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.     

Photodegradation of the synthetic fragrance OTNE and the bactericide triclosan adsorbed on dried loamy sand--results from models and experiments

Fragrances such as OTNE (marketed as Iso-E-Super®) and bactericides such as triclosan (marketed as Igrasan) are present in waste water and thus finally sorbed to sewage sludge. With that sludge they can reach agricultural fields where they potentially can undergo photodegradation processes. In this study the photodegradation of OTNE and triclosan on dried loamy sand was measured under artificial sunlight conditions in laboratory experiments. These compounds were artificially added with concentrations of 1 μg g⁻¹ on pre-rinsed dried loamy sand. The decrease in concentration with light irradiation was measured for 32 d in comparison to soil samples without light irradiation. The estimated light source intensity was 27 W m⁻². Within the experiment, the apparent half-life was 7 and 17 d for OTNE and triclosan respectively. The decrease did not simply follow first-order kinetics. The apparent rate constant decreased in the latter stage of reaction, suggesting that part of the chemicals were inaccessible for degradation. Two models, i.e., a diffusion-limited model, and a light penetration-limited model, were used in comparison to the measured data to explain the observed degradation limitations in the latter stages of the experiments. Comparing the hereby obtained model parameters with estimated physico-chemical parameters for the soil and the two chemical compounds, the light penetration-limited model, in which the degradation in the soil surface layer is assumed to be limited due to the shading effect of light in the upper thin soil layer, showed to be the most realistic in describing the photodegradation.     

Nitrate-induced photodegradation of atenolol in aqueous solution: kinetics, toxicity and degradation pathways

The extensive utilization of β-blockers worldwide led to frequent detection in natural water. In this study the photolysis behavior of atenolol (ATL) and toxicity of its photodegradation products were investigated in the presence of nitrate ions. The results showed that ATL photodegradation followed pseudo-first-order kinetics upon simulated solar irradiation. The photodegradation was found to be dependent on nitrate concentration and increasing the nitrate from 0.5 mM L⁻¹ to 10 mM L⁻¹ led to the enhancement of rate constant from 0.00101 min⁻¹ to 0.00716 min⁻¹. Hydroxyl radical was determined to play a key role in the photolysis process by using isopropanol as molecular probe. Increasing the solution pH from 4.8 to 10.4, the photodegradation rate slightly decreased from 0.00246 min⁻¹ to 0.00195 min⁻¹, probably due to pH-dependent effect of nitrate-induced OH formation. Bicarbonate decreased the photodegradation of ATL in the presence of nitrate ions mainly through pH effect, while humic substance inhibited the photodegradation via both attenuating light and competing radicals. Upon irradiation for 240 min, only 10% reduction of total organic carbon (TOC) can be achieved in spite of 72% transformation rate of ATL, implying a majority of ATL transformed into intermediate products rather than complete mineralization. The main photoproducts of ATL were identified by using solid phase extraction-liquid chromatography-mass spectrometry (SPE-LC-MS) techniques and possible nitrate-induced photodegradation pathways were proposed. The toxicity of the phototransformation products was evaluated using aquatic species Daphnia magna, and the results revealed that photodegradation was an effective mechanism for ATL toxicity reduction in natural waters.     

Kinetics of nitromusk compounds degradation in water by ultraviolet radiation and hydrogen peroxide

The photodegradation of five representative nitromusk compounds in water has been performed in a stirred batch photoreactor with a UV low-pressure immersed mercury lamp, at constant temperature and different doses of hydrogen peroxide. The rate constants have been calculated on the basis of experimental data and a postulated first-order kinetic model. The rate constants, at 298 K and a dose of 1.1746 μmol l⁻¹ H₂O₂ ranges from 0.3567 × 10⁻³ s⁻¹ for musk tibetene, to 1.785 × 10⁻³ s⁻¹ for musk ambrette.     

Study on photocatalytic degradation of gaseous dichloromethane using pure and iron ion-doped TiO2 prepared by the sol-gel method

The synthesis of TiO₂ and Fe–TiO₂ by sol–gel method is demonstrated and characterized. The characterization of TiO₂ and Fe–TiO₂ is performed with instruments, including TGA/DTA, FTIR, UV–Vis, N₂ adsorption and SEM. Dichloromethane is used for the photocatalytic activity test. From the results of dichloromethane photocatalyitc degradation, the calcined temperature of TiO₂ and the presence of water vapor influence the photocatalytic activity. The optimum doping amount of iron ions is 0.005 mol%, and this can enhance the photocatalytic activity, while too great an amount will make the iron ions become recombination centers for the electron–hole pairs and reduce the photocatalytic activity. UV–Vis diffuse reflectance spectra of Fe–TiO₂ show an increase in absorbency in the visible light region with the increase in iron ions doping concentration The intermediate of dichloromethane photodegradation includes CHCl₃, CCl₄, CH₂Cl₂ and COCl₂. The presence of iron ions may reduce the adsorption of Cl element on the surface of the photocatalyst.     

