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Stratigraphy, mineralogy, and genesis of the Bigadic borate deposits, western Turkey
Abstract and Figures
The Bigadic borates are the largest colemanite and ulexite deposits in the world. The Bigadic deposits formed within Neogene perennial saline lakes sediments located in a northeast-southwest-trending basin. The volcano-sedimentary sequence in the deposits consists of (from bottom to top) basement volcanics, lower limestone, lower tuff, lower borate zone, upper tuff, upper borate zone, and olivine basalt. The borate deposits formed under arid conditions in perennial saline lakes fed by hydrothermal springs associated with local volcanic activity. The deposits are interbedded with tuffs, clays, and limestones. -from Author
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... The Borate Basin around Bigadiç in Western Anatolia is extensively recognized with its Miocene borate deposits attracting widespread interest. On-going explorations and exploitation activities in the basin revealed the clay layers of the deposits are Lithium-rich [29][30][31][32][33][34][35][36]. The initial investigation of Li leaching was conducted by [37] utilizing sulfuric acid solution from ulexite-clay samples sourced from the Kırka borate deposit, including dolomite, montmorillonite, and hectorite. ...
... In the lower section, the units enriched in borate minerals consist of intercalations of clayey limestone, marl, claystone, mudstone and tuff. In the upper section, the lithological sequence is very closely similar to that of the lower section, where units such as limestone, claystone, clayey limestone, marl and tuff are intercalated [30,41] (Figure 1, stratigraphic section, left). This study used samples from the upper borate zone of the Simav quarry. ...
... for EG-solvated and thermally treated samples. (the formation colors correspond to the generalized stratigraphic section) (Modified from [30,41]). ...
... The Borate Basin around Bigadiç in Western Anatolia is extensively recognized with its Miocene borate deposits attracting widespread interest. On-going explorations and exploitation activities in the basin revealed the clay layers of the deposits are Lithium-rich [29][30][31][32][33][34][35][36]. The initial investigation of Li leaching was conducted by [37] utilizing sulfuric acid solution from ulexite-clay samples sourced from the Kırka borate deposit, including dolomite, montmorillonite, and hectorite. ...
... In the lower section, the units enriched in borate minerals consist of intercalations of clayey limestone, marl, claystone, mudstone and tuff. In the upper section, the lithological sequence is very closely similar to that of the lower section, where units such as limestone, claystone, clayey limestone, marl and tuff are intercalated [30,41] (Figure 1, stratigraphic section, left). This study used samples from the upper borate zone of the Simav quarry. ...
... for EG-solvated and thermally treated samples. (the formation colors correspond to the generalized stratigraphic section) (Modified from [30,41]). ...
Although lithium is a common element worldwide, it is primarily concentrated in specific areas, including pegmatites, granites, and clays, as well as brine. Today, research in various countries is exploring experimental techniques for extracting Li from Li rich rocks and clays. The Bigadiç boron deposits form in a volcano-sedimentary environment in western Turkey, and their boron minerals interlayer with significant amounts of Li-rich hectorite. However, the clays' high Mg content presents a significant complication, increasing the cost of lithium processes and necessitating an intricate extraction process. In this study, a solution with high Li and low Mg content was obtained by a two-step extraction process from raw Bigadiç clays with high Li content. Raw hectorite samples NaCl, CaCl2 and FeCl3 cation sources were mixed by the mechanical mixing method to provide cation absorption on the clay surface. The targeted ion, Li, was transferred from the clay to the solution by preferential displacement using acid treatment. The findings produced through DLi =[Li(clay)]/[Li(aq)] (ppm/ppm) and logDLi= 1319/T(K) + 5.5 ([Li(aq)]) -0.0806 formulae were analyzed and interpreted. The investigation has demonstrated the viability of selective cation exchange procedures upon rich lithium clay reserves present in Bigadiç.
