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R. E. Rathbun

Publications and source records attributed to R. E. Rathbun.

At least 37 records · Page 2Linked to original sources
USGS1991

Fate of acetone in an outdoor model stream with a nitrate supplement, southern Mississippi, U.S.A.

The fate of acetone in an outdoor model stream to which nitrate was added as a nutrient supplement was determined. The stream, in southern Mississippi, U.S.A. was 234 m long. Water was supplied to the stream by an artesian well at about 1.21 s −1 , resulting in a mean water velocity of about 0.5 m min −1 . Acetone was injected continuously for 26 days resulting in concentrations of 20–40 mg l −1 . A nitrate solution was injected for 21 days resulting in an instream concentration of about 1.7 mg l −1 at the upstream end of the stream. Rhodamine-WT dye was used to determine the travel time and dispersion characteristics of the stream, and t-butyl alcohol was used to determine the volatilization characteristics. Volatilization controlled the fate of acetone in the model stream. The lack of substantial bacterial degradation of acetone was contrary to expectations based on the results of laboratory degradation studies using model stream water enriched with nitrate. A possible explanation for the lack of significant degradation in the model stream may be the limited 6-h residence time of the acetone in the stream.

Journal of Hydrology↗
USGS1989

Determination of stream reaeration coefficients by use of tracers

Stream reaeration is the physical absorption of oxygen from the atmosphere by a flowing stream. This is the primary process by which a stream replenishes the oxygen consumed in the biodegradation of organic wastes. Prior to 1965, reaeration rate coefficients could be estimated only by indirect methods. In 1965, a direct method of measuring stream reaeration coefficients was developed whereby a radioactive tracer gas was injected into a stream-the principle being that the tracer gas would be desorbed from the stream inversely to how oxygen would be absorbed. The technique has since been modified by substituting hydrocarbon gases for the radioactive tracer gas. This manual describes the slug-injection and constant-rate-injection methods of measuring gas-tracer desorption. Emphasis is on the use of rhodamine WT dye as a relatively conservative tracer and propane as the nonconservative gas tracer, on planning field tests, on methods of injection, sampling, and analysis, and on techniques for computing desorption and reaeration coefficients.

Techniques of Water-Resources Investigations↗
USGS1988

Fate of acetone in an outdoor model stream in southern Mississippi, U.S.A.

The fate of acetone in water was investigated in an outdoor model stream located in southern Mississippi, U.S.A. Acetone was injected continuously for 32 days resulting in small milligram-perliter concentrations in the stream. Rhodamine-WT dye was injected at the beginning and at the end of the study to determine the time-of-travel and dispersion characteristics of the stream. A 12-h injection of t-butyl alcohol (TBA) was used to determine the volatilization characteristics of the stream. Volatilization controlled the acetone concentration in the stream. Significant bacterial degradation of acetone did not occur, contrary to expectations based on previous laboratory studies. Attempts to induce degradation of the acetone by injecting glucose and a nutrient solution containing bacteria acclimated to acetone were unsuccessful. Possible explanations for the lack of bacterial degradation included a nitrate limitation and a limited residence time in the stream system.

Mississippi↗
USGS1988

Photolysis of rhodamine-WT dye

Photolysis of rhodamine-WT dye under natural sunlight conditions was determined by measuring the loss of fluorescence as a function of time. Rate coefficients at 30° north latitude ranged from 4.77 × 10 −2 day −1 for summer to 3.16 × 10 −2 day −2 for winter. Experimental coefficients were in good agreement with values calculated using a laboratory-determined value of the quantum yield.

Chemosphere↗
USGS1988

Application of the two-film model to the volatilization of acetone and t-butyl alcohol from water as a function of temperature

