Wot. 2011 ELSEVIER Journal of South American Earth Seances x (2007) x04 098 PUBE- 64 200931408 3] South American Earth Sciences Hydrocarbon source potential of the Santiago Formation, Oriente Basin, SE of Ecuador J. Gaibor **, J.P.A. Hochuli “®, W. Winkler * Geological Insite, ETH Zentrum, Som ches Init eid Musetn, Unverstt Zieh. Karl Sl Abstract cc, Petr * J. Toro © CH Larch 8 4, CH8006 Zarich, Swit Quits, Hewat ir, P.O. Box 17-50 smiago Formation (Late Hettangian- Sinemurian), described in the area of Santiago inthe Oriente fasin of eastern Eeusdor. consists ‘oF three distint sedimentary members. The Santiago River Member is composed of limestones and caleareous sundstoness. The Vuguianvat Member sit monotonous sequence of black shales, The Patuca Membr consists ofa sequence of sandstones, greywackes, and shales. inter= cealated with lav flows ind dikes, The fine-grained sediments ofthe thn e members are characterized by a high content of particulate or nic matter POM, Palynofucies and rock-eval analyses indicate the predominance of kerogen types Hand Il, with HI values that indicate 8 nuelerate to low source potential. At the type locality the or ©2007 Elevior Lidl Allghts reserves Resumca {La Formacién Santiago (Hetiangiano Superior: Sinerauriano) descr a en el rea de Santiago on la Cuenca Or! os. EI Miembro Ric presenta tre distintos miembros Yuquianza es una sequenci monde steretladas por fujos de laa v dikes, Los sed do hideogeno indian an moderado 207 Elsevier Lid, All rights reserved 1 de luitas negras. El Micmbr Patuca consiste de una ssqusncia de arenisets greywackes | ntos de grano tne ae Jos tes miembros es eat 2, Los analisis de palinoracies y Rocke iil muesten un predomnvo dei kerogeno sp nd locally overmatures, surds: Cordillera of Cutueis Jurassic; Kerogen: Source tock: Pe-roleum potential: Palsnofcies| este de Bead reas, El Mier sta compuesto por ealizas y rams xlos por un sito contend baje potent de roca madre. Fn la tovaiidad tipo. a materia organica esta termalmente madura y Palabras clace: Cordillera del Cutwed; Jurisie. Kerdgeno; roca madre: Palinofacies 1. Introduction The Santiago Formation is u sedimentary sequence composed cf organicaich: shuts, sandstones, sand limes stones. It can be studied in scarce outcrops ia the Cordit Jers of Cutued in the southern sub-Andean zone of eastern Ecuador (Fig. 1). Sedimenis of the Santiago For ine author aheassen . Gaibor (0895981118 «soe Hom! matter © 2007 Ekevier Lid. AM rights rons 4010.10 ses. 2007.07.002 {20077 doi: 10, 10167 jsames 2007 07.002 Pee ee arin pena Galo Teal, Pra 9 ws potenti fhe Sant mation were deposited in an extensive basin with @ connec- tion to the sea and restricted circulation (Pindell and Tebbutt, 1995), The org F the formation ~e considered potential source rocks for oil in the Orient Resin (Pindell and Tabbutt, 1995, Vallejo et al., 2003: Diaz et al, 2003), However, no existing geochemical studies sap= port this interpretstion. tn this article, we present the results of an organic matier study in rocks of the Suntiag Formation, The analyzed samples were collected from the type locality along Patuea-Santi rich levels g0 road (Pig 1). Tae wos EPN - BIBLIOTECA PROYECTOS w Iti4, Goitor etal | Jena of South American Earth Srenes xxx (2007) ¥¥¥-¥ Te coLoMels Hottin Fm, eee + Sample cations (Lover Cretaceous) sens = ctepiea Fm Sa @ fomordis + soseen seniago Fn ee ecm clogs (Lower Jurassic saz Subsndean Zone Fig. 1. (A) Location of sty urea und (B) simpli geoloical map of the Corilers of Cute Please cite this article in press as: Gaibor, J. et eee Tecate ese ete Formion, 5.8. Am, Barth Sei. (2007), do101016)ssames. 