Source Rock Evaluation in the Central-Western Flank of the Tampico Misantla T Basin, Mexico ∗ Carlos Vega-Ortiza, , Dhrupad R

Home , Agua Nueva Formation, Misantla, Pimienta Formation

Journal of South American Earth Sciences 100 (2020) 102552

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Journal of South American Earth Sciences

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Source rock evaluation in the central-western flank of the Tampico Misantla T Basin, Mexico ∗ Carlos Vega-Ortiza, , Dhrupad R. Betia,b, Eiichi Setoyamab, John D. McLennana, Terry A. Ringa, Raymond Leveyb, Néstor Martínez-Romeroc a Department of Chemical Engineering, The University of Utah, Salt Lake City, UT 84112, USA b Energy & Geoscience Institute, The University of Utah, Salt Lake City, UT 84108, USA c National Autonomous University of Mexico, Mexico City, Mexico

ARTICLE INFO ABSTRACT

Keywords: Source rock evaluation is performed in a prospective block on the western-central flank of the Tampico Misantla Pyrolysis Basin (TMB), Mexico, analyzing the Agua Nueva, Pimienta and Taman formations. The rock samples are drilling Tampico Misantla Basin cores and cuttings obtained from legacy wells in an area delimited geographically on the west by the Sierra Agua nueva Madre Oriental. The area is located within the unconventional land region designated by Mexico's Ministry of Taman Energy (SENER). Pyrolysis analyses on 167 samples were performed using the HAWK℠ instrument. The results Pimienta of these source rock assessments indicate that most of the samples are classified in the oil to gas condensate Unconventional Mexico Geochemistry window, with low Total Organic Content (TOC) -dominated by non-generative organic carbon- and low Hydrogen Index (HI). A few wells showing higher S1/TOC ratio are recommended for further investigation. There is a general trend of increasing thermal maturity from southern to central-western Tampico Misantla Basin. The geochemical results were integrated with previously published data, thus enhancing our inter- pretations and providing additional insight on the thermal maturity and the phase of hydrocarbons of the Jurassic–Cretaceous source rock intervals in the region.

1. Introduction year plan for the development of domestic hydrocarbon exploration and production projects (SENER, 2015). This plan includes unconventional The petroleum industry in Mexico started with the discovery of the resources over a gross area of 69,670 km2 in the TMB. As of 2019, the prolific Golden Lane field located in the southeast part of theTampico TMB has proved reserves (1P) of 804 MMBOE, 2P of 3098 MMBOE and Misantla Basin (TMB) (Viniegra and Castillo-Tejero, 1970). Initially, the 3P of 5570 MMBOE (CNIH Reservas, 2019). The Area of Interest (AOI) oil production in the TMB targeted the Upper Cretaceous “El Abra” for the current study (Fig. 1A) is a 1735 km2 block located within the Formation (Aguayo-Camargo, 1998). In the early 2000s, exploration in TMB prospective unconventional resources area, in central-western the TMB was focused in the Chicontepec Basin (CB), which has pro- edge of the TMB at 150 km NW from the CB. Fig. 1B indicates the wells duced an accumulative 474 MMBOE (Oil = 333.4 MMB, Gas 724.3 with retrieved samples from CNH Geological Core Repository (Litoteca MMMCF) (CNIH Recursos, 2019), from the fields mentioned in the Nacional) for the source rock analysis. Although the AOI was first ex- Proyecto Aceite Terciario del Golfo (CNH-SENER, 2010). However, plored in 1912, no significant production was achieved (López-Ramos, operational difficulties associated with the highly complex turbidite 1952). Later, in the late 1950s, exploration in the AOI continued dril- depositional systems limited further development of the CB ling a total of 41 wells - the last drilled in 2000-, resulting in mostly dry (Hernández-Mendoza et al., 2011). Thus, a different approach for oil wells with a few isolated gas occurrences and oil-stained drilling cut- and gas production is required to overcome the decline from conven- tings and cores (CNH, 2018; Cruz-Luque et al., 2018). tional reservoirs. The TMB is geographically situated in the coastal plain of the Gulf of In light of the successful unconventional shale gas and oil produc- Mexico. It extends 50 km to the east, including shallow water fields. tion in North America (Bowker, 2007; Pollastro, 2007; Stevens and The basin is delimited to the west by the Sierra Madre Oriental, to the Moodhe, 2015), Mexico's Ministry of Energy (SENER), in collaboration north by the Tamaulipas arch and to the south by the Teziutlán Massif with the National Hydrocarbon Commission (CNH), established a five- (Fitz-Díaz et al., 2018). Fig. 2 is the stratigraphic column of the TMB

