The Roles of Oil-Water Interfaces in Forming Ultrasmall CaSO4 Nanoparticles.

In natural and engineered environmental systems, calcium sulfate (CaSO4) nucleation commonly occurs at dynamic liquid-liquid interfaces. Although CaSO4 is one of the most common minerals in oil spills and oil-water separation, the mechanisms driving its nucleation at these liquid-liquid interfaces remain poorly understood. In this study, using in situ small-angle X-ray scattering (SAXS), we examined CaSO4 nucleation at oil-water interfaces and found that within 60 minutes of reaction, short rod-shaped nanoparticles (with a radius of gyration (Rg) of 17.2 ± 2.7 nm and a length of 38.2 ± 5.8 nm) had formed preferentially at the interfaces. Wide-angle X-ray scattering (WAXS) analysis identified these nanoparticles as gypsum (CaSO4·2H2O). In addition, spherial nanoparticles measuring 4.1 nm in diameter were observed at oil-water interfaces, where surface-enhanced Raman spectroscopy (SERS) revealed an elevated pH compared to the bulk solution. The negatively charged oil-water interfaces preferentially adsorb calcium ions, collectively promoting CaSO4 formation there. CaSO4 particle formation at the oil-water interface follows a nonclassical nucleation (N-CNT) pathway by forming ultrasmall amorphous spherical particles which then aggregate to form intermediate nanoparticles, subsequently growing into nanorod-shaped gypsum. These findings of this study provide insights into mineral scaling during membrane separation and can inform more efficient oil transport in energy recovery systems.

Controls on Barite (BaSO4) Precipitation in Unconventional Reservoirs.

Barite (BaSO4) precipitation is one of the most ubiquitous examples of secondary sulfate mineral scaling in shale oil and gas reservoirs. Often, a suite of chemical additives is used during fracturing operations to inhibit the accumulation of mineral scales, though their efficacy is widely varied and poorly understood. This study combines experimental data and multi-component numerical reactive transport modeling to offer a more comprehensive understanding of the geochemical behavior of barite accumulation in shale matrices under conditions typical of fracturing operations. A variety of additives and conditions are individually tested in batch reactor experiments to identify the factors controlling barite precipitation. Our experimental results demonstrate a pH dependence in the rate of barite precipitation, which we use to develop a predictive model including a pH-dependent term that satisfactorily reproduces our observations. This model is then extended to consider the behavior of three major shale samples of highly variable mineralogy (Eagle Ford, Marcellus, and Barnett). This data-validated model offers a reliable tool to predict and ultimately mitigate against secondary mineral accumulation in unconventional shale reservoirs.

Thin continuous membrane coating with high surface energy for comprehensive antifouling seawater distillation.

Membrane distillation (MD) has prominent advantages such as treating high-salinity wastewater with a low-grade thermal energy, high salt rejection, and zero discharge. However, organic fouling and mineral scaling are two major challenges for hydrophobic MD membranes when used for practical applications. Commonly, improving organic fouling- and mineral scaling-resistance require oppositely enhanced wetting properties of membrane, thus is difficult to simultaneously realize dual resistance with one membrane. Here, we proposed to use underwater thermodynamically stable high-surface-energy coating to modify the hydrophobic membrane with Janus structures comprising different surface energy. The underlayered structure meets the hydrophobicity requirements of the MD membrane, while the coating layer realizes dual resistance to organic and inorganic foulants. Theoretical analysis and experimental proof reveal that the membrane with the high-surface-energy coating layer outperforms the pristine one with approximately 10 times of longevity. This strategy provides a new way for the use of high-surface-energy materials in versatilely fouling-resistant MD process.

Evaluating the Efficiency of Magnetic Treatment for Feed Water in Reverse Osmosis Processes.

The paper presents a new methodology for short-term (5-25 min) benchtop tests to evaluate the effectiveness of magnetic treatment of feed water for reducing mineral scaling on a reverse osmosis (RO) membrane. Scale deposition is measured at a controlled level of salt supersaturation in water flowing through an RO unit in once-through mode. A magnetic water conditioner is tested in a transient flow regime when variations of the permeate flux along the flow path are insignificant. Scale formation under these conditions is governed by salt crystallization on the membrane surface. The proposed method was implemented to investigate the influence of magnetic treatment on gypsum deposition on RO membranes in supersaturated aqueous CaSO4/NaCl solutions. The effects of magnetic water treatment on scale formation under our experimental conditions were found to be statistically insignificant with a confidence level of 95%. However, this outcome should not be considered to negate the potential efficiency of magnetic water treatment in specific applications. The proposed methodology of testing under a controlled level of salt supersaturation will also be useful for evaluating the efficiency of other water treatment technologies.

