The removal of chlorinated organic herbicide in water by gamma-irradiation

In this study, the radiation-induced degradation of 2,4-dichlorophenoxyacetic acid (2,4-D) herbicide in aqueous solution was studied under various conditions as a function of irradiation dose in the absence and presence of hydrogen peroxide. The obtained data confirmed that largest yield of radiolytic degradation is obtained in oxidation processes/ionizing radiation, where oxidation is carried out with hydroxyl radicals. For complete degradation of 50?ppm 2,4-D, a required dose was lower in the presence of hydrogen peroxide. The formed major toxic phenolic intermediates were 2,4-dichlorophenol (2,4-DCP) and 4-chlorophenol (4-CP). The chemical analysis of the 2,4-D and the intermediates resulted from the radiolytic degradation were performed using a gas chromatography associated to mass spectrometry (GC?CMS) with ion trap dedector (ITD) and ion chromatography (IC). The formation of chlorophenols in addition to chloride, formaldehyde and carboxylic acids was studied as a function of absorbed dose.     

Use of reversed-phase HPLC with solid-phase extraction for monitoring of radiolytic degradation of chlorophenols for environmental protection

The efficiency of radiation induced decomposition of chlorophenols depends substantially on the radiation dose used and the presence of specific scavengers in the irradiated samples. Due to the use of HPLC for decomposition control it was shown, for the first time, that the increase of radiation dose results in gradual elimination of chlorine atoms from the chlorophenols molecules. The efficiency of radiolytic degradation of phenol and chlorophenols was monitored by reversed-phase HPLC. Prior to the chromatography the products of radiolytic degradation were preconcentrated using solid-phase extraction with phenyl columns. The most difficult to decompose is the simple phenol, which is also a product of radiolysis of all chlorophenols. Doses up to 2.0 kGy have not decomposed it completely in experimental conditions used. Degradation of chlorophenols in synthetic aqueous solutions takes place at doses from 0.2 to 2.0 kGy at ppm level of substrates depending on the number of chlorine atoms in molecule, however, for river water matrix containing scavengers such as carbonates or oxygen it requires larger doses.     

Photodegradation of dye pollutants on TiO<Subscript>2</Subscript> pillared bentonites under UV light irradiation

TiO₂ pillared bentonite samples dried under different conditions are used to degrade 2,4-dichlorophenol and orange II under UV light irradiation. The supercritical dried sample exhibits a high activity for the photodegradation of 2,4-dichlorophenol and orange II due to its structural features. TOC and COD are measured during the degradation of 2,4-dichlorophenol under UV light irradiation using P25 and TiO₂ pillared bentonite samples dried under different conditions. The clay-based catalysts can be readily separated by filtration or sedimentation.     

氮掺杂Bi2O3光催化剂可见光催化降解2,4-二氯酚

采用自制的Bi2O3及氮掺杂Bi2O3(N-Bi2O3)光催化剂,以卤钨灯为光源,在可见光下对2,4-二氯酚进行光催化降解.结果表明,N-Bi2O3较Bi2O3具有更高的可见光催化活性.当N-Bi2O3光催化剂投加量为2.0 g/L、2,4-二氯酚初始浓度为20 mg/L和pH =7时,光催化反应320 min,2,4-二氯酚的降解率最高可达到91.5％.2,4-二氯酚的光催化反应初活性与其浓度之间的关系符合Langmuir-Hinshelwood动力学速率模型.对降解过程中总有机碳及Cl-测试结果表明,N-Bi2O3光催化剂能较好地完成对2,4-二氯酚的深度矿化及脱氯.     

Pervaporation separation of aqueous chlorophenols by a novel polyurethane urea–poly (methyl methacrylate) interpenetrating network membrane

A novel polymer membrane system consisting of interpenetrating network (IPN) of hydroxy terminated polybutadiene (HTPB) based polyurethane urea (PUU)–poly (methyl methacrylate) (PMMA) has been designed and developed as highly permselective membrane for pervaporation separation of toxic p-chlorophenol and 2,4-dichlorophenol from their dilute aqueous solutions. It was observed that 3 ppm 2,4-dichlorophenol in water could be reduced to 0.3 ppm 2,4-dichlorophenol using a PUU–PMMA IPN membrane of 28 cm² area and 150 μm thickness. This membrane has shown high selectivity towards p-chlorophenol and 2,4-dichlorophenol at very low concentration in feed. Feed concentration of p-chlorophenol was varied from 1000 to 7000 ppm and that of 2,4-dichlorophenol was varied from 3 to 4000 ppm. Fifty seven percent 2,4-dichlorophenol in permeate was obtained from 3 ppm concentration in feed compared to 87% 2,4-dichlorophenol in permeate from 1000 ppm in feed. Pervaporation studies were carried out by varying the temperature of feed, membrane thickness and PMMA content in the membrane. The results of this investigation have revealed that these membranes would be suitable for separation of chlorophenols from industrial effluents.     

