Reactive transport modeling of produced water disposal into dolomite saline aquifers: Controls of barium transport.

Experimental results on barium transport in dolomite are used to formulate, calibrate, and validate a reactive transport model of produced water disposal into dolomite saline aquifers. The model accounts for sorption, dissolution/precipitation reactions of minerals (dolomite, calcite, barite, gypsum, and witherite) and complexation and acid-base reactions of most abundant ionic species (H+, HCO3-, SO42-, Ca2+, Mg2+, and Cl-) in produced waters including Ba2+ which is the most common and abundant heavy metal present in produced water from oil and gas reservoirs. The model is applied to determine the chemical controls of barium transport in Arbuckle dolomite aquifers. The simulated scenario corresponds to produced water disposal through a Class II injection well located near an abandoned well that can facilitate the transport of barium to underground sources of drinking water (USDW). Simulation results reveal that most suitable dolomite aquifers to prevent the contamination of USDW by barium are dolomite aquifers of high SO42- content (>1000 mg/L). The mobility of barium which is promoted by the formation of Ba(Cl)+ and competition of cations (Ca2+ and Mg2+) for hydration sites of dolomite can be suppressed by the precipitation of barium as barite in dolomite saline aquifers of high SO42- content. A sensitivity analysis conducted using a two-level factorial design of experiments indicates that barium transport can be controlled by the initial concentration of a single ionic specie (mostly SO42-) or the concentration of various ionic species (e.g., SO42-, Cl-, and Mg2+). This depends on the chemical composition of both the dolomite saline aquifer and injection produced water. This work highlights the potentiality of a reactive transport simulation approach to conduct compatibility analysis of dolomite saline aquifers and produced waters to select dolomite aquifers and/or decide on treatment methods to prevent the contamination of USDW by barium.

Candidatus Mcinerneyibacterium aminivorans gen. nov., sp. nov., the first representative of the candidate phylum Mcinerneyibacteriota phyl. nov. recovered from a high temperature, high salinity tertiary oil reservoir in north central Oklahoma, USA.

We report on the characterization of a novel genomic assembly (ARYD3) recovered from formation water (17.6% salinity) and crude oil enrichment amended by isolated soy proteins (0.2%), and incubated for 100 days under anaerobic conditions at 50°C. Phylogenetic and phylogenomic analysis demonstrated that the ARYD3 is unaffiliated with all currently described bacterial phyla and candidate phyla, as evident by the low AAI (34.7%), shared gene content (19.4%), and 78.9% 16S rRNA gene sequence similarity to Halothiobacillus neapolitanus, its closest cultured relative. Genomic characterization predicts a slow-growing, non-spore forming, and non-motile Gram-negative rod. Adaptation to high salinity is potentially mediated by the production of the compatible solutes cyclic 2,3-diphosphoglycerate (cDPG), α-glucosylglycerate, as well as the uptake of glycine betaine. Metabolically, the genome encodes primarily aminolytic capabilities for a wide range of amino acids and peptides. Interestingly, evidence of propionate degradation to succinate via methyl-malonyl CoA was identified, suggesting possible capability for syntrophic propionate degradation. Analysis of ARYD3 global distribution patterns identified its occurrence in a very small fraction of Earth Microbiome Project datasets examined (318/27,068), where it consistently represented an extremely rare fraction (maximum 0.28%, average 0.004%) of the overall community. We propose the Candidatus name Mcinerneyibacterium aminivorans gen. nov, sp. nov. for ARYD3T, with the genome serving as the type material for the novel family Mcinerneyibacteriaceae fam. nov., order Mcinerneyibacteriales ord. nov., class Mcinerneyibacteria class nov., and phylum Mcinerneyibacteriota phyl. nov. The type material genome assembly is deposited in GenBank under accession number VSIX00000000.

Transport of barium in fractured dolomite and sandstone saline aquifers.

