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.     

Photodegradation of the antibiotic spiramycin studied by high-performance liquid chromatography-electrospray ionization-quadrupole time-of-flight mass spectrometry

The degradation of spiramycin induced by ultraviolet (UV) irradiation was studied at pH 3–4, 6–7 and 8–9 using high-performance liquid chromatography-electrospray ionization-quadrupole time-of-flight mass spectrometry. Furthermore, the influence of hydrogen peroxide and oxygen on the photodegradation was investigated. Three degradation products were observed in the presence of oxygen and four in the absence of oxygen. The degradation kinetics were monitored as mass area-time curves, analyzed and described using subsequent follow-up reaction first-order models. The m/z values of the degradation products were determined to be 160, 322 and 366, the latter representing two separate products, the sugar moieties of spiramycin. Remainders of the macrocycle or the intact lactone ring of spiramycin were not observed, since the conjugated π-electron system was assumed photoexcited and thus undergoing photodegradation and fast destruction of the ring. The kinetic of the degradation of spiramycin itself was described using a first-order model. The degradation was accelerated upon addition of hydrogen peroxide. In contrast, systematic acceleration depending on pH could not be found. The absence of oxygen did not lead to any significant acceleration. The findings are interpreted in terms of the effectiveness of advanced oxidation processes and their potential use as a fourth purification step in wastewater treatment plants.     

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.     

Sunlight-induced degradation of soil-adsorbed veterinary antimicrobials Marbofloxacin and Enrofloxacin

Marbofloxacin (MAR) and Enrofloxacin (ENR), two largely employed veterinary Fluoroquinolones (FQs), were found to be present at the micrograms per kilogram level in agricultural soils of South Lombardy (Italy) several months after manuring. Distribution coefficients (K_d) from sorption experiments indicated a strong binding to the soil. Soil samples fortified with environmentally significant FQs amounts (0.5 mg kg⁻¹) were exposed to solar light that promoted extensive degradation (80%) of both drugs in 60-150 h. Thus, photochemistry could be considered a significant depollution path in the soil, although it was two orders of magnitudes slower than in aqueous solution and a fraction of the drug (ca. 20%) remained unaffected. For MAR the photoprocess was the same as in solution, and involved cleavage of the tetrahydrooxadiazine ring. On the contrary, with ENR only some of the photoproducts determined in water (those arising from a stepwise oxidation of the piperazine side chain) were observed. Substitution of the 6-fluoro by a hydroxyl group and reduction did not occur in the soil, supporting the previous contention that such processes required polar solvation of FQs. Consistently with this rationalization, the irradiation of thin layers of solid drugs led to essentially the same products distribution as in the soil. From the environmental point of view it is important to notice that photodegradation mainly affects the side-chains, while the fluoroquinolone ring, to which the biological effect is associated, is conserved up to the later stages of the degradation.     

Direct and indirect photolysis of cyhalofop in aqueous systems

The photodegradation of the aryloxyphenoxy propionic herbicide cyhalofop-butyl (2R)-2-[4-(4-cyano-2-fluorophenoxy)phenoxy]butylpropanoate (CyB), and of its primary metabolite (2R)-2-[4-(4-cyano-2-fluorophenoxy)phenoxy]propanoic acid (CyA) was studied in water at different irradiation wavelengths. The sunlight irradiation was investigated also in the presence of humic acid (HA), Fe oxide, titanium dioxide (TiO₂) and zinc oxide (ZnO) as photocatalysts.CyB and CyA were rapidly degraded by UV irradiation. CyB afforded the butyl ester of 2-[3-(4-cyano-2-fluorophenyl)-4-hydroxy-phenoxy]propanoic acid (CyI), a metabolite arising from a photo-Fries rearrangement. Instead, CyA yielded (R)-2-4-(4-carboxyl-2-fluorophenoxy)phenoxypropanoic acid (CyD), a dicarboxylic acid arising from the photo-hydrolysis of cyano group via amide. CyB was stable in simulated sunlight also in the presence of the catalysts tested.The irradiation of a CyA solution, in the presence of HA or Fe oxide, with simulated sunlight did not produce any significant degradation. In the same experimental conditions, CyA was totally mineralized in the presence of TiO₂ and ZnO.     

Photodegradation of methylmercury in Jialing River of Chongqing, China

Photodegradation(PD) of methylmercury(MMHg) is a key process of mercury(Hg) cycling i water systems, maintaining MMHg at a low level in water systems. However, we posses little knowledge of this important process in the Jialing River of Chongqing, China. In sit incubation experiments were thus performed to measure temporal patterns and influencin factors of MMHg PD in this river. The results showed that MMHg underwent a ne demethylation process under solar radiation in the water column, which predominantl occurred in surface waters. For surface water, the highest PD rate constants were observed i spring(12 × 10-3± 1.5 × 10~(-3)m~2/E), followed by summer(9.0 × 10~(-3)± 1.2 × 10~(-3)m~2/E), autum(1.4 × 10~(-3)± 0.12 × 10~(-3)m~2/E), and winter(0.78 × 10~(-3)± 0.11 × 10~(-3)m~2/E). UV-A radiatio(320–400 nm), UV-B radiation(280–320 nm), and photosynthetically active radiation(PAR400–700 nm) accounted for 43%–64%, 14%–31%, and 16%–45% of MMHg PD, respectively. PD rat constants varied substantially with the treatments that filtered the river water and amended with chemicals(i.e., Cl-, NO_3~-, dissolved organic matter(DOM), Fe(III)), which reveals tha suspended particulate matter and water components are important factors in affecting the PD process. For the entire water column, the PD rate constant determined for each wavelengt range decreased rapidly with water depth. UV-A, UV-B, and PAR contributed 27%–46%, 6.2%12%, and 42%–65% to the PD process, respectively. PD flux was estimated to be 4.7 μg/(m~2·yea in the study site. Our results are very important to understand the cycling characteristics o MMHg in the Jialing River of Chongqing, China.     

