Chromatographic separation of the platinum-group elements, gold, base metals and sulfur during degassing of a compacting and solidifying igneous crystal pile

NASA Astrophysics Data System (ADS)

Boudreau, A. E.; Meurer, W. P.

The major platinum-group elements (PGE) concentrations in layered intrusions are typically associated with zones in which the sulfide abundance begins to increase. In a number of layered intrusions, there is also a distinct stratigraphic separation in the peak concentrations of the PGE from those of the base metals, gold and sulfur through these zones. These stratigraphic ``offsets'' are characterized by a lower, typically S-poor, Pt- and Pd-enriched zone overlain by a zone enriched in the base metals, S and Au. The separations amount to a few decimeters to several tens of meters. In some instances, the high Pt and Pd concentrations are associated with trivial amounts of sulfide. Theoretical considerations suggest that these offsets can be modeled as chromatographic peaks that develop during an infiltration/reaction process. Using Pd as a typical PGE and Cu as a typical base metal, a numeric model is developed that illustrates how metal separations can develop in a vapor-refining zone as fluid evolved during solidification of a cumulus pile leaches sulfide and redeposits it higher in the crystal pile. The solidification/degassing ore-element transport is coupled with a compaction model for the crystal pile. Solidification resulting from conductive cooling through the base of the compacting column leads to an increasing volatile concentration in the intercumulus liquid until it reaches fluid saturation. Separation and upward migration of this fluid lead to an upward-migrating zone of increasingly higher bulk water contents as water degassed from underlying cumulates enriches overlying, fluid-undersaturated interstitial liquids. Sulfide is resorbed from the degassing regions and is reprecipitated in these vapor-undersaturated interstitial liquids, producing a zone of relatively high modal sulfide that also migrates upward with time. Owing to its strong preference for sulfide, Pd is not significantly mobile until all sulfide is resorbed. The result is a zone of increasing PGE enrichment that follows the sulfide resorption front as solidification/degassing continues. In detail, the highest Pd concentrations occur stratigraphically below the peak in S and base metals. The high Pd/S ratio mimics values conventionally interpreted as the result of high (silicate liquid)/(sulfide liquid) mass ratios (``R'' values). However, in this case, the high Pd/S ratio is the result of a chromatographic/reaction front enrichment and not a magmatic sulfide-saturation event.

Dueling Mechanisms for Dry Zones around Frozen Droplets

NASA Astrophysics Data System (ADS)

Bisbano, Caitlin; Nath, Saurabh; Boreyko, Jonathan

2016-11-01

Ice acts as a local humidity sink, due to its depressed saturation pressure relative to that of supercooled water. Hygroscopic chemicals typically exhibit annular dry zones of inhibited condensation; however, dry zones do not tend to form around ice because of inter-droplet frost growth to nearby liquid droplets that have already condensed on the chilled surface. Here, we use a humidity chamber with an embedded Peltier stage to initially suppress the growth of condensation on a chilled surface containing a single frozen droplet, in order to characterize the dry zone around ice for the first time. The length of the dry zone was observed to vary by at least two orders of magnitude as a function of surface temperature, ambient humidity, and the size of the frozen droplet. The surface temperature and ambient humidity govern the magnitudes of the in-plane and out-of-plane gradients in vapor pressure, while the size of the frozen droplet effects the local thickness of the concentration boundary layer. We develop an analytical model that reveals two different types of dry zones are possible: one in which nucleation is inhibited and one where the net growth of condensate is inhibited. Finally, a phase map was developed to predict the parameter space in which nucleation dry zones versus flux dry zones are dominant.

Ore deposits and epithermal evidences associated with intra-magmatic faults at Aïn El Araâr-Oued Belif ring structure (NW of Tunisia)

NASA Astrophysics Data System (ADS)

Aissa, Wiem Ben; Aissa, Lassaâd Ben; Amara, Abdesslem Ben Haj; Tlig, Said; Alouani, Rabah

2017-03-01

Hydrothermal ore deposits at Aïn El Araâr-Oued Belif location are classified as epithermal deposits type. The ore bodies are hosted by upper Turonian (8-9 M.y) volcanic rhyodacitic complex. Polymetallic sulfide orebodies are mainly concentrated within intra-magmatic faults. Petrographic, XRD, and TEM-STEM investigations revealed that ore minerals are essentially, arsenopyrite, pyrite, chalcopyrite, pyrrhotite, hematite, goethite and magnetite with Au, Ag and Pt trace metals. Gangue minerals are mainly adularia, quartz, sericite, alunite, tridymite, chlorite, phlogopite and smectite. Epithermal alteration is well zoned with four successive characteristic zones: (1) zone of quartz-adularia-sericite and rare alunite; (2) zone of kaolinite and plagioclase albitization; (3) intermediate zone of illite-sericite; (4) sapropelic alteration type zone of chlorite-smectite and rare illite. This can be interpreted as a telescoping of two different acidity epithermal phases; low sulfidation (adularia-sericite) and high sulfidation (quartz-alunite), separated in time or due to a gradual increase of fluids acidity and oxicity within the same mineralization phase. Brecciated macroscopic facies with fragments hosting quartz-adularia-sericite minerals (low-sulfidation phase) without alunite, support the last hypothesis. Geodynamic context and mineral alteration patterns are closely similar to those of Maria Josefa gold mine at SE of Spain which exhibit a volcanic-hosted epithermal ore deposit in a similar vein system, within rhyolitic ignimbrites, altered to an argillic assemblage (illite-sericite abundant and subordinate kaolinite) that grades outwards into propylitic alteration (Sanger-von Oepen et al. (1990)). Mineralogical and lithologic study undertaken in the volcanic host rock at Aïn El Araâr-Oued Belif reveals a typical epithermal low-sulfidation and high-sulfidation ore deposits with dominance of low-sulfidation. Host rocks in these systems range from silicic to intermediate for adularia-sericite type (low sulfidation) to rhyodacite for quartz-alunite type (high sulfidation).

Internal flow inside droplets within a concentrated emulsion during droplet rearrangement

NASA Astrophysics Data System (ADS)

Leong, Chia Min; Gai, Ya; Tang, Sindy K. Y.

2018-03-01

Droplet microfluidics, in which each droplet serves as a micro-reactor, has found widespread use in high-throughput biochemical screening applications. These droplets are often concentrated at various steps to form a concentrated emulsion. As part of a serial interrogation and sorting process, such concentrated emulsions are typically injected into a tapered channel leading to a constriction that fits one drop at a time for the probing of droplet content in a serial manner. The flow physics inside the droplets under these flow conditions are not well understood but are critical for predicting and controlling the mixing of reagents inside the droplets as reactors. Here we investigate the flow field inside droplets of a concentrated emulsion flowing through a tapered microchannel using micro-particle image velocimetry. The confining geometry of the channel forces the number of rows of drops to reduce by one at specific and uniformly spaced streamwise locations, which are referred to as droplet rearrangement zones. Within each rearrangement zone, the phase-averaged velocity results show that the motion of the droplets involved in the rearrangement process, also known as a T1 event, creates vortical structures inside themselves and their adjacent droplets. These flow structures increase the circulation inside droplets up to 2.5 times the circulation in droplets at the constriction. The structures weaken outside of the rearrangement zones suggesting that the flow patterns created by the T1 process are transient. The time scale of circulation is approximately the same as the time scale of a T1 event. Outside of the rearrangement zones, flow patterns in the droplets are determined by the relative velocity between the continuous and disperse phases.

Role of degassing of the Noril’sk nickel deposits in the Permian–Triassic mass extinction event

PubMed Central

Barnes, Stephen J.; Mungall, James E.

2017-01-01

The largest mass extinction event in Earth's history marks the boundary between the Permian and Triassic Periods at circa 252 Ma and has been linked with the eruption of the basaltic Siberian Traps large igneous province (SLIP). One of the kill mechanisms that has been suggested is a biogenic methane burst triggered by the release of vast amounts of nickel into the atmosphere. A proposed Ni source lies within the huge Noril’sk nickel ore deposits, which formed in magmatic conduits widely believed to have fed the eruption of the SLIP basalts. However, nickel is a nonvolatile element, assumed to be largely sequestered at depth in dense sulfide liquids that formed the orebodies, preventing its release into the atmosphere and oceans. Flotation of sulfide liquid droplets by surface attachment to gas bubbles has been suggested as a mechanism to overcome this problem and allow introduction of Ni into the atmosphere during eruption of the SLIP lavas. Here we use 2D and 3D X-ray imagery on Noril’sk nickel sulfide, combined with simple thermodynamic models, to show that the Noril’sk ores were degassing while they were forming. Consequent “bubble riding” by sulfide droplets, followed by degassing of the shallow, sulfide-saturated, and exceptionally volatile and Cl-rich SLIP lavas, permitted a massive release of nickel-rich volcanic gas and subsequent global dispersal of nickel released from this gas as aerosol particles. PMID:28223492

Light-Dependent Sulfide Oxidation in the Anoxic Zone of the Chesapeake Bay Can Be Explained by Small Populations of Phototrophic Bacteria

PubMed Central

Bennett, Alexa J.; Hanson, Thomas E.; Luther, George W.

2015-01-01

Microbial sulfide oxidation in aquatic environments is an important ecosystem process, as sulfide is potently toxic to aerobic organisms. Sulfide oxidation in anoxic waters can prevent the efflux of sulfide to aerobic water masses, thus mitigating toxicity. The contribution of phototrophic sulfide-oxidizing bacteria to anaerobic sulfide oxidation in the Chesapeake Bay and the redox chemistry of the stratified water column were investigated in the summers of 2011 to 2014. In 2011 and 2013, phototrophic sulfide-oxidizing bacteria closely related to Prosthecochloris species of the phylum Chlorobi were cultivated from waters sampled at and below the oxic-anoxic interface, where measured light penetration was sufficient to support populations of low-light-adapted photosynthetic bacteria. In 2012, 2013, and 2014, light-dependent sulfide loss was observed in freshly collected water column samples. In these samples, extremely low light levels caused 2- to 10-fold increases in the sulfide uptake rate over the sulfide uptake rate under dark conditions. An enrichment, CB11, dominated by Prosthecochloris species, oxidized sulfide with a Ks value of 11 μM and a Vmax value of 51 μM min−1 (mg protein−1). Using these kinetic values with in situ sulfide concentrations and light fluxes, we calculated that a small population of Chlorobi similar to those in enrichment CB11 can account for the observed anaerobic light-dependent sulfide consumption activity in natural water samples. We conclude that Chlorobi play a far larger role in the Chesapeake Bay than currently appreciated. This result has potential implications for coastal anoxic waters and expanding oxygen-minimum zones as they begin to impinge on the photic zone. PMID:26296727

As, Bi, Hg, S, Sb, Sn and Te geochemistry of the J-M Reef, Stillwater Complex, Montana: constraints on the origin of PGE-enriched sulfides in layered intrusions

USGS Publications Warehouse

Zientek, M.L.; Fries, T.L.; Vian, R.W.

1990-01-01

The J-M Reef is an interval of disseminated sulfides in the Lower Banded series of the Stillwater Complex that is enriched in the platinum group elements (PGE). Palladium and Pt occur in solid solution in base-metal sulfides and as discrete PGE minerals. PGE minerals include sulfides, tellurides, arsenides, antimonides, bismuthides, and alloys with Fe, Sn, Hg, and Au. Several subpopulations can be delineated based on whole-rock chemical analyses for As, Bi, Cu, Hg, Pd, Pt, S, Sb and Te for samples collected from and adjacent to the J-M Reef. In general, samples from within the reef have higher Pt/Cu, Pd/Cu, Pd/Pt, Te/Bi and S/(Te+Bi) than those collected adjacent to the reef. Vertical compositional profiles through the reef suggest that Pd/Cu and Pt/Cu decrease systematically upsection from mineralized to barren rock. The majority of samples with elevated As, Sb and Hg occur adjacent to the reef, not within it, or in sulfide-poor rocks. Neither magma mixing nor fluid migration models readily explain why the minor quantities of sulfide minerals immediately adjacent to the sulfide-enriched layers that form the J-M Reef have different element ratios than the sulfide minerals that form the reef. If all the sulfides formed by exsolution during a magma mixing event and the modal proportion of sulfide now in the rocks are simply the result of mechanical processes that concentrated the sulfides into some layers and not others, then the composition of the sulfide would not be expected to be different. Models that rely upon ascending liquids or fluids are incompatible with the presence of sulfides that are not enriched in PGE immediately below or interlayered with the PGE-enriched sulfides layers. PGE-enriched postcumulus fluids should have reacted to the same extent with sulfides immediately outside the reef as within the reef. One explanation is that some of the sulfide minerals in the rocks outside the reef have a different origin than those that make up the reef. The sulfide minerals that form the reef may represent a cumulus sulfide phase that formed as the result of a magma-mixing event, achieved its high PGE contents at that time, and accumulated to form a layer. The rocks outside the reef may contain a large proportion of postcumulus sulfide minerals that formed as the last dregs of intercumulus liquids trapped in the interstitial spaces between the cumulus grains reached sulfur saturation and exsolved a sulfide liquid or precipitated a sulfide mineral. The PGE contents of these sulfides would be expected to be less than the cumulus sulfides that form the reef since they would have equilibrated with a much smaller volume of silicate liquid. Another explanation is that some of the sulfide droplets that formed as a result of the mixing event were trapped as inclusions in silicate minerals soon after they formed. This would reduce the amount of magma these sulfide droplets could equilibrate with and effectively reduce their PGE tenor. ?? 1990.

Competition for sulfide among colorless and purple sulfur bacteria in cyanobacterial mats

NASA Technical Reports Server (NTRS)

Jorgensen, B. B.; Des Marais, D. J.

1986-01-01

The vertical zonation of light, O2, H2S, pH, and sulfur bacteria was studied in two benthic cyanobacterial mats from hypersaline ponds at Guerrero Negro, Baja California, Mexico. The physical-chemical gradients were analyzed in the upper few mm at < or = 100 micrometers spatial resolution by microelectrodes and by a fiber optic microprobe. In mats, where oxygen produced by photosynthesis diffused far below the depth of the photic zone, colorless sulfur bacteria (Beggiatoa sp.) were the dominant sulfide oxidizing organisms. In a mat, where the O2-H2S interface was close to the photic zone, but yet received no significant visible light, purple sulfur bacteria (Chromatium sp.) were the dominant sulfide oxidizers. Analysis of the spectral light distribution here showed that the penetration of only 1% of the incident near-IR light (800-900 nm) into the sulfide zone was sufficient for the mass development of Chromatium in a narrow band of 300 micromoles thickness. The balance between O2 and light penetration down into the sulfide zone thus determined in micro-scale which type of sulfur bacteria became dominant.

Hydrodynamics and PIV study in the impingement zone formed by a droplet train

NASA Astrophysics Data System (ADS)

Kanjirakat, Anoop; Sadr, Reza; Zhang, Taolue; Muthusamy, Jayaveera; Alvarado, Jorge; Texas A; M University at Qatar Collaboration; Texas A; M University College Station Collaboration

2016-11-01

Droplet impingement is encountered in numerous technical applications, such as ink jet printing, spray cooling, and fuel injection in internal combustion engines. Even though many studies in droplet impingement were conducted in past, not many have measured the near-wall velocities in the droplet impingement zone. With the goal of gaining a better understanding of the hydrodynamics in the impingement zone, well-controlled experiments are performed in combination with micro-PIV measurements and numerical simulations. Hydrodynamics of HFE-7100 droplets generated using a piezoelectric droplet generator, impinging on a pre-wetted surface is investigated. Micro-PIV studies in the high-velocity impingement zone are performed using one-micron meter fluorescent particles dispersed in HFE-7100 along with the double exposed images. Three-dimensional and 2D-axisymmetric numerical modeling for a transient droplet crown development is performed. The interface between the gas and the liquid is modeled using a Volume of Fluid (VOF) method. Numerical simulation results obtained are observed to be in good agreement with that of the experimental observations. Supported by National Priority Research Program (NPRP) of Qatar National Research Fund (QNRF), Grant No.: NPRP 6-1304-2-525.

On the existence of free and metal complexed sulfide in the Arabian Sea and its oxygen minimum zone

NASA Astrophysics Data System (ADS)

Theberge, Stephen M.; Luther, George W.; Farrenkopf, Anna M.

Free hydrogen sulfide was not detected in the oxygen minimum zone (OMZ) of the Arabian Sea during legs D1 (September 1992) and D3 (October-November 1992) of the Netherlands Indian Ocean Programme (NIOP). However, sulfide complexed to metals was detected by cathodic stripping square wave voltammetry at 2 nM or less throughout the water column. A slight increase in sulfide was measured in the OMZ relative to the surface waters and may be related to sulfur release from organic matter during decomposition. Sulfide complexes are of two general types at low concentrations of metal and sulfide. First, metals such as Mn, Fe, Co and Ni form complexes with bisulfide ion (HS -) that are kinetically labile to dissociation and are reactive. Second, metals such as Cu and Zn form multinuclear complexes with sulfide (S 2-) that are kinetically inert to dissociation; thus, they are less reactive than free (bi)sulfide and the labile metal bisulfide complexes. Zinc and copper sulfide complexes are important in allowing hydrogen sulfide to persist in seawater which contains measurable oxygen.

Influence of water mist on propagation and suppression of laminar premixed flame

NASA Astrophysics Data System (ADS)

Belyakov, Nikolay S.; Babushok, Valeri I.; Minaev, Sergei S.

2018-03-01

The combustion of premixed gas mixtures containing micro droplets of water was studied using one-dimensional approximation. The dependencies of the burning velocity and flammability limits on the initial conditions and on the properties of liquid droplets were analyzed. Effects of droplet size and concentration of added liquid were studied. It was demonstrated that the droplets with smaller diameters are more effective in reducing the flame velocity. For droplets vaporizing in the reaction zone, the burning velocity is independent of droplet size, and it depends only on the concentration of added liquid. With further increase of the droplet diameter the droplets are passing through the reaction zone with completion of vaporization in the combustion products. It was demonstrated that for droplets above a certain size there are two stable stationary modes of flame propagation with transition of hysteresis type. The critical conditions of the transition are due to the appearance of the temperature maximum at the flame front and the temperature gradient with heat losses from the reaction zone to the products, as a result of droplet vaporization passing through the reaction zone. The critical conditions are similar to the critical conditions of the classical flammability limits of flame with the thermal mechanism of flame propagation. The maximum decrease in the burning velocity and decrease in the combustion temperature at the critical turning point corresponds to predictions of the classical theories of flammability limits of Zel'dovich and Spalding. The stability analysis of stationary modes of flame propagation in the presence of water mist showed the lack of oscillatory processes in the frames of the assumed model.

Inhalation of expiratory droplets in aircraft cabins.

PubMed

Gupta, J K; Lin, C-H; Chen, Q

2011-08-01

Airliner cabins have high occupant density and long exposure time, so the risk of airborne infection transmission could be high if one or more passengers are infected with an airborne infectious disease. The droplets exhaled by an infected passenger may contain infectious agents. This study developed a method to predict the amount of expiratory droplets inhaled by the passengers in an airliner cabin for any flight duration. The spatial and temporal distribution of expiratory droplets for the first 3 min after the exhalation from the index passenger was obtained using the computational fluid dynamics simulations. The perfectly mixed model was used for beyond 3 min after the exhalation. For multiple exhalations, the droplet concentration in a zone can be obtained by adding the droplet concentrations for all the exhalations until the current time with a time shift via the superposition method. These methods were used to determine the amount of droplets inhaled by the susceptible passengers over a 4-h flight under three common scenarios. The method, if coupled with information on the viability and the amount of infectious agent in the droplet, can aid in evaluating the infection risk. The distribution of the infectious agents contained in the expiratory droplets of an infected occupant in an indoor environment is transient and non-uniform. The risk of infection can thus vary with time and space. The investigations developed methods to predict the spatial and temporal distribution of expiratory droplets, and the inhalation of these droplets in an aircraft cabin. The methods can be used in other indoor environments to assess the relative risk of infection in different zones, and suitable measures to control the spread of infection can be adopted. Appropriate treatment can be implemented for the zone identified as high-risk zones. © 2011 John Wiley & Sons A/S.

Sulfur isotope patterns of iron sulfide and barite nodules in the Upper Cretaceous Chalk of England and their regional significance in the origin of coloured chalks

NASA Astrophysics Data System (ADS)

Jeans, Christopher V.; Turchyn, Alexandra V.; Hu, Xu-Fang

2016-06-01

The relationship between the development of iron sulfide and barite nodules in the Cenomanian Chalk of England and the presence of a red hematitic pigment has been investigated using sulfur isotopes. In southern England where red and pink chalks are absent, iron sulfide nodules are widespread. Two typical large iron sulfide nodules exhibit δ34S ranging from -48.6‰ at their core to -32.6‰ at their outer margins. In eastern England, where red and pink chalks occur in three main bands, there is an antipathetic relationship between the coloured chalks and the occurrence of iron sulfide or barite nodules. Here iron sulfide, or its oxidised remnants, are restricted to two situations: (1) in association with hard grounds that developed originally in chalks that contained the hematite pigment or its postulated precursor FeOH3, or (2) in regional sulfidization zones that cut across the stratigraphy. In the Cenomanian Chalk exposed in the cliffs at Speeton, Yorkshire, pyrite and marcasite (both iron sulfide) nodules range in δ34S from -34.7‰ to +40.0‰. In the lower part of the section δ34S vary from -34.8‰ to +7.8‰, a single barite nodule has δ34S between +26.9‰ and +29.9‰. In the middle part of the section δ34S ranges from +23.8‰ to +40.0‰. In the sulfidization zones that cut across the Cenomanian Chalk of Lincolnshire the iron sulfide nodules are typically heavily weathered but these may contain patches of unoxidised pyrite. In these zones, δ34S ranges from -32.9‰ to +7.9‰. The cross-cutting zones of sulfidization in eastern England are linked to three basement faults - the Flamborough Head Fault Zone, the Caistor Fault and the postulated Wash Line of Jeans (1980) - that have affected the deposition of the Chalk. It is argued that these faults have been both the conduits by which allochthonous fluids - rich in hydrogen sulfide/sulfate, hydrocarbons and possibly charged with sulfate-reducing bacteria - have penetrated the Cenomanian Chalk as the result of movement during the Late Cretaceous or Cenozoic. These invasive fluids are associated with (1) the reduction of the red hematite pigment or its praecursor, (2) the subsequent development of both iron sulfides and barite, and (3) the loss of overpressure in the Cenomanian Chalk and its late diagenetic hardening by anoxic cementation. Evidence is reviewed for the origin of the red hematite pigment of the coloured chalks and for the iron involved in the development of iron sulfides, a hydrothermal or volcanogenic origin is favoured.

30 CFR 250.808 - Hydrogen sulfide.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 30 Mineral Resources 2 2013-07-01 2013-07-01 false Hydrogen sulfide. 250.808 Section 250.808 Mineral Resources BUREAU OF SAFETY AND ENVIRONMENTAL ENFORCEMENT, DEPARTMENT OF THE INTERIOR OFFSHORE OIL... § 250.808 Hydrogen sulfide. Production operations in zones known to contain hydrogen sulfide (H2S) or in...

30 CFR 250.808 - Hydrogen sulfide.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 30 Mineral Resources 2 2014-07-01 2014-07-01 false Hydrogen sulfide. 250.808 Section 250.808 Mineral Resources BUREAU OF SAFETY AND ENVIRONMENTAL ENFORCEMENT, DEPARTMENT OF THE INTERIOR OFFSHORE OIL... § 250.808 Hydrogen sulfide. Production operations in zones known to contain hydrogen sulfide (H2S) or in...

30 CFR 250.808 - Hydrogen sulfide.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 30 Mineral Resources 2 2012-07-01 2012-07-01 false Hydrogen sulfide. 250.808 Section 250.808 Mineral Resources BUREAU OF SAFETY AND ENVIRONMENTAL ENFORCEMENT, DEPARTMENT OF THE INTERIOR OFFSHORE OIL... § 250.808 Hydrogen sulfide. Production operations in zones known to contain hydrogen sulfide (H2S) or in...

Method and apparatus for electrostatically sorting biological cells

DOEpatents

Merrill, John T.

1982-01-01

An improved method of sorting biological cells in a conventional cell sorter apparatus includes generating a fluid jet containing cells to be sorted, measuring the distance between the centers of adjacent droplets in a zone thereof defined at the point where the fluid jet separates into descrete droplets, setting the distance between the center of a droplet in said separation zone and the position along said fluid jet at which the cell is optically sensed for specific characteristics to be an integral multiple of said center-to-center distance, and disabling a charger from electrically charging a specific droplet if a cell is detected by the optical sensor in a position wherein it will be in the neck area between droplets during droplet formation rather than within a predetermined distance from the droplet center.

Compositions and microstructures of CB sulfides: Implications for the thermal history of the CB chondrite parent body

NASA Astrophysics Data System (ADS)

Srinivasan, Poorna; Jones, Rhian H.; Brearley, Adrian J.

2017-10-01

We studied textures and compositions of sulfide inclusions in unzoned Fe,Ni metal particles within CBa Gujba, CBa Weatherford, CBb HH 237, and CBb QUE 94411 in order to constrain formation conditions and secondary thermal histories on the CB parent body. Unzoned metal particles in all four chondrites have very similar metal and sulfide compositions. Metal particles contain different types of sulfides, which we categorize as: homogeneous low-Cr sulfides composed of troilite, troilite-containing exsolved daubreelite lamellae, arcuate sulfides that occur along metal grain boundaries, and shock-melted sulfides composed of a mixture of troilite and Fe, Ni metal. Our model for formation proposes that the unzoned metal particles were initially metal droplets that formed from splashing by a partially molten impacting body. Sulfide inclusions later formed as a result of precipitation of excess S from solid metal at low temperatures, either during single stage cooling or during a reheating event by impacts. Sulfides containing exsolution lamellae record temperatures of ≪600 °C, and irregular Fe-FeS intergrowth textures suggest localized shock melting, both of which are indicative of heterogeneous heating by impact processes on the CB parent body. Our study shows that CBa and CBb chondrites formed in a similar environment, and also experienced similar secondary impact processing.

Cu, Fe, and Zn Isotope Variations Within a High-Temperature Mid-Ocean Ridge Sulfide Structure

NASA Astrophysics Data System (ADS)

Ewing, S. M.; Nelson, B. K.; Kelley, D. S.; Nielsen, D. C.

2006-12-01

Hydrothermal processes at mid-ocean ridges play an important role in controlling the transition metal budget of seawater and the crust through which it circulates. Preliminary work has shown stable metal isotope variations accompany these processes. We report Cu, Zn, and Fe isotope analyses of transects through a high temperature sulfide structure ("Fin") collected during the 1998 Edifice Rex Sulfide Recovery Project. We analyzed two horizontal transects through the sulfide edifice, from inner conduit to outer surface. Transects A and F are 9 and 6 cm in length, respectively. Each displays radially zoned mineralogy progressing from a chalcopyrite (ccp) zone through zones of zinc sulfide, pyrite-anhydrite (pyr-anh) matrix, zinc sulfide-anhydrite (zns-anh) matrix, to an outer well-cemented silica (Si) zone. Additional ccp and pyr-anh zones appear in transect A resulting from a smaller breakout conduit. In transect A, Cu displays the most isotopic variation, with little variation in Fe and Zn isotopes. From the inner ccp zone outward, the Cu isotope profile shows a 0.4‰ (±0.05‰ 2σ) increase in the first pyr-anh zone over the coarse-grained ccp zone. The δ65Cu drops by 0.6‰ in the secondary ccp zone and recovers to values of the innermost wall in the following zone where it is constant until the outermost portion of the Si rich zone, which shows a 1.3‰ increase over inner zone values. The Zn isotope profile has a total variation of 0.27‰ (±0.05‰ 2σ), with a 0.2‰ increase in the first pyr- anh zone followed by a .27‰ decrease in the adjacent zone, and recovering to its heaviest values in the second pyr-anh zone. The Zn profile lacks any significant increase of the δ^{64}Zn in the outermost zones. The Fe isotope profile shows very little variation across the chimney wall, but does have a sharp 0.7‰ (±0.1‰ 2σ) increase in the δ56Fe in the well-cemented Si rich zone. In transect F, the Cu isotope profile again shows the most variation, but displays a more pronounced jump of 1.3‰ at the zinc sulfide boundary and no obvious increase of the δ65Cu in the Si rich zone. Similarly with Zn, there is a 0.35‰ increase of the δ^{64}Zn, but no outer wall increase. Fe, on the other hand, has variation of the same order as transect A, and shows a 0.6‰ increase of the δ56Fe in both the zns-anh and Si rich zones. These profiles are likely the result of a combination of diffusion and advection processes, fluid mineral equilibria, and mineral-mineral equilibria. High δ values of the outer zones likely reflect oxidation reactions with seawater. Processes responsible for isotopic variations within interior zones of the structure are ambiguous. Kinetic effects and biological activity may play a role, as Zn, which is not redox sensitive and only minimally coordination sensitive, has profiles that are qualitatively similar to Cu and Fe, but less analytically pronounced. Our findings are within the range of other published results, and further illustrate such measurable metal isotope variation exists not only on the vent field scale among chimneys, but systematically within chimney walls.

30 CFR 250.504 - Hydrogen sulfide.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 30 Mineral Resources 2 2010-07-01 2010-07-01 false Hydrogen sulfide. 250.504 Section 250.504... OPERATIONS IN THE OUTER CONTINENTAL SHELF Oil and Gas Well-Completion Operations § 250.504 Hydrogen sulfide. When a well-completion operation is conducted in zones known to contain hydrogen sulfide (H2S) or in...

30 CFR 250.604 - Hydrogen sulfide.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 30 Mineral Resources 2 2010-07-01 2010-07-01 false Hydrogen sulfide. 250.604 Section 250.604... OPERATIONS IN THE OUTER CONTINENTAL SHELF Oil and Gas Well-Workover Operations § 250.604 Hydrogen sulfide. When a well-workover operation is conducted in zones known to contain hydrogen sulfide (H2S) or in...

Improved method and apparatus for electrostatically sorting biological cells. [DOE patent application

DOEpatents

Merrill, J.T.

An improved method of sorting biological cells in a conventional cell sorter apparatus includes generating a fluid jet containing cells to be sorted, measuring the distance between the centers of adjacent droplets in a zone thereof defined at the point where the fluid jet separates into descrete droplets, setting the distance between the center of a droplet in said separation zone and the position along said fluid jet at which the cell is optically sensed for specific characteristics to be an integral multiple of said center-to-center distance, and disabling a charger from electrically charging a specific droplet if a cell is detected by the optical sensor in a position wherein it will be in the neck area between droplets during droplet formation rather than within a predetermined distance from the droplet center.

Sulfur cycling in an iron oxide-dominated, dynamic marine depositional system: The Argentine continental margin

NASA Astrophysics Data System (ADS)

Riedinger, Natascha; Brunner, Benjamin; Krastel, Sebastian; Arnold, Gail L.; Wehrmann, Laura M.; Formolo, Michael J.; Beck, Antje; Bates, Steven M.; Henkel, Susann; Kasten, Sabine; Lyons, Timothy W.

2017-05-01

The interplay between sediment deposition patterns, organic matter type and the quantity and quality of reactive mineral phases determines the accumulation, speciation and isotope composition of pore water and solid phase sulfur constituents in marine sediments. Here, we present the sulfur geochemistry of siliciclastic sediments from two sites along the Argentine continental slope—a system characterized by dynamic deposition and reworking, which result in non-steady state conditions. The two investigated sites have different depositional histories but have in common that reactive iron phases are abundant and that organic matter is refractory—conditions that result in low organoclastic sulfate reduction rates. Deposition of reworked, isotopically light pyrite and sulfurized organic matter appear to be important contributors to the sulfur inventory, with only minor addition of pyrite from organoclastic sulfate reduction above the sulfate-methane transition (SMT). Pore-water sulfide is limited to a narrow zone at the SMT. The core of that zone is dominated by pyrite accumulation. Iron monosulfide and elemental sulfur accumulate above and below this zone. Iron monosulfide precipitation is driven by the reaction of low amounts of hydrogen sulfide with ferrous iron and is in competition with the oxidation of sulfide by iron (oxyhydr)oxides to form elemental sulfur. The intervals marked by precipitation of intermediate sulfur phases at the margin of the zone with free sulfide are bordered by two distinct peaks in total organic sulfur. Organic matter sulfurization appears to precede pyrite formation in the iron-dominated margins of the sulfide zone, potentially linked to the presence of polysulfides formed by reaction between dissolved sulfide and elemental sulfur. Thus, SMTs can be hotspots for organic matter sulfurization in sulfide-limited, reactive iron-rich marine sedimentary systems. Furthermore, existence of elemental sulfur and iron monosulfide phases meters below the SMT demonstrates that in sulfide-limited systems metastable sulfur constituents are not readily converted to pyrite but can be buried to deeper sediment depths. Our data show that in non-steady state systems, redox zones do not occur in sequence but can reappear or proceed in inverse sequence throughout the sediment column, causing similar mineral alteration processes to occur at the same time at different sediment depths.

Slags in a Large Variation Range of Oxygen Potential Based on the Ion and Molecule Coexistence Theory

NASA Astrophysics Data System (ADS)

Yang, Xue-Min; Li, Jin-Yan; Zhang, Meng; Chai, Guo-Min; Zhang, Jian

2014-12-01

A thermodynamic model for predicting sulfide capacity of CaO-FeO-Fe2O3-Al2O3-P2O5 slags in a large variation range of oxygen potential corresponding to mass percentage of FetO from 1.88 to 55.50 pct, i.e., IMCT- model, has been developed by coupling with the deduced desulfurization mechanism of the slags based on the ion and molecule coexistence theory (IMCT). The developed IMCT- model has been verified through comparing the determined sulfide capacity after Ban-ya et al.[20] with the calculated by the developed IMCT- model and the calculated by the reported sulfide capacity models such as the KTH model. Mass percentage of FetO as 6.75 pct corresponding to the mass action concentration of FetO as 0.0637 or oxygen partial as 2.27 × 10-6 Pa is the criterion for distinguishing reducing and oxidizing zones for the slags. Sulfide capacity of the slags in reducing zone is controlled by reaction ability of CaO regardless of slag oxidization ability. However, sulfide capacity of the slags in oxidizing zone shows an obvious increase tendency with the increasing of slag oxidization ability. Sulfide capacity of the slags in reducing zone keeps almost constant with variation of the simplified complex basicity (pct CaO)/((pct Al2O3) + (pct P2O5)), or optical basicity, or the mass action concentration ratios of N FeO/ N CaO, , , and . Sulfide capacity of the slags in oxidizing zone shows an obvious increase with the increasing of the simplified complex basicity (pct CaO)/((pct Al2O3) + (pct P2O5)) or optical basicity, or the aforementioned mass action concentration ratios. Thus, the aforementioned mass action concentration ratios and the corresponding mass percentage ratios of various iron oxides to basic oxide CaO are recommended to represent the comprehensive effect of various iron oxides and basic oxide CaO on sulfide capacity of the slags.

A cryptic sulfur cycle driven by iron in the methane zone of marine sediment (Aarhus Bay, Denmark)

NASA Astrophysics Data System (ADS)

Holmkvist, Lars; Ferdelman, Timothy G.; Jørgensen, Bo Barker

2011-06-01

Sulfate reduction and sulfur-iron geochemistry were studied in 5-6 m deep gravity cores of Holocene mud from Aarhus Bay (Denmark). A goal was to understand whether sulfate is generated by re-oxidation of sulfide throughout the sulfate and methane zones, which might explain the abundance of active sulfate reducers deep below the main sulfate zone. Sulfate penetrated down to 130 cm where methane started to build up and where the concentration of free sulfide peaked at 5.5 mM. Below this sulfate-methane transition, sulfide diffused downwards to a sulfidization front at 520 cm depth, below which dissolved iron, Fe 2+, accumulated in the pore water. Sulfate reduction rates measured by 35S-tracer incubations in the sulfate zone were high due to high concentrations of reactive organic matter. Within the sulfate-methane transition, sulfate reduction was distinctly stimulated by the anaerobic oxidation of methane. In the methane zone below, sulfate remained at positive "background" concentrations of <0.5 mM down to the sulfidization front. Sulfate reduction decreased steeply to rates which at 300-500 cm depth were 0.2-1 pmol SO 42- cm -3 d -1, i.e., 4-5 orders of magnitude lower than rates measured near the sediment surface. The turn-over time of sulfate increased from 3 years at 12 cm depth to 100-1000 years down in the methane zone. Sulfate reduction in the methane zone accounted for only 0.1% of sulfate reduction in the entire sediment column and was apparently limited by the low pore water concentration of sulfate and the low availability of organic substrates. Amendment of the sediment with both sulfate and organic substrates immediately caused a 10- to 40-fold higher, "potential sulfate reduction" which showed that a physiologically intact community of sulfate reducing bacteria was present. The "background" sulfate concentration appears to be generated from the reaction of downwards diffusing sulfide with deeply buried Fe(III) species, such as poorly-reactive iron oxides or iron bound in reactive silicates. The oxidation of sulfide to sulfate in the sulfidic sediment may involve the formation of elemental sulfur and thiosulfate and their further disproportionation to sulfide and sulfate. The net reaction of sulfide and Fe(III) to form pyrite requires an additional oxidant, irrespective of the formation of sulfate. This could be CO 2 which is reduced with H 2 to methane. The methane subsequently diffuses upwards to become re-oxidized at the sulfate-methane transition and thereby removes excess reducing power and enables the formation of excess sulfate. We show here how the combination of these well-established sulfur-iron-carbon reactions may lead to the deep formation of sulfate and drive a cryptic sulfur cycle. The iron-rich post-glacial sediments underlying Holocene marine mud stimulate the strong sub-surface sulfide reoxidation observed in Aarhus Bay and are a result of the glacial to interglacial history of the Baltic Sea area. Yet, processes similar to the ones described here probably occur widespread in marine sediments, in particular along the ocean margins.

Experimentally Determined Phase Diagram for the Barium Sulfide-Copper(I) Sulfide System Above 873 K (600 °C)

NASA Astrophysics Data System (ADS)

Stinn, Caspar; Nose, Katsuhiro; Okabe, Toru; Allanore, Antoine

2017-12-01

The phase diagram of the barium sulfide-copper(I) sulfide system was investigated above 873 K (600 °C) using a custom-built differential thermal analysis (DTA) apparatus. The melting point of barium sulfide was determined utilizing a floating zone furnace. Four new compounds, Ba2Cu14S9, Ba2Cu2S3, Ba5Cu4S7, and Ba9Cu2S10, were identified through quench experiments analyzed with wavelength dispersive X-ray spectroscopy (WDS) and energy dispersive X-ray analysis (EDS). A miscibility gap was observed between 72 and 92 mol pct BaS using both DTA experiments and in situ melts observation in a floating zone furnace. A monotectic was observed at 94.5 mol pct BaS and 1288 K (1015 °C).

A multi-module microfluidic platform for continuous pre-concentration of water-soluble ions and separation of oil droplets from oil-in-water (O/W) emulsions using a DC-biased AC electrokinetic technique.

PubMed

Das, Dhiman; Phan, Dinh-Tuan; Zhao, Yugang; Kang, Yuejun; Chan, Vincent; Yang, Chun

2017-03-01

A novel continuous flow microfluidic platform specifically designed for environmental monitoring of O/W emulsions during an aftermath of oil spills is reported herein. Ionized polycyclic aromatic hydrocarbons which are toxic are readily released from crude oil to the surrounding water phase through the smaller oil droplets with enhanced surface area. Hence, a multi-module microfluidic device is fabricated to form ion enrichment zones in the water phase of O/W emulsions for the ease of detection and to separate micron-sized oil droplets from the O/W emulsions. Fluorescein ions in the water phase are used to simulate the presence of these toxic ions in the O/W emulsion. A DC-biased AC electric field is employed in both modules. In the first module, a nanoporous Nafion membrane is used for activating the concentration polarization effect on the fluorescein ions, resulting in the formation of stable ion enrichment zones in the water phase of the emulsion. A 35.6% amplification of the fluorescent signal is achieved in the ion enrichment zone; corresponding to 100% enrichment of the fluorescent dye concentration. In this module, the main inlet is split into two channels by using a Y-junction so that there are two outlets for the oil droplets. The second module located downstream of the first module consists of two oil droplet entrapment zones at two outlets. By switching on the appropriate electrodes, either one of the two oil droplet entrapment zones can be activated and the droplets can be blocked in the corresponding outlet. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Iron Isotope Fractionation in the Bushveld Igneous Complex Provide Insight into Fractional Crystallization

NASA Astrophysics Data System (ADS)

Rios, K. L.; Feineman, M. D.; Bybee, G. M.

2016-12-01

Dated at 2.056 Ga and encompassing an estimated 65,000 km2 in surface area and 650,000 km3 in volume the Bushveld Igneous Complex in South Africa contains the largest and most unique layered mafic intrusion in the world. It contains 80-90% of the world's minable platinum group elements. Scientists are interested in understanding the origin of this intrusion due to its massive size, unique assemblage of minerals, and strongly zoned stratigraphy. Iron isotopes may help us to understand the roles of partial mantle melting and fractional crystallization in magma genesis and differentiation. For example, it may be possible to determine what role fractional crystallization of oxides and sulfides played in the formation of the Rustenburg Layered Suite (RLS) by comparing δ56Fe in samples from the Lower, Critical, Main and Upper Zones. The use of MC-ICPMS has made it more routine to study the fractionation of stable iron isotopes in natural systems; however, this technique has only been applied in a few studies of the RLS, mostly restricted to the Upper Main and Upper Zones. In this study δ56Fe was determined in Upper Zone magnetite, Critical Zone chromitite and Critical Zone sulfides using MC-ICP-MS. Previous research has shown that early crystallizing mafic phases incorporate the lighter 54Fe isotope leaving a residual magma with a higher δ56Fe value. Therefore, if the Upper Zone magma represents a high-degree differentiate of the parental Bushveld magma, then magmas from the Upper Zone would be expected to have a higher δ56Fe than magmas contributing to the Lower, Critical and Main Zones. The results of this experiment were indeed consistent with this hypothesis. The δ56Fe values recorded for the three sample types were: magnetite 0.19 ±0.03‰; sulfides -0.45 ±0.03‰ to -0.81 ±0.03‰; and chromitite 0.03 ±0.05‰. The sulfides of the Critical Zone are isotopically lighter than would be predicted based on equilibrium sulfide-melt fractionation, if the parental melt of the Critical Zone were in equilibrium with previously published whole rock data for Upper Zone. This is consistent with interpretations of the Upper Zone as a high degree differentiate of the Bushveld Parental Magma.

30 CFR 250.808 - Hydrogen sulfide.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 30 Mineral Resources 2 2011-07-01 2011-07-01 false Hydrogen sulfide. 250.808 Section 250.808 Mineral Resources BUREAU OF OCEAN ENERGY MANAGEMENT, REGULATION, AND ENFORCEMENT, DEPARTMENT OF THE... Safety Systems § 250.808 Hydrogen sulfide. Production operations in zones known to contain hydrogen...

Dynamic Model of Basic Oxygen Steelmaking Process Based on Multi-zone Reaction Kinetics: Model Derivation and Validation

NASA Astrophysics Data System (ADS)

Rout, Bapin Kumar; Brooks, Geoff; Rhamdhani, M. Akbar; Li, Zushu; Schrama, Frank N. H.; Sun, Jianjun

2018-04-01

A multi-zone kinetic model coupled with a dynamic slag generation model was developed for the simulation of hot metal and slag composition during the basic oxygen furnace (BOF) operation. The three reaction zones (i) jet impact zone, (ii) slag-bulk metal zone, (iii) slag-metal-gas emulsion zone were considered for the calculation of overall refining kinetics. In the rate equations, the transient rate parameters were mathematically described as a function of process variables. A micro and macroscopic rate calculation methodology (micro-kinetics and macro-kinetics) were developed to estimate the total refining contributed by the recirculating metal droplets through the slag-metal emulsion zone. The micro-kinetics involves developing the rate equation for individual droplets in the emulsion. The mathematical models for the size distribution of initial droplets, kinetics of simultaneous refining of elements, the residence time in the emulsion, and dynamic interfacial area change were established in the micro-kinetic model. In the macro-kinetics calculation, a droplet generation model was employed and the total amount of refining by emulsion was calculated by summing the refining from the entire population of returning droplets. A dynamic FetO generation model based on oxygen mass balance was developed and coupled with the multi-zone kinetic model. The effect of post-combustion on the evolution of slag and metal composition was investigated. The model was applied to a 200-ton top blowing converter and the simulated value of metal and slag was found to be in good agreement with the measured data. The post-combustion ratio was found to be an important factor in controlling FetO content in the slag and the kinetics of Mn and P in a BOF process.

Localized sulfate-reducing zones in a coastal plain aquifer

USGS Publications Warehouse

Brown, C.J.; Coates, J.D.; Schoonen, M.A.A.

1999-01-01

High concentrations of dissolved iron in ground water of coastal plain or alluvial aquifers contribute to the biofouling of public supply wells for which treatment and remediation is costly. Many of these aquifers, however, contain zones in which microbial sulfate reduction and the associated precipitation of iron-sulfide minerals decreases iron mobility. The principal water-bearing aquifer (Magothy Aquifer of Cretaceous age) in Suffolk County, New York, contains localized sulfate-reducing zones in and near lignite deposits, which generally are associated with clay lenses. Microbial analyses of core samples amended with [14C]-acetate indicate that microbial sulfate reduction is the predominant terminal-electron-accepting process (TEAP) in poorly permeable, lignite-rich sediments at shallow depths and near the ground water divide. The sulfate-reducing zones are characterized by abundant lignite and iron-sulfide minerals, low concentrations of Fe(III) oxyhydroxides, and by proximity to clay lenses that contain pore water with relatively high concentrations of sulfate and dissolved organic carbon. The low permeability of these zones and, hence, the long residence time of ground water within them, permit the preservation and (or) allow the formation of iron-sulfide minerals, including pyrite and marcasite. Both sulfate-reducing bacteria (SRB) and iron-reducing bacteria (IRB) are present beneath and beyond the shallow sulfate-reducing zones. A unique Fe(III)-reducing organism, MD-612, was found in core sediments from a depth of 187 m near the southern shore of Long Island. The distribution of poorly permeable, lignite-rich, sulfate-reducing zones with decreased iron concentration is varied within the principal aquifer and accounts for the observed distribution of dissolved sulfate, iron, and iron sulfides in the aquifer. Locating such zones for the placement of production wells would be difficult, however, because these zones are of limited aerial extent.

Magnetic detection of underground pipe using timed-release marking droplets

DOEpatents

Powell, J.R.; Reich, M.

1996-12-17

A system and method are disclosed of detecting an underground pipe by injecting magnetic marking droplets into the underground pipe which coat the inside of the pipe and may be detected from aboveground by a magnetometer. The droplets include a non-adhesive cover which allows free flow through the pipe, with the cover being ablatable for the timed-release of a central core containing magnetic particles which adhere to the inside of the pipe and are detectable from aboveground. The rate of ablation of the droplet covers is selectively variable to control a free flowing incubation zone for the droplets and a subsequent deposition zone in which the magnetic particles are released for coating the pipe. 6 figs.

Reducing mode circulating fluid bed combustion

DOEpatents

Lin, Yung-Yi; Sadhukhan, Pasupati; Fraley, Lowell D.; Hsiao, Keh-Hsien

1986-01-01

A method for combustion of sulfur-containing fuel in a circulating fluid bed combustion system wherein the fuel is burned in a primary combustion zone under reducing conditions and sulfur captured as alkaline sulfide. The reducing gas formed is oxidized to combustion gas which is then separated from solids containing alkaline sulfide. The separated solids are then oxidized and recycled to the primary combustion zone.

Sulfide enrichment at an oceanic crust-mantle transition zone: Kane Megamullion (23°N, MAR)

NASA Astrophysics Data System (ADS)

Ciazela, Jakub; Koepke, Juergen; Dick, Henry J. B.; Botcharnikov, Roman; Muszynski, Andrzej; Lazarov, Marina; Schuth, Stephan; Pieterek, Bartosz; Kuhn, Thomas

2018-06-01

The Kane Megamullion oceanic core complex located along the Mid-Atlantic Ridge (23°30‧N, 45°20‧W) exposes lower crust and upper mantle directly on the ocean floor. We studied chalcophile elements and sulfides in the ultramafic and mafic rocks of the crust-mantle transition and the mantle underneath. We determined mineralogical and elemental composition and the Cu isotope composition of the respective sulfides along with the mineralogical and elemental composition of the respective serpentines. The rocks of the crust-mantle transition zone (i.e., plagioclase harzburgite, peridotite-gabbro contacts, and dunite) overlaid by troctolites are by one order of magnitude enriched in several chalcophile elements with respect to the spinel harzburgites of the mantle beneath. Whereas the range of Cu concentrations in spinel harzburgites is 7-69 ppm, the Cu concentrations are highly elevated in plagioclase harzburgites with a range of 90-209 ppm. The zones of the peridotite-gabbro contacts are even more enriched, exhibiting up to 305 ppm Cu and highly elevated concentrations of As, Zn, Ga, Sb and Tl. High Cu concentrations show pronounced correlation with bulk S concentrations at the crust-mantle transition zone implying an enrichment process in this horizon of the oceanic lithosphere. We interpret this enrichment as related to melt-mantle reaction, which is extensive in crust-mantle transition zones. In spite of the ubiquitous serpentinization of primary rocks, we found magmatic chalcopyrites [CuFeS2] as inclusions in plagioclase as well as associated with pentlandite [(Fe,Ni)9S8] and pyrrhotite [Fe1-xS] in polysulfide grains. These chalcopyrites show a primary magmatic δ65Cu signature ranging from -0.04 to +0.29 ‰. Other chalcopyrites have been dissolved during serpentinization. Due to the low temperature (<300 °C) of circulating fluids chalcophile metals from primary sulfides have not been mobilized and transported away but have been trapped in smaller secondary sulfides and hydroxides. Combined with the Cu deposits documented in the crust-mantle transition zones of various ophiolite complexes, our results indicate that the metal enrichment, increased sulfide modes, and potentially formation of small sulfide deposits could be expected globally along the petrological Moho.

Application of a long-lasting colloidal substrate with pH and hydrogen sulfide control capabilities to remediate TCE-contaminated groundwater.

PubMed

Sheu, Y T; Chen, S C; Chien, C C; Chen, C C; Kao, C M

2015-03-02

A long-lasting emulsified colloidal substrate (LECS) was developed for continuous carbon and nanoscale zero-valent iron (nZVI) release to remediate trichloroethylene (TCE)-contaminated groundwater under reductive dechlorinating conditions. The developed LECS contained nZVI, vegetable oil, surfactants (Simple Green™ and lecithin), molasses, lactate, and minerals. An emulsification study was performed to evaluate the globule droplet size and stability of LECS. The results show that a stable oil-in-water emulsion with uniformly small droplets (0.7 μm) was produced, which could continuously release the primary substrates. The emulsified solution could serve as the dispensing agent, and nZVI particles (with diameter 100-200 nm) were distributed in the emulsion evenly without aggregation. Microcosm results showed that the LECS caused a rapid increase in the total organic carbon concentration (up to 488 mg/L), and reductive dechlorination of TCE was significantly enhanced. Up to 99% of TCE (with initial concentration of 7.4 mg/L) was removed after 130 days of operation. Acidification was prevented by the production of hydroxide ion by the oxidation of nZVI. The formation of iron sulfide reduced the odor from produced hydrogen sulfide. Microbial analyses reveal that dechlorinating bacteria existed in soils, which might contribute to TCE dechlorination. Copyright © 2014 Elsevier B.V. All rights reserved.

Locus-specific microemulsion catalysts for sulfur mustard (HD) chemical warfare agent decontamination.

PubMed

Fallis, Ian A; Griffiths, Peter C; Cosgrove, Terence; Dreiss, Cecile A; Govan, Norman; Heenan, Richard K; Holden, Ian; Jenkins, Robert L; Mitchell, Stephen J; Notman, Stuart; Platts, Jamie A; Riches, James; Tatchell, Thomas

2009-07-22

The rates of catalytic oxidative decontamination of the chemical warfare agent (CWA) sulfur mustard (HD, bis(2-chlororethyl) sulfide) and a range (chloroethyl) sulfide simulants of variable lipophilicity have been examined using a hydrogen peroxide-based microemulsion system. SANS (small-angle neutron scattering), SAXS (small-angle X-ray scattering), PGSE-NMR (pulsed-gradient spin-echo NMR), fluorescence quenching, and electrospray mass spectroscopy (ESI-MS) were implemented to examine the distribution of HD, its simulants, and their oxidation/hydrolysis products in a model oil-in-water microemulsion. These measurements not only present a means of interpreting decontamination rates but also a rationale for the design of oxidation catalysts for these toxic materials. Here we show that by localizing manganese-Schiff base catalysts at the oil droplet-water interface or within the droplet core, a range of (chloroethyl) sulfides, including HD, spanning some 7 orders of octanol-water partition coefficient (K(ow)), may be oxidized with equal efficacy using dilute (5 wt. % of aqueous phase) hydrogen peroxide as a noncorrosive, environmentally benign oxidant (e.g., t(1/2) (HD) approximately 18 s, (2-chloroethyl phenyl sulfide, C(6)H(5)SCH(2)CH(2)Cl) approximately 15 s, (thiodiglycol, S(CH(2)CH(2)OH)(2)) approximately 19 s {20 degrees C}). Our observations demonstrate that by programming catalyst lipophilicity to colocalize catalyst and substrate, the inherent compartmentalization of the microemulsion can be exploited to achieve enhanced rates of reaction or to exert control over product selectivity. A combination of SANS, ESI-MS and fluorescence quenching measurements indicate that the enhanced catalytic activity is due to the locus of the catalyst and not a result of partial hydrolysis of the substrate.

Method of treating alkali metal sulfide and carbonate mixtures

DOEpatents

Kohl, Arthur L.; Rennick, Robert D.; Savinsky, Martin W.

1978-01-01

A method of removing and preferably recovering sulfur values from an alkali metal sulfide and carbonate mixture comprising the steps of (1) introducing the mixture in an aqueous medium into a first carbonation zone and reacting the mixture with a gas containing a major amount of CO.sub.2 and a minor amount of H.sub.2 S; (2) introducing the resultant product from step 1 into a stripping zone maintained at subatmospheric pressure, and contacting this product with steam to produce a gaseous mixture, comprising H.sub.2 S and water vapor, and a liquor of reduced sulfide content; (3) introducing the liquor of reduced sulfide content into a second carbonation zone, and reacting the liquor with substantially pure gaseous CO.sub.2 in an amount sufficient to precipitate bicarbonate crystals and produce an offgas containing CO.sub.2 and H.sub.2 S for use in step 1; (4) recovering the bicarbonate crystals from step 3, and thermally decomposing the crystals to produce an alkaline metal carbonate product and a substantially pure CO.sub.2 offgas for use in step 3.

Oil biodegradation. Water droplets in oil are microhabitats for microbial life.

PubMed

Meckenstock, Rainer U; von Netzer, Frederick; Stumpp, Christine; Lueders, Tillmann; Himmelberg, Anne M; Hertkorn, Norbert; Schmitt-Kopplin, Philipp; Harir, Mourad; Hosein, Riad; Haque, Shirin; Schulze-Makuch, Dirk

2014-08-08

Anaerobic microbial degradation of hydrocarbons, typically occurring at the oil-water transition zone, influences the quality of oil reservoirs. In Pitch Lake, Trinidad and Tobago--the world's largest asphalt lake--we found that microorganisms are metabolically active in minuscule water droplets (1 to 3 microliters) entrapped in oil. Pyrotag sequencing of individual droplet microbiomes revealed complex methanogenic microbial communities actively degrading the oil into a diverse range of metabolites, as shown by nuclear magnetic resonance and Fourier transform ion cyclotron resonance mass spectrometry. High salinity and water-stable isotopes of the droplets indicate a deep subsurface origin. The 13.5% water content and the large surface area of the droplets represent an underestimated potential for biodegradation of oil away from the oil-water transition zone. Copyright © 2014, American Association for the Advancement of Science.

Magnetic detection of underground pipe using timed-release marking droplets

DOEpatents

Powell, James R.; Reich, Morris

1996-12-17

A system 10 and method of detecting an underground pipe 12 injects magnetic marking droplets 16 into the underground pipe 12 which coat the inside of the pipe 12 and may be detected from aboveground by a magnetometer 28. The droplets 16 include a non-adhesive cover 32 which allows free flow thereof through the pipe 12, with the cover 32 being ablatable for the timed-release of a central core 30 containing magnetic particles 30a which adhere to the inside of the pipe 12 and are detectable from aboveground. The rate of ablation of the droplet covers 32 is selectively variable to control a free flowing incubation zone 12a for the droplets 16 and a subsequent deposition zone 12b in which the magnetic particles 30a are released for coating the pipe 12.

Theory of the Effects of Small Gravitational Levels on Droplet Gasification

NASA Technical Reports Server (NTRS)

Beitelmal, A.; Shaw, B. D.

1995-01-01

A mathematical model taking into account small (and constant) gravitational levels is developed for vaporization of an isolated liquid droplet suspended in a stagnant atmosphere. A goal of the present analysis is to see how small gravitational levels affect droplet gasification characteristics. Attention is focused upon determining the effects on gas-phase phenomena. The conservation equations arc normalized and nondimensionalized, and a small parameter that accounts for the effects of gravity is identified. This parameter is the square of the inverse of a Froude number based on the gravitational acceleration, the droplet radius, and a characteristic gas-phase velocity at the droplet surface. Asymptotic analyses are developed in terms of this parameter. In the analyses, different spatial regions are identified. Near a droplet, gravitational effects are negligible in the first approximation, and the flowfield is spherically symmetric to the leading order. Analysis shows, however, that outer zones exist where gravitational effects cannot be neglected; it is expected that a stagnation point will be present in an outer zone that is not present when gravity is totally absent. The leading order and higher-order differential equations for each zone are derived and solved. The solutions allow the effects of gravity on vaporization rates and temperature, velocity and species fields to be determined.

Method for reducing nitrogen oxides in combustion effluents

DOEpatents

Zauderer, Bert

2000-01-01

Method for reducing nitrogen oxides (NO.sub.x) in the gas stream from the combustion of fossil fuels is disclosed. In a narrow gas temperature zone, NO.sub.x is converted to nitrogen by reaction with urea or ammonia with negligible remaining ammonia and other reaction pollutants. Specially designed injectors are used to introduce air atomized water droplets containing dissolved urea or ammonia into the gaseous combustion products in a manner that widely disperses the droplets exclusively in the optimum reaction temperature zone. The injector operates in a manner that forms droplet of a size that results in their vaporization exclusively in this optimum NO.sub.x -urea/ammonia reaction temperature zone. Also disclosed is a design of a system to effectively accomplish this injection.

Tracing sources of crustal contamination using multiple S and Fe isotopes in the Hart komatiite-associated Ni-Cu-PGE sulfide deposit, Abitibi greenstone belt, Ontario, Canada

NASA Astrophysics Data System (ADS)

Hiebert, R. S.; Bekker, A.; Houlé, M. G.; Wing, B. A.; Rouxel, O. J.

2016-10-01

Assimilation by mafic to ultramafic magmas of sulfur-bearing country rocks is considered an important contributing factor to reach sulfide saturation and form magmatic Ni-Cu-platinum group element (PGE) sulfide deposits. Sulfur-bearing sedimentary rocks in the Archean are generally characterized by mass-independent fractionation of sulfur isotopes that is a result of atmospheric photochemical reactions, which produces isotopically distinct pools of sulfur. Likewise, low-temperature processing of iron, through biological and abiotic redox cycling, produces a range of Fe isotope values in Archean sedimentary rocks that is distinct from the range of the mantle and magmatic Fe isotope values. Both of these signals can be used to identify potential country rock assimilants and their contribution to magmatic sulfide deposits. We use multiple S and Fe isotopes to characterize the composition of the potential iron and sulfur sources for the sulfide liquids that formed the Hart deposit in the Shaw Dome area within the Abitibi greenstone belt in Ontario (Canada). The Hart deposit is composed of two zones with komatiite-associated Ni-Cu-PGE mineralization; the main zone consists of a massive sulfide deposit at the base of the basal flow in the komatiite sequence, whereas the eastern extension consists of a semi-massive sulfide zone located 12 to 25 m above the base of the second flow in the komatiite sequence. Low δ56Fe values and non-zero δ34S and Δ33S values of the komatiitic rocks and associated mineralization at the Hart deposit is best explained by mixing and isotope exchange with crustal materials, such as exhalite and graphitic argillite, rather than intrinsic fractionation within the komatiite. This approach allows tracing the extent of crustal contamination away from the deposit and the degree of mixing between the sulfide and komatiite melts. The exhalite and graphitic argillite were the dominant contaminants for the main zone of mineralization and the eastern extension zone of the Hart deposit, respectively. Critically, the extent of contamination, as revealed by multiple S and Fe isotope systematics, is greatest within the deposit and decreases away from it within the komatiite flow. This pattern points to a local source of crustal contamination for the mantle-derived komatiitic melt and a low degree of homogenization between the mineralization and the surrounding lava flow. Coupled S and Fe isotope patterns like those identified at the Hart deposit may provide a useful tool for assessing the potential of a komatiitic sequence to host Ni-Cu-(PGE).

Monodisperse, polymeric microspheres produced by irradiation of slowly thawing frozen drops

NASA Technical Reports Server (NTRS)

Rhim, Won-Kyu (Inventor); Hyson, Michael T. (Inventor); Chung, Sang-Kun (Inventor); Colvin, Michael S. (Inventor); Chang, Manchium (Inventor)

1991-01-01

Monodisperse, polymeric microspheres are formed by injecting uniformly shaped droplets of radiation polymerizable monomers, preferably a biocompatible monomer, having covalent binding sites such as hydroxyethylmethacrylate, into a zone, impressing a like charge on the droplet so that they mutually repel each other, spheroidizing the droplets within the zone and collecting the droplets in a pool of cryogenic liquid. As the droplets enter the liquid, they freeze into solid, glassy microspheres, which vaporizes a portion of the cryogenic liquid to form a layer. The like-charged microspheres, suspended within the layer, move to the edge of the vessel holding the pool, are discharged, fall and are collected. The collected microspheres are irradiated while frozen in the cryogenic liquid to form latent free radicals. The frozen microspheres are then slowly thawed to activate the free radicals which polymerize the monomer to form evenly-sized, evenly-shaped, monodisperse polymeric microspheres.

Extreme enrichment of Se, Te, PGE and Au in Cu sulfide microdroplets: evidence from LA-ICP-MS analysis of sulfides in the Skaergaard Intrusion, east Greenland

NASA Astrophysics Data System (ADS)

Holwell, David A.; Keays, Reid R.; McDonald, Iain; Williams, Megan R.

2015-12-01

The Platinova Reef, in the Skaergaard Intrusion, east Greenland, is an example of a magmatic Cu-PGE-Au sulfide deposit formed in the latter stages of magmatic differentiation. As is characteristic with such deposits, it contains a low volume of sulfide, displays peak metal offsets and is Cu rich but Ni poor. However, even for such deposits, the Platinova Reef contains extremely low volumes of sulfide and the highest Pd and Au tenor sulfides of any magmatic ore deposit. Here, we present the first LA-ICP-MS analyses of sulfide microdroplets from the Platinova Reef, which show that they have the highest Se concentrations (up to 1200 ppm) and lowest S/Se ratios (190-700) of any known magmatic sulfide deposit and have significant Te enrichment. In addition, where sulfide volume increases, there is a change from high Pd-tenor microdroplets trapped in situ to larger, low tenor sulfides. The transition between these two sulfide regimes is marked by sharp peaks in Au, and then Te concentration, followed by a wider peak in Se, which gradually decreases with height. Mineralogical evidence implies that there is no significant post-magmatic hydrothermal S loss and that the metal profiles are essentially a function of magmatic processes. We propose that to generate these extreme precious and semimetal contents, the sulfides must have formed from an anomalously metal-rich package of magma, possibly formed via the dissolution of a previously PGE-enriched sulfide. Other processes such as kinetic diffusion may have also occurred alongside this to produce the ultra-high tenors. The characteristic metal offset pattern observed is largely controlled by partitioning effects, producing offset peaks in the order Pt+Pd>Au>Te>Se>Cu that are entirely consistent with published D values. This study confirms that extreme enrichment in sulfide droplets can occur in closed-system layered intrusions in situ, but this will characteristically form ore deposits that are so low in sulfide that they do not conform to conventional deposit models for Cu-Ni-PGE sulfides which require very high R factors, and settling of sulfide liquids.

Magmatic structure and geochemistry of the Luanga Mafic-Ultramafic Complex: Further constraints for the PGE-mineralized magmatism in Carajás, Brazil

NASA Astrophysics Data System (ADS)

Mansur, Eduardo Teixeira; Ferreira Filho, Cesar Fonseca

2016-12-01

The Luanga Complex is part of the Serra Leste Magmatic Suite, a cluster of PGE-mineralized mafic-ultramafic intrusions located in the northeastern portion of the Carajás Mineral Province. The Luanga Complex is a medium-sized layered intrusion consisting of three main zones: i. the lower Ultramafic Zone comprising ultramafic adcumulates (peridotite), ii. the Transition Zone comprising interlayered ultramafic and mafic cumulates (harzburgite, orthopyroxenite and norite) and iii. the upper Mafic Zone comprising a monotonous sequence of mafic cumulates (norite) with minor orthopyroxenite layers. Several PGE-mineralized zones occur in the Transition Zone but the bulk of the PGE resources are hosted within a 10-50 meter thick interval of disseminated sulfides at the contact of the Ultramafic and Transition Zones. The compositional range of cumulus olivine (Fo78.9-86.4) is comparable to those reported for layered intrusions originated from moderate primitive parental magmas. Mantle normalized alteration-resistant trace element patterns of noritic rocks are fractionated, as indicated by relative enrichment in LREE and Th, with negative Nb and Ta anomalies, suggesting assimilation of older continental crust. Ni contents in olivine in the Luanga Complex (up to 7500 ppm) stand among the highest values reported in layered intrusions globally. The highest Ni contents in olivine in the Luanga Complex occur in distinctively PGE enriched (Pt + Pd > 1 ppm) intervals of the Transition Zone, in both sulfide-poor and sulfide bearing (1-3 vol.%) rocks. The origin of the PGE- and Ni-rich parental magma of the Luanga Complex is discussed considering the upgrading of magmas through dissolution of previously formed Ni-rich sulfide melts. Our results suggest that high Ni contents in olivine and/or orthopyroxene provide an additional exploration tool for Ni-PGE deposits, particularly useful for target selection in large magmatic provinces.

Repulsive Interaction of Sulfide Layers on Compressor Impeller Blades Remanufactured Through Plasma Spray Welding

NASA Astrophysics Data System (ADS)

Chang, Y.; Zhou, D.; Wang, Y. L.; Huang, H. H.

2016-12-01

This study investigated the repulsive interaction of sulfide layers on compressor impeller blades remanufactured through plasma spray welding (PSW). Sulfide layers on the blades made of FV(520)B steel were prepared through multifarious corrosion experiments, and PSW was utilized to remanufacture blade specimens. The specimens were evaluated through optical microscopy, scanning electron microscopy, energy-dispersive spectroscopy, 3D surface topography, x-ray diffraction, ImageJ software analysis, Vicker's micro-hardness test and tensile tests. Results showed a large number of sulfide inclusions in the fusion zone generated by sulfide layers embodied into the molten pool during PSW. These sulfide inclusions seriously degraded the mechanical performance of the blades remanufactured through PSW.

A comprehensive sulfur and oxygen isotope study of sulfur cycling in a shallow, hyper-euxinic meromictic lake

NASA Astrophysics Data System (ADS)

Gilhooly, William P.; Reinhard, Christopher T.; Lyons, Timothy W.

2016-09-01

Mahoney Lake is a permanently anoxic and sulfidic (euxinic) lake that has a dense plate of purple sulfur bacteria positioned at mid-water depth (∼7 m) where free sulfide intercepts the photic zone. We analyzed the isotopic composition of sulfate (δ34SSO4 and δ18OSO4), sulfide (δ34SH2S), and the water (δ18OH2O) to track the potentially coupled processes of dissimilatory sulfate reduction and phototrophic sulfide oxidation within an aquatic environment with extremely high sulfide concentrations (>30 mM). Large isotopic offsets observed between sulfate and sulfide within the monimolimnion (δ34SSO4-H2S = 51‰) and within pore waters along the oxic margin (δ34SSO4-H2S > 50‰) are consistent with sulfate reduction in both the sediments and the anoxic water column. Given the high sulfide concentrations of the lake, sulfur disproportionation is likely inoperable or limited to a very narrow zone in the chemocline, and therefore the large instantaneous fractionations are best explained by the microbial process of sulfate reduction. Pyrite extracted from the sediments reflects the isotopic composition of water column sulfide, suggesting that pyrite buried in the euxinic depocenter of the lake formed in the water column. The offset between sulfate and dissolved sulfide decreases at the chemocline (δ34SSO4-H2S = 37‰), a trend possibly explained by elevated sulfate reduction rates and inconsistent with appreciable disproportionation within this interval. Water column sulfate exhibits a linear response in δ18OSO4-δ34SSO4 and the slope of this relationship suggests relatively high sulfate reduction rates that appear to respond to seasonal changes in the productivity of purple sulfur bacteria. Although photosynthetic activity within the microbial plate influences the δ18OSO4-δ34SSO4 relationship, the biosignature for photosynthetic sulfur bacteria is restricted to the oxic/anoxic transition zone and is apparently minor relative to the more prevalent process of sulfate reduction operative throughout the light-deprived deeper anoxic water column and sediment pore waters.

Catalytic hydrotreating process

DOEpatents

Karr, Jr., Clarence; McCaskill, Kenneth B.

1978-01-01

Carbonaceous liquids boiling above about 300.degree. C such as tars, petroleum residuals, shale oils and coal-derived liquids are catalytically hydrotreated by introducing the carbonaceous liquid into a reaction zone at a temperature in the range of 300.degree. to 450.degree. C and a pressure in the range of 300 to 4000 psig for effecting contact between the carbonaceous liquid and a catalytic transition metal sulfide in the reaction zone as a layer on a hydrogen permeable transition metal substrate and then introducing hydrogen into the reaction zone by diffusing the hydrogen through the substrate to effect the hydrogenation of the carbonaceous liquid in the presence of the catalytic sulfide layer.

Volcanic sulfur degassing and the role of sulfides in controlling volcanic metal emissions

NASA Astrophysics Data System (ADS)

Edmonds, M.; Liu, E.

2017-12-01

Volcanoes emit prodigious quantities of sulfur and metals, their behaviour inextricably linked through pre-eruptive sulfide systematics and through degassing and speciation in the volcanic plume. Fundamental differences exist in the metal output of ocean island versus arc volcanoes, with volcanoes in Hawaii and Iceland outgassing large fluxes of gaseous and particulate chalcophiles; and arc volcanoes' plumes, in contrast, enriched in Zn, Cu, Tl and Pb. Metals and metalloids partition into a magmatic vapor phase from silicate melt at crustal pressures. Their abundance in magmatic vapor is influenced strongly by sulfide saturation and by the composition of the magmatic vapor phase, particularly with respect to chloride. These factors are highly dependent on tectonic setting. Metal outgassing is controlled by magma water content and redox: deep saturation in vapor and minimal sulfide in arc basalts yields metal-rich vapor; shallow degassing and resorption of sulfides feeds the metal content of volcanic gas in ocean islands. We present a detailed study of the sulfide systematics of the products of the 2014-2015 Holuhraun basaltic fissure eruption (Bárðarbunga volcanic system, Iceland) to illustrate the interplay between late water and sulfur outgassing; sulfide saturation and breakdown; and metal partitioning into a vapor phase. Sulfide globules, representing quenched droplets of an immiscible sulfide liquid, are preserved within erupted tephra. Sulfide globules in rapidly quenched tephra are preserved within both matrix glass and as inclusions in crystals. The stereologically-corrected 3D size distribution of sulfide globules ranges from <1 µm to 43 µm, with a modal diameter of 14-17 µm (by number). Sulfides are not uniformly distributed, and are commonly observed in association with either sub-millimetre-scale plagioclase-clinopyroxene-olivine glomerocrysts or with bubbles. Maximum dissolved sulfur concentrations of 1750 ppm in melt inclusions and matrix glass next to sulfides are consistent with empirical determinations of the sulfur content at sulfide saturation for MORB. The Holuhraun magma was sulfide-saturated on eruption and co-existed with an immiscible sulfide liquid throughout much of ol-cpx-plag crystallisation. Individual globules are associated with locally elevated dissolved sulfur concentrations, with concentration gradients away from sulfides preserved over distances of 10-40 µm from the melt-sulfide interfaces. We discuss the mechanisms of sulfide breakdown and its importance in supplying sulfur and metals to the atmosphere during eruption.

A simple device using magnetic transportation for droplet-based PCR.

PubMed

Ohashi, Tetsuo; Kuyama, Hiroki; Hanafusa, Nobuhiro; Togawa, Yoshiyuki

2007-10-01

The Polymerase chain reaction (PCR) was successfully and rapidly performed in a simple reaction device devoid of channels, pumps, valves, or other control elements used in conventional lab-on-a-chip technology. The basic concept of this device is the transportation of aqueous droplets containing hydrophilic magnetic beads in a flat-bottomed, tray-type reactor filled with silicone oil. The whole droplets sink to the bottom of the reactor because their specific gravity is greater than that of the silicone oil used here. The droplets follow the movement of a magnet located underneath the reactor. The notable advantage of the droplet-based PCR is the ability to switch rapidly the proposed reaction temperature by moving the droplets to the required temperature zones in the temperature gradient. The droplet-based reciprocative thermal cycling was performed by moving the droplets composed of PCR reaction mixture to the designated temperature zones on a linear temperature gradient from 50 degrees C to 94 degrees C generated on the flat bottom plate of the tray reactor. Using human-derived DNA containing the mitochondria genes as the amplification targets, the droplet-based PCR with magnetic reciprocative thermal cycling successfully provided the five PCR products ranging from 126 to 1,219 bp in 11 min with 30 cycles. More remarkably, the human genomic gene amplification targeting glyceraldehyde-3-phosphate dehydrogenase (GAPDH) gene was accomplished rapidly in 3.6 min with 40 cycles.

Chapter C: Hydrothermal Enrichment of Gallium in Zones of Advanced Argillic Alteration-Examples from the Paradise Peak and McDermitt Ore Deposits, Nevada

USGS Publications Warehouse

Rytuba, James J.; John, David A.; Foster, Andrea; Ludington, Steven D.; Kotlyar, Boris

2003-01-01

Gallium is produced as a byproduct from bauxite and zinc sulfide ores and rarely from primary Ga ores. High Ga contents (>60 ppm) can occur in zones of advanced argillic alteration consisting of alunite+kaolinite+quartz associated with quartz-alunite (high sulfidation Au-Ag) deposits. In a magmatic-hydrothermal environment, the zones of advanced argillic alteration associated with quartz-alunite (high sulfidation) Au-Ag deposits have the highest Ga contents (max 120 ppm). In these Au deposits, Ga is enriched in the zone of alunite+kaolinite alteration and depleted in the zone of quartz-rich alteration within acid-leached rocks. Peripheral zones of argillic alteration have Ga contents and Al/Ga ratios similar to those in unaltered volcanic rocks. The zones of advanced argillic alteration that formed in a steam-heated environment in association with hot-spring-type Hg-Au deposits are not Ga enriched, and residual silicified zones have very low Ga contents. The McDermitt Hg and Paradise Peak Au-Hg deposits, Nev., have zones of advanced argillic alteration that are Ga enriched. At the Paradise Peak Au-Hg deposits, Ga is enriched in the zone of alunite+jarosite alteration that formed in a magmatic-hydrothermal environment. Ga is depleted in the zone of opal+alunite alteration formed in a steam-heated environment, in residual silicified zones formed in a magmatic-hydrothermal environment, and in zones of supergene jarosite alteration. At the McDermitt Hg deposit, Ga is enriched in the zone of alunite+kaolinite alteration below the zone of adularia-quartz alteration that coincides with the Hg ore body. The spatial relation of Ga enrichment to alunite-kaolinite alteration suggests that formation in a magmatic-hydrothermal environment. X-ray-absorption spectra of Ga-enriched samples from the McDermitt Hg deposit are similar to that of gallium sulfate and support the association of Ga enrichment with alunite alteration.

A study of the trace sulfide mineral assemblages in the Stillwater Complex, Montana, USA

NASA Astrophysics Data System (ADS)

Aird, Hannah M.; Ferguson, Katherine M.; Lehrer, Malia L.; Boudreau, Alan E.

2017-03-01

The sulfide assemblages of the Stillwater Complex away from the well-studied ore zones are composed mainly of variable proportions of pyrrhotite, chalcopyrite, pentlandite, and ±pyrite. Excluding vein assemblages and those affected by greenschist and lower temperature alteration, the majority can be classified into two broad assemblages, defined here as pristine (multiphase, often globular in shape) or volatile-bearing (multiphase, high-temperature, volatile-rich minerals such as biotite, hornblende, or an unmixed calcite-dolomite assemblage). The volatile-bearing assemblages are mainly found within and below the J-M reef, where native copper and sphalerite are also locally present. Pristine sulfides are found throughout the stratigraphy. Both groups can be affected by apparent S loss in the form of pyrite being converted to magnetite and chalcopyrite to a Cu-Fe-oxide (delafossite), with little to no silicate alteration. An upward trend from pentlandite-rich to pyrrhotite-rich to pyrite-rich assemblages is observed in the footwall rocks in upper GN-I, and the same trend repeats from just below the reef and continues into the overlying N-II and GN-II. Modeling suggests that the sulfide Ni in the Peridotite Zone is largely controlled by silicate Ni. When taken together, observations are most readily explained by the remobilization of selected elements by a high-temperature fluid with the apparent loss of S > Cu > Ni. This could concentrate ore metals by vapor refining, eventually producing a platinum group element-enriched sulfide ore zone, such as the J-M reef.

Geology, ore facies and sulfur isotopes geochemistry of the Nudeh Besshi-type volcanogenic massive sulfide deposit, southwest Sabzevar basin, Iran

NASA Astrophysics Data System (ADS)

Maghfouri, Sajjad; Rastad, Ebrahim; Mousivand, Fardin; Lin, Ye; Zaw, Khin

2016-08-01

The southwest Sabzevar basin is placed in the southwestern part of a crustal domain known as the Sabzevar zone, at the north of Central Iranian microcontinent. This basin hosts abundant mineral deposits; particularly of the Mn exhalative and Cu-Zn volcanogenic massive sulfide (VMS) types. The evolution of this basin is governed by the Neo-tethys oceanic crust subduction beneath the Central Iranian microcontinent and by the resulting continental arc (Sanandaj-Sirjan) and back-arc (Sabzevar-Naien). This evolution followed two major sequences: (I) Lower Late Cretaceous Volcano-Sedimentary Sequence (LLCVSS), which is indicated by fine-grained siliciclastic sediments, gray basic coarse-grained different pyroclastic rocks and bimodal volcanism. During this stage, tuff-hosted stratiform, exhalative Mn deposits (Nudeh, Benesbourd, Ferizy and Goft), oxide Cu deposits (Garab and Ferizy) and Cu-Zn VMS (Nudeh, Chun and Lala) deposits formed. (II) Upper Late Cretaceous Sedimentary Dominated Sequence (ULCSS), including pelagic limestone, marly tuff, silty limestone and marl with minor andesitic tuff rocks. The economically most important Mn (Zakeri and Cheshmeh-sefid) deposits of Sabzevar zone occur within the marly tuff of this sequence. The Nudeh Cu-Zn volcanogenic massive sulfide (VMS) deposit is situated in the LLCVSS. The host-rock of deposits consists of alkali olivine basalt flow and tuffaceous silty sandstone. Mineralization occurs as stratiform blanket-like and tabular orebodies. Based on ore body structure, mineralogy, and ore fabric, we recognize three different ore facies in the Nudeh deposit: (1) a stringer zone, consisting of a discordant mineralization of sulfides forming a stockwork of sulfide-bearing quartz veins cutting the footwall volcano-sedimentary rocks; (2) a massive ore, consisting of massive replacement pyrite, chalcopyrite, sphalerite and Friedrichite with magnetite; (3) bedded ore, with laminated to disseminated pyrite, and chalcopyrite. Chloritization, silicification, sericitization and epidotization are the main wall-rock alterations; alteration intensity increases towards the stringer zone. The δ34S composition of the sulfides ranges from -1.5‰ to +3.69‰ with a general increase of δ34S ratios of massive ore facies to stockwork zone. The heavier values indicate that some of the sulfur was derived from seawater sulfate that was ultimately thermochemically reduced in deep hydrothermal reaction zones. Sulfur isotopes, along with sedimentological, textural, petrological, mineralogical, and geochemical evidences, suggest that this deposit should be classified as a Besshi-type VMS ore deposit.

The role of diallyl sulfides and dipropyl sulfides in the in vitro antimicrobial activity of the essential oil of garlic, Allium sativum L., and leek, Allium porrum L.

PubMed

Casella, Sergio; Leonardi, Michele; Melai, Bernardo; Fratini, Filippo; Pistelli, Luisa

2013-03-01

The in vitro antibacterial activity of essential oils (EOs) obtained from fresh bulbs of garlic, Allium sativum L., and leek, Allium porrum L. ( Alliaceae), was studied. A. sativum (garlic) EO showed a good antimicrobial activity against Staphylococcus aureus (inhibition zone 14.8 mm), Pseudomonas aeruginosa (inhibition zone 21.1 mm), and Escherichia coli (inhibition zone 11.0 mm), whereas the EO of A. porrum (leek) had no antimicrobial activity. The main constituents of the garlic EO were diallyl monosulfide, diallyl disulfide (DADS), diallyl trisulfide, and diallyl tetrasulfide. The EO of A. porrum was characterized by the presence of dipropyl disulfide (DPDS), dipropyl trisulfide, and dipropyl tetrasulfide. The antimicrobial activities of the DADS and DPDS were also studied. The results obtained suggest that the presence of the allyl group is fundamental for the antimicrobial activity of these sulfide derivatives when they are present in Allium or in other species (DADS inhibition zone on S. aureus 15.9 mm, P. aeruginosa 21.9 mm, E. coli 11.4 mm). Copyright © 2012 John Wiley & Sons, Ltd.

Metal sulfide initiators for metal oxide sorbent regeneration

DOEpatents

Turk, Brian S.; Gupta, Raghubir P.

2001-01-01

A process of regenerating a sulfided sorbent is provided. According to the process of the invention, a substantial portion of the energy necessary to initiate the regeneration reaction is provided by the combustion of a particulate metal sulfide additive. In using the particulate metal sulfide additive, the oxygen-containing gas used to regenerate the sulfided sorbent can be fed to the regeneration zone without heating or at a lower temperature than used in conventional processes wherein the regeneration reaction is initiated only by heating the oxygen-containing gas. The particulate metal sulfide additive is preferably an inexpensive mineral ore such as iron pyrite which does not adversely affect the regeneration or corresponding desulfurization reactions. The invention further includes a sorbent composition comprising the particulate metal sulfide additive in admixture with an active metal oxide sorbent capable of removing one or more sulfur compounds from a sulfur-containing gas stream.

Metal sulfide initiators for metal oxide sorbent regeneration

DOEpatents

Turk, Brian S.; Gupta, Raghubir P.

1999-01-01

A process of regenerating a sulfided sorbent is provided. According to the process of the invention, a substantial portion of the energy necessary to initiate the regeneration reaction is provided by the combustion of a particulate metal sulfide additive. In using the particulate metal sulfide additive, the oxygen-containing gas used to regenerate the sulfided sorbent can be fed to the regeneration zone without heating or at a lower temperature than used in conventional processes wherein the regeneration reaction is initiated only by heating the oxygen-containing. The particulate metal sulfide additive is preferably an inexpensive mineral ore such as iron pyrite which does not adversely affect the regeneration or corresponding desulfurization reactions. The invention further includes a sorbent composition comprising the particulate metal sulfide additive in admixture with an active metal oxide sorbent capable of removing one or more sulfur compounds from a sulfur-containing gas stream.

Metal sulfide initiators for metal oxide sorbent regeneration

DOEpatents

Turk, B.S.; Gupta, R.P.

1999-06-22

A process of regenerating a sulfided sorbent is provided. According to the process of the invention, a substantial portion of the energy necessary to initiate the regeneration reaction is provided by the combustion of a particulate metal sulfide additive. In using the particulate metal sulfide additive, the oxygen-containing gas used to regenerate the sulfided sorbent can be fed to the regeneration zone without heating or at a lower temperature than used in conventional processes wherein the regeneration reaction is initiated only by heating the oxygen-containing gas. The particulate metal sulfide additive is preferably an inexpensive mineral ore such as iron pyrite which does not adversely affect the regeneration or corresponding desulfurization reactions. The invention further includes a sorbent composition comprising the particulate metal sulfide additive in admixture with an active metal oxide sorbent capable of removing one or more sulfur compounds from a sulfur-containing gas stream. 1 fig.

Significance of archaeal nitrification in hypoxic waters of the Baltic Sea

NASA Astrophysics Data System (ADS)

Berg, C.; Vandieken, V.; Thamdrup, B.; Jürgens, K.

2012-04-01

Marine oxygen deficient areas are sites of important microbially mediated transformations within the nitrogen cycle. In the Baltic Sea, suboxic waters (oxygen below 5 μmol L-1) are considered to be a major nitrification zone within the water column. Recent evidence indicates that Archaea and not Bacteria are here the major ammonium oxidizers. In a Baltic Sea pelagic redoxcline, the crenarchaeotal subcluster GD2 which is related to the first cultivated ammonia-oxidizing crenarchaeote Candidatus Nitrosopumilus maritimus occurs in high abundance. However, little is known about its function and importance for the nitrogen and carbon cycles in oxygen minimum zones of the Baltic Sea. To approach this question, we sampled pelagic redoxclines in the Baltic Sea and determined the rates of nitrification and light-independent, inorganic carbon fixation via 15N and 14C isotope incubations, and quantified the abundance of putative ammonia-oxidizing Crenarchaeota by catalyzed reporter deposition fluorescence in situ hybridization (CARD-FISH). Nitrification was detectable throughout the suboxic zone with maxima of 122-131 nmol L-1 d-1 in layers with 1.8-7.1 μmol oxygen L-1 and ammonium below 0.2 μmol L-1. However, a nitrification potential was detected even in the upper anoxic, sulfidic zone. Crenarchaeotal abundance correlated strongly with nitrification rates and accounted for up to 24% of total prokaryotic cells. In contrast, the CO2 fixation in the suboxic zone was with 1.6-19.6 nmol L-1 d-1 rather low when compared to the subjacent anoxic, sulfidic waters. Our study indicates that ammonia oxidation in the suboxic zone of the Baltic Sea is mainly driven by Crenarchaeota. Their occurrence also in the anoxic, sulfidic water masses and the maintained nitrification potential point to special adaptations in this habitat with a potentially reduced sensitivity against hydrogen sulfide.

Sulfide petrology and highly siderophile element geochemistry of abyssal peridotites: a coupled study of samples from the Kane Fracture Zone (45°W 23°20N, MARK area, Atlantic Ocean)

NASA Astrophysics Data System (ADS)

Luguet, Ambre; Lorand, Jean-Pierre; Seyler, Monique

2003-04-01

Nineteen samples from the Kane Fracture Zone have been studied for sulfide mineralogy and analyzed for S, Se, platinum-group elements (PGE), and Au to assess the effect of refertilization processes on the PGE systematics of abyssal peridotites. The lherzolites show broadly chondritic PGE ratios and sulfide modal abundances (0.01 to 0.03 wt%) consistent with partial melting models, although the few pyroxene-hosted sulfide inclusions and in situ LAM-ICPMS analyses provide evidence for in situ mobilization of a Cu-Ni-rich sulfide partial melt. The most refractory harzburgites (spinel Cr# > 29) are almost devoid of magmatic sulfides and show uniformly low Pd N/Ir N (<0.5) for variable Pt N/Ir N (0.8 to 1.2). The compatible behavior of Os, Ir, Ru, Rh, and Pt reflects the presence of primary Os-Ru alloys. Some harzburgites displaying petrographic evidence for refertilization by incremental melts en route to the surface are enriched in sulfides (up to 0.1 wt%). Some of these sulfides are concentrated in small veinlets of clinopyroxene and spinel crystallized from these melts. These S-rich harzburgites display superchondritic Pd N/Ir N (up to 2.04) positively correlated with sulfide modal contents. It is concluded that refertilization processes resulting in precipitation of metasomatic sulfides may significantly enhance Pd concentrations of abyssal peridotites while marginally affecting Pt (Pt N/Ir N ≤ 1.24) and Rh (Rh N/Ir N ≤ 1.23) as well. When the effects of such processes are screened out, our database suggests PGE relative abundances in the DMM (Depleted MORB Mantle; MORB: Mid-Ocean Ridge) within the uncertainty range of chondritic meteorites, without evidence of superchondritic Pt/Ir and/or Rh/Ir ratios.

Effectiveness of a personalized ventilation system in reducing personal exposure against directly released simulated cough droplets.

PubMed

Pantelic, J; Tham, K W; Licina, D

2015-12-01

The inhalation intake fraction was used as an indicator to compare effects of desktop personalized ventilation and mixing ventilation on personal exposure to directly released simulated cough droplets. A cough machine was used to simulate cough release from the front, back, and side of a thermal manikin at distances between 1 and 4 m. Cough droplet concentration was measured with an aerosol spectrometer in the breathing zone of a thermal manikin. Particle image velocimetry was used to characterize the velocity field in the breathing zone. Desktop personalized ventilation substantially reduced the inhalation intake fraction compared to mixing ventilation for all investigated distances and orientations of the cough release. The results point out that the orientation between the cough source and the breathing zone of the exposed occupant is an important factor that substantially influences exposure. Exposure to cough droplets was reduced with increasing distance between cough source and exposed occupant. The results from this study show that an advanced air distribution system such as personalized ventilation reduces exposure to cough-released droplets better than commonly applied overhead mixing ventilation. This work can inform HVAC engineers about different aspects of air distribution systems’ performance and can serve as an aid in making critical design decisions. © 2015 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

A Bridge Too Far: Suppressing Frost Using an Out-of-Plane Dry Zone

NASA Astrophysics Data System (ADS)

Spohn, Corey; Ahmadi, Farzad; Nath, Saurabh; Boreyko, Jonathan

2017-11-01

It has recently been shown that ice can suppress the formation of any nearby condensation or frost on a substrate. However, these in-plane dry zones require the hygroscopic ice features to be placed on the same surface they are helping to keep dry, which makes it impossible to achieve complete anti-frosting. Here, we create an out-of-plane dry zone by holding two aluminum surfaces parallel to each other, where a uniform sheet of frost was grown on one surface to keep the other surface completely dry. The critical separation required to keep the test surface dry was found to be a function of the ambient supersaturation. We also show that inter-droplet ice bridging, now known to be a primary mechanism for in-plane frost growth, can be similarly extended to an out-of-plane configuration. We freeze a droplet on a hydrophobic surface and suspend a water droplet above it, such that an ice bridge grows toward the water droplet. More generally, these findings show that the recently discovered phenomena of dry zones and ice bridging can be extended to out-of-plane scenarios, which could lead to a better understanding of the behavior of mixed-phase systems. This work was supported by the National Science Foundation (CBET-1604272) and by the 3M Company (Non-Tenured Faculty Award).

Fe-C-S systematics in Bengal Fan sediments

NASA Astrophysics Data System (ADS)

Volvoikar, S. P.; Mazumdar, A.; Goswami, H.; Pujari, S.; Peketi, A.

2017-12-01

Global biogeochemical cycles of iron, carbon and sulfur (Fe-C-S) are interrelated. Sulfate reduction in marine sediments is the major factor controlling the cycling and burial of carbon, sulfur and iron. Organoclastic sulfate reduction and anaerobic oxidation of methane (AOM) are the two main processes responsible for sulfate reduction in marine sediments. The amount and reactivity of organic matter, iron minerals and concentrations of dissolved sulfide in pore water control the burial of iron sulfide and organic bound sulfur in marine sediments. Here we investigate the sulfidization process in a sediment core from the western part of upper Bay of Bengal fan characterized by efficient burial of organic matter with siliclastic load. A 30 m long sediment core (MD 161/29, Lat. 170 18.04' N, Long. 870 22.56' E, water depth: 2434m) was collected onboard Marion Dufresne (May, 2007) and studied for Fe-S speciation and organic matter characterization. Buffered dithionite extractable iron (FeD) varies from 0.71 to 1.43 wt % (Avg. 0.79 wt %). FeD represents Fe oxides and oxyhydroxides mainly, ferrihydrite, lepidocrocite, goethite and hematite. Acid volatile sulfur (AVS) varies from 0.0015 to 0.63 wt % (avg: 0.058 wt %), while chromium reducible sulfur (CRS) varies from 0.00047 to 0.29 wt % (avg. 0.054 wt %). Based on the vertical distribution patterns of FeD, AVS and CRS, the core is divided into three zones, the lower (3000 to 1833 cm), middle (1833 to 398 cm) and upper (398 cm to surface) zones. FeD shows higher concentration in the lower zone. FeTR (FeOx + FeD + FeCRS + FeAVS) also exhibit higher concentration in this zone, suggesting higher availability of reactive iron for iron sulfide precipitation. AVS, elemental sulfur, spikes of CRS and gradual enrichment of δ34SAVS and δ34SCRS with sharp peaks in-between is noted in the lower zone. The gradual enrichment of δ34SAVS and δ34SCRS is the outcome of late diagenetic pyritization with higher availability of sulfide (HS- and H2S) from AOM.

Immiscibility of Fluid Phases at Magmatic-hydrothermal Transition: Formation of Various PGE-sulfide Mineralization for Layered Basic Intrusions

NASA Astrophysics Data System (ADS)

Zhitova, L.; Borisenko, A.; Morgunov, K.; Zhukova, I.

2007-12-01

Fluid inclusions in quartz of the Merensky Reef (Bushveld Complex, South Africa) and the Chineisky Pluton (Transbaikal Region, Russia) were studied using cryometry, microthermometry, Raman-spectroscopy, LA ICP- MS, scanning electronic microscopy, gas-chromatography and isotopic methods. This allowed us to document some examples of fluid phase separation resulting in formation of different types of PGE-sulfide mineralization for layered basic intrusions. The results obtained show at least three generations of fluid separated from boiling residual alumosilicate intercumulus liquid of the Merensky Reef. The earliest fluid phase composed of homogenous high-dense methane and nitrogen gas mixture was identified in primary gas and co-existing anomalous fluid inclusions from symplectitic quartz. The next generation, heterophase fluid, composed of brines containing a free low-dense (mostly of carbon dioxide) gas phase, was observed in primary multiphase and coexisting gas-rich inclusions of miarolitic quartz crystals. The latest generation was also a heterophase fluid (low salinity water-salt solution and free low-dense methane gas phase) found in primary water-salt and syngenetic gas inclusions from peripheral zones of miarolitic quartz crystals. For the Chineisky Pluton reduced endocontact magmatogene fluids changed to oxidized low salinity hydrothermal fluids in exocontact zone. This resulted in formation of sulfide-PGE enrichment marginal zones of intrusion. The results obtained give us a possibility to suggest that: 1) Fluid phase separation is a typical feature of magmatogene fluids for layered basic intrusions. 2) Reduced fluids can extract and transport substantial PGE and sulfide concentrations. 3) Oxidation of reduced fluids is one of the most important geochemical barriers causing abundant PGE minerals and sulfides precipitation. This in turn results in both formation of PGE reefs or enriched contact zones of layered basic intrusions. This work was supported by the Ministry for Russian Science and Education, Grant DSP.2.1.1.702, by RFBR Grants ## 07-05-00685, 07-05-00803, Grant VMTK-2007 IGM SB RAS.

Mineralogy, paragenesis, and mineral zoning of the Bulldog Mountain vein system, Creede District, Colorado

USGS Publications Warehouse

Plumlee, Geoffrey S.; Heald Whitehouse-Veaux, Pamela

1994-01-01

The Bulldog Mountain vein system, Creede district, Colorado, is one of four major epithermal vein systems from which the bulk of the district's historical Ag-Pb-Zn-Cu production has come. Ores deposited along the vein system were discovered in 1965 and were mined from 1969 to 1985.Six temporally gradational mineralization stages have been identified along the Bulldog Mountain vein system, each with a characteristic suite of minerals deposited or leached and a characteristic distribution within the vein system; some of these stages are also strongly zoned within the vein system. Stage A was dominated by deposition of rhodochrosite along the lower levels of the Bulldog Mountain ore zone. Stage B in the northern parts of the ore zone is characterized by abundant fine-grained sphalerite and galena, with lesser tetrahedrite and minor chlorite and hematite. With increasing elevation to the south, stage B ores become progressively more barite and silver rich, with alternating barite and fine-grained sphalerite + galena generations; native silver + or - acanthite assemblages are also locally abundant within southern stage B barite sulfide ores, whereas chalcopyrite and other Cu and Ag sulfides and sulfosalts are present erratically in minor amounts. Stage C in the upper and northern portions of the ore zone is characterized by abundant quartz and fluorite, minor adularia, hematite, Mn siderite, sphalerite, and galena, and major leaching of earlier barite; to the south, some barite and sulfides may have been deposited. Stage D sphalerite and galena were deposited in the upper and northern portions of the ore zone; a barite- and silver-rich facies of this stage may also be present in the southern portions of the vein system. Late in stage D, mineralogically complex assemblages containing chalcopyrite, tetrahedrite, polybasite, bornite, pyrargyrite, and a variety of other sulfides and sulfosalts were deposited in modest amounts throughout the vein system. This complex assemblage marked the transition to stage E. During stage E, the final sulfide stage, abundant botryoidal pyrite and marcasite with lesser stibnite, sphalerite, and sulfosalts were deposited primarily along the top of the Bulldog Mountain ore zone. Stage F, the final mineralization stage along the vein system, is marked by wire silver and concurrent leaching of earlier sulfides and sulfosalts; this stage may reflect the transition to a supergene environment.The sequence of mineralization stages identified in this study along the Bulldog Mountain system can be correlated with corresponding stages identified by other researchers along the OH and P veins, and the southern Amethyst vein system. Mineral zoning patterns identified along the Bulldog Mountain vein system also parallel larger scale zoning patterns across the central and southern Creede district.The complex variations in mineral assemblages documented in time and space along the Bulldog Mountain vein system were produced by the combined effects of many processes. Large-scale changes in vein mineralogy over time produced discrete mineralization stages. Short-term mineralogical fluctuations produced complex interbanding of mineralogically distinct generations. Fluid chemistry evolution within the vein system produced large-scale lateral zoning patterns within certain stages. Hypogene leaching substantially modified the distributions of some minerals. Finally, structural activity, mineral deposition, and mineral leaching modified fluid flow pathways repeatedly during mineralization, and so added to the complex mineral distribution patterns within the vein system.

Study of Reaction Mechanism in Tracer Munitions

DTIC Science & Technology

1974-12-01

Effect of Fuel Particle Size on Reaction Zone Thickness 39 10 Temperature Distribution in Solid 41 11 Computed Reaction Rates as Func’ion of Heat Flux...dissociation (cal/g) R = gan constant (cal/mole K) r radius of fuel droplet (cm) s or x = distance increments in solid phase (cm) T = surface temperature ...of solid (*K) S T = arerage temperature in the reaction zone (°K) a t = ti-ne (sec) tb = avaporation time for droplet (sec) v = regression or burning

Material forming apparatus using a directed droplet stream

DOEpatents

Holcomb, David E.; Viswanathan, Srinath; Blue, Craig A.; Wilgen, John B.

2000-01-01

Systems and methods are described for rapidly forming precision metallic and intermetallic alloy net shape parts directly from liquid metal droplets. A directed droplet deposition apparatus includes a crucible with an orifice for producing a jet of material, a jet destabilizer, a charging structure, a deflector system, and an impact zone. The systems and methods provide advantages in that fully dense, microstructurally controlled parts can be fabricated at moderate cost.

Hydrothermal and metamorphic berthierine from the Kidd Creek volcanogenic massive sulfide deposit, Timmins, Ontario

USGS Publications Warehouse

Slack, J.F.; Wei-Teh, Jiang; Peacor, D.R.; Okita, P.M.

1992-01-01

Berthierine, a 7 A?? Fe-Al member of the serpentine group, occurs in the footwall stringer zone of the Archean Kidd Creek massive sulfide deposit, associated with quartz, muscovite, chlorite, pyrite, sphalerite, chalcopyrite, and local tourmaline, cassiterite, and halloysite. Petrographic and scanning electron microscopic (SEM) studies reveal different types of berthierine occurrences, including interlayers within the rims on deformed chlorite, intergrowths with muscovite and halloysite, and discrete coarse grains. This is the first reported occurrence of berthierine from volcanogenic massive sulfide deposits. Textural relations suggest that most of the berthierine formed as a primary hydrothermal mineral at relatively high temperatures (~350??C) in the footwall stringer zone, probably by the replacement of a pre-existing aluminous phase such as muscovite or chlorite. However, the intergrowth textures observed by SEM and TEM suggest that some of the berthierine originated by syn- or post-metamorphic replacement of chlorite. -from Authors

Copper isotopic zonation in the Northparkes porphyry Cu-Au deposit, SE Australia

NASA Astrophysics Data System (ADS)

Li, Weiqiang; Jackson, Simon E.; Pearson, Norman J.; Graham, Stuart

2010-07-01

Significant, systematic Cu isotopic variations have been found in the Northparkes porphyry Cu-Au deposit, NSW, Australia, which is an orthomagmatic porphyry Cu deposit. Copper isotope ratios have been measured in sulfide minerals (chalcopyrite and bornite) by both solution and laser ablation multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS). The results from both methods show a variation in δ 65Cu of hypogene sulfide minerals of greater than 1‰ (relative to NIST976). Significantly, the results from four drill holes through two separate ore bodies show strikingly similar patterns of Cu isotope variation. The patterns are characterized by a sharp down-hole decrease from up to 0.8‰ (0.29 ± 0.56‰, 1 σ, n = 20) in the low-grade peripheral alteration zones (phyllic-propylitic alteration zone) to a low of ˜-0.4‰ (-0.25 ± 0.36‰, 1 σ, n = 30) at the margins of the most mineralized zones (Cu grade >1 wt%). In the high-grade cores of the systems, the compositions are more consistent at around 0.2‰ (0.19 ± 0.14‰, 1 σ, n = 40). The Cu isotopic zonation may be explained by isotope fractionation of Cu between vapor, solution and sulfides at high temperature, during boiling and sulfide precipitation processes. Sulfur isotopes also show an isotopically light shell at the margins of the high-grade ore zones, but these are displaced from the low δ 65Cu shells, such that there is no correlation between the Cu and S isotope signatures. Fe isotope data do not show any discernable variation along the drill core. This work demonstrates that Cu isotopes show a large response to high-temperature porphyry mineralizing processes, and that they may act as a vector to buried mineralization.

Zonal differences in the distribution and morphology of lipid droplets using 4-amino-pyrazolo-(3,4 d) pyrimidine to lower cholesterol level in the rat adrenal.

PubMed

Szabó, D; Somogyi, J; Acs, Z; Mihály, K

1980-01-01

The effect of reduced blood and adrenal cholesterol levels on adrenocortical lipid droplets have been examined by treating adult rats with 4-amino-pyrazolo-(3,4 d) pyrimidine (4-APP), a drug that inhibits hepatic secretion of lipoproteins. Lowering the blood cholesterol level and the cholesterol content of the adrenals was associated with a marked reduction in the lipid droplets and with a simultaneous increase in their electron density in the inner cortical zones. In the zona glomerulosa cells, no perceptible differences were found in the quantity and morphology of lipid droplets. These data suggest that reduced blood and adrenal cholesterol levels do not affect lipids located in the zona glomerulosa and in the inner cortical zones in the same way, probably due to differences in their intracellular lipid dynamism. Noteworthy, that in spite of the marked lipid depletion, the adrenal glands retained their responsiveness to ACTH stimulation.

