Effect of Native Reservoir State and Oilfield Operations on Clay Mineral Surface Chemistry.

An understanding of clay mineral surface chemistry is becoming critical as deeper levels of control of reservoir rock wettability via fluid-solid interactions are sought. Reservoir rock is composed of many minerals that contact the crude oil and control the wetting state of the rock. Clay minerals are one of the minerals present in reservoir rock, with a high surface area and cation exchange capacity. This is a first-of-its-kind study that presents zeta potential measurements and insights into the surface charge development process of clay minerals (chlorite, illite, kaolinite, and montmorillonite) in a native reservoir environment. Presented in this study as well is the effect of fluid salinity, composition, and oilfield operations on clay mineral surface charge development. Experimental results show that the surface charge of clay minerals is controlled by electrostatic and electrophilic interactions as well as the electrical double layer. Results from this study showed that clay minerals are negatively charged in formation brines as well as in deionized water, except in the case of chlorite, which is positively charged in formation water. In addition, a negative surface charge results from oilfield operations, except for operations at a high alkaline pH range of 10-13. Furthermore, a reduction in the concentrations of Na, Mg, Ca, and bicarbonate ions does not reverse the surface charge of the clay minerals; however, an increase in sulfate ion concentration does. Established in this study as well, is a good correlation between the zeta potential value of the clay minerals and contact angle, as an increase in fluid salinity results in a reduction of the negative charge magnitude and an increase in contact angle from 63 to 102 degree in the case of chlorite. Lastly, findings from this study provide vital information that would enhance the understanding of the role of clay minerals in the improvement of oil recovery.

Investigating the mechanism of interfacial tension reduction through the combination of low-salinity water and bacteria.

In the enhanced oil recovery (EOR) process, interfacial tension (IFT) has become a crucial factor because of its impact on the recovery of residual oil. The use of surfactants and biosurfactants can reduce IFT and enhance oil recovery by decreasing it. Asphaltene in crude oil has the structural ability to act as a surface-active material. In microbial-enhanced oil recovery (MEOR), biosurfactant production, even in small amounts, is a significant mechanism that reduces IFT. This study aimed to investigate fluid/fluid interaction by combining low biosurfactant values and low-salinity water using NaCl, MgCl2, and CaCl2 salts at concentrations of 0, 1000, and 5000 ppm, along with Geobacillus stearothermophilus. By evaluating the IFT, this study investigated different percentages of 0, 1, and 5 wt.% of varying asphaltene with aqueous bulk containing low-salinity water and its combination with bacteria. The results indicated G. Stearothermophilus led to the formation of biosurfactants, resulting in a reduction in IFT for both acidic and basic asphaltene. Moreover, the interaction between asphaltene and G. Stearothermophilus with higher asphaltene percentages showed a decrease in IFT under both acidic and basic conditions. Additionally, the study found that the interaction between acidic asphaltene and G. stearothermophilus, in the presence of CaCl2, NaCl, and MgCl2 salts, resulted in a higher formation of biosurfactants and intrinsic surfactants at the interface of the two phases, in contrast to the interaction involving basic asphaltene. These findings emphasize the dependence of the interactions between asphaltene and G. Stearothermophilus, salt, and bacteria on the specific type and concentration of asphaltene.

Theoretical and experimental investigation of the impact of oil functional groups on the performance of smart water in clay-rich sandstones.

This research investigated the effect of ion concentration on the performance of low salinity water under different conditions. First, the effect of injection water composition on interparticle forces in quartz-kaolinite, kaolinite-kaolinite, and quartz-oil complexes was tested and modeled. The study used two oil samples, one with a high total acid number (TAN) and the other with a low TAN. The results illustrated that reducing the concentration of divalent ions to 10 mM resulted in the electric double layer (EDL) around the clay and quartz particles and the high TAN oil droplets, expanding and intensifying the repulsive forces. Next, the study investigated the effect of injection water composition and formation oil type on wettability and oil/water interfacial tension (IFT). The results were consistent with the modeling of interparticle forces. Reducing the divalent cation concentration to 10 mM led to IFT reduction and wettability alteration in high TAN oil, but low TAN oil reacted less to this change, with the contact angle and IFT remaining almost constant. Sandpack flooding experiments demonstrated that reducing the concentration of divalent cations incremented the recovery factor (RF) in the presence of high TAN oil. However, the RF increment was minimal for the low TAN oil sample. Finally, different low salinity water scenarios were injected into sandpacks containing migrating fines. By comparing the results of high TAN oil and low TAN oil samples, the study observed that fine migration was more effective than wettability alteration and IFT reduction mechanisms for increasing the RF of sandstone reservoirs.

