BENEFICIATION OF HIGH-MgO SEDIMENTARY PHOSPHATE ORES

Dolomite [CaMg(CO3)2] is an intolerable impurity in phosphate ores due to its MgO content. Traditionally, the Florida phosphate industry has avoided mining high-MgO phosphate reserves due to the lack of an economically viable process for removal of dolomite. However, as the high grade phosphate reserves become depleted, more emphasis is being put on the development of a cost effective method for separating dolomite from high-MgO phosphate ores. In general, the phosphate industry demands a phosphate concentrate containing less than 1%MgO. Dolomite impurities have mineralogical properties that are very similar to the desired phosphate minerals (francolite), making the separation of the two minerals very difficult. Magnesium is primarily found as distinct dolomite-rich pebbles, very fine dolomite inclusions in predominately francolite pebbles, and magnesium substituted into the francolite structure. Jigging is a gravity separation process that attempts to take advantage of the density difference between the dolomite and francolite pebbles. A unique laboratory scale jig was designed and built at Michigan Tech for this study. Through a series of tests it was found that a pulsation rate of 200 pulse/minute, a stroke length of 1 inch, a water addition rate of 0.5gpm, and alumina ragging balls were optimum for this study. To investigate the feasibility of jigging for the removal of dolomite from phosphate ore, two high-MgO phosphate ores were tested using optimized jigging parameters: (1) Plant #1 was sized to 4.00x0.85mm and contained 1.55%MgO; (2) Plant #2 was sized to 3.40mmx0.85mm and contained 3.07% MgO. A sample from each plant was visually separated by hand into dolomite and francolite rich fractions, which were then analyzed to determine the minimum achievable MgO levels. For Plant #1 phosphate ore, a concentrate containing 0.89%MgO was achieved at a recovery of 32.0%BPL. For Plant #2, a phosphate concentrate containing 1.38%MgO was achieved at a recovery of 74.7%BPL. Minimum achievable MgO levels were determined to be 0.53%MgO for Plant #1 and 1.15%MgO for Plant #2.

Leached zone : phosphate recovery /

"U.S. AEC Contract AT(49-1)-545."

The influence of bacterial activity on phosphorite formation in the Miocene Monterey Formation, California

Authigenic phosphorites from the Miocene Monterey Formation (California) including an autochthonous phosphatic laminite were analyzed for molecular biomarkers, element content, and sulfur isotopic composition of associated pyrite and sulfate to evaluate the role of bacterial activity in the precipitation of phosphate minerals. The phosphorites formed in a depositional environment typified by upwelling with dynamic bottom currents and hardground formation. Pyrite enclosed in the phosphorites shows delta S-34 values as low as -36.5 parts per thousand VCDT, which is consistent with bacterial sulfate reduction. In a three-step extraction phosphorite dissolution extraction procedure, molecular fossils of sulfate-reducing bacteria (di-O-alkyl glycerol ethers and short-chain branched fatty acids i- and ai-C-15:0, i- and ai-C-17:0, and 10MeC(16:0)) were preferentially released from the mineral lattice. This suggests that the molecular fossils were tightly bound to carbonate fluorapatite, indicating that sulfate-reducing bacteria were involved in mineral formation. A close association of sulfate-reducing bacteria with large sulfide-oxidizing bacteria, which was previously suggested to favor carbonate fluorapatite precipitation, could neither be confirmed nor excluded for the Miocene Monterey Formation phosphorites. (C) 2012 Elsevier B.V. All rights reserved.

Effects of Different Swimming Exercise Intensities on Bone Tissue Composition in Mice: A Raman Spectroscopy Study

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Experimental study of a methodology for Fission-track Dating without neutron irradiation

To carry out the dating by the Fission Track Method (FTM) the international community that works with this method employs methodologies in which the mineral to be dated must be irradiated with neutrons. Such irradiation, performed in a nuclear reactor, demand a relatively long waiting time so that the activity of the sample attain a proper level for handling. The present work aims to establish a methodology that makes possible the dating by FTM using a mass spectrometer instead of a nuclear reactor. This methodology was applied to apatite samples from Durango, Mexico. © 2009 Elsevier Ltd. All rights reserved.