Iron Transformation Pathways and Redox Micro-Environments in Seafloor Sulfide-Mineral Deposits: Spatially Resolved Fe XAS and δ(57/54)Fe Observations.

PubMed

Toner, Brandy M; Rouxel, Olivier J; Santelli, Cara M; Bach, Wolfgang; Edwards, Katrina J

2016-01-01

Hydrothermal sulfide chimneys located along the global system of oceanic spreading centers are habitats for microbial life during active venting. Hydrothermally extinct, or inactive, sulfide deposits also host microbial communities at globally distributed sites. The main goal of this study is to describe Fe transformation pathways, through precipitation and oxidation-reduction (redox) reactions, and examine transformation products for signatures of biological activity using Fe mineralogy and stable isotope approaches. The study includes active and inactive sulfides from the East Pacific Rise 9°50'N vent field. First, the mineralogy of Fe(III)-bearing precipitates is investigated using microprobe X-ray absorption spectroscopy (μXAS) and X-ray diffraction (μXRD). Second, laser-ablation (LA) and micro-drilling (MD) are used to obtain spatially-resolved Fe stable isotope analysis by multicollector-inductively coupled plasma-mass spectrometry (MC-ICP-MS). Eight Fe-bearing minerals representing three mineralogical classes are present in the samples: oxyhydroxides, secondary phyllosilicates, and sulfides. For Fe oxyhydroxides within chimney walls and layers of Si-rich material, enrichments in both heavy and light Fe isotopes relative to pyrite are observed, yielding a range of δ(57)Fe values up to 6‰. Overall, several pathways for Fe transformation are observed. Pathway 1 is characterized by precipitation of primary sulfide minerals from Fe(II)aq-rich fluids in zones of mixing between vent fluids and seawater. Pathway 2 is also consistent with zones of mixing but involves precipitation of sulfide minerals from Fe(II)aq generated by Fe(III) reduction. Pathway 3 is direct oxidation of Fe(II) aq from hydrothermal fluids to form Fe(III) precipitates. Finally, Pathway 4 involves oxidative alteration of pre-existing sulfide minerals to form Fe(III). The Fe mineralogy and isotope data do not support or refute a unique biological role in sulfide alteration. The findings reveal a dynamic range of Fe transformation pathways consistent with a continuum of micro-environments having variable redox conditions. These micro-environments likely support redox cycling of Fe and S and are consistent with culture-dependent and -independent assessments of microbial physiology and genetic diversity of hydrothermal sulfide deposits.

Large Solid Rocket Motor Safety Analyses: Thermal Effects Issues

DTIC Science & Technology

2010-07-01

aluminium combustion and condensation of oxide complete - The tertiary cone where flame plume mixes with air and where Al droplet combustion can occur... aluminium droplet combustion and aluminium oxide condensation complete. Flame true temperature drops to 2235 ±7 °K and 2206 ±7 °K respectively at 26...may occur in this zone where condensation of aluminium oxides and Al droplet combustion are being completed. So flame emissivity that is much weaker

Undercooling and solidification behavior in the InSb-Sb system. M.S. Thesis. Final Report

NASA Technical Reports Server (NTRS)

Graves, J. A.

1985-01-01

Use of the droplet emulsion technique has been successful in studying the undercooling and crystallization behavior of Sb, InSb, and an InSb-Sb eutectic alloy. Both droplet size and imposed cooling rate were influential in controlling the extent of liquid undercooling. The droplet surface coating was of significant importance in determining the resultant solidification product structure through its effect on nucleation kinetics. The maximum undercooling for pure Sb was extended from 0.08 to 0.23 T sub m. While simple crushing techniques provided a dramatic increase in droplet undercooling over the bulk material, emulsification treatments both enhanced this undercooling and allowed successful formation of a metastable simple cubic Sb phase. This phase was stable to temperatures approaching the melting point. The simple cubic phase was detected in droplet samples processed using DTA, air and water quenching, and drop tube processing under a helium gas atmosphere. A deviation in the InSb parent ingot composition limited interpretation of the line compound results, however, emulsification techniques extended the undercooling of this material to 0.17 T sub L and provided a stable, protective surface coating for the droplets. Emulsification of the eutectic alloy was effective at producing various levels of undercooling from 0.1 to 0.2 T sub E. Microstructural examination revealed a normal-type eutectic structure in the undercooled droplets indicating that solidification occurred within the coupled zone and that this zone is somewhat symmetric about the eutectic composition.

Gold deposits of the Carolina Slate Belt, southeastern United States--Age and origin of the major gold producers

USGS Publications Warehouse

Foley, Nora K.; Ayuso, Robert A.

2012-01-01

Gold- and iron sulfide-bearing deposits of the southeastern United States have distinctive mineralogical and geochemical features that provide a basis for constructing models of ore genesis for exploration and assessment of gold resources. The largest (historic) deposits, in approximate million ounces of gold (Moz Au), include those in the Haile (~ 4.2 Moz Au), Ridgeway (~1.5 Moz Au), Brewer (~0.25 Moz Au), and Barite Hill (0.6 Moz Au) mines. Host rocks are Late Proterozoic to early Paleozoic (~553 million years old) metaigneous and metasedimentary rocks of the Carolina Slate Belt that share a geologic affinity with the classic Avalonian tectonic zone. The inferred syngenetic and epithermal-subvolcanic quartz-porphyry settings occur stratigraphically between sequences of metavolcanic rocks of the Persimmon Fork and Uwharrie Formations and overlying volcanic and epiclastic rocks of the Tillery and Richtex Formations (and regional equivalents). The Carolina Slate Belt is highly prospective for many types of gold ore hosted within quartz-sericite-pyrite altered volcanic rocks, juvenile metasedimentary rocks, and in associated shear zones. For example, sheared and deformed auriferous volcanogenic massive sulfide deposits at Barite Hill, South Carolina, and in the Gold Hill trend, North Carolina, are hosted primarily by laminated mudstone and felsic volcanic to volcaniclastic rocks. The high-sulfidation epithermal style of gold mineralization at Brewer and low-sulfidation gold ores of the Champion pit at Haile occur in breccias associated with subvolcanic quartz porphyry and within crystal-rich tuffs, ash flows, and subvolcanic rhyolite. The Ridgeway and Haile deposits are primarily epithermal replacements and feeder zones within (now) metamorphosed crystal-rich tuffs, volcaniclastic sediments, and siltstones originally deposited in a marine volcanic-arc basinal setting. Recent discoveries in the region include (1) extensions of known deposits, such as at Haile where drilling has identified an extensive gold-rich feeder system; and (2) newly discovered prospects like the porphyry-style gold-copper-molybdenum occurrence reported at Deep River, N.C. Gold ores at Ridgeway and Haile represent the low-sulfidation, disseminated, shallow subaqueous tuffaceous equivalents of intrusion-related high-sulfidation ores such as those at Brewer. Haile also has mineralogical features that support a stockwork disseminated model of pyrite-gold-sericite mineralization in which a significant amount of ore was deposited in sediments at or near the surface. The potential is high for gold-rich ore at depth in the funnel-shaped feeder zones that likely underlie such surface variants of high sulfidation–low sulfidation epithermal systems and for new discoveries of similar deposits in areas undercover. Exploration strategies for large-scale gold-mineralizing systems applied to rocks of the Carolina Slate Belt, and by extension, the Carolinian-Avalonian tectonic zone of North America, benefit from applying subvolcanic and basinal epithermal models for gold mineralization.

Rare-Earth Elements from Modern Mineral-Organic Associations in the Zone of Sulfide Ore Hypergenesis

NASA Astrophysics Data System (ADS)

Vakh, E. A.; Vakh, A. S.; Petukhov, V. I.; Barinov, N. N.

2018-01-01

The REE composition of modern mineral-organic associations in the sulfide ore hypergenesis zone of the Berezitovoe deposit in the Russian Far East was studied for the first time. It is shown that the mineral-organic associations widely abundant in the valley of Konstantinovskii Creek and represented by bright brown crusts on the surface of deluvial deposits were formed at the expense of the influence of acid highly mineralized mine waters from the Berezitovoe deposit. The mineral-organic associations found in the Creek valley may be considered as a new indicator for evaluation of the geoecological state of modern technogenic landscapes.

Sulfide-associated mineral assemblages in the Bushveld Complex, South Africa: platinum-group element enrichment by vapor refining by chloride-carbonate fluids

NASA Astrophysics Data System (ADS)

Kanitpanyacharoen, W.; Boudreau, A. E.

2013-02-01

The petrology of base metal sulfides and associated accessory minerals in rocks away from economically significant ore zones such as the Merensky Reef of the Bushveld Complex has previously received only scant attention, yet this information is critical in the evaluation of models for the formation of Bushveld-type platinum-group element (PGE) deposits. Trace sulfide minerals, primarily pyrite, pyrrhotite, pentlandite, and chalcopyrite are generally less than 100 microns in size, and occur as disseminated interstitial individual grains, as polyphase assemblages, and less commonly as inclusions in pyroxene, plagioclase, and olivine. Pyrite after pyrrhotite is commonly associated with low temperature greenschist alteration haloes around sulfide grains. Pyrrhotite hosted by Cr- and Ti-poor magnetite (Fe3O4) occurs in several samples from the Marginal to Lower Critical Zones below the platiniferous Merensky Reef. These grains occur with calcite that is in textural equilibrium with the igneous silicate minerals, occur with Cl-rich apatite, and are interpreted as resulting from high temperature sulfur loss during degassing of interstitial liquid. A quantitative model demonstrates how many of the first-order features of the Bushveld ore metal distribution could have developed by vapor refining of the crystal pile by chloride-carbonate-rich fluids during which sulfur and sulfide are continuously recycled, with sulfur moving from the interior of the crystal pile to the top during vapor degassing.

Germanium geochemistry and mineralogy

USGS Publications Warehouse

Bernstein, L.R.

1985-01-01

Germanium is enriched in the following geologic environments: 1. (1) iron meteorites and terrestrial iron-nickel; 2. (2) sulfide ore deposits, particularly those hosted by sedimentary rocks; 3. (3) iron oxide deposits; 4. (4) oxidized zones of Ge-bearing sulfide deposits; 5. (5) pegmatites, greisens, and skarns; and 6. (6) coal and lignitized wood. In silicate melts, Ge is highly siderophile in the presence of native iron-nickel; otherwise, it is highly lithophile. Among silicate minerals, Ge is concentrated in those having less polymerized silicate tetrahedra such as olivine and topaz. In deposits formed from hydrothermal solutions, Ge tends to be enriched mostly in either sulfides or in fluorine-bearing phases; it is thus concentrated both in some hydrothermal sulfide deposits and in pegmatites, greisens, and skarns. In sulfide deposits that formed from solutions having low to moderate sulfur activity, Ge is concentrated in sphalerite in amounts up to 3000 ppm. Sulfide deposits that formed from solutions having higher sulfur activity allowed Ge to either form its own sulfides, particularly with Cu, or to substitute for As, Sn, or other metals in sulfosalts. The Ge in hydrothermal fluids probably derives from enrichment during the fractional crystallization of igneous fluids, or is due to the incorporation of Ge from the country rocks, particularly from those containing organic material. Germanium bonds to lignin-derivative organic compounds that are found in peat and lignite, accounting for its common concentration in coals and related organic material. Germanium is precipitated from water together with iron hydroxide, accounting for its concentration in some sedimentary and supergene iron oxide deposits. It also is able to substitute for Fe in magnetite in a variety of geologic environments. In the oxidized zone of Ge-bearing sulfide deposits, Ge is concentrated in oxides, hydroxides, and hydroxy-sulfates, sometimes forming its own minerals. It is particularly enriched in some iron- and manganese-bearing oxides and hydroxides, including goethite (up to 5300 ppm) and hematite (up to 7000 ppm). ?? 1985.

The Spar Lake strata-Bound Cu-Ag deposit formed across a mixing zone between trapped natural gas and metals-bearing brine

USGS Publications Warehouse

Hayes, Timothy S.; Landis, Gary P.; Whelan, Joseph F.; Rye, Robert O.; Moscati, Richard J.

2012-01-01

Ore formation at the Spar Lake red bed-associated strata-bound Cu deposit took place across a mixing and reaction zone between a hot oxidized metals-transporting brine and a reservoir of “sour” (H2S-bearing) natural gas trapped in the host sandstones. Fluid inclusion volatile analyses have very high CH4 concentrations (≥1 mol % in most samples), and a sample from the fringe of the deposit has between 18 and 36 mol % CH4. The ratio of CH4/CO2 in fluid inclusions appears to vary regularly across the deposit, with the lowest CH4/CO2 ratios from high-grade chalcocite-bearing ore, and the highest from the chalcopyrite-bearing fringe. The helium R/Ra isotope ratios (0.23–0.98) and concentrations define a mixture between crustal and atmospheric helium. The volatiles in fluid inclusions (CH4, CO2, H2S, SO2, H2, H2O, and other organic gases) and values of fO2 and temperature calculated from the volatiles data all show gradations across the deposit that are completely consistent with such a mixing and reaction zone. Other volatiles from the fluid inclusions (HCl, HF, 3He, Msup>4He, N2, Ar) characterize the brine and give evidence for only shallow crustal fluids with no magmatic influences. The brine entered the gas reservoir from below and along the axis of the deposit and migrated out along bedding to the southwest, northeast, and northwest. Metals-transporting brines may have been fed into the host sandstones from the East Fault, but that remains uncertain. Abundant ore-stage Fe and Mn calcite cements from the reduced fringe have δ13C values as low as −18.4‰, and many values less than −10‰, which indicate that significant carbonate was generated by oxidation of organic carbon from the natural gas. The zone of calcite cements with very low δ13C values approximately envelopes chalcocite-bearing ore. Sulfur isotope data of Cu, Pb, and Fe sulfides and barite indicate derivation of roughly half of the orebody sulfide directly from sour gas H2S. That sour gas H2S had developed in steps known from other sedimentary basins, starting with (1) bacterial sulfate reduction (BSR) of seawater sulfate having δ34S of about 20‰ and sequestering of the sulfide in organic matter in source rocks stratigraphically below the deposit host rocks, followed by (2) maturation of the sulfide-bearing organic matter into liquid petroleum with relatively homogeneous sulfide having δ34S of 5 ± 5‰, then by (3) thermal cracking of the oil to CH4 and H2S with relatively homogeneous sulfide having δ34S closely distributed, about 6‰. The CH4 and H2S migrated and were trapped in sandstones of the upper member of the Revett Formation, where they were later met by the 200°C metals-transporting brine. There was additional contribution of sulfide to ore from later thermochemical sulfate reduction (TSR) operating on sulfate δ34S of 20 to 29‰ in both formation waters and metals-transporting solutions. A large range of δ34S in sulfides resulted as the 6‰ sour gas sulfide was supplemented with varying proportions of 20 to 29‰ sulfide from TSR.

Gasification of black liquor

DOEpatents

Kohl, A.L.

1987-07-28

A concentrated aqueous black liquor containing carbonaceous material and alkali metal sulfur compounds is treated in a gasifier vessel containing a relatively shallow molten salt pool at its bottom to form a combustible gas and a sulfide-rich melt. The gasifier vessel, which is preferably pressurized, has a black liquor drying zone at its upper part, a black liquor solids gasification zone located below the drying zone, and a molten salt sulfur reduction zone which comprises the molten salt pool. A first portion of an oxygen-containing gas is introduced into the gas space in the gasification zone immediately above the molten salt pool. The remainder of the oxygen-containing gas is introduced into the molten salt pool in an amount sufficient to cause gasification of carbonaceous material entering the pool from the gasification zone but not sufficient to create oxidizing conditions in the pool. The total amount of the oxygen-containing gas introduced both above the pool and into the pool constitutes between 25 and 55% of the amount required for complete combustion of the black liquor feed. A combustible gas is withdrawn from an upper portion of the drying zone, and a melt in which the sulfur content is predominantly in the form of alkali metal sulfide is withdrawn from the molten salt sulfur reduction zone. 2 figs.

Gasification of black liquor

DOEpatents

Kohl, Arthur L.

1987-07-28

A concentrated aqueous black liquor containing carbonaceous material and alkali metal sulfur compounds is treated in a gasifier vessel containing a relatively shallow molten salt pool at its bottom to form a combustible gas and a sulfide-rich melt. The gasifier vessel, which is preferably pressurized, has a black liquor drying zone at its upper part, a black liquor solids gasification zone located below the drying zone, and a molten salt sulfur reduction zone which comprises the molten salt pool. A first portion of an oxygen-containing gas is introduced into the gas space in the gasification zone immediatley above the molten salt pool. The remainder of the oxygen-containing gas is introduced into the molten salt pool in an amount sufficient to cause gasification of carbonaceous material entering the pool from the gasification zone but not sufficient to create oxidizing conditions in the pool. The total amount of the oxygen-containing gas introduced both above the pool and into the pool constitutes between 25 and 55% of the amount required for complete combustion of the black liquor feed. A combustible gas is withdrawn from an upper portion of the drying zone, and a melt in which the sulfur content is predominantly in the form of alkali metal sulfide is withdrawn from the molten salt sulfur reduction zone.

Combustion process for synthesis of carbon nanomaterials from liquid hydrocarbon

DOEpatents

Diener, Michael D.; Alford, J. Michael; Nabity, James; Hitch, Bradley D.

2007-01-02

The present invention provides a combustion apparatus for the production of carbon nanomaterials including fullerenes and fullerenic soot. Most generally the combustion apparatus comprises one or more inlets for introducing an oxygen-containing gas and a hydrocarbon fuel gas in the combustion system such that a flame can be established from the mixed gases, a droplet delivery apparatus for introducing droplets of a liquid hydrocarbon feedstock into the flame, and a collector apparatus for collecting condensable products containing carbon nanomaterials that are generated in the combustion system. The combustion system optionally has a reaction zone downstream of the flame. If this reaction zone is present the hydrocarbon feedstock can be introduced into the flame, the reaction zone or both.

Inclusions of Sulphide Immiscible Melts in Primitive Olivine Phenocrysts from Mantle-Derived Magmas; Preliminary Results

NASA Astrophysics Data System (ADS)

Danyushevsky, L.; Ryan, C.; Kamenetsky, V.; Crawford, A.

2001-12-01

Sulphide inclusions have been identified in olivine phenocrysts (and in one case in a spinel phenocryst) in primitive volcanic rocks from mid- ocean ridges, subduction-related island arcs and backarc basins. These inclusions represent droplets of an immiscible sulphide melt and are trapped by olivine crystals growing from silicate melts. Sulphide melt is usually trapped as separate inclusions, however combined inclusions of sulphide and silicate melts have also been observed. Sulphide inclusions have rounded shapes and vary in size from several up to 100 microns in diameter. At room temperature sulphide inclusions consist of several phases. These phases are formed as a result of crystallisation of the sulphide melt after it was trapped. Crystallisation occurs due to decreasing temperature in the magma chamber after trapping and/or when magma ascents from the magma chamber during eruptions. In all studied sulphides three different phases can be identified: a high- Fe, low-Ni, low-Cu phase; a high-Fe, high-Ni, low-Cu phase; and high-Fe, low-Ni, high-Cu phase. Low-Cu phases appear to be monomineralic, whereas the high-Cu phase is usually composed of a fine intergrowth of high- and low-Cu phases, resembling the quench 'spinifex' structure. Fe, Ni and Cu are the major elements in all sulphides studied. The amount of Ni decreases with decreasing forsterite content of the host olivine phenocryst, which is an index of the degree of silicate magma fractionation. Since Ni content of the silicate magma is decreasing during fractionation, this indicates either that the immiscible sulfide melt remains in equilibrium with the silicate melt continuously changing its composition during fractionation, or that the sulfide melt is continuously separated from the silicate melt during fractionation, with later formed droplets having lower Ni content due to the lower Ni content of the evolved, stronger fractionated silicate melt. Trace element contents of the sulfide inclusions have been analysed on the proton microprobe at CSIRO in Sydney. The main trace elements in the sulfide inclusions are Zn, Pb, Ag, and Se. Other trace elements are below detection limits, which are normally at a level of several ppm. Zn concentrations (120 +/- 40 ppm) in sulphides are similar to those in silicate melts. This indicates that separation of the sulfide melt does not affect Zn contents of silicate melts. On the contrary, Ag (30 +/- 10 ppm) and Pb (40 +/- 10 ppm) contents in sulphides are at least in order of magnitude higher than in the silicate melt, and thus separation of the immiscible sulfide melt can significantly decrease Pb and Ag contents of the silicate magma. The widespread occurrence of sulfide inclusions, which were also described in olivine phenocrysts from ocean island basalts, indicates common saturation at low pressure of mantle-derived magmas with reduced sulfur.

Uranium-bearing copper deposits in the Coyote district, Mora County, New Mexico

USGS Publications Warehouse

Zeller, H.D.; Baltz, Elmer Harold

1954-01-01

Uranium-bearing copper deposits occur in steeply dipping beds of the Sangre de Cristo formation of Pennsylvanian and Permian(?) age south of Coyote, Mora County, N. Mex. Mapping and sampling of these deposits indicate that they are found in lenticular carbonaceous zones in shales and arkosic sandstones. Samples from these zones contain as much as 0.067 percent uranium and average 3 percent copper. Metatyuyamunite is dissemihatedin some of the arkosic sandstone beds, and uraninite is present in some of the copper sulfide nodules occurring in the shale. These sulfide nodules are composed principally of chalcocite but include some bornite, covellite, pyrite, and malachite. Most of the samples were collected near the surface from the weathered zone. The copper and uranium were probably deposited with the sediments and concentrated into zones during compaction and lithification. Carbonaceous material in the Sangre de Cristo formation provided the environment that precipitated uranium and copper from mineral-charged connate waters forced from the clayey sediments.

Success of chemolithoautotrophic SUP05 and Sulfurimonas GD17 cells in pelagic Baltic Sea redox zones is facilitated by their lifestyles as K- and r-strategists.

PubMed

Rogge, Andreas; Vogts, Angela; Voss, Maren; Jürgens, Klaus; Jost, Günter; Labrenz, Matthias

2017-06-01

Chemolithoautotrophic sulfur-oxidizing and denitrifying Gamma- (particularly the SUP05 cluster) and Epsilonproteobacteria (predominantly Sulfurimonas subgroup GD17) are assumed to compete for substrates (electron donors and acceptors) in marine pelagic redox gradients. To elucidate their ecological niche separation we performed 34 S 0 , 15 NO3- and H 13 CO3- stable-isotope incubations with water samples from Baltic Sea suboxic, chemocline and sulfidic zones followed by combined phylogenetic staining and high-resolution secondary ion mass spectrometry of single cells. SUP05 cells were small-sized (0.06-0.09 µm 3 ) and most abundant in low-sulfidic to suboxic zones, whereas Sulfurimonas GD17 cells were significantly larger (0.26-0.61 µm 3 ) and most abundant at the chemocline and below. Together, SUP05 and GD17 cells accumulated up to 48% of the labelled substrates but calculation of cell volume-specific rates revealed that GD17 cells incorporated labelled substrates significantly faster throughout the redox zone, thereby potentially outcompeting SUP05 especially at high substrate concentrations. Thus, in synopsis with earlier described features of SUP05/GD17 we conclude that their spatially overlapping association in stratified sulfidic zones is facilitated by their different lifestyles: whereas SUP05 cells are streamlined, non-motile K-strategists adapted to low substrate concentrations, GD17 cells are motile r-strategists well adapted to fluctuating substrate and redox conditions. © 2017 Society for Applied Microbiology and John Wiley & Sons Ltd.

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

Toner, Brandy M.; Rouxel, Olivier J.; Santelli, Cara M.

Hydrothermal sulfide chimneys located along the global system of oceanic spreading centers are habitats for microbial life during active venting. Hydrothermally extinct, or inactive, sulfide deposits also host microbial communities at globally distributed sites. The main goal of this study is to describe Fe transformation pathways, through precipitation and oxidation-reduction (redox) reactions, and examine transformation products for signatures of biological activity using Fe mineralogy and stable isotope approaches. The study includes active and inactive sulfides from the East Pacific Rise 9°50'N vent field. First, the mineralogy of Fe(III)-bearing precipitates is investigated using microprobe X-ray absorption spectroscopy (μXAS) and X-ray diffractionmore » (μXRD). Second, laser-ablation (LA) and micro-drilling (MD) are used to obtain spatially-resolved Fe stable isotope analysis by multicollector-inductively coupled plasma-mass spectrometry (MC-ICP-MS). Eight Fe-bearing minerals representing three mineralogical classes are present in the samples: oxyhydroxides, secondary phyllosilicates, and sulfides. For Fe oxyhydroxides within chimney walls and layers of Si-rich material, enrichments in both heavy and light Fe isotopes relative to pyrite are observed, yielding a range of δ 57Fe values up to 6‰. Overall, several pathways for Fe transformation are observed. Pathway 1 is characterized by precipitation of primary sulfide minerals from Fe(II)aq-rich fluids in zones of mixing between vent fluids and seawater. Pathway 2 is also consistent with zones of mixing but involves precipitation of sulfide minerals from Fe(II)aq generated by Fe(III) reduction. Pathway 3 is direct oxidation of Fe(II) aq from hydrothermal fluids to form Fe(III) precipitates. Finally, Pathway 4 involves oxidative alteration of pre-existing sulfide minerals to form Fe(III). The Fe mineralogy and isotope data do not support or refute a unique biological role in sulfide alteration. The findings reveal a dynamic range of Fe transformation pathways consistent with a continuum of micro-environments having variable redox conditions. Lastly, these micro-environments likely support redox cycling of Fe and S and are consistent with culture-dependent and -independent assessments of microbial physiology and genetic diversity of hydrothermal sulfide deposits.« less

Sulfur, carbon, and oxygen isotope variations in submarine hydrothermal deposits of Guaymas Basin, Gulf of California, USA

USGS Publications Warehouse

Peter, J.M.; Shanks, Wayne C.

1992-01-01

Sulfur, carbon, and oxygen isotope values were measured in sulfide, sulfate, and carbonate from hydrothermal chimney, spire, and mound samples in the southern trough of Guaymas Basin, Gulf of California, USA. ??34S values of sulfides range from -3.7 to 4.5%. and indicate that sulfur originated from several sources: 1. (1) dissolution of 0??? sulfide contained within basaltic rocks, 2. (2) thermal reduction of seawater sulfate during sediment alteration reactions in feeder zones to give sulfide with positive ??34S, and 3. (3) entrainment or leaching of isotopically light (negative-??34S) bacteriogenic sulfide from sediments underlying the deposits. ??34S of barite and anhydrite indicate sulfur derivation mainly from unfractionated seawater sulfate, although some samples show evidence of sulfate reduction and sulfide oxidation reactions during mixing within chimneys. Oxygen isotope temperatures calculated for chimney calcites are in reasonable agreement with measured vent fluid temperatures and fluid inclusion trapping temperatures. Hydrothermal fluids that formed calcite-rich chimneys in the southern trough of Guaymas Basin were enriched in 18O with respect to seawater by about 2.4??? due to isotopic exchange with sedimentary and/or basaltic rocks. Carbon isotope values of calcite range from -9.6 to -14.0??? ??34CpDB, indicating that carbon was derived in approximately equal quantities from the dissolution of marine carbonate minerals and the oxidation of organic matter during migration of hydrothermal fluid through the underlying sediment column. Statistically significant positive, linear correlations of ??34S, ??34C, and ??18O of sulfides and calcites with geographic location within the southern trough of Guaymas Basin are best explained by variations in water/rock ( w r) ratios or sediment reactivity within subsurface alteration zones. Low w r ratios and the leaching of detrital carbonates and bacteriogenic sulfides at the southern vent sites result in relatively high ??13C and low ??34S in chimney carbonates and sulfides, respectively. In the north, where the depletion of alkalis in vent fluids indicates higher w r ratios, positive ??34S and more negative ??13c are due to increased contributions from organic matter oxidation and sulfate reduction reactions. ?? 1992.

Method for continuous synthesis of metal oxide powders

DOEpatents

Berry, David A.; Haynes, Daniel J.; Shekhawat, Dushyant; Smith, Mark W.

2015-09-08

A method for the rapid and continuous production of crystalline mixed-metal oxides from a precursor solution comprised of a polymerizing agent, chelated metal ions, and a solvent. The method discharges solution droplets of less than 500 .mu.m diameter using an atomizing or spray-type process into a reactor having multiple temperature zones. Rapid evaporation occurs in a first zone, followed by mixed-metal organic foam formation in a second zone, followed by amorphous and partially crystalline oxide precursor formation in a third zone, followed by formation of the substantially crystalline mixed-metal oxide in a fourth zone. The method operates in a continuous rather than batch manner and the use of small droplets as the starting material for the temperature-based process allows relatively high temperature processing. In a particular embodiment, the first zone operates at 100-300.degree. C., the second zone operates at 300-700.degree. C., and the third operates at 700-1000.degree. C., and fourth zone operates at at least 700.degree. C. The resulting crystalline mixed-metal oxides display a high degree of crystallinity and sphericity with typical diameters on the order of 50 .mu.m or less.

In situ observations of Arctic cloud properties across the Beaufort Sea marginal ice zone

NASA Astrophysics Data System (ADS)

Corr, C.; Moore, R.; Winstead, E.; Thornhill, K. L., II; Crosbie, E.; Ziemba, L. D.; Beyersdorf, A. J.; Chen, G.; Martin, R.; Shook, M.; Corbett, J.; Smith, W. L., Jr.; Anderson, B. E.

2016-12-01

Clouds play an important role in Arctic climate. This is particularly true over the Arctic Ocean where feedbacks between clouds and sea-ice impact the surface radiation budget through modifications of sea-ice extent, ice thickness, cloud base height, and cloud cover. This work summarizes measurements of Arctic cloud properties made aboard the NASA C-130 aircraft over the Beaufort Sea during ARISE (Arctic Radiation - IceBridge Sea&Ice Experiment) in September 2014. The influence of surface-type on cloud properties is also investigated. Specifically, liquid water content (LWC), droplet concentrations, and droplet size distributions are compared for clouds sampled over three distinct regimes in the Beaufort Sea: 1) open water, 2) the marginal ice zone, and 3) sea-ice. Regardless of surface type, nearly all clouds intercepted during ARISE were liquid-phase clouds. However, differences in droplet size distributions and concentrations were evident for the surface types; clouds over the MIZ and sea-ice generally had fewer and larger droplets compared to those over open water. The potential implication these results have for understanding cloud-surface albedo climate feedbacks in Arctic are discussed.

Tracking photosynthetic sulfide oxidation in a meromictic lake using sulfate δ34S and δ18O

NASA Astrophysics Data System (ADS)

Gilhooly, W. P.; Reinhard, C.; Lyons, T. W.; Glass, J. B.

2012-12-01

Phototrophic sulfur bacteria oxidize sulfide and fix carbon dioxide in the presence of sunlight without producing oxygen. Environmental conditions in the Paleo- and Mesoproterozoic, when atmospheric oxygen concentrations were at low levels and portions of the oceans were anoxic and sulfidic (euxinic), were conducive to widespread carbon fixation by anoxygenic photosynthesis. This pathway may have helped sustain euxinic conditions in the Proterozoic water column. With limited organic biomarker and geochemical evidence for widespread production of anoxygenic phototrophs, however, additional proxies are needed to fingerprint paleoecological and biogeochemical signals associated with photic zone euxinia. Paired δ34S and δ18O from ancient sulfates (gypsum, barite, or CAS) may offer an added constraint on the history and ecological dominance of photosynthetic S-oxidation. Sulfate-oxygen can fractionate during sulfate reduction, but the extent of isotopic enrichment is controlled either by kinetic isotope effects imparted during intracellular enzymatic steps or equilibrium oxygen exchange with ambient water. An improved understanding of these processes can be gained from modern natural environments. Mahoney Lake is a density-stratified lake located within the White Lake Basin of British Columbia. The euxinic water column supports a dense plate of purple sulfur bacteria (Amoebobacter purpureus) that thrives where free sulfide intercepts the photic zone at ~7 m water depth. We analyzed the isotopic composition of sulfate (δ34SSO4 and δ18OSO4), sulfide (δ34SH2S), and water (δ18OH2O) to track the potentially coupled processes of dissimilatory sulfate reduction and phototrophic sulfide oxidation within this meromictic lake. Large isotopic offsets observed between sulfate and sulfide within the monimolimnion (δ34SSO4-H2S = 51‰) and within pore waters along the oxic margin (δ34SSO4-H2S >50‰) are consistent with sulfate reduction in both the sediments and the anoxic water column. Given the high sulfide concentrations of the lake ([H2S] = 30 mM), sulfur disproportionation is likely inoperable, and so the large instantaneous fractionations are best explained by single-step sulfate reduction. The offset between sulfate and sulfide decreases at the chemocline (δ34SSO4-H2S = 37‰), a trend possibly explained by sulfide oxidation or decreasing sulfate reduction rates. Sulfate exhibits a curvilinear response in δ18OSO4/δ34SSO4 that approaches δ18OSO4 values (~24-33‰) in equilibrium with ambient water (δ18OH2O = -2.2‰). Although an inverse relationship between δ18OSO4/δ18OH2O is inconsistent with chemical sulfide oxidation (typically a positive relationship), fine-scale variations in δ34SSO4 and δ18OSO4 at the chemocline imply sulfate reduction coupled with near quantitative reoxidation by A. purpureus. Although observed within the microbial plate, this photosynthetic S-bacteria biosignature is restricted to the oxic/anoxic transition zone and is apparently swamped by the more prevalent process of sulfate reduction operative throughout the anoxic water column and sediment pore waters.

Iron Transformation Pathways and Redox Micro-Environments in Seafloor Sulfide-Mineral Deposits: Spatially Resolved Fe XAS and δ57/54Fe Observations

PubMed Central

Toner, Brandy M.; Rouxel, Olivier J.; Santelli, Cara M.; Bach, Wolfgang; Edwards, Katrina J.

2016-01-01

Hydrothermal sulfide chimneys located along the global system of oceanic spreading centers are habitats for microbial life during active venting. Hydrothermally extinct, or inactive, sulfide deposits also host microbial communities at globally distributed sites. The main goal of this study is to describe Fe transformation pathways, through precipitation and oxidation-reduction (redox) reactions, and examine transformation products for signatures of biological activity using Fe mineralogy and stable isotope approaches. The study includes active and inactive sulfides from the East Pacific Rise 9°50′N vent field. First, the mineralogy of Fe(III)-bearing precipitates is investigated using microprobe X-ray absorption spectroscopy (μXAS) and X-ray diffraction (μXRD). Second, laser-ablation (LA) and micro-drilling (MD) are used to obtain spatially-resolved Fe stable isotope analysis by multicollector-inductively coupled plasma-mass spectrometry (MC-ICP-MS). Eight Fe-bearing minerals representing three mineralogical classes are present in the samples: oxyhydroxides, secondary phyllosilicates, and sulfides. For Fe oxyhydroxides within chimney walls and layers of Si-rich material, enrichments in both heavy and light Fe isotopes relative to pyrite are observed, yielding a range of δ57Fe values up to 6‰. Overall, several pathways for Fe transformation are observed. Pathway 1 is characterized by precipitation of primary sulfide minerals from Fe(II)aq-rich fluids in zones of mixing between vent fluids and seawater. Pathway 2 is also consistent with zones of mixing but involves precipitation of sulfide minerals from Fe(II)aq generated by Fe(III) reduction. Pathway 3 is direct oxidation of Fe(II) aq from hydrothermal fluids to form Fe(III) precipitates. Finally, Pathway 4 involves oxidative alteration of pre-existing sulfide minerals to form Fe(III). The Fe mineralogy and isotope data do not support or refute a unique biological role in sulfide alteration. The findings reveal a dynamic range of Fe transformation pathways consistent with a continuum of micro-environments having variable redox conditions. These micro-environments likely support redox cycling of Fe and S and are consistent with culture-dependent and -independent assessments of microbial physiology and genetic diversity of hydrothermal sulfide deposits. PMID:27242685

Iron transformation pathways and redox micro-environments in seafloor sulfide-mineral deposits: Spatially resolved Fe XAS and δ 57/54Fe observations

DOE PAGES

Toner, Brandy M.; Rouxel, Olivier J.; Santelli, Cara M.; ...

2016-05-10

Hydrothermal sulfide chimneys located along the global system of oceanic spreading centers are habitats for microbial life during active venting. Hydrothermally extinct, or inactive, sulfide deposits also host microbial communities at globally distributed sites. The main goal of this study is to describe Fe transformation pathways, through precipitation and oxidation-reduction (redox) reactions, and examine transformation products for signatures of biological activity using Fe mineralogy and stable isotope approaches. The study includes active and inactive sulfides from the East Pacific Rise 9°50'N vent field. First, the mineralogy of Fe(III)-bearing precipitates is investigated using microprobe X-ray absorption spectroscopy (μXAS) and X-ray diffractionmore » (μXRD). Second, laser-ablation (LA) and micro-drilling (MD) are used to obtain spatially-resolved Fe stable isotope analysis by multicollector-inductively coupled plasma-mass spectrometry (MC-ICP-MS). Eight Fe-bearing minerals representing three mineralogical classes are present in the samples: oxyhydroxides, secondary phyllosilicates, and sulfides. For Fe oxyhydroxides within chimney walls and layers of Si-rich material, enrichments in both heavy and light Fe isotopes relative to pyrite are observed, yielding a range of δ 57Fe values up to 6‰. Overall, several pathways for Fe transformation are observed. Pathway 1 is characterized by precipitation of primary sulfide minerals from Fe(II)aq-rich fluids in zones of mixing between vent fluids and seawater. Pathway 2 is also consistent with zones of mixing but involves precipitation of sulfide minerals from Fe(II)aq generated by Fe(III) reduction. Pathway 3 is direct oxidation of Fe(II) aq from hydrothermal fluids to form Fe(III) precipitates. Finally, Pathway 4 involves oxidative alteration of pre-existing sulfide minerals to form Fe(III). The Fe mineralogy and isotope data do not support or refute a unique biological role in sulfide alteration. The findings reveal a dynamic range of Fe transformation pathways consistent with a continuum of micro-environments having variable redox conditions. Lastly, these micro-environments likely support redox cycling of Fe and S and are consistent with culture-dependent and -independent assessments of microbial physiology and genetic diversity of hydrothermal sulfide deposits.« less

Geology of the Barite Hill gold-silver deposit in the southern Carolina slate belt

USGS Publications Warehouse

Clark, S.H.B.; Gray, K.J.; Back, J.M.

1999-01-01

Barite Hill is a stratiform gold-silver deposit associated with base metal sulfides and barite in greenschist facies rocks. The deposit, southernmost of four recently mined gold deposits in the Carolina slate belt, is located in the Lincolnton-McCormick district of Georgia and South Carolina, which includes several known gold-silver and base metal deposits in a Kuroko-type geological setting along with deposits of kyanite and manganese. Approximately 1,835,000 g of gold was produced mainly from oxidized ores in the Main and Rainsford pits from 1990 until their closing in 1994. Ore is hosted by sericitically altered felsic metavolcanic and metasedimentary rocks of the Late Proterozoic Persimmon Fork Formation. The deposit is stratigraphically below an overturned contact between upper and lower pyroclastic units, which overlie the Lincolnton metarhyolite, an intrusive unit. Gold-silver-rich zones in the Main pit are partly coincident with lenses of siliceous barite rock, but not confined to them, and occur more commonly in pyrite-quartz-altered fragmental rock. The Main pit ore is stratigraphically overlain by a zone of base metal and barite enrichment, which is, in turn, overlain by a talc-tremolite alteration zone locally. Siliceous barite zones are absent in the Rainsford pit, and gold-silver minerals are associated with silicified rocks and chert. The Barite Hill deposit is interpreted to be the result of Kuroko-type, volcanogenic, base metal sulfide mineralization, followed by gold-silver mineralization under epithermal conditions with the following stages of evolution: (1) massive sulfides, barite, and fine-grained siliceous exhalites were deposited during Late Proterozoic to Cambrian submarine volcanism, which was related to plate convergence and subduction in a microcontinental or island-arc setting distant from the North American continental plate; (2) Au-Ag-Te and base and precious metal Te-Se-Bi minerals were deposited either during waning stages of hydrothermal activity in a failed massive sulfide system or in a separate event; (3) sulfides and silica-barite rock recrystallized during regional deformation and greenschist facies metamorphism related to the Middle to Late Ordovician collision of the Carolina terrane with the North American continental plate; (4) quartz, barite, and gold were remobilized and formed veins that cut across cleavage; (5) orebodies were offset along high-angle faults; and (6) during weathering, base metal sulfides and barite dissolved and reprecipitated as supergene euhedral barite crystals that line ferric iron oxide-hydroxide gossans.

Investigation of the potential for concealed base-metal mineralization at the Drenchwater Creek Zn-Pb-Ag occurrence, northern Alaska, using geology, reconnaissance geochemistry, and airborne electromagnetic geophysics

USGS Publications Warehouse

Graham, Garth E.; Deszcz-Pan, Maria; Abraham, Jared E.; Kelley, Karen D.

2011-01-01

No drilling has taken place at the Drenchwater occurrence, so alternative data sources (for example, geophysics) are especially important in assessing possible indicators of mineralization. Data from the 2005 electromagnetic survey define the geophysical character of the rocks at Drenchwater and, in combination with geological and surface-geochemical data, can aid in assessing the possible shallow (up to about 50 m), subsurface lateral extent of base-metal sulfide accumulations at Drenchwater. A distinct >3-km-long electromagnetic conductive zone (observed in apparent resistivity maps) coincides with, and extends further westward than, mineralized shale outcrops and soils anomalously high in Pb concentrations within the Kuna Formation; this conductive zone may indicate sulfide-rich rock. Models of electrical resistivity with depth, generated from inversion of electromagnetic data, which provide alongflight-line conductivity-depth profiles to between 25 and 50 m below ground surface, show that the shallow subsurface conductive zone occurs in areas of known mineralized outcrops and thins to the east. Broader, more conductive rock along the western ~1 km of the geophysical anomaly does not reach ground surface. These data suggest that the Drenchwater deposit is more extensive than previously thought. The application of inversion modeling also was applied to another smaller geochemical anomaly in the Twistem Creek area. The results are inconclusive, but they suggest that there may be a local conductive zone, possibly due to sulfides.

Geological and geochemical studies of the Shujiadian porphyry Cu deposit, Anhui Province, Eastern China: Implications for ore genesis

NASA Astrophysics Data System (ADS)

Wang, Shiwei; Zhou, Taofa; Yuan, Feng; Fan, Yu; White, Noel C.; Lin, Fengjie

2015-05-01

Most porphyry deposits in the world occur in magmatic arc settings and are related to subduction of oceanic plates. A small proportion of porphyry deposits occur in intracontinental settings, however they are still poorly understood. Shujiadian, a newly-discovered porphyry Cu deposit, is located in the Middle-Lower Yangtze River Valley metallogenic belt and belongs to the intracontinental class. The deposit has classic alteration zones defined by a core of potassic alteration and local Ca-silicate alteration, which is overprinted by a feldspar-destructive alteration zone and cut by veins containing epidote and chlorite. Wallrocks of the deposit are unreactive quartz-rich sedimentary rocks. Three main paragenetic stages have been recognized based on petrographic observations; silicate stage, quartz-sulfide stage, and sulfide-carbonate stage. Quartz + pyrite + chalcopyrite ± molybdenite veins, and quartz + chalcopyrite + pyrite veins of the quartz-sulfide stage contribute most of the copper, and chalcopyrite + chlorite ± pyrite ± pyrrhotite ± quartz ± illite veins of the sulfide-carbonate stage also contribute part of the copper; all the mineralized veins are associated with feldspar-destructive alteration. Investigations on the fluid inclusions in Shujiadian indicate that the ore-forming fluids had four evolutionary episodes: immiscibility and overpressure in the silicate stage, boiling in the quartz-sulfide stage and mixing with meteoric water in the sulfide-carbonate stage. Sulfur and strontium isotope studies suggest that ore metals were mainly derived from magmatic-hydrothermal fluids, and combined with our study of fluid inclusions, we infer that decompression, changes in oxygen fugacity and sulfur content were the main factors that caused Cu precipitation. Compared with porphyry deposits in magmatic arc settings, there are some differences in the ore-bearing rock, alteration, and the composition of ore-forming fluids.

Dynamic Model of Basic Oxygen Steelmaking Process Based on Multizone Reaction Kinetics: Modeling of Decarburization

NASA Astrophysics Data System (ADS)

Rout, Bapin Kumar; Brooks, Geoffrey; Akbar Rhamdhani, M.; Li, Zushu; Schrama, Frank N. H.; Overbosch, Aart

2018-06-01

In a previous study by the authors (Rout et al. in Metall Mater Trans B 49:537-557, 2018), a dynamic model for the BOF, employing the concept of multizone kinetics was developed. In the current study, the kinetics of decarburization reaction is investigated. The jet impact and slag-metal emulsion zones were identified to be primary zones for carbon oxidation. The dynamic parameters in the rate equation of decarburization such as residence time of metal drops in the emulsion, interfacial area evolution, initial size, and the effects of surface-active oxides have been included in the kinetic rate equation of the metal droplet. A modified mass-transfer coefficient based on the ideal Langmuir adsorption equilibrium has been proposed to take into account the surface blockage effects of SiO2 and P2O5 in slag on the decarburization kinetics of a metal droplet in the emulsion. Further, a size distribution function has been included in the rate equation to evaluate the effect of droplet size on reaction kinetics. The mathematical simulation indicates that decarburization of the droplet in the emulsion is a strong function of the initial size and residence time. A modified droplet generation rate proposed previously by the authors has been used to estimate the total decarburization rate by slag-metal emulsion. The model's prediction shows that about 76 pct of total carbon is removed by reactions in the emulsion, and the remaining is removed by reactions at the jet impact zone. The predicted bath carbon by the model has been found to be in good agreement with the industrially measured data.

Dynamic Model of Basic Oxygen Steelmaking Process Based on Multizone Reaction Kinetics: Modeling of Decarburization

NASA Astrophysics Data System (ADS)

Rout, Bapin Kumar; Brooks, Geoffrey; Akbar Rhamdhani, M.; Li, Zushu; Schrama, Frank N. H.; Overbosch, Aart

2018-03-01

In a previous study by the authors (Rout et al. in Metall Mater Trans B 49:537-557, 2018), a dynamic model for the BOF, employing the concept of multizone kinetics was developed. In the current study, the kinetics of decarburization reaction is investigated. The jet impact and slag-metal emulsion zones were identified to be primary zones for carbon oxidation. The dynamic parameters in the rate equation of decarburization such as residence time of metal drops in the emulsion, interfacial area evolution, initial size, and the effects of surface-active oxides have been included in the kinetic rate equation of the metal droplet. A modified mass-transfer coefficient based on the ideal Langmuir adsorption equilibrium has been proposed to take into account the surface blockage effects of SiO2 and P2O5 in slag on the decarburization kinetics of a metal droplet in the emulsion. Further, a size distribution function has been included in the rate equation to evaluate the effect of droplet size on reaction kinetics. The mathematical simulation indicates that decarburization of the droplet in the emulsion is a strong function of the initial size and residence time. A modified droplet generation rate proposed previously by the authors has been used to estimate the total decarburization rate by slag-metal emulsion. The model's prediction shows that about 76 pct of total carbon is removed by reactions in the emulsion, and the remaining is removed by reactions at the jet impact zone. The predicted bath carbon by the model has been found to be in good agreement with the industrially measured data.

New constraints on the origin of the Skaergaard intrusion Cu-Pd-Au mineralization: Insights from high-resolution X-ray computed tomography

NASA Astrophysics Data System (ADS)

Godel, Bélinda; Rudashevsky, Nikolay S.; Nielsen, Troels F. D.; Barnes, Stephen J.; Rudashevsky, Vladimir N.

2014-03-01

This contribution presents the first detailed three-dimensional (3D) in situ analysis of samples from the Platinova Reef using high-resolution X-ray computed tomography (HRXCT) and 3D image processing and quantification coupled with microscopic and mineralogical investigations. Our HRXCT analyses reveal the complex textural relationships between Cu-rich sulfides (bulk composition close to bornite), skaergaardite (PdCu), Au-rich phases, silicates and Fe-Ti oxides and provide unequivocal textural evidences, not observed previously. The association in 3D between Cu-rich sulfide globules, PdCu alloy and ilmenite is inconsistent with a hydrothermal origin of the Cu-Pd mineralization. In contrast, our results combined with phase diagrams strongly support a primary magmatic origin for the Cu-Pd mineralization where Cu and Pd-rich, Fe-poor sulfide liquid represents a cumulus phase that forms by in-situ nucleation. These sulfide droplets and attached skaergaardite grains were trapped during the formation and crystallization of the Fe-Ti oxides. Subsequent, post-cumulus processes led to the partial to total dissolution of the sulfide not entirely enclosed by the Fe-Ti oxides (i.e., not protected from reaction) leading to the observed variability in Cu and Pd composition at the aggregate (sulfide + PdCu) scale and to the occurrence of free PdCu alloys. In contrast to the PdCu alloy, gold-bearing minerals are never observed entirely enclosed within the Fe-Ti oxide. Two hypotheses can be envisaged for the formation of the gold enriched layer in the upper part of the section. Gold may have either precipitated from high-temperature late magmatic Cl-rich fluids. Alternatively, gold may have been enriched during fractional crystallization after sulfide had been suppressed from the liquidus after the Pd layer crystallized and then deposited along redox barriers.

Oscillatory bursting of gel fuel droplets in a reacting environment.

PubMed

Miglani, Ankur; Nandagopalan, Purushothaman; John, Jerin; Baek, Seung Wook

2017-06-12

Understanding the combustion behavior of gel fuel droplets is pivotal for enhancing burn rates, lowering ignition delay and improving the operational performance of next-generation propulsion systems. Vapor jetting in burning gel fuel droplets is a crucial process that enables an effective transport (convectively) of unreacted fuel from the droplet domain to the flame zone and accelerates the gas-phase mixing process. Here, first we show that the combusting ethanol gel droplets (organic gellant laden) exhibit a new oscillatory jetting mode due to aperiodic bursting of the droplet shell. Second, we show how the initial gellant loading rate (GLR) leads to a distinct shell formation which self-tunes temporally to burst the droplet at different frequencies. Particularly, a weak-flexible shell is formed at low GLR that undergoes successive rupture cascades occurring in same region of the droplet. This region weakens due to repeated ruptures and causes droplet bursting at progressively higher frequencies. Contrarily, high GLRs facilitate a strong-rigid shell formation where consecutive cascades occur at scattered locations across the droplet surface. This leads to droplet bursting at random frequencies. This method of modulating jetting frequency would enable an effective control of droplet trajectory and local fuel-oxidizer ratio in any gel-spray based energy formulation.

Mineralogical and geochemical characterization of supergene Cu-Pb-Zn-V ores in the Oriental High Atlas, Morocco

NASA Astrophysics Data System (ADS)

Verhaert, Michèle; Bernard, Alain; Dekoninck, Augustin; Lafforgue, Ludovic; Saddiqi, Omar; Yans, Johan

2017-10-01

In the Moroccan High Atlas, two sulfide deposits hosted by Jurassic dolostones underwent significant weathering. In the Cu deposit of Jbel Klakh, several stages of supergene mineralization are distinguished: (1) the replacement of hypogene sulfides in the protolith (chalcopyrite) by secondary sulfides in the cementation zone (bornite, digenite, chalcocite, covellite), (2) the formation of oxidized minerals in the saprolite (malachite, azurite, brochantite) where the environment becomes more oxidizing and neutral, and (3) the precipitation of late carbonates (calcite) and iron (hydr-)oxides in the laterite. The precipitation of carbonates is related to the dissolution of dolomitic host rocks, which buffers the fluid acidity due to the oxidation of sulfides. In the Jbel Haouanit Pb-Zn deposit, the mineral assemblage is dominated by typical calamine minerals, Cu minerals (chalcocite, covellite, malachite), and a Cu-Pb-Zn vanadate (mottramite). Galena is successively weathered in anglesite and cerussite. Sphalerite is weathered in smithsonite, which is rapidly replaced by hydrozincite. Late iron (hydr-)oxides are mainly found at the top of both deposits (laterite). Both deposits are thus characterized by specific mineral zoning, from laterite to protolith, related to variations in the mineralogy and ore grades and probably caused by varying Eh-pH conditions.

Nature and origin of the nonsulfide zinc deposits in the Sierra Mojada District, Coahuila, Mexico: constraints from regional geology, petrography, and isotope analyses

NASA Astrophysics Data System (ADS)

Kyle, J. Richard; Ahn, Hyein; Gilg, H. Albert

2018-02-01

The Sierra Mojada District comprises multiple types of near-surface mineral concentrations ranging from polymetallic sulfide zones, "nonsulfide Zn" (NSZ) deposits, and a silver-rich Pb carbonate deposit hosted by lower Cretaceous carbonate strata. Hypogene concentrations of Fe-Zn-Pb-Cu-Ag sulfides and sulfosalts are locally preserved and are associated with hydrothermal dolomite and silica. Alteration mineralogy and sulfur isotope data suggest primary Zn-Pb-Ag mineralization from circa 200 °C hydrothermal fluids. The NSZ deposits dominantly consist of smithsonite and hemimorphite associated with local Mn-Fe oxides. The Red Zinc Zone consists of strata-bound zones dominantly of hemimorphite that fills pores in residual and resedimented Fe oxides. The White Zinc Zone shows local dissolution features, including internal sediments interbanded with and cemented by smithsonite. Similar Pb isotopic compositions of smithsonite, hemimorphite, and cerussite to Sierra Mojada galena document that the NSZ deposits originated from polymetallic carbonate-replacement sulfide deposits, with flow of metal-bearing groundwater being controlled by local topography and structural features in this extensional terrane. Oxygen isotope values for Sierra Mojada smithsonite are relatively constant (δ18OVSMOW = 20.9 to 23.3‰) but are unusually low compared to other supergene smithsonites. Using δ18OVSMOW (- 8‰) of modern groundwater at nearby Cuatrociénegas, smithsonite formational temperatures are calculated to have been between 26 to 35 °C. Smithsonite precipitation was favored by near-neutral conditions typical of carbonate terranes, whereas hemimorphite precipitated by reaction with wallrock silica and locally, or episodically, more acidic conditions resulting from sulfide oxidation. Transition to, and stabilization of, the modern desert climate over the past 9000 years from the Late Pleistocene wetter, cooler climate of northern Mexico resulted in episodic drawdown of the water table and termination of local supergene metal mobilization.

Influence of sea level rise on iron diagenesis in an east Florida subterranean estuary

USGS Publications Warehouse

Roy, M.; Martin, J.B.; Cherrier, J.; Cable, J.E.; Smith, C.G.

2010-01-01

Subterranean estuary occupies the transition zone between hypoxic fresh groundwater and oxic seawater, and between terrestrial and marine sediment deposits. Consequently, we hypothesize, in a subterranean estuary, biogeochemical reactions of Fe respond to submarine groundwater discharge (SGD) and sea level rise. Porewater and sediment samples were collected across a 30-m wide freshwater discharge zone of the Indian River Lagoon (Florida, USA) subterranean estuary, and at a site 250. m offshore. Porewater Fe concentrations range from 0.5 ??M at the shoreline and 250. m offshore to about 286 ??M at the freshwater-saltwater boundary. Sediment sulfur and porewater sulfide maxima occur in near-surface OC-rich black sediments of marine origin, and dissolved Fe maxima occur in underlying OC-poor orange sediments of terrestrial origin. Freshwater SGD flow rates decrease offshore from around 1 to 0.1. cm/day, while bioirrigation exchange deepens with distance from about 10. cm at the shoreline to about 40. cm at the freshwater-saltwater boundary. DOC concentrations increase from around 75 ??M at the shoreline to as much as 700 ??M at the freshwater-saltwater boundary as a result of labile marine carbon inputs from marine SGD. This labile DOC reduces Fe-oxides, which in conjunction with slow discharge of SGD at the boundary, allows dissolved Fe to accumulate. Upward advection of fresh SGD carries dissolved Fe from the Fe-oxide reduction zone to the sulfate reduction zone, where dissolved Fe precipitates as Fe-sulfides. Saturation models of Fe-sulfides indicate some fractions of these Fe-sulfides get dissolved near the sediment-water interface, where bioirrigation exchanges oxic surface water. The estimated dissolved Fe flux is approximately 0.84 ??M Fe/day per meter of shoreline to lagoon surface waters. Accelerated sea level rise predictions are thus likely to increase the Fe flux to surface waters and local primary productivity, particularly along coastlines where groundwater discharges through sediments. ?? 2010 Elsevier Ltd.

Giant Hydrogen Sulfide Plume in the Oxygen Minimum Zone off Peru Supports Chemolithoautotrophy

PubMed Central

Großkopf, Tobias; Kalvelage, Tim; Löscher, Carolin R.; Paulmier, Aurélien; Contreras, Sergio; Siegel, Herbert; Holtappels, Moritz; Rosenstiel, Philip; Schilhabel, Markus B.; Graco, Michelle; Schmitz, Ruth A.; Kuypers, Marcel M. M.; LaRoche, Julie

2013-01-01

In Eastern Boundary Upwelling Systems nutrient-rich waters are transported to the ocean surface, fuelling high photoautotrophic primary production. Subsequent heterotrophic decomposition of the produced biomass increases the oxygen-depletion at intermediate water depths, which can result in the formation of oxygen minimum zones (OMZ). OMZs can sporadically accumulate hydrogen sulfide (H2S), which is toxic to most multicellular organisms and has been implicated in massive fish kills. During a cruise to the OMZ off Peru in January 2009 we found a sulfidic plume in continental shelf waters, covering an area >5500 km2, which contained ∼2.2×104 tons of H2S. This was the first time that H2S was measured in the Peruvian OMZ and with ∼440 km3 the largest plume ever reported for oceanic waters. We assessed the phylogenetic and functional diversity of the inhabiting microbial community by high-throughput sequencing of DNA and RNA, while its metabolic activity was determined with rate measurements of carbon fixation and nitrogen transformation processes. The waters were dominated by several distinct γ-, δ- and ε-proteobacterial taxa associated with either sulfur oxidation or sulfate reduction. Our results suggest that these chemolithoautotrophic bacteria utilized several oxidants (oxygen, nitrate, nitrite, nitric oxide and nitrous oxide) to detoxify the sulfidic waters well below the oxic surface. The chemolithoautotrophic activity at our sampling site led to high rates of dark carbon fixation. Assuming that these chemolithoautotrophic rates were maintained throughout the sulfidic waters, they could be representing as much as ∼30% of the photoautotrophic carbon fixation. Postulated changes such as eutrophication and global warming, which lead to an expansion and intensification of OMZs, might also increase the frequency of sulfidic waters. We suggest that the chemolithoautotrophically fixed carbon may be involved in a negative feedback loop that could fuel further sulfate reduction and potentially stabilize the sulfidic OMZ waters. PMID:23990875

Giant hydrogen sulfide plume in the oxygen minimum zone off Peru supports chemolithoautotrophy.

PubMed

Schunck, Harald; Lavik, Gaute; Desai, Dhwani K; Großkopf, Tobias; Kalvelage, Tim; Löscher, Carolin R; Paulmier, Aurélien; Contreras, Sergio; Siegel, Herbert; Holtappels, Moritz; Rosenstiel, Philip; Schilhabel, Markus B; Graco, Michelle; Schmitz, Ruth A; Kuypers, Marcel M M; Laroche, Julie

2013-01-01

In Eastern Boundary Upwelling Systems nutrient-rich waters are transported to the ocean surface, fuelling high photoautotrophic primary production. Subsequent heterotrophic decomposition of the produced biomass increases the oxygen-depletion at intermediate water depths, which can result in the formation of oxygen minimum zones (OMZ). OMZs can sporadically accumulate hydrogen sulfide (H2S), which is toxic to most multicellular organisms and has been implicated in massive fish kills. During a cruise to the OMZ off Peru in January 2009 we found a sulfidic plume in continental shelf waters, covering an area >5500 km(2), which contained ∼2.2×10(4) tons of H2S. This was the first time that H2S was measured in the Peruvian OMZ and with ∼440 km(3) the largest plume ever reported for oceanic waters. We assessed the phylogenetic and functional diversity of the inhabiting microbial community by high-throughput sequencing of DNA and RNA, while its metabolic activity was determined with rate measurements of carbon fixation and nitrogen transformation processes. The waters were dominated by several distinct γ-, δ- and ε-proteobacterial taxa associated with either sulfur oxidation or sulfate reduction. Our results suggest that these chemolithoautotrophic bacteria utilized several oxidants (oxygen, nitrate, nitrite, nitric oxide and nitrous oxide) to detoxify the sulfidic waters well below the oxic surface. The chemolithoautotrophic activity at our sampling site led to high rates of dark carbon fixation. Assuming that these chemolithoautotrophic rates were maintained throughout the sulfidic waters, they could be representing as much as ∼30% of the photoautotrophic carbon fixation. Postulated changes such as eutrophication and global warming, which lead to an expansion and intensification of OMZs, might also increase the frequency of sulfidic waters. We suggest that the chemolithoautotrophically fixed carbon may be involved in a negative feedback loop that could fuel further sulfate reduction and potentially stabilize the sulfidic OMZ waters.

Formation of unequilibrated R chondrite chondrules and opaque phases

NASA Astrophysics Data System (ADS)

Miller, K. E.; Lauretta, D. S.; Connolly, H. C.; Berger, E. L.; Nagashima, K.; Domanik, K.

2017-07-01

Sulfide assemblages are commonly found in chondritic meteorites as small inclusions in the matrix or in association with chondrules. These assemblages are widely hypothesized to form through pre-accretionary corrosion of metal by H2S gas or through parent body processes. We report here on two unequilibrated R chondrite samples that contain large, chondrule-sized sulfide nodules in the matrix. Both samples are from Mount Prestrud (PRE) 95404. Chemical maps and spot and broad-beam electron microprobe analyses (EMPA) were used to assess the distribution, stoichiometry, and bulk composition of sulfide nodules and silicate chondrules in the clasts. Oxygen isotope data were collected via secondary ion mass spectrometry (SIMS) to assess the relationship of chondrules to other chondrite groups. Scanning electron microscopy (SEM), focused ion beam (FIB), and transmission electron microscopy (TEM) analyses were used to assess fine-scale features and identify crystal structures in sulfide assemblages. Thermodynamic models were used to assess the temperature, sulfur fugacity (fS2), total pressure, dust-to-gas ratio, and oxygen fugacity (fO2) conditions during sulfide nodule and chondrule formation. The unequilibrated clasts include a mixture of type I and type II chondrules, as well as non-porphyritic chondrules. Chondrule oxygen isotopes overlap with ordinary-chondrite chondrules. Sulfide nodules average 200 μm in diameter, have rounded shapes, and are primarily composed of pyrrhotite, pentlandite, and magnetite. Some are deformed around chondrules in a petrologic relationship similar in appearance to compound chondrules. Both nodules and sulfides in chondrules include phosphate inclusions and Cu-rich lamellae, which suggests a genetic relationship between sulfides in chondrules and in the matrix. Ni/Co ratios for matrix and chondrule sulfides are solar, while Fe and Ni are non-solar and inversely related. We hypothesize that sulfide nodules formed via pre-accretionary melt processes. During chondrule formation, precursors composed of a mixture of silicate and sulfide material were heated to form immiscible melt droplets, which separated and cooled to form Si-rich chondrules and S-rich nodules. Sulfide melt was stabilized by a high total pressure (∼1 atm) in a dust- or ice-enriched environment. Heating of this material contributed to a high fS2 (2 × 10-3 atm at 1138 °C), and high fO2 (IW - 1 to IW - 4), in an environment with peak temperatures between 1539 °C and 1750 °C. Oxygen isotopic compositions in this region were similar to those recorded by the LL-chondrite chondrules.

The evolution of droplet impacting on thin liquid film at superhydrophilic surface

NASA Astrophysics Data System (ADS)

Li, Yun; Zheng, Yi; Lan, Zhong; Xu, Wei; Ma, Xuehu

2017-12-01

Thin films are ubiquitous in nature, and the evolution of a liquid film after droplet impact is critical in many industrial processes. In this paper, a series of experiments and numerical simulations are conducted to investigate the distribution and evolution features of local temperature as the droplet impacts a thin film on the superhydrophilic surface by the thermal tracing method. A cold area is formed in the center after droplet impacts on heated solid surfaces. For the droplet impact on thin heated liquid film, a ring-shaped low temperature zone is observed in this experiment. Meanwhile, numerical simulation is adopted to analyze the mechanism and the interaction between the droplet and the liquid film. It is found that due to the vortex velocity distribution formed inside the liquid film after the impact, a large part of the droplet has congested. The heating process is not obvious in the congested area, which leads to the formation of a low-temperature area in the results.

Iron sulfide deposits at Wadi Wassat, Kingdom of Saudi Arabia

USGS Publications Warehouse

Roberts, R.J.; Rossman, D.L.; Bagdady, A.Y.; Conway, C.M.; Helaby, A.M.

1981-01-01

Massive and disseminated iron sulfide deposits in Wadi Wassat form lenticular, stratabound deposits in cherty Precambrian sedimentary rocks interlayered with Precambrian calcareous sedimentary rocks, pyroclastic rocks, and andesitic flow rocks. These rocks have been cut by a wide variety of plutonic and dike rocks including gabbro, diorite, granodiorite, diabase, rhyolite, and granite. The zone containing the sulfide lenses is nearly 16 km long and is cut off by granitic rocks at both the northern and southern ends. The lenses are as much as 200 m thick; one can be traced along strike for more than 4 km. The lenses consist mostly of iron sulfides. Pyrite is the principal sulfide mineral; near intrusive bodies the pyrite has been partially converted to pyrrhotite and locally mobilized into fractures. The sulfides have been oxidized to a depth of about 25 m. Preliminary calculations indicate that about 107,500,000 tons of sulfides, averaging 40 percent iron and 35 percent sulfur, are available to a depth of i00 m. Small amounts of nickel, cobalt, zinc, and copper are also present, but at metal prices prevailing in early 1981, these do not constitute significant resources.

investigating the use of geophysical techniques to detect hydrocarbon seeps

NASA Astrophysics Data System (ADS)

Somwe, Vincent Tambwe

In the Cement oil field, seeps occur in the Hydrocarbon Induced Diagenetic Aureole (HIDA).This 14 square km diagenetic alteration region is mainly characterized by the: (1) secondary carbonate minerals deposition that tends to form ridges throughout the oil field; (2) disseminated pyrite in the vicinity of the fault zones; (3) uranium occurrence and the change in color pattern from red to bleached red sandstone. Generally the HIDA of the Cement oil field is subdivided into four zones: (1) carbonate cemented sandstone zone (zone 1), (2) altered sandstone zone (zone 2), (3) sulfide zone (zone 3) and (4) unaltered sandstone zone (zone 4). This study investigated the use of geophysical techniques to detect alteration zones over the Cement oil field. Magnetic and electromagnetic data were acquired at 5 m interval using the geometric G858 magnetometer and the Geonics EM-31 respectively. Both total magnetic intensity and bulk conductivity were found to decrease across boundaries between unaltered and altered sandstones. Boundaries between sulfide and carbonate zones, which in most cases were located in fault zones, were found to be characterized by higher magnetic and bulk conductivity readings. The contrast between the background and the highest positive peak was found to be in the range of 0.5-10% for total magnetic intensity and 258-450% for bulk conductivity respectively; suggesting that the detection of hydrocarbon seeps would be more effective with EM techniques. The study suggests that geophysical techniques can be used to delineate contact between the different alteration zones especially where metallic minerals such as pyrite are precipitated. The occurrence of carbonate cemented sandstone in the Cement oil field can be used as a pathfinder for hydrocarbon reservoir. The change in color in the altered sandstone zone can still be useful in the hydrocarbon exploration.

Dusty plasmas in the lunar exosphere: Effects of meteoroids

NASA Astrophysics Data System (ADS)

Popel, S. I.; Golub', A. P.; Zelenyi, L. M.; Horányi, M.

2018-01-01

A possibility of the formation in the lunar exosphere of dust cloud due to meteoroid impacts onto the lunar surface is studied. The main attention is paid to the high altitudes over the lunar surface including the range of the altitudes between 30 and 110 km where the measurements of dust were performed within the NASA LADEE mission. From the viewpoint of the formation of dust cloud at high altitudes over the Moon, the most important zone formed by the meteoroid impact is the zone of melting of substance. Only the droplets originated from this zone have the speeds between the first and second astronautical velocities (for the Moon). Correspondingly, only such droplets can perform finite movement around the Moon. The liquid droplets harden when rising over the lunar surface. Furthermore, they aquire electric charges due to the action, in particular, of the solar wind electrons and ions, as well as of the solar radiation. Thus dusty plasmas exist in the lunar exosphere with the characteristic number density ≲ 10-2 m-3 of dust particles with the sizes from 300 nm to 1 μm which is in accordance with the results of measurements performed by LADEE.

Phase 3 geophysical studies in the Wadi Bidah District, Kingdom of Saudi Arabia

USGS Publications Warehouse

Flanigan, V.J.; Sadek, Hamdy; Smith, C.W.

1982-01-01

Detailed geophysical measurements have been made in the Rabathan area, Wadi Bidah district, Kingdom of Saudi Arabia, at the site of diamond drill holes RAB-1, -2, and -3; these measurements suggest that the causative source for the anomalous EM (electromagnetic) and SP (self-potential) responses is probably highly conductive zones of Precambrian siliceous-carbonaceous rocks. Although many of the zones are no more than a few meters wide, they commonly contain 50 to 80 percent carbonaceous material and locally abundant pyrite. In places, several thin layers of highly concentrated carbonaceous material interlayered with chert form a multiple conductive zone that is seen in the geophysical data as complex anomaly patterns. In the geologic environment of Wadi Bidah, massive sulfide-bearing zones cannot be distinguished from siliceous-carbonaceous zones on the basis of the EM-SP responses. In North America in similar environments, complex resistivity methods used in experimental research have successfully discriminated between sulfide and carbonaceous conductors. Tests of such methods in the Wadi Bidah district are recommended. Geologic, geochemical, and geophysical data at the Jabal Mohr prospect suggest the possibility of mineralized rocks at depth over a possible strike length of 400 m.

Substrate system for spray forming

DOEpatents

Chu, Men G.; Chernicoff, William P.

2000-01-01

A substrate system for receiving a deposit of sprayed metal droplets including a movable outer substrate on which the sprayed metal droplets are deposited. The substrate system also includes an inner substrate disposed adjacent the outer substrate where the sprayed metal droplets are deposited on the outer substrate. The inner substrate includes zones of differing thermal conductivity to resist substrate layer porosity and to resist formation of large grains and coarse constituent particles in a bulk layer of the metal droplets which have accumulated on the outer substrate. A spray forming apparatus and associated method of spray forming a molten metal to form a metal product using the substrate system of the invention is also provided.

Substrate system for spray forming

DOEpatents

Chu, Men G.; Chernicoff, William P.

2002-01-01

A substrate system for receiving a deposit of sprayed metal droplets including a movable outer substrate on which the sprayed metal droplets are deposited. The substrate system also includes an inner substrate disposed adjacent the outer substrate where the sprayed metal droplets are deposited on the outer substrate. The inner substrate includes zones of differing thermal conductivity to resist substrate layer porosity and to resist formation of large grains and coarse constituent particles in a bulk layer of the metal droplets which have accumulated on the outer substrate. A spray forming apparatus and associated method of spray forming a molten metal to form a metal product using the substrate system of the invention is also provided.

Spatial-temporal and genetic relationships between gold and antimony mineralization at gold-sulfide deposits of the Ob-Zaisan folded zone

NASA Astrophysics Data System (ADS)

Kalinin, Yu. A.; Naumov, E. A.; Borisenko, A. S.; Kovalev, K. R.; Antropova, A. I.

2015-05-01

The Ob-Zaisan folded zone is a fragment of a single structure composed of Paleozoic sedimentary and volcanogenic rocks (mainly black shale), which was formed at the margin of the Siberian continent and features a common set of magmatic complexes and mineral systems. However, there are some differences that determine the specific geological and metallogenic features of the Irtysh-Zaisan and Kolyvan-Tomsk fragments of the Ob-Zaisan folded zone. In the gold deposits of the West Kalba and Kolyvan-Tomsk auriferous belt, the main gold-sulfide mineralization is controlled by zones of shearing and dynamic metamorphism in carbonaceous carbonate-terrigenous rocks. This type of mineralization was formed in tectonic blocks in a compressional setting. Antimony mineralization is characterized by brecciated textures and the vein-like morphology of ore bodies, reflecting extensional tectonics. At some deposits (Zherek, Mirazh, Dalny), Sb mineralization is spatially separated from the main gold-sulfide ores and shows cross-cutting relations to the principal ore-controlling structures. In other gold deposits, stibnite is spatially associated with disseminated gold-sulfide ores and forms mineral assemblages with Ni, Co, Au, Pb, and Fe (Alimbet, Zhanan, Legostaevskoe, Semiluzhenskoe, and Kamenskoe deposits). This study reveals no direct correlation between Au and Sb in gold-sulfide ores of these deposits. SEM analysis indicated the absence of free gold in stibnite veins. However, atomic absorption and electron microprobe analysis indicated the presence of "invisible gold" from a few ppm to several tens of ppm in the stibnite. High gold contents in the gold-sulfide ores overprinted by antimony mineralization (Suzdalskoe, Zhanan, and Legostaevskoe deposits) can be explained by the processes of regeneration and redeposition. The results of microstructural observations, isotope geochronology, studies of mineral assemblages and fluid inclusions in the ores from gold deposits of the Ob-Zaisan folded zone suggest that antimony mineralization was formed at gold-polysulfide stage, which was separated from the early ore pyrite-arsenopyrite stage by a 30 Ma time gap. It can be assumed that the essentially stibnite mineralization was formed at a separate stage and was separated from the gold-polysulfide mineralization by a 7 Ma interval of tectonic activity. Our Ar-Ar data on sericite from ore samples, combined with U-Pb data on zircons from igneous rocks and previous data from the literature show that there were two major stages of ore formation: the Early Permian (282-270 Ma) and the Early Triassic (250-240 Ma). Most researchers suggest that these stages of mineralization can be related to the epochs of intraplate magmatism that led to the formation of the Tarim (280 Ma) and Siberian (250 Ma) large igneous provinces. These global geological events are generally connected with the influence of Tarim and Siberian mantle plumes.

Biotinylated vanadium and chromium sulfide nanoparticles as probes for colocalization of membrane proteins.

PubMed

Loukanov, Alexandre; Emin, Saim

2016-09-01

We report the microemulsion synthesis of vanadium and chromium sulfide nanoparticles (NPs) and their biological application as nanoprobes for colocalization of membrane proteins. Spherical V2 S3 and Cr2 S3 NPs were prepared in reverse microemulsion droplets, as nanoreactors, obtained by the surfactant sodium bis(2-ethylhexyl) sulfosuccinate (AOT) in nonpolar organic phase (heptane). Electron microscopic data indicated that the size distribution of the nanoparticles was uniform with an average diameter between 3 ÷ 5 nm. The prepared hydrophobic nanocrystals were transferred in aqueous phase by surface cap exchange of AOT with biotin-dihydrolipoic ligands. This substitution allows the nanoparticles solubility in aqueous solutions and confer their bioactivity. In addition, we report the conjugation procedure between α-Lipoic acid (LA) and biotin (abbreviated as biotin-LA). The biotin-LA structure was characterized by 1D and 2D NMR spectroscopy. The biotinylated vanadium and chromium sulfide nanoparticles were tested as probes for colocalization of glutamate receptors on sodium-dodecyl-sulfate-digested replica prepared from rat hippocampus. The method suggests their high labeling efficiency for study of membrane biological macromolecules. Microsc. Res. Tech. 79:799-805, 2016. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

The geology of the Morro Velho gold deposit in the Archean Rio das Velhas greenstone belt, Quadrilátero Ferrífero, Brazil

USGS Publications Warehouse

Vial, Diogenes Scipioni; DeWitt, Ed; Lobato, Lydia Maria; Thorman, Charles H.

2007-01-01

The Morro Velho gold deposit, Quadrilátero Ferrífero region, Minas Gerais, Brazil, is hosted by rocks at the base of the Archean Rio das Velhas greenstone belt. The deposit occurs within a thick carbonaceous phyllite package, containing intercalations of felsic and intermediate volcaniclastic rocks and dolomites. Considering the temporal and spatial association of the deposit with the Rio das Velhas orogeny, and location in close proximity to a major NNW-trending fault zone, it can be classified as an orogenic gold deposit. Hydrothermal activity was characterized by intense enrichment in alteration zones of carbonates, sulfides, chlorite, white mica±biotite, albite and quartz, as described in other Archean lode-type gold ores. Two types of ore occur in the deposit: dark gray quartz veins and sulfide-rich gold orebodies. The sulfide-rich orebodies range from disseminated concentrations of sulfide minerals to massive sulfide bodies. The sulfide assemblage comprises (by volume), on average, 74% pyrrhotite, 17% arsenopyrite, 8% pyrite and 1% chalcopyrite. The orebodies have a long axis parallel to the local stretching lineation, with continuity down the plunge of fold axis for at least 4.8 km. The group of rocks hosting the Morro Velho gold mineralization is locally referred to as lapa seca. These were isoclinally folded and metamorphosed prior to gold mineralization. The lapa seca and the orebodies it hosts are distributed in five main tight folds related to F1 (the best examples are the X, Main and South orebodies, in level 25), which are disrupted by NE- to E-striking shear zones. Textural features indicate that the sulfide mineralization postdated regional peak metamorphism, and that the massive sulfide ore has subsequently been neither metamorphosed nor deformed. Lead isotope ratios indicate a model age of 2.82 ± 0.05 Ga for both sulfide and gold mineralization. The lapa seca are interpreted as the results of a pre-gold alteration process and may be divided into carbonatic, micaceous and quartzose types. The carbonatic lapa seca is subdivided into gray and brown subtypes. Non-mineralized, gray carbonatic lapa seca forms the hanging wall to the orebodies, and is interpreted as the product of extreme CO2 metasomatism during hydrothermal alteration. This dolomitic lapa seca ranges in composition from relatively pure limestone and dolomite to silty limestone and dolomite. The brown carbonatic and micaceous lapa secas are the host rocks to gold. These units are interpreted to correspond to the sheared and hydrothermal products of metamorphosed volcaniclastic and/or volcanic rocks of varying composition from dacitic to andesitic, forming various types of schists and phyllites. The high-grade, massive sulfide orebodies occur at the base of the gray carbonatic lapa seca. Both disseminated mineralization and quartz veins are hosted by micaceous lapa seca. The data are consistent with a model of epigenetic mineralization for the lapa seca, from a hydrothermal fluid derived in part from the Archean basement or older crust material.

Arsenic repartitioning during biogenic sulfidization and transformation of ferrihydrite

NASA Astrophysics Data System (ADS)

Kocar, Benjamin D.; Borch, Thomas; Fendorf, Scott

2010-02-01

Iron (hydr)oxides are strong sorbents of arsenic (As) that undergo reductive dissolution and transformation upon reaction with dissolved sulfide. Here we examine the transformation and dissolution of As-bearing ferrihydrite and subsequent As repartitioning amongst secondary phases during biotic sulfate reduction. Columns initially containing As(V)-ferrihydrite coated sand, inoculated with the sulfate reducing bacteria Desulfovibrio vulgaris (Hildenborough), were eluted with artificial groundwater containing sulfate and lactate. Rapid and consistent sulfate reduction coupled with lactate oxidation is observed at low As(V) loading (10% of the adsorption maximum). The dominant Fe solid phase transformation products at low As loading include amorphous FeS within the zone of sulfate reduction (near the inlet of the column) and magnetite downstream where Fe(II) (aq) concentrations increase; As is displaced from the zone of sulfidogenesis and Fe(III) (s) depletion. At high As(V) loading (50% of the adsorption maximum), sulfate reduction and lactate oxidation are initially slow but gradually increase over time, and all As(V) is reduced to As(III) by the end of experimentation. With the higher As loading, green rust(s), as opposed to magnetite, is a dominant Fe solid phase product. Independent of loading, As is strongly associated with magnetite and residual ferrihydrite, while being excluded from green rust and iron sulfide. Our observations illustrate that sulfidogenesis occurring in proximity with Fe (hydr)oxides induce Fe solid phase transformation and changes in As partitioning; formation of As sulfide minerals, in particular, is inhibited by reactive Fe(III) or Fe(II) either through sulfide oxidation or complexation.

Arsenic Repartitioning during Biogenic Sulfidization and Transformation of Ferrihydrite

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

Kocar, B.; Borch, T; Fendorf, S

Iron (hydr)oxides are strong sorbents of arsenic (As) that undergo reductive dissolution and transformation upon reaction with dissolved sulfide. Here we examine the transformation and dissolution of As-bearing ferrihydrite and subsequent As repartitioning amongst secondary phases during biotic sulfate reduction. Columns initially containing As(V)-ferrihydrite coated sand, inoculated with the sulfate reducing bacteria Desulfovibrio vulgaris (Hildenborough), were eluted with artificial groundwater containing sulfate and lactate. Rapid and consistent sulfate reduction coupled with lactate oxidation is observed at low As(V) loading (10% of the adsorption maximum). The dominant Fe solid phase transformation products at low As loading include amorphous FeS within themore » zone of sulfate reduction (near the inlet of the column) and magnetite downstream where Fe(II){sub (aq)} concentrations increase; As is displaced from the zone of sulfidogenesis and Fe(III){sub (s)} depletion. At high As(V) loading (50% of the adsorption maximum), sulfate reduction and lactate oxidation are initially slow but gradually increase over time, and all As(V) is reduced to As(III) by the end of experimentation. With the higher As loading, green rust(s), as opposed to magnetite, is a dominant Fe solid phase product. Independent of loading, As is strongly associated with magnetite and residual ferrihydrite, while being excluded from green rust and iron sulfide. Our observations illustrate that sulfidogenesis occurring in proximity with Fe (hydr)oxides induce Fe solid phase transformation and changes in As partitioning; formation of As sulfide minerals, in particular, is inhibited by reactive Fe(III) or Fe(II) either through sulfide oxidation or complexation.« less

Arsenic repartitioning during biogenic sulfidization and transformation of ferrihydrite

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

Kocar, Benjamin D.; Borch, Thomas; Fendorf, Scott

Iron (hydr)oxides are strong sorbents of arsenic (As) that undergo reductive dissolution and transformation upon reaction with dissolved sulfide. Here we examine the transformation and dissolution of As-bearing ferrihydrite and subsequent As repartitioning amongst secondary phases during biotic sulfate reduction. Columns initially containing As(V)-ferrihydrite coated sand, inoculated with the sulfate reducing bacteria Desulfovibrio vulgaris (Hildenborough), were eluted with artificial groundwater containing sulfate and lactate. Rapid and consistent sulfate reduction coupled with lactate oxidation is observed at low As(V) loading (10% of the adsorption maximum). The dominant Fe solid phase transformation products at low As loading include amorphous FeS within themore » zone of sulfate reduction (near the inlet of the column) and magnetite downstream where Fe(II)(aq) concentrations increase; As is displaced from the zone of sulfidogenesis and Fe(III)(s) depletion. At high As(V) loading (50% of the adsorption maximum), sulfate reduction and lactate oxidation are initially slow but gradually increase over time, and all As(V) is reduced to As(III) by the end of experimentation. With the higher As loading, green rust(s), as opposed to magnetite, is a dominant Fe solid phase product. Independent of loading, As is strongly associated with magnetite and residual ferrihydrite, while being excluded from green rust and iron sulfide. Our observations illustrate that sulfidogenesis occurring in proximity with Fe (hydr)oxides induce Fe solid phase transformation and changes in As partitioning; formation of As sulfide minerals, in particular, is inhibited by reactive Fe(III) or Fe(II) either through sulfide oxidation or complexation.« less

The north-subducting Rheic Ocean during the Devonian: consequences for the Rhenohercynian ore sites

NASA Astrophysics Data System (ADS)

von Raumer, Jürgen F.; Nesbor, Heinz-Dieter; Stampfli, Gérard M.

2017-10-01

Base metal mining in the Rhenohercynian Zone has a long history. Middle-Upper Devonian to Lower Carboniferous sediment-hosted massive sulfide deposits (SHMS), volcanic-hosted massive sulfide deposits (VHMS) and Lahn-Dill-type iron, and base metal ores occur at several sites in the Rhenohercynian Zone that stretches from the South Portuguese Zone, through the Lizard area, the Rhenish Massif and the Harz Mountain to the Moravo-Silesian Zone of SW Bohemia. During Devonian to Early Carboniferous times, the Rhenohercynian Zone is seen as an evolving rift system developed on subsiding shelf areas of the Old Red continent. A reappraisal of the geotectonic setting of these ore deposits is proposed. The Middle-Upper Devonian to Early Carboniferous time period was characterized by detrital sedimentation, continental intraplate and subduction-related volcanism. The large shelf of the Devonian Old Red continent was the place of thermal subsidence with contemporaneous mobilization of rising thermal fluids along activated Early Devonian growth faults. Hydrothermal brines equilibrated with the basement and overlying Middle-Upper Devonian detrital deposits forming the SHMS deposits in the southern part of the Pyrite Belt, in the Rhenish Massif and in the Harz areas. Volcanic-hosted massive sulfide deposits (VHMS) formed in the more eastern localities of the Rhenohercynian domain. In contrast, since the Tournaisian period of ore formation, dominant pull-apart triggered magmatic emplacement of acidic rocks, and their metasomatic replacement in the apical zones of felsic domes and sediments in the northern part of the Iberian Pyrite belt, thus changing the general conditions of ore precipitation. This two-step evolution is thought to be controlled by syn- to post-tectonic phases in the Variscan framework, specifically by the transition of geotectonic setting dominated by crustal extension to a one characterized by the subduction of the supposed northern slab of the Rheic Ocean preceding the general Late Variscan crustal shortening and oroclinal bending.

NOx formation from the combustion of monodisperse n-heptane sprays doped with fuel-nitrogen additives

NASA Technical Reports Server (NTRS)

Sarv, Hamid; Cernansky, Nicholas P.

1989-01-01

A series of experiments with simulated synthetic fuels were conducted in order to investigate the effect of droplet size on the conversion of fuel-nitrogen to NOx. Pyridine and pyrrole were added to n-heptane as nitrogen-containing additives and burned as monodisperse fuel droplets under various operating conditions in a spray combustion facility. The experimental results indicate that under stoichiometric and fuel-rich conditions, reducing the droplet size increases the efficiency of fuel-N conversion to NOx. This observation is associated with improved oxidation of the pyrolysis fragments of the additive by better oxygen penetration through the droplet flame zone. The dominant reactions by which fuel-N is transformed to NOx were also considered analytically by a premixed laminar flame code. The calculations are compared to the small droplet size results.

Atacamite and paratacamite from the ultramafic-hosted Logatchev seafloor vent field (14°45′N, Mid-Atlantic Ridge)

USGS Publications Warehouse

Dekov, Vesselin; Boycheva, Tanya; Halenius, Ulf; Petersen, Sven; Billstrom, Kjell; Stummeyer, Jens; Kamenov, G.; Shanks, W.

2011-01-01

Atacamite and paratacamite are ubiquitous minerals associated with Cu-rich massive sulfides at the Logatchev hydrothermal field (Mid-Atlantic Ridge). In this work we provide new details on the mineralogy and geochemistry of these basic cupric chlorides. Our data support the notion that atacamite and paratacamite formation at submarine vent fields is an alteration process of hydrothermal Cu-sulfides. Secondary Cu-sulfides (bornite, covellite) are unstable at ambient seawater conditions and will dissolve. Dissolution is focused at the sulfide–seawater contact, leading to release of Fe2+ and Cu+ and formation of residual chalcocite through an intermediate Cu5S4 phase. Most of the released Fe2+ oxidizes immediately and precipitates as FeOOH directly on the chalcocite rims whereas Cu as chloride complexes (CuCl2−, CuCl32-) remains in solution at the same Eh. Cuprous–chloride complexes migrate from the reaction zone and upon increasing Eh precipitate as Cu2Cl(OH)3. As a consequence of this, the sulfide–seawater reaction interface is clearly marked by thin chalcocite–FeOOH bands and the entire assemblage is mantled by atacamite (or paratacamite). Our mineralogical, petrographic, geochemical and isotopic studies suggest that there are two types of atacamite (and/or paratacamite) depending on their mode of precipitation. Type 1 atacamite precipitated directly on the parent sulfides as evidenced by mantling of the sulfides, absence of detrital mineral grains, a preserved conspicuous positive Eu anomaly and a negligible negative Ce anomaly similar to those of the parent sulfide. In addition, Au concentrations are slightly lower than those of the parent sulfides, which suggest minimal transport of Au-ions after their release from the sulfides. Furthermore, the low content of the rare earth elements implies short contact time with the ambient seawater. The Sr–Nd–Pb-isotopic signatures of type 1 atacamite confirm the genetic association with the parent sulfides and indicate formation spatially very close to the latter. Type 2 atacamite precipitated at some distance from the parent sulfides, which means that the cuprous–chloride complexes have moved away from the sulfide alteration zone before precipitation. The evidence for this is absence of direct association of atacamite with sulfides. In addition, this atacamite contains a substantial proportion of detrital minerals, which implies precipitation in the sediments, distal to the parent sulfides. As a consequence of the detrital impurities the contents of elements like Cr, Cs, Hf, Nb, Rb, Th and Zr are higher than in type 1 atacamite (and/or paratacamite). Au contents are lower than those of type 1 atacamite (and/or paratacamite) which implies prolonged Au transport in solution before precipitation. Furthermore, the rare earth element distribution patterns have no positive Eu anomaly suggesting that the positive Eu anomaly of the parent sulfide has been erased after dissolution and prolonged contact of the fluid with ambient seawater (with negative Eu anomaly). Finally, the Sr–Nd-isotope signature differs from that of the parent sulfide and indicates a considerable terrigenous input.

Genetic Pd, Pt, Au, Ag, and Rh mineralogy in Noril'sk sulfide ores

NASA Astrophysics Data System (ADS)

Spiridonov, E. M.; Kulagov, E. A.; Serova, A. A.; Kulikova, I. M.; Korotaeva, N. N.; Sereda, E. V.; Tushentsova, I. N.; Belyakov, S. N.; Zhukov, N. N.

2015-09-01

The undeformed ore-bearing intrusions of the Noril'sk ore field (NOF) cut through volcanic rocks of the Late Permian-Early Triassic trap association folded in brachysynclines. Due to the nonuniform load on the roof of intrusive bodies, most sulfide melts were squeezed, up to the tops of ore-bearing intrusions; readily fusible Ni-Fe-Cu sulfide melts were almost completely squeezed. In our opinion, not only one but two stages of mineralization developed at the Noril'sk deposits: (i) syntrap magmatic and (ii) epigenetic post-trap metamorphic-hydrothermal. All platinum-group minerals (PGM) and minerals of gold are metasomatic in the Noril'sk ores. They replaced sulfide solid solutions and exsolution structures. All types of PGM and Au minerals occur in the ores, varying in composition from pyrrhotite to chalcopyrite, talnakhite, mooihoekite, and rich in galena; they are localized in the inner and outer contact zones and differ only in the quantitative proportions of ore minerals. The aureoles of PGM and Au-Ag minerals are wider than the contours of sulfide bodies and coincide with halos of fluid impact on orebodies and adjacent host rocks. The pneumatolytic PGM and Au-Ag minerals are correlated in abundance with the dimensions of sulfide bodies. Their amounts are maximal in veins of late fusible ore composed of eutectic PbS ss and iss intergrowths, as well as at their contacts. The Pd and Pt contents in eutectic sulfide ores of NOF are the world's highest. In the process of noble-metal mineral formation, the fluids supply Pd, Pt, Au, As, Sb, Sn, Bi, and a part of Te, whereas Fe, Ni, Cu, Pb, Ag, Rh, a part of Te and Pd are leached from the replaced sulfide minerals. The pneumatolytic PGM of the early stage comprises Pd and Pt intermetallic compounds enriched in Au along with Pd-Pt-Fe-Ni-Cu-Sn-Pb(As) and (Pd,Pt,Au)(Sn,Sb,Bi,Te,As) solid solutions. Pneumatolytic PGM and Au minerals of the middle stage are products of solid-phase transformation and recrystallization of early PGM in combination with the newly formed mineral species Sb-paolovite-insizwaite-geversite-maslovite, niggliite, tetraferroplatinum, rustenburgite-atokite-zvyagintsevite, moncheite, majakite, plumbopalladinite, polarite in association with altaite. The late minerals of the middle stage include stannopalladinite, tatianaite-taimyrite, Ag-Pd-Pt tetraauricupride, and cuproauride. PGM and Au-Ag minerals of the late stage are represented by sobolevskite-sudburyite-kotulskite, maslovite-michenerite, low-Sb paolovite, hessite, cabriite, Au-Ag minerals with fineness of 870-003, froodite, Sb-free insizwaite, Bi-free geversite, and Sb-free niggliite. Electrum and küstelite in PGM aggregates are not zoned. Crystals of Au-Ag minerals that grow over PGM minerals are smoothly zoned. Their zoning may be direct (crystal margins are enriched in Ag), inverse, oscillatory, and complex. Despite favorable annealing conditions, exsolution structures are not identified in Au-Ag minerals from the Noril'sk ores. Sperrylite—the latest of pneumatolytic PGM—occurs as metacrysts up to 14 cm in size. Sperrylite, which replaces high-Sb minerals, contains up to 11 wt % Sb. Pneumatolytic noble-metal minerals originated under the effect of the fluids released during crystallization of sulfide melts in an extremely reductive setting and at extremely low fS2; temperature drops from ~450 to ~350°C. Metamorphic-hydrothermal Ag mineralization (native silver, Hg-silver, sulfides and selenides, chalcopyrite-lenaite solid solutions, argentopentlandite), Pd mineralization (vysotskite, palladoarsenide, vincentite, Sb-free Ag-paolovite, malyshevite, native palladium), and Pt mineralization (kharaelakhite, cooperite, native platinum) develop in those parts of orebodies that are affected by low-grade metamorphism.

Platinum mineralization in the Kapalagulu Intrusion, western Tanzania

NASA Astrophysics Data System (ADS)

Wilhelmij, Harry R.; Cabri, Louis J.

2016-03-01

Low-grade copper and nickel mineralization was found near the eastern shore of Lake Tanganyika at Kungwe Bay in the early part of the twentieth century. The mineralization occurs in harzburgite at the base of a layered gabbro complex known as the Kapalagulu Intrusion, emplaced between the Paleoproterozoic Ubendian basement and overlying Neoproterozoic Itiaso Group metasediments. Several mining and exploration companies continued the geophysical and drilling exploration for base metals throughout the last century culminating in the discovery of high-grade platinum-group element (PGE) mineralization associated with chromitite and sulfide-bearing harzburgite within the southeastern extension of the Kapalagulu Intrusion (known as the Lubalisi Zone) that is covered by a layer of nickel-rich laterite regolith. The poorly layered southeastern harzburgite forms part of the >1500 m-thick Lower Ultramafic Sequence and resembles a dike-like body that flares upwards into a succession of well-layered gabbroic rocks of the Upper Mafic Sequence. No PGE mineralization has been found in the layered gabbro; all the mineralization is associated with the chromite- and sulfide-rich harzburgite of the Lower Ultramafic Sequence and the laterite regolith overlying the mineralized harzburgite. The Lubalisi Zone harzburgite is underlain by basal dunite and overlain by an interval of layered harzburgite and troctolite and this ultramafic sequence is folded into a syncline that plunges towards the northwest that has been modified by major dolerite-filled faults orientated subparallel to the fold axial surface. Extensive deep drilling in the Lubalisi Zone of the Kapalagulu Intrusion shows that the folded harzburgite can be subdivided into a lower feldspathic harzburgite, a harzburgite containing chromitite seams and intervals of sulfide and chromite mineralization known as the Main Chromite Sulfide Succession (MCSS), an overlying sulfide-rich harzburgite, and an upper feldspathic harzburgite. Impersistent, stratiform PGE mineralized horizons occur within the MCSS harzburgite from which drill core samples were taken for platinum-group mineral (PGM) characterization from two drill holes. Where the PGE reefs reach the surface there is residual PGE mineralization within the laterite regolith from which drill core samples were taken from various laterite lithological units for PGM characterization. As the harzburgite PGE reefs contain significant concentrations of both sulfide and chromite (including chromitite seams) they resemble the PGE-rich chromitite seams of the Bushveld Complex rather than the PGE-bearing Main Sulfide Zone of the Great Dyke and Main Sulfide Layer of the Munni Munni Complex. The dominant Pd PGM in three PGE reef samples varies, ranging ( n = 164, relative wt%) from bismuthides (63 %), bismuthtellurides (19 %), and tellurides (6 %), to tellurides (39 %), bismuthtellurides (24 %), stannides (14 %), and alloys (13 %), and to antimon-arsenides (33 %), stannides (21 %), bismuthides (17 %), tellurides (13 %), and alloys (10 %). From 13.5 % to 21.0 % of the total Pd occurs as a solid solution in pentlandite. The three samples have similar Pt PGM modal distributions ( n = 172, relative wt%); the dominant Pt mineral is sperrylite (79, 58, and 47 %) followed by tellurides (15, 17, 21 %), alloys (2, 1, 1 %), and sulfides (2, 1, 0 %). Comparison of Pd/Pt ratios from assays to those calculated from minerals show that the data for the Pt and Pd PGM are very robust, confirming the concentration methodology and characterization. Study of samples from a shallow drill hole penetrating the laterite regolith shows that the primary Pd mineralization has not survived oxidation, is mainly dispersed, but some was reconstituted to form secondary minerals: cabriite, unnamed tellurides, a selenide, a Pd-Te-Hg mineral, alloys and Pd-bearing secondary sulfides (millerite and heazlewoodite). The primary Pt minerals are more resistant to oxidation and dissolution, especially sperrylite and isoferroplatinum, but it is likely that other Pt alloys (tetraferroplatinum and tulameenite) are of secondary origin after dissolution of Pt tellurides.

Millisecond-Timescale Monitoring of PbS Nanoparticle Nucleation and Growth Using Droplet-Based Microfluidics.

PubMed

Lignos, Ioannis; Stavrakis, Stavros; Kilaj, Ardita; deMello, Andrew J

2015-08-26

The early-time kinetics (<1 s) of lead sulfide (PbS) quantum dot formation are probed using a novel droplet-based microfluidic platform, which allows for high-throughput and real-time optical analysis of the reactive process with millisecond time resolution. The reaction platform enables the concurrent investigation of the emission characteristics of PbS quantum dots and a real-time estimation of their size and concentration during nucleation and growth. These investigations reveal a two-stage mechanism for PbS nanoparticle formation. The first stage corresponds to the fast conversion of precursor species to PbS crystals, followed by the growth of the formed particles. The growth kinetics of the PbS nanoparticles follow the Lifshitz-Slyozov-Wagner model for Ostwald ripening, allowing direct estimation of the rate constants for the process. In addition, the extraction of absorption spectra of ultrasmall quantum dots is demonstrated for first time in an online manner. The droplet-based microfluidic platform integrated with online spectroscopic analysis provides a new tool for the quantitative extraction of high temperature kinetics for systems with rapid nucleation and growth stages. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Siderophile and chalcophile metals as tracers of the evolution of the Siberian Trap in the Noril'sk region, Russia

NASA Astrophysics Data System (ADS)

Brügmann, G. E.; Naldrett, A. J.; Asif, M.; Lightfoot, P. C.; Gorbachev, N. S.; Fedorenko, V. A.

1993-05-01

In this study Cu, Ni, and platinum-group elements (PGE) were determined in a sequence of basaltic and picritic lavas from the Siberian Trap in the Noril'sk area of Russia to constrain genetic relationships between the basalts and the petrogenesis of Ni-Cu-PGE sulfide deposits associated with the Talnakh and Noril'sk intrusions. In the most primitive basalts (8-19 wt% MgO) of the Tuklonsky (Tk) suite, Pt and Pd concentrations range from 4-13 ppb, increasing with decreasing MgO content; whereas Ir contents decrease with MgO from 0.8-0.05 ppb. The contrasting behavior of these elements, which all have very high sulfide-silicate partition coefficients, as well as the primitive mantle-like ratios of Cu/Y and Pd/Y, suggests that these magmas were not sulfide-saturated. The high PGE abundances imply that their parental magmas were also not sulfide saturated during partial melting in the mantle. Due to sulfide segregation, the overlying basalts of the Nadezhdinsky (Nd) series are low in Cu and Ni (52 and 38 ppm, respectively); highly depleted in all PGE; and have very low Cu/Y, Pd/Y, and Pd/Cu ratios. However, in stratigraphically higher levels, Cu, Ni, and PGE concentrations increase systematically through the Morongovsky (Mr) suite to reach a concentration plateau in the uppermost Mokulaevsky (Mk) suite (Pt 8 ppb; Pd: 9 ppb; Ir: 0.12 ppb; Rh: 0.4 ppb). At the same time, ratios such as Cu/Y increase and approach primitive mantle values. However, ratios involving PGE, such as Pd/Y, remain low, suggesting the removal of small amounts of sulfide (0.01-0.03%). The compositional variations in the basalts and the sulfide liquids can be quantitatively described by fractional segregation of a sulfide liquid in an open- or closed-system magma chamber. The latter model suggests that the basalts represent the eruption products of a zoned magma chamber in which light magma, with crustal components contaminated, overlies less contaminated, denser magma. Crustal contamination caused sulfide saturation, and the resulting sulfide liquids settled through a magma column and accumulated at the bottom of the chamber. In this model, the sulfide liquid is not in equilibrium with the whole magma mass, and sulfide segregation is compared with the zone-refining process of metallurgy. The sulfides become more enriched as they move through the magma; and although the magma left behind is depleted in PGE, Cu, and Ni, their concentrations also increase with depth. Eventually, the magma chamber is emptied from the top to the bottom, producing the flood basalt sequence and the associated intrusions and ore deposits. In the open-system model, sulfide saturation was initially caused by assimilation of crustal material by the Tuklonsky magma. Continuous and simultaneous replenishment, assimilation, and crystallization processes formed the lower Nd lavas. The concurrent removal of 0.5-1% sulfide strongly depleted these magmas in chalcophile and siderophile metals. Due to the continuous replenishment of the magma chamber with uncontaminated PGE-rich magma, succeeding lavas (Mr, Mk) show diminishing signs of crustal contamination and become less sulfide-saturated, as indicated by the increasing Ni, Cu, and PGE abundances. During the evolution of the chamber, the magma remained sulfur-saturated, and sulfides accumulated at the base. The composition of the sulfide ores could be regarded as a mixture consisting of low Ni-, Cu-, and PGE-sulfides derived with a low silicate/sulfide ratio (100) from the Tk-Nd magma and high Ni-, Cu-, and PGE-sulfides formed with a high ratio (10,000) from the Mr-Mk magma.

Droplet burning at zero G

NASA Technical Reports Server (NTRS)

Williams, F. A.

1978-01-01

Questions of the importance and feasibility of performing experiments on droplet burning at zero gravity in Spacelab were studied. Information on the physics and chemistry of droplet combustion, with attention directed specifically to the chemical kinetics, heat and mass transfer, and fluid mechanics of the phenomena involved, are presented. The work was divided into three phases, the justification, the feasibility, and the conceptual development of a preliminary design. Results from the experiments performed revealed a few new facts concerning droplet burning, notably burning rates in excess of theoretical prediction and a phenomenon of flash extinction, both likely traceable to accumulation of carbon produced by gas-phase pyrolysis in the fuel-rich zone enclosed by the reaction surface. These experiments also showed that they were primarily due to timing difficulties.

