Equilibrium and kinetic modelling of chromium(III) sorption by animal bones

The paper discusses sorption of Cr(III) ions from aqueous solutions by animal bones. Animal bones were found to be an efficient sorbent with the maximum experimentally determined sorption capacity in the range 29-194 mg g(-1) that depended on pH and temperature. The maximum experimentally determined sorption capacity was obtained at 50 degrees C, pH 5. Batch kinetics and equilibrium experiments were performed in order to investigate the influence of contact time, initial concentration of sorbate and sorbent, temperature and pH. It was found that sorption capacity increased with increase of Cr(III) concentration, temperature and initial pH of metal solution. Mathematical models describing kinetics and statics of sorption were proposed. It was found that process kinetics followed the pseudo-second-order pattern. The influence of sorbent concentration was described with Langmuir-type equation and the influence of sorbate concentration was described with empirical dependence. The models were positively verified.     

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.     

Sorption of 1-hydroxy-2-naphthoic acid to goethite, lepidocrocite and ferrihydrite: batch experiments and infrared study

The adsorption of naphthoic acids to iron oxides and hydroxides influences strongly their mobility in soils and sediments. Sorption of 1-hydroxy-2-naphthoic acid (HNA) to three iron oxides was examined over a wide range of conditions (pH, ionic strength, sorbate and sorbent concentrations). In the examination of HNA sorption, Tempkin model was performed to fit sorption data of HNA onto all iron oxides. The adsorption in the Henry law range increases in the order: goethite相似文献   

Sorption of Zn(II) in aqueous solutions by scoria

We conducted kinetic and equilibrium sorption experiments on removal of Zn(II) from aqueous solutions by scoria (a vesicular pyroclastic rock with basaltic composition) from Jeju Island, Korea, in order to examine its potential use as an efficient sorbent. The batch-type kinetic sorption tests under variable conditions indicated that the percentage of Zn(II) removal by scoria increases with decreasing initial Zn(II) concentration, particle size, and sorbate/sorbent ratio. However, the sorption capacity decreases with the decrease of the initial Zn(II) concentration and sorbate/sorbent ratio. Equilibrium sorption tests show that Jeju scoria has a larger capacity and affinity for Zn(II) sorption than commercial powdered activated carbon (PAC); at initial Zn(II) concentrations of more than 10mM, the sorption capacity of Jeju scoria is about 1.5 times higher than that of PAC. The acquired sorption data are better fitted to the Langmuir isotherm than the Freundlich isotherm. Careful examination of ionic concentrations in sorption batches suggests that the sorption behavior is mainly controlled by cation exchange and typically displays characteristics of 'cation sorption'. The Zn(II) removal capacity decreases when solution pH decreases because of the competition with hydrogen ions for sorption sites, while the Zn(II) removal capacity increases under higher pH conditions, likely due to hydroxide precipitation. At an initial Zn(II) concentration of 5.0mM, the removal increases from 70% to 96% with the increase of initial pH from 3.0 to 7.0. We recommend Jeju scoria as an economic and efficient sorbent for Zn(II) in contaminated water.     

Sorption of organic contaminants to a low carbon subsurface core

Sorption of 1,2,4-trichlorobenzene, o-chlorotoluene and dimethylphthalate to a series of subsurface samples collected with depth is reported. Desorption of sorbate from the sorbent matrix provides better precision than conventional solution phase concentration differences when sorption is low. Clay mineral content influences sorption on low carbon sorbents.     

Phenanthrene sorption/desorption sequences provide new insight to explain high sorption coefficients in field studies

The sorption coefficients obtained in field investigation vary greatly from laboratory sorption experiments. The possible reasons were discussed in literature. Observing the commonly reported desorption hysteresis, this study proposed that the unclear sorption history of the field study could also result in the diverse sorption coefficients. This study conducted a comparative study regarding phenanthrene sorption/desorption behavior in low-concentration multi-time sorption process and the commonly applied high-concentration one-time sorption process. The sorption coefficients determined during the desorption process were much higher than those at sorption process. Thus, the prediction of sorption coefficient should be related with sorption history. Desorption hysteresis was increased with increased equilibration time and decreased solid-phase concentration. In addition, although the apparent contact time between sorbate and sorbent was shorter for low-concentration multi-time sorption, the desorption hysteresis was much stronger, which consequently result in higher sorption coefficients in comparison to high-concentration one-time sorption. Pore swelling or diffusion-controlled sorption kinetics could not explain this phenomenon. This study calls for research attention on sorption history, especially for field investigations.     

