Journal of Geochemical Exploration 89 (2006) 276 279 www.elsevier.

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Chemistry of petroleum brines from oil-producing wells in Cretaceous rocks from Southeast Mexico
B.A. Mndez-Ortiz a , A. Carrillo-Chvez a,, E. Gonzlez-Partida a , J. Tritlla a , G. Levresse a , F. Gonzlez-Posadas b , H. Martnez-Kemp b
a

Geofluidos, Centro de Geociencias-UNAM Campus Juriquilla, AP 15, Juriquilla, Quertaro 76230, Mxico b Activo de Exploracin, Pemex Exploracin y Produccin, Villahermosa, Tabasco, Mxico Received 16 August 2005; accepted 14 December 2005 Available online 20 March 2006

Abstract Brine chemical data obtained from oil wells in Cretaceous oilfields in the Southeastern Basin of Mexico show a complex evolution, with the following main hydrochemical processes: (1) mixing of highly evaporated brines, past the point of halite precipitation with seawater; (2) water/rock interactions between brines and carbonated rocks (dolostones). 2006 Elsevier B.V. All rights reserved.
Keywords: Oil field brines; Halogen composition; Mixing; Southeastern basins; Mexico

1. Introduction Tracing the origin, transport and accumulation mechanisms that drive the mobilization of hydrocarbons is of paramount importance for the oil industry in order to evaluate and discover new oil and gas fields worldwide. Among other tools (petrography, geochemistry of oils, etc.), the chemical characterization of oil brines (formation water that accompanies the hydrocarbons), their geochemical evolution and their water to rock interactions have proved to be reliable tools (Bally and Snelson, 1980). Petroleum brines contain part of the registry of migration and hydrocarbon accumulation within the sedimentary basin. The correct interpretation of the chemical data allow the researchers to decipher the thermal and dynamic history of the basin as well as to determine the present day
Corresponding author. E-mail address: ambiente@geociencias.unam.mx (A. Carrillo-Chvez). 0375-6742/$ - see front matter 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.gexplo.2005.12.020

pressure and flow path history of the hydrocarbons and associated brines, in addition to waterrock interaction processes (Holser, 1979; Hunt, 1996). This paper presents new data on the hydrochemical composition of formation waters from 23 PEMEX oil wells located at Southeastern Mexico (Agave and Cactus Cretaceous oil fields, and Saramako Tertiary oil field). Major and minor element compositions are used to reconstruct the hydrochemical processes that affected the evolution and waterrock interactions of the brines during their migration. The ultimate goal of this ongoing project between Geociencias-UNAM and PEMEX is to help the latter to understand the migration and accumulation processes of hydrocarbons at the Southeastern Mexican Basin. 2. Geological background The Southeastern Mexican Basin is located between the ChiapasTabasco Mesozoic and Tertiary oil fields and

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Cretaceous, and the Tertiary terrigenous with coalrelated organic matter in shales (Ricoy-Saldaa, 1989; Gonzlez-Posadas, 2003). 3. Methods Brines were sampled from 23 production wells at the Agave, Cactus and Saramako oil fields. The sampled waters come mainly from Cretaceous oil-producing horizons (Agave and Cactus) and a non-productive horizon (Saramako). In order to compare these results, some water samples were also recovered form Tertiaryproducing horizons (gas and condensate) in Saramako. The water fraction was separated from the petroleum phase by heat and gravity accumulation. The obtained water fraction was immediately analyzed for pH, electric conductivity, carbonate alkalinity and density. The water samples were subsequently filtered using 5 m Whatman membrane filters, acidified with HNO3 to pH = 2 for cation analyses; for anion analyses no acidification was carried out. Cations were measured using inductively coupled plasma-mass spectrometry (ICP-MS) technique and anions by ion chromatography (IC) at the Laboratory of Geochemistry of the University of Wyoming. 4. Results and discussion 4.1. Chemical composition The analyzed brines have a very variable electrolyte composition, with salinities ranging from 12,736 (Cactus 4-D) to 222,355 (Cactus 302) mg/kg.

