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.     

Photochemical Degradation of Hydrophilic Xenobiotics in the UV/H2O2-process. Influence of Bicarbonate on the Degradation Rate of EDTA, 2-Amino-1-naphthalenesulfonate,Diphenyl-4-sulfonate,and 4,4′-Diaminostilbene-2,2′-disulfonate

Hydrophilic xenobiotics can be eliminated in the UV/H₂O₂-process. The oxidation in this process is enhanced by the photolytically generated HO radicals. Bicarbonate is able to scavenge HO radicals. So it was expected that the degradation rates of the investigated xenobiotics were affected by the influence of bicarbonate. In contrast to the widely described decrease of the degradation rate, a much more complex situation was found in this investigation. The degradation rates of 2-amino-1-naphthalenesulfonate and diphenyl-4-sulfonate were decreased and reached for high concentrations of bicarbonate the values of the photolytical degradation rate. The degradation of 4,4′-diaminostilbene-2,2′-disulfonate was accelerated significantly in the presence of bicarbonate. The degradation rate of EDTA was increased at small concentrations of bicarbonate and decreased at higher concentrations.     

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.     

Production of Laccase from Coriolus versicolor and Its Application in Dye Decolorization in Combination with UV/H2O2 Technique

The relative ability of Coriolus versicolor to grow on coir fiber as a ligninocellulosic material was examined. Addition of yeast extract to the culture increased laccase activity, which was further enhanced to the level of 1976 U/L by addition of 1 mM copper sulfate. Laccase thus produced was used without further purification for the decolorization of various dye solutions. Decolorization efficiency was compared with the conventional environment friendly oxidation technique using hydrogen peroxide in the presence of UV radiations. Laccase showed good decolorization in most of the cases. Excellent results were achieved when the dye solution was treated successively with laccase and UV/H₂O₂ wherein more than 80% decolorization was achieved. This value is remarkably higher than that attained either by the enzyme or UV/H₂O₂ photolysis alone.     

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.     

Treatment of Refractory Organics Contained in Actual Agro‐Industrial Wastewaters by UV/H2O2

In this work, the treatment of actual agro‐industrial wastewaters (IWW) by a UV/H₂O₂ process has been investigated. The aqueous wastes were received from industrial olive oil mills and then treated by laboratory scale physicochemical methods, i. e., coagulation using ferrous and aluminum sulfate, decantation, filtration and adsorption on activated carbon. These wastes are brown colored effluents and have a residual chemical oxygen demand (COD) in the range of 1800 to 3500 mgO₂ L^–1, which cannot be further eliminated with physicochemical processes. The UV/H₂O₂ treatments were carried out under monochromatic irradiation at 254 nm using a thermostated reactor equipped with a mercury vapor lamp located in an axial position. The effects of initial H₂O₂ concentration, initial COD, pH and temperature have been studied in order to determine the optimum conditions for maximum color and COD removals. The experimental results reveal the suitability of the UV/H₂O₂ process for both removal of high levels of COD and effectively decolorizing the solution. In particular, 95% of color removal and 90% of COD removal were obtained under conditions of pH = 5 and 32°C using 2.75 g H₂O₂ g^–1 COD L^–1 during 6 h of UV‐irradiation. The treatment is unaffected by pH over the range 2 to 9. In addition, the COD removal is improved by increasing the temperature, whereas the color removal has not been affected by this parameter. The results show that the hydroxyl radicals generated from the catalytic decomposition of H₂O₂ by UV‐irradiation of the solution could be successfully used to mineralize the organics contained in IWW. The mineralization of the organics seems to occur in three main sequential steps: the first is the rapid decomposition of tannins leading to aromatic compounds, which are confirmed by the decolorization of the IWW; the second step corresponds to the oxidation of aromatics leading to aliphatic intermediates, which occurs by the cleavage of an aromatic ring, and is established by the removal of aromatics, and the final step is the slow oxidation of the aliphatic intermediates, which is measured by the COD removal.     

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 of organic matter from wastewater using advanced primary treatment by O3 and O3/UV in a pilot plant

The oxidation of organic matter from wastewater using ozone, ultraviolet radiation and ozone/UV oxidation was evaluated in a pilot plant, applying a continuous effluent arising from the Autonomous Metropolitan University wastewater treatment plant. The oxidation was measured as the efficiency to remove organic load, measured as chemical oxygen demand. The use of ozone and UV was evaluated separately and in combination through a continuous process. Three different ozone doses (0.6–1.2 mg O₃/L) and three different UV radiation fluencies (6.7–20.12 mJ/cm²) were assessed. A synergistic effect of the combined process ozone/UV was demonstrated, and a maximal chemical oxygen demand reduction was achieved both processes. Due to residence times used (less than 1 min), 36% of chemical oxygen demand reduction was obtained when ozone treatment was evaluate separately and only 9% using ultraviolet radiation.     

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.     