Electric coupling between distant nitrate reduction and sulfide oxidation in marine sediment

PubMed Central

Marzocchi, Ugo; Trojan, Daniela; Larsen, Steffen; Louise Meyer, Rikke; Peter Revsbech, Niels; Schramm, Andreas; Peter Nielsen, Lars; Risgaard-Petersen, Nils

2014-01-01

Filamentous bacteria of the Desulfobulbaceae family can conduct electrons over centimeter-long distances thereby coupling oxygen reduction at the surface of marine sediment to sulfide oxidation in deeper anoxic layers. The ability of these cable bacteria to use alternative electron acceptors is currently unknown. Here we show that these organisms can use also nitrate or nitrite as an electron acceptor thereby coupling the reduction of nitrate to distant oxidation of sulfide. Sulfidic marine sediment was incubated with overlying nitrate-amended anoxic seawater. Within 2 months, electric coupling of spatially segregated nitrate reduction and sulfide oxidation was evident from: (1) the formation of a 4–6-mm-deep zone separating sulfide oxidation from the associated nitrate reduction, and (2) the presence of pH signatures consistent with proton consumption by cathodic nitrate reduction, and proton production by anodic sulfide oxidation. Filamentous Desulfobulbaceae with the longitudinal structures characteristic of cable bacteria were detected in anoxic, nitrate-amended incubations but not in anoxic, nitrate-free controls. Nitrate reduction by cable bacteria using long-distance electron transport to get privileged access to distant electron donors is a hitherto unknown mechanism in nitrogen and sulfur transformations, and the quantitative importance for elements cycling remains to be addressed. PMID:24577351

Formation of mercury sulfide from Hg(II)−thiolate complexes in natural organic matter

USGS Publications Warehouse

Alain Manceau,; Cyprien Lemouchi,; Mironel Enescu,; Anne-Claire Gaillot,; Martine Lanson,; Valerie Magnin,; Pieter Glatzel,; Poulin, Brett; Ryan, Joseph N.; Aiken, George R.; Isabelle Gautier-Lunea,; Kathryn L. Nagy,

2015-01-01

Methylmercury is the environmental form of neurotoxic mercury that is biomagnified in the food chain. Methylation rates are reduced when the metal is sequestered in crystalline mercury sulfides or bound to thiol groups in macromolecular natural organic matter. Mercury sulfide minerals are known to nucleate in anoxic zones, by reaction of the thiol-bound mercury with biogenic sulfide, but not in oxic environments. We present experimental evidence that mercury sulfide forms from thiol-bound mercury alone in aqueous dark systems in contact with air. The maximum amount of nanoparticulate mercury sulfide relative to thiol-bound mercury obtained by reacting dissolved mercury and soil organic matter matches that detected in the organic horizon of a contaminated soil situated downstream from Oak Ridge, TN, in the United States. The nearly identical ratios of the two forms of mercury in field and experimental systems suggest a common reaction mechanism for nucleating the mineral. We identified a chemical reaction mechanism that is thermodynamically favorable in which thiol-bound mercury polymerizes to mercury–sulfur clusters. The clusters form by elimination of sulfur from the thiol complexes via breaking of mercury–sulfur bonds as in an alkylation reaction. Addition of sulfide is not required. This nucleation mechanism provides one explanation for how mercury may be immobilized, and eventually sequestered, in oxygenated surface environments.

Hydrothermal mineralization at seafloor spreading centers

NASA Astrophysics Data System (ADS)

Rona, Peter A.

1984-01-01

The recent recognition that metallic mineral deposits are concentrated by hydrothermal processes at seafloor spreading centers constitutes a scientific breakthrough that opens active sites at seafloor spreading centers as natural laboratories to investigate ore-forming processes of such economically useful deposits as massive sulfides in volcanogenic rocks on land, and that enhances the metallic mineral potential of oceanic crust covering two-thirds of the Earth both beneath ocean basins and exposed on land in ophiolite belts. This paper reviews our knowledge of processes of hydrothermal mineralization and the occurrence and distribution of hydrothermal mineral deposits at the global oceanic ridge-rift system. Sub-seafloor hydrothermal convection involving circulation of seawater through fractured rocks of oceanic crust driven by heat supplied by generation of new lithosphere is nearly ubiquitous at seafloor spreading centers. However, ore-forming hydrothermal systems are extremely localized where conditions of anomalously high thermal gradients and permeability increase hydrothermal activity from the ubiquitous low-intensity background level (⩽ 200°C) to high-intensity characterized by high temperatures ( > 200-c.400°C), and a rate and volume of flow sufficient to sustain chemical reactions that produce acid, reducing, metal-rich primary hydrothermal solutions. A series of mineral phases with sulfides and oxides as high- and low-temperature end members, respectively, are precipitated along the upwelling limb and in the discharge zone of single-phase systems as a function of increasing admixture of normal seawater. The occurrence of hydrothermal mineral deposits is considered in terms of spatial and temporal frames of reference. Spatial frames of reference comprise structural features along-axis (linear sections that are the loci of seafloor spreading alternating with transform faults) and perpendicular to axis (axial zone of volcanic extrusion and marginal zones of active extension) common to all spreading centers, regional tectonic setting determined by stage (early, advanced), and rate (slow, intermediate-to-fast) of opening of an ocean basin about a spreading center, and local tectonic sub-setting that incorporates anomalous structural and thermal conditions conducive to mineral concentration (thermal gradient, permeability, system geometry, leaky versus tight hydrothermal systems). Temporal frames of reference comprise the relation between mineral concentration and timing of regional plutonic, volcanic and tectonic cycles and of episodic local physical and chemical events (transient stress, fluctuating heat transfer, intrusion-extrusion, fracturing, sealing, etc.). Types of hydrothermal deposits are not uniquely associated with specific tectonic settings and subsettings. Similar types of hydrothermal deposits may occur in different tectonic settings as a consequence of convergence of physical and chemical processes of concentration. Local tectonic sub-settings with conditions conducive to hydrothermal mineralization at slow-spreading centers (half rate ≤ 2cm y -1; length c. 28,000 km), characterized by an estimated average convective heat transfer of 15.1·10 8 cal. cm -2, deep-level ( > 3 km), relative narrow (< 5 km wide at base) magma chambers, and high topographic relief (1-5 km) are: (1) basins along linear sections of the axial zone of volcanic extrusion near transform faults at an early stage of opening, represented by a large stratiform sulfide deposit (estimated 32.5·10 6 metric tons) of the Atlantis II Deep of the Red Sea; (2) the wall along linear sections of the rift valley in the marginal zone of active extension at an advanced stage of opening, represented by encrustations and layered deposits of manganese and iron oxides, hydroxides and silicates inferred to be underlain by stockwork sulfides at the TAG Hydrothermal Field at latitude 26°C on the Mid-Atlantic Ridge; (3) transform faults, especially those with large ridge-ridge offset ( > 30 km), at an advanced stage of opening, represented by stockwork sulfides exposed in the walls of equatorial fracture zones of the Atlantic Ocean and Indian Ocean; (4) the axial zone of volcanic extrusion at an advanced stage of opening. Local tectonic sub-settings with conditions conducive to hydrothermal mineralization at intermediate- to fast-spreading centers (half rate > 2cm y -1; length c. 22,000 km) characterized by an estimated average convective heat transfer of 11.5·10 8 cal. cm -2, relatively wide (up to 20 km at base), shallow-level (c. 1-3 km) magma chambers, and low topographic relief (< 1 km), are: (1) basins along linear sections of the axial zone of volcanic extrusion at an early stage of opening, represented by massive sulfide deposits of the Guaymas Basin of the Gulf of California; (2) the axial zone of volcanic extrusion at an advanced stage of opening, represented by individually small (c. 1·10 3 metric tons), massive sulfide mounds surmounted by chimneys of the East Pacific Rise at latitude 21°N; (3) the marginal zone of active extension at an advanced stage of opening represented by a large, massive sulfide deposit (preliminary tentative estimate c.10·10 6 metric tons) at a double-rifted section of the Galapagos Spreading Center; (4) transform faults, especially those with large ridge-ridge offset ( > 50 km) represented by manganese encrustations in a transform fault at the Galapagos Spreading Center; (5) volcanic seamounts related to persistent hot spots at spreading centers, represented by oxide and sulfide deposits on seamounts off the axis of the East Pacific Rise; (6) portions of spreading centers with anomalous configurations such as multiple, bent or extended rifts, represented by massive sulfide deposits at a double-rifted section of the Galapagos Spreading Center, suggesting the operation of a thermal-structural feedback mechanism indicative of the presence of hydrothermal mineralization; (7) discrete spreading centers in back-arc basins represented by hydrothermal deposits at sites in marginal seas of the western Pacific. Ore-forming processes appear to be least efficient in the axial zone of volcanic extrusion of oceanic ridges at an advanced stage of opening irrespective of spreading rate, where tight hydrothermal systems dissipate a major portion of contained metals by precipitation and dispersion in particulate form from "black smokers" that discharge into the water column. Ore-forming processes appear to be most efficient at sites in basins at linear sections of the axial zone of volcanic extrusion near transform faults during an early stage of opening, and at marginal zones of active extension along linear sections of a spreading center during an advanced stage of opening, irrespective of spreading rate, where both tight and leaky hydrothermal systems may conserve their contained metals to concentrate large sulfide deposits. Resemblances in mineralization between stockwork sulfides at seafloor spreading centers and porphyry copper-type deposits in volcanogenic rocks on land suggest the possibility for the occurrence of large tonnage, low-grade porphyry copper-like deposits concentrated by leaky hydrothermal systems at spreading centers. Systematic application of composite exploration procedures is leading to the discovery of numerous additional deposits. It is inferred from the limited data base available that the occurrence of hydrothermal mineral deposits is more frequent at intermediate-to-fast-than at slow-spreading centers, but the potential for the accumulation of large hydrothermal mineral deposits is greater at slow-spreading centers. Current knowledge of the distribution of hydrothermal mineral deposits at seafloor spreading centers is limited to about 55 sites at this early stage of exploration. Estimates of the distribution of either fields of hydrothermal mineral deposits or high-intensity ore-forming hydrothermal systems at seafloor spreading centers, deduced from various considerations, range from one such occurrence between 15 and 265 km along slow-spreading centers, and 1 and 100 km along intermediate- to fast-spreading centers. However, the distribution of sizable deposits will remain sporadic owing to the special structural and thermal conditions necessary to sustain and to retain high-intensity ore-forming hydrothermal systems.

Rock magnetic properties in the sulfate reduction zone in IODP 350 Hole 1437B, Izu Bonin rear arc: preliminary results

NASA Astrophysics Data System (ADS)

Musgrave, R. J.; Kars, M. A. C.; Kodama, K.

2014-12-01

During the northern Spring 2014 (April-May), IODP Expedition 350 drilled a 1806.5 m deep hole at Site U1437 in the Izu-Bonin rear arc, in order to understand, among other objectives, the compositional evolution of the arc since the Miocene and track the missing half of the subduction factory. The good recovery of mostly fine grained sediments at this site enables a high resolution paleomagnetic and rock magnetic study. Particularly, variations in magnetic properties and mineralogy are well documented. The onboard magnetostratigraphy established from the study of the archive halves highlighted remagnetized intervals that produced "ghost" repetitions of geomagnetic reversals ~10's meters below their actual stratigraphic position in specific intervals. Onboard paleo- and rock magnetic analyses showed that remagnetization is probably due to a chemical remanence carried by iron sulfides (putatively identified as greigite). The rock magnetic parameters, SIRM/k and the S-ratio are consistent with the presence of ferromagnetic iron sulfides in Site U1437. A mixture of iron oxides and iron sulfides was found within the sulfate reduction zone, which was identified by onboard pore water analyses at ~50-60 meters below sea floor (mbsf) by a minimum in sulfate (~5 mM) coupled with a maximum in alkalinity. Below 50 mbsf, the sulfate content increases up to ~29 mM at ~460 mbsf. The particular downhole profile of the sulfate content in Site U1437 is probably triggered by fluid circulation. Evolution of sulfate content, pyritization process and fluid circulation are closely linked. Onshore research is focusing on further downhole characterization of the iron sulfides including their abundance, grain size and composition. Routine magnetic properties (NRM, magnetic susceptibility) and rock magnetic analyses at high resolution (every ~20-50 cm), including hysteresis properties and low temperature magnetic measurements, have been conducted on about 400 discrete samples in the first 200 m of Hole 1437B (Cores 1H to 30X). As suggested by the onboard data, hysteresis measurements showed the occurrence of both single domain-pseudo single domain iron oxides and iron sulfides in the sulfate reduction zone. Preliminary results will be compared with the geochemical data.

The Anarraaq Zn-Pb-Ag and barite deposit, northern Alaska: Evidence for replacement of carbonate by barite and sulfides

USGS Publications Warehouse

Kelley, K.D.; Dumoulin, Julie A.; Jennings, S.

2004-01-01

The Anarraaq deposit in northern Alaska consists of a barite body, estimated to be as much as 1 billion metric tons, and a Zn-Pb-Ag massive sulfide zone with an estimated resource of about 18 Mt at 18 percent Zn, 5.4 percent Pb, and 85 g/t Ag. The barite and sulfide minerals are hosted by the uppermost part of the Mississippian Kuna Formation (Ikalukrok unit) that consists of carbonaceous and siliceous mudstone or shale interbedded with carbonate. The amount of interbedded carbonate in the Anarraaq deposit is atypical of the district as a whole, comprising as much as one third of the section. The total thickness of the Ikalukrok unit is considerably greater in the area of the deposit (210 to almost 350 m) than to the north and south (maximum of 164 m). The mineralized zone at Anarraaq is lens shaped and has a relatively flat top and a convex base. It also ranges greatly in thickness, from a few meters to more than 100 m. Textures of some of the carbonate layers are distinctive, consisting of nodules within siliceous mudstone or layers interbedded with shale. Many of the layers contain calcitized sponge spicules or radiolarians in a carbonate matrix. Textures of barite and sulfide minerals mimic those of carbonate and provide unequivocal evidence that replacement of precursor carbonate was an important process. Barite and sulfide textures include either nodular, bladed grains of various sizes that resemble spicules (observed only with iron sulfides) or well-rounded forms that are replaced radiolarians. Mineralization at Anarraaq probably occurred in a fault-bounded Carboniferous basin during early diagenesis in the shallow subsurface. The shape and size of the mineralized body suggest that barite and sulfides replaced calcareous mass flow deposits in a submarine channel. The distribution of biogenic and/or early diagenetic silica may have served as impermeable barriers to the fluids, thereby focusing and controlling fluid flow through unreplaced carbonate layers. ?? 2004 by Economic Geology.

Sulfur and Metal Fertilization of the Lower Continental Crust

NASA Technical Reports Server (NTRS)

Locmelis, Marek; Fiorentini, Marco L.; Rushmer, Tracy; Arevalo, Ricardo, Jr.; Adam, John; Denyszyn, Steven W.

2015-01-01

Mantle-derived melts and metasomatic fluids are considered to be important in the transport and distribution of trace elements in the subcontinental lithospheric mantle. However, the mechanisms that facilitate sulfur and metal transfer from the upper mantle into the lower continental crust are poorly constrained. This study addresses this knowledge gap by examining a series of sulfide- and hydrous mineral-rich alkaline mafic-ultramafic pipes that intruded the lower continental crust of the Ivrea-Verbano Zone in the Italian Western Alps. The pipes are relatively small (<300 m diameter) and primarily composed of a matrix of subhedral to anhedral amphibole (pargasite), phlogopite and orthopyroxene that enclose sub-centimeter-sized grains of olivine. The 1 to 5 m wide rim portions of the pipes locally contain significant blebby and disseminated Fe-Ni-Cu-PGE sulfide mineralization.Stratigraphic relationships, mineral chemistry, geochemical modeling and phase equilibria suggest that the pipes represent open-ended conduits within a large magmatic plumbing system. The earliest formed pipe rocks were olivine-rich cumulates that reacted with hydrous melts to produce orthopyroxene, amphibole and phlogopite.Sulfides precipitated as immiscible liquid droplets that were retained within a matrix of silicate crystals and scavenged metals from the percolating hydrous melt. New high-precision chemical abrasion TIMS-UPb dating of zircons from one of the pipes indicates that these pipes were emplaced at 249.1+/-0.2 Ma, following partial melting of lithospheric mantle pods that were metasomatized during the Eo-Variscan oceanic to continental subduction (approx. 420-310 Ma). The thermal energy required to generate partial melting of the metasomatized mantle was most likely derived from crustal extension, lithospheric decompression and subsequent asthenospheric rise during the orogenic collapse of the Variscan belt (<300 Ma). Unlike previous models, outcomes from this study suggest a significant temporal gap between the occurrence of mantle metasomatism, subsequent partial melting and emplacement of the pipes.We argue that this multi-stage process is a very effective mechanism to fertilize the commonly dry and refractory lower continental crust in metals and volatiles. During the four-dimensional evolution of the thermo-tectonic architecture of any given terrain, metals and volatiles stored in the lower continental crust may become available as sources for subsequent ore-forming processes, thus enhancing the prospectivity of continental block margins for a wide range of mineral systems.

Sulfide oxidation and acid mine drainage formation within two active tailings impoundments in the Golden Quadrangle of the Apuseni Mountains, Romania.

PubMed

Sima, Mihaela; Dold, Bernhard; Frei, Linda; Senila, Marin; Balteanu, Dan; Zobrist, Jurg

2011-05-30

Sulfidic mine tailings have to be classified as one of the major source of hazardous materials leading to water contamination. This study highlights the processes leading to sulfide oxidation and acid mine drainage (AMD) formation in the active stage of two tailings impoundments located in the southern part of the Apuseni Mountains, in Romania, a well-known region for its long-term gold-silver and metal mining activity. Sampling was undertaken when both impoundments were still in operation in order to assess their actual stage of oxidation and long-term behavior in terms of the potential for acid mine drainage generation. Both tailings have high potential for AMD formation (2.5 and 3.7 wt.% of pyrite equivalent, respectively) with lesser amount of carbonates (5.6 and 3.6 wt.% of calcite equivalent) as neutralization potential (ABA=-55.6 and -85.1 tCaCO(3)/1000 t ) and showed clear signs of sulfide oxidation yet during operation. Sequential extraction results indicate a stronger enrichment and mobility of elements in the oxidized tailings: Fe as Fe(III) oxy-hydroxides and oxides (transformation from sulfide minerals, leaching in oxidation zone), Ca mainly in water soluble and exchangeable form where gypsum and calcite are dissolved and higher mobility of Cu for Ribita and Pb for Mialu. Two processes leading to the formation of mine drainage at this stage could be highlighted (1) a neutral Fe(II) plume forming in the impoundment with ferrihydrite precipitation at its outcrop and (2) acid mine drainage seeping in the unsaturated zone of the active dam, leading to the formation of schwertmannite at its outcrop. Copyright © 2011 Elsevier B.V. All rights reserved.

Dynamics of Droplet Extinction in Slow Convective Flows

NASA Technical Reports Server (NTRS)

Nayagam, V.; Haggard, J. B., Jr.; Williams, F. A.

1999-01-01

The classical model for droplet combustion predicts that the square of the droplet diameter decreases linearly with time. It also predicts that a droplet of any size will burn to completion over a period of time. However, it has been known for some time that under certain conditions flames surrounding a droplet, in a quiescent environment, could extinguish because of insufficient residence time for the chemistry to proceed to completion. This type of extinction that occurs for smaller droplets has been studied extensively in the past. Large droplets, on the other hand, exhibit a different type of extinction where excessive radiative heat loss from the flame zone leads to extinction. This mode of "radiative extinction" was theoretically predicted for droplet burning by Chao et al. and was observed in recent space experiments in a quiescent environment. Thus far, the fundamental flammability limit prescribed by radiative extinction of liquid droplets has been measured only under quiescent environmental conditions. In many space platforms, however, ventilation systems produce small convective flows and understanding of the influences of this convection on the extinction process will help better define the radiative extinction flammability boundaries. Boundaries defined by experiments and captured using theoretical models could provide enhanced fire safety margin in space explor1999063d investigation of convective effects will help in interpretations of burning-rate data obtained during free-floated droplet combustion experiments with small residual velocities.

Numerical simulation of the gas-liquid interaction of a liquid jet in supersonic crossflow

NASA Astrophysics Data System (ADS)

Li, Peibo; Wang, Zhenguo; Sun, Mingbo; Wang, Hongbo

2017-05-01

The gas-liquid interaction process of a liquid jet in supersonic crossflow with a Mach number of 1.94 was investigated numerically using the Eulerian-Lagrangian method. The KH (Kelvin-Helmholtz) breakup model was used to calculate the droplet stripping process, and the secondary breakup process was simulated by the competition of RT (Rayleigh-Taylor) breakup model and TAB (Taylor Analogy Breakup) model. A correction of drag coefficient was proposed by considering the compressible effects and the deformation of droplets. The location and velocity models of child droplets after breakup were improved according to droplet deformation. It was found that the calculated spray features, including spray penetration, droplet size distribution and droplet velocity profile agree reasonably well with the experiment. Numerical results revealed that the streamlines of air flow could intersect with the trajectory of droplets and are deflected towards the near-wall region after they enter into spray zone around the central plane. The analysis of gas-liquid relative velocity and droplet deformation suggested that the breakup of droplets mainly occurs around the front region of the spray where gathered a large number of droplets with different sizes. The liquid trailing phenomenon of jet spray which has been discovered by the previous experiment was successfully captured, and a reasonable explanation was given based on the analysis of gas-liquid interaction process.

Technetium Reduction and Permanent Sequestration by Abiotic and Biotic Formation of Low-Solubility Sulfide Mineral Phases

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

Tratnyek, Paul G.; Tebo, Bradley M.; Fan, Dimin

One way to minimize the mobility of the Tc VII oxyanion pertechnetate (TcO 4 -) is to effect reduction under sulfidogenic conditions (generated abiotically by Fe 0 or biotically) to form TcS x, which is significantly slower to oxidize than Tc IVO 2. In sediment systems, TcS x and other precipitates may oxidize more slowly due to oxygen diffusion limitations to these low permeability precipitate zones. In addition, the TcO 4 - reduction rate may be more rapid in the presence of sediment because of additional reductive surface phases. This project aims to provide a fundamental understanding of the feasibilitymore » of immobilization of TcO 4 - as TcS x in the vadose zone or groundwater by application nano zero-valent iron (nZVI), and sulfide or sulfate. Biotic batch experiments have used the sulfate-reducing bacterium (SRB) Desulfotomaculum reducens. The iron sulfide mineral mackinawite was generated under these conditions, while vivianite was formed in nZVI only controls. The sulfide/bacteria-containing system consistently reduced aqueous pertechnetate rapidly (> 95% in the first hour), a rate similar to that for the sulfide-free, nZVI only system. Reduced Tc (aged for 3 months) generated in both SRB/nZVI systems was highly resistant to reoxidation. In reduced samples, Tc was found associated with solid phases containing Fe and S (D. reducens/nZVI) or Fe (nZVI only). Experiments using D. reducens without nZVI provided some additional insights. Firstly, stationary phase cultures were able to slowly reduce pertechnetate. Secondly, addition of pertechnetate at the beginning of cell growth (lag phase) resulted in a faster rate of Tc reduction, possibly indicating a direct (e.g. enzymatic) role for D. reducens in Tc reduction. Abiotic batch experiments were conducted with Na 2S as the sulfide source. Pertechnetate reduction was rapid in the presence of sulfide and nZVI, although the rate was suppressed at the higher S/Fe ratios tested. This suppression appeared to be due to the formation of Tc-containing colloids. As with the biotic experiments, pertechnetate reduced under sulfidic conditions was highly resistant to reoxidation. The microscopic morphology of abiotically-transformed nZVI particles varied significantly with those in the biotic experiment, although mackinawite was formed in both systems (as indicated by μXRD and Mössbauer spectroscopy). Preliminary XAS analysis pointed to a mixture of Tc-O and Tc-S binding in the abiotic sulfide/nZVI system, while the major reduced solids under non-sulfidic conditions were TcO 2•nH 2O. The presence of sediment and advective flow to the TcO 4 -/nZVI/sulfide system results in additional processes occurring. Although the natural Hanford sediment used has sufficient available ferrous iron to slowly reduce TcO 4 -, under anaerobic conditions, that rate is orders of magnitude slower than reduction by nZVI/sulfide. Batch and 1-D column experiments showed that the TcO 4 - reduction rate increased with the sediment surface area (with the same nZVI mass). As in batch systems, column studies showed that the presence of sulfide with TcO 4 - at low (2-5 mM) concentrations increased the TcO 4 - reduction rate and high (10-30 mM) sulfide decreased the rate. This change is attributed to the formation of sulfide precipitates on the nZVI and sediment surfaces. Injection of low and high sulfide (i.e. pretreatment) prior to TcO 4 -/sulfide injection also greatly decreased the TcO 4 - reduction rate, likely decreasing the generation of ferrous iron from the nZVI. Although the high sulfide systems have slower Tc reduction rates, 190 times more Tc mass precipitated than in the low sulfide systems and the highest fraction of Tc mass remained immobilized.« less

Mineralogy, textures, and relative age relationships of massive sulfide ore in the West Shasta district, California ( USA).

USGS Publications Warehouse

Howe, S.S.

1985-01-01

The Devonian massive sulfide orebodies of the West Shasta district in N California are composed primarily of pyrite, with lesser amounts of other sulfide and gangue minerals. Examination of polished thin sections of more than 100 samples from the Mammoth, Shasta King, Early Bird, Balaklala, Keystone, and Iron Mountain mines suggests that mineralization may be divided into 6 paragenetic stages, the last 5 each separated by an episode of deformation: 1) precipitation of fine-grained, locally colloform and framboidal pyrite and sphalerite; 2) deposition of fine-grained arsenopyrite and coarse-grained pyrite; 3) penetration and local replacement of sulfide minerals of stages 1 and 2 along growth zones and fractures by chalcopyrite, sphalerite, galena, tennantite, pyrrhotite, bornite, and idaite; 4) recrystallization and remobilization of existing minerals; 5) deposition of quartz, white mica, chlorite, and calcite; and 6) formation of bornite, digenite, chalcocite, and covellite during supergene enrichment of several orebodies at the Iron Mountain mine. Mineralogic and textural evidence do not support a second major episode of massive sulfide mineralization during the Permian. -from Author

Seawater sulfate reduction and sulfur isotope fractionation in basaltic systems: interaction of seawater with fayalite and magnetite at 200–350°C

USGS Publications Warehouse

Shanks, Wayne C.; Bischoff, James L.; Rosenbauer, Robert J.

1981-01-01

Systematics of sulfur isotopes in the 250 and 350°C experiments indicate that isotopic equilibrium is reached, and can be modeled as a Rayleigh distillation process. Isotopic composition of hydrothermally produced H2S in natural systems is strongly dependent upon the seawater/basalt ratio in the geothermal system, which controls the relative sulfide contributions from the two important sulfur sources, seawater sulfate and sulfide phases in basalt. Anhydrite precipitation during geothermal heating severely limits sulfate ingress into high temperature interaction zones. Quantitative sulfate reduction can thus be accomplished without producing strongly oxidized rocks and resultant sulfide sulfur isotope values represent a mixture of seawater and basaltic sulfur.

Polysulfides as Intermediates in the Oxidation of Sulfide to Sulfate by Beggiatoa spp.

PubMed Central

Schwedt, Anne; Kreutzmann, Anne-Christin; Kuypers, Marcel M. M.; Milucka, Jana

2014-01-01

Zero-valent sulfur is a key intermediate in the microbial oxidation of sulfide to sulfate. Many sulfide-oxidizing bacteria produce and store large amounts of sulfur intra- or extracellularly. It is still not understood how the stored sulfur is metabolized, as the most stable form of S0 under standard biological conditions, orthorhombic α-sulfur, is most likely inaccessible to bacterial enzymes. Here we analyzed the speciation of sulfur in single cells of living sulfide-oxidizing bacteria via Raman spectroscopy. Our results showed that under various ecological and physiological conditions, all three investigated Beggiatoa strains stored sulfur as a combination of cyclooctasulfur (S8) and inorganic polysulfides (Sn2−). Linear sulfur chains were detected during both the oxidation and reduction of stored sulfur, suggesting that Sn2− species represent a universal pool of bioavailable sulfur. Formation of polysulfides due to the cleavage of sulfur rings could occur biologically by thiol-containing enzymes or chemically by the strong nucleophile HS− as Beggiatoa migrates vertically between oxic and sulfidic zones in the environment. Most Beggiatoa spp. thus far studied can oxidize sulfur further to sulfate. Our results suggest that the ratio of produced sulfur and sulfate varies depending on the sulfide flux. Almost all of the sulfide was oxidized directly to sulfate under low-sulfide-flux conditions, whereas only 50% was oxidized to sulfate under high-sulfide-flux conditions leading to S0 deposition. With Raman spectroscopy we could show that sulfate accumulated in Beggiatoa filaments, reaching intracellular concentrations of 0.72 to 1.73 M. PMID:24212585

'Scaling' analysis of the ice accretion process on aircraft surfaces

NASA Technical Reports Server (NTRS)

Keshock, E. G.; Tabrizi, A. H.; Missimer, J. R.

1982-01-01

A comprehensive set of scaling parameters is developed for the ice accretion process by analyzing the energy equations of the dynamic freezing zone and the already frozen ice layer, the continuity equation associated with supercooled liquid droplets entering into and impacting within the dynamic freezing zone, and energy equation of the ice layer. No initial arbitrary judgments are made regarding the relative magnitudes of each of the terms. The method of intrinsic reference variables in employed in order to develop the appropriate scaling parameters and their relative significance in rime icing conditions in an orderly process, rather than utilizing empiricism. The significance of these parameters is examined and the parameters are combined with scaling criteria related to droplet trajectory similitude.

Possible roles of manganese redox chemistry in the sulfur cycle

NASA Technical Reports Server (NTRS)

Nealson, K. H.

1985-01-01

Sulfate reducing bacteria (SRB) are very potent MnO2 reducers by virtue of their sulfide production: H2S reacts rapidly with MnO2 to yield Mn(2), elemental sulfur, and water. In manganese rich zones, Mn cycles rapidly if sulfate is present to drive the reduction and the MnO2 precipitates and sinks into anaerobic zones. The production of sulfide (by organisms requiring organic carbon compounds) to reduce manganese oxides might act to couple the carbon and sulfur cycles in water bodies in which the two cycles are physically separated. Iron has been proposed for this provision of reducing power by (Jorgensen, 1983), but since MnS is soluble and FeS is very insoluble in water, it is equally likely that manganese rather than iron provides the electrons to the more oxidized surface layers.

Alternative waste residue materials for passive in situ prevention of sulfide-mine tailings oxidation: a field evaluation.

PubMed

Nason, Peter; Johnson, Raymond H; Neuschütz, Clara; Alakangas, Lena; Öhlander, Björn

2014-02-28

Novel solutions for sulfide-mine tailings remediation were evaluated in field-scale experiments on a former tailings repository in northern Sweden. Uncovered sulfide-tailings were compared to sewage-sludge biosolid amended tailings over 2 years. An application of a 0.2m single-layer sewage-sludge amendment was unsuccessful at preventing oxygen ingress to underlying tailings. It merely slowed the sulfide-oxidation rate by 20%. In addition, sludge-derived metals (Cu, Ni, Fe, and Zn) migrated and precipitated at the tailings-to-sludge interface. By using an additional 0.6m thick fly-ash sealing layer underlying the sewage sludge layer, a solution to mitigate oxygen transport to the underlying tailings and minimize sulfide-oxidation was found. The fly-ash acted as a hardened physical barrier that prevented oxygen diffusion and provided a trap for sludge-borne metals. Nevertheless, the biosolid application hampered the application, despite the advances in the effectiveness of the fly-ash layer, as sludge-borne nitrate leached through the cover system into the underlying tailings, oxidizing pyrite. This created a 0.3m deep oxidized zone in 6-years. This study highlights that using sewage sludge in unconventional cover systems is not always a practical solution for the remediation of sulfide-bearing mine tailings to mitigate against sulfide weathering and acid rock drainage formation. Copyright © 2014 Elsevier B.V. All rights reserved.

Sulfur transformations at the hydrogen sulfide/oxygen interface in stratified waters and in cyanobacterial mats

NASA Technical Reports Server (NTRS)

Cohen, Y.

1985-01-01

Stratified water bodies allow the development of several microbial plates along the water column. The microbial plates develop in relation to nutrient availability, light penetration, and the distribution of oxygen and sulfide. Sulfide is initially produced in the sediment by sulfate-reducing bacteria. It diffuses along the water column creating a zone of hydrogen sulfide/oxygen interface. In the chemocline of Solar Lake oxygen and sulfide coexist in a 0 to 10 cm layer that moves up and down during a diurnal cycle. The microbial plate at the chemocline is exposed to oxygen and hydrogen sulfide, alternating on a diurnal basis. The cyanobacteria occupying the interface switch from anoxygenic photosynthesis in the morning to oxygenic photosynthesis during the rest of the day which results in a temporal build up of elemental sulfur during the day and disappears at night due to both oxidation to thiosulfate and sulfate by thiobacilli, and reduction to hydrogen sulfide by Desulfuromonas sp. and anaerobically respiring cyanobacteria. Sulfate reduction was enhanced in the light at the surface of the cyanobacterial mats. Microsulfate reduction measurements showed enhanced activity of sulfate reduction even under high oxygen concentrations of 300 to 800 micrometer. Apparent aerobic SO sub 4 reduction activity is explained by the co-occurrence of H sub 2. The physiology of this apparent sulfate reduction activity is studied.

Alternative waste residue materials for passive in situ prevention of sulfide-mine tailings oxidation: A field evaluation

USGS Publications Warehouse

Nason, Peter; Johnson, Raymond H.; Neuschutz, Clara; Alakangas, Lena; Ohlander, Bjorn

2014-01-01

Novel solutions for sulfide-mine tailings remediation were evaluated in field-scale experiments on a former tailings repository in northern Sweden. Uncovered sulfide-tailings were compared to sewage-sludge biosolid amended tailings over 2 years. An application of a 0.2 m single-layer sewage-sludge amendment was unsuccessful at preventing oxygen ingress to underlying tailings. It merely slowed the sulfide-oxidation rate by 20%. In addition, sludge-derived metals (Cu, Ni, Fe, and Zn) migrated and precipitated at the tailings-to-sludge interface. By using an additional 0.6 m thick fly-ash sealing layer underlying the sewage sludge layer, a solution to mitigate oxygen transport to the underlying tailings and minimize sulfide-oxidation was found. The fly-ash acted as a hardened physical barrier that prevented oxygen diffusion and provided a trap for sludge-borne metals. Nevertheless, the biosolid application hampered the application, despite the advances in the effectiveness of the fly-ash layer, as sludge-borne nitrate leached through the cover system into the underlying tailings, oxidizing pyrite. This created a 0.3 m deep oxidized zone in 6-years. This study highlights that using sewage sludge in unconventional cover systems is not always a practical solution for the remediation of sulfide-bearing mine tailings to mitigate against sulfide weathering and acid rock drainage formation.

Chalcophile element geochemistry of the Boggy Plain zoned pluton, southeastern Australia: a S-saturated barren compositionally diverse magmatic system

NASA Astrophysics Data System (ADS)

Park, Jung-Woo; Campbell, Ian H.; Ickert, Ryan B.; Allen, Charlotte M.

2013-02-01

The behavior of the platinum group elements (PGE) and Re in felsic magmas is poorly understood due to scarcity of data. We report the concentrations of Ni, Cu, Re, and PGE in the compositionally diverse Boggy Plain zoned pluton (BPZP), which shows a variation of rock type from gabbro through granodiorite and granite to aplite with a SiO2 range from 52 to 74 wt %. In addition, major silicate and oxide minerals were analyzed for Ni, Cu, and Re, and a systematic sulfide study was carried out to investigate the role of silicate, oxide, and sulfide minerals on chalcophile element geochemistry of the BPZP. Mass balance calculation shows that the whole rock Cu budget hosted by silicate and oxide minerals is <13 wt % and that Cu is dominantly located in sulfide phases, whereas most of the whole rock Ni budget (>70 wt %) is held in major silicate and oxide minerals. Rhenium is dominantly hosted by magnetite and ilmenite. Ovoid-shaped sulfide blebs occur at the boundary between pyroxene phenocrysts and neighboring interstitial phases or within interstitial minerals in the gabbro and the granodiorite. The blebs are composed of pyrrhotite, pyrite, chalcopyrite, and S-bearing Fe-oxide, which contain total trace metals (Co, Ni, Cu, Ag, Pb) up to ~16 wt %. The mineral assemblage, occurrence, shape, and composition of the sulfide blebs are a typical of magmatic sulfide. PGE concentrations in the BPZP vary by more than two orders of magnitude from gabbro (2.7-7.8 ppb Pd, 0.025-0.116 ppb Ir) to aplite (0.05 ppb Pd, 0.001 ppb Ir). Nickel, Cu, Re, and PGE concentrations are positively correlated with MgO in all the rock types although there is a clear discontinuity between the granodiorite and the granite in the trends for Ni, Rh, and Ir when plotted against MgO. Cu/Pd values gradually increase from 6,100 to 52,600 as the MgO content decreases. The sulfide petrology and chalcophile element geochemistry of the BPZP show that sulfide saturation occurred in the late gabbroic stage of magma differentiation. Segregation and distribution of these sulfide blebs controlled Cu and PGE variations within the BPZP rocks although the magma of each rock type may have experienced a different magma evolution history in terms of crustal assimilation and crystal fractionation. The sulfide melt locked in the cumulate rocks must have sequestered a significant portion of the chalcophile elements, which restricted the availability of these metals to magmatic-hydrothermal ore fluids. Therefore, we suggest that the roof rocks that overlay the BPZP were not prospective for magmatic-hydrothermal Cu, Au, or Cu-Au deposits.

Trace Metal Distribution and Speciation in Pore Water of Hydrothermal Sediments From the Guaymas Basin, Gulf of California

NASA Astrophysics Data System (ADS)

Morales-Villafuerte, M.; Ortega-Osorio, A.; Wheat, G.; Seewald, J.

2004-12-01

Thirteen sediment cores were collected through out direct sampling with the MBARI/ ROV "Tiburon" in the southern trough of the Guaymas Basin in March 2003. Pore water samples from regular 2.5 cm intervals of sediment cores were extracted onboard by centrifugation. The supernatants were collected in clean polystyrene vials and stored at 4° C until analytical work on shore. Dissolved Fe, Mn, Cu, Pb, Zn and Ni concentrations in extracted fluid samples were analyzed by direct injection of atomic absorption spectrometry. Four zones in the hydrothermal field were classified according to their physical characteristics. A core located away from the influence of active vents was recovered as a background site. The second zone is characterized by low temperatures (4.2-80° C) and sediments saturated in hydrocarbons. Sulfides formation and higher temperatures (4-166° C) were observed in the third zone. Precipitation of carbonates on top of the sediment characterizes the fourth zone. Concentration of trace metals at the water-sediment interface appears to be the highest, probably due to metal precipitation from the hydrothermal plume, followed by diffusion into the pore water. A decrease in concentration is observed between 5-12 cm depth, suggesting that biological activity is consuming essential metals (zone of bioturbation). Metal concentrations in zones where sulfide phases are rich, exhibit smaller values in pore water (Fe=2.4-3.8 μ mol/kg, Cu=0.6-0.8 μ mol/kg, Pb=1.2-1.5 μ mol/kg, Zn=0.4-0.5 μ mol/kg and Ni= 3.4-4.4 μ mol/kg) relative to samples located at hydrocarbon sites (Fe= 2.7-11.4, Cu= 0.7-1.0 μ mol/kg, Pb= 1.2-2.2 μ mol/kg, Zn= 0.4-0.7 μ mol/kg and Ni= 3.4-5.2 μ mol/kg). At sulfide zones, pH and Eh conditions help to precipitate their stable sulfides as opposed to the hydrocarbon areas, where conditions are not favorable for sulfide formation due to the absence of H2S. In general, Fe concentrations in pore water are lower than that of Mn, very likely due to the easier precipitation and greater stability of FeS relative to MnS. As an attempt to reconstruct predominant species and their abundance in the system, aqueous chemical models were applied. The codes EQBRM and SUPCRT92 were run with total concentrations to calculate, concentrations, activity coefficients and thermodynamic properties of aqueous species. Experimental data such as total chloride, total sulfur and measured pH were used in the model. According to the prevailing conditions in the Guaymas Basin, all metals studied form chloride complexes. Iron, lead, and zinc exist mainly as hydroxy complexes, manganese as free ion and copper as CuHS. Speciation results are well supported by the Pearson's hard-soft rule which states that soft metal ion Cu++ bonds with soft bisulfide ligand, likewise, borderline metal ions as Fe2+, Mn2+, Pb2+ and Zn2+ bond with chloride, hydroxyl or water ligands. The results reported here provide a greater insight into the behavior of trace metals in pore waters of hydrothermal sediments.

Droplet-based micro oscillating-flow PCR chip

NASA Astrophysics Data System (ADS)

Wang, Wei; Li, Zhi-Xin; Luo, Rong; Lü, Shu-Hai; Xu, Ai-Dong; Yang, Yong-Jun

2005-08-01

Polymerase chain reactions (PCR), thermally activated chemical reactions which are widely used for nucleic acid amplification, have recently received much attention in microelectromechanical systems and micro total analysis systems because a wide variety of DNA/RNA molecules can be enriched by PCR for further analyses. In the present work, a droplet-based micro oscillating-flow PCR chip was designed and fabricated by the silicon microfabrication technique. Three different temperature zones, which were stable at denaturation, extension and annealing temperatures and isolated from each other by a thin-wall linkage, were integrated with a single, simple and straight microchannel to form the chip's basic functional structure. The PCR mixture was injected into the chip as a single droplet and flowed through the three temperature zones in the main microchannel in an oscillating manner to achieve the temperature maintenance and transitions. The chip's thermal performance was theoretically analyzed and numerically simulated. The results indicated that the time needed for the temperature of the droplet to change to the target value is less than 1 s, and the root mean square error of temperature is less than 0.2 °C. A droplet of 1 µl PCR mixture with standard HPV (Human Papilloma Virus)-DNA sample inside was amplified by the present chip and the results were analyzed by slab gel electrophoresis with separation of DNA markers in parallel. The electrophoresis results demonstrated that the micro oscillating-flow PCR chip successfully amplified the HPV-DNA, with a processing time of about 15 min which is significantly reduced compared to that for the conventional PCR instrument.

Laser Assisted Micro Wire GMAW and Droplet Welding

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

FUERSCHBACH, PHILLIP W.; LUCK, D. L.; BERTRAM, LEE A.

2002-03-01

Laser beam welding is the principal welding process for the joining of Sandia weapon components because it can provide a small fusion zone with low overall heating. Improved process robustness is desired since laser energy absorption is extremely sensitive to joint variation and filler metal is seldom added. This project investigated the experimental and theoretical advantages of combining a fiber optic delivered Nd:YAG laser with a miniaturized GMAW system. Consistent gas metal arc droplet transfer employing a 0.25 mm diameter wire was only obtained at high currents in the spray transfer mode. Excessive heating of the workpiece in this modemore » was considered an impractical result for most Sandia micro-welding applications. Several additional droplet detachment approaches were investigated and analyzed including pulsed tungsten arc transfer(droplet welding), servo accelerated transfer, servo dip transfer, and electromechanically braked transfer. Experimental observations and rigorous analysis of these approaches indicate that decoupling droplet detachment from the arc melting process is warranted and may someday be practical.« less

Relationships between microbial communities and environmental parameters at sites impacted by mining of volcanogenic massive sulfide deposits, Prince William Sound, Alaska

USGS Publications Warehouse

Foster, A.L.; Munk, L.; Koski, R.A.; Shanks, Wayne C.; Stillings, L.L.

2008-01-01

The relations among geochemical parameters and sediment microbial communities were examined at three shoreline sites in the Prince William Sound, Alaska, which display varying degrees of impact by acid-rock drainage (ARD) associated with historic mining of volcanogenic massive sulfide deposits. Microbial communities were examined using total fatty acid methyl esters (FAMEs), a class of compounds derived from lipids produced by eukaryotes and prokaryotes (bacteria and Archaea); standard extraction techniques detect FAMEs from both living (viable) and dead (non-viable) biomass, but do not detect Archaeal FAMEs. Biomass and diversity (as estimated by FAMEs) varied strongly as a function of position in the tidal zone, not by study site; subtidal muds, Fe oxyhydroxide undergoing biogenic reductive dissolution, and peat-rich intertidal sediment had the highest values. These estimates were lowest in acid-generating, intertidal zone sediment; if valid, the estimates suggest that only one or two bacterial species predominate in these communities, and/or that Archeal species are important members of the microbial community in this sediment. All samples were dominated by bacterial FAMEs (median value >90%). Samples with the highest absolute abundance of eukaryotic FAMEs were biogenic Fe oxyhydroxides from shallow freshwater pools (fungi) and subtidal muds (diatoms). Eukaryotic FAMEs were practically absent from low-pH, sulfide-rich intertidal zone sediments. The relative abundance of general microbial functional groups such as aerobes/anaerobes and gram(+)/gram(-) was not estimated due to severe inconsistency among the results obtained using several metrics reported in the literature. Principal component analyses (PCAs) were performed to investigate the relationship among samples as separate functions of water, sediment, and FAMEs data. PCAs based on water chemistry and FAMEs data resulted in similar relations among samples, whereas the PCA based on sediment chemistry produced a very different sample arrangement. Specifically, the sediment parameter PCA grouped samples with high bulk trace metal concentration regardless of whether the metals were incorporated into secondary precipitates or primary sulfides. The water chemistry PCA and FAMEs PCA appear to be less prone to this type of artifact. Signature lipids in sulfide-rich sediments could indicate the presence of acid-tolerant and/or acidophilic members of the genus Thiobacillus or they could indicate the presence of SO4-reducing bacteria. The microbial community documented in subtidal and offshore sediments is rich in SRB and/or facultative anaerobes of the Cytophaga-Flavobacterium group; both could reasonably be expected in PWS coastal environments. The results of this study provide evidence for substantial feedback between local (meter to centimeter-scale) geochemical variations, and sediment microbial community composition, and show that microbial community signatures in the intertidal zone are significantly altered at sites where ARD drainage is present relative to sites where it is not, even if the sediment geochemistry indicates net accumulation of ARD-generated trace metals in the intertidal zone. ?? 2007 Elsevier Ltd. All rights reserved.

Iron catalyzed coal liquefaction process

DOEpatents

Garg, Diwakar; Givens, Edwin N.

1983-01-01

A process is described for the solvent refining of coal into a gas product, a liquid product and a normally solid dissolved product. Particulate coal and a unique co-catalyst system are suspended in a coal solvent and processed in a coal liquefaction reactor, preferably an ebullated bed reactor. The co-catalyst system comprises a combination of a stoichiometric excess of iron oxide and pyrite which reduce predominantly to active iron sulfide catalysts in the reaction zone. This catalyst system results in increased catalytic activity with attendant improved coal conversion and enhanced oil product distribution as well as reduced sulfide effluent. Iron oxide is used in a stoichiometric excess of that required to react with sulfur indigenous to the feed coal and that produced during reduction of the pyrite catalyst to iron sulfide.

Identification and characterization of the active hydrothermal deposits in Okinawa Trough, SW Japan: Estimates from logging-while-drilling

NASA Astrophysics Data System (ADS)

Saito, S.; Sanada, Y.; Moe, K.; Kido, Y. N.; Hamada, Y.; Kumagai, H.; Nozaki, T.; Takai, K.; Suzuki, K.

2015-12-01

A scientific drilling expedition was conducted at an active hydrothermal field on the Iheya-North Knoll by D/V Chikyu in 2014 (Expedition 907) as a part of "Next-generation Technology for Ocean Resources Survey" of the Cross-ministerial Strategic Innovation Promotion Program. During the expedition logging while drilling (LWD) was deployed to constrain the area of the fluid reservoir beneath seafloor followed by three coring holes down to 150 meter below the seafloor (mbsf). The LWD system is composed of arcVISION for resistivity and natural gamma ray measurement and TeleScope for real-time transmission of drilling parameters and arcVISION data. Five sites (C9011-15) at the Iheya-North Original Site and one site (C9016) at Aki Site were drilled with LWD. At C9012 and C9016, the arcVISION detected temperature anomaly up to 84℃ at 234 mbsf and up to 39℃ at 80 mbsf, respectively. The temperature quickly increases at that depth and it would reflect the existence of high-temperature heat source along borehole. Due to the continuous fluid circulation during drilling, the measured temperature does not indicate in-situ temperature, but it reflects the heat disturbed by the cold circulated water instead. High quality resistivity and natural gamma ray data were acquired at six sites. The log curves at Site C9016 show characteristic response; the natural gamma ray log exhibits extremely high radiation (>500 gAPI) at 7-13 and 23-31 mbsf (Zone A). In the underlying interval of 31-40 mbsf, the resistivity log exhibits extremely low value (<0.2 ohm-m) (Zone B). Then the resistivity log exhibits higher value (~10 ohm-m) and the natural gamma ray log shows very low radiation (<50 gAPI) at the interval of 41-48 mbsf (Zone C). The log characteristics in Zone A, B, and C can be interpreted as a series of K-rich alteration zone, sulfide zone, and low-K hard (silicified) sediments, respectively. The LWD-based lithological interpretation was confirmed by the following core description. Zones A and B can be correlated to altered clay zone and sulfide zone including sphalerite, galena, chalcopyrite, and pyrite. Our results show that LWD is a powerful tool for the identification and characterization of submarine hydrothermal deposits and LWD survey enhances the successful recovery of sulfide samples.

Carbothermic Reduction Reactions at the Metal-Slag Interface in Ti-Bearing Slag from a Blast Furnace

NASA Astrophysics Data System (ADS)

Wang, Yao-Zu; Zhang, Jian-Liang; Liu, Zheng-Jian; Du, Cheng-Bo

2017-11-01

Carbothermic reduction reactions at the metal-slag interface and the mechanisms of iron loss during the smelting of vanadium-bearing titanomagnetite in a blast furnace are still not clear as a result of the limited ability to observe the high-temperature zone of a blast furnace. The chemical composition of a Ti-bearing slag was determined by x-ray fluorescence and x-ray diffraction. The interfaces were characterized by scanning electron microscopy coupled with energy-dispersive x-ray spectroscopy. The interfacial chemical reactions were deduced based on the characterization results and on the thermodynamic calculations performed using Factsage 6.4. The results indicated that the forms of iron in the slag were iron droplets wetted by Ti(C x , N1- x ), mechanically separated by iron and iron oxide. The different forms possessed unique characteristics and were formed by different mechanisms. Iron droplets wetted by Ti(C x , N1- x ) were generated through a series of interfacial reactions between TiO2 in the slag and [C] and [N] in the metal. Iron droplets without attached Ti(C x , N1- x ) were mainly located on the edges of pores and were attributed to the reduction of Fe x O in the slag. Insufficient reduction of iron-bearing minerals made it difficult for iron droplets to aggregate and separate from the slag, which created an Fe x O-enriched zone.

Ignition of an organic water-coal fuel droplet floating in a heated-air flow

NASA Astrophysics Data System (ADS)

Valiullin, T. R.; Strizhak, P. A.; Shevyrev, S. A.; Bogomolov, A. R.

2017-01-01

Ignition of an organic water-coal fuel (CWSP) droplet floating in a heated-air flow has been studied experimentally. Rank B2 brown-coal particles with a size of 100 μm, used crankcase Total oil, water, and a plasticizer were used as the main CWSP components. A dedicated quartz-glass chamber has been designed with inlet and outlet elements made as truncated cones connected via a cylindrical ring. The cones were used to shape an oxidizer flow with a temperature of 500-830 K and a flow velocity of 0.5-5.0 m/s. A technique that uses a coordinate-positioning gear, a nichrome thread, and a cutter element has been developed for discharging CWSP droplets into the working zone of the chamber. Droplets with an initial size of 0.4 to 2.0 mm were used. Conditions have been determined for a droplet to float in the oxidizer flow long enough for the sustainable droplet burning to be initiated. Typical stages and integral ignition characteristics have been established. The integral parameters (ignition-delay times) of the examined processes have been compared to the results of experiments with CWSP droplets suspended on the junction of a quick-response thermocouple. It has been shown that floating fuel droplets ignite much quicker than the ones that sit still on the thermocouple due to rotation of an CWSP droplet in the oxidizer flow, more uniform heating of the droplet, and lack of heat drainage towards the droplet center. High-speed video recording of the peculiarities of floatation of a burning fuel droplet makes it possible to complement the existing models of water-coal fuel burning. The results can be used for a more substantiated modeling of furnace CWSP burning with the ANSYS, Fluent, and Sigma-Flow software packages.

Pattern-Directed Ordering of Spin-Dewetted Liquid Crystal Micro- or Nanodroplets as Pixelated Light Reflectors and Locomotives.

PubMed

Ravi, Bolleddu; Chakraborty, Snigdha; Bhattacharjee, Mitradip; Mitra, Shirsendu; Ghosh, Abir; Gooh Pattader, Partho Sarathi; Bandyopadhyay, Dipankar

2017-01-11

Chemical pattern directed spin-dewetting of a macroscopic droplet composed of a dilute organic solution of liquid crystal (LC) formed an ordered array of micro- and nanoscale LC droplets. Controlled evaporation of the spin-dewetted droplets through vacuum drying could further miniaturize the size to the level of ∼90 nm. The size, periodicity, and spacing of these mesoscale droplets could be tuned with the variations in the initial loading of LC in the organic solution, the strength of the centripetal force on the droplet, and the duration of the evaporation. A simple theoretical model was developed to predict the spacing between the spin-dewetted droplets. The patterned LC droplets showed a reversible phase transition from nematic to isotropic and vice versa with the periodic exposure of a solvent vapor and its removal. A similar phase transition behavior was also observed with the periodic increase or reduction of temperature, suggesting their usefulness as vapor or temperature sensors. Interestingly, when the spin-dewetted droplets were confined between a pair of electrodes and an external electric field was applied, the droplets situated at the hydrophobic patches showed light-reflecting properties under the polarization microscopy highlighting their importance in the development of micro- or nanoscale LC displays. The digitized LC droplets, which were stationary otherwise, showed dielectrophoretic locomotion under the guidance of the external electric field beyond a threshold intensity of the field. Remarkably, the motion of these droplets could be restricted to the hydrophilic zones, which were confined between the hydrophobic patches of the chemically patterned surface. The findings could significantly contribute in the development of futuristic vapor or temperature sensors, light reflectors, and self-propellers using the micro- or nanoscale digitized LC droplets.

Interfacial Reduction-Oxidation Mechanisms Governing Fate and Transport of Contaminants in the Vadose Zone

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

Principal Investigator: Baolin Deng, University of Missouri, Columbia, MO; Co-Principal Investigator: Silvia Sabine Jurisson, University of Missouri, Columbia, MO; Co-Principal Investigator: Edward C. Thornton, Pacific Northwest National Laboratory Richland, WA

2008-05-12

There are many soil contamination sites at the Department of Energy (DOE) installations that contain radionuclides and toxic metals such as uranium (U), technetium (Tc), and chromium (Cr). Since these contaminants are the main 'risk drivers' at the Hanford site (WA) and some of them also pose significant risk at other DOE facilities (e.g., Oak Ridge Reservation - TN; Rocky Flats - CO), development of technologies for cost effective site remediation is needed. Current assessment indicates that complete removal of these contaminants for ex-situ disposal is infeasible, thus in-situ stabilization through reduction to insoluble species is considered one of themore » most important approaches for site remediation. In Situ Gaseous Reduction (ISGR) is a technology developed by Pacific Northwest National Laboratory (PNNL) for vadose zone soil remediation. The ISGR approach uses hydrogen sulfide (H{sub 2}S) for reductive immobilization of contaminants that show substantially lower mobility in their reduced forms (e.g., Tc, U, and Cr). The technology can be applied in two ways: (i) to immobilize or stabilize pre-existing contaminants in the vadose zone soils by direct H{sub 2}S treatment, or (ii) to create a permeable reactive barrier (PRB) that prevents the migration of contaminants. Direct treatment involves reduction of the contaminants by H{sub 2}S to less mobile species. Formation of a PRB is accomplished through reduction of ferric iron species in the vadose zone soils by H{sub 2}S to iron sulfides (e.g., FeS), which provides a means for capturing the contaminants entering the treated zone. Potential future releases may occur during tank closure activities. Thus, the placement of a permeable reactive barrier by ISGR treatment can be part of the leak mitigation program. Deployment of these ISGR approaches, however, requires a better understanding of the immobilization kinetics and mechanisms, and a better assessment of the long-term effectiveness of treatment. The primary objective of this project was to understand the complex interactions among the contaminants (i.e., Cr, Tc, and U), H{sub 2}S, and various soil constituents. The reaction with iron sulfide is also the focus of the research, which could be formed from iron oxide reduction by hydrogen sulfide. Factors controlling the reductive immobilization of these contaminants were identified and quantified. The results and fundamental knowledge obtained from this project shall help better evaluate the potential of in situ gaseous treatment to immobilize toxic and radioactive metals examined.« less

Fractional crystallization-induced variations in sulfides from the Noril’sk-Talnakh mining district (polar Siberia, Russia)

USGS Publications Warehouse

Duran, C.J.; Barnes, S-J.; Pleše, P.; Prašek, M. Kudrna; Zientek, Michael L.; Pagé, P.

2017-01-01

The distribution of platinum-group elements (PGE) within zoned magmatic ore bodies has been extensively studied and appears to be controlled by the partitioning behavior of the PGE during fractional crystallization of magmatic sulfide liquids. However, other chalcophile elements, especially TABS (Te, As, Bi, Sb, and Sn) have been neglected despite their critical role in forming platinum-group minerals (PGM). TABS are volatile trace elements that are considered to be mobile so investigating their primary distribution may be challenging in magmatic ore bodies that have been somewhat altered. Magmatic sulfide ore bodies from the Noril’sk-Talnakh mining district (polar Siberia, Russia) offer an exceptional opportunity to investigate the behavior of TABS during fractional crystallization of sulfide liquids and PGM formation as the primary features of the ore bodies have been relatively well preserved. In this study, new petrographic (2D and 3D) and whole-rock geochemical data from Cu-poor to Cu-rich sulfide ores of the Noril’sk-Talnakh mining district are integrated with published data to consider the role of fractional crystallization in generating mineralogical and geochemical variations across the different ore types (disseminated to massive). Despite textural variations in Cu-rich massive sulfides (lenses, veins, and breccias), these sulfides have similar chemical compositions, which suggests that Cu-rich veins and breccias formed from fractionated sulfide liquids that were injected into the surrounding rocks. Numerical modeling using the median disseminated sulfide composition as the initial sulfide liquid composition and recent DMSS/liq and DISS/liq predicts the compositional variations observed in the massive sulfides, especially in terms of Pt, Pd, and TABS. Therefore, distribution of these elements in the massive sulfides was likely controlled by their partitioning behavior during sulfide liquid fractional crystallization, prior to PGM formation. Our observations indicate that in the Cu-poor massive sulfides the PGM formed as the result of exsolution from sulfide minerals whereas in the Cu-rich massive sulfides the PGM formed by crystallization from late-stage fractionated sulfide liquids. We suggest that the significant amount of Sn-bearing PGM may be related to crustal contamination from granodiorite, whereas As, Bi, Te, and Sb were likely added to the magma along with S from sedimentary rocks. Large PGM that are scarce and randomly distributed may account for most of the whole-rock Pt budget. Based on our results, we propose a holistic genetic model for the formation of the magmatic sulfide ore bodies of the Noril’sk-Talnakh mining district.

Chemistry and isotope ratios of sulfur in basalts and volcanic gases at Kilauea volcano, Hawaii

USGS Publications Warehouse

Sakai, H.; Casadevall, T.J.; Moore, J.G.

1982-01-01

Eighteen basalts and some volcanic gases from the submarine and subaerial parts of Kilauea volcano were analyzed for the concentration and isotope ratios of sulfur. By means of a newly developed technique, sulfide and sulfate sulfur in the basalts were separately but simultaneously determined. The submarine basalt has 700 ?? 100 ppm total sulfur with ??34S??s of 0.7 ?? 0.1 ???. The sulfate/sulfide molar ratio ranges from 0.15 to 0.56 and the fractionation factor between sulfate and sulfide is +7.5 ?? 1.5???. On the other hand, the concentration and ??34S??s values of the total sulfur in the subaerial basalt are reduced to 150 ?? 50 ppm and -0.8 ?? 0.2???, respectively. The sulfate to sulfide ratio and the fractionation factor between them are also smaller, 0.01 to 0.25 and +3.0???, respectively. Chemical and isotopic evidence strongly suggests that sulfate and sulfide in the submarine basalt are in chemical and isotopic equilibria with each other at magmatic conditions. Their relative abundance and the isotope fractionation factors may be used to estimate the f{hook}o2 and temperature of these basalts at the time of their extrusion onto the sea floor. The observed change in sulfur chemistry and isotopic ratios from the submarine to subaerial basalts can be interpreted as degassing of the SO2 from basalt thereby depleting sulfate and 34S in basalt. The volcanic sulfur gases, predominantly SO2, from the 1971 and 1974 fissures in Kilauea Crater have ??34S values of 0.8 to 0.9%., slightly heavier than the total sulfur in the submarine basalts and definitely heavier than the subaerial basalts, in accord with the above model. However, the ??34S value of sulfur gases (largely SO2) from Sulfur Bank is 8.0%., implying a secondary origin of the sulfur. The ??34S values of native sulfur deposits at various sites of Kilauea and Mauna Loa volcanos, sulfate ions of four deep wells and hydrogen sulfide from a geothermal well along the east rift zone are also reported. The high ??34S values (+5 to +6%.o) found for the hydrogen sulfide might be an indication of hot basaltseawater reaction beneath the east rift zone. ?? 1982.

Genesis of copper-lead mineralization in the regionally zoned Agnigundala Sulfide Belt, Cuddapah Basin, Andhra Pradesh, India

NASA Astrophysics Data System (ADS)

Bhattacharya, H. N.; Bandyopadhyay, Sandip

2018-03-01

Shallow marine sandstone-shale-carbonate sedimentary rocks of the Paleoproterozoic northern Cuddapah basin host copper (Nallakonda deposit), copper-lead (Dhukonda deposit), and lead mineralization (Bandalamottu deposit) which together constitute the Agnigundala Sulfide Belt. The Cu sulfide mineralization in sandstone is both stratabound and disseminated, and Pb sulfide mineralization occurs as stratabound fracture filling veins and/or replacement veins within dolomite. Systematic mineralogical and sulfur, carbon, and oxygen isotope studies of the three deposits indicate a common ore-fluid that deposited copper at Nallakonda, copper-lead at Dhukonda, and lead at Bandalamottu under progressive cooling during migration through sediments. The ore-fluid was of low temperature (< 200 °C) and oxidized. Thermochemical reduction of basinal water sulfate produced sulfide for ore deposition. It is envisaged that basal red-bed and evaporite-bearing rift-related continental to shallow marine sediments might have acted as the source for the metals. Rift-related faults developed during sedimentation in the basin might have punctured the ore-fluid pool in the lower sedimentary succession and also acted as conduits for their upward migration. The ore-bearing horizons have participated in deformations during basin inversion without any recognizable remobilization.

The variability of biogenic sulfur flux from a temperate salt marsh on short time and space scales

NASA Astrophysics Data System (ADS)

Morrison, Michael C.; Hines, Mark E.

Three emission chambers were deployed simultaneously to measure rates of emission of dimethyl sulfide, methane thiol and carbonyl sulfide within or across vegetation zones in a New Hampshire salt marsh. Short term (a few hours) variation in fluxes of all S gases from replicate sites were small within a monospecific stand of either Spartina alterniflora or S. patens. The quantity of emergent biomass and the type of vegetation present were the primary factors regulating the rate of emission. Dimethyl sulfide fluxes from the S. alterniflora soils ranged from 800 to 18,000 nmol m -2 h -1 compared to emissions of 25-120 nmol m -2 h -1 from S. patens. This difference was probably due to the presence of the dimethyl-sulfide precursor dimethylsulfoniopropionate which is an osmoregulator in S. alterniflora but not in S. patens. Methane thiol emissions from S. alterniflora were 20-280 nmol m -2 h -1 and they displayed a similar diel trend as dimethyl sulfide, although at much lower rates, suggesting that methane thiol is produced primarily by leaves. Methane thiol emissions from S. patens were 20-70 nmol m -2 h -1. Net uptake of carbonyl sulfide of 25-40 nmol m -2 h -1 occurred in stands of S. alterniflora while net efflux of 10-36 nmol m -2 h -1 of carbonyl sulfide occurred in stands of S. patens. In general, ranges of emissions of sulfur gases were similar to most other published values.

Characterization of sulfur oxidizing bacteria related to biogenic sulfuric acid corrosion in sludge digesters.

PubMed

Huber, Bettina; Herzog, Bastian; Drewes, Jörg E; Koch, Konrad; Müller, Elisabeth

2016-07-18

Biogenic sulfuric acid (BSA) corrosion damages sewerage and wastewater treatment facilities but is not well investigated in sludge digesters. Sulfur/sulfide oxidizing bacteria (SOB) oxidize sulfur compounds to sulfuric acid, inducing BSA corrosion. To obtain more information on BSA corrosion in sludge digesters, microbial communities from six different, BSA-damaged, digesters were analyzed using culture dependent methods and subsequent polymerase chain reaction denaturing gradient gel electrophoresis (PCR-DGGE). BSA production was determined in laboratory scale systems with mixed and pure cultures, and in-situ with concrete specimens from the digester headspace and sludge zones. The SOB Acidithiobacillus thiooxidans, Thiomonas intermedia, and Thiomonas perometabolis were cultivated and compared to PCR-DGGE results, revealing the presence of additional acidophilic and neutrophilic SOB. Sulfate concentrations of 10-87 mmol/L after 6-21 days of incubation (final pH 1.0-2.0) in mixed cultures, and up to 433 mmol/L after 42 days (final pH <1.0) in pure A. thiooxidans cultures showed huge sulfuric acid production potentials. Additionally, elevated sulfate concentrations in the corroded concrete of the digester headspace in contrast to the concrete of the sludge zone indicated biological sulfur/sulfide oxidation. The presence of SOB and confirmation of their sulfuric acid production under laboratory conditions reveal that these organisms might contribute to BSA corrosion within sludge digesters. Elevated sulfate concentrations on the corroded concrete wall in the digester headspace (compared to the sludge zone) further indicate biological sulfur/sulfide oxidation in-situ. For the first time, SOB presence and activity is directly relatable to BSA corrosion in sludge digesters.

Droplet-based microfluidic flow injection system with large-scale concentration gradient by a single nanoliter-scale injection for enzyme inhibition assay.

PubMed

Cai, Long-Fei; Zhu, Ying; Du, Guan-Sheng; Fang, Qun

2012-01-03

We described a microfluidic chip-based system capable of generating droplet array with a large scale concentration gradient by coupling flow injection gradient technique with droplet-based microfluidics. Multiple modules including sample injection, sample dispersion, gradient generation, droplet formation, mixing of sample and reagents, and online reaction within the droplets were integrated into the microchip. In the system, nanoliter-scale sample solution was automatically injected into the chip under valveless flow injection analysis mode. The sample zone was first dispersed in the microchannel to form a concentration gradient along the axial direction of the microchannel and then segmented into a linear array of droplets by immiscible oil phase. With the segmentation and protection of the oil phase, the concentration gradient profile of the sample was preserved in the droplet array with high fidelity. With a single injection of 16 nL of sample solution, an array of droplets with concentration gradient spanning 3-4 orders of magnitude could be generated. The present system was applied in the enzyme inhibition assay of β-galactosidase to preliminarily demonstrate its potential in high throughput drug screening. With a single injection of 16 nL of inhibitor solution, more than 240 in-droplet enzyme inhibition reactions with different inhibitor concentrations could be performed with an analysis time of 2.5 min. Compared with multiwell plate-based screening systems, the inhibitor consumption was reduced 1000-fold. © 2011 American Chemical Society

Metal Transport, Heavy Metal Speciation and Microbial Fixation Through Fluvial Subenvironments, Lower Coeur D'Alene River Valley, Idaho

NASA Astrophysics Data System (ADS)

Hooper, R. L.; Mahoney, J. B.

2001-12-01

The lower Coeur d'Alene River Valley of northern Idaho is the site of extensive lead and zinc contamination resulting from both direct riverine tailings disposal and flood remobilization of contaminated sediments derived from the Coeur d'Alene mining district upstream. Variations in the hydrologic regime, redox conditions, porosity/permeability, organic content and microbial activity results in complicated metal transport pathways. Documentation of these pathways is a prerequisite to effective remediation, and requires accurate analysis of lateral and vertical variations. An analytical approach combining sequential extraction, electron microscopy, and microanalysis provides a comprehensive assessment of particulate speciation in this complex hydrologic system. Rigorously controlled sample preparation and a new sequential extraction protocol provide unprecedented insight into the role of metal sequestration in fluvial subenvironments. Four subenvironments were investigated: bedload, overbank (levee), marsh, and lacustrine. Periodic floods remobilize primary ore minerals and secondary minerals from upstream tailings (primarily oxyhydroxides, sulfides and carbonates). The bedload in the lower valley is a reducing environment and acts as a sink for detrital carbonates and sulfides moving downstream. In addition, authigenic/biogenic Fe, Pb and Zn sulfides and phosphates are common in bedload sediments near the sediment/water interface. Flood redistribution of oxide, sulfide and carbonate phases results in periodic contaminant recharge generating a complex system of metal dissolution, mobilization, migration and precipitation. In levee environments, authigenic sulfides from flood scouring are quickly oxidized resulting in development of oxide coated grain surfaces. Stability of detrital minerals on the levee is variable depending on sediment permeability, grain size and mineralogy resulting in a complex stratigraphy of oxide zones mottled with zones dominated by detrital and authigenic carbonate and sulfide phases. Marshes subjected to periodic subaerial exposure/flooding are even more complex and dominated by authigenic and biogenic mineralization. Lacustrine environments are dominated by nanocrystalline inorganic and biogenic sulfide minerals in the upper third of the contaminated sediment column with increasing amounts of silt sized detrital sulfides (especially sphalerite) closer to the premining surface. In pH-neutral subenvironments within the wetlands and lateral lakes of the lower Coeur d'Alene River Valley, microbial fixation plays a critical role in sequestering metals. Complex metal oxyhydroxide phases provided via flood recharge to river edge, marsh and lacustrine environments rapidly dissolve upon encountering anoxic conditions. Microbial activity is extremely effective in removing heavy metals from the water column, producing a nanocrystalline biofilm substrate characterized by ZnS (sphalerite) and non-stoichiometric PbS, FeS, and mixed metal sulfides. These solid phases are inherently unstable, and the sequestered metals become readily available through changes in redox or pH conditions, particularly dam-controlled annual fluctuations in base level, or during removal by bottom-feeding aquatic water fowl. The recognition of the inherent complexity and instability of microbially produced sulfidic material in a pH-neutral environment has important implications for remediation efforts utilizing wetland filtration methods.

An Interactive Microsoft(registered tm) Excel Program for Tracking a Single Evaporating Droplet in Crossflow

NASA Technical Reports Server (NTRS)

Liew, K. H.; Urip, E.; Yang, S. L.; Marek, C. J.

2004-01-01

Droplet interaction with a high temperature gaseous crossflow is important because of its wide application in systems involving two phase mixing such as in combustion requiring quick mixing of fuel and air with the reduction of pollutants and for jet mixing in the dilution zone of combustors. Therefore, the focus of this work is to investigate dispersion of a two-dimensional atomized and evaporating spray jet into a two-dimensional crossflow. An interactive Microsoft Excel program for tracking a single droplet in crossflow that has previously been developed will be modified to include droplet evaporation computation. In addition to the high velocity airflow, the injected droplets are also subjected to combustor temperature and pressure that affect their motion in the flow field. Six ordinary differential equations are then solved by 4th-order Runge-Kutta method using Microsoft Excel software. Microsoft Visual Basic programming and Microsoft Excel macrocode are used to produce the data and plot graphs describing the droplet's motion in the flow field. This program computes and plots the data sequentially without forcing the user to open other types of plotting programs. A user's manual on how to use the program is included.

230Th/238U dating of hydrothermal sulfides from Duanqiao hydrothermal field, Southwest Indian Ridge

NASA Astrophysics Data System (ADS)

Yang, Weifang; Tao, Chunhui; Li, Huaiming; Liang, Jin; Liao, Shili; Long, Jiangping; Ma, Zhibang; Wang, Lisheng

2017-06-01

Duanqiao hydrothermal field is located between the Indomed and Gallieni fracture zones at the central volcano, at 50°28'E in the ultraslow-spreading Southwest Indian Ridge (SWIR). Twenty-eight subsamples from a relict chimney and massive sulfides were dated using the 230Th/238U method. Four main episodes of hydrothermal activity were determined according to the restricted results: 68.9-84.3, 43.9-48.4, 25.3-34.8, and 0.7-17.3 kyrs. Hydrothermal activity of Duanqiao probably started about 84.3 (±0.5) kyrs ago and ceased about 0.737 (±0.023) kyrs ago. The periodic character of hydrothermal activity may be related to the heat source provided by the interaction of local magmatism and tectonism. The estimated mean growth rate of the sulfide chimney is <0.02 mm/yr. This study is the first to estimate the growth rate of chimneys in the SWIR. The maximum age of the relict chimney in Duanqiao hydrothermal filed is close to that of the chimneys from Mt. Jourdanne (70 kyrs). The hydrothermal activity in Dragon Flag field is much more recent than that of Duanqiao or Mt. Jourdanne fields. The massive sulfides are younger than the sulfides from other hydrothermal fields such as Rainbow, Sonne and Ashadze-2. The preliminarily estimated reserves of sulfide ores of Duanqiao are approximately 0.5-2.9 million tons.

Particle dispersion and turbulence modification in a dilute mist non-isothermal turbulent flow downstream of a sudden pipe expansion

NASA Astrophysics Data System (ADS)

Terekhov, V. I.; Pakhomov, M. A.

2011-12-01

Flow, particles dispersion and heat transfer of dilute gas-droplet turbulent flow downstream of a pipe sudden expansion have been numerically investigated for the conditions of heated dry wall. An Euler two-fluid model with additional turbulence transport equations for gas and particulate phases was employed in the study. Gas phase turbulence was modelled using the elliptic blending Reynolds stress model of Fadai-Ghotbi et al. (2008). Two-way coupling is achieved between the dispersed and carrier phases. The partial equations of Reynolds stresses and temperature fluctuations, and the turbulent heat flux equations in dispersed phase by Zaichik (1999) were applied. Fine droplets get readily entrained with the detached flow, spread throughout the whole pipe cross-section. On the contrary, large particles, due to their inertia, do not appear in the recirculation zone and are presented only in the shear layer region. The presence of fine dispersed droplets in the flow attenuates the gas phase turbulence of up 25 %. Heat transfer in the mist flow increased (more than twice in comparison with the single-phase air flow). Intensification of heat transfer is observed both in the recirculation zone and flow development region in the case of fine particles. Large particles enhanced heat transfer only in the reattachment zone. Comparison between simulated results and experimental data of Hishida et al. (1995) for mist turbulent separated flow behind a backward-facing step shows quite good agreement.

Geologic map of the Strawberry Butte 7.5’ quadrangle, Meagher County, Montana

USGS Publications Warehouse

Reynolds, Mitchell W.; Brandt, Theodore R.

2017-06-19

The 7.5′ Strawberry Butte quadrangle in Meagher County, Montana near the southwest margin of the Little Belt Mountains, encompasses two sharply different geologic terranes.  The northern three-quarters of the quadrangle are underlain mainly by Paleoproterozoic granite gneiss, across which Middle Cambrian sedimentary rocks rest unconformably.  An ancestral valley of probable late Eocene age, eroded northwest across the granite gneiss terrane, is filled with Oligocene basalt and overlying Miocene and Oligocene sandstone, siltstone, tuffaceous siltstone, and conglomerate.  The southern quarter of the quadrangle is underlain principally by deformed Mesoproterozoic sedimentary rocks of the Newland Formation, which are intruded by Eocene biotite hornblende dacite dikes.  In this southern terrane, Tertiary strata are exposed only in a limited area near the southeast margin of the quadrangle.  The distinct terranes are juxtaposed along the Volcano Valley fault zone—a zone of recurrent crustal movement beginning possibly in Mesoproterozoic time and certainly established from Neoproterozoic–Early Cambrian to late Tertiary time.  Movement along the fault zone has included normal faulting, the southern terrane faulted down relative to the northern terrane, some reverse faulting as the southern terrane later moved up against the northern terrane, and lateral movement during which the southern terrane likely moved west relative to the northern terrane.  Near the eastern margin of the quadrangle, the Newland Formation is locally the host of stratabound sulfide mineralization adjacent to the fault zone; west along the fault zone across the remainder of the quadrangle are significant areas and bands of hematite and iron-silicate mineral concentrations related to apparent alteration of iron sulfides.  The map defines the distribution of a variety of surficial deposits, including the distribution of hematite-rich colluvium and iron-silicate boulders.  The southeast corner of the quadrangle is the site of active exploration and potential development for copper from the sulfide-bearing strata of the Newland Formation.

Association of a new type of gliding, filamentous, purple phototrophic bacterium inside bundles of Microcoleus chthonoplastes in hypersaline cyanobacterial mats

NASA Technical Reports Server (NTRS)

D'Amelio, E. D.; Cohen, Y.; Des Marais, D. J.

1987-01-01

An unidentified filamentous purple bacterium, probably belonging to a new genus or even a new family, is found in close association with the filamentous, mat-forming cyanobacterium Microcoleus chthonoplastes in a hypersaline pond at Guerrero Negro, Baja California Sur, Mexico, and in Solar Lake, Sinai, Egypt. This organism is a gliding, segmented trichome, 0.8-0.9 micrometer wide. It contains intracytoplasmic stacked lamellae which are perpendicular and obliquely oriented to the cell wall, similar to those described for the purple sulfur bacteria Ectothiorhodospira. These bacteria are found inside the cyanobacterial bundle, enclosed by the cyanobacterial sheath. Detailed transmission electron microscopical analyses carried out in horizontal sections of the upper 1.5 mm of the cyanobacterial mat show this cyanobacterial-purple bacterial association at depths of 300-1200 micrometers, corresponding to the zone below that of maximal oxygenic photosynthesis. Sharp gradients of oxygen and sulfide are established during the day at this microzone in the two cyanobacterial mats studied. The close association, the distribution pattern of this association and preliminary physiological experiments suggest a co-metabolism of sulfur by the two-membered community. This probable new genus of purple bacteria may also grow photoheterotrophically using organic carbon excreted by the cyanobacterium. Since the chemical gradients in the entire photic zone fluctuate widely in a diurnal cycle, both types of metabolism probably take place. During the morning and afternoon, sulfide migrates up to the photic zone allowing photoautotrophic metabolism with sulfide as the electron donor. During the day the photic zone is highly oxygenated and the purple bacteria may either use oxidized species of sulfur such as elemental sulfur and thiosulfate in the photoautotrophic mode or grow photoheterotrophically using organic carbon excreted by M. chthonoplastes. The new type of filamentous purple sulfur bacteria is not available yet in pure culture, and its taxonomical position cannot be fully established. This organism is suggested to be a new type of gliding, filamentous, purple phototroph.

Mechanisms controlling Cu, Fe, Mn, and Co profiles in peat of the Filson Creek Fen, northeastern Minnesota

USGS Publications Warehouse

Walton-Day, K.; Filipek, L.H.; Papp, C.S.E.

1990-01-01

Filson Creek Fen, located in northeastern Minnesota, overlies a Cu-Ni sulfide deposit. A site in the fen was studied to evaluate the hydrogeochemical mechanisms governing the development of Fe, Mn, Co, and Cu profiles in the peat. At the study site, surface peat approximately 1 m thick is separated from the underlying mineralized bedrock by a 6-12 m thickness of lake and glaciofluvial sediments and till. Concentrations of Fe, Mn, Co, and Cu in peat and major elements in pore water delineate a shallow, relatively oxidized, Cu-rich zone overlying a deeper, reduced, Fe-, Mn-, and Co-rich zone within the peat. Sequential metal extractions from peat samples reveal that 40-55% of the Cu in the shallow zone is associated with organic material, whereas the remaining Cu is distributed between iron-oxide, sulfide, and residual fractions. Sixty to seventy percent of the Fe, Mn, and Co concentrated in the deeper zone occur in the residual phase. The metal profiles and associations probably result from non-steady-state input of metals and detritus into the fen during formation of the peat column. The enrichment of organic-associated Cu in the upper, oxidized zone represents a combination of Cu transported into the fen with detrital plant fragments and soluble Cu, derived from weathering of outcrop and subcrop of the mineral deposit, transported into the fen, and fixed onto organic matter in the peat. The variable stratigraphy of the peat indicates that weathering processes and surface vegetation have changed through time in the fen. The Fe, Mn, and Co maxima at the base of the peat are associated with a maximum in detrital matter content of the peat resulting from a transition between the underlying inorganic sedimentary environment to an organic sedimentary environment. The chemistry of sediments and ground water collected beneath the peat indicate that mobilization of metals from sulfide minerals in the buried mineral deposit or glacial deposits is minimal. Therefore, the primary source of Cu to the peat at the study site is outcrops and shallow subcrops of the mineral deposit adjacent to the fen. ?? 1990.

Evaporation-induced gas-phase flows at selective laser melting

NASA Astrophysics Data System (ADS)

Zhirnov, I.; Kotoban, D. V.; Gusarov, A. V.

2018-02-01

Selective laser melting is the method for 3D printing from metals. A solid part is built from powder layer-by-layer. A continuum-wave laser beam scans every powder layer to fuse powder. The process is studied with a high-speed CCD camera at the frame rate of 104 fps and the resolution up to 5 µm per pixel. Heat transfer and evaporation in the laser-interaction zone are numerically modeled. Droplets are ejected from the melt pool in the direction around the normal to the melt surface and the powder particles move in the horizontal plane toward the melt pool. A vapor jet is observed in the direction of the normal to the melt surface. The velocities of the droplets, the powder particles, and the jet flow and the mass loss due to evaporation are measured. The gas flow around the vapor jet is calculated by Landau's model of submerged jet. The measured velocities of vapor, droplets, and powder particles correlate with the calculated flow field. The obtained results show the importance of evaporation and the flow of the vapor and the ambient gas. These gas-dynamic phenomena can explain the formation of the denudated zones and the instability at high-energy input.

Gold enrichment and the Bi-Au association in pyrrhotite-rich massive sulfide deposits, Escanaba trough, Southern Gorda Ridge

USGS Publications Warehouse

Tormanen, T.O.; Koski, R.A.

2005-01-01

High gold contents (to 10.1 ppm, avg 1.4 ppm, n = 34) occur in pyrrhotite-rich massive sulfide samples from the sediment-covered floor of the Escanaba trough, the slow-spreading, southernmost segment of Gorda Ridge. These concentrations reflect the presence of primary gold, formed during high-temperature hydrothermal activity in mounds and chimneys, and secondary gold deposited during sea-floor weathering of massive sulfide. Primary gold occurs as fine-grained (2 ??m) secondary gold grains have a porous, flaky morphology and occur in samples in which pyrrhotite is oxidized and replaced by Fe oxyhydroxides, Fe sulfate, and sulfur. Mounds and chimneys dominated by pyrrhotite and containing lesser amounts of isocubanite, chalcopyrite, and Fe-rich sphalerite were formed by high-temperature (estimated range 325??-275??C), reduced, low-sulfur vent fluids. The mineral and fluid compositions during this main stage of hydrothermal venting reflect subsurface interaction between circulating hydrothermal fluids and turbiditic sediment containing as much as 1.1 percent organic carbon. As the deposition of pyrrhotite, Cu-Fe sulfides, and sphalerite waned, a volumetrically minor suite of sulfarsenide, arsenide, Bi, and Au minerals was deposited from highly reduced, late main-stage fluids diffusing through mounds and chimneys. The low solubility of Au as a bisulfide complex and the absence of fluid mixing during this stage of hydrothermal activity apparently inhibited the precipitation of gold directly from solution. Instead, gold precipitation is thought to be linked to elevated concentrations of Bi in the late main-stage fluids. The textural relationships of Au and Bi minerals in pyrrhotite-rich samples, low melting point of native bismuth (271.4??C), and recent experimental results on Au and Bi in hydrothermal fluids contribute to the hypothesis that gold was effectively scavenged from the Escanaba trough vent fluids by coexisting droplets of liquid bismuth. Additional phase relationships of alloys in the Au-Bi system indicate that deposition of native bismuth and maldonite occurred at temperatures as low as 241??C. Bismuth droplets trapped in void space between main-stage mineral grains scavenged gold from ambient hydrothermal fluid to a greater extent than bismuth enclosed by late-forming pyrrhotite. The limited solid solution of Au in Bi can explain the apparent exsolution texture in which gold blebs are hosted by native bismuth. The electrum, native bismuth (with gold inclusions), and galena represent the last traces of gold mineralization from late main-stage fluids. During sea-floor weathering and the oxidation of pyrrhotite in the mounds and chimneys, secondary gold formed as aggregates of colloidal particles along pH gradients between acidic pore waters and ambient seawater. Gold was mobilized from earlier formed primary gold minerals and transported as aqueous chloride complexes. The reduction of Au(III) by residual Fe2+ in partly altered pyrrhotite and adsorption of colloids by Fe oxyhydroxides may have influenced the location of secondary gold grains within the alteration front. Solubility differences between gold and silver chloride complexes at low temperature account for the low Ag content of secondary gold grains. The high concentrations of Bi, and thus the association of Au and Bi minerals in pyrrhotite-rich massive sulfide, can be ascribed to the extensive interaction of hydrothermal fluids with sediment in the Escanaba trough. In contrast, the absence of the Au-Bi association in massive sulfides at other ridges, including other sediment-covered sites at Middle Valley and the Guaymas basin

Mineral potential tracts for polymetallic Pb-Zn-Cu vein deposits (phase V, deliverable 71): Chapter I in Second projet de renforcement institutionnel du secteur minier de la République Islamique de Mauritanie (PRISM-II)

USGS Publications Warehouse

Beaudoin, Georges

2015-01-01

In Mauritania, mineral occurrences of the polymetallic Pb-Zn-Cu vein deposit type are found near the Florence-El Khdar shear zone in northeast Mauritania. The deposits visited were deemed representative of other similar occurrences and consist of quartz veins with trace sulfides. The low sulfide and Pb-Zn-Cu content in the quartz veins is unlike producing polymetallic Pb-Zn-Cu vein deposits, such that the veins are not considered to belong to this deposit type. Mineral potential tracts for polymetallic Pb-ZnCu veins are highly speculative considering the lack of known mineralization belonging to this deposit type. Mineral potential tracts for polymetallic Pb-Zn-Cu veins are associated with and surround major shear zones in the Rgueïbat Shield and zones of complex faulting in the southern Mauritanides, at the exclusion of the imbricated thrust faults that are not considered favorable for this deposit type. No skarn and replacement deposits have been documented in Mauritania and the low mineral potential is indicated by lack of causative Mesozoic and Cenozoic mafic to felsic stocks.

[Effect of microorganisms and seasonal factors on the isotope composition of organic carbon from Black Sea suspensions].

PubMed

Ivanov, M V; Lein, A Iu; Miller, Iu M; Iusunov, S K; Pimenov, N V; Wehrli, B; Rusanov, I I; Zehnder, A

2000-01-01

The isotopic composition of particulate organic carbon (POC) from the Black Sea deep-water zone was studied during a Russian-Swiss expedition in May 1998. POC from the upper part of the hydrogen sulfide zone (the C-layer) was found to be considerably enriched with the 12C isotope, as compared to the POC of the oxycline and anaerobic zone. In the C-layer waters, the concurrent presence of dissolved oxygen and hydrogen sulfide and an increased rate of dark CO2 fixation were recorded, suggesting that the change in the POC isotopic composition occurs at the expense of newly formed isotopically light organic matter of the biomass of autotrophic bacteria involved in the sulfur cycle. In the anaerobic waters below the C-layer, the organic matter of the biomass of autotrophs is consumed by the community of heterotrophic microorganisms; this results in weighting of the POC isotopic composition. Analysis of the data obtained and data available in the literature allows an inference to be made about the considerable seasonable variability of the POC delta 13C value, which depends on the ratio of terrigenic and planktonogenic components in the particulate organic matter.

Sulfide and methane production in sewer sediments.

PubMed

Liu, Yiwen; Ni, Bing-Jie; Ganigué, Ramon; Werner, Ursula; Sharma, Keshab R; Yuan, Zhiguo

2015-03-01

Recent studies have demonstrated significant sulfide and methane production by sewer biofilms, particularly in rising mains. Sewer sediments in gravity sewers are also biologically active; however, their contribution to biological transformations in sewers is poorly understood at present. In this study, sediments collected from a gravity sewer were cultivated in a laboratory reactor fed with real wastewater for more than one year to obtain intact sediments. Batch test results show significant sulfide production with an average rate of 9.20 ± 0.39 g S/m(2)·d from the sediments, which is significantly higher than the areal rate of sewer biofilms. In contrast, the average methane production rate is 1.56 ± 0.14 g CH4/m(2)·d at 20 °C, which is comparable to the areal rate of sewer biofilms. These results clearly show that the contributions of sewer sediments to sulfide and methane production cannot be ignored when evaluating sewer emissions. Microsensor and pore water measurements of sulfide, sulfate and methane in the sediments, microbial profiling along the depth of the sediments and mathematical modelling reveal that sulfide production takes place near the sediment surface due to the limited penetration of sulfate. In comparison, methane production occurs in a much deeper zone below the surface likely due to the better penetration of soluble organic carbon. Modelling results illustrate the dependency of sulfide and methane productions on the bulk sulfate and soluble organic carbon concentrations can be well described with half-order kinetics. Copyright © 2014 Elsevier Ltd. All rights reserved.

Biological treatment process of air loaded with an ammonia and hydrogen sulfide mixture.

PubMed

Malhautier, Luc; Gracian, Catherine; Roux, Jean-Claude; Fanlo, Jean-Louis; Le Cloirec, Pierre

2003-01-01

The physico-chemical characteristics of granulated sludge lead us to develop its use as a packing material in air biofiltration. Then, the aim of this study is to investigate the potential of unit systems packed with this support in terms of ammonia and hydrogen sulfide emissions treatment. Two laboratory scale pilot biofilters were used. A volumetric load of 680 g H2S m(-3) empty bed day(-1) and 85 g NH3 m(-3) empty bed day(-1) was applied for eight weeks to a unit called BGSn (column packed with granulated sludge and mainly supplied with hydrogen sulfide); a volumetric load of 170 g H2S m(-3) empty bed day(-1) and 340 g NH3 m(-3) empty bed day(-1) was applied for eight weeks to the other called BGNs (column packed with granulated sludge and mainly supplied with ammonia). Ammonia and hydrogen sulfide elimination occur in the biofilters simultaneously. The hydrogen sulphide and ammonia removal efficiencies reached are very high: 100% and 80% for BGSn; 100% and 80% for BGNs respectively. Hydrogen sulfide is oxidized into sulphate and sulfur. The ammonia oxidation products are nitrite and nitrate. The nitrogen error mass balance is high for BGSn (60%) and BGNs (36%). This result could be explained by the denitrification process which would have occurred in anaerobic zones. High percentages of ammonia or hydrogen sulfide are oxidized on the first half of the column. The oxidation of high amounts of hydrogen sulfide would involve some environmental stress on nitrifying bacterial growth and activity.

Chromite and olivine in type II chondrules in carbonaceous and ordinary chondrites - Implications for thermal histories and group differences

NASA Technical Reports Server (NTRS)

Johnson, Craig A.; Prinz, Martin

1991-01-01

Unequilibrated chromite and olivine margin compositions in type II chondrules are noted to differ systematically among three of the chondrite groups, suggesting that type II liquids differed in composition among the groups. These differences may be interpreted as indicators of different chemical compositions of the precursor solids which underwent melting, or, perhaps, as differences in the extent to which immiscible metal sulfide droplets were lost during chondrule formation. Because zinc is detectable only in type II chromites which have undergone reequilibration, the high zinc contents reported for chondritic chromites in other studies probably reflect redistribution during thermal metamorphism.

Seismic valve as the main mechanism for sedimentary fluid entrapment within extensional basin: example of the Lodève Permian Basin (Hérault, South of France).

NASA Astrophysics Data System (ADS)

Laurent, D.; Lopez, M.; Chauvet, A.; Imbert, P.; Sauvage, A. C.; Martine, B.; Thomas, M.

2014-12-01

During syn-sedimentary burial in basin, interstitial fluids initially trapped within the sedimentary pile are easily moving under overpressure gradient. Indeed, they have a significant role on deformation during basin evolution, particularly on fault reactivation. The Lodève Permian Basin (Hérault, France) is an exhumed half graben with exceptional outcrop conditions providing access to barite-sulfides mineralized systems and hydrocarbon trapped into rollover faults of the basin. Architectural studies shows a cyclic infilling of fault zone and associated S0-parallel veins according to three main fluid events during dextral/normal faulting. Contrasting fluid entrapment conditions are deduced from textural analysis, fluid inclusion microthermometry and sulfide isotope geothermometer: (i) the first stage is characterized by an implosion breccia cemented by silicifications and barite during abrupt pressure drop within fault zone; (ii) the second stage consists in succession of barite ribbons precipitated under overpressure fluctuations, derived from fault-valve action, with reactivation planes formed by sulphide-rich micro-shearing structures showing normal movement; and (iii) the third stage is associated to the formation of dextral strike-slip pull-apart infilling by large barite crystals and contemporary hydrocarbons under suprahydrostatic pressure values. Microthermometry, sulfide and strontium isotopic compositions of the barite-sulfides veins indicate that all stages were formed by mixing between deep basinal fluids at 230°C, derived from cinerite dewatering, and formation water from overlying sedimentary cover channelized trough fault planes. We conclude to a polyphase history of fluid trapping during Permian synrift formation of the basin: (i) a first event, associated with the dextral strike-slip motion on faults, leads to a first sealing of the fault zone; (ii) periodic reactivations of fault planes and bedding-controlled shearing form the main mineralized ore bodies by the single action of fluid overpressure fluctuations, undergoing changes in local stress distribution and (iii) a final tectonic activation of fault linked to last basinal fluid and hydrocarbon migration during which shear stress restoration on fault plane is faster than fluid pressure build-up.

Depositionally controlled recycling of iron and sulfur in marine sediments and its isotopic consequences

NASA Astrophysics Data System (ADS)

Riedinger, N.; Formolo, M.; Arnold, G. L.; Vossmeyer, A.; Henkel, S.; Sawicka, J.; Kasten, S.; Lyons, T. W.

2011-12-01

The continental margin off Uruguay and Argentina is characterized by highly dynamic depositional conditions. This variable depositional regime significantly impacts the biogeochemical cycles of iron and sulfur. Mass deposit related redeposition of reduced minerals can lead to the reoxidation of these phases and thus to an overprint of their geochemical primary signatures. Due to rapid burial these oxidized phases are still present in deeper subsurface sediments. To study the effects of sediment relocation on the sulfur and iron inventory we collected shallow and deep subsurface sediment samples via multicorer and gravity cores, respectively, in the western Argentine Basin during the RV Meteor Expedition M78/3 in May-July 2009. The samples were retrieved from shelf, slope and deep basin sites. The concentration and sulfur isotope composition of acid volatile sulfur (AVS), chromium reducible sulfur (CRS), elemental sulfur and total organic sulfur were determined. Furthermore, sequential iron extraction techniques were applied assess the distribution of iron oxide phases within the sediment. The investigated sediments are dominated by terrigenous inputs, with high amounts of reactive ferric iron minerals and only low concentrations of calcium carbonate. Total organic carbon concentrations show strong variation in the shallow subsurface sediments ranging between approximately 0.7 and 6.4 wt% for different sites. These concentrations do not correlate with water depths. Pore water accumulations of hydrogen sulfide are restricted to an interval at the sulfate-methane transition (SMT) zone a few meters below the sediment surface. In these deeper subsurface sediments pyrite is precipitated in this zone of hydrogen sulfide excess, whereas the accumulation of authigenic AVS and elemental sulfur (up to 2000 ppm) occurs at the upper and lower boundary of the sulfidic zone due the reaction of iron oxides with limited amounts of sulfide. Furthermore, our preliminary results indicate that there is a link between modern deposition in the shallow subsurface sediments and the long-term signals being buried and preserved in the deep subsurface layers. The data show that the burial of elemental sulfur into deep subsurface sediments can fuel the deep biosphere and has consequences for isotopic overprints tied, for example, to oxidation and disproportionation processes in the deeper sediments.

Numerical Simulation of the Combustion of Fuel Droplets: Finite Rate Kinetics and Flame Zone Grid Adaptation (CEFD)

NASA Technical Reports Server (NTRS)

Gogos, George; Bowen, Brent D.; Nickerson, Jocelyn S.

2002-01-01

The NASA Nebraska Space Grant (NSGC) & EPSCoR programs have continued their effort to support outstanding research endeavors by funding the Numerical Simulation of the Combustion of Fuel Droplets study at the University of Nebraska at Lincoln (UNL). This team of researchers has developed a transient numerical model to study the combustion of suspended and moving droplets. The engines that propel missiles, jets, and many other devices are dependent upon combustion. Therefore, data concerning the combustion of fuel droplets is of immediate relevance to aviation and aeronautical personnel, especially those involved in flight operations. The experiments being conducted by Dr. Gogos and Dr. Nayagam s research teams, allow investigators to gather data for comparison with theoretical predictions of burning rates, flame structures, and extinction conditions. The consequent improved hndamental understanding droplet combustion may contribute to the clean and safe utilization of fossil hels (Williams, Dryer, Haggard & Nayagam, 1997, 72). The present state of knowledge on convective extinction of he1 droplets derives fiom experiments conducted under normal gravity conditions. However, any data obtained with suspended droplets under normal gravity are grossly affected by gravity. The need to obtain experimental data under microgravity conditions is therefore well justified and addresses one of the goals of NASA s Human Exploration and Development of Space (HEDS) microgravity combustion experiment.

Post-depositional behavior of Cu in a metal-mining polishing pond (East Lake, Canada).

PubMed

Martin, Alan J; Jambor, John L; Pedersen, Tom F; Crusius, John

2003-11-01

The post-depositional behavior of Cu in a gold-mining polishing pond (East Lake, Canada) was assessed after mine closure by examination of porewater chemistry and mineralogy. The near-surface (upper 1.5 cm) sediments are enriched in Cu, with values ranging from 0.4 to 2 wt %. Mineralogical examination revealed that the bulk of the Cu inventory is present as authigenic copper sulfides. Optical microscopy, energy-dispersion spectra, and X-ray data indicate that the main Cu sulfide is covellite (CuS). The formation of authigenic Cu-S phases is supported by the porewater data, which demonstrate that the sediments are serving as a sink for dissolved Cu below sub-bottom depths of 1-2 cm. The zone of Cu removal is consistent with the occurrence of detectable sulfide and the consumption of sulfate. The sediments can be viewed as a passive bioreactorthat permanently removes Cu as insoluble copper sulfides. This process is not unlike that which occurs in other forms of bioremediation, such as wetlands and permeable reactive barriers. Above the zone of Cu removal, dissolved Cu maxima in the interfacial porewaters range from 150 to 450 microg L(-1) and reflect the dissolution of a Cu-bearing phase in the surface sediments. The reactive phase is thought to be a component of treatment sludges delivered to the lake as part of cyanide treatment. Flux calculations indicate that the efflux of dissolved Cu from the sediments to the water column (14-51 microg cm(-2) yr(-1)) can account for the elevated levels of dissolved Cu in lake waters (approximately 50 microg L(-1)). Implications for lake recovery are discussed.

Arsenic transport between surface and groundwater in a moderately reducing zone: Geochemical approach

NASA Astrophysics Data System (ADS)

Khaska, Mahmoud; Le Gal La Salle, Corinne; Verdoux, Patrick

2015-04-01

Arsenic contamination represents a major risk to human health as one of the most prominent environmental causes of cancer mortality. Mining activities, particularly those involving arsenic rich ores have an impact on the environment and on human health that may persist for many decades after mine closure. The relationships between As released from alluvial aquifer in the vicinity of the sulfide-rich mine dumps was demonstrated with geochemical and isotopic tracers (major and traces elements, 87Sr/86Sr, 18O, 2H). Strontium isotopes were used to trace the transport of As downstream from a As rich tailing dam. Increasing As and Fe concentrations in surface water are explained by As release associated with alluvial groundwater discharge to the stream. This process occurs in a moderately reduced section of the stream downgradient from the sulfide-rich tailing dam. High As, total Fe and low Eh in groundwater confirm the discharge of alluvial groundwater and explain its impact on surface water. Transport of As between surface and groundwater can be described as follows: 1- Subsurface moderately reducing conditions prevail in groundwater downgradient from the tailing dams. This suggests a flux of reduced water from sulfide-rich tailing dams which is characterized by its high As and Fe content resulting from the reduction of Fe-sulfides. 2- Upon mixing with surface water, oxidizing conditions prevails and precipitate as Fe hydroxide on the stream bed. As and Sr subsequently adsorbed on the Fe -oxyhydroxide surface. This process contributes to the immobilization of As in surface water. Remaining dissolved As in surface water can be re-introduced in alluvial groundwater downstream of the reducing zone.

Post-Depositional Behavior of Cu in a Metal-Mining Polishing Pond (East Lake, Canada)

USGS Publications Warehouse

Martin, A.J.; Jambor, J.L.; Pedersen, Thomas F.; Crusius, John

2003-01-01

The post-depositional behavior of Cu in a gold-mining polishing pond (East Lake, Canada) was assessed after mine closure by examination of porewater chemistry and mineralogy. The near-surface (upper 1.5 cm) sediments are enriched in Cu, with values ranging from 0.4 to 2 wt %. Mineralogical examination revealed that the bulk of the Cu inventory is present as authigenic copper sulfides. Optical microscopy, energy-dispersion spectra, and X-ray data indicate that the main Cu sulfide is covellite (CuS). The formation of authigenic Cu-S phases is supported by the porewater data, which demonstrate that the sediments are serving as a sink for dissolved Cu below sub-bottom depths of 1-2 cm. The zone of Cu removal is consistent with the occurrence of detectable sulfide and the consumption of sulfate. The sediments can be viewed as a passive bioreactor that permanently removes Cu as insoluble copper sulfides. This process is not unlike that which occurs in other forms of bioremediation, such as wetlands and permeable reactive barriers. Above the zone of Cu removal, dissolved Cu maxima in the interfacial porewaters range from 150 to 450 ??g L-1 and reflect the dissolution of a Cu-bearing phase in the surface sediments. The reactive phase is thought to be a component of treatment sludges delivered to the lake as part of cyanide treatment. Flux calculations indicate that the efflux of dissolved Cu from the sediments to the water column (14-51 ??g cm-2 yr-1) can account for the elevated levels of dissolved Cu in lake waters (???50 ??g L-1). Implications for lake recovery are discussed.

The Formation and Chronology of the PAT 91501 Impact-Melt L-Chondrite with Vesicle-Metal-Sulfide Assemblages

NASA Technical Reports Server (NTRS)

Benedix, G. K.; Ketcham, R. A.; Wilson, L.; McCoy, T. J.; Bogard, D. D.; Garrison, D. H.; Herzog, G. F.; Xue, S.; Klein, J.; Middleton, R.

2007-01-01

The L chondrite Patuxent Range (PAT) 41 91501 is an 8.5-kg unshocked, homogeneous, igneous-textured impact melt that cooled slowly compared to other meteoritic impact melts in a crater floor melt sheet or sub-crater dike. We conducted mineralogical and tomographic studies of previously unstudied mm- to cm-sized metal-sulfide-vesicle assemblages and chronologic studies of the silicate host. Metal-sulfide clasts constitute about 1 vol.%, comprise zoned taenite, troilite and pentlandite, and exhibit a consistent orientation between metal and sulfide and of metal-sulfide contacts. Vesicles make up approximately 2 vol.% and exhibit a similar orientation of long axes. Ar-39-Ar-40 measurements date the time of impact at 4.461 +/- 0.008 Gyr B.P. Cosmogenic noble gases and Be-10 and Al-2l activities suggest a pre-atmospheric radius of 40-60 cm and a cosmic ray exposure age of 25-29 Myr, similar to ages of a cluster of L chondrites. PAT 91501 dates the oldest known impact on the L chondrite parent body. The dominant vesicle-forming gas was S2 (approximately 15-20 ppm), which formed in equilibrium with impact-melted sulfides. The meteorite formed in an impact melt dike beneath a crater, as did other impact melted L chondrites, such as Chico. Cooling and solidification occurred over approximately 2 hours. During this time, approximately 90% of metal and sulfide segregated from the local melt. Remaining metal and sulfide grains oriented themselves in the local gravitational field, a feature nearly unique among meteorites. Many of these metal sulfide grains adhered to vesicles to form aggregates that may have been close to neutrally buoyant. These aggregates would have been carried upward with the residual melt, inhibiting further buoyancy-driven segregation. Although similar processes operated individually in other chondritic impact melts, their interaction produced the unique assemblage observed in PAT 91501.

