Methidathion Complexes with Homoionic and Surfactant-Modified Montmorillonites

Abstract

The formation of the insecticide methidathion (S-[(5-methoxy-2-oxo-1,3,4-thiadiazol-3(2H)-yl)methyl] O,O-dimethyl phosphorodithioate) complexes with inorganic cation-saturated (Mg²⁺, Ca²⁺, Cu²⁺, and Ni²⁺) montmorillonites was investigated. The nature and structure of the complexes was determined by X-ray diffraction and infrared spectroscopy. The arrangement of the pesticide molecule in the interlayer space was also considered from ab initio calculations using simpler related molecules. The insecticide methidathion penetrated the interlayer spaces of the homoionic clay samples. The ligand–cation interactions in these complexes depend on the nature and characteristics of the saturating cations. Mechanisms involving water bridges and direct coordination with the exchange cation were proposed for the adsorption of methidathion by inorganic cation-saturated montmorillonites. The effect of the inorganic cations on the sorption of the cationic surfactant tetradecyltrimethylammonium bromide (TDTMA) by montmorillonite was also studied and the subsequent sorption of methidathion in TDTMA⁺-Montmorillonite determined. Van der Waals bonds constitute the methidathion adsorption mechanism by montmorillonite saturated with TDTMA⁺. The arrangements of methidathion and of the cationic surfactant molecules in the montmorillonite interlayer space were demostrated.     

Sorption of chlorimuron-ethyl on montmorillonite clays: effects of exchangeable cations,pH, and ionic strength

Sorption interaction of chlorimuron-ethyl with montmorillonite clays was investigated under varied types of exchangeable cation, pH, and ionic strength conditions. Chlorimuron-ethyl sorption on bentonites exhibited pronounced cation dependency, and the sorption ability increased as the sequence Ca²⁺- < Na⁺- < Al³⁺- < Fe³⁺-bentonite, due to different sorption mechanisms, whereas the cation dependency was influenced by the clay type and much weaker for montmorillonites. The decrease of pH at the range of 4.0–6.0 prominently increased sorption of chlorimuron-ethyl on all cation-exchanged montmorillonite clays, and nearly a neglected sorption (about 2 %) can be observed at pH over 7.0. In the presence of CaCl₂, sorption of chlorimuron-ethyl on Fe³⁺-bentonite was promoted because of complexion of Ca²⁺ and the surface of Fe³⁺-bentonite. However, as the concentration of CaCl₂ increased, chlorimuron-ethyl sorption on Ca²⁺- and Fe³⁺-exchanged bentonite decreased, suggesting that Ca bridging was not the prevailing mechanism for sorption of chlorimuron-ethyl on these clays. Furthermore, chlorimuron-ethyl sorption was relatively sensitive to pH, and the change of pH may obscure effect of other factors on the sorption, so it was quite necessary to control pH at a constant value when the effect of other factor was being studied.     

Characterization of carbonic anhydrase II from Chlorella vulgaris in bio-CO2 capture

Carbonic anhydrase II (CA II) can catalyze the reversible hydration reaction of CO₂ at a maximum of 1.4?×?10⁶ molecules of CO₂ per second. The crude intracellular enzyme extract containing CA II was derived from Chlorella vulgaris. A successful CO₂ capture experiment with the presence of calcium had been conducted on the premise that the temperature was conditioned at a scope of 30?C40?°C, that the biocatalyst-nurtured algal growth period lasted 3?days, and that pH ranged from7.5 to 8.5. Ions of K⁺, Na⁺, Ca²⁺, Co²⁺, Cu²⁺, Fe³⁺, Mg²⁺, Mn²⁺, and Zn²⁺ at 0.01, 0.1, and 0.5?M were found to exhibit no more than 30?% inhibition on the residual activity of the biocatalyst. It is reasonable to expect that calcification catalyzed by microalgae presents an alternative to geological carbon capture and sequestration through a chain of fundamental researches carried on under the guidance of sequestration technology.     