Carbamazepine Removal from Groundwater: Effectiveness of the TiO2/UV,Nanoparticulate Zero‐Valent Iron,and Fenton (NZVI/H2O2) Processes

Pharmaceutical compounds, widely produced and used all around the world, are partly responsible for the widespread water pollution in the environment. Carbamazepine (CBZ) is an antiepileptic drug that persists in the environment for many years. In the present study, we used the TiO₂/UV, nanoparticulate zero‐valent iron (NZVI), and NZVI/H₂O₂ treatment processes to compare efficiency of CBZ removal from water. Influence of NZVI loading, H₂O₂ concentration, TiO₂ loading, UV lamp power, and the matrix (distilled water and groundwater) on CBZ removal efficiency was evaluated using full factorial design. Results indicated that the NZVI/H₂O₂ process oxidized CBZ within 5 min. On the other hand, the NZVI process alone did not reduce CBZ concentration after 120 min of process time. The NZVI/H₂O₂ process was equally effective in CBZ removal from both distilled water and groundwater whereas the TiO₂/UV process was less effective due to the presence of ions in groundwater. CBZ removal efficiency of the TiO₂/UV process declined 30% when the matrix was changed from distilled water to groundwater. Negative divalent ions, i.e., and , were the main cause of reduction of CBZ removal efficiency from groundwater. It is likely that these two ions adsorb onto, and consequently prevent the superoxide anion and hydroxyl radical OH^? from being generated on, the surface of the TiO₂.     

D/H and O/O ratios of water in the crater lake at Kusatsu-Shirane volcano, Japan

The D/H and ¹⁸O/¹⁶O ratios of water in the active crater lake situated on the Kusatsu-Shirane volcano, Japan are about 20 and 6‰, respectively, higher than local meteoric water. The ratios show seasonal variations superimposed on a gradual change over nine years. The isotopic ratios started to increase in early 1990 and decrease in the spring of 1995. The seasonal variation which is high in winter and low in summer correlates with the temperature difference between lake water and ambient air. The large temperature difference in winter enhances the evaporation of lake water and produces the enriched isotopic ratios relative to the ratios in summer. The accumulation of snow and the decrease in the flux of meteoric water into the lake strengthens the winter-time isotopic enrichment. The enriched isotopic ratios of the lake water over a long time result from the addition of an end member with heavy isotopic ratios contained in a thermal fluid supplied to the lake. Considering the water balance in the lake, the isotopic ratios of the thermal fluid were found to be close to the lake water itself, suggesting the circulation of the lake water seeping through lake floor. Based on the correlation between Cl⁻concentration and the isotopic ratios, the contribution by the heavy end member was estimated to be 25–36% relative to the enrichment by evaporation. The heavy end member could be a liquid phase evolved from a parental fluid, which is a mixture of local meteoric water and a magmatic fluid as found in high-temperature volcanic gases.     

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.     

Identifying the source of atmospheric moisture over arid deserts using stable isotopes (2H and 18O) in precipitation

Precipitation is a major component of the hydrologic cycle in arid desert areas. To date, however, few studies have been conducted on investigating the isotope characteristics and moisture sources of precipitation in arid desert environments. The Alxa Desert Plateau is a critical arid desert area in North China. This study is the first to analyse the stable isotopic composition of precipitation to identify the sources of atmospheric moisture over this plateau. Our results show that the δD and δ¹⁸O values of precipitation across the plateau change greatly at both daily and monthly timescales, and exhibit seasonal variations. Among the main meteorological parameters, atmospheric temperature is the most predominant factor controlling the isotopic composition and the δD–δ¹⁸O relationship of local precipitation. Analyses of the precipitation isotopes with the Hybrid Single Particle Lagrangian Integrated Trajectory (HYSPLIT) model reveal that (a) the westerly and polar moisture sources are the dominant controls on summer and winter precipitation and (b) the evaporation of local lake water significantly affects winter precipitation even though it only represents a small amount. Based on the isotope data of 2013–2016 precipitation, a local meteoric water line (LMWL) is derived: δD = (8.20 ± 0.22)·δ¹⁸O + (8.15 ± 2.16)‰ for the study site. Compared to the global meteoric water line, the LMWL has a greater slope and lower d‐excess. This can be explained by admixing of atmospheric moisture resulting from the evaporation of local lake water. Based on this LMWL, we are able to trace that groundwater of the Badain Jaran Desert originates from the surrounding mountains with altitudes of <4,000 m. The newly derived LMWL shows that the recharge altitudes of desert groundwater are overestimated on the basis of the previous LMWLs. This study not only provides insights into the hydrological cycle but also offers guidance for water resource management in arid desert areas of China. Additionally, this study provides techniques that can be applied to the analyses of precipitation isotopes in similar arid regions of the world.     

