Geochemistry of Late Cretaceous phosphorites in Egypt: Implication for their genesis and diagenesis

NASA Astrophysics Data System (ADS)

Baioumy, H. M.; Tada, R.; Gharaie, M. H. M.

2007-09-01

Phosphorite deposits in Egypt, known as the Duwi Formation, are a part of the Middle East to North Africa phosphogenic province of Late Cretaceous to Paleogene age. Phosphatic grains in these deposites are classified into phosphatic mudclasts and phosphatic bioclasts. Phosphatic bioclasts are subdivided into fish bone fragments and shark tooth fragments. All phosphatic grains are composed of francolite. Chemical mapping of the phosphatic grains using Electron Probe Microanalysis (EPMA) indicated that the phosphatic mudclasts are homogeneous in their chemical composition and no concentric texture nor chemical zoning are observed. Some of the bone fragments show Fe and S zoning. No significant difference in chemical composition is observed between the phosphatic mudclasts and bioclasts. Acid-insoluble residues of the phosphorites show lower values of the Chemical Index of Alteration (CIA) compared to the associated rocks. Structural CO 2 contents in the francolites range from 3.32% to 7.21% with an average of 5.3%. The δ13C PDB values range from -4.04‰ to -8.7‰, while the δ18O PDB values range from -4.3‰ to -10.3‰. The compositional homogeneity of the mudclasts, Fe and S zoning in some of the bone fragments and the difference in the Chemical Index of Alteration between the acid-insoluble residues of the phosphorites and the associated rocks suggest that the phosphatic grains in the Duwi Formation are derived from pre-existing authigenic phosphorites, which reworked and concentrated afterward. Negative δ13C values of structural CO 2 suggest that the CO 2 was derived from degradation of organic matter. Low δ18O values of structural CO 2 can be attributed to the influence of meteoric water. Higher CO 2, SO 3 and F contents compared to the recent authigenic phosphorites and negative δ13C and δ18O values of structural CO 2 indicate that diagenesis plays an important role in the modification of the chemical composition of phosphatic grains and that the studied apatite was francolitized during diagenesis.

Paleontologic and stratigraphic relations of phosphate beds in Upper Cretaceous rocks of the Cordillera Oriental, Colombia

USGS Publications Warehouse

Maughan, Edwin K.; Zambrano O., Francisco; Mojica G., Pedro; Abozaglo M., Jacob; Pachon P., Fernando; Duran R., Raul

1979-01-01

Phosphorite crops out in the Cordillera Oriental of the Colombian Andes in rocks of Late Cretaceous age as strata composed mostly of pelletal carbonate fluorapatite. One stratum of Santonian age near the base of the Galembo Member of the La Luna Formation crops out at many places in the Departments of Santander and Norte de Santander and may be of commercial grade. This stratum is more than one meter thick at several places near Lebrija and near Sardinata, farther south it is locally one meter thick or more near the base of the Guadalupe Formation in the Department of Boyaca. Other phosphorite beds are found at higher stratigraphic levels in the Galembo Member and the Guadalupe Formation, and at some places these may be commercial also. A stratigraphically lower phosphorite occurs below the Galembo Member in the Capacho Formation (Cenomanian age) in at least one area near the town of San Andres, Santander. A phosphorite or pebbly phosphate conglomerate derived from erosion of the Galembo Member forms the base of the Umir Shale and the equivalent Colon Shale at many places. Deposition of the apatite took place upon the continental shelf in marine water of presumed moderate depth between the Andean geosyncline and near-shore detrital deposits adjacent to the Guayana shield. Preliminary calculations indicate phosphorite reserves of approximately 315 million metric tons in 9 areas, determined from measurements of thickness, length of the outcrop, and by projecting the reserves to a maximum of 1,000 meters down the dip of the strata into the subsurface. Two mines were producing phosphate rock in 1969; one near Turmeque, Boyaca, and the other near Tesalia, Huila.

Origin of Cretaceous phosphorites from the onshore of Tamil Nadu, India

NASA Astrophysics Data System (ADS)

Purnachandra Rao, V.; Kessarkar, Pratima M.; Nagendra, R.; Babu, E. V. S. S. K.

2007-12-01

Cretaceous phosphorites from the onshore of Tamil Nadu have been investigated for their origin and compared with those in the offshore. Cretaceous phosphorites occur as light brown to yellowish brown or white nodules in Karai Shale of the Uttatur Group in the onshore Cauvery basin. Nodules exhibit phosphatic nucleus encrusted by a chalky shell of carbonate. The nucleus of the nodules consists of light and dark coloured laminae, phosphate peloids/coated grains and detrital particles interspersed between the laminae. Scanning electron microscope (SEM) studies reveal trapping and binding activity of microbial filaments. A mat structure with linearly arranged microbial filaments and hollow, cell-based coccoid cyanobacterial mat are present. Nodules contain abundant carbonate fluorapatite, followed by minor calcite, quartz and feldspar. The P2O5 content of the phosphorites ranges from 18 to 26%. The CaO/P2O5, Sr and F contents are higher than that of pure carbonate fluorapatite. Concentrations of Si, Al, K, Fe, and Ti are low. We suggest that the nuclei of the nodules represent phosphate clasts related to phosphate stromatolites formed at intertidal conditions. At high energy levels the microbial mats were disintegrated into phosphate clasts, coated with carbonate and then reworked into Karai Shale. On the other hand, Quaternary phosphorites occur as irregular to rounded, grey coloured phosphate clasts at water depths between 180 and 320m on the continental shelf of Tamil Nadu. They exhibit grain-supported texture. Despite Quaternary in age, they also resemble phosphate stromatolites of intertidal origin and reworked as phosphate clasts onto the shelf margin depressions. Benthic microbial mats probably supplied high phosphorus to the sediments. Availability of excess phosphorus seems to be a pre-requisite for the formation of phosphate stromatolites.

Rare earth elements in sedimentary phosphate deposits: Solution to the global REE crisis?

USGS Publications Warehouse

Emsbo, Poul; McLaughlin, Patrick I.; Breit, George N.; du Bray, Edward A.; Koenig, Alan E.

2015-01-01

The critical role of rare earth elements (REEs), particularly heavy REEs (HREEs), in high-tech industries has created a surge in demand that is quickly outstripping known global supply and has triggered a worldwide scramble to discover new sources. The chemical analysis of 23 sedimentary phosphate deposits (phosphorites) in the United States demonstrates that they are significantly enriched in REEs. Leaching experiments using dilute H2SO4 and HCl, extracted nearly 100% of their total REE content and show that the extraction of REEs from phosphorites is not subject to the many technological and environmental challenges that vex the exploitation of many identified REE deposits. Our data suggest that phosphate rock currently mined in the United States has the potential to produce a significant proportion of the world's REE demand as a byproduct. Importantly, the size and concentration of HREEs in some unmined phosphorites dwarf the world's richest REE deposits. Secular variation in phosphate REE contents identifies geologic time periods favorable for the formation of currently unrecognized high-REE phosphates. The extraordinary endowment, combined with the ease of REE extraction, indicates that such phosphorites might be considered as a primary source of REEs with the potential to resolve the global REE (particularly for HREE) supply shortage.

Eumetazoan fossils in terminal Proterozoic phosphorites?

PubMed Central

Xiao, Shuhai; Yuan, Xunlai; Knoll, Andrew H.

2000-01-01

Phosphatic sedimentary rocks preserve a record of early animal life different from and complementary to that provided by Ediacaran fossils in terminal Proterozoic sandstones and shales. Phosphorites of the Doushantuo Formation, South China, contain eggs, egg cases, and stereoblastulae that document animals of unspecified phylogenetic position; small fossils containing putative spicules may specifically record the presence of sponges. Microfossils recently interpreted as the preserved gastrulae of cnidarian and bilaterian metazoans can alternatively be interpreted as conventional algal cysts and/or egg cases modified by diagenetic processes known to have had a pervasive influence on Doushantuo phosphorites. Regardless of this interpretation, evidence for Doushantuo eumetazoans is provided by millimeter-scale tubes that display tabulation and apical budding characteristic of some Cnidaria, especially the extinct tabulates. Like some Ediacaran remains, these small, benthic, colonial fossils may represent stem-group eumetazoans or stem-group cnidarians that lived in the late Proterozoic ocean. PMID:11095754

The controversial "Cambrian" fossils of the Vindhyan are real but more than a billion years older.

PubMed

Bengtson, Stefan; Belivanova, Veneta; Rasmussen, Birger; Whitehouse, Martin

2009-05-12

The age of the Vindhyan sedimentary basin in central India is controversial, because geochronology indicating early Proterozoic ages clashes with reports of Cambrian fossils. We present here an integrated paleontologic-geochronologic investigation to resolve this conundrum. New sampling of Lower Vindhyan phosphoritic stromatolitic dolomites from the northern flank of the Vindhyans confirms the presence of fossils most closely resembling those found elsewhere in Cambrian deposits: annulated tubes, embryo-like globules with polygonal surface pattern, and filamentous and coccoidal microbial fabrics similar to Girvanella and Renalcis. None of the fossils, however, can be ascribed to uniquely Cambrian or Ediacaran taxa. Indeed, the embryo-like globules are not interpreted as fossils at all but as former gas bubbles trapped in mucus-rich cyanobacterial mats. Direct dating of the same fossiliferous phosphorite yielded a Pb-Pb isochron of 1,650 +/- 89 (2sigma) million years ago, confirming the Paleoproterozoic age of the fossils. New U-Pb geochronology of zircons from tuffaceous mudrocks in the Lower Vindhyan Porcellanite Formation on the southern flank of the Vindhyans give comparable ages. The Vindhyan phosphorites provide a window of 3-dimensionally preserved Paleoproterozoic fossils resembling filamentous and coccoidal cyanobacteria and filamentous eukaryotic algae, as well as problematic forms. Like Neoproterozoic phosphorites a billion years later, the Vindhyan deposits offer important new insights into the nature and diversity of life, and in particular, the early evolution of multicellular eukaryotes.

Depositional setting and geochemistry of phosphorites and metalliferous black shales in the Carboniferous-Permian Lisburne Group, Northern Alaska

USGS Publications Warehouse

Dumoulin, Julie A.; Slack, John F.; Whalen, Michael T.; Harris, Anita G.

2011-01-01

Phosphatic rocks are distributed widely in the Lisburne Group, a mainly Carboniferous carbonate succession that occurs throughout northern Alaska. New sedimentologic, paleontologic, and geochemical data presented here constrain the geographic and stratigraphic extent of these strata and their depositional and paleogeographic settings. Our findings support models that propose very high oxygen contents of the Permo-Carboniferous atmosphere and oceans, and those that suggest enhanced phosphogenesis in iron-limited sediments; our data also have implications for Carboniferous paleogeography of the Arctic. Lisburne Group phosphorites range from granular to nodular, are interbedded with black shale and lime mudstone rich in radiolarians and sponge spicules, and accumulated primarily in suboxic outer- to middle-ramp environments. Age constraints from conodonts, foraminifers, and goniatite cephalopods indicate that most are middle Late Mississippian (early Chesterian; early late Visean). Phosphorites form 2- to 40-cm-thick beds of sand- to pebble-sized phosphatic peloids, coated grains, and (or) bioclasts cemented by carbonate, silica, or phosphate that occur through an interval =12 m thick. High gamma-ray response through this interval suggests strongly condensed facies related to sediment starvation and development of phosphatic hardgrounds. Phosphorite textures, such as unconformity-bounded coated grains, record multiple episodes of phosphogenesis and sedimentary reworking. Sharp bed bases and local grading indicate considerable redeposition of phosphatic material into deeper water by storms and (or) gravity flows. Lisburne Group phosphorites contain up to 37 weight percent P2O5, 7.6 weight percent F, 1,030 ppm Y, 517 ppm La, and 166 ppm U. Shale-normalized rare earth element (REE) plots show uniformly large negative Ce anomalies Ce/Ce*=0.11 + or - 0.03) that are interpreted to reflect phosphate deposition in seawater that was greatly depleted in Ce due to increased oxygenation of the atmosphere and oceans during the Carboniferous evolution of large vascular land plants. Black shales within the phosphorite sections have up to 20.2 weight percent Corg and are potential petroleum source rocks. Locally, these strata also are metalliferous, with up to 1,690 ppm Cr, 2,831 ppm V, 551 ppm Ni, 4,670 ppm Zn, 312 ppm Cu, 43.5 ppm Ag, and 12.3 ppm Tl; concentrations of these metals covary broadly with Corg, suggesting coupled redox variations. Calculated marine fractions (MF) of Cr, V, and Mo, used to evaluate the paleoredox state of the bottom waters, show generally high CrMF/MoMF and VMF/MoMF ratios that indicate deposition of the black shales under suboxic denitrifying conditions; Re/Mo ratios also plot mainly within the suboxic field and support this interpretation. Predominantly seawater and biogenic sources are indicated for Cr, V, Mo, Zn, Cd, Ni, and Cu in the black shales, with an additional hydrothermal contribution inferred for Zn, Cd, Ag, and Tl in some samples. Lisburne Group phosphorites formed in the Ikpikpuk Basin and along both sides of the mud- and chert-rich Kuna Basin, which hosts giant massive sulfide and barite deposits of the Red Dog district. Lisburne Group phosphatic strata are coeval with these deposits and formed in response to a nutrient-rich upwelling regime. Phosphate deposition occurred mainly in suboxic bottom waters based on data for paleoredox proxies (Cr, V, Mo, Re) within contemporaneous black shales. Recent global reconstructions are consistent with Carboniferous upwelling in northern Alaska, but differ in the type of upwelling expected (zonal versus meridional). Paleoenvironmental data suggest that meridional upwelling may better explain phosphorite deposition in the Lisburne Group.

Nanometer-scale characterization of exceptionally preserved bacterial fossils in Paleocene phosphorites from Ouled Abdoun (Morocco).

PubMed

Cosmidis, J; Benzerara, K; Gheerbrant, E; Estève, I; Bouya, B; Amaghzaz, M

2013-03-01

Micrometer-sized spherical and rod-shaped forms have been reported in many phosphorites and often interpreted as microbes fossilized by apatite, based on their morphologic resemblance with modern bacteria inferred by scanning electron microscopy (SEM) observations. This interpretation supports models involving bacteria in the formation of phosphorites. Here, we studied a phosphatic coprolite of Paleocene age originating from the Ouled Abdoun phosphate basin (Morocco) down to the nanometer-scale using focused ion beam milling, transmission electron microscopy (TEM), and scanning transmission x-ray microscopy (STXM) coupled with x-ray absorption near-edge structure spectroscopy (XANES). The coprolite, exclusively composed of francolite (a carbonate-fluroapatite), is formed by the accumulation of spherical objects, delimited by a thin envelope, and whose apparent diameters are between 0.5 and 3 μm. The envelope of the spheres is composed of a continuous crown dense to electrons, which measures 20-40 nm in thickness. It is surrounded by two thinner layers that are more porous and transparent to electrons and enriched in organic carbon. The observed spherical objects are very similar with bacteria encrusting in hydroxyapatite as observed in laboratory experiments. We suggest that they are Gram-negative bacteria fossilized by francolite, the precipitation of which started within the periplasm of the cells. We discuss the role of bacteria in the fossilization mechanism and propose that they could have played an active role in the formation of francolite. This study shows that ancient phosphorites can contain fossil biological subcellular structures as fine as a bacterial periplasm. Moreover, we demonstrate that while morphological information provided by SEM analyses is valuable, the use of additional nanoscale analyses is a powerful approach to help inferring the biogenicity of biomorphs found in phosphorites. A more systematic use of this approach could considerably improve our knowledge and understanding of the microfossils present in the geological record. © 2012 Blackwell Publishing Ltd.

The controversial “Cambrian” fossils of the Vindhyan are real but more than a billion years older

PubMed Central

Bengtson, Stefan; Belivanova, Veneta; Rasmussen, Birger; Whitehouse, Martin

2009-01-01

The age of the Vindhyan sedimentary basin in central India is controversial, because geochronology indicating early Proterozoic ages clashes with reports of Cambrian fossils. We present here an integrated paleontologic–geochronologic investigation to resolve this conundrum. New sampling of Lower Vindhyan phosphoritic stromatolitic dolomites from the northern flank of the Vindhyans confirms the presence of fossils most closely resembling those found elsewhere in Cambrian deposits: annulated tubes, embryo-like globules with polygonal surface pattern, and filamentous and coccoidal microbial fabrics similar to Girvanella and Renalcis. None of the fossils, however, can be ascribed to uniquely Cambrian or Ediacaran taxa. Indeed, the embryo-like globules are not interpreted as fossils at all but as former gas bubbles trapped in mucus-rich cyanobacterial mats. Direct dating of the same fossiliferous phosphorite yielded a Pb–Pb isochron of 1,650 ± 89 (2σ) million years ago, confirming the Paleoproterozoic age of the fossils. New U–Pb geochronology of zircons from tuffaceous mudrocks in the Lower Vindhyan Porcellanite Formation on the southern flank of the Vindhyans give comparable ages. The Vindhyan phosphorites provide a window of 3-dimensionally preserved Paleoproterozoic fossils resembling filamentous and coccoidal cyanobacteria and filamentous eukaryotic algae, as well as problematic forms. Like Neoproterozoic phosphorites a billion years later, the Vindhyan deposits offer important new insights into the nature and diversity of life, and in particular, the early evolution of multicellular eukaryotes. PMID:19416859

Sedimentary phosphate and associated fossil bacteria in a Paleoproterozoic tidal flat in the 1.85 Ga Michigamme Formation, Michigan, USA

NASA Astrophysics Data System (ADS)

Hiatt, Eric E.; Pufahl, Peir K.; Edwards, Cole T.

2015-04-01

Phosphorus is a nutrient fundamental to life and when it precipitates in modern environments bacteria are intimately involved in its release, concentration, and mineralization. Preserved fossil bacteria in phosphate crusts and grains from the ca. 1850 million-year-old Bijiki Iron Formation Member of the Michigamme Formation, Michigan provide insight into the longevity and nature of this relationship. The Michigamme Formation accumulated near the end of the Earth's initial phosphogenic episode (ca. 2.2 and 1.8 Ga) to produce one of the first granular phosphorites. Phosphatic lithofacies consist of fine- to medium-sand-sized francolite peloids concentrated on bedding surfaces in peritidal facies. Granular beds are up to 2 cm thick and peloids are often partially to completely replaced by dolomite and chert. The grains contain organic matter and pyrite framboids that suggest bacterial breakdown of organic matter and bacterial sulfate reduction. The peritidal nature of phosphorite in the Michigamme Formation is in sharp contrast to Phanerozoic phosphogenic environments in deeper coastal upwelling settings. Peritidal settings were well suited for phosphogenesis under the very low oxygen and low dissolved sulfate levels of the Paleoproterozoic as cyanobacteria produced oxygen in shallow water and evaporation led to increased sulfate concentrations. Such concomitant processes helped establish focused redox interfaces in the sediment that chemosynthetic bacterial communities (sulfur oxidizers, reducers, forms that concentrate P, and possibly iron oxidizers) could exploit. Phosphate released from organic matter by heterotrophic bacteria and Fe-redox pumping was further concentrated by these chemotrophs; a process that forms late Neoproterozoic to Phanerozoic phosphorites but on a much larger scale. This early example of a granular phosphorite demonstrates that, like their Phanerozoic counterparts, Paleoproterozoic phosphorites are the concentrated indirectly biomineralized products of bacterial communities. But unlike younger analogs, which accumulated across subtidal shelves and shelf margins, these ancient deposits formed only in tidal flat settings where phosphogenic redox processes could be established in the sediment. From this early beginning, the zone of phosphogenesis likely migrated into deeper water settings as oxygen and sulfate levels rose, expanding the zone of chemosynthetic bacterial and associated phosphogenesis across the shelf.

[Optimization of vermicomposting of organics enriched with phosphorites with participation of phosphate-mobilizing microorganisms].

PubMed

Hatsenko, M V; Volkohon, V V

2010-01-01

Active strains of microorganisms capable to mobilize phosphorus from poorly soluble compounds were isolated from the vermicompost. Representatives of Pseudomonas genus dominate in assemblages of phosphate-mobilizing humus microbiota. The strains Pseudomonas sp. 17 and Pseudomonas sp. 22, which promote liberation of the greatest quantity of water-soluble phosphorus were selected under vermicomposting of organics enriched with phosphorites with participation of active phosphate-mobilizing microorganisms. The use of compost derived with participation of Pseudomonas sp. 17 in cucumbers growth technologies makes the plants development better and raises the cultures productivity.

Phosphorite-hosted zinc and lead mineralization in the Sekarna deposit (Central Tunisia)

USGS Publications Warehouse

Garnit, Hechmi; Bouhel, Salah; Barca, Donatella; Johnson, Craig A.; Chtara, Chaker

2012-01-01

The Sekarna Zn–Pb deposit is located in Central Tunisia at the northeastern edge of the Cenozoic Rohia graben. Mineralization comprises two major ore types: (1) disseminated Zn–Pb sulfides that occur as lenses in sedimentary phosphorite layers and (2) cavity-filling zinc oxides (calamine-type ores) that crosscut Late Cretaceous and Early Eocene limestone. We studied Zn sulfide mineralization in the Saint Pierre ore body, which is hosted in a 5-m-thick sedimentary phosphorite unit of Early Eocene age. The sulfide mineralization occurs as replacements of carbonate cement in phosphorite. The ores comprise stratiform lenses rich in sphalerite with minor galena, Fe sulfides, and earlier diagenetic barite. Laser ablation–inductively coupled plasma mass spectrometry analyses of sphalerite and galena show a wide range of minor element contents with significant enrichment of cadmium in both sphalerite (6,000–20,000 ppm) and galena (12–189 ppm). The minor element enrichments likely reflect the influence of the immediate organic-rich host rocks. Fluid inclusions in sphalerite give homogenization temperatures of 80–130°C. The final ice melting temperatures range from −22°C to −11°C, which correspond to salinities of 15–24 wt.% NaCl eq. and suggest a basinal brine origin for the fluids. Sulfur isotope analyses show uniformly negative values for sphalerite (−11.2‰ to −9.3‰) and galena (−16‰ to −12.3‰). The δ34S of barite, which averages 25.1‰, is 4‰ higher than the value for Eocene seawater sulfate. The sulfur isotopic compositions are inferred to reflect sulfur derivation through bacterial reduction of contemporaneous seawater sulfate, possibly in restricted basins where organic matter was abundant. The Pb isotopes suggest an upper crustal lead source.

Phosphorite-hosted zinc and lead mineralization in the Sekarna deposit (Central Tunisia)

NASA Astrophysics Data System (ADS)

Garnit, Hechmi; Bouhlel, Salah; Barca, Donatella; Johnson, Craig A.; Chtara, Chaker

2012-06-01

The Sekarna Zn-Pb deposit is located in Central Tunisia at the northeastern edge of the Cenozoic Rohia graben. Mineralization comprises two major ore types: (1) disseminated Zn-Pb sulfides that occur as lenses in sedimentary phosphorite layers and (2) cavity-filling zinc oxides (calamine-type ores) that crosscut Late Cretaceous and Early Eocene limestone. We studied Zn sulfide mineralization in the Saint Pierre ore body, which is hosted in a 5-m-thick sedimentary phosphorite unit of Early Eocene age. The sulfide mineralization occurs as replacements of carbonate cement in phosphorite. The ores comprise stratiform lenses rich in sphalerite with minor galena, Fe sulfides, and earlier diagenetic barite. Laser ablation-inductively coupled plasma mass spectrometry analyses of sphalerite and galena show a wide range of minor element contents with significant enrichment of cadmium in both sphalerite (6,000-20,000 ppm) and galena (12-189 ppm). The minor element enrichments likely reflect the influence of the immediate organic-rich host rocks. Fluid inclusions in sphalerite give homogenization temperatures of 80-130°C. The final ice melting temperatures range from -22°C to -11°C, which correspond to salinities of 15-24 wt.% NaCl eq. and suggest a basinal brine origin for the fluids. Sulfur isotope analyses show uniformly negative values for sphalerite (-11.2‰ to -9.3‰) and galena (-16‰ to -12.3‰). The δ34S of barite, which averages 25.1‰, is 4‰ higher than the value for Eocene seawater sulfate. The sulfur isotopic compositions are inferred to reflect sulfur derivation through bacterial reduction of contemporaneous seawater sulfate, possibly in restricted basins where organic matter was abundant. The Pb isotopes suggest an upper crustal lead source.

3D-Mapping of Dolomitized Structures in Lower Cambrian Phosphorites

NASA Astrophysics Data System (ADS)

Hippler, Dorothee; Stammeier, Jessica A.; Brunner, Roland; Rosc, Jördis; Franz, Gerhard; Dietzel, Martin

2016-04-01

Dolomitization is a widespread phenomenon in ancient sedimentary rocks, particularly close to the Precambrian-Cambrian boundary. Dolomite can form in synsedimentary or hydrothermal environments, preferentially via the replacement of solid carbonate precursor phases. Synsedimentary dolomite formation is often associated with microbial activity, such as bacterial sulfate reduction or methanogenesis. In this study, we investigate dolomitic phosphorites from the Lowermost Cambrian Tal Group, Mussoori Syncline, Lesser Himalaya, India, using micro-CT 3D-mapping, in order to unravel the complex diagenetic history of the rocks. The selected sample shows alternating layering of phosphatic mudstones and sparitic dolostone, in which brecciated layers of phosphorite or phosphatic mudstones are immersed in a dolomite-rich matrix. Lamination occurs on a sub-millimetre scale, with lamination sometimes wavy to crinkly. This fabric is interpreted as former microbial mats, providing the environment for early diagenetic phosphatization. Preliminary electron backscatter imaging with scanning microscopy revealed that dolomite crystals often occur in spherical to ellipsoidal structures, typically with a high porosity. This dolomite is associated with botryoidal apatite, organic matter and small amounts of calcite. Micro-CT 3D-mappings reveal that dolomite structures are cigar-shaped, elongated and up to 600 μm long. They are further arranged in a Mikado-like oriented framework spanning a layer thickness of a few millimetres. Analyses of ambient pore space, with similar elongated outlines and filled with organic matter, suggest a potential coherence of ambient pore space and shape of the dolomite structures. Allowing for other associated mineral phases, such as pyrite and silicates, and their spatial distribution, the present approach can be used to unravel distinct diagenetic reaction pathways, and might thus constrain the proxy potential of these Lower Cambrian dolomitic phosphorites to reconstruct ambient environmental at the time of deposition.

Ediacaran stromatolites and intertidal phosphorite of the Salitre Formation, Brazil: Phosphogenesis during the Neoproterozoic Oxygenation Event

NASA Astrophysics Data System (ADS)

Caird, R. A.; Pufahl, P. K.; Hiatt, E. E.; Abram, M. B.; Rocha, A. J. D.; Kyser, T. K.

2017-04-01

The Ediacaran Nova America and Gabriel members of the Salitre Formation are composed of limestone and economic phosphorite that accumulated on an unrimmed epeiric ramp along the margins of the Irecê Basin, Brazil. Deposition occurred during a marine transgression punctuated by higher-order fluctuations in relative sea-level that produced m-scale, shallowing-upward peritidal cycles. Cycles consist of six lithofacies rich in microbial sedimentary structures including subtidal, cross-stratified grainstones and hemispheroidal columnar stromatolite reefs overlain by intertidal flat sediments indicative of decreasing accommodation. Phosphorite is restricted to the paleocoast where digitate stromatolite biostromes colonized tidal flats. Phosphorite accumulation is interpreted to have been associated with biostromes because photosynthetic oxygen production created a redox gradient beneath the seafloor that phosphogenic chemosynthetic bacteria exploited. The concentration of francolite or sedimentary apatite in microbial laminae suggests these bacteria actively stored, released, and concentrated phosphate to promote in situ precipitation. The sealing effect of interbedded, fine-grained tidal deposits was also critical for maintaining the high levels of pore water phosphate required. The absence of francolite in subtidal columnar stromatolite reefs implies phosphogenesis was prevented in deeper, more energetic environments because wave pumping of oxygenated seawater through reefs surrounded by constantly moving grainy sediment promoted the recycling of P directly back to the water column. The Salitre Formation has a complex paragenesis, including hydrothermal alteration that produced Mississippi Valley-type Pb-Zn mineralization. δ18O values of Nova America member dolomites range from - 10.2‰ to - 0.5‰ (mean = - 3.9‰) and δ13C ranges from - 9.2‰ to + 10.0‰ (mean = + 2.8‰). Samples contain varying proportions of low-Mg calcite and saddle dolomite. δ18O values of hydrothermal veins range from - 4.7‰ to - 3.0‰ (mean = - 4.2‰) reflecting equilibration with temperatures > 80 °C. δ13C values are between - 7.0‰ and + 5.6‰ (mean = - 1.8‰,). Late lateritic weathering produced calcretes with δ18O values between - 3.3‰ and - 1.3‰, and δ13C values from - 9.2‰ to - 8.0‰ (mean values are - 1.8‰ and - 8.7‰, respectively). Petrographic analysis, generally low δ18O, and high δ13C values suggest hydrothermal dolomitization and remobilization of P led to secondary phosphate mineralization of intertidal stromatolite biostromes to produce economic phosphorite. Collectively, these results suggest that the benthic P-cycle in the Neoproterozoic was more complex than previously surmised and emphasize the multifaceted significance of microbial, paleoenvironmental, and diagenetic processes that allowed phosphorite to accumulate on the São Franciscan craton. Such information further elucidates attributes of the onset of Earth's second major phosphogenic episode, which is roughly coincident with the Neoproterozoic Oxygenation Event (NOE) and the evolution of multicellular animals.

Phosphatized algal-bacterial assemblages in Late Cretaceous phosphorites of the Voronezh Anteclise

NASA Astrophysics Data System (ADS)

Maleonkina, Svetlana Y.

2003-01-01

Late Cretaceous phosphogenesis of the Voronezh Anteclise has occurred during Cenomanian and Early Campanian. SEM studies show the presence of phosphatized algal-bacterial assemblages both in Cenomanian and Campanian phosphorites. In some Cenomanian nodular phosphorite samples revealed empty tubes 1 - 5 microns in diameter, which are most likely trichomes of cyanobacterial filaments. Other samples contained accumulations of spheres 0,5-3 microns, similar to coccoidal bacteria. Complicated tubular forms with variable diameter 2 - 5 microns occur on surface of some quartz grains in nodules. They are probably pseudomorphs after algae. We found similar formations in the Campanian phosphate grains. Frequently, grain represents a cyanobacterial mat, which is sometimes concentrically coated by phosphatic films. The films of some grains retain the primary structure, their concentric layers are formed by pseudomorphs after different bacterial types and obviously they represent oncolite. In other cases, the primary structure is unobservable because of recrystallization process erases them. Occasionally, the central part retains the coccoidal structure and the recrystallization affects only films. Besides the core of such oncolite can be represented not only by phosphatic grain, but also by grains of other minerals, such as quartz, glauconite and heavy minerals, which serve as a substrate for cyanobacterial colonies. Bacteria also could settle on cavity surfaces and interiors frames of sponge fragments, teeth and bones.

Paleoclimatological change in the Late Neoproterozoic: Evidence from oxygen isotopes of phosphorite in Yangtze Platform, China

NASA Astrophysics Data System (ADS)

Ling, H.-F.; Jiang, S.-Y.; Feng, H.-Z.; Chen, J.-H.; Chen, Y.-Q.; Yang, J.-H.

