Estimating octanol-air partition coefficients with octanol-water partition coefficients and Henry's law constants

The octanol-air partition coefficient (K(OA)) is useful for predicting the partitioning behavior of organic compounds between air and environmental matrices such as soil, vegetation, and aerosol particles. At present, experimentally determined K(OA) values are available for only several hundred compounds. Therefore, the ability to estimate K(OA) is necessary for screening level evaluation of most chemicals. Although it is possible to estimate K(OA) from the octanol-water partition coefficient (K(OW)) and Henry's law constant (HLC), various concerns have been raised in regard to the usability of this estimation methodology. This work examines the accuracy and usability of K(OW) and HLC in application to a comprehensive database set of K(OA) values for screening level environmental assessment. Results indicate that K(OW) and HLC can be used to accurately predict K(OA) even when estimated K(OW) and HLC values are used. For an experimental dataset of 310log K(OA) values for different compounds, the K(OW)-HLC method was statistically accurate as follows: correlation coefficient (r2): 0.972, standard deviation: 0.526, absolute mean error: 0.358 using predominantly experimental K(OW) and HLC values. When K(OW) and HLC values were estimated (using the KOWWIN and HENRYWIN programs), the statistical accuracy was: correlation coefficient (r2): 0.957, standard deviation: 0.668, absolute mean error: 0.479.     

Molecular hologram derived quantitative structure-property relationships to predict physico-chemical properties of polychlorinated biphenyls

Polychlorinated biphenyls (PCBs) congeners with various degrees of chlorination and substitution patterns are among the most widespread and persistent man-made organic pollutants. They are toxic, lipophilic and tend to be bioaccumulated. The knowledge of the physico-chemical properties is very useful to explain the environmental behavior of PCBs and to perform an exposure assessment. In this paper, we have used a new molecular representation, the molecular hologram, to generate quantitative structure-property relationship models to predict the physico-chemical properties of biphenyl and all of its chlorinated congeners. The investigated properties include 1-octanol/water partition coefficient (logK(ow)), aqueous solubility (-logS(w)), aqueous activity coefficient (-logY(w)), Total molecular surface area, Henry's law constant (logH). The results show that this new quantitative structure-activity relationship approach presents highly predictive models for important physico-chemical properties of PCBs.     

Determination of octanol-air partition coefficients and supercooled liquid vapor pressures of organochlorine pesticides

Octanol-air partition coefficients (K_OA) and supercooled liquid vapor pressures (P_L) of nine organochlorine pesticides (OCPs) including p,p′-DDE, p,p′-DDD, o,p′-DDT, o,p′-DDE, o,p′-DDD, α-HCH, β-HCH, γ-HCH, δ-HCH were determined as functions of temperature using a gas chromatographic retention time method. Among them, the K_OA of o,p′-DDE and o,p′-DDD and the P_L of o,p′-DDE, o,p′-DDD, β-HCH and δ-HCH were determined for the first time. The determined K_OA and P_L values of investigated compounds at 25°C ranged from 3.14 × 10⁷ (α-HCH) to 3.76×10⁹ (p,p′-DDD), and 8.95×10^{? 4} Pa (p,p′-DDD) to 1.08×10^{? 1} Pa (α-HCH), respectively. The K_OA and P_L data were compared with published data. The K_OA values of o,p′-DDT at 25°C were 3.23×10⁹, higher than o,p′-DDE (1.02×10⁹) and o,p′-DDD (2.01×10⁹), indicating o,p′-DDT were more preferred to partition in soil compared with the metabolites. The K_OA values were lower and P_L values were higher for o,p′-DDE and o,p′-DDD, compared with their p,p′-isomeric counterparts, leading to a potential difference in behavior and fate of these isomers. The discrepancies among chemicals are obvious, which reflected in the increasing K_OA and decreasing P_L values in order of α-HCH, γ-HCH, β-HCH, δ-HCH, o,p′-DDE, p,p′-DDE, o,p′-DDD, o,p′-DDT, p,p′-DDD. For each compound, the LogK_OA decreased linearly with reciprocal absolute temperature, while LogP_L had a significant positive correlation with the inverse absolute temperature. The present study suggested that the method of gas chromatographic retention time was appropriate to measure the K_OA and P_L of a number of OCPs.     

