Adsorptive features of acid-treated olive stones for drin pesticides: Equilibrium,kinetic and thermodynamic modeling studies

The adsorption behavior of drin pesticides from aqueous solution onto acid treated olive stones (ATOS) was investigated using stir bar sorptive extraction and gas chromatography coupled with mass spectroscopy. The effects of sorbent particle size, adsorbent dose, contact time, concentration of pesticide solution and temperature on the adsorption processes were systematically studied in batch shaking sorption experiments. Maximum removal efficiency (94.8%) was reached for aldrin (0.5 mg L⁻¹) using the fraction 63–100 μm of ATOS (solid/liquid ratio: 1 g L⁻¹). Experimental data were modeled by Langmuir, Freundlich and Dubinin–Radushkevich (D–R) isotherms. The Freundlich isotherm model (R² = 0.98–0.99) fitted the equilibrium data better than the Langmuir and D–R isotherm models, with low sum of error values (SE = 1.4–9.2%). The mean adsorption free energy derived from the D–R isotherm model (R² = 0.95–0.99) showed that the adsorption of drin pesticides was taken place by weak physical forces, such as van der Waals forces and hydrogen bonding. The calculated thermodynamic parameters, ΔH, ΔS and ΔG prove that drin pesticides adsorption on ATOS was feasible, spontaneous and exothermic under examined conditions. The pseudo first order, pseudo second order kinetic and the intra-particle diffusion models were used to describe the kinetic data and rate constants were evaluated.     

Removal of prioritary pesticides contamining r'mel ground water by using organic waste residues

This study evaluated pesticide contamination of R'mel ground water located in northwest Morocco. The study area is densely populated and thriving, with intensive agriculture. Various techniques, including stir bar sorptive extraction (SBSE) and gas chromatography with mass spectroscopy detection (GC-MS), were used for the quantitative determination of 13 pesticides including alachlor, aldrin, atrazine, chlorpyrifos, chlorfenvinphos, dieldrin, alpha-endosulfan, endrin, hexachlorobenzene, beta-HCH, gamma-HCH (lindane), simazine and trifluralin. The survey results showed that contamination by pesticide residues is widespread in the area. With the exception of atrazine, the average concentrations were all below the regulatory limits established by the European Union. The potential of ten natural organic substances to eliminate pesticides included in the European Water Framework Directive was evaluated. The absorbents with the highest removal efficiency were date and olives stones and, to a Lesser degree, Raphanus raphanistrum and Cistus ladaniferus. The adsorption tests gave very satisfying results and pointed to the possible application of these supports as ecoLogical remediation techniques to prevent pesticide pollution of aquatic ecosystems.     

Removal of persistent organic pollutants from micro-polluted drinking water by triolein embedded absorbent

A new biomimetic absorbent, cellulose acetate (CA) embedded with triolein (CA-triolein), was prepared and applied for the removal of persistent organic pollutants (POPs) from micro-polluted aqueous solution. The comparison of CA-triolein, CA and granular activated carbon (GAC) for dieldrin removal was investigated. Results showed that CA-triolein absorbent gave a lowest residual concentration after 24 h although GAC had high removal rate in the first 4 h adsorption. Then the removal efficiency of mixed POPs (e.g. aldrin, dieldrin, endrin and heptachlor epoxide), absorption isotherm, absorbent regeneration and initial column experiments of CA-triolein were studied in detail. The linear absorption isotherm and the independent absorption in binary isotherm indicated that the selected POPs are mainly absorbed onto CA-triolein absorbent by a partition mechanism. The absorption constant, K, was closely related to the hydrophobic property of the compound. Thermodynamic calculations showed that the absorption was spontaneous, with a high affinity and the absorption was an endothermic reaction. Rinsing with hexane the CA-triolein absorbent can be regenerated after absorption of POPs. No significant decrease in the dieldrin removal efficiency was observed even when the absorption–regeneration process was repeated for five times. The results of initial column experiments showed that the CA-triolein absorbent did not reach the breakthrough point at a breakthrough empty-bed volume (BV) of 3200 when the influent concentration was 1–1.5 μg/L and the empty-bed contact time (EBCT) was 20 min.     