Phototransformation of Clodinafop-Propargyl

Abstract

Photodegradation of the herbicide clodinafop-propargyl was investigated on glass surface under sunlight and UV light. Four photoproducts were identified by NMR, IR, and MS. Major photolysis products were 2-[(5-chloro-3-fluoro-2-pyridyloxy) phenoxy] propanoic acid and prop-2-ynyl-2-[(5-chloro-3-hydroxy-2-pyridyloxy) phenoxy] propanoate, while minor were ethyl 2-[(5-chloro-3-fluoro-2-pyridyloxy) phenoxy] propanoate and 1-hydroxypropanyl-2-[(5-chloro-3-fluoro-2-pyridyloxy) phenoxy] propanoate. Rate of photodegradation followed first-order kinetics with significant correlation coefficient. The major photoproducts were observed in maximum quantity on the 7th and 10th day and further degraded within 15–20 days.     

腐殖质NAFA溶液中的扑热息痛光解研究

以中压汞灯为光源模拟阳光,研究了扑热息痛（ACT）在腐殖质NAFA中的光解行为,探讨了不同浓度的腐殖质、ACT、硝酸钠、碳酸氢钠、二价铁离子和pH值对ACT光解的影响,采用GC/MS技术鉴定了ACT的光解产物,并探讨其在腐殖质体系中可能的光解途径。研究结果表明,增加水体中的腐殖质、硝酸钠、二价铁离子浓度和pH值会促进ACT的光解,而增加水体中的ACT和碳酸氢钠浓度则会抑制ACT的光解。     

Identification of sources,characteristics and photochemical transformations of dissolved organic matter with EEM-PARAFAC in the Wei River of China

• The source of DOM in surface water and sediment is inconsistent. • The DOC content changes differently in surface water and sediment. • The content of DOC in the surface water is lower than that in the sediment. • The DOM in the surface water had higher photodegradation potentials than sediment. Dissolved organic matter (DOM) in rivers is a critical regulator of the cycling and toxicity of pollutants and the behavior of DOM is a key indicator for the health of the environment. We investigated the sources and characteristics of DOM in surface water and sediment samples of the Wei River, China. Dissolved organic carbon (DOC) concentration and ultraviolet absorbance at 254 nm (UV₂₅₄) increased in the surface water and were decreased in the sediment downstream, indicating that the source of DOM in the water differed from the sediment. Parallel factor (PARAFAC) analysis of the excitation-emission matrices (EEM) revealed the presence of terrestrial humus-like, microbial humus-like and tryptophan-like proteins in the surface water, whereas the sediment contained UVA humic-like, UVC humic-like and fulvic-like in the sediment. The DOM in the surface water and sediment were mainly derived from microbial metabolic activity and the surrounding soil. Surface water DOM displayed greater photodegradation potential than sediment DOM. PARAFAC analysis indicated that the terrestrial humic-like substance in the water and the fulvic-like component in the sediment decomposed more rapidly. These data describe the characteristics of DOM in the Wei River and are crucial to understanding the fluctuations in environmental patterns.     

Photosensitivity sources of dissolved organic matter from wastewater treatment plants and their mediation effect on 17α-ethinylestradiol photodegradation

● EE2 photodegradation behavior in the presence of four WWTPs’ DOM was explored. ● The ³DOM* played a major role in the EE2 photodegradation mediated by WWTPs’ DOM. ● The A²/O process DOM contained more aromatic and oxygen-containing substances. ● Possible photosensitivity sources of DOM in the A²/O process were proposed. Dissolved organic matter (DOM) from each treatment process of wastewater treatment plants (WWTPs) contains abundant photosensitive substances, which could significantly affect the photodegradation of 17α-ethinylestradiol (EE2). Nevertheless, information about EE2 photodegradation behavior mediated by DOM from diverse WWTPs and the photosensitivity sources of such DOM are inadequate. This study explored the photodegradation behavior of EE2 mediated by four typical WWTPs’ DOM solutions and investigated the photosensitivity sources of DOM in the anaerobic-anoxic-oxic (A²/O) process. The parallel factor analysis identified three varying fluorescing components of these DOM, tryptophan-like substances or protein-like substances, microbial humus-like substances, and humic-like components. The photodegradation rate constants of EE2 were positively associated with the humification degree of DOM (P < 0.05). The triplet state substances were responsible for the degradation of EE2. DOM extracted from the A²/O process, especially in the secondary treatment process had the fastest EE2 photodegradation rate compared to that of the other three processes. Four types of components (water-soluble organic matter (WSOM), extracellular polymeric substance, humic acid, and fulvic acid) were separated from the A²/O process DOM. WSOM had the highest promotion effect on EE2 photodegradation. Fulvic acid-like components and humic acid-like organic compounds in WSOM were speculated to be important photosensitivity substances that can generate triplet state substances. This research explored the physicochemical properties and photosensitive sources of DOM in WWTPs, and explained the fate of estrogens photodegradation in natural waters.