Sorption of naphthalene and phenanthrene by soil humic acids

Humic acids are a major fraction of soil organic matter (SOM), and sorption of hydrophobic organic chemicals by humic acids influences their behavior and fate in soil. A clear understanding of the sorption of organic chemicals by humic acids will help to determine their sorptive mechanisms in SOM and soil. In this paper, we determined the sorption of two hydrophobic organic compounds, naphthalene and phenanthrene by six pedogenetically related humic acids. These humic acids were extracted from different depths of a single soil profile and characterized by solid-state CP/MAS 13C nuclear magnetic resonance (NMR). Aromaticity of the humic acids increased with soil depth. Similarly, atomic ratios of C/H and C/O also increased with depth (from organic to mineral horizons). All isotherms were nonlinear. Freundlich exponents (N) ranged from 0.87 to 0.95 for naphthalene and from 0.86 to 0.92 for phenanthrene. The N values of phenanthrene were consistently lower than naphthalene for a given humic acid. For both compounds, N values decreased with increasing aromaticity of the humic acids, such an inverse relationship was never reported before. These results support the dual-mode sorption model where partitioning occurs in both expanded (flexible) and condensed (rigid) domains while nonlinear sorption only in condensed domains of SOM. Sorption in the condensed domains may be a cause for slow desorption, and reduced availability and toxicity with aging.     

Monitoring and toxicity of sulfonated derivatives of benzene and naphthalene in municipal sewage treatment plants

Monitoring benzenesulfonates (BS) and naphthalenesulfonates (NS) took place in five municipal sewage treatment plants (STP). A previously optimized method based on solid phase extraction with polymeric cartridges followed by ion-pair liquid chromatography-electrospray-mass spectrometry (SPE-IPC-ESI-MS) was used. This work confirmed the little or no effect of primary settlement on total organic carbon (TOC) and monosulfonated compounds removal, whereas the main reduction is obtained at the biological stage. However, the most polar compounds, such as naphthalenedisulfonates (NDS), were not effectively removed using the biological treatment. An aromatic sulfonated compound is suggested to be used as a tracer of the origin of industrial pollutants discharged into STPs. A bioluminescence inhibition test, Microtox assay, allowed toxicity determination of the most relevant aromatic sulfonated compounds detected and toxicity comparison between primary and secondary effluents.     

Sorption of naphthalene derivatives to soils from a long-term field experiment

The influence of long-term farming practices on the soil's behaviour to adsorb hydrophobic organic compounds (HOCs) over long times was investigated. Adsorption of five naphthalene derivatives (naphthalene, 1-naphthol, 1-naphthylamine, 1-hydroxy-2-naphthoic acid, 1,4-naphthoquinone) was examined on soils with varying amounts and origins of soil organic matter obtained after amendment with different organic materials over more than 40 years. Soil organic matter, pore sizes and aggregate stability were significantly altered influencing the adsorption behaviour of the soils. Samples of soil amended with peat having an organic carbon content of 3.4% sorbed naphthalene derivatives stronger than the soil treated with sewage sludge (2.6% C(org)). All other treatments, calcium nitrate, plots without nitrogen fertilizers, grassland, animal manure, green manure and the fallowed soil sorbed less and no significant difference was found between them although the organic carbon content ranged from 1.0% to 2.6%. Thus, a decrease of the carbon content of a soil does not necessarily imply a reduction of sorption capacities for hydrophobic compounds such as naphthalene derivatives. Furthermore, the importance of protonation of HOCs for the adsorption on soil surfaces was shown. Different polarities of electronic structures of HOCs distinctly influence their adsorption behaviour.     

The role of interfacial films in the mass transfer of naphthalene from creosotes to water

Viscous, semi-rigid interfacial films that are formed at the interface of certain multi-component non-aqueous phase liquid (NAPLs) and water can significantly reduce the rates of mass transfer of solutes. Creosote-water systems were investigated for their ability to form interfacial films. The effects of these films on the creosote-water partition and on mass transfer of a representative solute, naphthalene, were investigated in a series of experiments. The area-independent mass transfer coefficient of naphthalene contained in creosote decreased by 30% over a 1-week period in systems containing creosote and water. Further aging for up to 21 days did not result in significant additional decreases in the mass transfer coefficient. The creosote-water partition coefficient, however, did not change with extended contact. The presence of viscous interfacial films in creosote-water systems was demonstrated in pendant drop tests. These interfacial films most likely caused the reduction in solute mass transfer coefficients by providing significant resistance to the diffusion of solutes through the interfacial film. Results from mass transfer experiments conducted under different system conditions suggested that hindered diffusion of naphthalene through the bulk creosote phase, changes in composition of creosote as a result of extended dissolution, or changes in creosote-water interfacial area did not contribute to the decrease in naphthalene mass transfer coefficient.     