... The Li-bearing claystone, marl, carbonate, and silicified carbonate are associated with the Miocene Bigadiç colemanite-and ulexite-type borate deposits. These are the sediments of lacustrine volcanicsedimentary succession in the Bigadiç area, western Anatolia developed in a tectonically active closed basin hosting important resources of coal, bituminous shale, clay, borate, and zeolite deposits (Helvacı, 1995;Helvacı et al., 2004;Helvacı, 2015aHelvacı, , 2015b. ...
... The Bigadiç borate deposits and the surrounding region have been studied for their geology, mineralogy, and genesis (Ataman and Baysal, 1978;Helvacı, 1995;Helvacı, 1995, 1997;Floyd et al., 1998;Helvacı et al., 2004;Palmer et al., 2004;Küçük et al., 2002;Küçük and Kocakerim, 2005;García-Veigas et al., 2011;García-Veigas and Helvacı, 2013;Ortí et al., 2016;Helvacı, 2015aHelvacı, , 2015bHelvacı and Palmer, 2017;Seghedi et al., 2013;Seghedi and Helvacı, 2016). ...
... This research focuses on the mineralogy and Fig. 1. Geological maps of the Bigadiç borate deposit (modified from Helvacı, 1995 and. geochemistry of the Li-rich claystone alternated with the volcanic and carbonate units to determine the deposition and physicochemical conditions of the alteration processes and their genesis in the Bigadiç borate deposits. ...
Mineralogy, geochemistry, and genesis of lithium-bearing argillaceous
sediments associated with the borate deposit.
... The Li-bearing claystone, marl, carbonate, and silicified carbonate are associated with the Miocene Bigadiç colemanite-and ulexite-type borate deposits. These are the sediments of lacustrine volcanicsedimentary succession in the Bigadiç area, western Anatolia developed in a tectonically active closed basin hosting important resources of coal, bituminous shale, clay, borate, and zeolite deposits (Helvacı, 1995;Helvacı et al., 2004;Helvacı, 2015aHelvacı, , 2015b. ...
... The Bigadiç borate deposits and the surrounding region have been studied for their geology, mineralogy, and genesis (Ataman and Baysal, 1978;Helvacı, 1995;Helvacı, 1995, 1997;Floyd et al., 1998;Helvacı et al., 2004;Palmer et al., 2004;Küçük et al., 2002;Küçük and Kocakerim, 2005;García-Veigas et al., 2011;García-Veigas and Helvacı, 2013;Ortí et al., 2016;Helvacı, 2015aHelvacı, , 2015bHelvacı and Palmer, 2017;Seghedi et al., 2013;Seghedi and Helvacı, 2016). ...
... This research focuses on the mineralogy and Fig. 1. Geological maps of the Bigadiç borate deposit (modified from Helvacı, 1995 and. geochemistry of the Li-rich claystone alternated with the volcanic and carbonate units to determine the deposition and physicochemical conditions of the alteration processes and their genesis in the Bigadiç borate deposits. ...
Lithium distribution in Bigadiç Borate Deposit and lithium-borate relations
... Diğer kullanım alanları ise kimyasal gübreler, yangın geciktiriciler ve metal alaşımlarıdır [2]. Türkiye dünya bor rezervlerinin %70' inden fazlasına sahiptir [3][4]. Türkiye'de bor (B) içeren deterjanlar ve kimyasallar son yıllarda yaygın olarak kullanılmaya başlanmıştır. ...
