Tert-butyl Alcohol Concentration Research Articles

Assessment of the genotoxicity of tert-butyl alcohol in an in vivo thyroid comet assay.

Chronic exposure to high (20,000 ppm) concentrations of tert-butyl alcohol (TBA) in drinking water, equivalent to ~2100 mg/kg bodyweight per day, is associated with slight increases in the incidence of thyroid follicular cell adenomas and carcinomas in mice, with no other indications of carcinogenicity. In a recent toxicological review of TBA, the U.S. EPA determined that the genotoxic potential of TBA was inconclusive, largely based on non-standard studies such as in vitro comet assays. As such, the potential role of genotoxicity in the mode of action of thyroid tumors and therefore human relevance was considered uncertain. To address the potential role of genotoxicity in TBA-associated thyroid tumor formation, CD-1 mice were exposed up to a maximum tolerated dose of 1500 mg/kg-day via oral gavage for two consecutive days and DNA damage was assessed with the comet assay in the thyroid. Blood TBA levels were analyzed by headspace GC-MS to confirm systemic tissue exposure. At study termination, no significant increases (DNA breakage) or decreases (DNA crosslinks) in %DNA tail were observed in TBA exposed mice. In contrast, oral gavage of the positive control ethyl methanesulfonate significantly increased %DNA tail in the thyroid. These findings are consistent with most genotoxicity studies on TBA and provide mechanistic support for non-linear, threshold toxicity criteria for TBA. While the mode of action for the thyroid tumors remains unclear, linear low dose extrapolation methods for TBA appear more a matter of policy than science.

Theoretical Two Dimensional Infrared Spectroscopy of Aqueous Solutions of tert-Butyl Alcohol: Variation of the Dynamics of Spectral Diffusion along the Percolation Transition.

Binary mixtures of water and tert-butyl alcohol (TBA) are known to exhibit the so-called percolation transition where small clusters of TBA molecules span into large aggregates beyond a threshold concentration of the alcohol. In the present study, we have investigated the linear and two-dimensional infrared spectral features of aqueous solutions of TBA for varying concentration of the alcohol along the percolation transition. The percolation transition is characterized through calculations of intermolecular radial distribution functions and average size of the largest cluster of TBA molecules. It is found that, with variation of alcohol concentration, the radial distribution functions of the central carbon atoms of TBA molecules show a nonmonotonic change in the height of the first peak and also the size of the largest cluster of TBA molecules show a jump in the increase of its size for TBA mole fraction between 0.04 and 0.06 corresponding to a transition from smaller clusters to larger spanning aggregates. However, it is found that the linear infrared spectrum of water does not exhibit any noticeable changes on variation of TBA concentration along the percolation transition. Subsequently, two-dimensional infrared (2DIR) spectra and vibrational frequency time correlation function of water are calculated for all the TBA-water solutions considered in this study. The spectral diffusion of water calculated from 2DIR is found to slow down with increase of the TBA concentration. The time scales of spectral diffusion of water, as characterized by the relaxation of frequency time correlation function, 2DIR metric of central line slope, and also the hydrogen bond time correlation functions, are found to exhibit a noticeable jump along the percolation transition. The hydrophilic group of TBA is found to retard the water dynamics more effectively than the hydrophobic groups. Also, the jump in the dynamical slowdown along the percolation transition is found to be more significant for water molecules at the hydrophilic sites.

Chitosan/Diatom-Biosilica Aerogel with Controlled Porous Structure for Rapid Hemostasis.