An analytical quantification of mass fluxes and natural attenuation rate constants at a former gasworks site

A new integral groundwater investigation approach was used for the first time to quantify natural attenuation rates at field scale. In this approach, pumping wells positioned along two control planes were operated at distances of 140 and 280 m downstream of a contaminant source zone at a former gasworks site polluted with BTEX- (benzene, toluene, ethyl-benzene, o-, p-xylene) and PAH- (polycyclic aromatic hydrocarbons) compounds. Based on the quantified changes in total contaminant mass fluxes between the control planes, first-order natural attenuation rate constants could be estimated. For BTEX-compounds, these ranged from 1.4e-02 to 1.3e-01 day(-1) whereas for PAH-compounds natural attenuation rate constants of 3.7e-04 to 3.1e-02 day(-1) were observed. Microbial degradation activity at the site was indicated by an increase in dissolved iron mass flux and a reduction in sulphate mass flux between the two investigated control planes. In addition to information about total contaminant mass fluxes and average concentrations, an analysis of the concentration-time series measured at the control planes also allowed to semi-quantitatively delineate the aquifer regions most likely contaminated by the BTEX- and PAH-compounds.     

Contaminant degradation in physically and chemically heterogeneous aquifers

This paper examines the importance of the correlation between hydraulic conductivity (K) and degradation rate constant (k) during the transport of reactive contaminants in heterogeneous aquifers. We simulated reactive transport in an ensemble of two-dimensional heterogeneous aquifers. Two sets of transport simulations were conducted: one in which a perfect positive correlation was assumed between ln(K) and ln(k), and one in which a perfect negative correlation was assumed. We found that the sign of the correlation has important consequences for the contaminant transport. Qualitatively, a negative correlation leads to significantly more pronounced "fingering" of the contaminant plume than does a positive correlation, with potentially important consequences for downgradient receptors. Quantitatively, the expected behavior (as quantified by the contaminant mass remaining in the aquifer) is statistically different between the positive and negative cases: on average, more contaminant mass persists when K and k are negatively correlated. Also, the negative correlation leads to more variability between realizations of the ensemble, whereas a positive correlation induces relatively little variability between realizations. We discuss the implications of these findings for the management of contaminated aquifers.     

Sorption and leaching of flucetosulfuron in soil

Abstract

The adsorption–desorption and leaching of flucetosulfuron, a sulfonylurea herbicide, was investigated in three Indian soils. Freundlich adsorption isotherm described the sorption mechanism of herbicide with adsorption coefficients (K_f) ranging from 17.13 to 27.99 and followed the order: Clayey loam?>?Loam?>?Sandy loam. The K_f showed positive correlation with organic carbon (OC) (r?=?0.910) and clay content (r?=?0.746); but, negative correlation with soil pH (r = ?0.635). The adsorption isotherms were S-type suggesting that herbicide adsorption was concentration dependent and increased with increase in concentration. Desorption followed the sequence: sandy loam?>?clayey loam?>?loam . Hysteresis (H) was observed in all the three soils with H?<?1. Leaching of flucetosulfuron correlated positively with the soil pH; but, negatively with the OC content. Sandy loam soil (OC- 0.40%, pH ?7.25) registered lowest adsorption and highest leaching of flucetosulfuron while lowest leaching was found in the loam soil (pH ? 7.89, OC ? 0.65%). The leaching losses of herbicide increased with increase in the rainfall intensity. This study suggested that the soil OC content, pH and clay content played important roles in deciding the adsorption–desorption and leaching behavior of flucetosulfuron in soils.     

Sorption and desorption of sulfentrazone in Brazilian soils

This study was undertaken to obtain information about the behavior of sulfentrazone in soil by evaluating the sorption and desorption of the herbicide in different Brazilian soils. Batch equilibrium method was used and the samples were analyzed by high performance liquid chromatography. Based on the results obtained from the values of Freundlich constants (Kf), we determined the order of sorption (Haplic Planosol < Red-Yellow Latosol < Red Argisol < Humic Cambisol < Regolitic Neosol) and desorption (Regolitic Neosol < Red Argisol < Humic Cambisol < Haplic Planosol < Red-Yellow Latosol) of sulfentrazone in the soils. The process of pesticide sorption in soils was dependent on the levels of organic matter and clay, while desorption was influenced by the organic matter content and soil pH. Thus, the use of sulfentrazone in soils with low clay content and organic matter (low sorption) increases the probability of contaminating future crops.     