2003-04-01

Seawater and its isotopic composition is the most promising recorder for the climate change of the Earth. Chemical sediments such as carbonate and phosphorite has long been used to reveal the seawater chemistry in the past. The d13C of carbonate with least diagenesis has proved to be sensitive proxy for paleo-environment and paleo-productivity and for chemostratigrphy (e.g. Shen, 2002; Yang et al., 1999; Lambert et al., 1987). However, d18O of carbonate are more prone to suffering diagenesis, and therefore the implications of Phanerozoic d18O curve are controversial (cf. Veizer et al., 1999). Recent study of Wenzel et al. (2000) shows that Silurian phosphatic conodont retained primary oxygen isotopes whereas the d18O values of the coeval calcitic brachiopod shells were altered by diagenesis. Here, we presented and compared oxygen, carbon isotopic compositions and trace and rare earth element concentrations of Neoproterozoic phosphorite and coeval dolomite from the Yangtze platform in an attempt to reconstruct the paleoclimatological and paleooceanographic change during Neoproterozoic. The Yangtze platform possesses excellent record of Late Neoproterozoic-Cambrian strata. In this study, we collected samples systematically from late Neoproterozoic Doushantuo Formation at the Wengan section, Guizhou province. The Doushantuo Fm, overlying on the late Vendian tillite of Nantuo Fm and overlain by dolostone of Dengying Fm which underlain the basal Cambrian black shale, consists mainly of phosphorite and minor interbeded dolostone with total thickness of about 70 m. Our results show large variations of d18Odolo(SMOW) for the dolomite (17.6 ~ 25.9‰) which has no correlation with their d13Cdolo values and other geochemical parameters. In contrast, phosphorites display rather limited variations of the d18Ophos (SMOW) values (10.7 ~ 15.0‰). Further more, the d18Ophos and d13Cdolo values, Ce anomaly and Pb/Th ratio consistently increased from the lower to upper part of the section. It is suggested that the phosphorite studied preserved primary oxygen isotopes, whereas d18Odolo values of the dolomite were altered by diagenesis. Potential causes for the overall increase trend of d18Ophos include increase in seawater d18O values and decrease in temperature. During the time span of about 10 ~ 30 Ma for the section deposition when no glaciation occurred, it seems not completely in reality to attribute the variation of more than 4‰ of d18O values to seawater change alone. To cause ~4.3‰ variation of d18Ophos, temperature would decrease about 15-20˚C, which is possible to happen in the Earth history (Lecuyer and Allemand, 2002). The following lines of evidence also support this view. The studied phosphorites were deposited after thaw of the Snowball Earth. During the Snowball Earth period, continental weathering was in minimum due to little precipitation. This, together with existence of volcanic CO2 emitting through the snowball, CO2 accumulated in the atmosphere up to very high level and thus the temperature would be very high soon after thaw of the Snowball Earth. This, combined with more precipitation, would cause progressive weathering. Enhanced weathering of continental rocks would draw down the CO2 of atmosphere and in turn cause cooling, which is consistent with temperature lowering of the period. Increase trend of Pb/Th ratio during the period is in good agreement with enhanced weathering. Pb and Th are both highly particle reactive elements in the ocean. However, their geochemical behaviors in weathering processes are potentially different. Pb is mainly contained in feldspar while Th is mainly hosted in accessory minerals such as monazite. During enhanced weathering processes feldspar can be altered and release Pb whereas monazite would usually survive. Therefore Pb/Th ratio in hydrogenic sediments would be an indicator of weathering intensity. Enhanced weathering would also provide more nutrition elements to ocean, resulting in increase in productivity. The overall increasing trend of d13Cdolo agrees well with increasing productivity. Increased alga productivity would raise release of oxygen to the ocean by processes of photosynthesis, burial of light carbon and thus elevate heavy carbon in the ocean. This may also be the cause of increase in Ce anomaly. In conclusion, the above changes are consistent with each other. The overall increase trends of phosphorite d18O may imply decrease in temperature post the temperature maximum at thaw of the Snowball Earth.

Mineral resources of the Atlantic Exclusive Economic Zone

USGS Publications Warehouse

Dillon, William P.

1984-01-01

Potential mineral resources of the Atlantic Exclusive Economic Zone (including the Gulf of Mexico and US Caribbean areas) include petroleum, sand and gravel, phosphorite, placer deposits of heavy mineral sands, ferromanganese nodules, and fresh water. Although major efforts have been made to search for petroleum, the oil and gas resources of the region are well known only in the western Gulf Shelf and more exploration is under way. Heavy-mineral placer deposits, which may be sources of titanium, gold, rare earths, etc. , have been sampled, but the extent and, therefore, economic value of the deposits have not been identified. Sand and gravel, phosphorite, and ferromanganese nodules all are represented by fairly well established deposits, and only modified market conditions would be necessary to cause detailed exploration and mining.

Early Proterozoic (2.04 GA) Phoshorites of Pechenga Greenstone Belt and Their Origin

NASA Technical Reports Server (NTRS)

Rozanov, Alexei Yu.; Astafieva, Marina M.; Hoover, Richard B.

2007-01-01

No principal differences have been found between microfossils described from Cambrian and Phanerozoic and the 2000 Ma phosphorites. Numerous samples revealed diverse microbial microstructures interpreted as cyanobacterial mats consisting of filamentous (1-3 microns in diameter, 20 microns in length), coccoidal (0.8-1.0 microns) and ellipsoidal or rod-shaped microfossils (0.8 microns in diameter, around 2 microns in length) which morphologically resemble modern Microcoleus and Siphonophycus, Thiocapsa, and Rhabdoderma, respectively, reported from alkali ne or saline environment_ The sequence of the early Palaeoproterozoic events which point to a significant oxidation of the hydrosphere, including the formation of phosphorites and changes in the phosphorous cycle, mimics the sequence which was repeated at the Neoproterozoic-Cembrian transition, implying that oxidation of the terrestrial atmosphere-hydrosphere system experienced an irregular cyclic development.

Phosphorus as a potential guide in the search for extinct life on Mars.

PubMed

Weckwerth, G; Schidlowski, M

1995-03-01

In contrast to the search for extant organisms, the quest for fossil remains of life on Mars need not be guided by the presence of water and organic compounds on the present surface. An appropriate tracer might be the element phosphorus which is a common constituent of living systems. Utilizing terrestrial analogues, it should preferentially exist in the form of sedimentary calcium phosphate (phosphorites), which would have readily resisted changing conditions on Mars. Moreover, higher ratios of P/Th in phosphorites in comparison to calcium phosphates from magmatic rocks give us the possibility to distinguish them from inorganically formed phosphorus deposits at or close to the Martian surface. Identification of anomalous phosphorus enrichments by remote sensing or in situ analysis could be promising approaches for selecting areas preferentially composed of rocks with remains of extinct life.

Possible Roles of Fluoride and Carbonate in Biochemical Carbonated Apatite Formation

NASA Astrophysics Data System (ADS)

Meouch, Orysia; Omelon, Sidney

2016-04-01

Marine phosphorites are predominantly composed of carbonated fluorapatite (CFA = Ca10-a-b-cNaaMgb(PO4)6-x(CO3)x-y-z(CO3.F)y(SO4)zF2, where x=y+a+2c, and c represents the number of Ca vacancies, with a P2O5 content that ranges from 18-40 %. Sulphur-oxidizing bacteria of the Beggiatoa genus concentration phosphorous as intracellular polyphosphate ((PO3-)n) which is depolymerized into inorganic orthophosphate (Pi). Consequently, an increase in pore water Pi concentration favours carbonated apatite precipitation. The carbonate and fluoride that is characteristic of phosphorite CFA is also located in the vertebrate skeleton. This similarity suggests a biochemical pathway for CFA precipitation. Preliminary Raman spectroscopy and powder x-ray diffraction results that suggest a role for fluoride, and possibly carbonate, in the biochemical depolymerisation of polyphosphates with alkaline phosphatase will be presented.

Restoration of Soils and Vegetation on Reclamation Sites of the Kingisepp Phosphorite Field

NASA Astrophysics Data System (ADS)

Dmitrakova, Ya. A.; Abakumov, E. V.

2018-05-01

Processes of initial soil formation were studied on long-term monitoring plots on dump rocks of quarry no. 3 of the Phosphorite production company in Kingisepp district of Leningrad oblast. Observations were performed in 1998, 2004, and 2014. It was shown that vegetation succession on the plots proceeds relatively quickly, and that the species composition of phytocenoses formed is typical of the areas with soddy-calcareous soils. Soil development proved to be correlated with the development of vegetation. Maximum changes in soil characteristics were observed with an increase in the density of forest vegetation and a decrease in the role of herbs. The molecular composition of humic acids in the studied soils remained stable; in particular, the ratio of aliphatic to alkyl aromatic fragments was virtually constant. This phenomenon could be due to the great amount of aliphatic components in the falloff of coniferous species subjected to humification.

Origin of dolomite in the phosphatic Hawthorne Group of Florida

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

Compton, J.S.; Hall, D.L.; Mallinson, D.J.

1994-07-01

In addition to large amounts of phosphorite, the Miocene Hawthorn Group of Florida contains abundant dolomite. Dolomite is present as disseminated silt-size rhombs, as friable dolosilt beds, and as pore-filling cement in dolostone beds and clasts. The dolomite formed during early burial diagenesis both in the sulfate-reduction zone, overlapping and extending below sediment depths of phosphorite formation, and in adjacent, nonphosphatic, shallow-water lagoonal environments. Much of the dolomite is closely associated with the fibrous, Mg-rich clay minerals palygorskite and sepiolite. The percent carbonate in the Hawthorn Group increases from north to south; the dominant carbonate mineral in north Florida ismore » dolomite, whereas dolomite and calcite are both abundant in south Florida. The [delta][sup 13]C values of the dolomite, from +1.82 to [minus]6.21[per thousand] PDB, suggest that metastable biogenic carbonate (aragonite and high-Mg calcite) and seawater were the predominant sources of carbonate. However, negative [delta][sup 13]C values of dolomite from northeast Florida suggest that as much as 30--40% of the carbonate was derived from degradation of organic matter. Degradation of organic matter enhanced dolomitization by removing sulfate ion and increasing the carbonate alkalinity of the pore waters. The oxygen and strontium isotopic values along with moderate Na contents indicate a marine origin. Evaporation of seawater or mixing of seawater and meteoric water were apparently not major factors in dolomite formation. The presence of dolomite, along with phosphorite, in reworked sequences can indicate deposition of organic-rich sediments from which most of the organic matter has since been removed.« less

High phosphate availability as a possible cause for massive cyanobacterial production of oxygen in the Paleoproterozoic atmosphere

NASA Astrophysics Data System (ADS)

Papineau, Dominic; Purohit, Ritesh; Fogel, Marilyn L.; Shields-Zhou, Graham A.

2013-01-01

The deposition of major Precambrian phosphorites was restricted to times of global change and atmospheric oxygenation at both ends of the Proterozoic. Phosphorites formed after highly positive carbon isotope excursions in carbonates deposited during the Paleoproterozoic Lomagundi-Jatuli event and the Neoproterozoic Cryogenian and Ediacaran periods. The correlative step-wise rise in atmospheric oxygen over the Proterozoic has been linked to changes in the carbon cycle. However, the postulated relations between carbon isotope events, phosphorites, and atmospheric oxygenation remain unexplained. Paleoproterozoic carbonates of the Aravalli Supergroup, India, preserve evidence for cyanobacterial blooms in the form of tightly packed stromatolitic columns in the world's oldest significant sedimentary phosphate deposit. Restricted basins of the Lower Aravalli Group with stromatolitic phosphorites in Jhamarkotra, Udaipur, Jhabua, and Sallopat exhibit near-zero δ13Ccarb values and large ranges of δ13Corg values between -33.3‰ and -10.1‰, indicative of a complex carbon cycle. Because phosphate accumulates primarily in oxic sediments, these eutrophic microbial ecosystems likely developed within the photic zone of the shallow, oxygenated marine realm. This is consistent with deposition during the time of increasingly more oxidizing conditions, after the Great Oxidation Event (GOE). Approximately contemporaneous basins without phosphate deposits from Ghasiar, Karouli, Negadia, Umra, and Babarmal exhibit a range of positive δ13Ccarb excursions, some with values up to +11.2‰, that suggest high rates of organic carbon burial, and others with moderately high δ13Ccarb values around +6‰ or +3‰, that suggest smaller carbon cycle perturbations. The δ15N values of all these rocks vary between -0.7‰ and +3.4‰, and are consistent with the predominance of nitrogen fixation during cyanobacterial blooms in all basin types. Such low nitrogen isotope values are interpreted to have arisen from the biological response to high phosphate availability. We conclude that increased phosphate availability during and after the Paleoproterozoic Lomagundi-Jatuli event likely caused cyanobacterial blooms and was a key factor in the oxygenation of Earth's atmosphere. Increasing oxygenation of the shallow ocean seafloor favored the removal of excess phosphate as authigenic apatite, thus dampening effects of weathering increases on organic burial and marine δ13Ccarb after about 2.0 Ga.

Oceanographic controls on sedimentary and geochemical facies on the Peru outer shelf and upper slope

USGS Publications Warehouse

Arthur, Michael A.; Dean, Walter E.

2013-01-01

Concentrations and characteristics of organic matter in surface sediments deposited under an intense oxygen-minimum zone (OMZ) on the Peru margin were mapped and studied in samples from deck-deployed box cores and push cores acquired by submersible on two east-west transects spanning depths of 75 to 1,000 meters (m) at 12°S and 13.5°S. On the basis of sampling and analyses of the top 1–2 centimeters (cm) of available cores, three main belts of sediments were identified on each transect with increasing depth: (1) muds rich in organic carbon (OC); (2) authigenic phosphatic mineral crusts and pavements; and (3) glaucony facies.Sediments rich in OC on the 12°S transect were mainly located on the outer shelf and upper slope (150–350 m), but they occurred in much shallower water (approximately 100 m) on the 13.5°S transect. The organic matter is almost entirely marine as confirmed by Rock-Eval pyrolysis and isotopic composition of OC. Concentrations of OC are highest (up to 18 percent) in sediments within the OMZ where dissolved oxygen (DO) concentrations are <5 micromoles per kilogram (μM). Even at these low concentrations of DO, however, the surface sediments from within the OMZ are dominantly unlaminated. Concentrations of DO may have the dominant effect on organic matter characteristics, but reworking of fine-grained sediment and organic matter by strong bottom currents with velocities as high as 30 centimeters per second (cm/s) on the slope between 150 and 300 m and redeposition on the seafloor in areas of lower energy and higher DO concentration also exert important controls on OC concentration and degree of oxidation in this region.Phosphate-rich sediments and crusts occurred at depths of about 300 to 550 m on both transects. Nodular crusts of sediment cemented by carbonate-fluorapatite (CFA; phosphorite) or dolomite form within the OMZ. These phosphorite crusts evolve through cementation from light olive-green, stiff but friable, phosphatized claystone “protocrusts” through dense, dark phosphorite crusts, cemented breccias, and pavements. The degree of phosphatization and thickness of the crusts depend on the rates of sediment supply and on the strength and frequency of currents that re-expose crusts on the seafloor. Phosphorite crusts and pavements on the Peru margin can only become buried and incorporated into the geologic record once bottom currents slacken sufficiently to allow fine-grained sediment to accumulate.Glaucony-rich surface sediments, relatively undiluted by other components, were found mainly in deeper water on the 13.5°S transect (750 m to at least 1,067 m). These sediments consist almost entirely of sand-size glaucony pellets. These widespread glaucony sands formed in place and were then concentrated and reworked by strong currents that winnowed away the fine-grained matrix. Although the glaucony occurs in sand-size pellets, the pellets are made up of aggregates of authigenic, platy, micaceous clay minerals. Glaucony is predominantly a potassium (K), sodium (Na), iron (Fe), magnesium (Mg) aluminosilicate with an approximate formula of (K,Na)(Fe3+,Al,Mg)2(Si,Al)4O10(OH)2. The glaucony on the 13.5°S transect forms by alteration of one or more original “framework” minerals (carbonate and [or] aluminosilicates) to form pellital aggregates of Fe-, K-, and Mg-rich clay minerals. Because Fe, K, and Mg are derived from seawater, sedimentation rates must be extremely slow in order for the original framework minerals to remain in contact with seawater. The close association of glaucony and phosphorite indicates a delicate balance between the slightly oxidizing conditions at the base of the OMZ that form glaucony and the slightly reducing conditions that mobilize iron and phosphate to form phosphorite.

Phosphogenesis in the 2460 and 2728 million-year-old banded iron formations as evidence for biological cycling of phosphate in the early biosphere

PubMed Central

Li, Yi-Liang; Sun, Si; Chan, Lung S

2013-01-01

The banded iron formation deposited during the first 2 billion years of Earth's history holds the key to understanding the interplay between the geosphere and the early biosphere at large geological timescales. The earliest ore-scale phosphorite depositions formed almost at ∼2.0–2.2 billion years ago bear evidence for the earliest bloom of aerobic life. The cycling of nutrient phosphorus and how it constrained primary productivity in the anaerobic world of Archean–Palaeoproterozoic eons are still open questions. The controversy centers about whether the precipitation of ultrafine ferric oxyhydroxide due to the microbial Fe(II) oxidation in oceans earlier than 1.9 billion years substantially sequestrated phosphate, and whether this process significantly limited the primary productivity of the early biosphere. In this study, we report apatite radial flowers of a few micrometers in the 2728 million-year-old Abitibi banded iron formation and the 2460 million-year-old Kuruman banded iron formation and their similarities to those in the 535 million-year-old Lower Cambrian phosphorite. The lithology of the 535 Million-year-old phosphorite as a biosignature bears abundant biomarkers that reveal the possible similar biogeochemical cycling of phosphorus in the Later Archean and Palaeoproterozoic oceans. These apatite radial flowers represent the primary precipitation of phosphate derived from the phytoplankton blooms in the euphotic zones of Neoarchean and Palaoeproterozoic oceans. The unbiased distributions of the apatite radial flowers within sub-millimeter bands do not support the idea of an Archean Crisis of Phosphate. This is the first report of the microbial mediated mineralization of phosphorus before the Great Oxidation Event when the whole biosphere was still dominated by anaerobic microorganisms. PMID:23404127

Phosphogenesis in the 2460 and 2728 million-year-old banded iron formations as evidence for biological cycling of phosphate in the early biosphere.

PubMed

Li, Yi-Liang; Sun, Si; Chan, Lung S

2012-01-01

The banded iron formation deposited during the first 2 billion years of Earth's history holds the key to understanding the interplay between the geosphere and the early biosphere at large geological timescales. The earliest ore-scale phosphorite depositions formed almost at ∼2.0-2.2 billion years ago bear evidence for the earliest bloom of aerobic life. The cycling of nutrient phosphorus and how it constrained primary productivity in the anaerobic world of Archean-Palaeoproterozoic eons are still open questions. The controversy centers about whether the precipitation of ultrafine ferric oxyhydroxide due to the microbial Fe(II) oxidation in oceans earlier than 1.9 billion years substantially sequestrated phosphate, and whether this process significantly limited the primary productivity of the early biosphere. In this study, we report apatite radial flowers of a few micrometers in the 2728 million-year-old Abitibi banded iron formation and the 2460 million-year-old Kuruman banded iron formation and their similarities to those in the 535 million-year-old Lower Cambrian phosphorite. The lithology of the 535 Million-year-old phosphorite as a biosignature bears abundant biomarkers that reveal the possible similar biogeochemical cycling of phosphorus in the Later Archean and Palaeoproterozoic oceans. These apatite radial flowers represent the primary precipitation of phosphate derived from the phytoplankton blooms in the euphotic zones of Neoarchean and Palaoeproterozoic oceans. The unbiased distributions of the apatite radial flowers within sub-millimeter bands do not support the idea of an Archean Crisis of Phosphate. This is the first report of the microbial mediated mineralization of phosphorus before the Great Oxidation Event when the whole biosphere was still dominated by anaerobic microorganisms.

The quantitative determination of calcite associated with the carbonate-bearing apatites

USGS Publications Warehouse

Silverman, Sol R.; Fuyat, Ruth K.; Weiser, Jeanne D.

1951-01-01

The CO2 combined as calcite in carbonate-bearing apatites as been distinguished from that combined as carbonate-apatite, or present in some form other than calcite, by use of X-ray powder patterns, differential thermal analyses, and differential solubility tests. These methods were applied to several pure apatite minerals, to one fossil bone, and to a group of phosphorites from the Phosphoria formation of Permian age from Trail Canyon and the Conda mine, Idaho, and the Laketown district, Utah. With the exceptions of pure fluorapatite, pure carbonate-flueorapatite, and one phosphorite from Trail Canyon, these substances contain varying amounts of calcite, but in all the samples an appreciable part of the carbonite content is not present as calcite. The results of solubility tests, in which the particle size of sample and the length of solution time were varied, imply that the carbonate content is not due to shielded calcite entrapped along an internal network of surfaces.

Economic geology of the Isla de Mona Quadrangle, Puerto Rico

USGS Publications Warehouse

Briggs, Reginald Peter

1974-01-01

Limiting this tableland In the northern part of Isla de Mona are sheer sea cliffs chiefly exposing the Isla de Mona Dolomite. Around the southern part of the island are Irregular cliffs and steep slopes that chiefly expose the Lirio Limestone. The structure of Isla de Mona consists of two gentle complex folds a broad anticline that trends and plunges gently south-southeast through the central and western parts of Isla de Mona, and a parallel syncline through-the eastern part of the Island that also has a chiefly south-southeast plunge. A near-vertical fault that strikes northwest, then north from the central part to the north coast of Isla de Mona displaces bedrock of the eastern block downward about 10 m. Many caves, including one cave system more than 100,000 m2 in total area, are localized in the lower 10 m of the Lirio Limestone, adjacent to the cliffs peripheral to the upland surface, and numerous small caves occur higher in the Lirio. A few small caves also are found In the Isla de Mona Dolomite. However, the total floor area of all caves on Isla de Mona probably is less than 1 percent of the area of the Island. Almost all caves on Isla de Mona contain phosphorite, which was mined extensively during the late 19th and early 20th centuries. Phosphorite accumulation locally may have exceeded 3.5 m in thickness, but probably averaged less than 1.5 m thick. A fair estimate of original reserves of phosphorite in 12 surveyed caves is about 151,000 m3 of which about 125,500 m3 probably has been removed in mining. Original reserves in the entire island are estimated to have been in the range 158,000 to 235,500 m3. Converted to metric tons, remaining reserves of cave phosphorite probably are considerably less than 50,000. The very pure limestone and calcitic dolomite that form the bedrock of Isla de Mona are abundant industrial-mineral resources. In addition, these carbonate rocks and the beach deposits are sources of construction materials for some classes of engineering works. The structure of Isla de Mona suggests some possibility of favorable zones for accumulation of oil and gas, but no source rocks are known, and there are no confirmed reports of oil and gas from any nearby area. Known supplies of fresh water on Isla de Mona are very small, but wells dug in coastal lowlands or drilled In the upland surface might yield moderate quantities of groundwater.

Origin and history of the Charleston Bump - Geological formations, currents, bottom conditions, and their relationship to wreckfish habitats on the Blake Plateau

USGS Publications Warehouse

Popenoe, P.; Manheim, F.T.

2001-01-01

The Charleston Bump is a structural and topographic high on the northern Blake Plateau that overlies a seaward offset of the edge of continental crust. The feature causes the bottom to shoal and deflects the Gulf Stream offshore, causing an intensification of bottom currents. The area has been swept by strong currents since late Cretaceous time, but the strongest currents have occurred in the Neogene (last ???25 million years). Nondepositional conditions prevail at present, but erosion of the bottom is checked where the bottom is armored by a hard surficial layer of phosphorite pavement. The phosphorite pavements were formed by re-cementation of eroded residues of phosphorite-rich sediments of early-Neogene age. In some places there are multiple pavements separated by poorly lithified sediments. Submersible observations indicate that the south, or current-facing flank of the Charleston Bump has several deep (>100 m) scour depressions, the southern flanks of which form cliffs characterized by ledges and overhangs. In other areas discrete layers of older Paleogene rocks have been partly eroded away, leaving cliff-like steps of 5 m or more relief. Conglomeratic phosphorite pavement layers up to 1 m thick armor most of the bottom. Where breached by scour, these pavements form both low-relief ledges and rock piles. These features form a reef-like environment of caves and overhangs utilized by wreckfish Polyprion americanus and barrelfish Hyperoglyphe perciformis as shelter from the current and as staging areas to prey on passing schools of squid. Wreckfish and other large fish were often localized in rugged bottom habitat, including caves and other shelter areas. We observed wreckfish darting from shelters to feed on passing schools of squid. Present and past observations, are consistent with the concept that impingement of the Gulf Stream at the Charleston Bump compresses midwater fauna from much thicker water layers, providing food for a flourishing big-fish fauna. During our dives we noted currents often exceeding 1 knot, and ranging to 2.4 knots. Evidence of fossil, manganese-iron-encrusted megaripples suggest even greater current regimes in the past. Investigation of the site of an earlier report of possible freshwater discharge failed to find any evidence of a closed sinkhole or freshwater discharge. Rather, we concluded that the apparent loss of buoyancy experienced by the submarine was probably caused by downward-directed eddy currents generated by currents sweeping across the pavement/void interface of a more than 100-m high cliff 3 km south of the reported location.

A Geochemical Analysis of Rare Earth Elements Associated with Significant Phosphate Deposits of West-Central Florida

NASA Astrophysics Data System (ADS)

Turner, K. M.; Owens, J. D.

2017-12-01

Rare earth elements (REEs) such as the lanthanide series as well as yttrium, uranium, and thorium are an important industrial resource for expanding technological sectors; therefore, demand and production will continue to increase. Increased market prices resulting in decreased demand has led to new exploration for REE mineral resources in North America. Phosphorite deposits are being investigated as a possible supply but the overall concentrations, depositional environments, and ages are relatively unexplored. Phosphorite is commonly associated with ocean floor sediment deposition and upwelling; however, it may also form in estuarine and supratidal zones with low wave activity, present along Florida's west coast. Interestingly, it seems that major ancient phosphorite deposits are often, if not always, associated with major icehouse conditions (widespread glaciations) and rarely observed during greenhouse conditions. By analyzing a set of sonic drill cores, spatiotemporal REE concentrations can be better constrained for a wide-age range of the Miocene-Pliocene aged Bone Valley Member of the Peace River Formation, the largest North American phosphate deposit. We present concentrations from a depth-transect of samples collected in West-Central Florida, showing the phosphatic sands and silts of the area are highly enriched sedimentary archives for REE, yielding concentrations up to 200 ppm for some REE. The weathering and transport of igneous and metamorphic minerals from the southern Appalachians to the Florida coast where a series of winnowing events occurred may explain the enrichment seen by our data. Sediment cores showing well-rounded quartz sands, dolomitic silts, teeth, bones, and marine fossils commonly found in a near shore depositional environment support this hypothesis. Previous analysis of phosphate grains, teeth, bones, and bulk sediment indicate REE are not associated with and/or sourcing from biogenic components, but rather entering the lattice structure of the phosphate grains through secondary diagenetic processes. Though concentrations do not reach values as high as other mining sources the relative ease of extraction from sedimentary deposits may make them a valuable source.

Geochemistry of host rocks in the Howards Pass district, Yukon-Northwest Territories, Canada: implications for sedimentary environments of Zn-Pb and phosphate mineralization

USGS Publications Warehouse

Slack, John F.; Falck, Hendrik; Kelley, Karen D.; Xue, Gabriel G.

2017-01-01

Detailed lithogeochemical data are reported here on early Paleozoic sedimentary rocks that host the large Howards Pass stratiform Zn-Pb deposits in Yukon-Northwest Territories. Redox-sensitive trace elements (Mo, Re, V, U) and Ce anomalies in members of the Duo Lake Formation record significant environmental changes. During the deposition of lower footwall units (Pyritic siliceous and Calcareous mudstone members), bottom waters were anoxic and sulphidic, respectively; these members formed in a marginal basin that may have become increasingly restricted with time. Relative to lower members, a major environmental change is proposed for deposition of the overlying Lower cherty mudstone member, which contains phosphorite beds up to ∼0.8 m thick in the upper part, near the base of the Zn-Pb deposits. The presence of these beds, together with models for modern phosphorite formation, suggests P input from an upwelling system and phosphorite deposition in an upper slope or outer shelf setting. The overlying Active mudstone member contains stratabound to stratiform Zn-Pb deposits within black mudstone and gray calcareous mudstone. Data for unmineralized black mudstone in this member indicate deposition under diverse redox conditions from suboxic to sulphidic. Especially distinctive in this member are uniformly low ratios of light to heavy rare earth elements that are unique within the Duo Lake Formation, attributed here to the dissolution of sedimentary apatite by downward-percolating acidic metalliferous brines. Strata that overlie the Active member (Upper siliceous mudstone member) consist mainly of black mudstone with thin (0.5–1.5 cm) laminae of fine-grained apatite, recording continued deposition on an upper slope or outer shelf under predominantly suboxic bottom waters. Results of this study suggest that exploration for similar stratiform sediment-hosted Zn-Pb deposits should include the outer parts of ancient continental margins, especially at and near stratigraphic transitions from marginal basin facies to overlying slope or shelf facies.

Bacterial Paleontology and Studies of Carbonaceous Chondrites

NASA Technical Reports Server (NTRS)

Gerasimenko, L. M.; Hoover, Richard B.; Rozanov, Alexei Y.; Zhegallo, E. A.; Zhmur, S. I.

1999-01-01

The study of the fossilization processes of modern cyanobacteria provides insights needed to recognize bacterial microfossils. The fossilization of cyanobacteria is discussed and images of recent and fossil bacteria and cyanobacteria from the Early Proterozoic to Neogene carbonaceous rocks (kerites, shungites, and black shales) and phosphorites are provided. These are compared with biomorphic microstructures and possible microfossils encountered in-situ in carbonaceous meteorites.

Cell differentiation and germ-soma separation in Ediacaran animal embryo-like fossils

NASA Astrophysics Data System (ADS)

Chen, Lei; Xiao, Shuhai; Pang, Ke; Zhou, Chuanming; Yuan, Xunlai

2014-12-01

Phosphorites of the Ediacaran Doushantuo Formation (~600 million years old) yield spheroidal microfossils with a palintomic cell cleavage pattern. These fossils have been variously interpreted as sulphur-oxidizing bacteria, unicellular protists, mesomycetozoean-like holozoans, green algae akin to Volvox, and blastula embryos of early metazoans or bilaterian animals. However, their complete life cycle is unknown and it is uncertain whether they had a cellularly differentiated ontogenetic stage, making it difficult to test their various phylogenetic interpretations. Here we describe new spheroidal fossils from black phosphorites of the Doushantuo Formation that have been overlooked in previous studies. These fossils represent later developmental stages of previously published blastula-like fossils, and they show evidence for cell differentiation, germ-soma separation, and programmed cell death. Their complex multicellularity is inconsistent with a phylogenetic affinity with bacteria, unicellular protists, or mesomycetozoean-like holozoans. Available evidence also indicates that the Doushantuo fossils are unlikely crown-group animals or volvocine green algae. We conclude that an affinity with cellularly differentiated multicellular eukaryotes, including stem-group animals or algae, is likely but more data are needed to constrain further the exact phylogenetic affinity of the Doushantuo fossils.

Cell differentiation and germ-soma separation in Ediacaran animal embryo-like fossils.