Value recovery from spent alumina-base catalyst

DOEpatents

Hyatt, David E.

1987-01-01

A process for the recovery of aluminum and at least one other metal selected from the group consisting of molybdenum, nickel and cobalt from a spent hydrogenation catalyst comprising (1) adding about 1 to 3 parts H.sub.2 SO.sub.4 to each part of spent catalyst in a reaction zone of about 20.degree. to 200.degree. C. under sulfide gas pressure between about 1 and about 35 atmospheres, (2) separating the resultant Al.sub.2 (SO.sub.4).sub.3 solution from the sulfide precipitate in the mixture, (3) oxidizing the remaining sulfide precipitate as an aqueous slurry at about 20.degree. to 200.degree. C. in an oxygen-containing atmosphere at a pressure between about 1 and about 35 atmospheres, (4) separating the slurry to obtain solid molybdic acid and a sulfate liquor containing said at least one metal, and (5) recovering said at least one metal from the sulfate liquor in marketable form.

Geology and Mineral Deposits of the Snow Camp-Saxapahaw Area, Central North Carolina

USGS Publications Warehouse

Schmidt, Robert G.; Gumiel, Pablo; Payas, Alba

2006-01-01

The Snow Camp-Saxapahaw study area, in the Carolina slate belt in the Southeastern United States, is notable for large zones of high-sulfidation alteration in arc-related metavolcanic rocks. The area has potential for additional significant pyrophyllite and related aluminosilicate refractory mineral deposits and may have potential for small- to medium-size gold deposits also associated with the high-sulfidation hydrothermal systems. The Carolina slate belt is an elongate zone of mostly low-grade metamorphic rocks of Neoproterozoic to early Paleozoic age that extends from northeastern Georgia to southern Virginia. It is dominated by volcanic rocks but locally consists of fine-grained epiclastic sedimentary rocks. Plutons and subvolcanic bodies have intruded the rocks of the Carolina slate belt in many places and have been important in controlling the metamorphism and in localizing hydrothermal alteration. The Snow Camp-Saxapahaw area is mostly underlain by volcanic and volcaniclastic rocks and lesser amounts of intrusive shallow plutons. The volcanic rocks range in composition from basalt to rhyolite; however andesites, dacites, and rhyodacites are the most abundant. The intrusive bodies are largely granite and quartz monzonite; gabbroic bodies also are common. It was possible to establish the relative ages of only part of these rocks. Two northeast-trending fault zones and fractures divide the map area into three structural blocks; the central block was tilted down to the southwest to form a grabenlike structure. Most of the hydrothermally altered rocks and all of the intensely altered zones are confined to the downdropped block, which we think may have been calderalike in origin. A major volcanic unit, the Reedy Branch Tuff, is limited to the southwestern part of the graben and may be the youngest volcanic rock in the area. Layered rocks record one or more strong folding events, but the diversity of rock types, lack of recognizable stratigraphic markers, and uneven distribution of outcrops prevented comprehensive structural studies. Except for a few late plutons and dikes, all of the rocks of the area have been metamorphosed in middle to upper greenschist facies, and contact aureoles were recognized around some of the plutons. Several relatively small bodies of granitic rock contain plagioclase grains in which primary oscillatory zoning was unaffected by metamorphism. These were interpreted to be post-metamorphic. We think that there were three separate stages of hydrothermal alteration in the complex volcanic terrane in the area. The oldest, an area of at least 8.5 square miles (22 square kilometers), was subjected to an intense hydrothermal alteration, ranging from peripheral zones of quartz-sericite-paragonite through a patchy marginal zone of pyrophyllite, andalusite, and other high-alumina minerals, to almost totally silicified core zones. The second event resulted in large areas of weak to moderate sericitic and propylitic alteration recognizable only in the Reedy Branch Tuff. The last event was related to post-metamorphic plutons. All of the pyrophyllite-andalusite deposits and perhaps most of the gold and silver mineralization can be related to the first period of hydrothermal alteration. The subsequent metamorphism did not produce significant changes in mineral species in the zones of most intense hydrothermal alteration. Gold- and silver-bearing sulfide minerals in fracture zones along the southeastern margin of the graben may also have been deposited during this earliest alteration stage. No metallic mineralization appears to have occurred during the second event. A group of molybdenum-bearing greisenlike bodies formed during the emplacement of the youngest plutons during the post-metamorphic event. One gold-bearing sulfide zone occurs in the exocontact of one such porphyritic stock. Significant amounts of pyrophyllite-andalusite-bearing rock have been extracted from the Snow Camp Mine and from

Submarine fissure eruptions and hydrothermal vents on the southern Juan de Fuca Ridge: preliminary observations from the submersible Alvin

USGS Publications Warehouse

Normark, W.R.

1986-01-01

The submersible Alvin was used to investigate 3 active hydrothermal discharge sites along the S Juan de Fuca Ridge in September 1984. The hydrothermal zones occur within a 10-30m-deep, 30-50m-wide cleft marking the center of the axial valley. This cleft is the eruptive locus for the axial valley. The hydrothermal vents coincide with the main eruptive vents along the cleft. Each hydrothermal zone has multiple discharge sites extending as much as 500m along the cleft. Sulfide deposits occur as clusters (15-100m2 area) of small chimneys (= or <2m high) and as individual and clustered fields of large, branched chimneys (= or <10m high). Recovered sulfide samples are predominantly the tops of chimneys and spires and typically contain more than 80% sphalerite and wurtzite with minor pyrrhotite, pyrite, marcasite, isocubanite, chalcopyrite, anhydrite, anhydrite, and amorphous silica. The associated hydrothermal fluids have the highest chlorinity of any reported to date.-Authors

Effect of oxygen minimum zone formation on communities of marine protists

PubMed Central

Orsi, William; Song, Young C; Hallam, Steven; Edgcomb, Virginia

2012-01-01

Changes in ocean temperature and circulation patterns compounded by human activities are leading to oxygen minimum zone (OMZ) expansion with concomitant alteration in nutrient and climate active trace gas cycling. Here, we report the response of microbial eukaryote populations to seasonal changes in water column oxygen-deficiency using Saanich Inlet, a seasonally anoxic fjord on the coast of Vancouver Island British Columbia, as a model ecosystem. We combine small subunit ribosomal RNA gene sequencing approaches with multivariate statistical methods to reveal shifts in operational taxonomic units during successive stages of seasonal stratification and renewal. A meta-analysis is used to identify common and unique patterns of community composition between Saanich Inlet and the anoxic/sulfidic Cariaco Basin (Venezuela) and Framvaren Fjord (Norway) to show shared and unique responses of microbial eukaryotes to oxygen and sulfide in these three environments. Our analyses also reveal temporal fluctuations in rare populations of microbial eukaryotes, particularly anaerobic ciliates, that may be of significant importance to the biogeochemical cycling of methane in OMZs. PMID:22402396

Localization of mineralization, its age, and relationship to magmatism at the Mogot silver-base-metal deposit, North Stanovoi metallogenic zone in the southeastern framework of the North Asian Craton

NASA Astrophysics Data System (ADS)

Buchko, I. V.; Buchko, Ir. V.; Sorokin, A. A.; Ponomarchuk, V. A.; Travin, A. V.

2014-03-01

The results of studying the Mogot silver-base-metal deposit located in the Dzhugdzhur-Stanovoi Superterrane are discussed in this paper. The main ore-controlling structural elements of the studied district are near-latitudinal and NE-trending faults, which are accompanied by zones of hydrothermal metasomatic potassic, propylitic, and argillic alterations, breccias with quartz and quartz-carbonate cement replacing metamorphic rocks and granitoids of the Late Stanovoi Complex. The total sulfide content in ore is 2-3%. The high Ag, Pb, and Zn contents in ore allow us to consider the Mogot deposit as silver-base-metal, since except of orebody 4, there are no silver minerals proper. This indicates that silver is incorporated into crystalline lattice of sulfides. The results of 40Ar/39Ar geochronological investigations show that the hydrothermal ore deposition dated at 127-125 Ma was related to emplacement of intrusions pertaining to the Tynda-Bakaran Complex.

Geologic history of the Blackbird Co-Cu district in the Lemhi subbasin of the Belt-Purcell Basin

USGS Publications Warehouse

Bookstrom, Arthur A.; Box, Stephen E.; Cossette, Pamela M.; Frost, Thomas P.; Gillerman, Virginia; King, George; Zirakparvar, N. Alex

2016-01-01

The Blackbird cobalt-copper (Co-Cu) district in the Salmon River Mountains of east-central Idaho occupies the central part of the Idaho cobalt belt—a northwest-elongate, 55-km-long belt of Co-Cu occurrences, hosted in grayish siliciclastic metasedimentary strata of the Lemhi subbasin (of the Mesoproterozoic Belt-Purcell Basin). The Blackbird district contains at least eight stratabound ore zones and many discordant lodes, mostly in the upper part of the banded siltite unit of the Apple Creek Formation of Yellow Lake, which generally consists of interbedded siltite and argillite. In the Blackbird mine area, argillite beds in six stratigraphic intervals are altered to biotitite containing over 75 vol% of greenish hydrothermal biotite, which is preferentially mineralized.Past production and currently estimated resources of the Blackbird district total ~17 Mt of ore, averaging 0.74% Co, 1.4% Cu, and 1.0 ppm Au (not including downdip projections of ore zones that are open downward). A compilation of relative-age relationships and isotopic age determinations indicates that most cobalt mineralization occurred in Mesoproterozoic time, whereas most copper mineralization occurred in Cretaceous time.Mesoproterozoic cobaltite mineralization accompanied and followed dynamothermal metamorphism and bimodal plutonism during the Middle Mesoproterozoic East Kootenay orogeny (ca. 1379–1325 Ma), and also accompanied Grenvilleage (Late Mesoproterozoic) thermal metamorphism (ca. 1200–1000 Ma). Stratabound cobaltite-biotite ore zones typically contain cobaltite1 in a matrix of biotitite ± tourmaline ± minor xenotime (ca. 1370–1320 Ma) ± minor chalcopyrite ± sparse allanite ± sparse microscopic native gold in cobaltite. Such cobaltite-biotite lodes are locally folded into tight F2 folds with axial-planar S2 cleavage and schistosity. Discordant replacement-style lodes of cobaltite2-biotite ore ± xenotime2 (ca. 1320–1270 Ma) commonly follow S2fractures and fabrics. Discordant quartz-biotite and quartz-tourmaline breccias, and veins contain cobaltite3 ± xenotime3 (ca. 1058–990 Ma).Mesoproterozoic cobaltite deposition was followed by: (1) within-plate plutonism (530–485 Ma) and emplacement of mafic dikes (which cut cobaltite lodes but are cut by quartz-Fe-Cu-sulfide veins); (2) garnet-grade metamorphism (ca. 151–93 Ma); (3) Fe-Cu-sulfide mineralization (ca. 110–92 Ma); and (4) minor quartz ± Au-Ag ± Bi mineralization (ca. 92–83 Ma).Cretaceous Fe-Cu-sulfide vein, breccia, and replacement-style deposits contain various combinations of chalcopyrite ± pyrrhotite ± pyrite ± cobaltian arsenopyrite (not cobaltite) ± arsenopyrite ± quartz ± siderite ± monazite (ca. 144–88 Ma but mostly 110–92 Ma) ± xenotime (104–93 Ma). Highly radiogenic Pb (in these sulfides) and Sr (in siderite) indicate that these elements resided in Mesoproterozoic source rocks until they were mobilized after ca. 100 Ma. Fe-Cu-sulfide veins, breccias, and replacement deposits appear relatively undeformed and generally lack metamorphic fabrics.Composite Co-Cu-Au ore contains early cobaltite-biotite lodes, cut by Fe-Cu-sulfide veins and breccias, or overprinted by Fe-Cu-sulfide replacement-style deposits, and locally cut by quartz veinlets ± Au-Ag ± Bi minerals.

Labeled drawing of Jupiter showing its core and composition

NASA Technical Reports Server (NTRS)

1989-01-01

Labeled drawing of Jupiter identifies fluid molecular hydrogen, transition zone, fluid metallic hydrogen, and possible core and the composition of its atmosphere - cloud tops - aerosols, ammonia crystals, ammonium hydrosulfide clouds, ice crystal clouds, and water droplets.

Development of a computational testbed for numerical simulation of combustion instability

NASA Technical Reports Server (NTRS)

Grenda, Jeffrey; Venkateswaran, Sankaran; Merkle, Charles L.

1993-01-01

A synergistic hierarchy of analytical and computational fluid dynamic techniques is used to analyze three-dimensional combustion instabilities in liquid rocket engines. A mixed finite difference/spectral procedure is employed to study the effects of a distributed vaporization zone on standing and spinning instability modes within the chamber. Droplet atomization and vaporization are treated by a variety of classical models found in the literature. A multi-zone, linearized analytical solution is used to validate the accuracy of the numerical simulations at small amplitudes for a distributed vaporization region. This comparison indicates excellent amplitude and phase agreement under both stable and unstable operating conditions when amplitudes are small and proper grid resolution is used. As amplitudes get larger, expected nonlinearities are observed. The effect of liquid droplet temperature fluctuations was found to be of critical importance in driving the instabilities of the combustion chamber.

Metal mobilization under alkaline conditions in ash-covered tailings.

PubMed

Lu, Jinmei; Alakangas, Lena; Wanhainen, Christina

2014-06-15

The aim of this study was to determine element mobilization and accumulation in mill tailings under alkaline conditions. The tailings were covered with 50 cm of fly ash, and above a sludge layer. The tailings were geochemically and mineralogically investigated. Sulfides, such as pyrrhotite, sphalerite and galena along with gangue minerals such as dolomite, calcite, micas, chlorite, epidote, Mn-pyroxene and rhodonite were identified in the unoxidized tailings. The dissolution of the fly ash layer resulted in a high pH (close to 12) in the underlying tailings. This, together with the presence of organic matter, increased the weathering of the tailings and mobilization of elements in the uppermost 47 cm of the tailings. All primary minerals were depleted, except quartz and feldspar which were covered by blurry secondary carbonates. Sulfide-associated elements such as Cd, Fe, Pb, S and Zn and silicate-associated elements such as Fe, Mg and Mn were released from the depletion zone and accumulated deeper down in the tailings where the pH decreased to circum-neutral. Sequential extraction suggests that Cd, Cu, Fe, Pb, S and Zn were retained deeper down in the tailings and were mainly associated with the sulfide phase. Calcium, Cr, K and Ni released from the ash layer were accumulated in the uppermost depletion zone of the tailings. Copyright © 2014 Elsevier Ltd. All rights reserved.

Cryomilled zinc sulfide: A prophylactic for Staphylococcus aureus-infected wounds

DOE PAGES

Tran, Phat L.; Li, Jianqiang; Lungaro, Lisa; ...

2018-04-23

Bacterial pathogens that colonize wounds form biofilms, which protect the bacteria from the effect of host immune response and antibiotics. This paper examined the effectiveness of newly synthesized zinc sulfide in inhibiting biofilm development by Staphylococcus aureus (S. aureus) strains. Zinc sulfide (ZnS) was anaerobically biosynthesized to produce CompA, which was further processed by cryomilling to maximize the antibacterial properties to produce CompB. The effect of the two compounds on the S. aureus strain AH133 was compared using zone of inhibition assay. The compounds were formulated in a polyethylene glycol cream. We compared the effect of the two compounds onmore » biofilm development by AH133 and two methicillin-resistant S. aureus clinical isolates using the in vitro model of wound infection. Zone of inhibition assay revealed that CompB is more effective than CompA. At 15 mg/application, the formulated cream of either compound inhibited biofilm development by AH133, which was confirmed using confocal laser scanning microscopy. At 20 mg/application, CompB inhibited biofilm development by the two methicillin-resistant S. aureus clinical isolates. To further validate the effectiveness of CompB, mice were treated using the murine model of wound infection. Finally, colony forming cell assay and in vivo live imaging results strongly suggested the inhibition of S. aureus growth.« less

Cryomilled zinc sulfide: A prophylactic for Staphylococcus aureus-infected wounds

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

Tran, Phat L.; Li, Jianqiang; Lungaro, Lisa

Bacterial pathogens that colonize wounds form biofilms, which protect the bacteria from the effect of host immune response and antibiotics. This paper examined the effectiveness of newly synthesized zinc sulfide in inhibiting biofilm development by Staphylococcus aureus (S. aureus) strains. Zinc sulfide (ZnS) was anaerobically biosynthesized to produce CompA, which was further processed by cryomilling to maximize the antibacterial properties to produce CompB. The effect of the two compounds on the S. aureus strain AH133 was compared using zone of inhibition assay. The compounds were formulated in a polyethylene glycol cream. We compared the effect of the two compounds onmore » biofilm development by AH133 and two methicillin-resistant S. aureus clinical isolates using the in vitro model of wound infection. Zone of inhibition assay revealed that CompB is more effective than CompA. At 15 mg/application, the formulated cream of either compound inhibited biofilm development by AH133, which was confirmed using confocal laser scanning microscopy. At 20 mg/application, CompB inhibited biofilm development by the two methicillin-resistant S. aureus clinical isolates. To further validate the effectiveness of CompB, mice were treated using the murine model of wound infection. Finally, colony forming cell assay and in vivo live imaging results strongly suggested the inhibition of S. aureus growth.« less

Microbial communities in a porphyry copper tailings impoundment and their impact on the geochemical dynamics of the mine waste.

PubMed

Diaby, Nouhou; Dold, Bernhard; Pfeifer, Hans-Rudolf; Holliger, Christof; Johnson, D Barrie; Hallberg, Kevin B

2007-02-01

The distribution and diversity of acidophilic bacteria of a tailings impoundment at the La Andina copper mine, Chile, was examined. The tailings have low sulfide (1.7% pyrite equivalent) and carbonate (1.4% calcite equivalent) contents and are stratified into three distinct zones: a surface (0-70-80 cm) 'oxidation zone' characterized by low-pH (2.5-4), a 'neutralization zone' (70-80 to 300-400 cm) and an unaltered 'primary zone' below 400 cm. A combined cultivation-dependent and biomolecular approach (terminal restriction enzyme fragment length polymorphism and 16S rRNA clone library analysis) was used to characterize the indigenous prokaryotic communities in the mine tailings. Total cell counts showed that the microbial biomass was greatest in the top 125 cm of the tailings. The largest numbers of bacteria (10(9) g(-1) dry weight of tailings) were found at the oxidation front (the junction between the oxidation and neutralization zones), where sulfide minerals and oxygen were both present. The dominant iron-/sulfur-oxidizing bacteria identified at the oxidation front included bacteria of the genus Leptospirillum (detected by molecular methods), and Gram-positive iron-oxidizing acidophiles related to Sulfobacillus (identified both by molecular and cultivation methods). Acidithiobacillus ferrooxidans was also detected, albeit in relatively small numbers. Heterotrophic acidophiles related to Acidobacterium capsulatum were found by molecular methods, while another Acidobacterium-like bacterium and an Acidiphilium sp. were isolated from oxidation zone samples. A conceptual model was developed, based on microbiological and geochemical data derived from the tailings, to account for the biogeochemical evolution of the Piuquenes tailings impoundment.

Stratigraphic setting and mineralogy of the Arctic volcanogenic massive sulfide prospect, Ambler district, Alaska.

USGS Publications Warehouse

Schmidt, J.M.

1986-01-01

The Arctic prospect, south central Brooks Range, is among the 30 largest of 508 volcanic-hosted massive sulphide deposits in the world. The massive sulphide lenses are interlayered with graphitic schist between metamorphosed rhyolite porphyries in Middle Devonian to early Mississippian metamorphosed volcanic, volcaniclastic and sedimentary rocks. Hydrothermal alteration is of three types: chloritic, phyllic s.l., and pyrite-phengite, each type strata-distinctively and respectively below, in, and above the sulphides. Maximum alteration conforms with metal zoning in the sulfides to suggest predominantly northwestward dispersal from a linear vent area in the elongate basin containing the deposit.-G.J.N.

Copper isotope fractionation during partial melting and melt percolation in the upper mantle: Evidence from massif peridotites in Ivrea-Verbano Zone, Italian Alps

NASA Astrophysics Data System (ADS)

Huang, Jian; Huang, Fang; Wang, Zaicong; Zhang, Xingchao; Yu, Huimin

2017-08-01

To investigate the behavior of Cu isotopes during partial melting and melt percolation in the mantle, we have analyzed Cu isotopic compositions of a suite of well-characterized Paleozoic peridotites from the Balmuccia and Baldissero massifs in the Ivrea-Verbano Zone (IVZ, Northern Italy). Our results show that fresh lherzolites and harzburgites have a large variation of δ65Cu ranging from -0.133 to 0.379‰, which are negatively correlated with Al2O3 contents as well as incompatible platinum-group (e.g., Pd) and chalcophile element (e.g., Cu, S, Se, and Te) contents. The high δ65Cu can be explained by Cu isotope fractionation during partial melting of a sulfide-bearing peridotite source, with the light isotope (63Cu) preferentially entering the melts. The low δ65Cu can be attributed to precipitation of sulfides enriched in 63Cu during sulfur-saturated melt percolation. Replacive dunites from the Balmuccia massif display high δ65Cu from 0.544 to 0.610‰ with lower Re, Pd, S, Se, and Te contents and lower Pd/Ir ratios relative to lherzolites, which may result from dissolution of sulfides during interactions between S-undersaturated melts and lherzolites at high melt/rock ratios. Thus, our results suggest that partial melting and melt percolation largely account for the Cu isotopic heterogeneity of the upper mantle. The correlation between δ65Cu and Cu contents of the lherzolites and harzburgites was used to model Cu isotope fractionation during partial melting of a sulfide-bearing peridotite, because Cu is predominantly hosted in sulfide. The modelling results indicate an isotope fractionation factor of αmelt-peridotite = 0.99980-0.99965 (i.e., 103lnαmelt-peridotite = -0.20 to -0.35‰). In order to explain the Cu isotopic systematics of komatiites and mid-ocean ridge basalts reported previously, the estimated αmelt-peridotite was used to simulate Cu isotopic variations in melts generated by variable degrees of mantle melting. The results suggest that high degrees (>25%) of partial melting extracts nearly all source Cu and it cannot produce Cu isotope fractionation in komatiites relative to their mantle source, and that sulfide segregation during magma evolution have modified Cu isotopic compositions of mid-ocean ridge basalts.

Links between climate change, water-table depth, and water chemistry in a mineralized mountain watershed

USGS Publications Warehouse

Manning, Andrew H.; Verplanck, Philip L.; Caine, Jonathan S.; Todd, Andrew S.

2013-01-01

Recent studies suggest that climate change is causing rising solute concentrations in mountain lakes and streams. These changes may be more pronounced in mineralized watersheds due to the sensitivity of sulfide weathering to changes in subsurface oxygen transport. Specific causal mechanisms linking climate change and accelerated weathering rates have been proposed, but in general remain entirely hypothetical. For mineralized watersheds, a favored hypothesis is that falling water tables caused by declining recharge rates allow an increasing volume of sulfide-bearing rock to become exposed to air, thus oxygen. Here, we test the hypothesis that falling water tables are the primary cause of an increase in metals and SO4 (100-400%) observed since 1980 in the Upper Snake River (USR), Colorado. The USR drains an alpine watershed geologically and climatologically representative of many others in mineralized areas of the western U.S. Hydrologic and chemical data collected from 2005 to 2011 in a deep monitoring well (WP1) at the top of the USR watershed are utilized. During this period, both water table depths and groundwater SO4 concentrations have generally increased in the well. A numerical model was constructed using TOUGHREACT that simulates pyrite oxidation near WP1, including groundwater flow and oxygen transport in both saturated and unsaturated zones. The modeling suggests that a falling water table could produce an increase in metals and SO4 of a magnitude similar to that observed in the USR (up to 300%). Future water table declines may produce limited increases in sulfide weathering high in the watershed because of the water table dropping below the depth of oxygen penetration, but may continue to enhance sulfide weathering lower in the watershed where water tables are shallower. Advective air (oxygen) transport in the unsaturated zone caused by seasonally variable recharge and associated water table fluctuations was found to have little influence on pyrite oxidation rates near WP1. However, this mechanism could be important in the case of a shallow dynamic water table and more abundant/reactive sulfides in the shallow subsurface. Data from WP1 and numerical modeling results are thus consistent with the falling water table hypothesis, and illustrate fundamental processes linking climate and sulfide weathering in mineralized watersheds.

Seasonality of major redox constituents in a shallow subterranean estuary

NASA Astrophysics Data System (ADS)

O'Connor, Alison E.; Krask, Julie L.; Canuel, Elizabeth A.; Beck, Aaron J.

2018-03-01

The subterranean estuary (STE), the subsurface mixing zone of outflowing fresh groundwater and infiltrating seawater, is an area of extensive geochemical reactions that determine the composition of groundwater that flows into coastal environments. This study examined the porewater composition of a shallow STE (<5 m depth) in Gloucester Point, VA (USA) over two years to determine seasonal variations in dissolved organic carbon (DOC) and the reduced metabolites Fe, Mn, and sulfide. An additional aim of this study was to investigate the relative importance of salinity gradients (which have great geochemical influence in surface estuaries) versus redox gradients on STE geochemistry. Two freshwater endmembers were identified, between which redox potential and composition varied with depth-a shallow freshwater endmember was oxidizing and high in DOC, whereas a deep freshwater endmember was reducing, lower in DOC, and high in sulfide. Results showed that dissolved Fe, Mn, and sulfide varied along a redox gradient distinct from the salinity gradient, and that three-endmember mixing was required to quantify non-conservative chemical addition/removal in the STE. In addition to salinity, humic carbon was used as a quasi-conservative tracer to quantify mixing according to a three-endmember model. The vertical distributions of DOC and reduced metabolites remained approximately constant over time, but concentrations varied with season. Dissolved organic carbon concentrations were greatest in the summer, and shallow meteoric groundwater supplied the majority of DOC to the STE. In summer, there was additional evidence for shallow non-conservative addition of DOC. Dissolved Fe and Mn were highest in a subsurface plume through the middle of the STE (100-140 cm below sediment surface at the high tide line) which was characterized by higher concentrations and greater non-conservative addition in the winter. In contrast, sulfide was higher in summer at depths within the Fe and Mn plume (100-140 cm). We attribute the contrasting seasonal patterns of dissolved Fe, Mn, and sulfide to differences in microbial response to temperature changes and organic matter availability, and to competition at the ferrous-sulfidic transition zone between dissimilatory metal reduction and sulfate reduction, leading to sulfate/sulfur reducing bacteria (SRB) being more active in summer and metal reducers being more active in winter. Throughout the STE, seasonal temperature and DOC variations determined the spatial distribution and geochemical cycling of Fe, Mn, and sulfur.

Origin of stratiform sediment-hosted manganese carbonate ore deposits: Examples from Molango, Mexico, and TaoJiang, China

USGS Publications Warehouse

Okita, P.M.; Shanks, Wayne C.

1992-01-01

Carbonate and sulfide minerals from the Molango, Mexico, and TaoJiang, China, Mn deposits display similar and distinctive ??34S and ??13C patterns in intervals of manganese carbonate mineralization. ??13C-values for Mn-bearing carbonate range from -17.8 to +0.5??? (PDB), with the most negative values occurring in high-grade ore zones that are composed predominantly of rhodochrosite. In contrast, calcite from below, within and above Mn-carbonate zones at Molango has ??13C???0??? (PDB). Markedly negative ??13C data indicate that a large proportion of the carbon in Mn-carbonates was derived from organic matter oxidation. Diagenetic reactions using MnO2 and SO2-4 to oxidize sedimentary organic matter were the principle causes of such 12C enrichment. Pyrite content and sulfide ?? 34S-values also show distinctive variations. In unmineralized rocks, very negative ??34S-values (avg. < -21??? CDT) and abundant pyrite content suggest that pyrite formed from diagenetic, bacteriogenic sulfate reduction. In contrast, Mn-bearing horizons typically contain only trace amounts of pyrite (e.g., <0.5 wt% S with ??34S-values 34S-enriched, in some cases to nearly the value for contemporaneous seawater. 34S-enriched pyrite from the Mn-carbonate intervals indicates sulfide precipitation in an environment that underwent extensive SO2-4 reduction, and was largely a closed system with regard to exchange of sulfate and dissolved sulfide with normal seawater. The occasional occurrence of 34S-depleted pyrite within Mn-carbonate zones dominated by 34S-enriched pyrite is evidence that closed-system conditions were intermittent and limited to local pore waters and did not involve entire sedimentary basins. Mn-carbonate precipitation may have occluded porosity in the surficial sediments, thus establishing an effective barrier to SO2-4 exchange with overlying seawater. Similar isotopic and mineralogic characteristics from both the Molango and TaoJiang deposits, widely separated in geologic time and space, suggest they were formed similarly by MnO2 precipitation at the margins of dysaerobic to anoxic marine basins. Mn-carbonate formed predominantly by early-diagenetic reduction of Mn-oxides via oxidation of organic matter in near-surface sediments. In addition to MnCO3 precipitation, organic matter oxidation reactions resulted in oxidation of FeS to Fe-oxides such as magnetite, maghemite and hematite. The latter process explains anomalously low pyrite content and abundant Fe-oxide minerals in ore zones dominated by rhodochrosite. ?? 1992.

Satellite Remote Sensing of the Liquid Water Sensitivity in Water Clouds

NASA Technical Reports Server (NTRS)

Han, Qing-Yuan; Rossow, William B.; Welch, Ronald; Zeng, Jane; Jansen, James E. (Technical Monitor)

2001-01-01

In estimation of the aerosol indirect effect, cloud liquid water path is considered either constant (Twomey effect) or increasing with enhanced droplet number concentrations (drizzle-suppression effect, or Albrecht effect) if cloud microphysics is the prevailing mechanism during the aerosol-cloud interactions. On the other hand, if cloud thermodynamics and dynamics are considered, the cloud liquid water path may be decreased with increasing droplet number concentration, which is predicted by model calculations and observed in ship-track and urban influence studies. This study is to examine the different responses of cloud liquid water path to changes of cloud droplet number concentration. Satellite data (January, April, July and October 1987) are used to retrieve the cloud liquid water sensitivity, defined as the changes of liquid water path versus changes of column droplet number concentrations. The results of a global survey reveal that 1) in at least one third of the cases the cloud liquid water sensitivity is negative, and the regional and seasonal variations of the negative liquid water sensitivity are consistent with other observations; 2) cloud droplet sizes are always inversely proportional to column droplet number concentrations. Our results suggest that an increase of cloud droplet number concentration leads to reduced cloud droplet size and enhanced evaporation, which weakens the coupling between water clouds and boundary layer in warm zones, decreases water supply from surface and desiccates cloud liquid water. Our results also suggest that the current evaluations of negative aerosol indirect forcing by global climate models (GCM), which are based on Twomey effect or Albrecht effect, may be overestimated.

Fast Transport of Water Droplets over a Thermo-Switchable Surface Using Rewritable Wettability Gradient.

PubMed

Banuprasad, Theneyur Narayanaswamy; Vinay, Thamarasseril Vijayan; Subash, Cherumannil Karumuthil; Varghese, Soney; George, Sajan D; Varanakkottu, Subramanyan Namboodiri

2017-08-23

In spite of the reported temperature dependent tunability in wettability of poly(N-isopropylacrylamide) (PNIPAAm) surfaces for below and above lower critical solution temperature (32 °C), the transport of water droplets is inhibited by the large contact angle hysteresis. Herein, for the first time, we report on-demand, fast, and reconfigurable droplet manipulation over a PNIPAAm grafted structured polymer surface using temperature-induced wettability gradient. Our study reveals that the PNIPAAm grafted on intrinsically superhydrophobic surfaces exhibit hydrophilic nature with high contact angle hysteresis below 30 °C and superhydrophobic nature with ultralow contact angle hysteresis above 36 °C. The transition region between 30 and 36 °C is characterized by a large change in water contact angle (∼100°) with a concomitant change in contact angle hysteresis. By utilizing this "transport zone" wherein driving forces overcome the frictional forces, we demonstrate macroscopic transport of water drops with a maximum transport velocity of approximately 40 cm/s. The theoretical calculations on the force measurements concur with dominating behavior of driving forces across the transport zone. The tunability in transport velocity by varying the temperature gradient along the surface or the inclination angle of the surface (maximum angle of 15° with a reduced velocity 0.4 mm/s) is also elucidated. In addition, as a practical application, coalescence of water droplets is demonstrated by using the temperature controlled wettability gradient. The presented results are expected to provide new insights on the design and fabrication of smart multifunctional surfaces for applications such as biochemical analysis, self-cleaning, and microfluidics.

Measurement Sensitivity Of Liquid Droplet Parameters Using Optical Fibers

NASA Astrophysics Data System (ADS)

Das, Alok K.; Mandal, Anup K.

1990-02-01

A new clad probing technique is used to measure the size, number, refractive index and viscosity of liquid droplets sprayed from a pressure nozzle on an uncoated core-clad fiber. The probe monitors the clad mode power loss within the leaky ray zone represented as a three region fiber. Liquid droplets measured are Glycerine, commercial grade Turpentine, Linseed oil and some oil mixtures. The measurement sensitivity depends on probing conditions and clad diameter which is observed experimentally and verified analytically. A maximum sensitivity is obtained for the tapered probe-fiber diameter made equal to the clad thickness. A slowly tapered probe-fiber and a small end angle as well as separation of the sensor-fiber and the probe-fiber further improve the sensitivity. Under the best probing condition for 90-percent Glycerine droplets of - 50 micron diameter and a 50/125 micron sensor fiber with clad refractive index of 1.465 and 0.2 NA, the measured sensitivity per drop is 0.015 and 0.006 dB, respectively, for (10-20) and (100-200) droplets. Sensitivities for different systems are shown. The sensitivity is optimized by choosing proper fiber for known liquids.

Distribution of retinal cone photoreceptor oil droplets, and identification of associated carotenoids in crow (Corvus macrorhynchos).

PubMed

Rahman, Mohammad Lutfur; Yoshida, Kazuyuki; Maeda, Isamu; Tanaka, Hideuki; Sugita, Shoei

2010-06-01

The topography of cone oil droplets and their carotenoids were investigated in the retina of jungle crow (Corvus macrorhynchos). Fresh retina was sampled for the study of retinal cone oil droplets, and extracted retinal carotenoids were saponified using methods adapted from a recent study, then identified with reverse-phase high-performance liquid chromatography (HPLC). To assess the effects of saponification conditions on carotenoid recovery from crow retina, we varied base concentration and total time of saponification across a wide range of conditions, and again used HPLC to compare carotenoid concentrations. Based on colors, at least four types of oil droplets were recognized, i.e., red, orange, green, and translucent, across the retina. With an average of 91,202 /mm(2), density gradually declines in an eccentric manner from optic disc. In retina, the density and size of droplets are inversely related. In the peripheral zone, oil droplets were significantly larger than those of the central area. The proportion of orange oil droplets (33%) was higher in the central area, whereas green was predominant in other areas. Three types of carotenoid (astaxanthin, galloxanthin and lutein), together with one unknown carotenoid, were recovered from the crow retina; astaxanthin was the dominant carotenoid among them. The recovery of carotenoids was affected by saponification conditions. Astaxanthin was well recovered in weak alkali (0.06 M KOH), in contrast, xanthophyllic carotenoids were best recovered in strong alkali (0.6 M KOH) after 12 h of saponification at freeze temperature.

A paper-based analytical device for the determination of hydrogen sulfide in fuel oils based on headspace liquid-phase microextraction and cyclic voltammetry.

PubMed

Nechaeva, Daria; Shishov, Andrey; Ermakov, Sergey; Bulatov, Andrey

2018-06-01

An easily performed miniaturized, cheap, selective and sensitive procedure for the determination of H 2 S in fuel oil samples based on a headspace liquid-phase microextraction followed by a cyclic voltammetry detection using a paper-based analytical device (PAD) was developed. A modified wax dipping method was applied to fabricate the PAD. The PAD included hydrophobic zones of sample and supporting electrolyte connecting by hydrophilic channel. The zones of sample and supporting electrolyte were connected with nickel working, platinum auxiliary and Ag/AgCl reference electrodes. The analytical procedure included separation of H 2 S from fuel oil sample based on the headspace liquid-phase microextraction in alkaline solution. Then, sulfide ions solution obtained and supporting electrolyte were dropped on the zones followed by analyte detection at + 0.45 V. Under the optimized conditions, H 2 S concentration in the range from 2 to 20 mg kg -1 had a good linear relation with the peak current. The limit of detection (3σ) was 0.6 mg kg -1 . The procedure was successfully applied to the analysis of fuel oil samples. Copyright © 2018 Elsevier B.V. All rights reserved.

Application of Biostimulation for Remediation of Sulfate-Contaminated Groundwater at a Mining Site

NASA Astrophysics Data System (ADS)

Miao, Z.; Carroll, K. C.; Carreon, C.; Brusseau, M. L.

2011-12-01

There is growing concern regarding sulfate contamination of groundwater. One innovative in-situ remediation option under investigation is biostimulation through addition of electron-donor amendments to enhance sulfate reduction. Two pilot-scale ethanol-injection tests were conducted at a former uranium mining site that is contaminated with sulfate and nitrate (with a lack of heavy metals), and for which there appears to be minimal natural attenuation of sulfate. The first test was a push-pull test that had a limited zone of influence, while the second test was a single-well injection test in which additional downgradient wells were monitored. For both tests, sulfate concentrations began to decline within a few weeks of injection, after nitrate concentrations were significantly reduced. Concomitantly, aqueous concentrations of manganese, iron, and hydrogen sulfide increased from background. Monitoring over many months revealed that the declines in sulfate concentration conformed to exponential decay, with first-order decay rates of approximately 0.01 /d. Analysis of sulfur stable isotope data indicated that the decrease in sulfate concentrations was microbially mediated. The results also indicated that sulfides formed during sulfate reduction may have undergone partial re-oxidation. This study illustrates the feasibility of using ethanol injection for remediation of sulfate-contaminated groundwater. However, re-oxidation of sulfides (both metal sulfide precipitates and hydrogen sulfide gas) is a potential issue of significance that would need to be addressed.

The Archean komatiite-hosted, PGE-bearing Ni-Cu sulfide deposit at Vaara, eastern Finland: evidence for assimilation of external sulfur and post-depositional desulfurization

NASA Astrophysics Data System (ADS)

Konnunaho, J. P.; Hanski, E. J.; Bekker, A.; Halkoaho, T. A. A.; Hiebert, R. S.; Wing, B. A.

2013-12-01

Archean komatiites host important resources of Ni, Cu, Co, and PGE, particularly in Western Australia and Canada. In Finland, several small, low-grade sulfide deposits have been found in komatiites, including the ca. 2.8 Ga Vaara deposit in the Archean Suomussalmi greenstone belt. It occurs in the central part of the serpentinized olivine cumulate zone of a komatiitic extrusive body and is composed of disseminated interstitial sulfides consisting of pyrite, pentlandite, millerite, violarite, and chalcopyrite accompanied by abundant magnetite. Although currently subeconomic, the mineralization is interesting due to the very high chalcophile element contents of the sulfide fraction (38 wt% Ni, 3.4 wt% Cu, 0.7 wt% Co, 22.4 ppm Pd, and 9.5 ppm Pt). The sulfides occur in relatively Cr-poor olivine cumulates suggesting involvement of a chromite-undersaturated magma. The parental magma was an Al-undepleted komatiite with an estimated MgO content of at least 24 wt%. In contrast to the common komatiite types in the eastern Finland greenstone belts, the Vaara rocks are moderately enriched in LREE relative to MREE, suggesting that crustal contamination played an important role in the genesis of the Vaara deposit. Multiple sulfur isotope data reveal considerable mass-independent sulfur isotope fractionation both in country rock sedimentary sulfides (Δ33S ranges from -0.50 to +2.37 ‰) and in the Vaara mineralization (Δ33S ranges from +0.53 to +0.66 ‰), which provides strong evidence for incorporation of crustal sulfur. Extensive replacement of interstitial sulfides by magnetite and the presence of millerite- and violarite-bearing, pyrrhotite-free sulfide assemblages indicate significant post-magmatic, low-temperature hydrothermal oxidation of the primary magmatic pyrrhotite-pentlandite-chalcopyrite assemblages and associated sulfur loss that led to a significant upgrading of the original metal tenors of the Vaara deposit.

Diurnal shifts in co-distributions of sulfide and iron(II) and profiles of phosphate and ammonium in the rhizosphere of Zostera capricorni

NASA Astrophysics Data System (ADS)

Pagès, Anaïs; Welsh, David T.; Robertson, David; Panther, Jared G.; Schäfer, Jörg; Tomlinson, Rodger B.; Teasdale, Peter R.

2012-12-01

High resolution, two dimensional distributions of porewater iron(II) and sulfide were measured, using colourimetric DET (diffusive equilibration in a thin film) and DGT (diffusive gradients in a thin film) techniques, respectively, in Zostera capricorni colonised sediments under both light and dark conditions. Low resolution depth profiles of ammonium and phosphate were measured using conventional DET and DGT methods, respectively. Porewater iron(II) and sulfide distributions showed a high degree of spatial heterogeneity under both light and dark conditions, and distributions were characterised by a complex mosaic of sediment zones dominated by either iron(II) or sulfide. However, there was a clear shift in overall redox conditions between light and dark conditions. During light deployments, iron(II) and sulfide concentrations were generally low throughout the rhizosphere, apart from a few distinct "hotspots" of high concentration. Whereas during dark deployments, high concentrations of iron(II) were sometimes measured in the near surface sediments and sulfide depth distributions migrated towards the sediment surface. Profiles of porewater ammonium and phosphate demonstrated an increase in ammonium concentrations under dark compared to light conditions. Surprisingly, despite the large changes in iron(II) distributions between light and dark conditions, phosphate profiles remained similar, indicating that adsorption/release of phosphate by iron(III) hydr(oxide) mineral formation and reduction was not a major factor regulating porewater phosphate concentrations in these sediments or that phosphate uptake by the seagrass roots persisted during the dark period. Overall, the results demonstrate that the photosynthetic activity of the seagrass played a significant role in regulating sulfide, iron(II) and ammonium concentrations in the rhizosphere, due to rates of radial oxygen loss and ammonium uptake by the roots and rhizomes being lower under dark compared to light conditions. This cyclic production and reduction of iron(III) hydr(oxides) in the rhizosphere may act as a buffering system preventing sulfide accumulation.

Copper solubility in a basaltic melt and sulfide liquid/silicate melt partition coefficients of Cu and Fe

NASA Astrophysics Data System (ADS)

Ripley, Edward M.; Brophy, James G.; Li, Chusi

2002-09-01

The solubility of copper in a sulfur-saturated basaltic melt has been determined at 1245°C as a function of fO 2 and fS 2. Copper solubilities at log fO 2 values between -8 and -11 fall into two distinct populations as a function of fS 2. At log fS 2 values < -1.65, sulfide liquid that coexists with the basaltic glass quenches to sulfur-poor bornite solid solution. At log fS 2 values in excess of -1.65, the sulfide liquid quenches to a complex intergrowth of sulfur-rich bornite and intermediate solid solution. Copper solubilities in the low-fS 2 population range from 594 to 1550 ppm, whereas those in the high-fS 2 population range from 80 to 768 ppm. Sulfide liquid/silicate liquid partition coefficients (D) for Cu and Fe range from 480 to 1303 and 0.7 to 13.6, respectively. Metal-sulfur complexing in the silicate liquid is shown to be insignificant relative to metal-oxide complexing for Fe but permissible for Cu at high fS 2 values. On log D Fe (sulfide-silicate) and log D Cu (sulfide-silicate) vs. 1/2 (log fS 2 - log fO 2) diagrams, both fS 2 populations show distinct but parallel trends. The observation of two D values for any fS 2/fO 2 ratio indicates nonideal mixing of species involved in the exchange reaction. The two distinct trends observed for both Cu and Fe are thought to be due to variations in activity coefficient ratios (e.g., γ FeO/γ FeS and γ CuO 0.5/γ CuS 0.5). Results of the experiments suggest that accurate assessments of fS 2/fO 2 ratios are required for the successful numerical modeling of processes such as the partial melting of sulfide-bearing mantle and the crystallization of sulfide-bearing magmas, as well as the interpretation of sulfide mineralogical zoning. In addition, the experiments provide evidence for oxide or oxy-sulfide complexing for Cu in silicate magmas and suggest that the introduction of externally derived sulfur to mafic magma may be an important process for the formation of Cu-rich disseminated magmatic sulfide ore deposits.

Chip-based sequencing nucleic acids

DOEpatents

Beer, Neil Reginald

2014-08-26

A system for fast DNA sequencing by amplification of genetic material within microreactors, denaturing, demulsifying, and then sequencing the material, while retaining it in a PCR/sequencing zone by a magnetic field. One embodiment includes sequencing nucleic acids on a microchip that includes a microchannel flow channel in the microchip. The nucleic acids are isolated and hybridized to magnetic nanoparticles or to magnetic polystyrene-coated beads. Microreactor droplets are formed in the microchannel flow channel. The microreactor droplets containing the nucleic acids and the magnetic nanoparticles are retained in a magnetic trap in the microchannel flow channel and sequenced.

Impact of mixing time and energy on the dispersion effectiveness and droplets size of oil.

PubMed

Pan, Zhong; Zhao, Lin; Boufadel, Michel C; King, Thomas; Robinson, Brian; Conmy, Robyn; Lee, Kenneth

2017-01-01

The effects of mixing time and energy on Alaska Northern Slope (ANS) and diluted bitumen Cold Lake Blend (CLB) were investigated using EPA baffled flask test. Dispersion effectiveness and droplet size distribution were measured after 5-120 min. A modeling method to predict the mean droplet size was introduced for the first time to tentatively elucidate the droplet size breakup mechanism. The ANS dispersion effectiveness greatly increased with dispersant and mixing energy. However, little CLB dispersion was noted at small energy input (ε = 0.02 Watt/kg). With dispersant, the ANS droplet size distribution reached quasi-equilibrium within 10 min, but that of CLB seems to reach quasi-equilibrium after 120 min. Dispersants are assumed ineffective on high viscosity oils because dispersants do not penetrate them. We provide an alternative explanation based on the elongation time of the droplets and its residence in high intensity zones. When mixing energy is small, CLB did not disperse after 120 min, long enough to allow the surfactant penetration. Our findings suggest that dispersants may disperse high viscosity oils at a rougher sea state and a longer time. The latter could determine how far offshore one can intervene for effective responses to a high viscosity oil spill offshore. Copyright © 2016 Elsevier Ltd. All rights reserved.

Ultra-deep oxidation and exotic copper formation at the late pliocene boyongan and bayugo porphyry copper-gold deposits, surigao, philippines: Geology, mineralogy, paleoaltimetry, and their implications for Geologic, physiographic, and tectonic controls

USGS Publications Warehouse

Braxton, D.P.; Cooke, D.R.; Ignacio, A.M.; Rye, R.O.; Waters, P.J.

2009-01-01

The Boyongan and Bayugo porphyry copper-gold deposits are part of an emerging belt of intrusion-centered gold-rich deposits in the Surigao district of northeast Mindanao, Philippines. Exhumation and weathering of these Late Pliocene-age deposits has led to the development of the world's deepest known porphyry oxidation profile at Boyongan (600 m), and yet only a modest (30-70 m) oxidation profile at adjacent Bayugo. Debris flows, volcanic rocks, and fluviolacustrine sediments accumulating in the actively extending Mainit graben subsequently covered the deposits and preserved the supergene profiles. At Boyongan and Bayugo, there is a vertical transition from shallower supergene copper oxide minerals (malachite + azurite + cuprite) to deeper sulfide-stable assemblages (chalcocite ?? hypogene sulfides). This transition provides a time-integrated proxy for the position of the water table at the base of the saturated zone during supergene oxidation. Contours of the elevation of the paleopotentiometric surface based on this min- eralogical transition show that the thickest portions of the unsaturated zone coincided with a silt-sand matrix diatreme breccia complex at Boyongan. Within the breccia complex, the thickness of the unsaturated zone approached 600 in, whereas outside the breccia complex (e.g., at Bayugo), the thickness averaged 50 m. Contours of the paleopotentiometric surface suggest that during weathering, groundwater flowed into the breccia complex from the north, south, and east, and exited along a high permeability zone to the west. The high relief (>550 m) on the elevation of the paleopotentiometric surface is consistent with an environment of high topographic relief, and the outflow zone to the west of the breccia complex probably reflects proximity to a steep scarp intersecting the western breccia complex margin. Stable isotope paleoaltimetry has enabled estimation of the elevation of the land surface, which further constrains the physiographic setting during supergene oxidation. Isotopic measurements of oxygen in supergene kaolinite from Boyongan suggest that local paleometeoric water involved in weathering had a ??180 composition of approximately -5.7 per mil. At the latitude of the southern Philippines, this value corresponds to Pleistocene rain water condensing at elevations between 750 and 1,050 m above contemporary sea level, providing a maximum estimate for the surface elevation during weathering of the porphyry systems. Physiographic reconstuctions suggest that the deep oxidation profile at Boyongan formed in an environment of high topographic relief immediately east of a prominent (>550 m) escarpment. The high permeability contrast between the breccia complex and the surrounding wall rocks, coupled with the proximity of the breccia complex to the escarpment, led to a depressed groundwater table and a vertically extensive unsaturated zone in the immediate vicinity of Boyongan. This thick vadose zone and the low hypogene pyrite/copper sulfide ratios (0.6) at Boyongan promoted in situ oxidation of copper sulfides with only modest (<200 m) supergene remobilization of copper. In contrast, higher hypogene pyrite/chalcopyrite ratios (2.3) at Bayugo led to greater acid production during weathering and more complete leaching of copper above the base of oxidation. This process promoted significant (600 m) lateral dispersion of copper down the paleohydraulic gradient into the diatreme breccia comple, ultimately leading to the formation of an exotic copper deposit. ?? 2009 Society of Economices Geologists, Inc.

Response of gut health and microbiota to sulfide exposure in Pacific white shrimp Litopenaeus vannamei.

PubMed

Suo, Yantong; Li, Erchao; Li, Tongyu; Jia, Yongyi; Qin, Jian G; Gu, Zhimin; Chen, Liqiao

2017-04-01

Sulfide is a natural and widely distributed toxicant. It can be commonly found on the interface between water and sediment in the aquatic environment. The Pacific white shrimp Litopenaeus vannamei starts life in the benthic zone soon after the mysis stage, an early stage of post larvae. Therefore, L. vannamei is inevitably affected by exposure to sulfide released from pond sediment. This study explored the toxicant effect of different concentrations of sulfide on the intestinal health and microbiota of Pacific white shrimp by monitoring the change of expression of inflammatory, immune related cytokines, and the structure of the intestinal microbiota. The gut histology, expressions of inflammatory and immune related cytokines (tumor necrosis factor-alpha, C-type lectin 3, myostatin and heat shock transcription factor 1), and the microbiota were determined in L. vannamei after exposure to 0 (control), 425.5 (1/10 LC 50-96 h), and 851 μg/L (1/5 LC 50-96 h) of sulfide for 21 days. With the increase of sulfide concentration, intestinal injury was aggravated and the inflammatory and immune related cytokines generated a range of reactions. The expression of myostatin (MSTN) was significantly down-regulated by the concentration of sulfide exposure. No difference in the expression of heat shock transcription factor 1 (HSF1) was found between the control and shrimp exposed to 425.5 μg/L, but significantly higher HSF1 expression was found in shrimp exposed to 851 μg/L of sulfide. Significantly higher values of tumor necrosis factor-alpha (TNF-α) and C-type lectin 3 (CTL3) were found in the shrimp exposed to 425.5 μg/L of sulfide compared to the control, but a lower value was found in the shrimp exposed to 851 μg/L (P < 0.05). Sulfide also changed the intestinal microbial communities. The abundance of pathogenic bacteria, such as Cyanobacteria, Vibrio and Photobacterium, increased significantly with exposure to the increasing concentration of sulfide. The abundance of some anti-stress bacteria, such as Chlorobi and Fusobacterium, increased. Nitrospirae which can alleviate nitrite toxicity decreased. Microbacterium, Parachlamydia, and Shewanella were all commonly found and down-regulated in both sulfide groups, which is associated with an adaptation to sulfide stimulation. This study indicates that chronic exposure to sub-lethal levels of sulfide could lead to damage of the gut structure, stimulate the response of the inflammatory and immune systems, and shape the structure of the gut microbiota in L. vannamei. Copyright © 2017 Elsevier Ltd. All rights reserved.

Determination of acid forming potential of massive sulfide minerals and the tailings situated in lead/zinc mining district of Balya (NW Turkey)

NASA Astrophysics Data System (ADS)

Çelebi, E. Ender; Öncel, M. Salim

2016-12-01

Weathering of sulfide minerals is a major source of acid production in nature and especially in mining territories. Pyrite is not the only principal mineral that generates acid drainage: other sulfide minerals (sphalerite, galena, chalcopyrite, etc.) may also be responsible for acid production. In addition to massive sulfide minerals, sulfide-bearing mine tailings may also produce acid drainage due to oxidation and hydrolysis reactions in waste dumps. The lead/zinc (Pb/Zn) mining region in Balya and Balıkesir, in Turkey, has operated mines intensively since the 1860s; so that characterization of the sulfide minerals and tailings situated and formed around the mining site is of great importance to secure a sustainable environment. For this purpose, acid production and neutralization potentials of massive sulfide ores of the region, and in the Pb/Zn process facility mine tailings from ten different points of tailings dam, have been determined by applied conventional Acid-Base Accounting (ABA) and Net Acid Generation (NAG) static tests after chemical and mineralogical analysis. The NAG pH and net acid production potential (NAPP) values were compared on a chart in order to classify the samples as either acid generating or non-acid generating. According to the comparisons, the sulfide minerals were classified as potentially acid forming (PAF). Massive pyrite had the highest NAPP and NAG pH value of 1966.6 kg H2SO4/ton and 1.91, respectively and the galena had the lowest NAPP value of 558.9 kg H2SO4/ton. However, the sphalerite NAG leachate pH value of 4.30 was the highest in sulfide minerals so that the sphalerite plotted near the uncertainty reference border in the PAF zone. In the mine tailings, NAPP values of 105.9 kg H2SO4/ton on average and the NAG pH values of over 7.5 were determined. In addition to these tests, water leaching (agitation test) was carried out on tailings in order to generate more information. The tailings did not generate acidic leachates as they lie on limestone bed rock which neutralized the acidity.

The formation and chronology of the PAT 91501 impact-melt L chondrite with vesicle metal sulfide assemblages

NASA Astrophysics Data System (ADS)

Benedix, G. K.; Ketcham, R. A.; Wilson, L.; McCoy, T. J.; Bogard, D. D.; Garrison, D. H.; Herzog, G. F.; Xue, S.; Klein, J.; Middleton, R.

2008-05-01

The L chondrite Patuxent Range (PAT) 91501 is an 8.5-kg unshocked, homogeneous, igneous-textured impact melt that cooled slowly compared to other meteoritic impact melts in a crater floor melt sheet or sub-crater dike [Mittlefehldt D. W. and Lindstrom M. M. (2001) Petrology and geochemistry of Patuxent Range 91501 and Lewis Cliff 88663. Meteoritics Planet. Sci. 36, 439-457]. We conducted mineralogical and tomographic studies of previously unstudied mm- to cm-sized metal-sulfide-vesicle assemblages and chronologic studies of the silicate host. Metal-sulfide clasts constitute about 1 vol.%, comprise zoned taenite, troilite, and pentlandite, and exhibit a consistent orientation between metal and sulfide and of metal-sulfide contacts. Vesicles make up ˜2 vol.% and exhibit a similar orientation of long axes. 39Ar- 40Ar measurements probably date the time of impact at 4.461 ± 0.008 Gyr B.P. Cosmogenic noble gases and 10Be and 26Al activities suggest a pre-atmospheric radius of 40-60 cm and a cosmic ray exposure age of 25-29 Myr, similar to ages of a cluster of L chondrites. PAT 91501 dates the oldest known impact on the L chondrite parent body. The dominant vesicle-forming gas was S 2 (˜15-20 ppm), which formed in equilibrium with impact-melted sulfides. The meteorite formed in an impact melt dike beneath a crater, as did other impact melted L chondrites, such as Chico. Cooling and solidification occurred over ˜2 h. During this time, ˜90% of metal and sulfide segregated from the local melt. Remaining metal and sulfide grains oriented themselves in the local gravitational field, a feature nearly unique among meteorites. Many of these metal-sulfide grains adhered to vesicles to form aggregates that may have been close to neutrally buoyant. These aggregates would have been carried upward with the residual melt, inhibiting further buoyancy-driven segregation. Although similar processes operated individually in other chondritic impact melts, their interaction produced the unique assemblage observed in PAT 91501.

A geochemical evaluation of the Ash Sha'ib mineral prospect, Asir quadrangle, Kingdom of Saudi Arabia

USGS Publications Warehouse

Allcott, Glenn H.

1970-01-01

The mineralized zone at the remotely located Ash Sha'ib ancient mine contains only a small tonnage of moderately low grade sulfide- bearing rock. Based on present data the gross value of the deposit, with a value of $25.00 or more per ton, is $20,000,000. A belt of metasedimentary rocks, intruded by gabbro to the south and granite to the north, was the host for fissure vein-replacement type mineralization. Most of the mineralization is in a siliceous dolomite transected by fissures. The main sulfide mineral is sphalerite, but minor amounts of chalcopyrlte and argentlferous galena contribute to the value of the mineralized sections.

Metabolic potential and in situ activity of marine Marinimicrobia bacteria in an anoxic water column.

PubMed

Bertagnolli, Anthony D; Padilla, Cory C; Glass, Jennifer B; Thamdrup, Bo; Stewart, Frank J

2017-11-01

Marinimicrobia bacteria are widespread in subeuphotic areas of the oceans and particularly abundant in oxygen minimum zones (OMZs). Information on Marinimicrobia metabolism is sparse, making the biogeochemical influence of this group challenging to predict. Here, metagenome-assembled genomes representing Marinimicrobia subgroups PN262000N21 and ARCTIC96B-7 were retrieved to near completion (97% and 94%) from OMZ metagenomes, with contamination (14.1%) observed only in ARCTIC96B-7. Genes for aerobic carbon monoxide (CO) oxidation, polysulfide metabolism and hydrogen utilization were identified only in PN262000N21, while genes for partial denitrification occurred in both genomes. Transcripts mapping to these genomes increased from <0.3% of total mRNA from the oxic zone to a max of 22% under anoxia. ARCTIC96B-7 transcript representation decreased an order of magnitude from non-sulfidic to sulfidic depths. In contrast, PN262000N21 representation was relatively constant throughout the OMZ, although transcripts encoding sulfur-utilizing proteins, including sulfur transferases, were enriched at sulfidic depths. PN262000N21 transcripts encoding a protein with fibronectin domains similar to those in cellulosome-producing bacteria were also abundant, suggesting a potential for high molecular weight carbon cycling. These data provide omic-level descriptions of metabolic potential and activity in OMZ-associated Marinimicrobia, suggesting differentiation between subgroups with roles in carbon and dissimilatory inorganic nitrogen and sulfur cycling. © 2017 Society for Applied Microbiology and John Wiley & Sons Ltd.

An electrohydrodynamic technique for rapid mixing in stationary droplets on digital microfluidic platforms.

PubMed

Samiei, Ehsan; de Leon Derby, Maria Diaz; den Berg, Andre Van; Hoorfar, Mina

2017-01-17

This paper presents an electrohydrodynamic technique for rapid mixing of droplets in open and closed digital microfluidic (DMF) platforms. Mixing is performed by applying a high frequency AC voltage to the coplanar or parallel electrodes, inducing circulation zones inside the droplet which results in rapid mixing of the content. The advantages of the proposed method in comparison to conventional mixing methods that operate based on transporting the droplet back and forth and side to side include 1) a shorter mixing time (as fast as 0.25 s), 2) the use of a fewer number of electrodes, reducing the size of the chip, and 3) the stationary nature of the technique which reduces the chance of cross-contamination and surface biofouling. Mixing using the proposed method is performed to create a uniform mixture after merging a water droplet with another droplet containing either particles or dye. The results show that increasing the frequency, and or the amplitude of the applied voltage, enhances the mixing process. However, actuation with a very high frequency and voltage may result in shedding pico-liter satellite droplets. Therefore, for each frequency there is an effective range of the amplitude which provides rapid mixing and avoids shedding satellite droplets. Also, the increase in the gap height between the two plates (for the closed DMF platforms) significantly enhances the mixing efficiency due to the lower viscous effects. Effects of the addition of salts and DNA to the samples were also studied. The electrothermal effect decreased for these cases, which was solved by increasing the frequency of the applied voltage. To assure the high frequency actuation does not increase the sample temperature excessively, the temperature change was monitored using a thermal imaging camera and it was found that the increase in temperature is negligible.

Re-Os, Sm-Nd, U-Pb, and stepwise lead leaching isotope systematics in shear-zone hosted gold mineralization: genetic tracing and age constraints of crustal hydrothermal activity

NASA Astrophysics Data System (ADS)

Frei, R.; Nägler, Th. F.; Schönberg, R.; Kramers, J. D.

1998-06-01

A combined Re-Os, Sm-Nd, U-Pb, and stepwise Pb leaching (PbSL) isotope study of hydrothermal (Mo-W)-bearing minerals and base metal sulfides from two adjacent shear zone hosted gold deposits (RAN, Kimberley) in the Harare-Shamva greenstone belt (Zimbabwe) constrain the timing of the mineralizing events to two periods. During an initial Late Archean event (2.60 Ga) a first molybdenite-scheelite bearing paragenesis was deposited in both shear zone systems, followed by a local reactivation of the shear systems during an Early Proterozoic (1.96 Ga) tectono-thermal overprint, during which base metal sulfides and most of the gold was (re-)deposited. While PbSL has revealed an open-system behavior of the U-Pb systematics in molybdenite and wolframite from the RAN mine, initial Archean Re-Os ages are still preserved implying that this system in these minerals was more resistant to the overprint. A similar retentivity could be shown for the Sm-Nd system in scheelite and powellite associated with the above ore minerals. Re-Os isotopic data from the Proterozoic mineralization in the Kimberley mine point to a recent gain of Re, most pronouncedly affecting Fe-rich sulfides such as pyrrhotite. A significant Re-loss in powellitic scheelite (an alteration phase of molybdenite-bearing scheelite), coupled with a marked loss of U in W-Mo ore minerals, complements the observation of a major Re uptake in Fe-sulfides during oxidizing conditions in a weathering environment. Pyrrhotite under these conditions behaves as an efficient Re-sink. Lead isotope signatures from PbSL residues of molybdenite, powellite, and quartz indicate a continental crustal source and/or contamination for the mineralizing fluid by interaction of the fluids with older sedimentary material as represented by the direct host country rocks. Our investigation reveals the potential of the Re-Os isotopic system applied to crustal hydrothermal ore minerals for genetic tracing and dating purposes. The simplified chemical separation of Re and Os from geological material used in this study, together with improvements of chemical yields, will enable high precision data to be collected rapidly on crustal material with low Os concentrations in the future.

Relation of lineaments to sulfide deposits: Bald Eagle Mountain, Centre County, Pennsylvania

NASA Technical Reports Server (NTRS)

Mcmurtry, G. J.; Petersen, G. W. (Principal Investigator); Krohn, M. D.; Gold, D. P.

1975-01-01

The author has identified the following significant results. Discrete areas of finely-fractured and brecciated sandstone float are present along the crest of Bald Mountain and are commonly sites of sulfide mineralization, as evidenced by the presence of barite and limonite gossans. The frequency distributions of the brecciated float as the negative binomial distribution supports the interpretation of a separate population of intensely fractured material. Such zones of concentrated breccia float have an average width of one kilometer with a range from 0.4 to 1.6 kilometers and were observed in a quarry face to have subvertical dips. Direct spatial correlation of the Landsat-derived lineaments to the fractured areas on the ridge is low; however, the mineralized and fracture zones are commonly assymetrical to the lineament positions. Such a systematic dislocation might result from an inherent bias in the float population or could be the product of the relative erosional resistance of the silicified material in the mineralized areas in relation to the erosionally weak material at the stream gaps.

Geologic form and setting of a hydrothermal vent field at lat 10°56‧N, East Pacific Rise: A detailed study using Angus and Alvin

NASA Astrophysics Data System (ADS)

McConachy, T. F.; Ballard, R. D.; Mottl, M. J.; von Herzen, R. P.

1986-04-01

A hydrothermal vent field, here called the Feather Duster site, occurs on the eastern marginal high near the edge of a narrow (95-m) and shallow (15 20-m) axial graben, within an area dominated by sheet flows and collapse features. The sheet flows are intermediate in relative age between younger fluid-flow lavas on the floor of the axial graben and older pillow (constructional) lavas on the marginal highs. Hydrothermal activity occurs in two zones within a 65 by 45 m area. The main zone is located where a fissure system and sulfide-sulfate chimneys vent warm (9 47 °C) and hot (347 °C) hydrothermal fluids. Here, two mounds of massive sulfide totaling about 200 t are forming. One occurs at the base of a 3-m-high scarp which is the wall of a drained lava lake; the other is perched on top of the scarp. *Present address: Department of Geology, University of Toronto, Toronto, Ontario, Canada M5S 1A1

The role of ophiolite in metallogeny of the Sikhote-Alin region

NASA Astrophysics Data System (ADS)

Kazachenko, V. T.; Perevoznikova, E. V.; Lavrik, S. N.; Skosareva, N. V.

2012-06-01

Metalliferous sediments of the Triassic siliceous formation of the Sikhote-Alin (manganese-silicate rocks and cherts with dispersed rhodochrosite, silicate-magnetite ores, and jasper) and skarns of the Dalnegorsk and Olginsk ore districts were initially the wash away products (Late Anisian-end of the Triassic) of the lateritic weathering crust on ophiolite in the islands. Manganese, iron, and other metals were deposited in the sediments of both lagoons (present-day, skarns) and island water areas (manganese-silicate and siliceousrhodochrosite rocks, silicate-magnetite ores, and jasper). Skarns contain boric and polymetallic ores thus indicating the occurrence of both shallow (periodically drying up) and quite deep (with hydrogen sulfide contamination zones) lagoons. Lead was deposited in protoliths of the skarn deposits in lagoons from the beginning of the Carboniferous to the beginning of the Late Anisian (initial island submergence). Tin, tin-leadzinc (with Ag), and silver-lead-zinc (with Sn and Au) vein deposits (Late Cretaceous-Paleogene) of the Taukha and Zhuravlevka Terrains contain lead deposited in the sediments flanking the islands of water areas with the hydrogen sulfide contamination zones, in the Carboniferous-Permian and Triassic metalliferous sediments.

Geology of the Copper King Mine area, Prairie Divide, Larimer County, Colorado (Part 1)

USGS Publications Warehouse

Sims, Paul Kibler; Phair, George

1952-01-01

The Copper King mine, in Larimer County, Colo., in the northern part of the Front Range of Colorado, was operated for a short time prior to World War II for copper and zino, but since 1949, when pitchblende was discovered on the mine dump, it has been worked for uranium. The bedrock in the mine area consists predominantly of pre-Cambrian (Silver Plums) granite with minor migmatite and metasediments--biotite-quartz-plagioclase gneiss, biotite schist, quartzite, amphibolite, amphibole skarn, and biotite skols. The metasediments occur as inclusions that trend northeast in the granite. This trend is essentially parallel to the prevailing foliation in the granite. At places the metasediments are crosscut sharply by the granite to form angular, partly discordant, steep-walled bodies in the granite. Faults, confined to a narrow zone that extends through the mine, cut both the pre-Cambrian rocks and the contained sulfide deposits. The Copper King fault, a breccia zone, contains a deposit of pitchblende; the other faults are believed to be later than the ore. The two types of mineral deposits--massive sulfide and pitchblende deposits--in the mine area, are of widely different mineralogy, age, and origin. The massive sulfide deposits are small and consist of pyrite, sphalerite, chalcopyrite, pyrrhotite, and in places magnetite in amphibole skarn, mice skols, and quartzite. The deposit at the Copper King mine has yielded small quantities of high-grade sphalerite ore. The massive sulfides are pyrometasomatic deposits of pre-Cambrian age. The pitchblende at the Copper King mine is principally in the Copper King vein, a tight, hard breccia zone that cuts through both granite and the massive sulfide deposit. A small part of the pitchblende is in small fractures near the vein and in boxwork pyrite adjacent to the vein; the post-ore faults, close to their intersection with the Copper King vein, contain some radioactive material, but elsewhere, so far as is known, they are barren. The pitchblende in the deposit forms a steeply plunging ore shoot that has a horizontal length of more than 50 feet and a vertical height of about 85 feet. The thickness of the ore shoot averages about 2 feet, but it ranges from a feather edge to about 4 feet. The hard pitch-blende is intimately intergrown with siderite; other gangue minerals include pyrite, quartz, and finely comminuted fragments of the wall rocks. The vein was repeatedly reopened during mineral deposition as shown by several stages of brecciation and recommended by the vein matter. The pitchblende deposit probably formed at intermediate temperatures and depths and, according to the Pb/U ratio, is about 60 million years old--an early Tertiary age.

Chlorhexidine droplet splash from a skin preparation gallipot: effect of height of pouring.

PubMed

Evans, L; Cunningham, M; Tilakaratna, P

2013-12-01

Chlorhexidine contamination of equipment used in central neuraxial anaesthesia has been implicated in causing adhesive arachnoiditis. We measured the extent of chlorhexidine splash during pouring into a gallipot (antiseptic skin preparation container) from heights of 5 cm, 10 cm, 15 cm and 20 cm. Twenty experiments were performed at each height. Measurements made up to a horizontal distance of 40 cm radius from the gallipot showed a median (IQR [range]) maximum spread of splash droplets ≥ 2 mm diameter of 26.2 (10.2-36.4 [0-40]) cm. The 40-cm radius measurement area was divided into 5-cm-wide zones to assess spread. At pouring heights of 15 cm and 20 cm, all zones were contaminated. These results demonstrate that pouring chlorhexidine into a gallipot generates significant splash, and we recommend that this should be avoided near equipment used for neuraxial anaesthesia. © 2013 The Association of Anaesthetists of Great Britain and Ireland.

Oxygen and sulfur isotope fractionation during sulfide oxidation by anoxygenic phototrophic bacteria

NASA Astrophysics Data System (ADS)

Brabec, Michelle Y.; Lyons, Timothy W.; Mandernack, Kevin W.

2012-04-01

Sulfide-mediated anoxygenic photosynthesis (SMAP) carried out by anaerobic phototrophic bacteria may have played an important role in sulfur cycling, formation of sulfate, and, perhaps, primary production in the Earth’s early oceans. Determination of ε34SSO4-Sulfide- and ε18OSO4-H2O values for bacterial sulfide oxidation will permit more refined interpretation of the δ34S and δ18OSO4 values measured in modern anoxic environments, such as meromictic lakes where sulfide commonly extends into the photic zone, and in the ancient rock record, particularly during periods of the Precambrian when anoxic and sulfidic (euxinic) conditions were believed to be more pervasive than today. Laboratory experiments with anaerobic purple and green sulfur phototrophs, Allochromatium vinosum and Chlorobaculum tepidum, respectively, were conducted to determine the sulfur and oxygen isotope fractionation during the oxidation of sulfide to sulfate. Replicate experiments were conducted at 25 °C for A. vinosum and 45 °C for C. tepidum, and in duplicate at three different starting oxygen isotope values for water to determine sulfate-water oxygen isotope fractionations accurately (ε18OSO4-H2O). ε18OSO4-H2O values of 5.6 ± 0.2‰ and 5.4 ± 0.1‰ were obtained for A. vinosum and C. tepidum, respectively. Temperature had no apparent effect on the ε18OSO4-H2O values. By combining all data from both cultures, an average ε18OSO4-H2O value of 5.6 ± 0.3‰ was obtained for SMAP. This value falls between those previously reported for bacterial oxidation of sphalerite and elemental sulfur (7-9‰) and abiotic and biotic oxidation of pyrite and chalcopyrite (2-4‰). Sulfur isotope fractionation between sulfide and sulfate formed by A.vinosum was negligible (0.1 ± 0.2‰) during all experiments. For C. tepidum an apparent fractionation of -2.3 ± 0.5‰ was observed during the earlier stages of oxidation based on bulk δ34S measurements of sulfate and sulfide and became smaller (-0.7 ± 0.3‰) when sulfate concentrations rose above 0.5 mM and sulfide concentrations had became negligible.

Processing of Copper Zinc Tin Sulfide Nanocrystal Dispersions for Thin Film Solar Cells

NASA Astrophysics Data System (ADS)

Williams, Bryce Arthur

A scalable and inexpensive renewable energy source is needed to meet the expected increase in electricity demand throughout the developed and developing world in the next 15 years without contributing further to global warming through CO2 emissions. Photovoltaics may meet this need but current technologies are less than ideal requiring complex manufacturing processes and/or use of toxic, rare-earth materials. Copper zinc tin sulfide (Cu 2ZnSnS4, CZTS) solar cells offer a true "green" alternative based upon non-toxic and abundant elements. Solution-based processes utilizing CZTS nanocrystal dispersions followed by high temperature annealing have received significant research attention due to their compatibility with traditional roll-to-roll coating processes. In this work, CZTS nanocrystal (5-35 nm diameters) dispersions were utilized as a production pathway to form solar absorber layers. Aerosol-based coating methods (aerosol jet printing and ultrasonic spray coating) were optimized for formation of dense, crack-free CZTS nanocrystal coatings. The primary variables underlying determination of coating morphology within the aerosol-coating parameter space were investigated. It was found that the liquid content of the aerosol droplets at the time of substrate impingement play a critical role. Evaporation of the liquid from the aerosol droplets during coating was altered through changes to coating parameters as well as to the CZTS nanocrystal dispersions. In addition, factors influencing conversion of CZTS nanocrystal coatings into dense, large-grained polycrystalline films suitable for solar cell development during thermal annealing were studied. The roles nanocrystal size, carbon content, sodium uptake, and sulfur pressure were found to have pivotal roles in film microstructure evolution. The effects of these parameters on film morphology, grain growth rates, and chemical makeup were analyzed from electron microscopy images as well as compositional analysis techniques. From these results, a deeper understanding of the interplay between the numerous annealing variables was achieved and improved annealing processes were developed.

Integrated geophysical imaging of a concealed mineral deposit: a case study of the world-class Pebble porphyry deposit in southwestern Alaska

USGS Publications Warehouse

Shah, Anjana K.; Bedrosian, Paul A.; Anderson, Eric D.; Kelley, Karen D.; Lang, James

2013-01-01

We combined aeromagnetic, induced polarization, magnetotelluric, and gravity surveys as well as drillhole geologic, alteration, magnetic susceptibility, and density data for exploration and characterization of the Cu-Au-Mo Pebble porphyry deposit. This undeveloped deposit is almost completely concealed by postmineralization sedimentary and volcanic rocks, presenting an exploration challenge. Individual geophysical methods primarily assist regional characterization. Positive chargeability and conductivity anomalies are observed over a broad region surrounding the deposit, likely representing sulfide minerals that accumulated during multiple stages of hydrothermal alteration. The mineralized area occupies only a small part of the chargeability anomaly because sulfide precipitation was not unique to the deposit, and mafic rocks also exhibit strong chargeability. Conductivity anomalies similarly reflect widespread sulfides as well as water-saturated glacial sediments. Mineralogical and magnetic susceptibility data indicate magnetite destruction primarily within the Cu-Au-Mo mineralized area. The magnetic field does not show a corresponding anomaly low but the analytic signal does in areas where the deposit is not covered by postmineralization igneous rocks. The analytic signal shows similar lows over sedimentary rocks outside of the mineralized area, however, and cannot uniquely distinguish the deposit. We find that the intersection of positive chargeability anomalies with analytic signal lows, indicating elevated sulfide concentrations but low magnetite at shallow depths, roughly delineates the deposit where it is covered only by glacial sediments. Neither chargeability highs nor analytic signal lows are present where the deposit is covered by several hundred meters of sedimentary and volcanic rocks, but a 3D resistivity model derived from magnetotelluric data shows a corresponding zone of higher conductivity. Gravity data highlight geologic features within the deposit, including shallow diorite sills that locally contain higher-grade mineralization. The results thus show ways in which an integrated survey approach might be used to distinguish zones of potentially economic mineralization.

Mineralogy, fluid inclusion petrography, and stable isotope geochemistry of Pb-Zn-Ag veins at the Shizhuyuan deposit, Hunan Province, southeastern China

NASA Astrophysics Data System (ADS)

Wu, Shenghua; Mao, Jingwen; Yuan, Shunda; Dai, Pan; Wang, Xudong

2018-01-01

The Shizhuyuan polymetallic deposit is located in the central part of the Nanling region, southeastern China, and consists of proximal W-Sn-Mo-Bi skarns and greisens and distal Pb-Zn-Ag veins. The sulfides and sulfosalts in the distal veins formed in three distinct stages: (1) an early stage of pyrite and arsenopyrite, (2) a middle stage of sphalerite and chalcopyrite, and (3) a late stage of galena, Ag-, Sn-, and Bi-bearing sulfides and sulfosalts, and pyrrhotite. Combined sulfide and sulfosalt geothermometry and fluid inclusion analyses indicate that the early stage of mineralization occurred at a temperature of 400 °C and involved boiling under hydrostatic pressure ( 200 bar), with the temperature of the system dropping during the late stage to 200 °C. Laser Raman analysis indicates that the fluid inclusions within the studied minerals are dominated by H2O, although some contain carbonate solids and CH4 gas. Vein-hosted sulfides have δ34S values of 3.8-6.3‰ that are interpreted as indicative of a magmatic source of sulfur. The mineralization process can be summarized as follows: an aqueous fluid exsolved on final crystallization of the Qianlishan pluton, ascended along fracture zones, cooled to <400 °C, and boiled under hydrostatic conditions, and with decreasing temperature and sulfur fugacity, sulfide and sulfosalt minerals precipitated successively from the Ag-Cu-Zn-Fe-Pb-Sb-As-S-bearing fluid system.

Influence of iron sulfides on abiotic oxidation of UO2 by nitrite and dissolved oxygen in natural sediments.

PubMed

Carpenter, Julian; Bi, Yuqiang; Hayes, Kim F

2015-01-20

Iron sulfide precipitates formed under sulfate reducing conditions may buffer U(IV) insoluble solid phases from reoxidation after oxidants re-enter the reducing zone. In this study, sediment column experiments were performed to quantify the effect of biogenic mackinawite on U(IV) stability in the presence of nitrite or dissolved oxygen (DO). Two columns, packed with sediment from an abandoned U contaminated mill tailings site near Rifle, CO, were biostimulated for 62 days with an electron donor (3 mM acetate) in the presence (BRS+) and absence (BRS−) of 7 mM sulfate. The bioreduced sediment was supplemented with synthetic uraninite (UO2(s)), sterilized by gamma-irradiation, and then subjected to a sequential oxidation by nitrite and DO. Biogenic iron sulfides produced in the BRS+ column, mostly as mackinawite, inhibited U(IV) reoxidation and mobilization by both nitrite and oxygen. Most of the influent nitrite (0.53 mM) exited the columns without oxidizing UO2, while a small amount of nitrite was consumed by iron sulfides precipitates. An additional 10-day supply of 0.25 mM DO influent resulted in the release of about 10% and 49% of total U in BRS+ and BRS– columns, respectively. Influent DO was effectively consumed by biogenic iron sulfides in the BRS+ column, while DO and a large U spike were detected after only a brief period in the effluent in the BRS– column.

Biodegradation of p-cresol and sulfide removal by a marine-denitrifying consortium.

PubMed

Meza-Escalante, Edna R; Alvarez, Luis H; Serrano, Denisse; Mendoza, Erika; Bonola, Ramsés

2015-02-01

The simultaneous removal of sulfide and p-cresol was carried out by using a marine-denitrifying consortium collected in the coastal zone of Sonora, Mexico. Different experimental conditions were used to evaluate the capacity of the consortium to simultaneously eliminate nitrate, sulfide, and p-cresol. For instance, the first set of assays was conducted at different sulfide concentrations (20, 50, and 100 mg S(2À) L(À1) ), with a fixed concentration of p-cresol (45 mg C L(À1) ). The second set of assays was developed at different concentrations of p-cresol (45, 75, and 100 mg C L(-1) ), in the presence of 20 mg S(2À) L(À1) . In all cases, the concentration of nitrate was stoichiometrically added for the complete oxidization of the substrates. The results showed removal efficiencies up to 92% for p-cresol and nitrate at 20 and 50 mg S(2À) L(À1) ; whereas at 100 mg S(2À) L(À1) removal efficiencies were 77% and 59% for p-cresol and nitrate, respectively. On the other hand, sulfide (20 mg L(À1) ) was completely removed under different concentrations of p-cresol tested, with a partial accumulation of nitrite according to the increment of p-cresol concentration. The results obtained indicate that the marine consortium was able to simultaneously remove the pollutants studied. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Methanol Droplet Combustion in Oxygen-Inert Environments in Microgravity

NASA Technical Reports Server (NTRS)

Nayagam, Vedha; Dietrich, Daniel L.; Hicks, Michael C.; Williams, Forman A.

2013-01-01

The Flame Extinguishment (FLEX) experiment that is currently underway in the Combustion Integrated Rack facility onboard the International Space Station is aimed at understanding the effects of inert diluents on the flammability of condensed phase fuels. To this end, droplets of various fuels, including alkanes and alcohols, are burned in a quiescent microgravity environment with varying amounts of oxygen and inert diluents to determine the limiting oxygen index (LOI) for these fuels. In this study we report experimental observations of methanol droplets burning in oxygen-nitrogen-carbon dioxide and oxygen-nitrogen-helium gas mixtures at 0.7 and 1 atmospheric pressures. The initial droplet size varied between approximately 1.5 mm and 4 mm to capture both diffusive extinction brought about by insufficient residence time at the flame and radiative extinction caused by excessive heat loss from the flame zone. The ambient oxygen concentration varied from a high value of 30% by volume to as low as 12%, approaching the limiting oxygen index for the fuel. The inert dilution by carbon dioxide and helium varied over a range of 0% to 70% by volume. In these experiments, both freely floated and tethered droplets were ignited using symmetrically opposed hot-wire igniters and the burning histories were recorded onboard using digital cameras, downlinked later to the ground for analysis. The digital images yielded droplet and flame diameters as functions of time and subsequently droplet burning rate, flame standoff ratio, and initial and extinction droplet diameters. Simplified theoretical models correlate the measured burning rate constant and the flame standoff ratio reasonably well. An activation energy asymptotic theory accounting for time-dependent water dissolution or evaporation from the droplet is shown to predict the measured diffusive extinction conditions well. The experiments also show that the limiting oxygen index for methanol in these diluent gases is around 12% to 13% oxygen by volume.

Latent volcanic heat and further unique aspects of early diagenetic stratiform copper mineralization in the White Pine-Presque Isle District, northern Michigan

NASA Astrophysics Data System (ADS)

Brown, Alex C.

2018-06-01

The curious occurrence of copper-rich early diagenetic sediment-hosted stratiform copper mineralization in the finest-grained facies of Nonesuch greybeds in northern Michigan has been previously attributed to the warming of cupriferous brines in the footwall Copper Harbor Conglomerate by latent volcanic heat from the subjacent Porcupine Volcanics shield volcano. That anomalous footwall warming is employed here to explain other unique aspects of the White Pine-Presque Isle mineralization: the abrupt downward sulfide zoning from disseminated pyrite to chalcocite across the top of the cupriferous zone; the absence of bornite and chalcopyrite in the cupriferous zone proper; and the essential absence of pseudomorphs after pyrite euhedra and framboidal aggregates within the cupriferous zone proper, as well as the relatively coarse-grained character of disseminated chalcocite in the cupriferous zone.

Metabolism in the Uncultivated Giant Sulfide-Oxidizing Bacterium Thiomargarita Namibiensis Assayed Using a Redox-Sensitive Dye

NASA Astrophysics Data System (ADS)

Bailey, J.; Flood, B.; Ricci, E.

2014-12-01

The colorless sulfur bacteria are non-photosynthetic chemolithotrophs that live at interfaces between nitrate, or oxygen, and hydrogen sulfide. In sulfidic settings such as cold seeps and oxygen minimum zones, these bacteria are thought to constitute a critical node in the geochemical cycling of carbon, sulfur, nitrogen, and phosphorous. Many of these bacteria remain uncultivated and their metabolisms and physiologies are incompletely understood. Thiomargarita namibiensis is the largest of these sulfur bacteria, with individual cells reaching millimetric diameters. Despite the current inability to maintain a Thiomargarita culture in the lab, their large size allows for individual cells to be followed in time course experiments. Here we report on the novel use of a tetrazolium-based dye that measures the flux of NADH production from catabolic pathways via a colorimetric response. Staining with this dye allows for metabolism to be detected, even in the absence of observable cell division. When coupled to microscopy, this approach also allows for metabolism in Thiomargaritato be differentiated from that of epibionts or contaminants in xenic samples. The results of our tetrazolium dye-based assay suggests that Thiomargarita is the most metabolically versatile under anoxic conditions where it appears capable of using acetate, succinate, formate, thiosulfate, citrate, thiotaurine, hydrogen sulfide, and perhaps hydrogen as electron donors. Under hypoxic conditions, staining results suggest the utilization of acetate, citrate, and hydrogen sulfide. Cells incubated under oxic conditions showed the weakest tetrazolium staining response, and then only to hydrogen sulfide and questionably succinate. These initial results using a redox sensitive dye suggest that Thiomargarita is most metabolically versatile under anaerobic and hypoxic conditions. The results of this assay can be further evaluated using molecular approaches such as transcriptomics, as well as provide cultivation strategies.

Pediatric Cystic Fibrosis Sputum Can Be Chemically Dynamic, Anoxic, and Extremely Reduced Due to Hydrogen Sulfide Formation

PubMed Central

Cowley, Elise S.; Kopf, Sebastian H.; LaRiviere, Alejandro

2015-01-01

ABSTRACT Severe and persistent bacterial lung infections characterize cystic fibrosis (CF). While several studies have documented the microbial diversity within CF lung mucus, we know much less about the inorganic chemistry that constrains microbial metabolic processes and their distribution. We hypothesized that sputum is chemically heterogeneous both within and between patients. To test this, we measured microprofiles of oxygen and sulfide concentrations as well as pH and oxidation-reduction potentials in 48 sputum samples from 22 pediatric patients with CF. Inorganic ions were measured in 20 samples from 12 patients. In all cases, oxygen was depleted within the first few millimeters below the sputum-air interface. Apart from this steep oxycline, anoxia dominated the sputum environment. Different sputum samples exhibited a broad range of redox conditions, with either oxidizing (16 mV to 355 mV) or reducing (−300 to −107 mV) potentials. The majority of reduced samples contained hydrogen sulfide and had a low pH (2.9 to 6.5). Sulfide concentrations increased at a rate of 0.30 µM H2S/min. Nitrous oxide was detected in only one sample that also contained sulfide. Microenvironmental variability was observed both within a single patient over time and between patients. Modeling oxygen dynamics within CF mucus plugs indicates that anoxic zones vary as a function of bacterial load and mucus thickness and can occupy a significant portion of the mucus volume. Thus, aerobic respiration accounts only partially for pathogen survival in CF sputum, motivating research to identify mechanisms of survival under conditions that span fluctuating redox states, including sulfidic environments. PMID:26220964

Cu refertilization of abyssal harzburgites by melt percolation

NASA Astrophysics Data System (ADS)

Ciazela, Jakub; Dick, Henry; Koepke, Juergen; Botcharnikov, Roman; Muszynski, Andrzej; Kuhn, Thomas

2015-04-01

Primitive mantle is depleted in many elements by partial melting processes, but it can be subsequently refertilized by impregnation with percolating melts. It is known that Cu can be enriched in primitive melts, depleting mantle residue, due to the former process (Patten et al. 2013). However, the behavior of Cu in the processes of mantle-melt interaction is poorly understood. The only comprehensive study is based on compositions of orogenic peridotites, representing the subcontinental mantle (Lorand et al. 1993; 2013), where a moderate enrichment of the mantle in Cu (up to ~50 ppm) has been observed. Here, we present the first results obtained for a suite of rocks from an oceanic core complex (OCC), the Kane Megamullion at 22°30'N at the Mid-Atlantic Ridge (Dick et al. 2008). OCC's provide large exposures of mantle and lower crustal rocks on the seafloor on detachment fault footwalls at slow and ultraslow spreading ridges. The mantle rocks are composed of spinel and plagioclase harzburgites. The spinel harzburgites represent depleted mantle, whereas the plagioclase harzburgites were formed by subsequent late-stage melt impregnation in the depleted mantle (Dick et al. 2010). We have determined Cu concentrations in 22 residual spinel harzburgites and 4 plagioclase harzburgites using total digestion ICP-MS. The average Cu concentration in spinel harzburgites is 35±11 ppm Cu (2σ). The average Cu concentration obtained for plagioclase harzburgites is 131±33 ppm Cu (2σ). Additionally, we have analyzed one 1.5 cm thick contact zone between an oxide gabbro vein and residual peridotite. The contact zone, which has been heavily impregnated by the melt, contains 284 ppm Cu. In contrast, the neighboring oxide gabbro vein and the hosting peridotite contain 147 and 68 ppm Cu, respectively. Furthermore, we have determined the concentration of Cu in a dunite (118 ppm), formed in a reaction between the mantle and melt ascending through the lithosphere (Dick et al. 2010). Magmatic processes in the rocks coming from OCCs can be obscured by deformation and alteration. Plastically deformed rocks are common in the damaged zone related to the detachment fault. Metaperidotites from these zones, which show protomylonitic to ultramylonitic textures, are systematically depleted in Cu (15±5 ppm, 2σ) in comparison to non-deformed spinel harzburgites. We have not included the values obtained from non-deformed harzburgites in the calculation of the averages presented above. Thus, the effect of deformation processes does not influence our results. The relatively narrow 0.95 confidence intervals of the means obtained for non-deformed spinel and plagioclase harzburgite species and a large difference between the two means indicate a relatively low influence of alteration. Therefore, we believe the significant enrichment in Cu exhibited by the refertilized mantle rocks is caused exclusively by mantle impregnation with late-stage melts. Enhanced Cu concentrations indicate that the scale of this enrichment can be significantly underestimated in previous studies (Lorand et al. 2013). Dick, H.J.B., Tivey, M.A. & Tucholke, B.E., 2008. Plutonic foundation of a slow-spreading ridge segment: Oceanic core complex at Kane Megamullion, 23°30'N, 45°20'W. Geochemistry, Geophysics, Geosystems 9, Q05014. Dick, H.J.B., Lissenberg, C.J., & Warren, J.M., 2010. Mantle melting, melt transport, and delivery beneath a slow-spreading ridge: The paleo-MAR from 23°15'N to 23°45'N. Journal of Petrology 51, 425-467. Lorand, J.P., Keays, R.R. & Bodinier, J.L., 1993. Copper and noble metal enrichments across the lithosphere-astenosphere boundary of mantle diapirs: evidence from the Lanzo Lherzolite Massif. Journal of Petrology 34, 1111-1140. Lorand, J.P., Luguet, A. & Alard, O., 2013. Platinum-group element systematics and petrogenetics processing of the upper mantle: A review. Lithos 164-167, 2-21. Patten, C., Barnes, S.-J., Mathez, E.A. & Jenner, F.E., 2013. Partition coefficients of chalcophile elements between sulfide and silicate melts and the early crystallization history of sulfide liquid: LA-ICP-MS analysis of MORB sulfide droplets. Chemical Geology 358, 170-188.

Global Distribution of Cloud Droplet Number Concentration, Autoconversion Rate, and Aerosol Indirect Effect Under Diabatic Droplet Activation

NASA Technical Reports Server (NTRS)

Barahona, Donifan; Sotiropoulou, Rafaella; Nenes, Athanasios

2011-01-01

This study presents a global assessment of the sensitivity of droplet number to diabatic activation (i.e., including effects from entrainment of dry air) and its first-order tendency on indirect forcing and autoconversion. Simulations were carried out with the NASA Global Modeling Initiative (GMI) atmospheric and transport model using climatological metereorological fields derived from the former NASA Data Assimilation Office (DAO), the NASA Finite volume GCM (FVGCM) and the Goddard Institute for Space Studies version II (GISS) GCM. Cloud droplet number concentration (CDNC) is calculated using a physically based prognostic parameterization that explicitly includes entrainment effects on droplet formation. Diabatic activation results in lower CDNC, compared to adiabatic treatment of the process. The largest decrease in CDNC (by up to 75 percent) was found in the tropics and in zones of moderate CCN concentration. This leads to a global mean effective radius increase between 0.2-0.5 micrometers (up to 3.5 micrometers over the tropics), a global mean autoconversion rate increase by a factor of 1.1 to 1.7 (up to a factor of 4 in the tropics), and a 0.2-0.4 W m(exp -2) decrease in indirect forcing. The spatial patterns of entrainment effects on droplet activation tend to reduce biases in effective radius (particularly in the tropics) when compared to satellite retrievals. Considering the diabatic nature of ambient clouds, entrainment effects on CDNC need to be considered in GCM studies of the aerosol indirect effect.

Impact of hydrothermal alteration on time-dependent tunnel deformation in Neogene volcanic rock sequence in Japan: Petrology, Geochemistry and Geophysical investigation

NASA Astrophysics Data System (ADS)

Yamazaki, S.; Okazaki, K.; Niwa, H.; Arai, T.; Murayama, H.; Kurahashi, T.; Ito, Y.

2017-12-01

Time-dependent tunnel deformation is one of remaining geological problems for mountain tunneling. As a case study of time-dependent tunnel deformation, we investigated petrographical, mineral and chemical compositions of boring core samples and seismic exploration along a tunnel that constructed into Neogene volcanic rock sequence of andesite to dacite pyroclastic rocks and massive lavas with mafic enclaves. The tunnel has two zones of floor heaving that deformed time-dependently about 2 month after the tunnel excavation. The core samples around the deformed zones are characterized secondary mineral assemblages of smectite, cristobalite, tridymite, sulfides (pyrite and marcasite) and partially or completely reacted carbonates (calcite and siderite), which were formed by hydrothermal alteration under neutral to acidic condition below about 100 °C. The core samples also showed localized deterioration, such as crack formation and expansion, which occurred from few days to months after the drilling. The deterioration could be explained as a result of the cyclic physical and chemical weathering process with the oxidation of sulfide minerals, dissolution of carbonate mineral cementation and volumetric expantion of smectite. This weathering process is considered as a key factor for time-dependent tunnel deformation in the hydrothermally altered volcanic rocks. The zones of time-dependent deformation along a tunnel route can be predicted by the variations of whole-rock chemical compositions such as Na, Ca, Sr, Ba and S.

A subduction wedge origin for Paleoarchean peridotitic diamonds and harzburgites from the Panda kimberlite, Slave craton: evidence from Re-Os isotope systematics

NASA Astrophysics Data System (ADS)

Westerlund, K. J.; Shirey, S. B.; Richardson, S. H.; Carlson, R. W.; Gurney, J. J.; Harris, J. W.

2006-09-01

An extensive study of peridotitic sulfide inclusion bearing diamonds and their prospective harzburgitic host rocks from the 53 Ma Panda kimberlite pipe, Ekati Mine, NWT Canada, has been undertaken with the Re-Os system to establish their age and petrogenesis. Diamonds with peridotitic sulfide inclusions have poorly aggregated nitrogen (<30% N as B centers) at N contents of 200-800 ppm which differs from that of chromite and silicate bearing diamonds and indicates residence in the cooler portion of the Slave craton lithospheric mantle. For most of the sulfide inclusions, relatively low Re contents (average 0.457 ppm) and high Os contents (average 339 ppm) lead to extremely low 187Re/188Os, typically << 0.05. An age of 3.52 ± 0.17 Ga (MSWD = 0.46) and a precise initial 187Os/188Os of 0.1093 ± 0.0001 are given by a single regression of 11 inclusions from five diamonds that individually provide coincident internal isochrons. This initial Os isotopic composition is 6% enriched in 187Os over 3.5 Ga chondritic or primitive mantle. Sulfide inclusions with less radiogenic initial Os isotopic compositions reflect isotopic heterogeneity in diamond forming fluids. The harzburgites have even lower initial 187Os/188Os than the sulfide inclusions, some approaching the isotopic composition of 3.5 Ga chondritic mantle. In several cases isotopically distinct sulfides occur in different growth zones of the same diamond. This supports a model where C-O-H-S fluids carrying a radiogenic Os signature were introduced into depleted harzburgite and produced diamonds containing sulfides conforming to the 3.5 Ga isochron. Reaction of this fluid with harzburgite led to diamonds with less radiogenic inclusions while elevating the Os isotope ratios of some harzburgites. Subduction is a viable way of introducing such fluids. This implies a role for subduction in creating early continental nuclei at 3.5 Ga and generating peridotitic diamonds.

An interpretation of carbon and sulfur relationships in Black Sea sediments as indicators of environments of deposition

USGS Publications Warehouse

Leventhal, J.S.

1983-01-01

Syngenetic iron sulfides in sediments are formed from dissolved sulfide resulting from sulfate reduction and catabolism of organic matter by anaerobic bacteria. It has been shown that in recent marine sediments deposited below oxygenated waters there is a constant relationship between reduced sulfur and organic carbon which is generally independent of the environment of deposition. Reexamination of data from recent sediments from euxinic marine environments (e.g., the Black Sea) also shows a linear relationship between carbon and sulfur, but the slope is variable and the line intercepts the S axis at a value between 1 and 2 percent S. It is proposed that the positive S intercept is due to watercolumn microbial reduction of sulfate using metabolizable small organic molecules and the sulfide formed is precipitated and accumulates at the sediment-water interface. The variation in slope and intercept of the C to S plots for several cores and for different stratigraphic zones for the Black Sea can be interpreted in relation to thickness of the aqueous sulfide layer or thinness of the oxygen containing layer and to deposition rate, but also may be influenced by availability of iron, and perhaps the type of organic matter (Leventhal, 1979). ?? 1983.

The use of ERTS-1 images in the search for large sulfide deposits in the Chagai District, Pakistan

NASA Technical Reports Server (NTRS)

Schmidt, R. G. (Principal Investigator)

1974-01-01

The author has identified the following significant results. Visual examination of color composites was tested under relatively ideal conditions for direct detection of large hydrothermal sulfide deposits at the low-grade porphyry copper deposit at Saindak, western Chagai District, Pakistan. The Saindak deposit is characterized by an elongate zone of easily eroded sulfide-rich rock surrounded by a resistant rim of hornfels and propylitically altered rock. The geomorphic features related to the Saindak deposit are easily distinguished on ERTS-1 images. Attempts to detect a color anomaly using false-color composites were not successful. About 36,000 square km of the western Chagai District were examined on false-color composites for direct evidence of large sulfide deposits. New geologic information acquired from the images was used in conjunction with the known geology to evaluate two previously known proposed areas and to suggest seven additional targets for field checking, one of which is proposed on the basis of tonal anomaly alone. The study also showed that Saindak-type deposits are not likely to be present in some extensive areas of the Chagai District; and also that a rim like that at Saindak does not form if regional metamorphism has increased the resistance of the country rock to erosion.

Spray droplet size, drift potential, and risks to nontarget organisms from aerially applied glyphosate for coca control in Colombia.

PubMed

Hewitt, Andrew J; Solomon, Keith R; Marshall, E J P

2009-01-01

A wind tunnel atomization study was conducted to measure the emission droplet size spectra for water and Glyphos (a glyphosate formulation sold in Colombia) + Cosmo-flux sprays for aerial application to control coca and poppy crops in Colombia. The droplet size spectra were measured in a wind tunnel for an Accu-Flo nozzle (with 16 size 0.085 [2.16 mm] orifices), under appropriate simulated aircraft speeds (up to 333 km/h), using a laser diffraction instrument covering a dynamic size range for droplets of 0.5 to 3,500 microm. The spray drift potential of the glyphosate was modeled using the AGDISP spray application and drift model, using input parameters representative of those occurring in Colombia for typical aerial application operations. The droplet size spectra for tank mixes containing glyphosate and Cosmo-Flux were considerably finer than water and became finer with higher aircraft speeds. The tank mix with 44% glyphosate had a D(v0.5) of 128 microm, while the value at the 4.9% glyphosate rate was 140 microm. These are classified as very fine to fine sprays. Despite being relatively fine, modeling showed that the droplets would not evaporate as rapidly as most similarly sized agricultural sprays because the nonvolatile proportion of the tank mix (active and inert adjuvant ingredients) was large. Thus, longer range drift is small and most drift that does occur will deposit relatively close to the application area. Drift will only occur downwind and, with winds of velocity less than the modeled maximum of 9 km/h, the drift distance would be substantially reduced. Spray drift potential might be additionally reduced through various practices such as the selection of nozzles, tank mix adjuvants, aircraft speeds, and spray pressures that would produce coarser sprays. Species sensitivity distributions to glyphosate were constructed for plants and amphibians. Based on modeled drift and 5th centile concentrations, appropriate no-spray buffer zones (distance from the end of the spray boom as recorded electronically +/-5%) for protection of sensitive plants were 50-120 m for coca spray scenarios and considerably lower for poppy spray scenarios. The equivalent buffer zone for amphibia was 5 m. The low toxicity of glyphosate to humans suggests that these aerial applications are not a concern for human health.

Relationships among benthic green macroalgae, infaunal invertebrates, and dissolved sulfides in sediment pore waters, Yaquina Estuary, Oregon, USA

EPA Science Inventory

Relatively high abundances of benthic green macroalgae (Ulva spp.) have been measured in Yaquina Estuary on the central coast of the State of Oregon, USA. Band transects (30 meters in width) from the lower to the upper intertidal zone were established at two sites (Idaho Point a...

Vibration characteristics of aluminum surface subjected to ultrasonic waves and their effect on wetting behavior of solder droplets.

PubMed

Ma, Lin; Xu, Zhiwu; Zheng, Kun; Yan, Jiuchun; Yang, Shiqin

2014-03-01

The vibration characteristics of an aluminum surface subjected to ultrasonic waves were investigated with a combination of numerical simulation and experimental testing. The wetting behavior of solder droplets on the vibrating aluminum surface was also examined. The results show that the vibration pattern of the aluminum surface is inhomogeneous. The amplitude of the aluminum surface exceeds the excitation amplitude in some zones, while the amplitude decreases nearly to zero in other zones. The distribution of the zero-amplitude zones is much less dependent on the strength of the vibration than on the location of the vibration source. The surface of the liquid solder vibrates at an ultrasonic frequency that is higher than the vibration source, and the amplitude of the liquid solder is almost twice that of the aluminum surface. The vibration of the surface of the base metal (liquid solder) correlates with the oxide film removal effect. Significant removal of the oxide film can be achieved within 2s when the amplitude of the aluminum surface is higher than 5.4 μm or when the amplitude of the liquid solder surface is higher than 10.2 μm. Copyright © 2013 Elsevier B.V. All rights reserved.

Fundamental Study of a Single Point Lean Direct Injector. Part I: Effect of Air Swirler Angle and Injector Tip Location on Spray Characteristics

NASA Technical Reports Server (NTRS)

Tedder, Sarah A.; Hicks, Yolanda R.; Tacina, Kathleen M.; Anderson, Robert C.

