Photolysis of Enrofloxacin in aqueous systems under simulated sunlight irradiation: Kinetics, mechanism and toxicity of photolysis products

Photolysis of Enro in water was investigated under simulated sunlight irradiation using a Xenon lamp. The results showed that Enro photolysis followed apparent first-order kinetics. Increasing Enro concentration from 5.0 to 40.0 mg L⁻¹ led to the decrease of the photolysis rate constant from 1.6 × 10⁻² to 3.0 × 10⁻³ min⁻¹. Compared with the acidic and basic conditions, the photolysis rate was faster at neutral condition. Both of nitrate and humic acid can markedly decrease the photolysis rate of Enro because they can competitively absorb photons with Enro. The electron spin resonance and reactive oxygen species scavenging experiments indicated that Enro underwent self-sensitized photooxidation via OH and ¹O₂. After irradiation for 90 min, only 13.1% reduction of TOC occurred in spite of fast photolysis of 58.9% of Enro, indicating that Enro was transformed into intermediates without complete mineralization. The photolysis of Enro involved three main pathways: decarboxylation, defluorination, and piperazinyl N⁴-dealkylation. The bioluminescence inhibition rate using Vibrio fischeri increased to 67.2% at 60 min and then decreased to 56.9% at 90 min, indicative of the generation of some more toxic intermediates than Enro and then the degradation of the intermediates. The results will help us understand fundamental mechanisms of Enro photolysis and provide insight into the potential fate and transformation of Enro in surface waters.     

Decomposition of 14C-fenitrothion under the influence of UV and sunlight under tropical and subtropical conditions

The decomposition of (14)C-fenitrothion on silica gel chromatoplates as well as in polar and non polar solvents under sunlight and ultraviolet light was investigated, Its stability to sunlight on leaf surfaces of bean plants and on different surfaces (such as glass, quartz and plastic) was also determined. The main photoproducts were identified as carboxyfenitrothion, fenitrooxon, carboxyfenitrooxon and 3-methyl-4-nitrophenol and a small amount 3-caboxy-4-nitrophenol and methyl parathion. The addition of carbaryl and deltamethrin insecticides slightly accelerated the photodecomposition of fenitrothion on silica gel plates and in solution.     

Disappearance of polycyclic aromatic hydrocarbons sorbed on surfaces of pine [Pinua thunbergii] needles under irradiation of sunlight: Volatilization and photolysis

The solar photodegradation of 16 polycyclic aromatic hydrocarbons (PAHs), sorbed on surfaces of pine [Pinua thunbergii] needles was investigated. The PAHs were produced by combustion of polystyrene and exposed onto the surfaces of pine needles. The disappearance of PAHs sorbed on the pine needle surfaces is mainly caused by volatilization and photolysis, with photolysis playing a major role. The volatilization rates correlate with PAH molecular weight significantly. The photolysis of the 16 PAHs follows first-order kinetics and their photolysis half-lives (t_1/2,P) range from 12.9 h for naphthalene to 65.4 h for fluorene. The PAHs have similar half-lives whether they are sorbed on spruce or pine needles. Compared with water, the cuticular waxes of pine needles can stabilize photolysis of PAHs and facilitate accumulation of PAHs. t_1/2,P for selected PAHs correlate with semi-empirically calculated energy of the highest occupied orbital (E_HOMO). Photochemical behaviors of PAHs are dependent not only on their molecular structures but also the physical–chemical properties of the substrate on which they are adsorbed.     

Photolysis of pharmaceuticals and personal care products in the marine environment under simulated sunlight conditions: irradiation and identification

The photochemical fate of 16 pharmaceuticals and personal care products (PPCPs) found in the environment has been studied under controlled laboratory conditions applying a sunlight simulator. Aqueous samples containing PPCPs at environmentally relevant concentrations were extracted by solid-phase extraction (SPE) after irradiation. The exposed extracts were subsequently analysed by liquid chromatography combined with triple quadrupole mass spectrometry (HPLC-MS/MS) for studying the kinetics of photolytic transformations. Almost all exposed PPCPs appeared to react with a half-life time (τ _1/2) of less than 30 min. For ranitidine, sulfamethoxazole, diclofenac, warfarin, sulfamethoxazole and ciprofloxacin, τ_1/2 was found to be even less than 5 min. The structures of major photolysis products were determined using quadrupole-time-of-flight mass spectrometry (QToF) and spectroscopic data reported in the literature. For diclofenac, the transformation products carbazol-1-yl-acidic acid and 8-chloro-9H-carbazol-1-yl-acetic acid were identified based on the mass/charge ratio of protonated ions and their fragmentation pattern in negative electrospray ionization (ESI^?-QTOF). Irradiation of carbamazepine resulted in three known products: acridine, carbamazepine-10,11-epoxide, and 10,11-dihydro-10,11-dihydroxy-carbamazepine, whereas acetaminophen was photolytically transformed to 1-(2-amino-5 hydroxyphenyl) ethenone. These photochemical products were subsequently identified in seawater or fish samples collected at sites exposed to wastewater effluents on the Saudi Arabian coast of the Red Sea.     