Quasi-critical condition to balance the scaling and membrane lifespan tradeoff in hypersaline water concentration.

Mineral scaling is an inconvenient obstacle for membrane distillation in hypersaline wastewater concentration applications, compromising membrane lifespan to maintain high water recovery. Although various measures are devoted to alleviating mineral scaling, the uncertainty and complexity of scale characteristics make it difficult to accurately identify and effectively prevent. Herein, we systematically elucidate a practically applicable principle to balance the trade-off between mineral scaling and membrane lifespan. Through experimental demonstration and mechanism analysis, we find a consistent concentration phenomenon of hypersaline concentration in different situations. Based on the characteristics of the binding force between the primary scale crystal and the membrane, the quasi-critical concentration condition is sought to prevent the accumulation and intrusion of mineral scale. The quasi-critical condition achieves the maximum water flux on the premise of guaranteeing the membrane tolerance, and the membrane performance can be restored by undamaged physical cleaning. This report opens up an informative horizon for circumventing the inexplicable scaling explorations and develops a universal evaluation strategy to provide technical support for membrane desalination.

A Tale of Two Foulants: The Coupling of Organic Fouling and Mineral Scaling in Membrane Desalination.

Membrane desalination that enables the harvesting of purified water from unconventional sources such as seawater, brackish groundwater, and wastewater has become indispensable to ensure sustainable freshwater supply in the context of a changing climate. However, the efficiency of membrane desalination is greatly constrained by organic fouling and mineral scaling. Although extensive studies have focused on understanding membrane fouling or scaling separately, organic foulants commonly coexist with inorganic scalants in the feedwaters of membrane desalination. Compared to individual fouling or scaling, combined fouling and scaling often exhibits different behaviors and is governed by foulant-scalant interactions, resembling more complex but practical scenarios than using feedwaters containing only organic foulants or inorganic scalants. In this critical review, we first summarize the performance of membrane desalination under combined fouling and scaling, involving mineral scales formed via both crystallization and polymerization. We then provide the state-of-the-art knowledge and characterization techniques pertaining to the molecular interactions between organic foulants and inorganic scalants, which alter the kinetics and thermodynamics of mineral nucleation as well as the deposition of mineral scales onto membrane surfaces. We further review the current efforts of mitigating combined fouling and scaling via membrane materials development and pretreatment. Finally, we provide prospects for future research needs that guide the design of more effective control strategies for combined fouling and scaling to improve the efficiency and resilience of membrane desalination for the treatment of feedwaters with complex compositions.

Calcium Sulfate and Calcium Carbonate Scaling of Thin-Film Composite Polyamide Reverse Osmosis Membranes with Surface-Tethered Polyacrylic Acid Chains.

The gypsum and calcite scaling propensities of the thin-film composite polyamide (PA-TFC) reverse osmosis (RO) membrane, modified with a tethered surface layer of polyacrylic acid (PAA) chains, was evaluated and compared to the scaling of selected commercial RO membranes. The tethered PAA layer was synthesized onto a commercial polyamide membrane (i.e., base-PA) via atmospheric pressure plasma-induced graft polymerization (APPIGP). The PAA nano-structured (SNS) base-PA membrane (SNS-PAA-PA) was scaled to a lesser degree, as quantified by a lower permeate flux decline and surface imaging, relative to the tested commercial membranes (Dow SW30, Toray SWRO, and BWRO). The cleaning of gypsum-scaled membranes with D.I. water flushing achieved 100% water permeability recovery for both the SNS-PAA-PA and Dow SW30 membranes, relative to 92-98% permeability restoration for the Toray membranes. The calcium carbonate scaling of SNS-PAA-PA membranes was also lower relative to the commercial membranes, but permeability recovery after D.I. water cleaning was somewhat lower (94%) but consistent with the level of surface scale coverage. In contrast, the calcite and gypsum-scaled membrane areas of the commercial membranes post-cleaning were significantly higher than for the SNS-PAA-PA membrane but with 100% permeability recovery, suggesting the potential for membrane damage when mineral scaling is severe.

Which Surface Is More Scaling Resistant? A Closer Look at Nucleation Theories for Heterogeneous Gypsum Nucleation in Aqueous Solutions.