Guleman bölgesi, Türkiye' nin en önemli krom cevheri üreten bölgelerinden biri olup, geniş alanda serpantinli kayaçlar yüzeylemeler vermektedir. Bu çalışma Guleman serpantinli toprakları üzerinde yetişen Teucrium polium bitkisinin kök ve dalındaki bor akümülasyonlarını incelemiştir. Çalışma alanında serpantinli topraklar üzerinde yetişen 17 adet Teucrium polium bitkisi toprağı, kök ve dalı ile birlikte toplanarak, bor için ayrı ayrı kimyasal analizleri yapılmıştır. Kimyasal analizler ICP-MS (İndüktif Eşleşmiş Plazma-Kütle Spektrometresi)’de gerçekleştirilmiştir. Ortalama olarak toprakta 7,94 ppm, kökte 14,8 ppm ve dalda ise 70,06 ppm bor değerleri saptanmıştır. Bu bitkinin toprak, kök ve dallarındaki bor zenginleşme değerleri (ECR, ECS ve TLF) oldukça yüksek çıkmıştır. Bu değerler de Teucrium polium bitkisinin topraktan hem köke, hem de dala önemli oranda bor akümülasyonu gerçekleştirdiğini göstermiştir. Sonuç olarak bu bitki, özellikle bor ile kirlenmiş toprakların ıslah çalışmasında ve böyle alanların iyileştirilmesinde biyoakümülatör bitki olarak değerlendirilebileceğini göstermiştir.
... Celestines are associated commonly with gypsum, anhydrite, native sulphur (evaporites), strontianite, calcite, dolomite, anhydrite, gypsum and fluorite (cavities in carbonate rocks); and also occur jointly with analcime, natrolite, hydroxyapophyllite and celadonite (mafic volcanoclastics). The presence of celestine can be the mark of a redox environment (Hadji et al., 2019); however, anhydrite, celestine and analcime are rarely observed within borate deposits (Helvaci, 1995). Nakamura et al. (2010) describe an occurrence from the Bohemian massif, Czech Republic of eclogite as a carrier of Sr-sulfate celestine. ...
Five celestine crystals were sampled from the (palaeo)surface intervening between the late Miocene to Pleistocene basaltic sequences of the Jabal Eghei (Nuqay) volcanic province in southern Libya and then characterised by applying a combination of the SEM–WDS, ICP/OES, PXRD and IR methods. Colour variations and related minerogenetic frameworks were also investigated. Three samples have greenish-blue-to-blue colour (480.4–482.5 nm), whereas the other two samples have blue–green colour (cyan; 489.1–494.1 nm). The colour purity ranges from 1.36–7.16. Their composition is similar, end-member celestine, in which only 1.6–4.1 at.% of Sr ²⁺ content was substituted by Pb ²⁺ (0.7–0.9 at.%), Ba ²⁺ (0.5–0.7 at.%) and Ca ²⁺ (0.2–0.8 at.%). Three samples contained vacancies, from 1.0 to 1.9 at.%. The content of other chemical elements is minor. The resulting unit-cell parameters have the ranges: a 0 = 8.3578(9)–8.3705(6) Å; b 0 = 5.3510(5)–5.3568(4) Å; c 0 = 6.8683(7)–6.8767(2) Å and V 0 = 307.17(5)–308.34(4) Å ³ . The PXRD and IR results are mainly in accordance with the SEM–WDS results, with a high level of correlation. However, a few discrepancies were found, producing several possible interpretations, the primary cause being a slight unit-cell axial anisotropy i.e. thermal expansion. As a consequence these results yield a new geothermometric tool that is based on the unit-cell axial anisotropy. The celestines investigated were formed during a Miocene intraplate volcanism with basaltic magmas, and associated brines lifted by the structural conduits (normal faults crosscutting the Sirt basin). The Sr-bearing fluids then poured into and over the faulted and fractured lagoon-type gypsum, anhydrite Eocene sediments. The celestine mineralisation formed within a ~368–430 K (~95–157°C) temperature range. The celestine formed at slightly elevated temperature and pressure conditions, close to the shallow subsurface environment (over 250 bars).