∗ Corresponding author. E-mail address: [email protected] (C. Vega-Ortiz). https://doi.org/10.1016/j.jsames.2020.102552 Received 24 April 2019; Received in revised form 13 February 2020; Accepted 5 March 2020 Available online 19 March 2020 0895-9811/ © 2020 Elsevier Ltd. All rights reserved. C. Vega-Ortiz, et al. Journal of South American Earth Sciences 100 (2020) 102552

Fig. 1. A. Location of the area of study within the Tampico Misantla Basin (purple line). The basin is delimited on the west by the Sierra Madre Oriental mountain range and extends eastward toward the coastal plain of the Gulf of Mexico. The red square indicates the area of interest (AOI). The study area considered by Morelos- Garcia (1996) is located in the south of the Golden Lane field and the Chicontepec Basin (Adapted from CNIH Mapas, 2019). Fig. 1B is a close-up of the AOI. Wells are shown where Pimienta formation samples were obtained for geochemistry analyses. (Base map from SGM, 2018). (For interpretation of the references to colour in this figure legend, the reader is referred to the Web version of this article.) annotated with relevant geologic events. This study presents a source 2. Geological background rock evaluation of three formations: Agua Nueva, Pimienta and Taman. The Cenomanian-Turonian Agua Nueva Formation is part of the The rocks at the base of the TMB petroleum system were deposited stratigraphy in the area of study (García-Sandoval, 2016). An analysis during the Late Triassic. The basement rocks are part of a well-defined by Yallup and Bromhead (2018) evaluates the geological similarities metamorphic complex and characteristic red beds in the paleo-Pacific between the geologically contemporary Eagle Ford and Agua Nueva -western- margin of Pangea (Quezada-Flores, 1961; Cantú-Chapa, 1992; formations, that were deposited in the same paleo-shelf margin, al- Cantú-Chapa, 1998; Fastovsky et al., 2005; Barboza-Gudiño et al., though these similarities are bound to the proximal regions to the Sligo/ 2010; Barboza-Gudiño et al., 2004) formed on the active North Amer- Cupido margin in the Burgos and Sabinas basins in NE Mexico (Gold- ican continental margin (Barboza-Gudiño et al., 1998; Cantú-Chapa, hammer and Johnson, 2001). In the TMB, regional oceanic conditions 2001). and organic matter deposition produced lithofacies with oil window During the Early Jurassic, continental rifting related to the breakup and maturity of less than or equal to 1.3 Ro% and total organic carbon of Pangea created an alternating sequence of coastal plain and marine (TOC) on the order of 2%. The majority of the samples that have been transgression sedimentary environments in the ancestral Pacific Ocean evaluated were in the oil window, with Tmax ranging from 435 °C to (Cantú-Chapa, 2001). Variable depositional conditions from rifting to 465 °C (USGS Mexico Assessment Team, 2015). post-rift allowed basinal and shallow marine deposits in a paleo-bay, The Tithonian Pimienta Formation in the TMB has been identified as where the Huayacocotla fFormation was preserved as siltstones and one of the most prominent unconventional reservoirs in the world (US- sandstones in the lower section, and as black shales in the upper section EIA, 2015). Magoon et al. (2001) concluded that the Pimienta Forma- (Rueda-Gaxiola et al., 1993; CNH, 2018). The Rosario Formation is tion acted as the source rock that generated the vast reserves in the another sequence described as red alluvial fluvial, plant bearing de- southern Gulf of Mexico, including the giant offshore fields of the Sonda posits, composed of interbedded dark carbonaceous shales, siltstones de Campeche (Santamaría-Orozco, 2000). In a comprehensive study of and fine grained paralic sandstones (Salvador, 1987, Alzaga-Ruiz et al., the Upper Jurassic of the TMB, Jarvie and Maende (2016) reported an 2009). average TOC of 4.5 wt % and Hydrogen Indices (HI) ranging from 400 During Middle Jurassic times, as the Yucatan Platform drifted to 600 mg HC/g TOC. However, in a geochemical evaluation in a southward away from the North American Plate (Marton and Buffler, specific block located in the southern part of theTMB, Morelos-Garcia 2016), the opening of the Gulf of Mexico led to a marine regression and (1996) reported a lower average TOC of 1.65 wt % and lower HI values subsequent continental basin deposition (Pindell and Kennan, 2009), (most of them less than 350 mg HC/g TOC). Granados Hernandez et al. resulting in the deposition of the Cahuasas Formation. (2018) analyzed the Pimienta Formation for the areas Anhélido, In the Late Jurassic, a gradual continuous sea transgression flooded Punchut, and Tantocob, also located in the central and southeast areas the continental area, creating a shallow-water, low-energy sea with a of the TMB, reporting TOC within a 0.5 to 8 wt % range, and HI less reducing environment (Peterson, 1983). Goldhammer and Johnson than 600 mg HC/g TOC, dominated by kerogen type II and III. (2001) described the depositional setting as preexisting carbonate The Kimmeridgian Taman Formation was also studied by Morelos- ramps flooded with fine-grained, deep marine lithofacies. These de- Garcia (1996). Pyrolysis results indicated TOC of approximately 1.9 wt posits rich in organic matter would eventually become the source of % and HI less than 300 mg HC/g TOC. hydrocarbons in the TMB. The depositional environment in the AOI was Pyrolysis results have not been previously published for the AOI. dominated by the Valles-San Luis Platform (Carrillo-Bravo, 1971), The authors compare the obtained pyrolysis results from the AOI with where the exposed land and the transgressive ocean existed as a plat- the block studied by Morelos-Garcia (1996). form-margin environment. During the Oxfordian, two formations were deposited in the AOI:

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Fig. 2. Stratigraphic chart of the area of interest within the Tampico Misantla Basin (TMB) (adapted from Peterson, 1983 and CNH, 2018).

The Santiago and Zuloaga formations which are contemporaneous with present-day Mexico's territory. This event correlates with the higher the Smackover Formation in East Texas (Sassen et al., 1987). Oxfordian eustatic sea level shown in the stratigraphic column (Fig. 4). The deposits do not have a strong presence in the AOI. Drilling reports of the shoreline of the Valles-San Luis Platform generated a slope and shallow wells in the AOI show sparse occurrence of these formations (CNH, marine basin, which resulted in the deposition of the shaly limestone of 2018). the Pimienta Formation. This deposition created a conformable facies In the Kimmeridgian, three formations are identified in the AOI; on top of the Kimmeridgian strata. Deposition occurred in a relatively these include the San Andrés, Chipoco, and Taman formations (Fig. 3). steady and homogeneous, probably neritic environment, but with The San Andrés Formation was deposited in a continental environment varying bottom-water oxygenation (Morelos-Garcia, 1996). The Titho- on the northwest of the AOI (Salvador, 1987). The Chipoco Formation nian Pimienta Formation in the AOI is dark brown to black shaly formed on the slope dipping towards the southeast from the shoreline. limestone, with some recrystallized portions. There are very thin and This formation exhibits a mixture of continental and marine conditions isolated intercalations of gray to brown-gray cryptocrystalline lime- and contains oolitic limestone. In the southeast part of the AOI, the stone, black carbonaceous mudstone, and light gray carbonates. Taman Formation was deposited in an oxic to anoxic (or anoxic-hy- During Early Cretaceous times, the Farallon Plate subducted be- persaline), shallow marine environment. It is reputed for its high or- neath the North American Continent at a high angle (Martini, 2018). ganic carbon content (Morelos-Garcia, 1996). The Kimmeridgian This subduction initiated an extensive orogeny, uplifting the Sierra marine deposits consist of compact oolitic limestone that alternates at Madre Oriental (SMO) which runs from north to south parallel to the regular intervals with dark brown to black carbonaceous shaly lime- Gulf of Mexico. The Laramide tectonic events also caused tilting and stone, and occasionally with limited occurrences of gray dolomitic subsidence of the North American Plate (Mitrovica et al., 1989). This limestone. tilting, combined with a high sea level rise, caused a major oceanic In the Tithonian, marine transgression flooded a large portion of transgression of the North American Interior Seaway (Slattery et al.,

