Investigation of Drugs in Wastewater: Removal Efficiency in a Treatment Plant and Environmental Impact Assessment

Treball Final de Grau en Química. Codi: QU0943. Curs acadèmic: 2019/2020This study assessed the presence of 41 pharmaceuticalsin wastewater samples from the north of Spain. The samples under study were collected during a week, before the treatment (influent) and after treatment (effluent) in a wastewater treatment plant (WWTP). Additionally, samples reaching the inlet of the WWTP from hospital discharge were also collected. The wastewater samples were analysed by ultra-high performance liquid chromatography coupled to tandem mass spectrometry using triple quadrupole analyzer (UHPLC-MS/MS QqQ) due to its greatselectivity and sensitivity. Analyses were performed by direct injection (DI) of the samples; so, pre-concentration treatments were avoided. Moreover, in order to correct matrix effects, Isotopically-Labelled Internal Standards (ILIS) available for some pharmaceuticals were added to the samples. Acetaminophen and Gabapentin were the most frequently detected compounds in both influent wastewater (IWW) and Hospital discharge. In EWW, it was observed a decrease in the concentrations of pharmaceuticals in comparison to the influent samples. The removal efficiency (RE) (%) was calculated by comparing the mass load of the influent and the effluent samples. From the 30 compounds detected in wastewater, only three pharmaceuticals (Acetaminophen, Atorvastatin and Enalapril) presented a 100% RE, which means that they were completely eliminated after passing through the WWTP. The results of this work indicate that most of pharmaceuticals under study are present in treated wastewater, and consequently they reach the aquatic environment. Hazard quotients (HQ) were calculated to assess the potential environmental risks of these pharmaceuticals. The results showed that generally there are not significant risks associated to the presence of pharmaceuticals in the aquatic environment although Ciprofloxacin, Diclofenac, Norfloxacin and Venlafaxine presented an HQ > 1 implying that the amount of these compounds released into the environment is above the non-effect concentration. The results from this study contribute to the better understanding of potential risks associated to the presence of pharmaceuticals in urban wastewater and their impact on the aquatic environment

Design of a method for polycyclic aromatic hydrocarbons routine determination by liquid-liquid microextraction and GC-MS/MS: Optimisation and validation

Treball Final de Màster en Tècniques Cromatogràfiques Aplicades (Pla de 2013). Codi: SIY009 Curs acadèmic: 2020-2021This study focuses on the optimisation and validation of a method for the determination of Polycyclic Aromatic Hydrocarbons (PAHs) to be applied in real supply waters of the Zaragoza area. The supply water samples were analysed by gas chromatography coupled to tandem mass spectrometry using ion trap (GC-MS/MS IT) due to its great selectivity and sensitivity. Injections in GC were performed by programmable temperature vaporization (PTV) in solvent venting mode of the samples. A liquid-liquid microextraction (LLME) treatment was necessary to concentrate the sample for analysis. Moreover, in order to correct matrix effects, Isotopically-Labelled Internal Standard (ILIS) was added to the samples. Several experiments were carried out to optimise the PAHs extraction method, chromatography and MS/MS conditions. The study focused mainly on Acenaphthylene and Acenaphthene as these compounds were not included in the method in use at Valero Analítica. In addition, the research also focused on Benzo()fluoranthene, Benzo(g,h,i)perylene, Benzo()fluoranthene and Indeno(1,2,3-c,d)pyrene, compounds regulated by RD 140/2003. The results of this work indicate that a comprehensive study of the PAHs of interest can be performed on the optimised method. The validation provides positive data for all compounds except for Acenaphthylene and Acenaphthene, which have an (limit of quantification) LOQ more than three times higher than the rest of PAHs. The results of this study contribute to report more complete PAHs data and therefore to understand which compounds are found in drinking water

Analytical key issues and challenges in the LC-MS/MS determination of antibiotics in wastewater