The photolysis of organic substances under atmospheric conditions with a cylindrical photoreactor using ethyl nitrite and nitrogen dioxide

The first-order rate constants of 8 organic substances were measured using the ethyl nitrite and nitrogen dioxide photolyses and their relative rates with respect to n-hexane rate constant were calculated. These were compared with literature data. Relatively small photolysis rates of alkane and aromatics were shown for our photosystems and the alkenes were rapidly photolyzed. For mixed photooxidation reactions of various organics, it would be reasonable for organics of the group classified by their molecular structures to be discussed on their reactivities with OH radicals.     

Kinetic study of the OH reaction with some hydrochloroethers under simulated atmospheric conditions

Using the relative rate technique, rate constants for the gas-phase reactions of hydroxyl radicals with 2-chloroethyl methyl ether (k₁), 2-chloroethyl ethyl ether (k₂) and bis(2-chloroethyl) ether (k₃) have been measured. Experiments were carried out at (298 ± 2) K and atmospheric pressure using synthetic air as bath gas. Using n-pentane and n-heptane as reference compounds, the following rate constants were derived: k₁ = (5.2 ± 1.2) × 10^?12, k₂ = (8.3 ± 1.9) × 10^?12 and k₃ = (7.6 ± 1.9) × 10^?12, in units of cm³ molecule^?1 s^?1. This is the first experimental determination of k₂ and k₃ under atmospheric pressure. The rate constants obtained are compared with previous literature data and the observed trends in the relative rates of reaction of hydroxyl radicals with the ethers studied are discussed. The atmospheric implications of the results are considered in terms of lifetimes and fates of the hydrochloroethers studied.     

The effects of the rate for OH + HNO3 and HO2NO2 photolysis on stratospheric chemistry

The effects of the new estimates of the rate of the reaction of OH with HNO₃ and of HO₂NO₂ photolysis on models of stratospheric chemistry are discussed using a one-dimensional model. The new rates could lower the calculated OH concentrations in the altitude range 15–30 km with significant impact on the vertical profiles of ClO, HCl and NO₂ in the stratosphere and on the ozone perturbations due to fluorocarbons.     

Kinetic studies of the reaction of hydroxyl radicals with trichloroethylene and tetrachloroethylene

Rate coefficients are reported for the gas-phase reaction of the hydroxyl radical (OH) with C2HCl3 (k(1)) and C2Cl4 (k2) over an extended temperature range at 740+/-10 Torr in a He bath gas. These absolute rate measurements were accomplished using a laser photolysis/laser-induced fluorescence (LP/LIF) technique under slow flow conditions. The simple Arrhenius equation adequately describes the low temperature data for k1 (<650 K) and the entire data set for k2 and is given by (in units of cm3 molecule(-1) s(-1)): k1(291 - 650 K) = (9.73+/-1.15) x 10(-13) exp (158.7+/-44.0)/T, k2(293 - 720 K ) = (1.53+/-0.14) x 10(-12) exp (-688.2+/-67.5)/T. Error limits are 2sigma values. The room temperature values for k1 and k2 are within +/-2sigma of previous data using different techniques. The Arrhenius activation energies for k1 and k2 are a factor of 2-3 lower than previously reported values. The experimental measurements for both k1 and k2 in conjunction with transition state and variation transition state theory calculations infer an OH addition mechanism. The lack of a measurable kinetic isotope effect for k1 is consistent with this mechanism. Insight into the subsequent reactions of the chemically activated intermediate are presented in the form of potential energy diagrams derived from ab initio calculations.     

