Efficiency analysis of greenhouse gas sequestration during miscible CO2 injection in fractured oil reservoirs

During CO2 injection into naturally fractured oil reservoirs for enhanced oil recovery, the great portion of oil is recovered by matrix-fracture interaction. Diffusive mass transfer between matrix and fracture controls this process if CO2 is miscible with matrix oil. Oil expelled from matrix is replaced by CO2, and the matrix could be potentially a good storage medium for the long-term. For the cooptimization of the oil recovery and CO2 storage, i.e., maximizing the oil recovery while maximizing the amount of CO2 stored, we propose an efficiency analysis using a dimensionless term defined as the global effectiveness factor. The Biot number and Thiele modulus were incorporated in the development of the global effectiveness factor. Diffusion coefficients and the rate of mass-transfer constants were obtained from our previous finite element modeling study. We first defined and derived the dimensionless groups to be used in the efficiency analysis and then formulated a relationship between the dimensionless groups and the efficiency indicators, i.e., the ratios of total solute (oil) produced to total solvent injected and total solvent stored to total solvent injected. It was shown that the efficiency of the process can be represented by a dimensionless group that consists of well-known dimensionless numbers such as the Reynolds number, the Peclet number, the Sherwood number, and the global effectiveness factor.     

Effect of diet on fecal and urinary estrogenic activity

The United States Environmental Protection Agency has identified estrogens from animal feeding operations as a major environmental concern, but few data are available to quantify the excretion of estrogenic compounds by dairy cattle. The objectives of this study were to quantify variation in estrogenic activity in feces and urine due to increased dietary inclusion of phytoestrogens. Ten Holstein heifers were assigned to 2 groups balanced for age and days pregnant; groups were randomly assigned to treatment sequence in a 2-period crossover design. Dietary treatments consisted of grass hay or red clover hay, and necessary supplements. Total collection allowed for sampling of feed refusals, feces, and urine during the last 4 d of each period. Feces and urine samples were pooled by heifer and period, and base extracts were analyzed for estrogenic activity (estrogen equivalents) using the yeast estrogen screen bioassay. Feces and urine samples collected from 5 heifers were extracted and analyzed using liquid chromatography-tandem mass spectrometry (LC-MS/MS) to quantify excretion of 7 phytoestrogenic compounds. Excretion of 17-β estradiol equivalents in urine was higher and tended to be higher in feces for heifers fed red clover hay (84.4 and 120.2 mg/d for feces and urine, respectively) compared with those fed grass hay (57.4 and 35.6 mg/d). Analysis by LC-MS/MS indicated greater fecal excretion of equol, genistein, daidzein, coumestrol, and formononetin by heifers fed red clover hay (1634, 29.9, 96.3, 27.8, and 163 mg/d, respectively) than heifers fed grass hay (340, 3.0, 46.2, 8.8, and 18.3 mg/d, respectively). Diet had no effect on fecal biochanin A or 2-carbethoxy-5, 7-dihydroxy-4’-methoxyisoflavone. Four phytoestrogens were detected in urine (2-carbethoxy-5, 7-dihydroxy-4’-methoxyisoflavone, daidzein, equol, and formononetin) and their excretion was not affected by diet. Identifying sources of variation in estrogenic activity of manure will aid in the development of practices to reduce environmental estrogen accumulation.     

The aqueous degradation of butylated hydroxyanisole by UV/S2O8(2-): study of reaction mechanisms via dimerization and mineralization

Three distinctive phases of BHA reactivity toward UV/ S2O8(2-) at acidic, neutral, and basic pH range were examined, where 80-100% mineralization has been observed within an hour of irradiation under 254 nm. A reduction in solution pH during the reaction was observed mainly due to the complete conversion of S2O8(2-) to sulfate ion together with proton generation. Seven measurable intermediates were found via an oxidation and dimerization process at all tested pH levels. The BHA decay mechanisms are quite different in acidic condition and at other pH levels. There are three unique intermediates that are only detectable at pH 3 via two additional pathways. This is due to the generation of weaker oxidants or radicals which results in a slower degradation of the BHA, and therefore, the accumulation of these intermediates to detectable levels. The rate of BHA decay generally increases from low to high pH levels; however, the corresponding mineralization at higher pH is retarded due to the futile process of recombining radicals and involvement of intermediates. Therefore, neutral pH was suggested to be the optimum condition in terms of mineralization and moderate efficiency in removing BHA.     