Uncontrolled hemorrhage is the main reason of possible preventable death after accidental injury. It is necessary to develop a hemostatic agent with rapid hemostatic performance and good biocompatibility. In this study, a chitosan/diatom-biosilica-based aerogel is developed using dopamine as cross-linker by simple alkaline precipitation and tert-butyl alcohol replacement. The chitosan/diatom-biosilica aerogel exhibits favorable biocompatibility and multiscale hierarchical porous structure (from nanometer to micrometer), which can be controlled by the concentration of tert-butyl alcohol. The displacement of tert-butyl alcohol can keep the porosity of diatom-biosilica in aerogel and give it large surface with efficient water absorption ratio. 30% tert-butyl alcohol replacement of aerogel possesses the largest surface area (74.441 m2 g-1 ), water absorption capacity (316.83 ± 2.04%), and excellent hemostatic performance in vitro blood coagulation (≈70 s). Furthermore, this aerogel exhibits the shortest clotting time and lowest blood loss in rat hemorrhage model. The strong interface effect between aerogel and blood is able to promote erythrocytes aggregation, platelets adhesion, and activation, as well as, activate the intrinsic coagulation pathway to accelerate blood coagulation. All the above results demonstrate that chitosan/diatom-biosilica aerogel has great potential to be a safe and rapid hemostatic material.

Strategies to Reduce Reconstitution Time of Lyophilized Biotherapeutics

Lyophilized biotherapeutics with high protein concentration may have long reconstitution times, which pose an inconvenience to the end user. This report describes 2 approaches that lead to reduction of reconstitution time: (1) incorporation of tert-butyl alcohol (TBA) in the prelyophilization formulation and (2) decreased headspace pressure in the final lyophilized vial. Cakes made from prelyophilization formulations containing a range of TBA concentrations were physically characterized. The stability of antibodies with TBA in the liquid and lyophilized states was evaluated under stress conditions. Reconstitution time was minimized (>50% reduction) at a TBA concentration of 5% w/v. Reduced headspace pressure in the lyophilized vial demonstrated greater than 50% reduction in reconstitution time at headspace pressures of less than 50 Torr.

The in situ treatment of BTEX, MTBE, and TBA in saline groundwater

AbstractA pilot‐scale test was conducted in a saline aquifer to determine if a petroleum hydrocarbon (PHC) plume containing benzene (B), toluene (T), ethylbenzene (E), xylenes (X), methyl tert‐butyl ether (MTBE), and tert‐butyl alcohol (TBA) could be treated effectively using a sequential treatment approach that employed in situ chemical oxidation (ISCO) and enhanced bioremediation (EBR). Chemical oxidants, such as persulfate, have been shown to be effective in reducing dissolved concentrations of BTEX (B + T + E + X) and additives such as MTBE and TBA in a variety of geochemical environments including saline aquifers. However, the lifespan of the oxidants in saline environments tends to be short‐lived (i.e., hours to days) with their effectiveness being limited by poor delivery, inefficient consumption by nontargeted species, and back‐diffusion processes. Similarly, the addition of electron acceptors has also been shown to be effective at reducing BTEX and associated additives in saline groundwater through EBR, however EBR can be limited by various factors similar to ISCO. To minimize the limitations of both approaches, a pilot test was carried out in a saline unconfined PHC‐impacted aquifer to evaluate the performance of an engineered, combined remedy that employed both approaches in a sequence. The PHC plume had total BTEX, MTBE, and TBA concentrations of up to 4,584; 55,182; and 1,880 μg/L, respectively. The pilot test involved injecting 13,826 L of unactivated persulfate solution (19.4 weight percent (wt.%) sodium persulfate (Na2S2O8) solution into a series of injection wells installed within the PHC plume. Parameters monitored over a 700‐day period included BTEX, MTBE, TBA, sulfate, and sulfate isotope concentrations in the groundwater, and carbon and hydrogen isotopes in benzene and MTBE in the groundwater. The pilot test data indicated that the BTEX, MTBE, and TBA within the PHC plume were treated over time by both chemical oxidation and sulfate reduction. The injection of the unactivated persulfate resulted in short‐term decreases in the concentrations of the BTEX compounds, MTBE, and TBA. The mean total BTEX concentration from the three monitoring wells within the pilot‐test area decreased by up to 91%, whereas MTBE and TBA mean concentrations decreased by up to 39 and 58%, respectively, over the first 50 days postinjection in which detectable concentrations of persulfate remained in groundwater. Concentrations of the BTEX compounds, MTBE, and TBA rebounded at the Day 61 marker, which corresponded to no persulfate being detected in the groundwater. Subsequent monitoring of the groundwater revealed that the concentrations of BTEX continued to decrease with time suggesting that EBR was occurring within the plume. Between Days 51 and 487, BTEX concentrations decreased an additional 84% from the concentration measured on Day 61. Mean concentrations of MTBE showed a reduction during the EBR phase of remediation of 33% while the TBA concentration appeared to decrease initially but then increased as the sulfate concentration decreased as a result of MTBE degradation. Isotope analyses of dissolved sulfate (34S and 18O), and compound‐specific isotope analysis (CSIA) of benzene and MTBE (13C and 2H) supported the conclusions that ISCO and EBR processes were occurring at different stages and locations within the plume over time.