PubMed

Chen, Lei; Xiao, Shuhai; Pang, Ke; Zhou, Chuanming; Yuan, Xunlai

2014-12-11

Phosphorites of the Ediacaran Doushantuo Formation (∼600 million years old) yield spheroidal microfossils with a palintomic cell cleavage pattern. These fossils have been variously interpreted as sulphur-oxidizing bacteria, unicellular protists, mesomycetozoean-like holozoans, green algae akin to Volvox, and blastula embryos of early metazoans or bilaterian animals. However, their complete life cycle is unknown and it is uncertain whether they had a cellularly differentiated ontogenetic stage, making it difficult to test their various phylogenetic interpretations. Here we describe new spheroidal fossils from black phosphorites of the Doushantuo Formation that have been overlooked in previous studies. These fossils represent later developmental stages of previously published blastula-like fossils, and they show evidence for cell differentiation, germ-soma separation, and programmed cell death. Their complex multicellularity is inconsistent with a phylogenetic affinity with bacteria, unicellular protists, or mesomycetozoean-like holozoans. Available evidence also indicates that the Doushantuo fossils are unlikely crown-group animals or volvocine green algae. We conclude that an affinity with cellularly differentiated multicellular eukaryotes, including stem-group animals or algae, is likely but more data are needed to constrain further the exact phylogenetic affinity of the Doushantuo fossils.

Geological setting of oil shales in the Permian phosphoria formation and some of the geochemistry of these rocks

USGS Publications Warehouse

Maughan, E.K.

1983-01-01

Recent studies of the Meade Peak and the Retort Phosphatic Shale Members of the Phosphoria Formation have investigated the organic carbon content and some aspects of hydrocarbon generation from these rocks. Phosphorite has been mined from the Retort and Meade Peak members in southeastern Idaho, northern Utah, western Wyoming and southwestern Montana. Organic carbon-rich mudstone beds associated with the phosphorite in these two members also were natural sources of petroleum. These mudstone beds were differentially buried throughout the region so that heating of these rocks has been different from place to place. Most of the Phosphoria source beds have been deeply buried and naturally heated to catagenetically form hydrocarbons. Deepest burial was in eastern Idaho and throughout most of the northeastern Great Basin where high ambient temperatures have driven the catagenesis to its limit and beyond to degrade or to destroy the hydrocarbons. In southwest Montana, however, burial in some areas has been less than 2 km, ambient temperatures remained low and the kerogen has not produced hydrocarbons (2). In these areas in Montana, the kerogen in the carbonaceous mudstone has retained the potential for hydrocarbon generation and the carbon-rich Retort Member is an oil shale from which hydrocarbons can be synthetically extracted. The Phosphoria Formation was deposited in a foreland basin between the Cordilleran geosyncline and the North American craton. This foreland basin, which coincides with the area of deposition of the two organic carbon-rich mudstone members of the Phosphoria, has been named the Sublett basin (Maughan, 1979). The basin has a northwest-southeast trending axis and seems to have been deepest in central Idaho where deep-water sedimentary rocks equivalent to the Phosphoria Formation are exceptionally thick. The depth of the basin was increasingly shallower away from central Idaho toward the Milk River uplift - a land area in Montana, the ancestral Rocky Mountains. The basin is composed of land areas in Colorado, the Humboldt highland in northeastern Nevada and intervening carbonate shelves in Utah and Wyoming. The phosphorites and the carbonaceous mudstones were deposited on the foreslope between the carbonate and littoral sand deposits on the shelf and the dominantly cherty mudstone sediments in the axial part of the basin. Paleomagnetic evidence indicates that in the Permian the region would have been within the northern hemispheric trade wind belt; and wind-direction studies determined from studies of sand dunes, indicate that the prevailing winds from the Milk River uplift would have blown offshore across the Phosphoria sea. Offshore winds would have carried surface water away from the shore and generated upwelling in the sea in eastern Idaho and adjacent areas in Montana, Wyoming and Utah. Prior to deposition of the Phosphoria, the region was the site of extensive deposition of shallow-water carbonate sediments. Equivalent rocks in the northern part of the basin are dominantly sandstone derived from the adjacent Milk River uplift and similar sandstone strata in the southeastern sector were derived from the ancestral Rocky Mountains uplift. Tectonic subsidence of the Sublett basin in part of the region seems to have provided a sea-floor profile favorable for upwelling circulation and the shift in deposition from regional carbonates and local sandstone into a more complex depositional pattern that included the accumulation of the mudstone-chert-phosphorite facies that comprises the Phosphoria Formation. High biological productivity and the accumulation of sapropel on the sea floor is associated with contemporary coastal upwelling (1) and similar environmental and depositional conditions are attributed to the rich accumulations of organic matter in the Phosphoria Formation. Sapropelic mudstone and phosphorite composing the Meade Peak Member are approximately 60 m thick near the center of the Sublett basin. The Meade

USSR Report, Agriculture

DTIC Science & Technology

1984-04-13

and Lipetsk and Tambov oblasts. It is necessary to better utilize peat for fer- tilizers and litter , to apply phosphorite and gypsum in a high...concentrates. Equipment was inadequately cleaned in shifting to production of feed formula- tions for broilers following preparation of feed mix...not prepare prestarter mixes for 1 to 4-day broilers . The author of this article was employed for many years in the Ptitseprom system and recalls

New Insights into an Old Cycle: The Marine Phosphorus Cycle and the Formation of Critical Phosphate Rock Resources (Invited)

NASA Astrophysics Data System (ADS)

Filippelli, G. M.

2010-12-01

The cycling and geochemistry of phosphorus (P) in the marine environment is a critical component of biological productivity and of resource availability: P control the long-term carbon cycle via its role as a limiting nutrient, and the burial and concentration of P within marine sediments dictates the quality and availability of P as a fertilizer component from a resources standpoint. Given the projections of severe P fertilizer limitation over the next several centuries, understanding the controls on P geochemistry and concentration into a minable resource is critical in sustaining global populations. Several critical aspects of the marine P cycle have been uncovered over the past few decades which have clarified our understanding of P burial and concentration. First, the initial authigenic process of P mineralization within marine sediments, termed phosphogenesis, seems to occur regardless of marine setting. Phosphogenesis results from the release of P into sedimentary pore waters from organic and oxide-bound fractions, and the subsequent supersaturation with respect to carbonate fluorapatite. In sediment-starved basins with significant upwelling-driven productivity, the supply of P into sedimentary pore waters can be so high that visibly apparent layers of carbonate fluorapatite can be formed. Even in such environments, however, the mineral P content is too low to be of economic value unless it has undergone concentration via sediment reworking, a common occurrence in some dynamic continental margin environments. Thus, a combination of phosphogenesis in a high productivity setting plus sediment starvation plus condensation via reworking are necessary to produce phosphorites, sedimentary rocks with high P contents which are ideal as fertilizer-grade P resources. Given these special marine conditions, phosphorites are largely distributed along ancient marine environments (with the exception of the nearly-depleted atoll guano reserves). The largest currently-identified minable reservoirs of ore-grade P are found in the United States, in China, and in Morocco. Numerous less-economic sedimentary deposits exist, but these deposits are more dilute and represent former marine settings without the trifecta of productivity, geochemistry and sedimentology that makes phosphorites economically viable.

Incorporation of 210Pb and 210Po to Poultry through the Addition of Dicalcium Phosphate (DCP) to the Diet

NASA Astrophysics Data System (ADS)

Casacuberta, N.; Masqué, P.; Garcia-Orellana, J.; Gasa, J.; Anguita, M.

2008-08-01

Due to the replacement of calcium by uranium in the phosphorite, sedimentary phosphate rock contains high concentrations of 238U (i.e. from 1500 Bqṡkg-1 in Morocco to 4000 Bqṡkg-1 in Tanzania ores). Dicalcium Phosphate (DCP) is produced by the wet acid digestion of the phosphorite, and is used as a source of calcium and phosphorus for livestock feed supplement. If the phosphorite acid digestion is made with hydrochloric acid, DCP may present specific activities of about 103 Bqṡkg-1 of 238U and some of its decay chain daughters. In particular, due to its radiological implications, the presence of 210Pb and 210Po in DCP is of special relevance. The aim of this work was to investigate the potential incorporation of these radionuclides to poultry through its diet. Three different diets were therefore prepared with different contents of both DCP and 210Pb and 210Po. Diet A was used as a blank, and had a 2.5% in weight of monocalcium phosphate (MCP); diet B, with a 5% in weight of DCP; and diet C, with a 2.5% of DCP. Concentrations of 210Pb were 0.93, 101.4 and 51.2 Bqṡkg-1; whereas concentrations of 210Po were 0.92, 74 and 36 Bqṡkg-1 of food for diets A, B and C, respectively. Accumulation of 210Pb and 210Po was analysed at several times during poultry growth in samples of bone, liver, kidney, muscle, excrements as well as entire animals, with a total of 30 broilers fed with the 3 different diets. Results showed clear enhancements in the accumulation of both 210Pb and 210Po in chicken for diets B and C, and in particular in liver and bone. However, total accumulation of radionuclides in chicken, and especially in edible parts, is low compared to its expulsion through excrements. These results are interpreted in terms of the potential dose through consumption of chicken.

The Cretaceous glauconitic sandstones of Abu Tartur, Egypt

NASA Astrophysics Data System (ADS)

Pestitschek, Brigitte; Gier, Susanne; Essa, Mahmoud; Kurzweil, Johannes

2010-05-01

The Abu Tartur mine is located in the Western Desert of Egypt, 50 km west of El Kharga City. Geologically, the Abu Tartur plateau is built by a sequence of Upper Cretaceous (Campanian - Maastrichtian) phosphorites, black shales and glauconitic sandstones. The phosphate deposits are of great economic importance and have been mined since their discovery in 1967. Outcrop sections were measured, sampled, sedimentologically characterized and described. One specific glaucony layer was investigated mineralogically and chemically in detail and compared to a subsurface sample from the mine. Two depositional regimes can be interpreted based on sedimentary architecture and structures: 1) a deeper-water hemipelagic environment, where phosphorites and organic carbon-rich shales were deposited and 2) a shallower, prograding higher energy shelf environment with glauconies. From a sequence stratigraphic perspective 1) was deposited during the transgressive systems tract and the early highstand while 2) was deposited during the remaining highstand and a lowstand prograding wedge (Glenn & Arthur, 1990). Petrographic and SEM investigations show that the glaucony grains are of authochtonous origin. XRF, EMPA and thin-section analyses show that the glaucony grains from the outcrop differ significantly in their chemical composition, morphology and color from the grains of the mine sample. The fresh glauconies are enriched in Fe2O3 and K2O compared to the surface samples. XRD analyses of the clay fraction of the six outcrop samples and the mine sample show that the grains consist of illite(glauconite)/smectite mixed-layers, with more illite layers (80 %) in the mine sample. The charge distribution diagram muscovite-pyrophyllite-celadonite shows a clear trend from smectitic glaucony to illitic glaucony, the mine sample plots exactly in the field for glauconites. All these features indicate that the surface samples are strongly altered by weathering and that glauconite progressively transforms into iron-rich illte/smectite mixed layers and then into smectites. For any chemical and mineralogical characterization of glauconites at surface, these weathering effects have to be taken into consideration. GLENN, C. R. & ARTHUR, M. A. (1990): Anatomy and origin of a Cretaceous phosphorites-greensand giant, Egypt. Sedimentology, 37, 123-154.

Kinetics of selenium release in mine waste from the Meade Peak Phosphatic Shale, Phosphoria Formation, Wooley Valley, Idaho, USA

Treesearch

Lisa L. Stillings; Michael C. Amacher

2010-01-01

Phosphorite from the Meade Peak Phosphatic Shale member of the Permian Phosphoria Formation has been mined in southeastern Idaho since 1906. Dumps of waste rock from mining operations contain high concentrations of Se which readily leach into nearby streams and wetlands. While the most common mineralogical residence of Se in the phosphatic shale is elemental Se, Se(0...

Calcium-phosphate biomineralization induced by alkaline phosphatase activity in Escherichia coli: localization, kinetics and potential signatures in the fossil record

NASA Astrophysics Data System (ADS)

Cosmidis, Julie; Benzerara, Karim; Guyot, François; Skouri-Panet, Fériel; Duprat, Elodie; Férard, Céline; Guigner, Jean-Michel; Babonneau, Florence; Coelho, Cristina

2015-12-01

Bacteria are thought to play an important role in the formation of calcium-phosphate minerals composing marine phosphorites, as supported by the common occurrence of fossil microbes in these rocks. Phosphatase enzymes may play a key role in this process. Indeed, they may increase the supersaturation with respect to Ca-phosphates by releasing orthophosphate ions following hydrolysis of organic phosphorus. However, several questions remain unanswered about the cellular-level mechanisms involved in this model, and its potential signatures in the mineral products. We studied Ca-phosphate precipitation by different strains of Escherichia coli which were genetically modified to differ in the abundance and cellular localization of the alkaline phosphatase (PHO A) produced. The mineral precipitated by either E. coli or purified PHO A was invariably identified as a carbonate-free non-stoichiometric hydroxyapatite. However, the bacterial precipitates could be discriminated from the ones formed by purified PHO A at the nano-scale. PHO A localization was shown to influence the pattern of Ca-phosphate nucleation and growth. Finally, the rate of calcification was proved to be consistent with the PHO A enzyme kinetics. Overall, this study provides mechanistic keys to better understand phosphogenesis in the environment, and experimental references to better interpret the microbial fossil record in phosphorites.

The Peru Margin as an Authigenic Mineral Factory, Evidence From Surface Sediments and Oceanography

NASA Astrophysics Data System (ADS)

Dean, W. E.; Arthur, M. A.

2004-12-01

Characteristics of sediments deposited within an intense oxygen-minimum zone (OMZ) on the Peru continental margin were mapped by submersible, and studied in samples collected in deck-deployed box cores and submersible push cores on two east-west transects over water depths of 75 to 1000 m at 12 degrees and 13.5 degrees S. On the basis of sampling of the top 1-2 cm of available cores, three main belts of sediments were identified in each transect with increasing depth: 1) organic-carbon (OC)-rich muds; 2) authigenic phosphatic mineral crusts; and 3) glaucony facies. These facies patterns are primarily controlled by redox conditions and strength of bottom currents. OC-rich sediments on the 12-degree transect were mainly located on the outer shelf and upper slope (150-350 m), but they occurred in much shallower water (ca. 100 m) on the 13.5-degree transect. The organic matter is almost entirely marine, resulting from very high primary productivity. The OC concentrations are highest (up to 18%) in sediments where intermediate water masses with low dissolved oxygen concentrations (less than 5 micromoles/kg) impinge on the slope at water depths between 75 and 450 m. The region between 175 and 350 m depth is characterized by bedforms stabilized by bacterial mats, extensive authigenic mineral crusts, and (or) thick organic flocs. Currents as high as 30 cm/sec were measured over that depth interval. Current-resuspension of surficial organic matter, activity of organisms, and transport to and from more oxygenated zones contribute to greater oxidation and poorer preservation of organic matter than occur under oxygen-deficient conditions. Phosphate-rich sediments occurred at depths of about 300 to 550 m on both transects. Nodular crusts cemented by carbonate-fluorapatite (CFA; phosphorite) or dolomite form within the OMZ. The crusts start by cementation of sediment near the sediment-water interface forming stiff but friable phosphatizes claystone "protocrusts". The protocrusts evolve into dense, dark phosphorite crusts, cemented breccias, and pavements. The degree of phosphatization and thickness of the phosphorite crusts depends on rates of sediment supply and strength and frequency of currents that re-expose crusts on the seafloor. Glaucony-rich surficial sediments, relatively undiluted by other components, mainly were found in deeper water on the 13.5 degree transect (750 m to at least 1067 m). These sediments consist almost entirely of sand-size glaucony pellets (aggregates of clay minerals with pelletoid shapes). These widespread glaucony sands possibly formed in situ and were then concentrated and reworked by strong currents that winnowed away the fine-grained matrix. Overall, sedimentation rate must be slow in order for the glaucony minerals to remain in contact with seawater, which is the source of cations during growth. The close association of glaucony and phosphorite indicates that there is a delicate balance between slightly oxidizing and slightly reducing conditions at the base of the OMZ- slightly reducing to mobilize iron and phosphate, and slightly oxidizing to form glaucony.

Incorporation of {sup 210}Pb and {sup 210}Po to Poultry through the Addition of Dicalcium Phosphate (DCP) to the Diet

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

Casacuberta, N.; Masque, P.; Garcia-Orellana, J.

Due to the replacement of calcium by uranium in the phosphorite, sedimentary phosphate rock contains high concentrations of {sup 238}U (i.e. from 1500 Bq{center_dot}kg{sup -1} in Morocco to 4000 Bq{center_dot}kg{sup -1} in Tanzania ores). Dicalcium Phosphate (DCP) is produced by the wet acid digestion of the phosphorite, and is used as a source of calcium and phosphorus for livestock feed supplement. If the phosphorite acid digestion is made with hydrochloric acid, DCP may present specific activities of about 10{sup 3} Bq{center_dot}kg{sup -1} of {sup 238}U and some of its decay chain daughters. In particular, due to its radiological implications, themore » presence of {sup 210}Pb and {sup 210}Po in DCP is of special relevance. The aim of this work was to investigate the potential incorporation of these radionuclides to poultry through its diet. Three different diets were therefore prepared with different contents of both DCP and {sup 210}Pb and {sup 210}Po. Diet A was used as a blank, and had a 2.5% in weight of monocalcium phosphate (MCP); diet B, with a 5% in weight of DCP; and diet C, with a 2.5% of DCP. Concentrations of {sup 210}Pb were 0.93, 101.4 and 51.2 Bq{center_dot}kg{sup -1}; whereas concentrations of {sup 210}Po were 0.92, 74 and 36 Bq{center_dot}kg{sup -1} of food for diets A, B and C, respectively. Accumulation of {sup 210}Pb and {sup 210}Po was analysed at several times during poultry growth in samples of bone, liver, kidney, muscle, excrements as well as entire animals, with a total of 30 broilers fed with the 3 different diets. Results showed clear enhancements in the accumulation of both {sup 210}Pb and {sup 210}Po in chicken for diets B and C, and in particular in liver and bone. However, total accumulation of radionuclides in chicken, and especially in edible parts, is low compared to its expulsion through excrements. These results are interpreted in terms of the potential dose through consumption of chicken.« less

Precambrian animal diversity: putative phosphatized embryos from the Doushantuo Formation of China

NASA Technical Reports Server (NTRS)

Chen, J. Y.; Oliveri, P.; Li, C. W.; Zhou, G. Q.; Gao, F.; Hagadorn, J. W.; Peterson, K. J.; Davidson, E. H.

2000-01-01

Putative fossil embryos and larvae from the Precambrian phosphorite rocks of the Doushantuo Formation in Southwest China have been examined in thin section by bright field and polarized light microscopy. Although we cannot completely exclude a nonbiological or nonmetazoan origin, we identified what appear to be modern cnidarian developmental stages, including both anthozoan planula larvae and hydrozoan embryos. Most importantly, the sections contain a variety of small (

Evidence of Microfossils in Carbonaceous Chondrites

NASA Technical Reports Server (NTRS)

Hoover, Richard B.; Rozanov, Alexei Y.; Zhmur, S. I.; Gorlenko, V. M.

1998-01-01

Investigations have been carried out on freshly broken, internal surfaces of the Murchison, Efremovka and Orgueil carbonaceous chondrites using Scanning Electron Microscopes (SEM) in Russia and the Environmental Scanning Electron Microscope (ESEM) in the United States. These independent studies on different samples of the meteorites have resulted in the detection of numerous spherical and ellipsoidal bodies (some with spikes) similar to the forms of uncertain biogenicity that were designated "organized elements" by prior researchers. We have also encountered numerous complex biomorphic microstructures in these carbonaceous chondrites. Many of these complex bodies exhibit diverse characteristics reminiscent of microfossils of cyanobacteria such as we have investigated in ancient phosphorites and high carbon rocks (e.g. oil shales). Energy Dispersive Spectroscopy (EDS) analysis and 2D elemental maps shows enhanced carbon content in the bodies superimposed upon the elemental distributions characteristic of the chondritic matrix. The size, distribution, composition, and indications of cell walls, reproductive and life cycle developmental stages of these bodies are strongly suggestive of biology' These bodies appear to be mineralized and embedded within the meteorite matrix, and can not be attributed to recent surface contamination effects. Consequently, we have interpreted these in-situ microstructures to represent the lithified remains of prokaryotes and filamentous cyanobacteria. We also detected in Orgueil microstructures morphologically similar to fibrous kerite crystals. We present images of many biomorphic microstructures and possible microfossils found in the Murchison, Efremovka, and Orgueil chondrites and compare these forms with known microfossils from the Cambrian phosphate-rich rocks (phosphorites) of Khubsugul, Northern Mongolia.

Late Neogene foraminifera from the northern Namibian continental shelf and the transition to the Benguela Upwelling System

NASA Astrophysics Data System (ADS)

Bergh, Eugene W.; Compton, John S.; Frenzel, Peter

2018-05-01

Middle Miocene to Plio-Pleistocene foraminifera provide insights into the palaeoenvironment on the northern Namibian continental shelf located at the far northern end of the present-day Benguela Upwelling System (BUS). Biostratigraphy and Strontium Isotope Stratigraphy (SIS) of the recovered basal olive-green mud unit indicate an age of 16 to 14 Ma. A sharp, erosional contact separates the basal mud from the overlying Plio-Pleistocene gravelly pelletal phosphorite sands. Grain size data, P/B ratios and benthic diversity indices indicate a change between the middle Miocene and overlying Plio-Pleistocene palaeoenvironments linked to the timing and conditions associated with the initiation of the BUS. The different lithological units and microfossil assemblages in the olive-green mud unit and the overlying pelletal phosphorite units support the late Miocene initiation of the BUS and the northwards migration of the Angola-Benguela Front. Planktic foraminifera indicate a shift from warmer surface water conditions to cooler conditions during the initiation of the BUS. Benthic palaeobathymetric ranges and P/B ratios are consistent with outer shelf water depths suggesting a deeper palaeoenvironment during the Mid-Miocene Climatic Optimum (MMCO) than today. Benthic foraminifera in the middle Miocene are dominated by large (>1 mm) taxa and adapted to oligotrophic environments before the initiation of the BUS. The benthic assemblage composition indicates that bottom water conditions changed to eutrophic conditions during the Plio-Pleistocene under intensified upwelling conditions.

Evidence for Microfossils in Ancient Rocks and Meteorites

NASA Technical Reports Server (NTRS)

Hoover, Richard B.; Rozanov, A. Y.; Zhmur, S. I.; Gorlenko, V. M.

1998-01-01

The McKay et all. detection of chemical biomarkers and possible microfossils in an ancient meteorite from Mars (ALH84001) stimulated research in several areas of importance to the newly emerging field of Astrobiology. Their report resulted in a search for additional evidence of microfossils in ancient terrestrial rocks and meteorites. These studies of ancient rocks and meteorites were conducted independently (and later collaboratively) in the United States and Russia using the SEM, Environmental Scanning Electron Microscope (ESEM), and Field Emission Scanning Electron Microscope (FESEM). We have encountered in-situ in freshly broken carbonaceous chondrites a large number of complex microstructures that appear to be lithified microbial forms. The meteoritic microstructures have characteristics similar to the lithified remains of filamentous cyanobacteria and bacterial microfossils we have found in ancient phosphorites, ancient graphites and oil shales. Energy Dispersive Spectroscopy (EDS) and Link microprobe analysis shows the possible microfossils have a distribution of chemical elements characteristic of the meteorite rock matrix, although many exhibit a superimposed carbon enhancement. We have concluded that the mineralized bodies encountered embedded in the rock matrix of freshly fractured meteoritic surfaces can not be dismissed as recent surface contaminants. Many of the forms found in-situ in the Murchison, Efremovka, and Orgueil carbonaceous meteorites are strikingly similar to microfossils of coccoid bacteria, cyanobacteria and fungi such as we have found in the Cambrian phosphorites of Khubsugul, Mongolia and high carbon Phanerozoic and Precambrian rocks of the Siberian and Russian Platforms.

Phosphatization Associated Features of Ferromanganese Crusts at Lemkein Seamount, Marshall Islands

NASA Astrophysics Data System (ADS)

Choi, J.; Lee, I.; Park, B. K.; Kim, J.

2014-12-01

Old layers of ferromanganese crusts, especially in the Pacific Ocean, have been affected by phosphatization. Ferromanganese crusts on Lemkein seamount in Marshall Islands also are phosphatized (3.3 to 4.2 wt % of P concentration). Furthermore, they have characteristic features that are different from other ferromanganese crusts. These features occur near the phosphorite, which were thought to fill the pore spaces of ferromanganese crusts. Inside the features, ferromanganese crusts are botryoidally precipitated from the round-boundary. The features of the phosphatized lower crusts of Lemkein seamount are observed using microscope and SEM. Elemental compositions of the selected samples were analyzed by SEM-EDS. Based on the observation and analysis of samples, three characteristic structures are identified: (1) phosphate-filled circles, (2) tongue-shaped framboidal crust, and (3) massive framboidal crust. The phosphate-filled circles are mostly composed of phosphorite, and they include trace fossils such as foraminifera. Phosphatized ferromanganese crusts exist at the boundary of this structure. The tongue-shaped crust is connected with the lips downward, and ferromanganese crusts inside the tongue show distinct growth rim. The massive framboidal crust is located below the tongue. Ferromanganese crusts in the massive framboidal crust are enveloped by phosphate, and some of the crusts are phosphatized. Around the structures, Mn oxide phase is concentrated as a shape of corona on BSE image. All of the structures are in the phosphatized crusts that show columnar growth of ferromanganese crusts and have sub-parallel lamination. These observation and chemical analysis of the ferromanganese crusts can provide a clue of diagenetic processes during the formation of ferromanganese crusts.

Morphology and ultrastructure of epilithic versus cryptic, microbial growth in lower Cambrian phosphorites from the Montagne Noire, France.

PubMed

Alvaro, J J; Clausen, S

2010-03-01

The lower Cambrian grainy phosphorites of the northern Montagne Noire occur interbedded with grey to black, laminated to massive shales and limestones deposited along the edge of a continental shelf, associated with slope-related facies and unstable substrates. The concentration of phosphate took place by repeated alternations of low sedimentation rates and condensation (hardgrounds), in situ early-diagenetic precipitation of fluorapatite, winnowing and polyphase reworking of previously phosphatized skeletons and hardground-derived clasts. The succession of repeated cycles of sedimentation, phosphate concentration, and reworking led to multi-event phosphate deposits rich in allochthonous particles. Phosphogenesis was primarily mediated by microbial activity, which is evidenced by the abundance of phosphatized putative microbial remains. These occur as smooth and segmented filaments, sheaths, and ovoid-shaped coccoids. These simple morphologies commonly form composite frameworks as a result of their aggregation and entanglement, leading to the record of biofilms, microbial mats, and complex networks. These infested the calcitic skeletonized microfossils that littered the substrate. Microbial activity evidences epilithic (anisotropic coatings on skeletons), euendolithic (perforating skeletal walls), and cryptoendolithic (lining inter- and intraparticulate pores) strategies, the latter dominated by bundles of filaments and globular clusters that grew along the cavities of helcionellids and hyoliths. According to their epilithic versus cryptic strategies, microbial populations that penetrated and dwelled inside hard skeletal substrates show different network and colonial morphologies. These early Cambrian shell concentrations were the loci of a stepwise colonization made by saprophytic to mutualistic, cyanobacterial-fungal consortia. Their euendolithic and cryptoendolithic ecological niches provided microbial refugia to manage the grazing impact mainly led by metazoans.

Hierarchy of sedimentary discontinuity surfaces and condensed beds from the middle Paleozoic of eastern North America: Implications for cratonic sequence stratigraphy

USGS Publications Warehouse

McLaughlin, P.I.; Brett, Carlton E.; Wilson, M.A.

2008-01-01

Sedimentological analyses of middle Paleozoic epeiric sea successions in North America suggest a hierarchy of discontinuity surfaces and condensed beds of increasing complexity. Simple firmgrounds and hardgrounds, which are comparatively ephemeral features, form the base of the hierarchy. Composite hardgrounds, reworked concretions, authigenic mineral crusts and monomictic intraformational conglomerates indicate more complex histories. Polymictic intraformational conglomerates, ironstones and phosphorites form the most complex discontinuity surfaces and condensed beds. Complexity of discontinuities is closely linked to depositional environments duration of sediment starvation and degree of reworking which in turn show a relationship to stratigraphic cyclicity. A model of cratonic sequence stratigraphy is generated by combining data on the complexity and lateral distribution of discontinuities in the context of facies successions. Lowstand, early transgressive and late transgressive systems tracts are representative of sea-level rise. Early and late transgressive systems tracts are separated by the maximum starvation surface (typically a polymictic intraformational conglomerate or condensed phosphorite), deposited during the peak rate of sea-level rise. Conversely the maximum flooding surface, representing the highest stand of sea level, is marked by little to no break in sedimentation. The highstand and falling stage systems tracts are deposited during relative sea-level fall. They are separated by the forced-regression surface, a thin discontinuity surface or condensed bed developed during the most rapid rate of sea-level fall. The lowest stand of sea level is marked by the sequence boundary. In subaerially exposed areas it is occasionally modified as a rockground or composite hardground.

A Re-Interpretation of the Eocene Anuran Thaumastosaurus Based on MicroCT Examination of a ‘Mummified’ Specimen

PubMed Central

Laloy, Fabien; Rage, Jean-Claude; Evans, Susan E.; Boistel, Renaud; Lenoir, Nicolas; Laurin, Michel

2013-01-01

What originally appeared to be only an external cast of an anuran ‘mummy’ from the Quercy Phosphorites (southwestern France) was described as Rana plicata during the 19th century. Its geographical provenance is only vaguely known; therefore its precise age within the Paleogene was uncertain. The taxon was erected on the basis of the external morphology of the specimen, which includes few diagnostic characters. As a further complication, the name Rana plicata was recently shown to be unavailable at the time of the description, and the name Rana cadurcorum was proposed as a replacement. In order to see whether internal features were fossilized, the fossil was CT scanned. This showed that a large part of the skeleton is preserved. Unexpectedly, the scans revealed that the skull of the mummy is almost identical to that of Thaumastosaurus gezei, another anuran from the late middle or late Eocene of the Quercy Phosphorites. The few observed differences are attributable to intraspecific and ontogenetic variation, and R. cadurcorum is a junior subjective synonym of T. gezei. The mummy is therefore probably from the same time interval as T. gezei. The latter was previously known only by its skull, but the mummy provides important information on the postcranial skeleton. Earlier assessments, based only on the skull, placed Thaumastosaurus close to South American hyloid anurans, but a new phylogenetic analysis including postcranial characters reveals ranoid affinities. This study exemplifies the usefulness of modern imaging technologies that allow non-destructive study of previously inaccessible internal anatomical features. PMID:24086389

Selenium speciation in Lower Cambrian Se-enriched strata in South China and its geological implications

NASA Astrophysics Data System (ADS)

Fan, Haifeng; Wen, Hanjie; Hu, Ruizhong; Zhao, Hui

2011-12-01

To understand the impact of Selenium (Se) into the biogeochemical cycle and implications for palaeo-redox environment, a sequential extraction method was utilized for samples including black shales, cherts, a Ni-Mo-Se sulfide layer, K-bentonite and phosphorite from Lower Cambrian Se-enriched strata in southern China. Seven species (water-soluble, phosphate exchangeable, base-soluble, acetic acid-soluble, sulfide/selenide associated, residual Se) and different oxidation states (selenate Se(VI), selenite Se(IV), organic Se, Se (0) and mineral Se(-II)) were determinated in this study. We found that the Ni-Mo-Se sulfide layer contained a significantly greater amount of Se(-II) associated with sulfides/selenides than those in host black shales and cherts. Furthermore, a positive correlation between the degree of sulfidation of iron (DOS) and the percentage of the sulfide/selenide-associated Se(-II) was observed for samples, which suggests the proportion of sulfide/selenide-associated Se(-II) could serve as a proxy for palaeo-redox conditions. In addition, the higher percentage of Se(IV) in K-bentonite and phosphorite was found and possibly attributed to the adsorption of Se by clay minerals, iron hydroxide surfaces and organic particles. Based on the negative correlations between the percentage of Se(IV) and that of Se(-II) in samples, we propose that the K-bentonite has been altered under the acid oxic conditions, and the most of black shale (and cherts) and the Ni-Mo-Se sulfide layer formed under the anoxic and euxinic environments, respectively. Concerning Se accumulation in the Ni-Mo-Se sulfide layer, the major mechanism can be described by (1) biotic and abiotic adsorption and further dissimilatory reduction from oxidized Se(VI) and Se(IV) to Se(-II), through elemental Se, (2) contribution of hydrothermal fluid with mineral Se(-II).

