Criteria for choosing a least squares procedure to extract parameters from exponential decays

For analyzing A exp(-kx) data, least squares procedures cannot be appropriately weighted if the kind of random error in the data is not known. Analyses with both a nonlinear least squares and a log transformation method are tested on simulated data having known errors to determine if the kind of error can be distinguished with these analyses when weighting is not included. The results indicate that some criteria of smaller parameter errors or fit errors can give biased error estimates and/or mislead the experimenter about the underlying error structure. The cases of equal errors vs constant relative errors can be distinguished by using both least squares analyses provided the range of the data and the number of data sets are large enough, using the error in k as a guide.     

Washing of marine coastal sand in a batch reactor: sorption and desorption of BTEX

This study addresses the issues related to decontamination of marine beach sand accidentally contaminated by petroleum products. Sorption and desorption of BTEX (i.e., benzene, toluene, ethylbenzene, and xylene) onto the sand from Uran Beach, located near the city of Mumbai, India, were studied, and isotherms were determined using the bottle point method to estimate sorption coefficients. Alternatively, QSARs (i.e., quantitative structure activity relationships) were developed and used to estimate the sorption coefficients. Experiments for kinetics of volatilization as well as for kinetics of sorption and desorption in the presence of volatilization were conducted in a fabricated laboratory batch reactor. A mathematical model describing the fate of volatile hydrophobic organic pollutants like BTEX (via sorption and desorption in presence of volatilization) in a batch sediment-washing reactor was proposed. The experimental kinetic data were compared with the values predicted using the proposed models for sorption and desorption, and the optimum values of overall mass transfer coefficients for sorption (K(s)a(s)) and desorption (K(d)a(d)) were estimated. This was achieved by minimization of errors while using the sorption coefficients (Kp) obtained from either laboratory isotherm studies or the QSARs developed in the present study. Independent experimental data were also collected and used for calibration of the model for volatilization, and the values of the overall mass transfer coefficient for volatilization (K(g)a(g)) were estimated for BTEX. In these exercises of minimization of errors, comparable cumulative errors were obtained from the use of Kp values derived from experimental isotherms and QSARs.     

Washing of Marine Coastal Sand in a Batch Reactor: Sorption and Desorption of BTEX

ABSTRACT

This study addresses the issues related to decontamination of marine beach sand accidentally contaminated by petroleum products. Sorption and desorption of BTEX (i.e., benzene, toluene, ethylbenzene, and xylene) onto the sand from Uran Beach, located near the city of Mumbai, India, were studied, and isotherms were determined using the bottle point method to estimate sorption coefficients. Alternatively, QSARs (i.e., quantitative structure activity relationships) were developed and used to estimate the sorption coefficients. Experiments for kinetics of volatilization as well as for kinetics of sorption and desorption in the presence of volatilization were conducted in a fabricated laboratory batch reactor. A mathematical model describing the fate of volatile hydrophobic organic pollutants like BTEX (via sorption and desorption in presence of volatilization) in a batch sediment-washing reactor was proposed. The experimental kinetic data were compared with the values predicted using the proposed models for sorption and desorption, and the optimum values of overall mass transfer coefficients for sorption (K_sa_s) and desorption (K_da_d) were estimated.This was achieved by minimization of errors while using the sorption coefficients (K_p) obtained from either laboratory isotherm studies or the QSARs developed in the present study. Independent experimental data were also collected and used for calibration of the model for volatilization,and the values of the overall mass transfer coefficient for volatilization (K_ga_g) were estimated for BTEX. In these exercises of minimization of errors, comparable cumulative errors were obtained from the use of K_p values derived from experimental isotherms and QSARs.     

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.     

Volatilization of 1,2-dibromo-3-chloropropane (DBCP) from soils.

The volatilization of DBCP from soils, as affected by the soil characteristics and application techniques, was studied in a laboratory experiment. The volatilization rate of DBCP applied in water was higher from sandy and silty loam soils than from clay soil. Water added after DBCP application acted as a soil cover, decreasing the volatilization rate. The results obtained with DBCP application in hexane to air-dry soils, indicate that adsorption could be an important factor in reducing the volatilization losses. Diffusion coefficients were calculated from the volatilization parameters, by using a simplified relationship between volatilization losses and diffusion through soil.     

