Surface complexation at hydrous fluorapatite

The adsorption of H⁺, OH^– and ARS (Alizarin Red S) onto hydrous fluorapatite surfaces and Ca²⁺—ARS complexation in solution were studied by means of combined potentiometric and spectrophotometric titrations, as well as zeta potential and FT-IR measurements. Corresponding equilibrium constants of surface and solution reactions are determined. The application in flotation processes is discussed.     

Whole-rock, Phosphate, and Silicate Compositional Trends across an Amphibolite- to Granulite-facies Transition, Tamil Nadu, India

Chemical trends from north (amphibolite facies) to south (granulitefacies) along a 95 km traverse in Tamil Nadu, Southern India,include: whole-rock depletion of Rb, Cs, Th and U, enrichmentin Ti and F, and depletion in Fe and Mn in biotite and amphibole;increases in Al and decreases in Mn in orthopyroxene; enrichmentof fluorapatite in F. K-feldspar blebs are widespread alongquartz–plagioclase grain boundaries, and could indicateeither partial melting or metasomatism. In the northernmostportion of the traverse the principal rare earth element (REE)-bearingminerals are allanite and titanite. South of a clinopyroxeneisograd, monazite grains independent of fluorapatite are themajor REE- and Th-bearing phase. Further south independent monaziteis rare but Th-free monazite inclusions are common in fluorapatite.During prograde metamorphism, independent monazite was replacedby REE-rich fluorapatite in which the monazite inclusions laterformed. The loss of independent monazite was accompanied bya loss of whole-rock Th and possibly a small depletion in lightREE. Most mineralogical features along the traverse can be accountedfor by progressive dehydration and oxidation reactions. Trace-elementdepletion is best explained by the action of an externally derivedlow H₂O activity brine migrating from a source at greater depth,possibly preceded or accompanied by partial melting. KEY WORDS: granulite facies; charnockite; metasomatism; Archean; Tamil Nadu, India; fluorapatite; monazite; allanite; titanite; biotite     

Lake Boga Granite,northwestern Victoria: mineralogy,geochemistry and geochronology

The Devonian Lake Boga Granite in northern Victoria, while almost entirely under thin Murray Basin cover, is one of the largest plutons in the western Lachlan Fold Belt. Its only exposure is a quarry penetrating the Cenozoic sediments. In the quarry, prominent pod pegmatites and miarolitic cavities suggest a high level of emplacement. The granite, a non-magnetic, fractionated S-type, contains a large range of accessory minerals, including primary uranium- and REE-bearing phosphates and oxides, and primary copper sulfides. Monazite-series minerals show an exceptionally wide range of compositions, from normal monazite-(Ce) through cheralite (Ca – Th-rich) to rare huttonitic monazite (Th-rich) and brabantite; U contents in monazite also vary widely (0 – 7.9 wt%). Primary low-Ca uraninites are well preserved and are unusual in having low Th/U and LREE. Late-stage cavity fluorapatite crystals up to several centimetres across show intricate elemental zoning patterns with extreme U gradients (<10 – 6900 ppm) in some crystals. New ⁴⁰Ar – ³⁹Ar ages for magmatic biotite, muscovite and K-rich feldspar average 365 ± 3 Ma, which approximates the emplacement age of the granite. This is supported by a 377 ± 12 Ma U – Th – Pb (CHIME) age for primary uraninite. New whole-rock geochemical data support earlier observations: the granite is strongly fractionated (SiO₂ 70.7 – 76.0 wt%; 4.2 – 0.6 wt% FeO_t) and peraluminous (ASI = 1.23 – 1.45), and has slightly elevated Na₂O and P₂O₅ (0.30 wt%) contents compared with other fractionated S-type granites from the Lachlan Fold Belt. Trace-element abundances are typical of fractionated granites, although U and Cu concentrations vary strongly and reach >60 and ≈1400 ppm, respectively. REE patterns also vary strongly, from LREE-enriched with moderate Eu depletion, to flat with strong Eu depletion. The flattest of the REE patterns, in samples with FeO_total < 1%, are characterised by M-type tetrad effects. These and other samples also show low (subcrustal average) and variable Zr/Hf (35 – 16) and Nb/Ta (8 – 4) ratios; these and other unusual elemental fractionations are related to changes in elemental partitioning during the late magmatic stage, when felsic peraluminous magma and high-temperature magmatic fluid coexisted.     

震旦纪灯影组磷块岩及其生成特点

灯影组磷块岩有四种类型,即泥晶磷块岩、内碎屑磷块岩、藻磷块岩和细晶磷块岩。组成磷块岩的主要矿物是磷灰石、白云石、石英和少量伊利石等。磷块岩主要沉积在陆缘海内,它的沉积环境是与深水有联系的浅水地区。深水和浅水环境的地质背景分别为构造拗陷和碳酸盐岩台地。前者提供成矿物质,后者提供有利于磷质成矿的沉积环境。     

Diagenetic trends of fluorine concentration in Negev phosphorites, Israel: implications for carbonate fluorapatite composition during phosphogenesis

An electron probe and chemical study of bulk phosphorite samples and separated constituents from various Negev deposits was carried out together with XRD, FTIR spectroscopy and textural analysis. The results allow a better understanding of the distribution of fluorine in these Upper Cretaceous phosphorite sequences and shed light on variations in the composition of the carbonate fluorapatite (CFA) phase during phosphogenesis. Two facies are recognized: (1) a pristine, microbially generated phosphorite facies; (2) a recycled, peloidal and biodetrital facies. Fluorine distribution in the Negev phosphorites is facies controlled: F/P₂O₅ is much lower in the pristine facies (0·090–0·107) than in the recycled facies (0·107–0·120). In addition, F/P₂O₅ varies considerably between the various constituents of the phosphate fraction; F‐poor francolites (F/P₂O₅ as low as 0·080) co‐exist with F‐rich francolites (F/P₂O₅ as high as 0·135) in the same phosphorite bulk sample. A lower F/P₂O₅ in francolite is associated with higher Cd and Zn concentrations in the phosphorite, an increase in Fe‐rich smectites in the clay fraction and the presence of structural OH in the francolite. The lower F/P₂O₅ ratios in the pristine facies are attributed to high organic deposition rates during the formation of these matted sediments, leading to rapid burial of the in situ‐forming CFA. This is possibly coupled with diffusion of F from sea water into bottom sediments being hampered by microbial mat coatings. These conditions resulted in O₂‐depleted porefluids, inducing the precipitation of Cd‐rich Zn sulphides and the formation of Fe‐rich smectites. F‐enrichment probably takes place when the earlier formed F‐poor ‘primary’ CFA is relocated close to the sea floor and bathed with interstitial sea water solutions of higher F concentrations. Oxidation and removal of the sulphide‐bound Cd and Zn apparently occurred together with enrichment in F of the francolite. Combining chemical data with XRD and FTIR results suggests a multistage growth for the Negev phosphate constituents in shifting formational sites and porefluids of varying F concentrations. This multiphase growth is reflected in the patchy distribution of F in the Negev constituents and might explain the inverse correlation between mean CO₂/F and F/P₂O₅ ratios of the analysed phosphorites in the two facies. It also suggests that CFA (or an amorphous precursor) initially formed with some OH groups in the apatite structure, which were subsequently substituted by F ions in recycled francolite through re‐equilibration with porefluids of higher F concentrations.