Adsorptive removal of Pb(II) by activated carbon prepared from Spartina alterniflora: Equilibrium,kinetics and thermodynamics

Low-cost activated carbon was prepared from Spartina alterniflora by phosphoric acid activation for the removal of Pb(II) from dilute aqueous solution. The effect of experimental parameters such as pH, initial concentration, contact time and temperature on the adsorption was studied. The obtained data were fitted with the Langmuir and Freundlich equations to describe the equilibrium isotherms. The kinetic data were fitted with the Lagergren-first-order, pseudo-second-order and Elovich models. It was found that pH played a major role in the adsorption process. The maximum adsorption capacity for Pb(II) on S. alterniflora activated carbon (SAAC) calculated from Langmuir isotherm was more than 99 mg g⁻¹. The optimum pH range for the removal of Pb(II) was 4.8–5.6. The Freundlich isotherm model was found to best describe the experimental data. The kinetic rates were best fitted to the pseudo-second-order model. Thermodynamic study showed the adsorption was a spontaneous exothermic process.     

Performance of durian shell waste as high capacity biosorbent for Cr(VI) removal from synthetic wastewater

The capability of durian shell waste biomass as a novel and potential biosorbent for Cr(VI) removal from synthetic wastewater was studied. The adsorption study was performed in batch mode at different temperatures and pH. Langmuir and Freundlich isotherm models fit the equilibrium data very well (R² > 0.99). The maximum biosorption capacity of durian shell was 117 mg/g. On modeling its kinetic experimental data, the pseudo-first order prevails over the pseudo-second order model. Thermodynamically, the characteristic of Cr-biosorption process onto durian shell surface was spontaneous, irreversible and endothermic.     

Degradation of Endrin, Aldrin, and DDT by Soil Microorganisms

Twenty microbial cultures which had been shown to degrade dieldrin were tested to determine their ability to degrade endrin, aldrin, DDT, gamma isomers of benzenehexachloride (gamma-BHC), and Baygon. All isolates were able to degrade DDT and endrin, whereas 13 degraded aldrin. However, none of them was able to degrade Baygon or gamma-BHC.     

Adsorption of Victoria blue by carbon/Ba/alginate beads: Kinetics,thermodynamics and isotherm studies

The kinetic, thermodynamic and isotherm modeling studies were carried out on adsorptive removal of Victoria blue (VB) dye using activated carbon, Ba/alginate and modified carbon/Ba/alginate polymer beads. The feasibility of sorption process was determined by varying the experimental parameters viz., dye concentration (4–20 mg L⁻¹), contact time (10–90 min), pH (3–10), adsorbent dose (0.5–2.5 g) and temperature (303–343 K). Freundlich and Langmuir isotherms were determined and ascertained with the dimensionless separation factor (R_L). Lagergren's pseudo-first order, pseudo-second order and intraparticle diffusion model equations were used to analyze the kinetics of the adsorption process. The thermodynamic consistency of adsorption was found with Gibbs free energy (ΔG°), changes in enthalpy (ΔH°) and entropy (ΔS°) were calculated using the Van’t Hoff plot. The polymer beads were characterized using Fourier Transform Infrared Spectroscopy (FTIR) and their morphology was determined by scanning electron microscopy (SEM).     

The Systematic Separation and Identification of Pesticides in the First Division

The systematic identification and determination of many kinds of pesticides were tried by a combination of column, thin-layer and gas chromatography. Pesticides in the first division,¹⁾ e.g., aldrin, DMC ethylene, CPAS, DDDS, o,p′-DDT, p,p′-DDT, heptachlor, quintozene, Telodrin and tetrasul, were separated from pesticides in the second division,¹⁾ e.g., α-BHC, β-BHC, γ-BHC, trifluralin, CPA, CNP, nitrofen, endrin, dieldrin, dicofol, etc. by column chromatography. Further, pesticides in the first division were separated from each other and determined approximately by thin-layer and gas chromatography.

