Trace element (TE) partitioning in the system "mineral-hydrothermal solution" is studied by the method of thermo-gradient crystal growth coupled with internal sampling of a fluid phase. The analytical procedure used enables evaluating of structurally bound and superficially bound modes of TE in crystals and determining corresponding dual partition coefficients. The case of precious metals (PM-Au, Pt, Pd) at 450 and 500 • C and 100 MPa pressure is considered. The minerals are pyrite, As-pyrite, magnetite, Mn-magnetite and hematite and fluids are ammonium chloride-based hydrothermal solutions. The partition coefficients for structural and surficial modes, D str p and D sur p , are found to be unexpectedly high (except for Au in pyrite). High concentrations of PM are attributed to superficial nonautonomous phases (NAPs), which can be considered as primary concentrators of PM. We also have studied the co-crystallization (exchange) coefficients (D e) of REE (Ce, Eu, Er, Yb) and Fe in magnetite and hematite at 450 • C and 100 MPa. D sur e is elevated to two orders of magnitude as compared to D str e. It is shown that not only physicochemical parameters affect REE distribution in hydrothermal systems, but also NAP presence and its composition. The crystal growth mechanism specified by the agency of NAP is suggested. The study of PM distribution in natural pyrite of gold-ore deposits supported the importance of differentiating between structurally and superficially bound TE modes for correct use of experimental D values to determining element concentrations in ore-forming fluids.

The gold distribution in 32 pyrite samples and some samples of other ore minerals is studied using the method of statistical samplings of analytical data for single crystals. The samples were recovered from deposits of different genetic types within the largest gold provinces of Russia and Uzbekistan. The contents of uniformly distributed gold and the ratios of its structurally to superficially bound forms have been determined. According to the Au–As diagram for the chemical states of gold, uniformly distributed gold in pyrite is chemically bound in the overwhelming majority of cases. The previous experimental data suggest that it is partly incorporated into pyrite and partly into the structures of nanosized nonautonomous phases on the surface of the pyrite crystals. Micro- and nanoparticles of native gold might appear during postgrowth transformations of these phases. Data on the other ore minerals suggest that the dependence of the content of uniformly distributed gold on the size or specific surface area of the crystal and the superficial position of its considerable part are common to the ore minerals. It is shown for pyrite that the observed features are commonly found at deposits of different genetic types, only with differences in the slope and determination coefficients of the dependences. The size dependences of the contents of gold and other elements in pyrite are genetically significant, because they give an insight into the ore-forming processes. The data on structurally bound gold permit comparative evaluation of gold concentrations in ore fluids forming gold deposits of different genetic types.

No abstract

The interfacial crystal layer of poorly soluble mineral grown under hydrothermal conditions is modified chemically into a surficial nonautonomous phase (SNAP) and, in this capacity, takes part in growth process, doing several important functions. This paper considers some of them related to geochemistry and mineralogy. The new interpretation is given to the following phenomena: (1) selection of components during crystal growth in multiphase associations; (2) stability of multiphase parageneses having a common chemical component; (3) dual character of the distribution coefficients due to different properties of the crystal volume and SNAP; (4) formation of nano- and microinclusions of unusual composition different from the basic mineral phase; (5) spatial ordering of nano- and microparticles during their directed aggregation at the growing crystal face; (6) accumulation of valuable components (primarily noble metals), incompatible in most of mineral matrixes, in the surficial layer; and (7) effect of “hidden” metal content, associated with the presence of noble metals in the SNAP or of nano- and microinclusions formed during the SNAP evolution.

No abstract