The influence of some biological antioxid ants on the light emission from the oxytetracycline oxidation reaction

The effect of the Superoxide radical (O₂ ^–)‐, hydroxyl radical (HO')‐inhibitors, singlet oxygen (¹O₂)‐quenchers and catalase on the light emission during autoxidation reaction of oxytetracycline was measured. The influence of the ¹O₂‐quenchers was investigated quantitatively and the rate constants were established.     

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.     

Complexation of iron by salicylic acid and its effect on atrazine photodegradation in aqueous solution

The photodegradation of atrazine and the photochemical formation of Fe(II) and H₂O₂ in aqueous solutions containing salicylic acid and Fe(III) were studied under simulated sunlight irradiation. Atrazine photolysis followed first-order reaction kinetics, and the rate constant (k) corresponding to the solution of Fe(III)-salicylic acid complex (Fe(III)-SA) was only 0.0153 h^?1, roughly one eighth of the k observed in the Fe(III) alone solution (0.115 h^?1). Compared with Fe(III) solution, the presence of salicylic acid significantly enhanced the formation of Fe(II) but greatly decreased H₂O₂ generation, and their subsequent product, hydroxyl radical (˙OH), was much less, accounting for the low rate of atrazine photodegradation in Fe(III)-SA solution. The interaction of Fe(III) with salicylic acid was analyzed using Fourier-transform infrared (FTIR) spectroscopy and UV-visible absorption, indicating that Fe(III)-salicylic acid complex could be formed by ligand exchange between the hydrogen ions in salicylic acid and Fe(III) ions.     

Effect of natural aquatic humic substances on the photodegradation of bisphenol A

The photochemical degradation of bisphenol A (BPA) was studied in the presence of natural humic substances from different origins under simulated solar irradiation. BPA underwent insignificant direct photolysis in neutral water, but rapid photosensitized degradation in four humic substances solutions via pseudo-first-order reaction occurred. The photo-degradation rate of BPA was insensitive to the different initial BPA concentrations and was inhibited in aerated solution compared with the deoxygenated medium. The reactive oxygen species (ROS) such as ·OH and ¹O₂ produced from excitation of humic substances under irradiation was determined from the quenching kinetic experiment using molecular probe. The five main intermediate photoproducts of BPA in Nordic lake fulvic acid (NOFA) were tentatively identified using gas chromatography/mass spectrometer (GC/MS). Based on the identification of ROS and the analysis of photoproduct formation, the possible phototransformation pathways of BPA were proposed, involving the direct photolysis due to the energy transfer from the triplet state humic substance (³HS*) to BPA molecules and hydroxyl radical addition and oxidation as well.     

Effects of hypoxia on the respiratory and circulatory regulation of Nephrops norvegicus

The burrowing decapod Nephrops norvegicus (L.) was kept under various degrees of hypoxia in order to measure respiration, heart rate, scaphognathite rate, haemolymph oxygen content and pH. An emergence reaction to hypoxia occurred only in dim light (<10^-2 m-c) or darkness, but after 10 d of moderate hypoxia the decapods showed no emergence response at all. The weight specific respiration of quiescent individuals was relatively low and increased only slightly in hypoxia (P_wO₂=40 torr). Heart rate, about 50 beats min^-1, changed little during hypoxia, down to P_wO₂=40 torr, whereas scaphognathite rates rose from about 60 beats min^-1 at normoxia to peak at 120 beats min^-1 at P_wO₂=40 torr. The oxygen extraction efficiency (E) remained at 20 to 30% during the first hour of hypoxia then rose gradually to maximum values of 30 to 40%. A small respiratory alkalosis of the blood became evident only after 4h of hypoxia (P_wO₂=50 torr). Normoxic postbranchial O₂ tensions (P_aO₂) were low (25–30 torr) and showed only a small decline during hypoxia. Over 10 to 13 d in moderate hypoxia an effective biosynthesis of 0.024 mM haemocyanin individual^-1 d^-1 occurred in fed decapods, whereas controls (normoxic) showed no significant change in pigment levels. A linear relationship between oxygen carrying capacity and haemocyanin concentration was found. It is contended that N. norvegicus is better able to cope with periodic exposure to hypoxia when food of sufficient quantity and quality is available.     