The research on antibiotics occurrence in the aquatic environment has become a hot topic in the last years due to their potential negative effects, associated to possible bacterial antibiotic-resistance, after continuous exposure to these compounds. Most of antibiotic residues are not completely removed in the wastewater treatment plants (WWTPs) and end up in the aquatic environment through treated wastewater (WW). The development of reliable analytical methodologies for the determination of antibiotics in influent (IWW) and effluent wastewater (EWW) is needed with different purposes, among others: monitoring their occurrence in the aquatic environment, performing environmental risk assessment, estimating removal efficiencies of WWTPs, or estimating the consumption of these compounds. In this paper, we perform an in-depth investigation on analytical key issues that pose difficulties in the determination of antibiotics in complex matrices, such as WW, and we identify challenges to be properly addressed for successful analysis. The analytical technique selected was liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS), as it is the most powerful and widely applied at present for antibiotic residues determination. The mass spectrometric behavior of 18 selected antibiotics, the chromatographic performance, ion ratio variations associated to the sample matrix when using different precursor ions or protomers, and the macrolides adsorption to glass vial, were some of the issues studied in this work. On the basis of the detailed study performed, an analytical LC-MS/MS method based on sample direct injection has been developed for quantification of 18 antibiotics in IWW and EWW, allowing their determination at low ng L−1 levels.Funding for open access charge: CRUE-Universitat Jaume IDavid Fabregat-Safont acknowledges Ministerio de Universidades in Spain for his Margarita Salas postdoctoral grant (Ref. MGS/2021/15). Authors acknowledge financial support from General Directorate of Water (Conselleria de Agricultura, Desarrollo Rural, Emergencia Climática y Transición Ecológica) and Generalitat Valenciana (research group of excellence PROMETEO 2019/040). Authors also acknowledge to FACSA (Castelló, Spain) for the wastewater sample collection and the Ayuntamiento of Castelló for the authorization to collect wastewater samples from the WWTP of Castelló. Authors are very grateful to Alberto Celma for his comments on fluoroquinolones protomers evaluation

Three years of wastewater surveillance for new psychoactive substances from 16 countries

The proliferation of new psychoactive substances (NPS) over recent years has made their surveillance complex. The analysis of raw municipal influent wastewater can allow a broader insight into community consumption patterns of NPS. This study examines data from an international wastewater surveillance program that collected and analysed influent wastewater samples from up to 47 sites in 16 countries between 2019 and 2022. Influent wastewater samples were collected over the New Year period and analysed using validated liquid chromatography - mass spectrometry methods. Over the three years, a total of 18 NPS were found in at least one site. Synthetic cathinones were the most found class followed by phenethylamines and designer benzodiazepines. Furthermore, two ketamine analogues, one plant based NPS (mitragynine) and methiopropamine were also quantified across the three years. This work demonstrates that NPS are used across different continents and countries with the use of some more evident in particular regions. For example, mitragynine has highest mass loads in sites in the United States, while eutylone and 3-methylmethcathinone increased considerably in New Zealand and in several European countries, respectively. Moreover, 2F-deschloroketamine, an analogue of ketamine, has emerged more recently and could be quantified in several sites, including one in China, where it is considered as one of the drugs of most concern. Finally, some NPS were detected in specific regions during the initial sampling campaigns and spread to additional sites by the third campaign. Hence, wastewater surveillance can provide an insight into temporal and spatial trends of NPS use

Treatment with tocilizumab or corticosteroids for COVID-19 patients with hyperinflammatory state: a multicentre cohort study (SAM-COVID-19)

Objectives: The objective of this study was to estimate the association between tocilizumab or corticosteroids and the risk of intubation or death in patients with coronavirus disease 19 (COVID-19) with a hyperinflammatory state according to clinical and laboratory parameters. Methods: A cohort study was performed in 60 Spanish hospitals including 778 patients with COVID-19 and clinical and laboratory data indicative of a hyperinflammatory state. Treatment was mainly with tocilizumab, an intermediate-high dose of corticosteroids (IHDC), a pulse dose of corticosteroids (PDC), combination therapy, or no treatment. Primary outcome was intubation or death; follow-up was 21 days. Propensity score-adjusted estimations using Cox regression (logistic regression if needed) were calculated. Propensity scores were used as confounders, matching variables and for the inverse probability of treatment weights (IPTWs). Results: In all, 88, 117, 78 and 151 patients treated with tocilizumab, IHDC, PDC, and combination therapy, respectively, were compared with 344 untreated patients. The primary endpoint occurred in 10 (11.4%), 27 (23.1%), 12 (15.4%), 40 (25.6%) and 69 (21.1%), respectively. The IPTW-based hazard ratios (odds ratio for combination therapy) for the primary endpoint were 0.32 (95%CI 0.22-0.47; p < 0.001) for tocilizumab, 0.82 (0.71-1.30; p 0.82) for IHDC, 0.61 (0.43-0.86; p 0.006) for PDC, and 1.17 (0.86-1.58; p 0.30) for combination therapy. Other applications of the propensity score provided similar results, but were not significant for PDC. Tocilizumab was also associated with lower hazard of death alone in IPTW analysis (0.07; 0.02-0.17; p < 0.001). Conclusions: Tocilizumab might be useful in COVID-19 patients with a hyperinflammatory state and should be prioritized for randomized trials in this situatio

