Study on degradation process of famotidine hydrochloride in aqueous samples

The kinetics of famotidine (FAM) transformation under the influence of various factors, important from the environmental point of view, was investigated in aqueous solutions. The degradation processes using UV, H₂O₂, UV/H₂O₂, H₂O₂/Fe²⁺, and UV/H₂O₂/Fe²⁺ were studied. Direct photolysis and H₂O₂-assisted photolysis showed a pseudo-first-order kinetics, while the Fenton and the photo-Fenton processes fit second-order kinetics. The provided experiments proved a high resistance of FAM to direct photolysis. Its stability depends highly on the pH of the reaction solutions. The rate of FAM direct photolysis in acidic solutions was almost negligible. The reaction rate of FAM photolysis at pH 8–9 was 3.7 × 10^?3 min^?1 with DT₅₀ about 3 h 7 min. It was found that the presence of H₂O₂ in the reaction environment enhances the rate of photolysis of FAM. The observed rates of reaction were 5.1 × 10^?3 min^?1 and 3.7 × 10^?3 min^?1 in acidic and basic solutions, respectively. The used Fenton systems appeared to be the most efficient in FAM removal. The rate of reaction depends on concentration of Fe²⁺ and H₂O₂. It was observed that the presence of UV-light enhances the reaction rate by two to six times in comparison to the classical Fenton system. Additionally, FAM behavior in natural water under solar irradiation was examined. The irradiation experiments were carried out in batch experiments with simulated sunlight.     

Fe-pillared bentonite,a stable Fenton catalyst for treatment of petroleum refinery wastewater

Fe-pillared bentonite (Fe-Bent) was prepared by ion exchange as heterogeneous catalyst for degradation of organic contaminants in petroleum refinery wastewater. X-ray diffraction analysis showed the existence of α-Fe₂O₃. The effects of pH, H₂O₂ concentration, and catalyst dosage on the rate of lowering the chemical oxygen demand (COD) were investigated in detail. Removal efficiency of COD can be up to 92% under the following conditions: dosage of Fe-Bent 7 g L^?1, pH value 3, and H₂O₂ concentration 10 mmol L^?1. Fe-Bent showed good stability for the degradation of organics in petroleum refinery wastewater for five cycles. The adsorption of organics in wastewater onto Fe-Bent could be well described by a pseudo-second-order kinetic model.     

Solar-induced generation of singlet oxygen and hydroxyl radical in sewage wastewaters

Singlet oxygen (¹O₂) and hydroxyl radical (·OH) play an important role in the degradation of pollutants in surface waters. However, the mechanism underlying the photochemical generation of ¹O₂ and ·OH in wastewaters is poorly known. Here we studied the photo-induced generation of ¹O₂ and ·OH in different sewage treatment plant units. The correlation between the generation of ¹O₂ and ·OH and the water constituents was discussed. Our results show that in sewage units the ¹O₂ formation rate ranges from 2.19 × 10^?8 to 6.74 × 10^?8 mol L^?1 s^?1, and the ·OH formation rate ranges from 1.7 × 10^?11 to 3.06 × 10^?10 mol L^?1 s^?1. The average ¹O₂ formation rates in the various sewage units are similar to those in wetland and estuarine waters containing rich dissolved organic matter and 2–4 times higher than those in lake and seawater samples. The average ·OH formation rates of the sewage units are 5–50 times higher than for other water samples reported. The ·OH generation rate increased with the iron content with a correlation coefficient of 0.85, which indicates that the photo-Fenton reaction plays a dominant role in ·OH generation in sewage wastewater.     

Coupled electrocoagulation–electro-Fenton for efficient domestic wastewater treatment

