Partitioning of selected environmental pollutants into organic matter as determined by solid-phase microextraction

Partitioning/sorption of selected environmental pollutants (PCBs, organochlorine insecticides, triazine and amide herbicides) into dissolved humic acids (HA), soil and mineral substances was evaluated by measuring their free concentrations by solid-phase microextraction (SPME). Compounds were chosen to cover a wide range of logK(ow) (2.2-7.6). Two different types of partitioning behaviour for dissolved HA were observed. Compounds with logK(ow)>5 partitioned almost instantly into HA fraction and the remaining free fraction remained rather constant. LogK(HA) and logK(DOC) were calculated and found to be similar for commercial HA, HA standard and isolated HA. The behaviour of these compounds in soil suspension was similar, but strong sorption on CaCO3 and Florisil was also noticed. For compounds with logK(ow)<5, we have not noticed significant changes in free concentrations in HA solutions over time. In soil suspension, however, some sorption/partitioning was observed over time for some compounds, but it was matching the sorption on CaCO3 and Florisil.     

Partitioning of chloroaromatic compounds between the aqueous phase and dissolved and particulate soil organic matter at chlorophenol contaminated sites

The retention and mobility of hydrophobic organic contaminants (HOCs) in soil is mainly determined by hydrophobic partitioning to dissolved and particulate organic matter (DOM and POM, respectively). The aqueous phase, DOM, and POM fractions were extracted and separated from soils at three sites contaminated with technical chlorophenol formulations. Concentrations of chlorophenols (CP), polychlorinated phenoxyphenols (PCPP), polychlorinated diphenyl ethers (PCDE) and polychlorinated dibenzo-p-dioxins and furans (PCDD/F) were determined. The partitioning to POM, in relation to DOM, increased in all three soils with increasing hydrophobicity in the order CP < PCPP ~ PCDE ~ PCDF < PCDD. Differences in partitioning to DOM (logK(DOC)) and POM (logK(POC)) could not be explained by differences in gross organic C chemistry. Black carbon did not contribute significantly to the sorption of PCDDs, whereas >70% wood fibre in one soil resulted in a decrease of logK(POC) of 0.5 units for CPs and PCDDs. We conclude that logK(OC) for both DOM and POM need to be explicitly determined when the retention and mobility of HOCs is described and modelled in soils.     

Comparison of nonideal sorption formulations in modeling the transport of phthalate esters through packed soil columns

Sorption of dimethyl phthalate (DMP), diethyl phthalate (DEP) and dipropyl phthalate (DPP) to two soil materials that vary in organic matter content was investigated using miscible displacement experiments under saturated flow conditions. Generated breakthrough curves (BTCs) were inversely simulated using linear, equilibrium sorption (LE), nonlinear, equilibrium sorption (NL), linear, first-order nonequilibrium sorption (LFO), linear, radial diffusion (LRD), and nonlinear, first-order nonequilibrium sorption (NFO) models. The Akaike information criterion was utilized to determine the preferred model. The LE model could not adequately describe phthalate ester (PE) BTCs in higher organic matter soil or for more hydrophobic PEs. The LFO and LRD models adequately described the BTCs but a slight improvement in curve-fitting was gained in some cases when the NFO model was used. However, none of the models could properly describe the desorptive tail of DPP for the high organic matter soil. Transport of DPP through this soil was adequately predicted when degradation or sorption hysteresis was considered. Using the optimized parameter values along with values reported by others it was shown that the organic carbon distribution coefficient (K(oc)) of PEs correlates well with the octanol/water partition coefficient (K(ow)). Also, a strong relationship was found between the first-order sorption rate coefficient normalized to injection pulse size and compound residence time. A similar trend of timescale dependence was found for the rate parameter in the radial diffusion model. Results also revealed that the fraction of instantaneous sorption sites is dependent on K(ow) and appears to decrease with the increase in the sorption rate parameter.     

Acute toxicity of substituted phenols to Rana japonica tadpoles and mechanism-based quantitative structure-activity relationship (QSAR) study.

Acute 12 h and 24 h lethal toxicity (12 h-LC50 and 24 h-LC50) of 31 substituted phenols to Rana japonica tadpoles was determined. Results indicate that toxicity of phenols to tadpoles varied only slightly with length of exposure and the 12-h test could serve as surrogate of the 24-h test. A mechanism-based quantitative structure-activity relationship (QSAR) method was employed and 1-octanol/water partition coefficient (log K(ow))-dependent models were developed to study different modes of toxic action. Most phenols elicited their response via a polar narcotic mechanism and an excellent logK(ow)-dependent model was obtained. Soft electrophilicity and pro-electrophilicity were observed for some phenols and a good log K(ow)-dependent model was also achieved. Additionally, the significant dissociation of carboxyl on benzoic acid derivatives sharply reduced their toxicity. A statistically robust QSAR model was developed for all studied compounds with the combined application of log K(ow), energy of lowest unoccupied orbital (E(lumo)), heat of formation (HOF) and the first-order path molecular connectivity dices (1chi(p)).     

