Phosphate Recovery from Aqueous Solutions via Vivianite Crystallization: Interference of FeII Oxidation at Different DO Concentrations and pHs.

Vivianite (Fe3(PO4)2·8H2O) crystallization has attracted increasing attention as a promising approach for removing and recovering P from wastewaters. However, FeII is susceptible to oxygen with its oxidation inevitably influencing the crystallization of vivianite. In this study, the profile of vivianite crystallization in the presence of dissolved oxygen (DO) was investigated at pHs 5-7 in a continuous stirred-tank reactor. It is found that the influence of DO on vivianite crystallization was highly pH-related. At pH 5, the low rate of FeII oxidation at all of the investigated DO of 0-5 mg/L and the low degree of vivianite supersaturation resulted in slow crystallization with the product being highly crystalline vivianite, but the P removal efficiency was only 30-40%. The removal of P from the solution was substantially more effective (to >90%) in the DO-removed reactors at pH 6 and 7, whereas the efficiencies of P removal and especially recovery decreased by 10-20% when FeII oxidation became more severe at DO concentrations >2.5 mg/L (except at pH 6 with 2.5 mg/L DO). The elevated degree of vivianite supersaturation and enhanced rate and extent of FeII oxidation at the higher pHs led to decreases in the size and homogeneity of the products. At the same pH, amorphous ferric oxyhydroxide (AFO)─the product of FeII oxidation and FeIII hydrolysis─interferes with vivianite crystallization with the induction of aggregation of crystal fines by AFO, leading to increases in the size of the obtained solids.

Electrochemical Removal of Metal-Organic Complexes in Metal Plating Wastewater: A Comparative Study of Cu-EDTA and Ni-EDTA Removal Mechanisms.

Cu and Ni complexes with ethylenediaminetetraacetic acid (Cu/Ni-EDTA), which are commonly present in metal plating industry wastewaters, pose a serious threat to both the environment and human health due to their high toxicity and low biodegradability. In this study, the treatment of solutions containing either or both Cu-EDTA and Ni-EDTA using an electrochemical process is investigated under both oxidizing and reducing electrolysis conditions. Our results indicate that Cu-EDTA is decomplexed as a result of the cathodic reduction of Cu(II) with subsequent electrodeposition of Cu(0) at the cathode when the cathode potential is more negative than the reduction potential of Cu-EDTA to Cu(0). In contrast, the very negative reduction potential of Ni-EDTA to Ni(0) renders the direct reduction of EDTA-complexed Ni(II) at the cathode unimportant. The removal of Ni during the electrolysis process mainly occurs via anodic oxidation of EDTA in Ni-EDTA, with the resulting formation of low-molecular-weight organic acids and the release of Ni2+, which is subsequently deposited as Ni0 on the cathode. A kinetic model incorporating the key reactions occurring in the electrolysis process has been developed, which satisfactorily describes EDTA, Cu, Ni, and TOC removal. Overall, this study improves our understanding of the mechanism of removal of heavy metals from solution during the electrochemical advanced oxidation of metal plating wastewaters.

Electrochemical Reduction of Nitrate with Simultaneous Ammonia Recovery Using a Flow Cathode Reactor.

The presence of excessive concentrations of nitrate in industrial wastewaters, agricultural runoff, and some groundwaters constitutes a serious issue for both environmental and human health. As a result, there is considerable interest in the possibility of converting nitrate to the valuable product ammonia by electrochemical means. In this work, we demonstrate the efficacy of a novel flow cathode system coupled with ammonia stripping for effective nitrate removal and ammonia generation and recovery. A copper-loaded activated carbon slurry (Cu@AC), made by a simple, low-cost wet impregnation method, is used as the flow cathode in this novel electrochemical reactor. Use of a 3 wt % Cu@AC suspension at an applied current density of 20 mA cm-2 resulted in almost complete nitrate removal, with 97% of the nitrate reduced to ammonia and 70% of the ammonia recovered in the acid-receiving chamber. A mathematical kinetic model was developed that satisfactorily describes the kinetics and mechanism of the overall nitrate electroreduction process. Minimal loss of Cu to solution and maintenance of nitrate removal performance over extended use of Cu@AC flow electrode augers well for long-term use of this technology. Overall, this study sheds light on an efficient, low-cost water treatment technology for simultaneous nitrate removal and ammonia generation and recovery.

