Marcelo Luis Wilde

Oxidation-coagulation of β-blockers by K2FeVIO4 in hospital wastewater: assessment of degradation products and biodegradability.

This study investigated the degradation of atenolol, metoprolol and propranolol beta-blockers by ferrate (K2FeO4) in hospital wastewater and in aqueous solution. In the case of hospital wastewater, the effect of the independent variables pH and [Fe(VI)] was evaluated by means of response surface methodology. The results showed that Fe(VI) plays an important role in the oxidation-coagulation process, and the treatment of the hospital wastewater led to degradations above 90% for all the three β-blockers, and to reductions of aromaticity that were close to 60%. In addition, only 17% of the organic load was removed. In aqueous solution, the degradation of the β-blockers atenolol, metoprolol and propranolol was 71.7%, 24.7% and 96.5%, respectively, when a ratio of 1:10 [β-blocker]:[Fe(VI)] was used. No mineralization was achieved, which suggests that there was a conversion of the β-blockers to degradation products identified by liquid chromatography/mass spectrometry tandem. Degradation pathways were proposed, which took account of the role of Fe(VI). Furthermore, the ready biodegradability of the post-process samples was evaluated by using the closed bottle test, and showed an increase in biodegradability. The use of the ferrate advanced oxidation technology seems to be a useful means of ensuring the remediation of hospital and similar wastewater.

Degradation of 5-FU by means of advanced (photo)oxidation processes: UV/H2O2, UV/Fe2+/H2O2 and UV/TiO2--Comparison of transformation products, ready biodegradability and toxicity.

The present study investigates the degradation of the antimetabolite 5-fluorouracil (5-FU) by three different advanced photo oxidation processes: UV/H2O2, UV/Fe(2+)/H2O2 and UV/TiO2. Prescreening experiments varying the H2O2 and TiO2 concentrations were performed in order to set the best catalyst concentrations in the UV/H2O2 and UV/TiO2 experiments, whereas the UV/Fe(2+)/H2O2 process was optimized varying the pH, Fe(2+) and H2O2 concentrations by means of the Box-Behnken design (BBD). 5-FU was quickly removed in all the irradiation experiments. The UV/Fe(2+)/H2O2 and UV/TiO2 processes achieved the highest degree of mineralization, whereas the lowest one resulted from the UV/H2O2 treatment. Six transformation products were formed during the advanced (photo)oxidation processes and identified using low and high resolution mass spectrometry. Most of them were formed and further eliminated during the reactions. The parent compound of 5-FU was not biodegraded, whereas the photolytic mixture formed in the UV/H2O2 treatment after 256 min showed a noticeable improvement of the biodegradability in the closed bottle test (CBT) and was nontoxic towards Vibrio fischeri. In silico predictions showed positive alerts for mutagenic and genotoxic effects of 5-FU. In contrast, several of the transformation products (TPs) generated along the processes did not provide indications for mutagenic or genotoxic activity. One exception was TP with m/z 146 with positive alerts in several models of bacterial mutagenicity which could demand further experimental testing. Results demonstrate that advanced treatment can eliminate parent compounds and its toxicity. However, transformation products formed can still be toxic. Therefore toxicity screening after advanced treatment is recommendable.

Photocatalytic Degradation of Brilliant Red Dye and Textile Wastewater

The degradation of textile wastewater and brilliant red dye solutions in a coil photoreactor provided with recirculation, assisted by powdered TiO2 and medium-pressure mercury lamp irradiation, was investigated. Factorial design was used for the attainment of the best conditions for COD and color abatement. pH and TiO2 loading showed to be critical variables for the photocatalytic degradation process for both textile wastewater and aqueous reactive dye solutions (25 mg L−1). For both substrates, the optimized process conditions by factorial design were almost the same (pH 2–3, 444 mg TiO2 L−1 loading, 5 L h−1 recirculation flow-rate). A 41% COD abatement for textile wastewater was obtained with a 120 min treatment. For the Brilliant Red dye solutions, a 20 min treatment resulted in about 90% decolorization (517 nm, pH 5), as well as in a reduction of 66% of the integrated absorbance (200–600 nm, pH 5).

