Accepted Manuscript

Hydrocarbons in silica: PVTX properties of fluids and the genesis of diamond quartz
from Caravia-Berbes Fluorite district (Asturias, Spain)

Gilles Levresse, Jordi Tritlla, Aldo Ramos Rosique, Esteve Cardellach, Claire Rollion-
Bard, Jacques Pironon, Sergio Jiménez Sandoval

PII: S0264-8172(18)30517-8
DOI: https://doi.org/10.1016/j.marpetgeo.2018.11.039
Reference: JMPG 3606

To appear in: Marine and Petroleum Geology

Received Date: 9 May 2018

Revised Date: 9 October 2018
Accepted Date: 22 November 2018

Please cite this article as: Levresse, G., Tritlla, J., Rosique, A.R., Cardellach, E., Rollion-Bard, C.,
Pironon, J., Sandoval, Sergio.Jimé., Hydrocarbons in silica: PVTX properties of fluids and the genesis of
diamond quartz from Caravia-Berbes Fluorite district (Asturias, Spain), Marine and Petroleum Geology
(2019), doi: https://doi.org/10.1016/j.marpetgeo.2018.11.039.

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 ACCEPTED MANUSCRIPT
1 Hydrocarbons in silica: PVTX properties of fluids and the genesis of diamond

2 quartz from Caravia-Berbes Fluorite district (Asturias, Spain).

3 Gilles Levresse1, Jordi Tritlla2, Aldo Ramos Rosique1, Esteve Cardellach3, Claire

4 Rollion-Bard4, Jacques Pironon5, Sergio Jiménez Sandoval6

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6 1-Programa de Geofluidos, Centro de Geociencias UNAM-Campus Juriquilla, AP 1-

7 253, Querétaro, Mexico CP 76230, Mexico

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8 2- Repsol Exploración S.A., Méndez Alvaro 44, 28045 Madrid, Spain.

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3- Departament de Géologia, Facultat de Ciències, Universitat Autònoma de
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10 Barcelona, 08193 Bellaterra, Barcelona, Spain.
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11 4- Centre de Recherches Pétrographiques et Géochimiques, UMR7358, 15 rue Notre

12 Dame des Pauvres, F-54 501 Vandoeuvre-lès-Nancy Cédex, France

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13 5- Université de Lorraine, CNRS, CREGU, GeoRessources UMR 7359, BP 70239, F-

14 54506 Vandoeuvre-lès-Nancy, France

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15 6- Centro de Investigación y de Estudios Avanzados del Instituto Politecnico

16 Nacional, Unidad Querétaro, Apartado Postal 1-798, Querétaro, Qro. 76001, México
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18 Corresponding author: Dr. Gilles Levresse, glevresse@geociencias.unam.mx

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20

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21 Abstract

22 The fluid history of “diamond” quartz crystals from Caravia-Berbes Fluorite

23 district is intimately related with episodes of maturation and migration of

24 hydrocarbons within the Asturian basin, probably linked to the structural activation of

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25 a Mesozoic rift system. These “diamond” quartz record the migration of hydrothermal

26 silica-rich brines and associated hydrocarbons that recorded a temperature increase

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27 (outlined by fluid inclusion studies) from ∼90 to ∼140ºC. This gradient is also

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28 recorded by a change in the organic matter species trapped in quartz, from bitumen

29 located in the inner quartz growth zones to liquid hydrocarbons trapped within the

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30 outer quartz overgrowths. Secondary ion mass spectrometer (SIMS) oxygen isotope
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31 microanalyses allowed to differentiate two δ18OH2O values corresponding to the oil-

32 dominated zone (core) and the water-dominated zone (outer growth zone). The
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33 heavier δ18OH2O values in the water-dominated zone do not only record a higher

34 temperature of formation, but also an increase in the δ18OH2O of the parental fluid.
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35 Isotopic compositions of diamond quartz suggest a heterogeneous source of surficial

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36 fluids and formation-waters expelled from claystones.

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37 Within the basin history, the diamond quartz precipitation took place during

38 early Jurassic to Eocene subsidence periods. Pressure Temperature and composition

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39 (PTX) and δ18OH2O characteristics point out a probable relationship with Albian
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40 diagenetic events reported in Cantabrian and north Pyrenean basins.

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42 Keywords: Fluid inclusions, PT reconstruction, Hydrocarbon, Diamond Quartz,

43 Caravia-Berbes, Spain, Oxygen isotope.

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44

45 1. INTRODUCTION

46 In cemented sedimentary and crystalline rocks, fractures and veins provide the

47 main pathways for fluid circulation. Evidence of fluid migration through these

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48 fractures is provided by the presence of fluid inclusions (oil, brine, gas) trapped

49 within vein-filling minerals. In addition, some veins or fractures contain solid bitumen

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50 or other organic phases that may also represent remnants of ancient hydrocarbon

51 migration pulses (Baron et al., 2008; Bourdet and Pironon, 2008; Bourdet et al., 2012;

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52 Salardon et al., 2017). When such observations are placed within the geological and

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53 tectonic evolution of a sedimentary basin, they can be used to constrain the timing of
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54 oil and gas migration and identify their potential source rocks as well (Burruss et al.,

55 1985; Schubert et al., 2007).

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56 Double-terminated euhedral quartz crystals containing hydrocarbon fluid and

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57 solid inclusions are commonly observed in petroleum reservoirs (Murray, 1957;

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58 Touray and Sagon, 1967; Stalder and Touray, 1970; Burley et al., 1989; Marchand et

59 al., 2002; Teinturier et al., 2002; Bourdet et al., 2008; Ferket et al., 2010; Hartwood et
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60 al., 2013; among other). They have been found in fissures affecting low temperature

61 metamorphic and sedimentary rocks from many orogenic belts worldwide: Herkimer
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62 diamonds in the Appalachian Mountains (USA; Roedder, 1984; Parnell et al., 1996;
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63 Dix and Robinson, 2003); Marmarosh diamonds in the Carpathian mountains

64 (Ukraine and Poland; Lazarenko et al., 1976; Matkovskyi, 1961; Kazwowski and

65 Dorda, 1986; Hurai et al., 2006; Vitik et al., 1996; Dix and Robinson 2003;

66 Jarmolowicz-Szulc et al., 2006); euhedral quartz crystals in alpine fissures and

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67 septarias in the Alps (Switzerland, Italy and Germany; Mullis et al., 1994; Franzini et

68 al, 1992; Costagliola et al., 2006; Prüfer, 2003), double-terminated quartz crystals in

69 the Laramide thrust and fold belt of Mexico (Ramos-Rosique, 2007; Corona-Esquivel,

70 2009; Ferket et al., 2010); in the Balhan mega-anticline (Western Turkmenistan;

71 Bratus et al., 1975; Bratus and Pogrebnyak, 1982); in the Krym mountains (Ukraine;

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72 Gigashvili et al., 1975); in the Caucasus (Georgia; Akhvlediany and Gigashvili, 1975;

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73 Guilhaumou et al., 2000); and, finally, in the Caravia-Berbes fluorite stratabound

74 deposit in the foreland Pyrenean thrust in northern Spain (Garcia-Iglesias and Touray,

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75 1976, 1977; Garcia-Iglesias, 1978; Tejerina and Zorrilla, 1980; Gonzalez-Laguna et

76 al., 1996; Loredo, 1981; Garcia-Iglesias and Loredo, 1982, 1994; Arcos and Tornos,

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1997; Sanchez et al., 2005, 2006, 2009, 2010a; Symons et al., 2017). The conclusions
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78 of these studies on “diamond” quartz crystals can be summarized as follows: (1) most
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79 of the hydrocarbon-rich fluid inclusions coexist with water-rich fluid inclusions,

80 indicating the presence of immiscible fluids during mineral formation; (2) early
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81 primary hydrocarbon-bearing fluid inclusions trapped at the crystal core mostly

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82 contain methane; (3) brine-bearing fluid inclusions are scarce; (4) primary

83 hydrocarbon-bearing fluid inclusions trapped either at the outer growth zones of the
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84 crystals or in fractures as secondary/pseudosecondary fluid inclusions are usually rich

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85 in higher hydrocarbons (C2-C4) and gas; (5) calculated P-T trapping conditions for
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86 primary hydrocarbon-bearing fluid inclusions fall into a wide interval from 0.7-4.0

87 Kbar and 73-150ºC; (6) calculated fluid inclusions densities and trapping

88 temperatures decrease from the quartz crystal core to the outer growth zones; and (7)

89 most fluid inclusions show evidences of post-trapping re-equilibration (decrepitation

90 mainly).