Mineralogy and chemistry of archaeological ceramic fragments from archaeological Dark Earth site in Colombian Amazon

Vários sítios arqueológicos de Terra Preta Arqueológica (TPA) encontrados na floresta Amazônica Colombiana também contêm alto conteúdo de fragmentos cerâmicos semelhantes aqueles da Amazônia Brasileira, como mostra o sítio Quebrada Tacana. Seus fragmentos cerâmicos são amarelo a cinza, exibem matriz argilosa calcinada envolvendo fragmentos de cariapé, carvão e partículas de cinza, grãos de quartzo e micas. A matriz é composta de metacaulinita a material amorfo, quartzo, folhas de micas, clorita e sepiolita. Cariapé e cauixi são constituídos de cristobalita, da mesma forma o carvão e as cinzas. Embora não detectados pela difração de raios x, os fosfatos devem estar presentes, pois foram detectados teores de P2O5 de até 2,90 %, possivelmente como fosfatos de alumínio, já que o conteúdo de Ca está abaixo 0,1 %, o que elimina a possibilidade da presença de apatita. Estas características mineralógicas e químicas permitem relacionar estes fragmentos cerâmicos com aqueles encontrados nos sítios de TPA no Brasil e reforça o fósforo como um importante componente químico, originado pelo contato dos vasos cerâmicos com os alimentos do cotidiano dos povos amazônicos pré-históricos.

Fossilized bacteria in a Cretaceous pterosaur headcrest

Pinheiro F.L., Horn B.L.D., Schultz C.L., de Andrade J.A.F.G. and Sucerquia P.A., 2012: Fossilized bacteria in a Cretaceous pterosaur headcrest. Lethaia, Vol. 45, pp. 495-499. We report herein the first evidence of bacterial autolithification in the Crato Formation of Araripe Basin, Brazil. The fossilized bacteria are associated with a tapejarid pterosaur skull, replacing the soft-tissue extension of the headcrest. EDS analyses indicate that the bacteria were replaced by phosphate minerals, probably apatite. The bacterial biofilm was likely part of the prokaryotic mat that decomposed the pterosaur carcass at the bottom of the Araripe lagoon. This work suggests that bacterial autolithification could have played a key-role on soft-tissue preservation of Crato Formation Lagerstatte. ?Bacterial autolithification, Crato Formation, phosphatization, pterosaur, soft-tissue preservation.

The Application of Laser-Ablation Split-Stream ICP Petrochronology to Metamorphic Studies

Discussion of a new, innovative method for dating rocks, called laser ablation split stream (LASS) petrochronology, which is an in situ method that couples geochronological and geochemical data of minerals that remain in the rock matrix. The talk focuses on the application of this technique with U-Th-Pb dating of the phosphate minerals monazite and xenotine in metamorphic rocks. Examples from the Ruby Range in southwestern Montana and metamorphic core complexes in the northern Idaho panhandle will be explored.

Geochemistry of middle Eocene-lower Oligocene pelagic sediments of ODP Hole 105-647A

