Salts and brines have very low rare earth element (REE, La-Lu) concentrations. Thus, there is less knowledge of possible transfer of REE patterns during salt dissolution in water-rock interaction. REE levels in both media are close to or rather below limit of detection of commonly used methods. By dissolving salt samples in water followed by REE pre-concentration, REE contents of about 6.2 to 322 ng g−1 were measured for four samples from the Merkers salt mine, Germany. These salts previously were identified to consist mainly of carnallite, halite and/or sylvite. Assuming congruent dissolution, REE patterns of brines and salts differ. Thus, a more complex interaction with (secondary) phases and complexation of REE should be taken into account to explain REE patterns in brines. 相似文献
This study provides evidence for the existence of halite and sylvite solid inclusions in igneous quartz and feldspars, the first to be reported in intrusive rocks, and to partially constrain the physicochemical environment that lets halides crystallize under magmatic conditions.Halite and sylvite solid inclusions were found included in quartz and feldspars from a micrographic–granophyric assemblage in a miarolitic aplite and, rarer, in alkali-feldspar from a miarolitic monzogranite. Monzogranite and aplite represent I-type, K-enriched postcollisional rocks of the Late Cambrian–Early Ordovician Sierra Norte–Ambargasta batholith in the Eastern Sierras Pampeanas. Both granitoids fall among the most evolved felsic rocks of the batholith, with aplite approaching haplogranitic compositions. Halite is far more common than sylvite and the presence and distribution of one or both halides are erratic within the felsic intrusive bodies. Halides occur as small skeletal grains, commonly in cross-shaped aggregates of less than 50 μm. No K or Na was found at the detection limits of EDS in either halite or sylvite respectively. Textural relationships suggest that the alkali-chlorides separated from the melt near the minima along the quartz–feldspar cotectics of PH2O > 160 < 200 MPa in a silica-, and potassium-rich magmatic system at approximately 750–700 °C, prior to the H2O-vapor saturated miarole-forming stage.Computed ratios for the magmatic volatile phase (MVP) coexisting with melt at the early stage of aplite crystallization are: NaCl/HCl = 0.11–0.97 and KCl/HCl = 0.24–1.62, being the highest range of values (0.79–0.97 and 1.45–1.62, respectively) found in those alkali-chloride-bearing samples. Maximum HCl/ΣCl(MVP) (0.28 to 0.31) indicates higher total Cl concentration in the MVP of alkali-chloride-bearing aplites, which is much higher in the halite-free aplite samples (HCl/ΣCl(MVP) = 0.59 to 0.74). One miarolitic monzogranite sample, where halite solid inclusions are present, also yielded the highest ratios for NaCl/HCl(MVP) (0.91) and KCl/HCl(MVP) (1.46), and the HCl/ΣCl(MVP) is 0.30. A high HCl concentration in the fluid phase is suggested by the log f(HF)/f(H2O) = − 4.75 to − 4.95, log f(HCl)/f(H2O) = − 3.73 to − 3.86, and log f(HF)/f(HCl) = − 0.88 to − 1.22, computed at 750 °C after biotite composition. The Cl concentrations at 800 °C, computed with a Dv/lCl = 0.84 + 26.6P (P at 200 MPa), yielded values within the range of 70 to 700 ppm Cl in the melt and 4000 to 40 000 ppm Cl in the coexisting MVP. The preferential partitioning of Cl in the vapor phase is controlled by the Dv/lCl; however, the low concentration of Cl in the melt suggests that high concentrations of Cl are not necessary to saturate the melt in NaCl or KCl.Cl-saturation of the melt and coexisting MVP might have been produced by a drop in Cl solubility due to the near-haplogranitic composition of the granitoids after extreme fractionation, probably enhanced by fluctuating reductions of the emplacement pressure in the brittle monzogranite host. Liquid immiscibility, based in the differential viscosity and density among alkali-chloride saturated hydrosaline melt, aluminosilicate felsic melt, and H2O-rich volatiles is likely to have crystallized halite and sylvite from exsolved hydrosaline melt. High degrees of undercooling might have been important at the time of alkali-chloride exsolution. The effectiveness of alkali-chloride separation from the melt at magmatic temperatures is in line with the interpretation of “halite subtraction” as a necessary process to understand the origin of the “halite trend” in highly saline fluid inclusions from porphyry copper and other hydrothermal mineralizations, despite the absence of the latter in the Cerro Baritina aplites, where this process preceded the exsolution of halite-undersaturated fluids.Pervasive alteration of the monzogranite country rock as alkali-metasomatic mineral assemblages, the mineral chemistry of some species, and the association of weak molybdenite mineralization are compatible with the activity of alkaline hypersaline fluids, most likely exsolved during the earliest stages of aplite consolidation. 相似文献
