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1.
Lu C  Bjerg PL  Zhang F  Broholm MM 《Chemosphere》2011,83(11):1467-1474
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 (Kd 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 (Kd = 0.84-2.45 L kg−1), followed by trichloroethylene (TCE, Kd = 0.62-0.96 L kg−1), cis-dichloroethylene (cis-DCE, Kd = 0.17-0.82 L kg−1) and vinyl chloride (VC, Kd = 0.12-0.36 L kg−1). For chloroethanes, 1,1,1-trichloroethane (1,1,1-TCA) was most strongly sorbed (Kd = 0.2-0.45 L kg−1), followed by 1,1-dichloroethane (1,1-DCA, Kd = 0.16-0.24 L kg−1) and chloroethane (CA, Kd = 0.12-0.18 L kg−1). This is consistent with the order of hydrophobicity of the compounds. The octanol-water coefficient (log Kow) correlated slightly better with log Kd values than log Koc values indicating that the Kd values may be independent of the actual organic carbon content (foc). The estimated log Koc or log Kd 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 Kd 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.  相似文献   

2.
Wang L  Yang Z  Niu J 《Chemosphere》2011,82(6):895-900
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 Kd increasing 2-5 times as the temperature decreases 30 °C. The increase of Kd value was attributed primarily to the change of PAH water solubility, which predicted 40-75% of the increase of Kd in the sorption process. To provide insight into the sorption mechanism, enthalpy change (ΔHS) 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 ΔHS, 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.  相似文献   

3.
Sun K  Jin J  Gao B  Zhang Z  Wang Z  Pan Z  Xu D  Zhao Y 《Chemosphere》2012,88(5):577-583
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 Kd) 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 (Kd or KOC) 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 logKd 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.  相似文献   

4.
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 (Kd) 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 Kd values for soils of higher OC and lower Kd values with increasing pH and ionic strength.  相似文献   

5.
Wen Y  Su LM  Qin WC  Fu L  He J  Zhao YH 《Chemosphere》2012,86(6):634-640
The hydrophobic parameter represented by the octanol/water partition coefficient (log P) is commonly used to predict the soil sorption coefficient (Koc). However, a simple non-linear relationship between log Koc 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 Koc 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 Koc 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 Koc 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.  相似文献   

6.
Xiao D  Pan B  Wu M  Liu Y  Zhang D  Peng H 《Chemosphere》2012,86(2):183-189
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 (fOC) and single-point sorption coefficient (log Kd) was observed for all three chemicals in 10 soils/sediments. The large intercept in the log fOC − log Kd regression for PTR indicated that inorganic fractions control PTR sorption in soils/sediments. No relationship between specific surface area and Kd 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.  相似文献   

7.
Cyromazine (CY) is a triazine pesticide used as an insect growth inhibitor for fly control in cattle manure, field crops, vegetables, and fruits. Sorption of CY onto humic acid (HA) may affect its environmental fate. In this study, HA was used to investigate the sorption of CY at different solution chemistry conditions (pH, ionic strength) and in the presence of foreign ions and norfloxacin. All sorption isotherms fitted well with the Freundlich and Langmuir models. The sorption reached a maximum at initial pH 4.0 over the initial pH range of 3.0–7.0, implying that the primary sorption mechanism was cation exchange interaction between CY+ species and the negatively charged functional groups of HA. Increasing Ca2+ concentration resulted in a considerable reduction in the K d values of CY, hinting that Ca2+ had probably competed with CY+ for the cation exchange sites on the surfaces of HA. The sorption of CY on HA in different ionic media followed the order of NH4Cl ≈ KCl > K2SO4 > ZnCl2 ≈ CaCl2 at pH 5.0. Spectroscopic evidence demonstrated that the amino groups and triazine ring of CY was responsible for sorption onto HA, while the carboxyl group and the O-alkyl structure of HA participated in adsorbing CY.  相似文献   

8.
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, Kp, were calculated, and their relationship with the subcooled liquid vapor pressure pLo for both PAHs and PCBs was investigated. The regressions of log Kp vs. log pLo 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 KOA (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 KOA absorption model using the measured organic matter fraction (fOM) 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.  相似文献   

9.
When analyzing the sorption characteristics of weakly sorbing or labile pesticides, batch methods tend to yield a high margin of error attributable to errors in concentration measurement and to degradation, respectively. This study employs a recently developed unsaturated transient flow method to determine the sorption of isoxaflutole's herbicidally active diketonitrile degradate (DKN) and dicamba. A 20-cm acrylic column was packed with soils with varied texture that had been uniformly treated with 14C-labeled chemical.