Heterogeneous reactions of suspended parathion, malathion, and fenthion particles with NO(3) radicals

Organophosphorus pesticides (OPPs) emit into the atmosphere in both gas and particulate phases via spray drift from treatments and post-application emission, but most of their degradations in the atmosphere are not well known. In this study, the heterogeneous reactions of nitrate (NO₃) radicals with three typical OPPs (parathion, malathion, and fenthion) absorbed on azelaic acid particles are investigated using an online vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer (VUV-ATOFMS). The reaction products observed with the VUV-ATOFMS are identified on the basis of GC/MS analysis of the products in the reaction between NO₃ radicals and the coating of the pesticide. Paraoxon is identified as the only product of parathion; malaoxon and bis(1,2-bis-ethoxycarbonylethyl)disulfide as the products of malathion; fenoxon, fenoxon sulfoxide, fenthion sulfoxide, fenoxon sulfone, and fenthion sulfone as the products of fenthion. The degradation rates of parathion, malathion, and fenthion under the experimental conditions are 5.5 × 10⁻³, 5.6 × 10⁻², and 3.3 × 10⁻² s⁻¹, respectively. The pathways of the heterogeneous reactions between the three OPPs and NO₃ radicals are proposed. The experimental results reveal the possible transformations of these OPPs through the oxidation of NO₃ radicals in the atmosphere.     

Do aerosols act as catalysts in the OH radical initiated atmospheric oxidation of volatile organic compounds?

Smog chamber/FTIR techniques were used to study the relative reactivity of OH radicals with methanol, ethanol, phenol, C₂H₄, C₂H₂, and p-xylene in 750 Torr of air diluent at 296±2 K. Experiments were performed with, and without, 500–8000 μg m⁻³ (4000–50 000 μm² cm⁻³ surface area per volume) of NaCl, (NH₄)₂SO₄ or NH₄NO₃ aerosol. In contrast to the recent findings of Oh and Andino (Atmospheric Environment 34 (2000) 2901, 36 (2002) 149; International Journal of Chemical Kinetics 33 (2001) 422) there was no discernable effect of aerosol on the rate of loss of the organic compounds via reaction with OH radicals. Gas kinetic theory arguments cast doubt upon the findings of Oh and Andino. The available data suggest that the answer to the title question is “No”. As part of this work the rate constants for reactions of OH radicals with methanol, ethanol, and phenol in 750 Torr of air at 296 K were determined to be: k_OH+CH3OH=(8.12±0.54)×10⁻¹³, k_OH+C2H5OH=(3.47±0.32)×10⁻¹² and k_OH+phenol=(3.27±0.31)×10⁻¹¹ cm³ molecule⁻¹ s⁻¹.     

Synthesis and thermoluminescence properties of rare earth-doped NaMgBO<Subscript>3</Subscript> phosphor

Rare earth (Dy³⁺ and Sm³⁺)-doped sodium magnesium borate (NaMgBO₃) is synthesized by solution combustion synthesis method keeping their thermoluminescence properties in mind. The reaction produced very stable crystalline NaMgBO₃:RE (RE?=?Dy³⁺, Sm³⁺) phosphors. The phosphors are exposed to ⁶⁰Co gamma-ray radiations dose of varying rate from 5 to 25 Gy, and their TL characteristics with kinetic parameters are studied. NaMgBO₃:Dy³⁺ phosphor shows two peaks for lower doping concentration of Dy³⁺ while it reduced to single peak for the higher concentrations of activator Dy³⁺. NaMgBO₃:Dy³⁺ shows the major glow peak around 200 °C while NaMgBO₃:Sm³⁺ phosphors show two well-separated glow peaks at 200 and 332 °C respectively. The thermoluminescence intensity of these phosphors was compare with the commercially available TLD-100 (Harshaw) phosphor. The TL responses for gamma-ray radiations dose were found to be linear from 5 to 25 Gy for both phosphors while the fading in each case is calculated for the tenure of 45 days.     