Boron Removal from Reverse Osmosis Permeate Using an Electrosorption Process: Feasibility, Kinetics, and Mechanism.

Boron is present in the form of boric acid (B(OH)3 or H3BO3) in seawater, geothermal waters, and some industrial wastewaters but is toxic at elevated concentrations to both plants and humans. Effective removal of boron from solutions at circumneutral pH by existing technologies such as reverse osmosis is constrained by high energy consumption and low removal efficiency. In this work, we present an asymmetric, membrane-containing flow-by electrosorption system for boron removal. Upon charging, the catholyte pH rapidly increases to above ∼10.7 as a result of water electrolysis and other Faradaic reactions with resultant deprotonation of boric acid to form B(OH)4- and subsequent removal from solution by electrosorption to the anode. Results also show that the asymmetric flow-by electrosorption system is capable of treating feed streams with high concentrations of boron and RO permeate containing multiple competing ionic species. On the basis of the experimental results obtained, a mathematical model has been developed that adequately describes the kinetics and mechanism of boron removal by the asymmetric electrosorption system. Overall, this study not only provides new insights into boron removal mechanisms by electrosorption but also opens up a new pathway to eliminate amphoteric pollutants from contaminated source waters.

Significantly enhanced P release from vivianite as a fertilizer in rhizospheric soil: Effects of citrate.

The use of vivianite (Fe3(PO4)2∙8H2O) as a slow-release P fertilizer in agriculture could be a promising way for the utilization of the recovered vivianite products from sewage treatment systems but the efficiency of vivianite-P release in the rhizospheric soil was yet unclear. In this work the dissolution of vivianite was investigated under anoxic and aerobic conditions with the focus on the effects of citrate as a common organic matter in the rhizosphere by tracking the kinetics of P release and the variations of aqueous and solid phases. The results show that citrate effectively induced the dissolution of vivianite particles at pH 6 with simultaneous release of Fe and PO4-P. The enhancement of vivianite dissolution was positively correlated to the concentrations of citrate with complete dissolution observed when citrate was above 6 mM. Compared with anoxic conditions, aerobic conditions further enhanced the dissolution of vivianite to some extent, which could be partially attributed to the oxidation and removal of aqueous FeII in the solution that drove the equilibrium towards dissolution. In the presence of 2 mM citrate, the decrease in pH from 6.0 to 4.0 enhanced the vivianite-P release by 56.1%, indicating the pH dependence of the citrate-induced vivianite dissolution. This study has shown that the efficiency of P release from vivianite products as a fertilizer varies largely under different physico-chemical conditions in the rhizospheric microenvironment, which is critical for determining the dosage of vivianite for a specific soil.

Donnan Dialysis-Osmotic Distillation (DD-OD) Hybrid Process for Selective Ammonium Recovery Driven by Waste Alkali.

This work proposed an innovative and energy-efficient Donnan Dialysis (DD) and Osmotic Distillation (OD) hybrid process for alkali-driven ammonium recovery from wastewater. The efficiency and feasibility of ammonium removal and recovery from synthetic and real wastewater using NaOH and waste alkali were investigated. Ammonium in the feed first transported across the cation exchange membrane and accumulated in the receiver chamber. It is then deprotonated as ammonia, passing through the gas permeable membrane and finally is fixed as ammonium salt in the acid chamber. Our results indicated that employing waste alkali (red mud leachate) as driving solution led to excellent ammonium recovery performances (recovery efficiency of >80%), comparable to those of NaOH solution. When the initial ammonium concentration was 5 and 50 mM, the waste alkali driven DD-OD process achieved acceptable NH4+-N flux density of 16.8 and 169 g N m-2 d-1, at energy cost as low as 8.38 and 2.06 kWh kg-1 N, respectively. Since this alkali driven DD-OD hybrid process is based on solute concentration (or partial pressure) gradient, it could be an energy-effective technology capable of treating wastewaters containing ammonium using waste alkali to realize nutrients recovery in a sustainable manner.

Flow Electrode Capacitive Deionization (FCDI): Recent Developments, Environmental Applications, and Future Perspectives.