Evolution of Tethyan phosphogenesis along the northern edges of the Arabian--African shield during the Cretaceous--Eocene as deduced from temporal variations of Ca and Nd isotopes and rates of P accumulation

NASA Astrophysics Data System (ADS)

Soudry, D.; Glenn, C. R.; Nathan, Y.; Segal, I.; VonderHaar, D.

2006-09-01

The evolution of Tethyan phosphogenesis during the Cretaceous-Eocene is examined to try to explain fluctuations of phosphogenesis through time, and whether or not they reflect long-term changes in ocean circulation or in continental weathering. Twenty-seven time-stratigraphic phosphate levels in various Tethyan sites, covering a time span of about 90 Myr from the Hauterivian to the Eocene, were analyzed for 44Ca/ 42Ca and 143Nd/ 144Nd in their carbonate fluorapatite (CFA) fraction. P and Ca accumulation rates and bulk sedimentation rates were quantified throughout the Cretaceous-Eocene Negev sequence to examine how changes in 44Ca/ 42Ca and 143Nd/ 144Nd are reflected in the intensity of phosphogenesis. A clear-cut change occurs in ɛNd( T) and δ44Ca and in the rates of P and Ca accumulation and bulk sedimentation through the time analyzed. ɛNd( T) is much lower in the Hauterivian-Lower Cenomanian (- 12.8 to - 10.9) than in the Upper Cenomanian-Eocene (- 7.8 to - 5.9). Much lower δ44Ca values occur in the Hauterivian-Turonian (- 0.22 to + 0.02) than in the Coniacian-Eocene (+ 0.23 to + 0.40). P accumulation rates in the Negev steeply increase from < 200 μmol cm - 2 k yr - 1 in the Albian-Coniacian to ˜ 1500 μmol cm - 2 k yr - 1 in the Campanian, whereas a strong decrease is concomitantly recorded in the rates of Ca accumulation and bulk sedimentation. In addition, distinct ɛNd( T) values are shown by the phosphorites of the Negev (- 6.7 to - 6.4) and Egypt (- 9.1 to - 7.6) during the Campanian, and by those of the Negev (- 7.8 to - 6.3) and North Africa (- 10.1 to - 8.9) during the Maastrichtian-Eocene. The culmination of P accumulation rates in the Negev during the Campanian, occurring with a high in ɛNd( T) and δ44Ca and a low in sedimentation rates, indicates that paleoceanographic and paleogeographical factors mostly governed phosphorite accumulation in this area. The abrupt ɛNd( T) rise after the Cenomanian is attributed to increased incursion of Pacific (radiogenic) water masses into the Tethys, driven by the Late Cretaceous global sea-level rise, the connection between North and South Atlantic, the global post-Santonian cooling, and the progressive widening of the Caribbean threshold, all acting in combination to significantly intensify the Tethyan circumglobal current (TCC). It also reflects a weakening of the continental Nd signal due to a reduction of exposed landmasses caused by increased flooding of continental shelves. High δ44Ca values at those times also point to a decrease in weathering Ca +2 fluxes and expansion of carbonate sedimentation in shelves, both enriching seawater with isotopically heavy Ca +2. Deep ocean circulation intensified by the post-Santonian cooling of high latitudes increased P inventory in the Tethys basin, whereas the strengthened TCC and the folded shelf likely resulted in coastal and topographically-induced upwelling, supplying P-rich intermediate waters to southeastern Tethys shelves. Only in the Paleocene-Eocene, following major changes in global circulation produced by narrowing of Tethys and widening of the Atlantic, did phosphogenesis shifts its locus of high intensity to the western (Atlantic) Tethys and West African Atlantic coasts. This change in paleocirculation is expressed by distinctly differing ɛNd( T) in the Middle East and the North and West African phosphorites, suggesting different oceanic P sources and current systems for these two major groups of phosphorites. Our Nd isotope results further suggest a weaker TCC during the Mid-Cretaceous, becoming more intense in Late Cretaceous times. They also point to the North Pacific Ocean as major source of deep water formation for the intermediate-deep waters in the Tethys Basin during the Late Cretaceous.

Development and application of marine gamma-ray measurements: a review.

PubMed

Jones, D G

2001-01-01

The development of instruments to measure gamma radiation in the marine environment, particularly on the sea floor, and the range of uses to which they have been put is reviewed. Since the first steps in the late 1950s, systems have been developed in at least 10 countries with the main thrust occurring in the 1970s. Development has continued up to the present, primarily in Europe and the USA. Marine gamma-ray spectrometers have been used for a range of applications including the mapping of rocks and unconsolidated sediments, mineral exploration (mainly for heavy minerals and phosphorites), sediment transport studies and investigations in relation to discharged and dumped nuclear wastes and at nuclear weapon test sites.

Geographical coincidence of high heat flow, high seismicity, and upwelling, with hydrocarbon deposits, phosphorites, evaporites, and uranium ores.

PubMed

Libby, L M; Libby, W F

1974-10-01

Oil deposits occur in deep sediments, and appear to be organic matter that has been transformed through the action of geothermal heat and pressure. Deep sediments, rich in biological remains, are created by ocean upwelling, caused in part by high geothermal heat flow through the sea bottom. Such regions correlate with enhanced seismic activity. We look for correlations of seismicity, high heat flux, petroleum, uranium, phosphates, and salts, deposited from abundant plant life. These may be useful in discovering more petroleum and coal. We estimate that the known world reserves of petroleum and coal are about 10(-4) of the total of buried biogenic carbon.

Geographical Coincidence of High Heat Flow, High Seismicity, and Upwelling, with Hydrocarbon Deposits, Phosphorites, Evaporites, and Uranium Ores

PubMed Central

Libby, L. M.; Libby, W. F.

1974-01-01

Oil deposits occur in deep sediments, and appear to be organic matter that has been transformed through the action of geothermal heat and pressure. Deep sediments, rich in biological remains, are created by ocean upwelling, caused in part by high geothermal heat flow through the sea bottom. Such regions correlate with enhanced seismic activity. We look for correlations of seismicity, high heat flux, petroleum, uranium, phosphates, and salts, deposited from abundant plant life. These may be useful in discovering more petroleum and coal. We estimate that the known world reserves of petroleum and coal are about 10-4 of the total of buried biogenic carbon. Images PMID:16592185

On the mineral characteristics and geochemistry of the Florida phosphate of Four Corners and Hardee County mines

NASA Astrophysics Data System (ADS)

Baghdady, Ashraf R.; Howari, Fares M.; Al-Wakeel, Mohamed I.

2016-08-01

The Florida phosphate deposits in Four Corners and Hardee County mines are composed mainly of phosphate minerals and quartz in addition to subordinate proportions of feldspars, dolomite, calcite, gypsum, kaolinite, attapulgite and montmorillonite. These phosphorites contain three structurally different types of mudclasts: massive mudclasts, mudclasts with concentric structure and mudclasts consisting of agglomerates of apatite microparticles. The latter are represented by particles resembling phosphatized fossil bacteria associated with microbial filaments, and hollow apatite particles having surfacial coatings and connected to microbial filaments. The Florida phosphate particles are reworked and vary in mineral composition, color and shape. They are composed of a mixture of well-crystalline species including carbonate fluorapatite (francolite), carbonate apatite and fluorapatite. The color variation of the phosphate particles is related to difference in mineral composition, extent of diagenetic effects and reworking. The light-colored mudclasts are characterized by the presence of carbonate apatite and aluminum hydroxide phosphate minerals, whereas the dark mudclasts are rich in iron aluminum hydroxide phosphate minerals. The Florida phosphorites are suggested to be formed partially by authigenetic precipitation, replacement of the sea floor carbonate and diatomite, and microbial processes. With respect to elemental geochemistry, the analyzed particles contain small percentages of sulfur and iron which are related to the occurrence of pyrite. Traces of silica and alumina are recorded which may be attributed to the diagenetic. Some of the tested particles are relatively rich in phosphorous, fluorine, calcium, and magnesium, while poor in silicon, potassium and sulfur. Whereas, the bioclasts (especially teeth) are relatively rich in calcium, phosphorous and fluorine while poor in silicon, aluminum, magnesium and potassium. Hence, the microchemical analyses revealed that differential diagenesis affected mudclasts more than bioclasts. There is a complete compositional gradation between clay and phosphate particles which reflects their interaction. This involved kaolinitization of the phosphate particles, phosphatization of the clay mineral particles and production of silica.

U.s. Geological survey core drilling on the atlantic shelf.

PubMed

Hathaway, J C; Poag, C W; Valentine, P C; Manheim, F T; Kohout, F A; Bothner, M H; Miller, R E; Schultz, D M; Sangrey, D A

1979-11-02

The first broad program of scientific shallow drilling on the U.S. Atlantic continental shelf has delineated rocks of Pleistocene to Late Cretaceous age, including phosphoritic Miocene strata, widespread Eocene carbonate deposits that serve as reflective seismic markers, and several regional unconformities. Two sites, off Maryland and New Jersey, showed light hydrocarbon gases having affinity to mature petroleum. Pore fluid studies showed that relatively fresh to brackish water occurs beneath much of the Atlantic continental shelf, whereas increases in salinity off Georgla and beneath the Florida-Hatteras slope suggest buried evaporitic strata. The sediment cores showed engineering properties that range from good foundation strength to a potential for severe loss of strength through interaction between sediments and man-made structures.

Formation of the Shelf-edge Cretaceous-Tertiary contact off the southeastern U.S. Coast

USGS Publications Warehouse

Poppe, L.J.; Hathaway, J.C.; Hall, R.E.; Commeau, R.F.

1986-01-01

Submarine erosion, associated with changes in position of the proto-Gulf Stream, was the dominant mechanism controlling the formation of the Cretaceous-Tertiary unconformity in AMCOR borehole 6004. Paleontologic evidence indicates that this unconformity, which is marked by a gravelly-sand enriched in glauconitic and phosphoritic concretions, represents a hiatus of about 7 m.y. Both Cretaceous and Paleocene sediments contain middle-outer neritic foraminiferal assemblages that become more diverse with distance from the contact. Of the elemental abundances measured, Al, Ba, Co, Fe, Ga, K, Mg/Ca, Mo, Ni, P, Sr/Ca, V, Y, and Zn show a strong positive correlation with proximity to the contact, probably as a result of the concentration of authigenic and heavy minerals present as lag sediments on the erosion surface. ?? 1986.

The stable isotopic composition of a phosphorite deposit: δ13C, δ34S, and δ18O

USGS Publications Warehouse

Piper, D.Z.; Kolodny, Y.

1987-01-01

The stable isotopes of carbon and sulfur in a major marine sedimentary phosphate deposit from the northwestern United States (the Phosphoria Formation of Permian age) characterize the chemical properties of the depositional environment. The δ34S and δ13C analyses suggest deposition under conditions of variable redox from a solution the acidity of which was controlled by reaction with carbonate rocks and exchange with seawater. The δ18O concentration of apetite indicates phosphatization in a shallow sea, during three glacial and intervening interglacial stages. These data tend to corroborate the interpretation of field studies by others, that the apatite formed on a continental shelf in an area of intense oceanic upwelling during several episodes of sea level change. 

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.

Phosphorus in the ocean and marine sediments: similarities between present and past processes

NASA Astrophysics Data System (ADS)

Tamburini, F.

2004-12-01

Because phosphorus (P) is an essential nutrient, geochemical research has focused over the years on understanding the different aspects of the P cycle in the oceans, from the global to microbial scale. In the last 40 years, giant phosphorite deposits were largely studied, and their episodic occurrence in the geological record was alternatively interpreted as the product of shallow water environments, high productivity, low-sedimentation rates, and/or changes in sea level. Although research has focused more recently on the oceanic burial fluxes and residence time of P, there is still a general agreement on the need for more data. Thanks to new analytical techniques, allowing the detection of small quantities of phosphate (on the order of ?mol/g), and to the increased availability of sediment cores, P-bearing sediments have been found everywhere beneath the ocean floor. This finding has changed our understanding of P behavior in the ocean, and is redefining the role of P as an important nutrient, for example, over glacial-interglacial time scales. I will present glacial-interglacial reconstructions of burial and benthic fluxes of P, with the goal of understanding to which extent the P cycle is linked to global processes. The data, averaged to the whole ocean, indicate that burial fluxes of reactive P during glacial times are not considerably lower than during interglacials. This observation could lead to the conclusion that no changes occurred in P cycle on glacial-interglacial timescales and, therefore, that C cycle and climate variations were independent of P cycle. However, when the benthic flux estimates are taken into account, a different picture arises. During low sea level periods, the redistribution of sediments from shallow to deep waters, due to the reduction of the continental margin surface, fostered P regeneration during settling of organic matter. Even if P burial fluxes remain fairly constant, the oceanic phosphate inventory of glacial bottom waters was probably higher. On a different time scale, the shift in P behavior between glacial and interglacial periods could have been promoted by conditions similar to those that led to the formation of phosphorite deposits, which are abundant in the geological past but rare today.

Microbial pathways and palaeoenvironmental conditions involved in the formation of phosphorite grains, Safaga District, Egypt

NASA Astrophysics Data System (ADS)

Salama, Walid; El-Kammar, Ahmed; Saunders, Martin; Morsy, Rania; Kong, Charlie

2015-07-01

Phosphatic grains of the shallow marine phosphorite deposits of Egypt are classified as either phosphatic bioclasts preserving biological structure (e.g. skeletal fragments such as fish bones and teeth) or phosphatic peloids and intraclasts. This study describes the destructive and constructive microbial pathways represented by bioerosion of bones by endolithic cyanobacteria and accretion of phosphatic peloids by bacteria. The palaeoenvironmental conditions and post-depositional/diagenetic history of these grains have also been considered. Scanning and transmission electron microscopy showed that the phosphatic peloids under transmitted light microscopy are composed mainly of microspheres (0.5 to 2.5 μm) similar in shape and size to coccoid-like bacteria. Chemical mapping showed that these microspheres are composed of carbonate-fluorapatite (CFA) and surrounded by degraded carbonaceous matrix. These grains are suggested to be reworked from pre-existing microbial mats during transgressive-regressive cycles affecting the southern Tethyan Campanian-Maastrichtian shallow continental shelf. The bioerosion of phosphatic bones is characterized by a network of meandering microborings that penetrated inward from the bone surface by endolithic cyanobacteria. The bioerosion of bones resulted in a gradual centripetal digestion and conversion of bones into micritic phosphate peloids. The bioerosion mechanism is probably started in the acidic sheath surrounding cyanobacteria followed by supersaturation of PO4 and reprecipitation of crystalline CFA as electron dense remineralized rims. Electron microprobe microanalyses showed that the remineralized microbored areas are higher in CaO, P2O5, and F and depleted in Cl, relative to unaltered bones. A gradual demineralization of remineralized rims followed by dissolution of cyanobacterial cells is probably occurred during diagenesis and meteoric water alteration leaving behind empty microborings. Bone exposed to meteoric water alteration is lower in CaO and P2O5 and higher in F and Cl than the unaltered bones. Understanding bone bioerosion has significant implications for palaeoenvironmental and taphonomic reconstruction, archaeological applications and a regional correlation of the late Cretaceous to Palaeogene phosphogenic province extending from Middle East to North Africa.

Calculation of temperatures in condensed phase of burning PMMA by equation of Michelson, Mullar and Le Chatelier

NASA Astrophysics Data System (ADS)

Turgumbayeva, R. Kh; Abdikarimov, M. N.; Sagintayeva, S. S.

2018-05-01

Results of studying an aerosol of the dioxide of sulfur and pentoxide of phosphorus released into the atmosphere by the chemical company for processing of phosphorit are presented. Influence of the direction and speed of wind on sulfur dioxide distribution and pentoxide of phosphorus in a ground layer of the atmosphere is studied, and the points of the direction of wind leading to pollution of the atmosphere of the nearby city are allocated. The statistical analysis of environmental pollution is carried out by the method of the correlation and regression analysis. The equations of dependence of the amount of the sulfur dioxide and pentoxide of phosphorus, released into the atmosphere, on the volume, released by the enterprise of production, are defined. The obtained results are recommended for control, regulation and management of the environment.

Determination of the oxidation state of uranium in apatite and phosphorite deposits

USGS Publications Warehouse

Clarke, R.S.; Altschuler, Z.S.

1958-01-01

Geological and mineralogical evidence indicate that the uranium present in apatite may proxy for calcium in the mineral structure as U(IV). An experimental investigation was conducted and chemical evidence was obtained that establishes the presence of U(IV) in apatite. The following analytical procedure was developed for the determination of U(IV). Carbonatefluorapatite is dissolved in 1.5 M orthophosphoric acid at a temperature of 5??C or slightly below and fluorapatite is dissolved in cold 1.2 M hydrochloric acid (approximately 5??C) containing 1.5 g of hydroxylamine hydrochloride per 100 ml. Uranium(IV) is precipitated by cupferron using titanium as a carrier. The uranium in the precipitate is separated by use of the ethyl acetate extraction procedure and determined fluorimetrically. The validity and the limitations of the method have been established by spike experiments. ?? 1958.

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.

Phosphate Biomineralization of Cambrian Microorganisms

NASA Technical Reports Server (NTRS)

McKay, David S.; Rozanov, Alexei Yu.; Hoover, Richard B.; Westall, Frances

1998-01-01

As part of a long term study of biological markers (biomarkers), we are documenting a variety of features which reflect the previous presence of living organisms. As we study meteorites and samples returned from Mars, our main clue to recognizing possible microbial material may be the presence of biomarkers rather than the organisms themselves. One class of biomarkers consists of biominerals which have either been precipitated directly by microorganisms, or whose precipitation has been influenced by the organisms. Such microbe-mediated mineral formation may include important clues to the size, shape, and environment of the microorganisms. The process of fossilization or mineralization can cause major changes in morphologies and textures of the original organisms. The study of fossilized terrestrial organisms can help provide insight into the interpretation of mineral biomarkers. This paper describes the results of investigations of microfossils in Cambrian phosphate-rich rocks (phosphorites) that were found in Khubsugul, Northern Mongolia.

Mineralogical characterization of strata of the Meade Peak phosphatic shale member of the Permian Phosphoria Formation: channel and individual rock samples of measured section J and their relationship to measured sections A and B, central part of Rasmussen Ridge, Caribou County, Idaho

USGS Publications Warehouse

Knudsen, A.C.; Gunter, M.E.; Herring, J.R.; Grauch, R.I.

2002-01-01

The Permian Phosphoria Formation of southeastern Idaho hosts one of the largest phosphate deposits in the world. Despite the economic significance of this Formation, the fine-grained nature of the phosphorite has discouraged detailed mineralogical characterization and quantification studies. Recently, selenium and other potentially toxic trace elements in mine wastes have drawn increased attention to this formation, and motivated additional study. This study uses powder X-ray diffraction (XRD), with Rietveld quantification software, to quantify and characterize the mineralogy of composite channel samples and individual samples collected from the stratigraphic sections measured by the U.S. Geological Survey in the Meade Peak Member of the Permian Phosphoria Formation at the Enoch Valley mine on Rasmussen Ridge, approximately 15 miles northeast of Soda Springs, Idaho.

Lithofacies, Age, and Sequence Stratigraphy of the Carboniferous Lisburne Group in the Skimo Creek Area, Central Brooks Range

USGS Publications Warehouse

Dumoulin, Julie A.; Whalen, Michael T.; Harris, Anita G.

2008-01-01

The Lisburne Group, a mainly Carboniferous carbonate succession that is widely distributed across northern Alaska, contains notable amounts of oil and gas at Prudhoe Bay. Detailed studies of the Lisburne in the Skimo Creek area, central Brooks Range, delineate its lithofacies, age, conodont biofacies, depositional environments, and sequence stratigraphy and provide new data on its hydrocarbon source-rock and reservoir potential, as well as its thermal history, in this area. We have studied the Lisburne Group in two thrust sheets of the Endicott Mountains allochthon, herein called the Skimo and Tiglukpuk thrust sheets. The southern, Skimo Creek section, which is >900 m thick, is composed largely of even-bedded to nodular lime mudstone and wackestone intercalated with intervals of thin- to thick-bedded bioclastic packstone and grainstone. Some parts of the section are partially to completely dolomitized and (or) replaced by chert. A distinctive, 30-m-thick zone of black, organic-rich shale, lime mudstone, and phosphorite is exposed 170 m below the top of the Lisburne. The uppermost 40 m of section is also distinctive and made up of dark shale, lime mudstone, spiculite, and glauconitic grainstone. The northern, Tiglukpuk Creek section, which is similar to the Skimo Creek section but only ~760 m thick, includes more packstone and grainstone and less organic-rich shale. Analyses of conodonts and foraminifers indicate that both sections range in age from late Early Mississippian (Osagean) through Early Pennsylvanian (early Morrowan) and document a hiatus of at least 15 m.y. at the contact between the Lisburne and the overlying Siksikpuk Formation. No evidence of subaerial exposure was observed along this contact, which may represent a submarine erosional surface. Lithofacies and biofacies imply that the Lisburne Group in the study area was deposited mainly in midramp to outer-ramp settings. Deepest water strata are mud rich and formed below storm or fair-weather wave base on the outer ramp to outer midramp; shallowest facies are storm, sand-wave, and shoal deposits of the inner midramp to inner ramp. A relatively diverse, open-marine fauna occurs throughout much of the Lisburne in the study area, but some beds also contain clasts typical of more restricted, shallow-water environments that were likely transported seaward by storms and currents. Radiolarians are abundant in the shale and phosphorite unit at Skimo Creek and also occur in equivalent strata at Tiglukpuk Creek; high gamma-ray response and elevated total organic-carbon contents (max 5?8 weight percent) also characterize this unit at Skimo Creek. Lithologic, faunal, and geochemical data all suggest that these rocks formed mainly in an outer-ramp to basinal setting with low sedimentation rates, high productivity, and poorly oxygenated bottom water. Shale and mudstone at the top of the Lisburne Group accumulated in a similarly sediment starved, mainly outer ramp environment but lack comparable evidence for high nutrient and low oxygen levels during deposition. Vertical shifts in rock types and faunas delineate numerous parasequences and six probable third-order sequences in the study area; the same sequences are also recognized in the Lisburne Group to the east. Transgressive-system tracts in these sequences generally fine upward, whereas highstand-system tracts coarsen upward. Sequences in the Tiglukpuk Creek section are mostly thinner, contain thinner and more numerous parasequences, and accumulated in somewhat shallower settings than those in the Skimo Creek section. These differences reflect the more seaward position and, thus, increased accommodation space of the Skimo Creek section relative to the Tiglukpuk Creek section during deposition. Organic-rich calcareous shale in the shale and phosphorite unit has a cumulative thickness of at least 15 m and a lateral extent of >50 km; this lithology is the best potential hydrocarbon source rock in the Lisburne Group

Uranium provinces of North America; their definition, distribution, and models

USGS Publications Warehouse

Finch, Warren Irvin

1996-01-01

Uranium resources in North America are principally in unconformity-related, quartz-pebble conglomerate, sandstone, volcanic, and phosphorite types of uranium deposits. Most are concentrated in separate, well-defined metallogenic provinces. Proterozoic quartz-pebble conglomerate and unconformity-related deposits are, respectively, in the Blind River–Elliot Lake (BRELUP) and the Athabasca Basin (ABUP) Uranium Provinces in Canada. Sandstone uranium deposits are of two principal subtypes, tabular and roll-front. Tabular sandstone uranium deposits are mainly in upper Paleozoic and Mesozoic rocks in the Colorado Plateau Uranium Province (CPUP). Roll-front sandstone uranium deposits are in Tertiary rocks of the Rocky Mountain and Intermontane Basins Uranium Province (RMIBUP), and in a narrow belt of Tertiary rocks that form the Gulf Coastal Uranium Province (GCUP) in south Texas and adjacent Mexico. Volcanic uranium deposits are concentrated in the Basin and Range Uranium Province (BRUP) stretching from the McDermitt caldera at the Oregon-Nevada border through the Marysvale district of Utah and Date Creek Basin in Arizona and south into the Sierra de Peña Blanca District, Chihuahua, Mexico. Uraniferous phosphorite occurs in Tertiary sediments in Florida, Georgia, and North and South Carolina and in the Lower Permian Phosphoria Formation in Idaho and adjacent States, but only in Florida has economic recovery been successful. The Florida Phosphorite Uranium Province (FPUP) has yielded large quantities of uranium as a byproduct of the production of phosphoric acid fertilizer. Economically recoverable quantities of copper, gold, molybdenum, nickel, silver, thorium, and vanadium occur with the uranium deposits in some provinces.Many major epochs of uranium mineralization occurred in North America. In the BRELUP, uranium minerals were concentrated in placers during the Early Proterozoic (2,500–2,250 Ma). In the ABUP, the unconformity-related deposits were most likely formed initially by hot saline formational water related to diagenesis (»1,400 to 1,330 Ma) and later reconcentrated by hydrothermal events at »1,280–»1,000, »575, and »225 Ma. Subsequently in North America, only minor uranium mineralization occurred until after continental collision in Permian time (255 Ma). Three principal epochs of uranium mineralization occurred in the CPUP: (1) » 210–200 Ma, shortly after Late Triassic sedimentation; (2) »155–150 Ma, in Late Jurassic time; and (3) » 135 Ma, after sedimentation of the Upper Jurassic Morrison Formation. The most likely source of the uranium was silicic volcaniclastics for the three epochs derived from a volcanic island arc at the west edge of the North American continent. Uranium mineralization occurred during Eocene, Miocene, and Pliocene times in the RMIBUP, GCUP, and BRUP. Volcanic activity took place near the west edge of the continent during and shortly after sedimentation of the host rocks in these three provinces. Some volcanic centers in the Sierra de Peña Blanca district within the BRUP may have provided uranium-rich ash to host rocks in the GCUP.Most of the uranium provinces in North America appear to have a common theme of close associations to volcanic activity related to the development of the western margin of the North American plate. The south and west margin of the Canadian Shield formed the leading edge of the progress of uranium source development and mineralization from the Proterozoic to the present. The development of favorable hosts and sources of uranium is related to various tectonic elements developed over time. Periods of major uranium mineralization in North America were Early Proterozoic, Middle Proterozoic, Late Triassic–Early Jurassic, Early Cretaceous, Oligocene, and Miocene. Tertiary mineralization was the most pervasive, covering most of Western and Southern North America. 

Trace Elements in the Marine Sediments of the La Paz Lagoon, Baja California Peninsula, Mexico: Pollution Status in 2013.

PubMed

Pérez-Tribouillier, Habacuc; Shumilin, Evgueni; Rodríguez-Figueroa, Griselda Margarita

2015-07-01

To determine the actual concentrations of trace elements in surface sediments from the La Paz Lagoon, as well as their associations and possible origins, 91 sediment samples were analyzed for more than 50 elements using a combination of ICP-MS and ICP-AES. The results of a principal component analysis are used to distinguish four associative groups within the elements. Natural enrichment of As, Cd and U occurs due to the supply of weathered phosphorites from the El Cien formation located to the north-west of the lagoon. Sediment quality indices for potentially toxic trace elements do not show any probable impact on the biota of the lagoon. Only the concentrations of As in 30 % of the stations and Cu in 20 % of them exceed related effect range low levels. The highest concentration of Pb (36.8 mg kg(-1)) was measured in the sediments near the City of La Paz.

Chemotrophic Microbial Mats and Their Potential for Preservation in the Rock Record

NASA Astrophysics Data System (ADS)

Bailey, Jake V.; Orphan, Victoria J.; Joye, Samantha B.; Corsetti, Frank A.

2009-11-01

Putative microbialites are commonly regarded to have formed in association with photosynthetic microorganisms, such as cyanobacteria. However, many modern microbial mat ecosystems are dominated by chemotrophic bacteria and archaea. Like phototrophs, filamentous sulfur-oxidizing bacteria form large mats at the sediment/water interface that can act to stabilize sediments, and their metabolic activities may mediate the formation of marine phosphorites. Similarly, bacteria and archaea associated with the anaerobic oxidation of methane (AOM) catalyze the precipitation of seafloor authigenic carbonates. When preserved, lipid biomarkers, isotopic signatures, body fossils, and lithological indicators of the local depositional environment may be used to identify chemotrophic mats in the rock record. The recognition of chemotrophic communities in the rock record has the potential to transform our understanding of ancient microbial ecologies, evolution, and geochemical conditions. Chemotrophic microbes on Earth occupy naturally occurring interfaces between oxidized and reduced chemical species and thus may provide a new set of search criteria to target life-detection efforts on other planets.

High-resolution seismic reflection profiling for mapping shallow aquifers in Lee County, Florida

USGS Publications Warehouse

Missimer, T.M.; Gardner, Richard Alfred

1976-01-01

High-resolution continuous seismic reflection profiling equipment was utilized to define the configuration of sedimentary layers underlying part of Lee County, Florida. About 45 miles (72 kilometers) of profile were made on the Caloosahatchee River Estuary and San Carlos Bay. Two different acoustic energy sources, a high resolution boomer and a 45-electrode high resolution sparker, both having a power input of 300 joules, were used to obtain both adequate penetration and good resolution. The seismic profiles show that much of the strata of middle Miocene to Holocene age apparently are extensively folded but not faulted. Initial interpretations indicate that: (1) the top of the Hawthorn Formation (which contains the upper Hawthorn aquifer) has much relief due chiefly to apparent folding; (2) the limestone, sandstone, and unconsolidated sand and phosphorite, which together compose the sandstone aquifer, appear to be discontinuous; (3) the green clay unit of the Tamiami Formation contains large scale angular beds dipping eastward; and (4) numerous deeply cut alluvium-filled paleochannels underlie the Caloosahatchee River. (Woodard-USGS)

Interactions of the marine phosphorus and carbon cycles

NASA Technical Reports Server (NTRS)

Froelich, P. N.

1984-01-01

About 30 to 50% of the fluvial P-input to the oceans derives from release of reactive-P from particles during their passage through estuaries. The input is matched by P-removal into three approximately equivalent sink: (1) burial in phosphorites on productive shelves; (2) burial with (org) in the deep-sea; and (3) burial with biogenic calcite in the deep-sea. The P/C burial ratio in these three phases is very different: P/C (org) approximately .004; P/C (CaCO3) approximately .001; and P/C (PHOS) approximately .03. The removal mechanisms are all coupled to primary production in the surface ocean, but the details of the feedback mechanisms controlling the steady-state nutrient and carbon budgets in the sea are doscured by lack of knowledge of how the P/C ratios in the sinks adjust, and how shifts in oceanic nutrients affect oceanic ecology and the relative fraction of biogenic CaCO3 and (org) production.