... Different borate minerals are commonly interbedded in both Turkish and South American borate deposits (Helvaci and Alonso, 2000); hence, oxygen isotope analyses of closely coexisting borate minerals may aid in determining the extent to which changes in borate mineralogy reflect changing chemical and physical conditions. Oxygen isotope analyses may also help distinguish between borate minerals in deposits that were precipitated directly from lake waters versus those that precipitated within sediments (e.g., Helvaci, 1995) as the latter would be expected to record diagenetically altered porewater oxygen isotope compositions. ...
... The rapid tectonic denudation was due to differential footwall uplift during the early Miocene, and the formation of the Central Menderes Metamorphic Core Complex (CMCC; 'inner' axial zone) by late Miocene to recent detachment fault and normal fault systems, located between northern and southern (Çine) segments of the complex (Fig. 1b). The Menderes Massif includes the NE-SW trending Miocene Gördes, Demirci, Selendi, and Uşak-Güre basins in its northern part (Seyitoğlu & Scott, 1991;Seyitoğlu & Scott, 1994;Helvacı, 1995;Helvacı & Yağmurlu, 1995;Seyitoğlu, 1997;Yılmaz et al., 2000;Bozkurt, 2003;Purvis & Robertson, 2004;Westaway et al., 2004;Erkül et al., 2005;Ersoy & Helvacı, 2007;Ersoy et al., 2010;Karaoğlu et al., 2010;Ersoy et al., 2011Ersoy et al., , 2012. These basins were cut by seismically active E-W-trending obliquenormal faults, resulting in the formation of the Simav and Gediz grabens under the late Miocene to recent N-S rift-type extensional tectonics (Seyitoğlu, 1997;Cohen et al., 1995;Bozkurt & Sözbilir, 2004;Rojay et al., 2005;Emre & Sözbilir, 2007;Çiftçi & Bozkurt, 2009;Ersoy et al., 2010Ersoy et al., , 2011Ersoy et al., , 2012Hakyemez et al., 2013;Hetzel et al., 2013) (Fig 1b). ...
... En Hillsborough (Walker, 1921), New Brunswick y Wentworth (Goodman, 1957), Nova Scotia, Canadá. En Kirka, provincia de Eskiçehir (Innan et al., 1973;Helvaci & Ortí, 2004) y en la mina Büyük Günevi, en el distrito Bigadiç, provincia de Balikesir, Turquía (Helvaci, 1995;Helvaci & Alonso, 2000). Inyoíta primaria se presenta en A nicoles cruzados, el mineral muestra colores de interferencia de segundo orden y carácter óptico biáxico, con signo óptico negativo. ...
Luego de la Guerra del Pacífico de 1879, Chile anexó territorios de Perú y Bolivia y ocupó el actual territorio de la Puna Argentina. Entre 1884 y 1887 el gobierno de Chile envió numerosas misiones científicas con el objetivo de estudiar la geología y recursos del nuevo territorio, que recibía el nombre generalizado de Puna de Atacama, entre ellas las de Francisco J. San Román, Lorenzo Sundt y Alejandro Bertrand. San Román recorre la Puna en dos oportunidades y realiza valiosas observaciones que vuelca en libros y un mapa a escala 1:1.000.000 que publica en 1892. La lectura cuidadosa de ese material, que completará el geólogo noruego Lorenzo Sundt luego de la muerte inesperada de San Román, contiene datos valiosos para la geología regional. Se encuentran allí, entre muchas otras, las
primeras menciones de granitoides de la Faja Eruptiva de la Puna, las rocas metamórficas del complejo Antofalla (cratón Arequipa-Antofalla), los géiseres gigantes de Botijuelas y los boratos de las terrazas pleistocenas del salar de Pastos Grandes. Describe un perfil estratigráfico de lo que hoy se conoce como Formación Blanca Lila. Se detiene en la presentación de los boratos y sus texturas, especialmente ulexita y menciona la presencia de un “borato petrificado”. Ese borato resultó ser inyoíta, la que 30 años después sería descripta en California por Waldemar Schaller (1916). En este trabajo se analizan algunas de los principales aportes de San Román a la luz de las investigaciones actuales.