Sorption and desorption by ideal two-compartment systems: unusual behavior and data interpretation problems

This paper examines the current practices of fitting curves to sorption, desorption, and equilibrium data obtained from laboratory experiments. Systems of equations incorporating Freundlich isotherms and first-order kinetics for two different idealized sorbents, one "fast" and one "slow," were solved numerically to produce "data". Two-compartment curves were then fit to the data by nonlinear regression, and the parameters computed by the regression are compared with the original parameters used to produce the data. The results show that a sorbent with fast kinetics will not steadily accumulate sorbate until it reaches the equilibrium value but will overshoot equilibrium, accumulating an excess of sorbate. This overshoot will cause the sorption rates for both sorbents and the distribution between the fast and slow sorbents to be estimated incorrectly. The system may appear to be at equilibrium by external measures, but sorbate will slowly be redistributing from the fast to the slow sorbent. An isotherm constructed from data acquired during this process will have an incorrect coefficient and exponent. Consequently, the meaning of the results obtained by curve fitting may often be questionable and may say little about the phenomena occurring within the sorbate-sorbent-liquid system. Possible physical explanations for the effects observed are offered.     

Low cost sorbents for the removal of methyl parathion pesticide from aqueous solutions

Sorptive potential of selected agricultural waste materials i.e. rice (Oryza sativa) bran (RB), bagasse fly ash (BFA) of sugarcane (Saccharum officinarum), Moringa oleifera pods (MOP) and rice husk (RH) for the removal of methyl parathion pesticide (MP) from surface and ground waters has been investigated. Optimization of operating parameters of sorption process, i.e. sorbent dose, agitation time, pH, initial concentration of sorbate, and temperature have been studied. The sorption data fitted to Freundlich, Langmuir and Dubinin-Radushkevich (D-R) sorption isotherms. The maximum capacities of RB, BFA, MOP and RH for MP were calculated to be 3.6+/-0.8, 5.3+/-1.4, 5.2+/-1.5 and 4.7+/-1.0 mmolg(-1) by Freundlich, 0.39+/-0.009, 0.39+/-0.005, 0.36+/-0.004 and 0.35+/-0.008 mmolg(-1) by Langmuir and 0.9+/-0.08, 1.0+/-0.10, 1.0+/-0.10 and 0.9+/-0.07 mmolg(-1) by D-R isotherms respectively, employing 0.1g of each sorbent, at pH 6, 90 min agitation time and at 303 K. Application of first order Lagergren and Morris-Weber equations to the kinetic data yielded correlation coefficients, close to unity. Thermodynamic parameters of sorption process, i.e. DeltaH, DeltaS and DeltaG were computed and their negative values indicated the exothermic and spontaneous nature of sorption process. The pesticide may be stripped by sonication with methanol, making the regeneration and reutilization of sorbents promising. The sorbents investigated exhibited their potential applications in water decontamination, treatment of industrial and agricultural waste waters.     

An evaluation of the urban stormwater pollutant removal efficiency of catch basin inserts.

In a storm sewer system, the catch basin is the interface between surface runoff and the sewer. Responding to the need to improve the quality of stormwater from urban areas and transportation facilities, and spurred by Phase I and II Stormwater Rules from the U.S. Environmental Protection Agency, several companies market catch basin inserts as best management practices for urban water quality management. However, little data have been collected under controlled tests that indicate the pollutant removal efficiency of these inserts when the inflow is near what can be expected to occur in the field. A stormwater simulator was constructed to test inserts under controlled and replicable conditions. The inserts were tested for removal efficiency of total suspended solids (TSS) and total petroleum hydrocarbons (TPH) at an inflow rate of 757 to 814 L/min, with influent pollutant concentrations of 225 mg/L TSS and 30 mg/L TPH. These conditions are similar to stormwater runoff from small commercial sites in the southeastern United States. Results from the tests indicate that at the test flowrate and pollutant concentration, average TSS removal efficiencies ranged from 11 to 42% and, for TPH, the removal efficiency ranged from 10 to 19%.     

Bioretention column studies of phosphorus removal from urban stormwater runoff.

