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1.
Photolysis of oxyfluorfen, an herbicide of the nitrodiphenyl ether class, was studied in aqueous methanol under UV and sunlight. UV irradiation was carried out in a borosilicate glass photoreactor (containing 250 ppm oxyfluorfen in 50% aqueous methanol) equipped with a quartz filter and 125 watt mercury lamp (maximum output 254 nm) at 25 ± 1°C. Sunlight irradiation was conducted at 28 ± 1°C in borosilicate Erlenmeyer flasks containing 250 ppm oxyfluorfen in 50% aqueous methanol. The samples from both the irradiated conditions were withdrawn at a definite time interval and extracted to measure oxyfluorfen content by gas chromatography-flame ionization detector for rate study. The half-life values were 20 hours and 2.7 days under UV and sunlight exposure, respectively. Photolysis of oxyfluorfen yielded 13 photoproducts of which three were characterized by infrared spectrophotometer and 1H NMR and 13C NMR spectroscopy. The rest of the photoproducts were identified by gas chromatography-mass spectrometry (GC-MS) and thin layer chromatography (TLC). An ionization potential 70 eV was used for electron impact-mass spectrometry (EI-MS) and methane was used as reagent gas for chemical ionization-mass spectrometry (CI-MS). Two of the photoproducts were also synthesized for comparison. The main phototransformation pathways of oxyfluorfen involved nitro reduction, dechlorination, and hydrolysis as well as nucleophiles displacement reaction.  相似文献   

2.
Tetracycline antibiotics including tetracycline (TTC), oxytetracycline (OTC) and chlorotetracycline (CTC) undergo rapid transformation to yield various products in the presence of MnO2 at mild conditions (pH 4-9 and 22 °C). Reaction rates follow the trend of CTC > TTC > OTC, and are affected by pH and complexation of TCs with Mg2+ or Ca2+. Experimental results of TTC indicate that MnO2 promotes isomerization at the C ring to form iso-TTC and oxidizes the phenolic-diketone and tricarbonylamide groups, leading to insertion of up to 2 O most likely at the C9 and C2 positions. In contrast, reactions of OTC with MnO2 generate little iso-OTC, but occur mainly at the A ring’s dimethylamine group to yield N-demethylated products. CTC yields the most complicated products upon reactions with MnO2, encompassing transformation patterns observed with both TTC and OTC. The identified product structures suggest lower antibacterial activity than that of the parent tetracyclines.  相似文献   

3.
Oxytetracycline ((2Z,4S,4aR,5S,5aR,6S,12aS)-2-(amino-hydroxy-methylidene)-4-dimethylamino-5,6,10,11,12a-pentahydroxy-6-methyl-4,4a,5,5a-tetrahydrotetracene-1,3,12-trione) is a member of tetracycline antibiotics family and is widely administered to farm animals for the purpose of therapeutical treatment and health protection. Increasing attention has been paid to the environmental fate of oxytetracycline and other veterinary antibiotics with the occurrence of these antibiotics in the environment. The hydrolysis and photolysis degradation of oxytetracycline was investigated in this study. Oxytetracycline hydrolysis was found to obey the first-order model and similar rate constant values ranging from 0.094 ± 0.001 to 0.106 ± 0.003 day? 1 were obtained at different initial concentration ranging from 10 to 230 μ M. Solution pH and temperature were shown to have remarked effects on oxytetracycline hydrolysis. The hydrolysis in pH neutral solution appeared to be much faster than in both acidic and alkaline solutions. Oxytetracycline half-life decreased from 1.2 × 102 to 0.15 day with the increasing temperature from 4 ± 0.8 to 60 ± 1°C. The presence of Ca2 + made oxytetracycline hydrolytic degradation kinetics deviate from the simple first-order model to the availability-adjusted first-order model and greatly slowed down the hydrolysis. Oxytetracycline photolysis was found to be very fast with a degradation rate constant at 3.61 ± 0.06 day? 1, which is comparable to that of hydrolysis at 60°C. The presence of Ca2 + accelerated oxytetracycline photolysis, implying that oxytetracycline become more vulnerable to sunlight irradiation after chelating with Ca2 +. The photolysis may be the dominant degradation pathway of oxytetracycline in shallow transparent water environment.  相似文献   