2007070022. Gait eta | Jounal of South Americm Earth Sciences xxx of this study is to evaluate the oil source potential and reconstruct the depositional environments of the Santiago Formation, We do so using sedimentological characteris- ties, palynofacies, and rock-eval analysis, 2. Geological setting ‘The sub-Andean zone is a backare,fold-thrust belt tec= tonically associated with the Andes (Baldock, 1982). Itoccu- Pies the western margin of the Oriente Basin and includes ‘wo large-scale antiform structures, the Napo Uplitt to the north and the Cordillera of Cutucu to the south (Fig. 1). These two antiforms represent positive flower structures (Rivadeneira and Baby. 1999), developed mainly during the Neogene (Baby et al., 1999). The Santiago Formation ‘outcrops are restricted to the Cordillera of Cutuci. Chris- {ophout (1999) and Diaz et al. (2003) indicate that the Santi= :0 Formation was deposited during the aperture of an intraeratonic rift, which occurred in the Norian-Toarcian period (221-180 Ma). This interpretation is based on the presence of steeply dipping normal faults, grabens, and hall-grabens recognized in seismic profile, together with the occurrence of calc-alkaline and tholeitic basalts at the top of the Santiago Formation (Romeuf et al., 1997). There- fore, the Cordillera of Cutueti representsa tectonic inversion structure of the Triassic-Jurassie rit, The absence of Mio- ccene sediments of the Arajuno Formation in the Cordillera ‘of Cutuet and Napo Uplift suggests that these structures formed before the Miocene. This interpretation is also sup- ported by fission track data in the Napo Uplift (Ruiz, 2002), The best outcrops of the Santiago Formation are located in the Cordillera of Cutueti, along the Patuca-San- ‘ago road and Santiago River (Fig. 1). The complex tec- tonic setting anc dense vegetation in this area preclude a measure of the total thickness of the formation. However. Tschopp (1953) and Geyer (1974) estimate an approximate thickness of 1000-2700 m, Tschopp (1953) describes the Santiago Formation as a sequence of grey to black limestones and calcareous sand- stones with intercalations of micaveous and bituminous shales. In addition, Tschopp (1953) and Romeuf et al (1997) describe dikes, sills, and larger intrusions of felsic and basaltic igneous rocks. These voleanie intercalations are concentrated in the western border of the Cordillera of Cutued. This voleanism has cale-alkaline and tholeitic affinities (Romeuf et al., 1997). Caleareous sediments of the Santiago Formation outcrop along the Santiago River, whereas clastic and igneous rocks are best exposed along the road from Patuca to Santiago. ‘The Santiago Formation is absent in the northern part of the fat-lying Oriente Basin and the Napo Uplift. Red beds attributed to the Sacha Formation in the northern part of the Oriente Basin are interpreted as lateral equivalents of the Santiago Formation (Diaz et al., 2003). According to Diaz et al. (2003), the age of the Sacha Formation ranges from Early Triassic to Early Jurassic (Fig. 2). Several authors (ez, Romeut et al., 1997; Christophoul, 1999; Diaz eit 0p panera noes ape et al. 2003) propose that the Late Triassic Piuntza Forma= tion represents a lateral equivalent of the lower part of the Santiago Formation. The Piuntza Formation is a voleanie sedimentary sequence affected by contact metamorphism, defined from isolated outerops in the southern part of the Cordillera of Cutued, which includes calcareous metasilt- stones, comubianites, skarns, and impure quartzites (Asp- den and Iimey-Cook. 1992), The relationship between the Piuntza and Santiago formations is unclear, mainly because the contact between them has never been observed ‘Therefore, we consider that the Piuntza Formation repre- sents a separate formation (Fig. 2) The contact between the Santiago Formation and over- laying Chapiza Formation is an angular and erosional unconformity (Tschopp, 1953). Along the western border of the Cordillera of Cutued, in the Patucs area (Fig. 1), the Chapiza Formation consists of grey to red siltstones, sandstones, and conglomerates. In the eastern part of the Cordillera of Cutuei, the lithologies ate dominated by grey, green, and brown siltstones, The Chapiza Formation hhas never been directly dated, but volcanic rocks of the Misahualli and Yaupi formations, considered lateral equiv- alents of the Chapiza Formation (Rivadeneira and Baby 1999), yield radiometric ages (K/Ar, *Ar/Ar, zircon fi sion tracks) that range from 180 to 130 Ma (Hall and Calle 1982; Romeuf. 