Atrazine sorption on surface soils: time-dependent phase distribution and apparent desorption hysteresis

Non-equilibrium sorption-desorption behavior of atrazine was studied on two surface soils. Impact of sorption contact time was evaluated by interpreting temporal variations in Freundlich sorption isotherm parameters n(t) and K(F)(t) obtained from the phase distribution relationships. The extent of sorption linearity was very similar (n approximately 0.90) for the two soils at all sorption contact times. K(F)(t) increased with contact time and stabilized upon reaching apparent equilibrium. K(F) for woodland soil was significantly higher than that for agricultural soil. The Apparent Hysteresis Index (AHI) parameter was used to quantify sorption-desorption hysteresis arising from non-equilibrium sorption. AHI was a function of the sorption contact time and correlated well with K(F)(t). The woodland soil sorbed more herbicide due to its higher organic matter content. However, a larger fraction of the herbicide sorbed to this soil was released rapidly (within 24 h) following sorptive uptake. The differences in sorption-desorption behavior of atrazine in the two soils appear to be related to variations in the type and location of organic matter in the two soils. The parameters K(F)(t) and AHI(t) consistently demonstrated the effects that arise when batch systems are not brought to equilibrium during sorption studies.     

The use of indigenous coal reserves for the removal of lead(II) from the aquatic environment by adsorption

Activated carbon was prepared as an adsorbent from low cost Lakhra coal (LC) (Lignite grade) by chemical activation for the removal of Pb(II) from aqueous solution. The variables of pH, adsorbent dose, agitation time, ionic strength and temperature were investigated. The sorption process followed pseudo-first-order kinetics, intra-particle diffusion and Langmuir isotherm models. Evaluation of thermodynamic parameters affirmed the spontaneity of the process. The study also included the surface properties of activated Lakhra coal (ALC) by FTIR, scanning electron microscope and energy dispersive spectroscopy. The maximum Pb(II) removal capacity of ALC was 758?±?8?mg?g^?1 at 32?°C, approximately 300 times higher than without activation. This value was higher than other previously reported values. Thus, this study demonstrated that indigenous LC has excellent potential to be used as an economically feasible adsorbent after activation for the treatment of wastewater bearing Pb(II).     

Modeling, rate-limiting step investigation, and enhancement of the direct bio-regeneration of perchlorate laden anion-exchange resin

Anion-exchange with high perchlorate affinity resins is one of the most promising technologies for removing low levels of perchlorate. However, the traditional brine desorption technique is difficult and costly for regeneration of this type of resin. Previously, a direct bio-regeneration method by contacting the spent high perchlorate affinity resin with the perchlorate-reducing bacteria was proved feasible. This research is a further study of that method. Firstly, a direct bio-regeneration process model, based on the physicochemical and biological fundamentals, was developed and calibrated with experimental data. Thereafter, the rate-limiting step in regeneration of the high perchlorate affinity resin was investigated. Methods to enhance the regeneration efficiency were developed. The results indicated that the calibrated model well described the regeneration process. It thus might provide useful insights into the regeneration system. The results also demonstrated that the perchlorate desorption from the loaded resin could be the rate-limiting step. Addition of proper amount of counter anions such as chloride and sulfate improved the regeneration efficiency because these anions could promote both the extent and rate of perchlorate desorption from the loaded resin. These findings aided us in achieving good and efficient regeneration of high perchlorate affinity resins like the A-530E and SR-7 resins. The findings also suggested that the application of bacteria that could efficiently reduce perchlorate in highly saline solution would make the method more promising for the regeneration of high perchlorate affinity resins.     