Transport and fate of Fukushima-derived 137Cs and 134Cs in the seawater of the Northwest Pacific in 2015.

To understand the influence of the Fukushima accident on the Northwest Pacific, the distributions and transportations of 134Cs and 137Cs in the seawater in the Northwest Pacific in May and September 2015 were studied. The data showed that the Fukushima-derived 134Cs and 137Cs at some stations can still be distinguished from background level ~ 4 years later. On the whole, the activities of 137Cs and 134Cs in seawater were decreasing from May to Sep 2015. But the increased inventories and the surface activities of 137Cs imply that there has ever been an extra 137Cs from offshore water transported to this study area (from 31° N to 27° N, 145° E to 152.5° E) in May 2015. The average activities of 137Cs in subtropical gyre area in south of KE were the highest and the least were to the east of Luzon Strait in 2015. In vertical direction, 137Cs in subtropical gyre area were mainly distributed at 100 ~ 500 m layer and 137Cs only at 500 m layer in this area showed an increasing trend from May to Sep 2015 which reflects more 137Cs were still penetrating to deeper layer of 500 m from upper water. But they were almost not found below 1000 m layer. It was associated with the subsurface transport of radiocesiums by Northwest Pacific Mode Water (NPMW) and the diffusion of mesoscale eddy. Different distribution characteristics of 137Cs existed between north of KE and south of KE. The low-temperature-low-salinity water mass likely to be the first Oyashio Intrusion was the main factor that resulted in higher 137Cs appearing at the upper 100 m layers in north of KE.

Low-salinity water flooding by a novel hybrid of nano γ-Al2O3/SiO2 modified with a green surfactant for enhanced oil recovery.

This paper introduces a hybrid enhanced oil recovery (HEOR) method that combines a low-salinity water flooding (LSWF) and nanoparticles (NPs) stabilized with a green surfactant. We experimentally investigated the use of combinations of silica (SiO2) and gamma alumina (γ-Al2O3) nanohybrids stabilized with Gum Arabic (GA) at different water salinities. Nanofluids (NFs) were prepared by dispersing γ-Al2O3 and SiO2 NPs (0.1 wt%) in deionized water (DW), synthetic seawater (SSW), 2, 5, and 10 times diluted samples of synthetic seawater (in short 2-DSSW, 5-DSSW and 10-DSSW, respectively). The challenge is that NPs become unstable in the presence of cations in saline water. Moreover, an attempt was made to introduce NFs with high stability for a long period of time as the optimal NFs. The effects of temperature on the behaviour of optimal NFs in the presence of different base fluids, distinct mass ratios of γ-Al2O3/SiO2 and various concentrations of surfactant were analysed via interfacial tension (IFT) and viscosity measurements. The results of the viscosity measurement showed that with increasing temperature, the NPs dispersed in DW had lower viscosity than NPs dispersed in various salinities. However, the IFT measurement for NPs dispersed in different base-fluids revealed that with increasing temperature and presence of cations in saline water, IFT values decreases. Although, the minimum IFT for hybrid nanofluid (HNF) γ-Al2O3/SiO2 modified with GA and dispersed in 10-DSSW was reported 0.99 mN/m. Finally, according to the micromodel flooding results, in oil-wet conditions, the highest oil recovery for combination γ-Al2O3/SiO2 modified with GA and dispersed in 2-DSSW was reported 60.34%. It was concluded that NFs modified with GA could enhanced applicability of LSWF via delay in breakthrough time and improving sweep efficiency.

Pore-scale investigation of low-salinity water flooding in a heterogeneous-wet porous medium.

Low-Salinity Water Flooding (LSWF) is a technique aimed at modifying the interactions between rock and fluids particularly altering wettability and reducing interfacial tension (IFT). However, there remains limited understanding of how heterogeneous wettability and the presence of Initial Water Saturation (Swi) can impact the effectiveness of LSWF. This study contributes to a deeper understanding of LSWF mechanisms in the context of heterogeneous wettability, while also considering Swi. The simulations were conducted using OpenFOAM, employing a non-reactive quasi-three-phase flow solver that accounts for wettability alteration and IFT reduction during the mixing of Low-Salinity (LSW) and High-Salinity Water (HSW). A heterogeneous pore geometry is designed, and four distinct scenarios are simulated, encompassing both heterogeneous and homogeneous wettability conditions while considering the presence of Swi. These scenarios included secondary High-Salinity Water Flooding (HSWF), tertiary and secondary LSWF. Notably, the simulations reveal that secondary LSWF consistently yields the highest oil recovery across all scenarios, achieving recovery rates of up to 96.98 %. Furthermore, the presence of Swi significantly influences the performance of LSWF in terms of oil recovery, particularly in heterogeneous wettability conditions where it boosts recovery by up to 3.5 %, but in homogeneous wettability, it decreases recovery by nearly 26 %. These simulations also underscore the pivotal role played by the distribution of oil and HSW phases in profoundly affecting the outcomes of LSWF.