Monod kinetics for aerobic biodegradation of petroleum hydrocarbons in unsaturated soil microcosms

We use Monod kinetics to calibrate previously published data that documentthe aerobic biodegradation of hydrocarbon vapors in soil microcosms from a weathered petroleum spill site. Monod kinetics offer insight into biodegradation mechanics because they address biomass growth as well as substrate depletion. A blend of five aromatics and five alkanes dose the microcosm sets at four strengths, and a finite difference model describes the response superimposed across the constituent substrates. An observed initial biomass X0 of 125 g biomass/m(3) soil moisture and an endogendous decay rate b of 0.102 day(-1) calibrate all four dosages and agree with heterotrophic plate counts. Common maximum specific growth rates microMJ and half saturation constants KSJ calibrate each constituent across the four dosages. The biodegradable alkanes exhibit microMJ values ranging from 0.0190 to 0.0996 day(-1), while the aromatic rates vary from 0.0946 to 0.322 day(-1). One of the alkanes (2,2,4-trimethylpentane) is recalcitrant. The half saturation constants range from 0.000083 to 0.000355 g substrate/m(3) soil moisture for the biodegradable alkanes, which imply zero-order kinetics. The aromatic KSJ values vary from 5.02 to 14.3 g substrate/m(3) soil moisture, and suggest first-order kinetics. The yield YJ increases with dosage concentration for all the biodegradable constituents, varying from 0.0533 to 1.58 g biomass/g substrate.     

Formation of chloroform and other chlorinated byproducts by chlorination of triclosan-containing antibacterial products

Triclosan is a widely used antibacterial agent found in many personal hygiene products. Although it has previously been established that pure triclosan and free chlorine readily react, interactions between triclosan-containing consumer products and free chlorine have not previously been analyzed in great depth. Sixteen double-blinded solutions including both triclosan-containing (1.14-3.12 mg triclosan/g product) and triclosan-free products were contacted with free chlorine at pH 7. Products detected included (chlorophenoxy) phenols, 2,4-dichlorophenol, 2,4,6-trichlorophenol, and chloroform. The daughter product yields were found to be highly variable and were dependent on the antimicrobial product investigated, the free chlorine to triclosan ratio, and the temperature at which the study was conducted. Lowering the temperature from 40 to 30 degrees C resulted in a decreased average chloroform yield from 0.50 to 0.37 mol chloroform/mol triclosan consumed after 1 min of reaction time for an initial free chlorine concentration of 4.0 mg/L as Cl2. At 40 degrees C the average molar chloroform yields decreased to 0.29 and <0.1 when the initial free chlorine concentration was decreased to either 2.0 or 1.0 mg/L as Cl2, respectively. Field experiments, in which Atlanta, GA and Danville, VA tap waters were augmented with various soap products, exhibited results varying from the laboratory experiments in that different productyields were observed. These differences are attributed to the chlorine demand of constituents in the tap water. A simple exposure model suggests that exposure to chloroform can be significant under some conditions.     

Effect of flux (transmembrane pressure) and membrane properties on fouling and rejection of reverse osmosis and nanofiltration membranes treating perfluorooctane sulfonate containing wastewater

Perfluorooctane sulfonate (PFOS) is an emergent contaminant of substantial environmental concerns. In this study, reverse osmosis (RO) and nanofiltration (NF) membranes were used to remove this toxic and persistent compound from PFOS-containing wastewater. Five RO membranes and three NF membranes were tested at a feed concentration of 10 ppm PFOS over 4 days, and the PFOS rejection and permeate flux performances were systematically investigated. PFOS rejection was well correlated to sodium chloride rejection. The rejection efficiencies for the RO membranes were > 99%, and those for the NF membranes ranged from 90-99%. Improvement in PFOS rejection, together with mild flux reduction (< 16%), was observed at longer filtration time. Such shifts in rejection and flux performance were probably due to the increased PFOS accumulation at longer duration, as shown by X-ray photoelectron spectroscopy and liquid chromatograph and tandem mass spectrometry results. A fraction of PFOS molecules might be entrapped in the polyamide layer of the composite membranes, which hindered the further passage of both water and other PFOS molecules. In a similar fashion, PFOS rejection and fouling were enhanced for greater initial flux and/or applied pressure, where PFOS accumulation was promoted probably due to increased hydrodynamic permeate drag. Flux reduction was also shown to correlate to membrane roughness, with the rougher membranes tend to experience more flux reduction than the smoother ones.     

