QSPR study on soil sorption coefficient for persistent organic pollutants

Quantitative structure-property relationship (QSPR) models of soil sorption coefficients for 32 persistent organic pollutants were constructed using our recently introduced Lu index and novel distance-based atom-type DAI topological indices. Using multiple linear regression technique, a 6-variable model was obtained with the correlation coefficient of estimations (R) being 0.95, and the standard error of estimations (s) being 0.23, and the correlation coefficient (R(cv)) and the standard error (s(cv)) in the leave-4-out cross-validation procedure are 0.90 and 0.31, respectively. The results in this study indicate that soil sorption coefficients of POPs are dominated by molecular size while some DAI indices have smaller influence.     

A comparison of air quality indices for a port and harbour region in India

The present paper discusses and compares four different air quality indices, viz. arithmetic, multiplicative, unweighted arithmetic, and unweighted multiplicative, which were considered for characterising the coastal air quality at the Jawaharlal Nehru Port, Mumbai, India. Suspended particulate matter, oxides of nitrogen, and sulphur dioxide were used as the parameters of air quality indices. Value function graphs for above-mentioned variables were developed using Indian ambient air quality standards for different areas. Product moment correlation coefficients for various air quality indices were determined using the SPSS software package to evaluate correlation among various indices.     

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.     

A new method of predicting of gas chromatographic retention indices for polychlorinated dibenzofurans (PCDFs)

A new method has been developed to describe the quantitative relationship between molecular structures of PCDFs and their gas chromatographic retention indices on a 30-m fused silica column coated with DB-5 stationary phase. The regression equation is derived with a multiple correlation coefficient greater than 0.9995. The highest residual is 20 index units. The standard deviation is less than 7 index units. Using this regression equation, the retention indices of PCDFs for which data is not available have also been predicted.     

Comparison of screening methods for the estimation of adsorption coefficients on soil

The HPLC screening method for estimating soil sorption coefficients was compared to other QSAR approaches based on log P_ow, connectivity indices, molar refraction and molecular fragment approaches. For the data set under consideration (66 compounds from different chemical classes) only the HPLC screening method and, to a lesser extend, the log P_ow method proved to be suitable for predicting soil sorption coefficients with acceptable accuracy. The HPLC method and the regression with log P_ow were then cross-validated.     

Evaluating spectroscopic and chromatographic techniques to resolve dissolved organic matter via end member mixing analysis

Real-time or near real-time in-situ monitoring of dissolved organic matter (DOM) composition in natural waters and engineered treatment systems provides critical information to water quality scientists and engineers, particularly when the monitoring techniques can provide some information about the chemical nature of DOM. The efficacy of various indices derived from rapid, low-cost spectroscopic and chromatographic techniques to discriminate DOM composition was tested for samples prepared from well-defined mixtures of purified Aldrich humic acid (PAHA) and Suwannee River fulvic acid (SRFA). Sensitivities of the discrimination indices were examined by comparing (1) the differences between measured values and those predicted based from mass balance and the end member characteristics, and (2) the linear correlations between index values and mass ratios of the DOM mixtures. Size exclusion chromatography (SEC) results revealed that the weight-average molecular weight (MW(w)) may be a useful approach for tracking DOM mixing processes, although the number-average molecular weight (MW(n)) may be better for distinguishing different DOM compositions. Specific ultraviolet absorbance measured at 254 nm (SUVA(254)) performed better as a discrimination index than did two previously recommended absorbance ratios, both in terms of making better predictions of intermediate compositions and in exhibiting a more linear correlation with PAHA mass ratio. Several well-defined peaks in the derivative absorption spectra (301 and 314 nm for the first derivative, 217 nm for the third derivative, and 211 and 224 nm for the fourth derivative) also were found to be promising potential DOM discrimination indices. Finally, a fluorescence ratio based on humic- versus fulvic-like fluorescence proved to be a superior DOM discrimination index for the two DOM end members studied here. In general, this study illustrates the evaluation process that should be followed to develop rapid, low-cost discrimination indices to monitor DOM compositions based on end member mixing analyses.     

