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1.
A PAH contaminated river floodplain soil was separated according to grain size and density. Coal and coal-derived particles from coal mining, coal industry and coal transportation activities were identified by organic petrographic analysis in our samples. Distinct concentrations of PAHs were found in different grain size and density fractions, however, similar distribution patterns of PAHs indicated similar sources. In addition, although light fractions had the mass fraction by weight of less than 5%, they contributed almost 75% of the total PAHs in the soil. PAH concentrations of all sub fractions showed positive correlation with their TOC contents. Altogether, coal and coal-derived particles that were abundant in light fractions could be the dominant geosorbents for PAHs in our samples.  相似文献   

2.
3.
The aim of this study is to investigate how the presence of Cu influences tebuconazole (Teb) sorption onto contrasting soil types and two important constituents of the soil sorption complex: hydrated Fe oxide and humic substances. Tebuconazole was used in commercial form and as an analytical-grade chemical at different Teb/Cu molar ratios (1:4, 1:1, 4:1, and Teb alone). Increased Cu concentrations had a positive effect on tebuconazole sorption onto most soils and humic substances, probably as a result of Cu?Teb tertiary complexes on the soil surfaces. Tebuconazole sorption increased in the following order of different Teb/Cu ratios 1:4?>?1:1?>?4:1?>?without Cu addition, with the only exception for the Leptosol and ferrihydrite. The highest K f value was observed for humic substances followed by ferrihydrite, the Cambisol, the Arenosol, and the Leptosol. The sorption of analytical-grade tebuconazole onto all matrices was lower, but the addition of Cu supported again tebuconazole sorption. The Teb/Cu ratio with the highest Cu addition (1:4) exhibited the highest K f values in all matrices with the exception of ferrihydrite. The differences in tebuconazole sorption can be attributed to the additives present in the commercial product. This work proved the importance of soil characteristics and composition of the commercially available pesticides together with the presence of Cu on the behavior of tebuconazole in soils.  相似文献   

4.
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   

5.
Sequential supercritical fluid extraction (SFE) was performed in order to estimate desorption of PAHs from river floodplain soils which contain coal and coal-derived particles. Original soils, soils' light fractions (ρ < 2 g cm−3), and <63 μm fractions were studied for PAHs' desorption kinetics. Desorption data were successfully described using a two-site model. Desorption rate constants were one order of magnitude lower than those of “slow” and “very slow” desorption rates from other studies. This suggests very slow and extremely slow desorption. Estimated time scales releasing 99% of total extractable contaminants ranged from decades for 2-4-ring PAHs and hundreds of years for 5-6-ring PAHs. We demonstrate that, despite high soil PAH concentrations which are due to coal and coal-derived particles, the general environmental risk is reduced by the very slow and extremely slow desorption rates.  相似文献   

6.
Sorption–desorption of the insecticide imidacloprid 1-[(6-chloro-3-pyridinyl)-methyl]-N-nitro-2-imidazolidinimine onto a lacustrine sandy clay loam Egyptian soil and its clay and humic acid (HA) fractions was investigated in 24-h batch equilibrium experiments. Imidacloprid (IMDA) sorption–desorption isotherms onto the three sorbents were found to belong to a non-linear L-type and were best described by the Freundlich model. The value of the IMDA adsorption distribution coefficient, Kdads, varied according to its initial concentration and was ranged 40–84 for HA, 14–58 for clay and 1.85–4.15 for bulk soil. Freundlich sorption coefficient, Kfads, values were 63.0, 39.7 and 4.0 for HA, clay and bulk soil, respectively. The normalized soil Koc value for imidacloprid sorption was ~800 indicating its slight mobility in soils. Nonlinear sorption isotherms were indicated by 1/nads values <1 for all sorbents. Values of the hysteresis index (H) were <1, indicating the irreversibility of imidacloprid sorption process with all tested sorbents. Gibbs free energy (ΔG) values indicated a spontaneous and physicosorption process for IMDA and a more favorable sorption to HA than clay and soil. In conclusion, although the humic acid fraction showed the highest capacity and affinity for imidacloprid sorption, the clay fraction contributed to approximately 95% of soil-sorbed insecticide. Clay and humic acid fractions were found to be the major two factors controlling IMDA sorption in soils. The slight mobility of IMDA in soils and the hysteresis phenomenon associated with the irreversibility of its sorption onto, mainly, clay and organic matter of soils make its leachability unlikely to occur.  相似文献   