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91 Compared to other occurrences cited above, the Caravia-Berbes quartz crystals

92 present three particularities: (1) they are spatially related to Misssissipi Valley Type

93 (MVT) fluorite deposits (Arcos and Tornos 1997; Sanchez et al., 2009; 2010a); (2) the

94 early primary hydrocarbon-bearing fluid inclusions located at the core of the crystals

95 contain mostly bitumen (Garcia-Iglesias and Touray, 1976, 1977; Garcia-Iglesias,

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96 1978; Gonzalez-Laguna et al., 1996; Arcos and Tornos 1997; Sanchez et al., 2009);

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97 and (3) the majority of aqueous and hydrocarbon-bearing fluid inclusions show no

98 evidence of post-trapping re-equilibration.

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99 The main goal of this paper is to calculate and interpret the fluid PVTX

100 conditions and behavior during the hydrocarbon and brine migration recorded in the

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Caravia-Berbes double-terminated quartz crystal, using analytical data derived from
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102 fluid inclusion studies, quantitative spectroscopic analyses and oxygen isotope
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103 systematics. In addition, a discussion linking the formation of double-terminated

104 quartz crystals, the conditions of petroleum migration and their relationships in the
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105 regional geological context is given.

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107 2.- GEOLOGICAL SETTING

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108
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109 The Principality of Asturias is a Spanish Autonomous Community located on

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110 the north coast of Spain (Figure 1). In Asturias occurs the westernmost exposure of

111 the European Hercynides, where the largest outcrops of pre-Permian rocks within the

112 Iberian Peninsula appear, known as the Iberian Hercynian Massif. This Hercynian belt

113 has been classically divided into four zones (Julivert et al., 1972; Arenas et al., 1988;

114 Farias et al., 1987). From East to West, they include the Cantabrian zone, the Western

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115 Asturian-Leonese zone, the Central Iberian zone and the Galicia-Tras-os-Montes

116 Zone. This orogeny originated when Gondwana and Laurasia closed the Rheic Ocean

117 during the Devonian-Carboniferous and then collided (Pastor-Galán et al., 2015). The

118 studied area is located in the Western Asturian-Leonese zone, close to the contact with

119 the Cantabrian zone (Quesada, 1992). The westernmost area is composed of

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120 Precambrian and Paleozoic rocks (Figure 1) containing the folded and fractured

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121 Variscan basement. The central and easternmost areas of the region comprise

122 Mesozoic and Cenozoic units that unconformably overlie the Paleozoic basement

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123 (Julivert, 1972; Figure 1). The deformation caused imbrication, very low-grade

124 metamorphism and complex oroclinal rotation of the original linear collisional belt

125
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(Weil et al., 2013; Pastor-Galán et al., 2015). The older outcropping sedimentary
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126 formations are lower (299–271 Ma) and middle (271–260 Ma) Permian in age, and
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127 rest unconformably on either the basement or the lower Permian formation (Pieren et

128 al., 1995). These Permian materials are continental sedimentary formations resulting
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129 from uplift and erosion process, composed by intercalations of continental red shales,
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130 sandstones and conglomerates, with volcanic flows in the Villaviciosa area. Following

131 a period of uplift and erosion, the Caravia Formation was unconformably overlain by
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132 the marine Lower Jurassic Gijón Formation, which is composed of about 50 m of
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133 limestone with minor dolostone and black shales. From Jurassic to Paleocene, the
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134 Asturian basin was part of a large epicontinental sea, bounded by the Iberian Massif to

135 the southwest and by the Armorican Massif to the north (Julivert, 1972). Tectonic

136 activity is mainly extensional related to the Tethys Ocean, the central Atlantic and the

137 Bay of Biscay apertures respectively (Julivert, 1971; Salas et al. 2001). The early

138 Jurassic highlights the transition to oceanization. The marine early Jurassic

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139 sedimentary formations are rich in organic matter and generated hydrocarbons

140 (García-Ramos and Gutiérrez-Claverol, 1995). The Late Jurassic is composed by

141 siliciclastic formations (Nora, Vega, Teñeres and Lastres formations; Valenzuela et al.,

142 1986). The lower Cretaceous is still dominated by siliciclastic and conglomerate

143 formations. The upper Cretaceous is characterized by intercalations of carbonates and

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144 siliciclastic materials. The Alpine orogen generated a regional uplift and the

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145 reactivation of older structures as the Hercynian thrust (Figure 1).

146 Cenozoic convergence at the foot of the continental slope is also shown

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147 (modified from Sanchez et al., 2010). B: Simplified geological map of the Caravia-

148 Berbes fluorite district (modified from Symons et al., 2017). Schematic stratigraphic

149 column of the Asturias region.

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150 The Caravia-Berbes fluorite district spans along a NE-SW trend of around 10
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151 km long and 2 km wide in size (Figure 1B). The Caravia-Berbes fluorite district is

152 also well known for the presence of clear, euhedral quartz crystals (Herkimerr
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153 diamonds-like) found almost exclusively within clay pockets located in the upper
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154 Triassic (Keuper) claystones and breccia-conglomerates of Permo-Triassic age that

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155 unconformably overlie the Carboniferous limestones (Figure 1B). This idiomorphic

156 quartz postdates the fluorite formation, precipitating within residual void spaces with
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157 abundant calcite and minor sulphides and dolomite. These Caravia-Berbes quartz
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158 crystals are characterized by the presence of trapped large hydrocarbon-bearing fluid

159 inclusions (Arcos and Tornos 1997).

160

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161

162 Figure 1 A: Simplified geological map of the Asturias region showing the Variscan

163 thrust units and the location of the study area. Major Alpine structures over that zone

164 are highlighted. The location of the buried accretionary prism developed during

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165 The lower Jurassic series are locally intensively dolomitized (Symons et al.,

166 2017), and overly on top of the Triassic Keuper facies. Gasparrinia and co-workers

167 (2013) considered that dolomitization occurred during late-to-post-Variscan

168 extensional phases (Gasparrinia et al., 2003). Fluorite precipitation has been dated by

169 combining Sm/Nd isochrones and paleomagnetism to be between ∼206 to ∼185 Ma

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170 (Sanchez et al., 2010a; Symons et al., 2017). Symons and co-workers (in op. cit.)

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171 identify also a younger hydrothermal event, related to host rock silicification

172 alteration at ∼115 Ma.

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173

174 3.- ANALYTICAL METHODS

175
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Analytical procedures to carry out this study are summarized in table 1.
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176 The obtained thin sections were inspected using a petrographic Olympus® BX-
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177 50 petrographic microscope, equipped with a Qimage Micropublisher 5Mp digital

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178 camera with a Peltier cooled CCD, at the “Laboratorio de Fluidos Corticales” from
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179 the Centro de Geociencias (LFC-CGEO), Universidad Nacional Autonoma de Mexico

180 (UNAM), campus Querétaro (Querétaro, México).

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181
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182 3.1. CATODOLUMINESCENCE PETROLOGY

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183 Quartz ontogeny was studied using a Reliotron® cold cathode

184 cathodoluminescence (CL) device attached onto an Olympus SZ-X binocular

185 microscope and a Qimage Micropublisher 5Mp digital camera with a Peltier cooled

186 CCD at the CFL-CGEO-UNAM laboratory, (Querétaro, Mexico). The acceleration

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187 voltage of the electron beam was 15 kV with a probe current of 500 µA. CL emission

188 was enhanced by freezing the quartz samples using a copper plate previously cooled

189 by immersion into liquid nitrogen.