Reducing the environmental impact of surgery on a global scale: systematic review and co-prioritization with healthcare workers in 132 countries

Abstract Background Healthcare cannot achieve net-zero carbon without addressing operating theatres. The aim of this study was to prioritize feasible interventions to reduce the environmental impact of operating theatres. Methods This study adopted a four-phase Delphi consensus co-prioritization methodology. In phase 1, a systematic review of published interventions and global consultation of perioperative healthcare professionals were used to longlist interventions. In phase 2, iterative thematic analysis consolidated comparable interventions into a shortlist. In phase 3, the shortlist was co-prioritized based on patient and clinician views on acceptability, feasibility, and safety. In phase 4, ranked lists of interventions were presented by their relevance to high-income countries and low–middle-income countries. Results In phase 1, 43 interventions were identified, which had low uptake in practice according to 3042 professionals globally. In phase 2, a shortlist of 15 intervention domains was generated. In phase 3, interventions were deemed acceptable for more than 90 per cent of patients except for reducing general anaesthesia (84 per cent) and re-sterilization of ‘single-use’ consumables (86 per cent). In phase 4, the top three shortlisted interventions for high-income countries were: introducing recycling; reducing use of anaesthetic gases; and appropriate clinical waste processing. In phase 4, the top three shortlisted interventions for low–middle-income countries were: introducing reusable surgical devices; reducing use of consumables; and reducing the use of general anaesthesia. Conclusion This is a step toward environmentally sustainable operating environments with actionable interventions applicable to both high– and low–middle–income countries

Microrelatario

Basta/Prou es el resultado de El desafío por la erradicación de la violencia contra las mujeres que el Instituto Universitario de Estudios Feministas y de Género Purificación Escribano de la Universitat Jaume I lanzó en los Diez días contra la violencia de género 2012

Contemporary use of cefazolin for MSSA infective endocarditis: analysis of a national prospective cohort

Objectives: This study aimed to assess the real use of cefazolin for methicillin-susceptible Staphylococcus aureus (MSSA) infective endocarditis (IE) in the Spanish National Endocarditis Database (GAMES) and to compare it with antistaphylococcal penicillin (ASP). Methods: Prospective cohort study with retrospective analysis of a cohort of MSSA IE treated with cloxacillin and/or cefazolin. Outcomes assessed were relapse; intra-hospital, overall, and endocarditis-related mortality; and adverse events. Risk of renal toxicity with each treatment was evaluated separately. Results: We included 631 IE episodes caused by MSSA treated with cloxacillin and/or cefazolin. Antibiotic treatment was cloxacillin, cefazolin, or both in 537 (85%), 57 (9%), and 37 (6%) episodes, respectively. Patients treated with cefazolin had significantly higher rates of comorbidities (median Charlson Index 7, P <0.01) and previous renal failure (57.9%, P <0.01). Patients treated with cloxacillin presented higher rates of septic shock (25%, P = 0.033) and new-onset or worsening renal failure (47.3%, P = 0.024) with significantly higher rates of in-hospital mortality (38.5%, P = 0.017). One-year IE-related mortality and rate of relapses were similar between treatment groups. None of the treatments were identified as risk or protective factors. Conclusion: Our results suggest that cefazolin is a valuable option for the treatment of MSSA IE, without differences in 1-year mortality or relapses compared with cloxacillin, and might be considered equally effective