The recoveries of these pesticides, except for aldrin and CPAS, were about 100%. The recoveries of aldrin and CPAS were about 70 %, due to decomposition during the procedures, or to adsorption on the adsorbent during the column chromatography. It was presumed from GC-MS data that CPAS was decomposed to DDDS, tetrasul and other compounds during the procedures.     

Kinetic and Thermodynamic Studies of Phenolic Compounds’ Adsorption on River Sediment

Phenolic compounds have increasingly attracted global concerns in recent years due to their strong bioaccumulation and potential toxicity. In this study, the adsorption of 2, 4-Dichlorophenol (2, 4-DCP), 2, 4-Dinitrophenol (2, 4-DNP) and 2, 4-Dimethyphenol (2, 4-DMP) on sediment at different temperatures was studied. Adsorption isotherms fitted well to the Freundlich model and the adsorption capacity was increased when the temperature increased from 5°C to 25°C. It was found that the adsorption process could be modeled well using pseudo-second-order kinetic equation. The thermodynamic parameter ΔG° for 2, 4-DCP, 2, 4-DNP and 2, 4-DMP varied between ?8.82 and ?13.68, ?4.9 and ?8.05, and ?7.52 and ?10.55 kJ/mol, respectively, with ΔH° (kJ/mol) and ΔS°(J/(mol·K)) measuring 55.397 and 0.2263, 40.121 and 0.1585, and 38.012 and 0.16, respectively. The calculated thermodynamic parameters suggested that adsorption of the three selected phenolic compounds was a spontaneous (ΔG°< 0), endothermic (ΔH°> 0), and entropy-driven reaction (ΔS° > 0). The thermodynamic data also suggested that the three selected phenolic compounds to sediment were closed to chemisorption because ΔH° was around 40.     

Cyclodiene organochlorine insecticide-induced alterations in the sulfur-redox cycle in CHO-K1 cells

The effect of the cyclodiene organochlorine pesticides aldrin, dieldrin and endosulfan was assessed on CHO-K1 cultures at fractions of their lethal doses, determined by the neutral red (NRI) incorporation assay (NRI_6.25, NRI_12.5 and NRI₂₅). Glutathione peroxidase, reductase and S-transferase, and total and oxidised glutathione were evaluated along the standard growth curve of the cultures. After a 24-h incubation with each insecticide, glutathione peroxidase incurred a large increase, while glutathione reductase and S-transferase activities were slightly higher than untreated controls. Unlike oxidised glutathione, the content of total glutathione declined significantly after exposure to cyclodiene insecticides. Changes in cell membrane integrity were assessed by the lactate dehydrogenase (LDH) release assay and lipid peroxidation for a wide range of pesticide concentrations. Membrane leakage and peroxide production were significantly enhanced at concentrations of aldrin and as low as 12.5 μg/ml, whereas dieldrin and endosulfan increased membrane fragility at much higher concentrations.     

Using lignimerin (a recovered organic material from Kraft cellulose mill wastewater) as sorbent for Cu and Zn retention from aqueous solutions

Adsorption of copper and zinc in lignimerin (an organic material mainly composed by lignin, carbohydrate fragments and some extractives) and its acid derivative (H-lignimerin), recovered from Kraft cellulose mill wastewater was examined. A Box–Behnken experiment design, used to optimize lignimerin recovery process, revealed that the type of solvent used for precipitation is a determining factor in the amount of substance obtained. Conversely, batch adsorption studies at pH 4.0 revealed that the maximum adsorption capacities, modeled by the Langmuir equation, were 666.7 and 370.4 mmol kg⁻¹ for Cu(II) and Zn(II), respectively in lignimerin and 232.6 and 312.5 mmol kg⁻¹ for Cu(II) and Zn(II), respectively in H-lignimerin. The adsorption of Cu(II) and Zn(II) through deprotonated hydroxyl and carboxylic groups was the dominant mechanism that may explain the adsorption in both materials. The adsorption capacities indicated that lignimerin, with a molecular mass between 50 and 70 kDa, has a potential use as an organic sorbent for removing copper and zinc from liquid resources.     