Sustainable and easy recoverable magnetic TiO2-Lignocellulosic Biomass@Fe3O4 for solar photocatalytic water remediation

This work was undertaken to design a magnetic TiO2 hybridized with lignocellulosic biomass (olive pits: OP) for dyes and Cr(VI) photocatalytic removal from water. Firstly, TiO2-OP was synthetized by ultrasonic-assisted sol-gel process, and then TiO2-OP@Fe3O4 was obtained via hydrothermal magnetization at 180 °C. Materials were characterized by XRD, BET, UV-DRS and XPS. The as-prepared photocatalysts showed a visible light responsive, wherein, Eg values are 3.20, 3.02, 3.00 and 2.55 eV for TiO2, TiO2@Fe3O4, TiO2-OP and TiO2-OP@Fe3O4, respectively. While the specific surface area values were as follows: 22.94, 15, 55.1 and 104.7 m2/g for TiO2, TiO2@Fe3O4, TiO2-OP and TiO2-OP@Fe3O4, respectively. Photocatalytic activities of TiO2@Fe3O4, TiO2-OP and TiO2-OP@Fe3O4 were tested for the photocatalytic removal of three dyes (Rhodamine B (RhB), Methylene blue (MB) and Congo Red (CR)) and hexavalent chromium under visible light. It was found that TiO2-OP@Fe3O4 composite exhibited higher adsorption and photocatalytic abilities compared with TiO2@Fe3O4 and TiO2-OP. The oxidation rates using TiO2-OP@Fe3O4 were 100, 75 and 81% within 1 h for MB, RhB and CR, respectively, at a dye concentration of 10 ppm and photocatalyst mass of 0.25 g/L. While the photocatalytic reduction rates of Cr(VI) (10 ppm, pH 3) were 64% (within 60 min), 70% (within 60 min) and 100% (within 40 min) by TiO2@Fe2O3, TiO2-OP and TiO2-OP@Fe3O4, respectively. The effect of pH, MB concentration, photocatalyst dose, co-presence of metallic cations and Tert-butyl alcohol concentration (as OH scavenger) on the MB oxidation was studied. Since the composite showed an excellent magnetic recoverability and high photocatalytic efficiency, it could be a potential candidate in industrial wastewater treatment.

Improved Etherification of Glycerol with Tert-Butyl Alcohol by the Addition of Dibutyl Ether as Solvent

