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1.
Optimizing electron spin resonance detection of hydroxyl radical in water   总被引:20,自引:0,他引:20  
Cheng SA  Fung WK  Chan KY  Shen PK 《Chemosphere》2003,52(10):1797-1805
The parameters affecting the electron spin resonance (ESR) detection of hydroxyl free radical in water are studied and optimized. The hydroxyl radical is generated by the Fenton reaction with iron (II) ammonium sulfate and hydrogen peroxide reacting in a phosphate buffer using N-tert-butyl-alpha-phenylnitron as the spin trap. The concentrations of Fe2+, H2O2, and phosphate buffer are the parameters studied. The Taguchi method and the orthogonal experiment design were used to evaluate the effects of these parameters on the ESR signal intensity. By the analysis of the signal-to-noise ratio and the analysis of variance, the order of importance of the various parameters on the hydroxyl radical formation is determined for optimal ESR detection of hydroxyl radical. The results will help the development of water purification technologies using hydroxyl free radical as a green oxidant.  相似文献   

2.
Han SK  Hwang TM  Yoon Y  Kang JW 《Chemosphere》2011,84(8):1095-1101
The generation of reactive species in an aqueous goethite suspension, under room light and aeration conditions, was investigated using the electron paramagnetic resonance (EPR) technique employing spin trap agents. The trap reagents, including 5,5-dimethylpyrroline N-oxide (DMPO) and 2,2,6,6-tetramethylpiperidine (TEMP), were used for the detection of OH radicals (OH) and singlet oxygen (1O2), respectively. On the addition of DMPO to the goethite suspended solution, a DMPO-OH adduct was formed, which was not decreased, even in the presence of the OH scavenger, mannitol. This result implied a false positive interpretation from the DMPO-OH EPR signal. In the presence of TEMP reagent, a TEMP-O signal was detected, which was completely inhibited in the presence of the singlet oxygen scavenger, sodium azide. With both DMPO-OH and TEMP-O radicals in the presence and absence of radical scavengers, singlet oxygen was observed to be the key species formed in the room-light sensitized goethite suspension. In the goethite/H2O2 system; however, both OH and singlet oxygen were generated, with significant portions of DMPO-OH resulting from both OH and singlet oxygen. In fact, the DMPO-OH resulting from OH should be carefully calculated by correcting for the amount of DMPO-OH due to singlet oxygen. This study reports, for the first time, that the goethite suspensions may also act as a natural sensitizer, such as fulvic acids, to form singlet oxygen.  相似文献   

3.
Li F  Ji L  Luo Y  Oh K 《Chemosphere》2007,67(1):13-19
With Carassius auratus, one of the main economic fish species in Eastern China as test material, this paper studied the hydroxyl radical generation and oxidative stress in its liver under the effect of 2,4,6-trichlorophenol (2,4,6-TCP). Different doses of 2,4,6-TCP were injected intraperitoneally into the fishes, and the Electron paramagnetic resonance (EPR) spectra of hepatic free radicals, activities of superoxide dismutase (SOD), catalase (CAT) and glutathione-s-transferase (GST), levels of reduced glutathione (GSH) and oxidized glutathione (GSSG), and malondialdehyde (MDA) contents were determined 24h after injection. The results showed that under the effects of 2,4,6-TCP, the generation of free radical that was considered to be hydroxyl radical increased significantly, the activities of antioxidant enzymes decreased, with CAT most strongly affected and followed by SOD and GST, the GSH level decreased significantly while GSSG level had little difference, resulting in a decreased GSH/GSSG ratio, and the MDA content increased significantly. All the test parameters showed that C. auratus was subjected to oxidative stress and damage when exposed to 2,4,6-TCP.  相似文献   