This article reports the first use of coupled electrocoagulation and electro-Fenton (EF-EC) to clean domestic wastewater. Domestic wastewater contains high amounts of organic, inorganic and microbial pollutants that cannot be usually treated in a single step. Here, to produce an effluent suitable for discharge in a single process step, a hybrid process combining electrocoagulation and electro-Fenton was simultaneously used to decrease chemical oxygen demand (COD), turbidity and total suspended solids (TSS) from domestic wastewater. The electrocoagulation–electro-Fenton process was firstly tested for the production of H₂O₂ using Ti–IrO₂ and vitreous carbon- or graphite electrodes arranged at the anode and the cathode, respectively. The concentration of H₂O₂ recorded at 1.5 A of current intensity during 60 min of electrolysis using vitreous carbon- and graphite electrodes at the cathode was 4.18 and 1.62 mg L^?1, respectively. By comparison, when the iron electrode was used at the anode, 2.05 and 1.06 mg L^?1 of H₂O₂ were recorded using vitreous carbon and graphite, respectively. The H₂O₂ concentration decrease was attributed to hydroxyl radical formation generated by the Fenton reaction. Electro-Fenton using iron electrode at the anode and vitreous carbon at the cathode with a current density imposed of 0.34 A dm^?2 ensures the removal efficiency of 50.1 % COD_T, 70.8 % TSS and 90.4 % turbidity. The electrocoagulation–electro-Fenton technique is therefore a promising secondary treatment to simultaneously remove organic, inorganic and microbial pollutants from domestic, municipal and industrial wastewaters.     

Assessment of the role of thymol in combating chromium (VI)-induced oxidative stress in isolated rat erythrocytes in vitro

Thymol, the main phenolic compound in Thymus vulgaris, has been shown to have various biological effects. The main objective of this study was to investigate the efficacy of thymol on counteracting hexavalent chromium-induced oxidative damage in rat erythrocytes in vitro. The radical scavenging activity of thymol was examined using the 1, 1-diphenyl-2-picrylhydrazyl assay. Erythrocytes resistance to oxidative damage, lipid peroxidation, osmotic pressure, hemolysis as well as morphological alterations were evaluated in the presence of 2.5 µg thymol mL^?1 with or without 5 µmol hexavalent chromium mL^?1 of the incubation media. Results from the 1,1-diphenyl-2-picrylhydrazyl assay denoted good radical scavenging activity of thymol. Thymol caused a significant increase in superoxide dismutase and catalase activities and reduced glutathione content in erythrocytes intoxicated with hexavalent chromium. In contrast, the presence of thymol resulted in markedly less-elevated malondialdehyde levels, hemolysis, and destabilization of erythrocytes exposed to hexavalent chromium. Microscopically, thymol markedly reduced hexavalent chromium-induced morphological alterations in rat red blood cells. Conclusively, thymol counteracted hexavalent chromium-induced oxidative damage in rat erythrocytes.     

Evidence for a new mechanism of Fe2O3 decomposition in lightweight aggregate formation

Hematite (Fe₂O₃) chemical reduction into FeO and Fe₃O₄ by releasing O₂ at high temperatures is considered one of the generally accepted mechanisms for processing waste minerals and clay into lightweight aggregate construction materials. In many case studies, this mechanism has not been strictly confirmed. To verify whether hematite can effectively release O₂ at 1,000–1,260°C, a material containing hematite, simulating waste sediments from a Taiwanese reservoir, was shaped into pellets and fired into lightweight aggregates at high temperatures for 20 min and studied with various techniques. As revealed by the X-ray absorption near-edge structure technique, almost all the hematite remained as Fe(III) in the pellets when fired at 1,000–1,260°C, implying a negligible release of O₂ leading to the creation of pores. This finding shows that the generally accepted mechanism for lightweight aggregate formation associated with hematite decomposition into FeO, Fe₃O₄, and O₂ is invalid. Furthermore, Fe(III)-containing composites were formed in the fired pellets. Although firing at 1,000°C can trigger the decomposition of the components K₂CO₃, Na₂CO₃, and CaCO₃ with a release of CO₂, the sintering reaction was seemingly too weak to encapsulate the gases effectively. For pellets fired at 1,050–1,150°C, pores grew in size because the sintering reaction sufficed to generate a glassy phase that could better encapsulate gases.     

