ChromChem

Permanent URI for this collectionhttps://hdl.handle.net/10347/34311

O Grupo de Cromatografía e Quimiometría está formado por profesores e investigadores do Departamento de Química Analítica, Nutrición e Bromatoloxía da Universidade de Santiago de Compostela que desenvolven a súa actividade de investigación no Instituto de Investigación e Análises Alimentarias, pertencente tamén a esta Universidade.

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Integrated computational fluid dynamics and experimental evaluation of a tubular membrane photoreactor for UVC-driven advanced oxidation at bench- and pilot-scale
(Elsevier, 2026-04-13) Santos, Carla S.; Marrocos, Paulo H.; Passalía, Claudio; Labas, Marisol D.; Brandi, Rodolfo J.; Montes Goyanes, Rosa; Quintana Álvarez, José Benito; Gomes, Ana I.; Vilar, Vítor J. P.; Universidade de Santiago de Compostela. Instituto de Investigación do Medio Acuático para Unha Saúde Global (iARCUS); Universidade de Santiago de Compostela. Departamento de Química Analítica, Nutrición e Bromatoloxía
This study combines computational fluid dynamics (CFD) simulations and experimental data to examine the hydrodynamic and photonic behavior of tubular membrane photoreactors operated under UVC and UVC/persulfate (UVC/PDS) conditions for the removal of organic micropollutants (OMPs). At bench-scale, CFD simulations revealed that the tangential inlet generated a helical flow pattern in the annular reaction zone (ARZ), promoting interaction between radial and axial velocity components. The effect of reflective surfaces on photon delivery was evaluated across three configurations: no reflector and one- and three-sided reflectors (N = 1 and N = 3). Reflective surfaces increased photon delivery to the ARZ, with the N = 3 configuration providing the highest optical efficiency and the best photolytic removal of the selected OMP in both demineralized water (DW) and conventional activated sludge (CAS) effluent. Based on these findings, a pilot-scale reactor preserving the same cross-sectional geometry and incorporating the N = 3 reflector was evaluated. Residence time distribution (RTD) experiments indicated a non-ideal plug flow with moderate axial dispersion, while CFD confirmed the persistence of the characteristic helical flow pattern. Under UVC alone, venlafaxine (VLX) removal remained limited, whereas under UVC/PDS operation removal exceeded 85% across all evaluated conditions. Simulations of the local volumetric rate of photon absorption (LVRPA) and spatial species distributions revealed a strong correlation between photon availability, oxidant distribution, and OMP degradation along the reactor length. These results provide valuable insights into the design of tubular membrane photoreactors and support their applicability for advanced urban wastewater treatment systems.
Tracing illicit and prescription drug use in a Spanish prison by combining wastewater analysis and pharmaceutical dispensing data
(Elsevier, 2026-04-12) Egaña, Iker; Nogales-García, Maite; Akhrimenko, Vladimir; González Gómez, Xiana; Rodil Rodríguez, María del Rosario; Montes Goyanes, Rosa; Quintana Álvarez, José Benito; Mestre-Pintó, Juan Ignacio; Orive, Gorka; Lertxundi, Unax; Universidade de Santiago de Compostela. Instituto de Investigación do Medio Acuático para Unha Saúde Global (iARCUS); Universidade de Santiago de Compostela. Departamento de Química Analítica, Nutrición e Bromatoloxía
Background and aim We combined wastewater-based epidemiology (WBE) and pharmaceutical dispensing records to distinguish between illicit and prescription drug use. Methods We collected 24-h composite wastewater samples during three one-week campaigns in a prison in northern Spain. Samples were analysed for pharmaceuticals, illicit drugs, nicotine and alcohol. Population-normalised daily loads (PNDLs) were converted to consumption estimates and compared with Spanish population WBE estimates and pharmacy dispensing data. Results Wastewater analysis showed high use of several pharmaceuticals, with the highest average PNDL for gabapentinoids. Pregabalin and gabapentin estimates from wastewater exceeded pharmacy dispensing, suggesting internal diversion. Cannabis consumption was about four times higher than community estimates and cocaine was also higher in all campaigns. Ketamine and MDMA use were above community medians during the February campaign and nicotine use was nearly ten times higher than community levels. Conclusion WBE identifies prescription drug diversion, illicit drug markets and quantifies licit substance use in prisons.
Recent trends in wastewater-based epidemiology of pharmaceuticals. Methods and applications
(Elsevier, 2026-02-13) Pernas Fraguela, Carlos; Montes Goyanes, Rosa; Rodil Rodríguez, María del Rosario; Castro Bustelo, Verónica; Quintana Álvarez, José Benito; Estévez-Danta, Andrea; Universidade de Santiago de Compostela. Departamento de Química Analítica, Nutrición e Bromatoloxía; Universidade de Santiago de Compostela. Instituto de Investigación do Medio Acuático para Unha Saúde Global (iARCUS)
This review article discusses the latest research on wastewater-based epidemiology (WBE) of pharmaceuticals since 2020. It covers the analytical methods that have been used to measure pharmaceuticals and their metabolites, mostly relying on off-line solid-phase extraction followed by liquid chromatography-tandem mass spectrometry. Then, we focus on general considerations related to WBE, such as biomarkers stability or back-calculation of drug use by using correction factors. We found that over 130 drugs have been analyzed and their wastewater concentrations converted to pharmaceutical use estimations, of which those related with the nervous system (ATC level 1 code N) have been by far the most frequently investigated. Subsequently the review focusses on studies related to the spatio-temporal assessment of drug use, with a specific section devoted to the impact of COVID-19 pandemic. Then, it covers studies which contrast WBE estimations of drug use with pharmaceutical dispensing data and how they complement each other.
