Uptake of polychlorinated biphenyls and organochlorine pesticides from soil and air into radishes (Raphanus sativus)

Uptake of organochlorine pesticides and polychlorinated biphenyls from soil and air into radishes was measured at a heavily contaminated field site. The highest contaminant concentrations were found for DDT and its metabolites, and for β-hexachlorocyclohexane. Bioconcentration factor (BCF, defined as a ratio between the contaminant concentration in the plant tissue and concentration in soil) was determined for roots, edible bulbs and shoots. Root BCF values were constant and not correlated to log K_OW. A negative correlation between BCF and log K_OW was found for edible bulbs. Shoot BCF values were rather constant and varied between 0.01 and 0.22. Resuspended soil particles may facilitate the transport of chemicals from soil to shoots. Elevated POP concentrations found in shoots of radishes grown in the control plot support the hypothesis that the uptake from air was more significant for shoots than the one from soil. The uptake of POPs from air was within the range of theoretical values predicted from log K_OA.     

Respiratory uptake kinetics of neutral hydrophobic organic chemicals in a marine benthic fish, Pseudopleuronectes yokohamae

We investigated the respiratory uptake kinetics of polychlorinated biphenyls (PCBs), organohalogen pesticides (OCPs), polycyclic aromatic hydrocarbons (PAHs), and 2,2′,4,4′-tetrabrominated diphenyl ether (BDE #47) in a marine benthic fish, Pseudopleuronectes yokohamae. The respiratory uptake efficiencies (E_W) of the chemicals, of which there have been no reports for the majority of persistent organic pollutants (POPs), were obtained by measuring the respiratory uptake rate constants (k₁) and the oxygen consumption rates of fish. Fish were exposed to water in which these chemicals were dissolved at environmentally relevant concentrations for 28 d, followed by 168 d of depuration in clean seawater. The k₁ and E_W values for 99 compounds were obtained, and they ranged from 2000 to 42 000 L kg-lipid⁻¹ d⁻¹ and from 0.060 to 1.3, respectively. The E_W values of the chemicals, except for PAHs, tended to increase with increasing values of the log octanol–water partition coefficients (K_OW) of the chemicals up to a log K_OW of 5. For log K_OW in the range 3–5, the E_W values in this study were much lower than those in a published study (about one-third). As a result of analysis by a two-phase resistance model, the resistance of transport rates to the lipid phase in this study was lower than was the case in the published study. These findings indicate that the E_W predicted by the published study for log K_OW in the range 3–5 may differ among fish species and water temperature, and further study is needed.     

Hydroxypropyl-β-cyclodextrin as non-exhaustive extractant for organochlorine pesticides and polychlorinated biphenyls in muck soil

Hydroxypropyl-β-cyclodextrin (HPCD) was used as a non-exhaustive extractant for organochlorine pesticides (OCs) and polychlorinated biphenyls (PCBs) in muck soil. An optimized extraction method was developed which involved using a HPCD to soil mass ratio of 5.8 with a single extraction period of 20 h. An aging experiment was performed by spiking a muck soil with ¹³C-labeled OCs and non-labeled PCBs. The soil was extracted with the optimized HPCD method and Soxhlet apparatus with dichloromethane over 550 d periodically. The HPCD extractability of the spiked OCs was greater than of the native OCs. A decreased in HPCD extractability was observed for the spiked OCs after 550 d of aging and their extractability approached those of the natives. The partition coefficient between HPCD and soil (log K_CD-Soil) was negatively correlated with the octanol-water partition coefficient (log K_OW) with r² = 0.67 and p < 0.05.     

Dietary uptake kinetics of polychlorinated biphenyls from sediment-contaminated sandworms in a marine benthic fish (Pseudopleuronectes yokohamae)