190

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191 3.2. EPIFLUORESCENCE PETROLOGY

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192 Quartz double-polished wafers were studied using an Olympus BX-50

193 epifluorescence microscope equipped with an UV-light source (Mercury lamp, λ=365

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194 nm), a U-MNU2 excitation filter (straight band, 360-370 nm) and a LP400 longpass

195 emission filter (>400 nm), at the CFL-CGEO-UNAM laboratory, allowing the

196
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198 3.3. FLUID INCLUSIONS STUDIES

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199 Microthermometric data were obtained using a Linkam THMSG-600 stage

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200 attached to an Olympus® BX-50 petrographic microscope equipped with ultra-long

201 working distance objectives at the CFL-CGEO-UNAM laboratory. This stage allows
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202 the observation of phase transitions of the fluid inclusions between -193 to +600ºC,
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203 with an accuracy of ±0.1ºC. The stage was calibrated using Synflinc® synthetic fluid
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204 inclusions and Merck ultra-pure chemicals of known melting point.

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206 3.4. OXYGEN ISOTOPES ANALYSES

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207 In situ oxygen isotope analyses were obtained using a CAMECA IMS 1270

208 ion microprobe at the Centre de Recherches Pétrographiques et Géochimiques

209 (CNRS, Nancy, France). Methodology and procedures were described in detail by

210 Rollion-Bard et al. (2007). Briefly, the sample was bombarded with a 10 kV Cs+

211 primary beam of 5 nA intensity focused to 30x15 µm spots. The two oxygen isotopes

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212 O- and 18
O- were measured in multicollection mode using two off-axis Faraday

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213 Cups. The instrumental mass fractionation was determined using in-house quartz

214 reference materials (QZCWRU, δ18O=24.52 ‰, and Quartz-Brazil, δ18O=9.60 ‰).

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215 Internal precision was typically <0.1 ‰, and external reproducibility based on

216 multiple analysis of the reference materials was ±0.2 ‰ (1σ).

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218 3.5. FOURIER-TRANFORM INFRARED MICROSPECTROMETRY (FTIR)

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219 FTIR spectra were recorded on petroleum fluid inclusions using a Bruker
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220 Hyperion 3000 spectrometer, collecting the infrared signal with a Cassegrain
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221 objective (x15), at the CFL-CGEO-UNAM laboratory. The spectral range corresponds

222 to the mid-infrared; the spectral resolution was fixed at 4cm-1. Methodology and
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223 procedures are described in detail in Pironon (2004).

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224
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225 3.6. RAMAN MICROSPECTROMETRY

226 Qualitative and quantitative Raman microspectrometric analyses of aqueous

227 inclusions were performed using a ®Labram Jobin Yvon spectrometer, using a 514.5

228 nm radiation produced by an Argon laser, and a Linkam THMSG heating-freazing

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229 stage attached to an Olympus® microscope. Counting time, laser power and confocal

230 aperture were adapted for each inclusion measurement to obtain the best

231 signal/background ratio. Methane concentration (mCH4) in the liquid phase at

232 homogenization temperature was determined using the calibrations of Dubessy et al.

233 (2001) and Guillaume et al. (2003). Data were acquired at GeoRessources laboratory

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234 (Nancy, France).

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235

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236 3.7. CONFOCAL LASER SCANNING MICROSCOPY (CLSM)

237 Vapor volume fractions φvap at 20ºC for petroleum-bearing inclusions were

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determined using confocal laser scanning microscopy (CLSM) volumetric
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239 reconstructions, at the Instituto de Neurobiologia laboratory (UNAM, Querétaro,
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240 México) using a Zeiss LMS 700 adapted to a Zeiss inverted microscope, equipped

241 with long distance 40X and oil immersion 60x and 100x objectives. Double-polished
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242 wafers were fixed on a glass plate with paraffin for image acquisition. The detailed
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243 principles and procedures for CLSM fluid inclusion image acquisition are described

244 in Pironon et al. (1998). Incident radiation was obtained using an Argon laser at 488
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245 nm, and a diode laser at 405 nm in the case of deep-blue UV-fluorescent hydrocarbon-
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246 bearing fluid inclusions. This method allows volume estimation of the cavity of a
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247 petroleum inclusion with accuracy greater than 95%. The horizontal x–y resolution is

248 0.2 µm while resolution along the z-axis is approximately 0.5 µm. As suggested by

249 Pironon et al. (in op. cit.), the volumes of the spherical vapor bubbles were calculated

250 from its diameter measured in the image recorded by transmission. Each x–y plane

251 obtained by CLSM is treated as an independent image using the Image-J software

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252 (Schneider et al., 2012). This image processing softwear was used to threshold the

253 images, reconstruct the voxels (3D pixels) and, then, calculate the final volume for

254 each inclusion. The percentage of error on the estimate of φvap (20ºC) was calculated

255 assuming an error of ±0.2 µm on the measurement of the bubble diameter and an error

256 in oil volume measurement of 5% as well.

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257 The PVT modeling of the CH4-H2O-NaCl system is based on the Duan

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258 equation of state (Duan et al., 1992), which allows the calculation and plotting of the

259 isopleth (bubble point curve) on a PT diagram. The isochore of a fluid inclusion above

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260 the homogenization temperature in the CH4-H2O-NaCl system is calculated using the

261 method of Zhang and Frantz (1987) for aqueous-rich fluids with methane

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concentrations below 1 molal and various NaCl concentrations (mNaCl). Modeling of
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263 the petroleum inclusions composition is based on the Peng-Robinson equation of state
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264 (1976). It requires Th and φvap (20ºC) of oil inclusions as input data. PIT software

265 (Thiéry et al., 2000, 2002) allows to generate a PT diagram including isopleths and
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266 isochores for a given fluid inclusion and provides an estimate of composition and
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267 standard physical properties of the oil (API gravity, GOR).

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268

269 4.0 RESULTS

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271 Samples were collected at the La Cabaña fluorite deposit (Figure 1B), located

272 in the Caravia-Berbes mining district (Asturias, N Spain). Double terminated quartz

273 crystals are found in an argillaceous matrix filling karstified dolostones of the Caliza

274 de Montaña Formation (Late Carboniferous). According to Sanchez et al. (2009)

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275 this quartz generation corresponds to the latest episode of hydrothermal fluid

276 circulation in the Mesozoic basin.

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278 4.1 PETROGRAPHY OF CARAVIA-BERBES DIAMOND QUARTZ

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279 CRYSTALS

280

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281 At Caravia-Berbes, quartz crystals are in the range of 0.5–5.0 cm in size. They

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282 are colorless to brown-colored and present large hydrocarbon-bearing fluid and solid

283 bitumen inclusions, often big enough to be perceived with the naked eye. As quartz

284
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crystal sizes increase, the characteristic crystal habits of these quartz crystals
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285 (pseudohexagonal prism) change, loosing part of their luster and clarity.

286 A total of twenty-nine quartz crystals were sampled. Except for the six
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287 smallest crystals, all were prepared for microscopic observations. To order to better
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288 constrain the position of the fluid inclusions within the different growth zones, only
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289 the five biggest and more idiomorphic quartz crystals were used for detailed

290 petrographic studies. Under the petrographic microscope, the double polished quartz
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291 wafers display several non-concentric growing zones around a quartz core. The

292 number of zones and their thicknesses vary in each studied crystal. All crystals show
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293 an asymmetric growth, with no evidences of dissolution.

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294 Cathodoluminiscence (CL) studies helped to better outline the quartz

295 overgrowths already observed using optical microscopy. When the quartz core and

296 overgrowths present few hydrocarbon-bearing fluid inclusions, the quartz

297 luminescence is dull. Yellowish to bluish luminescence is restricted to the

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298 hydrocarbon-bearing quartz zones, fractures and zone boundaries (Figure 2 a and c).

299 When luminescence occurs, it could be sectorial (Figure 2 d) or present a succession

300 of colors (pale blue to brown) following the rims (Figure 2 b).

