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THE KAKOPETROS AND RAVDOUCHA IRON-OXIDE DEPOSITS, WESTERN CRETE, GREECE: FLUID TRANSPORT AND MINERALIZATION WITHIN A DETACHMENT ZONE

Markus Seidel^,* and Andreas Pack^**

Institut für Mineralogie and Geochemie, Universität zu Köln, 50674 Köln, Germany

Zachary D. Sharp

Department of Earth and Planetary Sciences, University of New Mexico, Albuquerque, New Mexico 87131-1116

Eberhard Seidel

Institut für Mineralogie and Geochemie, Universität zu Köln, 50674 Köln, Germany

e-mail, Markus.Seidel{at}gmx.net

	Abstract

Top Abstract Introduction Geologic Setting Iron-Oxide Deposits and Field... Mineralogy and Petrography Geochemistry and Oxygen Isotope... Discussion and Implications Conclusions APPENDIX References

 
Small iron deposits at Kakopetros and Ravdoucha in western Crete are hosted by an extensional detachment zone at the roof of the high-pressure–low-temperature metamorphic core complex known as the Phyllite-Quartzite unit. The iron oxides occur in a brecciated layer of phyllite, quartzite, and marble up to tens of meters thick. They fill fractures and vugs in the breccia and partly impregnate the marble. The iron oxides, which were formerly mined in open pits, are predominantly composed of goethite and subordinate oxyhydroxides of the manganomelane group. The field relationships and microstructures indicate that precipitation of the iron-oxide minerals was related to fluid flow focussed along the detachment fault. ¹⁸O values of goethite indicate crystallization at low temperatures (31°–40°C) and at a shallow depth of about 1 km. Microscopic investigations show that the deposition of iron oxides was syntectonic and occurred during deformation in the uppermost crust. Similar iron oxides are reported from low-angle brittle detachment horizons in the Cordilleran metamorphic core complexes of North America and suggest that small iron- and manganese-oxide deposits of this type may be a characteristic feature of detachment zones.

	Introduction

Top Abstract Introduction Geologic Setting Iron-Oxide Deposits and Field... Mineralogy and Petrography Geochemistry and Oxygen Isotope... Discussion and Implications Conclusions APPENDIX References

 
Distinctive mineralization related to detachment faulting and having characteristic mineral assemblages, alteration patterns, and structural features has been documented in the Basin and Range province in the western United States (e.g., Long, 1992). Similar iron-oxide deposits of western Crete (Fig. 1) are also located within a detachment zone setting (low-angle normal fault). However, the origins of this mineralization are not well understood (e.g., Spencer and Welty, 1986; Wilkins et al., 1986; Roddy et al., 1988; Spencer and Reynolds, 1989; Long, 1992). Such occurrences may be an indication of deep crustal fluid flow resulting from retrograde metamorphism in hot lower plate rocks or they may represent low-temperature circulation of fluids at shallower crustal levels. So-called ferruginous alteration is common along extensional detachment faults, such as in the Basin and Range (e.g., Buckskin Mountains, Arizona; Davis and Hardy, 1981). In this study, we examine the origins of two iron-oxide deposits associated with detachment faulting in western Crete and document the conditions and scale of hydrothermal fluid flowing along the detachment fault in this setting on the basis of petrographic, chemical, and oxygen isotope data.

View larger version (73K): [in this window] [in a new window]   FIG. 1. A. Generalized geologic and tectonic map of western Crete (modified from Creutzburg et al., 1977; and Kopp and Ott, 1977), showing the tectonic units, the detachment fault, and the two major iron-oxide deposits, located in the roof of the Phyllite-Quartzite unit. B. and C. Detailed geologic maps and cross sections of the Kakopetros and Ravdoucha iron-oxide deposits. Note vertical exaggeration of the cross sections.

