Experimental octanol/water partition coefficients of chlorinated paraffins

Octanol/water partition coefficients (K_OW) of chlorinated paraffins (CPs) from a commercial mixture (‘Cereclor 60L’) were determined using a “slow-stirring” method. Log K_OW values for the different congener groups ranged from 5.85 to 7.14. Equilibrium was reached within a few days, and K_OW values were the same at two CP-concentrations. A clear relationship is found between the total number of chlorine and carbon atoms and log K_OW for the CP-congener groups and a series of smaller chlorinated alkanes from the literature.     

Critical evaluation of the measurement of the 1- octanol / water partition coefficient of hydrophobic compounds

Data on the experimental measurement of the octanol/water partition coefficient (K_ow) with hydrophobic compounds was assembled from the literature. The precision, characterised by the standard deviation of mean K_ow values based on five commonly used experimental methods, over an extended K_ow range was found to generally decline with compounds having log K_ow > 5.5. In the log K_ow range from 2.0 to 5.5 there was little difference between the mean values of log K_ow determined by the different methods but major differences occured with compounds having log K_ow > 5.5. The agreement between calculated ClogP values and K_ow values derived from individual experimental methods indicated that ClogP overestimates log K_ow from all experimental methods with compounds having values greater than 5.5.     

Estimation of octanol/water partition coefficients for organic pollutants using reverse-phase HPLC

Octanol/water partition coefficients (K_ow's) of organic solutes are estimated with reasonable accuracy (standard deviation ± 0.25 log K_ow units) by elution from a C-18 column with 75:25 (v/v) MeOH-H₂O, based on results with 37 test compounds. Changes in solute activity coefficients from water to 75% MeOH account for the slope of the log K_ow-log k' plot, where k' is the HPLC capacity factor. The method is used to estimate K_ow's for 25 additional organic compounds, and some disparities between the results and those calculated using group additivity-constitutive factors are noted.     

Octanol/water partition coefficients for environmentally important organic compounds

Partition coefficients P_O,w ⁽ⁱ⁾ describing the distribution of a solute i onto coexisting phases of 1-octanol and water are needed in a large variety of applications. They can be measured directly by HPLC as long as log P_O,w ⁽ⁱ⁾≧ 3.5. For more hydrophobic substances, several experimental procedures have been proposed in the literature. The reliability of those methods is questionable. Therefore, in the present work, P_O,w ⁽ⁱ⁾ is determined experimentally by three HPLC methods using reversed-phase HPLC [1]. Results from different procedures are compared critically. The method of Braumann [2] proved to be superior over the OECD-guidelines [3]. It was therefore applied to determine octanol/water partition coefficients for 23 substances at 25 °C. For eight of those substances (4-methylindole; 9-(hydroxymethyl)anthracene; N-ethylcarbazol; ethylcyclohexane; trans-2-octene; l,l-dimethyl-(ethy])cyclohexane; heptylbenzene; 4-dodecyl-l,3-benzenediol) no experimentally determined number for P_O,w ⁽ⁱ⁾ has been published before.     

Temperature dependencies of Henry's law constants and octanol/water partition coefficients for key plant volatile monoterpenoids

To model the emission dynamics and changes in fractional composition of monoterpenoids from plant leaves, temperature dependencies of equilibrium coefficients must be known. Henry's law constants (H(pc), Pa m3 mol(-1) and octanol/water partition coefficients (K(OW), mol mol(-1)) were determined for 10 important plant monoterpenes at physiological temperature ranges (25-50 degrees C for H(pc) and 20-50 degrees C for K(OW)). A standard EPICS procedure was established to determine H(pc) and a shake flask method was used for the measurements of K(OW). The enthalpy of volatilization (deltaH(vol)) varied from 18.0 to 44.3 kJ mol(-1) among the monoterpenes, corresponding to a range of temperature-dependent increase in H(pc) between 1.3- and 1.8-fold per 10 degrees C rise in temperature. The enthalpy of water-octanol phase change varied from -11.0 to -23.8 kJ mol(-1), corresponding to a decrease of K(OW) between 1.15- and 1.32-fold per 10 degrees C increase in temperature. Correlations among physico-chemical characteristics of a wide range of monoterpenes were analyzed to seek the ways of derivation of H(pc) and K(OW) values from other monoterpene physico-chemical characteristics. H(pc) was strongly correlated with monoterpene saturated vapor pressure (P(v)), and for lipophilic monoterpenes, deltaH(vol) scaled positively with the enthalpy of vaporization that characterizes the temperature dependence of P(v) Thus, P(v) versus temperature relations may be employed to derive the temperature relations of H(pc) for these monoterpenes. These data collectively indicate that monoterpene differences in H(pc) and K(OW) temperature relations can importantly modify monoterpene emissions from and deposition on plant leaves.     

