Adsorption‐desorption hysteresis of α‐endosulfan in tropical soils using isotopic techniques

This study was designed to evaluate the adsorption‐desorption hysteresis of endosulfan (1,2,3,4, 7,7‐hexachlorobicyclo[2,2,1]‐2‐heptene‐5,6‐bisoxymethylene sulfite) in selected tropical soils. Two major tropical soils from Thailand were selected, Rangsit lowland soils (Rangsit series) and Phrabat upland soils (Pakchong series). The soil types were sub‐divided into plow soils, 0–20cm depth from the surface, and subsoils, 20–40cm depth. Adsorption was determined in 24h batch equilibrium, with five different concentrations of ¹⁴C endosulfan ranging from 1.04 to 16.64 ng/mg soils. Four successive desorption studies were performed continuously after three adsorption concentrations, 24h for each successive. Adsorption coefficient values (K _ads) as determined by Freundlich model ranged from 0.02 to 0.14 and found to be higher in Rangsit soils as expected when compared with Phrabat soils. Desorption was hysteresis in every desorption study. Desorption coefficient values (K _des) were higher than adsorption (K _des).     

Studies of thermodynamics of phosphomidon on fly ash

Adsorption thermodynamic studies of phosphomidon on fly ash at 25° and 50°C have been analysed as adsorption isotherms, Freundlich equations, K_d values and various other thermodynamic parameters. These data were in close agreement with Freundlich isotherms and yield ‘S’ type isotherms at both the temperatures. Thermodynamic constants (K_o) and standard free energy (ΔG°), enthalpy (ΔH°) and entropy changes (ΔS°) have been calculated for predicting the nature of adsorption.     

Retention of 137cesium in acid sulphate soils of South Central Thailand

Adsorption and desorption of ¹³⁷Cs by acid sulphate soils from the Nakhon Nayok province, South Central Plain of Thailand located near the Ongkarak Nuclear Research Center (ONRC) were investigated using a batch equilibration technique. The influence of added limestone (12 and 18 tons ha^?1) on ¹³⁷Cs adsorption–desorption was studied. Based on Freundlich isotherms, both adsorption and desorption of ¹³⁷Cs were nonlinear. A large portion (98.26–99.97%) of added ¹³⁷Cs (3.7?×?10³?7.03?×?10⁵ Bq l^?1) was sorbed by the soils with or without added lime. The higher lime treatments, however, favoured stronger adsorption of ¹³⁷Cs as compared with soil with no lime, which was supported by higher K _ads values. The addition of lime, the cation exchange capacity and pH of the soil increased and hence favoured the stronger adsorption of ¹³⁷Cs. Acid sulphate soils with a high clay content, medium to high organic matter, high CEC, and predominant clay types consisting of a mixture of illite, kaolinite, and montmorillonite were the main soil factors contributing to the high ¹³⁷Cs adsorption capacity. Competing cations such as NH₄ ⁺, K⁺, Na⁺, Ca²⁺, and Mg²⁺ had little influence on ¹³⁷Cs adsorption as compared with liming, where a significant positive correlation between K _ads and soil pH was observed. The ¹³⁷Cs adsorption–desorption characteristics of the acid sulphate soils studied exhibited a very strong irreversible sorption pattern. Only a small portion (0.09–0.58%) of ¹³⁷Cs adsorbed at the highest added initial ¹³⁷Cs concentration was desorbed by four successive soil extractions. Results clearly demonstrated that Nakhon Nayok province acid sulphate soils have a high ¹³⁷Cs adsorption capacity, which limits the ¹³⁷Cs bioavailability.     

