Artículos (Química Analítica)

URI permanente para esta colecciónhttps://hdl.handle.net/11441/10909

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AI-driven vibrational spectroscopic methods for evaluating antioxidant activity in food systems
(Elsevier, 2026-02-03) Zha, Rili; Ding, Fangchen; Nogales Bueno, Julio; Jara Palacios, María José; Baca Bocanegra, Berta; Hernanz Vila, María Dolores; Química Analítica; Ingeniería Química; Programa Iberoamericano de Ciencia y Tecnología para el Desarrollo, CYTED
Background: Food systems contain a wide array of bioactive compounds that exert beneficial effects on human health, among which antioxidant activity (AA) plays a pivotal role in mitigating oxidative stress-related disorders. Conventional analytical methods for evaluating AA are often labor-intensive, destructive and unsuitable for high-throughput or large-scale assessment, whereas AI-enhanced vibrational spectroscopy enables rapid, nondestructive, and sustainable evaluation of AA across diverse food matrices. Scope and approach: This review systematically summarizes the principles, applications, and limitations of promising vibrational spectroscopic techniques, including near- and mid-infrared spectroscopy, Raman spectroscopy, and hyperspectral imaging, in recent applications for predicting AA in foods. Notably, advances in AIenabled strategies integrating vibrational spectroscopy, hyperparameter optimization, explainable artificial intelligence, multimodal data fusion, and automated machine learning are leveraged to enhance the accuracy and reliability of AA assessment. Finally, this review outlines future directions toward large-scale and real-world AA sensing, emphasizing end-edge-cloud collaborative modeling, blockchain-enabled e-labeling, and portable smartphone spectrometers for consumer-level implementation. Key findings and conclusion: The integration of vibrational spectroscopy with advanced AI techniques enables rapid, non-destructive, and scalable evaluation of AA in complex food systems, bridging the gap between laboratory analysis and real-world applications. Deep learning-based spectral optimization, data fusion, explainable artificial intelligence, and automated machine learning frameworks significantly enhance model robustness, interpretability, and automation. Looking ahead, end-edge-cloud collaboration, blockchain-enabled traceability, and portable smartphone-based spectrometers will underpin large-scale AA prediction in food systems, fostering AI-driven evaluation of food nutritional quality and functional value.
Matrix solid-phase dispersion, combined with online SPE-LC-MS/MS, for the determination of tetracyclines and their main transformation products in sludge and agricultural soils
(Elsevier, 2025-10-04) García-Criado, Noelia; Martín Bueno, Julia; Santos Morcillo, Juan Luis; Aparicio Gómez, Irene; Alonso Álvarez, Esteban; Química Analítica; Ministerio de Ciencia, Innovación y Universidades (MICIU). España; Agencia Estatal de Investigación. España
Background Tetracyclines are frequently detected in the environment due to their persistence and extensive use as antibiotics in human and veterinary medicine. They can accumulate in sludge and in agricultural soils fertilised with treated sludge or manure. This behaviour may lead to ecological risk, propagation of antibiotic resistance and can affect crops and human health through the consumption of vegetables and fruits. Analytical methods for the determination of tetracyclines and their transformation products (TPs) in sludge and agricultural soils are scarce, include a small number of tetracyclines, do not include their TPs and are not specifically developed for their determination. Results A matrix solid-phase dispersion (MSPD) method has been optimised for the simultaneous determination of six tetracyclines and six of their main TPs in the types of sludge applied as soil fertiliser (digested sludge and composted sludge) and in agricultural soil. Analytical determination by online SPE-LC-MS/MS has also been optimised. The method was validated for each of the above-mentioned matrices, with good linearity (R2 ≥ 0.98), precision (RSD ≤12.3 %), accuracy (64–117 %) and method quantification limits (below 10 ng g−1 dry weight (dw) for most compounds). Application of the method to digested sludge, composted sludge and agricultural soils revealed high concentrations not only of the parent compounds (tetracycline and doxycycline, up to 353 ng g−1 dw and 1069 ng g−1 dw, respectively, in digested sludge) but also of their TPs (epitetracycline, anhydrotetracycline and 4-epioxytetracycline up to 327 ng g−1 dw, 117 ng g−1 dw and 10.2 ng g−1 dw, respectively, in digested sludge). Significance and novelty This method allows the specific simultaneous determination of six tetracyclines and six of their TPs in sludge and soils. The proposed method constitutes a starting point to extend the use of MSPD, that is being applied mainly to biota and food, as a low-cost and easy-to-perform technique that allows simultaneous extraction and clean-up. Application of the method revealed the significance of the determination of TPs of tetracyclines for a proper environmental risk assessment.