Differences in drug use across three neighbourhoods with varying socioeconomic levels: A wastewater-based surveillance study
(Elsevier, 2026-01-17) Corominas, Lluís; Pernas Fraguela, Carlos; Rodil Rodríguez, María del Rosario; Montes Goyanes, Rosa; Estévez-Danta, Andrea; Quintana Álvarez, José Benito; López de Alda, Miren; Universidade de Santiago de Compostela. Instituto de Investigación do Medio Acuático para Unha Saúde Global (iARCUS); Universidade de Santiago de Compostela. Departamento de Química Analítica, Nutrición e Bromatoloxía
This study measured 39 biomarkers of licit (e.g., alcohol, nicotine, benzodiazepines, antidepressants) and illicit drug consumption (e.g., cocaine, amphetamine, cannabis, new psychoactive substances) in wastewater from three neighbourhoods (NGBs) in Barcelona, each representing different socioeconomic and lifestyle profiles. Four weeklong sampling campaigns were conducted between March 2021 and March 2022. The results revealed significant differences in drug use across neighbourhoods that are not apparent in city-level analyses. These differences were particularly notable for illicit drugs—such as higher morphine and cannabis loads in socioeconomically disadvantaged areas—as well as for specific benzodiazepines and antidepressants, which varied in prevalence between neighbourhoods. Alcohol and nicotine patterns were more strongly associated with the local density of bars and restaurants than with socioeconomic status. A clear weekend peak was observed for substances like alcohol. Temporal analysis over the study period showed increased consumption of certain drugs at the end of 2021, likely linked to the reopening of nightlife venues and elevated anxiety related to the COVID-19 pandemic. This study highlights the value of applying wastewater-based epidemiology (WBE) at the intra-city level. By moving beyond aggregated citywide data, intra-urban WBE can reveal spatial and temporal variations in drug use that may otherwise go unnoticed. This approach also enables the identification of communities or socioeconomic groups at higher risk of substance use or mental health challenges, offering critical insights for public health authorities to develop targeted interventions and preventive strategies.
The role of syringe residue analysis in identifying substances consumed in sexualized drug use practices
(Elsevier, 2025-12-08) Pernas Fraguela, Carlos; Rodil Rodríguez, María del Rosario; Quintana Álvarez, José Benito; Sáez Maldonado, Antonio; Olmos Espinosa, Ruth; Mestre Pinto, Joan Ignaci; Isorna Folgar, Manuel; Montes Goyanes, Rosa; Universidade de Santiago de Compostela. Departamento de Química Analítica, Nutrición e Bromatoloxía; Universidade de Santiago de Compostela. Instituto de Investigación do Medio Acuático para Unha Saúde Global (iARCUS)
Chemsex is a practice mostly extended between men who have sex with men under drugs effects to enhance and/or prolong sexual activities. Within chemsex, slamming consists of intravenous consumption of substances such as cathinones and amphetamines. Syringe residue analysis is a relatively new alternative for knowing with accuracy the substances consumed by the users. Although several studies have been carried out applying the technique, none of them was focused on this population group. In this work, syringes were obtained from a drug addiction assistance centre from Madrid (Spain). Samples were processed by rinsing with methanol and injected in a liquid chromatography coupled to high resolution mass spectrometry system. Data (acquired in data dependent mode) were processed using a suspect screening approach. In total, 122 syringes from three sampling campaigns were analyzed. The compounds belonging to the cathinones’ group were the most frequently detected (99 %), followed by amphetamines and cocaine. The most consumed cathinone was chloromethcathinone, but also others as methylmethcathinone, pentedrone or N,N-dimethylpentylone were identified. Furthermore, temporal trends were detected during the different sampling campaigns. Thus, this technique allowed us to determine in an accurate way the substances consumed during slamming sessions, which may differ from the self-declared ones in surveys. Moreover, temporal trends were observed, that align with the market changes and regulation of cathinones
Selective prevention programs for substance and behavioral addictions in adolescents: a systematic review
(Frontiers, 2025-11-14) Villanueva-Blasco, Víctor José; Eslava, Dalila; Olave-Porrúa, Leticia; Quintana Álvarez, José Benito; Rodríguez de Fonseca, Fernando; Universidade de Santiago de Compostela. Departamento de Química Analítica, Nutrición e Bromatoloxía; Universidade de Santiago de Compostela. Instituto de Acuicultura (IA); Universidade de Santiago de Compostela. Instituto de Investigación e Análises Alimentarias
Justification: Selective prevention of substance use among adolescents and young people is a key strategy for reducing risks in vulnerable populations. However, there is a notable lack of systematization and scientific validation of the programs implemented in this field. The aim of this systematic review was to identify existing selective prevention programs, describe their main characteristics, and assess their effectiveness based on the available evidence. Method: A comprehensive search was conducted in scientific databases (Web of Science, PubMed/MEDLINE, Scopus, and Cochrane Library) and in best practice repositories (Xchange, EDDRA, Portal BBPP Adicciones), following PRISMA criteria and using the MMAT tool for methodological quality assessment. The review was registered in PROSPERO (CRD42024555838). Results: A total of 20 studies were included, analyzing 24 programs, of which only a portion showed robust evidence according to criteria adapted from the GRADE system. Preventure, Trampoline, ASSIST, and Project TND stood out for their theoretical foundations, methodological quality, and sustained positive outcomes. Nevertheless, significant limitations were identified: heterogeneity in study designs, limited evaluation in Southern European contexts, and a lack of gender perspective and cultural adaptation. Conclusions: The findings reveal a gap between practical implementation and empirical research, as many programs lack evaluation of their effectiveness through empirical studies. There is a pressing need to develop rigorously evaluated selective interventions, tailored to sociocultural contexts and aligned with clear quality standards.