	Geologic Setting

Top Abstract Introduction Geologic Setting Iron-Oxide Deposits and Field... Mineralogy and Petrography Geochemistry and Oxygen Isotope... Discussion and Implications Conclusions APPENDIX References

 
The island of Crete represents a horst structure in the fore arc of the Hellenic subduction zone. The geologic record of Crete documents the evolution of the plate boundary between Eurasia and Africa during the last 30 m.y. The architecture of Crete comprises a pile of nappes (Fig. 2) derived from different paleogeographic zones (for details, see Seidel and Wachendorf, 1986). During collision between Eurasia and the subducting African plate, the lower tectonic units (Plattenkalk unit, Phyllite-Quartzite unit) were overprinted by high-pressure–low-temperature metamorphism in the late Oligocene to early Miocene (Seidel et al., 1982; Jolivet et al., 1996). The higher tectonic units (Tripolitza unit, Pindos unit, Uppermost unit) were not affected by Tertiary high-pressure–low-temperature metamorphism. The metamorphosed rocks were exhumed within a very short time span (Thomson et al., 1998) after high-pressure–low-temperature metamorphism and now form the footwall of a major low-angle normal fault or extensional detachment fault (Seidel and Theye, 1993; Fassoulas et al., 1994; Jolivet et al., 1994, 1996; Kilias et al., 1994) of lower to middle Miocene age, separating the high-pressure–low-temperature units from the overlying unmetamorphosed units. The high-pressure–low-temperature rocks were returned to the upper crust by about 19 Ma (Thomson et al., 1998). The high rate of exhumation was a result of rollback of the subducting slab, as suggested in the "oblique buoyant escape" model of Thomson et al. (1998, 1999). Locally, in northwestern Crete, the anchimetamorphic Ravdoucha beds (Sannemann and Seidel, 1976) are sandwiched between the Phyllite-Quartzite and Tripolitza units.

View larger version (45K): [in this window] [in a new window]   FIG. 2. Schematic illustration of the tectonostratigraphy of Crete (modified after Seidel et al., 1982).

The Phyllite-Quartzite unit in western Crete experienced peak metamorphic conditions of about 400°C and 10 kbars (Theye et al., 1992) in a time span between 25 and 20 Ma (Seidel et al., 1982; Jolivet et al., 1996). The rocks cooled to temperatures below 290°C by 19 Ma and to less than 60°C by about 15 Ma. At temperatures of less than 300°C, extensive brittle deformation seems to have affected the Phyllite-Quartzite unit due to ongoing horizontal extension (Küster and Stöckhert, 1997; Thomson et al., 1998, 1999). The Phyllite-Quartzite unit was exposed at the surface by ca. 10 Ma at the latest, as documented by coarse sediments of undetermined stratigraphic age consisting predominantly of clasts derived from the Phyllite-Quartzite unit. These sediments in turn are overlain by marine strata (Frydas et al., 1999) of upper Miocene age (ca. 9 Ma).

	Iron-Oxide Deposits and Field Observations

Top Abstract Introduction Geologic Setting Iron-Oxide Deposits and Field... Mineralogy and Petrography Geochemistry and Oxygen Isotope... Discussion and Implications Conclusions APPENDIX References

 
The iron-oxide deposits of Kakopetros and Ravdoucha are located in western Crete, one in the vicinity of the small village Ravdoucha in the southern part of the Rhodopou peninsula, the other in a mountainous region in the middle of western Crete, south of the village of Kakopetros (Fig. 1). Documents from historical mining show that 25,000 t of iron ore were mined in Ravdoucha until 1952, whereas only 120 t of iron ore were extracted in the area of Kakopetros. The iron oxide was used for the fabrication of paint. The total tonnage of the Kakopetros deposit is estimated to have been between 0.5 and 4 Mt (Papastamatiou, 1952). However, the ore was mined only on a small scale in open pits. Iron ore mining throughout Greece ceased in 1965 (K. Zervantonakis, unpub. report, Newspaper Anatoli, December 30/31, 1977).

View larger version (69K): [in this window] [in a new window]   FIG. 3. A. Outcrop of iron oxide in the wall of a small open pit, southwest of Kakopetros. Hammer for scale. B. Brecciated quartzites of the Phyllite-Quartzite unit within the detachment zone. Fissures are filled by goethite. Coin for scale (25 mm).

View larger version (71K): [in this window] [in a new window]   FIG. 4. Backscattered electron photomicrographs of iron oxides. A. Fragments of phyllite, quartz (qtz), and goethite (gt) embedded in a fine-grained matrix composed predominantly of goethite (sample M2-215). B. Angular fragments of goethite and quartz in a matrix composed of goethite and small grains of quartz and phyllite (sample M2-218).