1994; Spikings et al.. 2001; Ruiz, 2002), indicating a Middle-Late Jurassic age. ‘The marine sequence of the Pucard Group in northern and central Peru is interpreted as a lateral equivalent of the Santiago Formation (Geyer, 1974: Geyer. 1980: Baby ct al., 1998; Diaz et l., 2003), Harrison (1943) and Mégard (1968) distinguish three units within the Pucard Group: the ‘Chambara, Aramachay, and Condorsinga formations. The Norian Chambara Formation consists of dolomites with dolomitic and cherty limestones (Louhgman and Hallam, 1982: Rosas, 1994). The Hettangian-Sinemurian Aramacr hay Formation includes organic-tich shales that pass to the top into phosphatic deposits (Louhgman and Hallam, 1982: Rosas, 1994). The organic-rich shales are regarded as the hydrocarbon source rock for the Maranon and Ucayali basins in eastern Peru (Mathalone and Montoya, 1995). The Pliensbachian-Tourcian Condorsinga For tion is restricted 10 central Peru and is a calcareous sequence with evaporites at the top (Louhgman and Hal- lam, 1982; Rosas, 1994) 3. Methods 3.4, Palynofacies analysis: ‘Twenty-five samples were selected for palynological and palynofacies analysis. The samples were treated according to standard palynological techniques and sieved to separate ‘material coarser than 15 ym for use in paalynofacies anally sis. The quantitative distribution of the particulate organic matter (POM) was determined by counting @ minimum of 300 particles per sample. For additional palynological4 4 Gabor eta. Journal of South American Earth riences xxx (2007) x84-¥¥x Chronos in Per. analysis, the sieved residue was oxidized with fuming HNO, In this study, two main types of POM were recognized: terrestrial and marine derived. The terrestrial-derived POM includes more plant debris, such as cuticles, membranes, ‘wood fragments, and opaque oxidized, structured material. These particles are referred to as phytoclasts (Tyson, 1995), Pollen and spores are listed as tcrrestrialderived pale ynomorphs. The marine-derived POM. is composed of amorphous organic matter (AOM) and marine pal yhomorphs. The latter group includes dinoflagellates, aerit- areas, and prasinophycean algae. In addition, different lypes of AOM are observed. The fluorescent’ AOM is assumed to be of marine origin, whereas non-fluorescent AOM is either of terrestrial origin or produced from the degradation of marine AOM (Steffen and Gorin, 1993: Tyson. 1995; Batten, 1996a). The state of preservation of AOM was determined on the basis of optical criteria. The thermal maturity of the sediments is related to the depth of burial heat flow, and igneous activity (Perregaard, and Schiener, 1979; Murchison and Raymond, 1989). Since the 1960s, several authors have defined numerical scales for the thermal alteration of the organic matter based on the colour of palynomorphs (Correia. 1967; Staplin, 1977; Fisher et al., 1980: Batten, 19965). Due the scarcity or Ecuador Peru North South North Central LV MisahualiFmi yy v VV Youpl Fm] Ve Fm. | Sorayaquil F Sarayequllo Fm. | Sarayoquilo Fm es Chepiza Fm. Blu [ve B| |v 3 ROA ASA AR i ‘Condorsinga Fm, I : 2 Condersings | a | 4 kd Ell Sacha km’ foe aoaacloin — S| Tavs Heber 2 F A 5) acaacnay Fn. ‘Pacamacay Fn 5 3 eee 8 { Fy 3 Chambara Fm, | Chambara Fm, | 2 g Piuntza Fm, | ? Sf 9 a 4 Cb 1 Manne sediments © Anmonocs Continental sediments T Bivalves [VV] Volcanics © Bractionods ae © payromorpns raphic chart ofthe Upper Triasc- Upper Jurassic formaticns nthe sut-Andean zone and Once ssn in Ecuador and correlate absence of palynomorphs in the studied material, the ther- ‘nal maturity is inferred from rock-eval analysis, 32, Rock-eval pyrolysis Analysis of the total organic carbon content (TOC) Was undertaken using the coulometer available at the Geological Institue, ETH Zarich. Samples with TOC greater than 2% were chosen for rock-eval pyrolysis, ‘The pyrolysis of 17 samples was carried out in the Labo. rutones for Geochemical and Environmental Analyses of the Geological Institute, University of Neuchatel, using the Rock-Eval 6 analyzer of VINCI Technologies. Data appear in Table 1 The rock-eval technique (Espitalig et al., 1977) is @ useful twol for characterizing source rock. The measurements include $1, $2, $3, total organic