Adsorptive removal of mercury from acid mine drainage: a comparison of silica and maghemite nanoparticles

Mercury adsorption by silica and maghemite nanoparticles (NPs) was studied with the aim of comparing their performance in the remediation of acid mine drainage (AMD) contaminated water. Calculated distribution coefficients (K_d) showed that both NPs are exceptional adsorbents. However, adsorbate coverage per unit area was 30 times higher for maghemite than for silica NPs, despite the latter having a surface area ～15 times greater. Maghemite adsorbed 75% of available Hg compared to 56% by silica, making it a more efficient sorbent than silica under AMD conditions. Kinetics and isotherm data for both adsorbents were fitted by the pseudo-second-order (R² = 1) and the Freundlich (R² ≥ 0.98) models, implying that adsorption to both NP types was by chemisorption. Adsorption increased with NP concentrations and pH and was enhanced in the presence of manganese and sulfate ions although adsorption to silica was inhibited in 1:2 Hg-to-Mn systems. Importantly, trends in simulated wastewater were replicated in actual AMD-contaminated water samples. This study highlights the fact that properties besides surface area and charge of adsorbents determine adsorbent performance, and superior attributes may not always lead to higher adsorption efficiencies.     

Sorption of cadmium(II) and copper(II) by soil humic acids: temperature effects and sorption heterogeneity

Sorption by humic acids is known to modify the bioavailability and toxicity of metals in soils and aquatic systems. The sorption of cadmium(II) and copper(II) to two soil humic acids was measured at pH 6.0 using ion-selective electrode potentiometric titration at different temperatures. Sorption reactions were studied with all components in aqueous solution, or with the humates in suspension. Adsorption reactions were described using a multiple site-binding model, and a model assuming a continuous log-normal distribution of adsorption constants. Adsorption of Cu²⁺ was more favourable than adsorption of Cd²⁺. The log-normal distribution model provided the closest fit to observations and allowed parameterisation of adsorption data using a mean adsorption constant (log K _μ). Sorption of Cd²⁺ to dissolved humic acids increased slightly in extent and sorption affinity with increasing temperature, but the effect was small (log K _μ 2.96–3.15). A slightly greater temperature effect occurred for sorption of Cd²⁺ to solid-phase humic acids (log K _μ 1.30–2.08). Sorption of copper(II) to both aqueous- and colloidal-phase humates showed more pronounced temperature dependence, with extent of sorption, and sorption affinity, increasing with increasing temperature (log K _μ 3.4–4.9 in solution and 1.4–4.5 in suspension). The weaker adsorption of Cd²⁺ than Cu²⁺, and smaller temperature effects for dissolved humates than suspended humates, suggested that the observed temperature effects had a kinetic, rather than thermodynamic, origin. For any metal-to-ligand ratio, free metal ion concentration, and by inference metal bioavailability, decreased with increasing temperature. The consistency of the data with kinetic rather than thermodynamic control of metal bioavailability suggests that equilibrium modelling approaches to estimating bioavailability may be insufficient.     

Adsorption and movement of carbaryl in soils: A verification of cosolvent theory and comparison of batch equilibrium and soil thin layer chromatography results

Batch equilibrium and soil thin layer chromatography (TLC) techniques were used to investigate the influence of different volume fractions of organic cosolvents (acetone and methanol) on the adsorption and movement of carbaryl in four different types of Indian soils. L-shaped isotherms were obtained for both the cosolvent–water mixtures at all f _s values and were in close agreement with the Freundlich equation. Higher adsorption was observed on F.R.I. soil (FSL) followed by Alampur soil (ASL), Kalai soil (KL), and Bhoran soil (BSL) at all f _s values for both the cosolvent systems as was anticipated from the K and K _D values. The K and K _D values also confirmed that carbaryl adsorption was higher in methanol–water mixture than acetone–water mixture and decreased with increasing f _s values. The frontal R _f values obtained from soil TLC studies were inversely proportional to the K and K _D values for both the cosolvent systems. The higher K and K _D values and lower R _f values in methanol–water mixtures relative to acetone–water mixtures for all the soils indicated that acetone had a greater potential for ground water contamination compared to methanol. The adsorption data were used to evaluate the cosolvent theory for describing adsorption of carbaryl in acetone–water and methanol–water mixtures. The aqueous phase partition coefficients, K _DW (mol g^?1), normalized with respect to f _oc for carbaryl was evaluated by extrapolating f _s → 0.     