Geochemical analyses of the middle Eocene through lower Oligocene lithologic Unit IIIC (260-518 meters below seafloor [mbsf]) indicate a relatively constant geochemical composition of the detrital fraction throughout this depositional interval at Ocean Drilling Program (ODP) Site 647 in the southern Labrador Sea. The main variability occurs in redox-sensitive elements (e.g., iron, manganese, and phosphorus), which may be related to early diagenetic mobility in anaerobic pore waters during bacterial decomposition of organic matter. Initial preservation of organic matter was mediated by high sedimentation rates (36 m/m.y.). High iron (Fe) and manganese (Mn) contents are associated with carbonate concretions of siderite, manganosiderite, and rhodochrosite. These concretions probably formed in response to elevated pore-water alkalinity and total dissolved carbon dioxide (CO2) concentrations resulting from bacterial sulfate reduction, as indicated by nodule stable-isotope compositions and pore-water geochemistry. These nodules differ from those found in upper Cenozoic hemipelagic sequences in that they are not associated with methanogenesis. Phosphate minerals (carbonate-fluorapatite) precipitated in some intervals, probably as the result of desorption of phosphorus from iron and manganese during reduction. The bulk chemical composition of the sediments differs little from that of North Atlantic Quaternary abyssal red clays, but may contain a minor hydrothermal component. The silicon/ aluminum (Si/Al) ratio, however, is high and variable and probably reflects original variations in biogenic opal, much of which is now altered to smectite and/or opal CT. An increase in the sodium/potassium (Na/K) ratio in the upper Eocene corresponds to the beginning of coarsergrained feldspar flux to the site, possibly marking the onset of more vigorous deep currents. Although the Site 647 cores provide a nearly complete high-resolution, high-latitude Eocene-Oligocene record, the high sedimentation rate and somewhat unusual diagenetic conditions have led to variable alteration of benthic foraminifers and fine-fraction carbonate and have overprinted the original stable-isotope records. Planktonic foraminifers are less altered, but on the whole, there is little chance of sorting out the nature and timing of environmental change on the basis of our stable-isotope analyses.

Dinâmica do fósforo no solo em função da adição de ácidos orgânicos de baixa massa molar

A baixa eficiência da adubação fosfatada em solos altamente intemperizados é devido, entre outros fatores, à adsorção do fósforo (P) à superfície das argilas silicatadas do tipo 1:1 e, principalmente, dos (hidr)óxidos de Fe e de Al. Manejos do solo que induzem a solubilização de formas de P indisponíveis para as plantas têm sido intensamente estudados nos últimos anos. Uma tentativa de aumentar a concentração de P disponível na solução do solo para sua absorção pelas plantas é a mobilização de P por ânions de ácidos orgânicos de baixa massa molar (AOBMM). Ânions derivados de AOBMM exsudados pelas raízes de plantas ou excretados por microrganismos são associados com algumas condições de rizosfera como deficiência de P e fitotoxidez de Al e interagem com o solo de forma a aumentar a biodisponibilidade de P. Dependendo dos atributos do solo, do grau de dissociação, das propriedades e do número de grupos carboxílicos dos ânions orgânicos, o P pode ser mobilizado do solo principalmente devido à dissolução complexométrica de minerais e à adsorção competitiva dos grupos funcionais carboxílicos e fosfato nos sítios de superfície coloidais. A capacidade dos ânions citrato, malato e oxalato em mobilizar P de amostras de um Neossolo Quartzarênico típico (RQ) e de um Latossolo Vermelho ácrico (LVwf) foi avaliada por meio de um estudo de lixiviação de ânions em colunas. Devido a não detecção de P nos efluentes das colunas com LVwf, foi realizado outro estudo em colunas, no qual somente citrato foi lixiviado, mas num volume maior, e as alterações das formas de P nas amostras desse solo induzidas pela lixiviação de citrato foram identificadas por espectroscopia de absorção de raios-X na borda K do fósforo (X-ray absorption near edge structure -XANES - spectroscopy). A capacidade dos ânions de AOBMM em solubilizar P foi mais dependente do teor de P disponível e de outros atributos do solo que do número de grupos funcionais carboxílicos dos ânions orgânicos. Somente o oxalato mobilizou P do RQ, enquanto todos os ânions de AOBMM foram capazes de mobilizar P do LVwf. Quando baixos volumes de solução contendo ânions de AOBMM foram lixiviados no solo, além do aumento do pH, a mobilização de P foi acompanhada pela mobilização de Al no RQ (pH água = 5), e pela mobilização de Ca no LVwf (pH água = 5.6), o que indica solubilização de P pela complexação de Al, Ca, ou Fe, de fosfatos insolúveis, ou pela inibição da precipitação de P com esses metais. Ao lixiviar um volume maior de citrato no LVwf, o P também não foi detectado nos efluentes das colunas, mas houve lixiviação intensa de Al e Fe, bem como mudanças nas proporções de formas de P no solo caracterizadas pelos espectros XANES. Embora tenhamos encontrado indícios da ação dos principais mecanismos de solubilização de P (dissolução complexométrica de minerais e troca de ligantes entre grupos funcionais carboxílicos e P adsorvido ao solo), os ânions de AOBMM mostraram pouco potencial de efetivamente aumentar a biodisponibilidade de P.

