Simultaneous sorption of lead and chlorobenzene by organobentonite

Clays or organoclays have been used as a barrier to prevent the transport of hazardous contaminants in landfills. However, clays are known to effectively sorb mostly inorganic contaminants, while organoclays are mainly used for organic contaminants. Since the organoclays are basically clay particles modified with cationic surfactants, there might exist an optimal coverage of cationic surfactant on the clay particles to sorb both inorganic and organic contaminants. In order to determine the optimal mass of cationic surfactants on the bentonites, sodium bentonites were treated with various ratios of hexadecyltrimethylammonium (HDTMA) to bentonites. Chlorobenzene and lead were selected as representative contaminants. When either chlorobenzene or lead exists as a single contaminant, chlorobenzene sorption increased with increasing HDTMA to bentonite ratios, and lead sorption decreased with increasing HDTMA to bentonite ratios. Sorption of chlorobenzene was a function of HDTMA coverage on the bentonites, while lead sorption was much more influenced by the initial lead concentration rather than the mass of HDTMA added to the bentonites.     

Influence of modified soils on the removal of diesel fuel oil from water and the growth of oil degradation micro-organism

Three soils were modified with two kinds of cationic surfactants in order to increase their sorptive capabilities for organic contaminants. Sorption of diesel fuel oil in water by these modified soils had been investigated. Modified soils can effectively sorb diesel fuel oil from water. The sorption capability of modified soils is: HDTMA-black soil > HDTMA-yellow brown soil > HDTMA-red soil > TMA-black soil > TMA-yellow brown soil > TMA-red soil. Sorption of diesel fuel oil by natural soils and HDTMA modified soils is via partition, the sorption isotherms can be expressed by Henry equation, and logK(SOM) is 2.42-2.80, logK(HDTMA) is 3.37-3.60. Sorption isotherms of TMA modified soils can be expressed by Langmuir equation, the saturation sorption capacities are 1150 (TMA-black soil), 750 (TMA-yellow-brown soil), 171 mg/kg (TMA-red soil), respectively. A diesel fuel oil degradation micro-organism (Pseudomonas sp.) was isolated in the lab. To test the influence of the modified soils on the micro-organism, various growth curves of Pseudomonas in different conditions were drawn. Pseudomonas can grow very well with natural soils and TMA modified soils. The acclimation period of Pseudomonas is reduced. As to HDTMA modified soils, HDTMA loading amount is very important. When HDTMA loading amount is no higher than 0.5 CEC, the micro-organism can grow very well after a long acclimation period.     

Pesticide adsorption on a calcareous soil modified with sewage sludge and quaternary alkyl-ammonium cationic surfactants

BACKGROUND, AIM AND SCOPE: Pesticides are often found in soil as a result of their application to control pests. They can be transported on soil particles to surface waters or they can lixiviate and reach other environmental compartments. Soil modification with amendments, such as sewage sludge, and with surfactants, h been proposed to reduce pesticide environmental fate. METHODS: The sorption of atrazine, methidathion and diazinon using the batch technique has been studied on non-modified soil and soil modified with sewage sludge and cationic surfactants, as well as the effect of their addition on soil properties such as organic carbon (OC) content and exchange cations. RESULTS AND DISCUSSION: The OC content of the surfactant modified soils was the highest with the surfactant with the longest hydrocarbon chain (hexadecyltrimethyl ammonium bromide, HDTMA). The results of the OC content run in parallel with the increase in pesticide retention. When the sorption was n malized to soil OC content, the retention induced by addition of HDTMA was still the highest, which is an indication that the organic matter derived from the organic cations is a more effective medium to retain dissolved contaminants, than organic matter from native soil. The addition of sewage sludge to the soil did only result in a slight increase of the soil CEC and, hence, moderately affected the ability of the cationic surfactant to retain the pesticides. CONCLUSIONS: The addition of cationic surfactants to soil would possibly reduce the movement to groundwater of atrazine, methidathion and diazinon. In the case of HDTMA, the decrease in sorption at high surfactant loadings was very slow, being that the surfactant was able to retain the pesticides at concentration values which clearly exceeded the monolayer coverage. RECOMMENDATIONS AND PERSPECTIVES: Contamination by pesticides, which are present in the soil due to their direct input in this medium or to spills or illegal tipping, may be hindered from migration to groundwater by application of a cationic surfactant.     