Application of Arthrospira (Spirulina) platensis biomass for silver removal from aqueous solutions

The cyanobacterium Arthrospira (Spirulina) platensis was used to study the process of silver biosorption. Effects of various parameters such as contact time, dosage of biosorbent, initial pH, temperature, and initial concentration of Ag(I) were investigated for a batch adsorption system. The optimal biosorption conditions were determined as pH 5.0, biosorbent dosage of 0.4 g, and initial silver concentration of 30 mg/L. Equilibrium adsorption data were analyzed by the Langmuir and Freundlich models – however, the Freundlich model provided a better fit to the experimental data. The kinetic data fit the pseudo-second-order model well, with a correlation coefficient of 0.99. The analysis of thermodynamic parameters (ΔG°, ΔH° and ΔS°) revealed that the adsorption process of silver ion by spirulina biomass was exothermic and spontaneous (ΔG° < 0), and exothermic (ΔH° < 0) process. The biosorption capacity of biomass A. platensis serves as a basis for the development of green technology for environmental remediation.     

Isolation of dieldrin- and endrin-degrading bacteria using 1,2-epoxycyclohexane as a structural analog of both compounds

This report describes the selective isolation of dieldrin- and endrin-degrading bacteria from soil with high degradation activity toward dieldrin and endrin. Several enrichment cultures from the soil were arranged with several structural analogs of dieldrin and endrin as a growth substrate and examined for their degradation activities toward dieldrin and endrin. An enrichment culture with 1,2-epoxycyclohexane (ECH) was found to aerobically degrade dieldrin and endrin. Denaturing gradient gel electrophoresis (DGGE) indicated that three types of bacteria were predominant in the ECH enrichment culture. Of the three major bacteria, two isolates, Burkholderia sp. strain MED-7 and Cupriavidus sp. strain MED-5, showed high degradation activity toward dieldrin and endrin. The degradation efficiencies of strain MED-7 and MED-5 were 49% and 38% toward dieldrin, respectively, and 51% and 40% toward endrin, respectively, in the presence of ECH for 14 days. These results indicated that ECH was a useful substrate for selective and efficient isolation of dieldrin- and endrin-degrading bacteria from soil containing numerous bacteria. Interestingly, the two isolates could also degrade dieldrin and endrin even in the absence of ECH. These are the first microorganisms demonstrated to grow on dieldrin and endrin as the sole carbon and energy source under aerobic conditions.     

Unfolding thermodynamics of the Delta-domain in the prohead I subunit of phage HK97: determination by factor analysis of Raman spectra

An early step in the morphogenesis of the double-stranded DNA (dsDNA) bacteriophage HK97 is the assembly of a precursor shell (prohead I) from 420 copies of a 384-residue subunit (gp5). Although formation of prohead I requires direct participation of gp5 residues 2-103 (Δ-domain), this domain is eliminated by viral protease prior to subsequent shell maturation and DNA packaging. The prohead I Δ-domain is thought to resemble a phage scaffolding protein, by virtue of its highly α-helical secondary structure and a tertiary fold that projects inward from the interior surface of the shell. Here, we employ factor analysis of temperature-dependent Raman spectra to characterize the thermostability of the Δ-domain secondary structure and to quantify the thermodynamic parameters of Δ-domain unfolding. The results are compared for the Δ-domain within the prohead I architecture (in situ) and for a recombinantly expressed 111-residue peptide (in vitro). We find that the α-helicity (∼ 70%), median melting temperature (T_m = 58 °C), enthalpy (ΔH_m = 50 ± 5 kcal mol^− 1), entropy (ΔS_m = 150 ± 10 cal mol^− 1 K^− 1), and average cooperative melting unit (〈n_c〉 ∼ 3.5) of the in situ Δ-domain are altered in vitro, indicating specific interdomain interactions within prohead I. Thus, the in vitro Δ-domain, despite an enhanced helical secondary structure (∼ 90% α-helix), exhibits diminished thermostability (T_m = 40 °C; ΔH_m = 27 ± 2 kcal mol^− 1; ΔS_m = 86 ± 6 cal mol^− 1 K^− 1) and noncooperative unfolding (〈n_c〉 ∼ 1) vis-à-vis the in situ Δ-domain. Temperature-dependent Raman markers of subunit side chains, particularly those of Phe and Trp residues, also confirm different local interactions for the in situ and in vitro Δ-domains. The present results clarify the key role of the gp5 Δ-domain in prohead I architecture by providing direct evidence of domain structure stabilization and interdomain interactions within the assembled shell.     