Leached zone : dissolution of values using heat treated feeds /

"U.S. AEC Contract AT(49-1)-545."

The provenance and technology of Near Eastern glass: Oxygen isotopes by laser fluorination as a complement to strontium

The ability to make rapid measurements on small samples using laser fluorination enhances the potential of oxygen isotopes in the investigation of early inorganic materials and technologies. delta O-18 and Sr-87/Sr-86 values are presented for glass from two primary production sites, four secondary production sites and a consumer site in the Near East, dating from Late Antiquity to the medieval period. delta O-18 is in general slightly less effective than Sr-87/Sr-86 in discriminating between sources, as the spread of measured values from a single source is somewhat broader relative to the available range. However, while Sr-87/Sr-86 is derived predominantly from either the lime-bearing fraction of the glass-making sand or the plant ash used as a source of alkali, delta O-18 derives mainly from the silica. Thus the two measurements can provide complementary information. A comparison of delta O-18 for late Roman - Islamic glasses made on the coast of Syria-Palestine with those of previously analysed glasses from Roman Europe suggests that the European glasses are relatively enriched in O-18. This appears to contradict the view that most Roman glass was made using Levantine sand and possible interpretations are discussed.

Sediment geochemistry PASOM research cruise (2009) - Murray Ridge region, northern Arabian Sea

In this study, we investigate phosphorus (P) and iron (Fe) cycling in sediments along a depth transect from within to well below the oxygen minimum zone (OMZ) in the northern Arabian Sea (Murray Ridge). Pore-water and solid-phase analyses show that authigenic formation of calcium phosphate minerals (Ca-P) is largely restricted to where the OMZ intersects the seafloor topography, likely due to higher depositional fluxes of reactive P. Nonetheless, increased ratios of organic carbon to organic P (Corg/Porg) and to total reactive P (Corg/Preactive) in surface sediments indicate that the overall burial efficiency of P relative to Corg decreases under the low bottom water oxygen concentrations (BWO) in the OMZ. The relatively constant Fe/Al ratio in surface sediments along the depth transect suggest that corresponding changes in Fe burial are limited. Sedimentary pyrite contents are low throughout the ~25 cm sediment cores at most stations, as commonly observed in the Arabian Sea OMZ. However, pyrite is an important sink for reactive Fe at one station in the OMZ. A reactive transport model (RTM) was applied to quantitatively investigate P and Fe diagenesis at an intermediate station at the lower boundary of the OMZ (bottom water O2: ~14 µmol/L). The RTM results contrast with earlier findings in showing that Fe redox cycling can control authigenic apatite formation and P burial in Arabian Sea sediment. In addition, results suggest that a large fraction of the sedimentary Ca-P is not authigenic, but is instead deposited from the water column and buried. Dust is likely a major source of this Ca-P. Inclusion of the unreactive Ca-P pool in the Corg/P ratio leads to an overestimation of the burial efficiency of reactive P relative to Corg along the depth transect. Moreover, the unreactive Ca-P accounts for ~85% of total Ca-P burial. In general, our results reveal large differences in P and Fe chemistry between stations in the OMZ, indicating dynamic sedimentary conditions under these oxygen-depleted waters.