4.
Zhao XH  Zhou PJ  Chen X  Dong YL  Jiang SY  Ding L 《Chemosphere》2011,83(4):422-428
As a new threat to environment all through the world, perchlorate (ClO(4)(-)) was predominantly a thyrotoxin, and its toxic manifestations in non-thyroid were also documented. However, little is known about the effects of ClO(4)(-) on cell and organelle. Therefore, the present study was designed to investigate the effects of ClO(4)(-) on hepatocytes and mitochondria isolated from Carassius auratus from the direct viewpoint of energy by using the microcalorimetric method. The metabolic thermogenic curves of hepatocytes and mitochondria at 25°C were obtained. And the thermokinetic parameters, such as growth rate constant (k), inhibitory ratio (I), maximum thermal power (P(max)) and total thermal effect (Q(total)) have been calculated. The results indicated that the toxicity of ClO(4)(-) on hepatocytes was relevant to the concentration of ClO(4)(-). However, 10-100mgL(-1)ClO(4)(-) stimulated the metabolic activity of mitochondria and the toxicity of ClO(4)(-) on mitochondria only occurrenced when treated with higher concentration of ClO(4)(-). This study shown that mitochondria has a major impact on the metabolic thermogenic of hepatocytes, but not the only factor. Meanwhile, it demonstrated that microcalorimetry was a powerful tool for understanding biological processes and studying on the toxic action of environmental contaminants in cell or subcellular level.  相似文献   

5.
Under laboratory conditions, ecotoxicological effects of chlorpromazine (CPZ) on freshwater goldfish (Carassius auratus) were examined using the toxic culture experiment. The results showed that the median lethal concentration (LC50) of CPZ toxic to Carassius auratus in 24, 48 and 96 h was 1.11, 0.43 and 0.32 mg/L, respectively. Thus, CPZ is an extreme toxicant to goldfish. Furthermore, there were significantly positive correlations between the ecotoxicological effects of CPZ and its concentrations, and the toxicity became higher as the exposure time increased. The activity of superoxide dismutase (SOD) and catalase (CAT) in goldfish livers was significantly influenced by CPZ. At the same exposure time, the activity of SOD reduced first, and increased then, whereas the activity of CAT enhanced first and decreased then. At the same exposure levels of CPZ, the activity of SOD and CAT changed similarly, decreased first, then increased and decreased at last. Within the range of exposure concentrations, the changes in the activity of CAT can more easily reflect the oxidation stress in Carassius auratus by CPZ than those of SOD.  相似文献   

6.
Cobalt is an essential element, but at high concentrations it is toxic. In addition to its well-known function as an integral part of cobalamin (vitamin B12), cobalt has recently been shown to be a mimetic of hypoxia and a stimulator of the production of reactive oxygen species. The present study investigated the responses of goldfish, Carassius auratus, to 96 h exposure to 50, 100 or 150 mg L−1 Co2+ in aquarium water (administered as CoCl2). The concentrations of cobalt in aquaria did not change during fish exposure. Exposure to cobalt resulted in increased levels of lipid peroxides in brain (a 111% increase after exposure to 150 mg L−1 Co2+) and liver (30-66% increases after exposure to 50-150 mg L−1 Co2+), whereas the content of protein carbonyls rose only in kidney (by 112%) after exposure to 150 mg L−1 cobalt. Low molecular mass thiols were depleted by 24-41% in brain in response to cobalt treatment. The activities of primary antioxidant enzymes, superoxide dismutase (SOD) and catalase, were substantially suppressed in brain and liver as a result of Co2+ exposure, whereas in kidney catalase activity was unchanged and SOD activity increased. The activities of glutathione-related enzymes, glutathione peroxidase and glutathione-S-transferase, did not change as a result of cobalt exposure, but glutathione reductase activity increased by ∼40% and ∼70% in brain and kidney, respectively. Taken together, these data show that exposure of fish to Co2+ ions results in the development of oxidative stress and the activation of defense systems in different goldfish tissues.  相似文献   

7.
Luo Y  Su Y  Lin RZ  Shi HH  Wang XR 《Chemosphere》2006,65(6):1064-1073
In the present study, a secondary spin trapping technique was used followed by electron paramagnetic resonance (EPR) analysis, to study the potential of reactive oxygen species (ROS) production after fish (Carassius auratus) were injected i.p. with different doses (50, 100, 200, 250, 500mgkg(-1)) of 2-chlorophenol (2-CP). The ROS signal intensity of the EPR spectrum showed a significant increase (p<0.05, compared with the control) when the 2-CP dose was as low as 50mgkg(-1). There is a good relationship between the 2-CP administered doses and ROS generation. Based on the hyperfine splitting constants and shape of the EPR spectrum, the ROS which was generated in fish liver after intraperitoneal (i.p.) injection of 2-CP was identified as ()OH. SOD and CAT activities were found to be induced at lower doses of 2-CP. GSH levels fell below the control level following all treatments with 2-CP, and GSSG levels changed along with those of GSH. These observations indicated that the fish experienced oxidative stress. The strong positive correlation (r=0.966, p<0.005) between ()OH radical and lipid peroxidation suggested that lipid peroxidation was possibly induced by ()OH. The phase II detoxification enzyme glutathione-S-transferase (GST) may play an important role in 2-CP metabolism or excretion and, consequently, reduce ROS production. This study provides strong evidence that level of ROS is significantly increased in 2-CP stressed fish, and ROS may serve as a potential biomarker to indicate 2-CP contamination.  相似文献   