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301

302 Figure 2: Images of a basal section (perpendicular section to the c axis) of a quartz
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303 crystal. a) Quartz-2 slide under transmitted light. b) Cathodoluminescence of quartz-2

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304 slide. c) Quartz-4 slide observed under transmitted light. d) Cathodoluminescence of

305 Quartz-4 slide.

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307 4.2 HYDROCARBON-BEARING AND BRINE-BEARING FLUID

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308 INCLUSIONS ASSOCIATION AND PETROGRAPHY

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310 These quartz crystals are very famous among mineralogists, fluid inclusionists

311 and mineral collectors as they contain abundant, large hydrocarbon-bearing fluid

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312 inclusions. Moreover, crystal facies and luster make them comparable with the

313 Herkimer diamonds.

314 Twenty doubly-polished thick sections (wafers) were prepared, cutting the

315 crystals perpendicular to the C axis from whom, after petrographic work, five

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316 prismatic quartz crystal sections were chosen to be studied.

317 All the studied quartz crystals present two very distinct zones: (i) an inner

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318 quartz crystal growth, characteristically rich in hydrocarbon-bearing fluid inclusions

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319 (HC-S) and solid bitumen; and (ii) an outer growth zone characterized by the presence

320 of both hydrocarbon-bearing and brine-bearing fluid inclusions (HCP and Aq).

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Petrographically, these quartz crystals contain abundant primary hydrocarbon-
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322 bearing fluid inclusions that are extremely large, commonly ranging from 10 to 1000
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323 µm (Figure 3). Most of the fluid inclusions present negative crystal shapes, but some

324 irregularly-shaped morphologies also occur. The biggest hydrocarbon-bearing fluid

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325 inclusions appear close to the outer rim and are always associated with smaller
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326 aqueous inclusions (Figure 3A and H). Some of them present recognizable water

327 meniscus in contact the liquid HC phase. Most of the hydrocarbon-bearing fluid
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328 inclusions are composed by two phases (L-V), a colorless to yellow liquid
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329 hydrocarbon and a gas phase. Primary hydrocarbon-bearing fluid inclusions (HCP-
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330 type, Figure 3C, 3E-G) are present throughout the outer overgrowths. Polyphase,

331 hydrocarbon-bearing fluid inclusions with trapped solid bitumen and/or spores (HC-S

332 type, Figure 3D) are only seen within the inner quartz core. Eventually, when water

333 phase is volumetrically important, three-phase fluid inclusions (LHC-LAq-V) can also

334 be observed. The oil-bearing fluid inclusions that are located at the boundary between

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335 two growth zones typically show irregular walls with possible corrosion pits, probably

336 linked to dissolution processes. Under long-wavelength UV excitation, all these

337 hydrocarbons present a light blue to white fluorescent emission

338 Late fractures crosscut partially or completely all the growth zones. Secondary

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339 hydrocarbon-bearing fluid inclusions (HCS type) trapped along these fractures are

340 scarce, present irregular shapes and range from 5 to 100 micrometers (Figure 3A, B,

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341 H) in size. These fluid inclusions are two-phase (L-V), with a light to dark brown-

342 colored liquid hydrocarbon. Necking down is the most common post-trapping

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343 modification detected (Figure 3G). Under UV light, secondary hydrocarbon-bearing

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344 fluid inclusions present a lighter blue fluorescence than their primary counterparts.
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345 Primary aqueous fluid inclusions (Aq type) are scarce and appear exclusively

346 within the outer growth zone. They usually present negative crystal shapes, but some
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347 irregular-shaped forms also occur. All these brine-bearing fluid inclusions are two-
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348 phase (L-V), with no trapped solids or daughter minerals. Primary aqueous fluid
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349 inclusions appear to be trapped along with primary hydrocarbon-bearing fluid

350 inclusions (Figure 3H). No secondary brine-bearing fluid inclusions were observed.
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351

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352 Figure 3: Fluid inclusions petrography: (A): wafer from quartz-2 crystal, with well

353 defined core and overgrowths. Primary hydrocarbon-bearing fluid inclusions are

354 trapped along the growing planes; secondary hydrocarbon-bearing fluid inclusions are

355 visible in fractures. (B) Close up from quartz-2 crystal in A. (C) Primary, elongated

356 colorless hydrocarbon-bearing fluid inclusions (HCP-type); elongation is growing

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357 zone. (D) Primary brownish hydrocarbon-bearing fluid inclusions (HC-S-type). (E)

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358 Primary (negative crystal shape) colorless hydrocarbon-bearing fluid inclusion with

359 trapped solid bitumen (HCP-type). (F) Rounded, primary colorless hydrocarbon-

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360 bearing fluid inclusion with an unidentified trapped solid (HCP-type). (G) Secondary

361 brownish hydrocarbon-bearing fluid inclusions trapped in a healed fracture (HCS-

362
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type), with very variable liquid-to-gas ratios due to post-trapping modifications
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363 (necking down). (H) Secondary brownish hydrocarbon-bearing fluid inclusions
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364 trapped in a healed fracture plane (HCS-type), crosscutting a primary fluid inclusion

365 assemblage.
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366
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367 4.3 HYDROCARBON–BEARING AND BRINE-BEARING FLUID

368 INCLUSIONS MICROTHERMOMETRIC STUDY

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369
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370 Fluid inclusion results are presented in Figures 4, 5 and 6. Homogenization

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371 temperatures should be regarded as minimum trapping temperatures and, thus a

372 correction is needed to determine the real trapping conditions.

373 Primary oil inclusions (HC-S; n=36) located at quartz core present

374 homogenization temperatures ranging from +91.6ºC to +125.8ºC, with a broad

375 maximum distribution located at 95-100ºC (Figures 4, 5 and 6). Despite the strong

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376 zoning displayed by quartz crystals, a clear temperature distribution from inner to

377 outer rims (excluding the core) cannot be drawn. In general, the outer rims present

378 (HCP; n=92) homogenization temperatures between +66.8 ºC and +128.2ºC, with a

379 well-defined maximum distribution at +120ºC (Figures 4, 5 and 6).

380 HCS-type fluid inclusions (n=171) also show a maximum located at +120ºC

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381 with homogenization temperatures located between +94ºC and +130.1ºC, (Figures 4,

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382 5 and 6).

383 Aq-type fluid inclusions (n=62) present homogenization temperatures ranging

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384 from 99ºC to 140ºC, with a well-defined Gaussian maximum distribution at ca. 130ºC

385 (Figures 5 and 6). The last ice melting temperature is between -1.6ºC and -0.8ºC, with

386
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387
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388
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389 Figure 4: Homogenization temperature histograms of hydrocarbon and aqueous fluid

390 inclusions for all the five studied quartz crystals. Qtz-1-green; Qtz-2: yellow; Qtz-3:
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391 Red; Qtz-4: grey; Qtz-5: blue

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392
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393 Figure 5: Distribution of fluid inclusion types with corresponding homogenization

394 temperatures range in a single slice of diamond quartz 4.

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395
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396 Figure 6: (A) Ice melting temperature vs. homogenization temperature plot for

397 aqueous fluid inclusions trapped in quartz overgrowths. Black dot: Qtz-1; open dot:
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398 Qtz-2; black star: Qtz-3; grey star: Qtz-4; open star: Qtz-5. (B) Ice melting
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399 temperature vs. homogenization temperature plot to compare Berbes diamond quartz

400 (grey area: Arco and Tornos, 1997) and North Sea diagenetic quartz (open dots:

401 Teinturier et al., 2002; Marchand et al., 2002; Harwood et al., 2013).

402

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403 4.4 BRINE-BEARING FLUID INCLUSIONS RAMAN

404 MICROSPECTROMETRY CHARATERIZATION

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406 Dissolved methane concentrations were measured at homogenization

407 temperature conditions on Aq-type fluid inclusions, spatially related to HCP-type fluid

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408 inclusions within the outer quartz rims (n=19). Methane concentrations are between

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409 0.12 and 0.32 molal. Results are compiled in Table 2 and salinity versus methane

410 content at Th is plotted in Figure 7.

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411

412 Figure 7: [CH4] vs. NaCl molalities plot for aqueous fluid inclusions trapped in outer
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413 quartz overgrowths. Black dot: Qtz-1; open dot: Qtz-2; black star: Qtz-3; grey star:
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414 Qtz-4; open star: Qtz-5.

415

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416 The salinity (recalculated as molality) versus methane plot presents a positive

417 correlation, suggesting that all the Aq-type fluid inclusions belong to a single family

418 and seems represent a single brine pulse.