With the increasing severity of global water scarcity, a myriad of scientific activities is directed toward advancing brackish water desalination and wastewater remediation technologies. Flow-electrode capacitive deionization (FCDI), a newly developed electrochemically driven ion removal approach combining ion-exchange membranes and flowable particle electrodes, has been actively explored over the past seven years, driven by the possibility of energy-efficient, sustainable, and fully continuous production of high-quality fresh water, as well as flexible management of the particle electrodes and concentrate stream. Here, we provide a comprehensive overview of current advances of this interesting technology with particular attention given to FCDI principles, designs (including cell architecture and electrode and separator options), operational modes (including approaches to management of the flowable electrodes), characterizations and modeling, and environmental applications (including water desalination, resource recovery, and contaminant abatement). Furthermore, we introduce the definitions and performance metrics that should be used so that fair assessments and comparisons can be made between different systems and separation conditions. We then highlight the most pressing challenges (i.e., operation and capital cost, scale-up, and commercialization) in the full-scale application of this technology. We conclude this state-of-the-art review by considering the overall outlook of the technology and discussing areas requiring particular attention in the future.

Carbon Black Flow Electrode Enhanced Electrochemical Desalination Using Single-Cycle Operation.

Flow-electrode electrochemical desalination (FEED) processes (e.g., flow-electrode capacitive deionization), which use flowable carbon particles as the electrodes, have attracted increasing attention, holding the promise for continuous desalination and high desalting efficiency. While it is generally believed that carbon particles with abundant microporous and large specific capacitances (e.g., activated carbon, AC) should be ideal candidates for FEED electrodes, we provide evidence to the contrary, showing that highly conductive electrodes with low specific surface area can outperform microporous AC-based electrodes. This study revealed that FEED using solely high surface area AC particles (∼2000 m2 g-1, specific capacitance of ∼44 F g-1, average salt adsorption rate of ∼0.15 µmol cm-2 min-1) was vastly outperformed by electrodes based solely on low-surface area carbon black (CB, ∼70 m2 g-1, ∼0.5 F g-1, ∼0.75 µmol cm-2 min-1). Electrochemical impedance spectroscopy results suggest that the electrode formed by CB particles led to more effective electronic charge percolation, likely contributing to the improved desalination performance. In addition, we propose and demonstrate a novel operation mode, termed single cycle (SC), which greatly simplified the FEED cell configuration and enabled simultaneous charging and discharging. Using SC mode with CB flow electrodes delivered an increased average salt removal rate relative to the more traditional short-circuited closed cycle (SCC) mode, achieving up to 1.13 µmol cm-2 min-1. Further investigations demonstrate that up to 50% of energy input would be avoided when using CB flow electrodes operated under SC mode as compared to that of AC flow electrodes operated under SCC mode. In summary, the FEED process presented in this study provided an innovative and promising approach toward high-efficient and low-cost brackish water desalination.

Effect of the Presence of Carbon in Ti4O7 Electrodes on Anodic Oxidation of Contaminants.

Magnéli phase titanium suboxide, Ti4O7, has attracted increasing attention as a potential electrode material in anodic oxidation as a result of its high efficiency and (electro)chemical stability. Although carbon materials have been amended to Ti4O7 electrodes to enhance the electrochemical performance or are present as an unwanted residual during the electrode fabrication, there has been no comprehensive investigation of how these carbon materials affect the electrochemical performance of the resultant Ti4O7 electrodes. As such, we investigated the electrochemical properties of Ti4O7 electrodes impregnated with carbon materials at different contents (and chemical states). Results of this study showed that while pure Ti4O7 electrodes exhibited an extremely low rate of interfacial electron transfer, the introduction of minor amounts of carbon materials (at values as low as 0.1 wt %) significantly facilitated the electron transfer process and decreased the oxygen evolution reaction potential. The oxygen-containing functional groups have been shown to play an important role in interfacial electron transfer with moderate oxidation of the carbon groups aiding electron uptake at the electrode surface (and consequently organic oxidation) while the generation of carboxyl groups-a process that is likely to occur in long-term operation-increased the interfacial resistance and thus retarded the oxidation process. Results of this study provide a better understanding of the relationship between the nature of the electrode surface and anodic oxidation performance with these insights likely to facilitate improved electrode design and optimization of operation of anodic oxidation reactors.

Iron Transformation and Its Role in Phosphorus Immobilization in a UCT-MBR with Vivianite Formation Enhancement.