Degradation of cyclophosphamide and 5-fluorouracil by UV and simulated sunlight treatments: Assessment of the enhancement of the biodegradability and toxicity

The presence of pharmaceuticals in the environment has triggered concern among the general population and received considerable attention from the scientific community in recent years. However, only a few publications have focused on anticancer drugs, a class of pharmaceuticals that can exhibit cytotoxic, genotoxic, mutagenic, carcinogenic and teratogenic effects. The present study investigated the photodegradation, biodegradation, bacterial toxicity, mutagenicity and genotoxicity of cyclophosphamide (CP) and 5-fluorouracil (5-FU). The photodegradation experiments were performed at a neutral to slight pH range (7-7.8) using two different lamps (medium-pressure mercury lamp and a xenon lamp). The primary elimination of the parent compounds was monitored by means of liquid chromatography tandem mass spectrometry (LC-IT-MS/MS). NPOC (non-purgeable organic carbon) analyses were carried out in order to assess mineralization rates. The Closed Bottle Test (CBT) was used to assess ready biodegradability. A new method using Vibrio fischeri was adopted to evaluate toxicity. CP was not degraded by any lamp, whereas 5-FU was completely eliminated by irradiation with the mercury lamp but only partially by the Xe lamp. No mineralization was observed for the experiments performed with the Xe lamp, and a NPOC removal of only 18% was registered for 5-FU after 256 min using the UV lamp. Not one of the parent compounds was readily biodegradable in the CBT. Photo transformation products (PTPs) resulting from photolysis were neither better biodegradable nor less toxic than the parent compound 5-FU. In contrast, the results of the tests carried out with the UV lamp indicated that more biodegradable and non-toxic PTPs of 5-FU were generated. Three PTPs were formed during the photodegradation experiments and were identified. The results of the in silico QSAR predictions showed positive mutagenic and genotoxic alerts for 5-FU, whereas only one of the formed PTPs presented positive alerts for the genotoxicity endpoint.

Advanced Oxidation Processes in the Treatment of Trifluraline Effluent

The treatment of an effluent from the production of trifluraline was studied using a 1-L, semi-batch, tank-stirred glass reactor for performing three different advanced oxidation processes (photoperoxidation, Fenton, photo-Fenton). A commercial, medium-pressure mercury lamp was used for sample irradiation. The degradation was monitored by measurements of absorptiometric color reduction, UV-visible absorption spectra, and chemical oxygen demand (COD). The obtained results showed that the photo-Fenton process was the most effective treatment for the trifluraline effluent.

Multivariate optimization of analytical methodology and a first attempt to an environmental risk assessment of β-blockers in hospital wastewater

O presente estudo avalia, preliminarmente, o risco da exposicao ambiental a β-bloqueadores em efluente de um hospital universitario (Hospital Universitario de Santa Maria (HUSM), Rio Grande do Sul). Propranolol mostrou o maior quociente de risco (0,56). A ocorrencia de β-bloqueadores foi avaliada com auxilio de metodologia de SPE-HPLC-FLD (extracao por fase solida-cromatografia liquida de alta eficiencia com deteccao por fluorescencia) otimizando-se multivariadamente as variaveis pH da amostra, pH da agua e a razao entre metanol:acetonitrila:acido formico. As concentracoes medias de atenolol, metoprolol e propranolol medidas durante o periodo de uma semana foram de 2,45 ± 1,14, 4,67 ± 1,63 e 0,70 ± 0,88 μg L-1 no efluente do pronto atendimento, 0,95 ± 0,68, 0,70 ± 0,33 e 0,315 ± 0,62 μg L-1 no efluente geral do hospital e 1,26 ± 0,47, 1,27 ± 0,35 e 0,56 ± 0,47 μg L-1 no corrego receptor, respectivamente. Propranolol mostrou razao MEC/PNEC > 1 (MEC: concentracao ambiental mensurada e PNEC: concentracao predita que nao causa efeito), exigindo maior atencao em termos de toxicidade. A ocorrencia de β-bloqueadores e o risco ambiental associado demonstram a necessidade de um sistema mais eficiente de tratamento do efluente hospitalar.