废液晶显示器偏光片水热产乳酸研究

以废液晶显示面板中的偏光片为原料,对其进行水热产乳酸研究,并考察了反应温度(250～375℃)、反应时间(1～11min)以及氧化剂(体积分数为30％的H2O2)投加量(0～1.0 mL)对乳酸产率的影响.结果表明,反应温度、反应时间均会对偏光片水热产乳酸产生一定影响,乳酸产率随反应温度和反应时间的增加呈现先增加后减少的趋势,最佳水热条件为反应温度350℃,反应时间5 min,此时乳酸产率达17％左右.投加氧化剂能显著提高乳酸的产率,在最佳水热条件下,氧化剂投加量为0.6 mL时乳酸的产率可提高到21％.     

Photodegradation of malachite green under natural sunlight irradiation: kinetic and toxicity of the transformation products

This article describes the photolytic degradation of malachite green (MG), a cationic triphenylmethane dye used worldwide as a fungicide and antiseptic in the aquaculture industry. Photolysis experiments were performed by direct exposure of a solution of MG in water to natural sunlight. The main transformation products (TPs) generated during the process were identified by liquid chromatography time-of-flight mass spectrometry (LC–TOF-MS) and gas chromatography mass spectrometry (GC–MS). The 28 TPs identified with this strategy indicate that MG undergoes three main reactions, N-demethylation, hydroxylation and cleavage of the conjugated structure forming benzophenone derivatives. These processes involve hydroxyl radical attack on the phenyl ring, the N,N-dimethylamine group and the central carbon atom. The Vibrio fischeri acute toxicity test showed that the solution remains toxic after MG has completely disappeared. This toxicity could be assigned, at least in part, to the formation of 4-(dimethylamine)benzophenone, which has an EC_50,30 min of 0.061 mg l⁻¹, and is considered “very toxic to aquatic organisms” by current EU legislation.     

Computer estimation of the Atmospheric gas-phase reaction rate of organic compounds with hydroxyl radicals and ozone

The Atmospheric Oxidation Program (AOP) is a computer program that estimates the rate constant for the atmospheric, gas-phase reaction between photochemically produced hydroxyl radicals (OH) and organic chemicals. It also estimates the rate constant for the gas-phase reaction between ozone and olefinic/acetylenic compounds. AOP, which uses estimation methods developed by Atkinson and co-workers, estimates more accurate rate constants than the PCFAP (Fate of Atmospheric Pollutants) program that was part of the U.S. EPA's Graphical Exposure Modeling System (GEMS). Due to its superior predictive ability, the EPA is currently using AOP to evaluate the atmospheric fate of compounds defined under Sections 4, 5 and 6 of the Toxic Substances Control Act (TSCA).     

Simultaneous Cr (VI) reduction and diazinon oxidation with organometallic sludge formation under photolysis: kinetics,degradation pathways,and mechanism

Environmental Science and Pollution Research - In this study, simultaneous removal of an organic matter (diazinon, DIZ) and an inorganic substance (chromium, Cr) was used. Breaking down of organic...     

Kinetics of IO radicals with C1, C2 aliphatic alcohols in tropospherically relevant conditions

Environmental Science and Pollution Research - Kinetics of the reaction of IO radicals with methanol (MeOH) and ethanol (EtOH) were experimentally studied in the gas phase using pulsed laser...     

Different reaction mechanisms of diphenylether and 4-bromodiphenylether with nitrous acid in the 355 nm laser flash photolysis of mixed aqueous solution

The microscopic reaction mechanisms of diphenylether (DPE) and 4-bromodiphenylether (4-BrDPE) with nitrous acid (HNO(2)) in the absence of O(2) have been explored by the 355nm laser flash photolysis. It was proposed that OH radical, from the photolysis of HNO(2), added to DPE forms the C(12)H(10)O-OH adduct while added to 4-BrDPE forms the 4-BrDPE-OH and 4-BrOH-DPE adducts. The first-order decay rate constants of the C(12)H(10)O-OH adduct, 4-BrDPE-OH adduct and 4-BrOH-DPE adduct were measured to be (1.86+/-0.14)x10(5)s(-1), (2.19+/-0.04)x10(5)s(-1) and (1.56+/-0.03)x10(5)s(-1), respectively. The final photolysis products of DPE and HNO(2) identified by GC/MS analysis were phenol, o-hydroxydiphenylether, p-hydroxydiphenylether and p-nitrodiphenylether, while the final photolysis product of 4-BrDPE and HNO(2) identified by LC/MS analysis was mainly the dimer.     