铈离子光催化降解茜素绿的性能和机理简

主要研究了简单铈离子（Ce³⁺）在紫外光（UV）的作用下对蒽醌染料茜素绿（AG）的光催化降解效果和反应机理。结果表明，UV/Ce³⁺体系能够有效降解AG，初始反应速率随AG浓度的倒数值和Ce³⁺浓度的增加而线性增加，随初始溶液pH的增加先降低后增加，在酸性条件下有很高的TOC去除率。荧光探针实验表明，反应过程中可以产生·OH自由基。UV/Ce³⁺体系对其他类型染料和对硝基苯酚都有较好的降解效果。     

Decomposition of phenylarsonic acid by AOP processes: degradation rate constants and by-products

The paper presents results of the studies photodegradation, photooxidation, and oxidation of phenylarsonic acid (PAA) in aquatic solution. The water solutions, which consist of 2.7 g dm^?3 phenylarsonic acid, were subjected to advance oxidation process (AOP) in UV, UV/H₂O₂, UV/O₃, H₂O₂, and O₃ systems under two pH conditions. Kinetic rate constants and half-life of phenylarsonic acid decomposition reaction are presented. The results from the study indicate that at pH 2 and 7, PAA degradation processes takes place in accordance with the pseudo first order kinetic reaction. The highest rate constants (10.45?×?10^?3 and 20.12?×?10^?3) and degradation efficiencies at pH 2 and 7 were obtained at UV/O₃ processes. In solution, after processes, benzene, phenol, acetophenone, o-hydroxybiphenyl, p-hydroxybiphenyl, benzoic acid, benzaldehyde, and biphenyl were identified.     

金属铁去除水中Cr6+的影响因素研究

研究Fe/Cr6+比值和不同浓度的NO3-、Cl-和SO42-对金属铁去除Cr6+效果的影响.结果表明,金属铁对水中Cr6+有很好的还原去除效果;当金属铁的使用量为Cr6+量的1/2000时,铁对Cr6+的去除效果较差且易失去活性,而当金属铁的使用量为Cr6+量的8 000倍时,铁对Cr6+的去除效果较好且其活性的持续...     

Electro-Fenton degradation of the antibiotic sulfanilamide with Pt/carbon-felt and BDD/carbon-felt cells. Kinetics,reaction intermediates,and toxicity assessment

The degradation of 230 mL of a 0.6-mM sulfanilamide solution in 0.05 M Na₂SO₄ of pH 3.0 has been studied by electro-Fenton process. The electrolytic cell contained either a Pt or boron-doped diamond (BDD) anode and a carbon-felt cathode. Under these conditions, organics are oxidized by hydroxyl radicals formed at the anode surface from water oxidation and in the bulk from Fenton’s reaction between initially added (and then electrochemically regenerated) Fe²⁺ and cathodically generated H₂O₂. From the decay of sulfanilamide concentration determined by reversed-phase liquid chromatography, an optimum Fe²⁺ concentration of 0.20 mM in both cells was found. The drug disappeared more rapidly using BDD than Pt, and, in both cases, it was more quickly removed with raising applied current. Almost total mineralization was achieved using the BDD/carbon-felt cell, whereas the alternative use of Pt anode led to a slightly lower mineralization degree. In both cells, the degradation rate was accelerated at higher current but with the concomitant fall of mineralization current efficiency due to the greater increase in rate of the parasitic reactions of hydroxyl radicals. Reversed-phase liquid chromatography allowed the identification of catechol, resorcinol, hydroquinone, p-benzoquinone, and 1,2,4-trihydroxybenzene as aromatic intermediates, whereas ion exclusion chromatography revealed the formation of malic, maleic, fumaric, acetic, oxalic, formic, and oxamic acids. NH₄ ⁺, NO₃ ^?, and SO₄ ^2? ions were released during the electro-Fenton process. A plausible reaction sequence for sulfanilamide mineralization involving all detected intermediates has been proposed. The toxicity of the solution was assessed from the Vibrio fischeri bacteria luminescence inhibition. Although it acquired its maximum value at short electrolysis time, the solution was completely detoxified at the end of the electro-Fenton treatment, regardless of the anode used.     