The host rocks consist of brecciated phyllite, quartzite, and marble of the high-pressure–low-temperature metamorphic Phyllite-Quartzite unit. The marble is strongly altered due to fluid-rock interaction along the detachment zone and has a friable and highly porous character. These rocks are impregnated by limonite, resulting in a yellow to reddish hue that is conspicuous in the field. The phyllite and quartzite are intensely brecciated with fractures filled by goethite (Fig. 3A-B). The goethite, itself, is brecciated with fragments of goethite embedded in a matrix of fine-grained goethite (Fig. 4A-B). This implies that deformation and brecciation was ongoing during mineralization. The goethite is powdery, friable, and porous but also occurs as hard crusts. Associated manganomelane group minerals are usually compact and massive with partly developed millimeter-scale botryoidal structures. Subordinate hematite is ubiquitous in the Phyllite-Quartzite unit.

	Mineralogy and Petrography

Top Abstract Introduction Geologic Setting Iron-Oxide Deposits and Field... Mineralogy and Petrography Geochemistry and Oxygen Isotope... Discussion and Implications Conclusions APPENDIX References

 
Scanning electron microscopy (SEM), backscattered-electron imaging (BSE), and electron probe microanalyses (EPMA) were used for mineral identification and investigations of the iron and manganese oxides (see Appendix for details). Qualitative powder X-ray diffraction analyses show that the fractures of the tectonic breccias are filled predominantly by goethite. The color of the iron oxides varies from typical ochre-brown through dark brownish-gray or nearly black, depending on different proportions of ferric iron hydroxides and tetravalent manganese oxides. The ochre-brown ore consists of goethite, whereas the dark, brown- to black-colored ore is rich in manganese oxides. BSE imaging reveals that the vein- and vug-filling goethite ore is very finely laminated, and EPMA reveals intercalated bands of manganese oxides at the micrometer to millimeter scale (Fig. 5A-B).

View larger version (56K): [in this window] [in a new window]   FIG. 5. A. Backscattered electron photomicrograph of laminated goethite. Lamination is due to slight differences in chemical composition, such as variable concentrations of alumina and manganese (sample M2-296). See text for details. B. i. Reflected light photomicrograph of laminated hardbands of Ba-rich cryptomelane and goethite (sample M2-296). ii, iii, and iv. Electron microprobe mapping of the same area, showing the relative content of potassium, iron, and manganese, respectively. Note that the cryptomelane is almost free of iron. C. Reflected-light photomicrograph showing a quartzite breccia with angular clasts. The veins are filled predominantly by goethite (sample M2-215).

	Geochemistry and Oxygen Isotope Geothermometry

Top Abstract Introduction Geologic Setting Iron-Oxide Deposits and Field... Mineralogy and Petrography Geochemistry and Oxygen Isotope... Discussion and Implications Conclusions APPENDIX References

The oxygen isotope fractionation between water and goethite is a low-temperature geothermometer (Yapp, 1987, 1990; Pack et al., 2000). Assuming that goethite crystallized in equilibrium with meteoric water, it is possible to estimate the temperature of the formation of goethite and, by inference, the thermal state during brittle deformation within the detachment zone. The ¹⁸O value for meteoric water is estimated to be similar to the present-day annual average value of –8.0 to –4.0 per mil (Rozanski et al., 1993; IAEA/WMO, Global Network for Isotopes in Precipitation Database, http://isohis.iaea.org). The geographic position of the island of Crete in the middle Miocene did not differ very much from its present-day position, and the existence of lower to upper Miocene terrestrial material filling half-graben provides evidence for climatic conditions resembling today’s conditions (e.g., Kopp and Richter, 1983; Postma et al., 1993; Seidel, 2002).

Yapp (1990) and O’Neil (1986) give a relationship between 1,000 ln ( ¹⁸O_goethite – ¹⁸O_water = _{goethite-water}) and temperature based on experimental data (measured for temperatures <100°C):

The geothermometer published by Zheng (1998) is based on a semiempirical approach and was calculated for a temperature range of 0° to 1,200°C:

EPMA data indicate that the studied goethite is not pure and contains considerable amounts of SiO₂ (2–4 wt %) and Al₂O₃ (0.1–1.4 wt %, Table 1). As a first approximation, it is assumed that SiO₂ and Al₃O₃ are present in 2 wt percent kaolinite and 1 wt percent quartz and/or chert. The oxygen isotope fractionation data for water-kaolinite (kaol-H₂O) and water-quartz (qtz-H₂O) were taken from Zheng (1993) and Kawabe (1978), respectively. At low temperatures, both quartz and kaolinite concentrate ¹⁸O relative to water.