Comparative evaluation of UV-driven processes for quaternary treatment of urban wastewaters: Trade-offs between micropollutants removal, toxicity reduction, and cost-effectiveness
(Elsevier, 2025-09-18) Gomes, Lúcio M. M. T.; Gomes, Ana I.; Montes Goyanes, Rosa; Quintana Álvarez, José Benito; Rodil Rodríguez, María del Rosario; Vilar, Vítor J. P.; Universidade de Santiago de Compostela. Departamento de Química Analítica, Nutrición e Bromatoloxía; Universidade de Santiago de Compostela. Instituto de Investigación e Análises Alimentarias; Universidade de Santiago de Compostela. Instituto de Acuicultura (IA)
Micropollutants (MP) in urban wastewater pose challenges, requiring advanced treatment solutions to ensure regulatory compliance and environmental safety. This study investigated UV-driven processes (UV-alone, UV/H2O2, and UV/PDS) in a FluHelik photoreactor operating in continuous mode (residence times: 1.0–6.5 min) to remove 19 MPs (spiked at 10 μg L−1 each) from urban wastewater after tertiary treatment. Preliminary trials included bench-scale testing and spiked demineralized water. Pilot-scale trials using real wastewater evaluated treatment performance across different UV lamp types: low-pressure (LP), medium-pressure mercury (MP_Hg), and medium-pressure iron-doped (MP_Fe). Treatment performance was assessed regarding MP removal, ecotoxicity (Chlorella vulgaris growth inhibition), and an integrated cost-effectiveness metric (expressed as € m−3 order−1). UV-alone treatments, particularly using medium-pressure lamps, effectively reduced urban wastewater toxicity but showed limited MP removal, especially for EU-prioritized compounds like carbamazepine and irbesartan. UV/H2O2 under MP_Hg lamp provided moderate removal (up to 56 % for 15 MPs) with acceptable operational costs (~0.09 € m−3), but increased post-treatment toxicity. UV/PDS consistently achieved the highest MP removal, namely for carbamazepine (82 %) and irbesartan (81 %), while also reducing effluent toxicity to C. vulgaris. Despite the higher cost of persulfate, UV/PDS proved more cost-effective when both pollutant removal and ecotoxicity were considered. Persistent MPs such as short-chain PFAS and melamine remained largely unaffected by all treatments. This study underscores the need to optimize UV-driven processes by tailoring UV spectra, oxidant choice, and operational conditions to balance contaminant removal, operational costs, and ecotoxicity.
Ozone injection system based on NETmix technology for quaternary treatment of urban wastewater
(Elsevier, 2025-04) Pituco, Mateus Mestriner; Marrocos, Paulo H.; Méndez, Sandra; Montes Goyanes, Rosa; Rodil Rodríguez, María del Rosario; Moreira, Francisca C.; Vilar, Vítor J. P.; Universidade de Santiago de Compostela. Departamento de Química Analítica, Nutrición e Bromatoloxía
An innovative high-intensity static mixer technology, known as NETmix, was applied as an ozone (O3) gas injection system to promote the quaternary treatment of urban wastewater (UWW), focusing on the elimination of contaminants of emerging concern (CECs). The NETmix network with an exclusive geometry boosts mass transfer rates and rapidly develops an O3-rich stream to react with CECs. The mixer operated in continuous mode promotes a rapid gas (O3)–liquid (water) dissolution. The ozonation process’ performance was evaluated for the abatement of 19 CECs spiked (10 μg dm−3 each) in demineralized water and two tertiary-treated UWW matrices, coming from (i) a secondary settler tank after a conventional activated sludge and (ii) the outlet of a membrane biological reactor (MBR). In addition, the ozonation system was tested for removing a broad range of CECs at natural trace levels from the UWW matrix coming from the MBR. In the realistic wastewater contamination scenario, a maximum transferred O3 dose of 1.28 and 0.76 resulted in removal values ≥80% for 12 out of the 19 spiked CECs from the secondary settler tank, and 9 out of the 19 spiked CECs from the post-MBR treatment, respectively, at a very short hydraulic residence time (55 s). Moreover, removals ≥80% were attained for 22 out of 25 CECs detected in the effluent from the MBR, applying a specific O3 dose of 0.6 . The enhanced ozone-water mass transfer provided by the NETmix technology enabled high removal efficiencies for CECs.