4.
Once released into the aquatic environment, pharmaceuticals may undergo different degradation processes. Photodegradation, for example, might be an important elimination process for light-sensitive pharmaceuticals, such as antibiotics. In this study, the fate of sulfonamides (sulfamethazine, sulfadiazine, and sulfamethoxazole) and their N 4-acetylated metabolites (N 4-acetylsulfadiazine, N 4-acetylsulfamethazine, and N 4-acetylsulfamethoxazole) under simulated sunlight irradiation was investigated. The irradiation resulted in total or almost total degradation (88 to 98 %) of the pharmaceuticals tested, except for sulfamethazine (52 %), during 24 h of irradiation. The photoproducts of all investigated pharmaceuticals have been analyzed using high-performance liquid chromatography coupled to electrospray ionization tandem mass spectrometry. Structure elucidation performed from photodegradation products of both, sulfonamides and their N 4-acetylated metabolites, clearly showed two major formation pathways. These were cleavage of the sulfonamide bond as well as SO2 extrusion. In total, nine photoproducts were elucidated. Among these photoproducts, the tautomers of sulfamethoxazole and desulfonated products of sulfadiazine and sulfamethazine were also present. Tautomers of sulfadiazine and sulfamethazine have been characterized here for the first time as well as some photoproducts of sulfadiazine, sulfametoxazole, and their metabolites N 4-acetylsulfadiazine and N 4-acetylsulfametoxazole. The obtained results are an important piece in the complex puzzle for assessing the environmental fate of sulfonamides and their metabolites in the environment.  相似文献   

5.
Understanding the removal mechanisms and kinetics of trace tetracycline by activated sludge is critical to both evaluation of tetracycline elimination in sewage treatment plants and risk assessment/management of tetracycline released to soil environment due to the application of biosolids as fertilizer. Adsorption is found to be the primary removal mechanism while biodegradation, volatilization, and hydrolysis can be ignored in this study. Adsorption kinetics was well described by pseudo-second-order model. Faster adsorption rate (k 2?=?2.04?×?10?2?g?min?1?μg?1) and greater adsorption capacity (q e?=?38.8 μg?g?1) were found in activated sludge treating freshwater sewage. Different adsorption rate and adsorption capacity resulted from chemical properties of sewage matrix rather than activated sludge surface characteristics. The decrease of tetracycline adsorption in saline sewage was mainly due to Mg2+ which significantly reduced adsorption distribution coefficient (K d) from 12,990?±?260 to 4,690?±?180 L?kg?1. Species-specific adsorption distribution coefficients followed the order of $ K_{\mathrm{d}}^{{ + 00}} \gg K_{\mathrm{d}}^{{ + - 0}} > K_{\mathrm{d}}^{{ + - - }} $ . Contribution of zwitterionic tetracycline to the overall adsorption was >90 % in the actual pH range in aeration tank. Adsorption of tetracycline in a wide range of temperature (10 to 35 °C) followed the Freundlich adsorption isotherm well.  相似文献   

6.
In August 2012, eight rainwater samples were collected and analyzed for pH and metal ions, viz., iron, copper, and manganese. The pH was within the range 6.84–7.65. The rate of oxidation of dissolved sulfur dioxide was determined using these rainwater samples as reaction medium. Kinetics was defined by the rate law: ?d[S(IV)]/dt = R o = k o[S(IV)]], where k o is the first-order rate constant and R o is the rate of the reaction. The effect of two volatile organic compounds—ethanol and 2-butanol—was examined and found to inhibit the oxidation as defined by the rate law: k obs = k o/(1 + B [Inh]), where k obs is the first-order rate constant in the presence of the inhibitor, [Inh] is the concentration of the inhibitor, and B is the inhibitor parameter—an empirical constant. In the pH range of collected rainwater samples, the values of first-order rate constants ranged from 3.1?×?10?5 to 1.5?×?10?4 s?1 at 25 °C. The values of inhibition parameter were found to be (5.99?±?3.91?×?104) (ethanol) and (3.95?±?2.36)?×?104 (2-butanol) at 25 °C.  相似文献   