To evaluate the dietary uptake of polychlorinated biphenyls (PCBs) from live food, we investigated the dietary uptake and depuration kinetics of PCBs in a marine benthic fish (marbled sole, Pseudopleuronectes yokohamae) by using as food live sandworms (Perinereis nuntia) that were laboratory-exposed to field-collected PCB-contaminated sediment. Marbled sole were fed the PCB-contaminated sandworms for 28 d and then uncontaminated sandworms for 56 d. The assimilation efficiencies (AEs) of 84 PCB congeners via the gastrointestinal tract (GIT) to the muscle of the fish ranged from 0.21 to 0.78; whole-body AEs would be lower than those of muscle because of the lower PCB concentrations, on a lipid basis. The AEs determined in this study were lower than those in other studies that used PCB-spiked commercial pelletized food. The lower AEs found in this study might be attributable to differences in the food administered (live sandworms vs. commercial pellet food), possibly because of low digestibility of sandworm lipids by marbled sole. In addition, the AEs in this study tended to increase with increasing log octanol-water partition coefficients (K_OW) up to about seven, although AEs in the other studies using commercial pelletized food did not increase with increasing log K_OW. This result suggests the co-transport of highly hydrophobic PCB congeners along with lipids and fatty acids from the digested sandworms into the GIT epithelium cells. The growth-corrected half-lives of 26 PCB congeners in the muscle of fish ranged from 20 to 107 d.     

Linear and non-linear relationships between soil sorption and hydrophobicity: model, validation and influencing factors

The hydrophobic parameter represented by the octanol/water partition coefficient (log P) is commonly used to predict the soil sorption coefficient (K_oc). However, a simple non-linear relationship between log K_oc and log P has not been reported in the literature. In the present paper, soil sorption data for 701 compounds was investigated. The results show that log K_oc is linearly related to log P for compounds with log P in the range of 0.5-7.5 and non-linearly related to log P for the compounds in a wide range of log P. A non-linear model has been developed between log K_oc and log P for a wide range of compounds in the training set. This model was validated in terms of average error (AE), average absolute error (AAE) and root-mean squared error (RMSE) by using an external test set with 107 compounds. Nearly the same predictive capacity was observed in comparison with existing models. However, this non-linear model is simple, and uses only one parameter. The best model developed in this paper is a non-linear model with six correction factors for six specific classes of compounds. This model can well predict log K_oc for 701 diverse compounds with AAE = 0.37. The reasons for systemic deviations in these groups may be attributed to the difference of sorption mechanism for hydrophilic/polar compounds, low solubility for highly hydrophobic compounds, hydrolysis of esters in solution, volatilization for volatile compounds and highly experimental errors for compounds with extremely high or low sorption coefficients.     

Salting-out phenomenon and 1-octanol/water partition coefficient of metalaxyl pesticide

In this paper, we present the effect of inorganic cations such as Na⁺, K⁺, Ca²⁺, Mg²⁺ on the salting-out phenomenon of metalaxyl from pure water to aqueous salt solutions. Moreover the 1-octanol/water partition coefficient in pure water is presented. To accomplish this, aqueous solubility of metalaxyl was determined in pure water, in different salt solution (NaCl, KCl, CaCl₂ and MgCl₂), and at different concentration level ranging from 0.01 to 1.5 M. The 1-octanol/water partition coefficient was determined using the static shake-flask method. Solubility was determined using dynamic saturation method for pure water in the range of 298.15-325.15 K and at 298.15 K for different salt solutions. The solubility value in pure water for studied interval was found constant (m = 3.118 × 10⁻² mol kg⁻¹).Solubility values were used to calculate the standard molar Gibbs free energy of dissolution (Δ_solG°) and transfer (Δ_trG°) at 298.15 K. The values of Δ_trG° from pure to all studied aqueous salt solutions did not exceed 2 kJ mol⁻¹, the value of Δ_solG° of dissolution is 18.5 ±0.72 kJ mol⁻¹. The 1-octanol/water partition coefficient in pure water log K_o/w is equal to 1.69. The obtained results confirm the classification of the neutral metalaxyl as a slightly hydrophobic molecule.     

Sorption of chlorinated solvents and degradation products on natural clayey tills

The sorption of chlorinated solvents and degradation products on seven natural clayey till samples from three contaminated sites was investigated by laboratory batch experiments in order to obtain reliable sorption coefficients (K_d values). The sorption isotherms for all compounds were nearly linear, but fitted by Freundlich isotherms slightly better over the entire concentration range. For chloroethylenes, tetrachloroethylene (PCE) was most strongly sorbed to the clayey till samples (K_d = 0.84-2.45 L kg⁻¹), followed by trichloroethylene (TCE, K_d = 0.62-0.96 L kg⁻¹), cis-dichloroethylene (cis-DCE, K_d = 0.17-0.82 L kg⁻¹) and vinyl chloride (VC, K_d = 0.12-0.36 L kg⁻¹). For chloroethanes, 1,1,1-trichloroethane (1,1,1-TCA) was most strongly sorbed (K_d = 0.2-0.45 L kg⁻¹), followed by 1,1-dichloroethane (1,1-DCA, K_d = 0.16-0.24 L kg⁻¹) and chloroethane (CA, K_d = 0.12-0.18 L kg⁻¹). This is consistent with the order of hydrophobicity of the compounds. The octanol-water coefficient (log K_ow) correlated slightly better with log K_d values than log K_oc values indicating that the K_d values may be independent of the actual organic carbon content (f_oc). The estimated log K_oc or log K_d for chlorinated solvents and degradation products determined by regression of data in this study were significantly higher than values determined by previously published empirical relationships. The site specific K_d values as well as the new empirical relationship compared well with calculations on water and soil core concentration for cis-DCE and VC from the Rugårdsvej site. In conclusion, this study with a wide range of chlorinated ethenes and ethanes - in line with previous studies on PCE and TCE - suggest that sorption in clayey tills could be higher than typically expected.     