Incomplete aerobic degradation of the antidiabetic drug Metformin and identification of the bacterial dead-end transformation product Guanylurea

Active pharmaceutical ingredients as well as personal care products are detected in increasing prevalence in different environmental compartments such as surface water, groundwater and soil. Still little is known about the environmental fate of these substances. The type II antidiabetic drug Metformin has already been detected in different surface waters worldwide, but concentrations were significantly lower than the corresponding predicted environmental concentration (PEC). In human and mammal metabolism so far no metabolites of Metformin have been identified, so the expected environmental concentrations should be very high.To assess the aerobic biodegradability of Metformin and the possible formation of degradation products, three Organisation of Economic Cooperation and Development (OECD) test series were performed in the present study.In the Closed Bottle test (OECD 301 D), a screening test that simulates the conditions of an environmental surface water compartment, Metformin was classified as not readily biodegradable (no biodegradation). In the Manometric Respiratory test (OEDC 301 F) working with high bacterial density, Metformin was biodegraded in one of three test bottles to 48.7% and in the toxicity control bottle to 57.5%. In the Zahn-Wellens test (OECD 302 B) using activated sludge, Metformin was biodegraded in both test vessels to an extent of 51.3% and 49.9%, respectively.Analysis of test samples by high performance liquid chromatography coupled to multiple stage mass spectrometry (HPLC-MS(n)) showed in the tests vessels were biodegradation was observed full elimination of Metformin and revealed Guanylurea (Amidinourea, Dicyandiamidine) as single and stable aerobic bacterial degradation product. In another Manometric Respiratory test Guanylurea showed no more transformation. Photodegradation of Guanylurea was also negative.A first screening in one of the greatest sewage treatment plant in southern Germany found Metformin with high concentrations (56.8 μg L⁻¹) in the influent (PEC = 79.8 μg L⁻¹), but effluent concentration was much lower (0.76 μg L⁻¹) whereas Guanylurea was detected in a low influent and high effluent concentration (1.86 μg L⁻¹). These data support the experimental findings in the OECD tests and analytical results of other studies, that Metformin under aerobic conditions can bacterially be degraded to the stable dead-end transformation product Guanylurea.     

Determination of o-phthalic acid in snow and its photochemical degradation by capillary gas chromatography coupled with flame ionization and mass spectrometric detection

Phthalic acid and its photochemical degradation has been determined in snow and rainwater samples collected during winters (2003-2010) in the Southeast of Massachusetts using capillary gas chromatography (GC) with flame ionization and mass spectrometric detection. Water samples were dried using a rotary evaporator and derivatized with a 14% BF₃/methanol reagent before GC analysis. The developed method proved simple and accurate. Phthalic acid was found in snow samples collected in a concentration range of 7.22-76.5 nM. The photodegradation of phthalate was carried out under 300 nm UV light. The direct photodecomposition of the acid is slow (5% h⁻¹). However, the addition of dissolved Fe(III) species at 2.0 μM accelerated the light-induced degradation of phthalic acid by 3.5 times in the atmospheric water samples. Photodegradation rates of phthalic acid increases with decreasing pH value of water samples in the range of pH 2.8-4.5.     

Modelling the environmental degradation of water contaminants. Kinetics and mechanism of the riboflavin-sensitised-photooxidation of phenolic compounds