A systematic and critical review of application of molecular dynamics simulation in low salinity water injection.

Low Salinity Water Injection (LSWI) has been a well-researched EOR method, with several experimental and theoretical scientific papers reported in the literature over the past few decades. Despite this, there is still an ongoing debate on dominant mechanisms behind this complex EOR process, and some issues remain elusive. Part of the complexity arises from the scale of investigation, which spans from sub-pore scale (atomic and electronic scale) to pore scale, core scale, and reservoir scale. Molecular Dynamics (MD) simulation has been used as a research tool in the past decade to investigate the nano-scale interactions among reservoir rock (e.g., calcite, silica), crude oil, and brine systems in presence of some impurities (e.g., clay minerals) and additives (e.g., nanoparticles). In this paper, fundamental concepts of MD simulation and common analyses driven by MD are briefly reviewed. Then, an overview of molecular models of the most common minerals encountered in petroleum reservoirs: quartz, calcite, and clay, with their most common types of potential function, is provided. Next, a critical review and in depth analysis of application of MD simulations in LSWI process in both sandstone and carbonate reservoirs in terms of sub-pore scale mechanisms, namely electrical double layer (EDL) expansion, multi-ion exchange (MIE), and cation hydration, is presented to scrutinize role of salinity, ionic composition, and rock surface chemistry from an atomic level. Some inconsistencies observed in the literature are also highlighted and the reasons behind them are explained. Finally, a future research guide is provided after critically discussing the challenges and potential of the MD in LSWI to shed more light on governing mechanisms behind LSWI by enhancing the reliability of MD outcomes in future researches. Such insights can be used for design of new MD researches with complementary experimental studies at core scale to capture the main mechanisms behind LSWI.

Enhanced oil recovery from fractured carbonate reservoirs using nanoparticles with low salinity water and surfactant: A review on experimental and simulation studies.

Nearly half of the world's oil reserves are found in carbonate reservoirs, which have heterogeneous formation characteristics and are naturally fractured. Because of the permeability contrast between the matrix and fracture network in these reservoirs, primary and secondary oil recovery processes are ineffective. Consequently, there has been a growing interest in enhanced oil recovery (EOR) from fractured carbonate reservoirs (FCRs) over the past years and many successful attempts have involved the use of different thermal or non-thermal EOR methods to improve oil recovery. Nonetheless, many researchers have recently directed their studies towards the use of low salinity water (LSW), nanoparticles (NPs), and surfactant (LNS) as EOR agents in carbonates because they are environmentally friendly and incur low costs. Several studies have reported the successful application of the solutions of LSW, NPs, and surfactants either as individual solutions or in combinations, to carbonate formations. The challenges associated with their implementations such as fines migration for LSW flooding, surfactant adsorption onto the pore walls, and instability of NPs under harsh conditions, have also been identified in literature and addressed. However, relatively few investigations have been conducted on FCRs to study the effectiveness of these LNS EOR applications in the presence of fractures. This review, therefore, presents the reports of EOR in FCRs using LNS and identifies the mechanisms that influence these results. It has been shown that fines migration could either promote EOR or reduce recovery based on the occurrence of formation damage. In addition, surfactants with the tendency to form micro-emulsions will be efficient for EOR applications in FCRs. Finally, LNS solutions show promising results with emerging techniques such as alternating injection, which could be applied in FCRs. The findings from this study set the stage for future investigations into EOR in FCRs.

Contribution of the offshore detached Changjiang (Yangtze River) Diluted Water to the formation of hypoxia in summer.