Volatilization of 1,2‐dibromo‐3‐chloropropane (DBCP) from soils

Abstract

The volatilization of DBCP from soils, as affected by the soil characteristics and application techniques, was studied in a laboratory experiment. The volatilization rate of DBCP applied in water was higher from sandy and silty loam soils than from clay soil. Water added after DBCP application acted as a soil cover, decreasing the volatilization rate. The results obtained with DBCP application in hexane to air‐dry soils, indicate that adsorption could be an important factor in reducing the volatilization losses.

Diffusion coefficients were calculated from the volatilization parameters, by using a simplified relationship between volatilization losses and diffusion through soil.     

Simultaneous determination of three herbicides by differential pulse voltammetry and chemometrics

A novel differential pulse voltammetry method (DPV) was researched and developed for the simultaneous determination of Pendimethalin, Dinoseb and sodium 5-nitroguaiacolate (5NG) with the aid of chemometrics. The voltammograms of these three compounds overlapped significantly, and to facilitate the simultaneous determination of the three analytes, chemometrics methods were applied. These included classical least squares (CLS), principal component regression (PCR), partial least squares (PLS) and radial basis function-artificial neural networks (RBF-ANN). A separately prepared verification data set was used to confirm the calibrations, which were built from the original and first derivative data matrices of the voltammograms. On the basis relative prediction errors and recoveries of the analytes, the RBF-ANN and the DPLS (D – first derivative spectra) models performed best and are particularly recommended for application. The DPLS calibration model was applied satisfactorily for the prediction of the three analytes from market vegetables and lake water samples.     

Simultaneous determination of three herbicides by differential pulse voltammetry and chemometrics

A novel differential pulse voltammetry method (DPV) was researched and developed for the simultaneous determination of Pendimethalin, Dinoseb and sodium 5-nitroguaiacolate (5NG) with the aid of chemometrics. The voltammograms of these three compounds overlapped significantly, and to facilitate the simultaneous determination of the three analytes, chemometrics methods were applied. These included classical least squares (CLS), principal component regression (PCR), partial least squares (PLS) and radial basis function-artificial neural networks (RBF-ANN). A separately prepared verification data set was used to confirm the calibrations, which were built from the original and first derivative data matrices of the voltammograms. On the basis relative prediction errors and recoveries of the analytes, the RBF-ANN and the DPLS (D - first derivative spectra) models performed best and are particularly recommended for application. The DPLS calibration model was applied satisfactorily for the prediction of the three analytes from market vegetables and lake water samples.     

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.     

Formaldehyde Concentrations in Wisconsin Mobile Homes

Mobile homes utilize a class of prefabricate construction techniques which rely greatly upon the use of particle board and hardwood plywood paneling for structural components. This has resulted In household sources which may emit formaldehyde into the home, since urea-formaldehyde resins are used as the bonding agent in most pressed wood stocks. A series of 137 mobile home households was investigated to determine indoor formaldehyde exposure concentrations. Homes were selected based on the estimated age of the construction components. Homes were studied serially for a nine-month period, with formaldehyde samples obtained on a monthly basis using a modified NIOSH chromotropic acid procedure. Formaldehyde concentrations were found to range from less than 0.10 ppm to 2.84 ppm. The median exposure concentration was 0.39 ppm. Analysis of variance was performed on each home to discern visit and room measurement effects. Eighty-nine percent of the homes exhibited no measurement placement effects, while only 10 percent failed to demonstrate between-visit variance effects. Regression models were constructed to predict household formaldehyde concentrations. Concentrations exhibited an inverse relationship with the age of the construction materials. A weighted least squares regression model of log of home age predicting temperature-corrected log formaldehyde explained 82 percent of the formaldehyde variation.     

Correlation relationships between physico-chemical properties and gas chromatographic retention index of polychlorinated-dibenzofurans

Correlation relationships between physico-chemical properties including vapor pressures (P), water solubilities (S), Henry's law constants (H(c)), n-octanol-water partition coefficients (K(ow)), sediment-water partition coefficient (K(pw)) and biotic lipid-water partition coefficient (K(bw), bioconcentration factor) of polychlorinated-dibenzofurans (PCDFs) and their gas chromatographic retention indices (GC-RIs) were established. A model equation between GC-RIs (= RI) and these physico-chemical properties (K) of PCDFs was in a form of log K = aRI2 + bRI + c with correlation coefficients (R2) greater than 0.94, except H(c). These equations were derived from six experimental data (five experimental data for log K(bw)) in each physico-chemical properties of PCDFs reported previously. The values of log P, log S, log H(c), log K(ow), log K(pw) and log K(bw) of PCDFs predicted by these equations based on their GC-RIs in the present study derviated from those calculated by the solubility parameters for fate analysis method in a previous study by 0.49, 0.32, 0.11, 0.34, 0.14 and 0.22 log units, respectively.     

