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.     

Adsorption and desorption of tetraalkyllead and dibutyltin compounds on contaminated soils

Adsorption and desorption of di-n-butyltin (IV) (DBT), tetramethyllead (TML), and tetraethyllead (TEL) on four types of soil were studied. Although, all K _d values for desorption are higher than the K _d values for adsorptions, which shows that the adsorption process is reversible, the lower percentages of desorption indicate that very low concentration of these organometallic compounds can be more easily leached from the soil. The adsorption ranging between 48.8% and 88.3% for DBT, between 9.1% and 38.3% for TEL, and between 24.9% and 44.2% for TML was measured. The desorption was obtained between 9.4% and 23.7% for DBT, between 19.3% and 38.9% for TEL, and between 21.5% and 32.7% for TML. These results show that the nonpolar (TML, TEL) organometallic compounds can be easier leached than the ionic forms (DBT). Adsorption kinetics and adsorption as a function of pH were also evaluated. DBT and tetraalkyllead adsorption equilibrium were reached after 12 and 24 h, respectively. The tetraalkyllead is strongly adsorbed at pH 7–8 and DBT at pH 6.     

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.     

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).     

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.     

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.     

Regression models for some solute distribution equilibria in the terrestrial environment

Sorption coefficients (K_p) of several organochlorine insecticides (OCs) in volcanic ash silt from Central Java are presented.

Selected experimental and estimated octanol‐water partition coefficient (P) values are used to study log‐log regressions with K_p data collected from the literature (PAHs, chlorophenols, phenylureas, chloro‐s‐triazines, carbamates and organophosphorus insecticides) and those of the OCs determined in the present study. Leaching distances and bioactivities in soil are correlated with the K_p values of the pesticides, and with the organic matter and the water content of the soil.     

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.     

Sensitized photooxygenation of mononitrophenols in micellar media

The singlet molecular oxygen‐mediated photooxidation of simple nitrophenols was studied in micellar (CTAB) alkaline solutions.

A different behaviour for the values of the overall rate constant (K_t ) and the reactive rate constant (K_t ) in the interaction nitrophenol‐singlet molecular oxygen was observed as a function of surfactant concentration. The former decreases as [CTAB] increases, from values of 1–3 × 10⁹ M^–1 s^–1 in the absence of surfactant to values at least one order of magnitude lower at [CTAB] ～0.1 M. Parallel, k_t remains practically unaffected, in values of the order of 10⁶ — 10⁷ M^–l s^–1, depending on the particular nitrophenol, within the same [CTAB] range. The quantum yield of nitrophenols photooxidation reaches a maximum at [CTAB] ～0.1 M.

The results are discussed in terms of a combination of causes, the polarity of the nitrophenolic microenvironment being the driving effect. The implication of the results on environmental decontamination are also analyzed.     

除草定在土壤中的降解和移动特性研究

除草定是一种新型嘧啶类除草剂,其在环境中的归趋备受关注。采用室内模拟试验方法,研究了除草定在不同土壤中的降解性、吸附性和移动特性。结果表明,除草定在江西红壤、太湖水稻土和东北黑土中的降解半衰期分别为693.1、173.3、138.6 d,该药在土壤中降解较慢,影响其在土壤中降解速率的主要因素为土壤有机质。除草定在江西红壤、太湖水稻土与东北黑土中的吸附较好地符合Freundlich方程,Kd值分别为0.34、1.86和2.94;3种土壤对除草定的吸附过程为自发的物理吸附。薄层层析试验显示,当溶剂展开至11.5 cm处,除草定在江西红壤、太湖水稻土和东北黑土中最远移至8~10 cm处。影响除草定在土壤中吸附性和移动性的主要因素为土壤有机质含量。除草定存在对地下水污染的潜在风险性,使用除草定应该引起足够重视。     

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.     

Growth kinetics and nutrient requirements of two tropical marine phytoplankters

Growth rates of nutrient-depleted cells of Biddulphia sinensis Greville and Ceratium furca (Ehrenberg) Claparède et Lachmann as a function of phosphate and nitrate, follow the hyperbolic expression of the Michaelis-Menten equation. variations in the half-saturation constants (K _s) for both species in each nutrient gave an index of their capacity to utilize these two nutrients when available either singly or in combination. The maximum growth rates (_max) of the two species did not follow the trends shown by K _s. Seasonal abundance of the two species in the Cochin Backwater (an Indian tropical estuary) showed that, at low concentrations of nutrients, C. furca becomes predominant; high nutrient concentrations present in the estuary during the monsoon months tend to increase the abundance of B. sinensis. The differences in the K _s values of the two organisms seem to reflect their observed seasonal abundance in the estuary.     

Development and validation of a spectrophotometric method for soil adsorption study of malathion on three Indian soils

In view of the widespread use of pesticides in agriculture and its associated toxic effects on environment and human beings, the fate of these chemicals in soil is of major concern. The pesticide adsorption process is one of the major factors affecting its persistence and movement in the soil. With a view of studying the fate of malathion in soil, the adsorption of this insecticide was studied on three Indian soils by using batch equilibrium method. To carry out the adsorption study, a new simple, sensitive, and rapid method was developed, based on microwave-assisted alkaline hydrolysis of insecticide to the dimethyl dithiophosphate and its subsequent reaction with copper(I) perchlorate in acetonitrile. On mixing the reagents, a yellow color developed, which was stable for 120?min and was measured at 419?nm. The adsorption of malathion was studied by using Freundlich's adsorption equation and n _f values were observed less than 1 in all the soils. The leaching behavior of the insecticide was studied in terms of ground ubiquity score, which was below 1.8, classifying malathion as non-leacher pesticide, and hence it is not hazardous.     