The Changjiang (Yangtze River) Diluted Water (CDW) plume substantially impacts the biogeochemical processes off the estuary and its adjacent area, resulting in considerable environmental and ecological effects. Based on survey data in the northeastern area off the Changjiang Estuary (CE) obtained in the summers of 2008 and 2013, the hypoxia induced by the offshore detached CDW plume and the associated controlling mechanisms were investigated. The results show that the offshore transport of the CDW plume caused a dispersed low-salinity area in the northeastern area off the CE during summer, in sharp contrast with the surrounding high-salinity and high-density waters. There was a hypoxic area with low-pH (i.e., acidification) near the 40-m isobath in bottom waters in the northeastern area off the CE, and its position generally corresponded to the surface offshore CDW plume. In the area affected by the offshore low-salinity water, the surface patch-like phytoplankton bloom and the organic debris produced in situ were the material drivers of the bottom oxygen consumption and led to the corresponding relationship between the bottom hypoxic zone and the high chlorophyll-a (Chl-a) area at the surface. We consider that the local stratification caused by the offshore low-salinity water and the stable environment within the detached CDW plume constituted the external dynamic conditions for maintaining the bottom hypoxia. Our results demonstrate that the offshore detached CDW plume in the northeastern area off the CE may contribute to the formation of a local hypoxic center with low pH. This study would provide basis for understanding of the physical-biogeochemical processes and environmental responses in the offshore areas of the CDW plume.

Effect of salinity, Mg2+ and SO42- on "smart water"-induced carbonate wettability alteration in a model oil system.

HYPOTHESIS: We present a systematic study of the "smart water" induced wettability alteration. This process is believed to be greatly affected by the brine salinity and the presence of Mg2+ and SO42- in the brine. EXPERIMENTS AND MODELLING: To characterize the wettability alteration, we perform spontaneous imbibition measurement using Indiana limestone cores and a model oil with added naphthenic acid. Both single-electrolyte-based and seawater-based "smart water" are tested to investigate the effect of Mg2+, SO42- and salinity on wettability alteration. Rock/brine and oil/brine zeta potentials are measured, and the electrostatic component of disjoining pressure is calculated to understand the role of electrostatics in the wettability alteration. The surface concentration of charged species on the limestone surface is analyzed based on a natural carbonate surface complexation model (SCM). FINDINGS: Both the reduction of Na+ and addition of SO42- are found to contribute to wettability alteration. Mg2+ is found to be unfavorable for wettability alteration. Ca2+ is believed to facilitate SO42- with wettability alteration based on the comparison between the single-electrolyte-based and seawater-based brines. The reduction of the Na+ surface complexation (>CaOH⋯Na+0.25) in low salinity brines is believed to be a critical mechanism responsible for wettability alteration based on the SCM calculations.

Pore-scale numerical simulation of low salinity water flooding using the lattice Boltzmann method.

HYPOTHESIS: The change of wettability toward more water-wet by the injection of low salinity water can improve oil recovery from porous rocks, which is known as low salinity water flooding. To simulate this process at the pore-scale, we propose that the alteration in surface wettability mediated by thin water films which are below the resolution of simulation grid blocks has to be considered, as observed in experiments. This is modeled by a wettability alteration model based on rate-limited adsorption of ions onto the rock surface. SIMULATIONS: The wettability alteration model is developed and incorporated into a lattice Boltzmann simulator which solves both the Navier-Stokes equation for oil/water two-phase flow and the advection-diffusion equation for ion transport. The model is validated against two experiments in the literature, then applied to 3D micro-CT images of a rock. FINDINGS: Our model correctly simulated the experimental observations caused by the slow wettability alteration driven by the development of water films. In the simulations on the 3D rock pore structure, a distinct difference in the mixing of high and low salinity water is observed between secondary and tertiary low salinity flooding, resulting in different oil recoveries.

Chattonella (Raphidophyceae) bloom spatio-temporal variations in Tachibana Bay and the southern area of Ariake Sea, Japan: Interregional displacement patterns with Skeletonema (Bacillariophyceae).

In 2010, a massive bloom of the raphidophycean flagellate Chattonella occurred in the Ariake Sea and Tachibana Bay. Bloom dynamics and hydrographical conditions were examined by field survey. The development and decline of the bloom occurred three times in Tachibana Bay. First and third bloom developments synchronized with precipitation, and the second bloom developed in synchronization with a salinity decrease which occurred in relation to an increase of river discharge from the Chikugo River which takes several days to flow from the Ariake Sea. These results imply that the bloom was transported with the low salinity water from the Ariake Sea to Tachibana Bay. During blooms along the northern coast of Shimabara Peninsula, the predominant phytoplankton species changed from Chattonella to Skeletonema. Low salinity water intrusion induced an interregional difference of the Chattonella and Skeletonema bloom spatially-differentiated by the salinity in the Ariake Sea and Tachibana Bay.