Isotopic exchangeability as a measure of the available fraction of the human pharmaceutical carbamazepine in river sediment

Cabamazepine (CBZ), an antiepileptic pharmaceutical compound, is a pollutant of aquatic ecosystems entering via wastewater treatment plants that is considered to be persistent to degradation. An isotope exchange technique was employed using radiolabelled CBZ as a model compound, to determine the amount of isotopic exchangeability of CBZ in river sediment. The amount of isotopically exchangeable CBZ was used as an estimate of the extent of desorption hysteresis in solution from river sediment, including a treatment where the sediment was amended with black carbon. The isotopically exchangeable CBZ was measured by equilibrating ¹²C-CBZ with sediment for 0 to 28 days followed by a 24 hour equilibration with ¹⁴C-CBZ at the end of the incubation period. The isotopically exchangeable fraction of CBZ decreased over time in the sediment, particularly following amendment with black carbon. This has important implications for the fate of CBZ, which, apart from being resistant to degradation, is constantly released into aquatic ecosystems from wastewater treatment plants. This study demonstrates the availability of a relatively quick and simple alternative to batch desorption techniques for the assessment of the available fraction of organic compounds in sediments following their release into aquatic ecosystems.     

Modelling of hysteresis influence on mass transfer in building materials

The processes of mass transfer in the material influence not only the conditions within the material but also inside the connected air spaces. A new module for precise representation of mass transfer in materials in contact with the indoor air, called Humi-mur, was elaborated and validated in this work. It allows for the precise representation of sorption isotherm and vapour permeability dependence on relative humidity. Also the sorption curve hysteresis has been implemented. The new module was then applied to estimate the sensitivity of the results to uncertainty in measured material properties and the impact of hysteresis effect. Reasonable estimation of experimental uncertainty resulted in the deviation of approximately 6% in the calculated results. Hysteresis quite strongly influences the dynamic behaviour of materials. Concerning hysteresis in the sorption isotherm, we showed that the average of the adsorption and desorption equations is a reasonable approximation of mean behaviour for coarse calculation. In case when precise results of the relative humidity (absolute humidity) are needed, the hysteresis effect should be taken into account.     

Implications of short and long term (30 days) sorption on the desorption kinetic of trace metals (Cd, Zn, Co, Mn, Fe, Ag, Cs) associated with river suspended matter

The desorption kinetic of trace elements (Cd, Zn, Co, Mn, Fe, Ag, and Cs) associated with Loire river natural suspended particulate matter (SPM; 0.4-63 microm) was followed up on times varying from 0.5 h to 30 days, from SPM previously contaminated during 1 h, 24 h and 30 days. Long term sorption kinetics indicated that the difference between sorption occurring during the period 0-30 days (time investigated in this study) and the period 0-48 h (time often used for sorption experiments) ranges from few to 25% according to the element. Desorption kinetics show that, whatever the age of the complex formed during the sorption step, the release tends to equilibrium between complexed and dissolved elements equivalent to the equilibrium obtained for sorption after a given time. However, the time to get this equilibrium depends on the aging of the complex and on the element. All the above features indicate different types of complexes formation and strength of the binding according to the age of the complex and according to the element. Using a multi-compartmental model, simulating the transfer of metals between water and different types of particulate sites, the relationships between the parameters describing slow and rapid processes helped in explaining the "aging" effect observed.     

Sorption and desorption of atrazine and diuron onto water dispersible soil primary size fractions

In this study, a low energy separation method was employed to separate water dispersible clay-, silt-, and sand-sized fractions. The batch equilibrium method was used to conduct atrazine and diuron sorption/desorption experiments with the bulk soils and their size fractions separately. A Freundlich sorption model provided the best fit for all sorption and desorption data. A mass balance calculation, taking into account the pesticide concentration differences in the size fraction and bulk soil, showed that pesticide sorption onto the different size fractions reproduces well the total amount of the pesticide sorbed onto the bulk soils. Due to their higher soil organic carbon content, the clay fractions were much more effective sorbents for the pesticides than the bulk soils, silt, and sand fractions. For all soils, the amount of the pesticide sorbed onto the clay fractions was more than 20% of the total amount of the pesticide sorbed by the bulk soils even though the clay fractions in these soils were only 5.3-14.0% (by weight). The clay fractions had the highest desorption hysteresis among all size fractions and the bulk soils, followed by silt fractions, implying the clay fractions had the strongest bound and least desorbable pesticide molecules. Our results suggest that attention should be paid to the pesticide sorbed to the smallest colloids, the water dispersible fraction, which can be potentially mobilized under field conditions, leading to wide spreading of contamination.     