This study investigated the effectiveness of bioretention as a stormwater management practice using repetitive bioretention columns for phosphorus removal. Bioretention media, with a higher short-term phosphorus sorption capacity, retained more phosphorus from infiltrating runoff after 3 mg/L phosphorus loading. A surface mulch layer prevented clogging after repetitive total suspended solids input. Evidence suggests that long-term phosphorus reactions will regenerate active short-term phosphorus adsorption sites. A high hydraulic conductivity media overlaying one with low hydraulic conductivity resulted in a higher runoff infiltration rate, from 0.51 to 0.16 cm/min at a fixed 15-cm head, and was more efficient in phosphorus removal (85% mass removal) than a profile with low conductivity media over high (63% mass removal). Media extractions suggest that most of the retained phosphorus in the media layers is available for vegetative uptake and that environmental risk thresholds were not exceeded.     

Stabilization of the initial electrochemical potential for a metal-based potentiometric titration study of a biosorption process

An interactive metal-based potentiometric titration method has been developed using an ion selective electrode for studying the sorption of metal cations. The accuracy of this technique was verified by analyzing the metal sorption mechanism for the biomass of Rhizopus arrhizus fungus and diatomite, two dissimilar materials (organic and mineral, strong sorbent and weak sorbent) of a different order of cation exchange capacity. The problem of the initial electrochemical potential was addressed identifying the usefulness of a Na-sulfonic resin as a strong chelating agent applied before the beginning of sorption titration experiments so that the titration curves and the sorption uptake could be quantitatively compared. The resin stabilized the initial electrochemical potential to -405+/-5 mV corresponding to 2 micro gl(-1) of lead concentration in solution. The amounts of lead sorbed by R. arrhizus biomass and diatomite were 0.9 mmol g(-1) (C(e)=5.16 x 10(-2)mM) and 0.052 mmol g(-1) (C(e)=5.97 x 10(-2) mM), respectively. Lead sorption by the fungal biomass was pinpointed to at least two types of chemical active sites. The first type was distinguished by high reactivity and a low number of sites whereas the other was characterized by their higher number and lower reactivity.     

Assessing biological and chemical signatures related to nutrient removal by floating islands in stormwater mesocosms

Aquatic floating plants on BioHaven mats were tested for their potential use as a Best Management Practice to be incorporated within existing stormwater detention ponds. Plants were analyzed for their capability to remove nutrient-pollution in parallel with the study of ecological dynamics. Experiments were carried out in cylindrical mesocosms of 5 m diameter and 1.2 m height, above-ground pools with a water volume of 14 m³. The design parameters tested were for 5% and 10% vegetated floating island coverage of the mesocosm, both with and without shoreline plants called littoral zone. This littoral shelf was 0.5 m thick, graded at a downward slope of 1:5 toward the center using loamy soil with low organic matter content, excavated from below turf grass. Endemic plant species were chosen for the experimental location in central Florida based on a wetland identification manual by the Florida Department of Environmental Protection to ensure the study was not compromised by unique climate requirements of the plants. Nutrient and aquatic chemical conditions such as pH, dissolved oxygen, temperature, turbidity, and chlorophyll a were monitored to understand their relationships to the general wetland ecosystem. Real-time polymerase chain reaction analysis identified the microbial activity near the rhizospheric zone. Logistical placement considerations were made using spatial sampling across the horizontal plane of the mesocosms, beneath and around the root zone, to determine if nutrients tend to aggregate around the floating island. This study concluded that the application of floating islands as a stormwater technology can remove nutrients through plant uptake and biological activity. The most cost-effective size in the outdoor mesocosms was 5% surface area coverage of the mat.     

Distribution of organophosphate insecticides in a Thai biomass-water system

Sorption and leaching of the organophosphate (OP) pesticides chlorpyrifos, profenofos, methyl parathion and malathion were investigated with four different types of biomass: coconut husk, rice husk, peat moss and peanut shell. Organic carbon contents of the biomass were in the range of 35.4–45.4%. Sorption studies were carried out by the batch (equilibrium) method at 4 different OP spike concentrations and at pH 3–7. Sorption isotherms conformed to a linear Freundlich equation and the Freundlich constant or sorption coefficient (K_D) confirmed that biomass organic carbon content was the principal sorbent factor affecting OP sorption. For a given sorbent, correlation of the extent of sorption with sorbate chemical properties was examined. Column leaching experiments involving different masses of coconut husk and peanut shell pre-spiked with OPs at the level equivalent to actual spraying concentrations in some Thai tangerine orchards were conducted. These experiments included repeated spikings and leaching. A water flow rate of 20 mL min^?1 was employed corresponding to the current average watering regime. Retardation and biodegradation with these sorbents were also examined.     