8.
Sun Y  Yu H  Zhang J  Yin Y  Shi H  Wang X 《Chemosphere》2006,63(8):1319-1327
In this study, laboratory experiment was carried out to determine phenanthrene bioaccumulation, depuration in whole fish and oxidative stress in the liver of freshwater fish Carassius auratus. Fish were exposed to 0.05 mg/l phenanthrene for different periods, while one control group was designated for each exposure group. Some fish after 7 days of exposure were transferred to diluted water. The concentrations of phenanthrene in fish were analyzed by HPLC. Twenty-four hours after the exposure, reactive oxygen species (ROS) were trapped by phenyl-tert-butylnitrone and detected by electron paramagnetic resonance (EPR). The activities of superoxide dismutase (SOD), catalase (CAT), and glutathione-s-transferase (GST) were also determined. The concentrations of phenanthrene in fish increased rapidly shortly after the start of the exposure, reached a maximum level at the 2 days, and then it declined quickly to low-level-steady state. The elimination process of phenanthrene could be divided into two periods-a fast elimination period following a slower loss period. The elimination curve could be fitted mathematically as the sum of two exponential functions according to two-compartment model: C(t)=2.72e(-1.065t) + 0.68e(-0.0364t). The PBN-radical adducts were detected in fish liver samples following the exposure 24h. The hyperfine splitting constants for the PBN-radical adducts were aN = 13.5 G, aH = 1.77 G and g value was 2.0058, which were consistent with those of PBN/()OH. The results indicated that the hydroxyl radical was probably significantly induced during the exposure of phenanthrene, as compared to the control group. The changes of activities of the antioxidant enzymes also were observed. In addition, after fish were removed from phenanthrene exposure, the recovery status of these antioxidant indices was explored. These results clearly indicated phenanthrene could be accumulated in fish and similar redox cyclings were produced, resulting in the changes of the activities of the antioxidant enzymes and the production of ROS with the oxidative stress.  相似文献   

9.
研究了含硫"类二噁英"化合物多氯代二苯并噻吩(PCDTs)中的2,3,7,8-四氯代二苯并噻吩(2,3,7,8-TCDT)在锦鲫(Carassius auratus)不同组织中的生物富集规律和对肝脏的氧化损伤.结果表明,2,3,7,8-TCDT在锦鲫各组织中的富集能力表现为肝脏>鳃>肌肉.2,3,7,8-TCDT在锦鲫...  相似文献   

10.
Roundup® is a glyphosate-based herbicide containing a mixture of surfactants. This paper evaluates the toxic effects of Roundup® and its main constituents on the goldfish, Carassius auratus, after 7 days exposure. Fish were exposed to 0.16, 0.032 and 0.0064 mg/L of Roundup® [containing 41% isopropylamine salt of glyphosate (G.I.S) and 18% polyoxyethylene amine (POEA)], G.I.S, and POEA. Their livers were taken for determining reactive oxygen species (ROS), superoxide dismutase (SOD) activity, malondialdehye (MDA) content and acetylcholinesterase (AChE) activity. Hydroxyl radical (·OH) could be induced by exposing Roundup® at a rate of 43%–111%, G.I.S at 90%–124% and POEA at142%–157%. A decreased SOD activity was observed in fish exposed to G.I.S and POEA. The contents of MDA significantly increased when exposed to Roundup® at all concentrations, 0.16 mg/L G.I.S and 0.032 mg/L POEA. The exposure led to an inhibition of AChE in livers overall during the experimental periods. POEA was more toxic than Roundup® or G.I.S during this experiment. AChE and ·OH are supposed to be sensitive biomarkers of the exposure of Roundup® and its main constituents to C. auratus.  相似文献   