For pure goethite and ¹⁸O of water of –6.0 per mil the calculated temperature of formation would be between 31° and 23°C, using the thermometers of Yapp (1990) and Zheng (1998), respectively. At a temperature of 28°C (average value of the calculated temperatures) and –6.0 per mil for the ¹⁸O value of water, the ¹⁸O value for kaolinite is +22 per mil (Zheng, 1993) and the ¹⁸O value for quartz is +28 per mil (Kawabe, 1978). If the goethite samples contain 2 wt percent kaolinite and 1 wt percent quartz, having the isotopic composition noted above, the ¹⁸O value of pure goethite would be –1.7 per mil, which would correspond to an equilibrium temperature for goethite and water of 40°C (Yapp, 1990) and 31°C (Zheng, 1998), respectively.

	Discussion and Implications

Top Abstract Introduction Geologic Setting Iron-Oxide Deposits and Field... Mineralogy and Petrography Geochemistry and Oxygen Isotope... Discussion and Implications Conclusions APPENDIX References

 
Ferruginous alteration and precipitation of iron oxides occur along the entire length of the detachment zone on Crete, which extends for 250 km in an east-west direction. A relationship to recent weathering is excluded, because the iron oxides do not occur in the present-day weathering profile. The source of the iron was probably hematite, which is ubiquitous in the Phyllite-Quartzite unit, and other iron-bearing minerals, such as chlorite (cf. Davis and Hardy, 1981). Similar detachment faults in the Basin and Range province locally host massive deposits or veins of iron and copper oxides with locally abundant sulfides, veins of barite and/or fluorite, and veins of manganese oxides (Spencer and Welty, 1986). However, the deposits in western Crete contain only iron oxides and subordinate manganese oxides. The difference in the type of mineralization is interpreted to be related to differences in temperature. Alteration and associated mineralization in the Basin and Range province resulted from retrograde metamorphism as hot lower plate rocks were brought up to shallower depth. Detachment fault-related polymetallic deposits with mainly Cu, Fe, and Mn formed at low pressures and temperatures, ranging between 90° to 350°C, as shown by fluid inclusion data (e.g., Long, 1992). By contrast, iron-oxide mineralization in western Crete appears to be related to the circulation of fluids at shallow crustal levels and lower temperatures.

The age of mineralization in the detachment zone on Crete can be constrained by the thermochronology of the high-pressure–low-temperature metamorphic rocks of the Phyllite-Quartzite unit (Seidel et al., 1982; Küster and Stöckhert, 1997; Thomson et al., 1998, 1999). The apparent syntectonic origin of the goethite suggests that precipitation of the iron oxides occurred during late-stage brittle deformation in the detachment zone, following exhumation of the core complex between 19 and 15 Ma. Genesis of the iron-oxide deposits prior to the late Miocene is indicated by the presence of marine Neogene sediments which overlie the iron-oxide deposits of Ravdoucha and by limonite clasts in basal conglomerates of Tortonian sediments (Kopp and Ott, 1977). Oxygen isotope data on the goethite samples indicate temperatures of formation between 31° and 40°C, consistent with the middle Miocene exhumation history and thermochronology of the Phyllite-Quartzite unit. For an average geothermal gradient, this temperature indicates contemporaneous deformation and formation of the deposits at a shallow crustal depth, ca. 1 to 1.5 km beneath the surface.

Fractured and brecciated rocks within the detachment zone are characterized by a high permeability, and these breccias were possible feeder channels for aqueous fluids driven by differential stress along the fault (e.g., Tobin et al., 2001). Goethite was precipitated mainly in fissures between the rock fragments in breccias of the Phyllite-Quartzite unit, whereas the alteration of the marbles resulted from mechanical disintegration and chemical decomposition during displacement and fluid flow (Fig. 6A). Maximum fluid transport took place within the phyllite and quartzite breccias beneath the dislocation plane, and the massive iron-oxide deposits are restricted to this domain. This unit accommodated downward flow of fluids, which led to the precipitation of the low-temperature iron oxides.