The etherification of glycerol with tert-butyl alcohol in the presence of acid catalysts gives rise to the production of ethers (monoethers, diethers and triethers) of high added-value, which can be used as oxygenated additives in fuels. This reaction is limited by the thermodynamic equilibrium, which can be modified by the addition of solvents that selectively solubilize the products of interest along with tert-butyl alcohol, leading to the progress of the reaction. In this work, it has been demonstrated that the addition of dibutyl ether allows shifting the reaction equilibrium, increasing the production of diethers. From the study of the main operating conditions, it was determined that an increase in the concentration of the solvent has a positive effect on the selectivity towards the production of diethers, the concentration of the catalyst (a commercial ion exchange resin, Amberlyst 15, named A-15) and the reaction temperature were also determining variables. Working with concentrations of tert-butyl alcohol above the stoichiometric one did not report great advantages. The optimal operating conditions to maximize the conversion of glycerol and the selectivity towards diethers were: 70 °C, 20% catalyst (referred to the total starting mass of the system), the stoichiometric ratio of glycerol:tert-butyl alcohol (G:TB = 1:3) and 1:2 molar ratio of dibutyl ether:tert-butyl alcohol. A study of three consecutive reaction cycles showed the high stability of the catalyst, obtaining identical results.

Advanced oxidation of formaldehyde in the aqueous solutions using UVC/S2 O8 2- process: Degradation and mineralization

Background: As a human carcinogen, formaldehyde is a toxic chemical imposing adverse effects on public health and environment. Due to its high reactivity, colorless nature, sustainability, purity in commercial forms, and low prices, the production and consumption of this compound has expanded vastly in industries. Methods: In this study, a UVC photoreactor with a total volume of 120 mL was used and operated in a rotary mode. To determine the residual concentration, high-performance liquid chromatography (HPLC) device was applied whose detector was set at a wavelength of 355 nm and equipped with C18 column (with dimensions of 25 × 4.6 mm i.d, and particle size of 5 µm). Total organic carbon (TOC) was determined using a TOC analyzer. Results: The optimal condition in this study was obtained at pH=3 and formaldehyde concentration of 350 mg, so that the removal of formaldehyde and TOC was 98.2% and 95.1%, respectively, after 35 minutes reaction time. The formaldehyde removal efficiency was assessed in the presence of methanol (MeOH), tert-butyl alcohol (TBA), and salicylic acid (SA) scavengers, and it was indicated that SO4 •- radicals were the most effective factors in formaldehyde destruction. By increasing the concentrations of MeOH, TBA, and SA to 2.5 g/L, the degradation efficiency of formaldehyde dropped from 98.02% to 69.78%, 64.68%, and 45.14%, respectively, at 35 minutes reaction time. The removal of formaldehyde in the presence of nitrate was significantly reduced and it had a significant effect on the removal of formaldehyde. Conclusion: In this study, the removal of formaldehyde was investigated in the presence of various anions including bicarbonate, carbonate, chloride, sulfate, and nitrate. According to the results, the UVC/S2 O8 2- process is a convenient and cost-effective method for the removal of formaldehyde.

Porous and highly dispersible voriconazole dry powders produced by spray freeze drying for pulmonary delivery with efficient lung deposition

Systemic administration of antifungal agents for the treatment of pulmonary aspergillosis is limited by the poor lung deposition and severe adverse effects. In contrast, pulmonary delivery allows a higher amount of drug to be delivered directly to the infection site and therefore a lower dose is required. This study aimed to develop porous and inhalable voriconazole dry powder with good lung deposition by spray freeze drying (SFD), using tert-butyl alcohol (TBA) as a co-solvent. A three-factor two-level full factorial design approach was used to investigate the effect of total solute concentration, drug content and co-solvent composition on the aerosol performance of the SFD powder. In general, the SFD voriconazole powder exhibited porous and spherical structure, and displayed crystalline characteristics. The analysis of factorial design indicated that voriconazole content was the most significant variable that could influence the aerosol performance of the SFD powders. The formulations that contained a high voriconazole content (40% w/w) and high TBA concentration in the feed solution (70% v/v) displayed the highest fine particle fraction of over 40% in the Next Generation Impactor study in which the powder was dispersed with a Breezhaler® at 100 L/min. In addition, the fine particle dose of the SFD powder showed a faster dissolution rate when compared to the unformulated voriconazole. Intratracheal administration of SFD voriconazole powder to mice resulted in a substantially higher drug concentration in the lungs when comparing to the group that received an equivalent dose of liquid voriconazole formulation intravenously, while a clinically relevant plasma drug concentration was maintained for at least two hours. Overall, an inhalable voriconazole dry powder formulation exhibiting good aerosol property and lung deposition was developed with clinical translation potential.

