Costas Michael

Drugs degrading photocatalytically: Kinetics and mechanisms of ofloxacin and atenolol removal on titania suspensions

The conversion of the antibiotic ofloxacin and the beta-blocker atenolol by means of TiO(2) photocatalysis was investigated. Irradiation was provided by a UVA lamp at 3.37x10(-6)einstein/s photon flux, while emphasis was given on the effect of catalyst type and loading (50-1500mg/L), initial substrate concentration (5-20mg/L), initial pH (3-10) and the effect of H(2)O(2) (0.07-1.4mM) as an additional oxidant on substrate conversion and mineralization in various matrices (i.e. pure water, groundwater and treated municipal effluent). Conversion was assessed measuring sample absorbance at 288 and 224nm for ofloxacin and atenolol, respectively, while mineralization measuring the dissolved organic carbon. Degussa P25 TiO(2) was found to be more active than other TiO(2) samples for either substrate degradation, with ofloxacin being more reactive than atenolol. Conversion generally increased with increasing catalyst loading, decreasing initial substrate concentration and adding H(2)O(2), while the effect of solution pH was substrate-specific. Reaction rates, following a Langmuir-Hinshelwood kinetic expression, were maximized at a catalyst to substrate concentration ratio (w/w) of 50 and 15 for ofloxacin and atenolol, respectively, while higher ratios led to reduced efficiency. Likewise, high concentrations of H(2)O(2) had an adverse effect on reaction, presumably due to excessive oxidant scavenging radicals and other reactive species. The ecotoxicity of ofloxacin and atenolol to freshwater species Daphnia magna was found to increase with increasing substrate concentration (1-10mg/L) and exposure time (24-48h), with atenolol being more toxic than ofloxacin. Photocatalytic treatment eliminated nearly completely toxicity and this was more pronounced for atenolol.

Dissolved effluent organic matter: Characteristics and potential implications in wastewater treatment and reuse applications

Wastewater reuse is currently considered globally as the most critical element of sustainable water management. The dissolved effluent organic matter (dEfOM) present in biologically treated urban wastewater, consists of a heterogeneous mixture of refractory organic compounds with diverse structures and varying origin, including dissolved natural organic matter, soluble microbial products, endocrine disrupting compounds, pharmaceuticals and personal care products residues, disinfection by-products, metabolites/transformation products and others, which can reach the aquatic environment through discharge and reuse applications. dEfOM constitutes the major fraction of the effluent organic matter (EfOM) and due to its chemical complexity, it is necessary to utilize a battery of complementary techniques to adequately describe its structural and functional character. dEfOM has been shown to exhibit contrasting effects towards various aquatic organisms. It decreases metal uptake, thus potentially reducing their bioavailability to exposed organisms. On the other hand, dEfOM can be adsorbed on cell membranes inducing toxic effects. This review paper evaluates the performance of various advanced treatment processes (i.e., membrane filtration and separation processes, activated carbon adsorption, ion-exchange resin process, and advanced chemical oxidation processes) in removing dEfOM from wastewater effluents. In general, the literature findings reveal that dEfOM removal by advanced treatment processes depends on the type and the amount of organic compounds present in the aqueous matrix, as well as the operational parameters and the removal mechanisms taking place during the application of each treatment technology.

Solar Fenton and solar TiO2 catalytic treatment of ofloxacin in secondary treated effluents: Evaluation of operational and kinetic parameters

Two different technical approaches based on advanced oxidation processes (AOPs), solar Fenton homogeneous photocatalysis (hv/Fe(2+)/H(2)O(2)) and heterogeneous photocatalysis with titanium dioxide (TiO(2)) suspensions were studied for the chemical degradation of the fluoroquinolone ofloxacin in secondary treated effluents. A bench-scale solar simulator in combination with an appropriate photochemical batch reactor was used to evaluate and select the optimal oxidation conditions of ofloxacin spiked in secondary treated domestic effluents. The concentration profile of the examined substrate during degradation was determined by UV/Vis spectrophotometry. Mineralization was monitored by measuring the dissolved organic carbon (DOC). The concentrations of Fe(2+) and H(2)O(2) were the key factors for the solar Fenton process, while the most important parameter of the heterogeneous photocatalysis was proved to be the catalyst loading. Kinetic analyses indicated that the photodegradation of ofloxacin can be described by a pseudo-first-order reaction. The rate constant (k) for the solar Fenton process was determined at different Fe(2+) and H(2)O(2) concentrations whereas the Langmuir-Hinshelwood (LH) kinetic expression was used to assess the kinetics of the heterogeneous photocatalytic process. The conversion of ofloxacin depends on several parameters based on the various experimental conditions, which were investigated. A Daphnia magna bioassay was used to evaluate the potential toxicity of the parent compound and its photo-oxidation by-products in different stages of oxidation. In the present study solar Fenton has been demonstrated to be more effective than the solar TiO(2) process, yielding complete degradation of the examined substrate and DOC reduction of about 50% in 30 min of the photocatalytic treatment.