7.
Yang Y  Ligouis B  Pies C  Achten C  Hofmann T 《Chemosphere》2008,71(11):2158-2167
Organic petrographic analysis was applied to provide direct information on carbonaceous geosorbents for PAHs in river floodplain soils. The anthropogenic OM group (primarily coal and coal-derived particles) displayed large volume amounts for all the soil samples. Distinct PAH concentrations with similar PAH distribution patterns were determined in grain size and density fractions for each sample. Two-ring PAHs had stronger correlation to organic carbon (OC) than black carbon (BC) contents, while heavier PAHs showed correlation to BC, rather than OC. In this study, we combined grain size and density separation, PAH determinations, TOC and BC measurements, and organic petrographic identification, and concluded that two-ring PAHs in soils were associated to coal particles. Other heavier PAHs could be more controlled by black carbon (BC), which were mostly coal-derived particles from former coal mining and coal industrial activity.  相似文献   

8.
Marbofloxacin (MAR) and Enrofloxacin (ENR), two largely employed veterinary Fluoroquinolones (FQs), were found to be present at the micrograms per kilogram level in agricultural soils of South Lombardy (Italy) several months after manuring. Distribution coefficients (Kd) from sorption experiments indicated a strong binding to the soil. Soil samples fortified with environmentally significant FQs amounts (0.5 mg kg−1) were exposed to solar light that promoted extensive degradation (80%) of both drugs in 60-150 h. Thus, photochemistry could be considered a significant depollution path in the soil, although it was two orders of magnitudes slower than in aqueous solution and a fraction of the drug (ca. 20%) remained unaffected. For MAR the photoprocess was the same as in solution, and involved cleavage of the tetrahydrooxadiazine ring. On the contrary, with ENR only some of the photoproducts determined in water (those arising from a stepwise oxidation of the piperazine side chain) were observed. Substitution of the 6-fluoro by a hydroxyl group and reduction did not occur in the soil, supporting the previous contention that such processes required polar solvation of FQs. Consistently with this rationalization, the irradiation of thin layers of solid drugs led to essentially the same products distribution as in the soil. From the environmental point of view it is important to notice that photodegradation mainly affects the side-chains, while the fluoroquinolone ring, to which the biological effect is associated, is conserved up to the later stages of the degradation.  相似文献   

9.
Pharmaceuticals and personal care products (PPCPs) are one class of the most urgent emerging contaminants, which have drawn much public and scientific concern due to widespread contamination in aquatic environment. Most studies on the environmental fate and behavior of PPCPs have focused on nonsteroidal anti-inflammatory drugs. Some other compounds with high concentrations were less mentioned. In this study, sorption and degradation of five selected PPCPs, including bisphenol A (BPA), carbamazepine (CBZ), gemfibrozil (GFB), octylphenol (OP), and triclosan (TCS) have been investigated using three different soils. Sorption isotherms of all tested PPCPs in soils were well described by Freundlich equation. TCS and OP showed moderate to strong sorption, while the sorption of GFB and CBZ in soils was negligible. Degradation of PPCPs in three soils was generally fitted first-order exponential decay model, with half-lives (t 1/2) varying from 9.8 to 39.1 days. Sterilization could prolong the t 1/2 of PPCPs in soil, indicating that microbial activity played an important role in the degradation of these chemicals in soils. Degradation of PPCPs in soils was also influenced by the soil organic carbon (f oc) contents. Results from our data show that sorption to the soils varied among the different PPCPs, and their sorption affinity on soil followed the order of TCS > OP > BPA > GFB > CBZ. The degradation of the selected PPCPs in soil was influenced by the microbial activity and soil type. The poor sorption and relative persistence of CBZ suggest that it may pose a high leaching risk for groundwater contamination when recycled for irrigation.  相似文献   