In-vitro metabolites characterization of 1,3-diphenylguanidine and 1,3-di-o-tolylguanidine by high-resolution mass spectrometry and urinary profiling
(Elsevier, 2025-08-23) Estévez-Danta, Andrea; Riveiro Rodríguez, Iago; Lage Díaz, María; Quintana Álvarez, José Benito; Montes Goyanes, Rosa; Rodil Rodríguez, María del Rosario; Universidade de Santiago de Compostela. Departamento de Química Analítica, Nutrición e Bromatoloxía; Universidade de Santiago de Compostela. Instituto de Acuicultura (IA); Universidade de Santiago de Compostela. Instituto de Investigación e Análises Alimentarias
The discovery of the hazardous effects associated with the polymer additives 1,3-diphenyl guanidine (DPG) and 1,3-di-o-tolylguanidine (DTG) has prompted the need for biomonitoring studies to detect human exposure. However, limited information is available about their metabolism. To address this gap, this study investigates the Phase I and II in-vitro biotransformation of both chemicals using human liver microsomes and cytosol. The samples were analyzed using liquid chromatography coupled to high resolution-(tandem) mass spectrometry through suspect (of in-silico predicted metabolites) and non-target screening. The analysis revealed four Phase I and two Phase II metabolic products for both DPG and DTG. Hydroxylation of the benzene ring led to the tentative identification of mono- and di-hydroxylated metabolites. Subsequent Phase I deamination followed by oxidation resulted in the formation of hydroxy-phenylurea and an intramolecular cyclization resulted in the formation of hydroxy-cyclic products. Furthermore, N-glucuronidation and O-glucuronidation products were identified for the first time. After performing urinalysis, DPG and DTG could be quantified in the 0.02–0.23 μg L−1 range, and DPG-227 (mono-hydroxylated DPG) was estimated to be present at ca. 0.01–0.10 μg L−1 range, using DPG response as quantification surrogate. Finally, toxicity assessment using an in-silico tool indicated the need to consider these human metabolites in (eco)toxicological assessments, as they may have the same or even greater effects on humans and the environment.
Screening of organic pollutants in mollusc and fish samples from the Portuguese coast by combining liquid and gas chromatography with high resolution mass spectrometry
(Elsevier, 2025-08-27) Méndez, Sandra; Montes Goyanes, Rosa; Raimundo, Joana; López Castillo, Daylin; López Vázquez, Javier; Caetano, Miguel; Lopes, Clara; Figueiredo, Cátia; Pinheiro, Marlene; Alves, Nélson; Capela, Ricardo; Barros, Susana; Morais, Hugo; Neuparth, Teresa; Santos, Miguel M.; Quintana Álvarez, José Benito; Rodil Rodríguez, María del Rosario; Universidade de Santiago de Compostela. Departamento de Química Analítica, Nutrición e Bromatoloxía; Universidade de Santiago de Compostela. Instituto de Acuicultura (IA); Universidade de Santiago de Compostela. Instituto de Investigación e Análises Alimentarias
In recent years, the presence of organic pollutants (OPs) in biota samples, especially in species which are intended for human consumption, has generated major concern. Thus, legislation on presence and levels has been created and/or updated in order to achieve safe food products for consumers. During the years 2020 and 2022 in the frame of the project “Contaminant levels in species of commercial interest captured in the Portuguese Maritime Area - CEIC”, different species of fish and molluscs were collected in 4 main areas of the Portuguese coast. Samples were processed by matrix solid-phase dispersion (MSPD) and injected into gas and liquid chromatographic systems coupled to high resolution mass spectrometry analysers. A total of 82 OPs were identified using liquid chromatography (LC), most being pharmaceuticals, 56 OPs were identified by gas chromatography (GC) using a high-resolution mass spectra library. In addition, 38 chlorine/bromine-containing compounds were tentatively identified using the low resolution NIST 2017 database, most of which are used as industrial chemicals. Cluster analysis of samples revealed grouping according to the type of analysed tissue, sampling area and campaign. For the per- and polyfluoroalkyl substances (PFAS) detected, a quantitative methodology was applied to evaluate concentration levels. Several fish muscle and bivalve mollusc samples exhibited PFAS concentrations that exceeded the permitted levels established by current regulations, with perfluorooctanoic acid (PFOA) showing particularly elevated levels in the analysed samples. In conclusion, the study highlights the widespread occurrence of organic pollutants, particularly PFAS, in commercial marine species along the Portuguese coast, underscoring the urgent need for continued monitoring.
Wastewater Based Epidemiology for the Surveillance of Illicit Drug and Substance of Abuse Use in Prison Settings: A Critical Review
(Wiley, 2025-04-07) Egaña, Iker; Nogales-García, Maite; Akhrimenko, Vladimir; González Gómez, Xiana; Quintana Álvarez, José Benito; Villanueva-Blasco, Víctor José; Orive, Gorka; Lertxundi, Unax; Universidade de Santiago de Compostela. Departamento de Química Analítica, Nutrición e Bromatoloxía; Universidade de Santiago de Compostela. Instituto de Investigación e Análises Alimentarias; Universidade de Santiago de Compostela. Instituto de Acuicultura (IA)
People held in prison suffer from drug use disorders, with important health and safety implications. In order to design strategies to reduce drug consumption and for the provision of services, reliable data is necessary. In this study, a review of published works that have applied wastewater-based epidemiology (WBE) in prison settings was performed in order to evaluate its utility. The study also explored future options for WBE in correctional settings. A search of MEDLINE was conducted using the following PubMed query terms: (“Wastewater” OR “Sewage”) AND (“Prisons” OR “Health Care Correctionals”) AND (“Abuse, substance” OR “illicit drugs”) since 2005 (first report of WBE applied to illicit drug consumption) to February 26, 2025. Then, it was complemented by a Google Scholar citation analysis. We found 8 studies, half of which have been conducted in Australia. Cocaine, cannabis, methamphetamine, and methadone have been the most widely monitored substances (5 studies). Different studies have also monitored various new psychoactive substances (NPS). So far, estimated consumption in prison settings has generally been lower than in the community, with the exception of cannabis and cocaine in French prisons. WBE has proven to be a valuable complementary tool to inform drug consumption in prison settings, as it can offer objective data. However, the number of publications is still limited. Studies focusing on gabapentinoids, synthetic cannabinoids, or enantiomeric profiling should be considered in future research. Additionally, the use of WBE to monitor the effectiveness of interventions offers a great potential as well.