Can trimethylamine-N-oxide act to influence the self-aggregation of tert-butyl alcohol?

ABSTRACTWe report classical molecular dynamics simulation studies of aqueous solution consisting of water, tert-butyl alcohol (TBA) and trimethylamine-N-oxide (TMAO). In spite of the fact that both TBA and TMAO molecules have very similar geometry with hydrophobic and hydrophilic groups, they behave very differently in aqueous solutions. Our aim is to see the role of TMAO on the self-aggregation (or association) of TBA molecules. We observe that, TMAO acts to postpone the aggregation of TBA molecules (takes place via the hydrophobic ends) to some extent. Addition of 0.10 mole fraction of TMAO shifts the aggregation concentration of TBA from xtba = 0.025 to xtba = 0.06. From the excess coordination number, calculation it is noticed that up to xtba = 0.06, TBA molecules are favourably solvated by TMAO by replacing water molecules from TBA solvation shell but above this concentration, TBA–TMAO interaction decreases. This is further confirmed by water–TMAO interactions which shows a shift above xtba = 0.06 indicating more preferred interactions between them. We also observe a noticeable increase in the water–water hydrogen bond life time in presence of TBA molecules indicating more structuring of water molecules.

The Comparative and Combined Inhibitory Effects of MTBE and TBA on the Activities of Soil Exoenzymes

ABSTRACTMethyl tert-butyl ether (MTBE) and tert-butyl alcohol (TBA) are major soil contaminants, and they have been actively investigated for their toxic effects on living organisms in soil ecosystems. Although previous studies have been used as tools to evaluate the health of soil, they have been limited in scope and ability to analyze the overall microbial activity. In the present study, the effects of MTBE and TBA on the activity of soil exoenzymes including urease, acid phosphatase, arylsulfatase, β-glucosidase, dehydrogenase, and fluorescein diacetate hydrolase, which are involved in nutrient cycles and overall microbial activities, were investigated. Soil samples were treated with 0–2% of MTBE and TBA solutions, and the comparative effects and combined effects on quantity of active soil exoenzymes were determined. The activity of six exoenzymes exposed solely to MTBE and TBA did not significantly change with dose concentration or exposure time, but did show significant changes when exposed to high concentrations of MTBE and TBA combined, with dehydrogenase being the most affected. Therefore, we proposed dehydrogenase as a potential biomarker to assess the risk of co-contamination of MTBE and TBA.

Hydrophobic Hydration in Water-tert-Butyl Alcohol Solutions by Extended Depolarized Light Scattering.

Molecular dynamics and structural properties of water-tert-butyl alcohol (TBA) mixtures are studied as a function of concentration by extended depolarized light scattering (EDLS) experiments. The wide frequency range, going from fraction to several thousand GHz, explored by EDLS allows distinguishing TBA rotational dynamics from structural relaxation of water and intermolecular vibrational and librational modes of the solution. Contributions to the water relaxation originating from two distinct populations, i.e. hydration and bulk water, are clearly identified. The dynamic retardation factor of hydration water with respect to the bulk, ξ ≈ 4, almost concentration independent, is one of the smallest found by EDLS among a variety of systems of different nature and complexity. This result, together with the small number of water molecules perturbed by the presence of TBA, supports the idea that hydrophobic simple molecules are less effective than hydrophilic and more complex molecules in perturbing the H-bond network of liquid water. At increasing TBA concentrations the average number of perturbed water molecules shows a pronounced decrease and the characteristic frequency of librational motions reduces significantly, both of which are results consistent with the occurrence of self-aggregation of TBA molecules.