Characterization of disinfection byproduct precursors based on hydrophobicity and molecular size

Natural organic matter (NOM) from five water sources was fractionated using XAD resins and ultrafiltration membranes into different groups based on hydrophobicity and molecular weight (MW), respectively. The disinfection byproduct formation from each fraction during chlorination and chloramination was studied. In tests using chlorination, hydrophobic and high MW (e.g., >0.5 kDa) precursors produced more unknown total organic halogen (UTOX) than corresponding hydrophilic and low MW (e.g., <0.5 kDa) precursors. Trihaloacetic acid (THAA) precursors were more hydrophobic than trihalomethane (THM) precursors. The formation of THM and THAA was similar among different fractions for a water with low humic content. Hydrophilic and low MW (<0.5 kDa) NOM fractions gave the highest dihaloacetic acid (DHAA) yields. No significant difference was found for DHAA formation among different NOM fractions during chloramination. Increasing pH from 6 to 9 led to lower TOX formation for hydrophobic and high MW NOM fractions but had little impact on TOX yields from hydrophilic and low MW fractions. Bromine and iodine were more reactive with hydrophilic and low MW precursors as measured by THM or HAA formation than their corresponding hydrophobic and high MW precursors. However, hydrophobic and high MW precursors produced more UTOX when reacting with bromine and iodine.     

Performance characterization of nanofiltration membranes based on rigid star amphiphiles

The objective of this study was to develop new nanofiltration (NF) membranes capable of providing significantly greater water permeability and higher rejection of water contaminants compared to state-of-the-art NF membranes. The active layer of the new NF membranes is prepared with rigid star amphiphiles (RSAs) synthesized as part of this study. Performance characterization for a first generation of RSA membranes in a bench-scale apparatus reveals that most of the new membranes provide water permeability of 1.3-3.1 times that of two commercial NF membranes with polyamide active layers while providing comparable rejection of the organic contaminant surrogate Rhodamine WT. However, the rejection of arsenious acid (H3AsO3) by most new NF membranes was found to be lower than that by the two commercial NF membranes tested. Future research efforts of this study will focus on exploring if H3AsO3 rejection could be significantly increased, without negatively affecting water permeability and organic contaminant rejection, by addition of various chemical groups to RSA hydrophobic cores and hydrophilic branches, and by RSA cross-linking.     

Comparative life-cycle air emissions of coal, domestic natural gas, LNG, and SNG for electricity generation

The U.S. Department of Energy (DOE) estimates that in the coming decades the United States' natural gas (NG) demand for electricity generation will increase. Estimates also suggest that NG supply will increasingly come from imported liquefied natural gas (LNG). Additional supplies of NG could come domestically from the production of synthetic natural gas (SNG) via coal gasification-methanation. The objective of this study is to compare greenhouse gas (GHG), SOx, and NOx life-cycle emissions of electricity generated with NG/LNG/SNG and coal. This life-cycle comparison of air emissions from different fuels can help us better understand the advantages and disadvantages of using coal versus globally sourced NG for electricity generation. Our estimates suggest that with the current fleet of power plants, a mix of domestic NG, LNG, and SNG would have lower GHG emissions than coal. If advanced technologies with carbon capture and sequestration (CCS) are used, however, coal and a mix of domestic NG, LNG, and SNG would have very similar life-cycle GHG emissions. For SOx and NOx we find there are significant emissions in the upstream stages of the NG/ LNG life-cycles, which contribute to a larger range in SOx and NOx emissions for NG/LNG than for coal and SNG.