Photochemical Degradation of Hydrophilic Xenobiotics in the UV/H2O2-process. Influence of Humic Matter on the Degradation Rate of 2-Amino-1-naphthalenesulfonate and Ethylenediaminetetraacetate

Photochemical oxidation methods are able to eliminate hydrophilic xenobiotics with a high efficiency. In waters with high DOC values caused by humic substances (HS) which are able to absorb UV light, problems can result. The degradation rates of the micropollutants using irradiation wavelengths in the range between λ = 200 nm to λ = 260 nm are significantly influenced by HS. This is mainly caused by the high absorption of the HS at shorter wavelength. In the presence of HS, the photolytic degradation of EDTA and FeEDTA was slowed down by an inner filter effect. A similar tendency could be seen for the photolytic degradation of 2-amino-1-naphthalenesulfonate where additional effects to the inner filter effect were also operating. In the UV/H₂O₂-process, the decrease of the degradation rate could be assigned to the ability of the HS to scavenge HO radicals.     

Degradation of Aqueous Atrazine and Metazachlor Solutions by UV and UV/H2O2 — Influence of pH and Herbicide Concentration Abbau von Atrazin und Metazachlor in wäßriger Lösung durch UV und UV/H2O2 — Einfluß von pH und Herbizid-Konzentration

The degradation of two pesticides: atrazine and metazachlor was investigated in aqueous solution under UV-irradiation with and without H₂O₂. Rate constants of the photochemical degradation were determined applying a first order kinetics and quantum yields of the processes were calculated. This approach leads to an apparent decrease of the quantum yield with increasing initial pesticide concentration. At low H₂O₂ initial concentrations, the pesticide degradation was shown to be much more efficient than the degradation under UV-irradiation only. However, at high H₂O₂ concentrations (>2 mmol L^?1), the efficiency of the UV/H₂O₂ system dropped down and the quantum yields of degradation were lower than for the direct photolysis. In the absence of H₂O₂, no influence of the pH value on the photodegradation of the pesticides could be noticed in a range between pH 3 and pH 11. At low H₂O₂ initial concentrations, the photochemical degradation of the pesticides was much faster at pH 3 and pH 7 compared with the degradation at pH 11. The results emphasize the potential of optimized reaction conditions in advanced oxidation.     

Photocatalytic Degradation of 17α‐Ethinylestradiol and Inactivation of Escherichia coli Using Ag‐Modified TiO2 Nanotube Arrays

Ag‐modified TiO₂ nanotube arrays (Ag/TiO₂ NAs) were prepared and employed as a photocatalyst for degradation of 17α‐ethinylestradiol (EE2) and inactivation of Escherichia coli. The as‐synthesized Ag/TiO₂ NAs were characterized by field‐emission scanning electron microscope (FESEM), X‐ray diffraction (XRD), and X‐ray photoelectron spectroscopy (XPS). It was found that metallic Ag nanoparticles were firmly deposited on the TiO₂ NAs with the pore diameter of 100 nm and the length of 550 nm. Photocatalytic degradation of EE2 and inactivation of E. coli were enhanced effectively in an analogical trend using Ag/TiO₂ NAs. In particular, Ag/TiO₂ NAs exhibited the antimicrobial activity even in the absence of light. The Ag acted as a disinfection agent as well as the dopant of the modified TiO₂ NAs photocatalysis by forming a Schottky barrier on the surface of TiO₂ NAs. Inorganic ions suppressed the rates of photocatalytic degradation of EE2, with HCO having a more pronounced effect than NO or SO. Humic acid (HA) was found to increase the rate of EE2 degradation.     

Electro‐Catalytic Degradation of Phenol Organics with SnO2‐Sb2O3/Ti Electrodes

The effect of extraordinary degradation of phenol organics on the SnO₂‐Sb₂O₃/Ti electrode is investigated through experimental research and theoretical analysis. The phenol organics contained 4‐chloro‐phenol, 4‐bromo‐phenol, and 2‐iodo‐phenol. At a current density of 4 mA cm^–2 and an electrolysis time of 12 h, the degradation efficiency of the phenols was over 98% with a relatively short degradation time, whereas the degradation time of the PbO₂/Ti electrode surpassed 40 h while delivering 100% disposal efficiency. Therefore, the effectiveness of electrochemical (EC) oxidation by the SnO₂‐Sb₂O₃/Ti was superior to that of the PbO₂/Ti electrode. At the same time, the SnO₂‐Sb₂O₃/Ti had higher oxygen generation potential and lower electron consumption than the other electrodes. This was mainly due to the effect of the middle Sb₂O₃ layer, which due to its high porosity and good catalytic effect, contributed to a better catalysis than the SnO₂ part.     