Fenton process on single and mixture components of phenothiazine pharmaceuticals: Assessment of intermediaries, fate, and preliminary ecotoxicity

Pharmaceuticals do not occur isolated in the environment but in multi-component mixtures and may exhibit antagonist, synergistic or additive behavior. Knowledge on this is still scarce. The situation is even more complicated if effluents or potable water is treated by oxidative processes or such transformations occur in the environment. Thus, determining the fate and effects of parent compounds, metabolites and transformation products (TPs) formed by transformation and degradation processes in the environment is needed. This study investigated the fate and preliminary ecotoxicity of the phenothiazine pharmaceuticals, Promazine (PRO), Promethazine (PRM), Chlorpromazine (CPR), and Thioridazine (THI) as single and as components of the resulting mixtures obtained from their treatment by Fenton process. The Fenton process was carried out at pH7 and by using 0.5-2mgL-1 of [Fe2+]0 and 1-12.5mgL-1 of [H2O2]0 at the fixed ratio [Fe2+]0:[H2O2]0 of 1:10 (w:w). No complete mineralization was achieved. Constitutional isomers and some metabolite-like TPs formed were suggested based on their UHPLC-HRMSn data. A degradation pathway was proposed considering interconnected mechanisms such as sulfoxidation, hydroxylation, N-dealkylation, and dechlorination steps. Aerobic biodegradation tests (OECD 301 D and OECD 301 F) were applied to the parent compounds separately, to the mixture of parent compounds, and for the cocktail of TPs present after the treatment by Fenton process. The samples were not readily biodegradable. However, LC-MS analysis revealed that abiotic transformations, such hydrolysis, and autocatalytic transformations occurred. The initial ecotoxicity tested towards Vibrio fischeri as individual compounds featured a reduction in toxicity of PRM and CPR by the treatment process, whereas PRO showed an increase in acute luminescence inhibition and THI a stable luminescence inhibition. Concerning effects of the mixture components, reduction in toxicity by the Fenton process was predicted by concentration addition and independent action models.

Combination of experimental and in silico methods for the assessment of the phototransformation products of the antipsychotic drug/metabolite Mesoridazine

The lack of studies on the fate and effects of drug metabolites in the environment is of concern. As their parent compounds, metabolites enter the aquatic environment and are subject to biotic and abiotic process. In this regard, photolysis plays an important role. This study combined experimental and in silico quantitative structure-activity relationship (QSAR) methods to assess the fate and effects of Mesoridazine (MESO), a pharmacologically active human drug and metabolite of the antipsychotic agent Thioridazine, and its transformation products (TPs) formed through a Xenon lamp irradiation. After 256min, the photodegradation of MESO⋅besylate (50mgL-1) achieved 90.4% and 6.9% of primary elimination and mineralization, respectively. The photon flux emitted by the lamp (200-600nm) was 169.55Jcm-2. Sixteen TPs were detected by means of liquid chromatography-high resolution mass spectrometry (LC-HRMS), and the structures were proposed based on MSn fragmentation patterns. The main transformation reactions were sulfoxidation, hydroxylation, dehydrogenation, and sulfoxide elimination. A back-transformation of MESO to Thioridazine was evidenced. Aerobic biodegradation tests (OECD 301 D and 301F) were applied to MESO and the mixture of TPs present after 256min of photolysis. Most of TPs were not biodegraded, demonstrating their tendency to persist in aquatic environments. The ecotoxicity towards Vibrio fischeri showed a decrease in toxicity during the photolysis process. The in silico QSAR tools QSARINS and US-EPA PBT profiler were applied for the screening of TPs with character of persistence, bioaccumulation, and toxicity (PBT). They have revealed the carbazole derivatives TP 355 and TP 337 as PBT/vPvB (very persistent and very bioaccumulative) compounds. In silico QSAR predictions for mutagenicity and genotoxicity provided by CASE Ultra and Leadscope® indicated positive alerts for mutagenicity on TP 355 and TP 337. Further studies regarding the carbazole derivative TPs should be considered to confirm their hazardous character.