This account presents detailed calibrations which can be used in other laboratories for the ultra-rapid X-ray chemical analysis of rock powders for 38 major and trace elements. The major element calibrations are based on 16,000 measurements on about 400 previously analysed rocks and working equations are given for rhyolites, granodiorites, granites etc., amphibolites, basalts, dolerites, pelites, semipelites, carbonate-rocks, and psammites. Trace elements have been calibrated by spiking nine carefully analysed rocks with 1,500 different amounts of added spectrographically pure chemicals. All the calibrations have been computer-calculated and are given in terms of ratios of counts relative to one rock, an amphibolite, which is available for general distribution and thus enables other laboratories to use the calibrations. By this ratio technique very high precision has been obtained. The results of extensive investigations into the optimum conditions for the determination of the 38 elements as regards X-ray tubes (Cr, W or Mo); kV and mA; analysing crystals; peak and background positions; counters etc. are summarised in tables.
A-ct -Borate minerals, such as colemanite, ulexite and borax, have been reported in Tertiary continental basins of West Anatolia, Turkey, and Samos Island, Greece. Tuffaceous rocks interbedded with the borates are rich in authigenic silicate minerals such as zeolites, potassium feldspar and opal-CT, all of which have a genetic association with the borates. Chemical analyses of the tuffaceous rocks show variation in major elements due to the varying per-centage of carbonaceous, detrital, and volcanic derived material. The volcanic activity in the vicinity of each particular lacustrine basin created ion-rich fluids from which a series of borates were precipitated under arid climate. Additionally, the We-alkaline character of these fluids was responsible for the diagenesis of the silicic glass of the tuffaceous rocks, altering them to silicates and silica polymorphs.
Most lakes are well flushed and the chemical constituents of their waters do not accumulate beyond the potable range. In unusual circumstances, however, the solute load may be increased and the lake then becomes saline. This is caused either by evaporation exceeding inflow or by the inflow being saline or both. Saline lakes are quite common in certain parts of the earth, but they have neither the size nor abundance of normal lakes. For this reason, few extensive studies have been made of such lakes and consequently their hydrologic, geochemical, sedimentological, and biological environments remain little explored. This is a pity, for saline lakes have much to teach us about processes under extreme conditions and, once we understand them, we will have greatly improved our understanding also of normal lakes. This paucity of studies is also surprising because saline lakes not only are of economic significance but are important in the geologic record as sensitive indicators of past tectonic and climatic events.
The Green River Formation of Wyoming was deposited in a large lake, Lake Gosiute, during Eocene time. Throughout Lake Gosiute's existence, nearby volcanism supplied debris to the lake basin. Tuffs are abundant and widespread in the formation and were highly reactive units. Reaction between glass and the lake waters produced authigenic clay minerals, mordenite or clinoptilolite, analcime, and potassium feldspar. Some tuffs are almost entirely replaced by authigenic aluminosilicate minerals. The alteration of the tuffs shows a systematic pattern with the clay mineral and zeolite alteration restricted to facies formed in relatively fresh water, and the feldspar alteration is confined to a hypersaline facies. We infer that the lake water ranged from fresh or brackish (SiO2 = 10 ppm, K = 50 ppm, Na = 1,000 ppm) at a pH of 8.0 during the "fresh-water stage" to hypersaline (SiO2 = 1,000 ppm, K = 5,000 ppm, Na = 100,000 ppm) at a pH of 9.0 to 10.0 during the most saline and alkaline stage. Brines were formed primarily by evaporative concentration. Organisms, reflected by abundant high-yield oil shales, thrived during the freshwater episodes, but were apparently absent or of minor significance during the hypersaline episodes; this is reflected by the presence of thick beds of trona and halite.