Effect of Branched Alcohols on Phase Behavior and Rheology of Nonionic Surfactant Systems

The effect of single- and double-branched alcohols on the phase and rheological behavior of the laurylsulfobetaine (LSB)/water system was studied, with special attention to the reverse micelles region. In our case, reverse micelle phases behaved as Newtonian fluids where alcohols play the role of solvent. Indeed, it can be concluded that the extension of the reverse micelles phase is determined by the alcohol miscibility in water. Regarding liquid crystals, it is observed that the lamellar phase exhibits gel-like behavior and is the most sensitive to the type of alcohol, affecting the elastic properties and the yield stress values. On the contrary, the hexagonal liquid crystal is barely sensitive to the kind of alcohol. In addition, a comparative study of the phase and rheological behavior of two dodecyl surfactants with different head groups (sulfobetaine LSB, and poly(oxyethylene) Brij-35) as a function of surfactant and tert-butyl alcohol concentrations was performed, revealing two completely different...

Fluctuating micro-heterogeneity in water-tert-butyl alcohol mixtures and lambda-type divergence of the mean cluster size with phase transition-like multiple anomalies.

Water-tert-butyl alcohol (TBA) binary mixture exhibits a large number of thermodynamic and dynamic anomalies. These anomalies are observed at surprisingly low TBA mole fraction, with x(TBA) ≈ 0.03-0.07. We demonstrate here that the origin of the anomalies lies in the local structural changes that occur due to self-aggregation of TBA molecules. We observe a percolation transition of the TBA molecules at x(TBA) ≈ 0.05. We note that "islands" of TBA clusters form even below this mole fraction, while a large spanning cluster emerges above that mole fraction. At this percolation threshold, we observe a lambda-type divergence in the fluctuation of the size of the largest TBA cluster, reminiscent of a critical point. Alongside, the structure of water is also perturbed, albeit weakly, by the aggregation of TBA molecules. There is a monotonic decrease in the tetrahedral order parameter of water, while the dipole moment correlation shows a weak nonlinearity. Interestingly, water molecules themselves exhibit a reverse percolation transition at higher TBA concentration, x(TBA) ≈ 0.45, where large spanning water clusters now break-up into small clusters. This is accompanied by significant divergence of the fluctuations in the size of largest water cluster. This second transition gives rise to another set of anomalies around. Both the percolation transitions can be regarded as manifestations of Janus effect at small molecular level.

Anaerobic biodegradation of methyl tert-butyl ether and tert-butyl alcohol in petrochemical wastewater

A laboratory-scale anaerobic sequencing batch reactor was used to evaluate treatment of a synthetic substrate mixture representing petrochemical wastewater containing methyl tert-butyl ether (MTBE), ethanol and acetic acid. Influent MTBE concentrations were 5, 10 and 50 mg/l (corresponding to MTBE loading rates of 0.2, 0.4 and 2 mg/l.d) with overall organic loading rates (OLRs) of 1.51, 3.23 and 3.25 g COD/l.d, respectively. These OLRs resulted in removal efficiencies for MTBE of 78%, 98% and 88%. Removal efficiencies for chemical oxygen demand were 85% and 90% with influent MTBE concentrations of 5 and 10 mg/l, but were significantly reduced to 72% with influent MTBE concentrations of 50 mg/l. During all reactor runs, effluent concentrations of tert-butyl alcohol (TBA) were below the detection limit. Batch degradation of the organic substrate mixture demonstrated initial inhibitory effects when exposed to MTBE concentrations of 50 mg/l and complete inhibition with MTBE concentrations above 2000 mg/l. It is interesting to note that in batch tests using MTBE as the sole organic substrate (initial MTBE concentrations of 50, 100 and 200 mg/l), the specific methanogenic activity decreased to below detection within the first 96 hours, but following a 72-hour lag phase the methane production increased again. Based on low volatile fatty acid (VFA) concentration, disappearance of TBA peaks and no findings of any other intermediate via gas chromatography/mass spectrometry, while the MTBE concentration is still high, it can be suggested that during the batch tests the breakdown of gas production and the following lag phase were the direct effect of higher MTBE concentrations (more than 50 mg/l) and not because of the TBA or VFA accumulations.

