Septarian concretions exhibit multiple generations of cements that include body, fringe, and spar phases. Classic paragenetic interpretations include initial precipitation of the body followed by fringe(s) and then by spar in more or less discrete events. Traditional approaches (e.g., carbon and oxygen isotope analyses) are generally unable to distinguish paragenetic trends as they relate to specific formation environments (e.g., precipitation during burial or with meteoric influx). Here we present carbonate clumped-isotope, δ13C (δ13Ccarb), and δ18O (δ18Ocarb) values for septarian concretions taken from four host units in order to assess cement paragenesis and overcome traditional shortcomings. Clumped-isotope and δ18Ofluid data exhibit a wide range of values, with carbonate precipitation temperatures between ~ 20 and 50°C and δ18Ofluid compositions of ~ -14 to +4% (VSMOW). In stable-isotope cross-plots, specific cement phases group together and confirm the paragenesis indicated by superposition. In some cases, samples analyzed from concretion bodies yield temperature and δ18Ofluid values that indicate formation at shallow depths, consistent with independent data (e.g., high minus-cement porosity, external laminae deflection). In contrast, other concretion-body analyses indicate relatively high body temperatures that conflict with shallow-formation indices. Petrographic and backscatter scanning electron microscopy (SEM) reveal that concretion bodies partially consist of a secondary, replacement phase, which could explain the higher temperatures expressed in bulk body samples. Based on data for different phases in these septarian concretions, we suggest that initial body-cement precipitation occurred at relatively shallow depths from unmodified seawater, followed by fringe formation at elevated temperatures that likely coincided with the emplacement of the secondary body phase. When considered together, late-stage spar phases exhibit temperatures and δ18Ofluid values supportive of spar precipitation from fluids with a significant meteoric component, possibly during uplift.

Over the past few decades, field- and laboratory-scale studies have shown enhancements in oil recovery when reservoirs, which contain high-salinity formation water (FW), are waterflooded with modified-salinity salt water (widely referred to as the low-salinity, dilution, or SmartWater effect for improved oil recovery). In this study, we investigated the time dependence of the physicochemical processes that occur during diluted seawater (i.e., SmartWater) waterflooding processes of specific relevance to carbonate oil reservoirs. We measured the changes to oil/water/rock wettability, surface roughness, and surface chemical composition during SmartWater flooding using 10-fold-diluted seawater under mimicked oil reservoir conditions with calcite and carbonate reservoir rocks. Distinct effects due to SmartWater flooding were observed and found to occur on two different timescales: (1) a rapid (<15 min) increase in the colloidal electrostatic double-layer repulsion between the rock and oil across the SmartWater, leading to a decreased oil/water/rock adhesion energy and thus increased water wetness and (2) slower (>12 h to complete) physicochemical changes of the calcite and carbonate reservoir rock surfaces, including surface roughening via the dissolution of rock and the reprecipitation of dissolved carbonate species after exchanging key ions (Ca²⁺, Mg²⁺, CO₃^2-, and SO₄^2- in carbonates) with those in the flooding SmartWater. Our experiments using crude oil from a carbonate reservoir reveal that these reservoir rock surfaces are covered with organic-ionic preadsorbed films (ad-layers), which the SmartWater removes (detaches) as flakes. Removal of the organic-ionic ad-layers by SmartWater flooding enhances oil release from the surfaces, which was found to be critical to increasing the water wetness and significantly improving oil removal from carbonates. Additionally, the increase in water wetness is further enhanced by roughening of the rock surfaces, which decreases the effective contact (interaction) area between the oil and rock interfaces. Furthermore, we found that the rate of these slower physicochemical changes to the carbonate rock surfaces increases with increasing temperature (at least up to an experimental temperature of 75 °C). Our results suggest that the effectiveness of improved oil recovery from SmartWater flooding depends strongly on the formation of the organic-ionic ad-layers. In oil reservoirs where the ad-layer is fully developed and robust, injecting SmartWater would lead to significant removal of the ad-layer and improved oil recovery.