Removal of hexavalent chromium upon interaction with biochar under acidic conditions: mechanistic insights and application

Environmental Science and Pollution Research - Chromium pollution of soil and water is a serious environmental concern due to potential carcinogenicity of hexavalent chromium [Cr(VI)] when...     

Acetamide hydrolyzing activity of Bacillus megaterium F-8 with bioremediation potential: Optimization of production and reaction conditions.

Bacillus megaterium F-8 exhibited an intracellular acetamide hydrolyzing activity (AHA) when cultivated in modified nutrient broth with 3 % tryptone, 1.5 % yeast extract, and 0.5 % sodium chloride, at pH 7.2, 45 °C for 24 h. Maximum AHA was recorded in the culture containing 0.1 M of sodium phosphate buffer, (pH 7.5) at 45 °C for 20 min with 0.2 % of acetonitrile and resting cells of B. megaterium F-8 equivalent to 0.2 ml culture broth. This activity was stable up to 55 °C and was completely inactivated at or above 60 °C. Maximum acyl transferase activity (ATA) was recorded in the reaction medium containing 0.1 M of potassium phosphate buffer, (pH 8.0) at 55 °C for 5 min with 0.85 mM of acetamide as acyl donor and hydroxylamine hydrochloride as acyl acceptor and resting cells of B. megaterium F-8 equivalent to 0.94 mg cells (dry weight basis). This activity was stable up to 60 °C and a rapid decline in enzyme activity was recorded above it. Under the optimized conditions, this organism hydrolyzed various nitriles and amides such as propionitrile, propionamide, caprolactam, acetamide, and acrylamide to corresponding acids. Acyl group transfer capability of this organism was used for the production of acetohydroxamic acid. ATA of B. megaterium F-8 showed broad substrate specificity such as for acetamide followed by propionamide, acrylamide, and lactamide. This amide hydrolyzing and amidotransferase activity of B. megaterium F-8 has potential applications in enzymatic synthesis of hydroxamic acids and bioremediation of nitriles and amides contaminated soil and water system.     

Atmospheric dispersion under non-homogeneous and unsteady conditions

Accidental releases of toxic material can give rise to serious air pollution situations. The behaviour of such releases is frequently quite different from that of normal chimney plumes and is highly unpredictable since their extent and occurrence cannot be known in advance. Thus one has to resort to computational simulation procedures for reasonable estimates of pollutant dispersion parameters in the atmosphere. In the present study efforts are made to develop such simulation procedures. Computer software is developed which can be obtained free of cost from the authors to simulate pollutant dispersal from continuous/short-term, steady/fluctuating, surface/elevated sources in stationary/non-stationary and homogeneous/non-homogeneous atmosphere using basic Gaussian theory. Validity and limitations of developed software are demonstrated through comparison of results obtained using different programs and field measurements. In general, the predicted results appear to be quite logical and the computer software prepared may prove to be a valuable aid in estimating the extent of air pollution.     

剩余污泥在微氧条件下利用VFAs合成PHAs的工况优化

针对2种脱氮除磷工艺的剩余污泥,在微氧条件下,以花生渣厌氧发酵产生的VFAs为碳源,控制反应时间为5 h,DO≤0.2 mg·L⁻¹,COD为650~750 mg·L⁻¹,对比2种不同工艺的剩余污泥合成聚羟基脂肪酸酯(PHAs)的量,并探究了增设前置曝气对微氧条件下剩余污泥合成PHAs的影响。结果表明,在微氧条件下,连续流中同步亚硝化反硝化脱氮除磷系统二沉池的剩余污泥(R1)和采用A²O工艺的实际水厂的剩余污泥(R2)合成PHAs最高量分别为108.6 mg·g⁻¹和58.58 mg·g⁻¹,R1比R2更具有合成PHAs的能力;在增设前置曝气实验中,曝气时间的延长和曝气量的增大均可促进PHAs的合成;当曝气气量为50 L·h⁻¹时,曝气20 min后,R1合成的PHAs最高为172.5 mg·g⁻¹。氧化还原电位(Eh)是微氧条件下PHAs合成过程中的重要指示参数,当Eh值为最低时,PHAs合成量最多。以上结果可为脱氮除磷工艺剩余污泥利用廉价碳源合成PHAs提供参考。