Degradation of Monoazo Pigments Red 53:1 and Red 48:2 by Fenton,Photo‐Fenton and UV/Peroxide Reactions

The degradation reactions of two monoazo pigments, namely, Red 53:1 and Red 48:2, by Fenton, photo‐Fenton and UV/H₂O₂ systems have been studied. The efficiencies of the Fenton reactions increased with temperature, but the formation of solid agglomerates was observed when the reactions were carried out above 50°C indicating a coagulant action of Fe⁺² or Fe⁺³. Photo‐Fenton reactions irradiated by sunlight presented the best rate constants for cleavage of the azo bond and the naphthalene rings. The UV/H₂O₂ system exhibited the highest efficiency with respect to the consumption of H₂O₂. The presence of a carbonyl group in the ortho position of the naphthol ring hampered the oxidation of pigment Red 48:2 by hydroxyl radicals. This finding may be explained in terms of the acceptor character of the COOH group, and suggests the formation of a complex containing two six‐membered rings between Fe⁺³ and the pigment molecule.     

Degradation of Bezafibrate with UV/H2O2 in Surface Water and Wastewater Treatment Plant Effluent

Bezafibrate (BZF), a widely used lipid regulator, is a potential threat to ecosystems and human health in water, and the recent research showed that advanced oxidation processes (AOPs) are much more effective for BZF degradation. In this study, we investigated the photochemical decomposition of BZF in surface water and effluent from waste water treatment plants (WWTP) by UV/H₂O₂ process. The results showed that the UV/H₂O₂ process was a promising method to remove BZF at low concentration, generally at µg L^?1 level. When initial concentrations reach 100 µg L^?1 in the deionized water, >99.8% of BZF could be removed in 16 min under UV intensity of 61.4 µm cm^?2, at the H₂O₂ concentration of 0.1 mg L^?1, and neutral pH condition. Moreover, BZF degradation was inhibited in this process when humic acid (HA) and inorganic solution anions were added to the deionized water solutions, including chloride, nitrate, bicarbonate, and sulfate, significantly. In the surface water and effluent of WWTP, however, the removal efficiency of BZF was lower than that in the deionized water because of the interference of complex constituents in the surface water and effluent. Some main intermediates at the m/z range of 100–400 were observed by high performance LC‐MS (HPLC/MS) and a simple pathway of BZF degradation by UV/H₂O₂ was proposed.     

Degradation Pathway of the Photochemical Oxidation of Ethylenediaminetetraacetate (EDTA) in the UV/H2O2-process

The degradation pathway for the oxidation of EDTA in the UV/H₂O₂-process was investigated. In absence of iron ions, the mineralization of EDTA is dominated by the reaction of the HO-radicals generated by the photolysis of H₂O₂. The organic degradation products iminodiacetate (IMDA), glycinate, oxamate, glyoxylate, oxalate and formate, and the inorganic degradation products carbon dioxide, ammonia, nitrate, nitrite, and cyanate were found. In the presence of iron ions, photolytic decarboxylation processes inside the complex get an important role during degradation, and the organic degradation products ethylenediaminetriacetate (ED3A), ethylenediaminediacetate (EDDA), ethylenediaminemonoacetate (EDMA) were also found. By combining product studies with balances of carbon and nitrogen, the degradation pathway in the UV/H₂O₂-process could be elucidated. The degradation of EDTA was fast (k_deg = 0.012 s^–1), and no toxic degradation products were identified. Therefore, the process is well suited for the elimination of EDTA in water treatment.     

Degradation of Acid Pharmaceuticals in the UV/H2O2 Process: Effects of Humic Acid and Inorganic Salts

The presence of acid pharmaceuticals in water environments poses a potential threat to ecosystems and human health. Recent research has shown that photo oxidation processes are much more effective for removing these pharmaceuticals. However, the existence of humic acid (HA) could inhibit the clearance efficiency of this process. In this study, we investigated the photochemical degradation of six selected acid pharmaceuticals in surface water and effluent from wastewater treatment plants using the UV/H₂O₂ process. The results showed that HA can act as a photo sensitizer or a ^. OH sink, and its concentration had a significant inhibitory effect on the degradation of acid pharmaceuticals. Most of these pharmaceuticals were inhibited during this process when HA was added to deionized water solutions. In addition, the effects of chloride, bicarbonate, and nitrate on the degradation of these pharmaceuticals were different. The removal efficiency of these acid pharmaceuticals is lower in natural samples than in deionized samples because of the complex constituents in the latter.     