Feasibility of a simple laboratory approach for determining temperature influence on SPMD–air partition coefficients of selected compounds

Semipermeable membrane devices (SPMDs) are a widely used passive sampling methodology for both waterborne and airborne hydrophobic organic contaminants. The exchange kinetics and partition coefficients of an analyte in a SPMD are mediated by its physicochemical properties and certain environmental conditions. Controlled laboratory experiments are used for determining the SPMD–air (K_sa's) partition coefficients and the exchange kinetics of organic vapors. This study focused on determining a simple approach for measuring equilibrium K_sa's for naphthalene (Naph), o-chlorophenol (o-CPh) and p-dichlorobenzene (p-DCB) over a wide range of temperatures. SPMDs were exposed to test chemical vapors in small, gas-tight chambers at four different temperatures (−16, −4, 22 and 40 °C). The exposure times ranged from 6 h to 28 d depending on test temperature. K_sa's or non-equilibrium concentrations in SPMDs were determined for all compounds, temperatures and exposure periods with the exception of Naph, which could not be quantified in SPMDs until 4 weeks at the −16 °C temperature. To perform this study the assumption of constant and saturated atmospheric concentrations in test chambers was made. It could influence the results, which suggest that flow through experimental system and performance reference compounds should be used for SPMD calibration.     

Assessment of reverse-phase chromatographic methods for determining partition coefficients

The possibility of using reverse-phase High Performance Liquid Chromatography (HPLC) and Thin Layer Chromatography (TLC) for determining partition coefficients is assessed. Whereas HPLC has been adequately validated and is recommended, TLC requires further validation. A method of calculating partition coefficients from molecular fragmental constants is also noted as being useful in certain cases.     

Salting-in and salting-out effects of ionic and neutral osmotica on limonene and linalool Henry's law constants and octanol/water partition coefficients

Foliar emission rates of plant-generated volatile monoterpenes depend on monoterpene partitioning between air, aqueous and lipid-phases in the leaves. While Henry's law constants (H pc, equilibrium gas/water partition coefficient) and octanol/water partition coefficients (K OW) for pure water have been previously used to simulate monoterpene emissions from the leaves, aqueous phase in plants is a complex solution of electrolytes and neutral osmotica. We studied the effects of dissociated compounds KCl and glycine and sugars glucose, sorbitol and sucrose with concentrations between 0 and 1M on H pc and K OW values for limonene and linalool. Linalool with ca. 1500-fold lower H(pc) (2.62 Pa m(3)mol(-1) for pure water at 30 degrees C) and ca. 30-fold lower K OW (955 mol mol(-1) for pure water at 25 degrees C) is the more hydrophilic compound of the two monoterpenes. H pc of both monoterpenes increased with increasing concentration of both ionic compounds and sorbitol, but decreased with increasing glucose and sucrose concentrations. The salting-out coefficients for H pc (kH) were ca. an order of magnitude larger for more hydrophilic compound linalool than for more hydrophobic limonene. For linalool, co-solutes modified H pc by 30-50% at the highest concentration (1M) tested. The effect of temperature on the salting-out coefficient of KCl was minor. As with H pc, K OW increased with increasing the concentration of KCl, glycine and sorbitol, and decreased with increasing glucose and sucrose concentrations. For limonene, co-solutes modified K OW by 20-50% at the highest concentration used. For linalool, the corresponding range was 10-35%. Salting-out coefficients for H pc and K OW were correlated, but the lipid-solubility was more strongly affected than aqueous solubility in the case of limonene. Overall, these data demonstrate physiologically important effects of co-solutes on H pc and K OW for hydrophilic monoterpenes and on K OW for hydrophobic monoterpenes that should be included in current emission models.     