Part V—sorption of pharmaceuticals and personal care products

Background, aim, and scope  Pharmaceuticals and personal care products (PPCPs) including antibiotics, endocrine-disrupting chemicals, and veterinary pharmaceuticals are emerging pollutants, and their environmental risk was not emphasized until a decade ago. These compounds have been reported to cause adverse impacts on wildlife and human. However, compared to the studies on hydrophobic organic contaminants (HOCs) whose sorption characteristics is reviewed in Part IV of this review series, information on PPCPs is very limited. Thus, a summary of recent research progress on PPCP sorption in soils or sediments is necessary to clarify research requirements and directions. Main features  We reviewed the research progress on PPCP sorption in soils or sediments highlighting PPCP sorption different from that of HOCs. Special function of humic substances (HSs) on PPCP behavior is summarized according to several features of PPCP–soil or sediment interaction. In addition, we discussed the behavior of xenobiotic chemicals in a three-phase system (dissolved organic matter (DOM)–mineral–water). The complexity of three-phase systems was also discussed. Results  Nonideal sorption of PPCPs in soils or sediments is generally reported, and PPCP sorption behavior is relatively a more complicated process compared to HOC sorption, such as the contribution of inorganic fractions, fast degradation and metabolite sorption, and species-specific sorption mechanism. Thus, mechanistic studies are urgently needed for a better understanding of their environmental risk and for pollution control. Discussion  Recent research progress on nonideal sorption has not been incorporated into fate modeling of xenobiotic chemicals. A major reason is the complexity of the three-phase system. First of all, lack of knowledge in describing DOM fractionation after adsorption by mineral particles is one of the major restrictions for an accurate prediction of xenobiotic chemical behavior in the presence of DOM. Secondly, no explicit mathematical relationship between HS chemical–physical properties, and their sorption characteristics has been proposed. Last but not least, nonlinear interactions could exponentially increase the complexity and uncertainties of environmental fate models for xenobiotics. Discussion on proper simplification of fate modeling in the framework of nonlinear interactions is still unavailable. Conclusions  Although the methodologies and concepts for studying HOC environmental fate could be adopted for PPCP study, their differences should be highly understood. Prediction of PPCP environmental behavior needs to combine contributions from various fractions of soils or sediments and the sorption of their metabolites and different species. Recommendations and perspectives  More detailed studies on PPCP sorption in separated soil or sediment fractions are needed in order to propose a model predicting PPCP sorption in soils or sediments based on soil or sediment properties. The information on sorption of PPCP metabolites and species and the competition between them is still not enough to be incorporated into any predictive models.     

Dissolved organic matter effects on the performance of a barrier to polycyclic aromatic hydrocarbon transport by groundwater

In order to contain the movement of organic contaminants in groundwater, a subsurface sorption barrier consisting of sand or clay minerals coated with a cationic surfactant has been proposed. The effectiveness of such a sorption barrier might be affected by the presence of dissolved organic matter (DOM) in the groundwater. To study the impact of DOM on barrier performance, a series of batch experiments were performed by measuring naphthalene and phenanthrene sorption onto sand coated with cetylpyridinium chloride (CPC) and bentonite coated with hexadecyltrimethylammonium bromide (HDTMA) in the presence of various concentrations of DOM. The overall soil-water distribution coefficient (K*) of naphthalene and phenanthrene onto CPC-coated sand decreased with increasing DOM concentration, whereas the K* of the compounds onto HDTMA-coated bentonite slightly increased with increasing DOM concentration. To describe the overall distribution of polycyclic aromatic hydrocarbons (PAHs) in the systems, a competitive multiphase sorption (CMS) model was developed and compared with an overall mechanistic sorption (OMS) model. The modeling studies showed that while the OMS model did not explain the CPC-coated sand experimental results, a model that included competitive sorption between DOM and PAH did. The experimental results and the modeling study indicated that there was no apparent competition between DOM and PAH in the HDTMA-coated bentonite system, and indicated that in groundwater systems with high DOM, a barrier using HDTMA-coated bentonite might be more effective.     

