The Biga Peninsula of NW Turkey is host to many kaolin and halloysite deposits with mineralization occurring at the intersections of fault zones in contact with Late Eocene-Miocene calc-alkaline volcanic rocks. Distinguishing between the relative overprinting of hypogene by supergene processes in these deposits is a challenge and important because they affect the physical-chemical properties of minerals and their potential for industrial applications. This study examines the Sarıbeyli-Sığırlı and Bodurlar kaolin deposits in NW Turkey, which were formed from similar volcanics as evidenced by 40Ar/39Ar. Late Eocene (34.2 ± 0.20 Ma) to Early Oligocene (32.7 ± 0.17 Ma) ages for both primary volcanic rocks and alunites are consistent with surrounding rocks in the Çanakkale region. Criteria used to distinguish hypogene alteration from supergene alteration processes come from X-ray diffraction (XRD), Fourier-transform infrared (FTIR) and Raman spectroscopies, thermal gravimetric analysis (TGA), scanning and transmission electron microscopy (SEM, TEM), and elemental analyses. Isotopic δ18O depletion and δD enrichment of the Sarıbeyli-Sığırlı deposit suggests that it was more influenced by magmatic waters than was the Bodurlar deposit. The Bodurlar deposit contains a paucity of dickite compared to the Sarıbeyli-Sığırlı deposit, which is evidenced by lower TGA endotherms, higher ratios of XRD intensities for reflections at 1.316 Å and 1.307 Å, distinctive FTIR absorbance bands at 3620 cm− 1 and 3652 cm−1, and relative Raman intensities of the γ1 and γ5 vibrational modes.A genetic model is proposed whereby these deposits are mainly formed through an acid-sulfate hydrothermal alteration, in what appears to be a volcanic-hydrothermal system. The extent of hydrothermal alteration was controlled by fault density and the initial texture of the volcanic rocks. These steam-heated environments included sulfide-enriched vapors and groundwater mixed to varying degrees in the vadose zone. The Sarıbeyli-Sığrlı and Bodurlar deposits, respectively, contain mineral assemblages that reflect both hypogene (kaolinite, alunite, dickite) and supergene (kaolinite, halloysite, jarosite) processes. These observations offer a basis for comparing and discriminating the relative influence of these two important alteration processes responsible for the formation of kaolin deposits in NW Turkey and around the world.

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Dacitic andesitic calc-alkaline lavas and their pyroclastic rocks of Upper Cretaceous age are widespread in the Ordu area, eastern Black Sea Coast of Turkey. Ca-bentonite and Ca/Nabentonite deposits with significant economic potential formed in the broader region. The mineralogy and geochemistry of these deposits were studied by X-ray diffraction (XRD), scanning electron microscopy (SEM) and chemical analyses. The parent rocks (PR) and bentonite samples were analysed for the major and trace element contents, including rare-earth elements, to understand the effect of differential alterations on element mobility. The bentonites contain mainly di-octahedral Ca-montmorillonite with minor amounts of illite, quartz, calcite, dolomite and feldspar. Primary K-feldspar and plagioclase phenocrysts were altered in the bentonite horizons, and were completely leached at greater depth. For this reason, the higher quality bentonites are found at deeper zones. Bentonite horizons are characterized by relatively high loss on ignition (LOI: 9.8–20.8%) and MgO content (3–5%) and low K2O (<0.5%) and Na2O (<2%) contents compared with the least altered parent rocks. Silicon, Ca, Mg, Mn and P are markedly enriched whereas Fe, Na, K and Ti are depleted in the bentonite samples. The chondrite-normalized rare earth element (REE) patterns show identical trends characterized by strong light rare earth element (LREE) enrichment in both the PR and bentonite samples. The LREE contents are higher than those of their heavy counterparts (HREE) in the samples. Alteration of the PR to bentonite is associated with intense chemical leaching and subsequent removal of K and Na in open-system conditions.

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