Partitioning of polycyclic aromatic hydrocarbons to solid-sorbed nonionic surfactants

The partition of hydrophobic organic compounds (HOCs) into solid-sorbed surfactant has a crucial role in describing and predicting the distribution of HOCs in solid-water-surfactant systems. The experimental results of this study indicated that the partition coefficients of polycyclic aromatic hydrocarbons (PAHs) into the solid-sorbed surfactant (Ksm) increased with an increase in the sorption amount of surfactants onto solid and reached a stable maximum value (Km sm) at the sorption of surfactants in saturation state, at which the solid surface was completely covered with the surface micelle (or admicelle). The fitted Km sm values for PAHs with different surfactants were found to have a good linear relationship with the corresponding partition coefficient of PAHs to surfactant micelles in solution (Kmc), and then a model was developed to describe and predict the distribution of PAHs in solid-water-surfactant systems. These results are of practical interest for developing effective and safe surfactant-enhanced remediation technologies.     

Retention behavior of hydrophobic organic chemicals as a function of temperature in soil leaching column chromatography

To study the transport mechanism of hydrophobic organic chemicals (HOCs) and the energy change in soil/solvent system, a soil leaching column chromatographic (SLCC) experiment at an environmental temperature range of 20-40 degrees C was carried out, which utilized a reference soil (SP 14696) packed column and a methanol-water (1:4 by volume ratio) eluent. The transport process quickens with the increase of column temperature. The ratio of retention factors at 30 and 40 degrees C (k'30/k'40) ranged from 1.08 to 1.36. The lower enthalpy change of the solute transfer in SLCC (from eluent to soil) than in conventional reversed-phase liquid chromatography (e.g., from eluent to C18) is consistent with the hypothesis that HOCs were dominantly and physically partitioned between solvent and soil. The results were also verified by the linear solvation energy relationships analysis. The chief factor controlling the retention was found to be the solute solvophobic partition, and the second important factor was the solute hydrogen-bond basicity, while the least important factors were the solute polarizability-dipolarity and hydrogen-bond acidity. With the increase of temperature, the contributions of the solute solvophobic partition and hydrogen-bond basicity gradually decrease, and the latter decreases faster than the former.     

Linear solvation energy relationships regarding sorption and retention properties of hydrophobic organic compounds in soil leaching column chromatography

The capacity factors of a series of hydrophobic organic compounds (HOCs) were measured in soil leaching column chromatography (SLCC) on a soil column, and in reversed-phase liquid chromatography on a C18 column with different volumetric fractions (phi) of methanol in methanol-water mixtures. A general equation of linear solvation energy relationships, log(XYZ) XYZ0 + mV(I)/100 + spi + bbetam + aalpham, was applied to analyze capacity factors (k'), soil organic partition coefficients (Koc) and octanol-water partition coefficients (P). The analyses exhibited high accuracy. The chief solute factors that control logKoc, log P, and logk' (on soil and on C18) are the solute size (V(I)/100) and hydrogen-bond basicity (betam). Less important solute factors are the dipolarity/polarizability (pi*) and hydrogen-bond acidity (alpham). Log k' on soil and log Koc have similar signs in four fitting coefficients (m, s, b and a) and similar ratios (m:s:b:a), while log k' on C18 and logP have similar signs in coefficients (m, s, b and a) and similar ratios (m:s:b:a). Consequently, logk' values on C18 have good correlations with logP (r > 0.97), while logk' values on soil have good correlations with logKoc (r > 0.98). Two Koc estimation methods were developed, one through solute solvatochromic parameters, and the other through correlations with k' on soil. For HOCs, a linear relationship between logarithmic capacity factor and methanol composition in methanol-water mixtures could also be derived in SLCC.     