Developing engineered surfaces with scaling resistance is an effective means to inhibit surface-mediated mineral scaling in various industries including desalination. However, contrasting results have been reported on the relationship between scaling potential and surface hydrophilicity. In this study, we combine a theoretical analysis with experimental investigation to clarify the effect of surface wetting property on heterogeneous gypsum (CaSO4·2H2O) formation on surfaces immersed in aqueous solutions. Theoretical prediction derived from classical nucleation theory (CNT) indicates that an increase of surface hydrophobicity reduces scaling potential, which contrasts our experimental results that more hydrophilic surfaces are less prone to gypsum scaling. We further consider the possibility of nonclassical pathway of gypsum nucleation, which proceeds by the aggregation of precursor clusters of CaSO4. Accordingly, we investigate the affinity of CaSO4 to substrate surfaces of varied wetting properties via calculating the total free energy of interaction, with the results perfectly predicting experimental observations of surface scaling propensity. This indicates that the interactions between precursor clusters of CaSO4 and substrate surfaces might play an important role in regulating heterogeneous gypsum formation. Our findings provide evidence that CNT might not be applicable to describing gypsum scaling in aqueous solutions. The fundamental insights we reveal on gypsum scaling mechanisms have the potential to guide rational design of scaling-resistant engineered surfaces.

Optimization of Polyacrylic Acid Coating on Graphene Oxide-Functionalized Reverse-Osmosis Membrane Using UV Radiation through Response Surface Methodology.

Reverse osmosis (RO) is affected by multiple types of fouling such as biofouling, scaling, and organic fouling. Therefore, a multi-functional membrane capable of reducing more than one type of fouling is a need of the hour. The polyacrylic acid and graphene oxide (PAA-GO) nanocomposite functionalization of the RO membrane has shown its effectiveness against both mineral scaling and biofouling. In this research, the polyacrylic acid concentration and irradiation times were optimized for the PAA-GO-coated RO membrane using the response surface methodology (RSM) approach. The effect of these parameters on pure water permeability and salt rejection was investigated. The models were developed through the design of the experiment (DoE), which were further validated through the analysis of variance (ANOVA). The optimum conditions were found to be: 11.41 mg·L-1 (acrylic acid concentration) and 28.08 min (UV activation times) with the predicted results of 2.12 LMH·bar-1 and 98.5% NaCl rejection. The optimized membrane was prepared as per the model conditions, which showed an increase in both pure water permeability and salt rejection as compared to the control. The improvement in membrane surface smoothness and hydrophilicity for the optimized membrane also helped to inhibit mineral scaling by 98%.

Geochemical Modeling of Celestite (SrSO4) Precipitation and Reactive Transport in Shales.

Celestite (SrSO4) precipitation is a prevalent example of secondary sulfate mineral scaling issues in hydraulic fracturing systems, particularly in basins where large concentrations of naturally occurring strontium are present. Here, we present a validated and flexible geochemical model capable of predicting celestite formation under such unconventional environments. Simulations were built using CrunchFlow and guided by experimental data derived from batch reactors. These data allowed the constraint of key kinetic and thermodynamic parameters for celestite precipitation under relevant synthetic hydraulic fracturing fluid conditions. Effects of ionic strength, saturation index, and the presence of additives were considered in the combined experimental and modeling construction. This geochemical model was then expanded into a more complex system where interactions between hydraulic fracturing fluids and shale rocks were allowed to occur subject to diffusive transport. We find that the carbonate content of a given shale and the presence of persulfate breaker in the system strongly impact the location and extent of celestite formation. The results of this study provide a novel multicomponent reactive transport model that may be used to guide future experimental design in the pursuit of celestite and other sulfate mineral scale mitigation under extreme conditions typical of hydraulic fracturing in shale formations.

Synergy of feed-side aeration and super slippery interface in membrane distillation for enhanced water flux and scaling mitigation.

Membrane distillation (MD) is an acknowledged promising technology for desalinating hypersaline brine, and as such can be a suitable candidate to further concentrate the seawater discharged from reverse osmosis process. Mineral scaling represents a major constraint against the application of MD for further desalination of concentrated seawater, especially when considering CaSO4 (gypsum) and NaCl. Up until now, it has been difficult to rely solely on membrane modification to mitigate CaSO4 scaling. Permeate-side aeration can lessen CaSO4 scaling, but does not permit to increase the water flux. Herein, we proposed the synergy of feed-side aeration and super slippery interface to perform concentrated seawater desalination via direct contact membrane distillation. The results of this study show that this synergistic effect could significantly increase the water flux, which was approximately 1.5 times higher in comparison to the membrane without aeration. Moreover, the synergistic effect effectively alleviates the complex scaling of concentrated seawater, achieving 90 wt% water recovery rate. Based on the observed results, we elucidated the mechanisms governing the enhanced water flux and scaling mitigation driven by the synergistic effect. In addition, we studied the optimal working condition for this system, unveiling that low-intensity large bubbles are more suitable as they lead to a better equilibrium between the economics and functionality of the process.