419

420 4.5 HYDROCARBON–BEARING FLUID INCLUSIONS FOURIER-

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421 TRANSFORM INFRARED MICROSPECTROMETRY RESULTS

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422

423 FTIR studies were performed on twenty-one oil-bearing fluid inclusions from

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424 five different quartz samples, taking special care to include all the hydrocarbon-

425 bearing fluid inclusions types (Table 3).

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All the analyzed inclusions present aliphatic compounds, CO2 and CH4. Water
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427 bands are always weak, probably due to the accumulation of water as meniscus
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428 wetting the walls of the HCP and HCS-type fluid inclusions located at the quartz outer

429 rims. The quantification of the gas contents is listed in Table 3.

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430 The CH4, CO2 and alkanes contents evolve from inner to outer quartz rims. In
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431 HC-S-type fluid inclusions, CO2 varies from 13 to 19 mole%; CH4 quantities are

432 between 34 to 37 mole%; the CH2/CH3 aliphatic ratio, that corresponds to the estimate
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433 of the aliphatic chain length, variation is estimated to be between 1.3 to 2.1.
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434 In HCP-type fluid inclusions, CO2 contents are between 14 to 21 mole%; CH4
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435 contents range from 32 to 39 mole%; and the CH2/CH3 aliphatic ratio is estimated to

436 be between 1.7 to 2.8. HCS-type fluid inclusions present CO2 contents between 15 and

437 19 mole%; CH4 contents between 32 to 35 mole%, and CH2/CH3 aliphatic ratios from

438 1.4 to 1.9. It is interesting to note that the non-colored, hydrocarbon-bearing fluid

439 inclusions present the lowest CH2/CH3 ratios.

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440

441 4.6 HYDROCARBON–BEARING FLUID INCLUSIONS CONFOCAL LASER

442 SCANNING MICROSCOPY (CLSM) CHARACTERIZATION

443

444 CLSM studies were performed on seventeen hydrocarbon-bearing fluid

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445 inclusions from five different quartz crystals, representing all hydrocarbon-bearing

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446 fluid inclusion types (see Table 3; Figure 8). Gas volume fractions at 20ºC (φgas) for

447 the HC-S-type fluid inclusions range between 7.4 and 19.1%; HCP-type fluid

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448 inclusions present gas volume fractions between 14.6 and 20.8%; whereas gas volume

449 fractions for the secondary HCS-type hydrocarbon inclusions range between 16.0 and

450
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25.1. The estimated φgas data plotted against homogenization temperature (Th) data
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451 (Figure 8; modified from Bourdet et al., 2008) allow a quick and effective
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452 classification of the trapped oils. The HC-S-type fluid inclusions plot in the black oil

453 field, while the HCP and HCS fluid inclusions types plot within the fields of black and
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454 light oils, with a trend towards lighter oil displayed by the HCP-type.
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455

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456 Figure 8. Vapor volume percentage (φvap) vs. homogenization temperature (Th) data

457 for petroleum inclusions in Berbes diamond quartz. Abacus with petroleum

458 composition curves modified from Bourdet et al. (2008).

459

460 4.7 PVT MODELING OF HYDROCARBON–BEARING AND BRINE-

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461 BEARING FLUID INCLUSIONS

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463 The bubble point curve and isochores for primary and secondary hydrocarbon

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464 fluid inclusions were calculated using PIT modeling software (Thiery et al., 2000),

465 based on our accurate volumetric measurements, FTIR CO2 and CH4 compositions

466
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and homogenization temperatures. Aqueous isopleths are calculated using Duan EOS
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467 (Duan et al., 1992). Petroleum and aqueous isopleths and isochores are calculated
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468 using data gathered from eighteen primary and secondary fluid inclusions. The P–T

469 phase diagram (Figure 9) displays several isopleths and isochores (n=15), belonging
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470 to all the hydrocarbon and aqueous fluid inclusion types found in Caravia-Berbes
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471 quartz samples. Accurate petrographic work indicated that HC-S-type fluid inclusions

472 were not coevally trapped with any aqueous-bearing fluid inclusions. In absence of
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473 trapped brine-bearing fluid inclusions, only a minimum trapping pressure can be
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474 determined, precisely located at the origin of the isochore on top of the corresponding
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475 isopleth. This give a P-T range of from ca. 110 to 220 bar for homogenization

476 temperatures ranging from 92ºC to 125ºC (Figure 9; Table 5) and an equivalent depth

477 range of 1 to 2,2 km under hydrostatic conditions. Petrographically, both HCP and Aq

478 fluid inclusion types found in the outer quartz rims are coeval. In this case, the

479 trapping P-T conditions can be estimated and corresponds to the intersection of the

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480 calculated isochores for both hydrocarbon and brine fluids. This allows to calculate

481 trapping P–T conditions of around 275 bars at 127ºC (Figure 9; Table 5) The

482 excursion of the calculated Aq-type fluid inclusions isopleths towards higher

483 pressures is due to methane enrichment as both fluid types were trapped coetaneously.

484 The P-T conditions calculated for the HCS-type fluid inclusions are also a minimum

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485 estimation, corresponding to the isochores starting point, with homogenization

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486 temperatures around 125ºC and pressures of around 200 bars (Figure 9; Table 5) or 2

487 km under hydrostatic conditions.

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488

489 Figure 9: PT diagram with calculated isopleths and isochores from PVTx analyses of

490 petroleum-bearing and brine-bearing fluid inclusions. Isopleths and isochores of the

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491 petroleum fluids are issued from PIT modeling whereas isopleths and isochores of the

492 aqueous fluids were calculated using Duan EOS (Duan et al., 1992).

493

494 4.8 DIAMOND QUARTZ OXYGEN ISOTOPIC COMPOSITION

495

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496 A transect composed by fifteen in-situ SIMS analyses was obtained from core

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497 to rim using the most representative sample (QUARTZ-2; Figure 10; Table 4). The

498 analytical points in a quartz wafer were selected using as a criterion the absence of oil

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499 or water fluid inclusions and CL patterns (Figure 2d and 10). Figure 10 provides the

500 distribution of the analytical points and the measured δ18Oquartz values, from core to

501
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rim. In addition, at the end of the analytical session, the sample was examined under
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502 an optical microscope to verify that all craters indeed did not affect any oil or aqueous

fluid inclusions. Values of δ18Oquartz along the transect from core to rim show a
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503

504 continuous trend with values ranging between 23.6±0.2‰ and 28.7 ±0.2‰. The water
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505 isotopic composition (δ18OH2O) in equilibrium with quartz was calculated using the
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506 equation of Méheut et al. (2007), calibrated for the adequate temperature range (0 to

507 130ºC; Table 4). Due to the absence of aqueous fluid inclusions in the inner quartz,
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508 the mean HC-bearing fluid inclusions homogenization temperature was considered as
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509 the minimum isotopic equilibrium temperature (ca. 115ºC). In the outer quartz rim,
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510 the minimum isotopic equilibrium temperature can be estimated as the

511 aqueous/hydrocarbon trapping temperature (ca. 127ºC; Figure 9). There is a different

512 trend in δ18OH2O compositions in the quartz core compared to the outer quartz fringe

513 (Figure 10). In the crystal nucleus, the calculated δ18OH2O compositions display a

514 narrow range between 1.9±0.2‰ and 2.9±0.2‰. In the outer quartz layers, the

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515 calculated δ18OH2O compositions display a wider range and higher values between

516 5.8±0.2‰ and 9.9±0.2‰.

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517
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518 Figure 10: Microanalyses for δ18OSMOW in quartz-2 from core to rim. Red line and

519 dots indicate the position of the analyzed spots.

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520
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521 5. DISCUSSION

522
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523 The petrographic study of Caravia-Berbes diamond quartz crystals allowed

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524 identifying two main growth stages during crystal ontogeny. Each stage is
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525 characterized by a distinctive cathodoluminescence response, different hydrocarbon

526 and aqueous fluid inclusions typology, and characteristic oxygen isotopic signatures.