Sorption and transport of trichloroethylene in caliche soil

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.     

Sorption and degradation of imidacloprid in soil and water

Imidacloprid, the major component of many widely used insecticide formulations, is highly persistent in soils. In this study, the sorption of imidacloprid by six soils as well as its photodegradation and hydrolysis in water were studied. The soils differed significantly in organic matter content and other physical and chemical properties. Sorption increased with increasing soil organic matter content but was not significantly correlated with other soil properties. Removal of organic matter via H2O2 oxidation decreased the sorption. By normalizing the Freundlich coefficients (Kf) to organic matter contents, the variability in obtained sorption coefficient (Kom) was substantially reduced. These results indicate that soil organic matter was the primary sorptive medium for imidacloprid. The low heat of sorption calculated from Kom suggests that partition into soil organic matter was most likely the mechanism. The photodegradation and hydrolysis of imidacloprid in water followed pseudo-first-order kinetics; however, the latter process needed a six-time-higher activation energy. While both processes produced the same main intermediate, they occurred via different pathways. The hydrolysis of imidacloprid was not catalyzed by the high interlayer pH in the presence of metal-saturated clays, which appeared to result from the lack of the pesticide adsorption in the interlayers of clays.     

Sorption and Desorption of Three Endocrine Disrupters in Soils

Sorption of the estrogens estrone (E1), 17β-estradiol (E2) and 17α-ethynylestradiol (EE2) on four soils was examined using batch equilibrium experiments with initial estrogen concentrations ranging from 10 to 1000 ng mL^?1. At all concentrations, >85% of the three estrogens sorbed rapidly to a sandy soil. E1 sorbed more strongly to soil than E2 or EE2. Partial oxidation of E2 to E1 was observed in the presence of soils. Autoclaving was more effective at reducing this conversion than inhibition with sodium azide or mercuric chloride, and had little effect on sorption, relative to the chemical microbial inhibitors. Sorption of EE2 was greater for fine-textured than coarse-textured soils, but greater than 90% of EE2 sorbed onto all four soils. The greatest degree of desorption of estrogens from the sandy soil occurred with the lowest initial concentration of 10 ng mL^?1 and reached levels ≥80% for E1 and E2. Desorption of EE2 was greater in coarser textured soils than finer-textured soils. Again, relative desorption from all soils was greatest with low initial concentrations. Therefore, at environmentally relevant concentrations, estrogens quickly sorb to soils, and soils have a large capacity to bind estrogens, but these endocrine-disrupting compounds can become easily desorbed and released into the aqueous phase.     

Sorption and predicted mobility of herbicides in Baltic soils

This study was undertaken to determine sorption coefficients of eight herbicides (alachlor, amitrole, atrazine, simazine, dicamba, imazamox, imazethapyr, and pendimethalin) to seven agricultural soils from sites throughout Lithuania. The measured sorption coefficients were used to predict the susceptibility of these herbicides to leach to groundwater. Soil-water partitioning coefficients were measured in batch equilibrium studies using radiolabeled herbicides. In most soils, sorption followed the general trend pendimethalin > alachlor > atrazine approximately amitrole approximately simazine > imazethapyr > imazamox > dicamba, consistent with the trends in hydrophobicity (log K(ow)) except in the case of amitrole. For several herbicides, sorption coefficients and calculated retardation factors were lowest (predicted to be most susceptible to leaching) in a soil of intermediate organic carbon content and sand content. Calculated herbicide retardation factors were high for soils with high organic carbon contents. Estimated leaching times under saturated conditions, assuming no herbicide degradation and no preferential water flow, were more strongly affected by soil textural effects on predicted water flow than by herbicide sorption effects. All herbicides were predicted to be slowest to leach in soils with high clay and low sand contents, and fastest to leach in soils with high sand content and low organic matter content. Herbicide management is important to the continued increase in agricultural production and profitability in the Baltic region, and these results will be useful in identifying critical areas requiring improved management practices to reduce water contamination by pesticides.     

