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.     

Modifications of black carbons and their influence on pyrene sorption

Sorption of pyrene on black carbons (BCs) obtained by heating sawdust at two temperatures (400 and 700 °C, denoted as 400BC and 700BC, respectively), as well as on modified BCs (via oxidation, oximation, and hydrolysis) was studied to investigate the role of BC structural characteristics in sorption of hydrophobic organic compounds. Pyrene was bound strongly by 700BC and 400BC, with organic carbon normalized distribution coefficients (K_oc) of 10^5.04-10^5.86 and 10^4.65-10^5.16, respectively, at equilibrium pyrene concentrations of 10-100 μg L⁻¹. Both chemical composition and pore distribution of the two BCs changed after modifications, which led to changes in their sorption characteristics for pyrene. After modifications, the linearity of pyrene sorption isotherm increased for 700BC but decreased for 400BC. For 700BC, both oxidation and oximation reduced pyrene sorption, with K_oc decreasing by 69.1-73.7% and 18.7-33.9%, respectively, whereas hydrolysis did not exert a significant influence. For 400BC, oxidation and hydrolysis reduced K_oc by 2.28-25.9% and 29.2-33.9%, respectively, while oximation increased K_oc. In most cases, the change in sorption capacity could be explained by the changes in C content and type, polarity, surface area, and micropore volume of the BCs; however, the role of conformation (the accessibility to sorption sites) could not be ignored.     

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.     

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.     

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.     

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.     

A flow-through passive dosing system for continuously supplying aqueous solutions of hydrophobic chemicals to bioconcentration and aquatic toxicity tests

A continuous supply of water with defined stable concentrations of hydrophobic chemicals is a requirement in a range of laboratory tests such as the OECD 305 protocol for determining the bioconcentration factor in fish. Satisfying this requirement continues to be a challenge, particularly for hydrophobic chemicals. Here we present a novel solution based on equilibrium passive dosing. It employs a commercially available unit consisting of ∼16 000 polydimethylsiloxane (PDMS) tubes connected to two manifolds. The chemicals are loaded into the unit by repeatedly perfusing it with a methanol solution of the substances that is progressively diluted with water. Thereafter the unit is perfused with water and the chemicals partition from the unit into the water. The system was tested with nine chemicals with log K_OW ranging from 4.1 to 6.3. The aqueous concentrations generated were shown to be largely independent of the water flow rate, and the unit to unit reproducibility was within a factor of ∼2. In continuous flow experiments the aqueous concentrations of most of the study chemicals remained constant over 8 d. A model was assembled that allows prediction of the operating characteristics of the system from the log K_OW or PDMS/water partition coefficient of the chemical. The system is a simple, safe, predictable and flexible tool that generates stable aqueous concentrations of hydrophobic chemicals.     

Sorption of 17α-ethinyl estradiol, bisphenol A and phenanthrene to different size fractions of soil and sediment

The potential for negative effects caused by endocrine disrupting chemicals (EDCs) release into the environment is a prominent concern and numerous research projects have investigated possible environmental fate and toxicity. However, their sorption behavior by size fractions of soil and sediment has not been systematically represented. The sorption of bisphenol A (BPA), 17α-ethinyl estradiol (EE2) and phenanthrene (Phen) by different size fractions of soil and sediment were investigated. Sorption isotherms of EE2, BPA, and Phen by size fractions of soil (SL) and sediment (ST) were well fitted to the Freundlich model. The positive correlation between EE2, BPA and Phen sorption capacity (log K_d) of size fractions and their organic carbon (OC) content suggests that OC of size fractions in SL and ST should regulate sorption, while the surface area (SA) of size fractions may not account for sorption of EE2, BPA and Phen. Each size fraction of ST had higher sorption capacity (K_d or K_OC) of EE2 and BPA than that of SL due to their difference in the polarity of organic matter (OM) between terrestrial and aquatic sources. Sorption capacity logK_d for size fractions of SL and ST did not follow the order: clay > silt > sand due to the difference in OM abundance and composition between the size fractions. Large particle fractions of ST contributed about 80% to the overall sorption for any EE2, BPA, and Phen. This study was significant to evaluate size fractions of soil and sediment as well as their associated OM affecting EE2 and BPA sorption processes.     