The formation of vivianite (Fe3(PO4)2·8H2O) in iron (Fe)-dosed wastewater treatment facilities has the potential to develop into an economically feasible method of phosphorus (P) recovery. In this work, a long-term steady FeIII-dosed University of Cape Town process-membrane bioreactor (UCT-MBR) system was investigated to evaluate the role of Fe transformations in immobilizing P via vivianite crystallization. The highest fraction of FeII, to total Fe (Fetot), was observed in the anaerobic chamber, revealing that a redox condition suitable for FeIII reduction was established by improving operational and configurational conditions. The supersaturation index for vivianite in the anaerobic chamber varied but averaged ∼4, which is within the metastable zone and appropriate for its crystallization. Vivianite accounted for over 50% of the Fetot in the anaerobic chamber, and its oxidation as it passed through the aerobic chambers was slow, even in the presence of high dissolved oxygen concentrations at circumneutral pH. This study has shown that the high stability and growth of vivianite crystals in oxygenated activated sludge can allow for the subsequent separation of vivianite as a P recovery product.

Water Recovery Rate in Short-Circuited Closed-Cycle Operation of Flow-Electrode Capacitive Deionization (FCDI).

While flow-electrode CDI is a promising desalination technology that has major advantages when the electrodes are operated in the short-circuited closed-cycle (SCC) mode, little attention has been paid to the water recovery rate, which, in the SCC mode, is determined by the need for partial replacement of the saline electrolyte of the flow electrodes. Results of this study show that an extremely high water recovery rate of ∼95% can be achieved when desalting a 1000 mg NaCl L-1 brackish influent to a potable level of 150 mg L-1. The improved performance with regard to the electrical cost is related, at least in part, to the alleviated concentration polarization at the membrane/electrolyte interface during electrosorption. In effect, the current efficiency decreases with an increase in the water recovery rate. This finding is ascribed to inevitable co-ion leakage since the flow electrodes reject ions with the same charge. In addition, water transport across the ion exchange membranes also influences the water recovery rate. The effect of partial replacement of the saline electrolyte during (semi-)continuous operation requires particular consideration because the associated dilution of the carbon content in the flow electrodes results in a decrease in process performance.

Integrated Flow-Electrode Capacitive Deionization and Microfiltration System for Continuous and Energy-Efficient Brackish Water Desalination.

Flow-electrode capacitive deionization (FCDI) is an emerging electrochemically driven technology for brackish and/or sea water desalination with merits of large salt adsorption capacity, high flow efficiency, and easy electrode management. While FCDI holds promise for continuous operation, there are very few investigations with regard to the regeneration/reuse of flowable electrodes and the separation of brine from electrodes with these operation prerequisites for real nonintermittent water desalination. In this study, we propose a novel module design to achieve these critical steps involving integration of an FCDI cell and a ceramic microfiltration (MF) contactor. Our investigations reveal that the brine discharge rate is the dominant factor for stable and efficient operation of the integrated module. Results obtained show that the integrated FCDI/MF system can be used to successfully separate brackish water (of salinities 1, 2 and 5 g L-1) into both a potable stream (<0.5 g L-1) and a brine stream (concentrated by 2-20 times) in a continuous manner with extremely high water recovery rates (up to 97%) and reasonable energy consumption. Another notable characteristic of the integrated system is the high thermodynamic energy efficiency (∼30%) with such efficiencies 4-5 times larger than those of conventional capacitive deionization units and comparable to reverse osmosis and electrodialysis systems achieving similar separation efficiencies. In brief, the results of studies described here indicate that continuous and efficient operation of FCDI is a real possibility and pave the way for scale-up of this emerging technology.

Short-Circuited Closed-Cycle Operation of Flow-Electrode CDI for Brackish Water Softening.

While flow-electrode capacitive deionization (FCDI) is an emerging desalination technology, reduction in water hardness using this technology has so far received minimal attention. In this study, treatment of influents containing both monovalent and divalent cations using FCDI was carried out with flow-electrodes operated in short-circuited closed-cycle (SCC) configuration. Divalent Ca2+ cations were selectively removed compared to monovalent Na+ with the selectivity becoming dominant when the FCDI unit was operated at lower current densities and hydraulic retention times. Results showed that SCC FCDI operation was much more energy-efficient for brackish water softening compared to operation in isolated closed-cycle (ICC) mode, particularly with implementation of energy recovery. This finding was largely ascribed to (i) charge neutralization of the flow-electrodes in SCC configuration and (ii) regeneration of the active materials to maintain pseudo "infinite" capacity during electrosorption. In addition, mixing of the flow-electrodes in SCC operation significantly inhibited pH excursion in the flow-electrode with resultant alleviation of calcium precipitation on the carbon surface.