Correlations of nonlinear sorption of organic solutes with soil/sediment physicochemical properties

The estimation of solute sorptive behaviors is essential when direct sorption data are unavailable and will provide a convenient way to assess the fate and the biological activity of organic solutes in soil/sediment environments. In this study, the sorption of 2,4-dichlorophenol (2,4-DCP) on 19 soil/sediment samples and the sorption of 13 organic solutes on one sediment were investigated. All sorption isotherms are nonlinear and can be described satisfactorily by a simple dual-mode model (DMM): q(e)=KpCe+Q0 . bCe/(1+bCe), where Kp (mlg(-1)) is the partition coefficient; Ce (microgml(-1)) is the equilibrium concentration; Q0 (microgg(-1)) is the maximum adsorption capacity; Q0 . b (mlg(-1)) is the Langmuir-type isotherm slope in the low concentration (Henry's law) range and b (mlmicrog(-1)) is a constant related to the affinity of the surface for the solute. Based on these nonlinear sorption isotherms and similar other nonlinear isotherms, it is observed that, for both polar 2,4-DCP and nonpolar phenanthrene, Kp, Q0 and Q0 . b are linearly correlated with soil/sediment organic carbon content (f(oc) in the range of 0.118-53.7%). The results indicate that the nonlinear sorption of organic solutes results primarily from interactions with soil/sediment organic matter. The K*oc K*oc=Kp/f(oc)), Qoc (Qoc=Q0/f(oc)), Loc (Loc=Q0 . b/f(oc)) and b for a given organic solute with different soils/sediments are largely invariant. Furthermore, logK*oc, logb and logLoc for various organic solutes are correlated significantly with the solute logKow or logSw (logKow in the range of 0.9 to 5.13 and logSw in the range of -6.176 to -0.070). A fundamental empirical equation was then established to calculate approximately the nonlinear sorption from soil/sediment f(oc) and solute Sw for a given solute equilibrium concentration.     

Predicting organic contaminant concentrations in sediment porewater using solid-phase microextraction

Because of its cost and time saving features, solid-phase microextraction (SPME) is a leading candidate as a biomimic technique in assessing the bioavailable fraction of hydrophobic organic contaminants (HOCs) in sediment porewater. However, no predictive modeling framework in which to systematically address the effect of key parameters on SPME performance for this application exists. In this study, we derived two governing equations to predict (1) the minimum sediment volume (V(s)min) required to achieve non-depletive conditions, and (2) dissolved phase HOC porewater concentrations (C(pw)) as functions of HOC- and sediment specific characteristics in a conceptual three compartment system. The resulting model predicted that V(s)min was independent of HOC concentrations both in sediment and porewater, but did vary with hydrophobicity (characterized by logK(ow)), the fraction of sediment porewater (f(pw)), and the volume (V(f)) of the SPME sorbent phase. Moreover, the effects of these parameters were minimized (i.e., V(s)min reached plateaus) as logK(ow) approached 4-5. Model predictions of C(pw), a surrogate for SPME-based detection limits in porewater, decreased with increasing sediment volume (V(s)) at low V(s) values, but rapidly leveled off as V(s) increased. A third result suggested that the sediment HOC concentration required for SPME is completely independent of K(ow). These results suggest that relatively small sediment volumes participate in exchange equilibria among sediment, porewater and the SPME fiber, and that large sediment HOC reservoirs are not needed to improve the detection sensitivity of SPME-based porewater samplers. The ultimate utility of this modeling framework will be to assist future experimental designs and help predict in situ bioavailability of sediment-associated HOCs.     

Accumulation of organochlorine pesticides by semipermeable membrane devices using composite complex

Semipermeable membrane devices (SPMDs) were developed for passive in situ monitoring of organochlorine pesticides (OCPs) in aqueous solution in both laboratory and field (Pearl River Delta, China) studies. The device consisted of a thin film of neutral lipid triolein, enclosed in thin-walled tubing made of composite cellulose acetate membrane (CA) supported by linear low density polyethylene (LLDPE) (CAPE). Results from the laboratory and field application indicated that triolein-CAPE (TCAPE) could quickly and efficiently accumulate hydrophobic OCPs in water and uptake equilibrium could reached within 20h in the laboratory. Some mathematical relationships of TCAPE-water partition coefficient (logK(sw)), triolein-water partition coefficient (logK(tw)) and octanol-water partition coefficient (logK(ow)) were developed under the laboratory conditions. A good correlation of accumulation in TCAPE with r(2) values ranging from 0.55 to 0.86 for individual OCPs (n=8) and an excellent correlation of logK(sw) and logK(ow) was also obtained under the field conditions. The average OCPs concentration in the surface water could be estimated by measuring OCPs concentration in the device under the field conditions.     