Factors Affecting UV/H2O2 Oxidation of 17α‐Ethynyestradiol in Water

In this study, bench‐scale experiments were conducted to examine the UV/H₂O₂ oxidation of 17α‐ethynyestradiol (EE2) in water in a batch operation mode. The EE2 degradation exhibited pseudo‐first‐order kinetics, and the removal was ascribed to the production of hydroxyl radicals (^?OH) by the UV/H₂O₂ system. Typically, the EE2 oxidation rate increased with increasing UV intensity and H₂O₂ dose, and with deceasing initial EE2 levels and solution pH. At EE2₀ = 650 µg/L, UV intensity = 154 µW/cm², H₂O₂ = 5 mg/L, and neutral pH, the UV/H₂O₂ treatment was able to remove 90% of the EE2 content within 30 min. Four anions commonly present in water were found to inhibit EE2 degradation to varying degrees: > > Cl^? > . Our results demonstrate that the described UV/H₂O₂ process is an effective method to control EE2 pollution in water.     

Oxidative Degradation of Orange II Dye in Water with Raw and Acid‐Treated ZnO,and MnO2

Commercial ZnO, MnO₂, and their acid‐treated forms were used as catalysts for oxidative degradation of Orange II dye in water. ZnO and MnO₂ were treated with 0.5, 0.75, or 1.0 N aqueous H₂SO₄. The acid treated oxides were found to be highly effective in bringing about degradation of Orange II in water. As much as 68.7% of the dye in an aqueous solution of 1 mg/L concentration could be degraded with untreated ZnO as the catalyst. The degradation increased to 79.5% with 1.0 N acid treated ZnO as the catalyst when the reaction was carried out at room temperature for 240 min. The catalytic activity was slightly affected by the solution pH in the range of 2.0–8.0. With MnO₂ as the catalyst, there was only 12.7% degradation of the dye, but this increased up to 100% when 0.5 N acid treated MnO₂ was used as the catalyst. It was found that a catalyst loading of 5.0 g/L of raw and acid‐treated ZnO and a loading of 0.5 g/L of raw and acid‐treated MnO₂ could bring about almost 100% degradation of Orange II in water in an interaction time of 240 min at room temperature.     

Effect of SO on 1,1,1‐Trichloroethane Degradation by Fe0 in Aqueous Solution

Sulfate in groundwater has been previously shown to change the reactivity of Fe⁰ in permeable reactive barriers for reducing chlorinated organics. To better understand the effect and mechanism of SO, the degradation of 1,1,1‐trichloroethane (TCA) by Fe⁰ in unbuffered aqueous solutions with and without SO was investigated. In a Fe⁰‐TCA‐H₂O system with initial pH of 2.0 to 10.0, the maximum removal rate of TCA was achieved at the initial pH 6.0 with pseudo‐first‐order constant K_obs 9.0 × 10^?3/min. But in a Fe⁰‐TCA‐Na₂SO₄‐H₂O system, the removal rate of TCA decreased remarkably with a reduction in K_obs to 1.0 × 10^?3/min, and the pH varied from 6.0 to 9.6, indicating an inhibition of TCA dehydrochlorination by SO. Sulfate remarkably inhibited TCA degradation via changing the route of Fe⁰ dissolution. It accelerated the dissolution of Fe⁰ and transformed the intermediate form Fe(OH)_ads to Fe₂(SO₄)_ads, which weakened the affinity between Fe and TCA, and thus depressed the degradation of TCA by Fe⁰.     