Enhanced Diclofenac Biodegradation by Bacterial Strains and a Microbial Consortium from Activated Sludge: Toxicity Assessment and Insights into Microbial Community Dynamics
(MDPI, 2026-02-02) Lara Moreno, Alba; Rodríguez Morillo, Belén; Madrid, Fernando; Villaverde, Jaime; Villaverde, Jaime; Mejías Padilla, Carmen; Alonso Álvarez, Esteban; Morillo, Esmeralda; Química Analítica; Microbiología y Parasitología; Junta de Andalucía; European Commission (EC). Fondo Europeo de Desarrollo Regional (FEDER)
Diclofenac (DCF) is a widely used non-steroidal anti-inflammatory drug whose presence in environmental matrices has led to its classification as an emerging contaminant. Developing effective and sustainable removal strategies is therefore essential. In this study, Pseudomonas aeruginosa CSWD.1, Pseudomonas sp. CSWD.2, and a microbial consortium (MC) were isolated from activated sludge through enrichment cultures with DCF and employed as laboratory models to investigate DCF biodegradation capacity under a biosafety-aware framework. Biodegradation assays supplemented with glucose showed limited removal (45.5%) by CSWD.1, whereas CSWD.2 and the MC achieved complete elimination (100%) of 10 mg L−1 DCF in 21 and 5 days, respectively. Three extracellular metabolites, 4’-hydroxy-diclofenac (4’-OH-DCF), 5-hydroxy-diclofenac (5-OH-DCF), and putative NO2-DCF, were detected, with concentrations varying during degradation. Persistence of 4’-OH-DCF and tentatively identified NO2-DCF after 28 days was potentially associated with increased toxicity relative to the abiotic control. Overall, the results suggest that evaluating metabolites and their toxicity is essential, requiring isolation of additional microorganisms able to degrade 4’-OH-DCF and NO2-DCF to combine with the microorganisms isolated in this study. Metabarcoding analysis of the microbial consortium after bioremediation revealed the dominant bacterial population of Burkholderia (88.9% relative abundance) and a predominant fungal genus Talaromyces (80.1%), indicating that both bacteria and fungi may be associated with DCF transformation. These results provide insights into microbial community dynamics and their potential application in designing effective consortia for DCF bioremediation.
Effects of water temperature increase on gene expression, biochemical, and histopathological responses of the bivalve species Mytilus galloprovincialis to the antineoplastic drug 5-fluorouracil
(Elsevier, 2025-06-27) Queirós, Vanessa; Leite, Carla; Azeiteiro, Ulisses M.; Casado Belloso, Marta; Navarro-Martín, Laia; Soares, Amadeu M.V.M.; Santos Morcillo, Juan Luis; Alonso Álvarez, Esteban; Química Analítica; Fundação para a Ciência e a Tecnologia, FCT, Portugal; Ministerio de Ciencia e Innovación (MICIN). España; Agencia Estatal de Investigación. España
The present study aimed to assess the potential ecotoxicological effects of 5-fluorouracil (5-FU), an antineoplastic already found in aquatic ecosystems, towards the bivalve Mytilus galloprovincialis, considering actual and warming temperature scenarios. To this end, organisms were exposed for 28 days to increasing 5-FU concentrations (10, 100, and 500 ng/L) at control (17 ± 1.0 °C) and warming (21 ± 1.0 °C) temperatures. Transcriptomic of selected target genes, biochemical responses, and histopathological alterations were used to assess possible detrimental effects. Results showed an overall down-regulation of mRNA transcripts related to xenobiotic metabolization pathways and cell apoptosis in organisms exposed to 5-FU, especially at 21 °C. While at 17 °C, the antioxidant defenses were not enough to avoid cell damage caused by 5-FU, at 21 °C the metabolic slowdown avoided further cell damage. However, histopathological alterations in the digestive gland at 21 °C at high concentrations of 5-FU were observed. Overall, the present results indicate that the warming temperature may enhance the detrimental effects of 5-FU on this species, with metabolism being particularly affected.
Could the Risk of Chronic Degenerative Valve Disease (CDVD) in Dogs Depend on Exposure to Endocrine-Disrupting Chemicals Polluting the Environment?