The two-film model is often used to describe the volatilization of organic substances from water. This model assumes uniformly mixed water and air phases separated by thin films of water and air in which mass transfer is by molecular diffusion. Mass-transfer coefficients for the films, commonly called film coefficients, are related through the Henry's law constant and the model equation to the overall mass-transfer coefficient for volatilization. The films are modeled as two resistances in series, resulting in additive resistances. The two-film model and the concept of additivity of resistances were applied to experimental data for acetone and t-butyl alcohol. Overall mass-transfer coefficients for the volatilization of acetone and t-butyl alcohol from water were measured in the laboratory in a stirred constant-temperature bath. Measurements were completed for six water temperatures, each at three water mixing conditions. Wind-speed was constant at about 0.1 meter per second for all experiments. Oxygen absorption coefficients were measured simultaneously with the measurement of the acetone and t-butyl alcohol mass-transfer coefficients. Gas-film coefficients for acetone, t-butyl alcohol, and water were determined by measuring the volatilization fluxes of the pure substances over a range of temperatures. Henry's law constants were estimated from data from the literature. The combination of high resistance in the gas film for solutes with low values of the Henry's law constants has not been studied previously. Calculation of the liquid-film coefficients for acetone and t-butyl alcohol from measured overall mass-transfer and gas-film coefficients, estimated Henry's law constants, and the two-film model equation resulted in physically unrealistic, negative liquid-film coefficients for most of the experiments at the medium and high water mixing conditions. An analysis of the two-film model equation showed that when the percentage resistance in the gas film is large and the gas-film resistance approaches the overall resistance in value, the calculated liquid-film coefficient becomes extremely sensitive to errors in the Henry's law constant. The negative coefficients were attributed to this sensitivity and to errors in the estimated Henry's law constants. Liquid-film coefficients for the absorption of oxygen were correlated with the stirrer Reynolds number and the Schmidt number. Application of this correlation with the experimental conditions and a molecular-diffusion coefficient adjustment resulted in values of the liquid-film coefficients for both acetone and t-butyl alcohol within the range expected for all three mixing conditions. Comparison of Henry's law constants calculated from these film coefficients and the experimental data with the constants calculated from literature data showed that the differences were small relative to the errors reported in the literature as typical for the measurement or estimation of Henry's law constants for hydrophilic compounds such as ketones and alcohols. Temperature dependence of the mass-transfer coefficients was expressed in two forms. The first, based on thermodynamics, assumed the coefficients varied as the exponential of the reciprocal absolute temperature. The second empirical approach assumed the coefficients varied as the exponential of the absolute temperature. Both of these forms predicted the temperature dependence of the experimental mass-transfer coefficients with little error for most of the water temperature range likely to be found in streams and rivers. Liquid-film and gas-film coefficients for acetone and t-butyl alcohol were similar in value. However, depending on water mixing conditions, overall mass-transfer coefficients for acetone were from two to four times larger than the coefficients for t-butyl alcohol. This difference in behavior of the coefficients resulted because the Henry's law constant for acetone was about three times larger than that of

Water Supply Paper↗
USGS1988

Volatilization of benzene and eight alkyl-substituted benzene compounds from water

Predicting the fate of organic compounds in streams and rivers often requires knowledge of the volatilization characteristics of the compounds. The reference-substance concept, involving laboratory-determined ratios of the liquid-film coefficients for volatilization of the organic compounds to the liquid-film coefficient for oxygen absorption, is used to predict liquid-film coefficients for streams and rivers. In the absence of experimental data, two procedures have been used for estimating these liquid-film coefficient ratios. These procedures, based on the molecular-diffusion coefficient and on the molecular weight, have been widely used but never extensively evaluated. Liquid-film coefficients for the volatilization of benzene and eight alkyl-substituted benzene compounds (toluene through n-octylbenzene) from water were measured in a constant-temperature, stirred water bath. Liquid-film coefficients for oxygen absorption were measured simultaneously. A range of water mixing conditions was used with a water temperature of 298.2 K. The ratios of the liquid-film coefficients for volatilization to the liquid-film coefficient for oxygen absorption for all of the organic compounds were independent of mixing conditions in the water. Experimental ratios ranged from 0.606 for benzene to 0.357 for n-octylbenzene. The molecular-diffusion-coefficient procedure accurately predicted the ratios for ethylbenzene through n-pentylbenzene with a power dependence of 0.566 on the molecular-diffusion coefficient, in agreement with published values. Predicted ratios for benzene and toluene were slightly larger than the experimental ratios. These differences were attributed to possible interactions between the molecules of these compounds and the water molecules and to benzene-benzene interactions that form dimers. Because these interactions also are likely to occur in natural waters, it was concluded that the experimental ratios are more correct than the predicted ratios for application purposes in the reference-substance concept. Predicted ratios for n-hexylbenzene, n-heptylbenzene, and n-octylbenzene were larger than the experimental ratios. These differences were attributed to a sorption-desorption process between these compounds and the surfaces of the constant-temperature water bath. Other experimental problems associated with preparing water solutions of these slightly soluble compounds also may have contributed to the differences. Because these processes are not part of the true volatilization process, it was concluded that the predicted ratios for these three compounds are probably more correct than the experimental ratios for application purposes in the reference-substance concept. Any model of the fate of these compounds in streams and rivers would have to include terms accounting for sorption processes, however. The molecular-weight procedure accurately predicted the ratios for ethylbenzene through n-pentylbenzene, but only if the power dependence on the molecular weight was decreased from the commonly used -0.500 to -0.427. Deviations for the low- and high-molecular-weight compounds were similar to those observed for the molecular-diffusion-coefficient procedure.