Kinetic study of dissociation of Eu(III) complex with H8dotp (H8dotp = 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetrakis(methylphosphonic acid))

The dissociation kinetics of the europium(III) complex with H₈dotp ligand was studied by means of molecular absorption spectroscopy in UV region at ionic strength 3.0 mol dm⁻³ (Na,H)ClO₄ and in temperature region 25-60 °C. Time-resolved laser-induced fluorescence spectroscopy (TRLIFS) was employed in order to determine the number of water molecules in the first coordination sphere of the europium(III) reaction intermediates and the final products. This technique was also utilized to deduce the composition of reaction intermediates in course of dissociation reaction simultaneously with calculation of rate constants and it demonstrates the elucidation of intimate reaction mechanism. The thermodynamic parameters for the formation of kinetic intermediate (ΔH⁰ = 11 ± 3 kJ mol⁻¹, ΔS⁰ = 41 ± 11 J K⁻¹ mol⁻¹) and the activation parameters (E_a = 69 ± 8 kJ mol⁻¹, ΔH^≠ = 67 ± 8 kJ mol⁻¹, ΔS^≠ = −83 ± 24 J K⁻¹ mol⁻¹) for the rate-determining step describing the complex dissociation were determined. The mechanism of proton-assisted reaction was proposed on the basis of the experimental data.     

A kinetic investigation of the oxidative addition reactions of the dimeric Bu4N[Ir2(μ-Dcbp)(cod)2] complex with iodomethane

The kinetic results of the oxidative addition of iodomethane to Bu₄N[Ir₂(μ-Dcbp)(cod)₂] (Dcbp = 3,5-dicarboxylatepyrazolate anion) show that oxidative addition can occur via a direct equilibrium pathway (K₁ = 88(22) acetone, 51(3) 1,2-dichloroethane, 55(4) dichloromethane, 52(12) acetonitrile and 43(5) M⁻¹ chloroform) or a solvent-assisted pathway (k₂, k₃). Oxidative addition occurs mainly along the direct pathway, which is a factor 10-40 faster than the solvent-assisted pathway. The observed solvent effect cannot be attributed to the donosity or polarity of the solvents. The fairly negative ΔS^≠ value (−110(7) J K⁻¹ mol⁻¹) and the positive ΔH^≠ value (+47(2) kJ mol⁻¹) for the oxidative addition step are indicative of an associative process.     

Isolation of four aquatic streptomycetes strains capable of growth on organochlorine pesticides

Ninety-three wild-type isolates identified as actinomycetes were tested against 11 organochlorine pesticides (OPs): aldrin, chlordane, DDD, DDE, DDT, dieldrin, heptachlor, and heptachlor epoxides, lindane, and methoxychlor. Qualitative screening agar assays displayed 62-78% tolerance of strains to OPs. Four strains designed M4, M7, M9 and M15 were selected based on multi-OP-tolerance, and identified as members of the streptomycetes group. Different growth profiles were observed in cultures of the four selected streptomycetes cultured in synthetic medium containing 5-50 microg x l(-1) aldrin or chlordane or lindane. Increase of aldrin removal by the selected microorganisms was concomitant with the 4.8-36.0 microg x l(-1) pesticide concentration range. After 72 h of streptomycete M7 growth in synthetic medium containing 48.0 microg x l(-1) aldrin, the remaining OP concentration in the supernatant was approximately 10% of the initial concentration. Also, in stationary growth phase less than 2.5 microg x l(-1) aldrin residual concentration was detected in the medium.     