Are Environmental Levels of Nonsteroidal Anti-Inflammatory Drugs a Reason for Concern? Chronic Life-Cycle Effects of Naproxen in Zebrafish
(ACS, 2024-10-24) Barros, Susana; Montes Goyanes, Rosa; Rodil Rodríguez, María del Rosario; Quintana Álvarez, José Benito; Neuparth, Teresa; Universidade de Santiago de Compostela. Departamento de Química Analítica, Nutrición e Bromatoloxía; Universidade de Santiago de Compostela. Instituto de Investigación e Análises Alimentarias; Universidade de Santiago de Compostela. Instituto de Acuicultura (IA)
The nonsteroidal anti-inflammatory drug naproxen (NPX) is among the most consumed pharmaceuticals worldwide, being detected in surface waters within the ng to μg/L range. Considering the limited chronic ecotoxicity data available for NPX in aquatic ecosystems, the present study aimed at evaluating its impact in the model organism Danio rerio, following a full life-cycle exposure to environmentally relevant concentrations (0.1 to 5.0 μg/L). An integration of apical endpoints, i.e., survival, growth, and reproduction, with gonad histopathology and gene transcription (RNA-seq) was performed to provide additional insights into the mode of action (MoA) of NPX. NPX decreased zebrafish growth and reproduction and led to histopathological alterations in gonads at concentrations as low as 0.1 μg/L. At the molecular level, 0.7 μg/L of NPX led to a disruption in gonads transcription of genes involved in several biological processes associated with reproduction, mainly involving steroid hormone biosynthesis and epigenetic/epitranscriptomic machineries. Collectively, these results show that environmentally realistic concentrations of NPX affect zebrafish reproduction and associated signaling pathways, indicating that current hazard and risk assessment data for NPX underestimate the environmental risk of this pharmaceutical.
Integration of a 3D-printed electrochemical reactor with a tubular membrane photoreactor to promote sulfate-based advanced oxidation processes
(Elsevier, 2024-10-24) Olivera, Agustina R. de; Montes Goyanes, Rosa; Quintana Álvarez, José Benito; Rodil Rodríguez, María del Rosario; Vilar, Vítor J. P.; Universidade de Santiago de Compostela. Departamento de Química Analítica, Nutrición e Bromatoloxía; Universidade de Santiago de Compostela. Instituto de Investigación e Análises Alimentarias; Universidade de Santiago de Compostela. Instituto de Acuicultura (IA)
This study investigates the integration of an in-house 3D printed electrochemical cell − SERPIC-UCLM® cell – for the in situ generation of peroxymonosulfuric acid (PMSA) with a lab-scale tubular membrane photoreactor (TMPr) to evaluate the effectiveness of sulfate-radical advanced oxidation processes (SR-AOPs) in eliminating contaminants of emerging concern (CECs) from reverse osmosis and nanofiltration concentrates (ROC and NFC, respectively). First, the SERPIC-UCLM® cell was evaluated in terms of mass transport features employing the limiting current technique, demonstrating favorable volumetric mass transport rates (kmA ∼ 10–3 s–1) and Sherwood values (Sh > 300) under the laminar flow regime (110 < Reynolds (Re) < 790). Afterward, the effect of the electrolyte (sulfuric acid, H2SO4) initial pH in the electrochemical generation of PMSA was studied, with an initial pH of 1 selected as optimal. PMSA is a highly reactive peroxyacid that undergoes self-decomposition at neutral pH media (e.g., ROC and NFC with a pH of 7.6 and 7.9, respectively), primarily existing in the form of peroxomonosulfate (PMS). Additionally, the phototreatment of the ROC and NFC was assessed using the electrogenerated PMS and commercial peroxydisulfate (PDS) under the same conditions. The results indicated comparable degradation patterns for CECs in both ROC and NFC. Furthermore, the application of 2.4 mM PMS resulted in removals higher than 60 % for 7 of the 11 CECs identified in the NFC, and ensured compliance with wastewater discharge regulations for pH, chemical oxygen demand (COD), and total suspended solids (TSS) levels. These findings emphasize the importance of this technology, showing its advantages in terms of versatility and logistics.
Bioaccessibility of plastic-related compounds from polymeric particles in marine settings: Are microplastics the principal vector of phthalate ester congeners and bisphenol A towards marine vertebrates?