Sorbed atrazine shifts into non-desorbable sites of soil organic matter during aging

Soil-chemical contact time (aging) is an important determinant of the sorption and desorption characteristics of the organic contaminants and pesticides in the environment. The effects of aging on mechanism-specific sorption and desorption of atrazine were studied in soil and clay slurries. Sorption isotherm and desorption kinetic experiments were performed, and soil-water distribution coefficients and desorption rate parameters were evaluated using linear and non-linear sorption equations and a three-site desorption model, respectively. Aging time for sorption of atrazine in sterilized soil and clay slurries ranged from 2 days to 8 months. Atrazine sorption isotherms were nearly linear (r(2)>0.97) and sorption coefficients were strongly correlated to soil organic carbon content. Sorption distribution coefficients (K(d)) increased with increase in age in all five soils studied, but not for K-montmorillonite. Sorption non-linearity did not increase with increase in age except for the Houghton muck soil. Desorption profiles were well described by the three-site desorption model. The equilibrium site fraction (f(eq)) decreased and the non-desorbable site fraction (f(nd)) increased as a function of aging time in all soils. For K-montmorillonite, f(nd) approximately 0 regardless of aging, showing that aging phenomena are sorbent/mechanism specific. In all soils, it was found that when normalized to soil organic matter content, the concentration of atrazine in desorbable sites was relatively constant, whereas that in non-desorbable site increased. This, and the lack of aging effects on desorption from montmorillonite, suggests that sorption into non-desorbable sites of soil organic matter is primary source of increased atrazine sorption in soils during aging.     

Sorption behavior of potential organic wastewater indicators with soils

Soil-aquifer treatment is a wastewater treatment and reclamation option to facilitate beneficial water reuse. The fate of wastewater originated micropollutants in the soil-aquifer system is important to understand. In the study the sorption behavior of potential wastewater indicators such as two antiepileptic drugs (carbamazepine, primidone), one sulfonamide (sulfamethoxazole), and one corrosion inhibitor (benzotriazole) were determined with three natural soils (Lufa 2.2, Euro Soil 5, and Wulpen sand) that differed in pH, organic carbon content and particle size distribution. As aqueous phase a 0.01 M CaCl₂ solution as well as the effluent of a municipal wastewater treatment plant was used. Affinities of all analytes to the soil increased from Wulpen sand, over Lufa 2.2 to Euro Soil 5, indicating that the organic carbon contents might be crucial for sorption. Isotherms were well described by the Freundlich model. Sorption was mainly close to linear (n = 0.93-1.07) for most target compounds and soils. Desorption gave rise to a small hysteresis only for Euro Soil 5 which was likely artificial, due to slow desorption kinetics beyond 24 h used in the experiment. All sorption studies confirmed that Carbamazepine, Benzotriazole and Primidone are appropriate to be used as wastewater indicator substances based on their low sorption affinity to soils, while the suitability of Sulfamethoxazole is limited due to the formation of non-extractable residues, especially at lower pH values.     