Radiolysis of aqueous solutions of ethylenediaminetetraacetatocerium(III)

The effect of γ-rays on acidic and alkaline solutions of ethylenediaminetetraacetatocerium(III) has been studied both in the presence and absence of oxygen. A mechanism is proposed, in which the radiolytic degradation of the complex is due only to OH, while the radiolytic oxidation of Ce(III) EDTA to Ce(IV) by γ-rays occurs via the formation of hydrogen peroxide.     

Photodegradation of dye pollutants on TiO_2 pillared bentonites under UV light irradiation

TiO2 pillared bentonite samples dried under different conditions are used to degrade 2,4-dichlorophenol and orange II under UV light irradiation. The supercritical dried sample exhibits a high activity for the photodegradation of 2,4-dichlorophenol and orange II due to its structural features. TOC and COD are measured during the degradation of 2,4-dichlorophenol under UV light irradiation using P25 and TiO2 pillared bentonite samples dried under different conditions. The clay-based catalysts can be readily separated by filtration or sedimentation.     

Destruction Kinetics of 2,4 Dichlorophenol Aqueous Solutions in an Atmospheric Pressure Dielectric Barrier Discharge in Oxygen

The processes of degradation of 2,4-dichlorophenol (2,4-DCP) aqueous solutions under the action of atmospheric pressure of DBD in oxygen were studied. The degradation of 2,4-DCP proceeds efficiently, the degree of decomposition reaching 100%. The degradation kinetics of 2,4-DCP obeys a formal first-order kinetic law on concentration of 2,4-DCP. The effective rate constants depend weakly on the experimental conditions and are equal to ~ 2 s^?1. Based on experimental data, the energy efficiency of 2,4-DCP decomposition was determined to be in the range of 0.039–0.173 molecules per 100 eV depending on the experimental conditions. The composition of the products was studied by gas chromatography, chromatography-mass spectrometry, UV/visible spectroscopy, fluorescent methods and some chemical methods. The main decomposition products present in the solution were found to be carboxylic acids, aldehydes and chloride ions, whereas carbon dioxide and molecular chlorine appear in the gas. The results obtained are compared with similar data from other advanced oxidation processes (AOP’s) methods.     

THE ROLE OF HUMIC SUBSTANCES IN THE PHOTOCATALYTIC DEGRADATION OF WATER CONTAMINANTS

Abstract

Photocatalysis over irradiated Ti0₂ has been proved to efficiently abate more than 80% of the organic carbon pertaining to a commercial humic acid (HA). The presence of HA up to 50 mg L^?1 has been found to decrease the degradation rate of some model pollutants, namely phenol, 2,4-dichlorophenol and tetrachloromethane. However, the total organic carbon measurements and chloride evolution ensure that the disappearance of the initial pollutants is not due to binding to HA structure, but to an efficient mineralization process. HA' s are able to scavenge both the oxidative and the reductive active species as shown by the inhibiting effect on the rate of disappearance of phenol and 2,4-dichlorophenol (essentially oxidative), and of CCI4 (initially reductive).     

Sample preparation procedure for PIXE elemental analysis on soft tissues

Neutral aqueous solutions of Nickel II-diethylenetriaminepentaacetate (DTPA) were irradiated using -rays both in the presence and in the absence of oxygen. A radiolytic mechanism has been proposed and discussed. It has been suggested that the radiolytic degradation of the ligand is due to the formation of OH^* during radiolysis.     

Photocatalytic degradation of chlorophenols under direct solar radiation in the presence of ZnO catalyst

The photocatalytic degradation of chlorophenols was evaluated under direct solar radiation using commercial ZnO catalyst. Effects of several parameters such as a catalyst loading, pH of solution and initial concentration on the degradation process have been investigated. The photocatalytic degradation efficiency of chlorophenols at the optimum value of the parameters was compared under similar experimental conditions. The results of efficiency and mineralization showed the degradation of 2-chlorophenol and 2,4-dichlorophenol compound with the first order kinetic rate and the rate constant decreases as the initial concentration of the chlorophenols increase. However, the rate constant was strongly affected by type of chlorophenols compound present either 2-chlorophenol or 2,4-dichlorophenol. The highest removal of chlorophenols was obtained after 120 min and the final intermediate compounds of chlorophenols degradation are lower molecular weight compound consisting of acetic acid which was analyzed through the HPLC.     