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.     

Structural and chromatographic predictors of n-octanol/water partition coefficients

The estimation of octanol/water coefficients by means of chromatographic and structural parameters may be a useful method for the prediction of ecotoxicological behaviour of chemical compounds. Experimental aspects and validity of some parameters are discussed with respect to heterocyclic aromatic hydrocarbons, including benzofurans. It is concluded that reverse phase chromatographic systems and molecular connectivities are promising predictors of log K_ow.     

Vapour pressures, aqueous solubilities, Henry's Law constants, and octanol/water partition coefficients of a series of mixed halogenated dimethyl bipyrroles

Basic physical-chemical properties of five bromine and chlorine containing mixed halogenated dimethyl bipyrroles (HDBPs) were determined using established methods. Subcooled liquid vapour pressures (P(o)(L,25)), aqueous solubilities (S(w,25)), and octanol/water partition coefficients (K(ow)) were determined using the gas chromatography-retention time, generator column, and slow-stirring methods, respectively. Henry's Law constants (H25) were estimated using experimentally-derived P(o)(L) and S(w,25) data. Values of all four properties were generally similar to those reported for other polyhalogenated aromatic compounds [P(o)(L,25) = (7.55-191) x 10(-6) Pa; S(w,25) = (1.0-1.9) x 10(-5) g/l; log K(ow) = 6.4-6.7; H25 = 0.0020-0.14 Pa m3/mol]. The effect of replacing a chlorine with a bromine atom significantly decreased P(o)(L,25) (log P(o)(L,25) = -0.4197 (# bromine atoms) - 2.643, p<0.01) and H25 (log H25 = -0.508 (# bromine atoms) + 0.394, p<0.02). There were no significant effects of bromine/chlorine substitution on S(w,25) or K(ow). A simple Level I equilibrium partitioning model predicted the environmental behaviour of HDBPs to be similar to a tetrabrominated diphenyl ether. Only slight differences in behaviour amongst HDBP congeners were predicted since substitution of a bromine for a chlorine (Cl/Br substitution) atom had less effect than H/Cl or H/Br substitution on P(o)(L,25), S(w,25), H25, and K(ow).     

N-octanol/water partition coefficients by reverse phase liquid chromatography/mass spectrometry for eight tetrachlorinated planar molecules

N-octanol/water partition coefficients (K_ow's) were determined using reverse phase liquid chromatography for eight tetrachlorinated planar molecules. The log K_ow's are as follows: 2,3,7,8-, 1,2,3,4-, 1,3,7,9-, and 1,3,6,8-tetrachlorodibenzo-p-dioxins, 7.02, 7.18, 7.06, and 7.20, respectively; 2,3,7,8-tetrachlorodibenzofuran, 5.82; 1,3,6,8-tetrachloro-9H-carbazole, 5.75; 2,3,6,7-tetrachlorobiphenylene, 6.14; and 3,3′,4,4′-tetrachlorobiphenyl, 5.81. The accuracy of these values was estimated to be ca. ± 0.50.Reevaluation of log K_ow's previously determined using reverse phase liquid chromatography for chlorinated dibenzofurans and dibenzo-p-dioxins yielded values of ca. 7.0 for the tetrachlorodibenzo-p-dioxins, also. This reevaluation was performed by using experimental rather than estimated log K_ow's in the correlative relationship. In addition, these values suggest that the log K_ow's for dibenzo-p-dioxins and dibenzofurans range from ca. 4.0 for the unsubstituted parent molecule to ca. 8.6 for the octachlorinated compounds; much lower than previously reported.     

Evaluation of reverse phase liquid chromatography/mass spectrometry for estimation of n-octanol/water partition coefficients for organic chemicals

A reverse-phase high pressure liquid chromatography/mass spectrometry (HPLC/MS method was developed for estimating n-octanol/water partition coefficients (K_ow) of anthropogenic molecules in complex chemical mixtures (e.g., complex effluents and solid waste leachates). The average error for an estimated log K_ow was ca. 0.5 and this error was similar for both aliphatic and aromatic compounds. The minimum level of detection using the total ion current profile generally decreased with increasing molecular weight between 100 and 600 daltons. Results obtained demonstrate that the HPLC/MS method is a viable technique for estimating log K_ow's of anthropogenic chemicals in complex environmental samples.     