Sulphur bacteria mediated formation of Palaeoproterozoic phosphorites

NASA Astrophysics Data System (ADS)

Joosu, Lauri; Lepland, Aivo; Kirsimäe, Kalle

2014-05-01

Modern phosphorite formation is typically associated with high productivity in upwelling areas where apatite (Ca-phosphate) precipitation is mediated by sulphur oxidising bacteria [1]. They inhabit the oxic/anoxic interface within the upper few centimetres of sediment column, accumulating phosphate in their cells under oxic conditions and releasing it rapidly when conditions become anoxic. Sulphur bacteria are known to live in close association with a consortium of anaerobic methane oxidising archaea and syntrophic sulphate-reducing bacteria. Paleoproterozoic, c. 2.0 Ga Zaonega Formation in Karelia, Russia contains several P-rich intervals in the upper part of 1500 m thick succession of organic-rich sedimentary rocks interlayered with mafic tuffs and lavas. Apatite in these P-rich intervals forms impure laminae, lenses and round-oval nodules which diameters typically range from 300 to 1000 μm. Individual apatite particles in P-rich laminae and nodules commonly occur as cylinders that are 1-8 μm long and have diameters of 0.5-4 μm. Cross-sections of best preserved cylindrical apatite particles reveal a thin outer rim whereas the internal parts consist of small anhedral elongated crystallites, intergrown with carbonaceous material. During recrystallization the outer rim thickens towards interior and cylinders may attain hexagonal crystal habit, but their size and shape remains largely unchanged [2]. The sizes of Zaonega nodules are similar to giant sulphide-oxidising bacteria known from modern and ancient settings [3, 4]. Individual apatite cylinders and aggregates have shapes and sizes similar to the methanotrophic archaea that inhabit microbial mats in modern seep/vent areas where they operate in close associations with sulphur-oxidising microbial communities [5]. Seep/vent influence during the Zaonega phosphogenesis is indicated by variable, though positive Eu anomaly, expected in magmatically active sedimentary environment experiencing several lava flows. Moreover, P-rich intervals in the Zaonega Formation are found in organic-rich sediments exhibiting strongly negative δ13Corg values (-37 to -34 per mil) which is interpreted to reflect the methanotrophic biomass. We conclude that modern-style phosphogenesis, mediated by sulphide-oxidising bacteria living in consortium with methanotrophs, was established at least 2 Ga ago. [1] Schulz and Schulz (2005) Science 307, 416-418 [2] Lepland, Joosu, Kirsimäe, Prave, Romashkin, Črne, Martin, Fallick, Somelar, Üpraus, Mänd, Roberts, van Zuilen, Wirth, Schreiber (2014) Nature geoscience 7, 20-24 [3] Bailey, Joye, Kalanetra, Flood, and Corsetti (2007) Nature 445, 198-201 [4] Schulz, Brinkhoff, Ferdelman, Marine, Teske and Jorgensen (1999) Science 284, 493-495 [5] Knittel, Losekann, Boetius, Kort and Amann (2005) Applied and Environmental Microbiology 71, 467-479.

Seawater as the source of minor elements in black shales, phosphorites and other sedimentary rocks

USGS Publications Warehouse

Piper, D.Z.

1994-01-01

Many of the minor elements in seawater today have a concentration-depth profile similar to that of the biologically essential nutrients, NO-3 and PO3-4. They show a relative depletion in the photic zone and enrichment in the deep ocean. The difference between their surface- and deep-ocean values, normalized to the change in PO3-4, approaches the average of measured minor-element: P ratios in marine plankton, although individual analyses of the latter show extreme scatter for a variety of reasons. Despite this scatter in the minor-element analyses of plankton, agreement between the two sets of data shows unequivocally that an important marine flux of many minor elements through the ocean is in the form of biogenic matter, with a composition approaching that of plankton. This interpretation is further supported by sediment studies, particularly of sediments which accumulate in shelf-slope environments where biological productivity in the photic zone is exceptionally high and organic carbon contents of the underlying sediment elevated. The interelement relations observed for some of these sediments approach the average values of plankton. These same interelement relations are observed in many marine sedimentary rocks such as metalliferous black shales and phosphorites, rocks which have a high content of marine fractions (e.g., organic matter, apatite, biogenic silica and carbonates). Many previous studies of the geochemistry of these rocks have concluded that local hydrothermal activity, and/or seawater with an elemental content different from that of the modern ocean, was required to account for their minor-element contents. However, the similarity in several of the minor-element ratios in many of these formations to minor-element ratios in modern plankton demonstrates that these sedimentary rocks accumulated in environments whose marine chemistry was virtually identical to that seen on continental shelf-slopes, or in marginal seas, of the ocean today. The accumulation of the marine fraction of minor elements on these ancient sea floors was determined largely by the accumulation of organic matter, settling from the photic zone and with a composition of average plankton. A second marine fraction of minor elements in these rocks accumulated through precipitation and adsorption from seawater. The suite of elements in this fraction reflects redox conditions in the bottom water, as determined by bacterial respiration. For example, high Mn, high Cr+V and high Mo concentrations, above those which can be attributed to the accumulation of planktonic matter, characterize accumulation under bottom-water oxidizing, denitrifying and sulfate-reducing conditions, respectively. ?? 1994.

A mid-Permian chert event: widespread deposition of biogenic siliceous sediments in coastal, island arc and oceanic basins

USGS Publications Warehouse

Murchey, B.L.; Jones, D.L.

1992-01-01

Radiolarian and conodont of Permian siliceous rocks from twenty-three areas in teh the circum-Pacific and Mediterranean regions reveal a widespread Permian Chert Event during the middle Leonardian to Wordian. Radiolarian- and (or) sponge spicule-rich siliceous sediments accumulated beneath high productivity zones in coastal, island arc and oceanic basins. Most of these deposits now crop out in fault-bounded accreted terranes. Biogenic siliceous sediments did not accumulate in terranes lying beneath infertile waters including the marine sequences in terranes of northern and central Alaska. The Permian Chert Event is coeval with major phosphorite deposition along the western margin of Pangea (Phosphoria Formation and related deposits). A well-known analogue for this event is middle Miocene deposition of biogenic siliceous sediments beneath high productivity zones in many parts of the Pacific and concurrent deposition of phosphatic as well as siliceous sediments in basins along the coast of California. Interrelated factors associated with both the Miocene and Permian depositional events include plate reorientations, small sea-level rises and cool polar waters. ?? 1992.

Regional analysis of spiculite faunas in the permian phosphoria basin: Implications for paleoceanography

USGS Publications Warehouse

Murchey, Benita L.

2004-01-01

During the Permian, the relative abundance and apparent diversity of siliceous sponges expanded over a wide range of depths in the basins from Nevada and Idaho to the open ocean. Radiolarian preservation and apparent diversity increased in the deeper Cordilleran basins as well. In the Arctic regions, significant sponge spiculites were deposited in epicratonic basins. At the same time that siliceous sponge populations expanded along the northwestern margin of Pangea, warm-water carbonate producers disappeared. Suppression of carbonate-producing organisms along the margin was critical to the accu- mulation and preservation of both the demosponge spiculites in the Eastern Belt and the spicule-rich argillites of the Central Belt. Vigorous thermohaline circulation was the major control on the paleobiogeography of the late Early, Middle, and early Late Permian along northwest Pangea. It was driven by cold, nutrient- and oxygen-rich northern waters and it produced a coastal current that swept down the margin of the supercontinent. The upwelling associated with deposition of world-class phosphorites in the Phosphoria basin was a part of this larger oceanographic system.

Geochemistry of Israeli oil shales - A review

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

Shirav, M.; Ginzbury, D.

1983-02-01

The oil shales in Israel are widely distributed throughout the country. Outcrops are rare and the information is based on boreholes data. The oil shale sequence is of UpperCampanian - Maastrichtian age and belongs to the Chareb Formation. In places, part of the phosphorite layer below the oil shales is also rich in kerogen. The host rocks are biomicritic limestones and marls, in which the organic matter is generally homogeneously and finely dispersed. The occurrence of authigenic feldspar and the preservation of the organic matter (up to 26% of the total rock) indicate euxinic hypersaline conditions which prevailed in themore » relative closed basins of deposition during the Maastrichtian. Current reserves of oil shales in Israel are about 3,500 million tons, located in the following deposits: Zin, Oron, Ef'e, Hartuv and Nabi-Musa. The 'En Bokek deposit, although thoroughly investigated, is of limited reserves and is not considered for future exploitation. Other potential areas, in the Northern Negev and along the Coastal Plain are under investigation. Future successful utilization of the Israeli oil shales, either by fluidizid-bed combustion or by retorting will contribute to the state's energy balance.« less

Mineral resources of Elko County, Nevada

USGS Publications Warehouse

Smith, Roscoe Maurice

1976-01-01

Of the 66 named mining districts in Elko County, 56 have been productive of one or more of 19 different commodities: 11 metals--copper, gold, silver, lead, zinc, mercury, tungsten, manganese, iron, uranium, and antimony; 8 nonmetals--sand and gravel, stone, barite, diatomite, gems, oil shale, volcanic ash, and clay. In addition to the commodities produced, at least 5 others--beryllium, molybdenum, tin, phosphorite, and petroleum, occur in amounts sufficient to warrant exploration. The other districts have been explored, but no production has been recorded. Total value-when-sold of production recorded through 1969 was nearly $91 million; actual production was considerably greater, especially if sand and gravel, barite, and other nonmetallic products before 1953 are included. In value of metals produced, the five highest districts are Mountain City ($26 million), Tuscarora ($11 million), Jarbidge ($10 million), Aura ($6 million), and Railroad (nearly $5 million). The Rio Tinto copper mine in the Mountain City district yielded $21 million. Of the 17 districts that produced nonmetallic minerals, Bootstrap .is the largest producer, containing the Rossi mine, one of the two largest barite mines in the United States. Most of /he metals produced name from veins and replacement deposits in limestone or dolomite near granitic stocks; exceptions are manganese and mercury, which are not associated with known or inferred stocks; mercury is further excepted because it occurs in volcanic rocks, as do a few deposits of the major metals. The largest deposit--the Rio Tinto lode--was a combination of fissure filling and replacement along a bedding plane shear zone 150 ft wide and 1,200 ft long in carbonaceous shale of the Valmy Formation; this deposit is apparently older than the Mountain City stock and its mineralization may be related to Paleozoic mafic volcanism later than a major thrust fault, inferred to underlie the area at a depth of about 5,000 ft. Most of the nonmetallic minerals mined were sedimentary bedded deposits, but mica was mined from pegmatite deposits, and turquoise from both placer and hydrothermal deposits. The largest known reserves of metals (1973) are of porphyry copper in the Dolly Varden district and gold in the Bootstrap district. Reserves of barite also are presumed to be large. The greatest potential for future production of metals, notably copper and gold, appears to be in the known districts or extensions of them and peripheral to deposits that are related to known or concealed plutons and thrust faults. Potential resources in deposits too low in grade to be worked profitably at the present time include all commodities that have been produced and, in addition, known, deposits of beryllium, molybdenum, tin, and phosphorite. Speculative resources in undiscovered deposits may reasonably be predicted to include all known commodities as well as others that are unsuspected. Petroleum may yet be produced from the Elko Formation and geothermal energy from the Ruby Valley and Elko areas.

Influence of substrate rocks on Fe Mn crust composition

NASA Astrophysics Data System (ADS)

Hein, James R.; Morgan, Charles L.

1999-05-01

Principal Component and other statistical analyses of chemical and mineralogical data of Fe-Mn oxyhydroxide crusts and their underlying rock substrates in the central Pacific indicate that substrate rocks do not influence crust composition. Two ridges near Johnston Atoll were dredged repetitively and up to seven substrate rock types were recovered from small areas of similar water depths. Crusts were analyzed mineralogically and chemically for 24 elements, and substrates were analyzed mineralogically and chemically for the 10 major oxides. Compositions of crusts on phosphatized substrates are distinctly different from crusts on substrates containing no phosphorite. However, that relationship only indicates that the episodes of phosphatization that mineralized the substrate rocks also mineralized the crusts that grew on them. A two-fold increase in copper contents in crusts that grew on phosphatized clastic substrate rocks, relative to crusts on other substrate rock types, is also associated with phosphatization and must have resulted from chemical reorganization during diagenesis. Phosphatized crusts show increases in Sr, Zn, Ca, Ba, Cu, Ce, V, and Mo contents and decreases in Fe, Si, and As contents relative to non-phosphatized crusts. Our statistical results support previous studies which show that crust compositions reflect predominantly direct precipitation from seawater (hydrogenetic), and to lesser extents reflect detrital input and diagenetic replacement of parts of the older crust generation by carbonate fluorapatite.

Influence of substrate rocks on Fe-Mn crust composition

USGS Publications Warehouse

Hein, J.R.; Morgan, C.L.

1999-01-01

Principal Component and other statistical analyses of chemical and mineralogical data of Fe-Mn oxyhydroxide crusts and their underlying rock substrates in the central Pacific indicate that substrate rocks do not influence crust composition. Two ridges near Johnston Atoll were dredged repetitively and up to seven substrate rock types were recovered from small areas of similar water depths. Crusts were analyzed mineralogically and chemically for 24 elements, and substrates were analyzed mineralogically and chemically for the 10 major oxides. Compositions of crusts on phosphatized substrates are distinctly different from crusts on substrates containing no phosphorite. However, that relationship only indicates that the episodes of phosphatization that mineralized the substrate rocks also mineralized the crusts that grew on them. A two-fold increase in copper contents in crusts that grew on phosphatized clastic substrate rocks, relative to crusts on other substrate rock types, is also associated with phosphatization and must have resulted from chemical reorganization during diagenesis. Phosphatized crusts show increases in Sr, Zn, Ca, Ba, Cu, Ce, V, and Mo contents and decreases in Fe, Si, and As contents relative to non-phosphatized crusts. Our statistical results support previous studies which show that crust compositions reflect predominantly direct precipitation from seawater (hydrogenetic), and to lesser extents reflect detrital input and diagenetic replacement of parts of the older crust generation by carbonate fluorapatite.

Characterizing the oxygen isotopic composition of phosphate sources to aquatic ecosystems

USGS Publications Warehouse

Young, M.B.; McLaughlin, K.; Kendall, C.; Stringfellow, W.; Rollog, M.; Elsbury, K.; Donald, E.; Paytan, A.

2009-01-01

The oxygen isotopic composition of dissolved inorganic phosphate (δ18Op) in many aquatic ecosystems is not in isotopic equilibrium with ambient water and, therefore, may reflect the source δ18Op. Identification of phosphate sources to water bodies is critical for designing best management practices for phosphate load reduction to control eutrophication. In order for δ18O p to be a useful tool for source tracking, the δ18Op of phosphate sources must be distinguishable from one another; however, the δ18Op of potential sources has not been well characterized. We measured the δ18O p of a variety of known phosphate sources, including fertilizers, semiprocessed phosphorite ore, particulate aerosols, detergents, leachates of vegetation, soil, animal feces, and wastewater treatment plant effluent. We found a considerable range of δ18Op values (from +8.4 to +24.9‰) for the various sources, and statistically significant differences were found between several of the source types. δ18Op measured in three different fresh water systems was generally not in equilibrium with ambient water. Although there is overlap in δ18Op values among the groups of samples, our results indicate that some sources are isotopically distinct and δ18Op can be used for identifying phosphate sources to aquatic systems.

Biogeochemical phosphorus mass balance for Lake Baikal, southeastern Siberia, Russia

USGS Publications Warehouse

Callender, E.; Granina, L.

1997-01-01

Extensive data for Lake Baikal have been synthesized into a geochemical mass balance for phosphorus (P). Some of the P budget and internal cycling terms for Baikal have been compared to similar terms for oligotrophic Lake Superior, mesotrophic Lake Michigan and the Baltic Sea, and the Ocean. Lake Baikal has a large external source of fluvial P compared to the Laurentian upper Great Lakes and the Ocean. The major tributary to Lake Baikal has experienced substantial increases in organic P loading during the past 25 years. This, coupled with potential P inputs from possible phosphorite mining, may threaten Baikal's oligotrophic status in the future. Water-column remineralization of particulate organic P is substantially greater in Lake Baikal than in the Laurentian Great Lakes. This is probably due to the great water depths of Lake Baikal. There is a gradient in P burial efficiency, with very high values (80%) for Lake Baikal and Lake Superior, lower values (50%) for Lake Michigan and the Baltic Sea, and a low value (13%) for the Ocean. The accumulation rate of P in Lake Baikal sediments is somewhat greater than that in the Laurentian upper Great Lakes and the Baltic Sea, and much greater than in the Ocean. Benthic regeneration rates are surprisingly similar for large lacustrine and marine environments and supply less than 10% of the P utilized for primary production in these aquatic environments.

Mapping mine wastes and analyzing areas affected by selenium-rich water runoff in southeast Idaho using AVIRIS imagery and digital elevation data

USGS Publications Warehouse

Mars, J.C.; Crowley, J.K.

2003-01-01

Remotely sensed hyperspectral and digital elevation data from southeastern Idaho are combined in a new method to assess mine waste contamination. Waste rock from phosphorite mining in the area contains selenium, cadmium, vanadium, and other metals. Toxic concentrations of selenium have been found in plants and soils near some mine waste dumps. Eighteen mine waste dumps and five vegetation cover types in the southeast Idaho phosphate district were mapped by using Airborne Visible-Infrared Imaging Spectrometer (AVIRIS) imagery and field data. The interaction of surface water runoff with mine waste was assessed by registering the AVIRIS results to digital elevation data, enabling determinations of (1) mine dump morphologies, (2) catchment watershed areas above each mine dump, (3) flow directions from the dumps, (4) stream gradients, and (5) the extent of downstream wetlands available for selenium absorption. Watersheds with the most severe selenium contamination, such as the South Maybe Canyon watershed, are associated with mine dumps that have large catchment watershed areas, high stream gradients, a paucity of downstream wetlands, and dump forms that tend to obstruct stream flow. Watersheds associated with low concentrations of dissolved selenium, such as Angus Creek, have mine dumps with small catchment watershed areas, low stream gradients, abundant wetlands vegetation, and less obstructing dump morphologies. ?? 2002 Elsevier Science Inc. All rights reserved.

Biomarkers and Microfossils in the Murchison, Rainbow, and Tagish Lake meteorites

NASA Astrophysics Data System (ADS)

Hoover, Richard B.; Jerman, Gregory A.; Rozanov, Alexei Y.; Davies, Paul C.

2003-02-01

During the past six years, we have conducted extensive scanning electron and optical microscopy investigations and x-ray analysis to determine the morphology, life cycle processes, and elemental distributions in living and fossil cyanobacteria, bacteria, archaea, fungi, and algae sampled from terrestrial environments relevant to Astrobiology. Biominerals, pseudomorphs and microfossils have been studied for diverse microbial groups in various states of preservation in many types of rocks (e.g., oil shales, graphites, shungites, bauxites, limestones, pyrites, phosphorites, and hydrothermal vent chimneys). Results of these studies have been applied to the search for biosignatures in carbonaceous chondrites, stony, and nickel iron meteorites. We review important biomarkers found in terrestrial rocks and meteorites and present additional evidence for the existence of indigenous bacterial microfossils in-situ in freshly fractured surfaces of the Murchison, Rainbow and Tagish Lake carbonaceous meteorites. We provide secondary and backscatter electron images and spectral data obtained with Field Emission and Environmental Scanning Electron Microscopes of biominerals and microfossils. We discuss techniques for discriminating indigenous microfossils from recent terrestrial contaminants. Images are provided of framboidal magnetites in oil shales and meteorites and images and 2D x-ray maps are shown of bacterial microfossils embedded in the mineral matrix of the Murchison, Rainbow and Tagish Lake Carbonaceous Meteorites. These microfossils exhibit characteristics that preclude their interpretation as post-arrival contaminants and we interpret them as indigenous biogenic remains.

Gondolellid conodonts and depositional setting of the Phosphoria Formation

USGS Publications Warehouse

Wardlaw, Bruce R.

2015-01-01

The Phosphoria Formation and related rocks were deposited over an 8.9 m.y. interval beginning approximately 274.0Ma and ending approximately 265.1Ma. The Meade Peak Phosphatic Shale Member was deposited in southeastern Idaho and adjacent Wyoming over 5.4 m.y. from approximately 273.2 to 268.6 Ma. The Retort Phosphatic Shale Member was deposited in southwestern Montana and west-central Wyoming over 1.3 m.y. from approximately 267.4 to 266.1Ma. The base of the Roadian Stage of the Middle Permian occurs within the lower phosphate zone of the Meade Peak. The base of the Wordian Stage occurs within the upper phosphate zone of the Meade Peak. The presence of a cool-water brachiopod fauna, cool-water conodont faunas, and the absence of fusulinids throughout the Phosphoria basin indicate the presence of pervasive cool, upwelling waters. Acritarchs are intimately associated with phosphorites and phosphatic shales and may have been the primary organic producer to help drive phosphate production. The gondolellid conodont fauna of the Phosphoria Formation links a geographic cline of Jinogondolella nankingensis from the Delaware basin, West Texas, to the Sverdrup basin, Canadian Arctic, and shows distinct differentiation in species distribution, as do other conodont groups, within the Phosphoria basin. Ten species and two subspecies of gondolellid conodonts are recognized from the Phosphoria Formation and related rocks that belong to Mesogondolella and Jinogondolella.

Summary of reconnaissance for radioactive deposits in Alaska, 1945-1954, and an appraisal of Alaskan uranium possibilities

USGS Publications Warehouse

Wedow, Helmuth

1956-01-01

In the period 1945-1954 over 100 investigations for radioactive source materials were made in Alaska. The nature of these investigations ranged from field examinations of individual prospects or the laboratory analysis of significantly radioactive samples submitted by prospectors to reconnaissance studies of large districts. In this period no deposits of uranium or thorium that would warrant commercial exploitation were discovered. The investigations, however, disclosed that radioactive materials occur in widely scattered areas of Alaska and in widely diverse environments. Many igneous rocks throughout Alaska are weakly radioactive because of uranium- and thorium-bearing accessory minerals, such as allanite, apatite, monazite, sphene, xenotime, and zircon; more rarely the radioactivity of these rocks is due to thorianite or thorite and their uranoan varieties. The felsic rocks, for example, granites and syenites, are generally more radioactive than the mafic igneous rocks. Pegmatites, locally, have also proved to be radioactive, but they have little commercial significance. No primary uranium oxide minerals have been found yet in Alaskan vein deposits, except, perhaps, for a mineral tentatively identified as pitchblende in the Hyder district of southeastern Alaska. However, certain occurrences of secondary uranium minerals, chiefly those of the uranite group, on the Seward Peninsula, in the Russian Mountains, and in the vicinity of Kodiak suggest that pitchblende-type ores may occur at depth beneath zones of alteration. Thorite-bearing veins have been discovered on Prince of Wales Island in southeastern Alaska. Although no deposits or carnotite-type minerals have been found in Alaska, several samples containing such minerals have been submitted by Alaskan prospectors. Efforts to locate the deposits from which these minerals were obtained have been unsuccessful, but review of available geologic data suggests that several Alaskan areas are potentially favorable for carnotite-type deposits. The chief of these areas is the Alaska Peninsula-Cook Inlet area which encompasses most of the reported occurrences of the prospectors' carnotite-type samples. Alaska is also potentially favorable for the occurrence of large bodies of the very low-grade uraniferous sedimentary rocks, such as phosphorites and black shales. This type of deposit, however, has not received much study because of the emphasis on the search for bonanza-type high-grade ores. Uraniferous phosphorites similar to those of Idaho, Montana, and Wyoming occur in northern Alaska on the north flank of the Brooks Range; black shales comparable to the uraniferous shales of the Chattanooga formation of southeastern United States have been noted along the Yukon River near the international boundary. Placer deposits in Alaska have some small potential for the production of the radioactive elements as byproducts of gold- and tin-placer mining. the placer area believed to have the relatively greatest potential in Alaska lies in the Kahiltna River valley where concentrates are known to contain such commercial minerals as ilmenite, cassiterite, platinum, and gold in addition to uranothorianite and monazite. The possibilities of the natural fluids--water and petroleum--have not yet been tested in Alaska to any great extent. Studies of fluids are in progress to determine whether they may be used to discover and define areas potentially favorable for the occurrence of uraniferous lodes.

Annotated checklist and fisheries interactions of cetaceans in Togo, with evidence of Antarctic minke whale in the Gulf of Guinea.

PubMed

Segniagbeto, Gabriel H; VAN Waerebeek, Koen; Bowessidjaou, Joseph E; Ketoh, Koffivi; Kpatcha, Takouda K; Okoumassou, Kotchikpa; Ahoedo, Kossi

2014-01-01

Based on strandings and captures, 9 cetacean species, including 6 odontocetes and 3 mysticetes, are documented (photos and specimens) in Togo's coastal waters (newly-recorded species marked with an asterisk): Antarctic minke whale (Balaenoptera bonaerensis*), Bryde's whale (Balaenoptera brydei or B. edeni), humpback whale (Megaptera novaeangliae), sperm whale (Physeter macrocephalus), pygmy sperm whale (Kogia breviceps*), short-finned pilot whale (Globicephala macrorhynchus*), pantropical spotted dolphin (Stenella attenuata*), common bottlenose dolphin (Tursiops truncatus) and common dolphin Delphinus sp. An anecdotal sighting record for killer whale (Orcinus orca) is considered reliable. The lack of Sousa teuszii records in Togo is consistent with its apparent contemporaneous absence in Ghana. The B. bonaerensis specimen, entangled in a purse seine set on small pelagics, is a first record for the Gulf of Guinea. The occurrence of this Southern Ocean species north of the equator underscores the severe gaps in our understanding of cetacean distribution off western Africa. The majority of artisanal fishermen operating in Togolese coastal waters are of Ghanaian origin and are thought to promote trade and consumption of cetacean bushmeat. Because captures are illegal, enforced with some success in the main fishing centers, covert landings of cetaceans are exceedingly difficult to monitor, quantify or sample. Concern is expressed about pollution of Togo's coastal waters with heavy metals due to phosphorite mining and export from the coastal basin near Hahotoé and Kpogamé. © 2012 Wiley Publishing Asia Pty Ltd, ISZS and IOZ/CAS.

Ferromanganese deposits from the Gulf of Alaska seamount province: mineralogy, chemistry, and origin.

USGS Publications Warehouse

Koski, R.A.

1988-01-01

Petrographic and chemical data presented and discussed permit the following conclusions regarding the high-latitude Gulf of Alaska (GA) Fe-Mn deposits: 1) thick (10-50 mm) Fe-Mn crusts form on alkali-basalt and volcaniclastic substrates by hydrogenetic processes, contain delta -MnO2 as the principal Mn phase, and have compositions similar to those of seamount crusts from comparable depths in the Hawaiian archipelago. GA crusts have higher Mn/Fe and lower Co contents than crusts from low-altitude, central Pacific seamounts; 2) thin (<10 mm) crusts on tuffaceous conglomerate, sandstone and phosphorite have a high proportion of crystalline Mn oxides and are genetically related to vein deposits; 3) vein deposits of todorokite and cryptomelane form during low-T oxidative diagenesis of volcanogenic sediment. Mn and other transition metals are supplied during the initial palagonitization of basaltic glass. The oxidation of Fe2+ to Fe3+ in palagonite and the dissolution of the diluted microfossil fraction of the sediment lower the Eh of the ambient pore fluid and enhance the solubility of Mn2+. The K released during the formation of palagonite may be redeposited in secondary phyllosilicate minerals, phillipsite, todorokite and cryptomelane; 4) the vein deposits formed soon after the deposition of sediment derived from the erosion and mass wasting of Mill Seamount but before crust deposition. Therefore, the deposition of hydrogenous crusts and the deposition of diagenetic veins are chemically distinct processes in time and space.-J.M.H.

Precambrian animal life: probable developmental and adult cnidarian forms from Southwest China

NASA Technical Reports Server (NTRS)

Chen, Jun-Yuan; Oliveri, Paola; Gao, Feng; Dornbos, Stephen Q.; Li, Chia-Wei; Bottjer, David J.; Davidson, Eric H.

2002-01-01

The evolutionary divergence of cnidarian and bilaterian lineages from their remote metazoan ancestor occurred at an unknown depth in time before the Cambrian, since crown group representatives of each are found in Lower Cambrian fossil assemblages. We report here a variety of putative embryonic, larval, and adult microfossils deriving from Precambrian phosphorite deposits of Southwest China, which may predate the Cambrian radiation by 25-45 million years. These are most probably of cnidarian affinity. Large numbers of fossilized early planula-like larvae were observed under the microscope in sections. Though several forms are represented, the majority display remarkable conformity, which is inconsistent with the alternative that they are artifactual mineral inclusions. Some of these fossils are preserved in such high resolution that individual cells can be discerned. We confirm in detail an earlier report of the presence in the same deposits of tabulates, an extinct crown group anthozoan form. Other sections reveal structures that most closely resemble sections of basal modern corals. A large number of fossils similar to modern hydrozoan gastrulae were also observed. These again displayed great morphological consistency. Though only a single example is available, a microscopic animal remarkably similar to a modern adult hydrozoan is also presented. Taken together, the new observations reported in this paper indicate the existence of a diverse and already differentiated cnidarian fauna, long before the Cambrian evolutionary event. It follows that at least stem group bilaterians must also have been present at this time.

An upwelling model for the Phosphoria sea: A Permian, ocean-margin sea in the northwest United States

USGS Publications Warehouse

Piper, D.Z.; Link, P.K.

2002-01-01

The Permian Phosphoria Formation, a petroleum source rock and world-class phosphate deposit, was deposited in an epicratonic successor basin on the western margin of North America. We calculate the seawater circulation in the basin during deposition of the lower ore zone in the Meade Peak Member from the accumulation rates of carbonate fluorapatite and trace elements. The model gives the exchange rate of water between the Phosphoria sea and the open ocean to the west in terms of an upwelling rate (84 m yr-1) and residence time (4.2 yr) of seawater in the basin. These hydrographic properties supported a mean rate of primary productivity of 0.87 g m-2 d-1 of carbon in the uppermost few tens of meters of the water column (the photic zone) and denitrifying redox conditions in the bottom water (below approximately 150 m depth). High rain rates, onto the sea floor, of the organic matter that hosted the phosphate and several trace elements contributed to the accumulation of phosphorite, chert, and black shales and mudstones. Evaporation in the Goose Egg basin to the east of the Phosphoria basin ensured the import of surface seawater from the Phosphoria sea. Budgets of water, salt, phosphate, and oxygen, plus the minor accumulation of the biomarker gammacerane, show that exchange of water between the two basins was limited, possibly by the shallow carbonate platform that separated the two basins.

A preliminary evaluation of the nonfuel mineral potential of Somalia

USGS Publications Warehouse

Greenwood, W.R.

1982-01-01

Additional exploration in Somalia is warranted for a wide variety of metallic and nonmetallic deposits. In Precambrian rocks, deposit types favorable for exploration include: a banded iron formation; platinum-bearing mafic-ultramafic complexes; tin-bearing quartz veins; phosphorite; stratabound base-metal deposits; uranium associated with Precambrian(?) syenite; apatite, molybdenum, and alumina in alkalic rocks; Jurassic and Cretaceous black shales; possible bedded-barite and massive base- and precious-metal sulfide deposits; vein barite in Tertiary rocks in fault zones; sepiolite and bentonite for drilling muds and other industrial uses; celestite; possible Tertiary zeolite; and uranium deposits. Several of these deposit types could be Jointly developed and integrated into domestic industries; for example, phosphate and gypsum, or bentonite for pelletized iron from the banded iron deposits. Other deposits such as barite and sepiolite are of value because of their proximity to major drilling operations in the Arabian Gulf. Still other deposits, such as alumina and banded iron, might be marketable because of proximity to aluminum and iron-refining industries now being constructed in Saudi Arabia. Some deposits, such as celestite, can be developed with little capital investment; others, such as the iron deposits, would require large capital commitments. Exploration and evaluation for many of these deposits can be accomplished by Somali geologists with a few advisors. Most of the deposits require feasibility studies conducted by teams of economic geologists, extractive metallurgists, and economists. Some marginal deposits could be exploited if cooperative development schemes could be negotiated with governments in nearby countries.