Kinetics of hexavalent chromium reduction by iron metal

The kinetics of Cr(VI) reduction to Cr(III) by metallic iron (Fe⁰) was studied in batch reactors for a range of reactant concentrations, pH and temperatures. Nearly 86.8% removal efficiency for Cr(VI) was achieved when Fe⁰ concentration was 6 g/L (using commercial iron powder (< 200 mesh) in 120 min). The reduction of hexavalent chromium took place on the surface of the iron particles following pseudo-first order kinetics. The rate of Cr(VI) reduction increased with increasing Fe⁰ addition and temperature but inversely with initial pH. The pseudo-first-order rate coefficients (k _obs) were determined as 0.0024, 0.010, 0.0268 and 0.062 8 min^?1 when iron powder dosages were 2, 6, 10 and 14 g/L at 25°C and pH 5.5, respectively. According to the Arrehenius equation, the apparent activation energy of 26.5 kJ/mol and pre-exponential factor of 3 330 min^?1 were obtained at the temperature range of 288–308 K. Different Fe⁰ types were compared in this study. The reactivity was in the order starch-stabilized Fe⁰ nanoparticles > Fe⁰ nanoparticles > Fe⁰ powder > Fe⁰ filings. Electrochemical analysis of the reaction process showed that Cr(III) and Fe(III) hydroxides should be the dominant final products.     

Catalytic ozonation performance and surface property of supported Fe3O4 catalysts dispersions

Fe₃O₄ was supported on mesoporous Al₂O₃ or SiO₂ (50 wt.%) using an incipient wetness impregnation method, and Fe₃O₄/Al₂O₃ exhibited higher catalytic efficiency for the degradation of 2,4-dichlorophenoxyacetic acid and para-chlorobenzoic acid aqueous solution with ozone. The effect and morphology of supported Fe₃O₄ on catalytic ozonation performance were investigated based on the characterization results of X-ray diffraction, X-ray photoelectron spectroscopy, BET analysis and Fourier transform infrared spectroscopy. The results indicated that the physical and chemical properties of the catalyst supports especially their Lewis acid sites had a significant influence on the catalytic activity. In comparison with SiO₂, more Lewis acid sites existed on the surface of Al₂O₃, resulting in higher catalytic ozonation activity. During the reaction process, no significant Fe ions release was observed. Moreover, Fe₃O₄/Al₂O₃ exhibited stable structure and activity after successive cyclic experiments. The results indicated that the catalyst is a promising ozonation catalyst with magnetic separation in drinking water treatment.     

Catalytic determination of ultratrace chromium based on gallocyanine‐hydrogen peroxide indicator reaction

A highly sensitive catalytic procedure for the determination of ultratrace chromium(VI) was developed based on its catalytic effect on the oxidation of gallocyanine by hydrogen peroxide in hexamine‐hydrochloric acid buffer solution. The reaction was followed spectrophotometrically by measuring the rate of change in the absorbance at 620 nm. The apparent active energy of the catalytic reaction is 6.84 kJ . mol^‐1. The calibration graph is linear for 0–150 ng.ml^‐1, and the detection limit is 0.8 ng.ml^‐1. Most foreign ions have no interfering effect on the determination of chromium(VI) except for Al³⁺, Cu²⁺, Fe³⁺and Fe²⁺. The interference of Al³⁺ is eliminated by masking with F^‐, and those of Cu²⁺, Fe³⁺ and Fe²⁺ are eliminated by adding appropriate amount of EDTA. The present procedure had been used for the determination of trace chromium(VI) in lake water, mine water and electroplating wastewater, and the results were satisfactory.     

Carbon paste electrode modified with chromium thiopental for the potentiometric flow injection analysis of chromium (III)

A chemically modified carbon paste electrode for chromium (III) based on the formation of ion-association complex of chromium with 5-ethyl-6-oxo-5-pentan-2-yl-sulfanyl-pyrimidin-4-olate (thiopental, THP) as electroactive ion-exchanger (Cr-THP) was prepared and investigated. The electrode has a linear dynamic range of 1.7?×?10^?6–1.3?×?10^?2?mol?L^?1, with a Nernstian slope of 19.6?±?0.5?mV per decade and a detection limit of 9.0?×?10^?7?mol?L^?1. It has a fast response time of <15?s and can be used for at least 7 weeks without any considerable divergence in potential. The proposed sensor revealed good selectivity for Cr(III) over a wide variety of mono-, di-, and trivalent cations and could be used in the pH range of 2.3–6.5. The proposed electrode was used in batch measurements and in flow injection analysis. The Cr-CMCPE was successfully applied for the determination of Cr(III) in real samples (wastewater of hot dip galvanizing unit and alloys). The present electrode was also used as an indicator electrode in potentiometric titration of Cr(III). The results were highly satisfactory.     