Slow and very slow desorption of organic compounds from sediment: influence of sorbate planarity

The kinetics of desorption of in situ chlorobenzenes, PAHs, and PCBs from four different sediments was studied employing Tenax beads as an infinite sink for sorbates. Rate constants for slow desorption were 2.9+/-0.4 x 10(-2) x h(-1), irrespective of the extent of sorbate planarity. Rate constants for very slow desorption were 2.1+/-0.5 x 10(-4) and 6.7+/-1.4 x 10(-4) x h(-1) for planar and non-planar compounds, respectively. Comparison with literature data suggests a priori estimates for rate constants for slow desorption to be 3 x 10(-2) x h(-1), and to be 2 x 10(-4) and 7 x 10(-4) x h(-1) for very slow desorption of planar and non-planar compounds, respectively. The ratio between the fractions in the very slowly desorbing domain and the rapidly desorbing domain was 15-38 for planar compounds which is higher than for non-planar compounds for which the ratio was 2.8-5.2. The ratio between the fractions in the slowly desorbing domain and the rapidly desorbing domain was 1.3-1.8 and independent of the sorbate planarity. The difference in influence of sorbate planarity on the very slowly desorbing domain as compared to the slowly desorbing domain points to different environments for the slowly and the very slowly desorbing fractions.     

Treatment of oily waters using vermiculite

The main objective of this study was to examine the removal of oil from water by expanded and hydrophobized vermiculite. A pH of 9 showed a higher removal efficiency of oil by vermiculite. Oil removal efficiencies at pH 9 were found to be 79%, 93%, 90%, 57% for standard mineral oil (SMO), Canola oil (CO), Kutwell oil (KUT45), refinery effluent (RE), respectively, in the case of expanded vermiculite, and 56%, 58%, 47%, 43% for SMO, CO, KUT45 and RE, respectively, for hydrophobized vermiculite. Kinetic data satisfied both the Lagergren and Ho models. Equilibrium studies showed that the Langmuir isotherm was the best-fit isotherm for oil removal by both expanded and hydrophobized vermiculite. The data showed a higher adsorptive capacity by the expanded vermiculite compared to the hydrophobized vermiculite. Desorption studies showed that the expanded vermiculite did not desorb oil to the same extent compared to hydrophobized vermiculite. The Freundlich isotherm was the best-fit model for desorption. Expanded vermiculite showed better retention than hydrophobic vermiculite. The results showed that the expanded vermiculite had a greater affinity for oil than hydrophobized vermiculite.     

Comparison between the short-term and the long-term toxicity of six triazine herbicides on photobacteria Q67

The bioluminescence inhibition of six triazine herbicides including desmetryne (DES), simetryn (SIM), velpar (VEL), prometon (PRO), metribuzin (MET), and aminotriazine (AMI) on Vibrio qinghaiensis sp.-Q67 (Q67) was determined to investigate the effects of exposure duration on the ecotoxicological relevance of triazine herbicides. Based on the short-term microplate toxicity analysis (MTA), a long-term MTA was established to assess the impact of exposure time on the toxicities of the herbicides. The results show that the long-term toxicities of DES and SIM are similar to their short-term toxicities, and the long-term toxicities of VEL, PRO, and MET are higher than their short-term toxicities, while AMI without short-term toxicity has a high long-term toxicity. In addition, a parabolic relationship was found between the pEC₅₀ (the negative logarithm of the EC₅₀, log 1/EC₅₀) and the logarithm of octanol-water partition coefficient (logK_ow). To better understand their toxicity process, the time-dependent toxicities of the six herbicides on Q67 were determined over a period of 12 h during which measurements were taken every 30 min to generate an integral effect surface related to both concentration and duration.     

Bismuth recovery from acidic solutions using Cyphos IL-101 immobilized in a composite biopolymer matrix

Impregnated resins prepared by the immobilization of an ionic liquid (IL, Cyphos IL-101, tetradecyl(trihexyl)phosphonium chloride) into a composite biopolymer matrix (made of gelatin and alginate) have been tested for recovery of Bi(III) from acidic solutions. The concentration of HCl slightly influenced Bi(III) sorption capacity. Bismuth(III) sorption capacity increased with IL content in the resin but non-linearly. Maximum sorption capacity reached 110-130mgBig(-1) in 1M HCl solutions. The mechanism involved in Bi recovery was probably an ion exchange mechanism, though it was not possible to establish the stoichiometric exchange ratio between BiCl(4)(-) and IL. Sorption kinetics were investigated through the evaluation of a series of parameters: metal concentration, sorbent dosage, type and size of sorbent particles and agitation speed. In order to reinforce the stability of the resin particles, the IL-encapsulated gels were dried; this may cause a reduction in the porosity of the resin particle and then diffusion limitations. The intraparticle diffusion coefficients were evaluated using the Crank's equation. Additionally, the pseudo-first-order and pseudo-second-order equations were systematically tested on sorption kinetics. Metal can be desorbed from loaded resins using either citric acid or KI/HCl solutions. The sorbent could be recycled for at least three sorption/desorption cycles.     