Regression method of the hydrophobicity ruler approach for determining octanol/water partition coefficients of very hydrophobic compounds

A regression method was developed for the hydrophobicity ruler approach, which is an indirect method for determining the octanol/water partition coefficients of very hydrophobic compounds. Two constants introduced into the mathematical model were obtained by regression of the absorption data sampled before the partition equilibrium. A water miscible organic solvent was used to increase the solubility of the very hydrophobic compounds in the aqueous solution so that the hydrophobicity scale was reduced and the equilibration was accelerated. Polydimethylsiloxane/methanol aqueous solution and a series of 21 polychlorinated biphenyls (PCBs) were used to demonstrate the regression method. The PCB compounds with known experimental logK(o/w) values served as reference compounds, while the PCB compounds without known logK(o/w) values were determined. The distribution coefficients (logK(p/s)), uptake and elimination rate constants were obtained from the two regression constants for each compound (reference or unknown). The correlation of the logK(p/s) values of the reference PCB compounds with their logK(o/w) values was linear (logK(o/w)=2.69logK(p/s)+0.76, R(2)=0.97). The logK(o/w) values were compared with literature values and suggested that some values from the literature far off the calibration line could be inaccurate. The critical experimental factors, the merits of the regression method were discussed.     

Estimating K(oc) for persistent organic pollutants: limitations of correlations with K(ow)

The n-octanol/water partition coefficient (K(ow)) is commonly used to predict the soil or aquatic particle water partition coefficient normalized to organic carbon (K(oc)). Many correlations are available covering several chemical classes and ranges of hydrophobicity. This work indicates the K(ow) may not be a strong predictor for persistent organic pollutants (POPs) which are defined here as chemicals with logK(ow) > 5.0. In addition, the correlation developed in this work for POPs will still result in a predicted value which is of by a factor of 15. Accordingly, care must be taken when applying K(oc) estimations using K(ow) for POPs until more suitable correlations are developed.     

Sorption of organic contaminants by biopolymers: role of polarity, structure and domain spatial arrangement

Sorption behavior of hydrophobic organic contaminants (HOCs) (i.e., pyrene, phenanthrene and naphthalene) by native and chemically modified biopolymers (lignin, chitin and cellulose) was examined. Lignins (native and treated) showed nonlinear sorption for all compounds studied, emphasizing their glassy character. Chitins and celluloses had linear isotherms for phenanthrene and naphthalene, illustrating the dominance of partitioning, while pyrene yielded nonlinear isotherms. Sorption capacity (K(oc)) of HOCs was negatively correlated with the polarity [(O+N)/C] of the biopolymers. Aromatic and alkyl+aromatic C percentages, rather than alkyl C content, demonstrated a better correlation with K(oc) values, indicating the importance of aromatic structures for HOC affinity. Hydrophobicity (K(ow))-normalized K(oc) values decreased sharply with increasing percentage of O-alkyl C versus total aliphatic C (O-alkyl C/total aliphatic C) or with polar C/(alkyl+aromatic C) ratio of the biopolymers until their values reached 80% and 4, respectively, illustrating the effect of surrounding polar groups on reducing affinity for HOCs. Overall, the results of this study highlight the role of spatial arrangement of domains within biopolymers in sorption of HOCs, and point to sorbent properties, such as functionality, polarity and structure, jointly regulating the sorption of HOCs in biopolymers.     

The partitioning of alkylphenolic surfactants and polybrominated diphenyl ether flame retardants in activated sludge batch tests

Polybrominated diphenyl ethers and nonylphenol polyethoxylates have been reported to be estrogenic and may enter the aquatic environment through the discharge of treated sewage effluent. Therefore, their fate during wastewater treatment processes is an important factor in determining their environmental impact. Batch tests with activated sludge from a Husmann apparatus were used to determine the effects of physico-chemical properties and sludge characteristics on the partitioning of polybrominated diphenyl ether flame retardants and nonylphenol polyethoxylate surfactants during biological wastewater treatment. Hydrophobic compounds, those with high logK(ow) values, were sorbed more rapidly and to a greater extent to the solid phase than more soluble compounds. For these hydrophobic compounds sorption may become an increasingly important removal mechanism as sludge age and therefore solids content increase. The initial rate of partitioning was greatest for the most hydrophobic compounds but all rates diminished with time as a result of progressive saturation of sorbent binding sites, a reduction of sorbate availability and as a consequence of the system reaching equilibrium. The sorption of polybrominated diphenyl ethers fit Freundlich adsorption isotherms demonstrating generally increasing adsorption capacity and efficiency with increasing hydrophobic nature. A correlation between increasing logK(ow) and increasing organic matter content was also observed for both polybrominated diphenyl ethers and nonylphenol polyethoxylates indicating the organic content of mixed liquor will also be influential in removing compounds during wastewater treatment.