Jurassic-Cretaceous paleogeography, paleoclimate and upwelling of the northern margin of Tethys

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

Golonka, J.; Krobicki, M.

The Jurassic and Cretaceous global paleogeographic reconstructions illustrate the changing configuration of mountains, land, shallow seas and deep ocean basins. Active plate boundaries, such as spreading centers and subduction zones, are also shown. The Pliensbachian, Toarcian, Bathonian, Oxfordian-Kimmeridgian, Tithonian-Berriasian, Valanginian, Albian, Turonian and Maastrichtian maps were generated The outlines of paleogeography are used as input for paleoclimatic modeling. The PALEOCLIMATE program models global atmospheric pressure, derive paleo-wind directions and estimate the likelihood of coastal upwelling. The program is based on the paleoclimatic methods first developed by Judith Parrish, adopted by C. R. Scotese and modified by M. I. Ross. Themore » maps depict air pressure, wind directions, humid zones and areas favorable for upwelling conditions plotted on the paleogeographic background. Paleoclimate modeling suggests that prevailing Jurassic-Cretaceous wind directions in the northern Tethys area were from north-northeast. These winds were parallel to the axis of Czorsztyn ridge. The ridge was uplifted between Magura and Pieniny basins as the result of extension during Jurassic supercontinent breakup. The upwelling may have been induced at the southeastern margin of the ridge. The model is consistent with rock records, especially from the upper part of ammonitico rosso type Czorsztyn formation. Mass occurrence of Tithonian and Berriasian brachiopods was probably controlled by upwelling-induced trophic relationships which is resulted in the intense growth of benthic organisms on the ridge. This is additionally supported by the presence of phosphorites at localities which corresponded to the continental shelf/slope transition.« less

Carbon emissions and resources use by Chinese economy 2007: A 135-sector inventory and input-output embodiment

NASA Astrophysics Data System (ADS)

Chen, G. Q.; Chen, Z. M.

2010-11-01

A 135-sector inventory and embodiment analysis for carbon emissions and resources use by Chinese economy 2007 is presented in this paper by an ecological input-output modeling based on the physical entry scheme. Included emissions and resources belong to six categories as: (1) greenhouse gas (GHG) in terms of CO 2, CH 4, and N 2O; (2) energy in terms of coal, crude oil, natural gas, hydropower, nuclear power, and firewood; (3) water in terms of freshwater; (4) exergy in terms of coal, crude oil, natural gas, grain, bean, tuber, cotton, peanut, rapeseed, sesame, jute, sugarcane, sugar beet, tobacco, silkworm feed, tea, fruits, vegetables, wood, bamboo, pulp, meat, egg, milk, wool, aquatic products, iron ore, copper ore, bauxite, lead ore, zinc ore, pyrite, phosphorite, gypsum, cement, nuclear fuel, and hydropower; (5) and (6) solar and cosmic emergies in terms of sunlight, wind power, deep earth heat, chemical power of rain, geopotential power of rain, chemical power of stream, geopotential power of stream, wave power, geothermal power, tide power, topsoil loss, coal, crude oil, natural gas, ferrous metal ore, non-ferrous metal ore, non-metal ore, cement, and nuclear fuel. Accounted based on the embodied intensities are carbon emissions and resources use embodied in the final use as rural consumption, urban consumption, government consumption, gross fixed capital formation, change in inventories, and export, as well as in the international trade balance. The resulted database is basic to environmental account of carbon emissions and resources use at various levels.

Paleoenvironmental signals and paleoclimatic condition of the Early Maastrichtian oil shales from Central Eastern Desert, Egypt

NASA Astrophysics Data System (ADS)

Fathy, Douaa; Wagreich, Michael; Zaki, Rafat; Mohamed, Ramadan S. A.

2016-04-01

Early Maastrichtian oil shales are hosted in the Duwi Formation of the Central Eastern Desert, Egypt. The examined member represents up to 20% of the total Duwi Formation. This interval is mainly composed of siliciclastic facies, phosphorites facies and carbonate facies. Oil shales microfacies is mainly composed of smectite, kaolinite, calcite, fluorapatite, quartz and pyrite. They are enriched in a number of major elements and trace metals in particular Ca, P, V, Ni, Cr, Sr, Zn, Mo, Nb, U and Y compared to the post-Archaean Australian shale (PAAS). Chondrite-normalized REEs patterns of oil shales for the studied area display light rare earth elements enrichment relatively to heavy rare earth elements with negative Ce/Ce* and Eu/Eu* anomalies. The most remarkable indicators for redox conditions are enrichments of V, Mo, Ni, Cr, U content and depletion of Mn content. Besides, V/V+Ni, V/Ni, U/Th, Ni/Co, authigentic uranium ratios with presence of framboidal shape of pyrite and its size are reflecting the deposition of these shales under marine anoxic to euxinic environmental conditions. Additionally, the ratio of Strontium (Sr) to Barium (Ba) Sr/Ba reflected highly saline water during deposition. Elemental ratios critical to paleoclimate and paleoweathering (Rb /Sr, Al2O3/TiO2), CIA values, binary diagram between (Al2O3+K2O+Na2O) and SiO2 and types of clay minerals dominated reflect warm to humid climate conditions prevailing during the accumulation of these organic-rich petroleum source rocks.

Wet separation processes as method to separate limestone and oil shale

NASA Astrophysics Data System (ADS)

Nurme, Martin; Karu, Veiko

2015-04-01

Biggest oil shale industry is located in Estonia. Oil shale usage is mainly for electricity generation, shale oil generation and cement production. All these processes need certain quality oil shale. Oil shale seam have interlayer limestone layers. To use oil shale in production, it is needed to separate oil shale and limestone. A key challenge is find separation process when we can get the best quality for all product types. In oil shale separation typically has been used heavy media separation process. There are tested also different types of separation processes before: wet separation, pneumatic separation. Now oil shale industry moves more to oil production and this needs innovation methods for separation to ensure fuel quality and the changes in quality. The pilot unit test with Allmineral ALLJIG have pointed out that the suitable new innovation way for oil shale separation can be wet separation with gravity, where material by pulsating water forming layers of grains according to their density and subsequently separates the heavy material (limestone) from the stratified material (oil shale)bed. Main aim of this research is to find the suitable separation process for oil shale, that the products have highest quality. The expected results can be used also for developing separation processes for phosphorite rock or all others, where traditional separation processes doesn't work property. This research is part of the study Sustainable and environmentally acceptable Oil shale mining No. 3.2.0501.11-0025 http://mi.ttu.ee/etp and the project B36 Extraction and processing of rock with selective methods - http://mi.ttu.ee/separation; http://mi.ttu.ee/miningwaste/

The geology of the Florida land-pebble phosphate deposits

USGS Publications Warehouse

Cathcart, J.B.; Blade, L.V.; Davidson, D.F.; Ketner, K.B.

1952-01-01

The land-pebble phosphate district is on the Gulf Coastal Plain of Florida. The phosphate deposits are in the Bone Valley formation, dated Pliocene by most writers. These strata overlie the Miocene Hawthorn formation and are overlain by consolidated sands 3 to 20 feet thick. The minable phosphate deposits, called “matrix” in the district, range from a featheredge to about 50 feet in thickness and consist of phosphatic pellets and nodules, quartz sand, and montmorillonitic clay in about equal proportions. Locally the matrix displays cross-bedding and horizontal laminations, but elsewhere it is structureless. The phosphorite particles, composed largely of carbonate-fluorapatite, range in diameter from less than 0.1 mm to about 60 cm and in P2O5 content from 30 to 36 percent. Coarse-pebble deposits, containing 30 to 34 percent P2O5 are found mainly on basement highs; and fine-pebble deposits, containing 32 to 36 percent P2O5 are, are found in basement lows. Deposits in the northern part of the field contain more phosphate particles and their P2O5 content is higher than those in the southern part. The upper part of the phosphatic strata is leached to an advanced degree and consists of quartz sand and clay-sized particules of pseudowavellite and wavellite. The leached zone ranges in thickness from a featheredge to 60 feet. The origin of the land-pebble deposits is incompletely known. Possible modes of origin are a residuum of Miocene age, or a reworked residuum of Pliocene or Quaternary age.

Ecosystem Services: a Framework for Environmental Management of the Deep Sea

NASA Astrophysics Data System (ADS)

Le, J. T.; Levin, L. A.; Carson, R. T.

2016-02-01

As demand for deep-sea resources rapidly expands in the food, energy, mineral, and pharmaceutical sectors, it has become increasingly clear that a regulatory structure for extracting these resources is not yet in place. There are jurisdictional gaps and a lack of regulatory consistency regarding what aspects of the deep sea need protection and what requirements might help guarantee that protection. Given the mining sector's intent to exploit seafloor massive sulphides, Mn nodules, cobalt crusts, and phosphorites in the coming years, there is an urgent need for deep-ocean environmental management. Here, we propose an ecosystem services-based framework to inform decisions and best practices regarding resource exploitation, and to guide baseline studies, preventative actions, monitoring, and remediation. With policy in early stages of development, an ecosystem services approach has the potential to serve as an overarching framework that takes protection of natural capital provided by the environment into account during the decision-making process. We show how an ecosystem services approach combined with economic tools, such as benefit transfer techniques, should help illuminate issues where there are direct conflicts among different industries, and between industry and conservation. We argue for baseline and monitoring measurements and metrics that inform about deep-sea ecosystem services that would be impaired by mining, and discuss ways to incorporate the value of those losses into decision making, mitigation measures, and ultimately product costs. This proposal is considered relative to current International Seabed Authority recommendations and contractor practices, and new actions are proposed. An ecosystem services-based understanding of how these systems work and their value to society can improve sustainability and stewardship of the deep ocean.

Origin of the anomalies in light and middle REE in sediments of an estuary affected by phosphogypsum wastes (south-western Spain).

PubMed

Borrego, J; López-González, N; Carro, B; Lozano-Soria, O

2004-12-01

Sc, Y, Th, Cu and rare earth elements (REE) concentrations have been analyzed in 14 samples of surface sediments and in two gravity cores by means of ICP-MS. Mean concentrations of Sc, Y and Th in surface sediments are 6.23, 4.76 and 16.30 ppm, respectively, lower than those present in the Upper Continental Crust (UCC). Cu concentration in these sediments is very high, 1466 ppm, and is caused by inputs from the Odiel and Tinto rivers, affected by acid mine drainage. SigmaREE mean concentration is 106.8 ppm, lower than that observed in other rivers and estuaries. In the cores, Sc, Y and Th concentrations show a significant increase in the intermediate levels, between 10 and 40 cm depth. The same pattern exists with Cu, where concentrations of 4440 ppm can be reached. Vertical evolution patterns for Sc, Y, Cu and heavy REE (HREE) are similar, and contrary to those shown by Th, light REE (LREE) and middle REE (MREE). Plots of North American Shale Composite (NASC)-normalized REE data of surface sediments show a slight depletion in REE concentrations. Most samples present with middle REE enrichment relative to light REE and heavy REE. Conversely, samples of the intermediate levels of the cores show significant enrichment of REE relative to NASC and high values in the (La/Gd)NASC and (La/Yb)NASC ratios. These anomalies in the fractionation patterns caused by enrichments in LREE and MREE concentrations is related to the presence of high concentrations of Th. They were generated by effluents from fertilizer factories between 1968 and 1998 which used phosphorite as source material.

Body temperatures of modern and extinct vertebrates from 13C-18O bond abundances in bioapatite

PubMed Central

Eagle, Robert A.; Schauble, Edwin A.; Tripati, Aradhna K.; Tütken, Thomas; Hulbert, Richard C.; Eiler, John M.

2010-01-01

The stable isotope compositions of biologically precipitated apatite in bone, teeth, and scales are widely used to obtain information on the diet, behavior, and physiology of extinct organisms and to reconstruct past climate. Here we report the application of a new type of geochemical measurement to bioapatite, a “clumped-isotope” paleothermometer, based on the thermodynamically driven preference for 13C and 18O to bond with each other within carbonate ions in the bioapatite crystal lattice. This effect is dependent on temperature but, unlike conventional stable isotope paleothermometers, is independent from the isotopic composition of water from which the mineral formed. We show that the abundance of 13C-18O bonds in the carbonate component of tooth bioapatite from modern specimens decreases with increasing body temperature of the animal, following a relationship between isotope “clumping” and temperature that is statistically indistinguishable from inorganic calcite. This result is in agreement with a theoretical model of isotopic ordering in carbonate ion groups in apatite and calcite. This thermometer constrains body temperatures of bioapatite-producing organisms with an accuracy of 1–2 °C. Analyses of fossilized tooth enamel of both Pleistocene and Miocene age yielded temperatures within error of those derived from similar modern taxa. Clumped-isotope analysis of bioapatite represents a new approach in the study of the thermophysiology of extinct species, allowing the first direct measurement of their body temperatures. It will also open new avenues in the study of paleoclimate, as the measurement of clumped isotopes in phosphorites and fossils has the potential to reconstruct environmental temperatures. PMID:20498092

Sedimentary condensation and authigenesis

NASA Astrophysics Data System (ADS)

Föllmi, Karl

2016-04-01

Most marine authigenic minerals form in sediments, which are subjected to condensation. Condensation processes lead to the formation of well individualized, extremely thin (< 1m) beds, which were accumulated during extremely long time periods (> 100ky), and which experienced authigenesis and the precipitation of glaucony, verdine, phosphate, iron and manganese oxyhydroxides, iron sulfide, carbonate and/or silica. They usually show complex internal stratigraphies, which result from an interplay of sediment accumulation, halts in sedimentation, sediment winnowing, erosion, reworking and bypass. They may include amalgamated faunas of different origin and age. Hardgrounds may be part of condensed beds and may embody strongly condensed beds by themselves. Sedimentary condensation is the result of a hydrodynamically active depositional regime, in which sediment accumulation, winnowing, erosion, reworking and bypass are processes, which alternate as a function of changes in the location and intensity of currents, and/or as the result of episodic high-energy events engendered by storms and gravity flow. Sedimentary condensation has been and still is a widespread phenomenon in past and present-day oceans. The present-day distribution of glaucony and verdine-rich sediments on shelves and upper slopes, phosphate-rich sediments and phosphorite on outer shelves and upper slopes, ferromanganese crusts on slopes, seamounts and submarine plateaus, and ferromanganese nodules on abyssal seafloors is a good indication of the importance of condensation processes today. In the past, we may add the occurrence of oolitic ironstone, carbonate hardgrounds, and eventually also silica layers in banded iron formations as indicators of the importance of condensation processes. Besides their economic value, condensed sediments are useful both as a carrier of geochemical proxies of paleoceanographic and paleoenvironmental change, as well as the product of episodes of paleoceanographic and paleoenvironmental change themselves.

Glacial-eustatic/climatic model for Upper Pennsylvanian marine and nonmarine cyclothems in the Appalachian basin

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

Heckel, P.H.

1992-01-01

Only glacial-eustatic sea-level fluctuations can account for all the characteristics of Upper Pennsylvanian marine cyclothems in the Midcontinent. Because this control is global, it must have affected deposition during this time everywhere. In the Appalachian basin widespread well developed paleosols represent long-term sea-level lowstand. During Conemaugh marine incursions, rising sea level ponded fresh-water influx to form peat swamps that migrated landward ahead of transgression and produced early transgressive coals. Marine highstand deposits commonly are conodont-rich limestones, typically skeletal packstone with glaucony and phosphorite. Regression resulted in progradation of detrital shorelines with local delta cycles, followed eventually by more paleosol formationmore » and local erosional incision that removed older sediments including the marine units in places. Fluvial sands filled many of these channels. During Monongahela deposition when marine incursions no longer entered the Appalachian basin, the climatic fluctuations recognized by Cecil can reasonably be related to sea-level fluctuations nearby, but with shifts in climatic significance of gross lithotopes. Coal swamps would more likely have formed at maximum marine highstand when the nearby sea would have provided both high base level and an abundant source of rainfall. Nonmarine limestones would more likely have formed at maximum lowstand when the sea was most distant and the climate driest. The intervening detrital deposits between the coals and limestones formed under intermediate seasonal rainfall regimes during both marine transgression and regression farther west in the Midcontinent. Conemaugh and Allegheny coals without overlying marine units probably also represent mainly marine highstand elsewhere, and nonmarine limestones of these ages typically are associated with lowstand paleosols.« less

Nutrient inputs into the Gulf of Finland: Trends and water protection targets

NASA Astrophysics Data System (ADS)

Knuuttila, Seppo; Räike, Antti; Ekholm, Petri; Kondratyev, Sergey

2017-07-01

The catchment area of the Gulf of Finland (GOF) is nearly 14 times larger than the sea area and is home to 12 million people. The GOF is thus heavily polluted by nutrients, and eutrophication is one of the major environmental concerns. The aim of this study was to estimate trends in the nutrient input and to evaluate whether current water protection targets (national, EU, HELCOM) will be achieved. We used both national and international (HELCOM) databases to evaluate nutrient inputs from the surrounding three countries (Estonia, Finland and Russia). The average nitrogen (N) input into the GOF was 112,000 t y- 1 for the period 2009-2013, with rivers responsible for 79%, direct point sources accounting for 10% and deposition for 11% of the input. Phosphorus (P) input was 4270 t y- 1, of which rivers were responsible for 88% and point sources for 12%. The largest proportions (61% for N and 73% for P) of the inputs came from Russia, despite the specific areal inputs (input divided by land area) being smaller than in Estonia and Finland. The changes in nutrient inputs into the GOF are largely due to the changes in Russian inputs, and in particular changes in the nutrient fluxes of the River Neva. The latest available flow-normalised data showed that N export decreased slightly from 1994 to 2010, while flow-normalised P export had clearly decreased by 2010. The P input ending up in the GOF as a whole has decreased significantly over the past 10 years as a result of the re-construction of wastewater treatment infrastructure in St Petersburg and following control of a P leak at the Phosphorit factory in 2012. This measure also explains the steep decrease in riverine P export during recent years. Further reduction of inputs to meet the ambitious nutrient reduction goals of HELCOM and of WFD seems to be a challenge for Finland and Estonia in particular. Russia appears to have already reached approximately 90% of the BSAP's reduction target, with fulfilment of the remainder of the P target appearing a fairly realistic aim as well.

Ordovician conodonts and stratigraphy of the ST. Peter sandstone and glen wood shale, central United States

USGS Publications Warehouse

Witzke, B.J.; Metzger, R.A.

2005-01-01

The age of the St. Peter Sandstone in the central and northern Midcontinent has long been considered equivocal because of the general absence of biostratigraphically useful fossils. Conodonts recovered from the St. Peter Sandstone in Iowa, Minnesota, Nebraska, and Kansas for this study help place some age constraints on this renowned formation in its northern and western extent. Faunas from the lower St. Peter include Phragmodus flexuosus, Cahabagnathus sp., and Leptochirognathus sp., and a late Whiterockian (Chazyan) correlation is indicated. Juvenile or immature elements of P. flexuosus from these collections show morphologies trending toward P. cognitus and P. inflexus, and paedomorphic derivation of these latter species is proposed. Diverse assemblages of hyaline forms also occur in the St. Peter strata (Erismodus spp., Erraticodon sp., Curtognathus sp., Coleodus sp., Archeognathus sp., Stereoconus sp., others) along with various albid elements (Plectodina sp., Eoplacognathus sp., others). The overlying Glenwood Shale contains abundant conodonts dominated by Phragmodus cognitus, Erismodus sp., and Chirognathus duodactylus, and the fauna is interpreted as an early Mohawkian (Blackriveran) association. Certain thin shale units in the St. Peter-Glenwood succession represent condensed intervals, in part reflected by their exceptionally high conodont abundances. Some organic-rich phosphatic shale units in the lower St. Peter of western Iowa have produced equivalent yields of tens of thousands of conodonts per kilogram, and many Glenwood Shale samples yield thousands of conodonts per kilogram. Previous depositional models have proposed that the St. Peter is primarily a succession of littoral and nearshore facies forming a broadly diachronous transgressive sheet sand. However, broad-scale diachroneity cannot be demonstrated with available biostratigraphic control. The recognition of condensed marine shale units, phosphorites, ironstones, and pyritic hardgrounds in the western facies tract of the St. Peter Sandstone has necessitated a re-evaluation of previous regional models of St. Peter deposition. The St. Peter is interpreted to be a composite stratigraphic interval deposited during a succession of transgressive-regressive sedimentary cycles. Transgressive episodes in some cycles were marked by offshore sediment condensation or starvation within a stratified seaway.

Rare-earth leaching from Florida phosphate rock in wet-process phosphoric acid production

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

Liang, Haijun; Zhang, Patrick; Jin, Zhen

Phosphorite, or phosphate rock, is the most significant secondary rare-earth resource. It contains high amounts of phosphate-bearing minerals along with low contents of rare earth elements (REEs). In Florida, about 19 Mt of phosphate rock are mined annually and most are used to manufacture fertilizers using a wet process, in which sulfuric acid reacts with phosphates to produce phosphoric acid and phosphogypsum. In the wet process, REEs are also leached out into solution and eventually get lost in the leaching residue and phosphate fertilizer. Recovering REEs from Florida phosphate rock in the wet process will be beneficial to broadening rare-earthmore » availability, improving the quality of phosphoric acid product and protecting the environment. Here, this study focuses on the influences of wet-process operating conditions on REE leaching efficiency. The results indicate that REE leaching efficiency increases with phosphoric acid addition in the initial pulp. At a temperature of 75 °C, a stoichiometric ratio of sulfuric acid (H2 SO4 ) to calcium oxide (CaO) of 1.05 and a weight ratio of liquid to solid of 3.5, REE leaching efficiency reached a relatively high value of 52.82 percent. The trends of REE leaching efficiency were similar to those for phosphoric acid (P2O5 ). Extensive tests on the leaching residue showed that during leaching, about 90 percent of the REEs were released from the phosphate rock but only 52.82 percent ended up in the leaching solution. This phenomenon can be attributed to two factors: (1) the effect of phosphate ions (PO43-) in the solution, which caused REE ions to form REE phosphates and be precipitated into the leaching residue, and (2) the influence of large amounts of anions such as sulfate (SO42-), dihydrogen phosphate (H2 PO4-) and hydrogen phosphate (HPO42-) anions as well as the polar molecule H3 PO4 , which surrounded the REE cations and formed an ion atmosphere that prevented the PO43- from contacting and combining with REE cations. Finally, interaction of these two opposite effects determined the REE distribution between leaching solution and residue.« less

Geochemistry of Permian rocks from the margins of the Phosphoria Basin

USGS Publications Warehouse

Perkins, Robert B.; McIntyre, Brandie; Hein, James R.; Piper, David Z.

2003-01-01

The Permian Phosphoria Formation and interbedded units of the Park City Formation and Shedhorn Sandstone in western Wyoming represent deposition along a carbonate ramp at the eastern margin of the Phosphoria Basin, with portions of the Phosphoria units reflecting periods of upwelling and widespread phosphogenesis. Thickness-weighted slab-samples of these units were collected at a maximum interval of 3 m along an 80+ m-length of unweathered core and analyzed for major-, minor-, and trace-element contents. Interpretations of geochemistry were made within the confines of a previously recognized sequence stratigraphy framework. Major shifts in element ratios characteristic of terrigenous debris that occur at sequence boundaries at the base of the Meade Peak and Retort Members of the Phosphoria Formation are attributed to changing sediment sources. Inter-element relationships in the marine fraction indicate that bottom waters of the Phosphoria Basin were predominantly denitrifying during deposition of the Ervay, Grandeur, and Phosphoria sediments, although sulfate-reducing conditions may have existed during deposition of the lower Meade Peak sediments. Oxic conditions were prevalent during deposition of a large part of the Franson Member, which represents sedimentation in a shallow, inner- to back-ramp setting. Variations in sediment facies and organic matter and trace element contents largely reflect changes in Permian sea level. Changes in sea level in basin-margin areas, such as represented by the study section, may have affected the oxidation of settling organic matter, the foci of intersection of upwelling bottom waters with the photic zone, the rate of terrigenous sedimentation, and, ultimately, the overall environment of deposition. Our study suggests that phosphogenesis can occur under lowstand, transgressive, and highstand conditions in marginal areas, assuming water depths sufficient for upwelling to occur. Formation of phosphorite layers under upwelling conditions appears to have been most dependent on a lack of dilution by terrigenous sedimentation and carbonate shoaling. Differences in the geochemistry between two similar environments represented by the upper and lower Phosphoria units are largely attributed to higher rates of diluting terrigenous sediment during deposition of the upper unit. This is consistent with prior interpretations of a more shoreward setting for the upper Phosphoria.

A modern vs. Permian black shale - the hydrography, primary productivity, and water-column chemistry of deposition

USGS Publications Warehouse

Piper, D.Z.; Perkins, R.B.

2004-01-01

The sediment currently accumulating in the Cariaco Basin, on the continental shelf of Venezuela, has an elevated organic-carbon content of approximately 5%; is accumulating under O2-depleted bottom-water conditions (SO42- reduction); is composed dominantly of foraminiferal calcite, diatomaceous silica, clay, and silt; and is dark greenish gray in color. Upon lithification, it will become a black shale. Recent studies have established the hydrography of the basin and the level of primary productivity and bottom-water redox conditions. These properties are used to model accumulation rates of Cd, Cr, Cu, Mo, Ni, V, and Zn on the seafloor. The model rates agree closely with measured rates for the uppermost surface sediment.The model is applied to the Meade Peak Phosphatic Shale Member of the Phosphoria Formation, a phosphate deposit of Permian age in the northwest United States. It too has all of the requisite properties of a black shale. Although the deposit is a world-class phosphorite, it is composed mostly of phosphatic mudstone and siltstone, chert, limestone, and dolomite. It has organic-carbon concentrations of up to 15%, is strongly enriched in several trace elements above a terrigenous contribution and is black. The trace-element accumulation defines a mean primary productivity in the photic zone of the Phosphoria Basin as moderate, at 500 g m-2 year-1 organic carbon, comparable to primary productivity in the Cariaco Basin. The source of nutrient-enriched water that was imported into the Phosphoria Basin, upwelled into the photic zone, and supported primary productivity was an O2 minimum zone of the open ocean. The depth range over which the water was imported would have been between approximately 100 and 600 m. The mean residence time of bottom water in the basin was approximately 4 years vs. 100 years in the Cariaco Basin. The bottom water was O2 depleted, but it was denitrifying, or NO3- reducing, rather than SO42- reducing. Published by Elsevier B.V.

Paleoenvironmental conditions and strontium isotope stratigraphy in the Paleogene Gafsa Basin (Tunisia) deduced from geochemical analyses of phosphatic fossils

NASA Astrophysics Data System (ADS)

Kocsis, László; Ounis, Anouar; Chaabani, Fredj; Salah, Neili Mohamed

2013-06-01

Fossil shark teeth and coprolites from three major phosphorite occurrences in the Gafsa Basin (southwestern Tunisia) were investigated for their geochemical compositions to improve local stratigraphy and to better assess paleoenvironmental conditions. 87Sr/86Sr isotope ratios of shark teeth from the Early Maastrichtian El Haria Formation and from the Early Eocene Métlaoui s.s. Formation yielded Sr isotope ages of 68 ± 1 and 47.9 ± 1.3 Ma, respectively, which accord with the expected stratigraphic positions of these sediments. Conversely, shark teeth from the Paleocene-Eocene Chouabine Formation have large variation in Sr isotope ratios even within individual layers. After statistical treatment and then elimination of certain outlier samples, three age-models are proposed and discussed. The most reasonable solution includes three subsequent Sr ages of 61.8 ± 2.2 Ma, 57.2 ± 1.8 and 54.6 ± 1.6 for layer IX, layers VIII-V and layers IV-0, respectively. Three scenarios are discussed for explanation of the presence of the outliers: (1) diagenesis, (2) re-working and (3) locally controlled seawater Sr isotope ratio. The most plausible account for the higher 87Sr/86Sr ratios relative to the global ocean in some fossils is enhanced intrabasinal re-working due to low sea level. Conversely, the sample with lower 87Sr/86Sr than the global seawater may link to diagenesis or to seawater influenced by weathering of Late Cretaceous marine carbonates, which latter is supported by model calculation as well. The ɛNd values of these fossils are very similar to those reported for Paleogene and Late Cretaceous Tethyan seawater and are compatible with the above interpretations. The relatively low oxygen isotope values in shark teeth from the topmost phosphate bed of the Chouabine Formation, together with the Sr isotope results, point toward recovering better connections with the open sea. These δ18O data reflect elevated ambient temperature, which may link to the Early Eocene Climatic Optimum.

Environmental significance of Upper Miocene phosphorites at hominid sites in the Lukeino Formation (Tugen Hills, Kenya)

NASA Astrophysics Data System (ADS)

Dericquebourg, Perrine; Person, Alain; Ségalen, Loïc; Pickford, Martin; Senut, Brigitte; Fagel, Nathalie

2015-08-01

The Lukeino Formation contains an important sedimentary and fossiliferous record of the late Miocene (6.09-5.68 Ma), which has in particular yielded the fossil remains of the oldest East African bipedal hominid called Orrorin tugenensis. This fluvio-lacustrine sedimentary succession crops out in the Kenyan part of the East African Rift. It is mainly composed of clay to sandy clay deposits intercalated with volcanic ash horizons, and localized layers of carbonates and diatomites. A detailed sedimentological and mineralogical study of the Lukeino Formation was conducted to throw light on the environmental conditions in which the hominids lived. Several centimetric, relatively continuous and indurated phosphatic horizons, of sedimentary origin, were identified at two sites (Sunbarua and Kapcheberek). Mineralogical (XRD) and geochemical analyses as well as observations by SEM, which was coupled with an energy dispersive spectroscopy (EDS) microprobe, indicate that the autochthonous phosphate layers are composed of a micritic matrix of francolite (38-93%), with incorporation of silicates in variable proportions from one layer to another. The phosphate matrix contains very well preserved and abundant diatom frustules in the basal phosphate layer. These diatoms are identified as Aulacoseira granulata, implying a pH of 7.8-8.2 for freshwaters of the Palaeolake Lukeino. Calcitic tubular structures, linked to a possible bacterial origin, are also observed locally. Phosphate layers occur abruptly within a thick clay-sandy series, associated with an intense runoff phase during the deposition of this interval of the Lukeino Formation. The massive and cyclic input of phosphorus to the lake promoted productivity to the stage where it caused a diatom bloom. The establishment of several phosphate horizons testifies to successive phases of eutrophication of Palaeolake Lukeino. The diatom cells provided some of the organic matter, which was decomposed by bacterial activity at the bottom of the lake in suboxic conditions, but in insufficient quantities to fully form the phosphatic materials. The rest of the organic matter needed for phosphogenesis came from terrigenous supply (plant debris), suggesting the presence of dense vegetation in the catchment of the Palaeolake Lukeino, during this well-drained interval of deposition of the Lukeino Formation.

Rare-earth leaching from Florida phosphate rock in wet-process phosphoric acid production

DOE PAGES

Liang, Haijun; Zhang, Patrick; Jin, Zhen; ...