The effects of soil properties and temperature on the adsorption isotherms of lead on some temperate and semiarid surface soils of Iran

Sorption of metal ions by soil and clay minerals is a complex process involving different mechanisms, and controlled by different variables that can interact. The aim of this work was to study the retention mechanisms of Pb ions on different soil samples. Surface soils were sampled from Guilan and Hamadan provinces in north and northwest of Iran with temperate and semiarid climates. The adsorption isotherms of Pb on the soils have been studied at 15, 27 and 37°C. The adsorption data for different soils were fitted into Langmuir and Freundlich models. Temperate soil samples had higher clay content, cation exchange capacity, dichromate (oxidable) organic carbon, total Kjeldahl-nitrogen, biological activity, amorphous and crystalline Fe and Al, but semiarid soil samples had higher sand content, pH, equivalent calcium carbonate, available P and K. Lead adsorption data obtained from semiarid soils against those obtained from temperate soils were better fitted in both Langmuir and Freundlich models. Langmuir constants Q ₀ for Pb adsorption in semiarid soils were considerably lower than those for Pb adsorption in temperate soils. However, the binding energy (K _L) of Pb and Freundlich constant n were higher for data of semiarid soils. The effect of temperature on the Pb adsorption was positive especially in temperate soils; however, soil properties had higher effects on Pb adsorption.     

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.     

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。     

Kinetics of the oxidation of endocrine disruptor nonylphenol by ferrate(VI)

The kinetics of the oxidation of endocrine disruptor nonylphenol (NP) by potassium ferrate(VI) (K₂FeO₄) in water as a function of pH 8.0–10.9 at 25°C is presented. The observed second-order rate constants, k _obs, decrease with an increase in pH 269–32 M^?1 s^?1. The speciation of Fe(VI) (HFeO ₄ ^? and FeO ₄ ^2? ) and NP (NP–OH and NP–O^?) species was used to explain the pH dependence of the k _obs values. At a dose of 10 mg L^?1 (50 μM) K₂FeO₄, the half-life for the removal of NP by Fe(VI), under water treatment conditions, is less than 1 min.     

In vitro kinetic characterization of inhibition of acetylcholinesterase by organophosphate and carbamate compounds in food animals

Organophosphate, dichlorvos (2,2-dichlorovinyldimethylphosphate, DDVP), and diazinon (DZN) as well as carbamates are currently found in contaminated water, dust, soil, agricultural waste, and elsewhere in the environment, and can be harmful after accidental or deliberate exposure. Intoxication by these compounds causes a generalized cholinergic crisis due to the inhibition of acetylcholinesterase (AChE), whose major physiological role in mammalian tissues is in nervous transmission. The half-maximal inhibitory concentration (IC₅₀) was found to be higher for carbaryl than DDVP and DZN, about 3–4 times in liver and about 4–6 times in muscles. The half time (t _1/2) of inhibition (8?µmol?L^?1 DDVP or DZN; 40?µmol?L^?1 carbaryl) ranged between 4 and 16?min and decreased as follows: pig?>?cattle?>?sheep for liver tissue, and cattle?>?sheep?>?pig for muscle. Rate constants of inhibition (k _i) ranged between 43?×?10^?3 and 168?×?10^?3?min^?1 for liver and from 46?×?10^?3 to 115?×?10^?3?min^?1 for muscles. Very little residual AChE activity (<6.1%) was seen in liver, but more was seen in muscle (<17%).     

Influence of some abiotic environmental factors on acute toxicity of inorganic lead to Cyprinus carpio var communis (Linn.) and Catla catla (Ham.) in simulated toxic aquatic environment

With the increase of water hardness from 60 to 720?mg/L CaCO₃, total alkalinity from 32 to 376?mg/L CaCO_3, pH from 7.6 to 7.9 and chloride from 28 to 350?mg/L, 96?h LC₅₀ on the basis of total lead increased from 8.2 to 1291?mg/L for Cyprinus carpio and 5.3 to 865?mg/L for Catla catla, when soil sediments were included these values were further raised to 1356 and 874?mg/L, respectively. The dissolved lead LC₅₀ values in all the treatments of soil and water was consistent with fixed amount of dissolved lead (1.04–1.78?mg/L) being needed for median lethal toxicity. Total lead toxicity also decreased with increase in pH from 6.3 to 11.3. 96?h LC₅₀ values increased for common carp 15 to 631?mg/L and for catla, 8 to 355?mg/L. But dissolved lead toxicity was found to increase with the increase of pH from 6.3 to 11.3 for both common carp (LC₅₀, 3.53 to 0.24?mg/L) and catla (LC₅₀, 2.21 to 0.09?mg/L). Removal of dissolved Pb with increasing carbonate content, particulate matter and pH due to adsorption, precipitation or coprecipitation reaction, reduced the dissolved lead concentration and thus the total lead toxicity. Increase in toxicity of lead with increase of exposure time was the biological response of longer contact time and decrease in dissolved lead toxicity with decrease in pH was due to increase H⁺ ion competition.