Fig. 1. Location of the study area, and the Southeastern Mexican Basin.

the Yucatan carbonate platform (Fig. 1). Northward, the basin extends towards the Campeche marine platform; the southern limit of the basin is the Sierra de Chiapas. The stratigraphic column comprises a thick sedimentary section ranging from Middle Jurassic to Recent. Overlaying the Middle Jurassic salt deposits, a marine sedimentary sequence starts with the Upper Jurassic materials (shales, sandstones, carbonates, anhydrite), ending with the deposition of the Tithonian marine organic-rich rocks, which is considered to be the major source rock in the area. The Cretaceous is characterized by a thick carbonate platform sequence. After the Chiapanecan orogeny, a thick Tertiary terrigenous sequence filled up a Foreland basin developed in front of the Chiapas Ranges (Garca-Molina, 1994). The three most important tectonic events (SantiagoAcevedo and Baro-Santos, 1992) are: (1) Jurassic to Early Cretaceous extension events; (2) Miocene compression, resulting in the formation of most of the major thrust-related structural traps; and (3) PlioceneHolocene extension, resulting in the formation of listric normal faults in the Neogene section and the reactivation of some of the JurassicCretaceous normal faults (Oviedo-Prez, 1996; Pindell and Kennan, 2001). Few published studies of the source rock potential and crude oil chemistry are available (Guzmn-Vega and Mello, 1999) indicating that the main potential source rocks in the Southeastern Mexican Basin are the marine formations of the Tithonian, the carbonate rocks of the

Fig. 2. Fingerprint diagram showing the major ions for brines from wells in Agave, Cactus and Saramako oil fields.

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Fig. 2 shows a fingerprint diagram for the seven analyzed major ions: Na, Ca, K, Mg, HCO3, SO4 and Cl. In general, all waters are NaCl-dominated fluids. All the water samples recovered from Cretaceous horizons display a similar pattern regardless their salinity, with enrichment in Mg due to their interaction with dolomitized carbonates. The negative sulphate could be due to the presence of a pervasive pyritization event in the dolostone. 4.2. Halogen chemistry Halogens are useful indicators of fluid source due to the largely conservative nature of chloride and bromide in solution. In the absence of halitebrine interactions, Cl concentration in brines is only modified by dilution or, more rarely, by fluidmineral reactions, as alteration of feldspars to clays. Halogen data are evaluated in Cl vs Br and Cl vs Cl / Br plots, compared with the seawater evaporation trend (SET) after data from Fontes and Matray (1993), and Matray et al. (1989). The data on a Cl vs Br plot display a trend of mixing between seawater and a highly evaporated seawater, past the point of halite dissolution. Whether this is just a binary mixing or not cannot be concluded from this plot (Fig. 3). Cl / Br ratio of a fluid is a valuable tool to discriminate between residual (bittern) fluids enriched in Br, derived from evaporation of seawater and secondary brines where the salinity is controlled by Cl, mostly formed after halite

Fig. 4. Cl / Br ratio and Cl content of the brines along the sea water evaporation line evolution. Saturation stages (open circles): seawater (SW); gypsum (G); halite beginning (HB); halite (H); epsomite beginning (EB); sylvite beginning (SB); carnallite beginning (CB); carnallite (C).

dissolution. Our data in a Cl vs Cl / Br plot into several trends that again suggests mixing among different end members, with compositions controlled by fluids that precipitated halite but before epsomite precipitation, and seawater. We modeled some mixing binary curves between seawater and different bittern compositions on the SET. It is noticeable that the shape of the calculated curves can reproduce the distribution of most of the samples, and that the latter plot near the change of slope of the mixing curves, suggesting an strong influence (N 70%) of little-evolved seawater in the mixing (Fig. 4). 5. Conclusions The brines collected from oil wells rooted into the Cretaceous series show a strong carbonate influence mostly indicated by the enrichment of Mg for the brines hosted, suggesting their equilibrium with dolostones. Halogen systematic in formation waters suggests their origin from Mesozoic evaporated seawater past the point of halite precipitation. These waters were trapped during sedimentation or, otherwise, flowed through the sedimentary column and reached equilibrium with the dolomitized host rocks. Afterwards, their undergone different degrees of mixing with little modified seawater probably during tertiary times.

Fig. 3. Diagram Cl vs Br showing brine evolution along the seawater evaporation line. Agave (black diamonds); Cactus (white triangles); Saramako (white boxes). Saturation stages (open circles); seawater (SW); gypsum (G); halite beginning (HB); halite (H); epsomite beginning (EB); sylvite beginning (SB); carnallite beginning (CB); carnallite (C).

Acknowledgements The realization of this work was possible to a joint Project between PEMEX Exploracion (PEP) Zona Sur

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and Geociencias-UNAM. The authors wish to acknowledge their recognition to PEMEX Exploracin (PEP) Zona Sur, especially to Ing. Adn Oviedo, Ing. Antonio Escalera, Dr. Javier Meneses, Ing. Jaime Patio, Ing. Miguel Varela, Ing. Lourdes Clara and Ing. Ernesto Caballero for their help and permission for the publication of the data. References
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