Phenol depletion by thermally activated peroxydisulfate at 70°C

The ability of thermal activated peroxydisulfate (PS) of mineralizing phenol at 70 °C from contaminated waters is investigated. Phenol in concentrations of 10⁻⁴ to 5 × 10⁻⁴ M is quantitatively depleted by 5 × 10⁻³ to 10⁻² M activated PS in 15 min of reaction. However, mineralization of the organic carbon is not observed. Instead, an insoluble phenol polymer-type product is formed. A reaction mechanism including the formation of phenoxyl radicals and validated by computer simulations is proposed. High molecular weight phenolic products are formed by phenoxyl radical H-abstraction reactions. This is not the case for the room temperature degradation of phenol by sulfate radicals where sulfate addition to the aromatic ring mainly leads to the generation of hydroxycyclohexadienyl radicals leading to hydroxybenzenes and oxidized open chain products. Therefore, a change in the reaction mechanism is observed with increasing temperature, and thermal activation of PS at 70 °C does not lead to the mineralization of phenol. Thus PS activation at 70 °C may be considered a potential method to reduce the load of phenol in polluted waters by polymerization.     

The Clean Air Act Amendments and Motor Vehicle Inspection/Maintenance

Seventeen days of detailed measurements of NO, NO₂, O₃, HNO₃ and the frequency of NO₂ photolysis—j(NO₂)—were carried out in Claremont, CA, in September 1980. Under conditions when the rate of change of NO concentration is small, there must be a balance between formation and loss processes. In the classical photostationary state this balance is between NO₂ photolysis: NO₂ + hv → NO + O and reaction with ozone: NO + O₃ → NO₂ + O₂. The results show that the latter reaction with ozone is inadequate to balance the formation step; a significant contribution is required from another NO oxidation process, possibly peroxy radical oxidation. If so, the inferred concentration of peroxy radicals shows a diurnal variation, peaking around solar noon.     

Activation of cadmium under simulated solar illumination and its impact on the mobility of Cd in flooded soils

In waterlogged paddy soils, cadmium (Cd) can be precipitated as cadmium sulfide (CdS) under reductive environment, thereby limiting the absorption of Cd by plants. Multiple environmental factors (such as water, pH, and Eh) played a role in the control of Cd mobility and bioavailability. In this study, we investigated the influence of the solar irradiation on the photodissolution of synthetic CdS-montmorillonite composites (CdS-M) in solution and the stability of Cd in natural soil. The release kinetic of Cd²⁺ showed that after the irradiation of simulated sunlight, CdS-M composites became less stable compared to the dark control. The solar irradiation seemed to enhance the release of Cd²⁺ from CdS significantly and continuously. Electron paramagnetic resonance (EPR) and quenching experiments confirmed that the photogenerated holes, ?O₂^? and ?OH, were possibly involved in the photo-induced release of Cd²⁺, while the holes was primarily responsible for the reaction. Irradiation under alkaline solution or the presence of DOM, PO₄^3?, CO₃^2?, and urea markedly inhibited the photodissolution process of CdS. The photo-mediated activation of Cd was further confirmed in paddy soil under natural sunlight, with a nearly threefold increase in concentration of extractable Cd during the 15 days of irradiation. This study highlights the importance of photochemical transformation of Cd in the environmental water and soil.

     

Inorganic nanoparticles enhance the production of reactive oxygen species (ROS) during the autoxidation of L-3,4-dihydroxyphenylalanine (L-dopa)

Public concerns over the toxicity of nanoparticles (NPs) are growing due to the rapid development of nanotechnology. An important mechanism of nanotoxicity is oxidative stress resulting from reactive oxygen species (ROS). In this study, the chemical production of ROS by inorganic NPs oxidizing the mammalian phenolic compound, l-3,4-dihydroxyphenylalanine (l-dopa) was evaluated using a ROS sensitive dye, 2′,7′-diclorodihydrofluorescin (DCFH). CeO₂, Fe₂O₃ and Fe⁰ NPs enhanced ROS production during the autoxidation of l-dopa by more than four-fold in reactions that were dependent on O₂. This is the first report of chemical ROS production due to interaction of phenolic compounds with NPs. Mn₂O₃ oxidized DCFH in a reaction that did not require O₂ or l-dopa, suggesting a direct redox reaction between the Mn₂O₃ and the dye. CeO₂, Mn₂O₃ and to a lesser extent Fe⁰ formed clear electron paramagnetic resonance (EPR) signature for hydroxyl radicals when incubated in aerobic aqueous suspensions with spin traps. The results indicate that NPs can generate ROS via chemical reactions with medium components and biomolecules susceptible to oxidation, such as l-dopa. NPs were reactive whereas micron-sized particles were not. The combined assay with l-dopa and DCFH is a method proposed to screen for chemical ROS production by NPs.     