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Fig. 3. Kimmeridgian paleogeographic map of Mexico. The deposition system in the area of study is a platform shoreline slope and basin environment (adapted from Salvador, 1987).

Fig. 4. Tithonian paleogeographic map. The Pimienta Formation was deposited in a relatively homogeneous environment, although the topography also contributes to the distribution of organic material concentration; deeper deposits contain higher organic content (adapted from Salvador, 1987).

Fig. 5. Late Cretaceous paleogeographic map. The Agua Nueva Formation was deposited in the edge of a barrier reef in the area of study, as a result of the marine transgression of the North America Interior Seaway (Adapted from Padilla y Sanchez, 2007 and Moore, 2010).

2015) and formed a foreland basin between the Valles-San Luis Potosí Cretaceous Tamaulipas Group and the Upper Cretaceous Agua Nueva Platform and the Tuxpan Platform. According to the morphostructural, Formation were deposited in a carbonate platform environment, paleogeographic and stratigraphic analysis by Eguiluz de Antuñano whereas the Upper Cretaceous San Felipe and Méndez formations have et al. (2000), the local sedimentary and structural environments were a deep-water marine origin (Aranda-Gómez et al., 2000). The Méndez dominated by the Huayacocotla sector of the SMO uplift; the high pa- Formation is described as a green-gray and brown marl, with thin in- leotectonic block was preserved to the Early Cretaceous and due to the tercalations of calcareous shale, often bentonitic (CNH, 2018). eustatic sea-level fluctuations, some areas were flooded developing Cenozoic tectonic events shaped the geology of Mexico to its pre- evaporitic-carbonate platforms. Shallow waters formed a reef boundary sent-day configuration. The Gulf of Mexico receded (Cossey et al., within the Gulf of Mexico (Fig. 5)(Salvador, 1987). The Lower 2016), and the deep foreland basin was filled with detrital and turbidite

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Fig. 6. Topographic map of the Pimienta Formation in the area of interest, obtained from the interpretation of seismic lines (Vega et al. In Preparation ‘A’). The formation follows a slope structure dipping from northwest to southeast, ending in a basin structure in the southeast. sediments of the Paleocene–lower Eocene Chicontepec Formation temperature is increased from 300 °C to 650 °C at 25 °C/min. The during the Laramide orogeny (Estrada et al., 2010). crucible containing the sample is then lowered from the oven but re- mains sealed, and the carrier gas is switched to air (oxidation mode). The crucible is reintroduced into the oven, where the sample tem- 3. Material and methods perature is increased from 300 °C to 750 °C at 25 °C/min, followed by a 3-min isotherm. Source rock evaluation was performed using an anhydrous pyrolysis The HAWK instrument, like other anhydrous pyrolysis instruments instrument. A total of 167 rock samples from nine different wells were such as the Rock-Eval and SRA devices, is equipped with three detec- obtained from the National Geologic Core Repository (Litoteca tors; flame ionization detector (FID), infra-red CO cell, and infra-red

