QSPR for prediction of subcooled vapor pressures (log PL) of polychlorinated trans-azobenzenes

In this study the values of subcooled vapor pressures (log P(L)) were estimated for 209 trans chloroazobenzenes (Ct-ABs) that fill some gaps in analytical and experimental data on these compounds. There are 209 chloro derivatives of trans azobenzenes that are relatively stable and more environmentally relevant than 209 chloro cis congeners. The calculations models were based on the Quantitative Structure-Property Relationship (QSPR) scheme using the semi-empirical method (PM6) in molecular package (MOPAC) software and density functional theory (DFT) method using B3LYP functional and 6-311++G** basis set) in Gaussian 03 software method and the artificial neural networks (ANNs) prediction. The values of log P(L) predicted by models used varied between -3.94 to -2.66 for Mono-; -4.85 to -2.97 for Di-; -5.18 to -3.17 for Tri-; -6.02 to -3.77 for Tetra-; -6.64 to -4.64 for Penta-; -7.36 to -4.76 for Hexa-; -7.54 to -5.79 for Hepta-; -7.75 to -6.64 for Octa-; -7.89 to -7.44 for Nona-Ct-Abs; and -8.09 and -8.13 for Deca-Ct-AB. Based on these values Ct-ABs can be grouped localized among relatively low (log P(L) -4 to -2) and low (log P(L) < -4) mobile Persistent Organic Pollutants (POPs). Both the calculation methods employed were characterized by similar prediction ability of subcooled vapor pressure values of Ct-ABs, while those of PM6 are much more efficient due to a cheaper hardware used and around 300-fold less time spent on calculations.     

Predicting logarithmic values of the subcooled liquid vapor pressure of halogenated persistent organic pollutants with QSPR: How different are chlorinated and brominated congeners?

Logarithmic values of the subcooled liquid vapor pressure (log P_L) were estimated for 1436 polychlorinated and polybrominated congeners of benzenes, biphenyls, dibenzo-p-dioxins, dibenzofurans, diphenyl ethers and naphthalenes by employing the Quantitative Structure–Property Relationships (QSPR) approach. The QSPR model developed with GA–PLS technique was characterized by satisfactory goodness-of-fit, robustness and the external predictive performance (R²Y = 0.970, Q_CV² = 0.970, Q_Ext² = 0.966, RMSE_C = 0.21, RMSE_CV = 0.22 and RMSE_P = 0.22). The externally validated model has been applied to predict subcooled liquid vapor pressure of uninvestigated halogenated persistent organic pollutants. Moreover, a simple arithmetic relationship between logarithmic values of subcooled liquid vapor pressures in pairs of chloro- and bromo-analogues has been found. This relationship can be used for estimating log P_L of a brominated compound, whenever log P_L of its chlorinated counterpart is known, without necessity of performing any time-consuming computations.     

Gas/particle partitioning of polychlorinated dibenzo-p-dioxins and dibenzofurans in atmosphere; evaluation of predicting models

The gas/particle partitioning of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) was measured at three sites for a year in order to monitor the variation of PCDD/Fs levels and describe their partitioning. The air concentrations of PCDD/Fs ranged from 71 to 1161 fg I-TEQ/m³ and large changes in these levels did not correlate with seasonal changes during this study. Different homolog patterns were observed in the gas/particle phase. High chlorinated dioxin/furans dominated the particle phase while low chlorinated dioxin/furans dominated the gas phase. The high correlation coefficient between log [(PCDD/Fs_vap)(TSP)/(PCDD/Fs_pat)] and 1/T was observed in lower chlorinated dioxin/furans unlike in OCDD/F. The slope of homolog ranged from −0.410 to −1.025 and that of 2,3,7,8-substituted isomers ranged from −0.379 to −0.772 in plots of the log partition coefficient (K_p) versus the log subcooled vapor pressure (P_L°).The octanol/air partition coefficient (K_oa)-based model of PCDD/Fs is more compatible with experimental data than those of the Junge–Pankow model that tends to overestimate results, even though both models include some level of uncertainty. However, both models can underestimate the particle phase of PCDD/Fs, especially when the ambient air temperature is extremely low in winter.     

Co-metabolic degradation of naphthalene and pyrene by acclimated strain and competitive inhibition kinetics

A dominant strain named Ochrobactrum sp. was isolated from soils contaminated with coal tar. The batch experiments were carried out to study the co-metabolic degradation of pyrene by Ochrobactrum MB-2 with naphthalene as the main substrate and the effects of several significant parameters such as naphthalene concentration, pH and temperature on removal efficiency were explored. The results showed that Ochrobactrum MB-2 effectively degraded naphthalene and that the addition of naphthalene favored the degradation of pyrene. The maximum elimination efficiency of naphthalene (10?mg?L^?1) and pyrene (1?mg?L^?1) was achieved at pH 7 and 25?°C, and the corresponding values were 99 and 41%, respectively. A competitive inhibition model based on the Michaelis–Menten equation was used to characterize the inhibitory effect of pyrene on naphthalene degradation. The values of the half-saturation coefficient for naphthalene (K_S) and dissociation constant of enzyme-inhibitor complex (K_C) were determined to be 4.93 and 1.38?mg?L^?1, respectively.     