Distribution of organophosphate insecticides in a Thai biomass-water system

Sorption and leaching of the organophosphate (OP) pesticides chlorpyrifos, profenofos, methyl parathion and malathion were investigated with four different types of biomass: coconut husk, rice husk, peat moss and peanut shell. Organic carbon contents of the biomass were in the range of 35.4-45.4%. Sorption studies were carried out by the batch (equilibrium) method at 4 different OP spike concentrations and at pH 3-7. Sorption isotherms conformed to a linear Freundlich equation and the Freundlich constant or sorption coefficient (KD) confirmed that biomass organic carbon content was the principal sorbent factor affecting OP sorption. For a given sorbent, correlation of the extent of sorption with sorbate chemical properties was examined. Column leaching experiments involving different masses of coconut husk and peanut shell pre-spiked with OPs at the level equivalent to actual spraying concentrations in some Thai tangerine orchards were conducted. These experiments included repeated spikings and leaching. A water flow rate of 20 mL min(-1) was employed corresponding to the current average watering regime. Retardation and biodegradation with these sorbents were also examined.     

Transport and attenuation of dissolved glyphosate and AMPA in a stormwater wetland

Glyphosate is an herbicide used widely and increasingly since the early 1990s in production of many crops and in urban areas. However, knowledge on the transport of glyphosate and its degradation to aminomethylphosphonic acid (AMPA) in ecosystems receiving urban or agricultural runoff is lacking. Here we show that transport and attenuation of runoff-associated glyphosate and AMPA in a stormwater wetland differ and largely vary over time. Dissolved concentrations and loads of glyphosate and AMPA in a wetland receiving runoff from a vineyard catchment were assessed during three consecutive seasons of glyphosate use (March to June 2009, 2010 and 2011). The load removal of glyphosate and AMPA by the wetland gradually varied yearly from 75% to 99%. However, glyphosate and AMPA were not detected in the wetland sediment, which emphasises that sorption on the wetland vegetation, which increased over time, and biodegradation were prevailing attenuation processes. The relative load of AMPA as a percentage of total glyphosate increased in the wetland and ranged from 0% to 100%, which indicates the variability of glyphosate degradation via the AMPA pathway. Our results demonstrate that transport and degradation of glyphosate in stormwater wetlands can largely change over time, mainly depending on the characteristics of the runoff event and the wetland vegetation. We anticipate our results to be a starting point for considering degradation products of runoff-associated pesticides during their transfer in wetlands, in particular when using stormwater wetlands as a management practice targeting pesticide attenuation.     

Nonideal transport of contaminants in heterogeneous porous media: 9 - impact of contact time on desorption and elution tailing

A series of miscible-displacement experiments was conducted to examine the impact of sorption contact time on desorption and elution of trichloroethene from a well-characterized soil. A large number of contact times were examined, spanning 1 h to 4 years (∼2 × 10⁶ h). Effluent trichloroethene concentrations were monitored over a range of greater than six orders of magnitude, allowing characterization of potential asymptotic tailing. The results of the column experiments showed that trichloroethene exhibited extensive elution tailing for all experiments. Each increase in contact time resulted in a successive increase in the extent of tailing. In total, the number of pore volumes of water flushing required to reach the analytical detection limit increased from approximately 1000 for the 1-h contact time to almost 9000 for the 4-year contact time. These results indicate that a contact time of less than 1 h produced a sorbed phase that is relatively resistant to desorption, and that a progressive increase in resistance to desorption occurred with increased contact time. A mathematical model incorporating nonlinear, rate-limited sorption/desorption described by a continuous-distribution reaction function was used to successfully simulate the measured data. The nonlinear sorption, the apparent rapid development of desorption resistance, and the progressive increase in resistance with increasing contact time are consistent with behavior anticipated for sorbate interactions with hard-carbon components of the soil.     

Diffusion mechanism of lindane into wood charcoal

Abstract

The wood charcoal treated by 1N HNO₃ (WCT) was used to remove toxic chlorinated pesticide lindane (y‐HCH) residue from water by the sorption process. Using a simple first order reversible kinetics constants and half time equations, the film and pore diffusion coefficients were determined. Film diffusion was found to be rate limiting step in sorbing lindane by WCT. This was further authenticated by kinetics studies at different initial sorbate concentrations, different sorbent sizes, and different agitation speeds besides interruption test. A pore diffusion model was used to fit the data of kinetics in continuously mixed batch reactors (CMBR), and the tortuosity, external resistance, and surface diffusion effects on lindane sorption by WCT were noticed. The tortuosity values of 15 to 28 were obtained for WCT‐lindane system.     