2017-08-01

Phosphorite, or phosphate rock, is the most significant secondary rare-earth resource. It contains high amounts of phosphate-bearing minerals along with low contents of rare earth elements (REEs). In Florida, about 19 Mt of phosphate rock are mined annually and most are used to manufacture fertilizers using a wet process, in which sulfuric acid reacts with phosphates to produce phosphoric acid and phosphogypsum. In the wet process, REEs are also leached out into solution and eventually get lost in the leaching residue and phosphate fertilizer. Recovering REEs from Florida phosphate rock in the wet process will be beneficial to broadening rare-earthmore » availability, improving the quality of phosphoric acid product and protecting the environment. Here, this study focuses on the influences of wet-process operating conditions on REE leaching efficiency. The results indicate that REE leaching efficiency increases with phosphoric acid addition in the initial pulp. At a temperature of 75 °C, a stoichiometric ratio of sulfuric acid (H2 SO4 ) to calcium oxide (CaO) of 1.05 and a weight ratio of liquid to solid of 3.5, REE leaching efficiency reached a relatively high value of 52.82 percent. The trends of REE leaching efficiency were similar to those for phosphoric acid (P2O5 ). Extensive tests on the leaching residue showed that during leaching, about 90 percent of the REEs were released from the phosphate rock but only 52.82 percent ended up in the leaching solution. This phenomenon can be attributed to two factors: (1) the effect of phosphate ions (PO43-) in the solution, which caused REE ions to form REE phosphates and be precipitated into the leaching residue, and (2) the influence of large amounts of anions such as sulfate (SO42-), dihydrogen phosphate (H2 PO4-) and hydrogen phosphate (HPO42-) anions as well as the polar molecule H3 PO4 , which surrounded the REE cations and formed an ion atmosphere that prevented the PO43- from contacting and combining with REE cations. Finally, interaction of these two opposite effects determined the REE distribution between leaching solution and residue.« less

Manganese and ferromanganese ores from different tectonic settings in the NW Himalayas, Pakistan

NASA Astrophysics Data System (ADS)

Tahir Shah, Mohammad; Moon, Charles J.

2007-02-01

In Pakistan manganese and ferromanganese ores have been reported from the Hazara area of North West Frontier Province, Waziristan agencies in the Federally Administered Tribal Areas and the Lasbela-Khuzdar regions of Baluchistan. This study is focused on comparison of mineralogy and geochemistry of the continental ferromanganese ores of Hazara and the ophiolitic manganese ores of the Waziristan area of Pakistan. In the Hazara area, ferromanganese ores occur at Kakul, Galdanian and Chura Gali, near Abbottabad, within the Hazira Formation of the Kalachitta-Margala thrust belt of the NW Himalayas of the Indo-Pakistan Plate. The Cambrian Hazira Formation is composed of reddish-brown ferruginous siltstone, with variable amounts of clay, shale, ferromanganese ores, phosphorite and barite. In Waziristan, manganese ores occur at Shuidar, Mohammad Khel and Saidgi, within the Waziristan ophiolite complex, on the western margin of the Indo-Pakistan Plate in NW Pakistan. These banded and massive ores are hosted by metachert and overlie metavolcanics. The ferromanganese ores of the Hazara area contain variable amount of bixbyite, partridgeite, hollandite, pyrolusite and braunite. Bixbyite and partridgeite are the dominant Mn-bearing phases. Hematite dominates in Fe-rich ores. Gangue minerals are iron-rich clay, alumino-phosphate minerals, apatite, barite and glauconite are present in variable amounts, in both Fe-rich and Mn-rich varieties. The texture of the ore phases indicates greenschist facies metamorphism. The Waziristan ores are composed of braunite, with minor pyrolusite and hollandite. Hematite occurs as an additional minor phase in the Fe-rich ores of the Shuidar area. The only silicate phase in these ores is cryptocrystalline quartz. The chemical composition of the ferromanganese ores in Hazara suggests that the Mn-Fe was contributed by both hydrogenous and hydrothermal sources, while the manganese ores of Waziristan originated only from a hydrothermal source. It is suggested that the Fe-Mn ores of the Hazara area originated from a mixed hydrothermal-hydrogenetic source in shallow water in a ontinental shelf environment due to the transgression and regression of the sea, while the Mn ores of Waziristan were formed at sea-floor spreading centers within the Neo-Tethys Ocean, and were later obducted as part of the Waziristan ophiolite complex.

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

NASA Astrophysics Data System (ADS)

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

2013-12-01

At the northwest corner of Africa excellent conditions existed for phosphate formation (i.e., stable upwelling system) during the late Cretaceous-early Eocene. This is probably in relation to stable tectonic evolution of shallow epicontinental basins at a passive continental margin and to their paleogeographic situation between the Atlantic and Tethys marine realms. To better comprehend paleoceanic conditions in this area, radiogenic isotope ratios (87Sr/86Sr and 143Nd/144Nd) and trace element compositions of fossil biogenic apatite are investigated from Maastrichtian to Ypresian shallow marine phosphorite deposits in Morocco (Ouled Abdoun and Ganntour Basins). Rare earth elements (REE) distributions in the fossils are compatible with early diagenetic marine pore fluid represented by negative Ce-anomaly and heavy REE enrichment. An overall shift in Ce-anomaly is apparent with gradually lower values in younger fossils along three distinct assemblages that correspond to Maastrichtian, Danian-Thanetian and Ypresian periods. The temporal change can be interpreted as presence of gradually more oxygenated seawater in the basins. Strontium isotopic ratios of the fossils follow the global Sr-evolution curve. However, the latest Cretaceous and the oldest Paleocene fossils yielded slightly higher ratios than the global ocean, which could reflect minor diagenetic alteration. Neodymium isotopic ratios are quite even along the phosphate series with ɛNd(t) values ranges from -6.8 to -5.8. These values are higher than those reported for average North Atlantic deep water and Tethyan seawater (e.g., Stille et al., 1996; Thomas et al., 2003). For the origin of the stable, high 143Nd/144Nd we propose three main hypotheses: (1) contribution of continental Nd-source, (2) locally controlled deep water Nd-isotope ratios near the coast from where upwelling originated in the area and (3) possible surface marine water contribution from the Pacific across the Atlantic. Stille, P., Steinmann, M., Riggs, R.S., 1996. Nd isotope evidence for the evolution of the paleocurrents in the Atlantic and Tethys Oceans during the past 180 Ma. Earth Planet. Sci. Lett. 144, 9-19. Thomas, J.D., Bralower, T.J., Jones, E.C., 2003. Neodymium isotopic reconstruction of late Paleocene-early Eocene thermohaline circulation. Earth Planet. Sci. Lett. 209, 309-322.

Geochemistry of Peruvian near-surface sediments

NASA Astrophysics Data System (ADS)

Böning, Philipp; Brumsack, Hans-Jürgen; Böttcher, Michael E.; Schnetger, Bernhard; Kriete, Cornelia; Kallmeyer, Jens; Borchers, Sven Lars

2004-11-01

Sixteen short sediment cores were recovered from the upper edge (UEO), within (WO) and below (BO) the oxygen minimum zone (OMZ) off Peru during cruise 147 of R/V Sonne. Solids were analyzed for major/trace elements, total organic carbon, total inorganic carbon, total sulfur, the stable sulfur isotope composition (δ 34S) of pyrite, and sulfate reduction rates (SRR). Pore waters were analyzed for dissolved sulfate/sulfide and δ 34S of sulfate. In all cores highest SRR were observed in the top 5 cm where pore water sulfate concentrations varied little due to resupply of sulfate by sulfide oxidation and/or diffusion of sulfate from bottom water. δ 34S of dissolved sulfate showed only minor downcore increases. Strong 32S enrichments in sedimentary pyrite (to -48‰ vs. V-CDT) are due to processes in the oxidative part of the sulfur cycle in addition to sulfate reduction. Manganese and Co are significantly depleted in Peruvian upwelling sediments most likely due to mobilization from particles settling through the OMZ, whereas release of both elements from reducing sediments only seems to occur in near-coastal sites. Cadmium, Mo and Re are exceptionally enriched in WO sediments (<600 m water depth). High Re and moderate Cd and Mo enrichments are seen in BO sediments (>600 m water depth). Re/Mo ratios indicate anoxic and suboxic conditions for WO and BO sediments, respectively. Cadmium and Mo downcore profiles suggest considerable contribution to UEO/WO sediments by a biodetrital phase, whereas Re presumably accumulates via diffusion across the sediment-water interface to precipitation depth. Uranium is distinctly enriched in WO sediments (due to sulfidic conditions) and in some BO sediments (due to phosphorites). Silver transfer to suboxic BO sediments is likely governed by diatomaceous matter input, whereas in anoxic WO sediments Ag is presumably trapped due to sulfide precipitation. Cadmium, Cu, Zn, Ni, Cr, Ag, and T1 predominantly accumulate via biogenic pre-concentration in plankton remains. Rhenium, Sb, As, V, U and Mo are enriched in accordance with seawater TE availability. Lead and Bi enrichment in UEO surface sediments is likely contributed by anthropogenic activity (mining). Accumulation rates of TOC, Cd, Mo, U, and V from Peruvian and Namibian sediments exceed those from the Oman Margin and Gulf of California due to enhanced preservation off Peru and Namibia.

Fluorine

USGS Publications Warehouse

Hayes, Timothy S.; Miller, M. Michael; Orris, Greta J.; Piatak, Nadine M.; Schulz, Klaus J.; DeYoung,, John H.; Seal, Robert R.; Bradley, Dwight C.

2017-12-19

Fluorine compounds are essential in numerous chemical and manufacturing processes. Fluorspar is the commercial name for fluorite (isometric CaF2), which is the only fluorine mineral that is mined on a large scale. Fluorspar is used directly as a fluxing material and as an additive in different manufacturing processes. It is the source of fluorine in the production of hydrogen fluoride or hydrofluoric acid, which is used as the feedstock for numerous organic and inorganic chemical compounds.The United States was the world’s leading producer of fluorspar until the mid-1950s. In the mid-1970s, the U.S. fluorspar mining industry began to decline because of foreign competition. By 1982, there was essentially only a single U.S. producer left, and that company ceased mining in 1996. Consumption of fluorspar in the United States peaked in the early 1970s, which was also the peak period of U.S. steel production. Since then, U.S. fluorspar consumption has decreased substantially; the United States has nonetheless increased its imports of downstream fluorine compounds, such as, in order of tonnage imported, hydrofluoric acid, aluminum fluoride, and cryolite. This combination of no U.S. production (until recently) and high levels of consumption has made the United States the world’s leading fluorspar-importing country, in all its various forms.The number of fluorspar-exporting countries has decreased substantially in recent decades, and, as a result, the United States has become dependent on just a few countries to supply its needs. In 2013, the United States imported the majority of its fluorspar from three countries, which were, in descending order of the amount imported, Mexico, China, and South Africa.Geologically, in igneous systems, fluorine is one of a number of elements that are “incompatible.” These incompatible elements become concentrated in the residual magma while the common silicates crystallize upon magma ascent and cooling, leading to relatively high fluorine concentrations in the more evolved or differentiated igneous rocks and in hydrothermal deposits associated with those evolved igneous rocks. In sedimentary rocks, fluorine’s highest concentrations are found in phosphorites because fluorine substitutes for hydroxyl ions in apatite, which leads to fluorine concentrations of, typically, from 2 to 4 weight percent in phosphorites. Because of the presence of fluorine, phosphate fertilizer manufacturers can produce a fluorosilicic acid byproduct. Most deposits mined for fluorine are hydrothermal, however, and consist of fluorine minerals that precipitated from hot water. Magmatic brines and brines from deep within sedimentary basins that have high concentrations of dissolved fluoride are the mineralizing fluids for various types of hydrothermal fluorspar deposits. Relatively dilute hydrothermal fluids that formed in some volcanic rocks can also transport sufficient fluoride to form a high-grade fluorspar deposit. Fluorite has low solubility in a common range of hydrothermal temperatures, particularly from about 160 degrees Celsius (°C) down to 60 °C. The increasing fluorite solubility below 60 °C partly explains why some water with exceptionally high levels of dissolved fluorine are found even at ambient temperatures in evaporitic lake basins in some East African Rift valleys in Kenya and Tanzania. The geologic conditions that led to the high concentrations there are known to exist in a number of other places in the world as well, including, perhaps, places in the Basin and Range province of the United States.Eight minerals or mineral groups have sufficient fluorine in their structures to be considered as possible ores of the element; they are bastnaesite (also spelled bastnäsite; and other fluorocarbonates), cryolite, sellaite, villiaumite, fluorite, fluorapatite (in phosphorites), various phyllosilicates, and topaz. Fluorite is currently the only mineral that is mined for fluorine, and nomineral except fluorite is likely to become a source of commercially produced fluorine as a primary product as long as supplies from relatively thick and high-grade fluorite deposits continue to be available.At least seven classes (which include one subclass) of hydrothermal fluorite deposits are recognized; they are classified according to their tectonic and (or) magmatic settings, as follows: (1) carbonatite-related fluorspar deposits; (2) alkaline-intrusion-related fluorspar deposits; (3) alkaline-volcanic-related epithermal fluorspar deposits; (4) Mississippi Valley-type fluorspar deposits (and a subclass of salt-related carbonate-hosted fluorspar deposits); (5) fluorspar deposits related to strongly differentiated granites; (6) subalkaline-volcanic-related epithermal fluospar deposits; and (7) fluorspar deposits that appear to be conformable within tuffaceous limy lacustrine sediments. An eighth class (not hydrothermal) is that of fluorspar deposits concentrated in soils and weathered zones; that is, residual fluorspar deposits. Generally, fluorspar deposits related to strongly differentiated granites have larger tonnages and lower grades than carbonatite-related fluorspar deposits, which, in turn, have larger tonnages and lower grades than fluorspar vein deposits from various other classes.The United States has a few identified resources of fluorspar, most notably the Klondike II property in the Illinois- Kentucky fluorspar district located about 8 kilometers southwest of Salem, Kentucky, which has a large vein that contains at least 1.6 million metric tons at a grade of 60 percent CaF2 (Feytis, 2009). Additional fluorspar resources of lower grade but larger tonnage have been identified at Hicks Dome in the Illinois-Kentucky fluorspar district and at Lost River near the western tip of the Seward Peninsula in Alaska, along with a couple of dozen smaller, higher grade resources.Internationally, new mines that either opened before the beginning of 2013 or were scheduled to open soon after that time include the Nui Phao tungsten-fluorspar-bismuth-copper-gold deposit in northern Vietnam; the St. Lawrence project in Newfoundland, Canada, which is located in a well-known fluorspar district; the Bamianshan deposit, which is related to a strongly differentiated granite in northwestern Zhejiang Province, China, near some of that Province’s large, subalkaline-volcanic-related epithermal veins; and the Nokeng project in South Africa, which is also related to a strongly differentiated granite. Other deposits in northwestern Australia, Nevada (United States), Norway, South Africa, and Sweden have been identified and could be put into production within just a few years.Among undiscovered resources, an interesting possibility might be to produce a fluorine product from evaporitic, high-fluorine, high-pH sodium-carbonate brines like Lake Magadi (Kenya) and Lake Natron (Tanzania) in Africa’s Eastern Rift Valley. In addition, apparently conformable fluorspar deposits in tuffaceous limy lacustrine sediments, such as those in Italy, are likely to occur in similar young alkalic volcanic settings elsewhere in the world.Modern geophysical and geochemical exploration techniques have typically not been brought to bear in exploration for new fluorspar deposits, although such techniques are likely to be used in future exploration. The tendency for fluorine to dissolve in significant concentrations in water at low temperature allows both surface water and groundwater to be used as sampling media in geochemical exploration. Evolved granite-related fluorspar deposits may be particularly susceptible to geophysical exploration methods because crystalline rocks that form a basement to sedimentary sections can be approximately defined with gravity and magnetic methods, and magnetite-bearing skarns can be directly detected with magnetic surveys.Environmental considerations of fluorine mining focus especially on drinking water, where high fluorine concentrations can lead to tooth decay; dental and skeletal fluorosis; and bone and cartilage conditions, including genu valgum, which is the crippling bone deformity more commonly known as knock knee. Trace amounts of other elements in fluorspar ores are a concern at some deposits; for example, high beryllium concentrations in alkaline-volcanic-related epithermal deposits or high cadmium concentrations associated with Mississippi Valley-type and salt-related carbonate-hosted fluorspar deposits.Future research might include testing whether fluorine can be extracted economically from high-pH, sodium-carbonate brines and exploring for new occurrences of apparently conformable fluorspar deposits in tuffaceous limy lacustrine sediments outside of the Latium Region of Italy. Other promising new areas of research could be studies of fluorspar deposit fluid inclusion compositions by quadrupole mass spectrometry, by noble gas mass spectrometry on irradiated fluid inclusions, or by chlorine isotopes, while also measuring the chemistry of the same fluid inclusions either by bulk crush-and-leach methods or by laser ablation-inductively coupled plasma mass spectrometry. Advanced studies of fluid inclusion chemistry could be applied beneficially to some of the enigmatic large epithermal fluorspar veins at various places in the world, where they might determine those deposits’ possible relationships to igneous intrusions, or to dissolved salt, or to heated meteoric water in volcanic sections, or perhaps to all three. This knowledge could help focus new exploration.

Kinetics of selenium release in mine waste from the Meade Peak Phosphatic Shale, Phosphoria Formation, Wooley Valley, Idaho, USA

USGS Publications Warehouse

Stillings, Lisa L.; Amacher, Michael C.

2010-01-01

Phosphorite from the Meade Peak Phosphatic Shale member of the Permian Phosphoria Formation has been mined in southeastern Idaho since 1906. Dumps of waste rock from mining operations contain high concentrations of Se which readily leach into nearby streams and wetlands. While the most common mineralogical residence of Se in the phosphatic shale is elemental Se, Se(0), Se is also an integral component of sulfide phases (pyrite, sphalerite and vaesite–pyritess) in the waste rock. It may also be present as adsorbed selenate and/or selenite, and FeSe2 and organo-selenides.Se release from the waste rock has been observed in field and laboratory experiments. Release rates calculated from waste rock dump and column leachate solutions describe the net, overall Se release from all of the possible sources of Se listed above. In field studies, Se concentration in seepage water (pH 7.4–7.8) from the Wooley Valley Unit 4 dump ranges from 3600 µg/L in May to 10 µg/L by Sept. Surface water flow, Q, from the seep also declines over the summer, from 2 L/s in May to 0.03 L/s in Sept. Se flux ([Se] ⁎ Q) reaches a steady-state of < 150 mg/day in 1–4 months, depending upon the volume of Q. Se release (mg/L) follows a first order reaction with a rate constant, k, = 1.35 – 6.35e−3 h− 1 (11.8–55.6 yr− 1).Laboratory experiments were performed with the waste shale in packed bed reactors; residence time varied from 0.09 to 400 h and outlet pH ∼ 7.5. Here, Se concentration increased with increasing residence time and release was modeled with a first order reaction with k = 2.19e−3 h− 1 (19.2 yr− 1).Rate constants reported here fall within an order of magnitude of reported rate constants for oxidation of Se(0) formed by bacterial precipitation. This similarity among rate constants from both field and laboratory studies combined with the direct observation of Se(0) in waste shales of the Phosphoria Formation suggests that oxidation of Se(0) may control steady-state Se concentration in water draining the Wooley Valley waste dump.

Cyclic and secular variation in microfossil biomineralization: clues to the biogeochemical evolution of Phanerozoic oceans

NASA Astrophysics Data System (ADS)

Martin, Ronald E.

1995-06-01

The stratigraphic occurrence and mineralogy of major protistan microfossil taxa tend to reflect evolutionary innovation in response to ocean chemistry and fertility. In foraminefera, the characteristic test composition—and, in some cases, ultrastructure—of each suborder is indicative of the degree of surface ocean CaCO 3 saturation, which varied in a cyclic manner through the Phanerozoic, at the time of origin of the suborder. High dissolved phosphate and low CaCO 3 saturation in late Precambrian-Early Cambrian surface waters may have prevented calcification in primitive non-calcareous (organic, agglutinated) foraminiferal stocks. Scattered reports of coccolithophorid-like microfossils from the Paleozoic are indicative of a secular trend in rising nutrient levels and marine productivity that controlled the initiation of calcareous oozes. Based on acritarch, carbon isotope, and phosphorite records, extremely low nutrient levels ("superligotrophic" conditions) in Cambrian-to-Devonian seas typically limited population densities of calcareous nannoplankton and prevented the formation of calcareous oozes. The overall "superoligotrophic" surface conditions of the Paleozoic were punctuated, though, by episodes of "catastrophic" eutrophication in the Late Ordovician, Late Devonia, and Late Carboniferous (Worsley et al., 1986). Following each episode, CaCO 3 rain rates were presumably enhanced because Marine C:P (MCP) burial ratios increased permanently above previous levels (Worsley et al., 1986). Nevertheless, it was not until the Carboniferous that the CCD had deepened sufficiently (via erosion of cratonic limestones) to allow pelagic calcareous oozes to begin to accumulate. Prior to this time, surface waters appear to have been sufficiently corrosive (high atmospheric pCO 2 and low CaCO 3 saturation), and the CCD sufficiently shallow, to dissolve virtually all incipient calcareous nannofossils. Following Late Permian extinctions, plankton re-expanded in response to both eustatic sea level rise (increased habitat availability) and increased nutrient levels ("mesotrophic" conditions). As organic matter (C org) and CaCO 3 rain rates increased, bioturbation rates also increased, thereby recycling nutrients back to the surface and accentuating productivity and calcareous ooze formation. MCP episodes further accelerated nutrient cycling and productivity in the Neogene, as indicated by the expansion of diatoms, which prefer nutrient-rich ("eutrophic") conditions. Ironically, while permanently increasing C:P burial ratios and productivity through the Phanerozoic, catastrophic fluctuations in nutrient levels may have also exacerbated mass extinctions via shortening of pelagic food chains. Nevertheless, re-expansion of the marine biosphere following each extinction episode resulted in a secular trend of increasing biomass and biotic diversity that may have contributed to the decline in background extinction rates through the Phanerozoic.

Genesis of iron-apatite ores in Posht-e-Badam Block (Central Iran) using REE geochemistry

NASA Astrophysics Data System (ADS)

Mokhtari, Mir Ali Asghar; Zadeh, Ghader Hossein; Emami, Mohamad Hashem

2013-06-01

Rare earth elements in apatites of different ore types show characteristic patterns which are related to different modes of formation of the ores. Most of the apatite-bearing iron ores are associated with alkaline magmas with LREE/HREE fractionation varying from moderate to steep. Iron-apatite deposits in Posht-e-Badam Block (Central Iran) have a high concentration of REE (more than 1000 ppm up to 2.5%), and show a strong LREE/HREE ratio with a pronounced negative Eu anomaly. This REE pattern is typical of magmatic apatite and quiet distinct from sedimentary apatites (phosphorites) which have a low REE contents and Ce negative anomalies. On the other hand, they are comparable to the REE patterns of apatites in Kiruna-type iron ores in different parts of the world. The REE patterns of apatites, iron-apatite ores and iron ores are similar and only have different REE contents. This similarity indicates a genetic relation for these rocks. Most of the iron-apatite deposits in Central Iran have similar REE patterns too, which in turn show a genetic relation for all of these deposits. This similarity indicates a similar origin and processes in their genesis. There are some small intrusions around some of the iron-apatite deposits that are petrographically identified as syenite and gabbro. These intrusions also have REE patterns similar to that of iron-apatite ores. This demonstrates a genetic relation between these intrusions and iron-apatite ores. The REE patterns of apatites in different deposits of Posht-e-Badam Block iron-apatite ores show an affinity to alkaline to sub-alkaline magmas and rifting environment. The alkaline host rocks of Central Iran iron-apatite ores are clearly related to an extensional setting where rifting was important (SSE-NNW fault lines). A probable source for this large scale ore forming processes is relatively low partial melting of mantle rocks. The ores have originated by magmatic differentiation as a late phase in the volcanic cycle forming sub-surface injections or surface flows. These ores have formed during magmatism as immiscible liquids (silicate and Fe-P-rich magmatic liquids) which separated from strongly differentiated magmas aided by a large volatile and alkali element content. Separation of an iron oxide melt and the ensuing hydrothermal processes dominated by alkali metasomatism were both involved to different degrees in the formation of Posht-e-Badam Block iron-apatite deposits. We proposed that the separation of an iron oxide melt and the ensuing hydrothermal processes dominated by alkali metasomatism were both involved to different degrees in the formation of Posht-e-Badam Block iron-apatite deposits.

Neoproterozoic Stromatolites and Microphytolites of the Spitsbergen Archipelago

NASA Astrophysics Data System (ADS)

Anisimov, Artem; Anisimova, Svetlana; Kosteva, Natalia

2017-04-01

The Svalbard archipelago is located in the extreme North-West of the Barents Sea. On the archipelago in the framework of large-scale exploration of the continental shelf exploration work carried out by employees of the Polar Marine Geological Expedition (PMGE). The authors were further explored and tested the Neoproterozoic sections of the Groups Veteranen, Akademikarbreen and Polarisbreen on the East and West banks of the Sorgfjorden (the Northern part of the Ny Friesland Peninsula) and in the moraine of the glacier Duner. The rocks carbonate-terrigenous Veteranen Group (upper Riphean) is set in the rocky outcrops on the Western and Eastern banks of Sorgfjorden and in ice-dressed rocks of the Bay. The Group consists of four Formations (bottom to top): Kortbreen, Kingbreen, Glasgowbreen and Oxfordbreen. The rocks carbonate-terrigenous Akademikarbreen Group (upper Riphean) have a lower areal distribution than the breed Veteranen Group in the project area is established only in the southern part of the Bay, in the valleys Kluftdalen, Rivnedalen and small-unnamed streams, as well as on the plateau Fleinfjellet and Vidarfjellet. The Groups consists of four formation (bottom to top): Grusdievbreen, Svanbergfjellet, Draken and Backlundtoppen. According to previous researchers, limestone in Kingbreen Formation (Veteranen Group) met with radial-rayed Microphytolites group Radiosus. And in light grey, cream, pink and red limestones of the Academikarbreen Group, in the Svanbergfjellet Formation defined columnar branching Stromatolites Inzeria djejimi Raab., Gymnosolen aff. ramsayi Steinm. Stromatolites of Conophyton miloradovichi Raab. in the dolomites of the overlying sediments Draken and Backlundtoppen Formations contain Vendian the bubbles Microphytolites Vesicularites bothrydioformis Krasnop. In carbonate rocks of the Akademikerbreen Group were confirmed by the finds of Neoproterozoic microbial entities identified by previous researchers, and identified new locations of columnar Stromatolites of the Conophyton garganicus Kor., columnar Stromatolites of the group Anabaria sp., Inseria chunnbergica Gol, Balcalia mariinica Dol., Lenia jacutica Dol., dome-columnar Stromatolites Tinnia patomica Dol. and formation Stromatolites Stratifera baracunica Dol. In the few carbonate interbeds of the Veteranen Group were found concentric layered Microphytolites of Osagia genuses. Upper Riphean sections of the Spitsbergen archipelago based on the paleontological and lithological-facial characteristics are correlated confidently with complex of Phytolites of the Riphean stratotype of the southern Urals of Russia. The results of the new biostratigraphic data can be used for paleogeographic reconstruction and recovery lithofacies of the Neoproterozoic of Spitsbergen. In future studies it is desirable to conduct mapping of fossil organogenic structures, setting their length, width, length, relationship with host sediments. This may have importance both for the solution of fundamental questions of evolution of life on Earth, and in the search of minerals such as manganese, cobalt, phosphorite, oil, natural gas.

The Itataia phosphate-uranium deposit (Ceará, Brazil) new petrographic, geochemistry and isotope studies

NASA Astrophysics Data System (ADS)

Veríssimo, César Ulisses Vieira; Santos, Roberto Ventura; Parente, Clóvis Vaz; Oliveira, Claudinei Gouveia de; Cavalcanti, José Adilson Dias; Nogueira Neto, José de Araújo

2016-10-01

The Itataia phosphate-uranium deposit is located in Santa Quitéria, in central Ceará State, northeastern Brazil. Mineralization has occurred in different stages and involves quartz leaching (episyenitization), brecciation and microcrystalline phase formation of concretionary apatite. The last constitutes the main mineral of Itatiaia uranium ore, namely collophane. Collophanite ore occurs in massive bodies, lenses, breccia zones, veins or episyenite in marble layers, calc-silicate rocks and gneisses of the Itataia Group. There are two accepted theories on the origin of the earliest mineralization phase of Itataia ore: syngenetic (primary) - where the ore is derived from a continental source and then deposited in marine and coastal environments; and epigenetic (secondary) - whereby the fluids are of magmatic, metamorphic and meteoric origin. The characterization of pre- or post-deformational mineralization is controversial, since the features of the ore are interpreted as deformation. This investigation conducted isotopic studies and chemical analyses of minerals in marbles and calc-silicate rocks of the Alcantil and Barrigas Formations (Itataia Group), as well as petrographic and structural studies. Analysis of the thin sections shows at least three phosphate mineral phases associated with uranium mineralizaton: (1) A prismatic fluorapatite phase associated with chess-board albite, arfvedsonite and ferro-eckermannite; (2) a second fluorapatite phase with fibrous radial or colloform habits that replaces calcium carbonate in marble, especially along fractures, with minerals such as quartz, chlorite and zeolite also identified in calc-silicate rocks; and (3) an younger phosphate phase of botryoidal apatite (fluorapatite and hydroxyapatite) related with clay minerals and probably others calcium and aluminum phosphates. Detailed isotopic analysis carried out perpendicularly to the mineralized levels and veins in the marble revealed significant variation in isotopic ratios. Mineralized zones exhibit a decrease in δ13C and δ18O isotope values and a higher 87Sr/86Sr ratio toward the center of the vein. In conjunction with petrographic studies, these changes contesting the hypothesis of a sedimentary origin for uranium and suggest a radiogenic Sr input by alkaline to peralkaline fluids from fertile granites of the end of Brasiliano/Pan-African orogeny, located outside the deposit. The origin of the phosphorous is associated with phosphorite deposits in the same depositional environment of the neoproterozoic supracrustal quartz-pelite-carbonate sediments of the Itataia Group. Considering the studies conducted here and available geological data, three main mineralizing events can be identified in Itataia: (1) an initial high temperature event connected with a sodium metasomatism-related uranium episode, taking place in Borborema Province and its African counterpart; (2) a second lower temperature stage, consisting of a multiphase cataclastic/hydrothermal event limited to fault and paleokarst zones; and (3) a third and final event, developed in frankly oxidizing conditions. The last two involving mixing of hydrothermal and meteoric fluids.

Temporal changes in Ce-anomalies in biogenic apatite from the Upper Cretaceous-Lower Eocene phosphate beds of Morocco. Is there a link to global paleoceanography?

NASA Astrophysics Data System (ADS)

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

2012-12-01

Shallow marine phosphorites are widespread along the western coast of Morocco. These sediments were deposited in three, first order transgressive-regressive cycles during the late Cretaceous-early Eocene. The layers are exceptionally rich in marine vertebrate fossils and three periods - Maastrichtian, Danian-Thanetian and Ypresian - can be distinguished by the especially abundant selachian fauna. A comprehensive geochemical study is carried out on these biogenic apatite fossils, and here we present trace element data analyzed on enameloid and dentin of shark teeth, coprolites, and bones coming from the Ouled Abdoun and Ganntour Basins. A clear separation is apparent between enameloid and the other archives in terms of the former has lower Cu, Ba, rare earth elements (REE) and U, and higher Zn and Sr concentrations. The REE and U in phosphatic fossils originate almost entirely from early diagenetic pore fluid and thus they can be used as a fingerprint of burial conditions. The above observed differences in the trace element concentrations relate to the originally different structure of these fossils, which means the better crystallized and denser enameloid interacted less with the burial fluid than the other remains. All the fossils revealed very similar shale normalized REE patterns, with negative Ce-anomaly and heavy REE enrichment, which mimics the REE distribution of typical modern seawater. This would indicate that the early diagenetic pore fluid was dominated by seawater, when these fossils gained their REE composition. However, the patterns show small differences with lower La/Sm, and higher La/Yb and Sm/Yb ratios in the coprolites, dentine and bones, which would appear as slight flattening of the patterns on the heavy REE end. This signifies again that these latter archives are more susceptible to interaction with the pore fluid. In contrast, the Ce-anomaly does not vary among the different remains and the values are very similar in a given layer. However, more interestingly a gradual shift towards lower Ce/Ce* values from older to younger beds is evident. Three major causes could be responsible for this temporal Ce-anomaly shift. First is enhanced REE uptake with time and gradually less oxygenated early diagenetic environment in the deeper and older beds. This would predict higher total REE content in the older fossils, which is not observable in our record. Second is varying water depth in the basins that may relate to alternation in redox conditions in the burial environment. Clearly, sea-level fluctuation had an impact on the sedimentation in these shallow marine basins. However, Ce-anomaly appears to change before major sedimentary gaps. Third and our preferred interpretation is the negative Ce-anomaly shift indicates the presence of more oxygenated seawater in the basins. This region was controlled by upwelling currents from the Atlantic Ocean, hence the observed changes are presumed to be in this source. This would point to development of more oxygenated deepwater in the North Atlantic by the end of the Paleocene, which may link to the extended opening of the North Atlantic and its connection to the South Atlantic.