carbon (TOC), and Tox values. The SI values correspond to the amount of hydro carbons present in the rock. S2 values correspond 10 the hydrocarbons generated from insoluble kerogen in the heat- ing process, and S3 values represent the amount of COs taleased during thermal alteration of oxigenated organic compounds (Tyson, 1995), Tyycx Vales express the temper= ature corresponding to the maximum of hydrocarbon ger eration during the pyrolysis (peak $2) (Tissot and Welte,4 Gite a Journal of South Ameri m Earth Sciences x (2007) Table | uate of Rock-Bval 6 ofthe Parva und Yuguinva Members eZ Semple «TOC or sr 2 6 ling Hie TOC) ___(mg COs TOC mg HCie) ime HCI) Pact Member 0 328108 s ost 351 1924 240 5 8 bas om 1925 3a on 0 22 086 ons “ a1 208 366 178 Masi 093 oor os M60 195 168 15 M36 2 7k OIG 02 Moa 16 som 003 Yuuguunva Member MAS 207 30” oe 192 3 @s om 0s Mar 461 0 3 sus Me 307 438078 585 M2 231 40 us on Mul 308 3810 sol mio De “01s 39 Ms 242 45010 4s Mo 201 a ot Los Ma 243 a8 036 138 1984), whieh indicates the maturity of the organic matter. Values between approximately 430 and 470°C correlate With the oil generation window (Hunt, 1996), ‘Two parameters. the hydrogen index (HT) and the oxy- gen index (Ol) are calculated from $1, $3, and TOC. These parameters define the kerogen type present in the rocks (Tissot and Welte, 1984: Tyson, 1995; Hunt, 1996). Tissot et al, (1974) differentiate the kerogen types I, 1, and TIT ‘on the basis of H/C and O/C ratios. Kerogen type I is char- acterized by high values of HI (700-900) and. represents ‘organic matter produced by algae or cyanobacteria, accu- mulated mainly in anoxic lacustrine and marine deposi- tional environments (Tyson, 1995). Kerozen type IT shows medium values of HI (150-700) and is composed cf mixtures of phytoplankton, zooplankton. and microor- anisms preserved in a marine-reducing environment (Tis- sot and Welte, 1984), Kerogen type III presents relatively low values of HI (25-250) and is essentially derived from land plants (Tissot and Welte, 1984; Tyson, 19 4. Results 44, Description and subdivision of the Santiago Formation Based on lithological and sedimentological criteria observed at the type locality. we subdivide the Santiago Formation into three members (Fig. 3). The calcareous sediments exposed along the Santiago River are attributed, to the Santiago River Member, which consists of thick beds, of grey and black limestones, black marls, and sporadic intra-formational breccias. Toward the top. fine-grained cealeareous sandstones show a variety of sedimentary struc- lures, such as centimetric ripples, planar laminations, hum- nioeky-cross stratification, and micro-slumps. A southward paleocurrent flow direction can be inferred from these structures. Along the Santiago River, the Santiago River Member is at least 300m thick. ‘The overlaying Yuquianza Member consists of black, partly micaceous and/or calcareous shales. and sporadic beds of green siltstones (Fig, 3). The black shales at the base contain ammonoids and bivalves. are thinly laminated, and show sporadic intercalations of centimetric sandstone Tenses. In thin sections, volcanic clasts and quartz grains cean be observed. Toward the top of the member, the black shales become increasingly calcareous. The Yuquianz ‘Member is at least 50 m thick, and crops out along the Pat- ‘uca-Santiago road, between the villages of Yuquianza and Suritak (Fig. 1), The contact between the Santiago River Member and the Yuguianza Member has not been observed: however, due to similar bed orientations and polarities. the Yuquianza Member is interpreted to rest conformably or paraconformably on the Santiago River Member. ‘The Patuea Member conformably overlies the Yuguianza Member and corresponds to a clastic sequence that includes thick beds of grey, green, and brown silt- stones and greywackes, as well as micaceous and/or calear> eous black shales, which are laminated. Fine-grained greywackes with graded bedding are observed within the Patuea Member and composed of voleanic lithoclasts, monocrystalline quartz, and plagioclase in a chloritized ‘matrix. Basaltic lava flows and dikes are