Effects of organic matter heterogeneity on sorption and desorption of organic contaminants by soils and sediments

This review highlights the major progress over the last decade on characterization of geochemically heterogeneous soil/sediment organic matter (SOM) and the impacts of SOM heterogeneity on sorption and desorption of hydrophobic organic contaminants (HOCs) under equilibrium and rate limiting conditions. Sorption and desorption by soils and sediments are fundamental processes controlling fate and transport of less polar and nonpolar organic pollutants in surface aquatic and groundwater systems. Recent studies have shown that soils and sediments exhibit an array of HOC sorption phenomena that are inconsistent with an early partition model based on an assumption of homogeneous gel-like SOM. Increasing data have revealed that isotherm nonlinearity, varied sorption capacity, sorption–desorption hysteresis, and slow rates of sorption and desorption are characteristics for HOC sorption by soils and sediments. These phenomena have been shown to result from different types of condensed SOM that exhibit capacity limiting sorption processes. Recent findings of glass transition phenomena and the nonlinear HOC sorption by humic acids provide a scientific foundation for drawing an analogy between humic acids and synthetic organic polymers that supports a dual mode model for sorption by soils and sediments. Humic acid is glassy or rigid at temperatures lower than its glass transition temperature and exhibits relatively nonlinear sorption isotherms for HOCs. Fractionation and quantification of SOM indicate that soils and sediments contain significant amounts of black carbon and kerogen of different origins. These particulate organic materials have rigid 3-dimensional structures and are often less polar compared to humic substances. Limited studies show that black carbon and kerogen exhibit nonlinear sorption for HOCs and may dominate the overall nonlinear sorption by soils and sediments.     

Effects of low molecular weight organic acids on sorption and desorption behavior of p-chlorophenol by yellow earth

Low molecular weight organic acids （LMWOAs） are important components of root exudates. They play an important role in immobilizing and remobilizing contaminants in rhizospheric soil. Effects of four LMWOAs on the sorption and desorption behavior of p-chlorophenol by yellow earth was studied in batch mode. The results showed that the previous application of LMWOAs to enhanced adsorption capacity of p-chlorophenol of the soil in the order of maleic acid〉malic acid〉oxalic acid〉citric acid. However, when LMWOAs were applied to soil where p-chlorophenol had been previously adsorbed, substantial p-chlorophenol was desorbed from soil by oxalic acid, whereas citric acid, malic acid and maleic acid didn＇t desorb as much p-chlorophenol from soil as deionized water.     

Effects of cations and anions on iron and manganese sorption and desorption capacity in calcareous soils from Iran

This study investigated the effect of cations and anions on the sorption and desorption of iron (Fe) and manganese (Mn) in six surface calcareous soil samples from Western Iran. Six 10 mM electrolyte background solutions were used in the study, i.e., KCl, KNO₃, KH₂PO₄, Ca(NO₃)₂, NaNO₃, and NH₄NO₃. NH₄NO₃ and NaNO₃ increased the soil retention of Fe and Mn, whereas Ca(NO₃)₂ decreased the soil retention of Fe and Mn. Iron and Mn sorption was decreased by NO₃ ^? compared with H₂PO₄ ^? or Cl^?. The Freundlich equation adequately described Fe and Mn adsorption, with all background electrolytes. The Freundlich distribution coefficient (K _F) decreased in the order H₂PO₄ ^? > Cl^? > NO₃ ^? for Mn and H₂PO₄ ^? > NO₃ ^? > Cl^? for Fe. The highest sorption reversibility was for Fe and Mn in competition with a Ca²⁺ background, indicating the high mobility of these two cations. A MINTEQ speciation solubility model showed that Fe and Mn speciation was considerably affected by the electrolyte background used. Saturation indices indicated that all ion background solutions were saturated with respect to siderite and vivianite at low and high Fe concentrations. All ion background solutions were saturated with respect to MnCO_3(am), MnHPO₄, and rhodochrosite at low and high Mn concentrations. The hysteresis indices (HI) obtained for the different ion backgrounds were regressed on soil properties indicating that silt, clay, sand, and electrical conductivity (EC) were the most important soil properties influencing Fe adsorption, while cation exchange capacity (CEC), organic matter (OM), and Mn-DTPA affected Mn adsorption in these soils.     