Water Supply Paper↗
USGS1987

Vapor pressures and gas-film coefficients for ketones

Comparison of handbook vapor pressures for seven ketones with more recent literature data showed large differences for four of the ketones. Gas-film coefficients for the volatilization of these ketones from water determined by two different methods were in reasonable agreement.

Chemosphere↗
USGS1987

Determination of stream reaeration coefficients by use of tracers

Stream reaeration is the physical absorption of oxygen from the atmosphere by a flowing stream. This is the primary process by which a stream replenishes the oxygen consumed in the biodegradation of organic wastes. Prior to 1965, reaeration rate coefficients could be estimated only by indirect methods. In 1965, a direct method of measuring stream reaeration coefficients was developed in which a radioactive tracer gas was injected into a stream--the tracer gas being desorbed from the stream inversely to how oxygen would be absorbed . The technique has since been modified by substituting hydrocarbon gases for the radioactive tracer gas. This manual describes the slug-injection and constant-rate injection methods of performing gas-tracer desorption measurements. Emphasis is on the use of rhodamine WT dye as a relatively conservative tracer and propane as the nonconservative gas tracer, on planning field tests, methods of injection, sampling and analysis, and computational techniques to compute desorption and reaeration coefficients.

Open-File Report↗
USGS1986

Gas-film coefficients for the volatilization of ketones from water

Volatilization is a significant process in determining the fate of many organic compounds in streams and rivers. Quantifying this process requires knowledge of the mass-transfer coefficient from water, which is a function of the gas-film and liquid-film coefficients. The gas-film coefficient can be determined by measuring the flux for the volatilization of pure organic liquids. Volatilization fluxes for acetone, 2-butanone, 2-pentanone, 3-pentanone, 4-methyl-2-pentanone, 2-heptanone, and 2-octanone were measured in the laboratory over a range of temperatures. Gas-film coefficients were then calculated from these fluxes and from vapor pressure data from the literature. An equation was developed for predicting the volatilization flux of pure liquid ketones as a function of vapor pressure and molecular weight. Large deviations were found for acetone, and these were attributed to the possibility that acetone may be hydrogen bonded. A second equation for predicting the flux as a function of molecular weight and temperature resulted in large deviations for 4methyl-2-pentanone. These deviations were attributed to the branched structure of this ketone. Four factors based on the theory of volatilization and relating the volatilization flux or rate to the vapor pressure, molecular weight, temperature, and molecular diffusion coefficient were not constant as suggested by the literature. The factors generally increased with molecular weight and with temperature. Values for acetone corresponded to ketones with a larger molecular weight, and the acetone factors showed the greatest dependence on temperature. Both of these results are characteristic of compounds that are hydrogen bonded. Relations from the literature commonly used for describing the dependence of the gas-film coefficient on molecular weight and molecular diffusion coefficient were not applicable to the ketone gas-film coefficients. The dependence on molecular weight and molecular diffusion coefficient was in general U-shaped with the largest coefficients observed for acetone, the next largest for 2octanone, and the smallest for 2-pentanone and 3-pentanone. The gas-film coefficient for acetone was much more dependent on temperature than were the coefficients for the other ketones. Such behavior is characteristic of hydrogen-bonded substances. Temperature dependencies of the other ketones were about twice the theoretical value, but were comparable to a literature value for water. Ratios of the ketone gas-film coefficients to the gasfilm coefficients for the evaporation of water were approximately constant for all the ketones except for acetone, whose values were considerably larger. The ratios increased with temperature; however, the increases were small except for acetone. These ratios can be combined with an equation from the literaure for predicting the gasfilm coefficient for evaporation of water from a canal to predict the gas-film coefficients for the volatilization of ketones from streams and rivers.

Water Supply Paper↗
USGS1985

VOLATILIZATION OF ALKYLBENZENES FROM WATER.

Volatilization is a physical process of importance in determining the fate of many organic compounds in streams and rivers. This process is frequently described by the conceptual-two-film model. The model assumes uniformly mixed water and air phases separated by thin films of water and air in which mass transfer is by molecular diffusion. Mass-transfer coefficients for the water and air films are related to an overall mass-transfer coefficient for volatilization through the Henry's law constant.

Conference Paper↗
USGS1984

Volatilization of chlorinated hydrocarbons from water

Coefficients for the volatilization from water of 1,1,1-trichloroethane and 1,2-dichloroethane were measured in a stirred tank. Experiments at constant mixing conditions over a wide range of concentrations showed that the volatilization coefficient was independent of concentration, confirming the assumption that volatilization is a first order process. Simultaneous measurements of the volatilization coefficient and the oxygen absorption coefficient over a wide range of mixing conditions showed that the chlorinated hydrocarbon/oxygen coefficient ratios for both compounds were independent of mixing conditions. Ratios of 0.596 and 0.621 were obtained for 1,1,1-trichloroethane and 1,2-dichloroethane, respectively.