(MDPI, 2025-11-28) Makowska, Krystyna; Martín Bueno, Julia; Pasławski, Robert; Rychlik, Andrzej; Aparicio Gómez, Irene; Santos Morcillo, Juan Luis; Alonso Álvarez, Esteban; Górecka-Politańska, Malgorzata; Gonkowski, Slawomir; Química Analítica; Minister of Science in Poland
Endocrine-disrupting chemicals (EDCs) pollute the environment and food, adversely affecting living organisms. It is known that exposure to EDCs increases the risk of various diseases in humans, but in veterinary medicine, the pathogenic impact of these substances is usually marginalised. Therefore, the aim of the present study was to determine whether exposure to EDCs is associated with a higher risk of chronic degenerative valve disease (CDVD) in dogs. The study included hair samples collected from 60 male and female dogs of various breeds and ages ranging from 9 months to 15 years. Hair samples collected from healthy dogs and dogs with CDVD were analysed for the presence of 15 EDCs (including bisphenol A, parabens, benzophenones and polyfluoroalkyl substances) using liquid chromatography and tandem mass spectrometry (LC-MS/MS) technique. Concentration levels of methylparaben, ethylparaben, propylparaben, perfluoroheptanoic acid and perfluorooctanoic acid in samples collected from dogs with CDVD were statistically significantly higher than those noted in healthy dogs. Differences in concentrations of other EDCs studied between ill and healthy dogs were not statistically significant. The results may suggest that greater exposure of dogs to certain EDCs (such as methylparaben, ethylparaben, propylparaben, perfluoroheptanoic acid, and perfluorooctanoic acid) may increase the risk of CDVD, but further comprehensive clinical and toxicological research is necessary to fully clarify this issue.
Volatile organic compounds, SO2 and NO2 capture by means of an indoor active living wall
(Elsevier, 2026-04-15) Fernández Espinosa, Antonio José; Montiel de la Cruz, J.M.; Fernández Cañero, Rafael; Pérez Urrestarazu, Luis; Rossini Oliva, Sabina; Química Analítica; Agronomía; Ingeniería Aeroespacial y Mecánica de Fluidos; Biología Vegetal y Ecología; Junta de Andalucía
The ability of an active living wall (ALW) to capture indoor air pollutants was studied. Five different species (Spathiphyllum wallisii, Tradescantia zebrina, Philodendron scandens, Ficus pumila and Chlorophytum comosum) were assessed. The experiments were performed inside a closed glass chamber for each species separately. Gas pol lutants (NO2 and SO2) and volatile organic compounds (formaldehyde, acetone, n-hexane and n-heptane) were introduced into the chamber monitoring concentration changes. High values of the Pollutant Reduction (PR%) indicator were recorded after releasing pollutants in the chamber, especially for CH2O and SO2. After 24 h, PR% in the chamber ranged 96-98% for all the plant species studied. The ALW was more efficient in removing CH2O and NO2 than other air contaminants. In addition, differences in Differential Reduction Efficiency (DRE%) in dicator were observed among plant species depending on the pollutant considered. After 15 min from the in jection of TVOCs, a reduction of 24-40% was achieved with all plant species but S. wallisii showed greater DRE for NO2, with 60% reduction in the first hour of exposure. The presented data demonstrates the effectiveness of active living wall systems for improving indoor air quality
Comparative study of hyperspectral imaging and portable spectroscopy techniques for selecting white grape pomace samples for fining agent production
(Elsevier, 2025-12-14) Gómez Pérez, Julia; Baca Bocanegra, Berta; Rodríguez Pulido, Francisco José; González-Miret Martín, María Lourdes; Nogales Bueno, Julio; Hernández Hierro, José Miguel; Nutrición y Bromatología, Toxicología y Medicina Legal; Química Analítica; Junta de Andalucía; Ministerio de Ciencia y Tecnología (MCYT). España
During wine production, grape pomace is generated as a by-product. Although its management poses challenge due to its large volume, it also offers opportunities thanks to its high content of valuable biopolymers. However, not all pomaces share the same properties or are suitable for the same applications. In this study, a total of 111 pomace samples from three white grape varieties were studied: Pedro Xim´enez (n = 40), Moscatel (n = 21), and Zalema (n = 50). Spectral data were collected using three different devices: a NIR hyperspectral camera (900–1700 nm), a portable visible-NIR hyperspectral camera (400–1000 nm), and a MicroNIR portable spectrometer (900–1700 nm). Measurements were taken from both whole pomace and isolated grape skins, the latter being of particular interest for future research and possible application as natural fining agents. This generated six spectral datasets, which were subsequently merged into three augmented matrices to assess sample heterogeneity (matrix effect) and, subsequently, the impact of the measuring device (device effect). Each dataset was processed using Principal Component Analysis (PCA), and representative samples were selected based on the Mahalanobis distance to the nearest neighbour (NH). The results were compared to highlight the strengths and limitations of each instrument and sample type in achieving an efficient, costeffective, and non-destructive selection method. Among the devices evaluated, MicroNIR proved to be the most cost-effective and portable solution for in-situ sample selection, enabling practical implementation in wineries. Finally, the selected samples were used as fining agents in red winemaking and their ability to clarify flavanols assessed.