7.
In this study, the effects of tetracycline exposure on wheat growth and the microbial community structure in the rhizosphere were investigated under hydroponic culture conditions. Exposure to various concentrations of tetracycline resulted in significant suppression of the growth of wheat roots and shoots, with minimum doses of 0.8 mg L?1 and 4 mg L?1 resulting in inhibition rates of 32% and 15.4%, respectively. Complete inhibition of the growth of these two parts of wheat plants was observed in response to treatment with tetracycline at 20 mg L?1 and 100 mg L?1, respectively. However, the germination of wheat seeds was not sensitive to exposure to tetracycline. The effects of tetracycline exposure on the microbial community in the wheat rhizosphere were evaluated through traditional cultivation and molecular biological analyses. The cultivation results indicated that bacteria were the dominant population, being present in concentrations of 1× 108–2.45× 109CFUs mL?1, although 39% to 87% inhibition occurred in response to tetracycline. The concentration of fungi increased in all tetracycline treated samples to 2.5 to 15.8 times that of the control. The highest concentration of fungi (4.27× 108 CFU mL?1) was observed in response to 60 mg L?1 tetracycline after 15 days of cultivation. In this stage, a large amount of fungal colonies was observed on the surface of the culture solution, the wheat roots became rotted and the plants became atrophic or even died. Molecular biological analysis indicated that the bacterial community structure was significantly different in samples that were exposed to high levels of tetracycline (over 20 mg L?1) than in samples that were exposed to lower concentrations. As the concentration of tetracycline increased, the diversity of the bacteria decreased. Additionally, several dominant sensitive species such as Sphingobacterium multivorum were suppressed by tetracycline, while some resistant species such as Acinetobacter sp. appeared or were conserved. The bacteria population tended to stabilize when the drug concentration exceeded 40 mg L?1.  相似文献   

8.
微波-Fenton对沼液中抗生素和激素的高级氧化   总被引:2,自引:1,他引:1  
采用微波强化Fenton氧化处理系统,研究H2O2浓度、Fe2+浓度、初始pH、微波辐射时间和微波辐射功率对沼液中喹乙醇、土霉素、四环素及金霉素降解效果的影响.结果发现,采用微波强化Fenton氧化降解沼液中抗生素与激素的最优条件是:H2O2浓度为40 mg/L、Fe2+浓度为12 mg/L、初始pH为4、微波辐射时间为2 min、微波辐射功率为中火(445W),沼液中喹乙醇、土霉素、四环素、金霉素和COD的去除率分别达到67%、93%、91%、88%和46%.在水浴条件下,与单独微波辐射和单独Fenton相比,微波强化Fenton氧化有明显的优越性.  相似文献   

9.
Azo dyes are recalcitrant and refractory pollutants that constitute a significant menace to the environment. The present study is focused on exploring the capability of Bacillus sp. strain UN2 for application in methyl red (MR) degradation. Effects of physicochemical parameters (pH of medium, temperature, initial concentration of dye, and composition of the medium) were studied in detail. The suitable pH and temperature range for MR degradation by strain UN2 were respectively 7.0–9.0 and 30–40 °C, and the optimal pH value and temperature were respectively 8.0 and 35 °C. Mg2+ and Mn2+ (1 mM) were found to significantly accelerate the MR removal rate, while the enhancement by either Fe3+ or Fe2+ was slight. Under the optimal degradation conditions, strain UN2 exhibited greater than 98 % degradation of the toxic azo dye MR (100 ppm) within 30 min. Analysis of samples from decolorized culture flasks confirmed biodegradation of MR into two prime metabolites: N,N′dimethyl-p-phenyle-nediamine and 2-aminobenzoic acid. A study of the enzymes responsible for the biodegradation of MR, in the control and cells obtained during (10 min) and after (30 min) degradation, showed a significant increase in the activities of azoreductase, laccase, and NADH-DCIP reductase. Furthermore, a phytotoxicity analysis demonstrated that the germination inhibition was almost eliminated for both the plants Triticum aestivum and Sorghum bicolor by MR metabolites at 100 mg/L concentration, yet the germination inhibition of parent dye was significant. Consequently, the high efficiency of MR degradation enables this strain to be a potential candidate for bioremediation of wastewater containing MR.  相似文献   