Sorption comparison between phenanthrene and its degradation intermediates, 9,10-phenanthrenequinone and 9-phenanthrol in soils/sediments

The degradation intermediates of phenanthrene (PHE) may have increased health risks to organisms than PHE. Therefore, environmental fate and risk assessment studies should take into considerations of PHE degradation products. This study compared the sorption properties of PHE and its degradation intermediates, 9,10-phenanthrenequinone (PQN) and 9-phenanthrol (PTR) in soils, sediments and soil components. A relationship between organic carbon content (f_OC) and single-point sorption coefficient (log K_d) was observed for all three chemicals in 10 soils/sediments. The large intercept in the log f_OC − log K_d regression for PTR indicated that inorganic fractions control PTR sorption in soils/sediments. No relationship between specific surface area and K_d was observed. This result indicated that determination of surface area based on gas sorption could not identify surface properties for PHE, PQN, and PTR sorption and thus provide limit information on sorption mechanisms. The high sorption and strong nonlinearity (low n values) of PTR in comparison to PHE suggested that the mobility of PTR could be lower than PHE. Increased mobility of PQN compared with PHE may be expected in soils/sediments because of PQN lower sorption. The varied sorption properties of the three chemicals suggested that their environmental risks should be assessed differently.     

Ozonation of azo dye Acid Red 14 in a microporous tube-in-tube microchannel reactor: decolorization and mechanism

Despite the great success of time-weighted average passive sampling of hydrophobic contaminants, such as PCBs and PAHs, the sampling of polar organic compounds still presents a challenge because the equilibrium between water and most sampling phases is attained in a relatively short time. In this study, we proposed a new time-integrative sampler using in situ solvent extraction (TISIS) for polar organic chemicals. The sampler was composed of a 15 cm poly(dimethylsiloxane) (PDMS) tubing, with an internal diameter of 0.5 mm and wall thickness of 0.5 mm, through which an extraction solvent (acetonitrile) was passed. Four polar organic contaminants, caffeine, atrazine, diuron and 17α-ethynylestradiol, were chosen for the evaluation of the performance of the sampler. Without the use of in situ solvent extraction, the PDMS tubing when exposed to a constant aqueous concentration of the four model compounds was able to linearly accumulate those compounds for less than 12 h and equilibrium between the PDMS tubing and water was attained in 2 d under our laboratory conditions. However, TISIS when exposed to a constant aqueous concentration was able to linearly accumulate all the model compounds without any exposure time limitation. The measured sampling rates at three different extraction flow rates (0.2, 0.5, 1.5 mL min⁻¹) were similar, regardless of the chemicals, indicating that the overall mass transfer from aqueous solution to the extraction solvent was most likely dominated by partitioning to the PDMS tubing and the internal diffusion within PDMS. In addition, a pulsed exposure experiment confirmed that TISIS operated in a time-integrative mode when the environmental concentration was highly fluctuated.     