Adsorption of pesticides by salorthids and camborthids of Punjab,Pakistan

This study was conducted to examine adsorption of pesticides bifenthrin, carbosulfan, λ-cyhalothrin, cypermethrin, endosulfan, parathion methyl, monocrotophos and 4-nitrophenol by sandy clay loam (S.C.L) and sandy loam (S.L) soils (with varying organic content). There was no significant difference between the observed soil water partitioning coefficient values (K _d) derived from linear and nonlinear Freundlich isotherms. Adsorption of pesticides on S.C.L soils was higher than those on S.L soils. K _d values showed significant correlations (r ²?=?0.8???0.99 and 0.65???0.97) with soil organic carbon content (OC) and weak correlations (r ²?=?0.2???0.29 and 0.1???0.18) with clay contents of S.C.L and S.L soil at p?≤?0.05, respectively for all pesticides (except monocrotophos). Observed K _oc values (soil-water partitioning constants based on the organic C fraction of the soil) were in accordance with the literature values of Wauchope and Tomlin with a maximum deviation of less than 0.5 log units. Ten Quantitative Property-Property Relationships (QPPR) among water solubility, n-octanol water coefficient (K _ow) and K _oc were proposed for studied pesticides except monocrotophos. The models were considered acceptable when predicted-observed difference for log?K _ow and log?K _oc were ≤?0.3 and ≤?0.5?log units, respectively, during the validation procedure. This work indicates that the log?K _oc derived from the log K_ow, from some of existing relationships, may be a fair predictor where observed values (i.e., K _d and K _oc) are not available. Furthermore, predicted leaching potential by groundwater ubiquity scores (GUS) equation was solved by using observed K _oc values and literature reported half lives of pesticides. GUS ranked the mobility of nonvolatile compounds i.e., bifenthrin, λ-cyhalothrin, cypermethrin and endosulfan extremely low; methyl parathion very low; 4-nitrophenol low; carbofuran and monocrotophos very high in S.C.L and S.L soils, respectively. Results discussed in this paper provide background to prioritize pesticides or chemical groups that should be evaluated under field conditions with regard to their leaching potential to groundwater in arid climates.     

Arachis hypogaea derived activated carbon steered remediation of Benzimidazole based fungicide adsorbed soils

Sorption characteristics of the Benzimidazole fungicide Carbendazim were assessed in seven different soils using batch equilibrium method and analysed by UV-Vis spectrophotometer. The values of adsorption co-efficient K_d ranged from 14.3 to 39.8?µg/mL depending upon unique physiochemical properties of soils. Negative values for Gibbs free energy (ΔG) proposed an exothermic and low interaction between Carbendazim and soil samples leading to physiosorption. Statistical analysis showed a negative correlation of soil pH and K_d (R²= ?0.80) and a positive correlation with organic matter (R^2?=?0.77). Activated carbon prepared from Arachis hypogaea (peanut shells) by acid activation for Carbendazim removal from soils was characterised by FTIR spectrometry, indicating the change in functional groups. The highest percentage removal observed was 70% in 5?ppm initial Carbendazim concentration while 65% in 7.5?ppm concentration. This method can be implied in agricultural soils as an efficient and cheap technique for removing the hazardous pesticides from the environment.     

A model of 90Sr distribution in the sea near Daya Bay Nuclear Power Plant in China

The impact on the environment ofradionuclide release from nuclear power plants has attracted increased attention, especially after the accident at Fukushima Daiichi Nuclear Power Plant in Japan. Based on the mechanisms of adsorption/desorption at solid/liquid interfaces and a surface micromorphology model of sediments, a theoretical expression of the distribution coefficient Kd is derived. This coefficient has significant effects on the distribution of radionuclide in seawater, suspended sediment and seabed sediment. Kd is then used to simulate ^90Sr transport in the sea near the Daya Bay Nuclear Power Plant. The simulation results are compared with field measurements of tidal level, current velocity, suspended sediment concentration and ^90Sr concentrations in the same period. Overall, the simulated results agree well with the field measured data. Thus, the derived expression for Ka is capable of interpreting realistic adsorption/desorption processes. What＇s more, conclusion is drawn that about 40% ^90Sr released by Daya Bay Nuclear Power Plant will be adsorbed by suspended sediment and 20% by seabed sediment, only about 40% ^90St will remain in the sea near Daya Bay Nuclear Power Plant in South China Sea.     