Chemical compatibility testing of geomembranes – sorption/desorption, diffusion, permeation and swelling phenomena

The laboratory test results of 14 organic liquids (widely varying in nature) for high density polyethylene, linear low density polyethylene, very low density polyethylene and polypropylene geomembranes are presented at 25, 50 and 70°C. The partition coefficients have been calculated by monitoring the increase in mass of geomembrane immersed in the fluid of interest from its initial value until the mass of geomembrane becomes constant. From such data, diffusion and permeation coefficients have been calculated using Fick's equation from the initial linear portions of the sorption curves. Swelling of the geomembranes has also been studied from a measurement of an increase in volume, thickness and diameter. From a temperature dependence of sorption, diffusion and permeation coefficients, the Arrhenius parameters have been calculated.     

Sorption of perfluorooctane sulfonate and perfluorooctanoate on activated carbons and resin: Kinetic and isotherm study

Perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) have increasingly attracted global concerns in recent years due to their global distribution, persistence, strong bioaccumulation and potential toxicity. The feasibility of using powder activated carbon (PAC), granular activated carbon (GAC) and anion-exchange resin (AI400) to remove PFOS and PFOA from water was investigated with regard to their sorption kinetics and isotherms. Sorption kinetic results show that the adsorbent size influenced greatly the sorption velocity, and both the GAC and AI400 required over 168 h to achieve the equilibrium, much longer than 4 h for the PAC. Two kinetic models were adopted to describe the experimental data, and the pseudo-second-order model well described the sorption of PFOS and PFOA on the three adsorbents. The sorption isotherms show that the GAC had the lowest sorption capacity both for PFOS and PFOA among the three adsorbents, while the PAC and AI400 possessed the highest sorption capacity of 1.04 mmol g⁻¹ for PFOS and 2.92 mmol g⁻¹ for PFOA according to the Langmuir fitting. Based on the sorption behaviors and the characteristics of the adsorbents and adsorbates, ion exchange and electrostatic interaction as well as hydrophobic interaction were deduced to be involved in the sorption, and some hemi-micelles and micelles possibly formed in the intraparticle pores.     

Partitioning of phenanthrene into surfactant hemi-micelles on the bacterial cell surface and implications for surfactant-enhanced biodegradation

Recent studies have suggested that the ability of a surfactant to enhance the bioavailability of hydrophobic organic compounds (HOC) requires the formation of surfactant hemi-micelles on the bacterial cell surface and subsequent partitioning of HOC into the hemi-micelles. However, the studies did not provide direct evidence of HOC partitioning into surfactant hemi-micelles on the bacterial cell surface. In this study, direct evidence is provided to demonstrate that the nonionic surfactant Brij 30 forms hemi-micelles on the bacterial cell surface and that phenanthrene sorption at the bacterial surface is enhanced by the surfactant. These results are in agreement with the current theory describing surfactant-enhanced HOC bioavailability. This enhanced bioavailability is put into context with microbial kinetics and system partitioning processes, and it is demonstrated that the addition of surfactant can enhance, have no effect, or inhibit HOC biodegradation depending upon surfactant concentration and microbial growth rate. Understanding these non-linear relationships between surfactant-enhanced HOC bioavailability, biodegradation kinetics, and system partitioning will assist in the design and implementation of surfactant-enhanced bioremediation programs.