10.
This paper studies the degradation reactions that 4-chloroaniline can naturally undergo in waters for the action of sun light. 10.00 mg L−1 4-chloroaniline aqueous solution, without any addition of organic solvent, are undergone to photoirradiation under conditions that simulate sun light. The degradation pathway, followed by HPLC-DAD-MS/MS methods, is complex since the pollutant gives rise to many photoproducts: the predominant species are characterized by m/z values of 217 (P5) and 218 (P6) and are compatible with dimeric structures of 4-chloroaniline. Vibrio fischeri tests indicate that the photoproducts of 4-chloroaniline are characterized by a toxicity level significantly greater than the precursor.  相似文献   

11.
The photochemistry of the herbicide chlorsulfuronR (2-chloro-N-[[4-methoxy-6-methyl-1.3.5-triazinyl-2-amino]carbonyl]benzene sulfonamide) was investigated in methanol, distilled water, natural creek-water, on silica gel and on montmorillonit surfaces. The rate of degradation was determined in outdoor and indoor experiments simulating tropospheric conditions (λ>290 nm). Two major photoproducts were identified in all cases.  相似文献   

12.
Abstract

The solubility products (Ksp) of 1:1 complexes of glyphosate, [N‐(phosphonomethyl)glycine], with Mg2+, Ca2+, Mn2+, Zn2+, Cu2+ and Fe3+, were determined in buffered (pH 7.0) distilled water, moist Ottawa sand, sandy loam and clay loam soils, each adjusted to 0.02 M with respect to KNO3. The Ksp values decreased in the order of Mg ? Ca > Mn > Zn > Cu > Fe, regardless of the medium in which they were determined. The constants measured in Ottawa sand were similar to those in water, but those in the forestry soils depended upon the type of metal ion involved. The values for the Mg, Ca, Mn and Zn complexes were about 2 to 3 times lower in sandy loam soil than those in water, but those in clay loam were about 3 to 10 times lower. The Ksp of the Cu and Fe complexes were similar to those in water regardless of the soil type used.

In a bioassay experiment using tomato plants, immersed in the saturated solutions of the complexes or planted in the sand and soils containing saturated solutions of the complexes, no mortality occurred although slight inhibition in growth was observed in all cases. The most soluble complexes of Mg and Ca caused the most reduction in plant height, while the least soluble complex of Fe caused little growth inhibition. The Zn, Cu and Mn complexes caused some growth inhibition depending on their Ksp values. The larger the solubility product, the greater the concentration of glyphosate ion in solution, and the greater the growth inhibition. In a similar experiment using white spruce seedlings, growth inhibition was insignificant over the 12‐d bioassay period.  相似文献   

13.
Photochemical degradation of methylparathion (O,O,–dimethyl O-4 nitrophenylphosphorothioate) in the presence of fulvic acid (FA) between pH 2 and 7 was studied by differential pulse polarography (DPP). Fulvic acid and its photoproducts were not electro-active under the experimental conditions used in this study, and only the pesticide exhibited polarographic signals. Photolysis of methylparathion in acid media was sensitized by fulvic acid since the pesticide did not degrade in the absence of this compound. Methylparathion degradation was observed at each of the studied pHs. The reaction was first-order with rate constant values ranging from 3.3 × 10?3 to 8.8 × 10?3min?1.  相似文献   