Binary gas sorption/desorption experiments on a bituminous coal: Simultaneous measurements on sorption kinetics,volumetric strain and acoustic emission

There is still no clear understanding of the specific interactions between coal and gas molecules. In this context sorption–desorption studies of methane and carbon dioxide, both in a single gas environment and gas mixtures, are of fundamental interest. This paper presents the results of unique simultaneous measurements of sorption kinetics, volumetric strain and acoustic emission (AE) on three tetragonal coal samples subjected to sorption of carbon dioxide and methane mixtures. The coal was a high volatile bituminous C coal taken from the Budryk mine in the Upper Silesia Basin, Poland. Three different gas mixtures were used in the sorption tests, with dominant CO₂, with dominant CH₄ and a 50/50 mixture.The experimental set-up was designed specially for this study. It consisted of three individual units working together: (i) a unit for gas sorption experiments using a volumetric method, (ii) an AE apparatus for detecting, recording and analysing AE, and (iii) a strain meter for measuring strains induced in the coal sample by gas sorption/desorption. All measurements were computer aided.The experiments indicated that the coal tested showed preferential sorption of CH₄ at 2.6 MPa pressure and exhibited comparable affinities for CH₄ and CO₂ at higher pressures (4.0 MPa). The results of chromatographic analysis of the gas released on desorption suggested that the desorption of methane from the coal was favoured. The relationship between the volumetric strain and the amount of sorbed gas was found to be non-linear. These results were contrary to common opinions on the coal behaviour. Furthermore, it appeared that the swelling/shrinkage of coal was clearly influenced by the network of fractures. Besides, the AE and strain characteristics suggested common sources of sorption induced AE and strain.The present results may have implications for the sequestration of carbon dioxide in coal seams and enhanced coalbed methane recovery (ECBM).     

孔隙溶液对膨胀土力学性质影响

为研究孔隙溶液的浓度和组分对膨胀土力学性质的影响规律,对含不同浓度的Na Cl、Ca Cl_2溶液的膨胀土进行自由膨胀率试验和直剪试验。试验结果表明,随着溶液浓度的增大,自由膨胀率先快速降低,再平缓下降;浓度相同时含Na Cl溶液的膨胀土其自由膨胀率比含Ca Cl_2溶液的稍大,随着溶液浓度的增大,土样的剪切强度和黏聚力降低;溶液对内摩擦角的影响较小。分析试验结果认为,膨胀土表面具有固定的负电荷,颗粒表面会形成双电层;随着盐溶液浓度的增大,双电层厚度降低,颗粒间斥力减小,使得粒间应力增大,土颗粒沉降,降低了自由膨胀率;阳离子化学价越高,半径越大,对双电层的影响越显著,因此Ca Cl_2溶液比Na Cl溶液对自由膨胀率的影响更大。另一方面,盐溶液会改变膨胀土的结构,使其从集聚状变成絮凝状。盐溶液增大粒间应力,使膨胀土的强度增大,结构的改变会使强度降低,上述两种影响因素对强度呈相反的趋势,对该广西膨胀土,结构的作用超过了粒间应力的影响。     

针铁矿和蒙脱石对菲的吸附解吸行为与热力学研究

采用批量振荡吸附平衡法设计针铁矿和蒙脱石对菲的吸附解吸试验,对比研究了针铁矿和蒙脱石对菲的吸附解吸行为,并考察了不同K＋浓度的溶液对蒙脱石吸附菲的影响,比较分析了线性吸附模型和Freundlich吸附模型描述矿物吸附等温线的准确性,并从吸附热力学角度探讨了矿物的吸附机理。结果表明：针铁矿和蒙脱石对菲的吸附解吸均表现出明显的非线性和解吸滞后现象;相对于线性吸附模型来说,针铁矿和蒙脱石对菲的吸附解吸更符合Freundiich吸附模型;与蒙脱石相比,针铁矿对菲的吸附更为显著,且具有更好的稳定性;溶液中软阳离子K＋的存在使蒙脱石对菲的吸附能力得到显著提高;菲在蒙脱石和针铁矿上的吸附过程是一个自发放热,同时伴随着熵值减小的过程;随着温度的升高,蒙脱石和针铁矿对菲的吸附能力均减弱。     