Biomonitoring of DAPs levels in urine and amniotic fluid of pregnant women in Seville (Spain): evaluation of prenatal exposure
(Elsevier, 2025-12-19) Sánchez Ruiz, Rocío; Hinojosa Hidalgo, María Gracia; Aranda Merino, Noemí; Fernández Torres, Rut; Cerrillos, Lucas; Ostos, Rosa; Fernández Palacín, Ana; Moreno Navarro, Isabel María; Nutrición y Bromatología, Toxicología y Medicina Legal; Química Analítica; Medicina Preventiva y Salud Pública; Ministerio de Ciencia, Innovación y Universidades (MICIU). España; European Union (UE); Junta de Andalucía
Among all population groups, pregnant women are one of the most vulnerable due to increasing concern about prenatal exposure to environmental pollutants, including pesticides such as organophosphates (OPs). In this regard, dialkyl phosphates (DAPs) are nonspecific metabolites excreted in urine and widely used to assess OP exposure. Thus, this study aimed to assess the risk of indirect OP exposure by determining six DAPs (dimethyl phosphate (DMP), O,O-dimethyl thiophosphate (DMTP), O,O-dimethyl dithiophosphate (DMDTP), diethyl phosphate (DEP), O,O-diethyl thiophosphate (DETP), and O,O-diethyl dithiophosphate (DEDTP)) in urine and amniotic fluid (AF) from a 74-pregnant-women cohort in Seville (Southern Spain). Sample preparation was based on electromembrane extraction (EME), a microextraction technique using an electric potential to selectively extract analytes across a supported liquid membrane (SLM). The analysis was performed using ion-pair ultrahigh-performance liquid chromatography coupled with electrospray ionization tandem mass spectrometry (UHPLC-ESI-MS/MS). Results showed that DAPs can cross the placental barrier, as most AF samples showed between 80 and 99 % positive levels, depending on the compound, however, the studies in this regard are very scarce. Nonetheless, these levels were slight, and both mean and maximum concentrations detected in AF were lower than urine levels in every case. Moreover, the percentage of positive samples in urine was lower (44–92 %). Thus, this research highlights the importance of studying the presence of these metabolites, both in urine and in AF, and the physiological outcomes that their presence may cause both in the mothers and infants.