Soil characterization in urban areas of the Bajo Segura Basin (Southeast Spain) using H/V, F-K and ESAC methods

Bajo Segura Basin, placed in the south of Alicante province (southeast Spain), is a region of moderate seismicity, which presents frequent seismic episodes. This region, as the rest of south-eastern part of Spain, is growing both economically and demographically. Hence, the presence of soft soils in a seismic region where many towns and villages are placed shows the importance of an adequate characterization of the site effects study in this area.The present work investigates the use of noise measurements for soil characterization by the application of H/V method and array techniques: extended spatial autocorrelation (ESAC) and frequency-wave number (F-K) in three urban areas of the Bajo Segura Basin. The application of these methods will help us to estimate the resonance frequencies, as well as shear-wave velocity profiles, having a better understanding of the sediment depth and site effects phenomena at the studied places.The estimated velocity profiles are used to model the fundamental mode Rayleigh wave ellipticity curves and the S-wave site transfer functions. Finally, the correlation between this curves and the experimental H/V analysis has allowed us a better assessment of the site response in the studied areas.     

Temporal and spatial variation of water stable isotopes (18O and 2H) in the Kaidu River basin,Northwestern China

Water resources are the most critical factors to ecology and society in arid basins, such as Kaidu River basin. Isotope technique was convenient to trace this process and reveal the influence from the environment. In this paper, we try to investigate the temporal and spatial characteristics in stable isotope (¹⁸O and ²H) of surface water and groundwater in Kaidu River. Through the water stable isotope composition measurement, spatial and temporal characteristics of deuterium (δ²H) and oxygen 18 (δ¹⁸O) were analysed. It is revealed that (1) comparing the stream water line with the groundwater line and local meteorological water line of Urumqi City, it is found that the contribution of precipitation to surface water in stream runoff is the main source, whereas the surface water is the main source of groundwater. Groundwater is mainly drainage of surface runoff in the river; (2) in the main stream of Kaidu River, the spatial variability of river water showed a ‘heavier‐lighter‐heavier’ change along with the main stream for δ¹⁸O, and temporal variability showed higher in summer and lower in winter; (3) the δ¹⁸O and δ²H values of groundwater samples ranged from ?11.36 to ?7.97‰ and ?73.45 to ?60.05‰, respectively. There is an increasing trend of isotopic values along the groundwater flow path. The seasonal fluctuation of δ¹⁸O is not clear in most samples. Copyright © 2012 John Wiley & Sons, Ltd.     

Molecular cloning and mRNA expression of cytochrome P4501A1 and 1A2 in the liver of common minke whales (Balaenoptera acutorostrata)

This study presents full-length cDNA sequences of CYP1A1 and 1A2, in common minke whale (Balaenoptera acutorostrata) from the North Pacific. Both CYP1A1 and CYP1A2 cDNAs had an open reading frame of 516 amino acid residues, and predicted molecular masses were 58.3 kDa and 58.1 kDa, respectively. The deduced full-length amino acid sequence of CYP1A1 revealed higher identities with those of sheep (86%) and pig (87%), and that of CYP1A2 was most closely related to human (82%) and monkey CYP1A2 (82%) among species from which CYP1A2 has been isolated so far. Differences in certain conserved and functional amino acid residues of CYP1A1 and 1A2 between common minke whale and other mammalian species indicate the possibility of their specific metabolic function. Concentrations of organochlorine compounds (OCs) including PCBs and DDTs analyzed in common minke whale liver showed no significant correlation with hepatic mRNA expression levels of CYP1A1 and CYP1A2, indicating no induction of these enzymes by such OCs.     

Origin and evolution of two contrasting thermal groundwaters (CO2-rich and alkaline) in the Jungwon area,South Korea: Hydrochemical and isotopic evidence

In the Jungwon area, South Korea, two contrasting types of deep thermal groundwater (around 20–33 °C) occur together in granite. Compared to shallow groundwater and surface water, thermal groundwaters have significantly lower δ¹⁸O and δD values (> 1‰ lower in δ¹⁸O) and negligible tritium content (mostly < 2 TU), suggesting a relatively high age of these waters (at least pre-thermonuclear period) and relatively long subsurface circulation. However, the hydrochemical evolution yielded two distinct water types. CO₂-rich water (P_CO2 = 0.1 to 2 atm) is characterized by lower pH (5.7–6.4) and higher TDS content (up to 3300 mg/L), whereas alkaline water (P_CO2 = 10^− 4.1–10^− 4.6 atm) has higher pH (9.1–9.5) and lower TDS (< 254 mg/L). Carbon isotope data indicate that the CO₂-rich water is influenced by a local supply of deep CO₂ (potentially, magmatic), which enhanced dissolution of silicate minerals in surrounding rocks and resulted in elevated concentrations of Ca²⁺, Na⁺, Mg²⁺, K⁺, HCO₃⁻ and silica under lower pH conditions. In contrast, the evolution of the alkaline water was characterized by a lesser degree of water–rock (granite) interaction under the negligible inflow of CO₂. The application of chemical thermometers indicates that the alkaline water represents partially equilibrated waters coming from a geothermal reservoir with a temperature of about 40 °C, while the immature characteristics of the CO₂-rich water resulted from the input of CO₂ in Na–HCO₃ waters and subsequent rock leaching.