Diffusive transport through compacted Na- and Ca-bentonite

The effect of exchangeable cation — Na⁺ and Ca ²⁺ — on the diffusive transport of I⁻, Sr ²⁺ and ³H (as HTO) in compacted bentonite was examined using a through-diffusion method. Total intrinsic diffusion coefficients, D_i, were determined from the steady-state flux of the diffusants through the clays, and apparent diffusion coefficients, D_a, were obtained from the time lag technique. The clays were compacted to a dry bulk density of 1.3 Mg/m³, and Na-bentonite was saturated with a solution of 100 mol NaCl/m3 and Ca-bentonite with one of 50 mol CaCl₂/m³. The D_i values for all diffusants are 2 to 6 times higher in the Ca- than Na-clay. We attribute this to the larger quasicrystal, or particle, size of Ca- compared to Na-bentonite. Hence, Ca-bentonite has a greater proportion of relatively large pores; this was confirmed by Hg intrusion porosimetry. This means the diffusion pathways in Ca-bentonite are less tortuous than those in Na-bentonite. Moreover, in some cases the effective porosity, or the porosity available for diffusive transport, may be greater in Ca-bentonite. The D_a values are inversely proportional to the distribution coefficients of the diffusants with the clays.     

Atmospheric degradation of fluoroesters (FESs): Gas-phase reactivity study towards OH radicals at 298 K

Using the relative technique, rate coefficients have been measured for the gas phase reactions of hydroxyl radicals with four fluoroacetates, methyl trifluoroacetate (CF₃COOCH₃), ethyl trifluoroacetate (CF₃COOCH₂CH₃), methyl difluoroacetate (CF₂HCOOCH₃) and 2,2,2-trifluoroethyl trifluoroacetate (CF₃COOCH₂CF₃). Experiments were carried out at 296±2 K and atmospheric pressure (∼750 Torr) using nitrogen or synthetic air as bath gases. The following rate coefficients were derived for the reaction of OH radicals (in units of cm³ mol⁻¹ s⁻¹) with CF₃COOCH₃, k=(4.97±1.04)×10⁻¹⁴, CF₃COOCH₂CH₃, k=(2.64±0.59)×10⁻¹³, CF₂HCOOCH₃, k=(1.48±0.34)×10⁻¹³ and CF₃COOCH₂CF₃, (1.05±0.23)×10⁻¹³. The rate constants obtained are compared with previous literature data of other volatile organic compounds to establish reactivity trends. Atmospheric implications are discussed in terms of lifetimes and fates of the fluoroacetates in the troposphere.     

The formation of dithionate during the iron(III)-catalysed autoxidation of sulfur(IV)-oxides

The iron(III)-catalyzed autoxidation of sulfur(IV)-oxides results in the formation of two different oxidation products of sulfur(IV): dithionate, S₂O₆²⁻, and sulfate, SO₄²⁻. The yield of these reaction products depends on the experimental conditions. Under the studied conditions ([Fe(III)] : [SIV)] = 1:10, pH = 2–4) dithionate is the minor reaction product. The formation of dithionate is influenced by the initial pH but not by the initial O₂ concentration. The presence of CO²⁺, Mn²⁺, and Ni²⁺ have no influence on the yield of dithionate, whereas in the presence of Cr³⁺ less and, in the presence of Cu²⁺, no dithionate is formed.     