Desupersaturation of RO concentrate and gypsum removal via seeded precipitation in a fluidized bed crystallizer.

The feasibility of a continuous chemically-enhanced seeded precipitation (CCESP) process was evaluated for desupersaturation of primary reverse osmosis (PRO) concentrate generated from RO desalting of inland agricultural drainage (AD) water with high gypsum scaling potential. The CCESP approach, comprised of partial lime treatment (PLT) followed by gypsum seeded precipitation (GSP), was assessed via laboratory and field tests, along with model simulations. PLT effectiveness was confirmed for residual antiscalant removal from the PRO concentrate, which otherwise would suppress gypsum crystallization. GSP was carried out in a fluidized bed crystallizer (FBC) demonstrating the feasibility of continuous PRO concentrate desupersaturation with suitable solids management. FBC operation was stable, with respect to desupersaturation performance, when operating over a sequence of periodic solids purge-only mode with intermittent seeds replenishment. The study suggests that CCESP integration with primary and secondary RO desalting (i.e., PRO-CCESP-SRO) can provide for significant enhancement of product water recovery for inland water of high gypsum scaling propensity. For example, source water of high salinity (14,347 mg/L total dissolved solid) AD water, nearly saturated with respect to gypsum, could be desalted up to a recovery of 88-96% (relative to merely 66% recovery feasible via PRO desalting. Moreover, net salt harvesting of 2.6-3.6 kg per m3 RO concentrate (with concentrate recycle) can be obtained from high recovery desalting of the above PRO concentrate.

Influence of Surface Modification of MK-40 Membrane with Polyaniline on Scale Formation under Electrodialysis.

A comprehensive study of the polyaniline influence on mineral scaling on the surface of the heterogeneous MK-40 sulfocationite membrane under electrodialysis has been conducted. Current-voltage curves and chronopotentiograms have been obtained and analyzed for the pristine MK-40 membrane and the MK-40 membrane which is surface-modified by polyaniline. The study of the electrochemical behavior of membranes has been accompanied by the simultaneous control of the pH of the solution outcoming from the desalination compartment. The mixture of Na2CO3, KCl, CaCl2, and MgCl2 is used as a model salt solution. Two limiting states are observed on the current-voltage curve of the surface-modified membrane. There is the first pseudo-limiting state in the range of small values of the potential drop. The second limiting current is comparable with that of the limiting current for the pristine membrane. It is shown that chronopotentiometry cannot be used as a self-sufficient method for membrane scaling identification on the surface-modified membrane at high currents. A mineral scale on the surfaces of the studied membranes has been found by scanning electron microscopy. The amount of precipitate is higher in the case of the surface-modified membrane compared with the pristine one.

Hydrophilic, bactericidal nanoheater-enabled reverse osmosis membranes to improve fouling resistance.

Polyamide (PA) semipermeable membranes typically used for reverse osmosis water treatment processes are prone to fouling, which reduces the amount and quality of water produced. By synergistically coupling the photothermal and bactericidal properties of graphene oxide (GO) nanosheets, gold nanostars (AuNS), and hydrophilic polyethylene glycol (PEG) on PA reverse osmosis membrane surfaces, we have dramatically improved fouling resistance of these membranes. Batch fouling experiments from three classes of fouling are presented: mineral scaling (CaCO3 and CaSO4), organic fouling (humic acid), and biofouling (Escherichia coli). Systematic analyses and a variety of complementary techniques were used to elucidate fouling resistance mechanisms from each layer of modification on the membrane surface. Both mineral scaling and organic fouling were significantly reduced in PA-GO-AuNS-PEG membranes compared to other membranes. The PA-GO-AuNS-PEG membrane was also effective in killing all near-surface bacteria compared to PA membranes. In the PA-GO-AuNS-PEG membrane, the GO nanosheets act as templates for in situ AuNS growth, which then facilitated localized heating upon irradiation by an 808 nm laser inactivating bacteria on the membrane surface. Furthermore, AuNS in the membrane assisted PEG in preventing mineral scaling on the membrane surface. In flow-through flux and foulant rejection tests, PA-GO-AuNS-PEG membranes performed better than PA membranes in the presence of CaSO4 and humic acid model foulants. Therefore, the newly suggested membrane surface modifications will not only reduce fouling from RO feeds, but can improve overall membrane performance. Our innovative membrane design reported in this study can significantly extend the lifetime and water treatment efficacy of reverse osmosis membranes to alleviate escalating global water shortage from rising energy demands.