11.
BACKGROUND: Most historical buildings in Bordeaux city are made of limestone. This yellowish-white rock is rather porous and highly sensitive to pollution. As a consequence of local weathering conditions, these buildings present a dark appearance due to the development of a superficial dark grey to black crust. METHODS: For the last decade, a campaign has been underway to clean these buildings. Eleven techniques of surface treatment have been used, including laser beam technology. As a contribution to the study of laser beam effects on stone buildings, two analytical methods have been used on clean versus unclean surfaces: Cathodoluminescence (CL) and Electron Paramagnetic Resonance (EPR), in addition to SEM-EDX and XRD. RESULTS: The black crust is composed of different types of particles: carbon porous micro-particles of industrial origin, atmospheric dust due to the erosion of soils and rocks, alumino-silicate particles from urban pollution; all these particles being cemented by gypsum. DISCUSSION: As far as heritage conservation is concerned, the laser surface treatment not only preserves the original patina of the stone, but also leaves surface smoothness unaltered. CONCLUSIONS AND PERSPECTIVES: CL and EPR data confirm that lasers--with highly controlled parameters--only get rid of the black crust and, thus, reveal the underneath layer, the so-called patina. This patina shows no luminescence, whereas the limestone on which it has grown shows a bright orange emission of CL. This indicates CL to be a fast and easy way to provide a high quality control for the restoration of polluted ancient stones.  相似文献   

12.
In this study, the bioavailability and accumulation of mercury from external environmental exposure to mixed, cured, milled, sieved and proportioned dental amalgam was examined in the common goldfish, Carassius auratus. Fish were exposed to dental amalgam (particle size range from < 0.10 to 3.15 mm) in order to represent the particle size and distribution of that found within the typical dental office wastewater discharge stream. Experimental amalgam water loadings were 0 g/l, 0.5 g/l and 1 g/l in glass aquaria at 15 degrees C for 28 days. Fish tissues were sampled at 5 min and 28 days of exposure, and the liver, brain, muscle and whole body analyzed for total mercury using cold vapor atomic fluorescence spectroscopy. Mercury was found in several tissues examined and generally increased with exposure to higher amounts of dental amalgam. The highest levels were found in the whole body (17.68 +/- 5.73 microg/g) followed by the liver (0.80 +/- 0.16 microg/g) and muscle (0.47 +/- 0.16 microg/g). The lowest concentrations were seen in the brain (0.28 +/- 0.19 microg/g). Compared to controls, concentrations in the whole body, muscle and liver in fish exposed for 28 days to the highest concentration of amalgam were 200-, 233-, and 40-fold higher, respectively. This study shows that mercury from an environmental exposure to representative samples of dental amalgam typically found within the dental wastewater discharge stream is bioavailable to fish and may accumulate in internal tissues.  相似文献   

13.
Lee C  Yoon J 《Chemosphere》2004,56(10):923-934
The thermal enhancement of the formation of *OH by the hv/Fe(III)/H2O2 system (including the Fe(III)/H2O2 system) was quantitatively investigated with reaction temperatures ranging from 25 to 50 degrees C. A temperature dependent kinetic model for the hv/Fe(III)/H2O2 system, incorporating 12 major reactions with no fitted rate constants or activation energies, was developed, and successfully explained the experimental measurements. Particularly, the thermal enhancement of Fe(OH)2+ photolysis which is the most significant step in the hv/Fe(III)/H2O2 system was effectively explained by two factors; (1) the variation of the Fe(OH)2+ concentration with temperature, and (2) the temperature dependence of the quantum yield for Fe(OH)2+ photolysis (measured activation energy=11.4 kJ mol(-1)). Although in both the hv/Fe(III)/H2O2 and Fe(III)/H2O2 systems, elevated temperatures enhanced the formation of *OH, the thermal enhancement was much higher in the dark Fe(III)/H2O2 system than the hv/Fe(III)/H2O2 system. Furthermore, it was found that the relative thermal enhancement of the formation of *OH in the presence of *OH scavengers (tert-butyl alcohol) was magnified in the Fe(III)/H2O2 system but was not in the hv/Fe(III)/H2O2 system.  相似文献   