Nacional) with the authorization of CNH (refer to Fig. 6 for well loca- CO2 cell. When experiments are performed, gases released from the tions). There are 39 cores and 16 cuttings samples from the Pimienta sample as a function of time (and/or temperature) are continuously Formation, 34 cuttings samples from the Taman Formation, and 78 sent to the three detectors by an inert carrier gas. The FID and IR signals cuttings samples from the Agua Nueva Formation. None of the samples plotted as a function of time constitute a pyrogram. The recorded FID had been preserved and no precautions were taken to prevent addi- and IR signals are then numerically processed using a calibration tional evaporative losses while the samples were in storage. standard, to determine S1, S2, S3, S4, S5, and Tmax. These parameters Source rock evaluation using pyrolysis was first introduced by are then used to calculate total organic carbon (TOC), hydrogen index Barker (1974). The anhydrous open system pyrolysis instrument (Rock- (HI), oxygen index (OI), and the oil saturation index (OSI). Eval) was first introduced by Espitalié and his colleagues in the 1970s and 1980s (Espitalié et al., 1977, 1985a; 1985b, 1986). All the ex- 4. Results and discussions periments presented in this study were performed using the standard/ classical pyrolysis temperature method (Bordenave, 1993; Behar et al., Table 1 is a summary of the results from the pyrolysis experiments 2001) using a Wildcat Technologies HAWK℠ (Hydrocarbon Analysis performed in this study (full details are provided in Appendix 1). With Kinetics) instrument. The key results are presented in three plots; a pseudo van Krevelen

Before the experiments were performed, all of the samples were diagram (HI versus OI), an HI versus Tmax plot indicating the thermal pulverized using a mortar and pestle to ~350 μm (U.S. std. Sieve 40 maturity, and an OSI versus Tmax plot showing the oil saturation index mesh). Nominal 75-mg aliquots of these pulverized drilling cuttings and versus thermal maturity. The interpretation templates for both the core chips were weighed and placed in the crucible for analysis. All the pseudo van Krevelen plot and the HI versus Tmax plot were modified samples obtained for analysis in this study had been exposed to water- from Bordenave (1993) and Huc (2013). The oil producibility onset is based drilling fluid. However, the drilling reports indicate the presence chosen at 100 mg HC/g TOC in the OSI versus Tmax plot, as suggested of organic solvent additives to the drilling mud (CNH, 2018). by Jarvie (2012). The key observations are as follows. In the standard temperature pyrolysis method, the oven temperature is programmed so that the sample, in a crucible placed on the ● In the HI versus OI plot (Fig. 7), most of the samples have low HI pedestal in the apparatus, is “equilibrated” at ~100 °C for 5 min in values (<200 mg HC/g TOC) and varying OI values (10–165 mg purge mode. Then, the sample is introduced into the oven in an inert CO2/g TOC). atmosphere, for a 3-min initial isotherm at 300 °C. Later, the sample

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Fig. 7. Modified pseudo van Krevelen plot indicating the highly mature kerogen of unknown type (HI versus OI), showing the data from the experiments performed in this study.

● In the HI versus Tmax plot (Fig. 8), most of the samples fall between The following observations are considered for the interpretation of the early mature - oil window and the oil-gas boundary - wet con- the results in this study: densate gas.

● In the OSI versus Tmax plot (Fig. 9), most of the samples from the ● The pseudo van Krevelen diagram enables kerogen type determi- wells GG and HH (located in the southeastern side of the AOI) show nation only when the samples are immature (Jones, 1984). The HI higher oil saturation than the other wells values presented in this study are all present-day values - they are

Fig. 8. HI versus Tmax plot indicating the thermal maturity, showing the data from the experiments performed in this study.