(Elsevier, 2024-09-25) López Vázquez, Javier; Miró, Manuel; Quintana Álvarez, José Benito; Cela Torrijos, Rafael; Ferriol, Pere; Rodil Rodríguez, María del Rosario; Universidade de Santiago de Compostela. Departamento de Química Analítica, Nutrición e Bromatoloxía; Universidade de Santiago de Compostela. Instituto de Acuicultura; Universidade de Santiago de Compostela. Instituto de Investigación e Análises Alimentarias
Marine vertebrates are known to ingest significant amounts of microplastics (MPs). Once ingested, MPs might cause gastrointestinal injuries and serve as a path of harmful plastic components, such as phthalate esters (PAEs) and bisphenol A (BPA) in the food chain. However, there is a lack of standardized in-vitro methods capable of simulating fish uptake of chemicals from MPs in the environment as potential vectors of such contaminants. In this work, leaching and in-vitro oral bioaccessibility testing of PAEs and BPA from MPs were conducted batchwise using artificial seawater and gut fluids mimicking gastric, intestinal, and gastrointestinal compartments of marine vertebrates at physiological temperature. The environmental and physiologically relevant extraction tests were applied to medium-density polyethylene (PE) and polyvinyl chloride (PVC) certified reference materials containing eight PAEs of varying hydrophobicity, namely, dimethyl phthalate (DMP), diethyl phthalate (DEP), di-n-butyl phthalate, benzylbutyl phthalate, diethylhexyl phthalate, di-n-octyl phthalate, diisononyl phthalate and diisodecyl phthalate, and BPA (only in PE) as MP surrogates with realistic analyte concentrations of additives for primary MPs. The analysis of the leachates/gut fluid extracts was performed via dilute-and-shoot by ultra-high performance liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS). Only the most hydrophilic compounds, i.e. DMP, DEP and BPA, were found to get released significantly in saline waters, and exhibited the highest oral bioaccessibility rates (34–83 %). Based on our results, a dual-compartment physiologically relevant gastrointestinal test is recommended for appropriate estimation of fish bioaccessibility. The fish daily intakes of DMP, DEP and BPA from MPs, and seawater ingestion as well were estimated using several contamination scenarios (10th percentile as the low level, 50th percentile as the medium level and 90th percentile as the high level) based on probabilistic distributions and cumulative probability curves of measured environmental concentrations of (i) MPs in seawater throughout the world, (ii) DMP, DEP and BPA in beached MPs and those sampled in the open ocean (including both incurred and adsorbed contaminants), and (iii) DMP, DEP and BPA in seawater as reported in recent literature. Under a medium-level concentration scenario (50th percentile) in marine settings, and taking the gastrointestinal bioaccessibility factor into account, the daily intake of DMP, DEP and BPA from MPs accounted for a mere 0.02 % of the waterborne contribution. Hence, the ingestion of MPs should not be considered the primary route of fish exposure to BPA and the most polar PAEs in marine environments. However, more studies on the local and the global scales for mass concentrations of MPs and additives in marine settings are needed for further confirmation of our findings.
Wastewater-based epidemiology to assess pharmaceutical consumption. Spanish perspective
(Elsevier, 2024-09-13) Fontanals Torroja, Núria; Marcé Recasens, Rosa Maria; Montes Goyanes, Rosa; Rodil Rodríguez, María del Rosario; González Mariño, Iria; Valcárcel, Yolanda; Rodríguez Mozaz, Sara; Borrull Ballarín, Francesc; Quintana Álvarez, José Benito; Pocurull, Eva; Universidade de Santiago de Compostela. Departamento de Química Analítica, Nutrición e Bromatoloxía; Universidade de Santiago de Compostela. Instituto de Acuicultura; Universidade de Santiago de Compostela. Instituto de Investigación e Análises Alimentarias
Wastewater-based epidemiology (WBE) is a well-established approach that can provide objective and real-time data on the consumption of substances such as pharmaceuticals. However, most of the studies reported so far compares consumption data obtained using WBE with those derived from prescription data from public health systems, which is often incomplete and might represent a source of uncertainty. This study aims to compare the measured pharmaceutical consumption back calculated with the WBE approach with consumption derived from dispensed pharmaceuticals in two regions of Spain, managed by two different Health Systems. To do so, a group of 17 pharmaceuticals, including the most representative ones of every therapeutic family, were monitored in influent wastewater (IWW) samples collected over a week campaign in spring 2022 at four different wastewater treatment plants (WWTPs) in Spain: two WWTPs in Madrid city (center of Spain) and two WWTPs in Catalonia (Northeast of Spain). Population-normalized daily loads (PNDL) revealed that the patterns of pharmaceutical occurrence in the different WWTPs are very similar, being acetaminophen, 4-acetamidoantipyrine and valsartan the pharmaceuticals with the highest PNDL values: 17162 ± 1457 mg day−1 1000 inh−1 for acetaminophen, 2365 ± 696 and 2429 ± 263 mg day−1 1000 inh−1 for 4-acetamidoantipyrine, 2006 ± 541 and 2041 ± 352 mg day−1 1000 inh−1 for valsartan. Pharmaceutical PNLDs were then transformed into measured pharmaceutical consumption (MC) and compared with dispensed consumption (DC) data obtained from the pharmacies in the catchment area where the WWTPs are located. A ratio MC/DC within 0.8 to 1.2 was obtained for 11 out of the 17 studied pharmaceuticals. Highlighting a match in all the cardiovascular system pharmaceuticals, with the exception of losartan (1.29–1.39 ratio) and valsartan (1.35–1.43) in all WWTPs. In summary, the degree of correlation between MC/DC is higher than those previously reported comparing with the prescribed pharmaceutical consumption.