Continuous Ammonia Recovery from Wastewaters Using an Integrated Capacitive Flow Electrode Membrane Stripping System.

We have previously described a novel flow-electrode capacitive deionization (FCDI) unit combined with a hydrophobic gas-permeable hollow fiber membrane contactor (designated "CapAmm") and presented results showing efficient recovery of ammonia from dilute synthetic wastewaters (Zhang et al., Environ. Sci. Technol. Lett. 2018, 5, 43-49). We extend this earlier study here with description of an FCDI system with integrated flat sheet gas permeable membrane with comprehensive assessment of ammonia recovery performance from both dilute and concentrated wastewaters. The integrated CapAmm cell exhibited excellent ammonia removal and recovery efficiencies (up to ∼90% and ∼80% respectively). The energy consumptions for ammonia recovery from low-strength (i.e., domestic) and high-strength (i.e., synthetic urine) wastewaters were 20.4 kWh kg-1 N and 7.8 kWh kg-1 N, respectively, with these values comparable to those of more conventional alternatives. Stable ammonia recovery and salt removal performance was achieved over more than two days of continuous operation with ammonia concentrated by ∼80 times that of the feed stream. These results demonstrate that the integrated CapAmm system described here could be a cost-effective technology capable of treating wastewaters and realizing both nutrient recovery and water reclamation in a sustainable manner.

Development of Redox-Active Flow Electrodes for High-Performance Capacitive Deionization.

An innovative flow electrode comprising redox-active quinones to enhance the effectiveness of water desalination using flow-electrode capacitive deionization (FCDI) is described in this study. The results show that, in addition to carbon particle contact, the presence of the aqueous hydroquinone (H2Q)/benzoquinone (Q) couple in a flowing suspension of carbon particles enhances charge transfer significantly as a result of reversible redox reactions of H2Q/Q. Ion migration through the micropores of the flow electrodes was facilitated in particular with the desalination rate significantly enhanced. The cycling behavior of the quinoid mediators in the anode flow electrode demonstrated a relatively high stability at the low pH induced, suggesting that the mediator would be suitable for long-term operation.

A ten liter stacked microbial desalination cell packed with mixed ion-exchange resins for secondary effluent desalination.

The architecture and performance of microbial desalination cell (MDC) have been significantly improved in the past few years. However, the application of MDC is still limited in a scope of small-scale (milliliter) reactors and high-salinity-water desalination. In this study, a large-scale (>10 L) stacked MDC packed with mixed ion-exchange resins was fabricated and operated in the batch mode with a salt concentration of 0.5 g/L NaCl, a typical level of domestic wastewater. With circulation flow rate of 80 mL/min, the stacked resin-packed MDC (SR-MDC) achieved a desalination efficiency of 95.8% and a final effluent concentration of 0.02 g/L in 12 h, which is comparable with the effluent quality of reverse osmosis in terms of salinity. Moreover, the SR-MDC kept a stable desalination performance (>93%) when concentrate volume decreased from 2.4 to 0.1 L (diluate/concentrate volume ratio increased from 1:1 to 1:0.04), where only 0.875 L of nonfresh water was consumed to desalinate 1 L of saline water. In addition, the SR-MDC achieved a considerable desalination rate (95.4 mg/h), suggesting a promising application for secondary effluent desalination through deriving biochemical electricity from wastewater.

Adaptation of Delftia acidovorans for degradation of 2,4-dichlorophenoxyacetate in a microfluidic porous medium.

Delftia acidovorans MC1071 can productively degrade R-2-(2,4-dichlorophenoxy)propionate (R-2,4-DP) but not 2,4-dichlorophenoxyacetate (2,4-D) herbicides. This work demonstrates adaptation of MC1071 to degrade 2,4-D in a model two-dimensional porous medium (referred to here as a micromodel). Adaptation for 2,4-D degradation in the 2 cm-long micromodel occurred within 35 days of exposure to 2,4-D, as documented by substrate removal. The amount of 2,4-D degradation in the adapted cultures in two replicate micromodels (~10 and 20 % over 142 days) was higher than a theoretical maximum (4 %) predicted using published numerical simulation methods, assuming instantaneous biodegradation and a transverse dispersion coefficient obtained for the same pore structure without biomass present. This suggests that the presence of biomass enhances substrate mixing. Additional evidence for adaptation was provided by operation without R-2,4-DP, where degradation of 2,4-D slowly decreased over 20 days, but was restored almost immediately when R-2,4-DP was again provided. Compared to suspended growth systems, the micromodel system retained the ability to degrade 2,4-D longer in the absence of R-2,4-DP, suggesting slower responses and greater resilience to fluctuations in substrates might be expected in the soil environment than in a chemostat.