湖泊污染底泥疏浚后新生沉积物-水界面溶解氧的动态响应

借助微氧电极测试技术对太湖贡湖湾试验区疏浚后的新生界面溶解氧动态进行一年的跟踪调研,分析溶解氧在新生微米级界面的分布特征、扩散通量以及界面附近有机质矿化速率.结果表明疏浚后半年内,溶解氧在表层沉积物的侵蚀深度增大,氧化层明显加厚.氧气在新生界面表层沉积物中呈指数下降,但衰减相对较缓.在连续一年的跟踪调查中发现,仅秋季新生界面附近溶解氧浓度明显高于对照,而在其他月份无差异.污染底泥疏浚后一个月内氧扩散通量及有机碳矿化速率下降最为明显,仅为疏浚前的13%,其他月份沉积物-水界面氧的扩散通量、氧气的消耗速率、有机碳的降解速率均有不同程度下降,疏浚后新生界面氧气交换速率下降以及由此导致的有机碳矿化过程变缓可能深刻影响界面生源要素的迁移过程.     

Soil H<Subscript>2</Subscript> and CO<Subscript>2</Subscript> Surveys at Several Active Faults in Japan

Soil H₂ and CO₂ surveys were carried out along seven active faults and around the aftershock region of the 2000 Tottori-ken Seibu earthquake in Japan. Diffuse CO₂ effluxes were also measured along one fault and around the 2000 aftershock region. The results show highly variable H₂ concentration in space and time and it seems that the maximum H₂ concentration at each active fault correlates with fault activity as exemplified by the time of the latest big earthquakes. Even though observed H₂ concentrations in four faults were markedly lower than those collected previously in the latter half of the 1970s, it is evident that the higher H₂ concentrations in this study are due to the addition of the fault gases. Comparing the chemical composition of trapped gases (H₂: 5–20% and CO₂/H₂: 0.5–12) in fractured rocks of drill cores bored at the Nojima fault, a soil gas sample with the highest H₂ concentration showed large amounts of the trapped fault gas, diluted with atmospheric component. The profile experiment across a fracture zone at the Yamasaki fault showed higher H₂ concentrations and lower CO₂/H₂ ratios as was observed in soil gas from the fracture zone. A few days after the 2000 Tottori-kei Seibu earthquake, no CO₂ effluxes related to the occurrence of earthquakes were observed at the aftershock region. However, only above the epicenter zone, relatively high H₂ concentrations in soil gases were observed.     

Glutamic Acid Modified Fenton System for Degradation of BTEX Contamination

The present study employed a modified Fenton system that aims to extend the optimum pH range towards neutral conditions for studying the oxidation of benzene, toluene, ethyl benzene, xylenes (BTEX) using glutamic acid (Glu) as an iron chelator. Addition of 20 mM Glu greatly enhanced the oxidation rate of BTEX in modified Fenton system at pH 5–7. A rapid mass destruction (>97% after 1 h) of BTEX as a water contaminant carried out in the presence of 500 mM H₂O₂, 10 mM Fe²⁺, and 20 mM Glu at pH 5 could be shown. The efficiency of this modified Fenton's system for mass destruction of BTEX in contaminated water was measured to estimate the impact of the major process variables that include initial concentrations of soluble Fe, H₂O₂, Glu (as metal chelating agent), and reaction time.     

Performance of A Combination Process of UV/H2O2/Micro‐Aeration for Oxidation of Dichloroacetic Acid in Drinking Water

The decomposition of dichloroacetic acid (DCAA) in water using a UV/H₂O₂/micro‐aeration process was investigated in this paper. DCAA cannot be removed by UV radiation, H₂O₂ oxidation or micro‐aeration alone, while UV/H₂O₂/micro‐aeration combination processes have proved effective and can degrade this compound completely. With initial concentrations of about 110 μg/L, more than 95.1% of DCAA can be removed in 180 min under UV intensity of 1048.7 μW/cm², H₂O₂ dosage of 30 mg/L and micro‐aeration flow rate of 2 L/min. However, more than 30 μg/L of DCAA was left after 180 min by UV/H₂O₂ combination process without micro‐aeration with the same UV intensity and H₂O₂ dosage. The effects of applied UV radiation intensity, H₂O₂ dose, initial DCAA concentration and pH on the degradation of DCAA have been examined in this study. Degradation mechanisms of DCAA with hydroxyl radical oxidation have been discussed. The removal rate of DCAA was sensitive to operational parameters. There was a linear relationship between rate constant k and UV intensity and initial H₂O₂ concentration, which indicated that a higher removal capacity can be achieved by improvement of both factors. A newly found nitrogenous disinfection by‐product (N‐DBP)‐DCAcAm, which has the potential to form DCAA, was easier to remove than DCAA by UV/H₂O₂ and UV/H₂O₂/micro‐aeration processes. Finally, a preliminary cost comparison revealed that the UV/H₂O₂/micro‐aeration process was more cost‐effective than the UV/H₂O₂ process in the removal of DCAA from drinking water.     