Removal of aqueous-phase polynuclear aromatic hydrocarbons using aspen wood fibers

Roadway runoff derived polynuclear aromatic hydrocarbons (PAHs) impact the quality of surface and ground water. Inexpensive aspen wood fibers have been investigated as a means to remove dissolved PAH under laboratory conditions. Our isotherm experiments demonstrated that the uptake of naphthalene, fluorene, anthracene, and pyrene required up to 12.5 days to reach equilibrium. Aspen wood-water sorption coefficients, Kww, were linearly correlated to octanol-water partition coefficients and the molecular weight of the studied PAH compounds. The correlation between Kww and molecular weight was the most significant. Column experiments were carried out to study the sorption and desorption of fluorene, anthracene, and pyrene under dynamic conditions. The results indicate linear sorption, but non-linear desorption behavior. The degree of desorption was inversely correlated to a compound's hydrophobicity. Flow interruption experiments showed that sorption and desorption was rate limited. A mass balance of the sorption and desorption tests indicated that sorptive uptake exceeded desorptive release over a given number of pore volumes. Further, absolute mass-removal efficiency increased with the molecular weight and hydrophobicity of the PAH compound. Batch and column studies demonstrated that aspen wood has the potential to become an effective remedial agent for PAH in stormwater runoff or other PAH contaminated waters.     

Prediction of octanol--air partition coefficients of semivolatile organic compounds based on molecular connectivity index

A new method has been developed to describe the quantitative relationship between the octanol-air partition coefficients and molecular connectivity indexes of semivolatile organic compounds such as polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated naphthalenes (PCNs), polycyclic aromatic hydrocarbons (PAHs), chlorobenzenes (CBs), polybrominated diphenyl ethers (PBDEs). The stepwise multiple linear regression was used to derive six equations with correlation coefficients greater than 0.99 except for PBDEs' (0.96). The largest relative error is 4.6%, and the standard deviation is less than 1.83 log units. Compared with the data obtained from the relevant experiments, the results of prediction are very accurate.     

Predicting aoueous solubility of organic nonelectrolytes from molar volume

Correlation equations relating aqueous solubility to molar volume and aqueous solubility to total molecular surface area were derived by regression analysis for several chemical classes which included both liquids and solids. These were similar to equations relating solubility with total molecular surface area and had similar correlation coefficients. The physical significance of the regression parameters obtained is discussed.     

Contamination by polycyclic aromatic hydrocarbons in the Jiulong River Estuary and Western Xiamen Sea, China

The distribution of 16 polycyclic aromatic hydrocarbons (PAHs) was determined in water, sediment and pore water of the Jiulong River Estuary and Western Xiamen Sea, China. Total PAH concentrations varied from 6.96 to 26.9 microg/l in water, 59-1177 ng/ g dry weight in surficial sediments, and 158-949 microg/l in pore water. The PAHs were present in higher levels in pore water than in surface water, due possibly to higher concentrations of dissolved organic carbon or colloids with which the hydrophobic pollutants were strongly associated. Such a concentration gradient implies a potential flux of pollutants from sediment pore water to overlying water. The levels of PAHs in water and pore water were significantly higher than those found in 1998, suggesting recent inputs of these compounds into the area and re-working of sediment phase. The composition pattern of PAHs in the three phases was dominated by high molecular weight PAHs, in particular 5-ring PAHs. The salinity profile of dissolved PAHs suggested that they all behaved non-conservatively due to deviation from the theoretical dilution line. No correlation was found between PAH concentrations in sediment and those in pore water, and the correlation between the partition coefficients of PAHs and sediment organic carbon content was not significant, suggesting the complexity of the partition behaviour of PAHs. As a result of high PAH concentrations in water and pore water, it is likely that they may have caused mortality to certain exposed organisms.     

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.     