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Fig. 9. OSI versus Tmax plot indicating the oil saturation, showing the data from the experiments performed in this study.

not to be confused with original HI values. rock and OSI greater than 200 mg HC/g TOC have been excluded. ● Although the HI vs OI plot (Fig. 7) shows TOC values ranging from This is justified because samples with lower S2 values tend tohave

0.2 to 6.3 wt %, the maximum generative organic carbon content less reliable Tmax values, and samples with higher OSI often skew recorded in the entire data set is only 0.49 wt %. The non-generative Tmax towards lower values (King et al., 2015). organic content recorded in the data set ranges from 0.2 to 5.9 wt %. ● Jarvie (2015) shows that cuttings samples undergo oxidation when Following Cooles et al. (1986), it can be stated that almost all the they experience prolonged storage times. He presented results that samples are dominated by inert organic carbon at the time of ana- show a general increase in carbonate carbon content and a decrease lysis. in TOC, S1, and S2 values as a result of oxidation. Since all of the ● In Figs. 8 and 9, data points with S2 values less than 0.5 mg HC/g samples from the Agua Nueva and Taman formations that were

Table 1 Pyrolysis experiments result summary showing the average values for each well and formation.

Well Total Wells Tmax TOC GOC NGOC HI OI S1 S2 OSI

[code] [qty] [°C] [Wt. %] [Wt. %] [Wt. %] [mgHC/gTOC] [mgCO2/gTOC] [mgHC/g rock] [mgHC/g rock] [mgHC/gTOC]

K Agua Nueva

CC 19 445 0.35 0.06 0.29 85 86 0.1 0.3 24 FF 38 441 0.58 0.08 0.50 74 69 0.2 0.4 33 GG 13 443 0.72 0.11 0.61 82 81 0.4 0.5 52 HH 8 446 1.02 0.23 0.79 97 46 1.3 0.9 123 AVG. 444 0.66 0.12 0.54 85 71 0.5 0.5 58

J Pimienta

AA 3 435 1.24 0.07 1.17 46 32 0.1 0.4 9 BB 14 450 0.44 0.07 0.38 119 85 0.0 0.4 12 DD 4 442 1.13 0.09 1.04 24 38 0.4 0.3 34 EE 3 448 0.67 0.05 0.63 24 55 0.1 0.1 12 GG 12 429 1.00 0.16 0.85 60 52 0.8 0.6 71 HH 9 432 0.74 0.10 0.64 73 48 0.3 0.5 44 II 8 450 0.39 0.06 0.33 94 91 0.1 0.3 21 AVG. 441 0.80 0.08 0.72 63 57 0.3 0.4 29

J Taman

FF 8 443 0.65 0.17 0.47 200 75 0.2 1.3 35 GG 26 425 1.59 0.23 1.36 49 34 1.7 0.7 111 AVG. 434 1.12 0.20 0.91 124 55 1.0 1.0 73

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analyzed in this study are cuttings - along with a few of the Pimienta except in well GG. A log display from well GG highlights the areas with samples - it is reasonable to assume that the results presented here large OSI (Fig. 12). may have been affected by oxidation. From Figs. 10 and 11 with data from Morelos-Garcia (1996), the immature Taman samples manifest a hybrid Type III and a mixture of 4.1. Agua Nueva Formation Type II and III kerogen.