Octanol–air partition coefficients of polybrominated biphenyls

The octanol–air partition coefficients (K_OA) for PBB15, PBB26, PBB31, PBB49, PBB103 and PBB153 were determined as a function of temperature using a gas chromatographic retention time technique with 1,1,1-trichloro-2,2-bis (4-chlorophenyl) ethane (p,p′-DDT) as a reference substance. The internal energies of phase change from octanol to air (Δ_OAU) were calculated for the six compounds and were in the range from 74 to 116 kJ mol⁻¹. Simple regression equations of log K_OA versus relative retention times (RRTs) on gas chromatography (GC), and log K_OA versus molecular connectivity indexes (MCI) were obtained, for which the correlation coefficients (r²) were greater than 0.985 at 283.15 K and 298.15 K. Thus the K_OA values of the remaining PBBs can be predicted by using their RRTs and MCI according to these relationships.     

Applications of polychlorinated biphenyls

Background, aim, and scope  

In the 50 years or so that polychlorinated biphenyls (PCBs) were manufactured in the USA and elsewhere, they were widely used in numerous applications because of their desirable properties. The purpose of this paper is to review and summarize in one place the factual information about the uses of PCBs, as well as to correct some misconceptions that have arisen over the years. The focus is on applications in the USA for which there is ample documentation. However, use patterns were probably similar worldwide.     

Reductive dechlorination for remediation of polychlorinated biphenyls

Technologies such as thermal, oxidative, reductive, and microbial methods for the remediation of polychlorinated biphenyls (PCBs) have previously been reviewed. Based on energy consumption, formation of PCDD/F, and remediation efficiency, reductive methods have emerged as being advantageous for remediation of PCBs. However, many new developments in this field have not been systematically reviewed. Therefore, reductive technologies published in the last decade related to remediation of PCBs will be reviewed here. Three categories, including catalytic hydrodechlorination with H₂, Fe-based reductive dechlorination, and other reductive dechlorination methods (e.g., hydrogen-transfer dechlorination, base-catalyzed dechlorination, and sodium dispersion) are specifically reviewed. In addition, the advantages of each remediation technology are discussed. In this review, 108 articles are referenced.     

Neurotoxicology of ortho-substituted polychlorinated biphenyls

Ortho-substituted, non-planar PCBs reduce dopamine content in both nonhuman primate brain and pheochromocytoma (PC12) cells. Planar, dioxin-like, congeners have no effect on dopamine content in PC12 cells. Additional in-vitro results indicate that dopamine reduction by PCBs is due to inhibition of tyrosine hydroxylase activity.     

Partitioning behavior of polychlorinated biphenyls

Partitioning of polychlorinated biphenyls (PCBs) among several idealized environmental compartments was investigated using equilibrium conditions. Simulations with single equilibrations suggested that PCB mixtures do not weather significantly. However, simulations with multiple equilibrations of a selected phase with renewed phases suggested that PCB mixtures have the potential to weather. These simulations were strongly influenced by temperature; both the compositions and total amount of the PCBs in each phase at equilibrium changed significantly with temperature. These simulations lend support to the hypothesis that lower and higher chlorinated PCBs behave differently in the environment.     

Mass transfer coefficients for volatilization of polychlorinated biphenyls from the Hudson River,New York measured using micrometeorological approaches

Air–water exchange is an important process controlling the fate of many organic chemicals in the environment. Modeling this process is hampered by the lack of direct observations. Thus, the purpose of this work was to derive direct measurements of the mass transfer coefficients for air–water exchange (v_aw) of polychlorinated biphenyls (PCBs) that may be used to check the validity of values derived from tracer gas experiments. v_aw values for PCBs were determined using previously published turbulent fluxes divided by the corresponding dissolved phase concentrations. The median v_aw values for each homolog decreased with increasing molecular weight and ranged from 0.29 for hexachlorobiphenyls to 2.2 m d^?1 for monochlorobiphenyls with a propagated uncertainty of about 70%, lower than in previous studies. Due to relatively low wind speeds and possible sorption of PCBs to colloids, these numbers may be biased low. These field measurements of v_aw differ by as much as a factor of 23 from predictions based on the widely-used Whitman two-film model. Therefore a new formulation for the calculation of v_aw based on field measurements is needed. This study demonstrates that micrometeorological approaches are a viable option for the measurement of v_aw for hydrophobic organics such as PCBs and should be used to generate enough field data on the air–water exchange of hydrophobic organics to allow the development of new predictive models.     

Ultrasonically-assisted electrocatalytic dechlorination of polychlorinated biphenyls

Commercial mixtures of PCB's (Aroclors) were dechlorinated to biphenyl by ultrasonically-assisted electroreduction with and without soluble catalysts. Ultrasound increased the rate of electrolysis at stirred-mercury-pool electrodes by 2- to 3-fold.