Stress-related phenomena and detoxification mechanisms induced by common pharmaceuticals in alfalfa (Medicago sativa L.) plants

Pharmaceutically active compounds (PhACs) have been recently shown to exert phytotoxic effects. The present study explores the uptake, systemic translocation, and abiotic stress responses and detoxification mechanisms induced by the exposure of alfalfa plants grown in sand under greenhouse conditions to four common, individually applied PhACs (10μgL(-1)) (diclofenac, sulfamethoxazole, trimethoprim, 17a-ethinylestradiol) and their mixture. Stress physiology markers (lipid peroxidation, proline, H2O2 and NO content, antioxidant activity assays) and gene expression levels of key plant detoxification components (including glutathione S-transferases, GST7, GST17; superoxide dismutases, CuZnSOD, FeSOD; proton pump, H(+)-ATP, and cytochrome c oxidase, CytcOx), were evaluated. PhACs were detected in significantly higher concentrations in roots compared with leaves. Stress related effects, manifested via membrane lipid peroxidation and oxidative burst, were local (roots) rather than systemic (leaves), and exacerbated when the tested PhACs were applied in mixture. Systemic accumulation of H2O2 in leaves suggests its involvement in signal transduction and detoxification responses. Increased antioxidant enzymatic activities, as well as upregulated transcript levels of GST7, GST17, H(+)-ATPase and CytcOx, propose their role in the detoxification of the selected PhACs in plants. The current findings provide novel biochemical and molecular evidence highlighting the studied PhACs as an emerging abiotic stress factor, and point the need for further research on wastewater flows under natural agricultural environments.

On the capacity of ozonation to remove antimicrobial compounds, resistant bacteria and toxicity from urban wastewater effluents.

The degradation of erythromycin (ERY) and ethylparaben (EtP) in urban wastewater effluents at low concentration level during ozonation was investigated under different experimental conditions. Both substrates were rapidly eliminated within 2min at low ozone dose of 0.3mgL-1 and the experimental data were well fitted in the pseudo-first-order kinetic model. The ratio of HO- and O3-exposure (Rct) at the inherent pH was found to be 1.9×10-8. The degradation of ERY and EtP was pronounced at pH 8 compared to acidic pH conditions, while the degradation rate of both substrates was found to be matrix-depended. It was also shown that both O3- and HO-mediated pathways are involved in the degradation of EtP, whereas the saturated-rich structure of ERY renders it O3-recalcitrant. Under the optimum O3 dose, the BrO3- concentration was found to be lower than 10μgL-1. Five and fifteen transformation products were elucidated during ERY and EtP oxidation, respectively. The root and shoot inhibition can be attributed to the oxidation products formed upon dissolved effluent organic matter transformation. Escherichia coli harbouring resistance to ERY survived ozonation better than EtP-resistant E. coli. However, neither ERY- nor EtP-resistant E. coli were detected after 15min of ozonation.

Wastewater reuse applications and contaminants of emerging concern

In response to the escalating problem of water shortage all over the world, treated wastewater is nowadays widely reused and is generally considered as a reliable alternative water source. Although the reuse practice is accompanied by a number of benefits relating to the enhancement of water balances and soil nutrition by the elements existing in the treated flows, a number of unanswered questions still puzzle scientists. Further to the lack of unequivocal knowledge on the possible elemental interactions that can affect the accumulation of heavy metals and other elements in the soil and their uptake by biota, during the last 2 decades, a number of organic contaminants of emerging concern has been identified and quantified in environmental compartments. The latter was made possible due to the remarkable technological progress in relation to analytical chromatographic methods, which enabled the identification and quantification of such compounds down to the ng/L level. Moreover, it is now known that the effluents’ remaining organic matter after conventional treatment consists of a number of recalcitrant organic xenobiotic compounds including potential endocrine disrupting compounds, antibiotics, and others. The fact that the currently applied treatment processes for urban wastewater abatement fail to remove completely such contaminants leading to their subsequent release in the terrestrial and aquatic environment through disposal and reuse applications is widely accepted. The number of studies focusing on the analysis and the toxicological assessment of such compounds in the environment is constantly increasing the aim being to bridge the various knowledge gaps associated with these issues. On the 13th and 14th of September 2012, approximately 80 scientists gathered in Limassol, Cyprus, to discuss the challenges of wastewater reuse practices with regard to contaminants of emerging concern, their transformation while in the environment, their potential uptake by plants and crops, the effects that these contaminants may induce in the environment, the evolution and release of antibiotic resistance, and the technologies that are able to remove such contaminants from wastewater. The workshop addressed the following themes:

Corrigendum to: “Long-term wastewater irrigation of vegetables in real agricultural systems: Concentration of pharmaceuticals in soil, uptake and bioaccumulation in tomato fruits and human health risk assessment.” [Water Res. 109 (2017) 24–34]

Corrigendum to: “Long-term wastewater irrigation of vegetables in real agricultural systems: Concentration of pharmaceuticals in soil, uptake and bioaccumulation in tomato fruits and human health risk assessment.” [Water Res. 109 (2017) 24e34] Anastasis Christou a, , Popi Karaolia b, , Evroula Hapeshi , Costas Michael , Despo Fatta-Kassinos b, c, * a Agricultural Research Institute, Ministry of Agriculture, Rural Development and Natural Recourses, P.O. Box 22016, 1516 Nicosia, Cyprus b Department of Civil and Environmental Engineering, University of Cyprus, P.O. Box 20537, 1678 Nicosia, Cyprus c NIREAS-International Water Research Center, University of Cyprus, P.O. Box 20537, 1678 Nicosia, Cyprus

Superiority of solar Fenton oxidation over TiO2 photocatalysis for the degradation of trimethoprim in secondary treated effluents

The overall aim of this work was to examine the degradation of trimethoprim (TMP), which is an antibacterial agent, during the application of two advanced oxidation process (AOP) systems in secondary treated domestic effluents. The homogeneous solar Fenton process (hv/Fe(2+)/H2O2) and heterogeneous photocatalysis with titanium dioxide (TiO2) suspensions were tested. It was found that the degradation of TMP depends on several parameters such as the amount of iron salt and H2O2, concentration of TiO2, pH of solution, solar irradiation, temperature and initial substrate concentration. The optimum dosages of Fe(2+) and H2O2 for homogeneous ([Fe(2+)] = 5 mg L(-1), [H2O2] = 3.062 mmol L(-1)) and TiO2 ([TiO2] = 3 g L(-1)) for heterogeneous photocatalysis were established. The study indicated that the degradation of TMP during the solar Fenton process is described by a pseudo-first-order reaction and the substrate degradation during the heterogeneous photocatalysis by the Langmuir-Hinshelwood kinetics. The toxicity of the treated samples was evaluated using a Daphnia magna bioassay and was finally decreased by both processes. The results indicated that solar Fenton is more effective than the solar TiO2 process, yielding complete degradation of the examined substrate within 30 min of illumination and dissolved organic carbon (DOC) reduction of about 44% whereas the respective values for the TiO2 process were ∼70% degradation of TMP within 120 min of treatment and 13% DOC removal.

Development and validation of a UPLC-MS/MS method for studying the degradation kinetics of ofloxacin and trimethoprim during the application of solar Fenton process in secondary treated sewage

In this work, a sensitive and highly selective method was developed and validated to study the degradation of two antibiotic compounds (ofloxacin (OFX) and trimethoprim (TMP)), spiked in secondary treated domestic effluents, by the solar Fenton process. Three different chromatographic columns were tested on a ultra performance liquid chromatography-tandem mass spectrometric (UPLC-MS/MS) instrument working in the electrospray ionization (ESI) mode with twelve combinations of eluting solvents. Samples were enriched prior to the analysis by solid phase extraction using the hydrophilic-lipophilic balanced (HLB) reversed phase polymeric sorbent. The method was optimized and showed very good performance characteristics and was successfully applied to study the degradation kinetics of the selected antibiotics during the solar Fenton process applied. The degradation was found to follow a pseudo first-order kinetics for both compounds at initial concentration of 100 μg L(-1) with k = 0.0345 min(-1) for OFX and k = 0.0768 min(-1) for TMP, whereas the complete removal was achieved after 120 min of treatment for both compounds.

Two important limitations relating to the spiking of environmental samples with contaminants of emerging concern: How close to the real analyte concentrations are the reported recovered values?

Occurrence and effects of contaminants of emerging concern pose a special challenge to environmental scientists. The investigation of these effects requires reliable, valid, and comparable analytical data. To this effect, two critical aspects are raised herein, concerning the limitations of the produced analytical data. The first relates to the inherent difficulty that exists in the analysis of environmental samples, which is related to the lack of knowledge (information), in many cases, of the form(s) of the contaminant in which is present in the sample. Thus, the produced analytical data can only refer to the amount of the free contaminant ignoring the amount in which it may be present in other forms; e.g., as in chelated and conjugated form. The other important aspect refers to the way with which the spiking procedure is generally performed to determine the recovery of the analytical method. Spiking environmental samples, in particular solid samples, with standard solution followed by immediate extraction, as is the common practice, can lead to an overestimation of the recovery. This is so, because no time is given to the system to establish possible equilibria between the solid matter—inorganic and/or organic—and the contaminant. Therefore, the spiking procedure need to be reconsidered by including a study of the extractable amount of the contaminant versus the time elapsed between spiking and the extraction of the sample. This study can become an element of the validation package of the method.