A comparison of octanol-water partitioning between organic chemicals and their metabolites in mammals

Bioaccumulation models take various elimination and uptake processes into account, estimating rates from chemical lipophilicity, expressed as the octanol-water partition ratio (K_ow). Here, we focussed on metabolism, which transforms parent compounds into usually more polar metabolites, thus enhancing elimination. The aim of this study was to quantify the change in lipophilicity of relevant organic pollutants undergoing various biotransformation reactions in mammals. We considered oxidation reactions catalyzed by three enzyme groups: cytochrome P450 (CYP), alcohol dehydrogenase (ADH), and aldehyde dehydrogenase (ALDH). Estimated log K_ow values of a selected dataset of parent compounds were compared with the log K_ow of their first metabolites. The log K_ow decreased by a factor that varies between 0 and −2, depending on the metabolic pathway. For reactions mediated by CYP, the decrease in K_ow was one order of magnitude for hydroxylated and epoxidated compounds and two orders of magnitude for dihydroxylated and sulphoxidated xenobiotics. On the other hand, no significant change in lipophilicity was observed for compounds N-hydroxylated by CYP and for alcohols and aldehydes metabolized by ADH and ALDH. These trends could be anticipated by the calculus method of log K_ow. Yet, they were validated using experimental log K_ow values, when available. These relationships estimate the extent to which the elimination of pollutants is increased by biotransformation. Thus, the quantification of the K_ow reduction can be considered as a first necessary step in an alternative approach to anticipate biotransformation rates, which are hard to estimate with existing methods.     

Biomagnification of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls in a highly contaminated freshwater food web from South China

To evaluate the biomagnification extent of polybrominated diphenyls ethers (PBDEs) and polychlorinated biphenyls (PCBs) in a highly contaminated freshwater food web from South China, trophic magnification factors (TMFs) for 18 PBDE congeners and 53 PCB congeners were calculated. The TMF values ranged 0.26-4.47 for PBDEs and 0.75-5.10 for PCBs. Forty-five of 53 PCBs and BDEs 47, 100 and 154 had TMFs greater than one, suggesting their biomagnification in the present food web. The TMFs for PBDEs were generally smaller than those for PCBs with the same degree of halogenation, indicating a lower biomagnification potential for PBDEs compared to PCBs. For PCBs, it followed a parabolic relationship between TMFs and log K_OW (octanol-water partition coefficient). However, this relationship was not significant for PBDEs, possibly due to the more complex behaviors of PBDEs in the food web (e.g., metabolism), compared to that of PCBs.     

Sorption of polycyclic aromatic hydrocarbons (PAHs) on glass surfaces

Sorption of polycyclic aromatic hydrocarbons (PAHs) to glass commonly used in laboratories was studied. Sorption coefficients (K_d) of five selected PAHs to borosilicate glass surfaces were measured using column chromatography. A linear relationship between log K_d and the corresponding water solubility of the subcooled liquid (log S_w) of the investigated PAHs was observed. Based on the determined sorption coefficients our data revealed that mass loss caused by sorption on glass walls strongly depends on the ratio of solution volume to contacted surface area (V/S). The influence of solution chemistry such as ionic strength, solution pH, presence of cosolvent, and the influence of temperature on the sorption process were investigated. In the presence of ionic strength, sorption coefficients concurrently increased but less than a factor of 2 up to 0.005 M calcium chloride concentration. However, further increasing ionic strength had no influence on K_d. The cosolvent reduced sorption at a concentration of methanol in water above 0.5% (v/v); however, for benzo[a]pyrene even with 10% (v/v) methanol the mass loss would be still higher than 10% (with a V/S ratio less than 0.25). Significant effects of the solution pH and temperature were not observed. These results suggest that van der Waal’s forces dominate the sorption process. In the analysis of highly hydrophobic PAHs in aqueous samples, mass loss due to sorption on glass walls should be accounted for in the final result if untreated glass is used. The presented relationship between log K_d and log S_w may help to decide if such a correction is necessary. Furthermore, the frequently used silanization of glass surfaces may not be sufficient to suppress sorption for large PAHs.     

Sorption influenced transport of ionizable pharmaceuticals onto a natural sandy aquifer sediment at different pH

The pH-dependent transport of eight selected ionizable pharmaceuticals was investigated by using saturated column experiments. Seventy-eight different breakthrough curves on a natural sandy aquifer material were produced and compared for three different pH levels at otherwise constant conditions. The experimentally obtained K_OC data were compared with calculated K_OC values derived from two different log K_OW-log K_OC correlation approaches. A significant pH-dependence on sorption was observed for all compounds with pK_a in the considered pH range. Strong retardation was measured for several compounds despite their hydrophilic character. Besides an overall underestimation of K_OC, the comparison between calculated and measured values only yields meaningful results for the acidic and neutral compounds. Basic compounds retarded much stronger than expected, particularly at low pH when their cationic species dominated. This is caused by additional ionic interactions, such as cation exchange processes, which are insufficiently considered in the applied K_OC correlations.     