Effect of soil application of chlorinated insecticides on amino acid composition of maize (Zea mays)

Summary Chlorinated insecticidesviz p,p-DDT, aldrin, endrin and lindane stimulated the synthesis of arginine+histidine, leucine, lysine, proline, and tyrosine in maize but decreased the content of tryptophan. However, synthesis of methionine was stimulated by the application of aldrin, endrin, and lindane only. On the otherhand, synthesis of valine was inhibited by aldrin, endrin and DDT only.     

Biosorption of acid violet dye from aqueous solutions using native biomass of a new isolate of Penicillium sp.

Laboratory investigation of the potential use of Penicillium sp. as biosorbent for the removal of acid violet dye from aqueous solution was studied with respect to pH, temperature, biosorbent, initial dye concentrations. Penicillium sp. decolourizes acid violet (30 mg l⁻¹) within 12 h agitation of 150 rpm at pH 5.7 and temperature of 35 °C. The pellets exhibited a high dye adsorption capacity (5.88 mg g⁻¹) for acid violet dye over a pH range (4–9); the maximum adsorption was obtained at pH 5.7. The increase of temperature favored biosorption for acid violet, but the optimum temperature was 35 °C. Adsorption kinetic data were tested using pseudo-first-order, pseudo-second-order and kinetic studies showed that the biosorption process follows pseudo-first-order rate kinetics with an average rate constant of 0.312 min⁻¹. Isotherm experiments were conducted to determine the sorbent–desorption behavior of examined dye from aqueous solutions using Langmuir and Freundlich equations. Langmuir parameter indicated a maximum adsorption capacity of 4.32 mg g⁻¹ for acid violet and R_L value of 0.377. Linear plot of log q_e vs log C_e shows that applicability of Freundlich adsorption isotherm model. These results suggest that this fungus can be used in biotreatment process as biosorbent for acid dyes.     

Mechanistic studies on monodentate-ligand substitution of five-coordinate trigonal-bipyramidal platinum (II) complexes with tris[2-(diphenylphosphino)ethyl]phosphine

Reaction of the five-coordinate trigonal-bipyramidal platinum(II) complex, [Pt(pt)(pp₃)](BF₄) (pt = 1-propanethiolate, pp₃ = tris[2-(diphenylphosphino)ethyl]phosphine), with I⁻ in chloroform gave the five-coordinate square-pyramidal complex with a dissociated terminal phosphino group and an apically coordinated iodide ion in equilibrium. The thermodynamic parameters for the equilibrium between the trigonal-bipyramidal and square-pyramidal geometries, [Pt(pt)(pp₃)]⁺ + I⁻ ? [PtI(pt) (pp₃)], and the kinetic parameters for the chemical exchange were obtained as follows: , ΔH⁰ = − 10 ± 2.4 kJ mol⁻¹, ΔS⁰ = − 36 ± 10 J K⁻¹ mol⁻¹, , ΔH^‡ = 34 ± 4.7 kJ mol⁻¹, ΔS^‡ = − 50 ± 21 J K⁻¹ mol⁻¹. The square-planar trinuclear platinum(II) complex was formed by bridging reaction of one of the terminal phosphino groups of trigonal-bipyramidal [PtCl(pp₃)]Cl with trans-[PtCl₂(NCC₆H₅)₂] in chloroform. From these facts, ligand substitution reactions of [PtX(pp₃)]⁺ (X = monodentate anion) are expected to proceed via an intermediate with a dissociated phosphino group. The rate constants for the chloro-ligand substitution reactions of [PtCl(pp₃)]⁺ with Br⁻ and I⁻ in chloroform approached the respective limiting values as concentrations of the entering halide ions are increased. These kinetic results confirmed the preassociation mechanism in which the square pyramidal intermediate with a dissociated phosphino group and an apically coordinated halide ion is present in the rapid pre-equilibrium.