Competitive sorption and desorption of cadmium and lead in paddy soils of eastern China

To assess the competitive sorption and desorption of cadmium (Cd) and lead (Pb), batch equilibrium experiments were performed using single- and binary-metal solutions in surface samples of three paddy soils from eastern China. Sorption isotherms were well fitted with one-metal and competitive Langmuir equation for single- and binary-metal system, respectively. The distribution coefficient (K _d) values were K _{d single} (Pb) > K _{d binary} (Pb) > K _{d single} (Cd) > K _{d binary} (Cd), indicating that Pb was stronger sorbed by these soils than Cd in binary metal system. Soils with high pH and clay content had the greatest sorption capacity as estimated by the maximum sorption parameter (Q). The co-existence of both metals reduces their tendency of sorption, whereas Cd sorption was affected to a greater extent than that of Pb. The Langmuir binding strength parameter (b) in binary sorption system was greater than that in single sorption system for all soils (b < b ₁), indicating that competition for sorption sites promote the retention of both metals into more specific sorption sites. Sorption of Cd and Pb decreased soil pH by 1.61 U for YRS, 1.39 U for PCS, and 0.91 U for SLS. The decreases of pH in binary metal system were greater than in single-metal system for three soils. Cadmium and Pb desorption increased with increasing Cd and Pb sorption saturation for all soils; however, Cd desorption ratio in binary metal system (d _Cd*) was much greater than Pb (d _Pb*), indicating that under the competitive sorption conditions, the sorbed Cd was more readily desorbed from the soils than the sorbed Pb.     

Kinetics of neptunium(V) sorption and desorption on goethite: An experimental and modeling study

Various sorption phenomena, such as aging, hysteresis and irreversible sorption, can cause differences between contaminant (ad)sorption and desorption behavior and lead to apparent sorption ‘asymmetry’. We evaluate the relevance of these characteristics for neptunium(V) (Np(V)) sorption/desorption on goethite using a 34-day flow-cell experiment and kinetic modeling. Based on experimental results, the Np(V) desorption rate is much slower than the (ad)sorption rate, and appears to decrease over the course of the experiment. The best model fit with a minimum number of fitting parameters was achieved with a multi-reaction model including (1) an equilibrium Freundlich site (site 1), (2) a kinetically-controlled, consecutive, first-order site (site 2), and (3) a parameter ψ_2,de, which characterizes the desorption rate on site 2 based on a concept related to transition state theory (TST). This approach allows us to link differences in adsorption and desorption kinetics to changes in overall reaction pathways, without assuming different adsorption and desorption affinities (hysteresis) or irreversible sorption behavior a priori. Using modeling as a heuristic tool, we determined that aging processes are relevant. However, hysteresis and irreversible sorption behavior can be neglected within the time-frame (desorption over 32 days) and chemical solution conditions evaluated in the flow-cell experiment. In this system, desorption reactions are very slow, but they are not irreversible. Hence, our data do not justify an assumption of irreversible Np(V) sorption to goethite in transport models, which effectively limits the relevance of colloid-facilitated Np(V) transport to near-field environments. However, slow Np(V) desorption behavior may also lead to a continuous contaminant source term when metals are sorbed to bulk mineral phases. Additional long-term experiments are recommended to definitely rule out irreversible Np(V) sorption behavior at very low surface loadings and environmentally-relevant time-scales.     

Polycyclic aromatic hydrocarbons (PAHs) in Chinese coal: occurrence and sorption mechanism