Synthesis and antibacterial activity of a Fe3O4–AgCl nanocomposite against Escherichia coli

In this investigation, Fe₃O₄ magnetic nanoparticles (MNPs) were prepared by the alkalinization of an aqueous medium containing ferrous sulfate and ferric chloride. In the next step, a Fe₃O₄–AgCl magnetic nanocomposite was fabricated by the drop-by-drop addition of silver nitrate solution into a NaCl solution containing Fe₃O₄ MNPs. All prepared nanoparticles were characterized by transition electron microscopy (TEM), X-ray diffraction (XRD), and energy-dispersive X-ray spectroscopy (EDS). Both particle types varied in size from 2.5 to 20?nm, with an average size of 7.5?nm for Fe₃O₄ MNPs and 12.5?nm for Fe₃O₄–AgCl nanocomposites. The antibacterial effect of the Fe₃O₄ MNPs and fabricated Fe₃O₄–AgCl nanocomposites against Escherichia coli (ATCC 35218) were investigated by conventional serial agar dilution method using the Müller–Hinton Agar medium. The minimum inhibitory concentration was 4?mg?mL^?1 for Fe₃O₄ MNPs and 2?mg?mL^?1 for the Fe₃O₄–AgCl magnetic nanocomposites. Time-kill course assays showed that the Fe₃O₄–AgCl magnetic nanocomposites successfully killed all inoculated bacterial cells during an exposure time of 60?min. The antibacterial activity of recycled Fe₃O₄–AgCl magnetic nanocomposites over four 60?min cycles of antibacterial treatment was further tested against E. coli by the colony-forming unit (CFU) method. The antibacterial efficiency of the nanocomposites was constant over two cycles of antibacterial testing.     

UV-C light-enhanced photo-Fenton oxidation of methyl parathion

The photodegradation of aqueous solutions containing 0.2 mM methyl parathion has been studied through the optimization of the [H₂O₂]/[Fe³⁺] ratio in a Fe³⁺/H₂O₂/UV-C flow system of 1.3 L capacity. The decay kinetics and TOC abatement have been analyzed for the experiments performed at pH 3.0 and room temperature. All experiments lead to the total methyl parathion destruction after a few minutes, following a pseudo-first-order decay kinetics. Total mineralization can be reached after 120 min at the optimum ratio found, due to the synergistic effect of the very oxidizing hydroxyl radical (^·OH) produced via the Fenton reagent and the effective photodecarboxylation at 253.7 nm.     

Removal of carbamazepine from urban wastewater by sulfate radical oxidation

The occurrence of bioactive trace pollutants such as pharmaceuticals in natural waters is an emerging issue. Numerous pharmaceuticals are not completely removed in conventional wastewater treatment plants. Advanced oxidation processes may represent an interesting alternative to completely mineralize organic trace pollutants. In this article, we show that sulfate radicals generated from peroxymonosulfate/Co^II are more efficient than hydroxyl radicals generated from the Fenton’s reagent (H₂O₂/Fe^II) for the degradation of the pharmaceutical compound, carbamazepine. The second-order rate constant for the reaction of SO₄ ^·− with carbamazepine is 1.92·10⁹ M⁻¹ s⁻¹. In laboratory grade water and in real urban wastewater, SO₄ ^·− yielded a faster degradation of carbamazepine compared to HO^· . Under strongly oxidizing conditions, a nearly complete mineralization of carbamazepine was achieved, while under mildly oxidizing conditions, several intermediates were identified by LC–MS. These results show for the first time in real urban wastewater that sulfate radicals are more selective than hydroxyl radicals for the oxidation of an organic pollutant and may represent an interesting alternative in advanced oxidation processes.     