Characterizing kinetics of transport and transformation of selenium in water-sediment microcosm free from selenium contamination using a simple mathematical model

This study developed a seven-compartment model for predicting the fate of selenium (Se) in an aquatic environment containing a water-sediment boundary. Speciation of Se in water-sediment microcosms under microaerobic conditions was measured to evaluate first-order kinetics of Se transportation and transformation. The microcosm consisted of a 10-ml solution containing 1mM soluble Se as selenate (Se6+) or selenite (Se4+) and 8 g wet sediment that was free from Se contamination, sampled from the Senri, Yamato, or Yodo Rivers in Osaka, Japan. Stepwise reaction coefficients describing transportation and transformation were determined using an inverse method on this model which includes: selenate (Se(W)6+) and selenite (Se(W)4+) in ponded water; selenate (Se(S)6+) and selenite (Se(S)4+), elemental Se (Se0), organic Se (Se2-) in sediment; and gaseous Se (DMSe). During this 1-month experiment, soluble Se was transported from ponded water to the sediment and Se was transformed sequentially to other Se species through biochemical reactions. Experimental and kinetic analyses indicated quantitatively that the Yamato River microcosm, with its high organic matter content, had a high adsorption rate of soluble Se. The Yodo River microcosm had a low adsorption rate for Se6+ and a low Se reduction rate. The Senri River microcosm had an apparent high volatilization rate of DMSe. The model developed in this study is extremely useful for predicting fate of Se in aquatic environment in the field.     

Effect of water content on transient nonequilibrium NAPL-gas mass transfer during soil vapor extraction

The effect of water content on the volatilization of nonaqueous phase liquid (NAPL) in unsaturated soils was characterized by one-dimensional venting experiments conducted to evaluate the lumped mass transfer coefficient. An empirical correlation based upon the modified Sherwood number, Peclet number, and normalized mean grain size was used to estimate initial lumped mass transfer coefficients over a range of water content. The effects of water content on the soil vapor extraction SVE process have been investigated through experimentation and mathematical modeling. The experimental results indicated that a rate-limited NAPL-gas mass transfer occurred in water-wet soils. A severe mass transfer limitation was observed at 61.0% water saturation where the normalized effluent gas concentrations fell below 1.0 almost immediately, declined exponentially from the initiation of venting, and showed long tailing. This result was attributed to the reduction of interfacial area between the NAPL and mobile gas phases due to the increased water content. A transient mathematical model describing the change of the lumped mass transfer coefficient was used. Simulations showed that the nonequilibrium mass transfer process could be characterized by the exponent beta, a parameter which described the reduction of the specific area available for NAPL volatilization. The nonequilibrium mass transfer limitations were controlled by the soil mean grain size and pore gas velocity, were well described by beta values below 1.0 at low water saturation, and were well predicted with beta values greater than 1.0 at high water saturation.     

Application of different RP-HPLC methods for the determination of the octanol/water partition coefficient of selected tetrachlorobenzyltoluenes.

Reversed-phase high-performance liquid chromatography (RP-HPLC) in both, isocratic and gradient elution mode (stationary phase: LiChrospher 100 RP-18; mobile phase: water/methanol or water/acetonitrile) was used for a renewed determination of octanol/water partition coefficients (Kow) of selected tetrachlorobenzyltoluene (TCBT) isomers. Reported Kow values identify this substance class as very hydrophobic but the data are relatively inconsistent. Based on a series of calibration runs with hydrophobic reference substances of different chemical structure at various eluent compositions we tested different approaches for the evaluation of isocratic retention factors (logk) and found substantial differences between the direct calibration procedure at special methanol volume fractions in the mobile phase (0.95-0.80) and the use of retention factors extrapolated to pure water as eluent (logkw). The logKow values obtained for the TCBTs with the latter approach are around 0.5 units higher and closer to literature data. The gradient elution experiments yield slightly better results compared to the isocratic direct calibration procedure, but not as good as the calibration with log kw. In addition, the use of the RP-HPLC retention factors for estimating sorption coefficients (Koc) of TCBT isomers is discussed.     