2014-01-01

Lean direct injection (LDI) is a combustion concept to reduce oxides of nitrogen (NOx) for next generation aircraft gas turbine engines. These newer engines have cycles that increase fuel efficiency through increased operating pressures, which increase combustor inlet temperatures. NOx formation rates increase with higher temperatures; the LDI strategy avoids high temperature by staying fuel lean and away from stoichiometric burning. Thus, LDI relies on rapid and uniform fuel/air mixing. To understand this mixing process, a series of fundamental experiments are underway in the Combustion and Dynamics Facility at NASA Glenn Research Center. This first set of experiments examines cold flow (non-combusting) mixing using air and water. Using laser diagnostics, the effects of air swirler angle and injector tip location on the spray distribution, recirculation zone, and droplet size distribution are examined. Of the three swirler angles examined, 60 deg is determined to have the most even spray distribution. The injector tip location primarily shifts the flow without changing the structure, unless the flow includes a recirculation zone. When a recirculation zone is present, minimum axial velocity decreases as the injector tip moves downstream towards the venturi exit; also the droplets become more uniform in size and angular distribution.

Fundamental Study of a Single Point Lean Direct Injector. Part I: Effect of Air Swirler Angle and Injector Tip Location on Spray Characteristics

NASA Technical Reports Server (NTRS)

Tedder, Sarah A.; Hicks, Yolanda R.; Tacina, Kathleen M.; Anderson, Robert C.

2015-01-01

Lean direct injection (LDI) is a combustion concept to reduce oxides of nitrogen (NOx) for next generation aircraft gas turbine engines. These newer engines have cycles that increase fuel efficiency through increased operating pressures, which increase combustor inlet temperatures. NOx formation rates increase with higher temperatures; the LDI strategy avoids high temperature by staying fuel lean and away from stoichiometric burning. Thus, LDI relies on rapid and uniform fuel/air mixing. To understand this mixing process, a series of fundamental experiments are underway in the Combustion and Dynamics Facility at NASA Glenn Research Center. This first set of experiments examines cold flow (non-combusting) mixing using air and water. Using laser diagnostics, the effects of air swirler angle and injector tip location on the spray distribution, recirculation zone, and droplet size distribution are examined. Of the three swirler angles examined, 60 degrees is determined to have the most even spray distribution. The injector tip location primarily shifts the flow without changing the structure, unless the flow includes a recirculation zone. When a recirculation zone is present, minimum axial velocity decreases as the injector tip moves downstream towards the venturi exit; also the droplets become more uniform in size and angular distribution.

Geochemical and Sulfur-Isotopic Signatures of Volcanogenic Massive Sulfide Deposits on Prince of Wales Island and Vicinity, Southeastern Alaska

USGS Publications Warehouse

Slack, John F.; Shanks, Wayne C.; Karl, Susan M.; Gemery, Pamela A.; Bittenbender, Peter E.; Ridley, W. Ian

2007-01-01

Stratabound volcanogenic massive sulfide (VMS) deposits on Prince of Wales Island and vicinity, southeastern Alaska, occur in two volcanosedimentary sequences of Late Proterozoic through Cambrian and of Ordovician through Early Silurian age. This study presents geochemical data on sulfide-rich samples, in situ laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) of sulfide minerals, and sulfur-isotopic analyses of sulfides and sulfates (barite) for identifying and distinguishing between primary sea-floor signatures and later regional metamorphic overprints. These datasets are also used here in an attempt to discriminate the VMS deposits in the older Wales Group from those in the younger Moira Sound unit (new informal name). The Wales Group and its contained VMS deposits have been multiply deformed and metamorphosed from greenschist to amphibolite grade, whereas the Moira Sound unit and related VMS deposits are less deformed and generally less metamorphosed (lower to middle greenschist grade). Variations in the sulfide mineral assemblages and textures of the VMS deposits in both sequences reflect a combination of processes, including primary sea-floor mineralization and sub-sea-floor zone refining, followed by metamorphic recrystallization. Very coarse grained (>1 cm diam) sulfide minerals and abundant pyrrhotite are restricted to VMS deposits in a small area of the Wales Group, at Khayyam and Stumble-On, which record high-grade metamorphism of the sulfides. Geochemical and sulfur-isotopic data distinguish the VMS deposits in the Wales Group from those in the Moira Sound unit. Although base- and precious-metal contents vary widely in sulfide-rich samples from both sequences, samples from the Moira Sound generally have proportionately higher Ag contents relative to base metals and Au. In situ LA-ICP-MS analysis of trace elements in the sulfide minerals suggests that primary sea-floor hydrothermal signatures are preserved in some samples (for example, Mn, As, Sb, and Tl in pyrite from the Moira Sound unit), whereas in other samples the signatures are varyingly annealed, owing to metamorphic overprinting. A limited LA-ICP-MS database for sphalerite indicates that low-Fe sphalerite is preferentially associated with the most Au rich deposits, the Niblack and Nutkwa. Sulfur-isotopic values for sulfide minerals in the VMS deposits in the Wales Group range from 5.9 to 17.4 permil (avg 11.5?2.7 permil), about 5 to 6 permil higher than those in the Moira Sound unit, which range from -2.8 to 10.4 permil (avg 6.1?4.0 permil). This difference in 34Ssulfide values reflects a dominantly seawater sulfate source of the sulfides and is linked to the 34S values of contemporaneous seawater sulfate, which were slightly higher during the Late Proterozoic through Cambrian than during the Ordovician through Early Silurian.

Magnetic anomalies associated with abundant production of pyrrhotite in a sulfide deposit in the Okinawa Trough, Japan

NASA Astrophysics Data System (ADS)

Honsho, Chie; Yamazaki, Toshitsugu; Ura, Tamaki; Okino, Kyoko; Morozumi, Haruhisa; Ueda, Satoshi

2016-11-01

We report here results from a deep-sea magnetic survey using an autonomous underwater vehicle over the Hakurei hydrothermal site, in the middle Okinawa Trough. Magnetic inversion revealed that the Hakurei site is associated with well-defined high-magnetization zones distributed within a broad low-magnetization zone. Results from rock magnetic measurements, performed on sulfide ore samples obtained by drilling, showed that some samples possessed extremely high natural remanent magnetization (NRM) (as much as 6.8-953.0 A/m), although most of the measured samples had much lower NRM. These high-NRM samples were characterized by high Königsberger ratios (101-103), indicating much larger NRM than induced magnetization, and contained pyrrhotite as the only magnetic mineral. This suggests that NRM carried by pyrrhotite is the source of the observed magnetic anomalies. The wide range of NRM intensity was considered to be due to a highly heterogeneous distribution of pyrrhotite, because pyrrhotite was commonly identified in both the high-NRM and low-NRM samples. Pyrrhotite production may have been occasionally drastically increased, with highly magnetic ores formed as a result. Rapid burial of active vents may result in the creation of an extensive reducing environment under the seafloor, which is favorable to pyrrhotite production, and may also prevent oxidation of pyrrhotite by isolating it from seawater. Because the magnetization intensity of sulfide ores was highly variable, it would not be straightforward to estimate the quantity of ore deposits from the magnetic anomalies. Nevertheless, this study demonstrates the usefulness of magnetic surveys in detecting hydrothermal deposits.

Nitrate-dependent iron oxidation limits iron transport in anoxic ocean regions

NASA Astrophysics Data System (ADS)

Scholz, Florian; Löscher, Carolin R.; Fiskal, Annika; Sommer, Stefan; Hensen, Christian; Lomnitz, Ulrike; Wuttig, Kathrin; Göttlicher, Jörg; Kossel, Elke; Steininger, Ralph; Canfield, Donald E.

2016-11-01

Iron is an essential element for life on Earth and limits primary production in large parts of the ocean. Oxygen-free continental margin sediments represent an important source of bioavailable iron to the ocean, yet little of the iron released from the seabed reaches the productive sea surface. Even in the anoxic water of oxygen minimum zones, where iron solubility should be enhanced, most of the iron is rapidly re-precipitated. To constrain the mechanism(s) of iron removal in anoxic ocean regions we explored the sediment and water in the oxygen minimum zone off Peru. During our sampling campaign the water column featured two distinct redox boundaries separating oxic from nitrate-reducing (i.e., nitrogenous) water and nitrogenous from weakly sulfidic water. The sulfidic water mass in contact with the shelf sediment contained elevated iron concentrations >300 nM. At the boundary between sulfidic and nitrogenous conditions, iron concentrations dropped sharply to <20 nM coincident with a maximum in particulate iron concentration. Within the iron gradient, we found an increased expression of the key functional marker gene for nitrate reduction (narG). Part of this upregulation was related to the activity of known iron-oxidizing bacteria. Collectively, our data suggest that iron oxidation and removal is induced by nitrate-reducing microbes, either enzymatically through anaerobic iron oxidation or by providing nitrite for an abiotic reaction. Given the important role that iron plays in nitrogen fixation, photosynthesis and respiration, nitrate-dependent iron oxidation likely represents a key-link between the marine biogeochemical cycles of nitrogen, oxygen and carbon.

Reduced Gravity Studies of Soret Transport Effects in Liquid Fuel Combustion

NASA Technical Reports Server (NTRS)

Shaw, Benjamin D.

2004-01-01

Soret transport, which is mass transport driven by thermal gradients, can be important in practical flames as well as laboratory flames by influencing transport of low molecular weight species (e.g., monatomic and diatomic hydrogen). In addition, gas-phase Soret transport of high molecular weight fuel species that are present in practical liquid fuels (e.g., octane or methanol) can be significant in practical flames (Rosner et al., 2000; Dakhlia et al., 2002) and in high pressure droplet evaporation (Curtis and Farrell, 1992), and it has also been shown that Soret transport effects can be important in determining oxygen diffusion rates in certain classes of microgravity droplet combustion experiments (Aharon and Shaw, 1998). It is thus useful to obtain information on flames under conditions where Soret effects can be clearly observed. This research is concerned with investigating effects of Soret transport on combustion of liquid fuels, in particular liquid fuel droplets. Reduced-gravity is employed to provide an ideal (spherically-symmetrical) experimental model with which to investigate effects of Soret transport on combustion. The research will involve performing reduced-gravity experiments on combustion of liquid fuel droplets in environments where Soret effects significantly influence transport of fuel and oxygen to flame zones. Experiments will also be performed where Soret effects are not expected to be important. Droplets initially in the 0.5 to 1 mm size range will be burned. Data will be obtained on influences of Soret transport on combustion characteristics (e.g., droplet burning rates, droplet lifetimes, gas-phase extinction, and transient flame behaviors) under simplified geometrical conditions that are most amenable to theoretical modeling (i.e., spherical symmetry). The experiments will be compared with existing theoretical models as well as new models that will be developed. Normal gravity experiments will also be performed.

Graphene doped ZnO films for photoelectrowetting on microchannels

NASA Astrophysics Data System (ADS)

Al-Aribe, Khaled; Knopf, George K.

2017-02-01

Photoelectrowetting on dielectric surfaces can be used to drive droplets of liquid along reconfigurable paths on a microfluidic chip using controlled optical signals. These electrostatically activated surfaces along the desired path eliminate the need for precision molded channels and discrete functional components such as microvalves and micropumps. The photoelectrowetting effect exploits the surface tension of the droplet to maintain its volume during the transportation pathway and the photoelectric properties of the substrate surface are used to induce reversible fluidic flow. The active light-driven substrate is structured from graphene doped zinc-oxide (ZnO-G) films deposited on ITO coated glass. This substrate is coated from the ZnO-G side with Ruthenium-based dye (N719) to maximize its absorbability. The light triggers two forces that enable the droplet to be transported along the substrate. The first arises from the induced hydrophobicity gradient formed across the droplet contact area with the substrate surface. Exposing the ZnO-G film to a broad spectrum white light source alters the surface's electric potential which induces a change in the droplet's contact angle and the associated hydrophobicity. Once the hydrophobicity gradient is generated the droplet will start to move in the direction of the wetting zone. The second force is also created by the optical input when the absorbed light generates a photoelectric potential that produces a piezo-electrical effect on the ZnO-G film. The light triggered piezo-electrical behavior of the ZnO-G film can be used to generate the erasable microchannels that can guide droplet movement through a microfluidic chip. Preliminary experiments are performed to investigate the photoelectric potential of light activated ZnO-G films.

Re-Os and S isotope evidence for the origin of Platreef mineralization (Bushveld Complex)

NASA Astrophysics Data System (ADS)

Yudovskaya, M.; Belousova, E.; Kinnaird, J.; Dubinina, E.; Grobler, D. F.; Pearson, N.

2017-10-01

The Bushveld Complex contains the largest platinum-group element (PGE) deposits of the world that are represented by persistent stratiform reefs highly enriched with PGE with respect to underlying and overlying rocks. New Re-Os isotope and elemental LA MC-ICPMS data on platinum-group minerals (PGM) from the mineralized reefs are presented with implications to correlation between the different segments of the Bushveld Complex and a role of superimposed processes at the reef formation. We analyzed laurite (RuS2), hollingworthite (RhAsS), sperrylite (PtAs2) and Pt-Fe alloys from the Merensky Reef, Pseudoreef and the PGE reef of the Platreef. The measured 187Os/188Os value for Platreef laurite is 0.1751 ± 0.0004 whereas the ratios for sperrylite and hollingworthite range to slightly higher values (0.1713-0.1818 and 0.1744-0.1835 respectively). The observed textures of the analyzed PGM, such as Pt-Fe symplectites in base metal sulfides (BMS), laurite inclusions in chromite and sperrylite rims around sulfide-silicate aggregates, are interpreted as features of primary magmatic crystallization whereas hollingworthite overgrowths and exsolutions in sperrylite are likely to have originated from later solid state transformation or metasomatic processes. The Platreef is a composite sill-like body in the northern limb correlative to the Critical Zone in terms of stratigraphic position, whole-rock geochemistry and isotope characteristics. The pristine magmatic character of sulfides and PGM in the stratiform reefs at the top of the Platreef strongly resembles the style of Merensky Reef mineralization. However, the basal part of the Platreef pyroxenitic sequence is variably contaminated and mineralized with a significant hydrothermal overprint. Sulfides from underlying Lower Zone peridotite yield δ34S values varying from +9‰ to +14.2‰ that are much higher than the values for the overlying Platreef and are a consequence of sulfur assimilation from sedimentary sulfates. The same homogeneous mantle-like S isotope compositions in the high-grade PGE reef of the Platreef and the Merensky Reef can be explained by enhanced S isotope exchange through the orthomagmatic process of sulfide upgrading. The similar values and the limited variations of the initial Os isotopic ratios of all PGMs in both reefs also support their magmatic crystallization and origin from a common source.

Constraints on the composition of ore fluids and implications for mineralising events at the Cleo gold deposit, Eastern Goldfields Province, Western Australia

USGS Publications Warehouse

Brown, S.M.; Johnson, C.A.; Watling, R.J.; Premo, W.R.

2003-01-01

The Cleo gold deposit, 55 km south of Laverton in the Eastern Goldfields Province of Western Australia, is characterised by banded iron-formation (BIF)-hosted ore zones in the gently dipping Sunrise Shear Zone and high-grade vein-hosted ore in the Western Lodes. There is evidence that gold mineralisation in the Western Lodes (which occurred at ca 2655 Ma) post-dates the majority of displacement along the Sunrise Shear Zone, but it remains uncertain if the ore in both structures formed simultaneously or separately. Overall, the Pb, Nd, Sr, C. O and S isotopic compositions of ore-related minerals from both the Western Lodes and ore zones in the Sunrise Shear Zone are similar. Early low-salinity aqueous-carbonic fluids and late high-salinity fluids with similar characteristics are trapped in inclusions in quartz veins from both the Sunrise Shear Zone and the Western Lodes. The early CO2, CO2-H2O, and H2O- dominant inclusions are interpreted as being related to ore formation, and to have formed from a single low-salinity aqueous-carbonic fluid as a result of intermittent fluid immiscibility. Homogenisation temperatures indicate that these inclusions were trapped at approximately 280??C and at approximately 4 km depth, in the deeper epizonal range. Differences between the ore zones are detected in the trace-element composition of gold samples, with gold from the Sunrise Shear Zone enriched in Ni, Pb, Sn, Te and Zn, and depleted In As, Bi, Cd, Cu and Sb, relative to gold from the Western Lodes. Although there are differences in gold composition between the Sunrise Shear Zone and Western Lodes, and hence the metal content of ore fluids may have varied slightly between the different ore zones, no other systematic fluid or solute differences are detected between the ore zones. Given the fact that the ore fluids in each zone have very similar bulk properties, the considerable differences in gold grade, sulfide mineral abundance, and ore textures between the two ore zones most likely result from different gold-deposition mechanisms. The association of ore zones in the Sunrise Shear Zone with pyrite-replaced BIF suggests that wall-rock sulfidation was the most significant mechanism of gold precipitation, through the destabilisation of gold-bisulfide complexes. The Western Lodes, however, do not exhibit any host-rock preference and multistage veins commonly contain coarse-grained gold. Fluid-inclusion characteristics and breccia textures in veins in the Western Lodes suggest that rapid pressure changes, brought about by intermittent release of overpressured fluids and concomitant phase separation, are likely to have caused the destabilisation of gold-thiocomplexes, leading to formation of higher-grade gold ore zones.

Magmatic-hydrothermal origin of the early Triassic Laodou lode gold deposit in the Xiahe-Hezuo district, West Qinling orogen, China: implications for gold metallogeny

NASA Astrophysics Data System (ADS)

Jin, Xiao-ye; Li, Jian-wei; Hofstra, Albert H.; Sui, Ji-xiang

2017-08-01

The Xiahe-Hezuo district in the West Qinling orogen contains numerous Au-(As-Sb) and Cu-Au-(W) deposits. The district is divided into eastern and western zones by the Xiahe-Hezuo Fault. The western zone is exposed at a shallow level and contains sediment-hosted disseminated Au-(As-Sb) deposits, whereas the eastern zone is exposed at a deeper level and contains Cu-Au-(W) skarn and lode gold deposits within or close to granitic intrusions. The Laodou gold deposit in the eastern zone consists of auriferous quartz-sulfide-tourmaline and minor quartz-stibnite veins that are structurally controlled by fault zones transecting the Laodou quartz diorite porphyry stock and enveloped by potassic and phyllic alteration. Both the veins and alteration halos commonly contain quartz, sericite, tourmaline, pyrite, and arsenopyrite, with minor galena, sphalerite, chalcopyrite, tetrahedrite, and enargite. Gold occurs mainly as invisible gold in pyrite or arsenopyrite and locally as inclusions less than 50 μm in diameter. The zircon U-Pb age of 247.6 ± 1.3 Ma (2 σ) on the host quartz diorite porphyry and the sericite 40Ar/39Ar plateau ages of 249.1 ± 1.6 and 249.0 ± 1.5 Ma (2 σ) on two ore-related hydrothermal sericite samples are within analytical errors of one another. At the formation temperature (275 °C) inferred from microthermometric measurements of fluid inclusion, sericite and tourmaline yield calculated δDH2O values of -70 to -45‰ and δ 18OH2O of 5.8 to 9.7‰, while quartz yields calculated δ 18OH2O values of 5.1˜5.7‰. Hydrothermal tourmaline in quartz-sulfide-tourmaline veins has δ 11B of -11.2 to -0.9‰ (mean of -6.3‰) that are similar to the values of magmatic tourmaline (-8.9 to -5.5‰ with a mean of -6.8‰) in the host quartz diorite porphyry. The δ 34S values of sulfide minerals range from -5.9 to +5.8‰ with a mean of -0.6‰ that is typical of magmatic sulfur. Pyrite from hydrothermally altered quartz diorite porphyry and quartz-sulfide-tourmaline veins have relatively homogeneous lead isotopic compositions, compatible with granitic intrusions in the district. The geochronological and isotopic data combined support a magmatic origin for the Laodou gold deposit, most likely formed from fluids exsolved from the Laodou quartz diorite porphyry or associated intrusive phases at deeper levels beneath the stock. Orogenic and Carlin-like gold deposits in the West Qinling orogen have been commonly thought to have formed from metamorphic fluids. This study, however, highlights the role of magmatic-derived fluids in the formation of lode gold deposits. Synthesis of geochronological, geological, and geochemical data on magmatic rocks and ore deposits in and surrounding the Xiahe-Hezuo district indicates that gold mineralization predominantly occurred within a subduction-related magmatic arc prior to collision between the Yangtze and North China cratons that produced the West Qinling orogen.

A cross-correlation optical velocimeter

NASA Astrophysics Data System (ADS)

Smrekar, J.; Oman, J.; Sirok, B.; Mori, M.; Hocevar, M.

2007-03-01

This study presents a newly developed approach to velocity measurements of moist air in a natural-draught cooling tower (CT). It is based on the cross-correlation of two signals acquired from infrared (IR) light-to-voltage optical sensors. The air flowing through the CT becomes supersaturated in CT packings and thus consists of small water droplets of size 4-12 µm. The same air usually contains droplets resulting from drift, which drags along too small droplets in the spray zone. When the moist-air droplet pattern crosses the beam emitted by IR light-emitting diodes (LEDs), the optical sensors detect a certain signal. The cross-correlation technique gives the time delay of the measured signals. Therefore, by knowing the distance between the sensors, it is possible to calculate the velocity of the moist air. The method has been developed for dynamic velocity measurements of moist air and has achieved a satisfactory precision. The optical velocimeter is a very practical device that makes it possible to carry out measurements on a local basis across the entire plane area of the CT. With the use of simultaneous measurements of velocities and temperatures, the exact location of problems with the packings, nozzles and water distribution system can be thus determined.

Removal of highly elevated nitrate from drinking water by pH-heterogenized heterotrophic denitrification facilitated with ferrous sulfide-based autotrophic denitrification.

PubMed

Huang, Bin; Chi, Guangyu; Chen, Xin; Shi, Yi

2011-11-01

The performance of acetic acid-supported pH-heterogenized heterotrophic denitrification (HD) facilitated with ferrous sulfide-based autotrophic denitrification (AD) was investigated in upflow activated carbon-packed column reactors for reliable removal of highly elevated nitrate (42 mg NO(3)-Nl(-1)) in drinking water. The use of acetic acid as substrate provided sufficient internal carbon dioxide to completely eliminate the need of external pH adjustment for HD, but simultaneously created vertically heterogenized pH varying from 4.8 to 7.8 in the HD reactor. After 5-week acclimation, the HD reactor developed a moderate nitrate removal capacity with about one third of nitrate removal occurring in the acidic zone (pH 4.8-6.2). To increase the treatment reliability, acetic acid-supported HD was operated under 10% carbon limitation to remove >85% of nitrate, and ferrous sulfide-based AD was supplementally operated to remove residual nitrate and formed nitrite without excess of soluble organic carbon, nitrite or sulfate in the final effluent. Copyright © 2011 Elsevier Ltd. All rights reserved.

Rapid Redox Signal Transmission by “Cable Bacteria” beneath a Photosynthetic Biofilm

PubMed Central

Meysman, F. J. R.

2014-01-01

Recently, long filamentous bacteria, belonging to the family Desulfobulbaceae, were shown to induce electrical currents over long distances in the surface layer of marine sediments. These “cable bacteria” are capable of harvesting electrons from free sulfide in deeper sediment horizons and transferring these electrons along their longitudinal axes to oxygen present near the sediment-water interface. In the present work, we investigated the relationship between cable bacteria and a photosynthetic algal biofilm. In a first experiment, we investigated sediment that hosted both cable bacteria and a photosynthetic biofilm and tested the effect of an imposed diel light-dark cycle by continuously monitoring sulfide at depth. Changes in photosynthesis at the sediment surface had an immediate and repeatable effect on sulfide concentrations at depth, indicating that cable bacteria can rapidly transmit a geochemical effect to centimeters of depth in response to changing conditions at the sediment surface. We also observed a secondary response of the free sulfide at depth manifest on the time scale of hours, suggesting that cable bacteria adjust to a moving oxygen front with a regulatory or a behavioral response, such as motility. Finally, we show that on the time scale of days, the presence of an oxygenic biofilm results in a deeper and more acidic suboxic zone, indicating that a greater oxygen supply can enable cable bacteria to harvest a greater quantity of electrons from marine sediments. Rapid acclimation strategies and highly efficient electron harvesting are likely key advantages of cable bacteria, enabling their success in high sulfide generating coastal sediments. PMID:25416774

Rapid redox signal transmission by "Cable Bacteria" beneath a photosynthetic biofilm.

PubMed

Malkin, S Y; Meysman, F J R

2015-02-01

Recently, long filamentous bacteria, belonging to the family Desulfobulbaceae, were shown to induce electrical currents over long distances in the surface layer of marine sediments. These "cable bacteria" are capable of harvesting electrons from free sulfide in deeper sediment horizons and transferring these electrons along their longitudinal axes to oxygen present near the sediment-water interface. In the present work, we investigated the relationship between cable bacteria and a photosynthetic algal biofilm. In a first experiment, we investigated sediment that hosted both cable bacteria and a photosynthetic biofilm and tested the effect of an imposed diel light-dark cycle by continuously monitoring sulfide at depth. Changes in photosynthesis at the sediment surface had an immediate and repeatable effect on sulfide concentrations at depth, indicating that cable bacteria can rapidly transmit a geochemical effect to centimeters of depth in response to changing conditions at the sediment surface. We also observed a secondary response of the free sulfide at depth manifest on the time scale of hours, suggesting that cable bacteria adjust to a moving oxygen front with a regulatory or a behavioral response, such as motility. Finally, we show that on the time scale of days, the presence of an oxygenic biofilm results in a deeper and more acidic suboxic zone, indicating that a greater oxygen supply can enable cable bacteria to harvest a greater quantity of electrons from marine sediments. Rapid acclimation strategies and highly efficient electron harvesting are likely key advantages of cable bacteria, enabling their success in high sulfide generating coastal sediments. Copyright © 2015, American Society for Microbiology. All Rights Reserved.

Fast Oxidation Processes in a Naturally Reduced Aquifer Zone Caused by Dissolved Oxygen

NASA Astrophysics Data System (ADS)

Davis, J. A.; Jemison, N. E.; Williams, K. H.; Hobson, C.; Bush, R. P.

2014-12-01

The occurrence of naturally reduced zones is quite common in alluvial aquifers in the western U.S.A. due to the burial of woody debris in flood plains. The naturally reduced zones are heterogeneously dispersed in such aquifers and are characterized by high concentrations of organic carbon and reduced phases, including iron sulfides and reduced forms of metals, including uranium(IV). The persistence of high concentrations of dissolved uranium(VI) at uranium-contaminated aquifers on the Colorado Plateau has been attributed to slow oxidation of insoluble uranium(IV) mineral phases that are found in association with these natural reducing zones, although there is little understanding of the relative importance of various potential oxidants. Three field experiments were conducted within an alluvial aquifer adjacent to the Colorado River near Rifle, CO wherein groundwater associated with naturally reduced zones was pumped into a gas-impermeable tank, mixed with a conservative tracer (Br-), bubbled with a gas phase composed of 97% O2 and 3% CO2, and then returned to the subsurface in the same well from which it was withdrawn. Within minutes of re-injection of the oxygenated groundwater, dissolved uranium(VI) concentrations increased from less than 1 μM to greater than 2.5 μM, demonstrating that oxygen can be an important oxidant for uranium in these field systems if supplied to the naturally reduced zones. Small concentrations of nitrate were also observed in the previously nitrate-free groundwater, and Fe(II) decreased to the detection limit. These results contrast with other laboratory and field results in which oxygen was introduced to systems containing high concentrations of mackinawite (FeS) rather than the more crystalline iron sulfides found in aged, naturally reduced zones. The flux of oxygen to the naturally reduced zones in the alluvial aquifers occurs mainly through interactions between groundwater and gas phases at the water table, and seasonal variations of the water table at the Rifle, CO site may play an important role in introducing oxygen into the system. Although oxygen was introduced directly to the naturally reduced zones in these experiments, delivery of oxidants to the system may normally be controlled by other oxidative pathways in which oxygen plays an indirect role.

Time variation in the reaction-zone structure of two-phase spray detonations.

NASA Technical Reports Server (NTRS)

Pierce, T. H.; Nicholls, J. A.

1973-01-01

A detailed theoretical analysis of the time-varying detonation structure in a monodisperse spray is presented. The theory identifies experimentally observed reaction-zone overpressures as deriving from blast waves formed therein by the explosive ignition of the spray droplets, and follows in time the motion, change in strength, and interactions of these blast waves with one another, and with the leading shock. The results are compared with experimental data by modeling the motion of a finite-size circular pressure transducer through the theoretical data field in an x-t space.

Specific effect of vincristine on epididymis.

PubMed

Averal, H I; Stanley, A; Murugaian, P; Palanisamy, M; Akbarsha, M A

1996-01-01

Wistar strain male albino rats were administered with vincristine (VCR) sulphate (10 micrograms/day for 15 days); epithelial cell types of the caput (zone II) and cauda (zone V) were studied light microscopically adopting semithin sectioning. VCR caused conspicuous pathological changes in the principal and apical cells of the caput and the clear cells of the cauda. The study points to toxic effect of VCR on these cell types, suggesting impairment of epididymal function, particularly concerning sperm maturation and endocytotic removal of the contents of the cytoplasmic droplets and dead sperm.

Focused ultrasound-facilitated brain drug delivery using optimized nanodroplets: vaporization efficiency dictates large molecular delivery

NASA Astrophysics Data System (ADS)

Wu, Shih-Ying; Fix, Samantha M.; Arena, Christopher B.; Chen, Cherry C.; Zheng, Wenlan; Olumolade, Oluyemi O.; Papadopoulou, Virginie; Novell, Anthony; Dayton, Paul A.; Konofagou, Elisa E.

2018-02-01

Focused ultrasound with nanodroplets could facilitate localized drug delivery after vaporization with potentially improved in vivo stability, drug payload, and minimal interference outside of the focal zone compared with microbubbles. While the feasibility of blood-brain barrier (BBB) opening using nanodroplets has been previously reported, characterization of the associated delivery has not been achieved. It was hypothesized that the outcome of drug delivery was associated with the droplet’s sensitivity to acoustic energy, and can be modulated with the boiling point of the liquid core. Therefore, in this study, octafluoropropane (OFP) and decafluorobutane (DFB) nanodroplets were used both in vitro for assessing their relative vaporization efficiency with high-speed microscopy, and in vivo for delivering molecules with a size relevant to proteins (40 kDa dextran) to the murine brain. It was found that at low pressures (300-450 kPa), OFP droplets vaporized into a greater number of microbubbles compared to DFB droplets at higher pressures (750-900 kPa) in the in vitro study. In the in vivo study, successful delivery was achieved with OFP droplets at 300 kPa and 450 kPa without evidence of cavitation damage using ¼ dosage, compared to DFB droplets at 900 kPa where histology indicated tissue damage due to inertial cavitation. In conclusion, the vaporization efficiency of nanodroplets positively impacted the amount of molecules delivered to the brain. The OFP droplets due to the higher vaporization efficiency served as better acoustic agents to deliver large molecules efficiently to the brain compared with the DFB droplets.

Microbial Remains in Middle Proterozoic Rocks of Northern Australia

NASA Technical Reports Server (NTRS)

Astafieva, Marina; Rozanov, Alexei Yu.; Hoover, Richard B.; Vickers-Rich, P.; Wilde, A.

2004-01-01

Investigation of the samples of the McArthur River complex ore deposit, one of the most zinc-lead m i n d provinces in the world, brings us to conclusion about the possibility of the biogenic origin of sulfides in McArthur River ore deposit and to make suppositions about the formation of the studied rocks in the photic zone of sea.

Effect of oxygen minimum zone formation on communities of marine protists.

PubMed

Orsi, William; Song, Young C; Hallam, Steven; Edgcomb, Virginia

2012-08-01

Changes in ocean temperature and circulation patterns compounded by human activities are leading to oxygen minimum zone (OMZ) expansion with concomitant alteration in nutrient and climate active trace gas cycling. Here, we report the response of microbial eukaryote populations to seasonal changes in water column oxygen-deficiency using Saanich Inlet, a seasonally anoxic fjord on the coast of Vancouver Island British Columbia, as a model ecosystem. We combine small subunit ribosomal RNA gene sequencing approaches with multivariate statistical methods to reveal shifts in operational taxonomic units during successive stages of seasonal stratification and renewal. A meta-analysis is used to identify common and unique patterns of community composition between Saanich Inlet and the anoxic/sulfidic Cariaco Basin (Venezuela) and Framvaren Fjord (Norway) to show shared and unique responses of microbial eukaryotes to oxygen and sulfide in these three environments. Our analyses also reveal temporal fluctuations in rare populations of microbial eukaryotes, particularly anaerobic ciliates, that may be of significant importance to the biogeochemical cycling of methane in OMZs. Eukaryotic 18S rRNA gene sequences recovered from the Saanich Inlet water column on were deposited in Genbank under accession numbers HQ864863–HQ871151.

An Experimental Examination of Combustion of Isolated Liquid Fuel Droplets with Polymeric and Nanoparticle Additives

NASA Astrophysics Data System (ADS)

Ghamari, Mohsen

In spite of recent attention to renewable sources of energy, liquid hydrocarbon fuels are still the main source of energy for industrial and transportation systems. Manufactures and consumers are consistently looking for ways to optimize the efficiency of fuel combustion in terms of cost, emissions and consumer safety. In this regard, increasing burning rate of liquid fuels has been of special interest in both industrial and transportation systems. Recent studies have shown that adding combustible nano-particles could have promising effects on improving combustion performance of liquid fuels. Combustible nano-particles could enhance radiative and conductive heat transfer and also mixing within the droplet. Polymeric additive have also shown promising effect on improving fire safety by suppressing spreading behavior and splatter formation in case of crash scenario. Polymers are also known to have higher burning rate than regular hydrocarbon fuels. Therefore adding polymeric additive could have the potential to increase the burning rate. In this work, combustion dynamics of liquid fuel droplets with both polymeric and nanoparticle additives is studied in normal gravity. High speed photography is employed and the effect of additive concentration on droplet burning rate, burning time, extinction and soot morphology is investigated. Polymer added fuel was found to have a volatility controlled combustion with four distinct regimes. The first three zones are associated with combustion of base fuel while the polymer burns last and after a heating zone because of its higher boiling point. Polymer addition reduces the burning rate of the base fuel in the first zone by means of increasing viscosity and results in nucleate boiling and increased burning rates in the second and third stages. Overall, polymer addition resulted in a higher burning rate and shorter burning time in most of the scenarios. Colloidal suspensions of carbon-based nanomaterials in liquid fuels were also tested at different particle loadings. It was found that dispersing nanoparticles results in higher burning rate by means of enhanced radiative heat absorption and thermal conductivity. An optimum particle loading was found for each particle type at which the maximum burning rate was achieved. It was observed that the burning rate again starts to reduce after this optimum point most likely due to the formation of large aggregates that reduce thermal conductivity and suppress the diffusion of species.

An anomalous Pt-Pd occurrence below the JM reef, Stillwater Complex, Montana

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

McIlveen, C.L.

1993-04-01

The late Archean Stillwater Complex, in south-central Montana, consists of the Basal, Ultramafic, and Banded series. The Lower Banded series contains several anomalous platinum-group element (PGE) occurrences, with the JM reef having the highest values (an average of 6,250 ppb Pt and 24,000 ppb Pd) and greatest lateral persistence. The Coors anomaly, below the reef, is near the middle of the complex. This zone contains bronzite cumulates which range from 100--14,600 ppb Pt, with an average of 1,250 ppb. Pt:Pd ratios in the Coors zone average 1:1.7, compared to 1:3.8 in the reef. Sulfides associated with the PGE's show immisciblemore » textures indicating a magmatic origin similar to the reef. The anomaly lies approximately 200 m below the reef along the Banded-Ultramafic series contact where the Gabbronorite 1 zone is virtually absent. Layering between the reef and the Ultramafic series bronzitite is irregular and thin compared to the normal 400-m thickness exposed elsewhere in the complex. Bronzitites which contain the PGE's are podiform and often pegmatoidal. Norites adjacent to the bronzities also tend to be pegmatoidal and sulfide-bearing, but contain an average of only 75 ppb Pt. Microprobe analyses of bronzites in this zone show abruptly lower Mg/(Mg + Fe) of 0.77 compared to 0.83 in the uppermost bronzitite. The disrupted layering and thinning in the Coors area may have formed by slumping, scouring, or thermal erosion in the cumulate pile during crystallization. Coors mineralization may have developed through processes similar to those in the JM reef. However, occurrence of the coors mineralization with irregular layering and higher PGE ratios suggest an origin different than that in the reef.« less

Soil contamination with emissions of non-ferrous metallurgical plants

NASA Astrophysics Data System (ADS)

Vodyanitskii, Yu. N.; Plekhanova, I. O.; Prokopovich, E. V.; Savichev, A. T.

2011-02-01

The upper soil horizons are strongly contaminated in the area influenced by the Mid-Urals copper smelter. In the technogenic desert and impact zones, the contents of a number of elements (Cu, Zn, As, Pb, P, and S) by many times exceed their clarke values and the maximum permissible concentrations (or provisional permissible concentrations). The degree of technogeneity (Tg) for these elements is very high in these zones. In the far buffer zone, Tg is about zero for many elements and increases up to Tg = 27-42% for four heavy elements (Cu, Zn, Pb, and As) and up to 81-98% for P and S. The buffer capacity of the humus horizon depends on the soil's location within the technogeochemical anomaly and also on the particular pollutant. In the impact zone, it is equal to 70-77% for lead and arsenic, although other technogenic elements (Zn, Cr, S, and P) are poorly retained and readily migrate into the deeper horizons (the buffer capacity is equal to 14-25%). Nearly all the heavy metals enter the soil in the form of sulfides. The soils in the area affected by the Noril'sk mining and smelting metallurgical enterprise are subdivided into two groups according to the degree of their contamination, i.e., the soils within Noril'sk proper and the soils in its suburbs to a distance of 4-15 km. The strongest soil contamination is recorded in the city: the clarke values are exceeded by 287, 78, 16, 4.1, and 3.5 times for Cu, Ni, Cr, Fe, and S, respectively. The major pollutants enter the soil from the ferruginous slag. The soil's contamination degree is lower in the suburbs, where heavy metal sulfides reach the soils with the aerial emission from the enterprise.

Are the stratospheric dust particles meteor ablation debris or interplanetary dust?

NASA Technical Reports Server (NTRS)

Blanchard, M. B.; Kyte, F. T.

1978-01-01

Natural and laboratory created fusion crusts and debris from artificial meteor samples were used to develop criteria for recognizing meteor ablation debris in a collection of 5 to 50 micron particles from the stratosphere. These laboratory studies indicate that meteor ablation debris from nickel-iron meteoroids produce spherules containing taenite, wuestite, magnetite, and hematite. These same studies also indicate that ablation debris from chondritic meteoroids produce spheres and fragmentary debris. The spheres may be either silicate rich, containing zoned olivine, magnetite, and glass, or sulfide rich, containing iron oxides (e.g., magnetite, wuestite) and iron sulfides (e.g., pyrrhotite, pentlandite). The fragmentary debris may be either fine-grained aggregates of olivine, magnetite, pyroxene, and occasionally pyrrhotite (derived from the meteorite matrix) or individual olivine and pyroxene grains (derived from meteorite inclusions).

Gases and trace elements in soils at the North Silver Bell deposit, Pima County, Arizona

USGS Publications Warehouse

Hinkle, M.E.; Dilbert, C.A.

1984-01-01

Soil samples were collected over the North Silver Bell porphyry copper deposit near Tucson, Arizona. Volatile elements and compounds in gases derived from the soils and metallic elements in the soils were analyzed in order: (1) to see which volatile constituents of the soils might be indicative of the ore body or the alteration zones; and (2) to distinguish the ore and alteration zones by comparison of trace elements in the soil. Plots of analytical data on trace elements in soils indicated a typical distribution pattern for metals around a porphyry copper deposit, with copper, molybdenum, and arsenic concentrations higher over the ore body, and zinc, lead, and silver concentrations higher over the alteration zones. Higher than average concentrations of helium, carbon disulfide, and sulfur dioxide adsorbed on soils were found over the ore body, whereas higher concentrations of carbon dioxide and carbonyl sulfide were found over the alteration zones. ?? 1984.

High-power laser radiation in atmospheric aerosols: Nonlinear optics of aerodispersed media

NASA Astrophysics Data System (ADS)

Zuev, V. E.; Zemlianov, A. A.; Kopytin, Iu. D.; Kuzikovskii, A. V.

The bulk of this book contains the results of investigations carried out at the Institute of Atmospheric Optics, Siberian Branch, USSR Academy of Science with the participation of the authors. The microphysical and optical characteristics of atmospheric aerosols are considered, taking into account light scattering by a single aerosol particle, light scattering by a system of particles, the scattering phase matrix, light scattering by clouds and fogs, light scattering by hazes, and scattering phase functions of polydispersed aerosols. Other topics studies are related to low-energy (subexplosive) effects of radiation on individual particles, the formation of clear zones in clouds and fogs due to the vaporization of droplets under regular regimes, self-action of a wave beam in a water aerosol under conditions of regular droplet vaporization, laser beam propagation through an explosively evaporating water-droplet aerosol, the propagation of high-power laser radiation through hazes, the ionization and optical breakdown in aerosol media, and laser monitoring of a turbid atmosphere using nonlinear effects.

Microbial oceanography of anoxic oxygen minimum zones.

PubMed

Ulloa, Osvaldo; Canfield, Donald E; DeLong, Edward F; Letelier, Ricardo M; Stewart, Frank J

2012-10-02

Vast expanses of oxygen-deficient and nitrite-rich water define the major oxygen minimum zones (OMZs) of the global ocean. They support diverse microbial communities that influence the nitrogen economy of the oceans, contributing to major losses of fixed nitrogen as dinitrogen (N(2)) and nitrous oxide (N(2)O) gases. Anaerobic microbial processes, including the two pathways of N(2) production, denitrification and anaerobic ammonium oxidation, are oxygen-sensitive, with some occurring only under strictly anoxic conditions. The detection limit of the usual method (Winkler titrations) for measuring dissolved oxygen in seawater, however, is much too high to distinguish low oxygen conditions from true anoxia. However, new analytical technologies are revealing vanishingly low oxygen concentrations in nitrite-rich OMZs, indicating that these OMZs are essentially anoxic marine zones (AMZs). Autonomous monitoring platforms also reveal previously unrecognized episodic intrusions of oxygen into the AMZ core, which could periodically support aerobic metabolisms in a typically anoxic environment. Although nitrogen cycling is considered to dominate the microbial ecology and biogeochemistry of AMZs, recent environmental genomics and geochemical studies show the presence of other relevant processes, particularly those associated with the sulfur and carbon cycles. AMZs correspond to an intermediate state between two "end points" represented by fully oxic systems and fully sulfidic systems. Modern and ancient AMZs and sulfidic basins are chemically and functionally related. Global change is affecting the magnitude of biogeochemical fluxes and ocean chemical inventories, leading to shifts in AMZ chemistry and biology that are likely to continue well into the future.

Quantitative Microbial Community Analysis of Three Different Sulfidic Mine Tailing Dumps Generating Acid Mine Drainage▿

PubMed Central

Kock, Dagmar; Schippers, Axel

2008-01-01

The microbial communities of three different sulfidic and acidic mine waste tailing dumps located in Botswana, Germany, and Sweden were quantitatively analyzed using quantitative real-time PCR (Q-PCR), fluorescence in situ hybridization (FISH), catalyzed reporter deposition-FISH (CARD-FISH), Sybr green II direct counting, and the most probable number (MPN) cultivation technique. Depth profiles of cell numbers showed that the compositions of the microbial communities are greatly different at the three sites and also strongly varied between zones of oxidized and unoxidized tailings. Maximum cell numbers of up to 109 cells g−1 dry weight were determined in the pyrite or pyrrhotite oxidation zones, whereas cell numbers in unoxidized tailings were significantly lower. Bacteria dominated over Archaea and Eukarya at all tailing sites. The acidophilic Fe(II)- and/or sulfur-oxidizing Acidithiobacillus spp. dominated over the acidophilic Fe(II)-oxidizing Leptospirillum spp. among the Bacteria at two sites. The two genera were equally abundant at the third site. The acidophilic Fe(II)- and sulfur-oxidizing Sulfobacillus spp. were generally less abundant. The acidophilic Fe(III)-reducing Acidiphilium spp. could be found at only one site. The neutrophilic Fe(III)-reducing Geobacteraceae as well as the dsrA gene of sulfate reducers were quantifiable at all three sites. FISH analysis provided reliable data only for tailing zones with high microbial activity, whereas CARD-FISH, Q-PCR, Sybr green II staining, and MPN were suitable methods for a quantitative microbial community analysis of tailings in general. PMID:18586975

Mineralogy and geochemistry of El Dorado epithermal gold deposit, El Sauce district, central-northern Chile

NASA Astrophysics Data System (ADS)

Carrillo-Rosúa, J.; Morales-Ruano, S.; Morata, D.; Boyce, A. J.; Belmar, M.; Fallick, A. E.; Fenoll Hach-Alí, P.

2008-03-01

The El Dorado Au-Cu deposit is located in an extensive intra-caldera zone of hydrothermal alteration affecting Upper Cretaceous andesites of the Los Elquinos Formation at La Serena (≈ 29°47'S Lat., 70°43'W Long., Chile). Quartz-sulfide veins of economic potential are hosted by N25W and N20E fault structures associated with quartz-illite alteration (+supergene kaolinite). The main ore minerals in the deposit are pyrite, chalcopyrite ± fahlore (As/(As + Sb): 0.06-0.98), with electrum, sphalerite, galena, bournonite-seligmanite (As/(As + Sb): 0.21-0.31), marcasite, pyrrhotite being accessory phases. Electrum, with an Ag content between 32 and 37 at.%, occurs interstitial to pyrite aggregates or along pyrite fractures. Pyrite commonly exhibits chemical zonation with some zones up to 1.96 at.% As. Electron probe microanalyses of pyrite indicate that As-rich zones do not exhibit detectable Au values. Fluid inclusion microthermometry shows homogenization temperatures between 130 and 352 °C and salinities between 1.6 and 6.9 wt.% NaCl eq. Isotope data for quartz, ankerite and phyllosilicates and estimated temperatures show that δ18O and δD for the hydrothermal fluids were between 3 and 10‰ and between -95 and -75‰, respectively. These results suggest the mineralizing fluids were a mixture of meteoric and magmatic waters. An epithermal intermediate-sulfidation model is proposed for the formation of the El Dorado deposit.

Microbial oceanography of anoxic oxygen minimum zones

PubMed Central

Ulloa, Osvaldo; Canfield, Donald E.; DeLong, Edward F.; Letelier, Ricardo M.; Stewart, Frank J.

2012-01-01

Vast expanses of oxygen-deficient and nitrite-rich water define the major oxygen minimum zones (OMZs) of the global ocean. They support diverse microbial communities that influence the nitrogen economy of the oceans, contributing to major losses of fixed nitrogen as dinitrogen (N2) and nitrous oxide (N2O) gases. Anaerobic microbial processes, including the two pathways of N2 production, denitrification and anaerobic ammonium oxidation, are oxygen-sensitive, with some occurring only under strictly anoxic conditions. The detection limit of the usual method (Winkler titrations) for measuring dissolved oxygen in seawater, however, is much too high to distinguish low oxygen conditions from true anoxia. However, new analytical technologies are revealing vanishingly low oxygen concentrations in nitrite-rich OMZs, indicating that these OMZs are essentially anoxic marine zones (AMZs). Autonomous monitoring platforms also reveal previously unrecognized episodic intrusions of oxygen into the AMZ core, which could periodically support aerobic metabolisms in a typically anoxic environment. Although nitrogen cycling is considered to dominate the microbial ecology and biogeochemistry of AMZs, recent environmental genomics and geochemical studies show the presence of other relevant processes, particularly those associated with the sulfur and carbon cycles. AMZs correspond to an intermediate state between two “end points” represented by fully oxic systems and fully sulfidic systems. Modern and ancient AMZs and sulfidic basins are chemically and functionally related. Global change is affecting the magnitude of biogeochemical fluxes and ocean chemical inventories, leading to shifts in AMZ chemistry and biology that are likely to continue well into the future. PMID:22967509

Quantitative microbial community analysis of three different sulfidic mine tailing dumps generating acid mine drainage.

PubMed

Kock, Dagmar; Schippers, Axel

2008-08-01

The microbial communities of three different sulfidic and acidic mine waste tailing dumps located in Botswana, Germany, and Sweden were quantitatively analyzed using quantitative real-time PCR (Q-PCR), fluorescence in situ hybridization (FISH), catalyzed reporter deposition-FISH (CARD-FISH), Sybr green II direct counting, and the most probable number (MPN) cultivation technique. Depth profiles of cell numbers showed that the compositions of the microbial communities are greatly different at the three sites and also strongly varied between zones of oxidized and unoxidized tailings. Maximum cell numbers of up to 10(9) cells g(-1) dry weight were determined in the pyrite or pyrrhotite oxidation zones, whereas cell numbers in unoxidized tailings were significantly lower. Bacteria dominated over Archaea and Eukarya at all tailing sites. The acidophilic Fe(II)- and/or sulfur-oxidizing Acidithiobacillus spp. dominated over the acidophilic Fe(II)-oxidizing Leptospirillum spp. among the Bacteria at two sites. The two genera were equally abundant at the third site. The acidophilic Fe(II)- and sulfur-oxidizing Sulfobacillus spp. were generally less abundant. The acidophilic Fe(III)-reducing Acidiphilium spp. could be found at only one site. The neutrophilic Fe(III)-reducing Geobacteraceae as well as the dsrA gene of sulfate reducers were quantifiable at all three sites. FISH analysis provided reliable data only for tailing zones with high microbial activity, whereas CARD-FISH, Q-PCR, Sybr green II staining, and MPN were suitable methods for a quantitative microbial community analysis of tailings in general.

Geochemical behavior of heavy metals in a Zn-Pb-Cu mining area in the State of Mexico (central Mexico).

PubMed

Lizárraga-Mendiola, L; González-Sandoval, M R; Durán-Domínguez, M C; Márquez-Herrera, C

2009-08-01

The geochemical behavior of zinc, lead and copper from sulfidic tailings in a mine site with potential to generate acidic drainage (pyrite (55%) and sphalerite (2%)) is reported in this paper. The mining area is divided in two zones, considering the topographic location of sampling points with respect to the tailings pile: (a) outer zone, out of the probable influence of acid mine drainage (AMD) pollution, and (b) inner zone, probably influenced by AMD pollution. Maximum total ions concentrations (mg/L) measured in superficial waters found were, in the outer zone: As (0.2), Cd (0.9), Fe (19), Mn (39), Pb (5.02), SO4(2-) (4650), Zn (107.67), and in the inner zone are As (0.1), Cd (0.2), Fe (88), Mn (13), Pb (6), SO4(2-) (4,880), Zn (46). The presence of these ions that exceeding the permissible maximum limits for human consume, could be associated to tailings mineralogy and acid leachates generated in tailings pile.

The Submarine 4-km diameter Corossol Crater, Eastern Canada: Evidence for an impact origin

NASA Astrophysics Data System (ADS)

Higgins, Michael D.; Lajeunesse, Patrick; St-Onge, Guillaume; Locat, Jacques; Sanfacon, Richard; Duchesne, Mathieu J.

2014-05-01

The newly-discovered Corossol Crater lies in the northwestern Gulf of St. Lawrence (Eastern Canada; 50°3'N, 66°23'W) and was found in 40-185 metres of water using high-resolution multibeam sonar. It is a 4 km in diameter complex circular structure with a central uplift and concentric rings. Glacial resurfacing indicates that it predates the last phase of glaciation in this area. Dredging on the central uplift recovered many angular clasts of hard grey limestone, which forms the bedrock in much of this area. One 4 cm clast of limestone breccia is somewhat different from the other blocks and has characteristics that suggest that it is an impact breccia. The block comprises fragments of calcite limestone up to 2 mm long. In many parts of the block these fragments have thin black rims. At the edges of the block these rims are brown, presumably reflecting aqueous alteration. Mineral grains in the rims are too small to characterize, but the fact that the ensemble can be oxidized suggests that it contains sulfides. In places the block is cut by veins of fine-grained calcite with euhedral dolomite crystals. The most unusual component is rare droplets up to 2 mm long, commonly fragmented. The droplets comprise a glassy matrix with a composition very close to fluorapatite and opaque crystals that have a composition close to pyrite. A few droplets have up to 5% vesicles. Fluorapatite requires fusion temperatures of about 1600 C, which cannot be achieved at the surface of the Earth by endogenous processes. A single fragmented quartz crystal with planar features was found close to one droplet. Universal stage measurements of the orientation of the planar features give an angle of 42 degrees which is close to that of {10-13} planes. This is the most common set of deformation planes produced during shock metamorphism of quartz. Unfortunately no other grains were found with similar planes. The glassy droplets and shocked quartz together suggest that the clast was produced by an impact, and hence that it is very likely that the Corossol Crater in which the clast was found is an astrobleme. The absolute age of this structure is unknown, but its geological setting indicates that it was formed long after the Mid-Ordovician and possibly before regional pre-Quaternary sea-level lowstand. We are now attempting to obtain a U-Th helium age for the droplets which will date the impact event.

Modern marine sediments as a natural analog to the chemically stressed environment of a landfill

USGS Publications Warehouse

Baedecker, M.J.; Back, W.

1979-01-01

Chemical reactions that occur in landfills are analogous to those reactions that occur in marine sediments. Lateral zonation of C, N, S, O, H, Fe and Mn species in landfills is similar to the vertical zonation of these species in marine sediments and results from the following reaction sequence: (1) oxidation of C, N and S species in the presence of dissolved free oxygen to HCO3-, NO3- and SO2-4; (2) after consumption of molecular oxygen, then NO3- is reduced, and Fe and Mn are solubilized; (3) SO2-4 is reduced to sulfide; and (4) organic compounds become the source of oxygen, and CH4 and NH4+ are formed as fermentation products. In a landfill in Delaware the oxidation potential increases downgradient and the redox zones in the reducing plume are characterized by: CH4, NH4+, Fe2+. Mn2+, HCO3- and NO3-. Lack of SO2-4 at that landfill eliminates the sulfide zone. Although it has not been observed at landfills, mineral alteration should result in precipitation of pyrite and/or siderite downgradient. Controls on the pH of leachate are the relative rates of production of HCO3-, NH4+ and CH4. Production of methane by fermentation at landfills results in 13C isotope fractionation and the accumulation of isotopically heavy ??CO2 (+10 to +18??? PDB). Isotope measurements may be useful to determine the extent of CO2 reduction in landfills and extent of dilution downgradient. The boundaries of reaction zones in stressed aquifers are determined by head distribution and flow velocity. Thus, if the groundwater flow is rapid relative to reaction rates, redox zones will develop downgradient. Where groundwater flow velocities are low the zones will overlap to the extent that they may be indeterminate. ?? 1979.

Formation and crystallisation of a liquid jet in a film exposed to a tightly focused laser beam

NASA Astrophysics Data System (ADS)

Anisimov, S. I.; Zhakhovsky, V. V.; Inogamov, N. A.; Murzov, S. A.; Khokhlov, V. A.

2017-06-01

This paper considers the effect of an ultrashort laser pulse on a thin gold film on a glass substrate at a focal spot size near 1 μm. We analyse the motion and thermal history of a film that has peeled off from the substrate in the heating spot as a consequence of melting. The detached zone is shown to form a domeshaped bump whose motion is hindered by surface tension. After the dome stops and turns back, towards the substrate, a jet begins to grow on its top. Concurrently, because of the heat dissipation in the film, melt recrystallisation begins, involving first the dome and then the jet. The liquid part of the jet elongates and breaks up into droplets because of the Plateau-Rayleigh instability development. The formation of a neck and the detachment of the last droplet occur in the solidification zone between the crystalline and liquid parts of the jet. The propagation of the crystallisation zone in the jet leads the necking process, so neck disruption occurs in the solid phase under nonequilibrium crystallisation conditions (the melt temperature is hundreds of kelvins lower than the melting point), at limiting mechanical stress and at high deformation rates. As a result, the jet transforms into a high needle with an extremely small tip radius (a few nanometres).

Sulfide oxidation and distribution of metals near abandoned copper mines in coastal environments, Prince William Sound, Alaska, USA

USGS Publications Warehouse

Koski, R.A.; Munk, L.; Foster, A.L.; Shanks, Wayne C.; Stillings, L.L.

2008-01-01

The oxidation of sulfide-rich rocks, mostly leftover debris from Cu mining in the early 20th century, is contributing to metal contamination of local coastal environments in Prince William Sound, Alaska. Analyses of sulfide, water, sediment, precipitate and biological samples from the Beatson, Ellamar, and Threeman mine sites show that acidic surface waters generated from sulfide weathering are pathways for redistribution of environmentally important elements into and beyond the intertidal zone at each site. Volcanogenic massive sulfide deposits composed of pyrrhotite and (or) pyrite + chalcopyrite + sphalerite with subordinate galena, arsenopyrite, and cobaltite represent potent sources of Cu, Zn, Pb, As, Co, Cd, and Hg. The resistance to oxidation among the major sulfides increases in the order pyrrhotite ??? sphalerite < chalcopyrite ??? pyrite; thus, pyrrhotite-rich rocks are typically more oxidized than those dominated by pyrite. The pervasive alteration of pyrrhotite begins with rim replacement by marcasite followed by replacement of the core by sulfur, Fe sulfate, and Fe-Al sulfate. The oxidation of chalcopyrite and pyrite involves an encroachment by colloform Fe oxyhydroxides at grain margins and along crosscutting cracks that gradually consumes the entire grain. The complete oxidation of sulfide-rich samples results in a porous aggregate of goethite, lepidocrocite and amorphous Fe-oxyhydroxide enclosing hydrothermal and sedimentary silicates. An inverse correlation between pH and metal concentrations is evident in water data from all three sites. Among all waters sampled, pore waters from Ellamar beach gravels have the lowest pH (???3) and highest concentrations of base metals (to ???25,000 ??g/L), which result from oxidation of abundant sulfide-rich debris in the sediment. High levels of dissolved Hg (to 4100 ng/L) in the pore waters probably result from oxidation of sphalerite-rich rocks. The low-pH and high concentrations of dissolved Fe, Al, and SO4 are conducive to precipitation of interstitial jarosite in the intertidal gravels. Although pore waters from the intertidal zone at the Threeman mine site have circumneutral pH values, small amounts of dissolved Fe2+ in the pore waters are oxidized during mixing with seawater, resulting in precipitation of Fe-oxyhydroxide flocs along the beach-seawater interface. At the Beatson site, surface waters funneled through the underground mine workings and discharged across the waste dumps have near-neutral pH (6.7-7.3) and a relatively small base-metal load; however, these streams probably play a role in the physical transport of metalliferous particulates into intertidal and offshore areas during storm events. Somewhat more acidic fluids, to pH 5.3, occur in stagnant seeps and small streams emerging from the Beatson waste dumps. Amorphous Fe precipitates in stagnant waters at Beatson have high Cu (5.2 wt%) and Zn (2.3 wt%) concentrations that probably reflect adsorption onto the extremely high surface area of colloidal particles. Conversely, crystalline precipitates composed of ferrihydrite and schwertmannite that formed in the active flow of small streams have lower metal contents, which are attributed to their smaller surface area and, therefore, fewer reactive sorption sites. Seeps containing precipitates with high metal contents may contribute contaminants to the marine environment during storm-induced periods of high runoff. Preliminary chemical data for mussels (Mytilus edulis) collected from Beatson, Ellamar, and Threeman indicate that bioaccumulation of base metals is occurring in the marine environment at all three sites.

Geochemistry of glacial sediments in the area of the Bend massive sulfide deposit, north-central Wisconsin

USGS Publications Warehouse

Woodruff, L.G.; Attig, J.W.; Cannon, W.F.

2004-01-01

Geochemical exploration in northern Wisconsin has been problematic because of thick glacial overburden and complex stratigraphic record of glacial history. To assess till geochemical exploration in an area of thick glacial cover and complex stratigraphy samples of glacial materials were collected from cores from five rotasonic boreholes near a known massive sulfide deposit, the Bend deposit in north-central Wisconsin. Diamond drilling in the Bend area has defined a long, thin zone of mineralization at least partly intersected at the bedrock surface beneath 30-40 m of unconsolidated glacial sediments. The bedrock surface has remnant regolith and saprolite resulting from pre-Pleistocene weathering. Massive sulfide and mineralized rock collected from diamond drill core from the deposit contain high (10s to 10,000s ppm) concentrations of Ag, As, Au, Bi, Cu, Hg, Se, Te, and Tl. Geochemical properties of the glacial stratigraphic units helped clarify the sequence and source areas of several glacial ice advances preserved in the section. At least two till sheets are recognized. Over the zone of mineralization, saprolite and preglacial alluvial and lacustrine samples are preserved on the bedrock surface in a paleoriver valley. The overlying till sheet is a gray, silty carbonate till with a source hundreds of kilometers to the northwest of the study area. This gray till is overlain by red, sandy till with a source to the north in Proterozoic rocks of the Lake Superior area. The complex glacial stratigraphy confounds down-ice geochemical till exploration. The presence of remnant saprolite, preglacial sediment, and far-traveled carbonate till minimized glacial erosion of mineralized material. As a result, little evidence of down-ice glacial dispersion of lithologic or mineralogic indicators of Bend massive sulfide mineralization was found in the samples from the rotasonic cores. This study points out the importance of determining glacial stratigraphy and history, and identifying favorable lithologies required for geochemical exploration. Drift prospecting in Wisconsin and other areas near the outer limits of the Pleistocene ice sheets may not be unsuccessful, in part, because of complex stratigraphic sequences of multiple glaciations where deposition dominates over erosion. ?? 2004 Elsevier B.V. All rights reserved.

Geochemical controls of elevated arsenic concentrations in groundwater, Ester Dome, Fairbanks district, Alaska

USGS Publications Warehouse

Verplanck, P.L.; Mueller, S.H.; Goldfarb, R.J.; Nordstrom, D. Kirk; Youcha, E.K.

2008-01-01

Ester Dome, an upland area near Fairbanks, Alaska, was chosen for a detailed hydrogeochemical study because of the previously reported elevated arsenic in groundwater, and the presence of a large set of wells amenable to detailed sampling. Ester Dome lies within the Fairbanks mining district, where gold-bearing quartz veins, typically containing 2-3??vol.% sulfide minerals (arsenopyrite, stibnite, and pyrite), have been mined both underground and in open cuts. Gold-bearing veins on Ester Dome occur in shear zones and the sulfide minerals in these veins have been crushed to fine-grained material by syn- or post-mineralization movement. Groundwater at Ester Dome is circumneutral, Ca-HCO3 to Ca-SO4 type, and ranges from dilute (specific conductance of 48????S/cm) to more concentrated (specific conductance as high as 2070????S/cm). In general, solute concentrations increase down hydrologic gradient. Redox species indicate that the groundwaters range from oxic to sub-oxic (low dissolved oxygen, Fe(III) reduction, no SO4 reduction). Waters with the highest Fe concentrations, as high as 10.7??mg/L, are the most anoxic. Dissolved As concentrations range from < 1 to 1160????g/L, with a median value of 146????g/L. Arsenic concentrations are not correlated with specific conductance or Fe concentrations, suggesting that neither groundwater residence time, nor reductive dissolution of iron oxyhydroxides, control the arsenic chemistry. Furthermore, As concentrations do not covary with other constituents that form anions and oxyanions in solution (e.g., HCO3, Mo, F, or U) such that desorption of arsenic from clays or oxides also does not control arsenic mobility. Oxidation of arsenopyrite and dissolution of scorodite, in the near-surface environment appears to be the primary control of dissolved As in this upland area. More specifically, the elevated As concentrations are spatially associated with sulfidized shear zones and localities of gold-bearing quartz veins. Consistent with this interpretation, elevated dissolved Sb concentrations (as high as 59????g/L), also correlated with occurrences of hypogene sulfide minerals, were measured in samples with high dissolved As concentrations.

Geoelectric structure of northern Cambay rift basin from magnetotelluric data

NASA Astrophysics Data System (ADS)

Danda, Nagarjuna; Rao, C. K.; Kumar, Amit

2017-10-01

Broadband and long-period magnetotelluric data were acquired over the northern part of the Cambay rift zone along an east-west profile 200 km in length. The decomposed TE- and TM-mode data were inverted using a 2-D nonlinear conjugate gradient algorithm to obtain the lithospheric structure of the region. A highly conductive ( 1000 S) layer was identified within the Cambay rift zone and interpreted as thick Quaternary and Tertiary sediments. The crustal conductors found in the profile were due to fluid emplacement in the western part, and the presence of fluids and/or interconnected sulfides caused by metamorphic phases in the eastern part. The demarcation of the Cambay rift zone is clearly delineated with a steeply dipping fault on the western margin, whereas the eastern margin of the rift zone gently dips along the NE-SW axis, representing a half-graben structure. A highly resistive body identified outside the rift zone is interpreted as an igneous granitic intrusive complex. Moderately conductive (30-100 Ω-m) zones indicate underplating and the presence of partial melt due to plume-lithosphere interactions.[Figure not available: see fulltext.

Continuous monitoring of bisulfide variation in microdialysis effluents by on-line droplet-based microfluidic fluorescent sensor.

PubMed

Zhu, Xiaocui; Xu, Lei; Wu, Tongbo; Xu, Anqin; Zhao, Meiping; Liu, Shaorong

2014-05-15

We demonstrate a novel fluorescent sensor for real-time and continuous monitoring of the variation of bisulfide in microdialysis effluents by using a nanoparticle-glutathione-fluorescein isothiocyanate (AuNP-GSH-FITC) probe coupled with on-line droplet-based microfluidic chip. The AuNP-GSH-FITC fluorescent probe was firstly developed and used for bisulfide detection in bulk solution by quantitative real-time PCR, which achieved a linear working range from 0.1 μM to 5.0 μM and a limit of detection of ~50 nM. The response time was less than 2 min. With the aid of co-immobilized thiol-polyethylene glycol, the probe exhibited excellent stability and reproducibility in high salinity solutions, including artificial cerebrospinal fluids (aCSF). By adding 0.1% glyoxal to the probe solution, the assay allowed quantification of bisulfide in the presence of cysteine at the micro-molarity level. Using the AuNP-GSH-FITC probe, a droplet-based microfluidic fluorescent sensor was further constructed for online monitoring of bisulfide variation in the effluent of microdialysis. By using fluorescence microscope-charge-coupled device camera as the detector, the integrated microdialysis/microfluidic chip device achieved a detection limit of 2.0 μM and a linear response from 5.0 μM to 50 μM for bisulfide in the tested sample. The method was successfully applied for the on-line measurement of bisulfide variation in aCSF and serum samples. It will be a very useful tool for tracking the variation of bisulfide or hydrogen sulfide in extracellular fluids. Copyright © 2013 Elsevier B.V. All rights reserved.

Biological nitrate transport in sediments on the Peruvian margin mitigates benthic sulfide emissions and drives pelagic N loss during stagnation events

NASA Astrophysics Data System (ADS)

Dale, A. W.; Sommer, S.; Lomnitz, U.; Bourbonnais, A.; Wallmann, K.

2016-06-01

Benthic N cycling in the Peruvian oxygen minimum zone (OMZ) was investigated at ten stations along 12 °S from the middle shelf (74 m) to the upper slope (1024 m) using in situ flux measurements, sediment biogeochemistry and modeling. Middle shelf sediments were covered by mats of the filamentous bacteria Thioploca spp. and contained a large 'hidden' pool of nitrate that was not detectable in the porewater. This was attributed to a biological nitrate reservoir stored within the bacteria to oxidize sulfide during 'dissimilatory nitrate reduction to ammonium' (DNRA). The extremely high rates of DNRA on the shelf (15.6 mmol m-2 d-1 of N), determined using an empirical steady-state model, could easily supply all the ammonium requirements for anammox in the water column. The model further showed that denitrification by foraminifera may account for 90% of N2 production at the lower edge of the OMZ. At the time of sampling, dissolved oxygen was below detection limit down to 400 m and the water body overlying the shelf had stagnated, resulting in complete depletion of nitrate and nitrite. A decrease in the biological nitrate pool was observed on the shelf during fieldwork concomitant with a rise in porewater sulfide levels in surface sediments to 2 mM. Using a non-steady state model to simulate this natural anoxia experiment, these observations were shown to be consistent with Thioploca surviving on a dwindling intracellular nitrate reservoir to survive the stagnation period. The model shows that sediments hosting Thioploca are able to maintain high ammonium fluxes for many weeks following stagnation, potentially sustaining pelagic N loss by anammox. In contrast, sulfide emissions remain low, reducing the economic risk to the Peruvian fishery by toxic sulfide plume development.

Platinum-group elements, S, Se and Cu in highly depleted abyssal peridotites from the Mid-Atlantic Ocean Ridge (ODP Hole 1274A): Influence of hydrothermal and magmatic processes

NASA Astrophysics Data System (ADS)

Marchesi, Claudio; Garrido, Carlos J.; Harvey, Jason; González-Jiménez, José María; Hidas, Károly; Lorand, Jean-Pierre; Gervilla, Fernando

2013-11-01

Highly depleted harzburgites and dunites were recovered from ODP Hole 1274A, near the intersection between the Mid-Atlantic Ocean Ridge and the 15°20'N Fracture Zone. In addition to high degrees of partial melting, these peridotites underwent multiple episodes of melt-rock reaction and intense serpentinization and seawater alteration close to the seafloor. Low concentrations of Se, Cu and platinum-group elements (PGE) in harzburgites drilled at around 35-85 m below seafloor are consistent with the consumption of mantle sulfides after high degrees (>15-20 %) of partial melting and redistribution of chalcophile and siderophile elements into PGE-rich residual microphases. Higher concentrations of Cu, Se, Ru, Rh and Pd in harzburgites from the uppermost and lowest cores testify to late reaction with a sulfide melt. Dunites were formed by percolation of silica- and sulfur-undersaturated melts into low-Se harzburgites. Platinum-group and chalcophile elements were not mobilized during dunite formation and mostly preserve the signature of precursor harzburgites, except for higher Ru and lower Pt contents caused by precipitation and removal of platinum-group minerals. During serpentinization at low temperature (<250 °C) and reducing conditions, mantle sulfides experienced desulfurization to S-poor sulfides (mainly heazlewoodite) and awaruite. Contrary to Se and Cu, sulfur does not record the magmatic evolution of peridotites but was mostly added in hydrothermal sulfides and sulfate from seawater. Platinum-group elements were unaffected by post-magmatic low-temperature processes, except Pt and Pd that may have been slightly remobilized during oxidative seawater alteration.

Analysis of Ecological Distribution and Genomic Content from a Clade of Bacteroidetes Endemic to Sulfidic Environments

NASA Astrophysics Data System (ADS)

Zhou, K.; Sylvan, J. B.; Hallam, S. J.

2017-12-01

The Bacteroidetes are a ubiquitous phylum of bacteria found in a wide variety of habitats. Marine Bacteroidetes are known to utilize complex carbohydrates and have a potentially important role in the global carbon cycle through processing these compounds, which are not digestible by many other microbes. Some members of the phylum are known to perform denitrification and are facultative anaerobes, but Bacteroidetes are not known to participate in sulfur redox cycling. Recently, it was shown that a clade of uncultured Bacteroidetes, including the VC2.1_Bac22 group, appears to be endemic to sulfidic environments, including hydrothermal vent sulfide chimneys, sediments and marine water column oxygen minimum zones (OMZs). This clade, dubbed the Sulfiphilic Bacteroidetes, is not detected in 16S rRNA amplicon studies from non-sulfidic environments. To test the hypothesis that the Sulphiphilic Bacteroidetes are involved in sulfur redox chemistry, we updated our meta-analysis of the clade using 16s rRNA sequences from public databases and employed single-cell genomics to survey their genomic potential using 19 single amplified genomes (SAGs) isolated from the seasonally anoxic Saanich Inlet, a seasonally hypoxic basin in British Columbia. Initial analysis of these SAGs indicates the Sulphiphilic Bacteroidetes may perform sulfur redox reactions using a three gene psrABC operon encoding the polysulfide reductase enzyme complex with a thiosulfate sulfurtransferase (rhodanese), which putatively uses cyanide to convert thiosulfate to sulfite, just upstream. Interestingly, this is the same configuration as discovered recently in some Marine Group A bacteria. Further aspects of the Sulphiphilic Bacteroidetes' genomic potential will be presented in light of their presence in sulfidic environments.

CFD simulation of pesticide spray from air-assisted sprayers in an apple orchard: Tree deposition and off-target losses

NASA Astrophysics Data System (ADS)

Hong, Se-Woon; Zhao, Lingying; Zhu, Heping

2018-02-01

The ultimate goal of a pesticide spraying system is to provide adequate coverage on intended canopies with a minimum amount of spray materials and off-target waste. Better spray coverage requires an understanding of the fate and transport of spray droplets carried by turbulent airflows in orchards. In this study, an integrated computational fluid dynamics (CFD) model was developed to predict displacement of pesticide spray droplets discharged from an air-assisted sprayer, depositions onto tree canopies, and off-target deposition and airborne drift in an apple orchard. Pesticide droplets discharged from a moving sprayer were tracked using the Lagrangian particle transport model, and the deposition model was applied to droplets entering porous canopy zones. Measurements of the droplet deposition and drift in the same orchard were used to validate the model simulations. Good agreement was found between the measured and simulated spray concentrations inside tree canopies and off-target losses (ground deposition and airborne drifts) with the overall relative errors of 22.1% and 40.6%, respectively, under three growth stages. The CFD model was able to estimate the mass balance of pesticide droplets in the orchard, which was practically difficult to investigate by measurements in field conditions. As the foliage of trees became denser, spray deposition inside canopies increased from 8.5% to 65.8% and airborne drift and ground deposition decreased from 25.8% to 7.0% and 47.8% to 21.2%, respectively. Higher wind speed also increased the spray airborne drift downwind of the orchard. This study demonstrates that CFD model can be used to evaluate spray application performance and design and operate sprayers with increased spray efficiencies and reduced drift potentials.

Petrology, chronology and sequence of vein systems: Systematic magmatic and hydrothermal history of a major intracontinental shear zone, Canadian Appalachians

NASA Astrophysics Data System (ADS)

Pe-Piper, Georgia; Piper, David J. W.; McFarlane, Chris R. M.; Sangster, Chris; Zhang, Yuanyuan; Boucher, Brandon

2018-04-01

Intra-continental shear zones developed during continental collision may experience prolonged magmatism and mineralization. The Cobequid Shear Zone formed part of a NE-SW-trending, orogen-parallel shear system in the late Devonian-early Carboniferous, where syn-tectonic granite-gabbro plutons and volcanic rocks 4 km thick were progressively deformed. In late Carboniferous to Permian, Alleghanian collision of Africa with Laurentia formed the E-W trending Minas Fault Zone, reactivating parts of the Cobequid Shear Zone. The 50 Ma history of hydrothermal mineralization following pluton emplacement is difficult to resolve from field relationships of veins, but SEM study of thin sections provides clear detail on the sequence of mineralization. The general paragenesis is: albite ± quartz ± chlorite ± monazite → biotite → calcite, allanite, pyrite → Fe-carbonates, Fe-oxides, minor sulfides, calcite and synchysite. Chronology was determined from literature reports and new U-Pb LA-ICPMS dating of monazite and allanite in veins. Vein mineralization was closely linked to magmatic events. Vein emplacement occurred preferentially during fault movement recognised from basin-margin inversion, as a result of fractures opening in the damage zone of master faults. The sequence of mineralization, from ca. 355 Ma riebeckite and albite veins to ca. 327 (-305?) Ma siderite-magnetite and sulfide mineralization, resembles Precambrian iron-oxide-copper-gold (IOCG) systems in the literature. The abundant magmatic Na, halogens and CO2 in veins and some magmatic bodies, characteristic of IOCG systems, were derived from the deeply subducted Rheic Ocean slab with little terrigenous sediment. Regional extension of the Magdalen Basin caused asthenospheric upwelling and melting of the previously metasomatized sub-continental lithospheric mantle. Crustal scale strike-slip faulting facilitated the rise of magmas, resulting in high heat flow driving an active hydrothermal system. Table S2 Location of all illustrated samples. Table S3 Monazite geochronology lab data. Table S4 Allanite geochronology lab data. Fig. S1 Monazite geochronology analytical spots. Fig. S2 Allanite geochronology analytical spots.

Empirical equations to predict the sulfur content of mafic magmas at sulfide saturation and applications to magmatic sulfide deposits

NASA Astrophysics Data System (ADS)

Li, Chusi; Ripley, Edward M.

2005-03-01

Empirical equations to predict the sulfur content of a mafic magma at the time of sulfide saturation have been developed based on several sets of published experimental data. The S content at sulfide saturation (SCSS) can be expressed as: ln X_{text S} = 1.229 - 0.74(10^4/T) - 0.021(P) - 0.311 ln X_{{text{FeO}}} - 6.166X_{{text{SiO}}_{text{2}}} - 9.153X_{{text{Na}}_{text{2}} {text{O + K}}_{text{2}} {text{O}}} - 1.914X_{{text{MgO}}} + 6.594X_{{text{FeO}}} where T is in degrees Kelvin, X is mole fraction and P is in kbar. The squared multiple correlation coefficient ( r 2) for the equation is 0.88. Application of the equation to data from sulfide-saturated mid-ocean ridge basalts (MORB) samples show that the SCSS is closely predicted for primitive MORBs, but that accuracy decreases for lower T (<1,130°C) and more evolved MORB samples. This suggests that because the calibrations are based on anhydrous experimental runs done at temperatures of 1,200°C and above, it is not possible to extrapolate them to significantly lower temperatures and hydrous conditions. Because the SCSS of a primitive MORB magma increases with decreasing P, sulfide saturation in MORB appears to be a function of the degree of en route assimilation of S from country rocks as well as the degree of fractional crystallization in shallow staging chambers. Application of the equation to the high- T impact melt sheet that produced the Sudbury Igneous Complex and associated Ni-Cu sulfide ores indicates that sulfide-saturation was reached at 1,500°C, well above the start of orthopyroxene crystallization at 1,190°C. This would permit ample time for the gravitational settling and collection of immiscible sulfide liquid that produced the high-grade ore bodies. The development of a platinum group element (PGE)-enriched layer in the Sonju Lake Intrusion of the Duluth Complex is thought to be due to the attainment of sulfide saturation in the magma after a period of fractional crystallization. Using the composition of the parent magma of the Sonju Lake Intrusion the presented equation indicates that sulfide saturation would have been reached at 60% crystallization, when iron oxide was a liquidus mineral; the prediction is in agreement with field evidence which indicates that PGE-enrichment occurs in the oxide-rich gabbro zone. Contamination and mixing processes that may be related to the attainment of sulfide saturation in mafic magmas can also be evaluated. Mixing of a siliceous melt and a liquid of olivine tholeiite composition, similar to that thought to be a reasonable parental composition for many Duluth Complex intrusions, can induce sulfide saturation at mixing ratios in excess of 0.1. If the contaminant contains low quantities of sulfur the mixing ratio required to promote saturation is reduced. Mixing of mafic magmas at various stages of fractionation is evaluated using magma compositions that are thought to be appropriate for the generation of the Merensky Reef in the Bushveld Complex. Magma mixing is shown to be an effective process for the attainment of sulfide saturation, depending strongly on the sulfur concentrations of the end-member magmas.

An Interactive Excel Program for Tracking a Single Droplet in Crossflow Computation

NASA Technical Reports Server (NTRS)

Urip, E.; Yang, S. L.; Marek, C. J.

2002-01-01

Spray jet in crossflow has been a subject of research because of its wide application in systems involving pollutant dispersion, jet mixing in the dilution zone of combustors, and fuel injection strategies. The focus of this work is to investigate dispersion of a 2-dimensional atomized spray jet into a 2-dimensional crossflow. A quick computational method is developed using available software. The spreadsheet can be used for any 2D droplet trajectory problem where the drop is injected into the free stream eventually coming to the free stream conditions. During the transverse injection of a spray into high velocity airflow, the droplets (carried along and deflected by a gaseous stream of co-flowing air) are subjected to forces that affect their motion in the flow field. Based on the Newton's Second Law of motion, four ordinary differential equations were used. These equations were then solved by a fourth-order Runge-Kutta method using Excel software. Visual basic programming and Excel macrocode to produce the data facilitate Excel software to plot graphs describing the droplet's motion in the flow field. This program computes and plots the data sequentially without forcing users to open other types of plotting programs. A user's manual on how to use the program is also included in this report.

Development of a model to compute the extension of life supporting zones for Earth-like exoplanets.

PubMed

Neubauer, David; Vrtala, Aron; Leitner, Johannes J; Firneis, Maria G; Hitzenberger, Regina

2011-12-01

A radiative convective model to calculate the width and the location of the life supporting zone (LSZ) for different, alternative solvents (i.e. other than water) is presented. This model can be applied to the atmospheres of the terrestrial planets in the solar system as well as (hypothetical, Earth-like) terrestrial exoplanets. Cloud droplet formation and growth are investigated using a cloud parcel model. Clouds can be incorporated into the radiative transfer calculations. Test runs for Earth, Mars and Titan show a good agreement of model results with observations.

The Kalatongke magmatic Ni-Cu deposits in the Central Asian Orogenic Belt, NW China: product of slab window magmatism?

NASA Astrophysics Data System (ADS)

Li, Chusi; Zhang, Mingjie; Fu, Piaoer; Qian, Zhuangzhi; Hu, Peiqing; Ripley, Edward M.

2012-01-01

The Permian Kalatongke Ni-Cu deposits in the Central Asian Orogenic Belt are among the most important Ni-Cu deposits in northern Xinjiang, western China. The deposits are hosted by three small mafic intrusions comprising mainly norite and diorite. Its tectonic context, petrogenesis, and ore genesis have been highly contested. In this paper, we present a new model involving slab window magmatism for the Kalatongke intrusions. The origin of the associated sulfide ores is explained in the context of this new model. Minor amounts of olivine in the intrusions have Fo contents varying between 71 and 81.5 mol%, which are similar to the predicted values for olivine crystallizing from coeval basalts in the region. Analytic modeling based on major element concentrations suggests that the parental magma of the Kalatongke intrusions and the coeval basalts represent fractionated liquids produced by ˜15% of olivine crystallization from a primary magma, itself produced by 7-8% partial melting of depleted mantle peridotite. Positive ɛ Nd values (+4 to +10) and significant negative Nb anomalies for both intrusive and extrusive rocks can be explained by the mixing of magma derived from depleted mantle with 6-18% of a partial melt derived from the lower part of a juvenile arc crust with a composition similar to coeval A-type granites in the region, plus up to 10% contamination with the upper continental crust. Our model suggests that a slab window was created due to slab break-off during a transition from oceanic subduction to arc-arc or arc-continent collision in the region in the Early Permian. Decompression melting in the upwelling oceanic asthenosphere produced the primary magma. When this magma ascended to pond in the lower parts of a juvenile arc crust, it underwent olivine crystallization and at the same time triggered partial melting of the arc crust. Mixing between these two magmas followed by contamination with the upper crust after the magma ascended to higher crustal levels formed the parental magma of the Kalatongke intrusions. The parental magma of the Kalatongke intrusions was saturated with sulfide upon arrival primarily due to olivine fractional crystallization and selective assimilation of crustal sulfur. Sulfide mineralization in the Kalatongke intrusions can be explained by accumulation of immiscible sulfide droplets by flow differentiation, gravitational settling, and downward percolation which operated in different parts of the intrusions. Platinum-group element (PGE) depletion in the bulk sulfide ores of the Kalatongke deposits was due to depletion in the parental magma which in turn was likely due to depletion in the primary magma. PGE depletion in the primary magma can be explained by a relatively low degree of partial melting of the mantle and retention of coexisting sulfide liquid in the mantle.

Porphyry-Style Petropavlovskoe Gold Deposit, the Polar Urals: Geological Position, Mineralogy, and Formation Conditions

NASA Astrophysics Data System (ADS)

Vikentyev, I. V.; Mansurov, R. Kh.; Ivanova, Yu. N.; Tyukova, E. E.; Sobolev, I. D.; Abramova, V. D.; Vykhristenko, R. I.; Trofimov, A. P.; Khubanov, V. B.; Groznova, E. O.; Dvurechenskaya, S. S.; Kryazhev, S. G.

2017-11-01

Geological and structural conditions of localization, hydrothermal metasomatic alteration, and mineralization of the Petropavlovskoe gold deposit (Novogodnenskoe ore field) situated in the northern part of the Lesser Ural volcanic-plutonic belt, which is a constituent of the Middle Paleozoic island-arc system of the Polar Urals, are discussed. The porphyritic diorite bodies pertaining to the late phase of the intrusive Sob Complex play an ore-controlling role. The large-volume orebodies are related to the upper parts of these intrusions. Two types of stringer-disseminated ores have been revealed: (1) predominant gold-sulfide and (2) superimposed low-sulfide-gold-quartz ore markedly enriched in Au. Taken together, they make up complicated flattened isometric orebodies transitory to linear stockworks. The gold potential of the deposit is controlled by pyrite-(chlorite)-albite metasomatic rock of the main productive stage, which mainly develops in a volcanic-sedimentary sequence especially close to the contacts with porphyritic diorite. The relationships between intrusive and subvolcanic bodies and dating of individual zircon crystals corroborate a multistage evolution of the ore field, which predetermines its complex hydrothermal history. Magmatic activity of mature island-arc plagiogranite of the Sob Complex and monzonite of the Kongor Complex initiated development of skarn and beresite alterations accompanied by crystallization of hydrothermal sulfides. In the Early Devonian, due to emplacement of the Sob Complex at a depth of approximately 2 km, skarn magnetite ore with subordinate sulfides was formed. At the onset of the Middle Devonian, the large-volume gold porphyry Au-Ag-Te-W ± Mo,Cu stockworks related to quartz diorite porphyry—the final phase of the Sob Complex— were formed. In the Late Devonian, a part of sulfide mineralization was redistributed with the formation of linear low-sulfide quartz vein zones. Isotopic geochemical study has shown that the ore is deposited from reduced, substantially magmatic fluid, which is characterized by close to mantle values δ34S = 0 ± 1‰, δ13C =-6 to-7‰, and δ18O = +5‰ as the temperature decreases from 420-300°C (gold-sulfide ore) to 250-130°C (gold-(sulfide)-quartz ore) and pressure decreases from 0.8 to 0.3 kbar. According to the data of microanalysis (EPMA and LA-ICP-MS), the main trace elements in pyrite of gold orebodies are represented by Co (up to 2.52 wt %), As (up to 0.70 wt %), and Ni (up to 0.38 wt %); Te, Se, Ag, Au, Bi, Sb, and Sn also occur. Pyrite of the early assemblages is characterized by high Co, Te, Au, and Bi contents, whereas the late pyrite is distinguished by elevated concentrations of As (up to 0.7 wt %), Ni (up to 0.38 wt %), Se (223 ppm), Ag (up to 111 ppm), and Sn (4.4 ppm). The minimal Au content in pyrite of the late quartz-carbonate assemblage is up to 1.7 ppm and geometric average is 0.3 ppm. The significant correlation between Au and As (furthermore, negative-0.6) in pyrite from ore of the Petropavlovskoe deposit is recorded only for the gold-sulfide assemblage, whereas it is not established for other assemblages. Pyrite with higher As concentration (up to 0.7 wt %) is distinguished only for the Au-Te mineral assemblage. Taking into account structural-morphological and mineralogical-geochemical features, the ore-magmatic system of the Petropavlovskoe deposit is referred to as gold porphyry style. Among the main criteria of such typification are the spatial association of orebodies with bodies of subvolcanic porphyry-like intrusive phases at the roof of large multiphase pluton; the stockwork-like morphology of gold orebodies; 3D character of ore-alteration zoning and distribution of ore components; geochemical association of gold with Ag, W, Mo, Cu, As, Te, and Bi; and predominant finely dispersed submicroscopic gold in ore.

Current COIL research in Samara

NASA Astrophysics Data System (ADS)

Nikolaev, Valeri D.

1996-02-01

Development of the high pressure singlet oxygen generator (SOG) is a very important aspect for chemical oxygen-iodine laser (COIL). Increasing of oxygen pressure up to 30 torr and more at conserving high O2(1(Delta) ) yield and maintaining BHP temperature at minus (10 divided by 20) degrees Celsius permits us to decrease ration [H2O]/[O2] to 5% and less. In this case COIL can operate successfully without a water vapor trap. With raising the total pressure Reynolds number increases too, diminishing boundary layers in supersonic nozzles and improving pressure recovery. The weight and dimensions of the SOG and laser become reduced for the same gas flow rate. For solving these problems the jet SOG has been suggested and developed in Lebedev Physical Institute, Samara Branch. The advantages of the jet SOG consist of the following: (1) Large and controlled specific surface of contact liquid-gas provides for high mass transfer efficiency. (2) High jets velocity guarantees fast basic hydrogen peroxide (BHP) surface renovation. (3) High gas velocity in the reaction zone diminishes O2(1(Delta) ) quenching. (4) Efficient gas-liquid heat exchange eliminates the gas heating and generation water vapor due O2(1(Delta) ) quenching. (5) Counterflowing design of the jet SOG produces the best conditions for self-cleaning gas flow of droplets in the reaction zone and gives the possibility of COIL operation without droplets separator. High pressure jet SOG has some features connected with intrachannel jet formation, free space jets reconstruction, interaction jets ensemble with counter moving gas flow and drag part of gas by jets, disintegrating jets, generation and separation of droplets, heat effects, surface renovation, impoverishment BHP surface by HO2- ions, moving solution film on the reaction zone walls, etc. In this communication our current understanding of the major processes in the jet SOG is set forth. The complex gas and hydrodynamic processes with heat and mass transfer, chemical reactions, generation of the relaxing components with high energy store take place in the SOG reaction zone. It is impossible to create a sufficiently exact model of such a jet SOG taking into account all the enumerated processes. But some approximations and simplifications allow us to determine what the main jet SOG parameters parts are for designing COIL.

Mapping the EEZ

NASA Astrophysics Data System (ADS)

Richman, Barbara T.

A cooperative, multi-year program to map the largely uncharted Exclusive Economic Zone (EEZ), begun last month, has the potential for piggybacking scientific observations and research. On March 10, 1983, President Ronald Reagan proclaimed the mineral-rich zone as the area between the U.S. shoreline and 200 nautical miles outward. The United States has sovereign rights for exploration, exploitation, conservation, and management of all living and nonliving resources within the zone.The National Oceanic and Atmospheric Administration (NOAA) and the U.S. Geological Survey (USGS) will cooperate in the project that will map an area nearly twice the area of U.S. land. USGS responsibilities include definition of seafloor geology and definition of geological processes and resources, including sand and gravel, placers, phosphorites, manganese nodules, cobalt crusts, and sulfides (Eos, March 20, 1984, p. 105). NOAA, meanwhile, will be surveying, mapping, analyzing resources, and managing fisheries.

Cerro de Pasco and other massive sulfide deposits of central Peru

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

Cheney, E.S.

1985-01-01

The famous Cerro de Pasco Pb-Zn-Ag deposit historically has been considered to be hydrothermally derived from an adjacent Tertiary volcanic vent. However, texturally massive pyrite-chert and pyrite-sphalerite-galena in the deposit have the same strike and cross folds as the adjacent pre-Tertiary strata. Both the deposit and the strata are cut by one of the large Longitudinal Faults. Both dikes and pyrite-enargite veins associated with the vent cut the massive sulfides; fragments of massive pyrite occur in the vent. A few examples of laminated pyrite and chert, banded pyrite and chert, banded pyrite and sphalerite, and banded pyrite, sphalerite, and galenamore » are preserved in the massive sulfide portion of the deposit. The deposit has the composition and zoning patterns typical of shale-hosted massive sulfides. Cerro de Pasco probably in part of the pelitic Devonian Excelsior formation. The Colquijirca deposit 8 km to the south and the San Cristobal district 110 km to the south likewise have been considered to be Tertiary volcanic hydrothermal deposits. Colquijirca consists of stratigraphically controlled mantos of layered pyrite, chert and tuff in the Tertiary Calera formation. The mantos of the San Cristobal district are along the upper contact of the pyritic, Permian, Catalina felsic volcanic rocks; some ore consists of laminated pyrite and sphalerite. Tertiary plutons are conspicuously absent at San Cristobal, and the ores are brecciated by Tertiary folding.« less

Evidence of Sulfate-Dependent Anaerobic Methane Oxidation within an Area Impacted by Coalbed Methane-Related Gas Migration

NASA Astrophysics Data System (ADS)

Wolfe, A. L.; Wikin, R. T.

2017-12-01

We evaluated water quality characteristics in the northern Raton Basin of Colorado and documented the response of the Poison Canyon aquifer system several years after upward migration of methane gas occurred from the deeper Vermejo Formation coalbed production zone. Over a 17-month study period, water samples were obtained from domestic water wells and monitoring wells located within the impacted area, and analyzed for 245 constituents, including organic compounds, nutrients, major and trace elements, dissolved gases, and isotopic tracers for carbon, sulfur, oxygen, and hydrogen. Multiple lines of evidence suggest that sulfate-dependent methane biodegradation, which involves the oxidation of methane (CH4) to carbon dioxide (CO2) using sulfate (SO42-) as the terminal electron acceptor, is occurring: (i) consumption of methane and sulfate and production of sulfide and bicarbonate, (ii) methane loss coupled to production of higher molecular weight (C2+) gaseous hydrocarbons, (iii) patterns of 13C enrichment and depletion in methane and dissolved inorganic carbon, and (iv) a systematic shift in sulfur and oxygen isotope ratios of sulfate, indicative of microbial sulfate reduction. Groundwater-methane attenuation is linked to the production of dissolved sulfide, and elevated dissolved sulfide concentrations represent an undesirable secondary water quality impact. The biogeochemical response of the aquifer system has not mobilized naturally occurring trace metals, including arsenic, chromium, cobalt, nickel, and lead, likely due to the microbial production of hydrogen sulfide, which favors stabilization of metals in aquifer solids.

The behaviour of antimony released from surface geothermal features in New Zealand

NASA Astrophysics Data System (ADS)

Wilson, Nathaniel; Webster-Brown, Jenny; Brown, Kevin

2012-12-01

Antimony-rich geothermal features in the Taupo Volcanic Zone (TVZ) of New Zealand's North Island drain directly into surface aquatic environments. The discharge from Champagne Pool, a mixed alkali-chloride/sulfate hot spring at Wai-O-Tapu Geothermal Field, contains up to 194 μg/L Sb. The discharge from Frying Pan Lake, a chloride-sulfate hot spring at Waimangu Geothermal Field, contains up to 21.5 μg/L Sb. At Champagne Pool, downstream concentrations of Sb show distinct diurnal variations, particularly in winter, when concentrations in the early morning were less than half those measured mid-afternoon. Changes in sulfide-sulfate equilibria and direct stibnite oxidation may explain this phenomenon. In the discharge from Frying Pan Lake, Sb exhibits little diurnal variation. Most (> 80%) of the dissolved Sb released from Champagne Pool is removed from solution at Alum Lake, an acid-sulfate hot pool containing elevated levels of dissolved sulfide. Therefore relatively little Sb is discharged into the freshwater drainage in the area. However, in the absence of a sulfide-rich feature at Waimangu, most of the Sb discharged from Frying Pan Lake remains dissolved, and is transported into the freshwater drainage system of Lake Rotomahana. The contrast in Sb behaviour between these two sites confirms the importance of dissolved sulfide and low (< 3) pH conditions in the precipitation and removal of dissolved Sb downstream of geothermal features. Otherwise, largely conservative behaviour can be expected.

Anoxygenic photosynthesis modulated Proterozoic oxygen and sustained Earth's middle age

PubMed Central

Johnston, D. T.; Wolfe-Simon, F.; Pearson, A.; Knoll, A. H.

2009-01-01

Molecular oxygen (O2) began to accumulate in the atmosphere and surface ocean ca. 2,400 million years ago (Ma), but the persistent oxygenation of water masses throughout the oceans developed much later, perhaps beginning as recently as 580–550 Ma. For much of the intervening interval, moderately oxic surface waters lay above an oxygen minimum zone (OMZ) that tended toward euxinia (anoxic and sulfidic). Here we illustrate how contributions to primary production by anoxygenic photoautotrophs (including physiologically versatile cyanobacteria) influenced biogeochemical cycling during Earth's middle age, helping to perpetuate our planet's intermediate redox state by tempering O2 production. Specifically, the ability to generate organic matter (OM) using sulfide as an electron donor enabled a positive biogeochemical feedback that sustained euxinia in the OMZ. On a geologic time scale, pyrite precipitation and burial governed a second feedback that moderated sulfide availability and water column oxygenation. Thus, we argue that the proportional contribution of anoxygenic photosynthesis to overall primary production would have influenced oceanic redox and the Proterozoic O2 budget. Later Neoproterozoic collapse of widespread euxinia and a concomitant return to ferruginous (anoxic and Fe2+ rich) subsurface waters set in motion Earth's transition from its prokaryote-dominated middle age, removing a physiological barrier to eukaryotic diversification (sulfide) and establishing, for the first time in Earth's history, complete dominance of oxygenic photosynthesis in the oceans. This paved the way for the further oxygenation of the oceans and atmosphere and, ultimately, the evolution of complex multicellular organisms. PMID:19805080

Anoxygenic photosynthesis modulated Proterozoic oxygen and sustained Earth's middle age.

PubMed

Johnston, D T; Wolfe-Simon, F; Pearson, A; Knoll, A H

2009-10-06

Molecular oxygen (O(2)) began to accumulate in the atmosphere and surface ocean ca. 2,400 million years ago (Ma), but the persistent oxygenation of water masses throughout the oceans developed much later, perhaps beginning as recently as 580-550 Ma. For much of the intervening interval, moderately oxic surface waters lay above an oxygen minimum zone (OMZ) that tended toward euxinia (anoxic and sulfidic). Here we illustrate how contributions to primary production by anoxygenic photoautotrophs (including physiologically versatile cyanobacteria) influenced biogeochemical cycling during Earth's middle age, helping to perpetuate our planet's intermediate redox state by tempering O(2) production. Specifically, the ability to generate organic matter (OM) using sulfide as an electron donor enabled a positive biogeochemical feedback that sustained euxinia in the OMZ. On a geologic time scale, pyrite precipitation and burial governed a second feedback that moderated sulfide availability and water column oxygenation. Thus, we argue that the proportional contribution of anoxygenic photosynthesis to overall primary production would have influenced oceanic redox and the Proterozoic O(2) budget. Later Neoproterozoic collapse of widespread euxinia and a concomitant return to ferruginous (anoxic and Fe(2+) rich) subsurface waters set in motion Earth's transition from its prokaryote-dominated middle age, removing a physiological barrier to eukaryotic diversification (sulfide) and establishing, for the first time in Earth's history, complete dominance of oxygenic photosynthesis in the oceans. This paved the way for the further oxygenation of the oceans and atmosphere and, ultimately, the evolution of complex multicellular organisms.

Regional variations in the diversity and predicted metabolic potential of benthic prokaryotes in coastal northern Zhejiang, East China Sea

PubMed Central

Wang, Kai; Ye, Xiansen; Zhang, Huajun; Chen, Heping; Zhang, Demin; Liu, Lian

2016-01-01

Knowledge about the drivers of benthic prokaryotic diversity and metabolic potential in interconnected coastal sediments at regional scales is limited. We collected surface sediments across six zones covering ~200 km in coastal northern Zhejiang, East China Sea and combined 16 S rRNA gene sequencing, community-level metabolic prediction, and sediment physicochemical measurements to investigate variations in prokaryotic diversity and metabolic gene composition with geographic distance and under local environmental conditions. Geographic distance was the most influential factor in prokaryotic β-diversity compared with major environmental drivers, including temperature, sediment texture, acid-volatile sulfide, and water depth, but a large unexplained variation in community composition suggested the potential effects of unmeasured abiotic/biotic factors and stochastic processes. Moreover, prokaryotic assemblages showed a biogeographic provincialism across the zones. The predicted metabolic gene composition similarly shifted as taxonomic composition did. Acid-volatile sulfide was strongly correlated with variation in metabolic gene composition. The enrichments in the relative abundance of sulfate-reducing bacteria and genes relevant with dissimilatory sulfate reduction were observed and predicted, respectively, in the Yushan area. These results provide insights into the relative importance of geographic distance and environmental condition in driving benthic prokaryotic diversity in coastal areas and predict specific biogeochemically-relevant genes for future studies. PMID:27917954

Controls on the emplacement and genesis of the MKD5 and Sarah's Find Ni Cu PGE deposits, Mount Keith, Agnew Wiluna Greenstone Belt, Western Australia

NASA Astrophysics Data System (ADS)

Fiorentini, M. L.; Rosengren, N.; Beresford, S. W.; Grguric, B.; Barley, M. E.

2007-11-01

The Mount Keith (MKD5) nickel sulfide deposit is one of the largest komatiite-hosted nickel sulfide deposits in the world; it is hosted by a distinctive spinifex-free, cumulate-rich, ultramafic horizon/unit termed the Mount Keith Ultramafic (MKU). The Mount Keith Ultramafic shows significant variation along its lateral extent. The internal architecture is made up of adcumulate-textured pods and lenses, which are flanked by thinner meso- and orthocumulate-textured units, overlain by pyroxenitic and gabbroic horizons. The lateral and vertical changes in the geometry and internal architecture reflect variations in the lithological association and emplacement conditions along the strike extent of the belt. The chilled margins of the Mount Keith Ultramafic unit contain ˜1,200 ppm Ni. Olivine cumulates average ˜2,500 3,500 ppm Ni, with few exceptions (Ni > 4,500 ppm) reflecting occurrence of minor nickel sulfides, whereas pyroxenites and gabbros generally contain, respectively, ˜1,500 2,000 and ˜100 1,000 ppm Ni. Olivine cumulates generally contain low Cr concentrations (<2,500 ppm Cr), with the rare presence of chromite-rich intervals containing anomalously high values (>5,000 ppm Cr). The internal stratigraphy of the Mount Keith Ultramafic unit may be subdivided into two groups based on rare earth element distribution. The chilled margins and the internal units of the Main Adcumulate domain display LREE-enriched patterns [(La/Sm) n > 1 3] and negative Eu, Hf, Zr, Nb, and Ti anomalies. The internal units in the Western Mineralized Zone generally display flat chondrite-normalized REE patterns and only minor negative Nb anomalies. The pattern of platinum-group element (PGE) distribution varies greatly along the strike extent of the Mount Keith Ultramafic unit. The chilled margins display relatively low absolute concentrations [PGE (excl. Os) ˜16 ppb] and relatively fractionated patterns, with subchondritic Pt/Pd ratios (˜1.5), and superchondritic Pd/Ir ratios (˜3). The PGE trends in the thick adcumulate-textured pods containing widespread nickel sulfide mineralization display positive correlation with sulfide abundance, whereas fractionated pyroxenites and gabbros in the thinner domains display highly depleted PGE concentrations and generally show compatible PGE trends. The nickel sulfide ore typology and style vary greatly along the strike extension of the Mount Keith Ultramafic unit. Basal massive nickel sulfide mineralization (e.g., Sarah’s Find) occurs in the thinner meso- and orthocumulate-textured units, whereas stratabound disseminated nickel sulfide mineralization (e.g., MKD5 Ni Deposit) is hosted in the adcumulate-textured pods. We hypothesize that the very low PGE content of the initial liquid of the Mount Keith Ultramafic unit indicates that the initial magma pulse that penetrated through the dacite host-rock had already equilibrated with sulfides at depth and/or carried entrained immiscible sulfide blebs. We argue that upon emplacement, the intruding magma experienced a significant thermal shock at the contact with water-saturated volcaniclastic breccias. The sudden chilling would have increased the viscosity of the magma, possibly to the point where it was no longer able to sustain the suspension of the immiscible sulfide liquid. As a result, the sulfide blebs coalesced and formed the basal massive sulfide nickel sulfide mineralization at the base of the sill (i.e., Sarah’s Find). Prolonged focused high volume magma flow within the sill resulted in the emplacement of a thick, lens-shaped accumulation of olivine adcumulate. Local variations in intensive parameters other than crustal assimilation (e.g., T, fO2, fS2) may be principally responsible for sulfide supersaturation and controlled the local distribution of stratabound disseminated nickel sulfide mineralization (e.g., MKD5 Ni Deposit), generally localized within the core of the thicker dunite lenses.