Aggregation in dilute aqueous tert-butyl alcohol solutions: Insights from large-scale simulations

Molecular dynamics simulations employing up to 64,000 particles are used to investigate aggregation and microheterogeneity in aqueous tert-butyl alcohol (TBA) solutions for TBA mole fractions X(t) ≤ 0.1. Four different force fields are considered. It is shown that the results obtained can be strongly dependent on the particular force field employed, and can be significantly influenced by system size. Two of the force fields considered show TBA aggregation in the concentration range X(t) ≈ 0.03 - 0.06. For these models, systems of 64,000 particles are minimally sufficient to accommodate the TBA aggregates. The structures resulting from TBA aggregation do not have a well-defined size and shape, as one might find in micellar systems, but are better described as TBA-rich and water-rich regions. All pair correlation functions exhibit long-range oscillatory behavior with wavelengths that are much larger than molecular length scales. The oscillations are not strongly damped and the correlations can easily exceed the size of the simulation cell, even for the low TBA concentrations considered here. We note that these long-range correlations pose a serious problem if one wishes to obtain certain physical properties such as Kirkwood-Buff integrals from simulation results. In contrast, two other force fields that we consider show little sign of aggregation for X(t) ≲ 0.08. In our 64,000 particle simulations all four models considered show demixing-like behavior for X(t) ≳ 0.1, although such behavior is not evident in smaller systems of 2000 particles. The meaning of the demixing-like behavior is unclear. Since real TBA-water solutions do not demix, it might be an indication that all four models we consider poorly represent the real system. Alternatively, it might be an artifact of finite system size. Possibly, the apparent demixing indicates that for X(t) ≳ 0.1, the stable TBA aggregates are simply too large to fit into the simulation cell. Our results provide a view of the possible nature of microheterogeneity in dilute TBA-water solutions, and of the associated long correlation lengths. It is clear that system size can be a very important factor in simulations of these solutions, and must be taken into account in the evaluation and development of TBA-water force fields.

An ex situ evaluation of TBA- and MTBE-baited bio-traps

Aquifer microbial communities can be investigated using Bio-traps® (“bio-traps”), passive samplers containing Bio-Sep® beads (“bio-beads”) that are deployed in monitoring wells to be colonized by bacteria delivered via groundwater flow through the well. When bio-beads are “baited” with organic contaminants enriched in 13C, stable isotope probing allows assessment of the composition and activity of the microbial community. This study used an ex situ system fed by groundwater continuously extracted from an adjacent monitoring well within an experimentally-created aerobic zone treating a tert-butyl alcohol (TBA) plume. The goal was to evaluate aspects of bio-trap performance that cannot be studied quantitatively in situ. The measured groundwater flow through a bio-trap housing suggests that such traps might typically “sample” about 1.8 L per month. The desorption of TBA or methyl tert-butyl ether (MTBE) bait from bio-traps during a typical deployment duration of 6 weeks was approximately 90% and 45%, respectively, of the total initial bait load, with initially high rate of mass loss that decreased markedly after a few days. The concentration of TBA in groundwater flowing by the TBA-baited bio-beads was estimated to be as high as 3400 mg/L during the first few days, which would be expected to inhibit growth of TBA-degrading microbes. Initial inhibition was also implied for the MTBE-baited bio-trap, but at lower concentrations and for a shorter time. After a few days, concentrations in groundwater flowing through the bio-traps dropped below inhibitory concentrations but remained 4–5 orders of magnitude higher than TBA or MTBE concentrations within the aquifer at the experimental site. Desorption from the bio-beads during ex situ deployment occurred at first as predicted by prior sorption analyses of bio-beads but with apparent hysteresis thereafter, possibly due to mass transfer limitations caused by colonizing microbes. These results suggest that TBA- or MTBE-baited bio-traps could be baited at lower initial total mass loading with no detriment to trapping ability. The bio-traps were able to collect detectable amounts of microbial DNA and thus allow some insight into the sparse microbial community present in the aquifer during remediation of the low concentration plume.

