Abstract

In regions where water resources are scarce and in high demand, it is important to safeguard against contamination of groundwater aquifers by oil-field fluids (water, gas, oil). In this context, the geochemical characterisation of these fluids is critical so that anthropogenic contaminants can be readily identified. The first step is characterising pre-development geochemical fluid signatures (i.e., those unmodified by hydrocarbon resource development) and understanding how these signatures may have been perturbed by resource production, particularly in the context of enhanced oil recovery (EOR) techniques. Here, we present noble gas isotope data in fluids produced from oil wells in several water-stressed regions in California, USA, where EOR is prevalent. In oil-field systems, only casing gases are typically collected and measured for their noble gas compositions, even when oil and/or water phases are present, due to the relative ease of gas analyses. However, this approach relies on a number of assumptions (e.g., equilibrium between phases, water-to-oil ratio (WOR) and gas-to-oil ratio (GOR) in order to reconstruct the multiphase subsurface compositions. Here, we adopt a novel, more rigorous approach, and measure noble gases in both casing gas and produced fluid (oil-water-gas mixtures) samples from the Lost Hills, Fruitvale, North and South Belridge (San Joaquin Basin, SJB) and Orcutt (Santa Maria Basin) Oil Fields. Using this method, we are able to fully characterise the distribution of noble gases within a multiphase hydrocarbon system. We find that measured concentrations in the casing gases agree with those in the gas phase in the produced fluids and thus the two sample types can be used essentially interchangeably.EOR signatures can readily be identified by their distinct air-derived noble gas elemental ratios (e.g., 20Ne/36Ar), which are elevated compared to pre-development oil-field fluids, and conspicuously trend towards air values with respect to elemental ratios and overall concentrations. We reconstruct reservoir 20Ne/36Ar values using both casing gas and produced fluids and show that noble gas ratios in the reservoir are strongly correlated (r2 = 0.88–0.98) to the amount of water injected within ~500 m of a well. We suggest that the 20Ne/36Ar increase resulting from injection is sensitive to the volume of fluid interacting with the injectate, the effective water-to-oil ratio, and the composition of the injectate. Defining both the pre-development and injection-modified hydrocarbon reservoir compositions are crucial for distinguishing the sources of hydrocarbons observed in proximal groundwaters, and for quantifying the transport mechanisms controlling this occurrence.

Highlights

  • The environmental effects of oil production, enhanced oil recovery (EOR) techniques, and hydraulic fracturing need to be understood in order to safeguard nearby water resources

  • In hydrocarbon systems that have been perturbed by anthropogenic processes such as EOR and hydraulic fracturing, defining end-members for evaluating potential mixing with groundwater requires the determination of the pre-development reser­ voir noble gas compositions and how these signatures have evolved with production, as well as with the secondary effects of EOR

  • Casing gases were collected from the Lost Hills, North and South Belridge and Orcutt Oil Fields; measured concentrations can be found in Supplementary Table 2 and isotope ratio data can be found in Supple­ mentary Table 3, as well in USGS data releases (Gannon et al, 2018; Seitz et al, 2021)

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Summary

Introduction

The environmental effects of oil production, enhanced oil recovery (EOR) techniques, and hydraulic fracturing need to be understood in order to safeguard nearby water resources. Hydrocarbon phases are initially devoid of all atmospheric noble gases and gain their unique signatures by interactions with airsaturated waters (ASW), which inherit their geochemical signature via atmospheric equilibration at recharge (e.g., Ballentine and Hall, 1999; Aeschbach-Hertig et al, 1999; Kipfer et al, 2002). This subsequent redistribution – from water to oil – is solubility controlled and is a function of the thermodynamic conditions and the relative volumes involved. In hydrocarbon systems that have been perturbed by anthropogenic processes such as EOR and hydraulic fracturing, defining end-members for evaluating potential mixing with groundwater requires the determination of the pre-development reser­ voir noble gas compositions and how these signatures have evolved with production, as well as with the secondary effects of EOR

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