Determination of regulated perfluoroalkyl substances (PFAS) in drinking water according to Directive 2020/2184/EU
(Springer, 2024-09-12) López Vázquez, Javier; Montes Goyanes, Rosa; Rodil Rodríguez, María del Rosario; Cela Torrijos, Rafael; Martínez-Pontevedra, José Ángel; Pena, María Teresa; Quintana Álvarez, José Benito; Universidade de Santiago de Compostela. Departamento de Química Analítica, Nutrición e Bromatoloxía
Perfluoroalkyl substances (PFAS) are chemical compounds that have been widely used in industry and manufacture. Occurrence, together with persistence and recent toxicological effects data, has promoted the regulation of 20 PFAS (carboxylic and sulfonic) acids in drinking water through the recent Directive 2020/2184/EU. This Regulation included PFAS with different carbon chain lengths (from C4 to C13) and limited the total PFAS concentration (as sum) to a maximum of 0.1 µg/L, for which law-enforcement analytical methods are required. In this work, three different methodologies have been developed and evaluated as regards their performance to determine those 20 PFAS in tap and bottled water, based on on-line and off-line solid-phase extraction (SPE) and direct injection. In all cases, ultra-high pressure liquid chromatography–tandem mass spectrometry (UHPLC-MS/MS) was used as a determination technique. Off-line SPE with Oasis Weak Anion Exchange (WAX) cartridges provided the best results in terms of limits of quantification (LOQ ≤ 0.3 ng/L) and accuracy (R ≥ 70%) in drinking water samples. On-line SPE and direct injection presented some drawbacks such as background contamination problems and lower accuracies for the least polar compounds. This off-line SPE methodology was then applied to the analysis of 46 drinking water samples (11 commercial bottled samples, 23 Spanish and 12 international tap water samples). Ten PFAS were quantified in such samples at concentrations and detection frequencies ranging from 0.1 to 20.1 ng/L and 2 to 91%, respectively. However, the sum concentration did not surpass the established limit in any sample.
Determination of the urinary concentrations of six bisphenols in public servants by online solid-phase extraction-liquid chromatography tandem mass spectrometry
(Springer, 2024-06-18) Estévez-Danta, Andrea; Rodil Rodríguez, María del Rosario; Quintana Álvarez, José Benito; Montes Goyanes, Rosa; Universidade de Santiago de Compostela. Departamento de Química Analítica, Nutrición e Bromatoloxía; Universidade de Santiago de Compostela. Instituto de Acuicultura; Universidade de Santiago de Compostela. Instituto de Investigación e Análises Alimentarias
Bisphenols are widely used as monomers and additives in plastic production. Thus, bisphenol A (BPA) and its most prominent substitutes have been detected in many environmental and human samples. This study proposes an online solid-phase extraction analytical methodology coupled to liquid chromatography with tandem mass spectrometry for the determination of six bisphenols (BPA and bisphenols F (BPF), S (BPS), AF (BPAF), B (BPB), and E (BPE)) in urine samples as an efficient and automated methodology. The method was developed and validated for all bisphenols with good recoveries (92–112%) and repeatability (RSD ≤ 10%) despite the variable matrix effects, except BPAF (which would require a dedicated internal standard), achieving method quantification limits in the 0.05–2.2 ng mL−1 range. The methodology was subsequently applied to 435 urine samples from a non-occupational exposure population (civil servants for the regional government) from Santiago de Compostela (Galicia, Spain). Only BPA, BPF, and BPS were positively detected; the last two presented higher detection frequencies than BPA. When the urinary concentrations are extrapolated to human intake and compared to the European Food Safety Agency (EFSA) tolerable daily intake (TDI) of 2 × 10−4 µg kg−1 day−1 (TDI), all BPA positively identified samples would surpass this threshold. Although no TDI exists currently for the other two identified bisphenols, it is evident that human exposure to bisphenols should be limited. Finally, the results stratification by gender revealed higher levels of exposure to BPF in the women group.
Wastewater-based epidemiology methodology to investigate human exposure to bisphenol A, bisphenol F and bisphenol S.