Carbon fluxes from eroding peatlands – the carbon benefit of revegetation following wildfire

Peatlands are among the largest long‐term soil carbon stores, but their degradation can lead to significant carbon losses. This study considers the carbon budget of peat‐covered sites after restoration, following degradation by past wildfires. The study measured the carbon budget of eight sites: four restored‐revegetated sites, two unrestored bare soil control sites, and two intact vegetated controls over two years (2006–2008). The study considered the following flux pathways: dissolved organic carbon (DOC); particulate organic carbon (POC); dissolved carbon dioxide (CO₂); primary productivity; net ecosystem respiration, and methane (CH₄). The study shows that unrestored, bare peat sites can have significant carbon losses as high as 522 ± 3 tonnes C/km²/yr. Most sites showed improved carbon budgets (decreased source and/or increased sink of carbon) after restoration; this improvement was mainly in the form of a reduction in the size of the net carbon source, but for one restored site the measured carbon budget after four years of restoration was greater than observed for vegetated controls. The carbon sequestration benefit of peatland restoration would range between 122 and 833 tonnes C/km²/yr. Copyright © 2011 John Wiley & Sons, Ltd.     

Photooxidation Degradation of Reactive Brilliant Red K‐2BP in Aqueous Solution by Ultraviolet Radiation/Sodium Hypochlorite

Photooxidation degradation of Reactive Brilliant Red K‐2BP (K‐2BP) aqueous solution by ultraviolet irradiation/sodium hypochlorite (UV/NaClO) was investigated. The effects of NaClO dosage, pH, temperature and initial dye concentrations were studied. A possible degradation pathway of K‐2BP was investigated. Acidic or neutral conditions were beneficial to the decolorization of K‐2BP aqueous solution. However, alkaline conditions facilitated chemical oxygen demand (COD) removal. Increasing the solution temperature from 20 to 50°C increased the removal of color and COD. However, at 60°C, the final percentage color and COD removal decreased by approximately 17 and 10%, respectively. Based on the products indentified and theoretical analysis, N=N cleavage and C‐N cleavage were possible initial steps in the degradation of K‐2BP. From the results of this work, we conclude that treatment of UV/NaClO is an efficient method to degrade K‐2BP in aqueous solution.     

Degradation of Malathion and Parathion by Ozonation,Photolytic Ozonation,and Heterogeneous Catalytic Ozonation Processes

The oxidation of organophosphorus pesticides (OPPs), such as malathion and parathion, in aqueous solution was studied using conventional ozonation (O₃), photolytic ozonation (O₃/UV, O₃/UV/H₂O₂), and heterogeneous catalytic ozonation (O₃/TiO₂/UV) processes. Experiments were performed in batch mode at laboratory scale and processes were compared in terms of disappearance kinetics. The best results of pesticide mineralization were obtained when TiO₂ particles in combination with ozone (O₃) and UV photolysis (λ = 254 nm) were applied. Decomposition of 99% of parent compounds were achieved in 10 min and oxon derivatives were completely removed in 30 min. The initial reaction rate increases linearly with increasing catalyst amount. Toxicity measurements of the treated solutions were carried out in order to evaluate the efficiency of the treatment methods. No detoxification was achieved for O₃ and O₃/UV applications. Heterogeneous photocatalytic ozonation was shown to be feasible for achieving complete decomposition of OPPs and their oxon intermediates.     

Hg2+对水鳖(Hydrocharis dubia)叶片生理生化及超微结构的毒害效应

研究了不同浓度Hg^2 对水鳖叶片光合放氧速率,呼吸速率、细胞膜透性、硝酸还原酶活性以及超微结构的毒害影响,结果表明,随着Hg^2 浓度的增加,水鳖叶片的光合放氧速率逐渐下降,呼吸速率、硝酸还原酶活性先升后降,而细胞膜透性则逐渐上升,电镜观察发现,水鳖叶细胞受Hg^2 毒初期,染色质凝集,叶绿体中类囊体片层以及线粒体嵴突膨胀,随着叶细胞遭受毒害程度的加深,核膜破裂,染色质与核质消失,叶绿体膨胀解体,线粒体空泡化。