527 Bitumen and heavy oil fluid inclusions are exclusively found in the quartz crystal core

528 area, whereas light oil-bearing and water-bearing fluid inclusions are only observed

529 either trapped within the last quartz growth band or within healed fractures.

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530 Primary hydrocarbon-bearing fluid inclusions, trapped within the diamond

531 quartz crystals core, are dominated by heavy oils. Contrastingly, primary

532 hydrocarbon-bearing fluid inclusions trapped in the outer rims are mainly composed

533 by light oil, with coeval poly-phase oil-gas-water fluid inclusions also present. These

534 observations suggest that water and petroleum coexisted during quartz formation, and

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535 that the ambient fluids from which the crystals precipitated were actually a petroleum

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536 aqueous emulsion.

537 FTIR results obtained are coherent with the first FTIR data reported by Arcos

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538 and Tornos (1997). The absence of the water band in HC-S-type fluid inclusions

539 suggests that the first stage of quartz precipitation occurred in an oil-dominated

540
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emulsion. Yellowish quartz CL luminescence is restricted to crystal core, while the
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541 outer overgrowths are dull. Yellow CL emission indicates high concentrations of
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542 defect centers, and probably amorphous micro-regions, all related to fast

543 crystallization rates in an oxygen-depleted, low-temperature hydrothermal

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544 environment (Götze et al., 2015; Kuchařová et al., 2016).

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545 The negative crystal morphology of some petroleum inclusions imply that the

546 host diamond quartz recrystallized probably driven by the presence of trapped brines.
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547 Also, based on Th values (66-140ºC), the temperature conditions for oil migration
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548 essentially coincides with the temperature required for the precipitation of SiO2 in oil
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549 systems (90-130ºC), as suggested by Parnell et al. (1996). Besides, Spirakis and Heyl,

550 (1995) proposed the transport of silica as organic complexes in the MVT systems and

551 its precipitation after heating of the hydrothermal fluid beyond the thermal stability of

552 these complexes. Silica sources may have been derived from an external supply from

553 enclosing Permotriassic sediments, with silica derived from loam clays.

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554 Solid bitumen is generally viewed as a residue of altered oils that undergone

555 severe biodegradation, water washing or de-asphalting processes (Blanc and Connan,

556 1994; Mossman and Nagy, 1996). Hydrocarbon fluid inclusion data plotted into the

557 abacus of Bourdet et al. (2008; Figure 8), allow to deduce that the early oils trapped in

558 inner quartz were initially similar to the later degraded oils trapped within the outer

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559 rims, composed by (residual?) black oils with associated bitumen (Figure 2 and 8).

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560 High CO2 concentrations found throughout the entire hydrocarbon and aqueous fluid

561 inclusions population are within the range reported for MVT deposits (Loredo, 1981;

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562 Loredo and García-Iglesias, 1984; Vityk et al., 1996; Guilhaumou et al., 2000;

563 Makhouki et al., 2003; Sanchez et al., 2005, 2009; Salardon et al., 2017). These high

564
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CO2 contents can be the result of organic matter/oil degradation or also the product of
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565 dissolution of carbonates during hostrock intensive dolomitization and silicification
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566 processes (Symons et al., 2017).

567 In Caravia-Berbes, bitumen occurrence in fluorite deposits and fractures may

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568 be the by-product of liquid oil migration subsequently in-situ degraded to bitumen.
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569

570 5.1 Oxygen isotopic compositions and nature of quartz-forming waters

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571
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572 Quartz chemistry should reflect the composition of the fluid which it
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573 precipitated from. The oxygen isotopic composition of quartz records forming

574 temperature conditions and fluid changes during mineral precipitation. Micro-

575 analytical measurements of δ18O in quartz can identify heterogeneities caused by

576 multiple fluids interacting with host-rock at different temperatures. This would allow

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577 better constraints on timing of quartz formation, source of silica and, ultimately, the

578 source of fluids during migration.

579 δ18Oquartz intra-quartz variability is on the order of 5‰ (from 23.6±0.2‰ to

580 28.7 ±0.2‰; Figure 10). The δ18Oquartz and δ18OH2O mean values (δ18Oquartz

581 =24.9±0.2‰; δ18OH2O =4.6±0.2‰) are comparable to the bulk data (δ18Oquartz

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582 =23.2±0.2‰; δ18OH2O =4.8±0.2‰) presented by Sanchez et al. (2009), and in the

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583 literature for comparable diamond quartz, (e.g. Marmarosh and Herkimmer; Dix and

584 Robinson, 2003; Jarmolowicz-Szulc et al., 2006) and quartz precipitated within

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585 sedimentary basins (Blatt, 1987; Lyon et al., 2000).

586 δ18OH2O values were calculated using fluid inclusions homogenization

587
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588 wide range of variation, intimately related with fluid inclusion homogenization
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589 temperature data, from 1.9±0,2‰ to 9.8±0,2‰ with two different zones: core

590 (1.9±0.2‰ to 2.9±0.2) and outer overgrowths (5.8±0.2‰ to 9.9±0.2‰) parts (Figure
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591 10). The δ18OH2O values are consistent with a mixing process between basinal
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592 brines/formation waters and surficial waters. The coincidence of aqueous fluid

593 inclusions trapped solely in the outer quartz overgrowths and its shift to heavier
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594 oxygen isotopes values, suggest that the δ18OH2O data range could be compatible with
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595 fluid mixing process between surficial and an increasing proportion of formation-
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596 waters. Pore waters expelled from a deeply buried shale would be expected to have

597 positive δ18OH2O of about 4 to 9 ‰ (Wilkinson et al., 1992). Considering the

598 depositional environment of the Caravia-Berbes F-district, the δ18OH2O values could

599 result from expelled pore waters fluids from deeply buried mudrocks, including

600 petroleum source rocks. The δ18OH2O values from core to overgrowths suggest an

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601 evolution within the hydrocarbon system from organic matter maturation (core) to oil

602 transport and potential reservoir charge (overgrowths).

603

604 5.2 The hydrocarbon system

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606 In the abacus of Figure 8, a petroleum inclusion with a fixed composition and

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607 trapped at a fixed P-T conditions plots on a single point. The decrease of density in

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608 the fluid trapped, after fluid inclusion stretching, moves the Th versus φvap point along

609 the curve towards higher Th values. Leakage of the inclusions is marked by

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611 has been trapped at a same PT conditions but subsequently re-equilibrated at different

612 PT conditions, the best preserved inclusions can be found at the lowest Th of the
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613 trend, (Bourdet et al., 2008).

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614 The early oil inclusions trapped at quartz core have heavier (black oil)
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615 compositions than those trapped within both the outer quartz layers and in healed

616 fractures (light oils). These late inclusions present comparable Th and φvap trends and
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617 can be classified between black to light oils. From the Th versus φvap trends, the

618 colorless and yellow oil inclusions from the outer part (HCP) can be interpreted as
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619 trapping a similar petroleum composition. This observation is an agreement with the
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620 temperature increase of the fluid flow system. The calculated P-T trapping conditions

621 displays a minor evolution from lower to higher temperatures and pressures (Figure

622 9).