Efficient oxidation of sulfides into sulfoxides catalyzed by a chitosan–Schiff base complex of Cu(II) supported on supramagnetic Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles

Sulfoxides are versatile synthetic intermediates for the preparation of biological products. Therefore, there is a need for efficient methods to oxidize sulfides into sulfoxides. Such oxidation may be catalyzed by magnetic nanocatalysts due to their good stability, easy synthesis, high surface area, low toxicity and easy separation by magnetic forces. Here we prepared a nanocatalyst by immobilization of the chitosan–Schiff base complex on supramagnetic Fe₃O₄ nanoparticles. The chitosan–Schiff base complex has been previously prepared by functionalization of chitosan with 5-bromosalicylaldehyde and metalation with copper(II) acetate. The catalyst was characterized by Fourier transform infrared, powder X-ray diffraction, transmission electron microscope, scanning electron microscopy, energy-dispersive X-ray spectroscopy and thermogravimetric analysis. Results show that the Fe₃O₄ nanoparticles and nanocatalyst were spherical in shape with an average size of 20 nm. Upon the covalently anchoring of chitosan–Schiff base Cu complex on the magnetic Fe₃O₄ nanoparticles, the average size increased to 60 nm. The prepared Fe₃O₄–chitosan–Schiff base Cu complex catalyzed very efficiently the oxidation of sulfides to sulfoxides with 100 % selectivity in all cases under green reaction conditions and excellent yields. Additionally, ease of recovery and reusability up to four cycles without noticeable loss of catalytic activity make the present protocol beneficial from industrial and environmental viewpoint.     

Metal Interactions in carcinogenesis†

Mixed exposures to a number of metallic compounds may give rise to a carcinogenic response in humans.

An interaction between occupational exposure to arsenic and cigarette smoking has been documented epidemiologically. A multiplicative effect was indicated concerning the occurrence of lung cancer when both of the exposures were present. Several experimental studies have been reported in the literature concerning interactions between benzo(a)pyrene and Fe₂O₃ as well as some other metallic compounds like Ni₃S₂, PbO, MgO and TiO₂ in relation to respiratory carcinogenicity. There is also limited evidence of a positive interaction between arsenic trioxide and benzo(a)pyrene. Particles containing V and Ni were obtained from the flue gases of power plants burning heavy fuel oil. Such particles were not carcinogenic themselves but enhanced the carcinogenicity of benzo(a)pyrene even more efficiently than Fe₂O₃.

Increased dietary selenium intakes can decrease the carcinogenicity of several organic carcinogens in animals and dietary zinc can effectuate both enhancement and inhibition of carcinogenicity depending on dietary concentration.     

High-valent iron-based oxidants to treat perfluorooctanesulfonate and perfluorooctanoic acid in water

Perfluoroalkyl and polyfluoroalkyl substances are occurring in consumer and industrial products. They have been found globally in the aquatic environment including drinking water sources and treated wastewater effluents, which has raised concern of potential human health effects because these substances may be bioaccumulative and extremely persistent. The saturated carbon–fluorine bonds of the substances make them resistant to degradation by physical, chemical, and biological processes. There is therefore a need for advanced remediation methods. Iron-based methods involving high-valent compounds are appealing to degrade these substances due to their high oxidation potentials and capability to generate environmentally friendly by-products. This article presents for the first time the oxidation ability of tetraoxy anions of iron(V) (Fe^VO₄ ^3?, Fe(V)), and iron(IV) (Fe^IVO₄ ^4?, Fe(IV)), commonly called ferrates, in neutral and alkaline solutions. Solid compounds of Fe(V) (K₃FeO₄) and Fe(IV) (Na₄FeO₄) were added directly into buffered solution containing perfluorooctansulfonate and perfluorooctanoic acid at pH 7.0 and 9.0, and mixed solutions were subjected to analysis for remaining fluoro compounds after 5 days. The analysis was performed by liquid chromatography–mass spectrometry/mass spectrometry technique. Fe(IV) showed the highest ability to oxidize the studied contaminants; the maximum removals were 34 % for perfluorooctansulfonate and 23 % for perfluorooctanoic acid. Both Fe(V) and Fe(IV) had slightly higher tendency to oxidize contaminants at alkaline pH than at neutral pH. Results were described by invoking reactions involved in oxidation of perfluorooctansulfonate and perfluorooctanoic acid by ferrates in aqueous solution. The results demonstrated potentials of Fe(V) and Fe(IV) to degrade perfluoroalkyl substances in contaminated water.     