The aerobic visible-light-photosensitised irradiation of methanolic solutions of either of the phenolic-type contaminants model compounds (ArOH) p-phenylphenol (PP), p-nitrophenol (NP) and phenol (Ph), and for two additional phenolic derivatives, namely p-chlorophenol (ClP) and p-methoxyphenol (MeOP), used in some experiments, was carried out. Employing the natural pigment riboflavin (Rf) as a sensitiser, the degradation of both the ArOH and the very sensitiser was observed. A complex mechanism, common for all the ArOH studied, operates. It involves superoxide radical anion (O₂^√−) and singlet molecular oxygen (O₂(¹Δ_g)) reactions. Maintaining Rf in sensitising concentrations levels (≈0.02 mM), the mechanism is highly dependent on the concentration of the ArOH. Kinetic experiments of oxygen and substrate consumption, static fluorescence, laser flash photolysis and time-resolved phosophorescence detection of O₂(¹Δ_g) demonstrate that at ArOH concentrations in the order of 10 mM, no chemical transformation occurs due to the complete quenching of Rf singlet excited state. When ArOH is present in concentrations in the order of mM or lower, O₂^√− is generated from the corresponding Rf radical anion, which is produced by electron transfer reaction from the ArOH to triplet excited Rf. The determined reaction rate constants for this step show a fairly good correlation with the electron-donor capabilities for Ph, PP, NP, ClP and MeOP. In this context, the main oxidative species is O₂^√−, since O₂(¹Δ_g) is quenched in an exclusive physical fashion by the ArOH. The production of O₂^√− regenerates Rf impeding the total degradation of the sensitiser. This kinetic scheme could partially model the fate of ArOH in aquatic media containing natural photosensitisers, under environmental conditions.     

壬基酚及其短链聚氧乙烯醚在污泥和土壤中的存在和降解

壬基酚聚氧乙烯醚(NPnEO)是广泛使用的表面活性剂．在污水处理厂中会降解为具有内分泌干扰效应的短链产物和最终产物壬基酚(NP)。剩余污泥是其进入环境的重要途径。介绍了NP和短链NPnEO在污泥中的存在情况、污泥处理过程对其存在的影响、以及这些物质随污泥处置过程进入土壤后的降解。     

Effects of Fe2O3, organic matter and carbonate on photocatalytic degradation of lindane in the sediment from the Liao River,China

Fourteen sediment samples with different content of Fe₂O₃ were collected from the lower reaches of the Liao River in China. The photodegradation of lindane on the surfaces of these sediments was investigated to observe the effects of Fe₂O₃ and other photoinducable substances, such as TiO₂ and organic substances, on photodegradation of lindane. A partial least-squares (PLS) analysis model was developed to find out the statistical relationship between the photodegradation and the contents of these photoinducable substances. It was concluded from the PLS analysis that inorganic carbon and organic carbon have negative effects, whereas Fe₂O₃ and TiO₂ accelerate the photodegradation of lindane in the sediment samples when 365 nm UV light was used as light source. In all cases of the experiments, the photodegradation of lindane in the sediment samples were fitted for pseudo-first-order kinetics.     

Fate and antibacterial potency of anticoccidial drugs and their main abiotic degradation products

The antibacterial potency of eight anticoccidial drugs was tested in a soil bacteria bioassay (pour plate method), EC₅₀-values between 2.4 and 19.6 μM were obtained; however, one compound, nicarbazin exhibited an EC₅₀-value above the maximum tested concentration (21 μM, 9.1 mg L⁻¹). The potency of mixtures of two of the compounds, narasin and nicarbazin, was synergistic (more than additive) with 10-fold greater antibacterial potency of the mixture than can be explained by their individual EC₅₀-values. The influence of pH, temperature, oxygen concentration and light on the transformation of robenidine and salinomycin was investigated. Robenidine was transformed by photolysis (DT₅₀ of 4.1 days) and was unstable at low pH (DT₅₀ of approximately 4 days); salinomycin was merely transformed at low pH, the latter into an unknown number of products. The antibacterial potency of the mixtures of transformation products of robenidine after photolysis and at low pH was comparable with that of the parent compound. Finally five photo-transformation products of robenidine were structural elucidated by accurate mass measurements, i-FIT values (isotopic pattern fit) and MS/MS fragmentation patterns.     

Plant uptake and in-soil degradation of PCB-5 under varying cropping conditions

A 60-d greenhouse experiment was conducted to investigate the uptake and in-soil degradation of PCB-5 under single cropping and intercropping conditions involving three crop plant species: pumpkin, soybean and corn. Volatilization of PCB-5 from the soil surface was also tested. The results show that while uptake of PCB-5 by the test plant species is possible and the root concentration of PCB-5 had a control on the upward transport of PCB-5 to the above-ground portion of the plants, the PCB-5 extracted by the plants mainly accumulated in the root materials. Phytoextraction contributed insignificantly toward the loss of the soil-borne PCB-5. Volatilization of PCB-5 from the soil was recorded but it appeared that this did not result in a marked loss of PCB-5 in the bulk soil though it might cause remarkable removal of PCB-5 in a thin layer of the topsoil (1 mm). It is likely that the in-soil biodegradation contributed markedly to the observed reduction in soil-borne PCB-5. The in-soil biodegradation of PCB-5 was significantly enhanced under intercropping conditions, which appeared to be related to increased microbial activities, particularly bacterial activities. The soil residual PCB-5 was correlated with the activity of the following enzymes: catalase (CAT), polyphenol oxidase (PPO) and peroxidase (POD).     