Iron-retrofitted anaerobic baffled reactor system for rural wastewater treatment: Stable performance of nutrients removal with phosphorus recovery and minimal sludge production.

An iron-retrofitted anaerobic baffled reactor (ABR) system was developed for the effective treatment of rural wastewater with reduced maintenance demand and aeration costs. Average removal efficiencies of chemical oxygen demand, total nitrogen and total phosphorus of 99.4%, 62.7% and 92.6% were achieved respectively, when the ABR system was operating at steady state. With effective bioreduction of FeIII in the anaerobic chambers, phosphorus was immobilized in the sludge as vivianite, the sole phosphorus-carrying mineral. The FeIII in the recirculated sludge induced Feammox in the ABR reactor, contributing 14.8% to total nitrogen removal. Biophase separation and enrichment of microorganisms associated with iron and nitrogen transformations were observed in the system after Fe dosing, which enhanced the removal of pollutants. The coupling of Feammox and vivianite crystallization to remove nitrogen and phosphorus in an iron-retrofitted ABR would appear to be a promising technology for rural wastewater treatment.

Micromodel investigation of transport effect on the kinetics of reductive dissolution of hematite.

Reductive dissolution of hematite in porous media was investigated using a micromodel (8.1 × 4.5 × 0.028 mm) with realistic pore network structures that include distinctive advection domain, macropores and micropores created in silicon substrate. The micromodel pore surface was sputter deposited with a thin layer (230 nm) of hematite. The hematite in the micromodel was reduced by injecting pH-varying solutions (pH 5.0, 6.0, 7.0) containing a reduced form of flavin mononucleotide (FMNH2, 100 µM), a biogenic soluble electron transfer mediator produced by Shewanella species. The reduction kinetics was determined by measuring effluent Fe(II) (aq) concentration and by spectroscopically monitoring the hematite dissolution front in the micromodel. Batch experiment was also performed to estimate the hematite reduction rate under the well-mixed condition. Results showed significant spatial variation in local redox reaction rate that was controlled by the coupled transport and reaction. The overall rate of the redox reaction in the micromodel required a three-domain numerical model to effectively describe reaction kinetics either with distinctive apparent rate parameters or mass transfer coefficients in different pore domains. Results from this study demonstrated the feasibility of a domain-based modeling approach for scaling reaction rates from batch to porous media systems where reactions may be significantly limited by transport.

Experimental study of crossover from capillary to viscous fingering for supercritical CO2-water displacement in a homogeneous pore network.

Carbon sequestration in saline aquifers involves displacing brine from the pore space by supercritical CO(2) (scCO(2)). The displacement process is considered unstable due to the unfavorable viscosity ratio between the invading scCO(2) and the resident brine. The mechanisms that affect scCO(2)-water displacement under reservoir conditions (41 °C, 9 MPa) were investigated in a homogeneous micromodel. A large range of injection rates, expressed as the dimensionless capillary number (Ca), was studied in two sets of experiments: discontinuous-rate injection, where the micromodel was saturated with water before each injection rate was imposed, and continuous-rate injection, where the rate was increased after quasi-steady conditions were reached for a certain rate. For the discontinuous-rate experiments, capillary fingering and viscous fingering are the dominant mechanisms for low (logCa ≤ -6.61) and high injection rates (logCa ≥ -5.21), respectively. Crossover from capillary to viscous fingering was observed for logCa = -5.91 to -5.21, resulting in a large decrease in scCO(2) saturation. The discontinuous-rate experimental results confirmed the decrease in nonwetting fluid saturation during crossover from capillary to viscous fingering predicted by numerical simulations by Lenormand et al. (J. Fluid Mech.1988, 189, 165-187). Capillary fingering was the dominant mechanism for all injection rates in the continuous-rate experiment, resulting in monotonic increase in scCO(2) saturation.