Novel coprecipitation–oxidation method for recovering iron from steel waste pickling liquor

Waste pickling liquors (WPLs) containing high concentrations of iron and acid are hazardous waste products from the steel pickling processes. A novel combined coprecipitation–oxidation method for iron recovery by Fe₃O₄ nanoparticle production from the WPLs was developed in this study. An oxidation–reduction potential monitoring method was developed for real-time control of the Fe²⁺/Fe³⁺ molar ratio. The key coprecipitation–oxidation parameters were determined using the orthogonal experimental design method. The use of promoters greatly improved the Fe₃O₄ nanoparticle crystallinity, size, magnetization, and dispersion. X-ray diffraction patterns showed that the produced Fe₃O₄ nanoparticles were single phase. The Fe₃O₄ nanoparticles were approximately spherical and slightly agglomerated. Vibrating sample magnetometry showed that the Fe₃O₄ nanoparticles produced from the WPLs had good magnetic properties, with a saturation magnetization of 80.206 emu·g^–1 and a remanence of 10.500 emu·g^–1. The results show that this novel coprecipitation–oxidation method has great potential for recycling iron in WPLs.

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Chromium recovery from solid leather waste by chemical treatment and optimisation by response surface methodology

The leather industry uses conventional tanning methods which cause environmental pollution due mainly to the presence of chromium. This study suggests a treatment for solid leather waste containing chromium as an ecological alternative to the pollution generated by tanneries. The study uses an original approach to the optimisation of chromium recovery by mathematical and statistical treatment of the experimental data. Several factors that influence recovery, such as temperature, concentration, time and solid/liquid ratio through acid and basic hydrolysis were analysed with the aid of experimental design. Tanning liquor was obtained by adjusting pH, alkalinity and concentration when hydrolysis finished. An appropriate response surface model was constructed using alkaline hydrolysis experiments with sodium hydroxide, leading to conditions for maximum recovery of Cr₂O₃. The optimal NaOH concentration (1.58%), temperature (63.7 °C), time (3 h) and solid/liquid ratio (1/70 g·mL^?1) were established. The results indicate that sodium hydroxide as an hydrolysis agent is a highly efficient means of recovering chromium from solid leather waste in order to produce tanning liquor.     

Removal of chromium (VI) from water streams: a thermodynamic study

The chemical speciation of water solutions containing chromium oxyanions in various ratios is calculated (with the aid of available computer code Mineql Plus, Geochemist Workbench and Visual Minteq) and discussed. The effect of solution pH, total concentration of each species studied, and the presence of other species in solution are calculated and presented in the form of thermodynamic speciation diagrams. Electrochemical diagram (correlating pH to Eh) has been calculated as well. The conditions of Cr(VI) reduction to Cr(III) and the subsequent solid phase precipitation are given as a function of redox potential and pH. Surface reactions that might occur between the chromate ions in the solution and redox couples as Fe²⁺/Fe³⁺ on the surface of sorbents are also discussed. Moreover, experimental sorption data of hexavalent chromium onto synthetic magnetite are presented and discussed with the aid of the calculated diagrams. A mechanism is elucidated for the efficient removal of Cr(VI) from water streams at low pH values, and zeta potential data of synthetic magnetite with and without Cr(VI) are presented, which agree well with the mechanism proposed.     

城市污水二级硝化出水的离子交换脱氮除磷

以城市污水二级硝化出水为原水,对比研究了3种强碱性阴离子交换树脂(201×4、D296、D301T)动态脱氮除磷情况,并以201×4树脂为模式树脂考察了树脂活化方式(常规酸碱交替活化与NaCl再生液活化)、腐殖酸(HA)浓度(1.1,2.8和9.4 mg·l~(-1))对树脂动态脱氮除磷的影响.结果表明,3种树脂都具有较好的脱氮除磷效果,达到TP穿透点(0.1 mg·l~(-1),去除率92%)时,201×4树脂具有最大的穿透体积(418 BV),但其对NO_3~--N的去除率(69%)明显低于其它树脂(97%-98%);3种树脂对SO_4~(2-)和HA的去除率分别为97%-99%,71%-80%;常规酸碱活化使树脂穿透体积较再生液活化仅提高了12%;超滤膜法和臭氧氧化法预处理对原水HA的去除率分别为27%和68%;原水HA浓度增加使树脂穿透体积从28lBV降至239BV,同时NO_3~-去除率从80%上升至92%.