Waters of widely differing chemical compositions have been considered at least in part volcanic in origin, and are commonly associated with each other in the same area. Do any or all of these types contain volcanic components, and if so, how are the different types derived? To determine the probable characteristics of volcanic waters, the writer has selected hot-spring groups that are particularly high in temperature and associated heat flow, are associated with late Tertiary or Quaternary volcanism, and are therefore most likely to contain some water and chemical components of direct volcanic origin. Of the different types of water that occur in these groups, one of the most common is characterized chemically by a dominance of sodium chloride. Isotopic evidence indicates that the contribution of water of direct volcanic origin is not large and is probably no more than 5 per cent in typical sodium-chloride springs. The compositions of volcanic waters are believed to be determined by: [1] type of magma and stage of crystallization; [2] temperature and pressure of the emanation at different stages during and after departure from the magma; [3] chemical composition, relative quantity, and depth of penetration of mixing meteoric water and water of other origin; and [4] reactions with wall rocks. Although the type of magma and its stage of crystallization are of major interest and have been emphasized in the past, the outstanding characteristics of volcanic emanations at and near the surface of the earth seem to be controlled for the most part by the other factors. Nonvolatile compounds are slightly to highly soluble in steam at high pressure, and high-density steam has solvent properties similar to those of liquid water. In the volcanic sodium-chloride waters, the high ratio of lithium to sodium and potassium is shown to indicate that alkalies were transported as alkali halides dissolved in a dense vapor. This in turn demands a deep circulation of meteoric water for steam to condense at high pressure and for the halides to remain in solution. The depth of circulation of meteoric water in the sodium-chloride spring systems is believed to be in the order of 2 miles. Where circulation of meteoric water is shallow, the vapors rise and expand at low pressure, which does not permit transport of substances of low volatility; some type of water other than the sodium-chloride type is formed. The common volcanic sodium-chloride waters are therefore concluded to be the diluted product of high-density emanations, modified by reactions with wall rocks and by precipitation of the less soluble components. Emanations at high temperature and relatively low pressure consist almost entirely of steam and volatile components. Their compositions are therefore relatively simple, and their ability to transport matter of low volatility is very limited. The sodium-chloride type is probably gradational into acid-sulfate-chloride waters. There is some evidence that, under conditions not well understood, sulfur may be emitted as SO(2), SO(3), or other sulfur species of intermediate valence, rather than as H(2)S or S. Other major types of volcanic waters are called sodium bicarbonate, acid sulfate, and calcium bicarbonate; the first two tend to be distinct, but the calcium-bicarbonate type clearly grades into the sodium-chloride type. The writer concludes that, in general, all these are derived from the sodium-chloride waters as a result of physical environment or of reactions with wall rocks.
Geological and K/Ar data are presented for 41 mines and prospects where Cu is present as a major ore element associated with subvolcanic igneous rocks. Each mine is associated with a different hypabyssal intrusive or breccia pipe. Mineralization occurs as dissemination, stockwork, breccia filling, replacement, skarn, pegmatite, manto and fissure vein occurrences. All but eight of the dated porphyry-Cu deposits were emplaced during the Laramide episode of maximum plate convergence. The porphyries appear to be apophyses of the batholiths. The relationships suggest that the ore components are contained within the calc-alkaline batholiths and were concentrated in the subvolcanic porphyries and wall rocks during transport of hydrothermal fluids to the volcanic orifice. The shape of the Cordilleran Cu belt is controlled by magma composition, protective capping, uplift, time and erosion. As the volcanic arc that produced the deposits progressed eastward, the associated magma became more alkalic and Cu-poor.-P.Br.
Occurrence, stratigrapliic position and genesis of the borate deposits in Puna, Argentina: Unpublished P1i.D. dissertation, AIgentina
- R N Alonso
Alonso, R.N., 1986, Occurrence, stratigrapliic position and genesis of the
borate deposits in Puna, Argentina: Unpublished P1i.D. dissertation, AIgentina, Universiclad Nacional de Salta, 196 p.