Sorption of atrazine and phenanthrene by organic matter fractions in soil and sediment

Atrazine and phenanthrene (Phen) sorption by nonhydrolyzable carbon (NHC), black carbon (BC), humic acid (HA) and whole sediment and soil samples was examined. Atrazine sorption isotherms were nearly linear. The single-point organic carbon (OC)-normalized distribution coefficients (K_OC) of atrazine for the isolated HA1, NHC1 and BC1 from sediment 1 (ST1) were 36, 550, and 1470 times greater than that of ST1, respectively, indicating the importance of sediment organic matter, particularly the condensed fractions (NHC and BC). Similar sorption capacity of atrazine and Phen by NHC but different isotherm nonlinearity indicated different sorption domains due to their different structure and hydrophobicity. The positive relationship between (O + N)/C ratios of NHC and atrazine log K_OC at low concentration suggests H-bonding interactions. This study shows that sediment is probably a less effective sorbent for atrazine than Phen, implying that atrazine applied in sediments or soils may be likely to leach into groundwater.     

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.     

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.     

Sorption of simazine to corn straw biochars prepared at different pyrolytic temperatures

Simazine sorption to corn straw biochars prepared at various temperatures (100-600 °C) was examined to understand its sorption behavior as influenced by characteristics of biochars. Biochars were characterized via elemental analysis, BET-N₂ surface area (SA), FTIR and ¹³C NMR. Freundlich and dual-mode models described sorption isotherms well. Positive correlation between log K_oc values and aromatic C contents and negative correlation between log K_oc values and (O + N)/C ratios indicate aromatic-rich biochars have high binding affinity to simazine (charge transfer (π-π*) interactions) and hydrophobic binding may overwhelm H-bonding, respectively. Dual-mode model results suggest adsorption contribution to total sorption increases with carbonization degree. Positive correlation between amounts of adsorption (Q_ad) and SA indicates pore-filling mechanism. Comparison between our results and those obtained with other sorbents indicates corn straw biochars produced at higher temperature can effectively retain simazine. These observations will be helpful for designing biochars as engineered sorbents to remove triazine herbicides.     

An integrated approach to understanding the sorption mechanism of phenanthrene by cork

Previous studies have shown the high sorption affinity of polycyclic aromatic hydrocarbons by cork. The aim of the present work is to go further by investigating the sorption mechanism of polycyclic aromatic hydrocarbons (exemplified by phenanthrene) on cork and the availability of the chemical components (i.e. lignin, suberin, holocellulose and extractives) to retain phenanthrene.Two approaches were integrated to reach this objective: (1) statistical multivariate analysis to obtain correlations between the sorption capacity, measured as K_oc, and the sorbent properties (i.e. polarity, acidic functional groups, %dichloromethane extractives, %ethanol and water extractives, %suberin, %lignin and %holocellulose) and (2) modeling calculations to obtain information on interaction at the molecular level.The statistical multivariate analysis demonstrated a strong and positive correlation between K_oc and the lignin content as well as negative correlations between K_oc and the phenolic groups and %dichloromethane extractives contents. The modeling study showed that the lignin–phenanthrene interaction is mostly hydrophobic in nature being largely determined by the π-stacking interaction between the aromatic groups of the interacting partners. This result justifies the observed correlations as dichloromethane extractives, being hydrophobic, compete with phenanthrene adsorption, whereas phenolic groups, as well as negatively charged groups, enhance the hydrophilic character of the sorbent surface, thus hindering the adsorption of phenanthrene.     