Optimization of arsenic removal water treatment system through characterization of terminal electron accepting processes.

PubMed

Upadhyaya, Giridhar; Clancy, Tara M; Brown, Jess; Hayes, Kim F; Raskin, Lutgarde

2012-11-06

Terminal electron accepting process (TEAP) zones developed when a simulated groundwater containing dissolved oxygen (DO), nitrate, arsenate, and sulfate was treated in a fixed-bed bioreactor system consisting of two reactors (reactors A and B) in series. When the reactors were operated with an empty bed contact time (EBCT) of 20 min each, DO-, nitrate-, sulfate-, and arsenate-reducing TEAP zones were located within reactor A. As a consequence, sulfate reduction and subsequent arsenic removal through arsenic sulfide precipitation and/or arsenic adsorption on or coprecipitation with iron sulfides occurred in reactor A. This resulted in the removal of arsenic-laden solids during backwashing of reactor A. To minimize this by shifting the sulfate-reducing zone to reactor B, the EBCT of reactor A was sequentially lowered from 20 min to 15, 10, and 7 min. While 50 mg/L (0.81 mM) nitrate was completely removed at all EBCTs, more than 90% of 300 μg/L (4 μM) arsenic was removed with the total EBCT as low as 27 min. Sulfate- and arsenate-reducing bacteria were identified throughout the system through clone libraries and quantitative PCR targeting the 16S rRNA, dissimilatory (bi)sulfite reductase (dsrAB), and dissimilatory arsenate reductase (arrA) genes. Results of reverse transcriptase (RT) qPCR of partial dsrAB (i.e., dsrA) and arrA transcripts corresponded with system performance. The RT qPCR results indicated colocation of sulfate- and arsenate-reducing activities, in the presence of iron(II), suggesting their importance in arsenic removal.

Combustion dynamics of low vapour pressure nanofuel droplets

NASA Astrophysics Data System (ADS)

Pandey, Khushboo; Chattopadhyay, Kamanio; Basu, Saptarshi

2017-07-01

Multiscale combustion dynamics, shape oscillations, secondary atomization, and precipitate formation have been elucidated for low vapour pressure nanofuel [n-dodecane seeded with alumina nanoparticles (NPs)] droplets. Dilute nanoparticle loading rates (0.1%-1%) have been considered. Contrary to our previous studies of ethanol-water blend (high vapour pressure fuel), pure dodecane droplets do not exhibit internal boiling after ignition. However, variation in surface tension due to temperature causes shape deformations for pure dodecane droplets. In the case of nanofuels, intense heat release from the enveloping flame leads to the formation of micron-size aggregates (of alumina NPS) which serve as nucleation sites promoting heterogeneous boiling. Three boiling regimes (A, B, and C) have been identified with varying bubble dynamics. We have deciphered key mechanisms responsible for the growth, transport, and rupture of the bubbles. Bubble rupture causes ejections of liquid droplets termed as secondary atomization. Ejection of small bubbles (mode 1) resembles the classical vapour bubble collapse mechanism near a flat free surface. However, large bubbles induce severe shape deformations as well as bulk oscillations. Rupture of large bubbles results in high speed liquid jet formation which undergoes Rayleigh-Plateau tip break-up. Both modes contribute towards direct fuel transfer from the droplet surface to flame envelope bypassing diffusion limitations. Combustion lifetime of nanofuel droplets consequently has two stages: stage I (where bubble dynamics are dominant) and stage II (formation of gelatinous mass due to continuous fuel depletion; NP agglomeration). In the present work, variation of flame dynamics and spatio-temporal heat release (HR) have been analysed using high speed OH* chemiluminescence imaging. Fluctuations in droplet shape and flame heat release are found to be well correlated. Droplet flame is bifurcated in two zones (I and II). Flame response is manifested in two frequency ranges: (i) buoyant flame flickering and (ii) auxiliary frequencies arising from high intensity secondary ejections due to bubble ruptures. Addition of alumina NPs enhances the heat absorption rate and ensures the rapid transfer of fuel parcels (detached daughter droplets) from droplet surface to flame front through secondary ejections. Therefore, average HR shows an increasing trend with particle loading rate (PLR). The perikinetic agglomeration model is used to explain the formation of gelatinous sheath during the last phase of droplet burning. Gelatinous mass formed results in bubble entrapment. SEM images of combustion precipitates show entrapped bubble cavities along with surface and sub-surface blowholes. Morphology of combustion precipitate shows a strong variation with PLRs. We have established the coupling mechanisms among heat release, shape oscillations, and secondary atomizations that underline the combustion behaviour of such low vapour pressure nanofuels.

Aerial ULV application of permethrin against adult mosquitoes over open field and medium density canopy habitat in a hot-temperate zone

USDA-ARS?s Scientific Manuscript database

Although aerial ULV application of adulticides is a common adult mosquito control strategy, not enough is known about the fate of the pesticide or its efficacy over different habitats. Dye labeling of droplets is used to evaluate ULV applications, and, by inference, their efficacy. Placement of cage...

The Tuscarora Au-Ag district: Eocene volcanic-hosted epithermal deposits in the Carlin gold region, Nevada

USGS Publications Warehouse

Castor, S.B.; Boden, D.R.; Henry, C.D.; Cline, J.S.; Hofstra, A.H.; McIntosh, W.C.; Tosdal, R.M.; Wooden, J.P.

2003-01-01

The Tuscarora mining district contains the oldest and the only productive Eocene epithermal deposits in Nevada. The district is a particularly clear example of association of low-sulfidation deposits with igneous activity and structure, and it is unusual in that it consists of two adjoining but physically and chemically distinct types of low-sulfidation deposits. Moreover, Tuscarora deposits are of interest because they formed contemporaneously with nearby, giant Carlin-type gold deposits. The Tuscarora deposits formed within the 39.9 to 39.3 Ma Tuscarora volcanic field, along and just outside the southeastern margin of the caldera-like Mount Blitzen volcanic center. Both deposit types formed at 39.3 Ma, contemporaneous with the only major intrusive activity in the volcanic field. No deposits are known to have formed during any of the intense volcanic phases of the field. Intrusions were the apparent heat source, and structures related to the Mount Blitzen center were conduits for hydrothermal circulation. The ore-forming fluids interacted dominantly with Eocene igneous rocks. The two deposit types occur in a northern silver-rich zone that is characterized by relatively high Ag/Au ratios (110-150), narrow alteration zones, and quartz and carbonate veins developed mostly in intrusive dacite, and in a southern gold-rich zone that is typified by relatively low Ag/Au ratios (4-14), more widespread alteration, and quartz-fissure and stockwork veins commonly developed in tuffaceous sedimentary rocks. The deposit types have similar fluid inclusion and Pb and S isotope characteristics but different geochemical signatures. Quartz veins from both zones have similar thermal and paragenetic histories and contain fluid inclusions that indicate that fluids cooled from between 260?? and 230??C to less than 200??C. Fluid boiling may have contributed to precious-metal deposition. Veins in both zones have relatively high As and Sb and low Bi, Te, and W. The silver zone has high Ca, Pb, Mn, Zn, Cd, Tl, and Se. The gold zone has high Hg and Mo. A few samples from an area of overlap between the two zones share chemical characteristics of both deposit types. The deposit types could represent a single zoned or evolving system in which hydrothermal fluids rose along structures within the silver zone, preferentially deposited Ag and base metals, and then spread into the gold zone. Alternatively, the deposit types could represent two distinct but temporally indistinguishable hydrothermal cells that only narrowly overlapped spatially. As noted in previous studies, the hydrothermal fluids that generated the Tuscarora and other epithermal deposits could have evolved from Carlin-type fluids by boiling and mixing with meteoric water. If so, the Tuscarora deposit may represent epithermal conditions above Carlin-type deposits, and Carlin-type deposits may lie beneath the district.

Search for the source of an apparent interfacial resistance to mass transfer of CnEm surfactants to the water/oil interface.

PubMed

Huston, Kyle J; Kiemen, Ashley; Larson, Ronald G

2018-06-12

Experiments have shown that relaxation of oil/water interfacial tension by adsorption of alkyl ethoxylate surfactants from water onto an oil droplet is delayed relative to diffusion-controlled adsorption. We examine possible causes of this delay, and we show that several are implausible. We find that re-dissolution of the surfactant in the oil droplet cannot explain the apparent interfacial resistance at short times, because the interface will preferentially fill before any such re-dissolution occurs. We also perform umbrella sampling with molecular dynamics simulation and do not find any evidence of a free energy barrier or low-diffusivity zone near the interface. Nor do we find evidence from simulation that pre-micellar aggregation slows diffusion enough to cause the observed resistance to interfacial adsorption. We are therefore unable to pinpoint the cause of the resistance, but we suggest that "dead time" associated with the experimental method could be responsible - specifically a local depletion of surfactant by the ejected droplet when creating the fresh interface between the oil and water.

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

Cayumil, R.; Khanna, R., E-mail: ritakhanna@unsw.edu.au; Ikram-Ul-Haq, M.

Highlights: • Recycling and material recovery from waste printed circuit boards is very complex. • Thermoset polymers, ceramics and metals are present simultaneously in waste PCBs. • Heat treatment of PCBs was carried out at 1150 °C under inert conditions. • Various metallic phases could be segregated out as copper based metallic droplets. • Carbon and ceramics residues can be further recycled in a range of applications. - Abstract: The rapid consumption and obsolescence of electronics have resulted in e-waste being one of the fastest growing waste streams worldwide. Printed circuit boards (PCBs) are among the most complex e-waste, containingmore » significant quantities of hazardous and toxic materials leading to high levels of pollution if landfilled or processed inappropriately. However, PCBs are also an important resource of metals including copper, tin, lead and precious metals; their recycling is appealing especially as the concentration of these metals in PCBs is considerably higher than in their ores. This article is focused on a novel approach to recover copper rich phases from waste PCBs. Crushed PCBs were heat treated at 1150 °C under argon gas flowing at 1 L/min into a horizontal tube furnace. Samples were placed into an alumina crucible and positioned in the cold zone of the furnace for 5 min to avoid thermal shock, and then pushed into the hot zone, with specimens exposed to high temperatures for 10 and 20 min. After treatment, residues were pulled back to the cold zone and kept there for 5 min to avoid thermal cracking and re-oxidation. This process resulted in the generation of a metallic phase in the form of droplets and a carbonaceous residue. The metallic phase was formed of copper-rich red droplets and tin-rich white droplets along with the presence of several precious metals. The carbonaceous residue was found to consist of slag and ∼30% carbon. The process conditions led to the segregation of hazardous lead and tin clusters in the metallic phase. The heat treatment temperature was chosen to be above the melting point of copper; molten copper helped to concentrate metallic constituents and their separation from the carbonaceous residue and the slag. Inert atmosphere prevented the re-oxidation of metals and the loss of carbon in the gaseous fraction. Recycling e-waste is expected to lead to enhanced metal recovery, conserving natural resources and providing an environmentally sustainable solution to the management of waste products.« less

Découverte et signification d'une paragenèse à ilménite zincifère dans les métapélites des Jebilet centrales (Maroc)Occurrence and significance of zincian ilmenite in low-pressure metapelites from central Jebilet (Morocco)

NASA Astrophysics Data System (ADS)

Essaifi, Abderrahim; Ballèvre, Michel; Marignac, Christian; Capdevila, Ramon

2001-10-01

A zincian ilmenite paragenesis is found in metapelites from a contact metamorphic zone (central Jebilet, Morocco) induced by the emplacement of microgranitic intrusions. The zincian ilmenite is mainly preserved in syntectonic andalusite porphyroblasts. The growth of zincian ilmenite is related either to sphalerite breakdown during prograde metamorphism, or to the pervasive flow of a mineralizing fluid within the metapelites. The chlorine-rich fluid carried zinc and other metals leached in the microgranites, during its flow to discharge zones which were probably the Jebilet sulfide deposits.

Hypoxic-Ischemic Encephalopathy-Associated Liver Fatty Degeneration and the Effects of Therapeutic Hypothermia in Newborn Piglets.

PubMed

Kubo, Hiroyuki; Shimono, Ryuichi; Nakamura, Shinji; Koyano, Kosuke; Jinnai, Wataru; Yamato, Satoshi; Yasuda, Saneyuki; Nakamura, Makoto; Tanaka, Aya; Fujii, Takayuki; Kanenishi, Kenji; Chiba, Yoichi; Miki, Takanori; Kusaka, Takashi; Ueno, Masaki

2017-01-01

Although liver can be injured under the hypoxic-ischemic encephalopathy (HIE) condition, there is currently no histopathological evidence. Therapeutic hypothermia is used to protect the brain; however, the therapeutic potential for concomitant liver injury is unknown. This study aimed to histopathologically prove HIE-associated liver injury and to investigate the influence of therapeutic hypothermia in a newborn piglet HIE model. Eighteen newborn piglets were divided into 3 groups: control (n = 4), HIE (n = 8), and therapeutic hypothermia (n = 6) groups. The hypoxic insult was induced by decreasing the fraction of inspiratory oxygen from 21 to 2-4% over 40 min while monitoring cerebral blood volume and cerebral hemoglobin oxygen saturation. For therapeutic hypothermia, whole-body cooling at 33-34°C was administered for 24 h after the hypoxic insult. We hematologically and histopathologically investigated the liver injury in all groups. Alanine transaminase and lactate dehydrogenase levels in the HIE group were significantly elevated compared with those in the control group. Micro-lipid droplet accumulation in the periportal zone, but not in the perivenous zone, was significantly greater in the HIE group than in the control group and significantly smaller in the therapeutic hypothermia group than in the HIE group. We demonstrated that micro-lipid droplet accumulation in the cytoplasm of hepatocytes in the periportal zone occurs under the HIE condition and that this accumulation is suppressed by therapeutic hypothermia. © 2016 S. Karger AG, Basel.

Geology and structural evolution of the Muruntau gold deposit, Kyzylkum desert, Uzbekistan

USGS Publications Warehouse

Drew, L.J.; Berger, B.R.; Kurbanov, N.K.

1996-01-01

The Muruntau gold deposit in the Kyzylkum desert of Uzbekistan is the largest single deposit (??? 1100 tonnes of gold) of the class of low-sulfide syndeformation/synigenous gold deposits formed in the brittle/ductile transition zone of the crust within transpressional shear zones. Hosted by the Cambrian to Ordovician Besopan Suite, the ores were deposited in pre-existing thrust-fault- and metamorphism-related permeabilities and in synmineralization dilational zones created in a large fault-related fold. The Besopan Suite is a 5,000-m-thick sequence of turbiditic siltstones, shales and sandstones. The ore is primarily localized at the base of the Besopan-3 unit, which is a 2,000-m-thick series of carbonaceous shales, siltstones, sandstones and cherts. Initial gold deposition took place within the Sangruntau-Tamdytau shear zone, which was developed along the stratigraphic contact between the Besopan-3 and Besopan-4 units. During the mineralization process, folding of the Besopan Suite and a left-step adjustment in the Sangruntau-Tamdytau shear zone were caused by two concurrent events: (1) the activation of the left-lateral Muruntau-Daugyztau shear zone that developed at nearly a 90?? angle to the preceding shear zone and (2) the intrusion of granitoid plutons. These structural events also resulted in the refocusing of hydrothermal fluid flow into new zones of permeability.

Spatial and temporal zoning of hydrothermal alteration and mineralization in the Sossego iron oxide-copper-gold deposit, Carajás Mineral Province, Brazil: Paragenesis and stable isotope constraints

USGS Publications Warehouse

Monteiro, Lena V.S.; Xavier, R.P.; Carvalho, E.R.; Hitzman, M.W.; Johnson, C.A.; Souza, Filho C.R.; Torresi, I.

2008-01-01

The Sossego iron oxide–copper–gold deposit (245 Mt @ 1.1% Cu, 0.28 g/t Au) in the Carajás Mineral Province of Brazil consists of two major groups of orebodies (Pista–Sequeirinho–Baiano and Sossego–Curral) with distinct alteration assemblages that are separated from each other by a major high angle fault. The deposit is located along a regional WNW–ESE-striking shear zone that defines the contact between metavolcano–sedimentary units of the ∼2.76 Ga Itacaiúnas Supergroup and tonalitic to trondhjemitic gneisses and migmatites of the ∼2.8 Ga Xingu Complex. The deposit is hosted by granite, granophyric granite, gabbro, and felsic metavolcanic rocks. The Pista–Sequeirinho–Baiano orebodies have undergone regional sodic (albite–hematite) alteration and later sodic–calcic (actinolite-rich) alteration associated with the formation of massive magnetite–(apatite) bodies. Both these alteration assemblages display ductile to ductile–brittle fabrics. They are cut by spatially restricted zones of potassic (biotite and potassium feldspar) alteration that grades outward to chlorite-rich assemblages. The Sossego–Curral orebodies contain weakly developed early albitic alteration and very poorly developed subsequent calcic–sodic alteration. These orebodies contain well-developed potassic alteration assemblages that were formed during brittle deformation that resulted in the formation of breccia bodies. Breccia matrix commonly displays coarse mineral infill suggestive of growth into open space. Sulfides in both groups of deposits were precipitated first with potassic alteration and more importantly with a later assemblage of calcite–quartz–epidote–chlorite. In the Sequeirinho orebodies, sulfides range from undeformed to deformed; sulfides in the Sossego–Curral orebodies are undeformed. Very late, weakly mineralized hydrolytic alteration is present in the Sossego/Currral orebodies. The sulfide assemblage is dominated by chalcopyrite with subsidiary siegenite, and millerite. Pyrrhotite and pyrite are minor constituents of ore in the Sequerinho orebodies while pyrite is relatively abundant in the Sossego–Curral bodies. Oxygen isotope partitioning between mineral pairs constrains temperatures in the deposit spatially and through time. In the Sequeirinho orebody, the early sodic–calcic alteration stage was characterized by temperatures exceeding 500°C and δ18OH2O values for the alteration fluid of 6.9 ± 0.9‰. Temperature declines outward and upward from the zone of most intense alteration. Paragenetically later copper–gold mineralization displays markedly lower temperatures (<300°C) and was characterized by the introduction of 18O-depleted hydrothermal fluids −1.8 ± 3.4‰. The calculated δDH2O and δ18OH2O values suggest that the fluids that formed the early calcic–sodic alteration assemblage were of formational/metamorphic or magmatic origin. The decrease of δ18OH2O values through time may reflect influx of surficially derived waters during later alteration and mineralization events. Influx of such fluids could be related to episodic fluid overpressure, resulting in dilution and cooling of the metalliferous fluid, causing deposition of metals transported as metal chloride complexes.

Origin and evolution of mineralizing fluids and exploration of the Cerro Quema Au-Cu deposit (Azuero Peninsula, Panama) from a fluid inclusion and stable isotope perspective

USGS Publications Warehouse

Corral, Isaac; Cardellach, Esteve; Corbella, Merce; Canals, Angels; Griera, Albert; Gomez-Gras, David; Johnson, Craig A.

2017-01-01

Cerro Quema is a high sulfidation epithermal Au-Cu deposit with a measured, indicated and inferred resource of 35.98 Mt. @ 0.77 g/t Au containing 893,600 oz. Au (including 183,930 oz. Au equiv. of Cu ore). It is characterized by a large hydrothermal alteration zone which is interpreted to represent the lithocap of a porphyry system. The innermost zone of the lithocap is constituted by vuggy quartz with advanced argillic alteration locally developed on its margin, enclosed by a well-developed zone of argillic alteration, grading to an external halo of propylitic alteration. The mineralization occurs in the form of disseminations and microveinlets of pyrite, chalcopyrite, enargite, tennantite, and trace sphalerite, crosscut by quartz, barite, pyrite, chalcopyrite, sphalerite and galena veins.Microthermometric analyses of two phase (L + V) secondary fluid inclusions in igneous quartz phenocrysts in vuggy quartz and advanced argillically altered samples indicate low temperature (140–216 °C) and low salinity (0.5–4.8 wt% NaCl eq.) fluids, with hotter and more saline fluids identified in the east half of the deposit (Cerro Quema area).Stable isotope analyses (S, O, H) were performed on mineralization and alteration minerals, including pyrite, chalcopyrite, enargite, alunite, barite, kaolinite, dickite and vuggy quartz. The range of δ34S of sulfides is from − 4.8 to − 12.7‰, whereas δ34S of sulfates range from 14.1 to 17.4‰. The estimated δ34SΣS of the hydrothermal fluid is − 0.5‰. Within the advanced argillic altered zone the δ34S values of sulfides and sulfates are interpreted to reflect isotopic equilibrium at temperatures of ~ 240 °C. The δ18O values of vuggy quartz range from 9.0 to 17.5‰, and the δ18O values estimated for the vuggy quartz-forming fluid range from − 2.3 to 3.0‰, indicating that it precipitated from mixing of magmatic fluids with surficial fluids. The δ18O of kaolinite ranges from 12.7 to 18.1‰ and δD from − 103.3 to − 35.2‰, whereas the δ18O of dickite varies between 12.7 and 16.3‰ and δD from − 44 to − 30. Based on δ18O and δD, two types of kaolinite/dickite can be distinguished, a supergene type and a hypogene type. Combined, the analytical data indicate that the Cerro Quema deposit formed from magmatic-hydrothermal fluids derived from a porphyry copper-like intrusion located at depth likely towards the east of the deposit. The combination of stable isotope geochemistry and fluid inclusion analysis may provide useful exploration vectors for porphyry copper targets in the high sulfidation/lithocap environment.

Oscillations and uniaxial mechanochemical waves in a model of an active poroelastic medium: Application to deformation patterns in protoplasmic droplets of Physarum polycephalum

NASA Astrophysics Data System (ADS)

Alonso, Sergio; Strachauer, Ulrike; Radszuweit, Markus; Bär, Markus; Hauser, Marcus J. B.

2016-04-01

Self-organization in cells often manifests itself in oscillations and waves. Here, we address deformation waves in protoplasmic droplets of the plasmodial slime mould Physarum polycephalum by modelling and experiments. In particular, we extend a one-dimensional model that considered the cell as a poroelastic medium, where active tension caused mechanochemical waves that were regulated by an inhibitor (Radszuweit et al., 2013). Our extension consists of a simple, qualitative chemical reaction-diffusion model (Brusselator) that describes the regulation of the inhibitor by another biochemical species. The biochemical reaction enhances the formation of mechanochemical waves if the reaction rates and input concentrations are near or inside an oscillatory regime. The period of the waves is found to be controlled by the characteristic oscillation period, whereas their wavelength is set by mechanical parameters. The model also allows for a systematic study of the chemical activity at the onset of mechanochemical waves. We also present examples for pattern formation in protoplasmic droplets of Physarum polycephalum including global oscillations where the central region of the droplets is in antiphase to the boundary zone, as well as travelling and standing wave-like uniaxial patterns. Finally, we apply our model to reproduce these experimental results by identifying the active tension inhibitor with the intracellular calcium concentration in the Physarum droplets and by using parameter values from mechanical experiments, respectively knowledge about the properties of calcium oscillations in Physarum. The simulation results are then found to be in good agreement with the experimental observations.

Cyanobacterial mats: Microanalysis of community metabolism

NASA Technical Reports Server (NTRS)

Cohen, Y.; Bermudes, D.; Fischer, U.; Haddad, R.; Prufert, L.; Scheulderman-Suylen, T.; Shaw, T.

1985-01-01

The microbial communities in two sites were studied using several approaches: (1) light microscopy; (2) the measurement of microprofiles of oxygen and sulfide at the surface of the microbial mat; (3) the study of diurnal variation of oxygen and sulfides; (4) in situ measurement of photosynthesis and sulfate reduction and study of the coupling of these two processes; (5) measurement of glutathione in the upper layers of the microbial mat as a possible oxygen quencher; (6) measurement of reduced iron as a possible intermediate electron donor along the established redoxcline in the mats; (7) measurement of dissolved phosphate as an indicator of processes of break down of organic matter in these systems; and (8) measurement of carbon dioxide in the interstitial water and its delta C-13 in an attempt to understand the flow of CO2 through the systems. Microbial processes of primary production and initial degradation at the most active zone of the microbial mat were analyzed.

High-temperature oxidation/corrosion of iron-based superalloys

NASA Technical Reports Server (NTRS)

Lemkey, F. D.; Smeggil, J. G.; Bailey, R. S.; Schuster, J. C.; Nowotny, H.

1987-01-01

The oxidation and sulfidation of several novel iron-base superalloys were evaluated in high-temperature cyclic tests. The experimental austenitic alloys examined were modifications of NASAUT-4GA which were developed for Stirling-engine application. The weight gains and resulting surface scales were measured and analyzed. Mixed oxide scales were found to form on all specimens exposed above 871 C. The build-up of these scales led to a depletion of Mn and Cr in a zone adjacent to the oxides. In addition, the initial oxidation of the Fe-rich alloy was inhibited by a thin but tenacious Si layer which formed at the interface between oxides and the parent layer. Sulfidation tests using Na2SO4 coatings resulted in the formation of a protective spinel and alpha-Fe2O3 phases. Preferential attack of the carbide phase by hydrogen was not observed after 350 h at 871 C.

Short-term effects of salinity reduction and drainage on salt-marsh biogeochemical cycling and Spartina (Cordgrass) production

USGS Publications Warehouse

Portnoy, J.W.; Valiela, I.

1997-01-01

To assess the biogeochemical effects of tidal restrictions on salt-marsh sulfur cycling and plant growth, cores of short-form Spartina alterniflora peat were desalinated and kept either waterlogged or drained in greenhouse microcosms. Changes in net Spartina production, and porewater and solid phase chemistry of treated cores were compared to natural conditions in the field collection site over a 21-mo period. Net production among treatments increased significantly in drained and waterlogged peat compared to field conditions during the first growing season. Constantly high sulfide in waterlogged cores accompanied reduced plant growth. Aeration invigorated growth in drained cores but led to oxidization of sulfide minerals and to lowered pH. During the second growing season, growth declined in the drained treatment, probably because of acidification and decreased dissolved inorganic nitrogen. Results are pertinent to the success of current wetland protection and restoration activities in the coastal zone.

Trace elements in tourmalines from massive sulfide deposits and tourmalinites: Geochemical controls and exploration applications

USGS Publications Warehouse

Griffin, W.L.; Slack, J.F.; Ramsden, A.R.; Win, T.T.; Ryan, C.G.

1996-01-01

Trace element contents of tourmalines from massive sulfide deposits and tourmalinites have been determined in situ by proton microprobe; >390 analyses were acquired from 32 polished thin sections. Concentrations of trace elements in the tourmalines vary widely, from <40 to 3,770 ppm Mn, <4 to 1,800 ppm Ni, <2 to 1,430 ppm Cu, <9 to 4,160 ppm Zn, 3 to 305 ppm Ga, <6 to 1,345 ppm Sr, <10 to 745 ppm Sn, <49 to 510 ppm Ba, and <3 to 4,115 ppm Pb. Individual grains and growth zones are relatively homogeneous, suggesting that these trace elements are contained within the crystal structure of the tourmaline, and are not present in inclusions. The highest base metal contents are in ore-related tourmaline samples from Kidd Creek (Ontario), Broken Hill (Australia), and Sazare (Japan). Tourmaline data from these and many other massive sulfide deposits cluster by sample and display broadly linear trends on Zn vs. Fe plots, suggesting chemical control by temperature and hydrothermal and/or metamorphic fluid-mineral equilibria. Significant Ni occurs only in samples from the Kidd Creek Cu-Zn-Pb-Ag deposit, which is associated with a large footwall ultramafic body. An overall antithetic relationship between Zn and Ni probably reflects fluid source controls. Mn is correlated with Fe in tourmalines from barren associations, and possibly in some tourmalines associated with sulfide vein deposits. Sn increases systematically with Fe content irrespective of association; the highest values are found in schorls from granites. Other trace elements are generally uncorrelated with major element concentrations (e.g., Sr-Ca). Base metal proportions in the tourmalines show systematic patterns on ternary Cu-Pb-Zn diagrams that correlate well with the major commodity metals in the associated massive sulfide deposits. For example, data for tourmalines from Cu-Zn deposits (e.g., Ming mine, Newfoundland) fall mainly on the Cu-Zn join, whereas those from Pb-Zn deposits (e.g., Broken Hill, Australia) plot on the Pb-Zn join; no data fall on the Cu-Pb join, consistent with the lack of this metal association in massive sulfide deposits. The systematic relationship between base metal proportions in the tourmalines and the metallogeny of the host massive sulfide deposits indicates that the analyzed tourmalines retain a strong chemical signature of their original hydrothermal formation, in spite of variable metamorphic recrystallization. Such trace element patterns in massive sulfide tourmalines may be useful in mineral exploration, specifically for the evaluation of tourmaline concentrations in rocks, soils, and stream sediments.

Sulfide saturation history of the Stillwater Complex, Montana: chemostratigraphic variation in platinum group elements

NASA Astrophysics Data System (ADS)

Keays, Reid R.; Lightfoot, Peter C.; Hamlyn, Paul R.

2012-01-01

A platinum group element (PGE) investigation of a 5.3 km-thick stratigraphic section of the Stillwater Complex, Montana was undertaken to refine and test a geochemical technique to explore for platiniferous horizons in layered mafic/ultramafic complexes. PGE, Au, major, and trace elements were determined in 92 samples from outcrops along traverses in the Chrome Mountain and Contact Mountain areas in the western part of the Stillwater Complex where the J-M reef occurs ˜1,460 m above the floor of the intrusion. A further 29 samples from a drill hole cored in the immediate vicinity of the J-M reef were analyzed to detail compositional variations directly above and below the J-M reef. Below the J-M reef, background concentrations of Pt (10 ppb) and Pd (7 ppb) are features of peridotites with intermediate S concentrations (mostly 100-200 ppm) and rocks from the Bronzitite, Norite I, and Gabbronorite I zones (mostly <100 ppm S). A sustained increase in S abundance commences at the J-M reef and continues to increase and peaks in the center of the 600 m-thick middle banded series. Over this same interval, Pt, Pd, and Au are initially elevated and then decrease in the order Pd > Pt > Au. Within the middle and upper banded series, S abundances fluctuate considerably, but exhibit an overall upward increase. The behavior of these elements records periodic sulfide saturation during deposition of the Peridotite zone, followed by crystallization under sulfide-undersaturated conditions until saturation is achieved at the base of the J-M reef. Following formation of the reef, sulfide-saturated conditions persisted throughout the deposition of most of the remaining Lower Layered Series. This resulted in a pronounced impoverishment in PGE abundance in the remaining magma, a condition that continued throughout deposition of the remainder of a succession, which is characterized by very low Pt (1.5 ppb) and Pd (0.7 ppb) abundances. Because only unmineralized rock was selected for study in the 5.3 km-thick section, the results provide an unbiased picture of the variation in background PGE levels during crystallization of the Stillwater Complex. In contrast, the variations in the drill core samples through the reef provide a detailed record of ore formation. Plots of Pt, Pd, Pd/S, and Pt + Pd as a function of stratigraphic height in the intrusion show that the location of the J-M reef is defined by an abrupt change in these concentrations and ratios. Although this is the most abrupt change, three other anomalies in PGE abundance and ratios are apparent in the profiles and coincide with known laterally extensive sub-economic sulfide concentrations above the J-M reef. The uppermost of these is the PGE-bearing Picket Pin sulfide horizon. The relative ease with which mineralized horizons can be pinpointed in these diagrams indicates that a similar approach could be used in exploration programs in other ultramafic/mafic intrusions. Our observations exclude the possibilities of either magma mixing within the Stillwater chamber or the fluxing of a volatile-rich fluid as the mechanisms responsible for the genesis of the J-M reef. Rather, our data indicate that the J-M reef formed from a parental magma that was strongly enriched in PGE; this magma likely formed at depth below the Stillwater magma chamber by the interaction of the parental magma with S-rich meta-sedimentary rocks, followed by the re-dissolution of these sulfides in the Stillwater magma.

Zoned Cr, Fe-spinel from the La Perouse layered gabbro, Fairweather Range, Alaska

USGS Publications Warehouse

Czamanske, G.K.; Himmelberg, G.R.; Goff, F.E.

1976-01-01

Zoned spinel of unusual composition and morphology has been found in massive pyrrhotite-chalcopyrite-pent-landite ore from the La Perouse layered gabbro intrusion in the Fairweather Range, southeastern Alaska. The spinel grains show continuous zoning from cores with up to 53 wt.% Cr2O3 to rims with less than 11 wt.% Cr2O3. Their composition is exceptional because they contain less than 0.32 wt.% MgO and less than 0.10 wt.% Al2O3 and TiO2. Also notable are the concentrations of MnO and V2O3, which reach 4.73 and 4.50 wt.%, respectively, in the cores. The spinel is thought to have crystallized at low oxygen fugacity and at temperatures above 900??C, directly from a sulfide melt that separated by immiscibility from the gabbroic parental magma. ?? 1976.

Generation of copper rich metallic phases from waste printed circuit boards.

PubMed

Cayumil, R; Khanna, R; Ikram-Ul-Haq, M; Rajarao, R; Hill, A; Sahajwalla, V

2014-10-01

The rapid consumption and obsolescence of electronics have resulted in e-waste being one of the fastest growing waste streams worldwide. Printed circuit boards (PCBs) are among the most complex e-waste, containing significant quantities of hazardous and toxic materials leading to high levels of pollution if landfilled or processed inappropriately. However, PCBs are also an important resource of metals including copper, tin, lead and precious metals; their recycling is appealing especially as the concentration of these metals in PCBs is considerably higher than in their ores. This article is focused on a novel approach to recover copper rich phases from waste PCBs. Crushed PCBs were heat treated at 1150°C under argon gas flowing at 1L/min into a horizontal tube furnace. Samples were placed into an alumina crucible and positioned in the cold zone of the furnace for 5 min to avoid thermal shock, and then pushed into the hot zone, with specimens exposed to high temperatures for 10 and 20 min. After treatment, residues were pulled back to the cold zone and kept there for 5 min to avoid thermal cracking and re-oxidation. This process resulted in the generation of a metallic phase in the form of droplets and a carbonaceous residue. The metallic phase was formed of copper-rich red droplets and tin-rich white droplets along with the presence of several precious metals. The carbonaceous residue was found to consist of slag and ∼30% carbon. The process conditions led to the segregation of hazardous lead and tin clusters in the metallic phase. The heat treatment temperature was chosen to be above the melting point of copper; molten copper helped to concentrate metallic constituents and their separation from the carbonaceous residue and the slag. Inert atmosphere prevented the re-oxidation of metals and the loss of carbon in the gaseous fraction. Recycling e-waste is expected to lead to enhanced metal recovery, conserving natural resources and providing an environmentally sustainable solution to the management of waste products. Copyright © 2014 Elsevier Ltd. All rights reserved.

GEOLOGY, SULFUR ISOTOPES AND THE ORIGIN OF THE HEATH STEELE ORE DEPOSITS, NEWCASTLE, N.B., CANADA

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

Dechow, E.

The Heath Steele mine is located 35 miles northwest of Newcastle, New Brunswick, Canada. Middle Ordovician Tetagouche Group rocks, consisting of siliceous and basic volcanic rocks, and fine-grained quartz sericite schists and porphyry, have been folded into a steeply plunging recumbent anticline. The ore deposits of zinc, lead, and copper are associated with minor folding and/or sheared dilatent zones at or near the contact between porphyry and fine-grained senicitic schist. Mineralogically the sulfide bodies consist of early, euhedral arsenopyrite, magnetite, and pyrite, followed by interstitial pyrrhotite, sphalerite, chalcopyrite and galena. Minor minerals are ternantite-tetrahedrite, bismuthinite, marcasite, hematite, and some graphite.more » Supergene minerals consist of chalcocite, covellite, and marcasite with a little native silver. Little hypogene replacement has taken place between the minerals, which show a "porphyritic" texture. Sulfur isotope ratios were determined for over 150 sulfide and sulfate specimens from five of the seven ore bodies, and from granite, acid and basic volcanics, porphyry, and sediments. The results indicate that there is no detectable fractionation either during hypogene mineralization or supergene enrichment. The spread (21.82 to 22.02) covered by the ratios is narrow, and suggestive of a well homogenized source of mineral solutions. The enrichment of S/sup 34/ in the ore sulfides and the presence of graphite, evident from mineralographic studies and mass spectrometric analysis, suggests reduction of original sulfates (known to be enriched in S/sup 34/) by organic carbon at temperatures in excess of 500 deg C. A calculation based on the isotopic exchange reaction between sulfide and sulfate under equilibrium conditions and the spread of the ratios indicates a temperature of 700 to 800 deg C for the source. Finally the ratios determined for sulfides in a gneissic granite close to Heath Steele have the same ratio as the ore. These factors are considered to be diagnostic of a magmatic hydrothermal origin for the orp deposits. It is believed that an original source bed has been buried until suitable temperatures were reached to cause granitization, reduction of sulfates, and mobilization of the resulting sulfides to form ore deposits at favorable loci. (auth)« less

Interplay of crystal fractionation, sulfide saturation and oxygen fugacity on the iron isotope composition of arc lavas: An example from the Marianas

NASA Astrophysics Data System (ADS)

Williams, H. M.; Prytulak, J.; Woodhead, J. D.; Kelley, K. A.; Brounce, M.; Plank, T.

2018-04-01

Subduction zone systems are central to a multitude of processes from the evolution of the continental crust to the concentration of metals into economically viable deposits. The interplay between oxygen fugacity, sulfur saturation, fluid exsolution and fractionating mineral assemblages that gives rise to typical arc magma chemical signatures is, however, still poorly understood and novel geochemical approaches are required to make further progress. Here we examine a well-characterized suite of arc lavas from the Marianas (W. Pacific) for their stable Fe isotope composition. In agreement with previous work and mass balance considerations, contributions from sediments and/or fluids are shown to have negligible effect on Fe isotopes. Instead, we focus on disentangling processes occurring during basalt through dacite differentiation using a sample suite from the island of Anatahan. Anatahan whole rock Fe isotope compositions (δ57Fe) range from -0.05 ± 0.05 to 0.17 ± 0.03 (2 S.D.)‰. A fractionation model is constructed, where three distinct stages of differentiation are required to satisfy the combined major and trace element and isotopic observations. In particular, the sequestration of isotopically heavy Fe into magnetite and isotopically light Fe into sulfide melts yields important constraints. The data require that lavas are first undersaturated with respect to crystalline or molten sulfide, followed by the crystallisation of magnetite, which then triggers late sulfide saturation. The model demonstrates that the final stage of removal of liquid or crystalline sulfide can effectively sequester Cu (and presumably other chalcophiles) and that late stage exsolution of magmatic fluids or brines may not be required to do this, although these processes are not mutually exclusive. Finally, the new Fe isotope data are combined with previous Tl-Mo-V stable isotope determinations on the same samples. Importantly, the multi-valent transition metal stable isotope systems of Fe and V are decoupled by sulfide saturation, thus providing a potential tool to constrain its somewhat intractable timing. The observed decoupling of notionally redox-sensitive tracers underlines the caution required in the application of transition metal isotopes as direct redox proxies.

Paleomagnetism and environmental magnetism of GLAD800 sediment cores from Bear Lake, Utah and Idaho

USGS Publications Warehouse

Heil, C.W.; King, J.W.; Rosenbaum, J.G.; Reynolds, R.L.; Colman, Steven M.

2009-01-01

A ???220,000-year record recovered in a 120-m-long sediment core from Bear Lake, Utah and Idaho, provides an opportunity to reconstruct climate change in the Great Basin and compare it with global climate records. Paleomagnetic data exhibit a geomagnetic feature that possibly occurred during the Laschamp excursion (ca. 40 ka). Although the feature does not exhibit excursional behavior (???40?? departure from the expected value), it might provide an additional age constraint for the sequence. Temporal changes in salinity, which are likely related to changes in freshwater input (mainly through the Bear River) or evaporation, are indicated by variations in mineral magnetic properties. These changes are represented by intervals with preserved detrital Fe-oxide minerals and with varying degrees of diagenetic alteration, including sulfidization. On the basis of these changes, the Bear Lake sequence is divided into seven mineral magnetic zones. The differing magnetic mineralogies among these zones reflect changes in deposition, preservation, and formation of magnetic phases related to factors such as lake level, river input, and water chemistry. The occurrence of greigite and pyrite in the lake sediments corresponds to periods of higher salinity. Pyrite is most abundant in intervals of highest salinity, suggesting that the extent of sulfidization is limited by the availability of SO42-. During MIS 2 (zone II), Bear Lake transgressed to capture the Bear River, resulting in deposition of glacially derived hematite-rich detritus from the Uinta Mountains. Millennial-scale variations in the hematite content of Bear Lake sediments during the last glacial maximum (zone II) resemble Dansgaard-Oeschger (D-O) oscillations and Heinrich events (within dating uncertainties), suggesting that the influence of millennial-scale climate oscillations can extend beyond the North Atlantic and influence climate of the Great Basin. The magnetic mineralogy of zones IV-VII (MIS 5, 6, and 7) indicates varying degrees of post-depositional alteration between cold and warm substages, with greigite forming in fresher conditions and pyrite in the more saline conditions. Copyright ?? 2009 The Geological Society of America.

Metalliferous sediment and a silica-hematite deposit within the Blanco fracture zone, Northeast Pacific

USGS Publications Warehouse

Hein, J.R.; Clague, D.A.; Koski, R.A.; Embley, R.W.; Dunham, R.E.

2008-01-01

A Tiburon ROV dive within the East Blanco Depression (EBD) increased the mapped extent of a known hydrothermal field by an order of magnitude. In addition, a unique opal-CT (cristobalite-tridymite)-hematite mound was discovered, and mineralized sediments and rock were collected and analyzed. Silica-hematite mounds have not previously been found on the deep ocean floor. The light-weight rock of the porous mound consists predominantly of opal-CT and hematite filaments, rods, and strands, and averages 77.8% SiO2 and 11.8% Fe2O3. The hematite and opal-CT precipitated from a low-temperature (???115?? C), strongly oxidized, silica- and iron-rich, sulfur-poor hydrothermal fluid; a bacterial mat provided the framework for precipitation. Samples collected from a volcaniclastic rock outcrop consist primarily of quartz with lesser plagioclase, smectite, pyroxene, and sulfides; SiO2 content averages 72.5%. Formation of these quartz-rich samples is best explained by cooling in an up-flow zone of silica-rich hydrothermal fluids within a low permeability system. Opal-A, opal-CT, and quartz mineralization found in different places within the EBD hydrothermal field likely reflects decreasing silica saturation and increasing temperature of the mineralizing fluid with increasing silica crystallinity. Six push cores recovered gravel, coarse sand, and mud mineralized variously by Fe or Mn oxides, silica, and sulfides. Total rare-earth element concentrations are low for both the rock and push core samples. Ce and Eu anomalies reflect high and low temperature hydrothermal components and detrital phases. A remarkable variety of types of mineralization occur within the EBD field, yet a consistent suite of elements is enriched (relative to basalt and unmineralized cores) in all samples analyzed: Ag, Au, S, Mo, Hg, As, Sb, Sr, and U; most samples are also enriched in Cu, Pb, Cd, and Zn. On the basis of these element enrichments, the EBD hydrothermal field might best be described as a base- and precious-metal-bearing, silica-Fe-oxide-barite deposit. Such deposits are commonly spatially and temporally associated with volcanogenic massive sulfide (VMS) ores. A plot of data for pathfinder elements shows a large hot spot at the northwestern margin of the field, which may mark a region where moderate to high temperature sulfide deposits are forming at depth; further exploration of the hydrothermal field to the northwest is warranted.

Lipid Biomarker Records Across the Permian-Triassic Boundary from Kap Stosch, Greenland

NASA Astrophysics Data System (ADS)

Hays, L. E.; Love, G. D.; Foster, C. B.; Grice, K.; Summons, R. E.

2006-12-01

The end-Permian extinction was the most severe in the past 500 million years of the Earth's history and evidence that an oceanic anoxic event (OAE) occurred contemporaneously has been presented previously [1,2]. OAEs have, therefore, been proposed as responsible for the mass mortality, and if the anoxic ocean was also euxinic, the release of hydrogen sulfide during upwelling and/or transgression provides an extinction agent in the ocean as well as on land. Chlorobiaceae, as indicators of photic zone euxinia (PZE), utilize hydrogen sulfide as an electron donor for anoxygenic photosynthesis. The detection of isorenieratane and a series of short-chain monoaromatic aryl isoprenoids, biomarkers for Chlorobiaceae, in sediments indicates the presence of hydrogen sulfide in the photic zone of the water column during sediment deposition. The Kap Stosch area in Eastern Greenland was identified as a Permian-Triassic boundary (PTB) outcrop of homogeneous shale, silty shale, and siltstone facies [3]. Another late Permian section in Eastern Greenland, the Ravnefjeld Formation, has framboidal pyrites indicative of sulfidic deep water [4]. A sample suite from the Kap Stosch region was studied using standard organic geochemistry methods including stable isotopic analyses of organic carbon, Rock-Eval pyrolysis, and biomarker hydrocarbon analysis. Aryl isoprenoids, including isorenieratane, were present in all samples studied and the concentrations were observed to fluctuate in tandem with TOC, similar to other Mesozoic OAEs. The molecular ratios of pristane/phytane and hopanes/steranes as well as the 2-methyl-hopane index (2-MHI) fluctuated dramatically through this section as they do at the type section at Meishan and in the Perth Basin [5]. The 2-MHI shows an inverse pattern to the total aryl isoprenoids, perhaps indicative of instability in the form of primary productivity in the water column during euxinic episodes. This can result in nitrogen limitation and a competitive advantage of cyanobacteria over microalgae for nutrient resources [6]. Overall, the biomarker patterns in these samples indicate the presence of PZE at this location leading up to and continuing through the PTB. 1. Isozaki Y., 1997. Science 276, 235. 2. Wignall P. and R. Twichett, 1996. Science 272, 1155. 3. Teichert C. and B. Kummel, 1972. Bull. Canadian Petrol. Geol. 20, 659. 4. Nielsen J. and Y. Shen, 2004. Geology 32, 1037. 5. Grice K., et al., 2005. Science 307, 706. 6. Kuypers M., et al., 2004. Geology 32, 853.

Geologic setting and genesis of the Mule Canyon low-sulfidation epithermal gold-silver deposit, north-central Nevada

USGS Publications Warehouse

John, D.A.; Hofstra, A.H.; Fleck, R.J.; Brummer, J.E.; Saderholm, E.C.

2003-01-01

The Mule Canyon mine exploited shallow, low-sulfidation, epithermal Au-Ag deposits that lie near the west side of the Northern Nevada rift in northern Lander County, Nevada. Mule Canyon consists of six small deposits that contained premining reserves of about 8.2 Mt at an average grade of 3.81 g Au/tonne. It is an uncommon mafic end member of low-sulfidation Au-Ag deposits associated with tholeiitic bimodal basalt-rhyolite magmatism. The ore is hosted by a basalt-andesite eruptive center that formed between about 16.4 to 15.8 Ma during early mafic eruptions related to regionally extensive bimodal magmatism. Hydrothermal alteration and Au-Ag ores formed at about 15.6 Ma and were tightly controlled by north-northwest- to north-striking high-angle fault and breccia zones developed during rifting, emplacement of mafic dikes, and eruption of mafic lava flows. Hydrothermal alteration assemblages are zoned outward from fluid conduits in the sequence silica-adularia, adularia-smectite, smectite (intermediate argillic), and smectite-carbonate (propylitic). All alteration types contain abundant pyrite and/or marcasite ?? arsenopyrite. Field relations indicate that silica-adularia alteration is superimposed on argillic and propylitic alteration. Little or no steam-heated acid-sulfate alteration is present, probably the result of a near-surface water table during hydrothermal alteration and ore deposition. Two distinct ore types are present at Mule Canyon: early replacement and later open-space filling. Replacement ores consist of disseminated and vesicle-filling pyrite, marcasite, and arsenopyrite in argillically altered or weakly silicified rocks. Ore minerals consist of Au-bearing arsenopyrite and arsenian pyrite overgrowths on earlier-formed pyrite and marcasite. Open-space filling ores include narrow stockwork quartz-adularia veins, banded and crustiform opaline and chalcedonic silica-adularia veins, silica-adularia cemented breccias, and sparse carbonate-pyrite and/or marcasite veins. Ore minerals consist mostly of electrum and Ag sulfide and selenide minerals, with minor to major amounts of pyrite, marcasite, and arsenopyrite, and local stibnite. Both types of ores have similar geochemical signatures, characterized by high Au, Ag, As, Sb, and Se contents, locally high Hg, Mo, Tl, and W contents, and low Cu, Pb, and Zn contents. Stable isotope data indicate that ore fluids consisted dominantly of meteoric water that evolved by deep circulation through Paleozoic sedimentary rocks at low water/rock ratios (about 1) and high temperatures (>200??C). Calculated isotopic compositions of ore fluids are ??18OH2O = -3 to -7 per mil, ??DH2O = -107 to -124 per mil, ??13CCO2 = 0 to -6 per mil, and ??34SH2S = -3 to +8 per mil. The ore fluids obtained much of their H2S and CO2 and probably scavenged ore metals and trace elements from the Paleozoic sedimentary rocks. Some H2S and CO2 may have been derived from degassing Miocene magmas. Mule Canyon formed at shallow depths, probably about 100 m below the paleosurface. Ore fluids were dilute, nearly neutral in pH, reduced, H2S-rich, and CO2-bearing. Peak temperatures in ore zones reached 230?? to 265??C at nearly lithostatic pressures when some crystalline quartz ?? adularia precipitated, but most ore formed at temperatures <200??C at near hydrostatic pressures and was accompanied by precipitation of opaline and chalcedonic silica ?? adularia ?? calcite and dolomite. Deposition of gold in As-rich overgrowths on pyrite and/or marcasite in disseminated ores occurred owing to decreasing H2S in the ore fluids resulting from sulfidation reactions. Later electrum and Ag selenide precipitation in open spaces occurred owing to boiling, loss of H2S to the vapor phase, and cooling. Mule Canyon is similar to most other low-sulfidation Au-Ag deposits associated with Miocene tholeiitic bimodal basalt-rhyolite magmatism in the Great Basin, such as Sleeper, Midas, and Buckhorn. Major differences at Mule Canyon are

Water characterization and seasonal heavy metal distribution in the Odiel River (Huelva, Spain) by means of principal component analysis.

PubMed

Montes-Botella, C; Tenorio, M D

2003-11-01

The Iberian Pyrite Belt is the largest mass of sulfide and manganese ores in Western Europe. Its sulfide oxidation is the origin of a heavily acidic drainage that affects the Odiel River in southwestern Huelva (Spain). To assess physicochemical, contamination parameters, heavy metal distribution and its seasonal variation in the upper Odiel River and in El Lomero mines, three water samplings were undertaken and analyzed between July 1998 and November 1999. Water from the Odiel River in the polluted zone showed low pH values (2.76-3.51), high heavy metal content, and high values of conductivity (1410-3648 microS/cm) and dissolved solids (1484-5602 mg/L). Principal Component Analysis (PCA) showed that variables related with the products of the pyrite oxidation and the salts that are solubilized by the high acidity generated in the oxidation of sulfides, grouped in the first component, accounted for 40.88% of total variance, and were the main influential factor in physicochemical water sample properties. The second influential factor was minority metals (nickel, cobalt, cadmium). Heavy metals showed three different seasonal patterns, closely related with saline efflorescences formed next to the river bed: majority metals (iron, copper, manganese, zinc); minority metals (lead, nickel, cobalt, cadmium); and chromium, which had a distinctive behavior.

Constraints from fluid inclusions on sulfide precipitation mechanisms and ore fluid migration in the Viburnum Trend lead district, Missouri

USGS Publications Warehouse

Rowan, E.L.; Leach, D.L.

1989-01-01

Homogenization temperatures and freezing point depressions were determined for fluid inclusions in Bonneterre Dolomite-hosted dolomite cements in mine samples, as well as drill core from up to 13 km outside of the district. A well-defined cathodoluminescent zonation distinguishes dolomite growth zones as older or younger than main-stage mineralization. Homogenization temperatures and salinities in samples from mines are not systematically different from those of samples outside of the district. The absence of a significant, recognizable decrease in temperature either vertically within the section or east-west across the district, coupled with the minor amount of silica in the district, argues against cooling as a primary cause of sulfide precipitation. In a reduced sulfur mineralization model with Pb carried as chloride complexes, dilution is also a possible sulfide precipitation mechanism. The difference in Pb solubility in the extremes of the chloride concentration range, 3.9 vs. 5.9 molal, reaches 1 ppm only for pH values below approximately 4.5. The distribution of warm inclusions beyond the Viburnum Trend district implies that fluid migration was regional in scale. Elevated temperatures observed in fluid inclusions at shallow stratigraphic depths are consistent with a gravity flow hydrologic system characterized by rapid flow rates and the capacity for advective heat transport. -from Authors

Uranium occurrences in the Golden Gate Canyon and Ralston Creek areas, Jefferson County, Colorado

USGS Publications Warehouse

Adams, John Wagstaff; Gude, A.J.; Beroni, E.P.

1953-01-01

Pitchblende, associated with base-metal sulfides, has been found at nine localities in the northern part of Jefferson County, Colo., in shear zones that cut pre-Cambrian metamorphic and igneous rocks, chiefly hornblende gneiss, biotite schist, and granite pegmatite. The known deposits are in the vicinity of Halston Creek and Golden Gate Canyon, in the foothills of the Colorado Front Range and about 15 miles east of the pitchblende-producing area of the Central City district. Two of the pitchblende occurrences were found by a local prospector in 1949; the seven other deposits were found by Geological Survey. personnel in 1951-52. The pitchblende deposits, with one exception, are in major shear zones that contain veinlike bodies of carbonate-rich breccia that ranges from 1 to 5 feet in thickness. The breccias probably are related to the Laramide faults, or 'breccia reefs' of similar trend, mapped by Loverinq and Goddard (1950). The breccias are composed of fragments of bleached and iron-stained wall rock, usually hornblende gneiss, that have been cut by veins and cemented by carbonate minerals, quartz, and orthoclase(?). Pitchblende and associated ore minerals, chiefly copper sulfides, occur in and along the margins of the breccias and apparently were introduced at a late stage of the carbonate deposition. At one deposit, the Buckman, the pitchblende is in narrow shear zones not closely related to any large breccia bodies. Secondary uranium minerals are subordinate except at the Schwartzwalder mine, where torbernite and metatorbernite are common. Some alteration of pitchblende to non-opaque materials, believed to be hydrated oxides, has been noted in ore from two of the deposits.

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.

Sources of sulfate supporting anaerobic metabolism in a contaminated aquifer

USGS Publications Warehouse

Ulrich, G.A.; Breit, G.N.; Cozzarelli, I.M.; Suflita, J.M.

2003-01-01

Field and laboratory techniques were used to identify the biogeochemical factors affecting sulfate reduction in a shallow, unconsolidated alluvial aquifer contaminated with landfill leachate. Depth profiles of 35S-sulfate reduction rates in aquifer sediments were positively correlated with the concentration of dissolved sulfate. Manipulation of the sulfate concentration in samples revealed a Michaelis-Menten-like relationship with an apparent Km and Vmax of approximately 80 and 0.83 ??M SO4-2??day-1, respectively. The concentration of sulfate in the core of the leachate plume was well below 20 ??M and coincided with very low reduction rates. Thus, the concentration and availability of this anion could limit in situ sulfate-reducing activity. Three sulfate sources were identified, including iron sulfide oxidation, barite dissolution, and advective flux of sulfate. The relative importance of these sources varied with depth in the alluvium. The relatively high concentration of dissolved sulfate at the water table is attributed to the microbial oxidation of iron sulfides in response to fluctuations of the water table. At intermediate depths, barite dissolves in undersaturated pore water containing relatively high concentrations of dissolved barium (???100 ??M) and low concentrations of sulfate. Dissolution is consistent with the surface texture of detrital barite grains in contact with leachate. Laboratory incubations of unamended and barite-amended aquifer slurries supported the field observation of increasing concentrations of barium in solution when sulfate reached low levels. At a deeper highly permeable interval just above the confining bottom layer of the aquifer, sulfate reduction rates were markedly higher than rates at intermediate depths. Sulfate is supplied to this deeper zone by advection of uncontaminated groundwater beneath the landfill. The measured rates of sulfate reduction in the aquifer also correlated with the abundance of accumulated iron sulfide in this zone. This suggests that the current and past distributions of sulfate-reducing activity are similar and that the supply of sulfate has been sustained at these sites.

Paragenesis of multiple platinum-group mineral populations in Shetland ophiolite chromitite: 3D X-ray tomography and in situ Os isotopes

NASA Astrophysics Data System (ADS)

Prichard, H. M.; Barnes, Stephen J.; Dale, C. W.; Godel, B.; Fisher, P. C.; Nowell, G. M.

2017-11-01

Chromitite from the Harold's Grave locality in the mantle section of the Shetland ophiolite complex is extremely enriched in Ru, Os and Ir, at μg/g concentrations. High-resolution X-ray computed tomography on micro-cores from these chromitites was used to determine the location, size, distribution and morphology of the platinum-group minerals (PGM). There are five generations of PGM in these chromitites. Small (average 5 μm in equivalent sphere diameter, ESD) euhedral laurites, often with Os-Ir alloys, are totally enclosed in the chromite and are likely to have formed first by direct crystallisation from the magma as the chromite crystallised. Also within the chromitite there are clusters of larger (50 μm ESD) aligned elongate crystals of Pt-, Rh-, Ir-, Os- and Ru-bearing PGM that have different orientations in different chromite crystals. These may have formed either by exsolution, or by preferential nucleation of PGMs in boundary layers around particular growing chromite grains. Thirdly there is a generation of large (100 μm ESD) composite Os-Ir-Ru-rich PGM that are all interstitial to the chromite grains and sometimes form in clusters. It is proposed that Os, Ir and Ru in this generation were concentrated in base metal sulfide droplets that were then re-dissolved into a later sulfide-undersaturated magma, leaving PGM interstitial to the chromite grains. Fourthly there is a group of almost spherical large (80 μm ESD) laurites, hosting minor Os-Ir-Ru-rich PGM that form on the edge or enclosed in chromite grains occurring in a sheet crosscutting a chromitite layer. These may be hosted in an annealed late syn- or post magmatic fracture. Finally a few of the PGM have been deformed in localised shear zones through the chromitites. The vast majority of the PGM - including small PGM enclosed within chromite, larger interstitial PGM and elongate aligned PGM - have Os isotope compositions that give Re-depletion model ages approximately equal to the age of the ophiolite at ∼492 Ma. A number of other PGM - not confined to a single textural group - fall to more or less radiogenic values, with four PGM giving anomalously unradiogenic Os corresponding to an older age of ∼1050 Ma. The 187Os/188Os isotopic ratios for PGM from Cliff and Quoys, from the same ophiolite section, are somewhat more radiogenic than those at Harold's Grave. This may be due to a distinct mantle source history or possibly the assimilation of radiogenic crustal Os.

Prospects of gold mineralization in the Gilgit-Baltistan Province of Pakistan

NASA Astrophysics Data System (ADS)

Shah, M. T.; Khan, S. D.; Tahirkheli, T.; Ahmad, L.; Miandad, S.; Rehman, A. U.; Ali, L.

2012-12-01

Gilgit-Baltistan province is the northern most province of Pakistan having its eastern, northern and western boarders with India, China and Afghanistan respectively. The geology of this province is unique as it has the spectacular tectonic entities of Asiatic plate (AP), Indian plate (IP) and the Kohistan-Ladakh arc (KLA). The Northern Suture Zone (NSZ) or Main Karakoram Thrust (MKT) separate the KLA from AP in the north while the Maim Mantle Thrust (MMT) separate the KLA from IP in the south. These different tectonic events have generated various types of igneous and metamorphic rocks in the form of gigantic mountain chains in the region. Considering the metallogenic provinces related to such types of tectonic environments world over, it can be suggested that the Gigit-Baltistan province may have the potential for the occurrence of economic mineral deposits. The present study is the follow-up of the previous studies for exploration of gold and base metals conducted by the Austrominerals and the Pakistan Mineral Development Corporation (PMDC) in the region. On the basis of PMDC extensive stream sediments geochemical survey of the province and delineated number of anomalous catchment areas for gold mineralization. In order to find the source bed-rock of gold, we have identified various alteration zones in these catchment areas by applying Remote sensing techniques by using both multispectral (LANDSAT, ASTER and Geoeye) and hyperspectral (Hyperion) data. Most of the alteration zones were found in steep high altitude inaccessible terrains. During this study, few of the accessible alteration zones in Golo Das, Bagrot valley, Shigri Bala, Machulu and Ranthak areas were selected for geological filed work and collection of proper samples from the alteration zones and host rocks for the identification of possible gold mineralization. In all these localities, the alteration zones are present along shear zones where the sulfide mineralization commonly occurs in the form of mainly pyrite and chalcopyrite with subordinate amount of bornite and tetrahedrite. Surface leaching of these phases to malachite, azurite and limonite is common. Quartz veining, silicification, carbonization and at places brecciation are the common features of these alteration zones. The concentrations of gold were found in the range of 3ppb to 112ppb, <5- 95ppb, 1ppb to 545ppb, 1ppb to 385 and 1ppb to 318ppb in the alteration zones of Golo Das, Bagrot valley, Shigri Bala, Machulu and Ranthak areas respectively. The barren rock samples have generally <5ppb gold. This is indicative of the multi-times enrichment of gold in the alteration zones. The sulfide mineralization along with gold in the alteration zones could be attributed to the hydrothermal/epithermal activity involving meteoric, igneous and or metamorphic fluid individually or mixture of these. The occurrence of dioritic intrusions (igneous fluid source) and the transitional dilated zones (metamorphic fluid source) on the major reactivated thrust fault (i.e., NSZ) in the vicinity of these alteration zones strengthen these observations. However, isotopic studies are underway to solve this problem. This study suggests that the alteration zones in the studied areas have the potential to be explored in detail for possible economical gold mineralization.

The geochemical cycling of trace elements in a biogenic meromictic lake

NASA Astrophysics Data System (ADS)

Balistrieri, Laurie S.; Murray, James W.; Paul, Barbara

1994-10-01

The geochemical processes affecting the behavior and speciation of As, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, V, and Zn in Hall Lake, Washington, USA, are assessed by examining dissolved and acid soluble particulate profiles of the elements and utilizing results from thermodynamic calculations. The water column of this meromictic lake is highly stratified and contains distinctive oxic, suboxic, and anoxic layers. Changes in the redox state of the water column with depth affect the distribution of all the elements studied. Most noticeable are increases in dissolved Co, Cr, Fe, Mn, Ni, Pb, and Zn concentrations across the oxic-suboxic boundary, increases in dissolved As, Co, Cr, Fe, Mn, and V concentrations with depth in the anoxic layer, significant decreases in dissolved Cu, Ni, Pb, and Zn concentrations in the anoxic region below the sulfide maximum, and large increases in acid soluble particulate concentrations of As, Cr, Cu, Fe, Mo, Ni, Pb, V, and Zn in the anoxic zone below the sulfide maximum. Thermodynamic calculations for the anoxic region indicate that all redox sensitive elements exist in their reduced forms, the primary dissolved forms of Cu, Ni, Pb, and Zn are metal sulfide solution complexes, and solid sulfide phases of Cu, Fe, Mo, and Pb are supersaturated. Calculations using a vertical diffusion and reaction model indicate that the oxidation rate constant for Mn(II) in Hall Lake is estimated to be 0.006 d -1 and is at the lower end of the range of microbial oxidation rates observed in other natural systems. The main geochemical processes influencing the distribution and speciation of trace elements in Hall Lake appear to be transformations of dissolved elements between their oxidation states (As, Cr, Cu, Fe, Mn, V), cocycling of trace elements with Mn and Fe (As, Co, Cr, Cu, Mo, Ni, Pb, V, Zn), formation of soluble metal sulfide complexes (Co, Cu, Ni, Pb, Zn), sorption (As, Co, Cr, Ni, V), and precipitation (Cu, Fe, Mn, Mo, Pb, Zn).

Porewater dynamics of silver, lead and copper in coastal sediments and implications for benthic metal fluxes

USGS Publications Warehouse

Kalnejais, Linda H.; Martin, W. R.; Bothner, Michael H.

2015-01-01

To determine the conditions that lead to a diffusive release of dissolved metals from coastal sediments, porewater profiles of Ag, Cu, and Pb have been collected over seven years at two contrasting coastal sites in Massachusetts, USA. The Hingham Bay (HB) site is a contaminated location in Boston Harbor, while the Massachusetts Bay (MB) site is 11 km offshore and less impacted. At both sites, the biogeochemical cycles include scavenging by Fe-oxyhydroxides and release of dissolved metals when Fe-oxyhydroxides are reduced. Important differences in the metal cycles at the two sites, however, result from different redox conditions. Porewater sulfide and seasonal variation in redox zone depth is observed at HB, but not at MB. In summer, as the conditions become more reducing at HB, trace metals are precipitated as sulfides and are no longer associated with Fe-oxyhydroxides. Sulfide precipitation close to the sediment–water interface limits the trace metal flux in summer and autumn at HB, while in winter, oxidation of the sulfide phases drives high benthic fluxes of Cu and Ag, as oxic conditions return. The annual diffusive flux of Cu at HB is found to be significant and contributes to the higher than expected water column Cu concentrations observed in Boston Harbor. At MB, due to the lower sulfide concentrations, the association of trace metals with Fe-oxyhydroxides occurs throughout the year, leading to more stable fluxes. A surface enrichment of solid phase trace metals was found at MB and is attributed to the persistent scavenging by Fe-oxyhydroxides. This process is important, particularly at sites that are less reducing, because it maintains elevated metal concentrations at the surface despite the effects of bioturbation and sediment accumulation, and because it may increase the persistence of metal contamination in surface sediments.

The geochemical cycling of trace elements in a biogenic meromictic lake

USGS Publications Warehouse

Balistrieri, L.S.; Murray, J.W.; Paul, B.

1994-01-01

The geochemical processes affecting the behavior and speciation of As, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, V, and Zn in Hall Lake, Washington, USA, are assessed by examining dissolved and acid soluble particulate profiles of the elements and utilizing results from thermodynamic calculations. The water column of this meromictic lake is highly stratified and contains distinctive oxic, suboxic, and anoxic layers. Changes in the redox state of the water column with depth affect the distribution of all the elements studied. Most noticeable are increases in dissolved Co, Cr, Fe, Mn, Ni, Pb, and Zn concentrations across the oxic-suboxic boundary, increases in dissolved As, Co, Cr, Fe, Mn, and V concentrations with depth in the anoxic layer, significant decreases in dissolved Cu, Ni, Pb, and Zn concentrations in the anoxic region below the sulfide maximum, and large increases in acid soluble particulate concentrations of As, Cr, Cu, Fe, Mo, Ni, Pb, V, and Zn in the anoxic zone below the sulfide maximum. Thermodynamic calculations for the anoxic region indicate that all redox sensitive elements exist in their reduced forms, the primary dissolved forms of Cu, Ni, Pb, and Zn are metal sulfide solution complexes, and solid sulfide phases of Cu, Fe, Mo, and Pb are supersaturated. Calculations using a vertical diffusion and reaction model indicate that the oxidation rate constant for Mn(II) in Hall Lake is estimated to be 0.006 d-1 and is at the lower end of the range of microbial oxidation rates observed in other natural systems. The main geochemical processes influencing the distribution and speciation of trace elements in Hall Lake appear to be transformations of dissolved elements between their oxidation states (As, Cr, Cu, Fe, Mn, V), cocycling of trace elements with Mn and Fe (As, Co, Cr, Cu, Mo, Ni, Pb, V, Zn), formation of soluble metal sulfide complexes (Co, Cu, Ni, Pb, Zn), sorption (As, Co, Cr, Ni, V), and precipitation (Cu, Fe, Mn, Mo, Pb, Zn). ?? 1994.

The polar sulfur cycle in the Werenskioldbreen, Spitsbergen: Possible implications for understanding the deposition of sulfate minerals in the North Polar Region of Mars

NASA Astrophysics Data System (ADS)

Szynkiewicz, Anna; Modelska, Magdalena; Buczyński, Sebastian; Borrok, David M.; Merrison, Jonathan P.

2013-04-01

In this study we investigated the polar cycling of sulfur (S) associated with the Werenskioldbreen glacier in Spitsbergen (Svalbard). Sulfide-derived S comprised 0.02-0.42 wt% of the fine-grained fraction of proglacial sediments. These sediments originated from glacial erosion of Precambrian sulfide-rich quartz and carbonate veins. In summer 2008, the δ34S of dissolved SO4 in glacier melt waters (+9‰ to +17‰) was consistent with SO4 generation from oxidation of primary sulfide minerals in the bedrock (+9‰ to +16‰). The calculated monthly SO4 load was ˜6881 kg/month/km2 in the main glacier stream. Subsequent evaporation and freezing of glacial waters lead to precipitation, accumulation, and temporary storage of sulfate salt efflorescences in the proglacial zone. These salts are presumably ephemeral, as they dissolve during annual snow/glacial melt events. Hydrated sulfates such as gypsum are also important constituents of the low-elevation areas around the polar ice cap of Planum Boreum on Mars. The origin of this gypsum on Mars might be better understood by using the investigated polar S cycle in Spitsbergen as a foundation. Assuming a trace sulfide content in the basaltic bedrock on Mars, the weathering of sulfides within the fine, porous texture of the ancient aeolian strata (basal unit) underlying Planum Boreum could have created elevated SO4 fluxes (and gypsum precipitation) during episodic thawing/melting events in the past. Limited water activity and prevailing dry conditions on the surface of Mars are the likely factors that accounted for the larger accumulation and preservation of polar gypsum on the surface and its broad aeolian distribution around Planum Boreum. This suggestion is also supported by an experiment showing that gypsum sand can be transported, under dry conditions, over great distances (˜2000 km) without a significant loss of mass.

Arsenic occurrence, mobility, and retardation in sandstone and dolomite formations of the Fox River Valley, Eastern Wisconsin.

PubMed

Thornburg, Katie; Sahai, Nita

2004-10-01

Elevated levels of groundwater arsenic (approximately 100 microg L(-1) = 1.3 x 10(-6) M) are found in the Fox River Valley, eastern Wisconsin. The goals of this study were to identifythe sources of As contamination and to determine the reactions responsible for As mobilization and retardation in areas lacking a discrete zone of As-enriched sulfides, shown previouslyto cause elevated arsenic in groundwater. Detailed mineralogical and chemical analyses were conducted on samples from the Sinnipee Group dolomite and St. Peter sandstone in eastern Wisconsin. Solution chemistry was monitored in batch reactions of dolomite, quartz, and sulfide mineral fractions with a 0.01 M CsCl solution at pH 7 for 3 weeks in air. Results indicate that arsenic is present in isomorphous substitution with pyrite/marcasite (FeS2), which occurs as disseminated veins, grains, and nodules in the dolomite and sandstone. The released As subsequently sorbs on the ferric oxyhydroxides formed or coprecipitates in a scorodite-like phase. Significantly, oxidative dissolution of the disseminated As-rich FeS2 grains and nodules is sufficient to explain the elevated As levels observed in eastern Wisconsin groundwater. Although complete uptake of As is observed in the batch experiments, persistent elevated As levels with spatial and temporal variations in regional groundwaters are attributed to differences in the type of sulfide occurrence (discrete horizon vs dispersed grains, veins, and nodules), variations in the dissolved oxygen content of the groundwater, and variable (limited) buildup of reacted surface layers on sulfide grains in the natural flow-through system. Discrete nanoparticulate As phases, As surface precipitates on sulfides, and sorbed As on dolomite and quartz are eliminated as major sources, and sorption of arsenic on dolomite and quartz is deemed less important than association with ferric oxyhydroxides for retardation in the regional system.

Spatial impacts of inorganic ligand availability and localized microbial community structure on mitigation of zinc laden mine water in sulfate-reducing bioreactors.

PubMed

Drennan, Dina M; Almstrand, Robert; Ladderud, Jeffrey; Lee, Ilsu; Landkamer, Lee; Figueroa, Linda; Sharp, Jonathan O

2017-05-15

Sulfate-reducing bioreactors (SRBRs) represent a passive, sustainable, and long-term option for mitigating mining influenced water (MIW) during release. Here we investigate spatial zinc precipitation profiles as influenced by substrate differentiation, inorganic ligand availability (inorganic carbon and sulfide), and microbial community structure in pilot-scale SRBR columns fed with sulfate and zinc-rich MIW. Through a combination of aqueous sampling, geochemical digests, electron microscopy and energy-dispersive x-ray spectroscopy, we were able to delineate zones of enhanced zinc removal, identify precipitates of varying stability, and discern the temporal and spatial evolution of zinc, sulfur, and calcium associations. These geochemical insights revealed spatially variable immobilization regimes between SRBR columns that could be further contrasted as a function of labile (alfalfa-dominated) versus recalcitrant (woodchip-dominated) solid-phase substrate content. Both column subsets exhibited initial zinc removal as carbonates; however precipitation in association with labile substrates was more pronounced and dominated by metal-sulfide formation in the upper portions of the down flow columns with micrographs visually suggestive of sphalerite (ZnS). In contrast, a more diffuse and lower mass of zinc precipitation in the presence of gypsum-like precipitates occurred within the more recalcitrant column systems. While removal and sulfide-associated precipitation were spatially variable, whole bacterial community structure (ANOSIM) and diversity estimates were comparatively homogeneous. However, two phyla exhibited a potentially selective relationship with a significant positive correlation between the ratio of Firmicutes to Bacteroidetes and sulfide-bound zinc. Collectively these biogeochemical insights indicate that depths of maximal zinc sulfide precipitation are temporally dynamic, influenced by substrate composition and broaden our understanding of bio-immobilized zinc species, microbial interactions and potential operational and monitoring tools in these types of passive bioreactors. Copyright © 2017 Elsevier Ltd. All rights reserved.

Simultaneous removal of nitrogen oxides and sulfur oxides from combustion gases

DOEpatents

Clay, David T.; Lynn, Scott

1976-10-19

A process for the simultaneous removal of sulfur oxides and nitrogen oxides from power plant stack gases comprising contacting the stack gases with a supported iron oxide catalyst/absorbent in the presence of sufficient reducing agent selected from the group consisting of carbon monoxide, hydrogen, and mixtures thereof, to provide a net reducing atmosphere in the SO.sub.x /NO.sub.x removal zone. The sulfur oxides are removed by absorption substantially as iron sulfide, and nitrogen oxides are removed by catalytic reduction to nitrogen and ammonia. The spent iron oxide catalyst/absorbent is regenerated by oxidation and is recycled to the contacting zone. Sulfur dioxide is also produced during regeneration and can be utilized in the production of sulfuric acid and/or sulfur.

Eutrophication, microbial-sulfate reduction and mass extinctions

PubMed Central

Schobben, Martin; Stebbins, Alan; Ghaderi, Abbas; Strauss, Harald; Korn, Dieter; Korte, Christoph

2016-01-01

ABSTRACT In post-Cambrian time, life on Earth experienced 5 major extinction events, likely instigated by adverse environmental conditions. Biodiversity loss among marine taxa, for at least 3 of these mass extinction events (Late Devonian, end-Permian and end-Triassic), has been connected with widespread oxygen-depleted and sulfide-bearing marine water. Furthermore, geochemical and sedimentary evidence suggest that these events correlate with rather abrupt climate warming and possibly increased terrestrial weathering. This suggests that biodiversity loss may be triggered by mechanisms intrinsic to the Earth system, notably, the biogeochemical sulfur and carbon cycle. This climate warming feedback produces large-scale eutrophication on the continental shelf, which, in turn, expands oxygen minimum zones by increased respiration, which can turn to a sulfidic state by increased microbial-sulfate reduction due to increased availability of organic matter. A plankton community turnover from a high-diversity eukaryote to high-biomass bacterial dominated food web is the catalyst proposed in this anoxia-extinction scenario and stands in stark contrast to the postulated productivity collapse suggested for the end-Cretaceous mass extinction. This cascade of events is relevant for the future ocean under predicted greenhouse driven climate change. The exacerbation of anoxic “dead” zones is already progressing in modern oceanic environments, and this is likely to increase due to climate induced continental weathering and resulting eutrophication of the oceans. PMID:27066181

Fabrication of glass microspheres with conducting surfaces

DOEpatents

Elsholz, William E.

1984-01-01

A method for making hollow glass microspheres with conducting surfaces by adding a conducting vapor to a region of the glass fabrication furnace. As droplets or particles of glass forming material pass through multiple zones of different temperature in a glass fabrication furnace, and are transformed into hollow glass microspheres, the microspheres pass through a region of conducting vapor, forming a conducting coating on the surface of the microspheres.

Fabrication of glass microspheres with conducting surfaces

DOEpatents

Elsholz, W.E.

1982-09-30

A method for making hollow glass microspheres with conducting surfaces by adding a conducting vapor to a region of the glass fabrication furnace. As droplets or particles of glass forming material pass through multiple zones of different temperature in a glass fabrication furnace, and are transformed into hollow glass microspheres, the microspheres pass through a region of conducting vapor, forming a conducting coating on the surface of the microspheres.

Periodic Vesicle Formation in Tectonic Fault Zones--an Ideal Scenario for Molecular Evolution.

PubMed

Mayer, Christian; Schreiber, Ulrich; Dávila, María J

2015-06-01

Tectonic fault systems in the continental crust offer huge networks of interconnected channels and cavities. Filled mainly with water and carbon dioxide (CO2), containing a wide variety of hydrothermal chemistry and numerous catalytic surfaces, they may offer ideal reaction conditions for prebiotic chemistry. In these systems, an accumulation zone for organic compounds will develop at a depth of approximately 1 km where CO2 turns sub-critical and dissolved components precipitate. At this point, periodic pressure changes caused for example by tidal influences or geyser activity may generate a cyclic process involving repeated phase transitions of carbon dioxide. In the presence of amphiphilic compounds, this will necessarily lead to the transient formation of coated water droplets in the gas phase and corresponding vesicular structures in the aqueous environment. During this process, the concentration of organic components inside the droplets and vesicles would be drastically increased, allowing for favorable reaction conditions and, in case of the vesicles generated, large trans-membrane concentration gradients. Altogether, the process of periodic formation and destruction of vesicles could offer a perfect environment for molecular evolution in small compartments and for the generation of protocells. The basic process of vesicle formation is reproduced experimentally with a lipid in a water/CO2 system.

Observed Spectral Invariant Behavior of Zenith Radiance in the Transition Zone Between Cloud-Free and Cloudy Regions

NASA Technical Reports Server (NTRS)

Marshak, A.; Knyazikhin, Y.; Chiu, C.; Wiscombe, W.

2010-01-01

The Atmospheric Radiation Measurement Program's (ARM) new Shortwave Spectrometer (SWS) looks straight up and measures zenith radiance at 418 wavelengths between 350 and 2200 nm. Because of its 1-sec sampling resolution, the SWS provides a unique capability to study the transition zone between cloudy and clear sky areas. A surprising spectral invariant behavior is found between ratios of zenith radiance spectra during the transition from cloudy to cloud-free atmosphere. This behavior suggests that the spectral signature of the transition zone is a linear mixture between the two extremes (definitely cloudy and definitely clear). The weighting function of the linear mixture is found to be a wavelength-independent characteristic of the transition zone. It is shown that the transition zone spectrum is fully determined by this function and zenith radiance spectra of clear and cloudy regions. This new finding may help us to better understand and quantify such physical phenomena as humidification of aerosols in the relatively moist cloud environment and evaporation and activation of cloud droplets.

Wire Composition: Its Effect on Metal Disintegration and Particle Formation in Twin-Wire Arc-Spraying Process

NASA Astrophysics Data System (ADS)

Tillmann, W.; Abdulgader, M.

2013-03-01

The wire tips in twin-wire arc-spraying (TWAS) are heated in three different zones. A high-speed camera was used to observe the melting behavior, metal breakup, and particle formation under different operating conditions. In zone (I), the wire tips are melted (liquidus metal) and directly atomized in the form of smaller droplets. Their size is a function of the specific properties of the molten metal and the exerting aerodynamic forces. Zone (II) is directly beneath zone (I) and the origin of the extruded metal sheets at the wire tips. The extruded metal sheets in the case of cored wires are shorter than those observed while using solid wires. In this study, the effects of adjustable parameters and powder filling on melting behavior, particle formation, and process instability were revealed, and a comparison between solid and cored wires was made. The findings can improve the accuracy of the TWAS process modeling.

High speed flow cytometer droplet formation system and method

DOEpatents

Van den Engh, Ger

2000-01-01

A droplet forming flow cytometer system allows high speed processing without the need for high oscillator drive powers through the inclusion of an oscillator or piezoelectric crystal such as within the nozzle volume or otherwise unidirectionally coupled to the sheath fluid. The nozzle container continuously converges so as to amplify unidirectional oscillations which are transmitted as pressure waves through the nozzle volume to the nozzle exit so as to form droplets from the fluid jet. The oscillator is directionally isolated so as to avoid moving the entire nozzle container so as to create only pressure waves within the sheath fluid. A variation in substance concentration is achieved through a movable substance introduction port which is positioned within a convergence zone to vary the relative concentration of substance to sheath fluid while still maintaining optimal laminar flow conditions. This variation may be automatically controlled through a sensor and controller configuration. A replaceable tip design is also provided whereby the ceramic nozzle tip is positioned within an edge insert in the nozzle body so as to smoothly transition from nozzle body to nozzle tip. The nozzle tip is sealed against its outer surface to the nozzle body so it may be removable for cleaning or replacement.

Constraints on formation processes of two coarse-grained calcium- aluminum-rich inclusions: a study of mantles, islands and cores

USGS Publications Warehouse

Meeker, G.P.

1995-01-01

Many coarse-grained calcium- aluminum-rich inclusions (CAIs) contain features that are inconsistent with equilibrium liquid crystallization models of origin. Spinel-free islands (SFIs) in spinel-rich cores of Type B CAIs are examples of such features. One model previously proposed for the origin of Allende 5241, a Type B1 CAI containing SFIs, involves the capture and assimilation of xenoliths by a liquid droplet in the solar nebula (El Goresy et al, 1985; MacPherson et al 1989). This study reports new textural and chemical zoning data from 5241 and identifies previously unrecognized chemical zoning patterns in the melilite mantle and in a SFI. -from Author

Origin of the world-class PGE-Au mineralisation in the Skaergaard intrusion by bulk S-saturation, accumulation, partial dissolution, and secondary reef formation.

NASA Astrophysics Data System (ADS)

Daugaard Nielsen, Troels Frederik

2013-04-01

The Skaergaard intrusion is the type locality for stratiform "Skaergaard-type" PGE-Au mineralisations with layers rich in PGE, followed by Au and Cu. Models for stratiform PGE mineralisations divide into uppers and downers models. Downers models assume bulk liquid S-saturation followed by a variety of accumulation processes and the second model the scavenging of metals by fluids deep in intrusions and deposition in chemical traps above. This investigation is based on continuous profiling in roof, walls and floor. Cu anomalies in roof, walls and floor are contemporaneous and systematics in Pd/Pt and Pd/Au ratios document bulk liquid S-saturation, no loss of precious metal below the mineralisation and no obvious chemical traps. A classic downers process is documented. The timing of the mineralisation is controlled by composition of liquidus plagioclase and fraction of residual magma (F). PGE concentrations are an order of magnitude higher in the floor mineralisation due to accumulation. Systematics across the mineralisation shows in the centre of the intrusion 5 main levels of Pd-concentration followed by an Au and a Cu-level. All levels PGE and Au levels have c. 100 ppm Cu and show no correlation to PGE and Au. 90% of all PGE is contained in one phase, skaergaardite (PdCu).The lower and main PGE concentration has moderate Pd/Pt ratios. Overlying secondary reefs have high, basal Pd/Pt and show local S-saturation reflecting d-values of PGE between sulphide and silicate liquid. No basal high Pd/Pt anomaly occurs at Au and Cu levels and the floor shows four types of mineralisation. The main PGE reef (Pd5) has gradual increase and decrease in PGE and Pd/Pt, dissolution of sulphide, increasing PGE+Au/Cu due to reaction between interstial and documented reactive Fe-rich silicate melt and the bulk magma sulfides. Dissolution of Cu-sulfide increases PGE/Cu, reduces the size of droplets to 30µ (av.) and provides metals for secondary reefs above - formed by migration of interstitial melt - and show expected decrease in Pd/Pt and increase in Au/Pd due to fractionation and substitutions in Skaergaardite (PdCu) and tetra-auricupride (AuCu). The main Au level is elevated relative to the top Pd-level (Pd1). High resolution X-ray tomography and petrography shows the precious metal phases on grain boundaries. The paragenesis is complex with many tellurides, arsenite and sulfides, and primary hydrous phases including amphiboles, ferrosaponite and chlorite. The Au mineralisation level is the residual of the Fe-rich interstitial silicate melt trapped by the layering of the gabbros. The Cu levels above are like the secondary Pd-levels secondary mineralisation levels caused by reaction between primary sulphide and Fe-rich melt. The Skaergaard-type mineralisation owes its characteristics to the concentration of Fe-rich interstitial melt and loss of immiscible granophyric melt from the mush zone at the floor of the residual bulk magma and a continuum of dissolution and S-saturation in an ever changing interstitial melt environment.

Vesicle-metal-sulfide assemblages from the Chelyabinsk meteorite

NASA Astrophysics Data System (ADS)

Andronikov, A.; Lauretta, D.; Hill, D.; Andronikova, I.

2014-07-01

On February 15, 2013, an ET object entered the Earth's atmosphere over the Russian city of Chelyabinsk. It entered at a preatmospheric velocity of 18.6 km/sec at the angle of 17--20°. The bolide responsible for this event was estimated to be 17-20 m in diameter and had a mass of ˜10 Ktons; the ensuing airburst occurred at an altitude >20 km and released a total energy of ˜440 kT [1,2]. The Chelyabinsk meteorite is an equilibrated LL5 ordinary chondrite, shock stage S4, and weathering grade WG0 similar to other LL5 falls [1,2]. Our studied sample is an impact melt breccia consisting of shock-darkened chondrite clasts (SDC) and vesicular impact melt lithology (IML). The SDC have recrystallized textures and contain barred- and porphyritic-olivine, porphyritic-olivine-pyroxene and radial-pyroxene chondrules in the intrachondrule matrix. A dense network of thin fractures in the SDC is filled up with opaque minerals [cf. 3]. Metals in the SDC are kamacite (4.7--8.5 % Ni), taenite (21.4--33.5 % Ni), and martensite (14.5--18.6 % Ni). The IML consists mostly of tiny (<10 microns) silicate grains surrounded by patches of glass. The IML is characterized by the presence of multiple vesicles (up to 1 mm) in silicate matrix. The vesicles are often filled up with sulfide-metal assemblages or only with sulfide. Metals in the IML are martensite (12.9--18.4 % Ni) and taenite (19.3--47.3 % Ni). Sulfides from both SDC and IML are Ni-bearing troilite (62.2--64.2 % Fe; 35.2--37.2 % S; 3000--5000 ppm Ni), with rare pentlandite (41.2--48.6 % Fe, 33.2--34.3 % S, 19.4--23.9 % Ni). The presence of abundant vesicles in the IML indicates strong heating and volatilization. Since no other phase except for sulfide-metal assemblages were observed to fill up vesicles, the likely source of volatiles is S vapor formed by vaporization of FeS during impact melting [cf. 4]. Molten metal and sulfide coalesced into droplets of metal-sulfide liquids forming eventually sulfide-metal assemblages. A notable compositional difference is observed between sulfides not containing metals and those with metals. The metal-free sulfides display higher concentrations of such elements as Ni, Co, Ga, Ge, As, Mo, Ru, Pd, Sn, Sb, Te, Au, and Hg, and lower amounts of Cu than their metal-bearing counterparts. The metal-free sulfides may represent loci of former ''parental'' Fe-S liquid where separation of Fe-Ni-rich from S-rich compositions had just begun and the process was ''frozen'' by rapid cooling. Troilites from the SDC are much more homogeneous in terms of the trace elements than troilites from the IML. These data suggest that the time was sufficient for equilibration of troilites in the SDC and they formed before the melting impact event, likely, during shock events at earlier stages of the asteroid evolution. The fact that there are so many vesicles in the IML, and that they grow to such a large size indicates that the melt must have been buried at some depth after formation but before solidification, otherwise volatiles would escape to space. After the impact and melting occurred on the asteroid body, the impact-induced pressure relieved sharply, causing ''boiling'' of volatiles and generation of vesicles filled later with S-rich liquid. Degassing of such liquid started immediately after the impact pressure was released, but a time lapse during which the degassing had been active was extremely short, i.e., silicate matrix solidified so quickly that cavities (resulted from the escape of some S-rich vapor) did not collapse, and survived in the meteor body until now. Benedix et al. [5] suggested that such solidification took place within a few hours in the case of the PAT 91501 L chondrite meteorite, and [4] calculated that the time of solidification of the impact melt in the case of the LAR 06299 LL chondrite was less than one hour. The absence of kamacite and instead the presence of martensite in metals from metal-sulfide assemblages of the IML also points to fast solidification after the impact-induced melting occurred. Compositions of martensite and coexisting taenite suggest that Fe-Ni partitioning stopped at temperatures ˜450°C [6] not allowing kamacite to crystallize. A high scatter of trace element amounts between sulfide individuals and between metal individuals in the IML also suggests that the inner equilibration was not reached during the cooling. Therefore, sulfide- metal assemblages were very quickly solidified and cooled down below the temperatures at which the diffusion stopped, which is consistent with fast cooling of the impact-induced melt.

"Sizing" Heterogeneous Chemistry in the Conversion of Gaseous Dimethyl Sulfide to Atmospheric Particles.

PubMed

Enami, Shinichi; Sakamoto, Yosuke; Hara, Keiichiro; Osada, Kazuo; Hoffmann, Michael R; Colussi, Agustín J

2016-02-16

The oxidation of biogenic dimethyl sulfide (DMS) emissions is a global source of cloud condensation nuclei. The amounts of the nucleating H2SO4(g) species produced in such process, however, remain uncertain. Hydrophobic DMS is mostly oxidized in the gas phase into H2SO4(g) + DMSO(g) (dimethyl sulfoxide), whereas water-soluble DMSO is oxidized into H2SO4(g) in the gas phase and into SO4(2-) + MeSO3(-) (methanesulfonate) on water surfaces. R = MeSO3(-)/(non-sea-salt SO4(2-)) ratios would therefore gauge both the strength of DMS sources and the extent of DMSO heterogeneous oxidation if Rhet = MeSO3(-)/SO4(2-) for DMSO(aq) + ·OH(g) were known. Here, we report that Rhet = 2.7, a value obtained from online electrospray mass spectra of DMSO(aq) + ·OH(g) reaction products that quantifies the MeSO3(-) produced in DMSO heterogeneous oxidation on aqueous aerosols for the first time. On this basis, the inverse R dependence on particle radius in size-segregated aerosol collected over Syowa station and Southern oceans is shown to be consistent with the competition between DMSO gas-phase oxidation and its mass accommodation followed by oxidation on aqueous droplets. Geographical R variations are thus associated with variable contributions of the heterogeneous pathway to DMSO atmospheric oxidation, which increase with the specific surface area of local aerosols.

40Ar/39Ar Dating of Zn-Pb-Ag Mineralization in the Northern Brooks Range, Alaska

USGS Publications Warehouse

Werdon, Melanie B.; Layer, Paul W.; Newberry, Rainer J.

2004-01-01

The 40Ar/39Ar laser step-heating method potentially can be used to provide absolute ages for a number of formerly undatable, low-temperature ore deposits. This study demonstrates the use of this method by determining absolute ages for Zn-Pb-Ag sediment-hosted massive sulfide deposits and vein-breccia occurrences found throughout a 300-km-long, east-west-trending belt in the northern Brooks Range, Alaska. Massive sulfide deposits are hosted by Mississippian to Pennsylvanian(?) black carbonaceous shale, siliceous mudstone, and lesser chert and carbonate turbidites of the Kuna Formation (e.g., Red Dog, Anarraaq, Lik (Su), and Drenchwater). The vein-breccia occurrences (e.g., Husky, Story Creek, West Kivliktort Mountain, Vidlee, and Kady) are hosted by a deformed but only weakly metamorphosed package of Upper Devonian to Lower Mississippian mixed continental and marine clastic rocks (the Endicott Group) that stratigraphically underlie the Kuna Formation. The vein-breccias are mineralogically similar to, but not spatially associated with, known massive sulfide deposits. The region's largest shale-hosted massive sulfide deposit is Red Dog; it has reserves of 148 Mt grading 16.6 percent zinc, 4.5 percent lead, and 77 g of silver per tonne. Hydrothermally produced white mica in a whole-rock sample from a sulfide-bearing igneous sill within the Red Dog deposit yielded a plateau age of 314.5 Ma. The plateau age of this whole-rock sample records the time at which temperatures cooled below the argon closure temperature of the white mica and is interpreted to represent the minimum age limit for massive sulfide-related hydrothermal activity in the Red Dog deposit. Sulfide-bearing quartz veins at Drenchwater crosscut a hypabyssal intrusion with a maximum biotite age of 337.0 Ma. Despite relatively low sulfide deposition temperatures in the vein-breccia occurrences (162°-251°C), detrital white mica in sandstone immediately adjacent to large vein-breccia zones was partially to completely recrystallized. The 40Ar/39Ar age spectra and inverse isochron plots of the multicomponent whole-rock sandstone samples are more complex than those of single minerals. However, different minerals have different Ca/K and Cl/K ratios and closure temperatures, and these properties were used to identify portions of spectra dominated by argon release from specific minerals. 40Ar/39Ar laser step-heating analyses of Late Devonian sandstone whole rocks produced spectra that record a two-stage resetting history: a Carboniferous hydrothermal event first and later Mesozoic to Tertiary events, which are in agreement with geologic constraints. The 40Ar/39Ar ages and the similar mineralogy, lead isotope composition, and relative stratigraphic positions support the interpretation that the shale-hosted massive sulfide deposits and most vein-breccia occurrences are temporally and genetically related, and that they are different expressions of Carboniferous basinal dewatering.

Exploiting the locality of periodic subsystem density-functional theory: efficient sampling of the Brillouin zone.

PubMed

Genova, Alessandro; Pavanello, Michele

2015-12-16

In order to approximately satisfy the Bloch theorem, simulations of complex materials involving periodic systems are made n(k) times more complex by the need to sample the first Brillouin zone at n(k) points. By combining ideas from Kohn-Sham density-functional theory (DFT) and orbital-free DFT, for which no sampling is needed due to the absence of waves, subsystem DFT offers an interesting middle ground capable of sizable theoretical speedups against Kohn-Sham DFT. By splitting the supersystem into interacting subsystems, and mapping their quantum problem onto separate auxiliary Kohn-Sham systems, subsystem DFT allows an optimal topical sampling of the Brillouin zone. We elucidate this concept with two proof of principle simulations: a water bilayer on Pt[1 1 1]; and a complex system relevant to catalysis-a thiophene molecule physisorbed on a molybdenum sulfide monolayer deposited on top of an α-alumina support. For the latter system, a speedup of 300% is achieved against the subsystem DTF reference by using an optimized Brillouin zone sampling (600% against KS-DFT).

Don't mess with H/sub 2/S

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

Not Available

1987-09-01

The American Petroleum Institute issued a report on ''Recommended Practices for Safe Drilling of Wells Containing Hydrogen Sulfide.'' The study (RP49) updates a first edition published in September 1974. It provides a solid overview of preventive steps that should be taken to safeguard crew and equipment when drilling through H/sub 2/S zones. Discussions cover personnel training, protective equipment, wellsite layout, rig and well equipment, general rig operations and contingency planning and emergency procedures. This article summarizes the report.

Analysis of borehole geophysical information across a uranium deposit in the Jackson Group, Karnes County, Texas

USGS Publications Warehouse

Daniels, Jeffrey J.; Scott, James Henry; Smith, Bruce D.

1979-01-01

Borehole geophysical studies across a uranium deposit in the Jackson Group, South Texas, show the three geochemical environments often associated with uranium roll-type deposits: an altered (oxidized) zone, an ore zone, and an unaltered (reduced) zone. Mineralogic analysis of the total sulfides contained in the drill core shows only slight changes in the total sulfide content among the three geochemical regimes. However, induced polarization measurements on the core samples indicate that samples obtained from the reduced side of the ore zone are more electrically polarizable than those from the oxidized side of the ore zone, and therefore probably contain more pyrite. Analysis of the clay-size fraction in core samples indicates that montmorillonite is the dominant clay mineral. High resistivity values within the ore zone indicate the presence of calcite cement concentrations that are higher than those seen outside of the ore zone. Between-hole resistivity and induced polarization measurements show the presence of an extensive zone of calcite cement within the ore zone, and electrical polarizable material (such as pyrite) within and on the reduced side of the ore zone. A quantitative analysis of the between-hole resistivity data, using a layered-earth model, and a qualitative analysis of the between-hole induced polarization measurements showed that mineralogic variations among the three geochemical environments were more pronounced than were indicated by the geophysical and geologic well logs. Uranium exploration in the South Texas Coastal Plain area has focused chiefly in three geologic units: the Oakville Sandstone, the Catahoula Tuff, and the Jackson Group. The Oakville Sandstone and the Catahoula Tuff are of Miocene age, and the Jackson Group is of Eocene age (Eargle and others, 1971). Most of the uranium mineralization in these formations is low grade (often less than 0.02 percent U3O8) and occurs in shallow deposits that are found by concentrated exploratory drilling programs. The sporadic occurrence of these deposits makes it desirable to develop borehole geophysical techniques that will help to define the depositional environments of the uranium ore, which is characterized by geochemical changes near the uranium deposits. Geochemical changes are accompanied by changes in the physical characteristics of the rocks that can be detected with borehole geophysical tools. This study is concerned with a uranium deposit within the Jackson Group that is located just east of Karnes City, Tex. Five holes were drilled on this property to obtain borehole geophysical data and cores. The cores were analyzed for mineralogic and electrical properties. The borehole geophysical information at this property included induced polarization, resistivity, gamma-gamma density, neutron-neutron, gamma-ray, caliper, and single-point-resistance logs. Between-hole resistivity and induced polarization measurements were made between hole pairs across the ore deposit and off the ore deposit.

Single-Cell RNA Sequencing of Lymph Node Stromal Cells Reveals Niche-Associated Heterogeneity.

PubMed

Rodda, Lauren B; Lu, Erick; Bennett, Mariko L; Sokol, Caroline L; Wang, Xiaoming; Luther, Sanjiv A; Barres, Ben A; Luster, Andrew D; Ye, Chun Jimmie; Cyster, Jason G

2018-05-15

Stromal cells (SCs) establish the compartmentalization of lymphoid tissues critical to the immune response. However, the full diversity of lymph node (LN) SCs remains undefined. Using droplet-based single-cell RNA sequencing, we identified nine peripheral LN non-endothelial SC clusters. Included are the established subsets, Ccl19 hi T-zone reticular cells (TRCs), marginal reticular cells, follicular dendritic cells (FDCs), and perivascular cells. We also identified Ccl19 lo TRCs, likely including cholesterol-25-hydroxylase + cells located at the T-zone perimeter, Cxcl9 + TRCs in the T-zone and interfollicular region, CD34 + SCs in the capsule and medullary vessel adventitia, indolethylamine N-methyltransferase + SCs in the medullary cords, and Nr4a1 + SCs in several niches. These data help define how transcriptionally distinct LN SCs support niche-restricted immune functions and provide evidence that many SCs are in an activated state. Copyright © 2018 Elsevier Inc. All rights reserved.

Isotopic insights into microbial sulfur cycling in oil reservoirs

PubMed Central

Hubbard, Christopher G.; Cheng, Yiwei; Engelbrekston, Anna; Druhan, Jennifer L.; Li, Li; Ajo-Franklin, Jonathan B.; Coates, John D.; Conrad, Mark E.

2014-01-01

Microbial sulfate reduction in oil reservoirs (biosouring) is often associated with secondary oil production where seawater containing high sulfate concentrations (~28 mM) is injected into a reservoir to maintain pressure and displace oil. The sulfide generated from biosouring can cause corrosion of infrastructure, health exposure risks, and higher production costs. Isotope monitoring is a promising approach for understanding microbial sulfur cycling in reservoirs, enabling early detection of biosouring, and understanding the impact of souring. Microbial sulfate reduction is known to result in large shifts in the sulfur and oxygen isotope compositions of the residual sulfate, which can be distinguished from other processes that may be occurring in oil reservoirs, such as precipitation of sulfate and sulfide minerals. Key to the success of this method is using the appropriate isotopic fractionation factors for the conditions and processes being monitored. For a set of batch incubation experiments using a mixed microbial culture with crude oil as the electron donor, we measured a sulfur fractionation factor for sulfate reduction of −30‰. We have incorporated this result into a simplified 1D reservoir reactive transport model to highlight how isotopes can help discriminate between biotic and abiotic processes affecting sulfate and sulfide concentrations. Modeling results suggest that monitoring sulfate isotopes can provide an early indication of souring for reservoirs with reactive iron minerals that can remove the produced sulfide, especially when sulfate reduction occurs in the mixing zone between formation waters (FW) containing elevated concentrations of volatile fatty acids (VFAs) and injection water (IW) containing elevated sulfate. In addition, we examine the role of reservoir thermal, geochemical, hydrological, operational and microbiological conditions in determining microbial souring dynamics and hence the anticipated isotopic signatures. PMID:25285094

Results of LA-ICP-MS sulfide mapping from Algoma-type BIF gold systems with implications for the nature of mineralizing fluids, metal sources, and deposit models

NASA Astrophysics Data System (ADS)

Gourcerol, B.; Kontak, D. J.; Thurston, P. C.; Petrus, J. A.

2018-01-01

Quantitative laser ablation inductively coupled plasma-mass spectrometry (LA-ICP-MS) element distribution maps combined with traverse mode analyses have been acquired on various sulfides (pyrite, pyrrhotite, arsenopyrite) from three Canadian Algoma-type BIF-hosted gold deposits ( 4 Moz Au Meadowbank, ≥ 2.8 Moz Au Meliadine district, 6 Moz Au Musselwhite). These data, in conjunction with detailed petrographic and SEM-EDS observations, provide insight into the nature and relative timing of gold events, the presence and implication of trace element zoning regarding crystallization processes, and elemental associations that fingerprint gold events. Furthermore, the use of an innovative method of processing the LA-ICP-MS data in map and traverse modes, whereby the results are fragmented into time-slice data, to generate various binary plots (Ag versus Ni) provides a means to identify elemental associations (Te, Bi) not otherwise apparent. This integrated means of treating geochemical data, along with petrography, allows multiple gold events and remobilization processes to be recognized and their elemental associations determined. The main gold event in each of these deposits is characterized by the coupling of an As-Se-Te-Ag element association coincident with intense stratabound sulfide-replacement of the Fe-rich host rock. Additionally, the data indicate presence of a later remobilization event, which upgraded the Au tenor, as either non-refractory or refractory type, along fracture networks due to the ingress of subsequent base metal-bearing metamorphic fluids (mainly a Pb-Bi association). Furthermore, the data reveal a stratigraphic influence, as reflected in the elemental associations and the elemental enrichments observed and the nature of the sulfide phase hosting the gold mineralization (arsenopyrite versus pyrite).