Selenium content of rice,mixed plant foods and fish from Bangladesh

Static and dynamic adsorption studies of Co (II) ions have been undertaken at fixed pH and ionic strength taking binary biopolymeric beads of cross-linked calcium alginate and carboxy methylcellulose as biosorbents. The adsorption data were applied to Langmuir and Freundlich isotherm equations and various static parameters were calculated. The dynamic nature of adsorption process was quantified in terms of several kinetic constants such as rate constants for adsorption (K) and Lagergreen rate constant (K _ad). The influence of various experimental parameters such as solid-to-liquid ratio, pH, and temperature, the presence of salts and chemical composition of biopolymeric beads were investigated on the adsorption of cobalt ions.     

pH dependence of copper adsorption in vineyard soils of Geneva

Copper adsorption by vineyard soils of the Geneva canton was evaluated by batch equilibration experiments in a pH range from 4 to 6. The adsorption curves fit significantly to Freundlich function log q = n log C + log K_f, where q is adsorbed Cu concentration on the solid phase and C is solution Cu concentration at the end of the equilibration time. Moreover, we found that Freundlich parameters n and log K_f are moderately correlated to pH, yielding the following equations: log K_f = 0.23 pH + 0.51 (R ² 0.59) and n = –0.12 pH + 1.06 (R ² 0.59). Such equations may be useful to predict Cu mobility for risk assessment studies.     

几类有机污染物的微塑料/水分配系数的线性溶解能关系模型

水体中的微塑料会吸附其中的有机污染物,影响有机污染物和微塑料的环境归趋和生态毒性。研究微塑料对有机污染物的吸附行为,对于评价有机污染物和微塑料的环境赋存、迁移及生物有效性有重要意义。污染物在微塑料与水之间的平衡分配系数(Kd),是表征微塑料对有机污染物吸附能力的重要参数。实验方法难以逐个测定众多有机污染物的Kd值,有必要发展其预测模型。本研究搜集了有机污染物的线性溶解能关系(LSER)参数及Kd值,构建了可预测有机污染物在聚丙烯微塑料与海水、聚乙烯微塑料与海水、聚乙烯微塑料与淡水之间Kd值的LSER模型。模型具有良好的拟合优度(R2adj介于0.794~0.903)、稳健性(Q2LOO和Q2BOOT分别介于0.763~0.863和0.720~0.804)和预测能力(R2ext和Q2ext分别介于0.886~0.971和0.825~0.954),能够用于预测多氯联苯、多环芳烃、六氯环已烷和氯苯类有机污染物的Kd值。     

Cationic dye adsorption onto natural and synthetic zeolites in the presence of Cs+ and Sr2+ ions

Adsorption of diazine dye safranine O (SO) in the presence of Cs⁺ and Sr²⁺ ions was investigated onto natural and synthetic zeolites in order to predict competition of cationic organic species with their radionuclides, which are the main fission products released into the environment. Adsorption of SO was measured up to the 40th day and the surface-diffusion coefficients (D_s) were estimated by applying Nernst–Planck approximation based on a homogeneous-surface-diffusion model. The values of D_s were 10 times higher on natural zeolite than those of synthesized zeolite from fly ash (FA) under hydrothermal conditions. Similarly, distribution coefficients (K_D) were considerably higher on the clinoptilolite-type natural zeolite. The zeolitized product of FA is mainly composed of analcime and sodalite. SO adsorption on natural zeolite was not influenced by Cs⁺ and Sr²⁺ ions, but it decreased at high concentrations on synthetic zeolite. The higher influence of the Sr²⁺ ions on SO⁺ adsorption showed that they compete with each other for the same adsorption sites. These results suggested that natural zeolite cannot be used for remediation of wastewater polluted with Cs and Sr radionuclides in the presence of organic cations, whilst FA zeolite has a potential for Sr removal.     