Reliable QSAR for estimating Koc for persistent organic pollutants: correlation with molecular connectivity indices

Several recent studies have shown that n-octanol/water partition coefficients may not be a good predictor for estimating soil sorption coefficients of persistent organic pollutants (POPs), defined here as chemicals with log Kow greater than 5. Thus, an alternative QSAR model was developed that seems to provide reliable estimates for the soil sorption coefficients of persistent organic pollutants. This model is based on a set of calculated molecular connectivity indices and evaluated soil sorption data for 18 POPs. The chemical's size and shape, quantified by 1chi, 3chiC and 4chiC(v) indices, have a dominant effect on the soil sorption process of POPs. The developed QSAR model was rationalized in terms of potential hydrophobic interactions between persistent organic pollutants and soil organic matrix. Its high predictive power has been verified by an extensive internal and external validation procedure.     

Lead adsorption to metal oxides and organic material of freshwater surface coatings determined using a novel selective extraction method

Surface coatings were collected in three lakes and a river in China to study the role of the components of natural surface coatings in controlling Pb adsorption. Chemical reagents, 0.02 mol/l NH2OH HCl+0.01 mol/l HNO3, 0.4 mol/l Na2S2O4 and 10% oxalic acid, were employed to extract one or more components from surface coatings, and then Pb adsorption to extracted and unextracted surface coatings was carried out. The observed Pb adsorption to extracted and Unextracted surface coatings were analyzed using the nonlinear least squares fitting (NLSF) to estimate the relative contribution of components to the total Pb adsorption. The amounts of Pb absorption to components described by estimated gamma(max) ranged from 0.1126 to 0.7291 (mol Pb/mol Mn) for Mn, 0.0528 to 0.1927 (mol Pb/mol Fe) for Fe and 0.0196 to 0.1020 (mol Pb/kg COD) for organic material, respectively. In all waters studied, metal oxides contributed most to Pb adsorption with a lesser role indicated for organic material.     

Comparison of photochemical behavior of various humic substances in water: III. Spectroscopic properties of humic substances

Spectral absorption coefficients and fluorescence quantum efficiencies were determined for humic substances from a variety of sources. Specific absorption coefficients k_h, for humic substances at wavelengths λ from 300 to 500 nm can be closely described by the relation Ae^B(450-λ), where A and B are constants. When the k_h values are in units of liter (mg organic carbon)^?1meter^?1 and wavelength λ is in nanometers, mean values of A and B for aquatic humus in the 12 water bodies studied were 0.6±0.3 and 0.014±0.001, respectively. Spectral absorption coefficients of dissolved organic matter in blackwater rivers, of the “yellow substance” in the sea, and of fulvic acids extracted from soils are very similar. Fluorescence quantum yields of humic substances were low and more variable than the absorption coefficients, ranging from 0.0005 to 0.012 with excitation at 350 nm (average of 0.0045±0.0038 for 6 waters). Fluorescence spectra for the humic substances were remarkably similar with maximum emission at 430 to 470 nm. Results of this study can be used to compute photolysis rates of pollutants as a function of depth in natural water bodies.     

Determination and partitioning behavior of perfluoroalkyl carboxylic acids and perfluorooctanesulfonate in water and sediment from Dianchi Lake, China

Perfluorinated compounds (PFCs) have received much attention on their distribution in various matrices including water bodies, precipitations, sediment and biota in different areas globally, however, little attention has been paid to their occurrence and distribution in urban lakes. In this study, water and sediment samples collected from 26 sites in Dianchi Lake, a plateau urban lake in the southwestern part of China were analyzed via high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) for ten analytes involving nine perfluoroalkyl carboxylic acids (PFOAs) and perfluorooctanesulfonate (PFOS). Total levels of PFCs were 30.98 ± 32.19 ng L(-1) in water and 0.95 ± 0.63 ng g(-1) in sediment. In water samples PFOA was the dominant PFC contaminant, with concentrations ranging from 3.41 to 35.44 ng L(-1), while in sediments PFOS was the main PFC contaminant at levels from 0.07-0.83 ng g(-1) dry weight. Field-based sediment water distribution coefficients (K(D)) were calculated and corrected for organic carbon content (K(oc)), which reduced variability among samples. The log K(oc) ranged from 2.54 to 3.57 for C8-C12 perfluorinated carboxylic acids, increasing by 0.1-0.4 log units with each additional CF2 moiety. The log K(oc) of PFOS was 3.35 ± 0.32. Magnitudes and trends in log K(D) or log K(oc) appeared to agree well with previously published laboratory data. Results showed that different PFC composition profiles were observed for samples from the lake water and sediments, indicating the presence of dissimilar characteristics of the PFCs compounds, which is important for PFC fate modeling and risk assessment.