10.
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   

11.
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   

12.
The sorption of 1,2,4-trichlorobenzene and tetrachloroethene was investigated in a series of well-controlled batch experiments, using authigenic soil materials from a profile extending to 2.5 m below ground surface. Batch experiment techniques were verified by study with both pulverized and unpulverized soil at different times of equilibration, using two widely different soil:water ratios, and at a wide range of aqueous concentration. Sorption isotherms were approximately linear, with sorption distribution coefficients (Kd) found to decrease roughly 100-fold down the soil profile. Kd decreased with depth to an extent greater than could be predicted on the basis of the only 10-fold decrease in natural solid organic matter (SOM) content and despite significantly higher specific surface area in the lower horizons. All base-extractable SOM in these deeper soil horizons was operationally defined as fulvic acid (FA), although there was also a significant fraction that was not extracted by the standard base technique. The lower Kd of the deeper soil horizons is believed to reflect a complex combination of (1) lower SOM content; (2) a more hydrophilic form of SOM; and (3) a more intimate association of the SOM with the mineral fraction, affecting its accessibility, sorptivity, or both. For the deeper horizons, an increase in overall Kd by more than 4-fold was observed on solids treated by either base extraction or H2O2 treatment, demonstrating that sorption to remaining soil components could be dramatically increased by fractional SOM removal and/or chemical alteration of the soil. A simple regression model that divides SOM into only two types (shallow and deep SOM) provides a reasonably good explanation of sorption in all seven horizons and suggests an order-of-magnitude variability in Koc among surface soil and deeper horizons.  相似文献   

13.
The efficiency of aided phytostabilization using organic amendments such as ramial chipped wood (RCW) and composted sewage sludge (CSS) was studied on contaminated techno-soils, on nine experimental plots. The objective was to characterize the role of fulvic (FA) and humic acids (HA) on the mobilization of trace elements, specifically As, Cu, Mo, Pb and Zn. Results showed that the addition of CSS increased the total organic carbon and nitrogen content more than with RCW and as a result, the C/N ratio in the CSS soil was higher than in the RCW and non-amended (NE) soil, reflecting the high decomposition of soil organic matter in the CSS soil compared with the other soils. The RCW and CSS amendments increased the hydrogen index (HI) values and the oxygen index (OI) values compared with the NE soil, especially for the soil treated with CSS which contained more aliphatic than aromatic compounds. The addition of CSS to the techno-soil significantly increased the percentage of C org associated with the HA fractions compared with the RCW and NE soils. The soil amended with CSS showed the highest E 4/E 6 ratio and the lowest E 2/E 3 ratio of FA. Zn and As were more abundant in the FA fraction than in the HA fraction, whereas Pb, Cu and Mo were more associated to HA than to FA in the treated and untreated soils, which may explain the difference in their mobility and availability.  相似文献   