14.
Europium (Eu3+)-labeled antibody was used as a fluorescent label to develop a highly sensitive time-resolved fluoroimmunoassay (TRFIA) for determination of clothianidin residues in agricultural samples. Toward this goal, the Eu3+-labeled polyclonal antibody and goat anti-rabbit antibody were prepared for developing and evaluating direct competitive TRFIA (dc-TRFIA) and indirect competitive TRFIA (ic-TRFIA). Under optimal conditions, the half-maximal inhibition concentration (IC50) and the limit of detection (LOD, IC10) of clothianidin were 9.20 and 0.0909 μg/L for the dc-TRFIA and 2.07 and 0.0220 μg/L for the ic-TRFIA, respectively. The ic-TRFIA has no obvious cross-reactivity with the analogues of clothianidin except for dinotefuran. The average recoveries of clothianidin from spiked water, soil, cabbage, and rice samples were estimated to range from 74.1 to 115.9 %, with relative standard deviations of 3.3 to 11.7 %. The results of TRFIA for the blind samples were largely consistent with gas chromatography (R 2?=?0.9902). The optimized ic-TRFIA might become a sensitive and satisfactory analytical method for the quantitative monitoring of clothianidin residues in agricultural samples.  相似文献   

15.

Photolysis behavior of a new herbicide propisochlor in water media as well as the effects of light sources, initial concentration of propisochlor, pH value, dissolved oxygen (DO) level, and salinity on the photolysis process was investigated. It was found that the relationship between initial concentration of propisochlor and its photodegradation rate was negatively correlated. The changes in acidity and alkalinity of the reaction medium influenced the photoreaction rate evidently. In the alkaline solution the degradation was accelerated. In the reaction media with different pH values, the photolysis followed the first-order kinetics. The presence of dissolved oxygen may promote the photolysis and there existed an optimum of dissolved oxygen concentrations. Increasing the DO level can weaken the promotion and even have an adverse effect. It was demonstrated that with dissolved oxygen the photodegradation of propisochlor followed the first-order kinetics equation. The addition of salt ions Ca2+ and Mg2+ changed the ionic strength and solvent polarity, resulting in the effect on propisochlor photolysis. The photoproducts were detected by both HPLC and GC-MS methods. It was found that photolysis products varied under different light sources. Conclusions may be reached that in the photodegradation of propisochlor, the benzene ring remained intact under irradiation of both solar light and high-pressure mercury lamp, and the amido link was relatively stable, while dechlorination was liable to take place; moreover, α-hydrogen at the substituent of benzene ring was active.  相似文献   

16.

In waterlogged paddy soils, cadmium (Cd) can be precipitated as cadmium sulfide (CdS) under reductive environment, thereby limiting the absorption of Cd by plants. Multiple environmental factors (such as water, pH, and Eh) played a role in the control of Cd mobility and bioavailability. In this study, we investigated the influence of the solar irradiation on the photodissolution of synthetic CdS-montmorillonite composites (CdS-M) in solution and the stability of Cd in natural soil. The release kinetic of Cd2+ showed that after the irradiation of simulated sunlight, CdS-M composites became less stable compared to the dark control. The solar irradiation seemed to enhance the release of Cd2+ from CdS significantly and continuously. Electron paramagnetic resonance (EPR) and quenching experiments confirmed that the photogenerated holes, ?O2? and ?OH, were possibly involved in the photo-induced release of Cd2+, while the holes was primarily responsible for the reaction. Irradiation under alkaline solution or the presence of DOM, PO43?, CO32?, and urea markedly inhibited the photodissolution process of CdS. The photo-mediated activation of Cd was further confirmed in paddy soil under natural sunlight, with a nearly threefold increase in concentration of extractable Cd during the 15 days of irradiation. This study highlights the importance of photochemical transformation of Cd in the environmental water and soil.

  相似文献   

17.