Micropollutants in urban stormwater: occurrence,concentrations, and atmospheric contributions for a wide range of contaminants in three French catchments

This study aimed at: (a) providing information on the occurrence and concentration ranges in urban stormwater for a wide array of pollutants (n?=?77); (b) assessing whether despite the differences between various catchments (land use, climatic conditions, etc.), the trends in terms of contamination level are similar; and (c) analyzing the contribution of total atmospheric fallout (TAF) with respect to sources endogenous to this contamination. The studied contaminants include conventional stormwater contaminants (polycyclic aromatic hydrocarbons (PAHs), Zn, Cu, Pb, etc.), in addition to poorly or undocumented pollutants such as nonylphenol and octylphenol ethoxylates (NPnEO and OPnEO), bisphenol A (BPA), polybrominated diphenyl ethers (PBDEs), a wide variety of pesticides, and various metals of relevance (As, Ti, Sr, V). Sampling and analysis were performed using homogeneous methods on three urban catchments with different land use patterns located in three distinct French towns. For many of these pollutants, the results do not allow highlighting a significant difference in stormwater quality at the scale of the three urban catchments considered. Significant differences were, however, observed for several metals (As, Cr, Cu, Ni, Sr and Zn), PAHs, and PBDEs, though this assessment would need to be confirmed by further experiments. The pollutant distributions between dissolved and particulate phases were found to be similar across the three experimental sites, thus suggesting no site dependence. Lastly, the contributions of TAF to stormwater contamination for micropollutants were quite low. This finding held true not only for PAHs, as previously demonstrated in the literature, but also for a broader range of molecules such as BPA, NPnEO, OPnEO, and PBDEs, whose high local production is correlated with the leaching of urban surfaces, buildings, and vehicles.     

Enhancement effect of water associated with natural organic matter (NOM) on organic compound-NOM interactions: a case study with carbamazepine

Natural organic matter (NOM) in soils and sediments is recognized to strongly affect environmental distributions of organic compounds. Water associated with NOM may have a significant impact on NOM-organic compound interactions. The objectives of this research were (1) to determine the effect of hydration of a model NOM sorbent on interactions with a probe organic compound, carbamazepine (CBZ), and (2) based on the comparison with the literature data, to evaluate the effect of organic compound structure on the cooperative participation of water molecules in organic sorbate-NOM interactions. CBZ is one of the most widely reported water pollutants from the pharmaceutical and personal care products family. Therefore, CBZ sorption on Pahokee peat was compared from water and from n-hexadecane, using solubility-normalized solute concentrations. CBZ-NOM interactions were enhanced by one to two orders of magnitudes when NOM became fully hydrated. This enhancement is associated with the distinct ability of CBZ to undergo strong, specific interactions with NOM which was revealed by comparing the transfer of CBZ and another model sorbate, phenanthrene, from solution in n-hexadecane to the hydrated NOM sorbent. The enhancing effect of NOM hydration on CBZ-NOM interactions was also observed when CBZ sorption was examined on partially hydrated NOM. In comparison with a smaller-size organic sorbate such as phenol, CBZ needs more NOM-associated water in order to demonstrate the strengthening of interactions with NOM. Therefore, for penetration of the larger sorbate molecules into the NOM interior, a greater number of water molecules are needed to compensate for the local NOM disintegration thus suggesting the greater extent of the cooperativity in an involvement of water molecules in the CBZ-NOM interactions.     

BDE-47 sorption and desorption to soil matrix in single- and binary-solute systems

Three loamy-clay soil samples (LC1-3) with different properties were collected as the geosorbents to preliminarily investigate the sorption and desorption of 2,2′,4,4′-tetrabromodiphenyl ether (BDE-47) in single system and binary system with the presence of decabromodiphenyl ether (BDE-209), which can provide information in order to further understand the sorption mechanisms and evaluate the adsorption sites. A concentration of 10 μg L⁻¹ BDE-209 suppressed the sorption of BDE-47, and the trend became more and more significant with the increase of BDE-47 equilibrium concentration, however, BDE-47 caused no competitive effect on BDE-209 sorption, which was related with the better accessibility of more hydrophobic molecules to adsorption sites. In the binary system, nonlinearity of the BDE-47 sorption isotherms for the three samples changed in different ways, which originated from the varied soil properties. Desorption hysteresis was observed in all cases, which was estimated due to irreversible surface adsorption between sorbent and sorbate. BDE-209 made desorption of BDE-47 more hysteretic from soil samples, which was estimated to be ascribed to the accelerated sorbent state transition and new sites creation caused by BDE-209 sorption.