14.
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   

15.
This investigation was undertaken to determine the effect of amendment of two fly ashes [Kota and Inderprastha (IP)] on sorption behavior of metsulfuron-methyl in three Indian soil types. Kota fly ash (5%) did not show any effect on herbicide sorption while IP fly ash significantly enhanced the sorption. Further studies on metsulfuron-methyl sorption-desorption behavior in 0.5, 1, 2, and 5% IP fly ash-amended soils suggested that effect of fly ash varied with soil type and better effect was observed in low organic carbon content soils. The sorption-desorption isotherms fitted very well to the Freundlich sorption equation and, in general, slope (1/n) values less than unity were observed. Metsulfuron-methyl sorption in the IP fly ash-amended soils showed strong correlation with the fly ash content and compared to the Freundlich sorption constant (K f), K FA values (sorption normalized to fly ash content) showed less variation. Metsulfuron-methyl leaching studies suggested greater retention of herbicide in the application zone in IP fly ash-amended soils, but effect varied with soil type and no herbicide leaching was observed in 5% fly ash-amended soils. The study suggested that all coal fly ashes are not effective in enhancing the sorption of metsulfuron-methyl in soils. However, one which enhanced herbicide sorption, could play an important role in reducing its leaching losses.  相似文献   

16.
Ding G  Rice JA 《Chemosphere》2011,84(4):519-526
The chemical composition and physical conformation of natural organic matter (NOM) play a major role in regulating its capacity to retain hydrophobic organic compounds. Naphthalene and phenanthrene were used to study the correlations between sorption/desorption isotherm nonlinearity and compositional data obtained from quantitative 13C solid-state DPMAS NMR spectroscopy for soil and peat organic matter with or without lipids. Sorption experiments were conducted using a batch equilibration method. Desorption experiments were carried out immediately following the sorption experiments by three successive decant-refill cycles. Hysteresis was observed in all samples. Nonlinear sorption behavior was increased by removal of lipids from the NOM. The hysteresis index, obtained from the ratio of the Freundlich exponents (N values) for the desorption and sorption isotherms, was lower in the lipid-extracted NOM samples than in the same samples without lipid extraction. The relationship between the extent of hysteresis and the characteristics of the 13C DPMAS NMR spectra indicates that altering NOM composition through lipid extraction not only increased the proportion of aromatic-C content, but also increased sorption/desorption hysteresis. Our data also suggest that the hysteresis index is negatively related to aromaticity.  相似文献   

17.
Khunjar WO  Love NG 《Chemosphere》2011,82(6):917-922
The sorption of carbamazepine (CBZ), iopromide (IOP), trimethoprim (TMP) and 17α-ethinylestradiol (EE2) was evaluated using four biomass types (pure ammonia oxidizing bacterial culture, two heterotrophic enrichment cultures with varying levels of oxygenase activity, and a full-scale nitrifying activated sludge (NAS) culture). CBZ and IOP did not sorb to the four biomass types. EE2 did not sorb to the pure culture but sorbed significantly to the heterotrophic cultures and NAS. TMP sorbed to the heterotrophic cultures and NAS, and was not evaluated for the pure culture. Three floc characteristics (hydrophobicity, median particle size, organic matter content) correlated moderately well with the EE2 organic matter sorption coefficient (KOM,EE2). Zeta potential did not correlate well with KOM,EE2 but did with KOM,TMP, indicating that TMP sorption is more influenced by electrostatic factors than EE2. Once divalent cation-linked exocellular polymeric substances (EPS) were removed from flocs, EE2 and TMP sorption to the non-EPS (cellular) fraction decreased by approximately 50%. The correlation between KOM,EE2 for the non-EPS cellular fraction deteriorated while the correlation between KOM,TMP improved. EE2 seemed to sorb more strongly to EPS protein whereas TMP sorbed equally to polysaccharide and protein EPS. Attempts to develop predictive models were not successful. Pharmaceuticals that sorbed to biomass samples underwent biodegradation whereas those that did not sorb were not biodegraded, suggesting a relationship between sorption and pharmaceutical biotransformation.  相似文献   