The dissipation rates of trichlorfon and its degradation product dichlorvos in cabbage and soil

The residual levels and dissipation rate of trichlorfon, and its degradation product, dichlorvos, in cabbage crops and the soil in which these were grown, were determined by gas chromatography at two geographically distant experimental sites, one in Kunming and one in Beijing, China. Trichlorfon was applied at two dosages (900 g ai ha⁻¹ and 1350 g ai ha⁻¹). Maximum final residues of trichlorfon in soil and cabbage were 1.23 mg kg⁻¹ and 1.81 mg kg⁻¹ respectively at Kunming, and 0.35 mg kg⁻¹ and 0.70 mg kg⁻¹ respectively at Beijing. However, the final residues of dichlorvos in both cabbage and soil was only 0.04 mg kg⁻¹ at Kunming, and only 0.03 mg kg⁻¹, or “not detectable”, at Beijing. The mean half-life of trichlorfon in cabbage was 1.80 d with a dissipation rate of 90% over 5 d, while that in soil was 3.05 d with a dissipation rate of 90% over 14 d at one experimental site. The dissipation rates of trichlorfon and its degradation product dichlorvos at the two experimental sites were different, suggesting that degradation of these pesticides was affected by local soil characteristics and climate. When applied at both the recommended dosage and at 1.5 times this, no detectable residues of either trichlorfon or dichlorvos were found in soil or cabbage at harvest. Although trichlorfon can easily degrade into dichlorvos, which is highly toxic to humans and other animals, the observed low residual levels of dichlorvos suggest that trichlorfon is safe when applied at the recommended dosage.     

Biological degradation of triclocarban and triclosan in a soil under aerobic and anaerobic conditions and comparison with environmental fate modelling

Triclocarban and triclosan are two antimicrobial agents widely used in many personal care products. Their biodegradation behaviour in soil was investigated by laboratory degradation experiments and environmental fate modelling. Quantitative structure-activity relationship (QSAR) analyses showed that triclocarban and triclosan had a tendency to partition into soil or sediment in the environment. Fate modelling suggests that either triclocarban or triclosan "does not degrade fast" with its primary biodegradation half-life of "weeks" and ultimate biodegradation half-life of "months". Laboratory experiments showed that triclocarban and triclosan were degraded in the aerobic soil with half-life of 108 days and 18 days, respectively. No negative effect of these two antimicrobial agents on soil microbial activity was observed in the aerobic soil samples during the experiments. But these two compounds persisted in the anaerobic soil within 70 days of the experimental period.     

Evidence of degradation of polybrominated biphenyls in soil samples from michigan

Abstract

Soil samples obtained from the former polybrominated biphenyls (PBB) manufacturing site in Michigan were analyzed by gas chromatography and gas chromatography with mass spectrometric detection. The results indicate significant degradation of the PBB residue in the soil sample. The soil sample with the highest concentration of PBB has the greatest degree of degradation. Principal degradation products include 2,3’,4,4’,5‐pentabromo‐biphenyl, 2,2’,4,4’,5‐pencabromobiphenyl and two unidentified tetrabromobiphenyls.

The degradation pattern observed supports a photochemical decomposition mechanism. These degraded residues may be more toxic than the original Firemaster residues. The implications of the results are discussed.     

Urbanisation-driven land degradation and socioeconomic challenges in peri-urban areas: Insights from Southern Europe

Climate change and landscape transformation have led to rapid expansion of peri-urban areas globally, representing new ‘laboratories’ for the study of human–nature relationships aiming at land degradation management. This paper contributes to the debate on human-driven land degradation processes by highlighting how natural and socioeconomic forces trigger soil depletion and environmental degradation in peri-urban areas. The aim was to classify and synthesise the interactions of urbanisation-driven factors with direct or indirect, on-site or off-site, and short-term or century-scale impacts on land degradation, focussing on Southern Europe as a paradigmatic case to address this issue. Assuming complex and multifaceted interactions among influencing factors, a relevant contribution to land degradation was shown to derive from socioeconomic drivers, the most important of which were population growth and urban sprawl. Viewing peri-urban areas as socio-environmental systems adapting to intense socioeconomic transformations, these factors were identified as forming complex environmental ‘syndromes’ driven by urbanisation. Based on this classification, we suggested three key measures to support future land management in Southern European peri-urban areas.     