Effects of surface coatings on electrochemical properties and contaminant sorption of clay minerals

Surface charges play a major role in determining the interactions of contaminants with soils. The most important sources of soil charges are clay mineral colloids, whose electrochemical properties are usually modified by metal-oxides and organic matter in natural environments. In this study, effects of coatings of organic matter and Fe- and Al-oxides on a series of electrochemical properties and heavy metal sorption of three clay minerals (kaolinite, montmorillonite and illite) predominant in natural soils were investigated using batch techniques. The results indicate that the coatings increased the specific surface area of the clay minerals, except for the Al-oxide coated montmorillonite and organic matter coated 2:1 clay minerals. The sesquioxide coatings increased amount of positive charges but decreased negative charges. This causes great reduction of the negative potential on the clay surfaces, shift of the zero point of charge to a higher pH, and promotion of fluoride sorption due to presence of more OH- and OH2 on the oxide surfaces than on the clay surfaces. In contrast, the organic coating significantly increased the negativity of surface charges, and thus the zero point of charge and zeta-potential of the clays dropped down. The organic coating also induced a reduction of fluoride sorption on the clays. With respect to the sorption of lead and cadmium, the sesquioxide coatings produced insignificant effects. The experiments of lead/cadmium competitive sorption show that on both the oxide-coated surface and the original clay surface there exist different types of sites, each of which preferentially binds with a heavy metal.     

Sorption and cosorption of organic contaminant on surfactant-modified soils

Three kinds of soils were modified with the cationic surfactants, hexadecyltrimethylammonium (HDTMA) bromide and tetramethylammonium (TMA) bromide to increase their sorptive capabilities. Sorption of chlorobenzene in simulated groundwater by these soils was investigated. HDTMA-modified soil has a higher ability to sorb chlorobenzene from simulated groundwater than unmodified soil. TMA-modified soil did not show the superiority. HDTMA thus can be used to modify soil to improve its sorption capability. Cosorption of chlorobenzene in simulated groundwater in the absence or presence of nitrobenzene and dichloromethane on HDTMA-modified soil was also investigated. Nitrobenzene facilitated sorption of chlorobenzene on all HDTMA-modified soil. Dichloromethane did not influence the sorption of chlorobenzene by HDTMA-modified soil. The results suggest that HDTMA-modified soil is a highly effective sorbent for chlorobenzene and multiple organic compounds did not impede the uptake of chlorobenzene.     

The effects of particle size, organic matter content, crop residues and dissolved organic matter on the sorption kinetics of atrazine and isoproturon by clay soil

Reliable predictions of the fate and behaviour of pesticides in soils is dependent on the use of accurate ‘equilibrium’ sorption constants and/or rate coefficients. However, the sensitivity of these parameters to changes in the physicochemical characteristics of soil solids and interstitial solutions remains poorly understood. Here, we investigate the effects of soil organic matter content, particle size distribution, dissolved organic matter and the presence of crop residues (wheat straw and ash) on the sorption of the herbicides atrazine and isoproturon by a clay soil. Sorption K_d's derived from batch ‘equilibrium’ studies for both atrazine and isoproturon by <2 mm clay soil were approximately 3.5 L/kg. The similarity of K_oc's for isoproturon sorption by the <2 mm clay soil and <2 mm clay soil oxidised with hydrogen peroxide suggested that the sorption of this herbicide was strongly influenced by soil organic matter. By contrast, K_oc's for atrazine sorption by oxidised soil were three times greater than those for <2 mm soil, indicating that the soil mineral components might have affected sorption of this herbicide. No significant differences between the sorption of either herbicide by <2 mm clay soil and (i) <250 μm clay soil, (ii) clay soil mixed with wheat straw or ash at ratios similar to those observed under field conditions, (iii) <2 mm clay soil in the presence of dissolved organic matter as opposed to organic free water, were observed.     

Time and pH-dependent sorption of the veterinary antimicrobial sulfathiazole to clay minerals and ferrihydrite