Habitat, Fauna, and Conservation of Florida's Deep-Water Coral Reefs

NASA Astrophysics Data System (ADS)

Reed, J. K.; Pomponi, S. A.; Messing, C. G.; Brooke, S.

2008-05-01

Various types of deep-water coral habitats are common off the southeastern United States from the Blake Plateau through the Straits of Florida to the eastern Gulf of Mexico. Expeditions in the past decade with the Johnson-Sea- Link manned submersibles, ROVs, and AUVs have discovered, mapped and compiled data on the status, distribution, habitat, and biodiversity for many of these relatively unknown deep-sea coral ecosystems. We have discovered over three hundred, high relief (15-152-m tall) coral mounds (depth 700-800 m) along the length of eastern Florida (700 km). The north Florida sites are rocky lithoherms, whereas the southern sites are primarily classic coral bioherms, capped with dense 1-2 m tall thickets of Lophelia pertusa and Enallopsammia profunda. Off southeastern Florida, the Miami Terrace escarpment (depth 300-600 m) extends nearly 150 km as a steep, rocky slope of Miocene-age phosphoritic limestone, which provides habitat for a rich biodiversity of fish and benthic invertebrates. Off the Florida Keys, the Pourtalès Terrace (depth 200- 460 m) has extensive high-relief bioherms and numerous deep-water sinkholes to depths of 250-610 m and diameters up to 800 m. The dominant, deep-water, colonial scleractinian corals in this region include Oculina varicosa, L. pertusa, E. profunda, Madrepora oculata, and Solenosmilia variabilis. Other coral species include hydrozoans (Stylasteridae), bamboo octocorals (Isididae), numerous other gorgonians, and black corals (Antipatharia). These structure-forming taxa provide habitat and living space for a relatively unknown but biologically rich and diverse community of crustaceans, mollusks, echinoderms, polychaete and sipunculan worms, and associated fishes. We have identified 142 taxa of benthic macro-invertebrates, including 66 Porifera and 57 Cnidaria. Nearly 100 species of fish have been identified to date in association with these deep-water coral habitats. Paull et al. (2000) estimated that over 40,000 individual deep-water lithoherms may occur on the Blake Plateau and Straits of Florida, perhaps exceeding the areal extent of all the shallow-water reefs of the southeastern U.S. Our research program has provided data on the status of knowledge concerning these deep-reef habitats to the South Atlantic Fishery Management Council (SAFMC). Currently pending is a proposal by the SAFMC for a deep- water coral Habitat Area of Particular Concern (HAPC) that would extend from North Carolina to south Florida (78,888 km2) to protect these diverse and irreplaceable resources from destructive fishing activities such as bottom trawling. Deep-water reefs worldwide have been severely impacted by bottom trawling, including the deep-water Oculina coral reefs off central eastern Florida, which are structurally similar to the Lophelia reefs. Over a 30-year period, up to 99% of unprotected portions of the Oculina reefs were destroyed by rock shrimp trawling, whereas reefs designated as the Oculina HAPC in 1984 were protected from trawling and long-lines and are still relatively healthy. Numerous fisheries may target the deep-water Lophelia reef habitat including royal red shrimp, golden crab, and various fin fish.

Composition of the Rex Chert and associated rocks of the Permian Phosphoria Formation: Soda Springs area, SE Idaho

USGS Publications Warehouse

Hein, James R.; McIntyre, Brandie; Perkins, Robert B.; Piper, David Z.; Evans, James

2002-01-01

This study, one in a series, reports bulk chemical and mineralogical compositions, as well as petrographic and outcrop descriptions of rocks collected from three measured outcrop sections of the Rex Chert member of the Phosphoria Formation in SE Idaho. The three measured sections were chosen from ten outcrops of Rex Chert that were described in the field. The Rex Chert overlies the Meade Peak Phosphatic Shale Member of the Phosphoria Formation, the source of phosphate ore in the region. Rex Chert removed as overburden comprises part of the material disposed in waste-rock piles during phosphate mining. It has been proposed that the chert be used to cap and isolate waste piles, thereby inhibiting the leaching of potentially toxic elements into the environment. It is also used to surface roads in the mining district. The rock samples studied here constitute a set of individual chert beds that are representative of each stratigraphic section sampled. The informally named cherty shale member that overlies the Rex Chert in measured section 1 was also described and sampled. The upper Meade Peak and the transition zone to the Rex Chert were described and sampled in section 7. The cherts are predominantly spicularite composed of granular and mosaic quartz, and sponge spicules, with various but minor amounts of other fossils and detrital grains. The cherty shale member and transition rocks between the Meade Peak and Rex Chert are siliceous siltstones and argillaceous cherts with ghosts of sponge spicules and somewhat more detrital grains than the chert. The overwhelmingly dominant mineral is quartz, although carbonate beds are rare in each section and are composed predominantly of calcite and dolomite in addition to quartz. Feldspar, mica, clay minerals, calcite, dolomite, and carbonate fluorapatite are minor to trace minerals in the chert. The mean concentrations of oxides and elements in the Rex Chert and the cherty shale member are dominated by SiO2, which averages 94.6%. Organic-carbon contents are generally very low in the chert, but are up to 1.8 wt. % in cherty shale member samples and up to 3.3% in samples from the transition between the Meade Peak and Rex Chert. Likewise, phosphate (P2O5) is generally low in the chert, but can be up to 3.1% in individual beds. Selenium concentrations in Rex Chert and cherty shale member samples vary from Q-mode factors are interpreted to represent the following rock and mineral components: chert-silica component consisting of Si (± Ba); phosphorite-phosphate component composed of P, Ca, As, Y, V, Cr, Sr, and La (± Fe, Zn, Cu, Ni, Li, Se, Nd, Hg); shale component composed of Al, Na, Zr, K, Ba, Li, and organic C (± Ti, Mg, Se, Ni, Fe, Sr, V, Mn, Zn); carbonate component (dolomite, calcite, silicified carbonates) composed of carbonate C, Mg, Ca, and Si (± Mn); tentatively organic matter-hosted elements (and/or sulfide-sulfate phases) composed of Cu (± organic C, Zn, Mn Si, Ni, Hg, and Li). Selenium shows a dominant association with the shale component, but correlations and Qmode factors also indicate that organic matter (within the shale component) and carbonate fluorapatite may host a portion of the Se. Consideration of larger numbers of factors in Qmode analysis indicates that native Se (a factor containing Se (± Ba)) may also comprise a minor component of the Se compliment.

Geology of Paleozoic Rocks in the Upper Colorado River Basin in Arizona, Colorado, New Mexico, Utah, and Wyoming, Excluding the San Juan Basin

USGS Publications Warehouse

Geldon, Arthur L.

2003-01-01

The geology of the Paleozoic rocks in the Upper Colorado River Basin in Arizona, Colorado, New Mexico, Utah, and Wyoming, was studied as part of the U.S. Geological Survey's Regional Aquifer-System Analysis Program to provide support for hydrogeological interpretations. The study area is segmented by numerous uplifts and basins caused by folding and faulting that have recurred repeatedly from Precambrian to Cenozoic time. Paleozoic rocks in the study area are 0-18,000 feet thick. They are underlain by Precambrian igneous, metamorphic, and sedimentary rocks and are overlain in most of the area by Triassic formations composed mostly of shale. The overlying Mesozoic and Tertiary rocks are 0-27,000 feet thick. All Paleozoic systems except the Silurian are represented in the region. The Paleozoic rocks are divisible into 11 hydrogeologic units. The basal hydrogeologic unit consisting of Paleozoic rocks, the Flathead aquifer, predominantly is composed of Lower to Upper Cambrian sandstone and quartzite. The aquifer is 0-800 feet thick and is overlain gradationally to unconformably by formations of Cambrian to Mississippian age. The Gros Ventre confining unit consists of Middle to Upper Cambrian shale with subordinate carbonate rocks and sandstone. The confining unit is 0-1,100 feet thick and is overlain gradationally to unconformably by formations of Cambrian to Mississippian age. The Bighom aquifer consists of Middle Cambrian to Upper Ordovician limestone and dolomite with subordinate shale and sandstone. The aquifer is 0-3,000 feet thick and is overlain unconformably by Devonian and Mississipplan rocks. The Elbert-Parting confining unit consists of Lower Devonian to Lower Mississippian limestone, dolomite, sandstone, quartzite, shale, and anhydrite. It is 0-700 feet thick and is overlain conformably to unconformably by Upper Devonian and Mississippian rocks. The Madison aquifer consists of two zones of distinctly different lithology. The lower (Redwall-Leadville) zone is 0-2,500 feet thick and is composed almost entirely of Upper Devonian to Upper Mississippian limestone, dolomite, and chert. The overlying (Darwin-Humbug) zone is 0-800 feet thick and consists of Upper Mississippian limestone, dolomite, sandstone, shale, gypsum, and solution breccia. The Madison aquifer is overlain conformably by Upper Mississippian and Pennsylvanian rocks. The Madison aquifer in most areas is overlain by Upper Mississippian to Middle Pennsylvanian rocks of the Four Comers confining unit. The lower part of this confining unit, the Belden-Molas subunit, consists of as much as 4,300 feet of shale with subordinate carbonate rocks, sandstone, and minor gypsum. The upper part of the confining unit, the Paradox-Eagle Valley subunit, in most places consists of as much as 9,700 feet of interbedded limestone, dolomite, shale, sandstone, gypsum, anhydrite, and halite. Locally, the evaporitic rocks are deformed into diapirs as much as 15,000 feet thick. The Four Corners confining unit is overlain gradationally to disconformably by Pennsylvanian rocks. The uppermost Paleozoic rocks comprise the Canyonlands aquifer, which is composed of three zones with distinctly different lithologies. The basal (Cutler-Maroon) zone consists of as much as 16,500 feet of Lower Pennsylvanian to Lower Permian sandstone, conglomerate, shale, limestone, dolomite, and gypsum. The middle (Weber-De Chelly) zone consists of as much as 4,000 feet of Middle Pennsylvanian to Lower Permian quartz sandstone with minor carbonate rocks and shale. The upper (Park City-State Bridge) zone consists of as much as 800 feet of Lower to Upper Permian limestone, dolomite, shale, sandstone, phosphorite, chert, and gypsum. The Canyonlands aquifer is overlain disconformably to unconformably by formations of Triassic and Jurassic age.

Hydrothermal, biogenic, and seawater components in metalliferous black shales of the Brooks Range, Alaska: Synsedimentary metal enrichment in a carbonate ramp setting

USGS Publications Warehouse

Slack, John F.; Selby, David; Dumoulin, Julie A.

2015-01-01

Trace element and Os isotope data for Lisburne Group metalliferous black shales of Middle Mississippian (early Chesterian) age in the Brooks Range of northern Alaska suggest that metals were sourced chiefly from local seawater (including biogenic detritus) but also from externally derived hydrothermal fluids. These black shales are interbedded with phosphorites and limestones in sequences 3 to 35 m thick; deposition occurred mainly on a carbonate ramp during intermittent upwelling under varying redox conditions, from suboxic to anoxic to sulfidic. Deposition of the black shales at ~335 Ma was broadly contemporaneous with sulfide mineralization in the Red Dog and Drenchwater Zn-Pb-Ag deposits, which formed in a distal marginal basin.Relative to the composition of average black shale, the metalliferous black shales (n = 29) display large average enrichment factors (>10) for Zn (10.1), Cd (11.0), and Ag (20.1). Small enrichments (>2–<10) are shown by V, Cr, Ni, Cu, Mo, Pd, Pt, U, Se, Y, and all rare earth elements except Ce, Nd, and Sm. A detailed stratigraphic profile over 23 m in the Skimo Creek area (central Brooks Range) indicates that samples from at and near the top of the section, which accumulated during a period of major upwelling and is broadly correlative with the stratigraphic levels of the Red Dog and Drenchwater Zn-Pb-Ag deposits, have the highest Zn/TOC (total organic carbon), Cu/TOC, and Tl/TOC ratios for calculated marine fractions (no detrital component) of these three metals.Average authigenic (detrital-free) contents of Mo, V, U, Ni, Cu, Cd, Pb, Ge, Re, Se, As, Sb, Tl, Pd, and Au show enrichment factors of 4.3 × 103 to 1.2 × 106 relative to modern seawater. Such moderate enrichments, which are common in other metalliferous black shales, suggest wholly marine sources (seawater and biogenic material) for these metals, given similar trends for enrichment factors in organic-rich sediments of modern upwelling zones on the Namibian, Peruvian, and Chilean shelves. The largest enrichment factors for Zn and Ag are much higher (1.4 × 107 and 2.9 × 107, respectively), consistent with an appreciable hydrothermal component. Other metals such as Cu, Pb, and Tl that are concentrated in several black shale samples, and are locally abundant in the Red Dog and Drenchwater Zn-Pb-Ag deposits, may have a partly hydrothermal origin but this cannot be fully established with the available data. Enrichments in Cr (up to 7.8 × 106) are attributed to marine and not hydrothermal processes. The presence in some samples of large enrichments in Eu (up to 6.1 × 107) relative to modern seawater and of small positive Eu anomalies (Eu/Eu* up to 1.12) are considered unrelated to hydrothermal activity, instead being linked to early diagenetic processes within sulfidic pore fluids.Initial Os isotope ratios (187Os/188Os) calculated for a paleontologically based depositional age of 335 Ma reveal moderately unradiogenic values of 0.24 to 0.88 for four samples of metalliferous black shale. A proxy for the ratio of coeval early Chesterian seawater is provided by initial (187Os/188Os)335 Ma ratios of four unaltered black shales of the coeval Kuna Formation that average 1.08, nearly identical to the initial ratio of 1.06 for modern seawater. Evaluation of possible sources of unradiogenic Os in the metalliferous black shales suggests that the most likely source was mafic igneous rocks that were leached by externally derived hydrothermal fluids. This unradiogenic Os is interpreted to have been leached by deeply circulating hydrothermal fluids in the Kuna basin, followed by venting of the fluids into overlying seawater.We propose that metal-bearing hydrothermal fluids that formed Zn-Pb-Ag deposits such as Red Dog or Drenchwater vented into seawater in a marginal basin, were carried by upwelling currents onto the margins of a shallow-water carbonate platform, and were then deposited in organic-rich muds, together with seawater- and biogenically derived components, by syngenetic sedimentary processes. Metal concentration in the black shales was promoted by high biologic productivity, sorption onto organic matter, diffusion across redox boundaries, a low sedimentation rate, and availability of H2S in bottom waters and pore fluids.

The source of phosphate in the oxidation zone of ore deposits: Evidence from oxygen isotope compositions of pyromorphite

NASA Astrophysics Data System (ADS)

Burmann, Fabian; Keim, Maximilian F.; Oelmann, Yvonne; Teiber, Holger; Marks, Michael A. W.; Markl, Gregor

2013-12-01

Pyromorphite (Pb5[PO4]3Cl) is an abundant mineral in oxidized zones of lead-bearing ore deposits and due to its very low solubility product effectively binds Pb during supergene alteration of galena (PbS). The capacity of a soil or near-surface fluid to immobilize dissolved Pb depends critically on the availability of phosphate in this soil or fluid. Potential phosphorus sources in soil include (i) release during biological processes, i.e. leaching from litter/lysis of microbial cells (after intracellular enzyme activity) in soil and hydrolysis from soil organic matter by extracellular enzymes and (ii) inorganic phosphate from the dissolution of apatite in the adjacent basement rocks. Intracellular enzyme activity in plants/microorganisms associated with kinetic fractionation produces an oxygen isotope composition distinctly different from inorganic processes in soil. This study presents the first oxygen isotope data for phosphate (δ18OP) in pyromorphite and a comprehensive data set for apatite from crystalline rocks. We investigated 38 pyromorphites from 26 localities in the Schwarzwald (Southwest Germany) and five samples from localities outside the Schwarzwald in addition to 12 apatite separates from gneissic and granitic host rocks. Pyromorphites had δ18OP values between +10‰ and +19‰, comparable to literature data on δ18OP in the readily available P fraction in soil (resin-extractable P) from which minerals potentially precipitate in soils. δ18OP values below the range of equilibrium isotope fractionation can be attributed either to apatites that formed geochemically (δ18OP of apatites:+6‰ to +9‰) or less likely to biological processes (extracellular enzyme activity). However, for most of our samples isotopic equilibrium with ambient water was indicated, which suggests biological activity. Therefore, we conclude that the majority of pyromorphites in oxidized zones of ore bodies formed from biologically cycled phosphate. This study highlights that biological activity and Pb mobilization are intimately connected: in humid regions with high biological activity in soil, Pb might be precipitated rapidly due to biologically-released phosphate, whereas Pb will be released to the environment from ore deposits or mine dumps much more easily in arid regions with low biological activity, because pyromorphite cannot form due to limited supply of phosphorus. Phosphate from magmatic, metamorphic or sedimentary rocks: The most important phosphate-bearing mineral in such rocks is apatite (Ca5[(PO4)3(F,Cl,OH)]). In magmatic and metamorphic rocks it generally occurs as fluorapatite (Piccoli and Candela, 2002; Filippelli, 2008), whereas sedimentary rocks may also contain considerable amounts of carbonate-fluorapatite. Phosphorites are present in the geological record since the Lower Proterozoic (Cook and McElhinny, 1979; Shemesh et al., 1983). Alteration with low-pH fluids can dissolve apatite and thereby release geochemical phosphate (Filippelli, 2008). Low pH values may be attained by dissolution of atmospheric CO2 or by reaction with sulfides present in the rocks or in adjacent ore deposits. Phosphate of organic origin, such as from plants, animals or microorganisms: Phosphorus is required in most biological systems, as it is an essential element in major organic molecules such as adenosine triphosphate in the energy cycle, or in phospholipids, which form cell walls (Bucher, 2007; Filippelli, 2008). Organisms take up phosphorus as dissolved inorganic phosphate and cycle it through metabolic processes (intracellular enzyme activity). Once entering the soil, the organic material is decomposed by extracellular enzyme activity (hydrolysis of ester bonds) and phosphate is being released (Bünemann et al., 2011). Phosphate of anthropogenic origin: Since phosphate is a limiting factor in organism growth, it is an important ingredient of fertilizers in the agricultural industry. Also, phosphate can be found as ingredients in detergents, toothpaste and as a release of waste water treatment plants (Young et al., 2009). Anthropogenic effects will not be discussed further in the following. On this basis, we consider three different cases of pyromorphite formation as illustrated on the conceptual scheme of Fig. 1. Case 1: Pyromorphite grown recently (within the last hundreds of years) on rock surfaces in former mines. Both, phosphate released geochemically from igneous rocks and phosphate released biologically during leaching from litter/lysis of microbial cells and soil organic matter decomposition are possible sources. Case 2: Pyromorphite formation on mine dumps, below vegetation (recent, during tens to hundreds of years). Based on the specific setting of these samples investigated here (they were found exclusively below a large fern; see more details in the section on sample description), biologically-mediated P release provides the phosphate for pyromorphite growth. Case 3: Pyromorphite growth in the oxidized zones of ore bodies prior to human interference. Most samples of our study belong to this case.Phosphorus generally forms very strong covalent bonds (Huminicki and Hawthorne, 2002) and there is only negligible exchange of oxygen isotopes between phosphate and ambient water under most near-surface conditions without biological activity (Winter et al., 1940; Longinelli, 1965). The only important exchange of oxygen isotopes between phosphate and ambient water involves biological activity and the oxygen isotope composition of phosphate (δ18OP) may be modified by different enzymatic/cellular processes. Once phosphate is taken up by organisms, intracellular pyrophosphatase mediates internal P cycling. This is associated with a temperature-dependent equilibrium isotope fractionation due to the reversible exchange of O atoms between the phosphate molecule and cell water. As a result the δ18OP is equilibrated with the ambient water, and the equilibrium temperature can be calculated following the revised empirical equation from Longinelli and Nuti (1973) presented by Puceat et al. (2010): T(°C)=118.7-4.22[(δ18OP+(22.6-δ18ONBS120c))-δ18OW] where T is the temperature of the ambient water, δ18OP is the oxygen isotope composition of the phosphate at equilibrium conditions, δ18ONBS120c is the oxygen isotope composition of reference material NBS120c according to Vennemann et al. (2002) and δ18OW is the oxygen isotope composition of the ambient water. Knowledge of the δ18OP of ambient water and its temperature renders it possible to calculate a theoretical equilibrium value for δ18OP. If phosphate is again released from organisms into the soil, it will reflect the δ18OP of the cell-internal P cycling. In addition, extracellular enzymes are released in soil if the demand for P requires the hydrolysis of organic P in soil (McGill and Cole, 1981). Extracellular enzymes also transfer O atoms from water to phosphate and thus, change δ18OP. The associated isotopic fractionation factors vary between -10‰ (enzyme: 5‧-nucleotidase) and -30‰ (enzyme: alkaline phosphatase; Liang and Blake, 2006, 2009). All recent publications on δ18OP of phosphate in the readily available P fraction in soil (resin P) showed δ18OP values in the range calculated for isotopic equilibrium fractionation irrespective of environmental conditions (parent material, climate, biome). At most 20% down to 0% of the measured δ18OP fell outside the calculated isotopic equilibrium range (Angert et al., 2011, 2012; Tamburini et al., 2012). We therefore infer a dominant role of intracellular enzyme activity for δ18OP values in resin P in soil.Theoretical calculations by Lecuyer et al. (1999) imply that oxygen isotope exchange between phosphate and water can also occur in the absence of biological activity. An extrapolation of their equations to temperatures of 10 °C shows, however, that it takes more than 6000 years to exchange 10% of the phosphate oxygen (Colman et al., 2005). Traditionally, the oxygen isotope composition of phosphate has been used as a tool for determining paleotemperatures (e.g., Longinelli, 1984), but recent studies suggested to test its suitability for tracing phosphate sources in aquatic systems (Gruau et al., 2005; Elsbury et al., 2009; Young et al., 2009). Most of these studies deal with short-term ecological cycles and therefore the inorganic exchange of oxygen is negligible. However, this effect has to be considered for processes that happen in geological timescales.Due to the low phosphate concentrations in natural waters (Blake et al., 2005) and the low solubility product of pyromorphite, it is reasonable to assume almost all phosphate to precipitate as pyromorphite without any fractionation. Accordingly, the δ18OP of pyromorphite reflects the oxygen isotope composition of the dissolved phosphate in the water from which it precipitated and records the source, if this phosphate was not modified during fluid transport.Different phosphate reservoirs differ in their oxygen-isotope composition and with more and more data available it is possible to discriminate between different sources. Data for phosphates in aquatic systems are provided by Young et al. (2009): Phosphates of anthropogenic origin (fertilizers and the corresponding processing stages, detergents and toothpaste) show δ18OP values between +13.3‰ and +22.3‰, for phosphates from organic sources (vegetation leachate and animal waste) values between +14.2‰ and +23.1‰ are reported and a range between +8.4‰ and +14.2‰ is covered by phosphates of waste water treatment plants. For terrestrial ecosystems, Tamburini et al. (2012) reported δ18OP values between +4.5‰ and +31.4‰ with most data falling in the range of +12.4‰ to +31.4‰ for phosphate in plants (N = 11). Microbial phosphate in soil covered a range of +11‰ to +19‰. Resin-extractable P in soil as the readily available P fraction in soil from which P-containing minerals would precipitate, showed a range of 14.5-20.0‰ (Angert et al., 2011, 2012; Weiner et al., 2011; Tamburini et al., 2012). Additionally, Tamburini et al., 2012 reported values for apatite, most likely from the metamorphosed granitic bedrock, to be about +7‰. This is consistent with theoretical considerations by Shemesh et al. (1983) and with data from a gabbro (+4.1‰) and a tonalite (+6.7‰) reported by Taylor and Epstein (1962). Mizota et al. (1992) analyzed δ18OP of apatites from carbonatites, volcanic ashes and hydrothermal vugs covering a range of +0.2 to +12.2‰ (N = 10), whereas phosphate from phosphorites have higher values of up to +20‰ (e.g., Shemesh et al. (1983).This study investigates the oxygen isotope composition of phosphate in pyromorphite and in apatite from crystalline rocks. To evaluate possible phosphate sources, the results will be checked for isotopic equilibrium with different ambient waters and possible phosphate sources will be discussed.

Site Selection for Mars Exopaleontology in 2001

NASA Technical Reports Server (NTRS)

Farmer, Jack

1998-01-01

The microbial fossil record encompasses a wide range of information, including cellular remains, stromatolites, biofabrics, trace fossils, biominerals and chemofossils. The preservation of fossils is strongly influenced by the physical, chemical and biological factors of the environment which, acting together, ultimately determine the types of information that will be captured and retained in the rock record. The critical factor in assessing the suitability of a site for a microbial fossil record is the paleoenvironment. The reconstruction of ancient sedimentary environments usually requires the integration of a wide variety of geological information, including the shape, geometry and internal structure of sedimentary deposits, their mineralogy, and geochemistry. For Mars, much of our knowledge about past environments is based on orbital imaging of geomorphic features. This evidence provides an important context and starting point for site selection. However, our knowledge of the martian surface is quite limited, and a major goal of the upcoming exploration effort is to reconstruct the history of Martian volatiles, climate, and hydrology as a context for the exploration for past or present life. Mineralogical mapping from orbit will be an important key in this effort. In exploring for evidence of past life, terrestrial experience suggests that the long-term preservation of biological information as fossils occurs under a fairly narrow range of geological conditions that are well known to paleontologists (1). In detrital sedimentary systems, microbial fossilization is favored by rapid burial in fine-grained, clay-rich sediments. In chemical sedimentary systems, preservation is enhanced by rapid entombment in fine-grained chemical precipitates. For long term preservation, host rocks must be composed of stable minerals that resist chemical weathering, and which form an impermeable matrix and closed chemical system that can protect biosignatures from alteration during subsequent diagenetic change or metamorphism. In this context, host rocks composed of highly ordered, chemically-stable mineral phases, like silica (forming cherts) or phosphate (forming phosphorites), are especially favored. Such lithologies tend to have very long crustal residence times and (along with carbonates and shales), are the most common host rocks for the Precambrian microfossil record on Earth. If we assume that a subsurface hydrosphere has been present throughout martian history, then life could have originated there at any time, perhaps emerging at the surface periodically when climate changes, induced by external forcing or endogenous processes (e.g. volcanism), allowed liquid water to exist at the surface. The recent discovery of subsurface chemolithoautotrophic organisms which are capable of synthesizing organic substrates from C02 and H2 liberated from the aqueous weathering of basalt, is especially. relevant as a model for martian life. While a subsurface habitable zone may yet exist on Mars, access to such environments will likely require drilling to depths of several kilometers. Given the technological challenge of deep drilling, this is unlikely to occur prior to human missions. So, even if there is extant life on Mars today in subsurface habitats, it may be much easier to find its fossil counterparts in ancient deposits exposed at the surface. In exploring for a fossil record in subsurface environments on Mars there are several geological situations that may provide access to the appropriate materials. These include 1) ejecta from impact craters, 2) talus slopes, debris flows or alluvial fans developed below the walls of deep canyons, and 3) the deposits of outflood channels. Examples of aqueous mineral deposits of formed in subsurface environments that could harbor a microbial fossil record include such things as cements in detrital sedimentary rocks, low temperature diagenetic minerals deposited in veins, or filling vesicles in volcanic rocks, and hydrothermal deposits formed below the upper temperature limit for life (about 160 degrees C). There are many sites within the present latitudinal constraints for the 2001 mission (15 deg S to 30 deg N) that meet these requirements. But the practical problem with these kinds of deposits is that they tend to be disseminated, making up only a small percentage of a host rock. Even with mineralogical information provided by the Thermal Emission Spectrometer (TES) presently in orbit around Mars, predicting their occurrence ahead of time may be quite difficult. The deposits of surficial aqueous sedimentary systems are likely to provide the largest targets for site selection in 2001. Of these, the deposits of hydrothermal systems (subaerial and subaqueous thermal springs) have been discussed previously. It is likely that hydrothermal systems were widespread on Mars early in its history and a number of common geo-tectonic settings on Mars are likely to have hosted hydrothermal activity. Most of these are represented within the latitudinal constraints presently identified for 2001. However, the deposits of surface spring systems are likely to be difficult to find as well. On Earth, exposure areas for hydrothermal spring mounds are typically a few square kms, less than a single TES pixel. But such deposits may be quite abundant within some volcanic terrains, It is estimated, for example, that between 15-20% of the floor of Yellowstone caldera is covered by thermal spring deposits. In such abundances, subaerial sinters could well be detected by TES. Where exposed, the shallow subsurface portions of these systems may be quite a lot larger (perhaps tens of square kms), although (as noted above) mineralization may be finely disseminated in the basement rock, making remote detection more difficult. Paleolake Basins. There are a large number of potential paleolake basins on Mars (inclusive of impact craters and volcanic calderas) that have been previously identified using Viking images. Most of these lie in the southern highlands beyond the l5 deg S constraint for 2001. However, deposits of paleolakes may offer the largest and most easily identified exopaleontological targets from orbit. Based on a variety of arguments, some workers have suggested that there was once an ancient ocean on the northern plains, and some sites of interest (potential shoreline terraces) fall within the 30 deg N constraint. From a paleontological standpoint the most interesting places of this type are terminal paleolake basins which are likely to have been both saline and alkaline. Models by Schaefer suggest such environments could be widespread on Mars. The conditions in terminal lake basin settings favor widespread chemical sedimentation, an important condition for microbial fossilization. Important lithological targets for a microbial fossil record in terminal lake basins include spring-deposited carbonates, shoreline cements, a wide variety of evaporite minerals and fine-grained detrital sediments including shales, marls, and water-lain volcanic ash deposits. In developing a strategy to explore for ancient hydrothermal deposits on Mars, we can learn from the methods that have been developed by explorationists to explore for economic mineral deposits on Earth. Due to their simple mineralogy, hydrothermal deposits can often be detected using remote sensing methods. Common thermal spring mineral assemblages include silica, carbonate, and various metallic oxides and sulfides. But there are also a number of diagnostic silicate minerals, including clays, formed by the hydrothermal alteration of country rocks. These hydrothermal minerals have characteristic spectral signatures that could be detected from Mars orbit using high resolution infrared remote sensing methods. In playa lake settings, evaporite deposits often form a predictable "bull's eye" pattern with carbonates being deposited in marginal basin areas, and sulfates and halides occurring progressively mo re basinward. The floors of some impact craters on Mars, such as "White Rock" and Bequeral Crater (see Oxia Palus NE, Site 148), have floor deposits that could be evaporites, inclusive of carbonates. Evaporite minerals possess characteristic spectral signatures in the infrared and could similarly be identified from Mars orbit using high resolution remote sensing methods. Clearly, utilization of TES data will be important for optimizing site selection for Exopaleontology, and every effort should be made to benefit from that data before a final decision is made.