intercalated within these sediments, The basalts are massive and occasionally show columnar joints. In thin sections, the basalt shows, porphyritic texture. The Patuca Member is at least 100 m thick and crops out along the Patuca-Santiago road, with the best exposures between the villages of Patuca and Yuquianza (Fig. 1). The contact between the Patuca and Yuquianza mem- bers is transitional. This limit is defined by a coarsening- upward trend and the first appearance of voleanic rocksDettaic environment UPPER MEMBER ;piza Formation ae PATUCAMEMBER SANTIAGO FORMATION Turbiditic environment LOWER MEMBER Calcareous platform YUQUIANZA MEMBER SANTIAGO RIVER MEMBER [=] Conglomerate FD] Breeia [1 Sandstone [4 ststone Ss shaes anc sandstones Shae [23 Catcareous shale F21 Limestone Basic lavas = _ Gap without scale aoe Sample fr Rock Eval analysis ®_—_Aimonoidfeune + Biales 2 Lelospnaera sp. (green algae)Journal of South American Earth Sciences xx (2007) sx3-0¥% Pnytociasts Opaque Praservation Particulate Organic Matter om 25% Sore 2H now tOH 100% PATUCA MEMBER SANTIAGO FORMATION YUQUIANZA MEMBER wood Lom <1 1 Nonnuorescent Marine palynomorphs Opaque sartcies PHYTOCLASTS PALYN es of phytoclass, average size of opaque particles, preservation, an! thermal leration of the organic matter, al for thology in Fig 3 POM assemblages See legend yee between 420 and 586°C (Fig. 5). Ing, whereas in the Patuca Member, the values range [rom the Vaquianza Member, values vary between 433 and 003 to 54¢.me HCis (Fi. 5 460°C. The samples from Patuca Member show mostly values of 422-450 °C; however, extreme values of S00, 5. Discussion and interpretation 578, and 586°C were measured in the middle part of this member (Fig. 5) 51, Santiago River Member ‘The values of the total genetic potential ($1 + $2) range From 0,03 to 7.31 mg HC/s, The samples of the Yuquianza This member was deposited on 1 calcareous platform, Member show values that range from 0.14 t0 7.31 mg HC/ with moderate to low energy and disoxic anoxic conditions J.S. Am, Barth Se. Please cite this article in. eee eee oli puaees Poration, (2007) doi 10-1016) jsumes 200707002" eerJ. Gabor eta. | Sournal of Soh American Eat Tmax. (C x04 PATUCA MEMBER SANTIAGO FORMATION YUQUIANZA MEMBER Oiwedoa Overman Big. 5. TOC, HI. scnctie potential (SI ‘The calcareous sandstones in the upper part of the Santi= ago River Member show common hummocky eross-strati- fication, suggesting the presence of tempestites. 5.2. Yuguianca Member The Yuquianza Member was deposited in a shallow marine basin with disoxie to anoxie conditions. On the basis of the characteristics of the POM assemblages, this member can be subdivided into two parts. In the lower part, the relatively low percentage of phytoclasis and small size of the equidimentional opaque particles suggest a dis- al marine environment (Steffen and Gorin, 1993). The presence of fluorescent and non-fluorescent AOM indicates, fi Please cite this article in press as: Gaibor, J. et al., Hydrocarbon so woe potential of the Santiago Formation, (2007), do: 10.1016/. james 2007 07.002 2, and Tra blues of Santiago Formation 2 continental and marine source or partial degradation of the AOM. In the upper part of the Yuquianza Member, the percentage of phytoclasts and size of the equidimen: sional opaque particles increase, suggesting a more proxi mal marine environment (Steffen and Gorin, 1993). The high TOC values in this member point to anoxic deposi- tional environment, i line with the moderate to good pres: ervation of the organic matter, as well as the consistent presence of the prasinophycean algae (Leiospha also suggests anoxic conditions in a shallow-marine envi- ronment (Batten, 1996). Tus Values from the Yuquianza Member suggest that the organic matter in this member is thermally mature, The HI versus Trax diagram indicates the dominance of 1.8, Am. Earth Se0 J. Guitar eva + Patuca Member Type! © Yuquianza Member 1000) Woe Hydrogen index (mgHO/gT0C) 460460500 6 ‘380400 420440 Tmax °C) ig. 6. Type of kerogen in the Yuguianza and Patuca members of Stati Formation 10000 w Patuca Member 2 Notuiona Member gow] otsouce g z A gas source -25 a 8 & 3 gas (?) 