Sorption and desorption of three endocrine disrupters in soils

Sorption of the estrogens estrone (E1), 17beta-estradiol (E2) and 17alpha-ethynylestradiol (EE2) on four soils was examined using batch equilibrium experiments with initial estrogen concentrations ranging from 10 to 1000 ng mL-1. At all concentrations, >85% of the three estrogens sorbed rapidly to a sandy soil. E1 sorbed more strongly to soil than E2 or EE2. Partial oxidation of E2 to E1 was observed in the presence of soils. Autoclaving was more effective at reducing this conversion than inhibition with sodium azide or mercuric chloride, and had little effect on sorption, relative to the chemical microbial inhibitors. Sorption of EE2 was greater for fine-textured than coarse-textured soils, but greater than 90% of EE2 sorbed onto all four soils. The greatest degree of desorption of estrogens from the sandy soil occurred with the lowest initial concentration of 10 ng mL-1 and reached levels >or=80% for E1 and E2. Desorption of EE2 was greater in coarser textured soils than finer-textured soils. Again, relative desorption from all soils was greatest with low initial concentrations. Therefore, at environmentally relevant concentrations, estrogens quickly sorb to soils, and soils have a large capacity to bind estrogens, but these endocrine-disrupting compounds can become easily desorbed and released into the aqueous phase.     

Sorption and predicted mobility of herbicides in Baltic soils

This study was undertaken to determine sorption coefficients of eight herbicides (alachlor, amitrole, atrazine, simazine, dicamba, imazamox, imazethapyr, and pendimethalin) to seven agricultural soils from sites throughout Lithuania. The measured sorption coefficients were used to predict the susceptibility of these herbicides to leach to groundwater. Soil-water partitioning coefficients were measured in batch equilibrium studies using radiolabeled herbicides. In most soils, sorption followed the general trend pendimethalin > alachlor > atrazine～ amitrole～ simazine > imazethapyr > imazamox > dicamba, consistent with the trends in hydrophobicity (log K_ow) except in the case of amitrole. For several herbicides, sorption coefficients and calculated retardation factors were lowest (predicted to be most susceptible to leaching) in a soil of intermediate organic carbon content and sand content. Calculated herbicide retardation factors were high for soils with high organic carbon contents. Estimated leaching times under saturated conditions, assuming no herbicide degradation and no preferential water flow, were more strongly affected by soil textural effects on predicted water flow than by herbicide sorption effects. All herbicides were predicted to be slowest to leach in soils with high clay and low sand contents, and fastest to leach in soils with high sand content and low organic matter content. Herbicide management is important to the continued increase in agricultural production and profitability in the Baltic region, and these results will be useful in identifying critical areas requiring improved management practices to reduce water contamination by pesticides.     

The dissolution of benzene, toluene, m-xylene and naphthalene from a residually trapped non-aqueous phase liquid under mass transfer limited conditions

The results of dissolution experiments for benzene, toluene, m-xylene and naphthalene (BTXN) from a relatively insoluble oil phase (tridecane), residually trapped in a non-sorbing porous medium, are described. This mixture was chosen to simulate dissolution of soluble aromatic compounds from a petroleum hydrocarbon mixture, e.g., crude oil, for which a large fraction of the mixture is relatively insoluble. The experiments were carried out at a small source length to interstitial velocity ratio, L/v, so that dissolution would be mass transfer limited (MTL). When fitted to data for toluene, a multiregion mass transfer model was found to predict the experimental data satisfactorily for the other components without adjustment of the mass transfer rate parameters. These results indicate that the dissolution process can be generalized for various hydrophobic organic compounds present in a multicomponent non-aqueous phase liquid (NAPL) when mass transfer limitations are present. This also suggests that dissolution data obtained for one compound can be useful for predicting the dissolution histories for other compounds from petroleum hydrocarbon mixtures.     