五氧化二钒类Fenton降解邻苯二甲酸二乙酯的机制研究

发展了基于五氧化二钒(V_2O_5)和过氧化氢(H_2O_2)的新型类Fenton体系,探索了此体系产生羟基(·OH)的机制及降解邻苯二甲酸二乙酯(DEP)的效率;并考察了V_2O_5投加量、H_2O_2浓度,以及草酸对DEP降解的影响。结果表明,当V_2O_5投加量为0.1 g·L-1,H_2O_2浓度为2.0 mmol·L-1,反应24 h后,对DEP(25 mg·L-1)的降解率可达61.1%,增加或降低V_2O_5投加量和H_2O_2浓度均不利于DEP的降解。利用电子顺磁共振技术(Electron Paramagnetic Resonance,EPR)耦合5,5-二甲基-1-吡咯啉氮氧化物(DMPO)为捕获剂对反应体系中的主导自由基进行鉴定,发现·OH是体系降解DEP的主要活性物种,利用苯甲酸作为探针分子实现了·OH的间接定量,并初步推测了V_2O_5活化H_2O_2的过程。     

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.     

Intra-colonial variability in light acclimation of zooxanthellae in coral tissues of Pocillopora damicornis

We investigated heterogeneity of light acclimation of photosynthesis in sun- and shade-adapted coenosarc and polyp tissues of Pocillopora damicornis. The zooxanthellar community within P. damicornis colonies at Heron Island is genetically uniform, yet they showed a large degree of plasticity in their photo-physiological acclimation linked to light microclimates characterised by fibre-optic microprobes. Microscale scalar irradiance measurements showed higher absorption in polyp than coenosarc tissues and higher absorption in the more densely pigmented shade-adapted polyps than in sun-adapted polyps. The combination of an O₂ microelectrode with a fibre-optic microprobe (combined sensor diameter 50–100 μm) enabled parallel measurements of O₂ concentration, gross photosynthesis rate and photosystem II (PSII) quantum yield at the coral surface under steady-state conditions as a function of increasing irradiances. Lower O₂ levels at the tissue surface and higher compensation irradiance indicated a higher respiration activity in sun-adapted polyp tissue as compared to shade-adapted polyps. Shade-adapted coenosarc and polyp tissues exhibited lower maxima of relative electron transport rates (rETR_max) (84±15 and 41±10, respectively) than sun-adapted coenosarc and polyp tissues (136±14 and 77±13, respectively). Shade-adapted tissues showed stronger decrease of rETR at high scalar irradiances as compared to sun-adapted tissues. The relationship between the relative PSII electron transport and the rate of gross photosynthesis, as well as O₂ concentration, was non-linear in sun-adapted tissues over the entire irradiance range, whereas for shade-adapted tissues the relationship became non-linear at medium to high scalar irradiances >200 μmol photons m⁻² s⁻¹. This suggests that rETR measurements should be used with caution in corals as a proxy for photosynthesis rates. The apparently high rates of photosynthesis (oxygen evolution rates) suggest that there must be a considerable electron transport rate through the photosystems that is not observed by the rETR measurements. This may be accounted for by vertical heterogeneity of zooxanthellae in the tissue and the operation of an alternative electron pathway such as cyclic electron flow around PSII.     

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.     

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.     

Removal of organophosphorus pesticides from water by electrogenerated Fenton's reagent

Aqueous solutions of organophosphorus pesticides were completely mineralized via in-situ generated hydroxyl radicals (HO^·) by the Electro-Fenton process. Formation of Fenton's reagent (H₂O₂, Fe²⁺) was carried out by simultaneous reduction of O₂ and Fe³⁺ on carbon cathode in acidic medium. The electrochemistry combined with Fenton's reagent provides an excellent way to continuously produce the hydroxyl radical, a powerful oxidant. We demonstrate the efficiency of the Electro-Fenton process to degrade three organophosphorus insecticides: malathion, parathion ethyl and tetra-ethyl-pyrophosphate (TEPP). Degradation kinetics and removals of chemical oxygen demand (COD) have been investigated. Here we show that the mineralization efficiency was over 80% for three organophosphorus pesticides.     