Substantial amounts of sulfonamides, ionizable, polar veterinary antimicrobials, may reach the environment by spreading of manure. Sorption to soils and sediments is a crucial but not sufficiently understood process influencing the environmental fate of sulfonamides. Therefore, we investigated sorption of sulfathiazole to clay minerals (montmorillonite, illite) and ferrihydrite for varying pH values and two contact times (1d, 14 d) under sterile conditions. Results were compared to sulfathiazole sorption to organic sorbents. Sulfathiazole sorption to inorganic sorbents exhibited pronounced pH dependence consistent with sorbate speciation and sorbent charge properties. While sulfathiazole cations were most important for sorption to clay minerals, followed by neutral species, ferrihydrite was a specific anion sorbent, showing significant sorption only between pH 5.5-7. Experiments revealed a substantial increase of sorption with time for ferrihydrite (pH 5.5-7) and illite (pH<5.5). Reasons may be disaggregation of clay minerals and, for ferrihydrite, diffusion and sorption of sulfathiazole in micropores. Independent of contact time and pH, sorption to inorganic sorbents was more than an order of magnitude lower than to organic sorbents. This implies that in many topsoils and sediments inorganic sorbents play a minor role. Our results highlight the need to account for contact time and speciation when predicting sulfonamide sorption in the environment.     

Potential contributions of clay minerals and organic matter to pentachlorophenol retention in soils

Sorption of pentachlorophenol (PCP) by pure minerals and humic acids were measured to obtain additional perspective on the potential contributions of both clay minerals and soil organic matter (SOM) to contaminants retention in soils. Four types of common soil minerals and two kinds of humic acids (HAs) were tested. The sorption affinity for PCP conformed to an order of HAs > K-montmorillonite > Ca-montmorillonite > goethite > kaolinite. Such a difference in sorption capacity could be attributed to the crucial control of HAs. Clay minerals also had their contribution, especially K-montmorillonite, which played an important, if not dominant, role in the controlling process of PCP sorption. By removing 80% (on average) of the organic carbon from the soils with H(2)O(2), the sorption decreased by an average of 50%. The sorption reversibility had been greatly favored as well. Considering the uncharged mineral fractions in soil before and after H(2)O(2)-treated, the main variation in sorption behavior of the soil might thus be related to the removed organic carbon and the reduced pH. This testified rightly the interactive effect of SOM and clay minerals on PCP sorption as a function of pH.     

Chromate transport through columns packed with surfactant-modified zeolite/zero valent iron pellets

Chromate transport through columns packed with zeolite/zero valent iron (Z/ZVI) pellets, either untreated or treated with the cationic surfactant hexadecyltrimethylammonium (HDTMA), was studied at different flow rates. In the presence of sorbed HDTMA, the chromate retardation factor increased by a factor of five and the pseudo first-order rate constant for chromate reduction increased by 1.5-5 times. The increase in rate constant from the column studies was comparable to a six-fold increase in the rate constant determined in a batch study. At a fast flow rate, the apparent delay in chromate breakthrough from the HDTMA modified Z/ZVI columns was primarily caused by the increase in chromate reduction rate constant. In contrast, at a slower flow rate, the retardation in chromate transport from the HDTMA modified Z/ZVI columns mainly originated from chromate sorption onto the HDTMA modified Z/ZVI pellets. Due to dual porosity, the presence of immobile water was responsible for the earlier breakthrough of chromate in columns packed with zeolite and Z/ZVI pellets. The results from this study further confirm the role of HDTMA in enhancing sorption and reduction efficiency of contaminants in groundwater remediation.     

Sorption of 3,4-dichloroaniline on four contrasting Greek agricultural soils and the effect of liming

Sorption of 3,4-dichloroaniline (3,4-DCA) on four typical Greek agricultural soils, with distinct texture, organic matter content and cation exchange capacities, was compared by using sorption isotherms and the parameters calculated from the fitted Freundlich equations. The sorption process of 3,4-DCA to the soil was completed within 48–72 h. The 3,4-DCA sorption on all soils was well described by the Freundlich equation and all sorption isotherms were of the L-type. The sandy clay loam soil with the highest organic matter content and a slightly acidic pH was the most sorptive, whereas the two other soil types, a high organic matter and neutral pH clay and a low organic matter and acidic loam, had an intermediate sorption capacity. A typical calcareous soil with low organic matter had the lowest sorption capacity which was only slightly higher than that of river sand. The 3,4-DCA sorption correlated best to soil organic matter content and not to clay content or cation exchange capacity, indicating the primary role of organic matter. The distribution coefficient (K _d) decreased with increasing initial 3,4-DCA concentration and the reduction was most pronounced with the highly sorptive sandy clay loam soil, suggesting that the available sorption sites of the soils are not unlimited. Liming of the two acidic soils (the sandy clay loam and the loam) raised their pH (from 6.2 and 5.3, respectively) to 7.8 and reduced their sorption capacity by about 50 %, indicating that soil pH may be the second in importance factor (after organic matter) determining 3,4-DCA sorption.     