Pencycuron application to soils: degradation and effect on microbiological parameters

Clay loam soil from agricultural fields of alluvial (AL) soil (typic udifluvent) and coastal saline (CS) soil (typic endoaquept) were investigated for the degradation and effect of pencycuron application at field rate (FR), 2-times FR (2FR) and 10-times FR (10FR) with and without decomposed cow manure (DCM) on soil microbial variables under laboratory conditions. Pencycuron degraded faster in CS soil and in soil amended with DCM. Pencycuron spiking at FR and 2FR resulted in a short-lived (in case of 10FR slightly longer) and transitory toxic effect on soil microbial biomass-C (MBC), ergosterol content and fluorescein diacetate hydrolyzing activity (FDHA). Amendment of DCM did not seem to have any counteractive effect of the toxicity of pencycuron on the microbial variables. The ecophysiological status of the soil microbial communities as expressed by microbial metabolic quotient (qCO2) and microbial respiration quotient (Q(R)) changed, but for a short period, indicating pencycuron induced disturbance. The duration of this disturbance was slightly longer at 10FR. Pencycuron was more toxic to the metabolically activated soil microbial populations, specifically the fungi. It is concluded that side effects of pencycuron at 10FR on the microbial variables studied were only short-lived and probably of little ecological significance.     

Occurrence and source analysis of typical veterinary antibiotics in manure, soil, vegetables and groundwater from organic vegetable bases, northern China

The residue of antibiotics is becoming an intractable environmental problem in many organic vegetable bases. However, their residual levels and distribution are still obscure. This work systematically analyzed the occurrence and migration of typical veterinary antibiotics in organic vegetable bases, northern China. The results showed that there was no obvious geographical difference in antibiotic distribution between soil and manure. A simple migration model can be easy and quick to predict the accumulation of antibiotics in soil. Antibiotics were mainly taken up through water transport and passive absorption in vegetables. The distribution of antibiotics in a plant was in the sequence leaf > stem > root, and performed biological accumulation. The residues of antibiotics in all samples in winter were significantly higher than those in summer. Overall, this work can lay the foundation for understanding ecological risk of antibiotics and their potential adverse effects on human health by food chain.     

Characterisation of the abiotic degradation pathways of oxytetracyclines in soil interstitial water using LC-MS-MS

The fate of oxytetracyclines (OTCs) in soil interstitial water was investigated and the structure of a number of degradation products elucidated in a time-related experiment. A previously developed separation method for LC–MS–MS able to base separate and quantify OTC and three of its epimers and degradation products was applied. Compounds detected were 4-epi-oxytetracycline (EOTC) (t_R=3.0 min), OTC (t_R=4.4 min), -apo-oxytetracycline (-apo-OTC) (t_R=11.4 min) and β-apo-oxytetracycline (β-apo-OTC) (t_R=18.4 min). Furthermore, we tentatively identified 4-epi-N-desmethyl-oxytetracycline (E-N-DM-OTC) (t_R=3.0 min), N-desmethyl-oxytetracycline (N-DM-OTC) (t_R=3.5), N-didesmethyl-oxytetracycline (N-DDM-OTC), 4-epi-N-didesmethyl-oxytetracycline (E-N-DDM-OTC) (t_R=3.7 and 4.7 min) and 2-acetyl-2-decarboxamido-oxytetracycline (t_R=8.7) in all samples. Most compounds were only present in trace concentrations (less than 2%) relative to the parent OTC. EOTC was on the other hand formed up to a ratio of 0.6 relative to parent OTC concentration. Only EOTC, E-N-DM-OTC, N-DM-OTC, N-DDM-OTC and E-N-DDM-OTC were formed during the time-related experiment. All other compounds were probably only present as impurities in the spiked OTC formulation as they declined in concentration from the start of the experiment. Half-lives (T_1/2, days) of the OTCs in soil interstitial water were in the order of 2 days (EOTC) to 270 days (β-apo-OTC).