Book chapter↗
USGS1984

Volatilization of ketones

Volatilization fluxes of seven ketones were measured over a range of temperatures. Gas-film coefficients were calculated from these volatilization fluxes and related to the gas-film coefficient for the evaporation of water. These relations, when combined with an equation for estimating the gas-film coefficient for evaporation of water from a canal, permit estimating gas-film coefficients for the volatilization of ketones from streams and rivers.

Chemosphere↗
USGS1984

Comparison of nonlinear least squares and log transformation procedures for calculating volatilization coefficients

A nonlinear least squares procedure and a log transformation procedure for calculating first-order rate coefficients from experimental concentration-versus-time data were compared using laboratory measurements of the volatilization from water of 1,1,1-trichloroethane and 1,2-dichloroethane and the absorption of oxygen by water. Ratios of the nonlinear least squares to log transformation volatilization and absorption coefficients for 77 tests ranged from 0.955 to 1.08 and averaged 1.01. Comparison of the maximum, minimum, and mean root-mean-square errors of prediction for six sets of coefficients showed that the errors for the nonlinear least squares procedure were almost always smaller than the errors for the log transformation procedure.

Chemosphere↗
USGS1984

Use of the routing procedure to study dye and gas transport in the West Fork Trinity River, Texas

Rhodamine-WT dye, ethylene, and propane were injected at three sites along a 21.6-kilometer reach of the West Fork Trinity River below Fort Worth, Texas. Complete dye concentration versus time curves and peak gas concentrations were measured at three cross sections below each injection. The peak dye concentrations were located and samples were collected at about three-hour intervals for as many as six additional cross sections. These data were analyzed to determine the longitudinal dispersion coefficients as well as the gas desorption coefficients using both standard techniques and a numerical routing procedure. The routing procedure, using a Lagrangian transport model to minimize numerical dispersion, provided better estimates of the dispersion coefficient than did the method of moments. At a steady flow of about 0.76 m2/s, the dispersion coefficient varied from about 0.7 m2/s in a reach contained within a single deep pool to about 2.0 m2/s in a reach containing riffles and small pools. The bulk desorption coefficients computed using the routing procedure and the standard peak method were essentially the same. The liquid film coefficient could also be obtained using the routing procedure. Both the bulk desorption coefficient and the liquid film coefficient were much smaller in the pooled reach than in the reaches containing riffles.

Water Supply Paper↗
USGS1983

Gas-film coefficients for streams

Equations for predicting the gas-film coefficient for the volatilization of organic solutes from streams are developed. The film coefficient is a function of windspeed and water temperature. The dependence of the coefficient on windspeed is determined from published information on the evaporation of water from a canal. The dependence of the coefficient on temperature is determined from laboratory studies on the evaporation of water. Procedures for adjusting the coefficients for different organic solutes are based on the molecular diffusion coefficient and the molecular weight. The molecular weight procedure is easiest to use because of the availability of molecular weights. However, the theoretical basis of the procedure is questionable. The diffusion coefficient procedure is supported by considerable data. Questions, however, remain regarding the exact dependence of the film coefficint on the diffusion coefficient. It is suggested that the diffusion coefficient procedure with a 0.68-power dependence be used when precise estimate of the gas-film coefficient are needed and that the molecular weight procedure be used when only approximate estimates are needed.

Journal of Environmental Engineering↗
USGS1982

Volatilization of ketones from water

The overall mass-transfer coefficients for the volatilization from water of acetone, 2-butanone, 2-pentanone, 3-pentanone, 4-methyl-2-pentanone, 2-heptanone, and 2-octanone were measured simultaneously with the oxygen-absorption coefficient in a laboratory stirred water bath. The liquid-film and gas-film coefficients of the two-film model were determined for the ketones from the overall coefficients, and both film resistances were important for volatilization of the ketones. The liquid-film coefficients for the ketones varied with the 0.719 power of the molecular-diffusion coefficient, in agreement with the literature. The liquid-film coefficients showed a variable dependence on molecular weight, with the dependence ranging from the −0.263 power for acetone to the −0.378 power for 2-octanone. This is in contrast with the literature where a constant −0.500 power dependence on the molecular weight is assumed. The gas-film coefficients for the ketones showed no dependence on molecular weight, in contrast with the literature where a −0.500 power is assumed.

Water, Air, & Soil Pollution↗
USGS1982

Fate of acetone in water

The physical, chemical, and biological processes that might affect the concentration of acetone in water were investigated in laboratory studies. Processes considered included volatilization, adsorption by sediments, photodecomposition, bacterial degradation, and absorption by algae and molds. It was concluded that volatilization and bacterial degradation were the dominant processes determining the fate of acetone in streams and rivers.

Chemosphere↗