Comparison of modified montmorillonite adsorbents. Part II: The effects of the type of raw clays and modification conditions on the adsorption performance

This paper builds on the preceding researches to study the effects of the type of clays (montmorillonites K10, KSF) and modifying conditions on the structure and adsorption behavior of resulting clay adsorbents. The raw clays were modified by polymeric Al/Fe species, hexadecyl-trimethylammonium (HDTMA) surfactant and a complex of polymeric Al/Fe-HDTMA. X-ray diffraction spectra was applied to analyze the structure of the raw and modified clays. After modification, the basal spacing of the clays varied, depending on the types of raw clay and modification conditions. Copper and phenol were selected as adsorbates for evaluating the adsorption performance of various clays, which was affected significantly by the types of raw clay and modification conditions. In general the inorganic contaminant (e.g., Cu) tend to be adsorbed by the polymeric Al/Fe modified clay and the organic impurities (e.g., phenol) will be preferably captured by the surfactant modified clay; both due to the specific surface properties resulting from introducing the modifiers. The complex modified clays possessed the ability of adsorbing both inorganic and organic contaminants. In addition, the d 0 0 1 spacing of modified KSF was greater than that of K10; the adsorption performance with modified KSF was thus greater than that with the modified K10. Finally, the ratio of modifiers to the clay (metal:surfactant:clay) has been observed to affect the adsorption performance; the optimal conditions have been defined.     

Sorption of 3,4-dichloroaniline on four contrasting Greek agricultural soils and the effect of liming

Sorption of 3,4-dichloroaniline (3,4-DCA) on four typical Greek agricultural soils, with distinct texture, organic matter content and cation exchange capacities, was compared by using sorption isotherms and the parameters calculated from the fitted Freundlich equations. The sorption process of 3,4-DCA to the soil was completed within 48-72 h. The 3,4-DCA sorption on all soils was well described by the Freundlich equation and all sorption isotherms were of the L-type. The sandy clay loam soil with the highest organic matter content and a slightly acidic pH was the most sorptive, whereas the two other soil types, a high organic matter and neutral pH clay and a low organic matter and acidic loam, had an intermediate sorption capacity. A typical calcareous soil with low organic matter had the lowest sorption capacity which was only slightly higher than that of river sand. The 3,4-DCA sorption correlated best to soil organic matter content and not to clay content or cation exchange capacity, indicating the primary role of organic matter. The distribution coefficient (K(d)) decreased with increasing initial 3,4-DCA concentration and the reduction was most pronounced with the highly sorptive sandy clay loam soil, suggesting that the available sorption sites of the soils are not unlimited. Liming of the two acidic soils (the sandy clay loam and the loam) raised their pH (from 6.2 and 5.3, respectively) to 7.8 and reduced their sorption capacity by about 50 %, indicating that soil pH may be the second in importance factor (after organic matter) determining 3,4-DCA sorption.     

Studies on the sorption and desorption characteristics of Zn(II) on the surface soils of nuclear power plant sites in India using a radiotracer technique

Zinc adsorption was studied in the soils of three nuclear power plant sites of India. 65Zn was used as a radiotracer to study the sorption characteristics of Zn(II). The sorption of zinc was determined at 25 and 45 degrees C at pH 7.8+/-0.2 in the solution of 0.01 M Ca(NO3)2 as supporting electrolyte. The sorption data was tested both in Freundlich and Langmuir isotherms and could be described satisfactorily. The effect of organic matter and other physico-chemical properties on the uptake of zinc was also studied in all the soil samples. The results showed that the cation exchange capacity, organic matter, pH and clay content were the main contributors to zinc sorption in these soils. The adsorption maximum was found to be higher in the soil on Kakarpara Atomic Power Plant sites soils having high organic matter and clay content. The zinc supply parameters of the soils are also discussed. In the desorption studies, the sequential extraction of the adsorbed zinc from soils showed that the diethylene triamine penta acetic acid extracted maximum amount of adsorbed zinc than CaCl2 and Mg(NO3)2. The zinc sorption on the soil and amount of zinc retention after extractants desorption shows a positively correlation with vermiculite and smectite mineral content present in the clay fraction of the soil. The amount desorbed by strong base (NaOH) and demineralised water was almost negligible from soils of all the sites, whereas the desorption by strong acid (HNO3) was 75-96% of the adsorbed zinc.     