Personal exposure to fine particulate matter in elderly subjects: relation between personal, indoor, and outdoor concentrations

The time-series correlation between ambient levels, indoor levels, and personal exposure to PM2.5 was assessed in panels of elderly subjects with cardiovascular disease in Amsterdam, the Netherlands, and Helsinki, Finland. Subjects were followed for 6 months with biweekly clinical visits. Each subject's indoor and personal exposure to PM2.5 was measured biweekly, during the 24-hr period preceding the clinical visits. Outdoor PM2.5 concentrations were measured at fixed sites. The absorption coefficients of all PM2.5 filters were measured as a marker for elemental carbon (EC). Regression analyses were conducted for each subject separately, and the distribution of the individual regression and correlation coefficients was investigated. Personal, indoor, and ambient concentrations were highly correlated within subjects over time. Median Pearson's R between personal and outdoor PM2.5 was 0.79 in Amsterdam and 0.76 in Helsinki. For absorption, these values were 0.93 and 0.81 for Amsterdam and Helsinki, respectively. The findings of this study provide further support for using fixed-site measurements as a measure of exposure to PM2.5 in epidemiological time-series studies.     

Three-dimensional quantitative structure-activity relationship study for phenylsulfonyl carboxylates using CoMFA and CoMSIA

From both the comparative molecular field analysis (CoMFA) and the comparative molecular similarity indices analysis (CoMSIA), the paper describes two three-dimensional quantitative structure-activity relationship (3D-QSAR) models for the acute toxicity logEC50 (15 min-EC50 in micromoll(-1)) of 56 phenylsulfonyl carboxylates on Photobacterium phosphoreum. Two models yield the leave-one-out cross-validated correlation coefficient q2 values of 0.823 and 0.713, and the conventional correlation coefficient r2 values of 0.958 and 0.933, respectively. The achievement of higher q2 and r2 values of CoMFA model indicates the significance of correlation of steric and electrostatic fields with biological activities. The key features in the CoMFA contour maps are critical to trace the important properties and gain insight into the toxic mechanism of tested compounds. The quality of CoMSIA model is slightly lower than that of CoMFA in terms of q2 and r2 values. Not requiring molecular superposition, CoMSIA is faster than CoMFA in data processing.     

有机蒸气-空气分子扩散系数实测数据及分析

利用自行研发的气体扩散系数测试装置,测定了烷烃、环烷烃、芳香烃、含氧化合物（酯类、醇类、酮类等）等21种挥发性有机化合物在空气中的分子扩散系数。测定结果表明：互为同系物的有机化合物在相同温度下,分子扩散系数随着分子链的增长而减小,与其沸点呈负相关;互为同分异构体的有机化合物在相同温度下,有支链的分子扩散系数比没有支链的要大。另外,将实验实测值与FSG方程计算值以及文献值进行了对比分析。通过比较实测值与计算值,认为大部分分子结构全部为单键并且不含环状结构的有机化合物的实测值与计算值吻合度比较高,但分子结构中含苯环、碳环和烷烃支链的有机化合物,实测值与计算值吻合度不是很高。建议FSG方程进一步考虑分子结构差异性的影响。     

Determination of sorption coefficients of pharmaceutically active substances carbamazepine, diclofenac, and ibuprofen, in sandy sediments

Laboratory batch studies were conducted to characterize the sorption behavior of three pharmaceutically active substances (carbamazepine, diclofenac, and ibuprofen) in different sediment types. The sediments were natural sandy sediments from the water saturated zone and the unsaturated zone in the Berlin (Germany) area. They are characterized as medium and fine-grained sands, both with low organic carbon content. The results of the experiments show that sorption coefficients were generally quite low. Distribution coefficients (K(d) values) determined by the batch experiments varied from 0.21 to 5.32 for carbamazepine, 0.55 to 4.66 for diclofenac, and 0.18 to 1.69 for ibuprofen. Comparison of the organic carbon normalized sorption coefficient K(OC) values based on correlation equations with actual experimental data revealed that the calculated data for carbamazepine is of the same order as the experimental data. For diclofenac and ibuprofen the calculated values are much higher than the experimental data, showing a much higher mobility of diclofenac and ibuprofen in natural aquifer sediments than indicated by correlation equations based on octanol water distribution coefficients.