(Elsevier, 2024-07-08) Estévez-Danta, Andrea; Montes Goyanes, Rosa; Prieto, Ailette; Santos, Miguel M.; Orive, Gorka; Lertxundi, Unax; Quintana Álvarez, José Benito; Rodil Rodríguez, María del Rosario; Universidade de Santiago de Compostela. Departamento de Química Analítica, Nutrición e Bromatoloxía; Universidade de Santiago de Compostela. Instituto de Acuicultura; Universidade de Santiago de Compostela. Instituto de Investigación e Análises Alimentarias
Wastewater-based epidemiology (WBE) has become an invaluable tool for tracking the evolution of use or exposure of/to numerous substances. Bisphenols, commonly utilized in manufacturing plastic goods, have been categorized as endocrine disrupting chemicals, underscoring the critical need for real-time data on their local-level exposure to safeguard public health. In this study, we have developed a novel analytical method and WBE framework for the assessment of population-level exposure to bisphenol A (BPA) and its most prominent substitutes, bisphenols F and S (BPF and BPS), through the determination their Phase II metabolites in wastewater by WBE. Stability and exclusivity tests denoted that glucuronides are not stable in sewage, whereas sulfate metabolites are good biomarkers. Therefore, a solid-phase extraction followed by liquid chromatography-tandem mass spectrometry method was developed for the bisphenols’ monosulfates and BPA bissulfate. The analytical method was validated with three different wastewater matrices, providing trueness (as recovery) in the 79–112 % range with relative standard deviations < 12 %, and method quantification limits below 2 ng L−1 for monosulfates, but higher (35 ng L−1) for BPA bissulfate. Subsequently, the method was applied to 24h-composite raw wastewater samples collected over a week in 4 different locations in Spain and Portugal. BPA bissulfate was not detected, but the three monosulfate metabolites of each bisphenol were positively detected in the samples, being the metabolite of BPA the most prevalent, followed by those of BPF and BPS. Community-wide BPA intake was then estimated to be higher than the European Food Safety Agency (EFSA) tolerable daily intake (TDI) of 2 × 10−4 µg kg−1day−1 in all locations. In the case of BPF and BPS, there is not enough metabolism data or even established limit, but they would also surpass safe levels in several locations if a similar metabolism and TDI would be assumed. This innovative method could be used to a larger set of wastewater-treatment plants as an early-warning approach on human exposure to bisphenols.
Selective electrochemical oxidation of organic compounds in a mass transfer-enhanced electrochemical flow reactor (esingle bondNETmix)
(Elsevier, 2024-07-13) Rosa, Clarissa H.; Montes Goyanes, Rosa; Rodil Rodríguez, María del Rosario; Quintana Álvarez, José Benito; Moreira, Francisca C.; Universidade de Santiago de Compostela. Departamento de Química Analítica, Nutrición e Bromatoloxía; Universidade de Santiago de Compostela. Instituto de Acuicultura; Universidade de Santiago de Compostela. Instituto de Investigación e Análises Alimentarias
esingle bondNETmix stands as an electrochemical flow reactor engineered to enhance mass transfer. This study aimed at assessing the performance of the esingle bondNETmix reactor in the realm of organic electrosynthesis. Specifically, the research focused on the selective electrochemical oxidation of 4-methoxybenzyl alcohol (4-MBA) to p-anisaldehyde (PAA) using a bare fluorine-doped tin oxide (FTO) anode. The efficiency of the process was assessed for distinct current densities (j), Reynolds numbers (Re), supporting electrolyte contents, and substrate initial contents. The esingle bondNETmix reactor was extensively compared to a commercial electrochemical flow reactor (MicroFlowCell from ElectroCell, Denmark). esingle bondNETmix facilitated the use of a broader range of j (0.8–2.0 mA cm−2 versus 0.8 mA cm−2) together with smaller Re (≥190 versus >1750), supporting electrolyte contents (≥1 mM versus ≥30 mM), and substrate initial contents (≥2.0 mM versus ≥3.0 mM) with no loss of PAA production or energy consumption. These findings underscore a remarkable suitability of esingle bondNETmix as a reactor for organic electrosynthesis.
In vitro biotransformation of 3-methylmethcathinone (3-MMC) through incubation with human liver microsomes and cytosol and application to in vivo samples
(Elsevier, 2024-07-06) Wichelen, Natan van; Estévez-Danta, Andrea; Quintana Álvarez, José Benito; Rodil Rodríguez, María del Rosario; Gys, Celine; Universidade de Santiago de Compostela. Departamento de Química Analítica, Nutrición e Bromatoloxía; Universidade de Santiago de Compostela. Instituto de Acuicultura; Universidade de Santiago de Compostela. Instituto de Investigación e Análises Alimentarias
Synthetic cathinones are the second largest group of new psychoactive substances (NPS) monitored by the European Monitoring Centre for Drugs and Drug Addiction. Although 3-methylmethcathinone (3-MMC, C11H15NO) is legally banned in many countries, it is readily available for purchase online and on the street. Due to the scarcity of information regarding the pharmacokinetic and toxicological profile of 3-MMC, understanding its biotransformation pathways is crucial in determining its potential toxicity in humans and in the development of analytical methods for screening of human matrices. To gain more insight, Phase I and Phase II in vitro biotransformation of 3-MMC was investigated using human liver microsomes and human liver cytosol. Suspect and non-target screening approaches were employed to identify metabolites. To confirm in vitro results in an in vivo setting, human matrices (i.e., plasma, urine, saliva and hair) positive for 3-MMC (n=31) were screened. In total three biotransformation products were identified in vitro: C11H15NO2 (a hydroxylated derivate), C11H17NO (a keto-reduced derivate) and C10H13NO (an N-desmethyl derivate). All three were confirmed as human metabolites in respectively 16 %, 52 % and 42 % of the analysed human samples. In total, 61 % of the analysed samples were positive for at least one of the three metabolites. Interestingly, three urine samples were positive for all three metabolites. The presence of 3-MMC in saliva and hair indicates its potential applicability in specific settings, e.g., roadside testing or chronic consumption analysis. To our knowledge, C11H17NO was not detected before in vivo. Although some of these metabolites have been previously suggested in vitro or in a single post mortem case report, a wide in vivo confirmation including the screening of four different human matrices was performed for the first time. These metabolites could serve as potential human biomarkers to monitor human 3-MMC consumption effectively.

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