Toxic effects of enrofloxacin on Scenedesmus obliquus

In this article, the toxic effects of Enrofloxacin (ENFX) on Scenedesmus obliquus were studied, through investigating the growth, photosynthetic pigments, and protein contents. The possible toxic mechanisms of ENFX were analyzed by determining the superoxide dismutase (SOD) activity, malondialdehyde (MDA) content, proline content, and superoxide anion (O ₂ ^? ) generation rate. Results showed that the growth of algae was inhibited by ENFX and the 50% effective concentration (EC₅₀) values for 24, 48, 72, and 96 h of ENFX were 88.39, 63.86, 45.10, and 59.16 mg·L^?1, respectively. After treated with ENFX for 96 h, the contents of photosynthetic pigments decreased with the increase of ENFX concentration, the content of soluble protein and the activity of SOD increased and then decreased, and the generation rate of superoxide anion (O ₂ ^? ) increased continually. The contents of MDA and proline changed little in lower ENFX concentration groups, but increased rapidly when treated with higher concentration groups. These results suggested that ENFX affected the growth of S. obliquus, and the main toxicity mechanism was that algal cells generated the reactive oxygen species under ENFX stress, and then the reactive oxygen species (ROS) induced the oxidation damages of biologic macromolecules and changed the biomembrane permeability further.     

Zur Abhängigkeit des Herzschlags vom O2-Gehalt des Wassers bei Carcinus maenas

Heart beats of unrestrained Carcinus maenas L. have been recorded by means of aspiration electrodes. The heart rate shows a clear dependence upon the oxygen content of the sea water under otherwise constant conditions. There is a high degree of correlation between heart rate and oxygen concentration in the range between 0 cm³ and ca. 6 cm³ O₂/I sea water. From this point upwards no further dependence could be found. Very low (beneath 0.5 cm³ O₂/I water) and very high (over 12 cm³ O₂/I water) concentrations lead to arrhythmia and often to long lasting intervals in the heart beats. It is suggested that this correlation is due to the oxygen-dependent excitability of the neurones generating the beats in the neurogenic hearts of crustaceans.     

Removal of acid yellow 36 using Box–Behnken designed photoelectro-Fenton: a study on removal mechanisms

Photoelectro-Fenton was applied for the removal of acid yellow 36 (AY36) from synthetic aqueous solution using iron electrodes. A Box–Behnken design was used for optimization of the effects of pH, H₂O₂ concentration, current density, and reaction time. Individual effects of these variables were more important than their interaction effects. The derived model was in good agreement with the experimental results. Total organic carbon was determined in solution and sludge in order to clarify the removal mechanism. Increase of H₂O₂ concentration and current density led to domination of oxidation and coagulation mechanisms, respectively. The effects of scavenging and inhibiting agents were also investigated: (1) presence of alcohols can reduce the efficiency through competition with dye for reaction with hydroxyl radicals; (2) anions (NO₃^?, HCO₃^?, and H₂PO₄^?) scavenged hydroxyl radicals and reduced decolorization of AY36.     

Sensitized photooxygenation of mononitrophenols in micellar media

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

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

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

Photocatalytic formation of hydrogen peroxide over highly porous illuminated ZnO and TiO2thin film

The photocatalytic formation of hydrogen peroxide over ZnO and TiO₂thin films has been investigated in aqueous phase in the presence of molecular oxygen as an electron acceptor. These films are highly porous and showed enhanced catalytic activity in the photochemical formation of hydrogen peroxide. The amount of H₂O₂formed during 2 hour light illumination is 4–6 μM and the rates of formation of hydrogen peroxide of both the films are almost comparable. The yield of hydrogen peroxide increases with the increase in irradiation time and a trend of steady state concentration of H₂O₂is observed in the case of TiO₂thin film. Photodissolution of ZnO particles is observed in some extent during the process of prolonged UV light illumination.     

Luminescence in the oxidation of isoproterenol by the superoxide anion radical in dimethyl sulfoxide

Chemiluminescence appearing during oxidation of isoproterenol using chemical system involving superoxide anion radical has been studied. Chemiluminescence and fluorescence spectra were measured. The chemiluminescence spectrum was measured with cut‐off filters and revealed bands with maximum at 440, 480, 550, 640 and 700 nm. The bands at 480, 640 and 700 nm were similar to those observed for singlet oxygen. The fluorescence spectrum exhibited maximum at 560 nm.