14.
15.
We investigated dioxin concentrations in freshwater fish in Japan by standardizing species to detect subtle decreasing trends of dioxin concentrations in the future with the reinforcement of regulations. The fish studied were crucian carp (Carassius auratus (gibelio) langsdorfii), an omnivorous species. Fish and sediments were collected from 14 rivers and lakes located in remote areas, agricultural areas, and small and large cities throughout Japan. The total toxic equivalent (TEQ) dioxin concentrations at the three remote sites were about 20% of the concentrations at the other 11 sites, which all had similar concentrations. The average concentrations in fish collected from these 11 sites were 0.69pgTEQg(-1) wet wt. (95% CI 0.52-0.85) or 57.3pgTEQg(-1) fat (95% CI 47.9-66.7). There were notable differences in congener profiles of polychlorinated p-dibenzodioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) between sampling areas. A chemical mass balance method was used to estimate the proportions of dioxin contributions from different sources. The sampling areas were classified into four groups on the basis of the predominant source of dioxin contamination: a combustion group, a chlornitrofen herbicide group, a chlornitrofen and pentachlorphenol herbicide group, and a remote group. The congener profiles of dioxin like polychlorinated biphenyls (DL-PCBs) were almost the same in all areas and close to those in Kanechlor, which indicates that pollution from PCB products has spread throughout Japan. From samples collected during the spawning season, it was determined that about 20% of the dioxins in adult females were transferred to the eggs, resulting in higher dioxin concentrations in adult males than in females. Biota-sediment accumulation factors (BSAFs) of 2,3,7,8-substituted PCDDs/DFs for crucian carp were larger than those of non-2,3,7,8-substituted congeners, and BASFs decreased with increasing number of chlorines. The BSAFs of DL-PCBs were 10 times greater than those of PCDDs/DFs, and BSAFs of mono-ortho type DL-PCBs were higher than those of non-ortho types.  相似文献   

16.
We have measured the concentration of hydroxyl radicals (OH) produced in the gas phase by a commercially available purifier for air and surfaces, using the time rate of decay of n-heptane added to an environmental chamber. The hydroxyl generator, an Odorox® BOSS? model, produces the OH through 185-nm photolysis of ambient water vapor. The steady-state concentration of OH produced in the 120 m3 chamber is, with 2σ error bars, (3.25 ± 0.80) × 106 cm?3. The properties of the hydroxyl generator, in particular the output of the ultraviolet lamps and the air throughput, together with an estimation of the water concentration, were used to predict the amount of OH produced by the device, with no fitted parameters. To relate this calculation to a steady-state concentration, we must estimate the OH loss rate within the chamber owing to reaction with the n-heptane and the 7 ppb of background hydrocarbons that are present. The result is a predicted steady-state concentration in excellent agreement with the measured value. This shows we understand well the processes occurring in the gas phase during operation of this hydroxyl radical purifier.

Implications: Hydroxyl radical air purifiers are used for cleaning both gaseous contaminants, such as volatile organic compounds (VOCs) or hazardous gases, and biological pathogens, both airborne and on surfaces. This is the first chemical kinetic study of such a purifier that creates gas-phase OH by ultraviolet light photolysis of H2O. It shows that the amount of hydroxyls produced agrees well with nonparameterized calculations using the purifier lamp output and device airflow. These results can be used for designing appropriate remediation strategies.  相似文献   

17.
Kim JK  Metcalfe IS 《Chemosphere》2007,69(5):689-696
The presence and impact of hydroxyl radicals generated via the catalytic decomposition of H(2)O(2) over heterogeneous copper catalysts were investigated by using two detection methods, an electron spin resonance-spin trapping method and a chemical probe method. Detection of the (5,5-dimethyl-1-pyrroline-N-oxide)-OH adduct signal and formation of 4-chlorocatechol during the oxidation of a 4-chlorophenol substrate demonstrated that the three heterogeneous copper catalysts employed here (CuO, Cu/Al(2)O(3) and CuO.ZnO/Al(2)O(3)) were capable of generating hydroxyl radicals in combination with H(2)O(2). The oxidative mechanism of the hydroxyl radical in the presence of heterogeneous copper catalysts is discussed with regard to the further oxidation of the (5,5-dimethyl-1-pyrroline-N-oxide)-OH adduct and hydroxylated products of 4-chlorophenol oxidation. Interestingly, integration of the 5,5-dimethyl-1-pyrroline-N-oxide-OH adduct signal could not be used to reliably measure the total amount of hydroxyl radicals generated as a result of oxidative attack on the adduct. This may be as a result of locally higher hydroxyl radical concentrations in the presence of a heterogeneous catalyst leading to further unwanted oxidation of the (5,5-dimethyl-1-pyrroline-N-oxide)-OH.  相似文献   