Elevated polycyclic aromatic hydrocarbon (PAH) concentrations were determined in different Chinese coals, with the highest concentrations in bituminous coals. Phenanthrene (Phen) was chosen as the probe compound for PAHs to study the sorption behavior of coal. No native Phen was detected in desorption experiments indicating irreversible sorption–desorption behavior of PAHs in raw coal samples. Sorption mechanism was further studied under varying conditions of pH value and ionic strength. Different ranks of coal showed different sorption behavior under acidic, neutral, and alkaline conditions. Batch experiments were further processed for the selected coals at pH values from 3 to 11 at a constant aqueous concentration. Sorption capacities of all coals decreased with increased pH except for YJ coal. Furthermore, although DOC-associated Phen mass contributed little to the total Phen mass under different pH values, the significant negative correlations between M _DOC and log K _OC values were observed for all coal samples, indicating a significant role played by DOC in the coal sorption. In addition, sorption experiments under varying ionic strength showed that the ionic strength influence was more obvious in sorption isotherms for higher rank coals with increasing ionic strength, and this effect was most significant when ionic strength increased from 0 to 0.15 M, especially at relatively low aqueous concentrations.     

Study of metal sorption/desorption processes on competing sediment components with a multichamber device

A new multichamber device was developed to study sorption/desorption reactions of metals on different competing sediment components and the influence of environmental factors on these reactions. The system consists of a central chamber connected with six external chambers and separated by 0.45-μm-diameter membranes. The diffusion kinetics of metals between the single chambers were determined. Equilibrium was attained within 24 h. Algal cell walls (Scenedesmus quadricauda), bentonite, aluminium oxide, managese oxide, quartz powder, and goethite were used as model sediment components. Determination of metal sorption on the solid phases resulted in a significant enrichment on the algal cell walls, particularly for Cu and Cd. It was concluded that sorption depends not only on ion exchange but also on complexing reactions which lead to relatively stable surface binding. A second series of experiments investigated the effect of seawater on sediment components and dredged mud. Cadmium was remobilized from all solid components, but Cu was not remobilized from algal cell walls and bentonite. The dominant role of organic substrates in the binding of metals such as Cd andCu is of particular relevance for the transfer of these elements into biological systems. Even relatively small percentages of organic substrates, if involved in metabolic processes, may constitute a major pathway by which metals are transferred within the food chain.     

Kinetics of Cd sorption, desorption and fixation by calcite: A long-term radiotracer study

Time-dependent sorption and desorption of Cd on calcite was studied over 210 days utilizing ¹⁰⁹Cd as a tracer to distinguish between ‘labile’ and ‘non-labile’ forms of sorbed Cd. Stabilizing the calcite suspensions for 12 months under atmospheric P_CO2 and controlled temperature was necessary to reliably follow Cd dynamics following initial sorption. Results revealed time-dependant Cd sorption and marked desorption hysteresis by calcite under environmentally relevant conditions. Data obtained were fitted to a first-order kinetic model and a concentric shell diffusion model. Both models described the progressive transfer of Cd²⁺ to a less reactive form within calcite and subsequent desorption of Cd subject to different initial contact times. The kinetic model provided a better fit to the combined sorption and desorption data (R² = 0.992). It differentiates between two ‘pools’ of sorbed Cd²⁺ on calcite, ‘labile’ and ‘non-labile’, in which labile sorbed Cd is in immediate equilibrium with the free Cd²⁺ ion activity in solution whereas non-labile Cd is kinetically restricted. For the diffusion model (R² = 0.959), the rate constants describing Cd dynamics in calcite produced a half-life for Cd desorption of ∼175 d, for release to a ‘zero-sink’ solution. Results from this study allow comment on the likely mechanisms occurring at the calcite surface following long-term Cd sorption.     

Phosphate sorption desorption characteristics of some ferruginous soils of tropical region in Eastern India

Phosphate sorption and desorption experiments were conducted with four ferruginous soils (alfisols) of Eastern India, in view of the low native phosphate concentrations in tropical Indian soils. From the P-isotherm curve, standard P requirement (SPR) of the soils was determined. Phosphate sorption data were fitted to both Langmuir and Freundlich equations and mean sorption maximum values obtained for the different soil series were in the decreasing order as Matimahal > Anandapur > Mrigindih > Kashipur. The fraction of added P sorbed followed the same trend as SPR, P sorption maximum (P_max), phosphate affinity constant (K), maximum phosphate buffering capacity (MPBC), Freundlich constant K′ and phosphate desorption values. Phosphate sorption maximum was significantly correlated with MPBC, Freundlich 1/n, SPR, clay and different forms of Fe and Al. The value of K (bonding energy) was significantly correlated with MPBC, Freundlich K′ and pyrophosphate extractable Fe and Al. The MPBC was significantly correlated with Freundlich K′, Freundlich constant 1/n, clay, oxalate and dithionite extractable, amorphous and crystalline form of Fe and Al. Freundlich K′ was significantly correlated with Freundlich 1/n, pH_water, clay, dithionite extractable and crystalline form of Fe and Al. The results suggested that the soils having higher amount of extractable and reactive Fe and Al shared higher P sorbtion capacity and such soils may need higher levels of P application     