Sedimentary sulfides in dune sands of Spiekeroog Island, southern North Sea: A biogeochemical study of sulfur isotope partitioning

NASA Astrophysics Data System (ADS)

Seibert, Stephan; Schubert, Florian; Schmiedinger, Iris; Böttcher, Michael E.; Massmann, Gudrun

2017-04-01

The formation of iron sulfides in sandy sediments and the associated development of stable isotope signatures is still mechanistically not understood. In dune sands under impact of both fresh and saline water several physico-chemical gradients may develop leading to distinctly different biogeochemical zones. In the present study, a 10 m long core from a dune base at the North Eastern part of Spiekeroog Island, southern North Sea, was investigated for the elemental and stable isotope composition. The pyrite (TRIS) content was quantitatively extracted via an acidic Cr(II) distillation procedure and the stable sulfur isotope composition was determined by means of C-irmMS. The pore waters display a downcore increase in salt contents and a mixing between fresh and salt water. The accumulation of metabolites at depth indicate an increasing superimposition of mixing by microbial decomposition of dissolved organic matter with only limited net sulfate reduction. This indicates an essential open system with respect to dissolved sulfate. The sands were found to be very low in TOC, TIC, and TRIS and dominated by quartz minerals. Under the assumption that North Sea water sulfate was the only substantial sulfate source (d34S = + 21per mil), the sedimentary sulfides indicate an overall sulfur isotope discrimination upon microbial sulfate reduction between 39 and 52 per mil, which is within the range of results from other fully marine sands from the Spiekeroog area and laboratory studies with pure cultures of sulfate-reducing bacteria under low cellular sulfate reduction rates. Further investigations are on the way to understand the processes leading to the iron sulfide formation in these organic-poor substrates.

The possible role of thiosulfate in the precipitation of 34S-rich barite in some Mississippi Valley-type deposits

USGS Publications Warehouse

Spirakis, C.S.

1991-01-01

The precipitation of extremely 34S-rich barite in the late stage of mineralization in the Mississippi Valleytype deposits of the Illinois-Kentucky district (U.S.A.) may be explained by reactions involving thiosulfate (S2O3=). Inorganic processes are known to concentrate 34S in the sulfonate site of thiosulfate and 32S in the sulfate site. In the mineralizing solution, these inorganic processes may have fractionated sulfur between the two sites by about 40 per mil. At the low temperatures of the late barite stage of mineralization, bacteria are known to metabolize thiosulfate by various reactions. In one of these, dissimilatory reduction, hydrogen sulfide and sulfite are produced. Isotopically light sulfite is preferentially reduced to sulfide by bacteria to leave a residual sulfite enriched in 34S. Part of the residual sulfite may be oxidized to form isotopically heavy sulfate; part may recombine with hydrogen sulfide to form thiosulfate. The recombination also enriches the sulfonate site in 34S and the sulfane site in 32S. Recycling the newly formed thiosulfate through the above steps further enriches sulfite and sulfate from oxidation of sulfite in 34S. During genesis of the ores, the aggregate effect of these reactions may have been the precipitation of extremely 34S-rich barite. The sequence of reactions suggested above requires the presence of organic matter. Previously proposed reactions to account for the precipitation of sulfide minerals and fluorite and for the carbonate paragenesis also require the presence of organic matter. Thus, organic matter in the host rocks may cause the various ore-zone reactions and account for the localization of the ores. ?? 1991 Springer-Verlag.

Formulation and characterization of garlic (Allium sativum L.) essential oil nanoemulsion and its acaricidal activity on eriophyid olive mites (Acari: Eriophyidae).

PubMed

Mossa, Abdel-Tawab H; Afia, Sahar I; Mohafrash, Samia M M; Abou-Awad, Badawi A

2018-04-01

Green and nanoacaricides including essential oil (EO) nanoemulsions are important compounds to provide new, active, safe acaricides and lead to improvement of avoiding the risk of synthetic acaricides. This study was carried out for the first time on eriophyid mites to develop nanoemulsion of garlic essential oil by ultrasonic emulsification and evaluate its acaricidal activity against the two eriophyid olive mites Aceria oleae Nalepa and Tegolophus hassani (Keifer). Acute toxicity of nanoemulsion was also studied on male rats. Garlic EO was analyzed by gas chromatography-mass spectrometry (GC-MS), and the major compounds were diallyl sulfide (8.6%), diallyl disulfide (28.36%), dimethyl tetrasulfide (15.26%), trisulfide,di-2-propenyl (10.41%), and tetrasulfide,di-2-propenyl (9.67%). Garlic oil nanoemulsion with droplet size 93.4 nm was formulated by ultrasonic emulsification for 35 min. Emulsification time and oil and surfactant ratio correlated to the emulsion droplet size and stability. The formulated nanoemulsion showed high acaricidal activity against injurious eriophyid mites with LC 50 298.225 and 309.634 μg/ml, respectively. No signs of nanoemulsion toxicity were noted in treating rats; thus, it may be considered non-toxic to mammals. Stability of garlic oil nanoemulsion, high acaricidal activity, and the absence of organic toxic solvents make the formulation that may be a possible acaricidal product. Results suggest the possibility of developing suitable natural nanoacaricide from garlic oil.

K/T spherules from Haiti and Wyoming: Origin, diagenesis, and similarity to some microtektites

NASA Technical Reports Server (NTRS)

Bohor, B. F.; Glass, B. P.; Betterton, W. J.

1993-01-01

Spherules with relict glass cores in the K/T boundary bed of Haiti allow for a comparison of these bodies with hollow goyazite shells in the K/T boundary claystone of Wyoming and with younger microtektites of the Ivory Coast strewn field. Samples of the Haitian beds from undisturbed sections at Beloc, as determined by Jehanno et al., contain both hollow shells and relict glass cores rimmed by palagonite that has been partially converted to smectite. These palagonite rims developed from hydration zones formed when hot, splash-form droplets of andesitic impact glass were deposited into water. Mutual collisions between these droplets in the ejecta curtain may have formed point-source stresses on their surfaces. Initiation of hydration would be facilitated at these surface stress points and propagated radially into the glass. The inner surface of these merged hemispherical fronts appears mammillary, which is reflected as scalloping in Haitian relict glass cores.

Use of ERTS-1 images in the search for porphyry copper deposits in Pakistani Baluchistan

NASA Technical Reports Server (NTRS)

Schmidt, R. G.

1973-01-01

Geomorphic features related to a known porphyry copper deposit at Saindak, western Chagai District, Pakistan, are easily distinguished on ERTS-1 images. New geologic information from the images was used in conjunction with known geology to evaluate one previously known prospect area and to suggest two additional ones, but no new prospects were recognized on the basis of the images alone. The study also showed that Saindak-type deposits are not likely to be present in some extensive areas of the Chagai District. The Saindak deposit is in an area of relatively easily eroded folded sedimentary and volcanic rocks. The deposit is characterized by an elongate zone of easily eroded sulfide-rich rock surrounded by this rim and the central sulfide-rich valley are conspicuous features on the images. Swarms of dikes are probably useful for distinguishing real rims from other resistant rock types, but there is no expression of them on the image, although they are easily seen on aerial photographs of the Saindak rim.

Effect of Sulfur and Chlorine on Fireside Corrosion Behavior of Inconel 740 H Superalloy

NASA Astrophysics Data System (ADS)

Jin-tao, Lu; Yan, Li; Zhen, Yang; Jin-yang, Huang; Ming, Zhu; Gu, Y.

2018-03-01

Fireside corrosion behavior of Inconel 740H superalloy was studied at 750 °C in simulated coal ash/flue gas environments by means of XRD, SEM and EDS. The results indicated that the corrosion behavior was strongly related to the SO2 levels and was significantly affected by NaCl additions. In presence of the atmospheres with 0.1 % SO2, the alloy exhibited the highest corrosion resistance due to formation of a stable and dense Cr2O3 film. In presence of the atmosphere with 1.5 % SO2, however, a non-coherent and porous Cr2O3 film was formed. The thickness of film and internal sulfides were substantially increased. The NaCl additions significantly accelerated the corrosion process. A non-protective outer oxide film was formed, composed by multiple layers with serious inner sulfide and spallation. The depths of internal oxidizing and sulfuration zones were significantly increased. The mechanism of ash corrosion formation was also discussed.

Geochronology, geochemistry, and tectonic environment of porphyry mineralization in the central Alaska Peninsula

USGS Publications Warehouse

Wilson, Frederic H.; Cox, Dennis P.

1983-01-01

Porphyry type sulfide systems on the central Alaska Peninsula occupy a transition zone between the Aleutian island magmatic arc and the continental magmatic arc of southern Alaska. Mineralization occurs associated with early and late Tertiary magmatic centers emplaced through a thick section of Mesozoic continental margin clastic sedimentary rocks. The systems are of the molybdenum-rich as opposed to gold-rich type and have anomalous tungsten, bismuth, and tin, attributes of continental-margin deposits, yet gravity data suggest that at least part of the study area is underlain by oceanic or transitional crust. Potassium-argon age determinations indicate a variable time span of up to 2 million years between emplacement and mineralization in a sulfide system with mineralization usually followed by postmineral intrusive events. Finally, mineralization in the study area occurred at many times during the time span of igneous activity and should be an expected stage in the history of a subduction related magmatic center.

Deformation, geochemistry, and origin of massive sulfide deposits, Gossan lead district, Virginia.

USGS Publications Warehouse

Gair, J.E.; Slack, J.F.

1984-01-01

Lenses and layers of massive sulphides comprise a discontinuous horizon in the late Proterozoic metasedimentary Ashe formation. The folded and brecciated sulphides include pyrrhotite, minor chalcopyrite, sphalerite and pyrite, and rare arsenopyrite and galena. The deposits were mined for supergene copper, later for gossan iron, and finally for sulphur. The Ashe formation is interpreted to be marine turbidites, and contains lenses of mafic rocks of probable tholeiitic basalt parentage. Mineralogically and chemically distinctive rocks - for the Ashe formation - are interbedded with the sulphides and may represent metamorphosed alteration zones and/or mixed chemical and clastic sediments. The sulphide deposits are interpreted as syngenetic sediments, modified by deformation during metamorphism. Their deposition occurred in a deep, elongate marine basin overlying a crustal rift zone.-G.J.N.

NONFUEL MINERAL RESOURCES OF THE PACIFIC EXCLUSIVE ECONOMIC ZONE.

USGS Publications Warehouse

Clague, David; Bischoff, James; Howell, David

1984-01-01

The Pacific Exclusive Economic Zone contains a variety of hard mineral resources. Sand and gravel and their associated placer deposits of heavy minerals are the most likely to be developed in the near future, but offshore and deep water deposits of phosphorite, abyssal manganese nodules, ferromanganese crusts enriched in cobalt, and massive sulfide deposits all represent future resources. The distribution, extent, and formation of these deposits are poorly understood and will be clarified only with additional exploration, framework geologic mapping, and study of the processes by which these resources form. It is pointed out that the initial discovery of most hard-mineral resources in the EEZ was made during routine scientific marine-geologic surveys aimed at understanding the framework geology and geologic processes of an offshore region.

Metal endowment reflected in chemical composition of silicates and sulfides of mineralized porphyry copper systems, Urumieh-Dokhtar magmatic arc, Iran

NASA Astrophysics Data System (ADS)

Zarasvandi, Alireza; Rezaei, Mohsen; Raith, Johann G.; Pourkaseb, Houshang; Asadi, Sina; Saed, Madineh; Lentz, David R.

2018-02-01

The present work attempts to discriminate between the geochemical features of magmatic-hydrothermal systems involved in the early stages of mineralization in high grade versus low grade porphyry copper systems, using chemical compositions of silicate and sulfide minerals (i.e., plagioclase, biotite, pyrite and chalcopyrite). The data indicate that magmatic plagioclase in all of the porphyry copper systems studied here has high An% and Al content with a significant trend of evolution toward AlAl3SiO8 and □Si4O8 endmembers, providing insight into the high melt water contents of the parental magmas. Comparably, excess Al and An% in the high grade deposits appears to be higher than that of selected low grade deposits, representing a direct link between the amounts of exsolving hydrothermal fluids and the potential of metal endowment in porphyry copper deposits (PCDs). Also, higher Al contents accompanied by elevated An% are linked to the increasing intensity of disruptive alteration (phyllic) in feldspars from the high grade deposits. As calculated from biotite compositions, chloride contents are higher in the exsolving hydrothermal fluids that contributed to the early mineralization stages of highly mineralized porphyry systems. However, as evidenced by scattered and elevated log (fH2O)/(fHF) and log (fH2O)/(fHCl) values, chloride contents recorded in biotite could be influenced by post potassic fluids. Geothermometry of biotite associated with the onset of sulfide mineralization indicates that there is a trend of increasing temperature from high grade to low grade porphyry systems. Significantly, this is coupled with a sharp change in copper content of pyrite assemblages precipitated at the early stages of mineralization such that Cu decreased with increasing temperature. Based on EMPA and detailed WDS elemental mapping, trace elements do not exhibit complex compositional zoning or solid solution in the sulfide structure. Nevertheless, significant amounts of Cu and Au are contained in pyrite assemblages as micro- to nano-sized inclusions, especially in the high grade fertile porphyry deposits. However, unexpectedly high concentrations of Te, Se, and Re may be associated with early stage of sulfide mineralization, especially when there is no epithermal lithocap. This may highlight the significance of trace metals partitioning in the sulfides formed at the early stages of mineralization in PCDs.

Potential for Sulfide Mineral Deposits in Australian Waters

NASA Astrophysics Data System (ADS)

McConachy, Timothy F.

The world is witnessing a paradigm shift in relation to marine mineral resources. High-value seafloor massive sulfides at active convergent plate boundaries are attracting serious commercial attention. Under the United Nations Convention on the Law of the Sea, maritime jurisdictional zones will increase by extending over continental margins and ocean basins. For Australia, this means a possible additional 3.37 million km2 of seabed. Australia's sovereign responsibility includes, amongst other roles, the management of the exploitation of nonliving resources and sea-bed mining. What, therefore, is the potential in Australia's marine jurisdiction for similar deposits to those currently attracting commercial attention in neighboring nations and for other types/styles of sulfide deposits? A preliminary review of opportunities suggests the following: (i) volcanogenic copper—lead—zinc—silver—gold mineralization in fossil arcs and back arcs in eastern waters Norfolk Ridge and the Three Kings Ridge; (ii) Mississippi Valley-type lead—zinc—silver mineralization in the NW Shelf area; (iii) ophiolite-hosted copper mineralization in the Macquarie Ridge Complex in the Southern Ocean; and (iv) submerged extensions of prospective land-based terranes, one example being offshore Gawler Craton for iron oxide—copper—gold deposits. These areas would benefit from pre-competitive surveys of detailed swath bathymetry mapping, geophysical surveys, and sampling to help build a strategic inventory of future seafloor mineral resources for Australia.

Toxicity of sediments and pore water from Brunswick Estuary, Georgia

USGS Publications Warehouse

Winger, Parley V.; Lasier, Peter J.; Geitner, Harvey

1993-01-01

A chlor-alkali plant in Brunswick, Georgia, USA, discharged >2 kg mercury/d into a tributary of the Turtle River-Brunswick Estuary from 1966 to 1971. Mercury concentrations in sediments collected in 1989 along the tributary near the chlor-alkali plant ranged from 1 to 27 μg/g (dry weight), with the highest concentrations found in surface (0–8 cm) sediments of subtidal zones in the vicinity of the discharge site. Toxicity screening in 1990 using Microtox® bioassays on pore water extracted on site from sediments collected at six stations distributed along the tributary indicated that pore water was highly toxic near the plant discharge. Ten-day toxicity tests on pore water from subsequent sediment samples collected near the plant discharge confirmed high toxicity to Hyalella azteca, and feeding activity was significantly reduced in whole-sediment tests. In addition to mercury in the sediments, other metals (chromium, lead, and zinc) exceeded 50 μg/g, and polychlorobiphenyl (PCB) concentrations ranged from 67 to 95 μg/g. On a molar basis, acid-volatile sulfide concentrations (20–45 μmol/g) in the sediments exceeded the metal concentrations. Because acid-volatile sulfides bind with cationic metals and form metal sulfides, which are generally not bioavailable, toxicities shown by these sediments were attributed to the high concentrations of PCBs and possibly methylmercury.

Residence time effects on technetium reduction in slag-based cementitious materials.

PubMed

Arai, Yuji; Powell, Brian A; Kaplan, D I

2018-01-15

A long-term disposal of technetium-99 ( 99 Tc) has been considered in a type of cementitious formulation, slag-based grout, at the U.S. Department of Energy, Savannah River Site, Aiken SC, U.S.A. Blast furnace slag, which contains S and Fe electron donors, has been used in a mixture with fly ash, and Portland cement to immobilize 99 Tc(VII)O 4 - (aq) in low level radioactive waste via reductive precipitation reaction. However the long-term stability of Tc(IV) species is not clearly understood as oxygen gradually diffuses into the solid structure. In this study, aging effects of Tc speciation were investigated as a function of depth (<2.5cm) in slag-based grout using X-ray absorption spectroscopy. All of Fe(II) in solids was oxidized to Fe(III) after 117d. However, elemental S, sulfide, and sulfoxide persists at the 0-8mm depths even after 485d, suggesting the presence of a reduced zone below the surface few millimeters. Pertechnetate was successfully reduced to Tc(IV) after 29d. Distorted hydrolyzed Tc(IV) octahedral molecules were partially sulfidized and or polymerized at all depths (0-8mm) and were stable in 485d aged sample. The results of this study suggest that variable S species contribute to stabilize the partially sulfidized Tc(IV) species in aged slag-based grout. Copyright © 2017 Elsevier B.V. All rights reserved.

Anomalous δ13C in POC at the chemoautotrophy maximum in the Cariaco Basin

NASA Astrophysics Data System (ADS)

Scranton, M. I.; Taylor, G. T.; Thunell, R.; Tappa, E.; benitez-Nelson, C. R.; Muller-Karger, F. E.; Lorenzoni, L.; Astor, Y. M.

2016-02-01

The Cariaco Basin is the world's largest truly marine, permanently anoxic basin and is located on the continental shelf of Venezuela which experiences strong seasonal upwelling. The CARIACO program has been studying the hydrography, biogeochemistry and properties of sinking flux of the Cariaco Basin since 1995. One of the major puzzles of CARIACO has been the nature of the chemoautotrophic maximum which is seen at depths just below the appearance of hydrogen sulfide ( 250-300 m). The identity and sources of oxidants and reductants to this active microbial community, and the identity of the chemoautotrophic organisms themselves, are still only partially known. Below about 50m (the euphotic zone), δ13C values of suspended particulates range from -23 to -26‰, typical of marine phytoplankton. However we have observed both enrichments (values of up to -16‰) and depletions (values of -28‰) near the redox interface. We had expected to see isotopically light POC in the chemoautotrophy maximum, since DIC δ13C should decrease with depth as organic carbon is remineralized. However both positive and negative isotopic excursions in POC occur at depths where dark carbon fixation is at a maximum, and at or near the transition from micro-oxic to sulfidic water. We postulate that this signal may help to define carbon fixation pathways (and dominant chemoautotrophic populations) in the oxic/sulfidic transition region.

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

Processes of high-T fluid-rock interaction during gold mineralization in carbonate-bearing metasediments: the Navachab gold deposit, Namibia

NASA Astrophysics Data System (ADS)

Dziggel, A.; Wulff, K.; Kolb, J.; Meyer, F. M.

2009-08-01

The Navachab gold deposit in the Damara belt of central Namibia is hosted by a near-vertical sequence of amphibolite facies shelf-type metasediments, including marble, calc-silicate rock, and biotite schist. Petrologic and geochemical data were collected in the ore, alteration halos, and the wall rock to evaluate transport of elements and interaction between the wall rock and the mineralizing fluid. The semi-massive sulfide lenses and quartz-sulfide veins are characterized by a complex polymetallic ore assemblage, comprising pyrrhotite, chalcopyrite, sphalerite, and arsenopyrite, native bismuth, gold, bismuthinite, and bismuth tellurides. Mass balance calculations indicate the addition of up to several orders of magnitude of Au, Bi, As, Ag, and Cu. The mineralized zones also record up to eightfold higher Mn and Fe concentrations. The semi-massive sulfide lenses are situated in the banded calc-silicate rock. Petrologic and textural data indicate that they represent hydraulic breccias that contain up to 50 vol.% ore minerals, and that are dominated by a high-temperature (T) alteration assemblage of garnet-clinopyroxene-K-feldspar-quartz. The quartz-sulfide veins crosscut all lithological units. Their thickness and mineralogy is strongly controlled by the composition and rheological behavior of the wall rocks. In the biotite schist and calc-silicate rock, they are up to several decimeters thick and quartz-rich, whereas in the marble, the same veins are only a few millimeters thick and dominated by sulfides. The associated alteration halos comprise (1) an actinolite-quartz alteration in the biotite schist, (2) a garnet-clinopyroxene-K-feldspar-quartz alteration in the marble and calc-silicate rock, and (3) a garnet-biotite alteration that is recorded in all rock types except the marble. The hydrothermal overprint was associated with large-scale carbonate dissolution and a dramatic increase in CO2 in the ore fluid. Decarbonation of wall rocks, as well as a low REE content of the ore fluid resulted in the mobilization of the REE, and the decoupling of the LREE from the HREE. The alteration halos not only parallel the mineralized zones, but may also follow up single layers away from the mineralization. Alteration is far more pronounced facing upward, indicating that the rocks were steep when veining occurred. The petrologic and geochemical data indicate that the actinolite-quartz- and garnet-clinopyroxene-K-feldspar-quartz alterations formed in equilibrium with a fluid (super-) saturated in Si, and were mainly controlled by the composition of the wall rocks. In contrast, the garnet-biotite alteration formed by interaction with a fluid undersaturated in Si, and was mainly controlled by the fluid composition. This points to major differences in fluid-rock ratios and changes in fluid composition during alteration. The alteration systematics and geometry of the hydrothermal vein system are consistent with cyclic fluctuations in fluid pressure during fault valve action.

Anoxygenic photosynthesis controls oxygenic photosynthesis in a cyanobacterium from a sulfidic spring.

PubMed

Klatt, Judith M; Al-Najjar, Mohammad A A; Yilmaz, Pelin; Lavik, Gaute; de Beer, Dirk; Polerecky, Lubos

2015-03-01

Before the Earth's complete oxygenation (0.58 to 0.55 billion years [Ga] ago), the photic zone of the Proterozoic oceans was probably redox stratified, with a slightly aerobic, nutrient-limited upper layer above a light-limited layer that tended toward euxinia. In such oceans, cyanobacteria capable of both oxygenic and sulfide-driven anoxygenic photosynthesis played a fundamental role in the global carbon, oxygen, and sulfur cycle. We have isolated a cyanobacterium, Pseudanabaena strain FS39, in which this versatility is still conserved, and we show that the transition between the two photosynthetic modes follows a surprisingly simple kinetic regulation controlled by this organism's affinity for H2S. Specifically, oxygenic photosynthesis is performed in addition to anoxygenic photosynthesis only when H2S becomes limiting and its concentration decreases below a threshold that increases predictably with the available ambient light. The carbon-based growth rates during oxygenic and anoxygenic photosynthesis were similar. However, Pseudanabaena FS39 additionally assimilated NO3 (-) during anoxygenic photosynthesis. Thus, the transition between anoxygenic and oxygenic photosynthesis was accompanied by a shift of the C/N ratio of the total bulk biomass. These mechanisms offer new insights into the way in which, despite nutrient limitation in the oxic photic zone in the mid-Proterozoic oceans, versatile cyanobacteria might have promoted oxygenic photosynthesis and total primary productivity, a key step that enabled the complete oxygenation of our planet and the subsequent diversification of life. Copyright © 2015, American Society for Microbiology. All Rights Reserved.

Cable Bacteria and the Bioelectrochemical Snorkel: The Natural and Engineered Facets Playing a Role in Hydrocarbons Degradation in Marine Sediments

PubMed Central

Matturro, Bruna; Cruz Viggi, Carolina; Aulenta, Federico; Rossetti, Simona

2017-01-01

The composition and metabolic traits of the microbial communities acting in an innovative bioelectrochemical system were here investigated. The system, known as Oil Spill Snorkel, was recently developed to stimulate the oxidative biodegradation of petroleum hydrocarbons in anoxic marine sediments. Next Generation Sequencing was used to describe the microbiome of the bulk sediment and of the biofilm growing attached to the surface of the electrode. The analysis revealed that sulfur cycling primarily drives the microbial metabolic activities occurring in the bioelectrochemical system. In the anoxic zone of the contaminated marine sediment, petroleum hydrocarbon degradation occurred under sulfate-reducing conditions and was lead by different families of Desulfobacterales (46% of total OTUs). Remarkably, the occurrence of filamentous Desulfubulbaceae, known to be capable to vehicle electrons deriving from sulfide oxidation to oxygen serving as a spatially distant electron acceptor, was demonstrated. Differently from the sediment, which was mostly colonized by Deltaproteobacteria, the biofilm at the anode hosted, at high extent, members of Alphaproteobacteria (59%) mostly affiliated to Rhodospirillaceae family (33%) and including several known sulfur- and sulfide-oxidizing genera. Overall, we showed the occurrence in the system of a variety of electroactive microorganisms able to sustain the contaminant biodegradation alone or by means of an external conductive support through the establishment of a bioelectrochemical connection between two spatially separated redox zones and the preservation of an efficient sulfur cycling. PMID:28611751

Undocumented water column sink for cadmium in open ocean oxygen-deficient zones

PubMed Central

Janssen, David J.; Conway, Tim M.; John, Seth G.; Christian, James R.; Kramer, Dennis I.; Pedersen, Tom F.; Cullen, Jay T.

2014-01-01

Cadmium (Cd) is a micronutrient and a tracer of biological productivity and circulation in the ocean. The correlation between dissolved Cd and the major algal nutrients in seawater has led to the use of Cd preserved in microfossils to constrain past ocean nutrient distributions. However, linking Cd to marine biological processes requires constraints on marine sources and sinks of Cd. Here, we show a decoupling between Cd and major nutrients within oxygen-deficient zones (ODZs) in both the Northeast Pacific and North Atlantic Oceans, which we attribute to Cd sulfide (CdS) precipitation in euxinic microenvironments around sinking biological particles. We find that dissolved Cd correlates well with dissolved phosphate in oxygenated waters, but is depleted compared with phosphate in ODZs. Additionally, suspended particles from the North Atlantic show high Cd content and light Cd stable isotope ratios within the ODZ, indicative of CdS precipitation. Globally, we calculate that CdS precipitation in ODZs is an important, and to our knowledge a previously undocumented marine sink of Cd. Our results suggest that water column oxygen depletion has a substantial impact on Cd biogeochemical cycling, impacting the global relationship between Cd and major nutrients and suggesting that Cd may be a previously unidentified tracer for water column oxygen deficiency on geological timescales. Similar depletions of copper and zinc in the Northeast Pacific indicate that sulfide precipitation in ODZs may also have an influence on the global distribution of other trace metals. PMID:24778239

Undocumented water column sink for cadmium in open ocean oxygen-deficient zones.

PubMed

Janssen, David J; Conway, Tim M; John, Seth G; Christian, James R; Kramer, Dennis I; Pedersen, Tom F; Cullen, Jay T

2014-05-13

Cadmium (Cd) is a micronutrient and a tracer of biological productivity and circulation in the ocean. The correlation between dissolved Cd and the major algal nutrients in seawater has led to the use of Cd preserved in microfossils to constrain past ocean nutrient distributions. However, linking Cd to marine biological processes requires constraints on marine sources and sinks of Cd. Here, we show a decoupling between Cd and major nutrients within oxygen-deficient zones (ODZs) in both the Northeast Pacific and North Atlantic Oceans, which we attribute to Cd sulfide (CdS) precipitation in euxinic microenvironments around sinking biological particles. We find that dissolved Cd correlates well with dissolved phosphate in oxygenated waters, but is depleted compared with phosphate in ODZs. Additionally, suspended particles from the North Atlantic show high Cd content and light Cd stable isotope ratios within the ODZ, indicative of CdS precipitation. Globally, we calculate that CdS precipitation in ODZs is an important, and to our knowledge a previously undocumented marine sink of Cd. Our results suggest that water column oxygen depletion has a substantial impact on Cd biogeochemical cycling, impacting the global relationship between Cd and major nutrients and suggesting that Cd may be a previously unidentified tracer for water column oxygen deficiency on geological timescales. Similar depletions of copper and zinc in the Northeast Pacific indicate that sulfide precipitation in ODZs may also have an influence on the global distribution of other trace metals.

Anoxygenic Photosynthesis Controls Oxygenic Photosynthesis in a Cyanobacterium from a Sulfidic Spring

PubMed Central

Al-Najjar, Mohammad A. A.; Yilmaz, Pelin; Lavik, Gaute; de Beer, Dirk; Polerecky, Lubos

2015-01-01

Before the Earth's complete oxygenation (0.58 to 0.55 billion years [Ga] ago), the photic zone of the Proterozoic oceans was probably redox stratified, with a slightly aerobic, nutrient-limited upper layer above a light-limited layer that tended toward euxinia. In such oceans, cyanobacteria capable of both oxygenic and sulfide-driven anoxygenic photosynthesis played a fundamental role in the global carbon, oxygen, and sulfur cycle. We have isolated a cyanobacterium, Pseudanabaena strain FS39, in which this versatility is still conserved, and we show that the transition between the two photosynthetic modes follows a surprisingly simple kinetic regulation controlled by this organism's affinity for H2S. Specifically, oxygenic photosynthesis is performed in addition to anoxygenic photosynthesis only when H2S becomes limiting and its concentration decreases below a threshold that increases predictably with the available ambient light. The carbon-based growth rates during oxygenic and anoxygenic photosynthesis were similar. However, Pseudanabaena FS39 additionally assimilated NO3− during anoxygenic photosynthesis. Thus, the transition between anoxygenic and oxygenic photosynthesis was accompanied by a shift of the C/N ratio of the total bulk biomass. These mechanisms offer new insights into the way in which, despite nutrient limitation in the oxic photic zone in the mid-Proterozoic oceans, versatile cyanobacteria might have promoted oxygenic photosynthesis and total primary productivity, a key step that enabled the complete oxygenation of our planet and the subsequent diversification of life. PMID:25576611

Toxic metal(loid) speciation during weathering of iron sulfide mine tailings under semi-arid climate

PubMed Central

Root, Robert A.; Hayes, Sarah M.; Hammond, Corin M.; Maier, Raina M.; Chorover, Jon

2015-01-01

Toxic metalliferous mine-tailings pose a significant health risk to ecosystems and neighboring communities from wind and water dispersion of particulates containing high concentrations of toxic metal(loid)s (e.g., Pb, As, Zn). Tailings are particularly vulnerable to erosion before vegetative cover can be reestablished, i.e., decades or longer in semi-arid environments without intervention. Metal(loid) speciation, linked directly to bioaccessibility and lability, is controlled by mineral weathering and is a key consideration when assessing human and environmental health risks associated with mine sites. At the semi-arid Iron King Mine and Humboldt Smelter Superfund site in central Arizona, the mineral assemblage of the top 2 m of tailings has been previously characterized. A distinct redox gradient was observed in the top 0.5 m of the tailings and the mineral assemblage indicates progressive transformation of ferrous iron sulfides to ferrihydrite and gypsum, which, in turn weather to form schwertmannite and then jarosite accompanied by a progressive decrease in pH (7.3 to 2.3). Within the geochemical context of this reaction front, we examined enriched toxic metal(loid)s As, Pb, and Zn with surficial concentrations 41.1, 10.7, 39.3 mM kg-1 (3080, 2200, and 2570 mg kg-1), respectively. The highest bulk concentrations of As and Zn occur at the redox boundary representing a 1.7 and 4.2 fold enrichment relative to surficial concentrations, respectively, indicating the translocation of toxic elements from the gossan zone to either the underlying redox boundary or the surface crust. Metal speciation was also examined as a function of depth using X-ray absorption spectroscopy (XAS). The deepest sample (180 cm) contains sulfides (e.g., pyrite, arsenopyrite, galena, and sphalerite). Samples from the redox transition zone (25-54 cm) contain a mixture of sulfides, carbonates (siderite, ankerite, cerrusite, and smithsonite) and metal(loid)s sorbed to neoformed secondary Fe phases, principally ferrihydrite. In surface samples (0-35 cm), metal(loid)s are found as sorbed species or incorporated into secondary Fe hydroxysulfate phases, such as schwertmannite and jarosites. Metal-bearing efflorescent salts (e.g., ZnSO4·nH2O) were detected in the surficial sample. Taken together, these data suggest the bioaccessibility and lability of metal(loid)s are altered by mineral weathering, which results in both the downward migration of metal(loid)s to the redox boundary, as well as the precipitation of metal salts at the surface. PMID:26549929

Uranium Bio-accumulation and Cycling as revealed by Uranium Isotopes in Naturally Reduced Sediments from the Upper Colorado River Basin

NASA Astrophysics Data System (ADS)

Lefebvre, Pierre; Noël, Vincent; Jemison, Noah; Weaver, Karrie; Bargar, John; Maher, Kate

2016-04-01

Uranium (U) groundwater contamination following oxidized U(VI) releases from weathering of mine tailings is a major concern at numerous sites across the Upper Colorado River Basin (CRB), USA. Uranium(IV)-bearing solids accumulated within naturally reduced zones (NRZs) characterized by elevated organic carbon and iron sulfide compounds. Subsequent re-oxidation of U(IV)solid to U(VI)aqueous then controls the release to groundwater and surface water, resulting in plume persistence and raising public health concerns. Thus, understanding the extent of uranium oxidation and reduction within NRZs is critical for assessing the persistence of the groundwater contamination. In this study, we measured solid-phase uranium isotope fractionation (δ238/235U) of sedimentary core samples from four study sites (Shiprock, NM, Grand Junction, Rifle and Naturita, CO) using a multi-collector inductively coupled plasma mass spectrometer (MC-ICP-MS). We observe a strong correlation between U accumulation and the extent of isotopic fractionation, with Δ238U up to +1.8 ‰ between uranium-enriched and low concentration zones. The enrichment in the heavy isotopes within the NRZs appears to be especially important in the vadose zone, which is subject to variations in water table depth. According to previous studies, this isotopic signature is consistent with biotic reduction processes associated with metal-reducing bacteria. Positive correlations between the amount of iron sulfides and the accumulation of reduced uranium underline the importance of sulfate-reducing conditions for U(IV) retention. Furthermore, the positive fractionation associated with U reduction observed across all sites despite some variations in magnitude due to site characteristics, shows a regional trend across the Colorado River Basin. The maximum extent of 238U enrichment observed in the NRZ proximal to the water table further suggests that the redox cycling of uranium, with net release of U(VI) to the groundwater by non-fractionating oxidation, is occurring within this zone. Thus, release of uranium from the NRZs may play a critical role in the persistence of groundwater contamination at these sites.

The carbonaceous phyllite rock-hosted Pedra Verde copper mine, Borborema Province, Brazil: Stable isotope constraints, structural controls and metallogenic evolution

NASA Astrophysics Data System (ADS)

da Silva Nogueira de Matos, José Henrique; Saraiva dos Santos, Ticiano José; Virgínia Soares Monteiro, Lena

2017-12-01

The Pedra Verde Copper Mine is located in the Viçosa do Ceará municipality, State of Ceará, NE Brazil. The copper mineralization is hosted by the Pedra Verde Phyllite, which is a carbonaceous chlorite-calcite phyllite with subordinate biotite. It belongs to the Neoproterozoic Martinópole Group of the Médio Coreaú Domain, Borborema Province. The Pedra Verde deposit is stratabound and its ore zoning is conspicuous, according to the following sequence, from bottom to top: marcasite/pyrite, native silver, chalcopyrite, bornite, chalcocite, native copper and hematite. Barite and carbonaceous material are reported in ore zones. Zoning reflects the ore formation within a redox boundary developed due to the interaction between oxidized copper- and sulfate-bearing fluids and the reduced phyllite. Structural control on mineralization is evidenced by the association of the ore minerals with veins, hinge folds, shadow pressures, and mylonitic foliation. It was mainly exercised by a dextral transcurrent shear zone developed during the third deformational stage identified in the Médio Coreaú Domain between 590 Ma and 570 Ma. This points to the importance of epigenetic, post-metamorphic deformational events for ore formation. Oxygen isotopic composition (δ18OH2O = 8.94 to 11.28‰, at 250 to 300 °C) estimated for the hydrothermal fluids in equilibrium with calcite indicates metamorphic or evolved meteoric isotopic signatures. The δ13CPDB values (-2.60 to -9.25‰) obtained for hydrothermal calcite indicate mixing of carbon sources derived from marine carbonate rocks and carbonaceous material. The δ34SCDT values (14.88 to 36.91‰) of sulfides suggest evaporites as sulfate sources or a closed system in relation to SO42- availability to form H2S. Carbonaceous matter had a key role in thermochemical sulfate processes and sulfide precipitation. The Pedra Verde Copper Mine is considered the first stratabound meta-sedimentary rock-hosted copper deposit described in Brazil and shares similarities with the syn-orogenic copper deposits of the Congo-Zambian Copperbelt formed during the Gondwana amalgamation.

Fe(II)- and sulfide-facilitated reduction of 99Tc(VII)O4- in microbially reduced hyporheic zone sediments

NASA Astrophysics Data System (ADS)

Lee, Ji-Hoon; Zachara, John M.; Fredrickson, James K.; Heald, Steve M.; McKinley, James P.; Plymale, Andrew E.; Resch, Charles T.; Moore, Dean A.

2014-07-01

Redox-reactive, biogeochemical phases generated by reductive microbial activity in hyporheic zone sediments from a dynamic groundwater-river interaction zone were evaluated for their ability to reduce soluble pertechnetate [99Tc(VII)O4-] to less soluble Tc(IV). The sediments were bioreduced by indigenous microorganisms that were stimulated by organic substrate addition in synthetic groundwater with or without sulfate. In most treatments, 20 μmol L-1 initial aqueous Tc(VII) was reduced to near or below detection (3.82 × 10-9 mol L-1) over periods of days to months in suspensions of variable solids concentrations. Native sediments containing significant lithogenic Fe(II) in various phases were, in contrast, unreactive with Tc(VII). The reduction rates in the bioreduced sediments increased with increases in sediment mass, in proportion to weak acid-extractable Fe(II) and sediment-associated sulfide (AVS). The rate of Tc(VII) reduction was first order with respect to both aqueous Tc(VII) concentration and sediment mass, but correlations between specific reductant concentrations and reaction rate were not found. X-ray microprobe measurements revealed a strong correlation between Tc hot spots and Fe-containing mineral particles in the sediment. However, only a portion of Fe-containing particles were Tc-hosts. The Tc-hot spots displayed a chemical signature (by EDXRF) similar to pyroxene. The application of autoradiography and electron microprobe allowed further isolation of Tc-containing particles that were invariably found to be ca 100 μm aggregates of primary mineral material embedded within a fine-grained phyllosilicate matrix. EXAFS spectroscopy revealed that the Tc(IV) within these were a combination of a Tc(IV)O2-like phase and Tc(IV)-Fe surface clusters, with a significant fraction of a TcSx-like phase in sediments incubated with SO42-. AVS was implicated as a more selective reductant at low solids concentration even though its concentration was below that required for stoichiometric reduction of Tc(VII). These results demonstrate that composite mineral aggregates may be redox reaction centers in coarse-textured hyporheic zone sediments regardless of the dominant anoxic biogeochemical processes.

Fe(II)- and Sulfide-Facilitated Reduction of 99Tc(VII)O4- in Microbially Reduced Hyporheic Zone Sediments

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

Lee, Ji-Hoon; Zachara, John M.; Fredrickson, Jim K.

Redox-reactive, biogeochemical phases generated by reductive microbial activity in hyporheic zone sediments from a dynamic groundwater-river interaction zone were evaluated for their ability to reduce soluble pertechnetate [99Tc(VII)O4-] to less soluble Tc(IV). The sediments were bioreduced by indigenous microorganisms that were stimulated by organic substrate addition in synthetic groundwater with or without sulfate. In most treatments, 20 µmol L-1 initial aqueous Tc(VII) was reduced to near or below detection (3.82×10-9 mol L-1) over periods of days to months in suspensions of variable solids concentrations. Native sediments containing significant lithogenic Fe(II) in various phases were, in contrast, unreactive with Tc(VII). Themore » reduction rates in the bioreduced sediments increased with increases in sediment mass, in proportion to weak acid-extractable Fe(II) and sediment-associated sulfide (AVS). The rate of Tc(VII) reduction was first order with respect to both aqueous Tc(VII) concentration and sediment mass, but correlations between specific reductant concentrations and reaction rate were not found. X-ray microprobe measurements revealed a strong correlation between Tc hot spots and Fe-containing mineral particles in the sediment. However, only a portion of Fe-containing particles were Tc-hosts. The Tc-hot spots displayed a chemical signature (by EDXRF) similar to pyroxene. The application of autoradiography and electron microprobe allowed further isolation of Tc-containing particles that were invariably found to be ca 100 µm aggregates of primary mineral material embedded within a fine-grained phyllosilicate matrix. EXAFS spectroscopy revealed that the Tc(IV) within these were a combination of a Tc(IV)O2-like phase and Tc(IV)-Fe surface clusters, with a significant fraction of a TcSx-like phase in sediments incubated with SO42-. AVS was implicated as a more selective reductant at low solids concentration even though its concentration was below that required for stoichiometric reduction of Tc(VII). These results demonstrate that composite mineral aggregates may be redox reaction centers in coarse-textured hyporheic zone sediments regardless of the dominant anoxic biogeochemical processes.« less

Laser-Induced Fluorescence and Synthetic Jet Fuel Analysis in the Ultra Compact Combustor

DTIC Science & Technology

2009-12-01

In the primary zone, high- temperature, high-pressure air enters from the compressor and flows around fuel injectors spraying atomized liquid -droplet...chemical reaction in which synthesis gas , a mixture of carbon monoxide and hydrogen, is converted into liquid hydrocarbons of various forms. The most...the fuel lines needed to be rebuilt due to a recent COAL lab renovation. The liquid fuel system had not been used for nearly two years so some

Investigation of surface water behavior during glaze ice accretion

NASA Technical Reports Server (NTRS)

Hansman, R. John, Jr.; Turnock, Stephen R.

1990-01-01

A series of experimental investigations that focused on isolating the primary factors that control the behavior of unfrozen surface water during glaze ice accretion were conducted. Detailed microvideo observations were made of glaze ice accretions on 2.54 cm diam cylinders in a closed-loop refrigerated wind tunnel. Distinct zones of surface water behavior were observed; a smooth wet zone in the stagnation region with a uniform water film, a rough zone where surface tension effects caused coalescence of surface water into stationary beads, and a zone where surface water ran back as rivulets. The location of the transition from the smooth to the rough zone was found to migrate towards the stagnation point with time. Comparative tests were conducted to study the effect of the substrate thermal and roughness properties on ice accretion. The importance of surface water behavior was evaluated by the addition of a surface tension reducing agent to the icing tunnel water supply, which significantly altered the accreted glaze ice shape. Measurements were made to determine the contact angle behavior of water droplets on ice. A simple multizone modification to current glaze ice accretion models was proposed to include the observed surface roughness behavior.

Constraints on Hf and Zr mobility in high-sulfidation epithermal systems: formation of kosnarite, KZr2(PO4)3, in the Chaquicocha gold deposit, Yanacocha district, Peru

NASA Astrophysics Data System (ADS)

Deditius, Artur P.; Utsunomiya, Satoshi; Sanchez-Alfaro, Pablo; Reich, Martin; Ewing, Rodney C.; Kesler, Stephen E.

2015-04-01

We report the first occurrence of Hf-rich kosnarite [K(Hf,Zr)2(PO4)3], space group R- 3c, Z = 6, in the giant Chaquicocha high-sulfidation epithermal gold deposit in the Yanacocha mining district, Peru. Kosnarite crystals are small (<100 μm) and occur in 2-3-mm-thick veins that cut intensively silicified rocks. The paragenesis includes a first stage of As-free pyrite and quartz (plus gratonite and rutile), followed by trace metal-rich pyrite [(Fe,As,Pb,Au)S2] and secondary Fe sulfates. Kosnarite is associated with quartz and is clearly late within the paragenetic sequence. Electron microprobe analyses (EMPA) of kosnarite show relatively high concentrations of HfO2 and Rb2O (7.61 and 1.05 wt.%, respectively). The re-calculated chemical formulas of kosnarite vary from KΣ1.00(Zr1.93Na0.01Hf0.01Mn0.01)Σ1.96(P3.04O4)Σ3 to (K0.92Rb0.05Na0.03)Σ1.00(Zr1.81Hf0.19)Σ2.00 [(P2.98Si0.02As0.01)Σ3.01O4]Σ3, where Hf and Rb are most likely incorporated according to a coupled substitution of Hf4+ + Rb+ ⇔ Zr4+ + K+. Back-scattered electron (BSE) images and elemental mapping of kosnarite reveal that Hf and Rb are enriched in 2-10-μm-wide oscillatory and/or sector zones. High-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) observations of such zones reveal a pattern of alternating, 5-50-nm-thick, Hf-rich and Zr-rich nanozones. These high-resolution observations indicate that the incorporation of Hf does not appear to cause significant distortion in the kosnarite structure. Semiquantitative TEM-energy-dispersive X-ray spectrometry (EDS) analyses of the nano-layers show up to 22 wt.% of HfO2, which corresponds to 31 mol% of the hypothetical, KHf2(PO4)3, end-member. The presence of kosnarite in the advanced argillic alteration zone at Yanacocha is indicative of Hf and Zr mobility under highly acidic conditions and points towards an unforeseen role of phosphates as sinks of Zr and Hf in high-sulfidation epithermal environments. Finally, potentially new geochronological applications of highly insoluble vein kosnarite, including Rb-Sr dating, may provide further age constraints in pervasively altered areas where other isotopic systems might have been reset.

Nanoparticles of noble metals in the supergene zone

NASA Astrophysics Data System (ADS)

Zhmodik, S. M.; Kalinin, Yu. A.; Roslyakov, N. A.; Mironov, A. G.; Mikhlin, Yu. L.; Belyanin, D. K.; Nemirovskaya, N. A.; Spiridonov, A. M.; Nesterenko, G. V.; Airiyants, E. V.; Moroz, T. N.; Bul'bak, T. A.

2012-04-01

Formation of noble metal nanoparticles is related to various geological processes in the supergene zone. Dispersed mineral phases appear during weathering of rocks with active participation of microorganisms, formation of soil, in aqueous medium and atmosphere. Invisible gold and other noble metals are incorporated into oxides, hydroxides, and sulfides, as well as in dispersed organic and inorganic carbonic matter. Sulfide minerals that occur in bedrocks and ores unaltered by exogenic processes and in cementation zone are among the main concentrators of noble metal nanoparticles. The ability of gold particles to disaggregate is well-known and creates problems in technological and analytical practice. When Au and PGE nanoparticles and clusters occur, these problems are augmented because of their unusual reactions and physicochemical properties. The studied gold, magnetite, titanomagnetite and pyrite microspherules from cementation zone and clay minerals of laterites in Republic of Guinea widen the knowledge of their abundance and inferred formation conditions, in particular, in the contemporary supergene zone. Morphology and composition of micrometer-sized Au mineral spherules were studied with SEM and laser microprobe. The newly formed segregations of secondary gold on the surface of its residual grains were also an object of investigation. The character of such overgrowths is the most indicative for nanoparticles. The newly formed Au particles provide evidence for redistribution of ultradispersed gold during weathering. There are serious prerequisites to state that microorganisms substantially control unusual nano-sized microspherical morphology of gold particles in the supergene zone. This is supported by experiments indicating active absorption of gold by microorganisms and direct evidence for participation of Ralstonia metallidurans bacteria in the formation of peculiar corroded bacteriomorphic surface of gold grains. In addition, the areas enriched in carbon and nitrogen have been detected with SEM on the surface of gold spherules from Guinea. Such organic compounds as serine, alanine, and glycine are identified on their surface with Raman spectroscopy. The experiments have been carried out and new data have been obtained indicating the role of micromycetes in concentration and distribution of noble metals in ferromanganese nodules of the World Ocean. Au and Pt were detected in the system with radioisotopes. It has been established that two forms of gold distribution develop within pseudomorphs of fungi colonies: (1) as pseudomorphic concentrates and (2) dispersed form unrelated to the colony structure. Inhomogeneities in distribution of dispersed platinum are manifested in the form of linear anomalies with elevated concentrations at the margins of the colonies.

Returning from the deep: Archean atmospheric fingerprints in modern hotspot lavas (Invited)

NASA Astrophysics Data System (ADS)

Jackson, M. G.; Cabral, R. A.; Rose-Koga, E. F.; Koga, K. T.; Whitehouse, M. J.; Antonelli, M. A.; Farquhar, J.; Day, J. M.; Hauri, E. H.

2013-12-01

Ocean plates transport surface materials, including oceanic crust and sediment, into the mantle at subduction zones. However, the fate of the subducted package--oceanic crust and sediment--in the mantle is poorly understood. A long-standing hypothesis maintains that subducted materials reside in the mantle for an extended, but unknown, period of time and are then recycled back to the Earth's surface in regions of buoyantly upwelling mantle and melted beneath hotspots. Sulfur isotopes provide an important new tool to evaluate the presence of ancient recycled materials in hotspot lavas. Widespread terrestrial mass independently fractionated sulfur (MIF-S) isotope signatures were generated exclusively through atmospheric photochemical reactions until ~2.45 Ga. In fact, the only significant reservoirs of MIF-S containing rocks documented so far are sediments and hydrothermal rocks older than ~2.45 Ga. Armed with this insight, we examined sulfur isotopes in olivine phenocrysts and olivine-hosted sulfides in lavas from the island of Mangaia, Cook Islands. Lavas from this location host unusually radiogenic Pb-isotopic compositions--referred to as a HIMU (high U/Pb) component--and this has been attributed to ancient recycled oceanic crust in the mantle source. In Cabral et al. (2013), we report MIF-S in olivine phenocrysts and olivine-hosted sulfides. The discovery of MIF-S isotopic signatures in young hotspot lavas appears to provide a "timestamp" and "signature" for preservation of subducted Archean surface materials in the mantle sourcing Mangaia lavas. We report new sulfur isotope data on olivine-hosted sulfides from the Mangaia lavas that reinforce our discovery of MIF-S anomalies reported in Cabral et al. (2013). We also report new sulfur isotopic data on Mangaia whole rock powders, and we find no evidence of MIF-S signatures. It is not yet clear why the individual Mangaia sulfides and the olivine separates have more extreme MIF-S than the whole rocks. We consider it likely that the MIF-S anomaly measured in the olivine separates was diminished relative to the olivine-hosted sulfides by incorporation of modern sulfur into the olivine separates by low-temperature processes operating on the rocks during the 20 Ma since eruption: The absence of a MIF-S anomaly in the whole rock that has olivine-hosted sulfides with MIF-S anomalies may be a result of near-complete replacement of the magmatic sulfur (with a MIF-S anomaly) with modern sulfur (with no MIF-S anomaly) during surficial weathering over 20 Ma. The sulfur in the olivine-hosted sulfides with the largest MIF-S anomalies represents a very small proportion of the sulfur in a bulk basaltic rock and therefore do not impart a clear MIF-S anomaly on the bulk rock analysis. Very few data are available to evaluate this hypothesis. Therefore, pairing sulfur isotope measurements with whole rocks, mineral separates and olivine-hosted sulfides with careful petrographic and electron probe analyses of the samples will be critical for evaluating the origin of the sulfides--primary magmatic or secondary--and the origin and distribution of the sulfur-isotopic signatures in OIB.

Self-focused acoustic ejectors for viscous liquids.

PubMed

Hon, S F; Kwok, K W; Li, H L; Ng, H Y

2010-06-01

Self-focused acoustic ejectors using the Fresnel zone plate (FZP) have been developed for ejecting viscous liquids, without nozzle, in the drop-on-demand mode. The FZP is composed of a lead zirconate titanate piezoelectric plate patterned with a series of annular electrodes, with the unelectroded region of the plate removed. Our results show that the acoustic waves are effectively self-focused by constructive interference in glycerin (with a viscosity of 1400 mPa s), giving small focal points with a high pressure. Due to the high attenuation, the wave pressure decreases significantly with the distance from the FZP. Nevertheless, the pressure at the focal points 2.5 and 6.5 mm from the FZP is high enough to eject glycerin droplets in the drop-on-demand mode. Driven by a simple wave train comprising a series of sinusoidal voltages with an amplitude of 35 V, a frequency of 4.28 MHz, and a duration of 2 ms, the ejector can eject fine glycerin droplets with a diameter of 0.4 mm at a repetition frequency of 120 Hz in a downward direction. Droplets of other viscous liquids, such as the prepolymer of an epoxy with a viscosity of 2000 mPa s, can also be ejected in the drop-on-demand mode under similar conditions.

Low Reynolds Number Droplet Combustion In CO2 Enriched Atmospheres In Microgravity

NASA Technical Reports Server (NTRS)

Hicks, M. C.

2003-01-01

The effect of radiative feedback from the gas phase in micro-gravity combustion processes has been of increasing concern because of the implications in the selection and evaluation of appropriate fire suppressants. The use of CO2, an optically thick gas in the infrared region of the electromagnetic spectrum, has garnered widespread acceptance as an effective fire suppressant for most ground based applications. Since buoyant forces often dominate the flow field in 1-g environments the temperature field between the flame front and the fuel surface is not significantly affected by gas phase radiative absorption and re-emission as these hot gases are quickly swept downstream. However, in reduced gravity environments where buoyant-driven convective flows are negligible and where low-speed forced convective flows may be present at levels where gas phase radiation becomes important, then changes in environment that enhance gas phase radiative effects need to be better understood. This is particularly true in assessments of flammability limits and selection of appropriate fire suppressants for future space applications. In recognition of this, a ground-based investigation has been established that uses a droplet combustion configuration to systematically study the effects of enhanced gas phase radiation on droplet burn rates, flame structure, and radiative output from the flame zone.

Experiments on Nitrogen Oxide Production of Droplet Arrays Burning under Microgravity Conditions

NASA Astrophysics Data System (ADS)

Moesl, Klaus; Sattelmayer, Thomas; Kikuchi, Masao; Yamamoto, Shin; Yoda, Shinichi

The optimization of the combustion process is top priority in current aero-engine and aircraft development, particularly from the perspectives of high efficiency, minimized fuel consumption, and a sustainable exhaust gas production. Aero-engines are exclusively liquid-fueled with a strong correlation between the combustion temperature and the emissions of nitric oxide (NOX ). Due to safety concerns, the progress in NOX reduction has been much slower than in stationary gas turbines. In the past, the mixing intensity in the primary zone of aero-engine combustors was improved and air staging implemented. An important question for future aero-engine combustors, consequently, is how partial vaporization influences the NOX emissions of spray flames? In order to address this question, the combustion of partially vaporized, linear droplet arrays was studied experimentally under microgravity conditions. The influence of fuel pre-vaporization on the NOX emissions was assessed in a wide range. The experiments were performed in a drop tower and a sounding rocket campaign. The microgravity environment provided ideal experiment conditions without the disturbing ef-fect of natural convection. This allowed the study of the interacting phenomena of multi-phase flow, thermodynamics, and chemical kinetics. This way the understanding of the physical and chemical processes related to droplet and spray combustion could be improved. The Bremen drop tower (ZARM) was utilized for the precursor campaign in July 2008, which was com-prised of 30 drops. The sounding rocket experiments, which totaled a microgravity duration of 6 minutes, were finally performed on the flight of TEXUS-46 in November 2009. On both campaigns the "Japanese Combustion Module" (JCM) was used. It is a cooperative experi-ment on droplet array combustion between the Japan Aerospace Exploration Agency (JAXA) and ESA's (European Space Agency) research team, working on the combustion properties of partially premixed sprays. One droplet array consisted of five droplets (for sounding rocket) and 9 -17 droplets (for drop tower) of the hydrocarbon n-decane (C10 H22 ). While keeping the pressure at 1.0 bar (+/-20 mbar), the combustion chamber temperature and the fuel vaporization time were varied in the range of 300 -500 K and 0.5 -18 s, respectively. Consequently, the total amount of fuel, the local equivalence ratio Φ along the droplet array, and the dimensionless droplet spacing S/d0 , with d0 being the initial droplet diameter, were adapted. Ignition was initiated by a hot-wire igniter from one end of the droplet array. Representative gas samples were collected from every single combustion sequence after flame extinction and stored in specially treated gas sampling cylinders for their succeeding analysis on ground. Visual observation of the combustion process, as well as temperature and pressure logging, supported the scientific interpretation of the gas analysis. With an increase of the preheating temperature, NOX emissions increase due to a higher effec-tive flame temperatures. However, with an increasing pre-vaporization, NOX emissions become lower due to the dropping number and the dropping size of burning droplets, acting as hot spots. A correction for the effect of the preheating temperature was developed. It reveals the effect of pre-vaporization and shows that the NOX emissions are almost independent of it for near-stoichiometric operation. At overall lean conditions the NOX emissions drop non-linearly with the degree of vaporization. Up to now, this leads to the conclusion that a high degree of vaporization is required in order to achieve substantial NOX abatement.

Molybdenum isotope fractionation and speciation in a euxinic lake—Testing ways to discern isotope fractionation processes in a sulfidic setting

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

Dahl, Tais W.; Wirth, Stefanie B.

The molybdenum (Mo) isotope composition in euxinic shales has been used as a proxy for the global distribution of anoxic conditions in ancient oceans, and since more recently also as a proxy for sulfide concentrations in depositional environments. However, there is currently no way to distinguish isotope fractionation at low bottom water sulfide concentrations in ‘local’ basins from ‘global’ secular isotope variations associated with changing seawater composition. This uncertainty is challenging the use of Mo isotopes for paleoceanographic reconstructions. To explore this further, we present new data from sediments deposited over the past ~ 9800 years in one of themore » best studied euxinic localities in the world: Lake Cadagno in Switzerland. The sample set allows us to test ways to discern isotope fractionation processes at play in a highly restricted euxinic basin. Most of our drill core samples (n = 18) show high δ98Mo values similar to previously studied shallow sediments, indicative of quantitative Mo removal from the water column (Dahl et al. 2010a). However, a few samples (n = 3) deposited between about 1200 and 3400 years ago carry low δ98Mo values and have been isotopically fractionated in the lake. Sedimentological and geochemical characterizations show that these δ98Mo-fractionated sediments formed during times of frequent injection of O2- and sediment-rich river water into the deep sulfidic water column. A positive correlation between δ98Mo and sedimentary Mo contents suggests that isotope fractionation occurred during times of non-quantitative Mo removal, although Mn-oxide cycling at the chemocline might also contribute a subordinate proportion of (98Mo-depleted) molybdenum into the sulfidic zone. Sedimentary Mo/U enrichments relative to oxic lake water further supports the hypothesis that a particulate Mo shuttle was most efficient during times of quantitative Mo removal. Therefore, periods with inefficient Mo capture are ascribed to incomplete conversion of molybdate to particle reactive Mo species when bottom water H2S levels were low or less stable than today. Using XAFS spectroscopy, we found that the two distinct Mo compounds predominating in the sediments (MoIV-S and MoVI-OS) are not diagnostic for isotope fractionation that has occurred in Lake Cadagno. Instead, we infer that δ98Mo-fractionated products (forming via a low-sulfide Mo pathway) can be subsequently altered with little or no isotopic imprint during remobilization and re-precipitation (e.g., at higher sulfide levels in the sediments) as well as during post-depositional oxidation. Future work could investigate local δ98Mo-fractionation processes expressed in other euxinic settings and explore other sedimentary metrics to constrain the steps involved in the euxinic burial pathway(s). One tantalizing prospect of this is to distinguish between local bottomwater sulfide levels and variations in the fraction of global seafloor anoxia from the Mo isotope composition in ancient euxinic mudrocks.« less

Geological Assessment of Cores from the Great Bay National Wildlife Refuge, New Hampshire

USGS Publications Warehouse

Foley, Nora K.; Ayuso, Robert A.; Ayotte, Joseph D.; Montgomery, Denise L.; Robinson, Gilpin R.

2007-01-01

Geological sources of metals (especially arsenic and zinc) in aquifer bedrock were evaluated for their potential to contribute elevated values of metals to ground and surface waters in and around Rockingham County, New Hampshire. Ayotte and others (1999, 2003) had proposed that arsenic concentrations in ground water flowing through bedrock aquifers in eastern New England were elevated as a result of interaction with rocks. Specifically in southeastern New Hampshire, Montgomery and others (2003) established that nearly one-fifth of private bedrock wells had arsenic concentrations that exceed the U.S. Environmental Protection Agency (EPA) maximum contamination level for public water supplies. Two wells drilled in coastal New Hampshire were sited to intersect metasedimentary and metavolcanic rocks in the Great Bay National Wildlife Refuge. Bulk chemistry, mineralogy, and mineral chemistry data were obtained on representative samples of cores extracted from the two boreholes in the Kittery and Eliot Formations. The results of this study have established that the primary geologic source of arsenic in ground waters sampled from the two well sites was iron-sulfide minerals, predominantly arsenic-bearing pyrite and lesser amounts of base-metal-sulfide and sulfosalt minerals that contain appreciable arsenic, including arsenopyrite, tetrahedrite, and cobaltite. Secondary minerals containing arsenic are apparently limited to iron-oxyhydroxide minerals. The geologic source of zinc was sphalerite, typically cadmium-bearing, which occurs with pyrite in core samples. Zinc also occurred as a secondary mineral in carbonate form. Oxidation of sulfides leading to the liberation of acid, iron, arsenic, zinc, and other metals was most prevalent in open fractures and vuggy zones in core intervals containing zones of high transmissivity in the two units. The presence of significant calcite and lesser amounts of other acid-neutralizing carbonate and silicate minerals, acting as a natural buffer to reduce acidity, forced precipitation of iron-oxyhydroxide minerals and the removal of trace elements, including arsenic and lead, from ground waters in the refuge. Zinc may have remained in solution to a greater extent because of complexing with carbonate and its solubility in near-neutral ground and surface waters. The regional link between anomalously high arsenic contents in ground water and a bedrock source as established by Ayotte and others (1999, 2003) and Montgomery and others (2003) was confirmed by the presence of some arsenic-bearing minerals in rocks of the Kittery and Eliot Formations. The relatively low amounts of arsenic and metals in wells in the Great Bay National Wildlife Refuge as reported by Ayotte and others (U.S. Geological Survey Water Resources Data, 2005) were likely controlled by local geochemical environments in partially filled fractures, fissures, and permeable zones within the bedrock formations. Carbonate and silicate gangue minerals that line fractures, fissures, and permeable zones likely limited the movement of arsenic from bedrock to ground water. Sources other than the two geologic formations might have been required to account for anomalously high arsenic contents measured in private bedrock aquifer wells of Rockingham County.

Distinguishing Indigenous from Contaminating Microorganisms in Rock Samples from a Deep Au Mine in South Africa

NASA Technical Reports Server (NTRS)

Onstott, T. C.; Moser, D. P.; Fredrickson, J. K.; Pfiffner, S. M.; Phelps, T. J.; White, D. C.; Peacock, A.; Balkwill, D.; Hoover, R. B.; Krumholz, L.;

Distribution and Composition of Thiotrophic Mats in the Hypoxic Zone of the Black Sea (150–170 m Water Depth, Crimea Margin)

PubMed Central

Jessen, Gerdhard L.; Lichtschlag, Anna; Struck, Ulrich; Boetius, Antje

2016-01-01

At the Black Sea chemocline, oxygen- and sulfide-rich waters meet and form a niche for thiotrophic pelagic bacteria. Here we investigated an area of the Northwestern Black Sea off Crimea close to the shelf break, where the chemocline reaches the seafloor at around 150–170 m water depth, to assess whether thiotrophic bacteria are favored in this zone. Seafloor video transects were carried out with the submersible JAGO covering 20 km2 on the region between 110 and 200 m depth. Around the chemocline we observed irregular seafloor depressions, covered with whitish mats of large filamentous bacteria. These comprised 25–55% of the seafloor, forming a belt of 3 km width around the chemocline. Cores from the mats obtained with JAGO showed higher accumulations of organic matter under the mats compared to mat-free sediments. The mat-forming bacteria were related to Beggiatoa-like large filamentous sulfur bacteria based on 16S rRNA sequences from the mat, and visual characteristics. The microbial community under the mats was significantly different from the surrounding sediments and enriched with taxa affiliated with polymer degrading, fermenting and sulfate reducing microorganisms. Under the mats, higher organic matter accumulation, as well as higher remineralization and radiotracer-based sulfate reduction rates were measured compared to outside the mat. Mat-covered and mat-free sediments showed similar degradability of the bulk organic matter pool, suggesting that the higher sulfide fluxes and subsequent development of the thiotrophic mats in the patches are consequences of the accumulation of organic matter rather than its qualitative composition. Our observations suggest that the key factors for the distribution of thiotrophic mat-forming communities near to the Crimean shelf break are hypoxic conditions that (i) repress grazers, (ii) enhance the accumulation and degradation of labile organic matter by sulfate-reducers, and (iii) favor thiotrophic filamentous bacteria which are adapted to exploit steep gradients in oxygen and sulfide availability; in addition to a specific seafloor topography which may relate to internal waves at the shelf break. PMID:27446049

Biogeochemical zonation of sulfur during the discharge of groundwater to lake in desert plateau (Dakebo Lake, NW China).

PubMed

Su, Xiaosi; Cui, Geng; Wang, Huang; Dai, Zhenxue; Woo, Nam-Chil; Yuan, Wenzhen

2018-06-01

As one of the important elements of controlling the redox system within the hyporheic and hypolentic zone, sulfur is involved in a series of complex biogeochemical processes such as carbon cycle, water acidification, formation of iron and manganese minerals, redox processes of trace metal elements and a series of important ecological processes. Previous studies on biogeochemistry of the hyporheic and hypolentic zones mostly concentrated on nutrients of nitrogen and phosphorus, heavy metals and other pollutants. Systematic study of biogeochemical behavior of sulfur and its main controlling factors within the lake hypolentic zone is very urgent and important. In this paper, a typical desert plateau lake, Dakebo Lake in northwestern China, was taken for example within which redox zonation and biogeochemical characteristics of sulfur affected by hydrodynamic conditions were studied based on not only traditional hydrochemical analysis, but also environmental isotope evidence. In the lake hypolentic zone of the study area, due to the different hydrodynamic conditions, vertical profile of sulfur species and environmental parameters differ at the two sites of the lake (western side and center). Reduction of sulfate, deposition and oxidation of sulfide, dissolution and precipitation of sulfur-bearing minerals occurred are responded well to Eh, dissolved oxygen, pH, organic carbon and microorganism according to which the lake hypolentic zone can be divided into reduced zone containing H 2 S, reduced zone containing no H 2 S, transition zone and oxidized zone. The results of this study provide valuable insights for understanding sulfur conversion processes and sulfur biogeochemical zonation within a lake hypolentic zone in an extreme plateau arid environment and for protecting the lake-wetland ecosystem in arid and semiarid regions.

The study of hydrothermal alteration zones in Kahang exploration area (north eastern of Isfahan, central of Iran) using microscopy studies and TM and Aster satellite data

NASA Astrophysics Data System (ADS)

Zahra Afshooni, Seyedeh; Esmaeily, Dariush

2010-05-01

Kahang ore deposit located in 73 km to the northeast of Isfahan city and 10 km to the east of Zefreh town, covering an area about 18.6 km2. This ore deposit is a part of Uromieh-Dokhtar volcanopolotonic belt. The rocks of the area included Andesite, Porphyritic Andesite, Dacite, Porphyritic, Rhyodacite, Diorite, Quartz Monzonite and Porphyry Micro Granite. In plutons, there is a trend from basic to acid features along with decreasing of age from margin to center of massive. Kahang region is an alteration and breccia zone. The occurrence of alteration zones and iron oxides were confirmed by satellite images processing. Generally, more than 90% of rocks of this region have been affected by hydrothermal fluids. Remote sensing refers to detection and measurement from a distance. For the first time, this exploration area was studied using satellite images processing (TM) and primary results showed that is suitable place for resources of Copper (Cu) and Molybdenum (Mo). Hydrothermal alteration commonly occurs in geothermal areas in association with ore deposits producing alteration assemblages typically dominated by silicates, sulfides, sulfates and carbonates. In the alteration zones studies the subject discussed is the study of existing minerals in such zones and study of chemical specifications of altering fluids. Four alteration zones Based on observations derived from the study of thin sections, XRD analysis and deep remote sensing using TM and Aster satellite images studies could be identified in this area: propylitic alteration zone with chlorite, epidot, calcite; argillic alteration zone with clay minerals; phyllic (qartz-sericite) alteration zone with quartz, sericite and pyrite and silicic alteration zone with abundant quartz.

Diffuse-flow hydrothermal field in an oceanic fracture zone setting, Northeast Pacific: Deposit composition

USGS Publications Warehouse

Hein, J.R.; Koski, R.A.; Embley, R.W.; Reid, J.; Chang, S.-W.

1999-01-01

This is the first reported occurrence of an active hydrothermal field in an oceanic fracture zone setting. The hydrothermal field occurs in a pull-apart basin within the Blanco Fracture Zone (BFZ), which has four distinct mineral deposit types: (1) barite mounds and chimneys, (2) barite stockwork breccia, (3) silica-barite beds, and (4) silica, barite, and Fe-Mn oxyhydroxide in sediments. All deposit types contain minor amounts of sulfides. In barite stockwork, silica-barite beds, and mineralized sediment, Ba, Ph, Ag, S, Au, Zn, Cu, Hg, TI, As, Mo, Sb, U, Cd, and Cu are enriched relative to unmineralized rocks and sediments of the BFZ. Fe and Mn are not enriched in the barite stockwork or silica-barite beds, but along with P, Co, and Mg are enriched in the mineralized sediments. Silver contents in deposits of the hydrothermal field range up to 86 ppm, gold to 0.7 ppm, zinc to 3.2%, copper to 0.8%, and barium to 22%. Mineralization occurred by diffuse, low to intermediate temperature (mostly <250??C) discharge of hydrothermal fluids through pillow lavas and ponds of mixed volcaniclastic and biosiliceous sediments. Bacterial mats were mineralized by silica, barite, and minor Fe hydroxides, or less commonly, by Mn oxyhydroxides. Pervasive mineralization of bacterial mats resulted in formation of silica-barite beds. Silica precipitated from hydrothermal fluids by conductive cooling and mixing with seawater. Sulfate, U, and rare earth elements (REEs) in barite were derived from seawater, whereas the REE content of hydrothermal silica deposits and mineralized sediments is associated with the aluminosilicate detrital fraction. Fe-, Zn-, Cu-, Pb-, and Hg-sulfide minerals, Ba in barite, and Eu in all mineralized deposits were derived from hydrothermal fluids. Manganese oxides and associated elements (Co, Sb, Mo, W, Cl, and Cu) and Fe oxides and associated elements (Be, B, P, and Mo) precipitated as the result of mixing of hydrothermal fluids with seawater. ?? 2001 Canadian Institute of Mining, Metallurgy and Petroleum. All rights reserved.

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.

Guidelines for Mass Casualty Decontamination During a HAZMAT/Weapon of Mass Destruction Incident. Volumes 1 and 2

DTIC Science & Technology

2009-04-01

Prioritization of victims for decontamination based on injury and evidence of contamination and/or exposure to the hazard. Fog nozzle - Firefighting hose nozzle...A thick, high-pressure hose used to carry water to a fire to extinguish it. Hot Zone - Contaminated area of HAZMAT incident that must be isolated and...evidence of contamination and/or exposure to the hazard. Fog nozzle - Firefighting hose nozzle that separates water into droplets. Hazardous Material

Origin of condensation nuclei in the springtime polar stratosphere

NASA Technical Reports Server (NTRS)

Zhao, Jingxia; Toon, Owen B.; Turco, Richard P.

1995-01-01

An enhanced sulfate aerosol layer has been observed near 25 km accompanying springtime ozone depletion in the Antarctic stratosphere. We use a one-dimensional aerosol model that includes photochemistry, particle nucleation, condensational growth, coagulation, and sedimentation to study the origin of the layer. Annual cycles of sunlight, temperature, and ozone are incorporated into the model. Our results indicate that binary homogeneous nucleation leads to the formation of very small droplets of sulfuric acid and water under conditions of low temperature and production of H2SO4 following polar sunrise. Photodissociation of carbonyl sulfide (OCS) alone, however, cannot provide sufficient SO2 to create the observed condensation nuclei (CN) layer. When subsidence of SO2 from very high altitudes in the polar night vortex is incorporated into the model, the CN layer is reasonably reproduced. The model predictions, based on the subsidence in polar vortex, agree with in situ measurements of particle concentration, vertical distribution, and persistence during polar spring.

Origin of Condensation Nuclei in the Springtime Polar Stratosphere

NASA Technical Reports Server (NTRS)

Zhao, Jingxia; Toon, Owen B.; Turco, Richard P.

1995-01-01

An enhanced sulfate aerosol layer has been observed near 25 km accompanying springtime ozone depletion in the Antarctic stratosphere. We use a one-dimensional aerosol model that includes photochemistry, particle nucleation, condensational growth, coagulation, and sedimentation to study the origin of the layer. Annual cycles of sunlight, temperature, and ozone are incorporated into the model. Our results indicate that binary homogeneous nucleation leads to the formation of very small droplets of sulfuric acid and water under conditions of low temperature and production of H2SO4 following polar sunrise. Photodissociation of carbonyl sulfide (OCS) alone, however, cannot provide sufficient SO2 to create the observed condensation nuclei (CN) layer. When subsidence of SO2 from very high altitudes in the polar night vortex is incorporated into the model, the CN layer is reasonably reproduced. The model predictions, based on the subsidence in polar vortex, agree with in situ measurements of particle concentration, vertical distribution, and persistence during polar spring.

The formation and potential importance of cemented layers in inactive sulfide mine tailings

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

Blowes, D.W.; Reardon, E.J.; Cherry, J.A.

Investigations of inactive sulfide-rich tailings impoundments at the Heath Steele (New Brunswick) and Waite Amulet (Quebec) minesites have revealed two distinct types of cemented layers or hardpans. That at Heath Steele is 10-15 cm thick, occurs 20-30 cm below the depth of active oxidation, is continuous throughout the tailings impoundment, and is characterized by cementation of tailings by gypsum and Fe(II) solid phases, principally melanterite. Hardpan at the Waite Amulet site is only 1-5 cm thick, is laterally discontinuous (10-100 cm), occurs at the depth of active oxidation, and is characterized by cementation of tailings by Fe(III) minerals, principally goethite,more » lepidocrocite, ferrihydrite, and jarosite. At Heath Steele, an accumulation of gas-phase CO{sub 2}, of up to 60{percent} of the pore gas, occurs below the hardpan. The calculated diffusivity of the hardpan layer is only about 1/100 that of the overlying, uncemented tailings. The pore-water chemistry at Heath Steele has changed little over a 10-year period, suggesting that the cemented layer restricts the movement of dissolved metals through the tailings and also acts as a zone of metal accumulation. Generation of a cemented layer therefore has significant environmental and economic implications. It is likely that, in sulfide-rich tailings impoundments, the addition of carbonate-rich buffering material during the late stages of tailings deposition would enhance the formation of hardpan layers.« less

Wüstite in the fusion crust of Almahata Sitta sulfide-metal assemblage MS-166: Evidence for oxygen in metallic melts

NASA Astrophysics Data System (ADS)

Horstmann, Marian; Humayun, Munir; Harries, Dennis; Langenhorst, Falko; Chabot, Nancy L.; Bischoff, Addi; Zolensky, Michael E.

2013-05-01

Meteorite fusion crusts form during the passage of a meteoroid through the Earth's atmosphere and are highly oxidized intergrowths as documented by the presence of e.g., oxides. The porous and irregular fusion crust surrounding the Almahata Sitta sulfide-metal assemblage MS-166 was found highly enriched in wüstite (Fe1-xO). Frictional heating of the outer portions of the assemblage caused partial melting of predominantly the Fe-sulfide and minor amounts of the outer Ni-rich portions of the originally zoned metal in MS-166. Along with melting significant amounts of oxygen were incorporated into the molten fusion crust and mainly FeS was oxidized and desulfurized to form wüstite. Considerable amounts of FeS were lost due to ablation, whereas the cores of the large metal grains appear largely unmelted leaving behind metal grains and surrounding wüstite-rich material (matte). Metal grains along with the surrounding matte typically form an often highly porous framework of globules interconnected with the matte. Although textures and chemical composition suggest that melting of Fe,Ni metal occurred only partially (Ni-rich rims), there is a trace elemental imprint of siderophile element partitioning influenced by oxygen in the metallic melt as indicated by the behavior of W and Ga, the two elements significantly affected by oxygen in a metallic melt. It is remarkable that MS-166 survived the atmospheric passage as troilite inclusions in iron meteorites are preferentially destroyed.

Microbial diversity and impact on carbonate geochemistry across a changing geochemical gradient in a karst aquifer

PubMed Central

Gray, Cassie J; Engel, Annette S

2013-01-01

Although microbes are known to influence karst (carbonate) aquifer ecosystem-level processes, comparatively little information is available regarding the diversity of microbial activities that could influence water quality and geological modification. To assess microbial diversity in the context of aquifer geochemistry, we coupled 16S rRNA Sanger sequencing and 454 tag pyrosequencing to in situ microcosm experiments from wells that cross the transition from fresh to saline and sulfidic water in the Edwards Aquifer of central Texas, one of the largest karst aquifers in the United States. The distribution of microbial groups across the transition zone correlated with dissolved oxygen and sulfide concentration, and significant variations in community composition were explained by local carbonate geochemistry, specifically calcium concentration and alkalinity. The waters were supersaturated with respect to prevalent aquifer minerals, calcite and dolomite, but in situ microcosm experiments containing these minerals revealed significant mass loss from dissolution when colonized by microbes. Despite differences in cell density on the experimental surfaces, carbonate loss was greater from freshwater wells than saline, sulfidic wells. However, as cell density increased, which was correlated to and controlled by local geochemistry, dissolution rates decreased. Surface colonization by metabolically active cells promotes dissolution by creating local disequilibria between bulk aquifer fluids and mineral surfaces, but this also controls rates of karst aquifer modification. These results expand our understanding of microbial diversity in karst aquifers and emphasize the importance of evaluating active microbial processes that could affect carbonate weathering in the subsurface. PMID:23151637

Microbial diversity and impact on carbonate geochemistry across a changing geochemical gradient in a karst aquifer.

PubMed

Gray, Cassie J; Engel, Annette S

2013-02-01

Although microbes are known to influence karst (carbonate) aquifer ecosystem-level processes, comparatively little information is available regarding the diversity of microbial activities that could influence water quality and geological modification. To assess microbial diversity in the context of aquifer geochemistry, we coupled 16S rRNA Sanger sequencing and 454 tag pyrosequencing to in situ microcosm experiments from wells that cross the transition from fresh to saline and sulfidic water in the Edwards Aquifer of central Texas, one of the largest karst aquifers in the United States. The distribution of microbial groups across the transition zone correlated with dissolved oxygen and sulfide concentration, and significant variations in community composition were explained by local carbonate geochemistry, specifically calcium concentration and alkalinity. The waters were supersaturated with respect to prevalent aquifer minerals, calcite and dolomite, but in situ microcosm experiments containing these minerals revealed significant mass loss from dissolution when colonized by microbes. Despite differences in cell density on the experimental surfaces, carbonate loss was greater from freshwater wells than saline, sulfidic wells. However, as cell density increased, which was correlated to and controlled by local geochemistry, dissolution rates decreased. Surface colonization by metabolically active cells promotes dissolution by creating local disequilibria between bulk aquifer fluids and mineral surfaces, but this also controls rates of karst aquifer modification. These results expand our understanding of microbial diversity in karst aquifers and emphasize the importance of evaluating active microbial processes that could affect carbonate weathering in the subsurface.

Geomicrobiology and hopanoid content of sulfidic subsurface vent biofilms, Little Salt Spring, Florida

NASA Astrophysics Data System (ADS)

Yang, E.; Schaperdoth, I.; Albrecht, H.; Freeman, K. H.; Macalady, J. L.

2008-12-01

Sulfide-rich, oxygen-poor environments are widespread in the subsurface and were prevalent at the earth's surface during critical intervals in the geologic past. Modern microbial communities in sulfidic niches have the potential to shed light on the biogeochemistry and biosignatures of anoxia and euxinia in earth history. Caves and sinkholes provide rare windows into microbially-dominated, sulfidic subsurface environments that are otherwise difficult and expensive to access. Little Salt Spring (Sarasota County, Florida) is a cover-collapse sinkhole lake with oxic surface water and anoxic, sulfidic bottom water (Alvarez Zarikian 2005). The site is famous for excellent preservation of human and animal archaeological remains (Clausen 1979), and its microbiology has never been investigated. Abundant white biofilms develop seasonally at a warm vent that feeds into the anoxic bottom water at 73 m depth below the water surface. The biofilms are of interest both as potential sources of biomarker compounds and because of their likely role in sulfuric acid production and limestone dissolution (speleogenesis). Biofilm samples were collected by expert science divers and investigated using microscopy, nucleic acid, and lipid analytical methods. Microscopy of the live biofilm revealed clusters of microbial filaments with holdfasts and dendritic, sulfur-rich colonial structures similar to those described in the 1960s for Thiobacterium, a sulfur-oxidizing genus with undetermined phylogeny. A 16S rDNA library constructed from the biofilm was split into three main phylotypes, with multiple clones representing (1) a Betaproteobacterial clade with no cultivated representatives, (2) filamentous Epsilonproteobacteria, and (3) a major bacterial lineage without named isolates (OP11/OD2). A full cycle rRNA approach is currently underway to link 16S rDNA phylotypes with specific populations in the biofilm. We confirmed using fluorescence in situ hybridization (FISH) that abundant filamentous cells with holdfasts are Epsilonproteobacteria. Additional FISH experiments will target the Betaproteobacterial and OP11/OD2 phylotypes retrieved by cloning. Based on HPLC-MS analyses, the biofilm contains at least 5 membrane hopanoid structures distinct from the suite of hopanoids present in sinking organic particles from the photic zone of the sinkhole. Future efforts will be aimed at linking hopanoid structures to specific sulfur-oxidizing populations and to geochemical parameters such as sulfide and oxygen concentrations. References Alvarez Zarikian,C. A., P. K. Swart, J. A. Gifford, P. L. Blackwelder, Palaeogeography, Palaeoclimatology, Palaeoecology 225, 134 (2005). Clausen, C. J., A. D. Cohen, C. Emiliani, J. A. Holman, J. J. Stipp, Science 203, 609 (1979).

An initial examination of tungsten geochemistry along groundwater flow paths

NASA Astrophysics Data System (ADS)

Dave, H. B.; Johannesson, K. H.

2008-12-01

Groundwater samples were collected along groundwater flow paths from the Upper Floridan (Florida), Carrizo Sand (Texas), and the Aquia (Maryland) aquifers and analyzed for tungsten (W) concentrations by high- resolution inductively couple plasma mass spectrometry. At each well head, groundwater samples were also analyzed for pH, specific conductance, temperature, alkalinity, dissolved oxygen (DO), oxidation-reduction potential (Eh), dissolved iron speciation, and dissolved sulfide [S(-II)] concentrations. Sediment samples from the Carrizo Sand and Aquia aquifers were also collected and subjected to sequential extractions to provide additional insights into the solid-phase speciation of W in these aquifers. Tungsten concentrations varied along the groundwater flow paths chiefly in response to changing pH, and to a lesser extent, variations in the redox conditions. For groundwater from the Carrizo Sand aquifer, W ranges between 3.64 and 1297 pmol/kg, exhibiting the lowest values proximal to the recharge zone. Tungsten concentrations progressively increase along the flow path, reaching 1297 pmol/kg in the sulfidic groundwaters located approximately 60 km downgradient from the recharge area. Tungsten is strongly correlated with S(-II) concentrations and pH in Carrizo groundwaters (r = 0.95 and 0.78, respectively). Within the Aquia aquifer, however, W generally occurs at lower concentrations than the Carrizo (14 to 184 pmol/kg; mean = 80 pmol/kg), and shows no systematic trends along the flow path (e.g., r = 0.08 and 0.4 for W vs. S(-II) and pH, respectively). Our data are consistent with the increase in W concentrations in Carrizo groundwaters reflecting, in part, pH-related desorption, which has been shown to be substantial for pH greater than 8. Moreover, because of the broad similarities in the chemistry of W and Mo, which forms thiomolybdates in sulfidic waters, we suggest that thiotungstate complexes may form in sulfidic groundwaters, thus partially explaining the elevated W in sulfidic waters of the Carrizo aquifer. We propose that the substantially lower W concentrations in Aquia groundwaters reflect the fact that these waters are suboxic and have not undergone sulfate reduction. Hence, the evolution of W concentrations in the Aquia aquifer is consistent with conservative behavior in these generally oxic to suboxic groundwaters. In summary, our data indicate that pH related adsorption/desorption reactions are the key factors controlling W concentrations in oxic and sub-oxic waters, whereas formation of thiotungstate complexes may be important in sulfidic/anoxic waters.

Trials of flexible pipe in sour service reveal degradation

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

Al-Maslamani, M.J.

Field trials on flexible pipe offshore Qatar have shown that, under sour conditions, the layered, composite material can suffer severe degradation leading to failure. The failure demonstrates the significant effects of stress level, environmental aggressiveness, and localized hard zones in promoting sulfide stress cracking. Permeability of the sour gas through the composite layer of the flexible pipe resulted in varying degrees of sulfide attack and hydrogen embrittlement, depending on the susceptibility of the multilayered material. In the trials, the material was used as a gas-lift line in a sour-oil field in the Arabian Gulf. Flexible pipes have been used successfullymore » for transporting methanol, benzene, and gas condensates in wet sweet environments at temperatures of up to 80 C. Little or no information, however, has been available as to its corrosion resistance in sour-service wells containing 6% CO{sub 2} with 3% H{sub 2}S partial pressures and at moderate temperatures. The paper discusses an underwater survey to evaluate the damage, visual inspection, mechanical tests, metallographic exam, and trial results.« less

Geochemistry of vanadium in an epigenetic, sandstone-hosted vanadium- uranium deposit, Henry Basin, Utah

USGS Publications Warehouse

Wanty, R.B.; Goldhaber, M.B.; Northrop, H.R.

1990-01-01

The epigenetic Tony M vanadium-uranium orebody in south-central Utah is hosted in fluvial sandstones of the Morrison Formation (Upper Jurassic). Measurements of the relative amounts of V+3 and V +4 in ore minerals show that V+3 is more abundant. Thermodynamic calculations show that vanadium was more likely transported to the site of mineralization as V+4. The ore formed as V+4 was reduced by hydrogen sulfide, followed by hydrolysis and precipitation of V+3 in oxide minerals or chlorite. Uranium was transported as uranyl ion (U+6), or some complex thereof, and reduced by hydrogen sulfide, forming coffinite. Detrital organic matter in the rocks served as the carbon source for sulfate-reducing bacteria. Vanadium most likely was derived from the dissolution of iron-titanium oxides. Uranium probably was derived from the overlying Brushy Basin Member of the Morrison Formation. Previous studies have shown that the ore formed at the density-stratified interface between a basinal brine and dilute meteoric water. The mineralization processes described above occurred within the mixing zone between these two fluids. -from Authors

Nanoparticulate, sub-micron and micron sized particles emanating from hydrothermal vents

NASA Astrophysics Data System (ADS)

Luther, G. W., III; Gartman, A.; Findlay, A.; Yucel, M.; Chan, C. S. Y.

2015-12-01

Recent data from Geotraces cruises over the MAR and SEPR indicate dissolved and particulate Fe enrichment in waters 1000 and 4000 km from their vent sources, respectively. Deep-sea hydrothermal vents and the waters in the reactive mixing zone above vent orifices have been suggested to be an important source of fine material that can pass through normal filters (0.2 and 0.4 μm). In this work, nanoparticles are defined operationally as that which can pass through a 0.2 μm filter. We investigated two vent sites (Lau Basin and the MAR). Chimneys from both vent sites have fluids that can be sulfide rich or metal rich. We also present chemical and physical chemical data (SEM-EDS, TEM, XRD, EELS) showing some of the materials found in these (nano)particulate phases including pyrite, metal sulfides, silicate and aluminosilicate material. Enrichment of Mg and K in the latter suggest that reverse weathering may occur in the waters within 1-2 meters of the vent orifice where vent waters mix with cold oxygenated bottom waters.

Faulting and off-axis submarine massive sulfide accumulation at slow spreading mid-ocean ridges: A numerical modeling perspective

NASA Astrophysics Data System (ADS)

Andersen, C.; Theissen-Krah, S.; Hannington, M.; Rüpke, L.; Petersen, S.

2017-06-01

The potential of mining seafloor massive sulfide deposits for metals such as Cu, Zn, and Au is currently debated. One key challenge is to predict where the largest deposits worth mining might form, which in turn requires understanding the pattern of subseafloor hydrothermal mass and energy transport. Numerical models of heat and fluid flow are applied to illustrate the important role of fault zone properties (permeability and width) in controlling mass accumulation at hydrothermal vents at slow spreading ridges. We combine modeled mass-flow rates, vent temperatures, and vent field dimensions with the known fluid chemistry at the fault-controlled Logatchev 1 hydrothermal field of the Mid-Atlantic Ridge. We predict that the 135 kilotons of SMS at this site (estimated by other studies) can have accumulated with a minimum depositional efficiency of 5% in the known duration of hydrothermal venting (58,200 year age of the deposit). In general, the most productive faults must provide an efficient fluid pathway while at the same time limit cooling due to mixing with entrained cold seawater. This balance is best met by faults that are just wide and permeable enough to control a hydrothermal plume rising through the oceanic crust. Model runs with increased basal heat input, mimicking a heat flow contribution from along-axis, lead to higher mass fluxes and vent temperatures, capable of significantly higher SMS accumulation rates. Nonsteady state conditions, such as the influence of a cooling magmatic intrusion beneath the fault zone, also can temporarily increase the mass flux while sustaining high vent temperatures.

Geology of the Shinarump No. 1 uranium mine, Seven Mile Canyon area, Grand County, Utah

USGS Publications Warehouse

Finch, Warren Irvin

1954-01-01

The geology of the Shinarump No. 1 uranium mine, located about 12 miles northwest of Moab, Utah, in the Seven Mile Canyon area, Grand County, Utah, was studied to determine the habits, ore controls, and possible origin of the deposit. Rocks of Permian, Triassic, and Jurassic age crop out in the area mapped, and uranium deposits are found in three zones in the lower 25 feet of the Chinle formation of Late Triassic age. The Shinarump No. 1 mine, which is in the lowermost zone, is located on the west flank of the Moab anticline near the Moab fault. The Shinarump No. 1 uranium deposit consists of discontinuous lenticular layers of mineralized rock, irregular in outline, that, in general, follow the bedding. Ore minerals, mainly uraninite, impregnate the rock. High-grade ore seams of uraninite and chalcocite occur along bedding planes. Uraninite formed later than, or simultaneous with, most sulfides, and the chalcocite may be of two ages, with some being later than uraninite. Uraninite and chalcocite are concentrated in the more poorly sorted parts of siltstones. In the Seven Mile Canyon area guides to ore inferred from the study of the Shinarump No. 1 deposit are the presence of bleached siltstone, carbonaceous matter, and copper sulfides. Results of spectrographic analysis indicate that the mineralizing solutions contained important amounts of barium, vanadium, uranium, and copper, as well as lesser amounts of strontium, chromium, boron, yttrium, lead, and zinc. The origin of the Shinarump No. 1 deposit is thought to be hydrothermal.

Geology of the Shinarump No. 1 uranium mine, Seven Mile Canyon area, Grand County, Utah

USGS Publications Warehouse

Finch, Warren Irvin

1953-01-01

The Shinarump No. 1 uranium mine is located about 12 miles northwest of Moab, Utah, in the Seven Mile Canyon area, Grand County, Utah. A study was made of the geology of the Shinarump No. 1 mine in order to determine the habits, ore controls, and possible origin of the deposit. Rocks of Permain, Triassic, and Jurassic age crop out in the area mapped. Uranium deposits are found in three zones in the lower 25 feet of the Upper Triassic Chinle formation. The Shinarump No. 1 mine, which is in the lowermost zone, is located on the west flank of the Moab anticline near the Moab fault. The Shinarump No. 1 uranium deposit consists of discontinuous lenticular layers of mineralized rock, irregular in outline, that, in general, follow the bedding. Ore minerals, mainly uranite, impregnate the rock. High-grade seams of uranite and chalcocite occur along bedding planes. Formation of unraninite is later than or simultaneous with most sulfides. Chalcocite may be of two ages, with some being later than uraninite. Uraninite and chalcocite are concentrated in the poorer sorted parts of siltstones. Guides to ore in the Seven Mile Canyon area inferred from the study of the Shinarump No. 1 deposit are the presence of bleached siltstone, copper sulfides, and carbonaceous matter. Results of spectrographic analysis indicated that the mineralizing solutions contained important amounts of barium, vanadium, uranium, and copper as well as lesser amounts of strontium, chromium, boron, yttrium, lead, and zinc. The origin of the Shinarump No. 1 deposit is thought to be hydrothermal, dated as later or early.

Hydrogen sulfide gas emissions in the human-occupied zone during disturbance and removal of stored spent mushroom compost.

PubMed

Velusami, B; Curran, T P; Grogan, H M

2013-10-01

Hydrogen sulfide (H2S) gas levels were monitored in the human-occupied zone at four spent mushroom compost (SMC) storage sites during removal of SMC for application on agricultural land. During SMC removal operations, H2S gas monitors were mounted on the outside of the tractor positioned at the SMC periphery, and worn by individual tractor drivers. The highest H2S concentrations (10 s average) detected outside the tractor, at the SMC periphery, and for the tractor driver were, respectively, 454, 249, and 100 ppm for the outdoor sites and 214, 75, and 51 ppm for the indoor sites. The highest short-term exposure values (STEV over a 15 min period) outside the tractor at the SMC periphery, and for the tractor driver were 147, 55, and 86 ppm for the outdoor sites and 19, 9, and 10 ppm for the indoor sites. The values exceeded the current maximum permissible concentration limit of 10 ppm for all the sites except for the SMC periphery and tractor driver at the indoor sites. Results suggest that H2S levels detected at indoor storage sites during SMC removal are lower compared to outdoor storage sites. Results indicate that there is a substantial health and safety risk associated with working in the vicinity of stored SMC when it is being disturbed and removed for land application, and that the risk is great for the tractor driver. This article discusses possible control measures and lists recommendations to reduce the risks.

Spray characteristics of two combined jet atomizers

NASA Astrophysics Data System (ADS)

Tambour, Y.; Portnoy, D.

The downstream changes in droplet volume concentration of a vaporizing fuel spray produced by two jet atomizers which form an overlapping zone of influence is theoretically analyzed, employing experimental data of Yule et al. (1982) for a single jet atomizer as initial conditions. One of the atomizers is located below the other at a certain distance downstream. Such an injection geometry can be found in afterburners of modern jet engines. The influence of various vertical and horizontal distances between the two atomizers on the downstream spray characteristics is investigated for a vaporizing kerosene spray in a 'cold' (293 K) and a 'hot' (450 K) environment. The analysis shows how one can control the downstream spray characteristics via the geometry of injection. Such geometrical considerations may be of great importance in the design of afterburner wall geometry and in the reduction of wall thermal damage. The injection geometry may also affect the intensity of the spray distribution which determines the mode of droplet group combustion. The latter plays an important role in improving afterburner combustion efficiency.

Homogeneous crystal nucleation in Ni droplets

NASA Astrophysics Data System (ADS)

Kožíšek, Zdeněk; Demo, Pavel

2017-10-01

Crystal nucleation kinetics is often represented by induction times or metastable zone widths (Kulkarni et al., 2013; Bokeloh et al., 2011). Repeating measurements of supercooling or time delay, at which phase transition is detected, are statistically processed to determine the so-called survivorship function, from which nucleation rate is computed. The size distribution of nuclei is difficult to measure near the critical size directly, and it is not clear which amount of nuclei is formed at the moment when the phase transition is detected. In the present paper, kinetic nucleation equations are solved for the crystal nucleation in Ni liquid droplet to determine the number of nuclei formed within a considered system. Analysis of supercooling experimental data, based on the classical nucleation theory CNT), computes appropriate values of the nucleation rate. However, CNT underestimates the number of nuclei F (F ≪ 1 for supercritical sizes). Taking into account the dependence of the surface energy on nucleus size to data analysis overcomes this discrepancy and leads to reasonable values of the size distribution of nuclei.

Investigation of Heat Transfer and Magnetohydrodynamic Flow in Electroslag Remelting Furnace Using Vibrating Electrode

NASA Astrophysics Data System (ADS)

Wang, Fang; Wang, Qiang; Lou, Yanchun; Chen, Rui; Song, Zhaowei; Li, Baokuan

2016-01-01

A transient three-dimensional (3D) coupled mathematical model has been developed to understand the effect of a vibrating electrode on the electromagnetic, two-phase flow and temperature fields as well as the solidification in the electroslag remelting (ESR) process. With the magnetohydrodynamic model, the Joule heating and Lorentz force, which are the source terms in the energy and momentum equations, are recalculated at each iteration as a function of the phase distribution. The influence of the vibrating electrode on the formation of the metal droplet is demonstrated by the volume of fluid approach. Additionally, the solidification of the metal is modeled by an enthalpy-based technique, in which the mushy zone is treated as a porous medium with porosity equal to the liquid fraction. The present work is the first attempt to investigate the innovative technology of the ESR process with a vibrating electrode by a transient 3D comprehensive model. A reasonable agreement between the experiment and simulation is obtained. The results indicate that the whole process is presented as a periodic activity. When the metal droplets fall from the tip of the electrode, the horizontal component of velocity will generate electrode vibration. This will lead to the distribution variation of the flow field in the slag layer. The variation of temperature distribution occurs regularly and is periodically accompanied by the behavior of the falling metal droplets. With the decreasing vibrating frequency and amplitude, the relative velocity of the electrode and molten slag increase accordingly. The diameter of the molten droplets, the maximum temperature and the depth of the molten pool gradually become smaller, lower and shallower.

Mount St. Augustine volcano fumarole wall rock alteration: Mineralogy, zoning, composition and numerical models of its formation process

USGS Publications Warehouse

Getahun, A.; Reed, M.H.; Symonds, R.

1996-01-01

Intensely altered wall rock was collected from high-temperature (640??C) and low-temperature (375??C) vents at Augustine volcano in July 1989. The high-temperature altered rock exhibits distinct mineral zoning differentiated by color bands. In order of decreasing temperature, the color bands and their mineral assemblages are: (a) white to grey (tridymite-anhydrite); (b) pink to red (tridymite-hematite-Fe hydroxide-molysite (FeCl3) with minor amounts of anhydrite and halite); and (c) dark green to green (anhydrite-halite-sylvite-tridymite with minor amounts of molysite, soda and potash alum, and other sodium and potassium sulfates). The alteration products around the low-temperature vents are dominantly cristobalite and amorphous silica with minor potash and soda alum, aphthitalite, alunogen and anhydrite. Compared to fresh 1986 Augustine lava, the altered rocks exhibit enrichments in silica, base metals, halogens and sulfur and show very strong depletions in Al in all alteration zones and in iron, alkali and alkaline earth elements in some of the alteration zones. To help understand the origins of the mineral assemblages in altered Augustine rocks, we applied the thermochemical modeling program, GASWORKS, in calculations of: (a) reaction of the 1987 and 1989 gases with wall rock at 640 and 375??C; (b) cooling of the 1987 gas from 870 to 100??C with and without mineral fractionation; (c) cooling of the 1989 gas from 757 to 100??C with and without mineral fractionation; and (d) mixing of the 1987 and 1989 gases with air. The 640??C gas-rock reaction produces an assemblage consisting of silicates (tridymite, albite, diopside, sanidine and andalusite), oxides (magnetite and hercynite) and sulfides (bornite, chalcocite, molybdenite and sphalerite). The 375??C gas-rock reaction produces dominantly silicates (quartz, albite, andalusite, microcline, cordierite, anorthite and tremolite) and subordinate amounts of sulfides (pyrite, chalcocite and wurtzite), oxides (magnetite), sulfates (anhydrite) and halides (halite). The cooling calculations produce: (a) anhydrite, halite, sylvite; (b) Cu, Mo, Fe and Zn sulfides; (c) Mg fluoride at high temperature (> 370??C); (d) chlorides, fluorides and sulfates of Mn, Fe, Zn, Cu and Al at intermediate temperature (170-370??C); and (e) hydrated sulfates, liquid sulfur, crystalline sulfur, hydrated sulfuric acid and water at low temperature ( 0.41 (> 628??C). This is followed by precipitation of sulfates of Fe, Cu, Pb, Zn and Al at lg/a ratios between 0.41 and -0.4 (628-178??C). At a lg/r ratio of < - 0.4 (178??C), anhydrous sulfates are replaced by their hydrated forms and hygroscopic sulfuric acid forms. At these low g/a ratios, hydrated sulfuric acid becomes the dominant phase in the system. Comparison of the thermochemical modeling results with the natural samples suggests that the alteration assemblages include: (1) minerals that precipitate from direct cooling of the volcanic gas; (2) phases that form by volcanic gases mixing with air; and (3) phases that form by volcanic gas-air-rock reaction. A complex interplay of the three processes produces the observed mineral zoning. Another implication of the numerical simulation results is that most of the observed incrustation and sublimate minerals apparently formed below 700??C.

Environmental geochemical study of Red Mountain--an undisturbed volcanogenic massive sulfide deposit in the Bonnifield District, Alaska range, east-central Alaska: Chapter I in Recent U.S. Geological Survey studies in the Tintina Gold Province, Alaska, United States, and Yukon, Canada--results of a 5-year project

USGS Publications Warehouse

Eppinger, Robert G.; Briggs, Paul H.; Dusel-Bacon, Cynthia; Giles, Stuart A.; Gough, Larry P.; Hammarstrom, Jane M.; Hubbard, Bernard E.

2007-01-01

Water samples with the lowest pH values, highest specific conductances, and highest major- and trace-element concentrations are from springs and streams within the quartz-sericite-pyrite alteration zone. Aluminum, As, Cd, Co, Cu, Fe, Mn, Ni, Pb, Y, and particularly Zn and the REEs are all found in high concentrations, ranging across four orders of magnitude. Waters collected upstream from the alteration zone have near-neutral pH values, lower specific conductances, lower metal concentrations, and measurable alkalinities. Water samples collected downstream of the alteration zone have pH values and metal concentrations intermediate between these two extremes. Stream sediments are anomalous in Zn, Pb, S, Fe, Cu, As, Co, Sb, and Cd relative to local and regional background abundances. Red Mountain Creek and its tributaries do not support, and probably never have supported, significant megascopic faunal aquatic life.

The formation age of ores from the Pebble Cu-Au-Mo giant deposit (Alaska, United States)

NASA Astrophysics Data System (ADS)

Kremenetskii, A. A.; Popov, V. S.; Gromalova, N. A.

2012-02-01

Zircons from the porphyry-like quartz-diorite boss of the Pebble Cu-Au-Mo deposit (southwest Alaska) have been examined. By their appearance and internal structure (cathode luminescence and electron probing), the zircons have been subdivided into four genetic groups: (1) xenogenic detrital (mainly rounded); (2) magmatogene (protolith crystal in the center and growth zone at the edge); (3) hydrothermally altered (with new-formed regeneration edges in growth zones); (4) metamict-altered (unconsolidated center of the crystal and sectoring in growth zones). Based on SHRIMP U-Pb dating for the principal heterogeneous elements in every group, the following stages of ore formation have been identified for the Pebble deposit: (a) crystallization of quartz diorite-porphyry bosses (95-92 Ma, the concordant age is 94.7 ± 1.5 Ma); (b) late magmatic metasomatic alterations with copper-molybdenum mineralization (92-85 Ma, the concordant age is 90.15 ± 0.78 Ma); (c) postmagmatic argillization with epithermal gold-sulfide mineralization (82-80 Ma, the concordant age is 82.9 ± 2.7 Ma).

Highly oxidising fluids generated during serpentinite breakdown in subduction zones.

PubMed

Debret, B; Sverjensky, D A

2017-09-04

Subduction zones facilitate chemical exchanges between Earth's deep interior and volcanism that affects habitability of the surface environment. Lavas erupted at subduction zones are oxidized and release volatile species. These features may reflect a modification of the oxidation state of the sub-arc mantle by hydrous, oxidizing sulfate and/or carbonate-bearing fluids derived from subducting slabs. But the reason that the fluids are oxidizing has been unclear. Here we use theoretical chemical mass transfer calculations to predict the redox state of fluids generated during serpentinite dehydration. Specifically, the breakdown of antigorite to olivine, enstatite, and chlorite generates fluids with high oxygen fugacities, close to the hematite-magnetite buffer, that can contain significant amounts of sulfate. The migration of these fluids from the slab to the mantle wedge could therefore provide the oxidized source for the genesis of primary arc magmas that release gases to the atmosphere during volcanism. Our results also show that the evolution of oxygen fugacity in serpentinite during subduction is sensitive to the amount of sulfides and potentially metal alloys in bulk rock, possibly producing redox heterogeneities in subducting slabs.