18.
The hydroxyl radical (*OH) is generated in polluted dew on the needle surfaces of Japanese red pine (Pinus densiflora Sieb. et Zucc.). This free radical, which is a potent oxidant, is assumed to be a cause of ecophysiological disorders of declining trees on the urban-facing side of Mt. Gokurakuji, western Japan. Mists of *OH-generating N(III) (HNO2 and NO2-) and HOOH + Fe + oxalate solutions (50 and 100 microM, pH 5.1-5.4) simulating the dew water were applied to the foliage of pine seedlings grown in open-top chambers in the early morning. Needles treated with 100 microM N(III) tended to have a greater maximum CO2 assimilation rate (Amax), a greater stomatal conductance (g(s)) and a greater needle nitrogen content (Nneedle), suggesting that N(III) mist acts as a fertilizer rather than as a phytotoxin. On the other hand, needles treated with 100 microM HOOH + Fe + oxalate solution showed the smallest Amax, g(s), and Nneedle, suggesting that the combination of HOOH + Fe + oxalate caused a decrease in needle productivity. The effects of HOOH + Fe + oxalate mist on pine needles were very similar to the symptoms of declining trees at Mt. Gokurakuji.  相似文献   

19.
Maezono T  Tokumura M  Sekine M  Kawase Y 《Chemosphere》2011,82(10):1422-1430
Dynamic behaviors of hydroxyl (OH) radical generation and consumption in photo-Fenton oxidation process were investigated by measuring OH radical concentration during the discoloration of azo-dye Orange II. The effects of operating parameters for photo-Fenton discoloration, i.e. dosages of H2O2 and Fe, initial dye concentration, solution pH and UV irradiation, on the generation and consumption of OH radicals playing the main role in advanced oxidation processes were extensively studied. The scavenger probe or trapping technique in which coumarin is scavenger of OH radical was applied to estimate OH radical concentration in the photoreactor during the photo-Fenton discoloration process. The OH radical generation was enhanced with increasing the dosages of Fenton regents, H2O2 and Fe. At the initial stage of photo-Fenton discoloration of Orange II, the OH radical concentration rapidly increased (Phase-I) and the OH radical concentration decreased after reaching of OH radical concentration at maximum value (Phase-II). The decrease in OH radical concentration started when the complete discoloration of Orange II was nearly achieved and the H2O2 concentration became rather low. The dynamic behavior of OH radical concentration during the discoloration of Orange II was found to be strongly linked with the change in H2O2 concentration. The generation of OH radical was maximum at solution pH of 3.0 and decreased with an increase of solution pH. The OH radical generation rate in the Fenton Process was rather slower than that in the photo-Fenton process.  相似文献   

20.
Atmospheric chemistry directly above snowpacks is strongly influenced by ultraviolet (UV) radiation initiated emissions of chemicals from the snowpack. The emission of gases from the snowpack to the atmosphere is in part due to chemical reactions between hydroxyl radical, OH (produced from photolysis of hydrogen peroxide (H2O2) or nitrate (NO3)) and impurities in the snowpack. The work presented here is a radiative-transfer modelling study to calculate the depth-integrated production rates of hydroxyl radical from the photolysis of hydrogen peroxide and nitrate anion in snow for four different snowpacks and for solar zenith angles 30°–90°. This work also demonstrates the importance of hydrogen peroxide photolysis to produce hydroxyl radical relative to nitrate photolysis with (a) different snowpacks, (b) different ozone column depths, and (c) snowpack depths. The importance of hydrogen peroxide photolysis over nitrate photolysis for hydroxyl radical production increases with increasing depth in snowpack, column ozone depth, and solar zenith angle. With a solar zenith angle of 60° the production of hydroxyl radical from hydrogen peroxide photolysis accounts for 91–99% of all hydroxyl radical production from hydrogen peroxide and nitrate photolysis.  相似文献   

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