A laboratory batch study on arsenic sorption and desorption on guava orchard soils of Baruipur,West Bengal,India

Groundwater contaminated with arsenic (As), when extensively used for irrigation, causes potentially long term detrimental effects to surface soils. Such contamination can also directly affect human health when irrigated crops, such as rice, vegetable and fruits, are used for human consumption. Therefore, an understanding of the sorption and desorption behavior of As in surface soils is of high importance, because these processes regulate the bioavailability of As in the soil environment. In this study, we have collected soils from guava orchards of Baruipur, West Bengal, and characterized soil chemistry and batch sorption and desorption behavior in the laboratory. The sorption and desorption behavior of As in the soils were examined using the Langmuir and Freundlich sorption equation. Regression analysis of the soil chemical characteristics and sorption equation parameters were also performed. The results suggest that the sorption behavior of arsenate is highly dependent on soil characteristics, specifically organic carbon, clay and Al₂O₃ content of the soils. Whereas desorption behavior is critically influenced by the presence of high concentrations of amorphous and/or crystalline Fe₂O₃ in the soils. Retention of the significant portion of As in the soils (~ 84% of the total) suggests that As in the orchard soils may not be highly bioavailable to plants for uptake. However, more detailed studies will be required to ascertain the role of individual soil components on the As sorption and desorption processes.     

Thorium sorption in the marine environment: Equilibrium partitioning at the hematite/water interface,sorption/desorption kinetics and particle tracing

Thorium(IV) sorption onto hematite (-Fe₂O₃) was examined as a function of pH and ionic strength. Sorption behaved Langmuirian over an eleven order of magnitude range in adsorption densities, : 10^–12 to 10^–1 moles Th sorbed per mole hematite sites, indicating that the overall free energy of Th adsorption is independent of adsorption density. Modeling of Th sorption was conducted with the Triple Layer Model of Davis and Leckie; reactions considered included solution-phase hydroxy and carbonato complexes of thorium, and carbonate/hematite surface complexes. The entire Th sorption isotherm can be modeled with a single surface complex formation reaction

Effects of orientation on the diffusive properties of fluid-filled grain boundaries during pressure solution

An unresolved issue in the study of pressure solution in rock materials is the dependence of grain boundary structure and diffusive properties on the mutual orientation of neighbouring grain lattices. We report electrical measurements yielding the diffusivity of differently oriented halite–glass and halite–halite contacts loaded in the presence of brine. The halite–glass contact experiments show pressure solution of the halite and an effect of halite lattice orientation on grain boundary transport. Post-mortem observations show an orientation-dependent grain boundary texture controlled by the periodic bond chains in the halite structure. It is inferred that this texture determines the internal grain boundary structure and properties during pressure solution. In the halite–halite experiments neck-growth occurred, its rate depending on twist-misorientation. The results imply that deformation by pressure solution may lead to lattice-preferred orientation development, and that polymineralic rocks may deform faster at lower stresses than monomineralic rocks.     

Fluoride sorption and desorption on soils located in the surroundings of an aluminium smelter in Galicia (NW Spain)