Partitioning behaviour of perfluorinated alkyl contaminants between water, sediment and fish in the Orge River (nearby Paris, France)

This paper reports on the partitioning behaviour of 15 perfluorinated compounds (PFCs), including C₄-C₁₀ sulfonates and C₅-C₁₄ carboxylic acids, between water, sediment and fish (European chub, Leuciscus cephalus) in the Orge River (nearby Paris). Total PFC levels were 73.0 ± 3.0 ng L⁻¹ in water and 8.4 ± 0.5 ng g⁻¹ in sediment. They were in the range 43.1-4997.2 ng g⁻¹ in fish, in which PFC tissue distribution followed the order plasma > liver > gills > gonads > muscle. Sediment-water distribution coefficients (log K_d) and bioaccumulation factors (log BAF) were in the range 0.8-4.3 and 0.9-6.7, respectively. Both distribution coefficients positively correlated with perfluoroalkyl chain length. Field-based biota-sediment accumulation factors (BSAFs) are also reported, for the first time for PFCs other than perfluorooctane sulfonate. log BSAF ranged between −1.3 and 1.5 and was negatively correlated with the perfluoroalkyl chain length in the case of carboxylic acids.     

Oxygen-containing polycyclic aromatic hydrocarbons (OPAHs) in urban soils of Bratislava, Slovakia: patterns, relation to PAHs and vertical distribution

We determined concentrations, sources, and vertical distribution of OPAHs and PAHs in soils of Bratislava. The ∑14 OPAHs concentrations in surface soil horizons ranged 88-2692 ng g⁻¹ and those of ∑34 PAHs 842-244,870 ng g⁻¹. The concentrations of the ∑9 carbonyl-OPAHs (r = 0.92, p = 0.0001) and the ∑5 hydroxyl-OPAHs (r = 0.73, p = 0.01) correlated significantly with ∑34 PAHs concentrations indicating the close association of OPAHs with parent-PAHs. OPAHs were quantitatively dominated by 9-fluorenone, 9,10-anthraquinone, 1-indanone and benzo[a]anthracene-7,12-dione. At several sites, individual carbonyl-OPAHs had higher concentrations than parent PAHs. The concentration ratios of several OPAHs to their parent-PAHs and contribution of the more soluble OPAHs (1-indanone and 9-fluorenone) to ∑14 OPAHs concentrations increased with soil depth suggesting that OPAHs were faster vertically transported in the study soils by leaching than PAHs which was supported by the correlation of subsoil:surface soil ratios of OPAH concentrations at several sites with K_OW.     

A rapidly equilibrating, thin film, passive water sampler for organic contaminants; characterization and field testing

Improving methods for assessing the spatial and temporal resolution of organic compound concentrations in marine environments is important to the sustainable management of our coastal systems. Here we evaluate the use of ethylene vinyl acetate (EVA) as a candidate polymer for thin-film passive sampling in waters of marine environments. Log K_EVA−W partition coefficients correlate well (r² = 0.87) with Log K_OW values for selected pesticides and polychlorinated biphenyls (PCBs) where Log K_EVA−W = 1.04 Log K_OW + 0.22. EVA is a suitable polymer for passive sampling due to both its high affinity for organic compounds and its ease of coating at sub-micron film thicknesses on various substrates. Twelve-day field deployments were effective in detecting target compounds with good precision making EVA a potential multi-media fugacity meter.     

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.     

Predicting bioavailability of PAHs in field-contaminated soils by passive sampling with triolein embedded cellulose acetate membranes

Triolein embedded cellulose acetate membrane (TECAM) was used for passive sampling of the fraction of naphthalene, phenanthrene, pyrene and benzo[a]pyrene in 18 field-contaminated soils. The sampling process of PAHs by TECAM fitted well with a first-order kinetics model and PAHs reached 95% of equilibrium in TECAM within 20 h. Concentrations of PAHs in TECAM (C_TECAM) correlated well with the concentrations in soils (r² = 0.693-0.962, p < 0.001). Furthermore, concentrations of PAHs determined in the soil solution were very close to the values estimated by C_TECAM and the partition coefficient between TECAM and water (K_TECAM-w). After lipid normalization nearly 1:1 relationships were observed between PAH concentrations in TECAMs and earthworms exposed to the soils (r² = 0.591-0.824, n = 18, p < 0.01). These results suggest that TECAM can be a useful tool to predict bioavailability of PAHs in field-contaminated soils.