Ackee apple (Blighia sapida) seeds: a novel adsorbent for the removal of Congo Red dye from aqueous solutions

The ability of ackee apple (AA) seeds to remove Congo Red (CR) dye from aqueous solution was investigated. AA was characterised using thermo gravimetric analyser, scanning electron microscopy, Braunauer Emmett Teller, pH_pzc, elemental analysis and Boehm titration. The effects of operational parameters such as adsorbent dosage, contact time, initial dye concentration and solution pH were studied in a batch system. pH has a profound influence on the adsorption process. Maximum dye adsorption was observed at pH 3.0. The reaction was fast, reaching equilibrium in 90 min. Adsorption data were best described by Langmuir isotherm and the pseudo-second-order kinetic model with a maximum monolayer coverage of 161.89 mg·g^?1. Both boundary layer and intraparticle diffusion mechanisms were found to govern the adsorption process. Thermodynamic parameters such as standard free energy change (Δ G ⁰), standard enthalpy change (Δ H ⁰), and standard entropy change (Δ S ⁰) were studied. Values of Δ G ⁰ varied between?30.94 and?36.56 kJ·mol^?1, Δ H ⁰ was 25.61 kJ·mol^?1, and Δ S ⁰ was 74.84 kJ·mol^?1·K^?1, indicating that the removal of CR from aqueous solution by AA was spontaneous and endothermic in nature. Regeneration and reusability studies were carried out using different eluents. AA gave the highest adsorption efficiency up to four cycles when treated with 0.3 M HCl. AA was found to be an effective adsorbent for the removal of CR dye from aqueous solution.     

Phenanthrene adsorption by soils treated with humic substances under different pH and temperature conditions

The mobility of phenanthrene (PHE) in soils depends on its sorption and is influenced by either the existing soil humus or exogenous humic substances. Exogenous humic acids (HAs) were added to soil to enhance the amount of soil organic carbon (SOC) by 2.5, 5.0, and 10.0 g kg⁻¹. PHE desorption of the treated soils was determined at two pH levels (3.0 and 6.0) and temperatures (15 and 25 °C). Soil PHE adsorption was related to pH and the type and quantity of added HAs. Humic acid (HA) and fulvic acid (FA) derived from peat had different effects on adsorption of PHE. Adsorption increased at first and then decreased with increasing quantity of exogenous FA. When the soil solution pH (in 0.005 M CaCl₂) was 4.5 or 3.0, the turning points were 2.5 g FA kg⁻¹ at pH 3.0 and 5 g FA kg⁻¹ at pH 4.5. When soil solution pH was 6, the amount of adsorbed PHE was enhanced with increasing exogenous HAs (HA or FA) and amount of adsorption by soil treated with FA was higher than with HA. Adsorption of PHE in the FA treatment at 10.0 g kg⁻¹ was lower than the controls (untreated soil or treatment with HAs at 0 g kg⁻¹) when the soil solution pH was 3.0. This suggests that FA adsorbed by soil was desorbed at low pH and would then increase PHE solubility, and PHE then combined with FA. PHE adsorption was usually higher under lower pH and/or lower temperature conditions. PHE sorption fitted the Freundlich isotherm, indicating that exogenous humic substances influenced adsorption of phenanthrene, which in turn was affected by environmental conditions such as pH and temperature. Thus, exogenous humic substances can be used to control the mobility of soil PAHs under appropriate conditions to decrease PAH contamination.     

Heavy metals uptake from aqueous solutions using marine algae (Colpomenia sinuosa): kinetics and isotherms

The adsorption of copper, zinc, cobalt, lead and cadmium ions onto Colpomenia sinuosa was studied as a function of contact time, initial metal ion concentration and initial pH. In addition, desorption studies were performed. Characterisation of this adsorbent was also confirmed by Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM) analysis. Batch adsorption experimental data were analysed using Langmuir, Freundlich and Dubinin–Raduschkevich (D–R) adsorption isotherms. The results indicated that the biosorption equilibrium was well described by both the Freudlich and D–R isotherms. Moreover, sorption kinetics was performed and it was observed that equilibrium was reached in<60 min, which could be described by the pseudo-second-order kinetic model for all heavy metals. The sorption of heavy metals onto the biomass was largely dependent on the initial solution pH. The elution efficiency for heavy metal ions desorption from C. sinuosa was determined for 0.1 M HCl, 1.0 M HCl and 1.0 M HNO₃. Desorption efficiency and also adsorption capacity were highest for Pb(II). The results indicate that C. sinuosa has great potential for the removal of heavy metals in an ecofriendly process.     