Compound dependence of the relationship log Kow and log BCFL

Linear relatinships between log bioconcentration factor (BCF) and log K^ow for a variety of compounds have been reported many times in the literature. Analysis of the thermodynamics of the two partition processes has, however, shown that they are not analogous and that linear relationships can be expected to have different slopes for structurally unrelated compounds. In this study a set of literature lipid normalized BCF (BCF_L) values of chlorbenzenes (CBs) for rainbow trout and polycyclic aromatic hydrocarbons (PAHs) forDaphnia was put together with literature K_ow values. The slopes of the regression lines for log BCF_L versus log K_ow for the two groups of compounds proved to differ significantly in a statistical test using analysis of variance (ANOVA). The difference, which is of significance for estimates of BCFs in environmental modelling of these types of compounds, is explained by the differences in chemical structure of the two groups of compounds.     

Determination of vapor pressures for chloroguaiacols,chloroveratroles, and nonylphenol by gas chromatography

Vapor pressures of six chlorinated phenols were measured by capillary gas chromatography using a 1.0-m BP-1 bonded phase column. GC-determined vapor pressures (P_GC) were correlated with known liquid-phase vapor pressures (P_L) by the equation: Log P_GC = 1.026 Log P_L — 0.132, r² = 0.975 (vapor pressures in pascals). This relationship was used to estimate P_L for chloroguaiacols, chloroveratroles, and 4-nonylphenol from their experimental P_GC.     

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.     

A study of gas/particle partitioning of SVOCs in the tropical atmosphere of Southeast Asia

Gas- and particle-phase polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) were collected at a tropical site in Southeast Asia over 12-h periods during November and December 2006 to determine their gas/particle distributions by analyzing integrated quartz filter and polyurethane foam samples. Gas/particle partitioning coefficients, K_p, were calculated, and their relationship with the subcooled liquid vapor pressure p_L^o for both PAHs and PCBs was investigated. The regressions of log K_p vs. log p_L^o for most of samples gave high correlations for both PAHs and PCBs and the slopes were statistically shallower than ?1, but they were relatively steeper than those obtained in temperate zones of the Northern Hemisphere. By comparison, the particle-bound fraction of low molecular weight (LMW) PAHs was underestimated by both Junge-Pankow adsorption and K_OA (octanol–air partition coefficient) absorption models, while the predicted values agree relatively better with those observed ones for high molecular weight (HMW) PAHs. In addition, the adsorption onto the soot phase (elemental carbon) predicted accurately the gas/particle partitioning of PAHs, especially for LMW compounds. On the other hand, the K_OA absorption model using the measured organic matter fraction (f_OM) value fitted the PCB data much better than the adsorption model did, indicating the sorption of nonpolar compounds to aerosols might be dominated by absorption into organic matters in this area.     

Determination of vapor pressure-temperature relationships of current–use pesticides and transformation products

Sub-cooled liquid vapor pressures (P_L ⁰) of current–use organochlorine and organophosphate pesticides (chlorothalonil, chlorpyrifos methyl, diazinon, fipronil) and selected transformation products (chlorpyrifos oxon, heptachlor epoxide, oxychlordane, 3,5,6-trichloro-2-pyridinol) were determined at multiple temperatures using the gas chromatography retention time technique. Results were utilized to determine vapor pressure-temperature relationships and to calculate enthalpies of vaporization (ΔH_vap). While results for chlorothalonil and diazinon were comparable with published values, the measured value for fipronil (1.82 × 10^{? 6} Pa) is almost an order of magnitude higher than the reported literature value (3.7 × 10^{? 7} Pa). The availability of vapor pressure temperature relationships for these chemicals will aid in pesticide risk assessment development and improve the effectiveness of mitigation and remediation efforts.     

Performance and efficiency of removal of pharmaceutical compounds from hospital wastewater by lab-scale biological treatment system

The fate of pharmaceuticals after discharged from hospital into wastewater was clarified experimentally by using a new lab-scale conventional activated sludge (CAS) treatment reactor. The 43 target compounds belong to nine therapeutic classes (antivirals, antibacterials, anticancer drugs, psychotropics, antihypertensives, analgesic–antipyretics, contrast media, herbal medicines, and phytoestrogens) were selected with inclusion of 16 newly estimated compounds. The efficiency of the present reactor was estimated by comparing the reaction rate constant of the solid-water partition coefficients (log K_d) between liquid and solid samples and half-life during 48-h experiment obtained by using hospital effluents with those obtained by using STP wastewater. The results that no significant difference in removal efficiency was observed between both water samples (P?>?0.05) indicate high reliability of the present lab-scale reactor. The actual rates of removal when hospital effluent was applied varied widely (mean, 59?±?40%) independent of type of the pharmaceuticals. More than 90% of 17 compounds were removed after 8 h of treatment. However, the values for psychotropics (mean, 19?±?26%) and contrast media (mean, 24?±?17%) were generally low, indicating high stability. The log K_d values ranged from 1.3 to 4.8. Notably, clarithromycin, acridine, and glycitein could be removed in both liquid and solid phases. The dominant removal mechanisms were found to be different for individual pharmaceutical. These results suggest the effectiveness of introduction of the lab-scale biological treatment system for development of a new solution for discharge of pharmaceuticals from hospital.