Preparation of 4′,4′′(5′′)-Di-tert-butyldibenzo-18-crown-6 Based on Electrophilic Aromatic Substitution

Abstract 4′,4′′(5′′)-Di-tert-butyldibenzo-18-crown-6 (DTBB18C6) was synthesized by improving the electrophilic aromatic substitution of dibenzo-18-crown-6 (DB18C6) using tert-butyl alcohol (TBA) as alkylation reagent, H3PO4 (85 wt %) as catalyst and CH2Cl2 as solvent. Experimental results show that the optimized reaction conditions were 0.03 mol L−1 for TBA concentration, 2.5 for TBA/DB18C6 molar ratio, 0.006 mol L−1 for H3PO4 concentration, 50 °C reaction temperature, and 6 h reaction time. Under the optimum reaction conditions, DTBB18C6 yield can reach 43.65%.

In Situ Biotreatment of TBA with Recirculation/Oxygenation

The potential for in situ biodegradation of tert-butyl alcohol (TBA) by creation of aerobic conditions in the subsurface with recirculating well pairs was investigated in two field studies conducted at Vandenberg Air Force Base (VAFB). In the first experiment, a single recirculating well pair with bromide tracer and oxygen amendment successfully delivered oxygen to the subsurface for 42 days. TBA concentrations were reduced from approximately 500 μg/L to below the detection limit within the treatment zone and the treated water was detected in a monitoring transect several meters downgradient. In the second experiment, a site-calibrated model was used to design a double recirculating well pair with oxygen amendment, which successfully delivered oxygen to the subsurface for 291 days and also decreased TBA concentrations to below the detection limit. Methylibium petroleiphilum strain PM1, a known TBA-degrading bacterium, was detectable at the study site but addition of oxygen had little impact on the already low baseline population densities, suggesting that there was not enough carbon within the groundwater plume to support significant new growth in the PM1 population. Given favorable hydrogeologic and geochemical conditions, the use of recirculating well pairs to introduce dissolved oxygen into the subsurface is a viable method to stimulate in situ biodegradation of TBA or other aerobically-degradable aquifer contaminants.

Role of back diffusion and biodegradation reactions in sustaining an MTBE/TBA plume in alluvial media

A methyl tert-butyl ether (MTBE) / tert-butyl alcohol (TBA) plume originating from a gasoline spill in late 1994 at Vandenberg Air Force Base (VAFB) persisted for over 15 years within 200 feet of the original spill source. The plume persisted until 2010 despite excavation of the tanks and piping within months after the spill and excavations of additional contaminated sediments from the source area in 2007 and 2008. The probable history of MTBE concentrations along the plume centerline at its source was estimated using a wide variety of available information, including published details about the original spill, excavations and monitoring by VAFB consultants, and our own research data. Two-dimensional reactive transport simulations of MTBE along the plume centerline were conducted for a 20-year period following the spill. These analyses suggest that MTBE diffused from the thin anaerobic aquifer into the adjacent anaerobic silts and transformed to TBA in both aquifer and silt layers. The model reproduces the observation that after 2004 TBA was the dominant solute, diffusing back out of the silts into the aquifer and sustaining plume concentrations much longer than would have been the case in the absence of such diffusive exchange. Simulations also suggest that aerobic degradation of MTBE or TBA at the water table in the overlying silt layer significantly affected concentrations of MTBE and TBA by limiting the chemical mass available for back diffusion to the aquifer.