Storage of bottled waters in varying ambient conditions affects its characteristics. Different storage conditions cause changes in the initial chemical composition of bottled water which lead to the occurrence of precipitates with various morphologies. In order to assess the relationship between water composition, storage conditions and precipitate morphology, a study of four brands of Slovenian bottled water stored in PET bottles was carried out. Chemical analyses of the main ions and measurements of the physical properties of water samples were performed before and after storage of water samples at different ambient conditions. SEM/EDS analysis of precipitates was performed after elapsed storage time. The results show that the presence of Mg2+, SO4 2−, SiO2, Al, Mn and other impurities such as K+, Na+, Ba and Sr in the water controlled precipitate morphology by inhibiting crystal growth and leading to elongated rhombohedral calcite crystal forms which exhibit furrowed surfaces and calcite rosettes. Different storage conditions, however, affected the number of crystallization nuclei and size of calcite crystals. Hollow calcite spheres composed of cleavage rhombohedrons formed in the water with variable storage conditions by a combination of evaporation and precipitation of water droplets during high temperatures or by the bubble templating method.

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18.
The present work compares the efficiency of homogenous Fenton and photo-Fenton processes in the presence of Fe(III)–EDDS complex under different experimental conditions. 4-tert-Butylphenol (4-t-BP), which is one of the endocrine disrupting chemicals, was used as a model pollutant to investigate the Fenton and photo-Fenton application. The efficiency of homogenous photo-Fenton process was significantly much higher than homogenous Fenton process, which is due to the rapid formation of Fe2+ under UV irradiation of the iron complex and the photochemical formation of HO? from the photolysis of the complex Fe(III)–EDDS. Through the degradation of 4-t-BP, the effect of Fe(III)–EDDS concentration, H2O2 concentration, pH, and oxygen was investigated in both processes. Such trend was also correlated with pH calculating the polychromatic Fe2+ quantum yield formation at pH 4.0, 6.0, and 8.6. The results showed that at high Fe(III)–EDDS and H2O2 concentrations, a negative effect was found. By the way, the Fenton process was found to be enhanced at basic pH. These results can be very useful for the use and optimization of such iron complex in water treatment process as function of different physico-chemical conditions.  相似文献   

19.
The rapid growth of urbanization and industrialization, along with dramatic climate change, has strongly influenced hydrochemical characteristics in recent decades in China and thus could cause the variation of pH and general total hardness of a river. To explore such variations and their potential influencing factors in a river of the monsoon climate region, we analyzed a long-term monitoring dataset of pH, SO4 2?, NOx, general total hardness (GH), Mg2+, Ca2+, and Cl? in surface water and groundwater in the Luan River basin from 1985 to 2009. The nonparametric Seasonal Kendall trend test was used to test the long-term trends of pH and GH. Relationship between the affecting factors, pH and GH were discussed. Results showed that pH showed a decreasing trend and that GH had an increasing trend in the long-term. Seasonal variation of pH and GH was mainly due to the typical monsoon climate. Results of correlation analysis showed that the unit area usage amounts of chemical fertilizer, NO3 ?, and SO4 2? were negatively correlated with pH in groundwater. In addition, mining activity affected GH spatial variation. Acid deposition, drought, and increasing the use of chemical fertilizers would contribute to the acidification trend, and mining activities would affect the spatial variation of GH. Variations of precipitation and runoff in semi-arid monsoon climate areas had significant influences on the pH and GH. Our findings implied that human activities played a critical role in river acidification in the semi-arid monsoon climate region of northern China.  相似文献   

20.
This paper investigates the potential of using the silver antibacterial properties combined with the metal ion exchange characteristics of silver-modified clinoptilolite to produce a treatment system capable of removing both contaminants from aqueous streams. The results have shown that silver-modified clinoptilolite is capable of completely eliminating Escherichia coli after 30-min contact time demonstrating its effectiveness as a disinfectant. Systems containing both E. coli and metals exhibited 100 % E. coli reduction after 15-min contact time and maximum metal adsorption removal efficiencies of 97, 98, and 99 % for Pb2+, Cd2+, and Zn2+ respectively after 60 min; 0.182–0.266 mg/g of metal ions were adsorbed by the zeolites in the single- and mixed-metal-containing solutions. Nonmodified clinoptilolite showed no antibacterial properties. This study demonstrated that silver-modified clinoptilolite exhibited high disinfection and heavy metal removal efficiencies and consequently could provide an effective combined treatment system for the removal of E. coli and metals from contaminated water streams.  相似文献   

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