623 The presence of high methane concentrations in aqueous inclusions and low

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624 homogenization temperatures in hydrocarbon-bearing fluid inclusions suggest high

625 pressure conditions during trapping. On the contrary, high Th values could indicate

626 low pressure trapping conditions. On Figure 9B the intersection between isochores of

627 aqueous and hydrocarbon fluid inclusions precisely corresponds to the

628 homogenization pressure for the two systems, suggesting that in this case water and

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629 oil are methane-saturated. In these conditions, a slight decrease of pressure could

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630 produce degassing. Compared to Herkimer and Marmarosh diamond quartzes (100 to

631 250ºC and 0.75-3.06 Kbar; Vityk et al., 1996; Dudok and Jarmolowicz-Szulc, K.,

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632 2000; Huray et al., 2006), the Caravia-Berbes quartz crystals present low pressure

633 (i.e., shallow ambient) precipitation conditions (<0.3 kbar). This low pressure could

634
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not be related to an orogeny geodynamic context, but is more in agreement with the P-
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635 T conditions determined for fluorite-MVT deposits in extensional conditions (90 to
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636 140ºC and 0.12 to 0.3 Kbar; Guilhaumou et al., 2000; Makhoukhi et al., 2003;

637 Gonzalez-Partida et al., 2003; Sanchez et al., 2005, 2009, 2010a, 2010b)
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638 The exact timing of these hydrocarbon charges is not known in the Asturian
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639 basin. From Jurassic to late Eocene, the Asturian basin is in extension and subsidence

640 (Lopez-Horgue et al., 2010). The inversion phase (Pyrenean orogeny) took place due
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641 to different tectonic pulses during the Eocene and could imply the erosion of more
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642 than 1300 m of sediments until present time (Gomez et al., 2002). The tectonic
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643 subsidence history shows phases of relative tectonic quiescence and low subsidence

644 rates, separated by a tectonically active phase with high subsidence rates, in particular

645 during Albian and Turonian (Lopez-Horgue et al., 2010). During subsidence, the

646 hydrostatic pressure gradient dominates (Warren, 2006). In such conditions the

647 trapping pressure determined in the Caravia-Berbes quartz (200 to 275 bars)

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648 corresponds to a water column (hydrostatic conditions) of 1.8 to 2.6 km and suggests

649 that the hydrocarbon maturation and diamond quartz precipitation occurred before to

650 the erosion process related to the Pyrenean orogeny. At this depth (1.8 to 2.6 km) and

651 with the trapping paleotemperatures determined in the aqueous and hydrocarbon fluid

652 systems, the geothermal gradient could be estimated around 30ºC/km. Such gradient

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653 is comparable to the Cantabrian and the North Pyrenean basin calculated gradient

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654 during Albian/Turonian subsidence (Lopez-Horgue et al., 2010; Salardon et al.,

655 2017). Temperatures from 90 to 140ºC recorded in the quartz overgrowths are

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656 abnormally high considering a standard thermal gradient during Aptian (Grobe et al.,

657 2010), implying a burial of more than 3 km. Considering this burial, the thermal

658
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659 Pyrenean Jurassic dolomites field (75ºC/km) in the Arzacq basin (Renard, 2010).
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660 Field observations indicate that the diamond quartz precipitation postdates the F-Ba

661 MVT mineralization (Symons et al., 2017). Between the early Jurassic fluorite
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662 precipitation (205 to 185 Ma; Sanchez et al., 2006; Symons et al., 2017) and the
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663 Pyrenean orogeny, only one hydrothermal event has been reported in the Asturian

664 basin at 115 Ma (Symons et al., 2017). This Aptian hydrothermal event is
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665 characterized by a pervasive silicification alteration event of the host rock (Symons et
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666 al., 2017). During Aptian times, thinning of the continental crust started and Atlantic
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667 sea floor spreading occurs around 118 Ma (Srivastava et al., 1990), corresponding to a

668 peak of extension intensity. Finally, the mantle exhumation was completed during the

669 Cenomanian (Masini et al., 2014). The temperatures determined for diamond quartzes

670 in the Caravia-Berbes F-district can be envisaged as the consequence of thermal

671 anomaly related to the mantle exhumation and the subsequent circulation of basinal

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672 brines during the Aptian. In a more regional perspective, the Caravia-Berbes Aptian

673 hydrothermal event is slightly older but comparable with the Albian/Cenomanian

674 extension in the Cantabrian and north Pyrenean basins, in relationship with the

675 thermobaric dolomitization events (Grobe et al., 2010; Lopez-Horgue et al., 2010;

676 Salardon et al., 2017). These authors point out that the most favorable conditions for

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677 thermobaric diagenesis within the respective basins (including isotherm ascent,

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678 subsidence and strike-slip fault development, deeply buried reservoir and pore fluids

679 expulsion) occurred during Albian/Cenomanian and Coniacian/Santonian (Figure 11).

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680

681 Figure 11. General model of the evolution of parent fluids according to the
682 geodynamics of the Asturian basin from lower Jurassic to Late Cretaceous.

683

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684 6. CONCLUSIONS

685

686 The conditions and timing of formation for the diamond quartzes from the

687 Caravia-Berbes area (Spain) have been constrained using catodoluminescence

688 petrography, fluid inclusion studies (microthermometry, CLSM, Raman, FTIR), fluid

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689 inclusions PVTX modeling and SIMS oxygen isotope analyses. Two differentiate

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690 quartz growth stages are characterized by the presence of distinct fluid inclusion

691 assemblages and compositions, paleo-temperatures, and δ18OQtz values, indicating an

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692 evolution in the precipitation conditions. The quartz fluid inclusion studies and PVTX

693 modeling allowed to obtain new insights into the evolution of the paleofluids in the

694
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Caravia-Berbes F-district. Hydrocarbons are represented by a wide variety of
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695 compositions, from solid black oils to light oils, with coeval solid bitumen. The
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696 variable liquid-vapor ratio, compositions and morphologies for all the petroleum fluid

697 inclusions have be interpreted as the result of a combination of increasing PT

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698 conditions correlated with higher organic matter maturation pressure. Two main
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699 episodes of fluid entrapment have been distinguished. The first appear as fluid

700 inclusions trapped at quartzes crystal core, characterized by the presence of heavy
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701 oils, with trapping conditions ranging from 90-120ºC and 100 to 200 bars. The second
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702 fluid episode is represented by primary hydrocarbon-bearing and brine-bearing fluid

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703 inclusions, both primary and secondary (along healed fractures), with temperatures

704 comprised between 110-130ºC and pressures of ca. 270 bars.

705 SIMS oxygen isotope microanalyses allowed to differentiate two δ18OH2O values

706 corresponding to the oil-dominated zone (core part) and the water-dominated zone

707 (outer growth zone). The heavier δ18OH2O values in the water-dominated zone do not

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708 only reflect a higher temperature formation, but also an increase in the δ18OH2O of the

709 parental fluid. Isotopic compositions of diamond quartz suggest a heterogeneous

710 source of surficial fluids and formation-water expelled from mud-rock.

711 Within the basin history the diamond quartz precipitation took place during

712 early Jurassic to Eocene subsidence. PTX and δ18OH2O characteristics point out a

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713 probable relationship with Albian diagenetic events reported in Cantabrian and north

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714 Pyrenean basins.

715

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716 Acknowledgments

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717 Special thanks to Marina Vega, Juan Tomas Vasquez Perez and Teresa Soledad
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718 Medina Malagón for their assistance at the CGEO laboratory. This study was financed

719 by UNAM-PAPIIT projects IN100707, IN109410-3 and CONACyT project 81584.

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720
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721 REFERENCES
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722
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723 Akhvlediany, R.A., Gigashvili, G.M., 1975. Inclusions of hydrocarbons in quartz from

724 hydrothermal veins on the Teletskiy Chain. En: Klyuzhnyi, V. A. (Ed.), Carbon
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725 and its Compounds in Endogenic Processes of Mineral Formation (Data on

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726 Studies of Fluid inclusions). Abstr. Reg. Meet., Lvov, September, 1975, 57-59

727 (In Russian; English translation en Fluid Incl. Res. Proc. COFFI, 1975, 8: 2)

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728 Arcos, D., Tornos, F. 1997. Hydrocarbon fluid inclusions in quartz crystals from the

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1026

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1027 Table caption

1028

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1029 Table 1: Summary of the techniques used to carry out this work
1030

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1031 Table 2: Microthermometric and Raman data of aqueous fluid inclusions trapped in

1032 the Caravia-Berbes diamond quartz crystals.

1033
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1034 Table 3: Microthermometry, petrography, FTIR and φgas data of hydrocarbon fluid

1035 inclusion in the Caravia-Berbes diamond quartz.

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1036
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1037 Table 4: δ18Oquartz and recalculated δ18OH2O isotopic composition of transect in

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1038 Caravia-Berbes diamond district.

1039
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1040 Table 5: Microthermometry, petrography, and trapping pressure and temperature in

1041 the Caravia-Berbes petroleum system.