Photocatalytic mineralization of chlorinated organic pollutants in water by polyoxometallates. Determination of intermediates and final degradation products

Homogeneous aqueous solutions of organochlorine pesticides and chlorophenols, namely, lindane, hexachlorobenzene and 2,4-dichlorophenol (2,4DCP), undergo effective photodegradation upon photolysis with UV and near visible light in the presence of a characteristic polyoxometallate catalyst PW₁₂O₄₀ ³⁻. These substrates remained, practically, intact (lindane, HCB) or underwent minor degradation under similar conditions in absence of catalyst. The main oxidant appears to be OH radicals formed by the reaction of the excited polyoxometallate with H₂O. The system compares with the widely published TiO₂. Chlorohydroquinone (ClHQ), hydroquinone (HQ), chlorobenzoquinone (ClBQ), benzoquinone (BQ), 3,5-dichlorocatechol (3,5DCC) and 4-chlorocatechol (4CC), among others, were identified as the main aromatic intermediates in the photodegradation of 2,4DCP. Acetic acid was detected as ring cleavage product. In all cases the final photodegradation leads to complete mineralization of substrates to CO₂ and HCl.     

Radiolytic degradation of malathion and lindane in aqueous solutions

Degradation of malathion and lindane pesticides present in an aqueous solution was investigated on a laboratory scale upon gamma-irradiation from a ⁶⁰Co source. The effects of pesticide group, presence of various additives and absorbed dose on efficiency of pesticide degradation were investigated. Gamma-irradiation was carried out in distilled water solutions (malathion and lindane) and in combination with humic solution (HS), nitrous oxide (N₂O) and HS/N₂O (lindane) over the range 0.1–2 kGy (malathion) and 5–30 kGy (lindane). Malathion was easily degraded at low absorbed doses compared to lindane in distilled water solutions. Absorbed doses required to remove 50% and 90% of initial malathion and lindane concentrations in distilled water solutions were 0.53 and 1.77 kGy (malathion) and 17.97 and 28.79 kGy (lindane), respectively. The presence of HS, N₂O and HS/N₂O additives in aqueous solutions, significantly improved the effectiveness of radiolytic degradation of lindane. Chemical analysis of the pesticides and the by-products resulted from the radiolytic degradation were made using a gas chromatography associated with mass spectrometry (GC–MS). Additionally, the final degradation products of irradiation as detected by ion chromatography (IC) were acetic acid and traces of some anions (phosphate and chloride).     

Absorption and fluorescence behavior of cytosine irradiated at different pH and in the presence of Cu(II) ions at neutral pH

Dilute aqueous solutions of cytosine were irradiated with⁶⁰Co -rays under N₂O saturated conditions at different pH and in the presence of Cu(II) ions at neutral pH. The base degradation decreased from neutral to acidic and basic conditions. In the presence of metal ions at neutral pH conditions there was a significant increase in the base degradation compared to that in the absence of metal ions under similar conditions. From the difference absorption spectra and fluorescence behavior of the irradiated solutions it was observed that the major radiolytic products of cytosine under different conditions are cytosine glycols, 5-hydroxycytosine, hydroxy-hydrocytosine and cytosine dimers. The yields of dimers is maximum in neutral conditions and it decreased from basic to acidic conditions. However, in the presence of Cu(II) ions formation of cytosine dimers is completely restricted and there is an increase in the yields of cytosine glycol, hydroxy-hydrocytosine and 5-hydroxycytosine. From the post-radiolytic changes in absorption and fluorescence behavior of irradiated solutions, it is revealed that some of the radiolytic products, namely cytosine glycol and hydroxy-hydrocytosine decompose to 5-hydroxycytosine and cytosine, respectively.     

Radiolytic degradation of 2,4-dichlorophenoxyacetic acid in dilute aqueous solution: pH dependence

The reactions of hydroxyl radical and hydrated electron intermediates of water radiolysis were studied in the radiolytic degradation of 2,4-dichlorophenoxyacetic acid (2,4-D) at pH values of 4, 6 and 8. The hydrated electron reactions are also suggested to contribute to the aromatic ring decomposition in addition to the highly effective hydroxyl radical reactions. The experimental results suggest also some contribution from the O₂^−•/HO₂^• pair to the degradation. The degradation efficiency was found to be the highest at pH 8 and the lowest at pH 6.     