(Figure 1 and 2) Phosphorus pools in the investigated sediments quantified by SEDEX sequential extraction and distribution of recovered 33P spike between sedimentary P pools after incubation

Phosphorus is an essential nutrient for life. In the ocean, phosphorus burial regulates marine primary production**1, 2. Phosphorus is removed from the ocean by sedimentation of organic matter, and the subsequent conversion of organic phosphorus to phosphate minerals such as apatite, and ultimately phosphorite deposits**3, 4. Bacteria are thought to mediate these processes**5, but the mechanism of sequestration has remained unclear. Here, we present results from laboratory incubations in which we labelled organic-rich sediments from the Benguela upwelling system, Namibia, with a 33P-radiotracer, and tracked the fate of the phosphorus. We show that under both anoxic and oxic conditions, large sulphide-oxidizing bacteria accumulate 33P in their cells, and catalyse the nearly instantaneous conversion of phosphate to apatite. Apatite formation was greatest under anoxic conditions. Nutrient analyses of Namibian upwelling waters and sediments suggest that the rate of phosphate-to-apatite conversion beneath anoxic bottom waters exceeds the rate of phosphorus release during organic matter mineralization in the upper sediment layers. We suggest that bacterial apatite formation is a significant phosphorus sink under anoxic bottom-water conditions. Expanding oxygen minimum zones are projected in simulations of future climate change**6, potentially increasing sequestration of marine phosphate, and restricting marine productivity.

Characterization and greenhouse evaluation of Brazilian calcined nonapatite phosphate rocks for rice

Little information is available on the agronomic effectiveness of calcined nonapatite phosphate rock (PR) sources containing crandallite minerals in the form of Ca-Fe-Al-P for flooded and upland rice (Oryza sativa L.). We conducted laboratory and greenhouse studies to (i) characterize the mineralogical composition, (ii) investigate the solubility and dissolution behavior, and (iii) evaluate the agronomic effectiveness of two nonapatite PR sources (Juquia and Sapucaia) from Brazil and compared them with (i) a highly reactive Gafsa PR (Tunisia) containing apatite in the form of Ca-P and (ii) a reference water-soluble triple superphosphate (TSP) for flooded and upland rice. After calcination at 500 degrees C for 4 h, the solubility of Juquia PR and Sapucaia PR in neutral ammonium citrate (NAC) significantly increased from almost nil to a maximum of 39.3 and 114 g P kg(-1), respectively. X-ray diffraction showed that crystalline crandallite mineral was transformed to an amophorus form after calcination. The solubility behavior of the two calcined PR sources followed the same trend as Gafsa PR, that is, P release decreased with increasing equilibrium pH in the 0.01 M KCl solution (PH 3.0-8.0). At PH 3, the solubility followed: Gafsa PR > calcined Sapucaia PR > calcined Juquia PR. No P release was detected from any of the PR sources at pH >= 5.0 in the solution, indicating the Ca-P characteristic of the Ca-Fe-Al-P mineral controlled P dissolution of the calcined PR. Without calcination, both Juquia PR and Sapucaia PR were totally ineffective for upland rice grown on a Hiwassee clay loam (fine, kaolinitic, thermic Rhodic Kanhapludult) with pH 5.4 whereas a significant P response was observed with the calcined PR samples. For flooded rice grown on Hiwassee soil, the calcined Juquia PR and Sapucaia PR were 66 and 72%, respectively, as effective as TSP in increasing rice grain yield whereas Gafsa PR was ineffective. For upland rice grown on the unlimed soil, Gafsa PR was as effective as TSP in increasing rice grain yield whereas calcined Juquia PR and Sapucaia PR were 89 and 83% of TSP. The effectiveness of Gafsa PR was reduced to 0% after the soil was limed to pH 7.0 whereas the two calcined PR sources were reduced to 49% of TSP. Soil available P extracted by iron oxide impregnated filter paper (Pi test) or anion-exchange resin after rice harvest correlated well with P uptake by rice grain for flooded and upland rice.