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Device Sample number Laboratory
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Petrology petrographic Olympus® BX-50 petrographic 29 qtz

microscope
Catodoluminescence petrology Reliotron® cold cathode cathodoluminescence 29 qtz
Olympus BX-50 epifluorescence microscope
equipped with an UV-light source (Mercury lamp, Laboratorio de Fluidos
Epifluorescence petrology λ=365 nm), a U-MNU2 excitation filter (straight 29 qtz Corticales, UNAM,
band, 360-370 nm) and a LP400 longpass emission Queretaro, Mexico
filter (>400 nm)
Linkam THMSG-600 stage attached to an
Fluid inclusion 5 qtz
Olympus® BX-50 petrographic microscope

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Fourier transform infrared microspectrometry (FTIR) Bruker Hyperion 3000 spectrometer 5 qtz
Instituto de Neurobiologia
Zeiss LMS 700 adapted to a Zeiss inverted
Confocal laser microscopy 5 qtz laboratory (UNAM,
microscope
Querétaro, México)

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GeoRessources laboratory
Raman spectrometry Labram Jobin Yvon spectrometer 5 qtz
(Nancy, France)
Centre de Recherches
Pétrographiques et

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Oxygen satble isotope CAMECA IMS 1270 ion microprobe 1
Géochimiques (CNRS,
Nancy, France)

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Qtz Part Th (ºC) Tf (ºC) NaCl wt % eq [NaCl]m [CH4]m

Qtz-1 outer 114.5 -0.9 1.6 0.3 0.15

Qtz-1 outer 127.7 -1.2 2.1 0.4 0.16
Qtz-1 outer 134.2 -1.2 2.1 0.4 0.19

Qtz-2 outer 132.3 -1.2 2.1 0.4 0.25

Qtz-2 outer 130.3 -1.2 2.1 0.4 0.25
Qtz-2 outer 131.1 -1.2 2.1 0.4 0.25
Qtz-2 outer 130.2 -0.8 1.4 0.3 0.32

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Qtz-2 outer 134 -1.3 2.3 0.4 0.28
Qtz-2 outer 134 -1.3 2.3 0.4 0.25
Qtz-2 outer 104.2 -1.6 2.8 0.5 0.32

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Qtz-2 outer 102 -1.6 2.8 0.5 0.26

Qtz-3 outer 131.4 -1.3 2.3 0.4 0.16

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Qtz-4 outer 104 -1.6 2.8 0.5 0.3
Qtz-4 outer 99 -1.6 2.8 0.5 0.24
Qtz-4 outer 140 -1.3 2.3 0.4 0.23

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Qtz-4 outer 109 -1 1.9 0.3 0.12
Qtz-4 outer 127.3 -1.4 2.4 0.4 0.15
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Qtz-5 outer 131.4 -1.3 2.3 0.4 0.16
Qtz-5 outer 130.8 -1 1.9 0.3 0.16
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Qtz Part Inc. Type Color (nat. light)Color (under UV) Th (ºC) [CH4]m [CO2]m [Alk]m CH2/CH3m φ vap Th φ vap

Qtz-1 inner HC-S coffe blue 66.8 36.8 12.8 50.3 1.3 7.4
Qtz-1 outer HCp pale yellow blue 116.8 35.1 16.2 48.6 1.7 16.2
Qtz-1 outer HCp pale yellow blue 113.0 33.7 18.3 48.0 2.0 20.8 2 fractura borde
Qtz-1 inner HCs yellow blue 34.5 15.2 50.2 1.4
Qtz-1 inner HCs coffe pale blue 111.9 33.7 16.2 50.1 1.5 15.7

Qtz-2 inner HC-S coffe blue 97.4 33.7 18.8 47.4 2.1 7.8 60x(agua) 116.8 16.24
Qtz-2 inner HC-S coffe blue 108.9 34.8 15.4 49.6 1.5 19.1 2 fractura borde

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Qtz-2 outer HCp translucide blue /white 34.7 19.3 45.9 2.8 60x(agua) 123 20.12
Qtz-2 outer HCp pale yellow blue 116.7 37.5 15.5 46.9 2.4 18.3 2 fractura borde
Qtz-2 outer HCp pale yellow blue 122.1 37.9 14.4 47.6 2.2 20.9 externo
Qtz-2 inner HCs yellow pale blue 123.0 34.8 15.7 49.4 1.6 20.1 externo

Qtz-3 inner HC-S coffe blue 97.4 34.3 16.8 48.8 1.7 11.5 5 fractura centro del

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Qtz-3 outer HCp pale yellow blue 33.5 19.6 46.8 2.3 100x(aceite) 111.1 17.8
Qtz-3 outer HCp translucide blue /white 129.3 38.7 14.5 46.7 2.6 14.6
Qtz-3 outer HCp pale yellow blue 119.2 34.2 18.3 47.3 2.1 16.4
Qtz-3 inner HCs yellow pale blue 125.3 35.3 16.3 48.3 1.9 20.0 cristal

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Qtz-4 inner HC-S coffe blue 92.7 33.8 17.9 48.2 1.8 9.5
Qtz-4 inner HC-S coffe blue 94.2 34.2 16.2 49.5 1.5 9.4
Qtz-4 outer HCp translucide blue /white 37.1 16.1 46.6 2.4
Qtz-4 outer HCp translucide blue /white 32.0 21.2 46.7 2.5
Qtz-4 inner HCs coffe pale blue 111.1 32.4 18.8 48.8 1.8 25.2

Qtz-5 inner HC-S coffe blue 34.1 14.2 51.7 1.5

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Qtz-5 inner HC-S coffe blue 34.9 16.3 48.8 1.7
Qtz-5 outer HCp pale yellow blue 114.0 36.8 17.7 45.5 2.7 17.8
Qtz-5 outer HCp pale yellow blue 34.9 18.2 46.9 2.3

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2 fractura borde

60x(agua) 116.8 16.24

2 fractura borde

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60x(agua) 123 20.12
2 fractura borde

5 fractura centro del

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100x(aceite) 111.1 17.8

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Quartz Zone Point d18OSMOW error Th mean (ºC) d18OH2O error

Qtz-2 Inner pt 1 23.6 0.2 115.0 1.9 0.2

Qtz-2 Inner pt 2 24.2 0.2 115.0 2.4 0.2
Qtz-2 Inner pt 3 24.8 0.2 115.0 3.0 0.2
Qtz-2 Inner pt 4 24.0 0.2 115.0 2.3 0.2
Qtz-2 Inner pt 5 24.3 0.2 115.0 2.5 0.2
Qtz-2 Inner pt 6 24.2 0.2 115.0 2.4 0.2
Qtz-2 Inner pt 7 24.3 0.2 115.0 2.6 0.2
Qtz-2 Inner pt 8 24.6 0.2 115.0 2.8 0.2
Qtz-2 Inner pt 9 24.6 0.2 115.0 2.9 0.2
Qtz-2 Outer pt 10 24.6 0.2 127.0 5.8 0.2
Qtz-2 Outer pt 11 25.3 0.2 127.0 6.4 0.2
Qtz-2 Outer pt 12 25.7 0.2 127.0 6.8 0.2
Qtz-2 Outer pt 13 26.4 0.2 127.0 7.6 0.2
Qtz-2 Outer pt 14 28.7 0.2 127.0 9.9 0.2
Qtz-2 Inner pt 15 23.6 0.2 127.0 1.9 0.2

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Crystal part Inc. Type Inclusion number Color (nat. light) Color (under UV) Th (ºC) Inc. Type Inclusion number Th (ºC) Trapping P Trapping T depth
n n bar ºC km
Inner HCs 171 coffe pale blue 111,1 - 125,3 - - - 200 111 - 125 >2
Outer HCp 92 pale yellow blue 113 - 129,2 Aq 62 102 - 140 275 127 2.7

All HC-S 36 coffe blue 66,8 - 108,9 - - - 110 - 220 92 - 125 >1 - 2,2

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CENTRO DE GEOCIENCIAS
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10th of May, 2018

Highlight:

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- We define the physic-chemical conditions of transport and precipitation of silica.

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- We define the fluid (hydrocarbon and water emulsion) source

- We discuss arguments considering the existence of hydrocarbon migration in Asturian basin

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- We discuss the timing of the hydrocarbon migration pointing out a probable relationship
with Albian diagenetic events reported in Cantabrian and north Pyrenean basins.
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