View larger version (89K): [in this window] [in a new window]   FIG. 6. A. Interpreted fluid-flow pattern within the detachment zone. High fluid flow is restricted to intensely brecciated rocks leading to precipitation of vein-filling iron oxides. By contrast, the relatively homogeneous marble is pervasively impregnated by fine-grained goethite. See text for discussion. B. Schematic diagram (not to scale) showing detachment fault–related mineralization in the roof of the Phyllite-Quartzite unit in western Crete (for comparison, see Long, 1992, fig. 36).

	Conclusions

Top Abstract Introduction Geologic Setting Iron-Oxide Deposits and Field... Mineralogy and Petrography Geochemistry and Oxygen Isotope... Discussion and Implications Conclusions APPENDIX References

These observations show that widespread and common ferruginous alteration in detachment faults can form at both high temperatures and deep crustal levels (e.g., as in the Basin and Range) and at much shallower crustal levels, such as the examples on Crete.

	APPENDIX

Top Abstract Introduction Geologic Setting Iron-Oxide Deposits and Field... Mineralogy and Petrography Geochemistry and Oxygen Isotope... Discussion and Implications Conclusions APPENDIX References

 
Analytical Techniques
A Philips PW 2400 X-ray fluorescence spectrometer equipped with an Rh tube (University of Cologne) was used for major and minor element analyses on glass disks that were made from 0.6 g of sample fused in a platinum crucible. Loss on ignition (L.O.I.) was determined in a muffle furnace at 1,000°C. Electron probe microanalyses (EPMA) at the University of Cologne were conducted with a wavelength dispersive JEOL JXA-8900RF electron microprobe, using 15 kV accelerating voltage and 20 nA probe current. Data were automatically processed by the ZAF method. Samples for powder X-ray diffraction were dried at 50°C for several hours and afterward ground to obtain a homogenous sample powder. A Philips PW 1800 X-ray powder diffractometer with Cu-K radiation was used for qualitative phase analyses.

Oxygen isotope analyses at the University of New Mexico were performed on 1- to 2-mg samples, using the IR laser fluorination technique with BrF₅ as oxidizing agent (Sharp, 1990). The samples were loaded along with laboratory mineral standards in an Ni sample holder. Samples were prefluorinated (100 mbars BrF₅) over night in order to remove moisture and surface-absorbed impurities. Fluorination of the samples was performed by laser heating, using a 25-W IR CO₂ gas laser ( = 10.6 µm) in a ~100-mbar BrF₅ atmosphere. Liberated oxygen was cleaned by conducting the gas mixture over heated KCl. Cl₂ was separated from the sample in a cold trap. The O₂ was collected on two successive molecular sieve traps (5Å) before it was expanded into the bellows of the dual inlet system of a Finnigan Delta Plus XL gas mass spectrometer. Accuracy and precision of the ¹⁷O and ¹⁸O determinations was within ±0.2 per mil. Due to the correlation between error of ¹⁷O and ¹⁸O, the error of ¹⁷O was less than ±0.05 per mil. All data are reported relative to V-SMOW (Gonfiantini, 1978).

	Acknowledgments

 
This work was funded by the Deutsche Forschungsgemeinschaft (DFG grants SE 282/15 and STO 196/14, PP 1006-ICDP) and the University of Cologne. AP gratefully appreciates the help of T. Larson and V. Atudorei during oxygen isotope measurements. The stay of AP at the University of New Mexico was funded by the Deutscher Akademischer Austauschdienst (DAAD). MS thanks G. Kostakis and E. Mistakidou for their scientific and logistical help. B. Stöckhert is thanked for fruitful discussions. We thank Crayton Yapp and Jens Gutzmer for their helpful suggestions on an earlier version of the manuscript. Furthermore, special thanks are given to John G. McLellan, an anonymous referee, and Mark D. Hannington for their critical reviews and useful comments, which greatly improved this manuscript.

December 30, 2002; November 25, 2004

	Footnotes

 
^* Present address: Döbrabergstrasse 4, 50765 Köln, NRW, Germany.

^** Present address: CNRS Centre de Recherches Pétrographiques et Géochimiques, 15 rue Notre Dame des Pauvres, 54501 Vandoeuvre-lès- Nancy, France.

December 30, 2002; November 25, 2004

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Top Abstract Introduction Geologic Setting Iron-Oxide Deposits and Field... Mineralogy and Petrography Geochemistry and Oxygen Isotope... Discussion and Implications Conclusions APPENDIX References

 

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