Sulfur and oxygen isotopic study of Paleozoic sediment-hosted Zn-Pb(-Ag-Au-Ba-F) deposits and associated hydrothermal alteration zones in the Nome Complex, Seward Peninsula, Alaska

USGS Publications Warehouse

Shanks, W.C. Pat; Slack, John F.; Till, Alison B.; Thurston, Roland; Gemery-Hill, Pamela

2014-01-01

The stratabound Nelson deposit, and the deformed veins at the Galena and Quarry deposits, may be older than the Aurora Creek-Christophosen and Wheeler North deposits. The Nelson deposit has a lower and narrower range of δ34S values (1.9 to 10.4‰), averaging about 8‰. The Galena and Quarry veins display δ34S values that are similar to those of the stratabound Nelson deposit. Barite samples from the Aurora Creek-Christophosen, Wheeler North, and Quarry deposits have 34S-enriched δ34S values between 25 and 30‰ that are consistent with derivation of the sulfur from coeval (Paleozoic) seawater sulfate. Given their δ34S values, it is likely that the Aurora Creek-Christophosen and Wheeler North deposits formed in closed sub-basins with euxinic conditions that led to extreme Rayleigh distillation to produce the very large range and very high δ34S values. The Nelson deposit probably formed within an anoxic but not euxinic sub-basin. At Nelson, sulfide was likely derived by a subsurface thermochemical sulfate reduction (TSR) reaction, similar to reactions that are inferred to have produced the sulfides in the Galena and Quarry deposits, which are interpreted as feeder veins for the stratabound deposits. Calculations of oxygen isotope temperatures are based on the assumption that evolved seawater with δ18O of 3‰ was the mineralizing and altering fluid related to the formation of the sulfide deposits. Temperatures of aluminous alteration and sulfide mineralization were between 109 and 209 °C, determined on the basis of oxygen isotope fractionations between the mineralizing fluid and proportionate amounts of quartz and muscovite in the rocks. These temperature estimates agree well with known temperatures of SEDEX mineralization worldwide. Sulfur isotope values also are generally consistent with the known ranges in SEDEX deposits worldwide (δ34S ≈ -5 to 25‰).

Formation of "Chemically Pure" Magnetite from Mg-Fe-Carbonates Implications for the Exclusively Inorganic Origin of Magnetite and Sulfides in Martian Meteorite ALH84001

NASA Technical Reports Server (NTRS)

Golden, D. C.; Ming, Douglas W.; Lauer, H. V., Jr.; Morris, R. V.; Trieman, A. H.; McKay, G. A.

2006-01-01

Magnetite and sulfides in the black rims of carbonate globules in Martian meteorite ALH84001 have been studied extensively because of the claim by McKay et al. that they are biogenic in origin. However, exclusively inorganic (abiotic) processes are able to account for the occurrence of carbonate-sulfide-magnetite assemblages in the meteorite. We have previously precipitated chemically zoned and sulfide-bearing carbonate globules analogous to those in ALH84001 (at less than or equal to 150 C) from multiple fluxes of variable-composition Ca-Mg-Fe-CO2-S-H2O solutions. Brief heating of precipitated globules to approx. 470 C produced magnetite and pyrrhotite within the globules by thermal decomposition of siderite and pyrite, respectively. We have also shown that morphology of magnetite formed by inorganic thermal decomposition of Fe-rich carbonate is similar to the morphology of so-called biogenic magnetite in the carbonate globules of ALH84001. Magnetite crystals in the rims of carbonate globules in ALH84001 are chemically pure [Note: "Chemically pure" is defined here as magnetite with Mg at levels comparable or lower than Mg detected by [8] in ALH84001 magnetite]. A debate continues on whether or not chemically pure magnetite can form by the thermal decomposition of mixed Mg-Fe-carbonates that have formed under abiotic conditions. Thomas-Keprta et al. argue that it is not possible to form Mg-free magnetite from Mg-Fe-carbonate based on thermodynamic data. We previously suggested that chemically pure magnetite could form by the thermal decomposition of relatively pure siderite in the outer rims of the globules. Mg-Fe-carbonates may also thermally decompose under conditions conducive for formation of chemically pure magnetite. In this paper we show through laboratory experiments that chemically pure magnetite can form by an inorganic process from mixed Mg-Fe-carbonates.

Mercury mobilization and speciation linked to bacterial iron oxide and sulfate reduction: A column study to mimic reactive transfer in an anoxic aquifer.

PubMed

Hellal, Jennifer; Guédron, Stéphane; Huguet, Lucie; Schäfer, Jörg; Laperche, Valérie; Joulian, Catherine; Lanceleur, Laurent; Burnol, André; Ghestem, Jean-Philippe; Garrido, Francis; Battaglia-Brunet, Fabienne

2015-09-01

Mercury (Hg) mobility and speciation in subsurface aquifers is directly linked to its surrounding geochemical and microbial environment. The role of bacteria on Hg speciation (i.e., methylation, demethylation and reduction) is well documented, however little data is available on their impact on Hg mobility. The aim of this study was to test if (i) Hg mobility is due to either direct iron oxide reduction by iron reducing bacteria (IRB) or indirect iron reduction by sulfide produced by sulfate reducing bacteria (SRB), and (ii) to investigate its subsequent fate and speciation. Experiments were carried out in an original column setup combining geochemical and microbiological approaches that mimic an aquifer including an interface of iron-rich and iron depleted zones. Two identical glass columns containing iron oxides spiked with Hg(II) were submitted to (i) direct iron reduction by IRB and (ii) to indirect iron reduction by sulfides produced by SRB. Results show that in both columns Hg was leached and methylated during the height of bacterial activity. In the column where IRB are dominant, Hg methylation and leaching from the column was directly correlated to bacterial iron reduction (i.e., Fe(II) release). In opposition, when SRB are dominant, produced sulfide induced indirect iron oxide reduction and rapid adsorption of leached Hg (or produced methylmercury) on neoformed iron sulfides (e.g., Mackinawite) or its precipitation as HgS. At the end of the SRB column experiment, when iron-oxide reduction was complete, filtered Hg and Fe concentrations increased at the outlet suggesting a leaching of Hg bound to FeS colloids that may be a dominant mechanism of Hg transport in aquifer environments. These experimental results highlight different biogeochemical mechanisms that can occur in stratified sub-surface aquifers where bacterial activities play a major role on Hg mobility and changes in speciation. Copyright © 2015 Elsevier B.V. All rights reserved.

Germanium enrichment in supergene settings: evidence from the Cristal nonsulfide Zn prospect, Bongará district, northern Peru

NASA Astrophysics Data System (ADS)

Mondillo, Nicola; Arfè, Giuseppe; Herrington, Richard; Boni, Maria; Wilkinson, Clara; Mormone, Angela

2018-02-01

Supergene nonsulfide ores form from the weathering of sulfide mineralization. Given the geochemical affinity of Ge to Si4+ and Fe3+, weathering of Ge-bearing sulfides could potentially lead to Ge enrichments in silicate and Fe-oxy-hydroxide minerals, although bulk rock Ge concentrations in supergene nonsulfide deposits are rarely reported. Here, we present the results of an investigation into Ge concentrations and deportment in the Cristal supergene Zn nonsulfide prospect (Bongará, northern Peru), which formed from the weathering of a preexisting Mississippi Valley-type (MVT) sulfide deposit. Material examined in this study originates from drillcore recovered from oxidized Zn-rich bodies 15-20 m thick, containing 5-45 wt% Zn and Ge concentrations 100 ppm. Microanalysis and laser ablation-ICP-MS show that precursor sphalerite is rich in both Fe (mean Fe = 8.19 wt%) and Ge (mean Ge = 142 ppm). Using the mineral geothermometer GGIMFis—geothermometer for Ga, Ge, In, Mn, and Fe in sphalerite—proposed by Frenzel et al. (Ore Geol Rev 76:52-78, 2016), sphalerite trace element data from the Cristal prospect suggest a possible formation temperature ( T GGIMFis) of 225 ± 50 °C, anomalously high for a MVT deposit. Germanium concentrations measured in both goethite (mean values 100 to 229 ppm, max 511 ppm) and hemimorphite (mean values 39 to 137 ppm, max 258 ppm) are similar to concentrations measured in hypogene sphalerite. Additionally, the Ge concentrations recorded in bulk rock analyses of sphalerite-bearing and oxidized samples are also similar. A persistent warm-humid climate is interpreted for the region, resulting in the development of an oxidation zone favoring the formation of abundant Zn hydrosilicates and Fe hydroxides, both able to incorporate Ge in their crystal structure. In this scenario, Ge has been prevented from dispersion during the weathering of the Ge-bearing sulfide bodies and remains in the resultant nonsulfide ore.

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.

Geochemical and isotopic evidence for paleoredox conditions during deposition of the Devonian-Mississippian New Albany Shale, southern Indiana

NASA Technical Reports Server (NTRS)

Beier, J. A.; Hayes, J. M.

1989-01-01

The upper part of the New Albany Shale is divided into three members. In ascending order, these are (1) the Morgan Trail Member, a laminated brownish-black shale; (2) the Camp Run Member, an interbedded brownish-black and greenish-gray shale; and (3) the Clegg Creek Member, also a laminated brownish-black shale. The Morgan Trail and Camp Run Members contain 5% to 6% total organic carbon (TOC) and 2% sulfide sulfur. Isotopic composition of sulfide in these members ranges from -5.0% to -20.0%. C/S plots indicate linear relationships between abundances of these elements, with a zero intercept characteristic of sediments deposited in a non-euxinic marine environment. Formation of diagenetic pyrite was carbon limited in these members. The Clegg Creek Member contains 10% to 15% TOC and 2% to 6% sulfide sulfur. Isotopic compositions of sulfide range from -5.0% to -40%. The most negative values occur in the uppermost Clegg Creek Member and are characteristic of syngenetic pyrite, formed within an anoxic water column. Abundances of carbon and sulfur are greater and uncorrelated in this member, consistent with deposition in as euxinic environment. In addition, DOP (degree of pyritization) values suggest that formation of pyrite was generally iron limited throughout Clegg Creek deposition, but sulfur isotopes indicate that syngenetic (water-column) pyrite becomes an important component in the sediment only in the upper part of the member. At the top of the Clegg Creek Member, a zone of phosphate nodules and trace-metal enrichment coincides with maximal TOC values. During euxinic deposition, phosphate and trace metals accumulated below the chemocline because of limited vertical circulation in the water column. Increased productivity would have resulted in an increased flux of particulate organic matter to the sediment, providing an effective sink for trace metals in the water column. Phosphate and trace metals released from organic matter during early diagenesis resulted in precipitation of metal-rich phosphate nodules.

Isotope geochemistry of waters affected by acid mine drainage in old labour sites (SE, Spain).

NASA Astrophysics Data System (ADS)

Pérez-Sirvent, Carmen; Martinez-Sanchez, Maria Jose; Garcia-Lorenzo, Maria Luz; Agudo, Ines; Hernandez-Cordoba, Manuel; Recio, Clemente

2015-04-01

The ore deposits of this zone have iron, lead and zinc as the main metal components. Iron is present in oxides, hydroxides, sulfides, sulfates, carbonates, and silicates; lead and zinc occur in sulfides (galena and sphalerite, respectively), carbonates, sulfates, and lead or zinc-bearing (manganese, iron) oxides. Mining started with the Romans and activity peaked in the second half of the 19th century and throughout the 20th century until the 1980's. From 1940 to 1957, mineral concentration was made by froth flotation and, prior to this, by gravimetric techniques. The mining wastes, or tailings, with a very fine particle size were deposited inland (tailings dams) and, since 1957, huge releases were made in directly the sea coast. The objective of this work was to evaluate processes affecting waters from abandoned mine sites by way of stable isotopic analysis, particularly H and O stable isotopes from water and S and O from dissolved sulfates. Several common chemical and physical processes, such as evaporation, water-rock interaction and mixing could alter water isotopic composition. Evaporation, which causes an enrichment in δD and δ18O in the residual water, is an important process in semiarid areas. The results obtained indicate that, for sites near the coast, waters are meteoric, and marine infiltration only takes place in the deepest layers near the shore or if water remains stagnated in sediments with low permeability. The main source of sulfate was the oxidation of sulfides, resulting in the liberation of acid, sulfate and metals. In order to assess the mechanism responsible for sulfide oxidation, the stoichiometric isotope balance model and the general isotope balance model were tested, suggesting that the oxidation via Fe3+ was predominant in the surface, and controlled by A. ferrooxidans, while at depth, sulfate reduction occurred.

The Lithospheric Structure of the Solonker Suture Zone and Adjacent Areas: Crustal Structure Revealed by a High-Resolution Magnetotelluric Study

NASA Astrophysics Data System (ADS)

Ye, Gaofeng; Jin, Sheng; Wei, Wenbo; Jing, Jian'en

2017-04-01

The closure of the Paleo-Asian Ocean along the Solonker Suture Zone (SSZ) during the Late Permian and Triassic represented the final stage in the formation of the Central Asian Orogenic Belt between the Siberian Craton and the North China Craton. In order to better understand the structure and formation of this ancient subduction zone, a high-resolution magnetotelluric (MT) profile was collected with both broadband and long-period MT data. The high resolution mapping of the lithosphere achieved in this study is due to the closely spaced MT stations (2-3 km). With the 2-D resistivity model, a south-dipping conductor was detected and extends through the entire crust. The geometry of this feature provides evidence that a southward directed subduction zone formed the Solonker suture. The enhanced conductivity was interpreted to subducted sulfide-bearing graphitic sediments. The resistive body beneath the northern margin of the North China Craton indicates a thickened lithosphere caused by the southward subduction at this region, and the resistive body beneath the Solonker Suture Zone indicates the subducted oceanic lithosphere. North-dipping low resistivity features were also detected in the crust of both the North China Craton and Central Asian Orogenic Belt, and were interpreted as post-collisional thrust faults. Strong anisotropy was found beneath the suture zone, and can be explained if the high strain rate has rotated the fold axes into the dip direction.

Comparison of geoelectrical/tectonic models for suture zones in the western U.S.A. and eastern Europe: are black shales a possible source of high conductivities?

USGS Publications Warehouse

Stanley, W.D.

1989-01-01

Large-scale geoelectrical anomalies have been mapped with geomagnetic depth sounding (GDS) and magnetotelluric (MT) surveys in the Carpathian Mountains region. These anomalies are associated with the zone of closure between stable Europe and a complex of microplates in front of the converging African plate. The zone of closure, or suture zone, is largely occupied by an extensive deformed flysch belt. The models derived to fit the observed geoelectrical data are useful in the study of other suture zones, and Carpathian structures have been compared with areas currently being studied in the western Cordillera of the U.S.A. Models derived for a smaller-scale suture zone mapped in western Washington State have features that are similar to the Carpathian models. The geoelectrical models for both the Carpathian and Washington anomalies require dipping conductive slabs of 1-5 ?? m material that extends to depths > 20 km. In both instances there is evidence that these materials may merge with lower crustal-mantle conductors along the down-dip margins of the slab. The main conductive units are interpreted to be sedimentary rocks that have been partially subducted due to collisional processes. Heat flow is low in both regions and it is difficult to explain fully the deep conduction mechanisms; however, evidence suggests that the conduction at depth may include electronic conduction in sulfide mineral or carbon films as well as ionic conduction in fluids or partial melt. ?? 1989.

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

Walsh, David A.; Zaikova, Elena; Howes, Charles L.

Oxygen minimum zones (OMZs), also known as oceanic"dead zones", are widespread oceanographic features currently expanding due to global warming and coastal eutrophication. Although inhospitable to metazoan life, OMZs support a thriving but cryptic microbiota whose combined metabolic activity is intimately connected to nutrient and trace gas cycling within the global ocean. Here we report time-resolved metagenomic analyses of a ubiquitous and abundant but uncultivated OMZ microbe (SUP05) closely related to chemoautotrophic gill symbionts of deep-sea clams and mussels. The SUP05 metagenome harbors a versatile repertoire of genes mediating autotrophic carbon assimilation, sulfur-oxidation and nitrate respiration responsive to a wide rangemore » of water column redox states. Thus, SUP05 plays integral roles in shaping nutrient and energy flow within oxygen-deficient oceanic waters via carbon sequestration, sulfide detoxification and biological nitrogen loss with important implications for marine productivity and atmospheric greenhouse control.« less

Continuous flow real-time PCR device using multi-channel fluorescence excitation and detection.

PubMed

Hatch, Andrew C; Ray, Tathagata; Lintecum, Kelly; Youngbull, Cody

2014-02-07

High throughput automation is greatly enhanced using techniques that employ conveyor belt strategies with un-interrupted streams of flow. We have developed a 'conveyor belt' analog for high throughput real-time quantitative Polymerase Chain Reaction (qPCR) using droplet emulsion technology. We developed a low power, portable device that employs LED and fiber optic fluorescence excitation in conjunction with a continuous flow thermal cycler to achieve multi-channel fluorescence detection for real-time fluorescence measurements. Continuously streaming fluid plugs or droplets pass through tubing wrapped around a two-temperature zone thermal block with each wrap of tubing fluorescently coupled to a 64-channel multi-anode PMT. This work demonstrates real-time qPCR of 0.1-10 μL droplets or fluid plugs over a range of 7 orders of magnitude concentration from 1 × 10(1) to 1 × 10(7). The real-time qPCR analysis allows dynamic range quantification as high as 1 × 10(7) copies per 10 μL reaction, with PCR efficiencies within the range of 90-110% based on serial dilution assays and a limit of detection of 10 copies per rxn. The combined functionality of continuous flow, low power thermal cycling, high throughput sample processing, and real-time qPCR improves the rates at which biological or environmental samples can be continuously sampled and analyzed.

Microbiological and Geochemical Characterization of Fluvially Deposited Sulfidic Mine Tailings

PubMed Central

Wielinga, Bruce; Lucy, Juliette K.; Moore, Johnnie N.; Seastone, October F.; Gannon, James E.

1999-01-01

The fluvial deposition of mine tailings generated from historic mining operations near Butte, Montana, has resulted in substantial surface and shallow groundwater contamination along Silver Bow Creek. Biogeochemical processes in the sediment and underlying hyporheic zone were studied in an attempt to characterize interactions consequential to heavy-metal contamination of shallow groundwater. Sediment cores were extracted and fractionated based on sediment stratification. Subsamples of each fraction were assayed for culturable heterotrophic microbiota, specific microbial guilds involved in metal redox transformations, and both aqueous- and solid-phase geochemistry. Populations of cultivable Fe(III)-reducing bacteria were most prominent in the anoxic, circumneutral pH regions associated with a ferricrete layer or in an oxic zone high in organic carbon and soluble iron. Sulfur- and iron-oxidizing bacteria were distributed in discrete zones throughout the tailings and were often recovered from sections at and below the anoxic groundwater interface. Sulfate-reducing bacteria were also widely distributed in the cores and often occurred in zones overlapping iron and sulfur oxidizers. Sulfate-reducing bacteria were consistently recovered from oxic zones that contained high concentrations of metals in the oxidizable fraction. Altogether, these results suggest a highly varied and complex microbial ecology within a very heterogeneous geochemical environment. Such physical and biological heterogeneity has often been overlooked when remediation strategies for metal contaminated environments are formulated. PMID:10103249

[Study on the arc spectral information for welding quality diagnosis].

PubMed

Li, Zhi-Yong; Gu, Xiao-Yan; Li, Huan; Yang, Li-Jun

2009-03-01

Through collecting the spectral signals of TIG and MIG welding arc with spectrometer, the arc light radiations were analyzed based on the basic theory of plasma physics. The radiation of welding arc distributes over a broad range of frequency, from infrared to ultraviolet. The arc spectrum is composed of line spectra and continuous spectra. Due to the variation of metal density in the welding arc, there is great difference between the welding arc spectra of TIG and MIG in both their intensity and distribution. The MIG welding arc provides more line spectra of metal and the intensity of radiation is greater than TIG. The arc spectrum of TIG welding is stable during the welding process, disturbance factors that cause the spectral variations can be reflected by the spectral line related to the corresponding element entering the welding arc. The arc spectrum of MIG welding will fluctuate severely due to droplet transfer, which produces "noise" in the line spectrum aggregation zone. So for MIG welding, the spectral zone lacking spectral line is suitable for welding quality diagnosis. According to the characteristic of TIG and MIG, special spectral zones were selected for welding quality diagnosis. For TIG welding, the selected zone is in ultraviolet zone (230-300 nm). For MIG welding, the selected zone is in visible zone (570-590 nm). With the basic theory provided for welding quality diagnosis, the integral intensity of spectral signal in the selected zone of welding process with disturbing factor was studied to prove the theory. The results show that the welding quality and disturbance factors can be diagnosed with good signal to noise ratio in the selected spectral zone compared with signal in other spectral zone. The spectral signal can be used for real-time diagnosis of the welding quality.

Trace-element fingerprints of chromite, magnetite and sulfides from the 3.1 Ga ultramafic-mafic rocks of the Nuggihalli greenstone belt, Western Dharwar craton (India)

NASA Astrophysics Data System (ADS)

Mukherjee, Ria; Mondal, Sisir K.; González-Jiménez, José M.; Griffin, William L.; Pearson, Norman J.; O'Reilly, Suzanne Y.

2015-06-01

The 3.1 Ga Nuggihalli greenstone belt in the Western Dharwar craton is comprised of chromitite-bearing sill-like ultramafic-mafic rocks that are surrounded by metavolcanic schists (compositionally komatiitic to komatiitic basalts) and a suite of tonalite-trondhjemite-granodiorite gneissic rocks. The sill-like plutonic unit consists of a succession of serpentinite (after dunite)-peridotite-pyroxenite and gabbro with bands of titaniferous magnetite ore. The chromitite ore-bodies (length ≈30-500 m; width ≈2-15 m) are hosted by the serpentinite-peridotite unit. Unaltered chromites from massive chromitites (>80 % modal chromite) of the Byrapur and Bhaktarhalli chromite mines in the greenstone belt are characterized by high Cr# (100Cr/(Cr + Al)) of 78-86 and moderate Mg# (100 Mg/(Mg + Fe2+)) of 45-55. In situ trace-element analysis (LA-ICPMS) of unaltered chromites indicates that the parental magma of the chromitite ore-bodies was a komatiite lacking nickel-sulfide mineralization. In the Ga/Fe3+# versus Ti/Fe3+# diagram, the Byrapur chromites plot in the field of suprasubduction zone (SSZ) chromites while those from Bhaktarhalli lie in the MOR field. The above results corroborate our previous results based on major-element characteristics of the chromites, where the calculated parental melt of the Byrapur chromites was komatiitic to komatiitic basalt, and the Bhaktarhalli chromite was derived from Archean high-Mg basalt. The major-element chromite data hinted at the possibility of a SSZ environment existing in the Archean. Altered and compositionally zoned chromite grains in our study show a decrease in Ga, V, Co, Zn, Mn and enrichments of Ni and Ti in the ferritchromit rims. Trace-element heterogeneity in the altered chromites is attributed to serpentinization. The trace-element patterns of magnetite from the massive magnetite bands in the greenstone belt are similar to those from magmatic Fe-Ti-V-rich magnetite bands in layered intrusions, and magnetites from andesitic melts, suggesting that magnetite crystallized from an evolved gabbroic melt. Enrichments of Ni, Co, Te, As and Bi in disseminated millerite and niccolite occurring within chromitites, and in disseminated bravoite within magnetites, reflect element mobility during serpentinization. Monosulfide solid solution inclusions within pyroxenes (altered to actinolite) in pyroxenite, and interstitial pyrites and chalcopyrites in magnetite, retain primary characteristics except for Fe-enrichment in chalcopyrite, probably due to sub-solidus re-equilibration with magnetite. Disseminated sulfides are depleted in platinum-group elements (PGE) due to late sulfide saturation and the PGE-depleted nature of the mantle source of the sill-like ultramafic-mafic plutonic rocks in the Nuggihalli greenstone belt.

Magmatic ore deposits in layered intrusions - Descriptive model for reef-type PGE and contact-type Cu-Ni-PGE deposits

USGS Publications Warehouse

Zientek, Michael L.

2012-01-01

Layered, ultramafic to mafic intrusions are uncommon in the geologic record, but host magmatic ore deposits containing most of the world's economic concentrations of platinum-group elements (PGE) (figs. 1 and 2). These deposits are mined primarily for their platinum, palladium, and rhodium contents (table 1). Magmatic ore deposits are derived from accumulations of crystals of metallic oxides, or immiscible sulfide, or oxide liquids that formed during the cooling and crystallization of magma, typically with mafic to ultramafic compositions. "PGE reefs" are stratabound PGE-enriched lode mineralization in mafic to ultramafic layered intrusions. The term "reef" is derived from Australian and South African literature for this style of mineralization and used to refer to (1) the rock layer that is mineralized and has distinctive texture or mineralogy (Naldrett, 2004), or (2) the PGE-enriched sulfide mineralization that occurs within the rock layer. For example, Viljoen (1999) broadly defined the Merensky Reef as "a mineralized zone within or closely associated with an unconformity surface in the ultramafic cumulate at the base of the Merensky Cyclic Unit." In this report, we will use the term PGE reef to refer to the PGE-enriched mineralization, not the host rock layer. Within a layered igneous intrusion, reef-type mineralization is laterally persistent along strike, extending for the length of the intrusion, typically tens to hundreds of kilometers. However, the mineralized interval is thin, generally centimeters to meters thick, relative to the stratigraphic thickness of layers in an intrusion that vary from hundreds to thousands of meters. PGE-enriched sulfide mineralization is also found near the contacts or margins of layered mafic to ultramafic intrusions (Iljina and Lee, 2005). This contact-type mineralization consists of disseminated to massive concentrations of iron-copper-nickel-PGE-enriched sulfide mineral concentrations in zones that can be tens to hundreds of meters thick. The modes and textures of the igneous rocks hosting the mineralization vary irregularly on the scale of centimeters to meters; autoliths and xenoliths are common. Mineralization occurs in the igneous intrusion and in the surrounding country rocks. Mineralization can be preferentially localized along contact with country rocks that are enriched in sulfur-, iron-, or CO2-bearing lithologies. Reef-type and contact-type deposits, in particular those in the Bushveld Complex, South Africa, are the world's primary source of platinum and rhodium (tables 2 and 3; fig. 2). Reef-type PGE deposits are mined only in the Bushveld Complex (Merensky Reef and UG2), the Stillwater Complex (J-M Reef), and the Great Dyke (Main Sulphide Layer). PGE-enriched contact-type deposits are only mined in the Bushveld Complex. The other deposits in tables 2 and 3 are undeveloped; some are still under exploration.

CFD Analysis of Spray Combustion and Radiation in OMV Thrust Chamber

NASA Technical Reports Server (NTRS)

Giridharan, M. G.; Krishnan, A.; Przekwas, A. J.; Gross, K.

1993-01-01

The Variable Thrust Engine (VTE), developed by TRW, for the Orbit Maneuvering Vehicle (OMV) uses a hypergolic propellant combination of Monomethyl Hydrazine (MMH) and Nitrogen Tetroxide (NTO) as fuel and oxidizer, respectively. The propellants are pressure fed into the combustion chamber through a single pintle injection element. The performance of this engine is dependent on the pintle geometry and a number of complex physical phenomena and their mutual interactions. The most important among these are (1) atomization of the liquid jets into fine droplets; (2) the motion of these droplets in the gas field; (3) vaporization of the droplets (4) turbulent mixing of the fuel and oxidizer; and (5) hypergolic reaction between MMH and NTO. Each of the above phenomena by itself poses a considerable challenge to the technical community. In a reactive flow field of the kind occurring inside the VTE, the mutual interactions between these physical processes tend to further complicate the analysis. The objective of this work is to develop a comprehensive mathematical modeling methodology to analyze the flow field within the VTE. Using this model, the effect of flow parameters on various physical processes such as atomization, spray dynamics, combustion, and radiation is studied. This information can then be used to optimize design parameters and thus improve the performance of the engine. The REFLEQS CFD Code is used for solving the fluid dynamic equations. The spray dynamics is modeled using the Eulerian-Lagrangian approach. The discrete ordinate method with 12 ordinate directions is used to predict the radiative heat transfer in the OMV combustion chamber, nozzle, and the heat shield. The hypergolic reaction between MMH and NTO is predicted using an equilibrium chemistry model with 13 species. The results indicate that mixing and combustion is very sensitive to the droplet size. Smaller droplets evaporate faster than bigger droplets, leading to a well mixed zone in the combustion chamber. The radiative heat flux at combustion chamber and nozzle walls are an order of negligible less than the conductive heat flux. Simulations performed with the heat shield show that a negligible amount of fluid is entrained into the heat shield region. However, the heat shield is shown to be effective in protecting the OMV structure surrounding the engine from the radiated heat.

The cuticular localization of integument peptides from particular routing categories.

PubMed

Locke, M; Kiss, A; Sass, M

1994-10-01

The distribution of integument peptides in relation to chitin and structural features has been studied in the surface epidermis of the caterpillar of Calpodes ethlius by immunoblotting and immunogold labelling using antibodies prepared to peptides isolated from lamellate endocuticle or from hemolymph. The intermoult cuticle consists of an epicuticle, an endocuticle of many chitin containing lamellae, and a chitin containing assembly zone directly above the apical epidermal microvilli and the perimicrovillar space. During the intermoult, the epidermis secretes peptides constitutively, that is, secretory vesicles containing peptides exocytose without accumulating, traverse the perimicrovillar space and form lamellae in the assembly zone. At moulting, the epidermis deposits ecdysial droplets in addition. These interrupt the last few lamellae which later go on to become the perforated ecdysial membrane. The integument is involved with four routing classes of peptide. Secretion is apical into the cuticle (C), basal into the hemolymph (H), bidirectional (BD), or transported to the cuticle across the epidermis from the hemolymph (T). Some peptides change their routing at moulting. There are several patterns of localization. (1) C and BD cuticular peptides occur mainly in chitin containing lamellate cuticle. (2) Some are also present in epicuticle, and are therefore not obligatorily linked to chitin or matrix between chitin fibers. Cuticular peptides that also occur in the hemolymph are glycosylated, whereas most that are only secreted apically into the cuticle are not. All BD but few C peptides carry alpha-D-glucose/alpha-D-mannose. Some C and BD peptides carry N-acetyl glucosamine. (3) C36 extracted from cuticle has most N-acetyl glucosamine and colocalizes with chitin rather than the protein matrix. It is therefore probably the main link between chitin fibers and the matrix. (4) H235 is barely detectable at the apical cell surface during the intermoult but is abundant at moulting around and below the ecdysial droplets. (5) T66 occurs in intermoult lamellate cuticle. At moulting, alone among the peptides examined, it is in ecdysial droplets. Intermoult C and BD peptides are not in ecdysial droplets but continue to be present in the ecdysial membrane, suggesting that constitutive secretion is independent from the exocytosis of transported moult peptides. T66 differs from most hemolymph peptides in that it does not carry N-acetyl glucosamine or alpha-D-glucose/alpha-D-mannose. (6) Weakly reacting BD peptides (and some H peptides barely detectable in cuticle) localize near the apical surface. Their distribution therefore favours apical secretion and retrieval as a mechanism for basal secretion.

Free-Surface flow dynamics and its effect on travel time distribution in unsaturated fractured zones - findings from analogue percolation experiments

NASA Astrophysics Data System (ADS)

Noffz, Torsten; Kordilla, Jannes; Dentz, Marco; Sauter, Martin

2017-04-01

Flow in unsaturated fracture networks constitutes a high potential for rapid mass transport and can therefore possibly contributes to the vulnerability of aquifer systems. Numerical models are generally used to predict flow and transport and have to reproduce various complex effects of gravity-driven flow dynamics. However, many classical volume-effective modelling approaches often do not grasp the non-linear free surface flow dynamics and partitioning behaviour at fracture intersections in unsaturated fracture networks. Better process understanding can be obtained by laboratory experiments, that isolate single aspects of the mass partitioning process, which influence travel time distributions and allow possible cross-scale applications. We present a series of percolation experiments investigating partitioning dynamics of unsaturated multiphase flow at an individual horizontal fracture intersection. A high precision multichannel dispenser is used to establish gravity-driven free surface flow on a smooth and vertical PMMA (poly(methyl methacrylate)) surface at rates ranging from 1.5 to 4.5 mL/min to obtain various flow modes (droplets; rivulets). Cubes with dimensions 20 x 20 x 20 cm are used to create a set of simple geometries. A digital balance provides continuous real-time cumulative mass bypassing the network. The influence of variable flow rate, atmospheric pressure and temperature on the stability of flow modes is shown in single-inlet experiments. Droplet and rivulet flow are delineated and a transition zone exhibiting mixed flow modes can be determined. Furthermore, multi-inlet setups with constant total inflow rates are used to reduce variance and the effect of erratic free-surface flow dynamics. Investigated parameters include: variable aperture widths df, horizontal offsets dv of the vertical fracture surface and alternating injection methods for both droplet and rivulet flow. Repetitive structures with several horizontal fractures extend arrival times but also complexity and variance. Finally, impacts of variable geometric features and flow modes on partitioning dynamics are highlighted by normalized fracture inflow rates. For higher flow rates, i.e. rivulet flows dominates, the effectiveness of filling horizontal fractures strongly increases. We demonstrate that the filling can be described by plug flow, which transitions into a Washburn-type flow at later times, and derive an analytical solution for the case of rivulet flows. Droplet flow dominated flow experiments exhibit a high bypass efficiency, which cannot be described by plug-flow, however, they also transition into a Washburn stage.

Sulfur speciation and stable isotope trends of water-soluble sulfates in mine tailings profiles.

PubMed

Dold, Bernhard; Spangenberg, Jorge E

2005-08-01

Sulfur speciation and the sources of water-soluble sulfate in three oxidizing sulfidic mine tailings impoundments were investigated by selective dissolution and stable isotopes. The studied tailings impoundments--Piuquenes, Cauquenes, and Salvador No. 1--formed from the exploitation of the Rio Blanco/La Andina, El Teniente, and El Salvador Chilean porphyry copper deposits, which are located in Alpine, Mediterranean, and hyperarid climates, respectively. The water-soluble sulfate may originate from dissolution of primary ore sulfates (e.g., gypsum, anhydrite, jarosite) or from oxidation of sulfide minerals exposed to aerobic conditions during mining activity. With increasing aridity and decreasing pyrite content of the tailings, the sulfur speciation in the unsaturated oxidation zones showed a trend from dominantly Fe(III) oxyhydroxide fixed sulfate (e.g., jarosite and schwertmannite) in Piuquenes toward increasing presence of water-soluble sulfate at Cauquenes and Salvador No. 1. In the saturated primary zones, sulfate is predominantly present in water-soluble form (mainly as anhydrite and/or gypsum). In the unsaturated zone at Piuquenes and Cauquenes, the delta34S(SO4)values ranged from +0.5 per thousand to +2.0 per thousand and from -0.4 per thousand to +1.4 per thousand Vienna Canyon Diablo Troilite (V-CDT), respectively, indicating a major sulfate source from pyrite oxidation (delta34S(pyrite) = -1.1 per thousand and -0.9 per thousand). In the saturated zone at Piuquenes and Cauquenes, the values ranged from -0.8 per thousand to +0.3 per thousand and from +2.2 per thousand to +3.9 per thousand, respectively. At Cauquenes the 34S enrichment in the saturated zone toward depth indicates the increasing contribution of isotopically heavy dissolved sulfate from primary anhydrite (approximately +10.9 per thousand). At El Salvador No. 1, the delta34S(SO4) average value is -0.9 per thousand, suggesting dissolution of supergene sulfate minerals (jarosite, alunite, gypsum) with a delta34S approximately -0.7 per thousand as the most probable sulfate source. The gradual decrease of delta18O(SO4) values from the surface to the oxidation front in the tailings impoundments at Piuquenes (from -4.5 per thousand to -8.6 per thousand Vienna Standard Mean Ocean Water, V-SMOW) and at Cauquenes (from -1.3 per thousand to -3.5 per thousand) indicates the increasing importance of ferric iron as the main electron acceptor in the oxidation of pyrite. The different delta18O(SO4) values between the tailings impoundments studied here reflect the local climates.

Fluid chemistry and evolution of hydrothermal fluids in an Archaean transcrustal fault zone network: The case of the Cadillac Tectonic Zone, Abitibi greenstone belt, Canada

USGS Publications Warehouse

Neumayr, P.; Hagemann, S.G.; Banks, D.A.; Yardley, B.W.D.; Couture, J.-F.; Landis, G.P.; Rye, R.

2007-01-01

Detailed fluid geochemistry studies on hydrothermal quartz veins from the Rouyn-Noranda and Val-d'Or areas along the transcrustal Cadillac Tectonic Zone (CTZ) indicate that unmineralized (with respect to gold) sections of the CTZ contained a distinct CO2-dominated, H2S-poor hydrothermal fluid. In contrast, both gold mineralized sections of the CTZ (e.g., at Orenada #2) and associated higher order shear zones have a H2O-CO2 ?? CH4-NaCl hydrothermal fluid. Their CO2/H2S ratios indicate H2S-rich compositions. The Br/Cl compositions in fluid inclusions trapped in these veins indicate that hydrothermal fluids have been equilibrated with the crust. Oxygen isotope ratios from hydrothermal quartz veins in the CTZ are consistently 2??? more enriched than those of associated higher order shear zones, which are interpreted to be a function of greater fluid/rock ratios in the CTZ and lower fluid/rock ratios, and more efficient equilibration of the hydrothermal fluid with the wall rock, in higher order shear zones. An implication from this study is that the lower metal endowment of the transcrustal CTZ, when compared with the higher metal endowment in higher order shear zones (ratio of about 1 : 1000), may be the result of the lack of significant amounts of H2O-H2S rich fluids in most of the CTZ. In contrast, gold mineralization in the higher order shear zones appear to be controlled by the high H2S activity of the aqueous fluids, because gold was likely transported in a bisulfide complex and was deposited during sulfidation reactions in the wall rock and phase separation in the quartz veins. ?? 2007 NRC Canada.

Mineral systems and the thermodynamics of selenites and selenates in the oxidation zone of sulfide ores - a review

NASA Astrophysics Data System (ADS)

Charykova, Marina V.; Krivovichev, Vladimir G.

2017-02-01

Contemporary mineralogy and geochemistry are concerned with understanding and deciphering processes that occur near the surface of the Earth. These processes are especially important for resolving ecological challenges and developing principles of good environmental management. Selenium oxysalts, selenites and selenates, are relatively rare as minerals; there are presently only 34 known mineral species. Thirty-one "pure" selenites, which contain only selenite anionic groups, are known to occur naturally. The other three minerals each contain two anionic groups: selenate and selenite (schmiederite), selenate and sulphate (olsacherite), and selenate and iodate (carlosruizite).

Effect of Pulse Parameters on Weld Quality in Pulsed Gas Metal Arc Welding: A Review

NASA Astrophysics Data System (ADS)

Pal, Kamal; Pal, Surjya K.

2011-08-01

The weld quality comprises bead geometry and its microstructure, which influence the mechanical properties of the weld. The coarse-grained weld microstructure, higher heat-affected zone, and lower penetration together with higher reinforcement reduce the weld service life in continuous mode gas metal arc welding (GMAW). Pulsed GMAW (P-GMAW) is an alternative method providing a better way for overcoming these afore mentioned problems. It uses a higher peak current to allow one molten droplet per pulse, and a lower background current to maintain the arc stability. Current pulsing refines the grains in weld fusion zone with increasing depth of penetration due to arc oscillations. Optimum weld joint characteristics can be achieved by controlling the pulse parameters. The process is versatile and easily automated. This brief review illustrates the effect of pulse parameters on weld quality.

Solidification Sequence of Spray-Formed Steels

NASA Astrophysics Data System (ADS)

Zepon, Guilherme; Ellendt, Nils; Uhlenwinkel, Volker; Bolfarini, Claudemiro

2016-02-01

Solidification in spray-forming is still an open discussion in the atomization and deposition area. This paper proposes a solidification model based on the equilibrium solidification path of alloys. The main assumptions of the model are that the deposition zone temperature must be above the alloy's solidus temperature and that the equilibrium liquid fraction at this temperature is reached, which involves partial remelting and/or redissolution of completely solidified droplets. When the deposition zone is cooled, solidification of the remaining liquid takes place under near equilibrium conditions. Scanning electron microscopy (SEM) and optical microscopy (OM) were used to analyze the microstructures of two different spray-formed steel grades: (1) boron modified supermartensitic stainless steel (SMSS) and (2) D2 tool steel. The microstructures were analyzed to determine the sequence of phase formation during solidification. In both cases, the solidification model proposed was validated.

Geology of the Vienna Mineralized Area, Blaine and Camas Counties, Idaho

USGS Publications Warehouse

Mahoney, J. Brian; Horn, Michael C.

2005-01-01

The Vienna mineralized area of south-central Idaho was an important silver-lead-producing district in the late 1800s and has intermittently produced lead, silver, zinc, copper, and gold since that time. The district is underlain by biotite granodiorite of the Cretaceous Idaho batholith, and all mineral deposits are hosted by the biotite granodiorite. The granodiorite intrudes Paleozoic sedimentary rocks of the Sun Valley Group, is overlain by rocks of the Eocene Challis Volcanic Group, and is cut by numerous northeast-trending Eocene faults and dikes. Two mineralogically and texturally distinct vein types are present in a northwest- and east-trending conjugate shear-zone system. The shear zones postdate granodiorite emplacement and joint formation, but predate Eocene fault and dike formation. Ribbon veins consist of alternating bands of massive vein quartz and silver-sulfide (proustite and pyrargyrite) mineral stringers. The ribbon veins were sheared and brecciated during multiple phases of injection of mineralizing fluids. A quartz-sericite-pyrite-galena vein system was subsequently emplaced in the brecciated shear zones. Both vein systems are believed to be the product of mesothermal, multiphase mineralization. K-Ar dating of shear-zone sericite indicates that sericitization occurred at 80.7?2.8 Ma; thus mineralization in the Vienna mineralized area probably is Late Cretaceous in age.

Water table dynamics and biogeochemical cycling in a shallow, variably-saturated floodplain

DOE PAGES

Yabusaki, Steven B.; Wilkins, Michael J.; Fang, Yilin; ...

2017-02-20

Three-dimensional variably saturated flow and multicomponent biogeochemical reactive transport modeling, based on published and newly generated data, is used to better understand the interplay of hydrology, geochemistry, and biology controlling the cycling of carbon, nitrogen, oxygen, iron, sulfur, and uranium in a shallow floodplain. In this system, aerobic respiration generally maintains anoxic groundwater below an oxic vadose zone until seasonal snowmelt-driven water table peaking transports dissolved oxygen (DO) and nitrate from the vadose zone into the alluvial aquifer. The response to this perturbation is localized due to distinct physico-biogeochemical environments and relatively long time scales for transport through the floodplainmore » aquifer and vadose zone. Naturally reduced zones (NRZs) containing sediments higher in organic matter, iron sulfides, and non-crystalline U(IV) rapidly consume DO and nitrate to maintain anoxic conditions, yielding Fe(II) from FeS oxidative dissolution, nitrite from denitrification, and U(VI) from nitrite-promoted U(IV) oxidation. Redox cycling is a key factor for sustaining the observed aquifer behaviors despite continuous oxygen influx and the annual hydrologically induced oxidation event. Furthermore, depth-dependent activity of fermenters, aerobes, nitrate reducers, sulfate reducers, and chemolithoautotrophs (e.g., oxidizing Fe(II), S compounds, and ammonium) is linked to the presence of DO, which has higher concentrations near the water table.« less

Predicting the denitrification capacity of sandy aquifers from in situ measurements using push-pull 15N tracer tests

NASA Astrophysics Data System (ADS)

Eschenbach, W.; Well, R.; Walther, W.

2015-04-01

Knowledge about the spatial variability of in situ denitrification rates (Dr(in situ)) and their relation to the denitrification capacity in nitrate-contaminated aquifers is crucial to predict the development of groundwater quality. Therefore, 28 push-pull 15N tracer tests for the measurement of in situ denitrification rates were conducted in two sandy Pleistocene aquifers in northern Germany. The 15N analysis of denitrification-derived 15N-labelled N2 and N2O dissolved in water samples collected during the push-pull 15N tracer tests was performed using isotope ratio mass spectrometry (IRMS) in the lab and additionally for some tracer tests online in the field with a quadrupole membrane inlet mass spectrometer (MIMS) in order to test the feasibility of on-site real-time 15N analysis. Aquifer material from the same locations and depths as the push-pull injection points was incubated, and the initial and cumulative denitrification after 1 year of incubation (Dcum(365)) as well as the stock of reduced compounds (SRC) was compared with in situ measurements of denitrification. This was done to derive transfer functions suitable to predict Dcum(365) and SRC from Dr(in situ). Dr(in situ) ranged from 0 to 51.5 μg N kg-1 d-1. Denitrification rates derived from on-site isotope analysis using MIMS satisfactorily coincided with laboratory analysis by conventional IRMS, thus proving the feasibility of in situ analysis. Dr(in situ) was significantly higher in the sulfidic zone of both aquifers compared to the zone of non-sulfidic aquifer material. Overall, regressions between the Dcum(365) and SRC of the tested aquifer material with Dr(in situ) exhibited only a modest linear correlation for the full data set. However, the predictability of Dcum(365) and SRC from Dr(in situ) data clearly increased for aquifer samples from the zone of NO3--bearing groundwater. In the NO3--free aquifer zone, a lag phase of denitrification after NO3- injections was observed, which confounded the relationship between reactive compounds and in situ denitrification activity. This finding was attributed to adaptation processes in the microbial community after NO3- injections. It was also demonstrated that the microbial community in the NO3--free zone just below the NO3--bearing zone can be adapted to denitrification by NO3- injections into wells for an extended period. In situ denitrification rates were 30 to 65 times higher after pre-conditioning with NO3-. Results from this study suggest that such pre-conditioning is crucial for the measurement of Dr(in situ) in deeper aquifer material from the NO3--free groundwater zone and thus for the prediction of Dcum(365) and SRC from Dr(in situ).

Euhedral metallic-Fe-Ni grains in extraterrestrial samples

NASA Technical Reports Server (NTRS)

Rubin, Alan E.

1993-01-01

Metallic Fe-Ni is rare in terrestrial rocks, being largely restricted to serpentinized peridotites and volcanic rocks that assimilated carbonaceous material. In contrast, metallic Fe-Ni is nearly ubiquitous among extraterrestrial samples (i.e., meteorites, lunar rocks, and interplanetary dust particles). Anhedral grains are common. For example, in eucrites and lunar basalts, most of the metallic Fe-Ni occurs interstitially between silicate grains and thus tends to have irregular morphologies. In many porphyritic chondrules, metallic Fe-Ni and troilite form rounded blebs in the mesostasis because their precursors were immiscible droplets. In metamorphosed ordinary chondrites, metallic Fe-Ni and troilite form coarse anhedral grains. Some of the metallic Fe-Ni and troilite grains has also been mobilized and injected into fractures in adjacent silicate grains where local shock-reheating temperatures reached the Fe-FeS eutectic (988 C). In interplanetary dust particles metallic Fe-Ni most commonly occurs along with sulfide as spheroids and fragments. Euhedral metallic Fe-Ni grains are extremely rare. Several conditions must be met before such grains can form: (1) grain growth must occur at free surfaces, restricting euhedral metallic Fe-Ni grains to systems that are igneous or undergoing vapor-deposition; (2) the metal (+/-) sulfide assemblage must have an appropriate bulk composition so that taenite is the liquidus phase in igneous systems or the stable condensate phase in vapor-deposition systems; and (3) metallic Fe-Ni grains must remain underformed during subsequent compaction, thermal metamorphism, and shock. Because of these restrictions, the occurrence of euhedral metallic Fe-Ni grains in an object can potentially provide important petrogenetic information. Despite its rarity, euhedral metallic Fe-Ni occurs in a wide variety of extraterrestrial materials. Some of these materials formed in the solar nebula; others formed on parent body surfaces by meteoroid impacts.

Sulfur and iron geochemistry of the dynamic sedimentary system at the Costa Rica margin, IODP Expedition 344

NASA Astrophysics Data System (ADS)

Gott, C.; Riedinger, N.; Formolo, M.; Solomon, E. A.; Torres, M. E.; Bates, S. M.; Lyons, T. W.; 344 Scientific Party, I.

2013-12-01

One of the major targets of the CRISP (Costa Rica Seismogenesis Project) was to explore diagenetic processes, including fluid flow, related to the complex sedimentary and tectonic behavior of the Costa Rica margin system. Here we present preliminary results of the iron and sulfur geochemistry from sediments collected during the IODP Expedition 344 at Holes U1413B and U1414A. Our specific goal was to investigate the impact of this dynamic system on biogeochemical processes - especially regarding the sulfur cycle - and how minerals record these processes in the geologic record. The sediments at both investigated locations display non-steady state pore water conditions. Specifically, the deposits at Hole U1413B are characterized by a shallow sulfate-methane transition zone (SMTZ; approximately 15 mbsf), where released hydrogen sulfide reacts with reactive iron minerals to form iron sulfides. At Hole U1414A pore water sulfate is present at several hundreds of meters sediment depth, while the concentration of hydrogen sulfide is low (<4 μM). The measured concentrations of solid phase iron sulfides in the sediments indicate that pyrite is the main sulfur-bearing phase, reaching concentrations of 2 and 3 wt.%, in U1413B and U1414A, respectively. Sequential extractions of iron oxides reveal the presence of reactive iron phases, although in low concentrations (total iron oxides are below 1.1 wt.%), indicating ongoing alteration of iron oxides. The occurrence of these reactive iron minerals in the deeply buried sediments at Hole U1414A has implications for the deep biosphere - as those minerals can still be utilized by the microbial community. The non-steady state condition of the sedimentary system at both locations is also mirrored in the S-isotopic signal in the pore fluids as well as solid phase. The 34S-enriched sulfate (δ34S >+60 ‰) in the deeper sediment column is reflected in the δ34S profile of the in situ formed iron sulfides - the results can have implications for the interpretation of ancient rocks from similar active systems throughout Earth's history. Comparing the results of the investigated sediments at both sites, our data show variability, which may be caused by different sulfur sources and biogeochemical sulfur cycling driven by the tectonic and sedimentary complexity of the Costa Rica margin system.

Sulfide geochronlogy along the Southwest Indian Ridge

NASA Astrophysics Data System (ADS)

Yang, W.; Tao, C.; Li, H.; Liang, J.; Liao, S.

2017-12-01

Dragon Flag and Duanqiao hydrothermal field is located between the Indomed and Gallieni fracture zones in the ultraslow-spreading Southwest Indian Ridge (SWIR). Ten subsamples from active and inactive vents of Dragon Flag hydrothermal field and twenty-eight subsamples from Duanqiao hydrothermal field were dated using the 230Th/238U method. Four main episodes of hydrothermal activity of Duanqiao were determined according to the restricted results: 68.9-84.3, 43.9-48.4, 25.3-34.8, and 0.7-17.3 kyrs. Hydrothermal activity of Duanqiao probably started about 84.3 (±0.5) kyrs ago and ceased about 0.737 (±0.023) kyrs ago. And sulfide samples from the nearby Dragon Flag filed at the same time and the results show that the ages of most sulfides from Dragon Flag field range from 1.496(±0.176) to 5.416 (±0.116) kyrs with the oldest age estimated at 15.997 (±0.155) kyrs Münch et al. (2001) reconstructed the evolution history of Mt. Jourdanne hydrothermal field. The age dating results indicate activity in two episodes, at 70-40 and 27-13 kyrs. The hydrothermal activity in Dragon Flag field is much more recent than that of Duanqiao or Mt. Jourdanne fields. The massive sulfides are younger than the sulfides from other hydrothermal fields such as Rainbow, Sonne and Ashadze-2. All these results suggest that hydrothermal activity of Dragon Flag field is much more recent than that of Duanqiao or Mt. Jourdanne fields. Mt. Jourdanne is situated on an axial volcanic ridge which has both volcanic and tectonic activity. This is necessary to develop the heat source and pathways for the fluid convection, which enables the hydrothermal circulation. Hydrothermal activity in Dragon Flag Field is located next to the detachment fault termination. The detachment fault system provides a pathway for hydrothermal convection. Such style of heat source can contribute to continuous hydrothermal activity for over 1000 years. Duanqiao field is located near the central volcano and there is a hot mantle and/or fertile melt beneath Duanqiao field. The crust thickness is 9.5 km, suggesting the existence of AMC (Axial Magma Chamber) which provides magma source to the field (Li et al. 2015; Mendel et al. 2003). The periodic hydrothermal activity at Duanqiao may be related to the heat source provided by the local interaction of magmatism and tectonism.

Hydrogen Sulfide Emissions from Sow Farm Lagoons across Climates Zones.

PubMed

Grant, Richard H; Boehm, Matthew T; Lawrence, Alfred J; Heber, Albert J

2013-11-01

Hydrogen sulfide (HS) emissions were measured periodically over the course of 2 yr at three sow waste lagoons representing humid mesothermal (North Carolina, NC), humid microthermal (Indiana, IN), and semiarid (Oklahoma, OK) climates. Emissions were determined using a backward Lagrangian stochastic model in conjunction with line-sampled HS concentrations and measured turbulence. The median annual sow-specific (area-specific) lagoon emissions at the OK farm were approximately 1.6 g head [hd] d (5880 µg m s), whereas those at the IN and NC sow farms were 0.035 g hd d (130 µg m s), and 0.041 g hd d (260 µg m s), respectively. Hydrogen sulfide emissions generally increased with wind speed. The daily HS emissions from the OK lagoon were greatest during the first half of the year and decreased as the year progressed. Emissions were episodic at the NC and IN lagoons. The generally low emissions at the NC and IN lagoons were probably a result of significant populations of purple sulfur bacteria maintained in the humid mesothermal and humid microthermal climates. Most of the large HS emission events at the NC and IN lagoons appeared to be a result of either precipitation events or liquid pump-out events. The high emissions at the OK lagoon in a semiarid climate were largely a result of high wind speeds enhancing both lagoon and air boundary layer mixing. The climate (air temperature, winds, and precipitation) appeared to influence the HS emissions from lagoons. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Environmental controls on sulfur isotopic composition of sulfide minerals in seep carbonates from the South China Sea

NASA Astrophysics Data System (ADS)

Gong, S.; Li, N.; Liang, Q.; Chen, D.; Feng, D.

2017-12-01

Authigenic carbonates and pyrite associated with sulfate-driven anaerobic oxidation of methane (AOM) at methane seeps provide archives to explore the biogeochemical processes involved and seepage dynamics over time. The wide range and extremely high δ34Spy value of authigenic sulfide has been used to trace the AOM-related processes. However, the detail mechanism for this is unknown. We proposed the δ34Spy characteristics result from high sulfate reduction rate and its competition with sulfate supply rate. To test this hypothesis, we investigated Mo content, Sr/Ca and Mg/Ca ratios, pyrite content, and its sulfur isotopic compositions in methane-derived carbonates from Site F and Haima in northern South China Sea. Calcite and aragonite were distinguished through the Sr/Ca and Mg/Ca ratios. The data show that aragonites are always associated with relatively low δ34Spy values compared to calcites. The Mo content and pyrite have good linear correlations in both aragonites and calcites, and aragonites have more positive slope than calcites. This indicates that there is more Mo available from seawater during the aragonite precipitation. The data suggest that the low δ34Spy values are formed at higher supply rate of sulfate under relatively open system, and high δ34Spy values result from a deep sulfate methane transition zone where dissolve sulfate near to complete exhausted via AOM. The combination of a detailed elemental study of authigenic carbonate with sulfur isotopes of sulfide minerals in carbonates are promising tools for reconstructing the dynamics of seep intensities in modern and, potentially, geological record.

Significance of tourmaline-rich rocks in the north range group of the cuyuna iron range, East-Central Minnesota

USGS Publications Warehouse

Cleland, J.M.; Morey, G.B.; McSwiggen, P.L.

1996-01-01

Concentrations of tourmaline in Early Proterozoic metasedirnentary rocks of the Cuyuna iron range, east-central Minnesota, provide a basis for redefinition of the evolutionary history of the area. Manganiferous iron ore forms beds within the Early Proterozoic Trommald Formation, between thick-bedded granular iron-formation having shallow-water depositional attributes and thin-bedded, nongranular iron-formation having deeper water attributes. These manganese-rich units were previously assumed to be sedimentary in origin. However, a revaluation of drill core and mine samples from the Cuyuna North range has identified strata-bound tourmaline and tourmalinite, which has led to a rethinking of genetic models for the geology of the North range. We interpret the tourmaline-rich rocks of the area to be a product of submarine-hydrothermal solutions flowing along and beneath the sedirnent-seawater interface. This model for the depositional environment of the tourmaline is supported by previously reported mineral assemblages within the Trommald Formation that comprise aegirine; barium feldspar; manganese silicates, carbonates, and oxides; and Sr-rich barite veins. In many places, tourmaline-rich metasedimentary rocks and tourmalinites are associated locally with strata-bound sulfide deposits. At those localities, the tourmaline-rich strata are thought to be lateral equivalents of exhalative sulfide zones or genetically related subsea-floor replacements. On the basis of the occurrence of the tourmaline-rich rocks and tourmalinites, and on the associated minerals, we suggest that there is a previously unrecognized potential for sediment-hosted sulfide deposits in the Cuyuna North range.

Characterization and origin of low-T willemite (Zn2SiO4) mineralization: the case of the Bou Arhous deposit (High Atlas, Morocco)

NASA Astrophysics Data System (ADS)

Choulet, Flavien; Barbanson, Luc; Buatier, Martine; Richard, James; Vennemann, Torsten; Ennaciri, Aomar; Zouhair, Mohamed

2017-10-01

Willemite (Zn2SiO4) usually reported in hypogene non-sulfide deposits is described as the main ore mineral in the carbonate-hosted Bou Arhous zinc deposit. This deposit is located in the High Atlas intracontinental range that formed during the Tertiary. Based on a set of microscopic observations, it was possible to establish that willemite replaces primary sphalerite. On the basis of cathodoluminescence imaging, three successive generations of willemite are distinguished, with evidence of dissolution-reprecipitation processes. Willemite is also variably enriched in Ge (up to 1000 ppm), while Ge contents lower than 100 ppm are reported in the primary sulfide minerals. Depending on the willemite generation, this substitution was positively or negatively correlated to the Zn-Pb substitution. According to the nature of zoning (sector versus oscillatory), the incorporation of Ge was either controlled by crystallographic factors or by the nature of the mineralizing fluids. Willemite is associated with other oxidation-related mineral species, like cerussite (PbCO3) but is not in isotopic equilibrium and therefore not considered to be cogenetic. Oxygen isotope compositions support the formation of willemite at temperatures below 130 °C, from mixed meteoric and deeper, hydrothermal fluids. The formation of the High Atlas Belt during the Tertiary has contributed to the exhumation of the sulfide minerals and the development of vertical conduits for percolation of meteoric water and ascending hydrothermal fluids. In addition to a local contribution of silicate minerals of the host limestone, hydrothermal fluids probably transported Si and Ge that are incorporated in willemite.

Frying of the Dispersion Droplets with Varying Contents of Chickpea Flour and Gum Arabic: Product Characterization and Modeling.

PubMed

Shanthilal, J; Babylatha, R; Navya, M C; Chakkaravarthi, A; Bhattacharya, Suvendu

2018-03-01

Dispersions having chickpea (37%, 40%, and 43%, w/w) and gum arabic (0%, 1%, 2%, 3%, 4%, and 5%, w/w) solids were prepared. These dispersion droplets were fried, and the physical, sensory, and microstructural characteristics of the fried products were determined. The oil content in the fried snack decreased up to 20.3% when the level of chickpea and/or gum in the dispersions was increased. The compression curve for fried snack showed 5 major zones and exhibited the failure phenomenon. Failure force (6.5 to 11.4 N) increased with chickpea flour in the dispersions. Fracture strain (12.0% to 19.5%) indicated that all the fried samples were soft-crisp products. An increase in chickpea flour concentration offered an ovoid/oblong shape of dispersion droplets while falling to oil, and changed the spherical shape of the fried snack. The near-spherical product could be obtained by using 37% chickpea flour containing 0 to 2% of gum arabic, or with the 40% and 0 to 1% combinations. The hue or dominant wavelength increased from 578.5 nm (flour) to 581.0 to 582.7 nm (product) indicating a shift toward red coloration. A porous microstructure with scattered small cavities and large vacuoles of the fried snack were observed; big vacuoles were located in the inner portion of the fried product. The cells were divided into closed and open cells and were characterized by image analysis. The air cells usually had an elliptical shape with varying sizes; the cell wall thickness was between 12 and 80 μm. An artificial neural network (ANN) structure of 2-9-2 was developed for the prediction of sensory overall acceptability and oil content of the fried snack. Chickpea flour is used in several food preparations. The addition of gum arabic affects the textural and structural characteristics, and the sensory acceptance; the fried dispersion droplets have a lower fat content when gum arabic is used compared to samples fried without the addition of gum arabic. The fried dispersion droplets change their shape with the level of the ingredients used in the dispersion. © 2018 Institute of Food Technologists®.

A novel method for improving cerussite sulfidization

NASA Astrophysics Data System (ADS)

Feng, Qi-cheng; Wen, Shu-ming; Zhao, Wen-juan; Cao, Qin-bo; Lü, Chao

2016-06-01

Evaluation of flotation behavior, solution measurements, and surface analyses were performed to investigate the effects of chloride ion addition on the sulfidization of cerussite in this study. Micro-flotation tests indicate that the addition of chloride ions prior to sulfidization can significantly increase the flotation recovery of cerussite, which is attributed to the formation of more lead sulfide species on the mineral surface. Solution measurement results suggest that the addition of chloride ions prior to sulfidization induces the transformation of more sulfide ions from pulp solution onto the mineral surface by the formation of more lead sulfide species. X-ray diffraction and energy-dispersive spectroscopy indicate that more lead sulfide species form on the mineral surface when chloride ions are added prior to sulfidization. These results demonstrate that the addition of chloride ions prior to sulfidization can significantly improve the sulfidization of cerussite, thereby enhancing the flotation performance.

Mesozoic Magmatism and Base-Metal Mineralization in the Fortymile Mining District, Eastern Alaska - Initial Results of Petrographic, Geochemical, and Isotopic Studies in the Mount Veta Area

USGS Publications Warehouse

Dusel-Bacon, Cynthia; Slack, John F.; Aleinikoff, John N.; Mortensen, James K.

2009-01-01

We present here the initial results of a petrographic, geochemical, and isotopic study of Mesozoic intrusive rocks and spatially associated Zn-Pb-Ag-Cu-Au prospects in the Fortymile mining district in the southern Eagle quadrangle, Alaska. Analyzed samples include mineralized and unmineralized drill core from 2006 and 2007 exploration by Full Metal Minerals, USA, Inc., at the Little Whiteman (LWM) and Fish prospects, and other mineralized and plutonic samples collected within the mining district is part of the USGS study. Three new ion microprobe U-Pb zircon ages are: 210 +- 3 Ma for quartz diorite from LWM, 187 +- 3 Ma for quartz monzonite from Fish, and 70.5 +- 1.1 Ma for altered rhyolite porphyry from Fish. We also present 11 published and unpublished Mesozoic thermal ionization mass spectrometric U-Pb zircon and titanite ages and whole-rock geochemical data for the Mesozoic plutonic rocks. Late Triassic and Early Jurassic plutons generally have intermediate compositions and are slightly foliated, consistent with synkinematic intrusion. Several Early Jurassic plutons contain magmatic epidote, indicating emplacement of the host plutons at mesozonal crustal depths of greater than 15 km. Trace-element geochemical data indicate an arc origin for the granitoids, with an increase in the crustal component with time. Preliminary study of drill core from the LWM Zn-Pb-Cu-Ag prospect supports a carbonate-replacement model of mineralization. LWM massive sulfides consist of sphalerite, galena, and minor pyrite and chalcopyrite, in a gangue of calcite and lesser quartz; silver resides in Sb-As-Ag sulfosalts and pyrargyrite, and probably in submicroscopic inclusions within galena. Whole-rock analyses of LWM drill cores also show elevated In, an important metal in high-technology products. Hypogene mineralized rocks at Fish, below the secondary Zn-rich zone, are associated with a carbonate host and also may be of replacement origin, or alternatively, may be a magnetite-bearing Zn skarn. Cu-Zn-Pb-Ag-Au showings at the Oscar pros-pect occur in marble-hosted magnetite and pyrrhotite skarn that is spatially related to the stocks, dikes, and sills of the Early Jurassic syenite of Mount Veta. Mineralized rocks at the Eva Creek Ag-Zn-Pb-Cu prospect are within 1.5 km of the Mount Veta pluton, which is epidotized and locally altered along its contact with metamorphosed country rock east of the prospect. We report five new sulfide Pb-isotopic analyses from the LWM, Oscar, and Eva Creek prospects and compare these sulfide Pb-isotopic ratios with those for sulfides from nearby deposits and prospects in the Yukon-Tanana Upland and with feldspar Pb-isotopic ratios for Mesozoic plutons in the region. Disparities between the Pb-isotopic ratios for sulfides and igneous feldspars are consistent with a carbonate-replacement model for both the LWM and Eva Creek prospects. The presence in the Fortymile district of base-metal sulfides within both calc-silicate-rich skarns and the calc-silicate-free carbonate replacement deposits may reflect multistage mineralization by magmatic-hydrothermal systems during the emplacement of two or more magmatically unrelated igneous intrusions. Alternatively, all of the mineralized occurrences could be products of one regionally zoned system that formed during the intrusion of a single pluton. In addition to the likely origin of some of the base-metal occurrences by intrusion-related hydrothermal fluids, proximity of the LWM prospect to the northeast-striking, high-angle Kechumstuk Fault suggests that fluid flow along the fault also played an important role during carbonate-replacement mineralization.

Dzhezkazgan and associated sandstone copper deposits of the Chu-Sarysu basin, Central Kazakhstan

USGS Publications Warehouse

Box, Stephen E.; Seltmann, Reimar; Zientek, Michael L.; Syusyura, Boris; Creaser, Robert A.; Dolgopolova, Alla

2012-01-01

Sandstone-hosted copper (sandstone Cu) deposits occur within a 200-km reach of the northern Chu-Sarysu basin of central Kazakhstan (Dzhezkazgan and Zhaman-Aibat deposits, and the Zhilandy group of deposits). The deposits consist of Cu sulfide minerals as intergranular cement and grain replacement in 10 ore-bearing members of sandstone and conglomerate within a 600- to 1,000-m thick Pennsylvanian fluvial red-bed sequence. Copper metal content of the deposits ranges from 22 million metric tons (Mt, Dzehzkazgan) to 0.13Mt (Karashoshak in the Zhilandy group), with average grades of 0.85 to 1.7% Cu and significant values for silver (Ag) and rhenium (Re). Broader zones of iron reduction (bleaching) of sandstones and conglomerates of the red-bed sequence extend over 10 km beyond each of the deposits along E-NE-trending anticlines, which began to form in the Pennsylvanian. The bleached zones and organic residues within them are remnants of ormer petroleum fluid accumulations trapped by these anticlines. Deposit sites along these F1anticlines are localized at and adjacent to the intersections of nearly orthogonal N-NW-trending F2synclines. These structural lows served to guide the flow of dense ore brines across the petroleum-bearing anticlines, resulting in ore sulfide precipitation where the two fluids mixed. The ore brine was sourced either from the overlying Early Permian lacustrine evaporitic basin, whose depocenter occurs between the major deposits, or from underlying Upper Devonian marine evaporites. Sulfur isotopes indicate biologic reduction of sulfate but do not resolve whether the sulfate was contributed from the brine or from the petroleum fluids. New Re-Os age dates of Cu sulfides from the Dzhezkazgan deposit indicate that mineralization took place between 299 to 309 Ma near the Pennsylvanian-Permian age boundary. At the Dzhezkazgan and some Zhilandy deposits, F2fold deformation continued after ore deposition. Copper orebodies in Lower Permian shale near the Zhaman-Aibat deposit indicate that at least some of the mineralization there is younger than at Dzhezkazgan, consistent with the Re-Os age and with differences in their ore Pb isotopes.

Nickel-cobalt-iron-copper sulfides and arsenides in solution-collapse breccia pipes, northwestern Arizona

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

Wenrich, K.J.; Hlava, P.F.

An extensive suite of Ni-Co-Fe-Cu sulfides and arsenides lies within the matrix of solution-collapse breccias buried deep within the plateaus of the Grand Canyon region. Ceilings over large caverns in the Redwall collapsed, brecciating the overlying sandstone and forming cylindrical breccia pipes up to 300 ft in diameter that extend vertically as much as 3,000 ft. These highly permeable breccias served as a host for the precipitation of a suite of over 100 minerals, including uraninite, sphalerite, galena and various copper phases, in addition to the Ni-Co-bearing-phase discussed here. Intricately zoned crystals of small (<1 mm), euhedral Ni-Co-Fe-As-S minerals weremore » the first to form during the second major episode of mineralization in these pipes. Several of these phases replace minerals, such as barite and anhydrite, from the first episode. Extensive microprobe work has been done on samples from two breccia pipe mines, the Hack 2 and Orphan, which are about 50 miles apart. Mineral compositions are similar except that no copper is found in the Ni-Co-Fe phases from the Hack 2 mine, while pyrites containing 1 wt % Cu are common from the Orphan, which was mined for copper. In some of these pyrites', Cu is dominant and the mineral is actually villamaninite. Pyrites from both mines characteristically contain 0.5 to 3 wt % As. Metal contents in zones pyrite-bravoite-vaesite (M[sub 1]S[sub 2]) crystals at the Hack 2 mine range from Fe[sub 1] to Fe[sub .12], Ni[sub 0] to Ni[sub .86], and Co[sub 0] to Co[sub .10]. The metal content for polydymite-siegenite-violarite averages about (Ni[sub 2.33]Co[sub .39]Fe[sub .23])(S[sub 3.9]As[sub .1]). Orphan mine pyrite-bravoite-vaesite-villamaninite ranges in composition from pure FeS[sub 2] to (Ni[sub .6]Fe[sub .21]Co[sub .17])S[sub 2], and (Cu[sub .46]Ni[sub .27]Fe[sub .21]Co[sub .13])S[sub 2]. Of all the sulfides or arsenides found in these breccia pipes, only nickeline consistently occurs as the pure end member.« less

Granitoid-associated gold mineralization in Egypt: a case study from the Atalla mine

NASA Astrophysics Data System (ADS)

Zoheir, Basem; Deshesh, Fatma; Broman, Curt; Pitcairn, Iain; El-Metwally, Ahmed; Mashaal, Shabaan

2018-06-01

Gold-bearing sulfide-quartz veins cutting mainly through the Atalla monzogranite intrusion in the Eastern Desert of Egypt are controlled by subparallel NE-trending brittle shear zones. These veins are associated with pervasive sericite-altered, silicified, and ferruginated rocks. The hosting shear zones are presumed as high-order structures of the Najd-style faults in the Central Eastern Desert ( 615-585 Ma). Ore minerals include an early pyrite-arsenopyrite (±pyrrhotite) mineralization, partly replaced by a late pyrite-galena-sphalerite-chalcopyrite (±gold/electrum ± tetrahedrite ± hessite) assemblage. Gold occurs as small inclusions in pyrite and arsenopyrite, or more commonly as intergrowths with galena and sphalerite/tetrahedrite in microfractures. Arsenopyrite geothermometry suggests formation of the early Fe-As-sulfide mineralization at 380-340 °C, while conditions of deposition of the late base metal-gold assemblage are assumed to be below 300 °C. Rare hessite, electrum, and Bi-galena are associated with sphalerite and gold in the late assemblage. The early and late sulfide minerals show consistently a narrow range of δ34S ‰ (3.4-6.5) that overlaps with sulfur isotopic values in ophiolitic rocks. The Au-quartz veins are characterized by abundant CO2 and H2O ± CO2 ± NaCl inclusions, where three-dimensional clusters of inclusions show variable aqueous/carbonic proportions and broad range of total (bimodal) homogenization temperatures. Heterogeneous entrapment of immiscible fluids is interpreted to be caused by unmixing of an originally homogenous, low salinity ( 2 eq. mass % NaCl) aqueous-carbonic fluid, during transition from lithostatic to hydrostatic conditions. Gold deposition occurred generally under mesothermal conditions, i.e., 1.3 kbar and 280 °C, and continued during system cooling to < 200 °C and pressure decrease to 0.1 kbar. Based on the vein textures, sulfur isotope values, composition of ore fluids, and conditions of ore formation, we suggest that the Atalla monzogranite intrusion acted only as a competent structural host for ore deposition from shear-related, metal-rich fluids migrated up from depth. This model is also presumed for most granitoid-associated Au deposits in the region, considering the similarity in their structural control, alteration pattern and mineralogy, and chemistry of the ore fluids.

Platinum and Palladium Exsolution Textures in Quenched Sulfide Melts

NASA Astrophysics Data System (ADS)

Reo, G.; Frank, M. R.; Loocke, M. P.; Macey, C. J.

2017-12-01

Magmatic sulfide ore deposits account for over 80% of the world's platinum group element (PGE) reserves. Layered mafic intrusions (LMIs), a type of magmatic sulfide ore deposit, contain alternating layers of silicate and sulfide mineralization that are thought to have coexisted as an immiscible silicate + sulfide melt pair. Platinum and palladium, the most common PGEs found in LMIs, heavily favor the sulfide melt. Nernst partition coefficients for Pt (D = wt% of Pt in sulfide/wt% of Pt in silicate) range from 102 to 109. This study examined the Pt- and Pd-bearing phases that formed from the quenched sulfide melts to better constrain the PGE-rich sulfide layers of LMIs system. Experiments were conducted with a basalt melt, sulfide melt, and Pt-Pd metal in a vertical tube furnace at 1100°C and 1 atm and with oxygen fugacity buffered to QFM (quartz-fayalite-magnetite). Following the experiments, run products containing both sulfide and silicate glasses (quenched melts) were analyzed by a Shimadzu EPMA-1720HT Electron Probe Microanalyzer. The focus here is on the quenched Fe-rich sulfides whereas data on the partitioning of Pt and Pd between the coexisting silicate and sulfide melts will be presented in the future. The sulfide samples were imaged in back-scattering mode and major and trace element concentrations of separate metal-rich phases in the sulfide matrix were ascertained through wavelength-dispersive x-ray spectroscopy. Three discernable PGE-rich phases were found to have exsolved from the sulfide matrix upon quenching of the sulfide melt. All of these phases had Fe and S of 21-24 and 16-22 wt.%, respectively. An irregularly shaped Pd- and Cu-rich sulfide phase ( 36 and 14 wt.%, respectively) makes up the majority of the exsolution product. A separate Pd- and Ni-rich phase ( 22 and 14 wt%, respectively) can be found as grains or rims adjacent to the exsolved Pd- and Cu-rich phase. A third Pd- and Pt-rich phase ( 26 and 18 wt.%, respectively) exhibits a dendritic quench texture and is usually surrounded by the sulfide matrix. These data indicate that multiple phases, each with a different Pt:Pd ratio can form upon quench of a homogenous sulfide melt. Thus, the analysis of PGE-rich sulfide domains within LMI may be best considered as a single phase when conducting exploration efforts.

Use of sulfide-containing liquors for removing mercury from flue gases

DOEpatents

Nolan, Paul S.; Downs, William; Bailey, Ralph T.; Vecci, Stanley J.

2006-05-02

A method and apparatus for reducing and removing mercury in industrial gases, such as a flue gas, produced by the combustion of fossil fuels, such as coal, adds sulfide ions to the flue gas as it passes through a scrubber. Ideally, the source of these sulfide ions may include at least one of: sulfidic waste water, kraft caustic liquor, kraft carbonate liquor, potassium sulfide, sodium sulfide, and thioacetamide. The sulfide ion source is introduced into the scrubbing liquor as an aqueous sulfide species. The scrubber may be either a wet or dry scrubber for flue gas desulfurization systems.

Use of sulfide-containing liquors for removing mercury from flue gases

DOEpatents

Nolan, Paul S.; Downs, William; Bailey, Ralph T.; Vecci, Stanley J.

2003-01-01

A method and apparatus for reducing and removing mercury in industrial gases, such as a flue gas, produced by the combustion of fossil fuels, such as coal, adds sulfide ions to the flue gas as it passes through a scrubber. Ideally, the source of these sulfide ions may include at least one of: sulfidic waste water, kraft caustic liquor, kraft carbonate liquor, potassium sulfide, sodium sulfide, and thioacetamide. The sulfide ion source is introduced into the scrubbing liquor as an aqueous sulfide species. The scrubber may be either a wet or dry scrubber for flue gas desulfurization systems.

Photosynthetic Microbial Mats are Exemplary Sources of Diverse Biosignatures (Invited)

NASA Astrophysics Data System (ADS)

Des Marais, D. J.; Jahnke, L. L.

2013-12-01

Marine cyanobacterial microbial mats are widespread, compact, self-contained ecosystems that create diverse biosignatures and have an ancient fossil record. Within the mats, oxygenic photosynthesis provides organic substrates and O2 to the community. Both the absorption and scattering of light change the intensity and spectral composition of incident radiation as it penetrates a mat. Some phototrophs utilize infrared light near the base of the photic zone. A mat's upper layers can become highly reduced and sulfidic at night. Counteracting gradients of O2 and sulfide shape the chemical environment and provide daily-contrasting microenvironments separated on a scale of a few mm. Radiation hazards (UV, etc.), O2 and sulfide toxicity elicit motility and other physiological responses. This combination of benefits and hazards of light, O2 and sulfide promotes the allocation of various essential mat processes between light and dark periods and to various depths in the mat. Associated nonphotosynthetic communities, including anaerobes, strongly influence many of the ecosystem's overall characteristics, and their processes affect any biosignatures that enter the fossil record. A biosignature is an object, substance and/or pattern whose origin specifically requires a biological agent. The value of a biosignature depends not only on the probability of life creating it, but also on the improbability of nonbiological processes producing it. Microbial mats create biosignatures that identify particular groups of organisms and also reveal attributes of the mat ecosystem. For example, branched hydrocarbons and pigments can be diagnostic of cyanobacteria and other phototrophic bacteria, and isoprenoids can indicate particular groups of archea. Assemblages of lipid biosignatures change with depth due to changes in microbial populations and diagenetic transformations of organic matter. The 13C/12C values of organic matter and carbonates reflect isotopic discrimination by particular microorganisms as well as networks of C flow within mats; thus they offer insights about community structure. For example, relative 13C/12C values of individual lipid biosignatures can indicate trophic relationships between key groups of microorganisms. Mat microenvironments can affect the stability of authigenic minerals and alter the chemical compositions and crystal forms of carbonate, sulfate and metal oxide minerals. Interactions between low molecular weight organic compounds and sulfides in mat pore waters can produce alkyl sulfide gases. Processes associated with these physically coherent biofilms can trap and bind detrital grains, enhance mineral precipitation or dissolution, and stabilize sediment surfaces. Accordingly mats can create distinctive sedimentary fabrics and structures. Stromatolites are the most ancient, widespread examples of such fabrics and structures. Thus photosynthetic microbial mats create diverse biosignatures that, when preserved in the geologic record, can help to identify the former presence of key populations of microorganisms and reveal key processes that occurred within ancient mats as well as the interactions between those ecosystems and their environment.

Influence of dissolved organic matter on the complexation of mercury under sulfidic conditions.

PubMed

Miller, Carrie L; Mason, Robert P; Gilmour, Cynthia C; Heyes, Andrew

2007-04-01

The complexation of Hg under sulfidic conditions influences its bioavailability for microbial methylation. Neutral dissolved Hg-sulfide complexes are readily available to Hg-methylating bacteria in culture, and thermodynamic models predict that inorganic Hg-sulfide complexes dominate dissolved Hg speciation under natural sulfidic conditions. However, these models have not been validated in the field. To examine the complexation of Hg in natural sulfidic waters, octanol/water partitioning methods were modified for use under environmentally relevant conditions, and a centrifuge ultrafiltration technique was developed. These techniques demonstrated much lower concentrations of dissolved Hg-sulfide complexes than predicted. Furthermore, the study revealed an interaction between Hg, dissolved organic matter (DOM), and sulfide that is not captured by current thermodynamic models. Whereas Hg forms strong complexes with DOM under oxic conditions, these complexes had not been expected to form in the presence of sulfide because of the stronger affinity of Hg for sulfide relative to its affinity for DOM. The observed interaction between Hg and DOM in the presence of sulfide likely involves the formation of a DOM-Hg-sulfide complex or results from the hydrophobic partitioning of neutral Hg-sulfide complexes into the higher-molecular-weight DOM. An understanding of the mechanism of this interaction and determination of complexation coefficients for the Hg-sulfide-DOM complex are needed to adequately assess how our new finding affects Hg bioavailability, sorption, and flux.

Geology and reconnaissance stable isotope study of the Oyu Tolgoi porphyry Cu-Au system, South Gobi, Mongolia

USGS Publications Warehouse

Khashgerel, B.-E.; Rye, R.O.; Hedenquist, J.W.; Kavalieris, I.

2006-01-01

The Oyu Tolgoi porphyry Cu-Au system in the South Gobi desert, Mongolia, comprises five deposits that extend over 6 km in a north-northeast-oriented zone. They occur in a middle to late Paleozoic are terrane and are related to Late Devonian quartz monzodiorite intrusions. The Hugo Dummett deposits are the northernmost and deepest, with up to 1,000 m of premineral sedimentary and volcanic cover rock remaining. They are the largest deposits discovered to date and characterized by high-grade copper (>2.5% Cu) and gold (0.5-2 g/t) mineralization associated with intense quartz veining and several phases of quartz monzodiorite intruded into basaltic volcanic host rocks. Sulfide minerals in these deposits are zoned outward from a bornite-dominated core to chalcopyrite, upward to pyrite ?? enargite and covellite at shallower depth. The latter high-sulfidation-state sulfides are hosted by advanced argillic alteration mineral associations. This alteration is restricted mainly to dacitic ash-flow tuff that overlies the basaltic volcanic rock and includes ubiquitous quartz and pyrophyllite, kaolinite, plus late dickite veins, as well as K alunite, Al phosphate-sulfate minerals, zunyite, diaspore, topaz, corundum, and andalusite. A reconnaissance oxygen-hydrogen and sulfur isotope study was undertaken to investigate the origin of several characteristic alteration minerals in the Oyu Tolgoi system, with particular emphasis on the Hugo Dummett deposits. Based on the isotopic composition of O, H, and S (??18O(SO4) = 8.8-20.1???, ??D = -73 to -43???, ??34S = 9.8-17.9???), the alunite formed from condensation of magmatic vapor that ascended to the upper parts of the porphyry hydrothermal system, without involvement of significant amounts of meteoric water. The isotopic data indicate that pyrophyllite (??18O = 6.5-10.9???, ??D = -90 to -106???) formed from a magmatic fluid with a component of meteoric water. Muscovite associated with quartz monzodiorite intrusions occurs in the core of the Hugo Dummett deposits, and isotopic data (??18O = 3.0-9.0???, ??D = -101 to -116%o) show it formed from a magmatic fluid with water similar in composition to that which formed the pyrophyllite. Mg chlorite (??18O = 5.5???, ??D = -126???) is a widespread mineral retrograde after hydrothermal biotite and may have formed from fluids similar to those related to the muscovite during cooling of the porphyry system. By contrast, paragenetically later and postmineralization alteration fluid, which produced dickite (??18O = -4.1 to +3.3???, ??D = -130 to -140???), shows clear evidence for mixing with substantial amounts of meteoric water. Relatively low ??D values (-140???) for this meteoric water component may indicate that its source was at high elevations. The geologic structure, nature of alteration, styles of mineralization, and stable isotope data indicate that the Oyu Tolgoi deposits constitute a typical porphyry system formed in an island-arc setting. The outward zonation of sulfide minerals for the Hugo Dummett deposits, from a bornite-dominated core to chalcopyrite and pyrite-enargite, can be interpreted to be related to a cooling magmatic hydrothermal system which transgressed outward over enclosing advanced argillic alteration. This resulted in some unusual alteration and sulfide parageneses, such as topaz, or pyrite, enargite, and tennantite, entrained by high-grade bornite. ?? 2006 by Economic Geology.

Fine structure of the retinal photoreceptors of the great horned owl (Bubo virginianus).

PubMed

Braekevelt, C R

1993-01-01

The retinal photoreceptors of the great horned owl (Bubo virginianus) consist of rods, single cones and unequal double cones present in a ratio of about 30:1.2. In the light-adapted state the rods are stout cells which are not felt to undergo retinomotor movements. The rod outer segment consists of a stack of scalloped membranous discs enclosed by the cell membrane. The rod inner segment shows an ellipsoid of mitochondria and a wealth of rough endoplasmic reticulum (RER) and polysomes, Golgi zones and autophagic vacuoles but not hyperboloid of glycogen. Single cones show a slightly tapered outer segment, a heterogenous oil droplet and an ellipsoid of mitochondria at the apex of the inner segment. Double cones consist of a larger chief member which also displays an oil droplet and a slightly smaller accessory member which does not. Both members of the double cone as well as the single cone show a prominent ellipsoid, plentiful polysomes and RER and Golgi zones in the inner segment. Neither single nor double cones possess a condensed paraboloid of glycogen but instead show plentiful scattered glycogen particles. Along the contiguous membranes between accessory and chief cones a few presumed junctional complexes are seen near the external limiting membrane. Judging by their morphology in light-adaptation the cones of this species do not undergo photomechanical movements. Rods and cones (both types) have both invaginated (ribbon) and numerous superficial (conventional) synaptic sites. Rods are more numerous in this nocturnally active bird than is usually noted in avian species.

In Situ Determination of Sulfide Turnover Rates in a Meromictic Alpine Lake

PubMed Central

Lüthy, Lucas; Fritz, Markus; Bachofen, Reinhard

2000-01-01

A push-pull method, previously used in groundwater analyses, was successfully adapted for measuring sulfide turnover rates in situ at different depths in the meromictic Lake Cadagno. In the layer of phototrophic bacteria at about 12 m in depth net sulfide consumption was observed during the day, indicating active bacterial photosynthesis. During the night the sulfide turnover rates were positive, indicating a net sulfide production from the reduction of more-oxidized sulfur compounds. Because of lack of light, no photosynthesis takes place in the monimolimnion; thus, only sulfide formation is observed both during the day and the night. Sulfide turnover rates in the oxic mixolimnion were always positive as sulfide is spontaneously oxidized by oxygen and as the rates of sulfide oxidation depend on the oxygen concentrations present. Sulfide oxidation by chemolithotrophic bacteria may occur at the oxicline, but this cannot be distinguished from spontaneous chemical oxidation. PMID:10653740

Modelling and intepreting the isotopic composition of water vapour in convective updrafts

NASA Astrophysics Data System (ADS)

Bolot, M.; Legras, B.; Moyer, E. J.

2012-08-01

The isotopic compositions of water vapour and its condensates have long been used as tracers of the global hydrological cycle, but may also be useful for understanding processes within individual convective clouds. We review here the representation of processes that alter water isotopic compositions during processing of air in convective updrafts and present a unified model for water vapour isotopic evolution within undiluted deep convective cores, with a special focus on the out-of-equilibrium conditions of mixed phase zones where metastable liquid water and ice coexist. We use our model to show that a combination of water isotopologue measurements can constrain critical convective parameters including degree of supersaturation, supercooled water content and glaciation temperature. Important isotopic processes in updrafts include kinetic effects that are a consequence of diffusive growth or decay of cloud particles within a supersaturated or subsaturated environment; isotopic re-equilibration between vapour and supercooled droplets, which buffers isotopic distillation; and differing mechanisms of glaciation (droplet freezing vs. the Wegener-Bergeron-Findeisen process). As all of these processes are related to updraft strength, droplet size distribution and the retention of supercooled water, isotopic measurements can serve as a probe of in-cloud conditions of importance to convective processes. We study the sensitivity of the profile of water vapour isotopic composition to differing model assumptions and show how measurements of isotopic composition at cloud base and cloud top alone may be sufficient to retrieve key cloud parameters.

Experience with flexible pipe in sour service environment: A case study (the Arabian Gulf)

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

Al-Maslamani, M.J.

The suitability of a flexible pipe was evaluated on a trial basis for a lift gas line in a sour oil field in the State of Qatar, in the Arabian Gulf. Flexible pipes have been successfully used in the oil and gas industries for transportation of methanol, benzene and gas condensates in wet sweet environment at temperatures of up to 80 C. However, there is little or no information available as to its corrosion resistance in sour service wells containing 6% CO{sub 2} with 3% mole H{sub 2}S and at moderate temperatures. The present experience with a flexible pipe inmore » the gas field of Qatar has shown that under sour service conditions, the layered, composite material can suffer severe degradation leading to failure. A detailed inspection and failure analysis of the flexible pipe forms the basis of this paper. The failure demonstrates the significant effects of stress level, environmental aggressiveness, and localized hard zones in promoting Sulfide Stress Cracking (SSC). Permeability of this sour gas through the composite layer of the flexible pipe resulted in varying degree of sulfide attack and hydrogen embrittlement depending on the susceptibility of the multi layered material.« less

Flux of the biogenic volatiles isoprene and dimethyl sulfide from an oligotrophic lake.

PubMed

Steinke, Michael; Hodapp, Bettina; Subhan, Rameez; Bell, Thomas G; Martin-Creuzburg, Dominik

2018-01-12

Biogenic volatile organic compounds (BVOCs) affect atmospheric chemistry, climate and regional air quality in terrestrial and marine atmospheres. Although isoprene is a major BVOC produced in vascular plants, and marine phototrophs release dimethyl sulfide (DMS), lakes have been widely ignored for their production. Here we demonstrate that oligotrophic Lake Constance, a model for north temperate deep lakes, emits both volatiles to the atmosphere. Depth profiles indicated that highest concentrations of isoprene and DMS were associated with the chlorophyll maximum, suggesting that their production is closely linked to phototrophic processes. Significant correlations of the concentration patterns with taxon-specific fluorescence data, and measurements from algal cultures confirmed the phototrophic production of isoprene and DMS. Diurnal fluctuations in lake isoprene suggested an unrecognised physiological role in environmental acclimation similar to the antioxidant function of isoprene that has been suggested for marine biota. Flux estimations demonstrated that lakes are a currently undocumented source of DMS and isoprene to the atmosphere. Lakes may be of increasing importance for their contribution of isoprene and DMS to the atmosphere in the arctic zone where lake area coverage is high but terrestrial sources of BVOCs are small.

Polyphase enrichment and redistribution processes in silver-rich mineral associations of the hydrothermal fluorite-barite-(Ag-Cu) Clara deposit, SW Germany

NASA Astrophysics Data System (ADS)

Keim, Maximilian F.; Walter, Benjamin F.; Neumann, Udo; Kreissl, Stefan; Bayerl, Richard; Markl, Gregor

2018-03-01

The silver-copper sulfide mineralization associated with the fluorite-barite vein system at the Clara deposit in SW Germany shows large scale vertical zoning. Low to moderate silver contents prevail in the upper 350 m, whereas high silver contents occur in the subsequent 450 m of the currently known vein system. This change in Ag tenor is related to conspicuous mineralogical changes with depth. A detailed petrographic and fluid inclusion study identifies evidence for five subsequent hydrothermal and one alteration stage—all contributing to mineralogical diversity. The vertical Ag zoning, however, is attributed only to the first of these stages. During this first stage, increasing oxidation of ascending hydrothermal fluids (90-160 °C, 24.2-26.7 wt% NaCl+CaCl2) led to the formation of high-Ag tetrahedrite-tennantite in the lower parts and basically Ag-free enargite in the upper parts of the vein system. The subsequent hydrothermal stage led to significant mineralogical changes, but inherited the pre-existing Ag zonation. In this second hydrothermal stage, which was related to fluids similar in composition to those of the first stage (70-125 °C, 23.1-26.5 wt% NaCl+CaCl2), dissolution of high Ag-tetrahedrite-tennantite resulted in the formation of complex Ag-sulfosalts together with moderately Ag-bearing tetrahedrite-tennantite and chalcopyrite. The first two stages were formed by fluid mixing of a sedimentary and a hot basement fluid. The influx of fluids with high Ag, Bi and Pb activity during stage 3 and 5 resulted in the local replacement of earlier Ag-sulfosalts by galena and Ag-(Bi)-sulfosalts. The fourth stage is marked by partial dissolution of sulfides and sulfosalts by a late, hot, undiluted basement fluid (250 °C, 18.7-20.9 wt% NaCl+CaCl2) precipitating fluorite, barite and quartz. Finally, supergene alteration lead to the dissolution of silver-bearing phases and the precipitation of acanthite and native silver. The study illustrates, how metal tenor and mineralogy are decoupled in vertically extensive, polyphase hydrothermal vein systems. This may be pertinent to similarly zoned polymetallic vein systems.

Effect of sulfide on As(III) and As(V) sequestration by ferrihydrite.

PubMed

Zhao, Zhixi; Wang, Shaofeng; Jia, Yongfeng

2017-10-01

The sulfide-induced change in arsenic speciation is often coupled to iron geochemical processes, including redox reaction, adsorption/desorption and precipitation/dissolution. Knowledge about how sulfide influenced the coupled geochemistry of iron and arsenic was not explored well up to now. In this work, retention and mobilization of As(III) and As(V) on ferrihydrite in sulfide-rich environment was studied. The initial oxidation states of arsenic and the contact order of sulfide notably influenced arsenic sequestration on ferrihydrite. For As(III) systems, pre-sulfidation of As(III) decreased arsenic sequestration mostly. The arsenic adsorption capacity decreased about 50% in comparison with the system without sulfide addition. For As(V) systems, pre-sulfidation of ferrihydrite decreased 30% sequestration of arsenic on ferrihydrite. Reduction of ferrihydrite by sulfide in As(V) system was higher than that in As(III) system. Geochemical modeling calculations identified formation of thioarsenite in the pre-sulfidation of As(III) system. Formation of arsenic thioanions enhanced As solubility in the pre-sulfidation of As(III) system. The high concentration of sulfide and Fe(II) in pre-sulfidation of ferrihydrite system contributed to saturation of FeS. This supplied new solid phase to immobilize soluble arsenic in aqueous phase. X-ray absorption near edge spectroscopy (XANES) of sulfur K-edge, arsenic K-edge and iron L-edge analysis gave the consistent evidence for the sulfidation reaction of arsenic and ferrihydrite under specific geochemical settings. Copyright © 2017 Elsevier Ltd. All rights reserved.

High-resolution measurement of DMS and volatile organic compounds dissolved in seawater using equilibrator inlet-proton transfer reaction-mass spectrometry (EI-PTR-MS)

NASA Astrophysics Data System (ADS)

Kameyama, S.; Tanimoto, H.; Inomata, S.; Tsunogai, U.; Ooki, A.; Yokouchi, Y.; Takeda, S.; Obata, H.; Tsuda, A.; Uematsu, M.

2010-12-01

We developed an equilibrator inlet-proton transfer reaction-mass spectrometry (EI-PTR-MS) for high-resolution measurement of multiple volatile organic compounds (VOCs) dissolved in seawater. The equilibration of six VOC species (dimethyl sulfide (DMS), isoprene, propene, acetone, acetaldehyde, and methanol) between seawater and carrier gas, and the response time of the system were evaluated in the laboratory. While isoprene and propene are not in equilibrium associated with slow response time (≈ 15 min) due to low solubility, other species achieve complete equilibrium with overall response time within 2 min under the condition without water droplets on the inner wall of the headspace of the equilibrator. The EI-PTR-MS instrument was deployed during a cruise in the western North Pacific. For DMS and isoprene, comparison of EI-PTR-MS with a membrane tube equilibrator-gas chromatography/mass spectrometry was made, showing generally good agreement. EI-PTR-MS captured temporal variations of dissolved VOCs including small-scale variability, demonstrating the performance of EI-PTR-MS technique for continuous measurement of multiple VOCs in seawater.

Alteration geochemistry of the volcanic-hosted Dedeninyurdu, Yergen and Fındıklıyar Fe-Cu mineralization at Gökçedoǧan, Çorum-Kargi region, Turkey

NASA Astrophysics Data System (ADS)

Gumus, Lokman; Öztürk, Sercan; Yalçın, Cihan; Abdelnasser, Amr; Hanilçi, Nurullah; Kumral, Mustafa

2016-04-01

This study is to determine the mass/volume gain and loss of the major and trace elements during the alteration processes on Dedeninyurdu, Yergen and Fındıklıyar Fe-Cu mineralizations of the area. Fe-Cu mineralization occurred in the spilitic volcanic a rock of Saraycık Formation is associated with the different types of alteration zones which are pyritization, silicification and sericitization. The study area comprises Bekirli Formation, Saraycık Formation, Beşpınar Formation, and Ilgaz Formation. Saraycık formation consists of spilitic volcanic rocks with pelagic limestone, siltstone and chert. The ore mineralogical data show that the pyrite, chalcopyrite, covellite, hematite, malachite and goethite formed during three phases of mineralization. As well as the geologic and petrographic studies reveal three alteration zones with definite mineral assemblages; phyllic alteration (quartz + sericite + pyrite) that represents the main alteration and mineralized zone; propylitic alteration; and carbonatized sericitic alteration zone. The boundaries between these zones are gradual. Mass balance calculations suggested that the phyllic alteration zone represented by gain in Si, Fe, K, S, and LOI and loss in Mg, Ca, and Na refers to silicification, sericitization and pyritization as well as replacement of Fe-Mg silicate and plagioclase. While, in the propylitic alteration zone, enrichment of Si, Fe, Mg, LOI and S occurred with depletions of Ca, Na, and K reflecting chloritization alteration type. On the other hand, carbonatized sericitic alteration zone shows local gain in Si, CaO and K reflects the occurrence of calc-silicate alteration. All alteration zones contain a large proportion of sulfide minerals (gain in S) with increase in loss on ignition (LOI). Keywords: Alteration geochemistry; Mass balance calculation, Fe-Cu mineralization; phyllic alteration, propylitic alteration.

Geochemical behavior of rare earth elements of the hydrothermal alterations within the Tepeoba porphyry Cu-Mo-Au deposits at Balikesir, NW Turkey

NASA Astrophysics Data System (ADS)

Doner, Zeynep; Abdelnasser, Amr; Kiran Yildirim, Demet; Kumral, Mustafa

2016-04-01

This work reports the geochemical characteristics and behavior of the rare earth elements (REE) of the hydrothermal alteration of the Tepeoba porphyry Cu-Mo-Au deposit located in the Anatolian tectonic belt at Biga peninsula (Locally Balikesir province), NW Turkey. The Cu-Mo-Au mineralization at this deposit hosted in the hornfels rocks and related to the silicic to intermediate intrusion of Eybek pluton. It locally formed with brecciated zones and quartz vein stockworks, as well as the brittle fracture zones associated with intense hydrothermal alteration. Three main alteration zones with gradual boundaries formed in the mine area in the hornfels rock that represents the host rock, along that contact the Eybek pluton; potassic, propylitic and phyllic alteration zones. The potassic alteration zone that formed at the center having high amount of Cu-sulfide minerals contains biotite, muscovite, and sericite with less amount of K-feldspar and associated with tourmalinization alteration. The propylitic alteration surrounds the potassic alteration having high amount of Mo and Au and contains chlorite, albite, epidote, calcite and pyrite. The phyllic alteration zone also surrounds the potassic alteration containing quartz, sericite and pyrite minerals. Based on the REE characteristics and content and when we correlate the Alteration index (AI) with the light REEs and heavy REEs of each alteration zone, it concluded that the light REEs decrease and heavy REEs increase during the alteration processes. The relationships between K2O index with Eu/Eu* and Sr/Sr* reveals a positive correlation in the potassic and phyllic alteration zones and a negative correlation in the propylitic alteration zone. This refers to the hydrothermal solution which is responsible for the studied porphyry deposits and associated potassic and phyllic alterations has a positive Eu and Sr anomaly as well as these elements were added to the altered rock from the hydrothermal solution. Keywords: Rare earth elements geochemistry; Tepeoba porphyry Cu-Mo-Au deposits; Balikesir; Turkey

Sulfide Intrusion and Detoxification in the Seagrass Zostera marina

PubMed Central

Hasler-Sheetal, Harald; Holmer, Marianne

2015-01-01

Gaseous sulfide intrusion into seagrasses growing in sulfidic sediments causes little or no harm to the plant, indicating the presence of an unknown sulfide tolerance or detoxification mechanism. We assessed such mechanism in the seagrass Zostera marina in the laboratory and in the field with scanning electron microscopy coupled to energy dispersive X-ray spectroscopy, chromatographic and spectrophotometric methods, and stable isotope tracing coupled with a mass balance of sulfur compounds. We found that Z. marina detoxified gaseous sediment-derived sulfide through incorporation and that most of the detoxification occurred in underground tissues, where sulfide intrusion was greatest. Elemental sulfur was a major detoxification compound, precipitating on the inner wall of the aerenchyma of underground tissues. Sulfide was metabolized into thiols and entered the plant sulfur metabolism as well as being stored as sulfate throughout the plant. We conclude that avoidance of sulfide exposure by reoxidation of sulfide in the rhizosphere or aerenchyma and tolerance of sulfide intrusion by incorporation of sulfur in the plant are likely major survival strategies of seagrasses in sulfidic sediments. PMID:26030258

Why does the Conductivity of a Nickel Catalyst Increase during Sulfidation? An Exemplary Study Using an In Operando Sensor Device.

PubMed

Fremerey, Peter; Jess, Andreas; Moos, Ralf

2015-10-23

In order to study the sulfidation of a catalyst fixed bed, an in operando single pellet sensor was designed. A catalyst pellet from the fixed bed was electrically contacted and its electrical response was correlated with the catalyst behavior. For the sulfidation tests, a nickel catalyst was used and was sulfidized with H₂S. This catalyst had a very low conductivity in the reduced state. During sulfidation, the conductivity of the catalyst increased by decades. A reaction from nickel to nickel sulfide occurred. This conductivity increase by decades during sulfidation had not been expected since both nickel and nickel sulfides behave metallic. Only by assuming a percolation phenomenon that originates from a volume increase of the nickel contacts when reacting to nickel sulfides, this effect can be explained. This assumption was supported by sulfidation tests with differently nickel loaded catalysts and it was quantitatively estimated by a general effective media theory. The single pellet sensor device for in operando investigation of sulfidation can be considered as a valuable tool to get further insights into catalysts under reaction conditions.

Catalyzed Preparation of Amorphous Chalcogenides

DTIC Science & Technology

1998-01-30

hydrogen sulfide through lanthanum isopropoxide in dry benzene, as the solvent. The powder obtained was heat-treated in hydrogen sulfide finally 15...producing single-phase crystalline lanthanum sulfide (La2S3) . Amorphous particles were also prepared by reacting titanium tetrapropoxide [Ti...OC3H7)4] and hydrogen sulfide. Resulting powder was heat-treated in flowing hydrogen sulfide to produce crystalline titanium sulfide (TiS2) . 20

Geological structure and prospects of noble metal ore mineralization of the Khayrkhan gabbroid massif (Western Mongolia)

NASA Astrophysics Data System (ADS)

Kurumshieva, K. R.; Gertner, I. F.; Tishin, P. A.

2017-12-01

An analysis of the distribution of noble metals in zones of sulfide mineralization makes it possible to justify the isolation of four ore-bearing horizons with a specific geochemical zonation. A rise in the gold content relative to palladium and platinum is observed from the bottom upwards along the section of the stratified series of gabbroids. The study of the mineral phases of sulphides and the noble minerals itself indicates the evolution of hydrothermal solutions, which determines the different activity and mobility of the fluid (mercury, tellurium, sulfur) and ore (copper, nickel, iron, platinum, gold and silver) components.