Synthesis of porous divinylbiphenyl copolymers and their sorptive properties towards phenol and its derivatives

Seven porous divinylbiphenyl polymers having the same nominal crosslinking degree (51.8 wt.%) have been synthesized using suspension polymerization method in the presence of the following inert diluents or their mixtures: toluene, heptane, dodecane, isooctane. The use of various inert diluents was aimed at changing the extent of polymeric network-diluent interactions. The obtained polymers have specific surface area in the range 50-300 m²/g depending on the type and amount of inert diluents used during polymerization. Their sorptive properties have been studied using dilute (0.5 mmol/l) aqueous solutions of phenol and its derivatives (2-chlorophenol, 2,4-dichlorophenol, 2,4,5-trichlorophenol, 2,6-dimethylphenol, 4-hydroxyphenol). It has been found that sorption, at low equilibrium concentration, follows the order: 2,4,5-trichlorophenol > 2,4-dichlorophenol > 2-chlorophenol > 2,6-dimethylphenol > phenol > 4-hydroxyphenol. Full characteristic of the porous structure of polymers has been obtained by nitrogen adsorption at 77K.     

A surface plasmon resonance immunosensor for detecting a dioxin precursor using a gold binding polypeptide

A surface plasmon resonance (SPR) based biosensor was developed for monitoring 2,4-dichlorophenol, a known dioxin precursor, using an indirect competitive immunoassay. The SPR sensor was fabricated by immobilizing a gold-thin layer on the surface of an SPR sensor chip with an anti-(2,4-dichlorophenol) antibody using a gold binding polypeptide (GBP) and protein G. The SPR response based on the antigen-antibody reaction in a flow system was measured by injecting a 2,4-dichlorophenol sample solution into the flow system in which the SPR sensor was located. In a direct immunoassay system using the modified sensor chip, no significant SPR angle shift less than 0.001° was observed when a 25 ppm of 2,4-dichlorophenol solution was injected. In order to improve the sensitivity of the SPR sensor, an indirect competitive immunoassay method was used in conjunction with the SPR sensor system using 2,4-dichlorophenol conjugated with bovine serum albumin (BSA). In the competitive assay, a 350 ppm 2,4-dichlorophenol-BSA conjugate solution containing 2,4-dichlorophenol at various concentrations (10-250 ppb) were injected into the SPR sensor system. The sensitivity of this indirect immunoassay was found to be extremely sensitive, compared to the direct one, and a detection limit of 20 ppb was estimated. Verification that the use of GBP for immobilizing the antibody on the sensor chip enhanced the sensitivity to 2,4-dichlorophenol was obtained by comparing the procedure with another modification, in which BSA was used instead of GBP for immobilizing the antibody on the sensor chip. The affinity constant of 2,4-dichlorophenol and its conjugate to the antibody were estimated form the SPR response.     

Synthesis of cubic Ag@AgCl and Ag@AgBr plasmonic photocatalysts and comparison of their photocatalytic activity for degradation of methyl orange and 2,4-dichlorophenol

Uniform cubic Ag@AgCl and Ag@AgBr plasmonic photocatalysts with side length of 0.7 µm were synthesized by a facile green route, in which a controllable double-jet precipitation technique was employed to fabricate homogeneous cubic AgCl and AgBr grains while a photoreduction process was used to produce Ag nanoparticles (NPs) on the surface of AgCl and AgBr grains. The synthesized samples were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) analysis, X-ray photoelectron spectroscopy (XPS), and ultraviolet–visible (UV–Vis) diffuse reflectance spectroscopy (DRS). The photocatalytic activities of Ag@AgCl and Ag@AgBr were compared using degradation of methyl orange (MO) dye and 2,4-dichlorophenol (2,4-DCP) under visible-light irradiation. Ag@AgBr showed higher photocatalytic activity for MO degradation but weaker activity for 2,4-DCP decomposition. Possible degradation mechanisms are proposed to interpret these contrary paradoxical experimental results.     

Radiolysis of aqueous solutions of cobalt/II/ and cobalt/III/ 2,2′-bis-[aminoethyl]ether-tetraacetate complexes

Radiolysis of aqueous solutions of di- and trivalent cobalt with 2,2-bis/aminoethyl/ether-tetraacetic acid /BAETA/ was investigated, both in absence and in presence of oxygen. A radiolytic mechanism has been proposed where it has been shown that the degradation of the chelation is due to OH only.     

Synthesis of 2,4-dichlorophenyl methanesulfonate labeled with 14C and 35S

Radioactive 2,4-dichlorophenyl methanesulfonate labeled with ¹⁴C and ³⁵S has been synthesized because it was needed to facilitate the study of the metabolic fate of this interesting nematicide. It was prepared from the reaction between methanesulfonyl chloride and 2,4-dichlorophenol in the presence of a base. Three hundred milligrams of each ¹⁴C- and ³⁵S-2,4-dichlorophenyl methanesulfonate was obtained in a yield of 87% based on ¹⁴C-2,4-dichlorophenol or ³⁵S-methanesulfonyl chloride, respectively. The specific activity was 3.8 mCi/mmol for the compound labeled with ³⁵S and 2.5 mCi/mmol for the ¹⁴C material. Both tracers assayed over 99% after purification.