To understand the advective-dispersive transport of Ba in fractured dolomite and sandstone saline aquifers, we conducted core-flooding experiments and reactive transport simulations. We used intact and synthetic fractured dolomite and sandstone cores collected from formations where hydraulic fracturing (HF) wastewater is disposed in Oklahoma, USA. The core-flooding experiments were conducted using saline water containing typical concentrations of NaCl (90 g/L), Ca (5 g/L), Mg (1 g/L), and Ba (100 mg/L) in HF wastewaters. At typical concentrations of NaCl, Ca, and Mg in HF wastewater, our experimental results show similar Ba transport rates in both intact and fractured dolomites but faster Ba transport rates in intact than in fractured sandstones. We found a match between measured and simulated breakthrough curves of Ba in intact and fractured sandstones. This supports the hypothesis that the inhibitory effect of salinity on Ba sorption increases Ba transport through matrix pores bordering the fracture while reducing its transport through the fracture. This is reflected by a reduction of the overall rate of Ba transport through fractured dolomites and sandstones. We found that the effect of salinity in retarding Ba transport through fractured dolomites and sandstones increases with increased matrix porosity and/or fracture aperture size. We implemented the multiple interacting continua (MINC) method developed for modeling fluid flow in fractured porous media to successfully capture the effect of salinity, matrix porosity and fracture aperture size on Ba transport in fractured sandstones. The measured and simulated results have significant implications on efforts of field-scale simulations of Ba transport in dolomite and sandstone saline aquifers where HF wastewater is disposed.

Petroleum produced water disposal: Mobility and transport of barium in sandstone and dolomite rocks.

To assess the risk of underground sources of drinking water contamination by barium (Ba) present in petroleum produced water disposed into deep saline aquifers, we examined the effect of salinity (NaCl), competition of cations (Ca, Mg), temperature (22 and 60°C), and organic fracturing additives (guar gum) on the sorption and transport of Ba in dolomites and sandstones. We found that at typical concentration levels of NaCl, Ca, and Mg in petroleum produced water, Ba sorption in both dolomites and sandstones is inhibited by the formation of Ba(Cl)+ complexes in solution and/or the competition of cations for binding sites of minerals. The inhibition of Ba sorption by both mechanisms is greater in dolomites than in sandstones. This is reflected by a larger decrease in the breakthrough times of Ba through dolomites than through sandstones. We found that the presence of guar gum has little influence on the sorption and thus the transport of Ba in both dolomites and sandstones. Contrary to most heavy metals, Ba sorption in both dolomites and sandstones decreases with increasing temperature, however the reducing effect of temperature on Ba sorption is relevant only at low salinity conditions. Higher inhibition of Ba sorption in dolomites than in sandstones is due to the greater reactivity of dolomite over sandstone. The results of this study which includes the formulation of a reactive transport model and estimation of partition coefficients of Ba in dolomites and sandstones have significant implications in understanding and predicting the mobility and transport of Ba in deep dolomite and sandstone saline aquifers.

Effect of brine salinity and guar gum on the transport of barium through dolomite rocks: Implications for unconventional oil and gas wastewater disposal.

This research aimed to elucidate the effect of brine salinity and guar gum on the sorption and transport of Ba in dolomite rocks collected from the Arbuckle formation in Oklahoma, USA. Guar gum represents the most important organic additive used in viscosified fracturing fluids, and Ba constitutes the most common and abundant heavy metal found in unconventional oil and gas (UOG) wastewater. Batch experiments conducted using powdered dolomite rocks (500-600 µm particle size) revealed that at brine salinities of UOG wastewater, chloro-complexation reactions between Ba and Cl ions and pH changes that results from dolomite dissolution are the controlling factors of Ba sorption on dolomite. Competition of Ba with common cations (Ca and Mg) for hydration sites of dolomite, plays a secondary role. Core-flooding experiments conducted to analyze the transport of Ba through natural and synthetic dolomite core plugs are in agreement with the batch sorption experimental results. The transport of Ba through dolomite rocks, increases with increasing brine salinity (0-180,000 mg-NaCl/L). The presence guar gum (50-500 mg/L) does not affect the transport of Ba through dolomite rocks of high flow properties (25-29.6% porosity, 9.6-13.7 mD permeability). However, core-flooding experiments conducted using tight dolomite rocks (6.5-8.6% porosity, 0.06-0.3 mD permeability), revealed that guar gum can retard the transport of Ba by clogging high permeability/porosity regions of tight dolomite rocks. The mechanism of Ba sorption on dolomite can be represented by a sorption model that accounts for both surface complexation reactions on three distinct hydration sites (>CaOHo, >MgOHo, and >CO3Ho), and the kinetic dissolution of dolomite. These results are important in understanding and predicting the fate of Ba present in UOG wastewater disposed into deep dolomite saline aquifers.