10 A 7 0 ToC (%) Fie. 7. Possible hydrocarbon ganerited from mutare samples of Yuguianza and Patucs members of Santiago Formato, type III kerogen, though in some intervals, type TI kerogen is quite abundant (Fig, 6). The $I + 82 values suggest that a few levels have « moderate to good source potential. The level of South American Earth Scenes xx (2007) xxx HI versus TOC diagram shows that the Yuguianza Mem ber is a potential gas source and that some levels can be oil prone (Fig. 7) 53, Patuca Member A shallowing-upward trend of the depositional environ- nent can be inferred in the transition from the Yuquianza Member to the Patuca Member, as is corroborated by the POM assemblages that indicate a change in the deposi- tional environment from an anoxic or disoxie to oxie con- ditions, Despite the absence of complete Bouma cycles, the presence of graded bedding and lamination in the sand- stones of the Patuca Member suggest a turbiditic origin for these sediments, probably associated with a delta Front ‘The deposition was apparently synchronous with a strong, voleanic activity that produced lava flows and dikes. ‘The POM assemblages in the Patuca Member are dom= inated by non-fluorescent AOM, indicating terrestrial ori- gin or strong degradation of the AOM of marine origin, ‘The important amounts of phytoclasts and the size of the equidimensional opaque particles. (25-50 um) suggest a proximal marine environment (Steffen and Gorin, 1993) Tua Values indicate the mature state of the organic mat- ter, though some levels show anomalously high values of Tax combined with a black AOM. These levels obviously hhave been exposed to increased heat flow within the sedi ments due to coeval volcanism, as manifested by the inter= calation of basaltic flows. Pyrolysis parameters from these levels are irrelevant for the evaluation of the POM. In sam= ples out of the range of contact metamorphism, the HI ver= 818 Tiyox diagram (Fig. 6) indicates the dominance of kerogen type II, which makes them gas-prone (Fig. 7) The low values of SI +2 indicate a poor to moderate source potential (Tissot and Welte. 1984), 6, Conclusions According to lithological and sedimentological criteria, the Santiago Formation can be subdivided into three mem- bers. The basal Santiago River Member consists of lime= scones and calcareous sandstones; the Yuquianza, Member includes organie-rich black shales: and the Patuea Member includes sandstones, siltstones, and black shales with basaltic intercalations. Fossil evidence indicates that the organic-rieh shales of the Santiago Formation (Yuquianza Member) are of Late Sinemurian age and can be correlated with part of the Aramachay Formation of the Pucari Group in Peru. The presence of volcanic material in the shales of the Yuquianza Member and the volcanic rocks interca- lied in the Patuca Member document volcanic activity during the deposition of the upper part of the Santiago Formation, As indicated by pyrolysis data and organic matter anal- ysis, the Santiago Formation is thermally mature in the Sudied area, The Yuquianza Member has a moderateJ. Gait eta Journal of South Americ m Earth Sciences ex (2007) xnxx " source potential, with kerogen type II and II], combined. with high TOC values and a moderate preservation. Com- pared with the Yuquianza Member, the source potential of the Patuea Member is distinetly lower because of the dom- nance of kerogen type III of terrestrial origin. In conclu sion, the Santiago Formation has some oil source potential, especially in the black shales of the Yuguianza Member. Considering the state of preservation of the rock Samples (e.g., outcrop weathering). the values measured at the type locality probably represent minimum values. The Source potential of the Santiago Formation could prove to be higher in unaltered material Acknowledgments A Swiss Government Grant to J.G. supported this work. We thank H. Rieber for the identification of the ammo- roids. This manuscript was significantly improved by crit sal comments of C. Vallejo and helpful reviews of G. Gorin and P. Baby. 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