18.
Abstract

The sorption and desorption of diuron by soil samples from Horizons A and B (HA and HB) and by their different clay fractions were investigated, using two soil samples, classified as Typic Argiudoll and Oxic Argiudoll. The sorption and desorption curves were adjusted to the Freundlich model and evaluated by parameters Kf, Kd and Koc. Based on the data of groundwater ubiquity score (GUS), leachability index (LIX) and hysteresis index (HI), the risk of groundwater pollution was evaluated. The Kd values obtained for soil samples were between 4.5?mL g?1 (Oxic Argiudoll – HB) and 15.9?mL g?1 (Typic Argiudoll – HA) and between 1.13 and 14.0?mL g?1 for the different mineral fractions, whereas the Koc values varied between 276 (Oxic Argiudoll – HB) and 462 (Typic Argiudoll – HA). According to the parameter GUS, only Oxic Argiudoll – HB presented leaching potential, and based on the LIX index this same soil presented the highest leaching potential. Some samples presented low LIX and GUS values, indicating no leaching potential, but none presented HI results indicative of hysteresis, suggesting weak bonds between diuron and the soil samples and, hence, the risk of groundwater pollution by diuron.  相似文献   

19.
为了研究土霉素在人工湿地基质床中的行为机制,本实验采用批量平衡方法研究了壤土、煤灰渣、粗砂和细砂等4种人工湿地基质材料对土霉素的吸附、解吸特性。结果表明,土霉素在人工湿地基质材料上的吸附可分为前4小时的快速吸附阶段和之后的慢速吸附阶段,14 h后达到吸附平衡,这一吸附平衡时间明显低于一般人工湿地系统的水力停留时间。可以认为,土霉素在人工湿地中有足够的时间吸附于基质层上,其吸附量的大小主要取决于基质材料的性质。土霉素在4种基质材料上的等温吸附实验表明,吸附等温线均呈非线性,用Freundlich方程能较好地对吸附数据进行非线性拟合。在4种人工湿地基质材料中,煤灰渣对土霉素的吸附作用最强,通过Freundlich方程拟合的吸附容量参数(KF)为280.2;其次为壤土,KF值为129.3;粗砂和细砂的吸附作用较弱,KF值分别为53.2和64.5。人工湿地基质材料对土霉素的吸附能力主要与基质有机质含量、粘粒含量、Fe2O3含量、阳离子交换量和Al2O3含量呈正相关。土霉素在4种人工湿地基质材料上的解吸均存在滞后现象,相对于壤土和煤灰渣,吸附于粗砂和细砂上的土霉素更容易被解吸下来。  相似文献   

20.
Sorption and transport of trichloroethylene in caliche soil   总被引:3,自引:0,他引:3  
Sorption of TCE to the caliche soil exhibited linear isotherm at the high TCE concentrations (Co = 122-1300 mg L−1) but Freundlich isotherm at the low concentration range (1-122 mg L−1). Sorption strength of the carbonate fraction of the soil was about 100-fold lower than the sorption strength of soil organic matter (SOM) in the caliche soil, indicating weak affinity of TCE for the carbonate fraction of the soil. Desorption of TCE from the caliche soil was initially rapid (7.6 × 10−4 s−1), then continued at a 100-fold slower rate (7.7 × 10−6 s−1). Predominant calcium carbonate fraction of the soil (96%) was responsible for the fast desorption of TCE while the SOM fraction (0.97%) controlled the rate-limited desorption of TCE. Transport of TCE in the caliche soil was moderately retarded with respect to the water (R = 1.75-2.95). Flow interruption tests in the column experiments indicated that the rate-limited desorption of TCE controlled the non-ideal transport of TCE in the soil. Modeling studies showed that both linear and non-linear nonequilibrium transport models provided reasonably good match to the TCE breakthrough curves (r2 = 0.95-0.98). Non-linear sorption had a negligible impact on both the breakthrough curve shape and the values of sorption kinetics parameters at the high TCE concentration (Co = 1300 mg L−1). However, rate-limited sorption/desorption processes dominated at this concentration. For the low TCE concentration case (110 mg L−1), in addition to the rate-limited sorption/desorption, contribution of the non-linear sorption to the values of sorption kinetics became fairly noticeable.  相似文献   

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