Adsorptive separation of phosphate oxyanion from aqueous solution using an inorganic adsorbent

Phosphate removal from aqueous solution was explored using granular ferric hydroxide (GFH) as an inorganic adsorbent. Adsorption, desorption and kinetic studies were conducted on laboratory scale to evaluate the performance of GFH as an adsorbent for low concentrations of phosphate solution. The effect of pH on adsorption was investigated, and phosphate uptake was shown to decrease with an increase in solution pH, with maximum removal seen to occur at pH 3. The experimental data best fit the Temkin isotherm at both pH 3 and 4. Uptake of phosphate by GFH follows second-order kinetics, with the small particle range (76–200 μm) removing phosphate from the solution more rapidly than the larger particle range (710–850 μm). The kinetic results suggest that intra-particle diffusion is an important factor in phosphate adsorption onto GFH. Thermodynamic parameters (ΔG°, ΔH°, ΔS°) were evaluated, and the results indicated that the adsorption process was endothermic and spontaneous. This study demonstrates that GFH has potential to be used as a cost-effective adsorbent for phosphate removal from aqueous solution.     

Turnover of tracer (14C, 3H labelled) alanine in inshore marine sediments

The turnover rate constants (k) of alanine in coastal marine sediments were measured using ³H-and ¹⁴C-alanine in tracer amounts (less than in situ concentrations of alanine in the porewater). After incubation ¹⁴C-label was recovered in free dissolved alanine, adsorbed alanine, volatile fatty acids and carbon dioxide pools. Alanine left the free dissolved pool by two processes: 1) adsorption (k=0.06 min^-1) and 2) biological uptake (k=0.16 min^-1). Adsorption of alanine was deduced from the persistence of ¹⁴C-alanine, which was slowly metabolized after an initial rapid rate of degradation. Adsorption was confirmed in biologically inactivated sediments. The adsorbed ¹⁴C-alanine was only partially exchanged by the addition of excess non-labelled alanine, indicating the existence of at least 2 different adsorbed pools. The rates of adsorption and desorption were equal, but the k-values were different, indicating that the adsorbed pool was 2500 fold greater than the free pool. From the biological turnover rate constant (0.16 min^-1), the mineralization percentage (80%) and the concentration of alanine (800 nmol l^-1 of porewater) a mineralization rate in the sediment of 75 nmol cm^-3 d^-1 was determined. This was in excess of the measured total NH ₄ ⁺ production. It is concluded that much of the dissolved alanine (800 nm) was biologically unavailable and a more realistic free dissolved pool would be 10 nM.     

Removal of chromium(VI) by ZnCl2 activated coir pith carbon

The adsorption of chromium(VI) onto ZnCl₂ activated carbon developed from coir pith was investigated to assess the possible use of this adsorbent. The influence of contact time, adsorbent dose, Cr(VI) concentration, pH and temperature were investigated. The two theoretical adsorption isotherms, namely, Langmuir and Freundlich were used to describe the experimental results. The Langmuir adsorption capacity (Q ₀) was found to be 120.5?mg Cr(VI) per g of the adsorbent. The adsorption followed the second-order kinetics and was found to be maximum at pH 2.0. The pH effect and the desorption studies showed that ion exchange mechanism might be involved in the adsorption process. The effects of foreign ions such as chloride, sulphate, phosphate, selenite, molybdate, nitrate and perchlorate on the removal of Cr(VI) have been investigated. The removal of Cr(VI) from synthetic ground water was also tested. The results show that ZnCl₂ activated coir pith carbon is effective for the removal of Cr(VI) from water.