The antecedent solution herbicide in equilibrium with sorbed phase herbicide was displaced by herbicide-free water, which was infiltrated into the column. Sorption coefficients, Kd, were obtained from a plot of total herbicide concentration in the soil versus water content in the region where the antecedent solution accumulated. DKN Kd values were ~2–3 times (average Kd = 0.71 L kg?1) greater using the unsaturated transient flow method as compared to the batch equilibration method in clay loam (Kd = 0.33 L kg?1), but similar for the two methods in sand (0.12 vs 0.09 L kg?1) soils. Dicamba Kd values were 3 times greater using the unsaturated transient flow method as compared to the batch equilibration method in the clay loam soil (0.38 vs 0.13 L kg?1), however, the Kd values were the same for the two methods in the sand (~0.06 L kg?1). This demonstrates that to determine sorption coefficients for labile hydrophilic pesticides, an unsaturated transient flow method may be a suitable alternative to the batch method. In fact, it may be better in cases where transport models have overpredicted herbicide leaching when batch sorption coefficients have been used.  相似文献   

10.
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 (KOC) 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 KOC 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.  相似文献   

11.
12.
《Chemosphere》2009,74(11):1832-1837
Sorption of nonpolar (phenanthrene and butylate) and polar (atrazine and diuron) organic chemicals to oil-contaminated soil was examined to investigate oil effects on sorption of organic chemicals and to derive oil–water distribution coefficients (Koil). The resulting oil-contaminated soil–water distribution coefficients (Kd) for phenanthrene demonstrated sorption-enhancing effects at both lower and higher oil concentrations (Coil) but sorption-reducing (competitive) effects at intermediate Coil (approximately 1 g kg−1). Rationalization of the different dominant effects was attempted in terms of the relative aliphatic carbon content which determines the accessibility of the aromatic cores to phenanthrene. Little or no competitive effect occurred for butylate because its sorption was dominated by partitioning. For atrazine and diuron, the changes in Kd at Coil above approximately 1 g kg−1 were negligible, indicating that the presently investigated oil has little or no effect on the two tested compounds even though the polarity of the oil is much less than soil organic matter (SOM). Therefore, specific interactions with the active groups (aromatic and polar domains) are dominantly responsible for the sorption of polar sorbates, and thus their sorption is controlled by available sorption sites. This study showed that the oil has the potential to be a dominant sorptive phase for nonpolar pollutants when compared to SOM, but hardly so for polar compounds. The results may aid in a better understanding of the role of the aliphatic and aromatic domains in sorption of nonpolar and polar organic pollutants.  相似文献   

13.
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 KOC data were compared with calculated KOC values derived from two different log KOW-log KOC correlation approaches. A significant pH-dependence on sorption was observed for all compounds with pKa in the considered pH range. Strong retardation was measured for several compounds despite their hydrophilic character. Besides an overall underestimation of KOC, 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 KOC correlations.  相似文献   

14.
Modifications of black carbons and their influence on pyrene sorption   总被引:2,自引:0,他引:2  
Zhang W  Wang L  Sun H 《Chemosphere》2011,85(8):1306-1311
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 (Koc) of 105.04-105.86 and 104.65-105.16, 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 Koc 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 Koc by 2.28-25.9% and 29.2-33.9%, respectively, while oximation increased Koc. 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.  相似文献   

15.
The adsorption behavior of 241Am, 60Co, 137Cs and 85Sr in the presence and absence of chelating ligands (ethylenediaminetetraacetic acid, ethylenediaminediacetic acid, hydroxyethyliminodiacetic acid, iminodiaceiticacid and methyliminodiacetic acid) was investigated. Sorption affinity in the absence of chelating ligands followed: Am(III) > Co(II) > Cs(I) > Sr(II). The presence of chelating ligands generally had little effect on sorption of 85Sr and 137Cs with Kd values 110 and 690 mL g−1, respectively. But at 0.02 M of ethylenediaminetetraacetic or hydroxyethyliminodiacetic, the Kd decreased to 5 or 63 mL g−1, respectively, where thermochemical modeling indicated almost all 85Sr is complexed with these ligands. The Kd values for 241Am and 60Co generally decreased with increasing chelating agent concentrations. In notable cases, the Kd values for Am increased at specific concentrations of 10−3 M for IDA, MIDA and 10−4 M for EDDA. This is proposed to be due to formation of a ternary surface complex.  相似文献   

16.

To assess the risk of a pesticide to leach to groundwater or to run off to surface water after application, it is necessary to characterize the sorption of the pesticide to soil. For pyrethroids, their hydrophobicity, strong sorption to various materials, and low solubility make it difficult to accurately characterize sorption processes. The objective of this research was to evaluate the variability in cyfluthrin ((RS)-α -cyano-4-fluoro-3-phenoxybenzyl (1RS,3RS;1RS,3SR)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate) sorption to soil as affected by experiment conditions. To minimize cyfluthrin sorption on the walls of glass, silanized-glass, stainless steel, and PTFE centrifuge tubes, cyfluthrin solution was added to aqueous soil slurries or directly to soil, after which it was equilibrated with aqueous solution. Depending on the soil, variation in sorption coefficients, K oc, obtained using different experimental methodologies with one soil can be comparable to the variation in K oc values obtained for soils with different physical and chemical properties using one method. K oc values for cyfluthrin ranged from 56,000 to 300,000 L kg?1. Sorption methodology needs to be evaluated before sorption coefficients are used in predictive transport models.  相似文献   