Activated soil filters for removal of biocides from contaminated run-off and waste-waters

Building facades can be equipped with biocides to prevent formation of algal, fungal and bacterial films. Thus run-off waters may contain these highly active compounds. In this study, the removal of several groups of biocides from contaminated waters by means of an activated soil filter was studied.A technical scale activated vertical soil filter (biofilter) with different layers (peat, sand and gravel), was planted with reed (Phragmites australis) and used to study the removal rates and fate of hydrophilic to moderate hydrophobic (log K_ow 1.8-4.4) biocides and biocide metabolites such as: Terbutryn, Cybutryn (Irgarol® 1051), Descyclopropyl-Cybutryn (Cybutryn and Terbutryn metabolite), Isoproturon, Diuron, and its metabolite Diuron-desmonomethyl, Benzo-isothiazolinone, n-Octyl-isothiazolinone, Dichloro-n-octylisothiazolinone and Iodocarbamate (Iodocarb). Three experiments were performed: the first one (36 d) under low flow conditions (61 L m⁻² d⁻¹) reached removal rates between 82% and 100%. The second one was performed to study high flow conditions: During this experiment, water was added as a pulse to the filter system with a hydraulic load of 255 L m⁻² within 5 min (retention time <1 h). During this experiment the removal rates of the compounds decreased drastically. For five compounds (Cybutryn, Descyclopropyl-Cybutryn, Diuron, Isoproturon, and Iodocarb) the removal dropped temporarily below 60%, while it was always above 70% for the others (Terbutryn, Benzo-isothiazolinone, n-Octyl-isothiazolinone, Dichloro-n-octylisothiazolinone). However, this removal is a considerable improvement compared to direct discharge into surface waters or infiltration into soil without appropriate removal. In the last experiment the removal efficiencies of the different layers were studied. Though the peat layer was responsible for most of the removal, the sand and gravel layers also contributed significantly for some compounds. All compounds are rather removed by degradation than by sorption.     

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.     

Sulfadimethoxine and sulfaguanidine: their sorption potential on natural soils

Sulfonamides (SAs) are one of the oldest groups of veterinary chemotherapeutic agents. As these compounds are not completely metabolized in animals, a high proportion of the native form is excreted in feces and urine. They are therefore released either directly to the environment in aquacultures and by grazing animals, or indirectly during the application of manure or slurry. Once released into the environment, SAs become distributed among various environmental compartments and may be transported to surface or ground waters. The physicochemical properties of SAs, dosage and nature of the matrix are the factors mainly responsible for their distribution in the natural environment. Although these rather polar compounds have been in use for over half a century, knowledge of their fate and behavior in soil ecosystems is still limited. Therefore, in this work we have determined the sorption potential of sulfadimethoxine and sulfaguanidine on various natural soils. The influence on sorption of external factors, such as ionic strength and pH, were also determined. The sorption coefficients (K_d) obtained for the sulfonamides investigated were quite low (from 0.20 to 381.17 mL g⁻¹ for sulfadimethoxine and from 0.39 to 35.09 mL g⁻¹ for sulfaguanidine), which indicated that these substances are highly mobile and have the potential to run off into surface waters and/or infiltrate ground water. Moreover, the sorption of these pharmaceuticals was found to be influenced by OC, soil solution pH and ionic strength, with higher K_d values for soils of higher OC and lower K_d values with increasing pH and ionic strength.     

Temperature-dependent sorption of polycyclic aromatic hydrocarbons on natural and treated sediments

In aqueous environment temperature is considered to play a significant role in the sorption process of polycyclic aromatic hydrocarbons (PAHs) and its influence on the sorption equilibrium is indicative of sorption energies and mechanisms. In this study, sorptions of five PAHs on three heterogeneous sorbents including one river sediment (YHR), one estuary sediment (YRD) and one treated sediment with organic matter removed (IM) were carried out at a range of temperature from 5 °C to 35 °C. Stronger sorptions were observed at lower temperatures, with the equilibrium sorption coefficient K_d increasing 2-5 times as the temperature decreases 30 °C. The increase of K_d value was attributed primarily to the change of PAH water solubility, which predicted 40-75% of the increase of K_d in the sorption process. To provide insight into the sorption mechanism, enthalpy change (ΔH_S) for the sorption process was calculated and the values were observed to be negative for all of the interactions, suggesting that the exothermal sorption of PAHs inversely dependents on temperature. Based on the values of ΔH_S, van der Waals forces were inferred as the main sorption mechanism for the PAHs, especially on the YHR sediment which contained more organic matter. For sorption of larger size PAHs on the sorbents with low organic matter, specific interactions were deduced to contribute to the overall sorption.