Correlation between the bioconcentration potential of organic environmental chemicals in humans and their n-octanol/water partition coefficients

A quantitative relationship was found to exist between the lipophilicity (n-octanol/water partition coefficient) of pentachlorophenol, dieldrin, hexachlorobenzene, 2,3,7,8-tetrachlorodibenzo-p-dioxin, Σ DDT, polychlorinated biphenyls, α-, β-, γ- and δ -hexachlorocyclohexane and their bioconcentration factor (BCF) in human adipose tissue. The equations were used to predict the bioconcentration factors of some chlorinated aromatic chemicals.     

Aqueous solubility, Henry's law constants and air/water partition coefficients of n-octane and two halogenated octanes

New data on the aqueous solubility of n-octane, 1-chlorooctane and 1-bromooctane are reported between 1 degree C and 45 degrees C. Henry's law constants, K(H), and air/water partition coefficients, K(AW), were calculated by associating the measured solubility values to vapor pressures taken from literature. The mole fraction aqueous solubility varies between (1.13-1.60)x10(-7) for n-octane with a minimum at approximately 23 degrees C, (3.99-5.07)x10(-7) for 1-chlorooctane increasing monotonically with temperature and (1.60-3.44)x10(-7) for 1-bromooctane with a minimum near 18 degrees C. The calculated air-water partition coefficients increase with temperature and are two orders of magnitude lower for the halogenated derivatives compared to octane. The precision of the results, taken as the average absolute deviations of the aqueous solubility, the Henry's law constants, or the air/water partition coefficients, from appropriate smoothing equations as a function of temperature is of 3% for n-octane and of 2% and 4% for 1-chlorooctane and 1-bromooctane, respectively. A new apparatus based on the dynamic saturation column method was used for the solubility measurements. Test measurements with n-octane indicated the capability of measuring solubilities between 10(-6) and 10(-10) in mole fraction, with an estimated accuracy better than +/-10%. A thorough thermodynamic analysis of converting measured data to air/water partition coefficients is presented.     

Vapour pressures, aqueous solubility, Henry's law constants and air/water partition coefficients of 1,8-dichlorooctane and 1,8-dibromooctane

New data on the vapour pressures and aqueous solubility of 1,8-dichlorooctane and 1,8-dibromooctane are reported as a function of temperature between 20 °C and 80 °C and 1 °C and 40 °C, respectively. For the vapour pressures, a static method was used during the measurements which have an estimated uncertainty between 3% and 5%. The aqueous solubilities were determined using a dynamic saturation column method and the values are accurate to within ±10%. 1,8-Dichlorooctane is more volatile than 1,8-dibromooctane in the temperature range covered (p_sat varies from 3 to 250 Pa and from 0.53 to 62 Pa, respectively) and is also approximately three times more soluble in water (mole fraction solubilities at 25 °C of 5.95 × 10⁻⁷ and 1.92 × 10⁻⁷, respectively). A combination of the two sets of data allowed the calculation of the Henry’s law constants and the air water partition coefficients. A simple group contribution concept was used to rationalize the data obtained.     

Techniques for determining the chemical composition of aerosol sulfur compounds

An extensive critical review is given of the methods presently available for the determination of the chemical composition of aerosol sulfur compounds. Some recent typical results employing the methods are presented. The advantages, limitations and future promises of the techniques are discussed. Potential problems associated with the alteration of chemical composition during sampling are illustrated. The utility of general analytical and wet chemical identification techniques are demonstrated. A sequential selective solvent separation scheme and the use of thermal volatilization for the determination of various sulfates are described and illustrative results given. The application of thermometric titrimetry and electron spectroscopy for the identification of oxidation states is presented and evaluated. A discussion is given for the use and utility of i.r. and laser Raman spectroscopic techniques for the identification of sulfate species. A diffusion battery processor technique for sampling suboptical particles is described and its utility in conjunction with chemical analysis of these size separated particles evaluated.