In subsurface imaging and oil recovery where temperatures and salinities are high, it is challenging to design polymer-coated nanoparticles with low retention (high mobility) in porous rock. Herein, the grafting of poly­(2-acrylamido-2-methyl-1-propanesulfonic acid-co-acrylic acid) (poly­(AMPS-co-AA)) on magnetic iron oxide nanoparticles was sufficiently uniform to achieve low adsorption on model colloidal silica and crushed Berea sandstone in highly concentrated API brine (8% NaCl and 2% CaCl2 by weight). The polymer shell was grafted via amide bonds to an aminosilica layer, which was grown on silica-coated magnetite nanoparticles. The particles were found to be stable against aggregation in American Petroleum Institute (API) brine at 90 °C for 24 h. For IO nanoparticles with ∼23% polymer content, Langmuir adsorption capacities on colloidal silica and crushed Berea Sandstone in batch experiments were extremely low at only 0.07 and 0.09 mg of IO/m2, respectively. Furthermore, upon injection of a 2.5 mg/mL IO suspension in API brine in a column packed with crushed Berea sandstone, the dynamic adsorption of IO nanoparticles was only 0.05 ± 0.01 mg/m2, which is consistent with the batch experiment results. The uniformity and high concentration of solvated poly­(AMPS-co-AA) chains on the IO surfaces provided electrosteric stabilization of the nanoparticle dispersions and also weakened the interactions of the nanoparticles with negatively charged silica and sandstone surfaces despite the very large salinities.

Petroleum sulfonate (PS) salt surfactants that are insoluble in high-salinity water were encapsulated into 10–60 nm oil swollen micelles dispersed by a cocamidopropyl hydroxysultaine zwitterionic cosurfactant to form a highly stable nanofluid at elevated salinity (∼56 000 mg/L) and temperature (∼100 °C). The resulting “Nano-Surfactant (NS)” fluid enables an economic, efficient, and environmentally friendly enhanced oil recovery (EOR) capable of targeted delivery of PS salt surfactantsone of the most abundant and inexpensive industrial surfactants, yet cannot be used in most EOR operations because of its insolubility in high-salinity waterto residual oil without the need of massive amounts of surfactants. The NS formulations presented here can be easily prepared in the field by a simple one-pot, one-step procedure at ambient temperatures and with a minimal energy input. This article reports the preparation method of the NS and results, demonstrating their long-term colloidal and chemical stability at 100 °C, reduction of crude oil–high-salinity water interfacial tension (IFT) by 3 orders of magnitude (from ∼10 to 0.008 mN/m), and improved mobilization of the trapped crude oil from the carbonate rock. Results point out the potential of NS formulations in enhancing oil mobilization under a variety of reservoir conditions. The NS platform described here can be utilized to encapsulate and deliver a variety of other chemical treatments, not only in oil recovery applications but also in others such as remediation of nonaqueous phase liquid-contaminated groundwater aquifers, well-drilling operations, and wellbore stimulation.

Engineered nanoparticles have been proposed for use as contrast agents to enhance geophysical characterization of oil and gas reservoirs. Under saline conditions and in the presence of fine materials, nanoparticle mobility in porous media can be severely limited. To address this issue, a series of column experiments was performed to evaluate the ability of selected polymers and surfactants to enhance the transport of magnetite nanoparticles (nMag) coated with cross-linked polymers in the presence of American Petroleum Institute (API) brine (8 wt % NaCl + 2 wt % CaCl2). Aqueous suspensions containing nMag and API brine were injected at pore-water velocities of 2 ± 0.04 m/day or 10 ± 0.40 m/day through columns packed with either 40–50 mesh Ottawa sand or 60–170 mesh crushed Berea sandstone. When nMag (2500 mg/L) was introduced into Ottawa sand, 97% of the injected mass was recovered in the column effluent, indicating high mobility under saline conditions. However, the injection of nMag (2500 mg/L) into crushed Berea sandstone resulted in >60% nMag retention within the column. In order to improve delivery, nMag (2500 mg/L) was co-injected with 1000 mg/L hydroxyethyl cellulose (HEC-10), which increased nMag mobility 2-fold (78% effluent recovery). Co-injection of nMag with 1000 mg/L Gum Arabic or Calfax 16L-35, an anionic surfactant, resulted in slightly lower effluent recoveries of 72% and 69%, respectively. A preflood with 1000 mg/L HEC-10, followed by the injection of nMag alone (2500 mg/L), yielded an additional 20% improvement in nMag mobility (93% effluent recovery), suggesting that HEC-10 screened nMag attachment sites. A multisite nanoparticle transport model that accounts for heterogeneous mineralogy with variable attachment kinetics was able to accurately reproduce the effluent concentration data. Coupled with the observed 7-fold reduction in maximum retention capacity, the model parameter fits provide further evidence to support a site-blocking mechanism. These findings demonstrate the potential for relatively small additions (0.1%) of commercially available polymers and surfactants to greatly improve nMag mobility in porous media.

We use terahertz transmission through limestone sedimentary rock samples to assess the macro and micro porosity. We exploit the notable water absorption in the terahertz spectrum to interact with the pores that are two orders of magnitude smaller (<1μm) than the terahertz wavelength. Terahertz water sensitivity provides us with the dehydration profile of the rock samples. The results show that there is a linear correlation between such a profile and the ratio of micro to macro porosity of the rock. Furthermore, this study estimates the absolute value of total porosity based on optical diffusion theory. We compare our results with that of mercury injection capillary pressure as a benchmark to confirm our analytic framework. The porosimetry method presented here sets a foundation for a new generation of less invasive porosimetry methods with higher penetration depth based on lower frequency (f<10THz) scattering and absorption. The technique has applications in geological studies and in other industries without the need for hazardous mercury or ionizing radiation.

Environmental tracing applications require materials that can be detected in complex fluids composed of multiple phases and contaminants. Moreover, large libraries of tracers are necessary in order to mitigate memory effects and to deploy multiple tracers simultaneously in complex oil fields. Herein, we disclose a novel approach based on the thermal decomposition of polymeric nanoparticles comprised of styrenic and methacrylic monomers. Polymeric nanoparticles derived from these monomers cleanly decompose into their constituent monomers at elevated temperatures, thereby maximizing atom economy wherein the entire nanoparticle mass contributes to the generation of detectable units. A total of ten unique single monomer particles and three dual-monomer particles were synthesized using semicontinuous monomer starved addition polymerization. The pyrolysis gas chromatography-flame ionization detection/mass spectrometry (GC-FID/MS) behavior of these particles was studied using high-pressure mass spectrometry. The programmable nature of our methodology permits simultaneous removal of contaminants and subsequent identification and quantification in a single analytical step.