     

Biosorption and degradation of decabromodiphenyl ether by <Emphasis Type="Italic">Brevibacillus brevis</Emphasis> and the influence of decabromodiphenyl ether on cellular metabolic responses

There is global concern about the effects of decabromodiphenyl ether (BDE209) on environmental and public health. The molecular properties, biosorption, degradation, accumulation, and cellular metabolic effects of BDE209 were investigated in this study to identify the mechanisms involved in the aerobic biodegradation of BDE209. BDE209 is initially absorbed by wall teichoic acid and N-acetylglucosamine side chains in peptidoglycan, and then, BDE209 is transported and debrominated through three pathways, giving tri-, hepta-, octa-, and nona-bromodiphenyl ethers. The C–C bond energies decrease as the number of bromine atoms on the diphenyl decreases. Polybrominated diphenyl ethers (PBDEs) inhibit protein expression or accelerate protein degradation and increase membrane permeability and the release of Cl^?, Na⁺, NH₄ ⁺, arabinose, proteins, acetic acid, and oxalic acid. However, PBDEs increase the amounts of K⁺, Mg²⁺, PO₄ ^3?, SO₄ ^2?, and NO₃ ^? assimilated. The biosorption, degradation, accumulation, and removal efficiencies when Brevibacillus brevis (1 g L^?1) was exposed to BDE209 (0.5 mg L^?1) for 7 days were 7.4, 69.5, 16.3, and 94.6 %, respectively.     

Estimation of K(OA) values of 209 polychlorinated trans-azobenzenes by PM6 and DFT methods

The octanol-air partition coefficients (K(OA)) of all 209 PCt-ABs were determined computationally to fill gaps on their environmentally relevant physical and chemical properties. These properties have been determined using two computational approaches: the semi-empirical quantum chemistry method for property parameterization (PM6) of the molecular orbital package (MOPAC) and density functional theory (DFT) method using B3LYP functional and 6-311++G** basis set in Gaussian 03 software and artificial neural network (ANN) predicting abilities. Both computational methods enabled estimation of log K(OA) partition coefficients of PCt-ABs with a similar accuracy and precision. The PM6 method compared to DFT was highly superior because it requires much less time, manpower and cost of hardware. The determined log K(OA) values of the investigated PCt-ABs for standard condition (25 °C) varied between 8.30 and 8.75 for Mono-; 8.71 and 9.92 for Di-; 9.58 and 10.72 for Tri-; 10.11 and 11.34 for Tetra-, 10.83 and 11.85 for Penta-; 11.24 and 12.36 for Hexa-; 11.87 and 12.66 for Hepta-; 12.31 and 12.97 for Octa-; 12.89 and 13.21 for Nona-Ct-ABs; and 13.17- and 13.49 for Deca-Ct-AB. PCt-ABs, in view of these log K(OA) values, can be classified as compounds of relatively low (Mono-, Di- and some of Tri- Ct-ABs with values of log K(OA) around 8 to 10) environmental mobility (most of Tri- to Nona-Ct-ABs and Deca-Ct-AB homologues with values of log K(OA) >10), and with a potential to be adsorbed by soil particles.     

Verteilungskoeffizienten chlorierter Kohlenwasserstoffe zwischen Muskulatur und Leber bei Fischen

Zusammenfassung  Lipidbezogene Verteilungskoeffizienten (KL_M/L) zwischen Muskelkonzentrationen-(C_ML) und Leberkonzentrationen (C_LL) zweier Friedfischarten Brassen (Abramis brama) und Aalmutter (Zoarces viviparus) ergeben theoriekonform (KL_M/L=C_ML/C_LL=1) nominale Werte um 1 für persistente (hochchlorierte PCB) und Werte über 1 für metabolisierbare lipophile Umweltchemikalien wie chlorierte Cyclohexane oder DDT.      

On-site and off-site atmospheric PBDEs in an electronic dismantling workshop in south China: gas-particle partitioning and human exposure assessment

Gas samples and total suspended particle during work and off work time were investigated on-site and off-site electronic waste dismantling workshop (I- and O-EWDW), then compared with plastic recycling workshop (PRW) and waste incineration plant (WIP). TSP concentrations and total PBDE were 0.36-2.21 mg/m³ and 27-2975 ng/m³ at different workshops, respectively. BDE-47, -99, and -209 were major ∑PBDE congeners at I-EWDW and WIP, while BDE-209 was only dominant congener in PRW and control sites during work time and all sites during off work time. The gas-particle partitioning result was well correlated with the subcooled liquid vapor pressure for all samples, except for WIP and I-EDWD, at park during work time, and residential area during off work time. The predicted urban curve fitted well with measured φ values at O-DEWD during work time, whereas it was slightly overestimated or underestimated for others. Exposure assessment revealed the highest exposure site was I-EDWD.