Selective removal of Cr(VI) from aqueous solution by adsorption on mangosteen peel

Mangosteen peel, rich in polyphenolic compounds, was used to prepare the adsorbent exhibiting highly selective adsorption for Cr(VI) over other metal ions such as Pb²⁺, Fe³⁺, Zn²⁺, Cd²⁺, and Cr³⁺ at the pH values of 1～4. The chemical modification method proposed by using calcium hydroxide is quite cost-effective and ecofriendly without using any toxic reagents or causing any secondary pollution. The adsorption isotherm results revealed that the adsorption of Cr(VI) on the gel fit well the Langmuir adsorption model, and the maximum adsorption capacity for Cr(VI) at pH levels 1, 2, 3, and 4 was evaluated to be 2.46, 2.44, 1.99, and 2.14 mol/kg, respectively. The adsorption mechanism for Cr(VI) on the saponified gel was verified to follow an esterifiaction reaction coupled with the reduction of Cr(VI) to Cr(III) in which H⁺ plays a role of promoter. Thus, modified mangosteen peel gel has the prominent selectivity and low cost for Cr(VI) removal.     

Adsorption and desorption of 2,4,6-trichlorophenol onto and from ash as affected by Ag+, Zn2+, and Al3+

Metal cations and organic pollutants mostly co-exist in the natural environment. However, their interactions in adsorption processes have yet to be adequately addressed. In the current study, the effect of inorganic cations with different charges (Ag⁺, Zn²⁺, and Al³⁺) on the adsorption and desorption of 2,4,6-trichlorophenol (TCP) onto and from processed ash derived from wheat (Triticum aestivum L.) straw was investigated. The adsorption and desorption of TCP were both nonlinear; the isotherm and kinetics curves fitted well using the Freundlich equation and a pseudo-second-order model, respectively. The presence of Ag⁺ promoted TCP adsorption, while Zn²⁺ and Al³⁺ reduced TCP adsorption onto ash. The desorption of TCP from ash showed obvious hysteresis, and the presence of Ag⁺, Zn²⁺, and Al³⁺ caused the desorption to be less hysteretic. The suppression of TCP adsorption by Zn²⁺ and Al³⁺ was ascribed to the partial overlapping of adsorption groups between TCP and metal ions. Al³⁺ had a stronger inhibition effect than that of Zn²⁺ due to its higher binding capacity and larger hydrated ionic radius than those of Zn²⁺. Enhanced adsorption of TCP onto ash by Ag⁺ was ascribed to its ability to reduce the competitive adsorption of water molecules on ash surface by replacing the original ions, such as Na⁺ and Ca²⁺, and compressing the hydrated ionic radius of these metal ions. In addition, Ag⁺ was able to bind with the aromatic organic compounds containing π-electrons, which resulted in a further increase of TCP adsorption by ash.     

Enhanced removal of tetracycline via advanced oxidation of sodium persulfate and biochar adsorption

Advanced oxidation of antibiotic tetracycline (TC) is becoming an accessible and efficient technology. The removal of TC from the complex wastewater needs to be lucubrated. In this study, a TC removal system involving degradation and adsorption was established. TC degradation was accomplished by enhanced advanced oxidation via the addition of sodium persulfate (SP) and biochar into simulated wastewater containing Mn²⁺ and TC wastewater. The adsorption of TC and its derivatives was removed by biochar. The results indicate that the optimized reaction parameters were 3.0 g/L of biochar prepared at 600 °C (B600) and 400 mg/L of SP under acidic condition, and the removal percentage of TC was 87.48%, including 74.23% of degradation and 13.28% of adsorption; the anions Cl^?, NO₃^?, and H₂PO₄^? had negligible effects on the removal of TC in this Mn²⁺/B600/SP system. The system also functioned well with an aqueous solution with a high chemical oxygen demand (COD) concentration. Electron paramagnetic resonance (EPR) analysis indicated that ·OH and SO₄^? free radicals were present in the Mn²⁺/B600/SP system. Based on the testing and analysis results, a removal mechanism and potential TC degradation pathway for this system were proposed. TC can be degraded by ·OH and SO₄^? via three degradation pathways. Mn²⁺ can be precipitated as MnO₂, and a part of the TC and its derivatives can be adsorbed on the biochar surface. The Mn²⁺/B600/SP system also performed satisfactorily for a complex aqueous solution with various cations and antibiotics.