A new model for the biodegradation kinetics of oil droplets: application to the Deepwater Horizon oil spill in the Gulf of Mexico.

Oil biodegradation by native bacteria is one of the most important natural processes that can attenuate the environmental impacts of marine oil spills. Existing models for oil biodegradation kinetics are mostly for dissolved oil. This work developed a new mathematical model for the biodegradation of oil droplets and applied the model to estimate the time scale for oil biodegradation under conditions relevant to the Deepwater Horizon oil spill in the Gulf of Mexico. In the model, oil is composed of droplets of various sizes following the gamma function distribution. Each oil droplet shrinks during the microbe-mediated degradation at the oil-water interface. Using our developed model, we find that the degradation of oil droplets typically goes through two stages. The first stage is characterized by microbial activity unlimited by oil-water interface with higher biodegradation rates than that of the dissolved oil. The second stage is governed by the availability of the oil-water interface, which results in much slower rates than that of soluble oil. As a result, compared to that of the dissolved oil, the degradation of oil droplets typically starts faster and then quickly slows down, ultimately reaching a smaller percentage of degraded oil in longer time. The availability of the water-oil interface plays a key role in determining the rates and extent of degradation. We find that several parameters control biodegradation rates, including size distribution of oil droplets, initial microbial concentrations, initial oil concentration and composition. Under conditions relevant to the Deepwater Horizon spill, we find that the size distribution of oil droplets (mean and coefficient of variance) is the most important parameter because it determines the availability of the oil-water interface. Smaller oil droplets with larger variance leads to faster and larger extent of degradation. The developed model will be useful for evaluating transport and fate of spilled oil, different remediation strategies, and risk assessment.

Bio-electrochemical property and phylogenetic diversity of microbial communities associated with bioelectrodes of an electromethanogenic reactor.

Electromethanogenesis is a new bio-electrochemical reaction potentially useful for energy conversion. As a first step toward its technical application, electromethanogenic reactors were built, and their bio-electrochemical properties were analyzed. Comparisons of the microbial compositions of the electromethanogenic cathode and the current-producing anode suggested an electromethanogenic pathway mediated by exoelectrogenic bacteria.

Electrochemical and phylogenetic analyses of current-generating microorganisms in a thermophilic microbial fuel cell.

To explore diversity of thermophilic exoelectrogens, a thermophilic microbial fuel cell was constructed. Population analysis of the anodic microorganisms suggested possible involvement of Caloramator-related bacteria in electricity generation. Pure culture of Caloramator australicus showed electricity-generating ability, indicating that the bacterium is a new thermophilic exoelectrogen.

Inhibitory effect of gamma-irradiated chitosan on the growth of denitrifiers.

In order to find an environmentally benign substitute to hazardous inhibitory agents, the inhibitory effect of gamma-irradiated chitosans against a mixed culture of denitrifying bacteria was experimentally evaluated. Unlike other studies using pure aerobic cultures, the observed effect was not a complete inhibition but a transient inhibition reflected by prolonged lag phases and reduced growth rates. Raw chitosan under acid conditions (pH 6.3) exerted the strongest inhibition followed by the 100 kGy and 500 kGy irradiated chitosans, respectively. Therefore, because the molecular weight of chitosan decreases with the degree of gamma-irradiation, the inhibitory properties of chitosan due to its high molecular weight were more relevant than the inhibitory properties gained due to the modification of the surface charge and/or chemical structure by gamma-irradiation. High dosage of gamma-irradiated appeared to increase the growth of mixed denitrifying bacteria in acid pH media. However, in neutral pH media, high dosage of gamma-irradiation appeared to enhance the inhibitory effect of chitosan.