Long-chain amines, used in potash ore flotation as collectors, are insoluble in NaCl–KCl saturated brine. In commercial applications, these amines are melted at 70–90 °C, dispersed in acidic solution of hydrochloric or acetic acids, and such emulsions are then introduced to the flotation pulp.To model the commercial potash ore flotation process, dodecyl amine, used in this study, was melted at 70 °C, dispersed in hydrochloric acid aqueous solution and was added to a KCl–NaCl saturated brine at room temperature. This results in the precipitation of the amine. The present study summarizes the influence of the conditions on the particle size and morphology of the precipitating amine particles. Methyl isobutyl carbinol (MIBC), common frother in flotation processes, was shown to affect amine dispersion when added into a hot amine emulsion prior to mixing with a saturated brine. This study demonstrates that the precipitating amine particles are selectively abstracted by KCl particles, but not by NaCl particles. 相似文献
Over the last decade, our studies in ancient evaporitic basins have been based on a detailed study of a single borehole record. The detailed findings in medium- to large-sized evaporitic basins were shadowed with a relevant question: can interpretations from a representative evaporitic record in a single borehole be extended to the whole evaporitic basin? This paper addresses that question; the results obtained are compared with results from another distant point within the basin. The general methodology not only proves its reliability in interpreting the evolution of evaporitic basins from a single borehole but reveals its capability to obtain detailed palaeoenvironmental interpretations.
The chemical evolution of an Upper Eocene evaporitic sequence from the South Pyrenean foreland basin (Spain) has been investigated along the Súria-19 borehole record. Detailed petrographic and mineralogical study, X-ray microanalysis of frozen primary inclusions trapped in halite (Cryo-SEM-EDS), systematic isotopic analysis (δ34S and δ18O in sulphates) and computer-based evaporation models have been integrated in a multi-proxy methodology. This study revealed that a variable amount of Ca excess is required throughout different parts of the marine Lower Halite Unit (LHU) for sylvite, instead of K–Mg sulphates, to form. This Ca excess is in turn different from that required for the western sector of the same evaporitic basin (Navarrese subbasin). Quick and variable changes in Ca-rich brines or equivalent dolomitization required are explained as internal processes within the basin rather than secular variations in seawater chemistry.
The general hydrological evolution of the Catalan subbasin is explained as a restricted subbasin with a first marine stage in which continental input (up to 50% of total input) had an important control on the geochemistry of the subbasin. A second stage was determined during potash precipitation, in which the subbasin was cut from any seawater input to end up in its last stage as a purely continental evaporitic basin. Coupling evaporation models and analytical results we have obtained the proportions of recycling and their sources, estimated to change from a 100% (total mass of sulphate) Eocene source to 20% Eocene and 80% Triassic (Keuper) towards the latest stage of potash precipitation. The results obtained have been compared with results from the Navarrese subbasin allowing an integrated interpretation of the hydrological evolution of the whole Upper Eocene South Pyrenean basin. Local geochemical variations within the Upper Eocene south Pyrenean basin are explained by the differences in paleogeographical setting of the Navarrese and Catalan subbasins. 相似文献