Adsorptive removal of naphthalene induced by structurally different Gemini surfactants in a soil-water system

A new generation of surfactant, Gemini surfactants, have been synthesized and have attracted the attention of various industrial and academic research groups. This study focused on the use of symmetric and dissymmetric quaternary ammonium Gemini surfactants to immobilize naphthalene onto soil particles, and is used as an example of an innovative application to remove HOC in situ using the surfactant-enhanced sorption zone. The sorption capacity of modified soils by Gemini surfactant and natural soils was compared and the naphthalene sorption efficiency, in the absence and presence of Gemini surfactants with different alkyl chain lengths, was investigated in the soil-water system. The results have shown that the increased added Gemini surfactant formed admicelles at the interface of soil/water having superior capability to retard contaminant. Symmetric and dissymmetric Gemini surfactants have opposite effect on the aspect of removing of PAH attributing to their solubilization and sorption behavior in soil-water system. Compared with the natural soil, sorption of naphthalene by Gemini-modified soil is noticeably enhanced following the order of C_12-2-16 < C_12-2-12 < C_12-2-8. However, the symmetric Gemini surfactant C_12-2-12 is the optimized one for in situ barrier remediation, which is not only has relative high retention ability but also low dosage.     

Sorption of polar and nonpolar aromatic compounds to four surface soils of eastern China

Improved predictions on the fate of organic pollutants in surface environments require a better understanding of the underlying sorption mechanisms that control their uptake by soils. In this study, we monitored sorption of nine aromatic compounds with varying physicochemical properties (hydrophobicity, electron-donor/acceptor ability and polarity), including two polycyclic aromatic hydrocarbons, two chlorobenzenes, two nitroaromatic compounds, dichlobenil, carbaryl and 2,4-dichlorophenol in aqueous suspension of four surface soils of eastern China. The tested soils were characterized with respect to organic carbon (OC) content, black carbon content, mineralogy, morphology and size fraction to assess the role of the diverse soil characteristics in sorption. The results of this study show that not only the solute hydrophobicity and the OC content of soil are important to the retention of organic pollutants, but also the solute molecular structure and the soil nature.     

Solvophobic approach for predicting sorption of hydrophobic organic chemicals on synthetic sorbents and soils

The application of a solvophobic approach for predicting the sorption of hydrophobic organic compounds (HOC) was evaluated with data collected using synthetic sorbents and soils. The experimental data consisted of batch equilibrium sorption coefficients (K_D), as well as soil-TLC and reversed-phase liquid chromatographic (RPLC) retention factors (κ′). All data were collected using aqueous solutions and binary or ternary solvent mixtures of water, methanol, acetone, and acetonitrile. As predicted by the theory, the chromatographic retention factors and sorption coefficients for HOC decreased log-linearly with increasing fraction of organic cosolvent in binary solvents. Model parameters estimated from the binary solvent data could be used to predict sorption (or retention) from ternary solvents. Reasonable agreement was found between model parameters reported in the literature and those estimated using the data from batch sorption, soil-TLC, and RPLC studies.     

2,4-Dichlorophenoxyacetic acid (2,4-D) sorption and degradation dynamics in three agricultural soils

The fate and transport of 2,4-dichlorophenoxyacetic acid (2,4-D) in the subsurface is affected by a complex, time-dependent interplay between sorption and mineralization processes. 2,4-D is biodegradable in soils, while adsorption/desorption is influenced by both soil organic matter content and soil pH. In order to assess the dynamic interactions between sorption and mineralization, 2,4-D mineralization experiments were carried using three different soils (clay, loam and sand) assuming different contact times. Mineralization appeared to be the main process limiting 2,4-D availability, with each soil containing its own 2,4-D decomposers. For the clay and the loamy soils, 45 and 48% of the applied dose were mineralized after 10 days. By comparison, mineralization in the sandy soil proceeded initially much slower because of longer lag times. While 2,4-D residues immediately after application were readily available (>93% was extractable), the herbicide was present in a mostly unavailable state (<2% extractable) in all three soils after incubation for 60 days. We found that the total amount of bound residue decreased between 30 and 60 incubation days. Bioaccumulation may have led to reversible immobilization, with some residues later becoming more readily available again to extraction and/or mineralization.