The inhibitory effect of several biologically important compounds known as O₂ ^?‐ HO^? and ¹O₂ scavengers on the light emission was studied.

The obtained results indicate that oxidation of isoproterenol by O₂ ^?‐ involves products in the electronically excited states. The data also seem to indicate the protective effect of isoproterenol on the deoxyribose degradation.     

Inhibitory effect of the iron chelator desferrioxamine (Desferal) on the generation of activated oxygen species by Chattonella marina

Recent studies demonstrated that the toxic red tide phytoplankton Chattonella spp. produce activated oxygen species such as superoxide anion (O ₂ ^- ), hydrogen peroxide (H₂O₂), and hydroxyl radicals (·OH), which may be responsible for the toxicity of this flagellate. However, the mechanism behind the production of these oxygen radicals and H₂O₂ by Chattonella spp. is largely unknown, and the physiological significance of activated oxygen species for Chattonella spp. is also unclear. In the present study, we investigated the involvement of iron in the generation of O ₂ ^- and H₂O₂ by C. marina. The generation of O ₂ ^- by C. marina was related to the growth phase; the highest rate of O ₂ ^- production was observed during the exponential growth phase. However, no such increase during the exponential growth phase was observed in C. marina growing in an iron-deficient medium, even though the growth of C. marina was not significantly affected by iron-deficiency during the first 4 d. In addition, the iron chelator desferrioxamine (Desferal) strongly inhibited the generation of both O ₂ ^- and H₂O₂ by C. marina in a concentration-dependent manner. The growth of C. marina was also inhibited by Desferal. Furthermore, in the presence of 500 M Desferal, C. marina-induced growth inhibition of the marine bacteria Vibrio alginolyticus was almost completely abolished. These results suggest that iron is required for the generation of activated oxygen species by C. marina, as well as for its own growth.     

Bioreduction of nitrate in groundwater using a pilot-scale hydrogen-based membrane biofilm reactor

A long-term pilot-scale H₂-based membrane biofilm reactor (MBfR) was tested for removal of nitrate from actual groundwater. A key feature of this second-generation pilot MBfR is that it employed lower cost polyester hollow fibers and still achieved high loading rate. The steady-state maximum nitrate surface loading at which the effluent nitrate and nitrite concentrations were below the Maximum Contaminant Level (MCL) was at least 5.9 g·N·(m²·d)^?1, which corresponds to a maximum volumetric loading of at least 7.7 kg·N·(m³·d) ^?1. The steady-state maximum nitrate surface area loading was higher than the highest nitrate surface loading reported in the first-generation MBfRs using composite fibers (2.6 g·N·(m²·d)^?1). This work also evaluated the H₂-utilization efficiency in MBfR. The measured H₂ supply rate was only slightly higher than the stoichiometric H₂-utilization rate. Thus, H₂ utilization was controlled by diffusion and was close to 100% efficiency, as long as biofilm accumulated on the polyester-fiber surface and the fibers had no leaks.     

Degradation of carbendazim by UV/H<Subscript>2</Subscript>O<Subscript>2</Subscript> investigated by kinetic modelling

The transformation of the fungicide carbendazim (methyl-2 benzimidazole carbamate) induced by hydroxyl radical generated by the UV photolysis of H₂O₂ has been studied in dilute aqueous solution. The efficient reaction of hydroxyl radicals with carbendazim led to the rapid degradation of carbendazim. The study of reaction kinetics yielded a second order rate constant of 2.2±0.3 10⁹ M⁻¹ s⁻¹ for HO^· radicals with carbendazim. This value is in agreement with a high reactivity of HO^· radicals with carbendazim. Most degradation products were identified by high performance liquid chromatography mass spectrometry (HPLC-MS). In the presence of hydrogenocarbonate and carbonate ions, hydroxyl radicals were quenched and in turn carbonate radicals CO₃ ^·− were formed. Carbonate radicals are indeed known to react efficiently with compounds containing electron-rich sites such as nitrogen or sulfur atoms. The use of a kinetic modelling software gave evidence for the occurrence of such reactions with carbendazim. The second order rate constant of carbonate radical with carbendazim was equal to 6±2 10⁶ M⁻¹ s⁻¹. Electronic Publication