The samples from the Agua Nueva Formation were obtained from 4.4. General observations the wells CC, FF, GG, and HH (Fig. 6). The average thickness of the formation recorded in these wells in the AOI is 200 m. The measured The overall pyrolysis results suggest that all three formations have TOC values ranged from 0.24 wt % to 2.8 wt %, with an average of very low (<0.5 wt %) generative organic carbon. The majority of the 0.6 wt %. All of the HI values are lower than 152 mg HC/g TOC, and the samples lie between the oil window and the wet gas window, with OI values range from 164 to 13 mg CO2/g TOC (Fig. 7). All the recorded unidentifiable kerogen types. The samples from the wells GG andHH Tmax values range from 433 to 457 °C (Fig. 8). This indicates that all of have higher OSI values recorded in the three the formations analyzed, the samples are thermally mature and lie in the oil window. Since the compared to the rest of the wells, except the HH well where the Taman samples are thermally mature, kerogen type determination is not pos- Formation is not present. This could be due to the higher relative S1/ sible using the pseudo van Krevelen diagram (Fig. 7). From a plot of OSI TOC ratio (dominated by migrated oil) and/or the reported presence of vs. Tmax (Fig. 9), it can be noted that while the majority of the samples organic solvent in the drilling (CNH, 2018). have lower OSI values (less than 100 mg HC/g TOC), all of the samples As mentioned, it is highly likely that the results presented here have from well HH have high OSI values. These locally high OSI values could been affected by oxidation. Since oxidation due to extended storage be due to a higher relative S1/TOC ratio and/or contamination caused time results in a decrease of TOC, S1 and S2 values, the HI and OSI by organic solvents added to the water-based drilling fluid. values presented here, along with TOC, S1 and S2 values, may have Although the experiments performed in this study do not confirm been higher if the samples were tested immediately after sample ac- kerogen type, Busch and Amado Govela (1974) attributed the Agua quisitions. In general, accurate results can only be achieved by testing Nueva Formation to a marine depositional environment. solvent-extracted rock samples immediately after sample acquisition, to avoid the influence of drilling fluid contamination and oxidation. 4.2. Pimienta Formation From the mineralogical compositional analysis (Vega-Ortiz et al. In Preparation ‘B’), it can be confirmed that the Pimienta Formation Samples from the Pimienta Formation were acquired in the wells samples from the northwestern portion of the AOI -closer to the AA, BB, DD, EE, GG, HH, and II (Fig. 6). The thickness of this formation shoreline-are more diluted with clastics (~50% Carbonates, ~40% in the AOI is between 30 and 60 m on the slope in the northwest, and Sands, ~10% Clays), classified as Silica-Rich Carbonate Mudstone using 80–120 m in the basin area in the southeast. TOC values range from the “sCore: A Classification for Organic Mudstones” by Gamero-Diaz 0.25 wt % to 2.3 wt %, with an average of 0.72 wt %. All of the re- et al. (2013), whereas the formations in the southeastern part of the corded HI values are lower than 179 mg HC/g TOC, and the OI values AOI (deeper marine environment) are Carbonate-Dominated Lithotype range from 151 to 20 mg CO2/g TOC (Fig. 7). Except for two outliers, (~95% Carbonates, ~3% Sands, ~2% Clays). all of the recorded Tmax values range from 425 °C to 451 °C (Fig. 8). The In comparison to pyrolysis results of Morelos-Garcia (1996), a few majority of the samples are thermally mature and lie in the oil window. immature samples from the Pimienta Formation sampled from the Kerogen type determination is not possible since the samples are mostly southern part of the TMB indicate the presence of Type II kerogen and a thermally mature. Fig. 9 shows that except for three samples from well hybrid source rock system with lean carbonate intervals (the same GG all of the samples have lower OSI values (less than 100). observations can be inferred from the Pimienta sample results pre- The Morelos-Garcia (1996) analyses of the Pimienta Formation sented in Granados-Hernández et al., 2018). On the other hand, a few sample are reproduced in the HI vs. Tmax (Fig. 10) and HI vs. OI immature samples from the Taman Formation in the same location (Fig. 11) plots. These samples were obtained from wells located indicate the presence of a hybrid Type III and mixed Type II and III southeast of the current AOI (Fig. 1A). The analysis by Granados- kerogen. Hernández et al. (2018) is also displayed in Fig. 10, although no HI and Evaluation of the presence and distribution of pure kerogen types OI information is available from the Puchut and Tantocob areas. requires visual kerogen or biomarker analysis of immature samples. The average Pimienta HI values (Figs. 10 and 11) do not entirely This is outside of the scope of the present study. reflect the kerogen type since they are also affected by thermalma- turity. A set of immature samples with higher HI values indicates the 5. Conclusions presence of Type II kerogen (Fig. 10). This is confirmed by biomarker analysis presented by Morelos-Garcia (1996). However, a few immature Almost all of the samples analyzed for this study lie between the oil samples with lower HI values may indicate a more hybrid source rock and wet gas windows. A few relatively deeper wells have higher S1/ system mainly due to lean carbonate intervals. TOC ratios (wells GG and HH). These wells are mostly dominated by contributions from the Taman and then the Agua Nueva formations 4.3. Taman Formation (and the lower interval of the Pimienta from the well GG). Discounting any organic solvent contamination, these samples may be targets for The only samples available for the Taman Formation were obtained future investigation. From this study it is clear that the Pimienta and from the wells GG and FF (Fig. 6), where the formation thickness in the Taman samples from the west-central TMB (current area of interest) are AOI is 560 m. These samples have TOC values ranging from 0.27 wt % more mature (oil window – onset of wet gas), whereas samples ana- to 6.36 wt %, with an average of 1.37 wt %. All of the recorded HI lyzed from the southern TMB (Figs. 9 and 10) are less mature (im- values are lower than 347 mg HC/g TOC, and the OI values range from mature - oil window). This increasing thermal maturity trend in the 139 to 10 mg CO2/g TOC (Fig. 7). Except for one outlier, all of the southern to central-western TMB is confirmed by the USGS Mexico recorded Tmax values range from 424 °C to 448 °C (Fig. 8). This tem- Assessment Team (2015). perature range indicates that most of the samples are thermally mature Although the lack of immature samples limited the scope for and lie in the oil window. Kerogen type determination is not possible kerogen type determination in this study, the Pimienta samples from because the samples are thermally mature. The samples from the the central-western TMB (area of interest) could be diluted with terri- Taman Formation have OSI values lower than 100 mg HC/g TOC, genous organic matter or other non-source sedimentary material,