17.
Abstract

Chemical transport in soil is a major factor influencing soil and water contamination. Four soils and turfgrass thatch, representing a wide range of organic carbon OC content were studied to determine sorption Kd and Kf parameters for the insecticides chlorpyrifos and fonofos. The batch equilibrium method was used. The concentration of insecticide was measured in the solution as well as in the solid phase to determine the most accurate sorption data. Four soils and thatch were equilibrated for 24 h at 22 ± 1OC with aqueous insecticide solutions. Four concentrations of the insecticides, each <50% of their respective water solubilities, were selected for the experiments. After extraction with an organic solvent, the concentration of insecticides in the aqueous solution was determined by gas liquid chromatography using electron capture detection for chlorpyrifos, and nitrogen/phosphorus detection for fonofos. Data obtained were fitted to the log and simple linear form of the Freundlich equation. Mass balance Freundlich isotherm exponents n ranged between 0.82 and 0.93 for chlorpyrifos. 0.82 and 1.21 for fonofos, with r2 ≥ 0.97. Koc (percent of organic carbon %OC normalized Sorption coefficient) values were calculated by using experimentally developed Kd and Kf coefficients in relation to OC levels from 0.29 to 34.85%. Kd and Kf coefficients of both insecticides were positively correlated with OC (r2 ≥ 0.96). organic matter OM (r2 0.96), and cation exchange capacity CEC (r2 ≥ 0.90).  相似文献   

18.
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 Kd) 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.  相似文献   

19.
ABSTRACT

This study addresses the issues related to decontamination of marine beach sand accidentally contaminated by petroleum products. Sorption and desorption of BTEX (i.e., benzene, toluene, ethylbenzene, and xylene) onto the sand from Uran Beach, located near the city of Mumbai, India, were studied, and isotherms were determined using the bottle point method to estimate sorption coefficients. Alternatively, QSARs (i.e., quantitative structure activity relationships) were developed and used to estimate the sorption coefficients. Experiments for kinetics of volatilization as well as for kinetics of sorption and desorption in the presence of volatilization were conducted in a fabricated laboratory batch reactor. A mathematical model describing the fate of volatile hydrophobic organic pollutants like BTEX (via sorption and desorption in presence of volatilization) in a batch sediment-washing reactor was proposed. The experimental kinetic data were compared with the values predicted using the proposed models for sorption and desorption, and the optimum values of overall mass transfer coefficients for sorption (Ksas) and desorption (Kdad) were estimated.This was achieved by minimization of errors while using the sorption coefficients (Kp) obtained from either laboratory isotherm studies or the QSARs developed in the present study. Independent experimental data were also collected and used for calibration of the model for volatilization,and the values of the overall mass transfer coefficient for volatilization (Kgag) were estimated for BTEX. In these exercises of minimization of errors, comparable cumulative errors were obtained from the use of Kp values derived from experimental isotherms and QSARs.  相似文献   

20.
Use of animal manure is a main source of veterinary pharmaceuticals (VPs) in soil and groundwater through a series of migration processes. The sorption–desorption and transport of four commonly used VPs including trimethoprim (TMP), sulfapyridine, sulfameter, and sulfadimethoxine were investigated in three soil layers taken from an agricultural field in Chongming Island China and two types of aqueous solution (0.01 M CaCl2 solution and wastewater treatment plant effluent). Results from sorption–desorption experiments showed that the sorption behavior of selected VPs conformed to the Freundlich isotherm equation. TMP exhibited higher distribution coefficients (K d?=?6.73–9.21) than other sulfonamides (K d?=?0.03–0.47), indicating a much stronger adsorption capacity of TMP. The percentage of desorption for TMP in a range of 8–12 % is not so high to be considered significant. Low pH (<pK a of tested VPs) and rich soil organic matter (e.g., 0–20 cm soil sample) had a positive impact on sorption of VPs. Slightly lower distribution coefficients were obtained for VPs in wastewater treatment plant (WWTP) effluent, which suggested that dissolved organic matter might affect their sorption behavior. Column studies indicated that the transport of VPs in the soil column was mainly influenced by sorption capacity. The weakly adsorbed sulfonamides had a high recovery rate (63.6–98.0 %) in the leachate, while the recovery rate of TMP was only 4.2–10.4 %. The sulfonamides and TMP exhibited stronger retaining capacity in 20–80 cm and 0–20 cm soil samples, respectively. The transport of VPs was slightly higher in the columns leached by WWTP effluent than by CaCl2 solution (0.01 M) due to their sorption interactions.  相似文献   

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