Sorption and desorption of sulfadiazine in soil and soil-manure systems

Sulfadiazine is a widely used veterinary medicine that has high potential to enter the environment, especially the soil compartment by the application of manure on agricultural land and grass land or by the deposition of dung pats on pasture. Once it reaches the soil environments, it may enter into surface and ground water. Therefore, sorption-desorption behavior of sulfadiazine was studied under laboratory conditions in five different soils varying in their physicochemical properties. A batch equilibration technique was used with initial aqueous solution concentration of sulfadiazine at 5, 0.5, 0.05, and 0.005 microg mL(-1). Sorption-desorption data in soils with and without manure were well fitted with Freundlich model in log form (r(2), 0.99). A sorption-desorption hysteresis effect was apparent in all soils. A significant amount of sulfadiazine was found tightly bound to the soil particles and did not desorb after the desorption process. Moreover, presence of manure enhanced hysteresis effect. Hysteresis coefficient (H) value from soils in absence of manure (0.9-1.0) increased to the soils in presence of manure (0.9-1.8). Soils in the absence of manure showed low level of K(D Sorp.) values ranging from 0.1 to 24.3, suggesting low level sorption of sulfadiazine with appreciable risk of run-off and leaching, and in turn, surface and ground water contamination. However, presence of manure increased the sorption tendency of sulfadiazine significantly (K(D Sorp.), 6.9-40.2). K(D) values pertaining to desorption cycle increased from 1.2-90.4 to 10.4-167.3 in absence and presence of manure, respectively.     

Sorption of thiamethoxam in three Indian soils

The sorption behavior of the insecticide thiamethoxam [3-(2-chloro-1,3-thiazol-5-ylmethyl)-5-methyl-1,3,5-oxadiazinan-4-ylidene(nitro)amine] on three Indian soils with different physico-chemical properties was investigated. The soils represent the major grapevine growing areas of India, where the vineyards frequently receive thiamethoxam applications as foliar spray, soil drenching and through drip irrigation for the management of various insect pests. The rate constants for adsorption and desorption at two different temperatures were obtained from the Lindstrom model, which simultaneously evaluated adsorption and desorption kinetics. The data for rate constants, activation energies, enthalpy of activation, entropy of activation and free energy indicated physical adsorption of thiamethoxam on soil. The adsorptivity of different soils might be attributed to the organic matter and clay contents. A good fit to the linear and Freundlich isotherms was observed for both adsorption as well as desorption. Thiamethoxam could be categorized as a chemical with medium leaching potential.     

Sorption of perfluoroalkyl substances in sewage sludge

The sorption behaviour of three perfluoroalkyl substances (PFASs) (perfluorooctanesulfonic acid (PFOS), perfluorooctanoic acid (PFOA) and perfluorobutanesulfonic acid (PFBS)) was studied in sewage sludge samples. Sorption isotherms were obtained by varying initial concentrations of PFOS, PFOA and PFBS. The maximum values of the sorption solid–liquid distribution coefficients (K_d,max) varied by almost two orders of magnitude among the target PFASs: 140–281 mL g^?1 for PFOS, 30–54 mL g^?1 for PFOA and 9–18 mL g^?1 for PFBS. Freundlich and linear fittings were appropriate for describing the sorption behaviour of PFASs in the sludge samples, and the derived K_F and K_d,linear parameters correlated well. The hydrophobicity of the PFASs was the key parameter that influenced their sorption in sewage sludge. Sorption parameters and log(K_OW) were correlated, and for PFOS (the most hydrophobic compound), pH and Ca?+?Mg status of the sludge controlled the variation in the sorption parameter values. Sorption reversibility was also tested from desorption isotherms, which were also linear. Desorption parameters were systematically higher than the corresponding sorption parameters (up to sixfold higher), thus indicating a significant degree of irreversible sorption, which decreased in the sequence PFOS?>?PFOA?>?PFBS.     

Sorption of organic gases in residential rooms

Experiments were conducted to characterize organic gas sorption in residential rooms studied “as-is” with furnishings and material surfaces unaltered and in a furnished chamber designed to simulate a residential room. Results are presented for 10 rooms (five bedrooms, two bathrooms, a home office, and two multi-function spaces) and the chamber. Exposed materials were characterized and areas quantified. A mixture of volatile organic compounds (VOCs) was rapidly volatilized within each room as it was closed and sealed for a 5-h Adsorb phase; this was followed by 30-min Flush and 2-h closed-room Desorb phases. Included were alkane, aromatic, and oxygenated VOCs representing a range of ambient and indoor air pollutants. Three organophosphorus compounds served as surrogates for Sarin-like nerve agents. Measured gas-phase concentrations were fit to three variations of a mathematical model that considers sorption occurring at a surface sink and potentially a second, embedded sink. The 3-parameter sink–diffusion model provided acceptable fits for most compounds and the 4-parameter two-sink model provided acceptable fits for the others. Initial adsorption rates and sorptive partitioning increased with decreasing vapor pressure for the alkanes, aromatics and oxygenated VOCs. Best-fit sorption parameters obtained from experimental data from the chamber produced best-fit sorption parameters similar to those obtained from the residential rooms.