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Fig. 10. HI versus Tmax plot indicating the thermal maturity, showing the data sourced from Morelos-Garcia (1996) and Granados-Hernández et al. (2018). whereas the samples analyzed from the southern TMB indicate the deposited in a purely anoxic environment. presence of Type II through immature samples, in accordance with the biomarker analysis by Morelos-Garcia (1996). In comparison, the Authorship statement Taman samples from the southern TMB are less dominated by Type II kerogen, mainly influenced by mixed oxic and anoxic deposition con- C. Vega Ortiz: Conception and design of study, acquisition of data, ditions. Alternatively, the Pimienta Formation was dominantly analysis and/or interpretation of data, Drafting the manuscript. D. Beti:

Fig. 11. Modified pseudo van Krevelen plot (HI versus OI), showing the data sourced from Morelos-Garcia (1996).

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Fig. 12. Geochemical log of well GG showing the oil crossover effect (Jarvie, 2012, 2014). The crossover is an indication of potential productive oil, occurring when the free oil (S1) obtained from pyrolysis experiments is larger than TOC although the S1 value may be overestimated if the measured oil is not indigenous or as the effect of additives used in the drilling fluid. Petrophysical logs are displayed for formation identification (CNH, 2018).

Conception and design of study, acquisition of data, analysis and/or acknowledge support from the Department of Chemical Engineering interpretation of data, Drafting the manuscript, revising the manuscript and the Energy & Geosciences Institute at the University of Utah. critically for important intellectual content. E. Setoyama: analysis and/ or interpretation of data, revising the manuscript critically for im- Appendix A. Supplementary data portant intellectual content, N. Martinez Romero: Approval of the version of the manuscript to be published. J. McLennan: Approval of the Supplementary data to this article can be found online at https:// version of the manuscript to be published. T. Ring: Approval of the doi.org/10.1016/j.jsames.2020.102552. version of the manuscript to be published. R. Levey: Approval of the version of the manuscript to be published References

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