Aluminium smelters are major sources of F emission to the environment. We studied, in laboratory experiments, the sorption and desorption of fluoride on organic and mineral horizons of soils located within 2 km from one of these factories, situated in the northern coast of Galicia (NW Spain). The soils, developed from granite, are acid (pH H₂O 3.9–5.5), rich in organic matter (4–16 % C in the A horizon) and most A horizons have high Al saturation in the exchange complex. All samples showed a notable F sorption, between 1,066 and 1,589 mg kg^?1, after adding 200 mg F L^?1, which accounts for 53–80 % of F added. The sorption was slightly higher in the A horizons than in the respective organic horizons (differences of up to 194 mg kg^?1). The fluoride sorption upon addition of 200 mg F L^?1 correlated significantly (p < 0.05) with soil pH in water (r = ?0.77), iron extracted by acid ammonium oxalate (r = 0.68), aluminium plus iron extracted by acid ammonium oxalate (r = 0.63), exchange aluminium (r = 0.52) and clay percentage in soil (r = 0.76). The F sorption fitted to both Langmuir and Freundlich models. Desorbed F accounted for only 12–22 % of sorbed fluoride and correlated (p < 0.05) negatively with non-crystalline (extracted by acid ammonium oxalate) Fe (r = ?0.51) and clay content (r = ?0.74) and positively with organic matter (r = 0.69) and with the effective cation exchange capacity of the soil (r = 0.50).     

Methane and CO2 sorption and desorption measurements on dry Argonne premium coals: pure components and mixtures

Sorption and desorption behaviour of methane, carbon dioxide, and mixtures of the two gases has been studied on a set of well-characterised coals from the Argonne Premium Coal Programme. The coal samples cover a maturity range from 0.25% to 1.68% vitrinite reflectance. The maceral compositions were dominated by vitrinite (85% to 91%). Inertinite contents ranged from 8% to 11% and liptinite contents around 1% with one exception (Illinois coal, 5%). All sorption experiments were performed on powdered (−100 mesh), dry coal samples.Single component sorption/desorption measurements were carried out at 22 °C up to final pressures around 51 bar (5.1 MPa) for CO₂ (subcritical state) and 110 bar (11 MPa) for methane.The ratios of the final sorption capacities for pure CO₂ and methane (in molar units) on the five coal samples vary between 1.15 and 3.16. The lowest ratio (1.15) was found for the North Dakota Beulah-Zap lignite (VR_r=0.25%) and the highest ratios (2.7 and 3.16) were encountered for the low-rank coals (VR_r 0.32% and 0.48%) while the ratio decreases to 1.6–1.7 for the highest rank coals in this series.Desorption isotherms for CH₄ and CO₂ were measured immediately after the corresponding sorption isotherms. They generally lie above the sorption isotherms. The degree of hysteresis, i.e. deviation of sorption and desorption isotherms, varies and shows no dependence on coal rank.Adsorption tests with CH₄/CO₂ mixtures were conducted to study the degree of preferential sorption of these two gases on coals of different rank. These experiments were performed on dry coals at 45 °C and pressures up to 180 bar (18 MPa). For the highest rank samples of this sequence preferential sorption behaviour was “as expected”, i.e. preferential adsorption of CO₂ and preferential desorption of CH₄ were observed. For the low rank samples, however, preferential adsorption of CH₄ was found in the low pressure range and preferential desorption of CO₂ over the entire pressure range.Follow-up tests for single gas CO₂ sorption measurements consistently showed a significant increase in sorption capacity for re-runs on the same sample. This phenomenon could be due to extraction of volatile coal components by CO₂ in the first experiment. Reproducibility tests with methane and CO₂ using fresh sample material in each experiment did not show this effect.     

Removal of bisphenol A from aqueous solution by hydrophobic sorption of hemimicelles

In this work, the hydrophobic sorption of hemimicelles was proposed as an innovative method for removing bisphenol A from aqueous solution with esterified carboxyl cotton as sorbent and cetyl trimethyl ammonium bromide as cationic surfactant. In order to optimize the sorption process, the effect of sorbent dose, initial pH, surfactant dose, sorbate concentration, contact time and temperature was investigated in batch system. The maximum value of bisphenol A removal appeared in the pH range 4–10. The bisphenol A removal ratio came up to the maximum value beyond 12 time of surfactant/bisphenol A. The isothermal data of bisphenol A sorption conformed well to the Langmuir model and the maximum sorption capacity (Q_m) of esterified carboxyl cotton for bisphenol A was 87.72 mg/g. The bisphenol A removal equilibrium was reached within about 4 h and the removal process could be described by the pseudo-second-order kinetic model. The thermodynamic study indicated that the bisphenol A sorption process was spontaneous and exothermic.