Rice husk ash–supported CdS composites for efficient photocatalytic degradation of metronidazole with minimized phytotoxicity
(Elsevier, 2026-01-21) Jerônimo, Aimée Giovanna; Amorim, Kallyandra; Albuquerque, Willams; Trigueiro, Pollyana; Romaguera-Barcelay, Y.; Prado Feitosa, Rodrigo; Orta Cuevas, María del Mar; Osajima, Josy A.; Peña García, Ramón Raudel; Química Analítica
In this work, cadmium sulfide–rice husk ash (CdS/RHA) composites were synthesized by co-precipitation of cadmium nitrate and ammonium sulfide, followed by dispersion and assembly of the resulting cadmium sulfide nanoparticles with rice husk ash at mass ratios of 1:1, 1:2, and 1:3. Structural analysis using X-ray diffraction (XRD) confirmed the presence of hexagonal and cubic cadmium sulfide, as well as α-quartz (SiO2). Additionally, Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy coupled with energy-dispersive analysis (EDS) demonstrated strong interfacial contact and a uniform dispersion of nanoparticles. Nitrogen adsorption–desorption measurements revealed mesoporous surfaces, with specific surface areas of 15.9, 9.3, and 6.1 m2 g-1 for the 1:1, 1:2, and 1:3 composites, respectively. Diffuse reflectance spectroscopy (DRS) showed negligible changes in the optical band gap (2.413–2.434 eV) but a 20–35% decrease in visible reflectance upon incorporation of ash. Photoluminescence measurements showed a quenching of near-band-edge emission for the CdS/RHA composites, indicating enhanced separation of photogenerated charges. Lettuce seed bioassays revealed that the control exhibited a germination rate of 76.5% under the test conditions, whereas pure cadmium sulfide and the CdS/RHA(1:1) composite completely inhibited germination, while the 1:2 and 1:3 composites restored germination rates to 31.5(2)% and 50.0(1)% at 1000 μg mL-1, respectively. Under UV irradiation, the CdS/RHA(1:1) composite achieved 83.5(2)% degradation of metronidazole (MNZ) in 150 minutes (apparent rate constant, k = 0.01239 min-1), outperforming the 1:2 (74.0(1) %, k = 0.01000 min-1) and 1:3 (74.8(1) %, k = 0.009713 min-1) materials. Complementary dark experiments revealed that adsorption alone was responsible for only 11.1%, 18.0%, and 15.2% removal in the 1:1, 1:2, and 1:3 composites, respectively, confirming that metronidazole removal was primarily photocatalytic. Scavenger tests identified photogenerated holes and electrons as the primary reactive species, with superoxide radicals playing a secondary role. The CdS/RHA(1:1) composite retained 40.3(1)% of its initial activity after three consecutive reuse cycles, with degradation efficiencies decreasing from 83.5% in the first cycle to 58.4% and 40.3% in the second and third cycles, respectively. These results demonstrate that integrating CdS with rice husk ash yields a recyclable, high-performance photocatalyst with reduced phytotoxicity at higher RHA loadings, suitable for sustainable pharmaceutical removal from water.
Occurrence of the main metabolites of the most recurrent pharmaceuticals and personal care products in Mediterranean soils
(Elsevier, 2021-01-15) Malvar Guzmán, José Luis; Santos Morcillo, Juan Luis; Martín Bueno, Julia; Aparicio Gómez, Irene; Alonso Álvarez, Esteban; Química Analítica; Ministerio de Economía y Competitividad (MINECO). España; Ministerio de Ciencia, Innovación y Universidades (MICIU). España; FQM344: Análisis Químico Industrial y Medioambiental
The use of sewage sludge and wastewater in agricultural lands provide contaminants to soils. As a result, a large number of contaminants can be present in soils. Among others, pharmaceuticals and personal care products (PPCPs) are two of the most studied families of emerging contaminants in wastewater. However, there is scarce information about their behaviour in soils. Occurrence, fate and behaviour in soils of metabolites are even less known. In this work, the degradation of most recurrent PPCPs in the environment and their main metabolites has been evaluated using batch experiments in three typical Mediterranean soils. Batch experiments were carried out in a climatic chamber using spiked soils under Mediterranean climatic conditions. The studied compounds were five pharmaceutically active compounds (carbamazepine, ibuprofen, caffeine, sulfamethoxazole and diclofenac), two parabens (methylparaben and propylparaben) and twelve of their main metabolites. Studied PPCPs and metabolites showed different adsorption capacity onto the studied soils. As results, despite of the compounds were spiked at the same concentrations, different contents were measured at the beginning of the batch experiments. The soil 3 showed the lowest degradation rate for all studied compounds what could be related with the higher adsorption capacity of this soil. A decrease of the measured contents was observed for all studied compounds, except in the case of CBZ and EP-CBZ. No transformations of parent compounds into their metabolites or vice versa were observed, except in the case of Ibuprofen and its metabolites. Although the results showed overall short degradation times for the most of the compounds studied, the evaluation of the environmental risks of the PPCPs and their metabolites should not be underestimated.
Comparison of ultrasound-assisted extraction, QuEChERS and selective pressurized liquid extraction for the determination of metabolites of parabens and pharmaceuticals in sludge
(Elsevier, 2020-09) Malvar Guzmán, José Luis; Santos Morcillo, Juan Luis; Martín Bueno, Julia; Aparicio Gómez, Irene; Alonso Álvarez, Esteban; Química Analítica; Ministerio de Economía y Competitividad (MINECO). España; Ministerio de Ciencia, Innovación y Universidades (MICIU). España; FQM344: Análisis Químico Industrial y Medioambiental
Analytical methods for the determination of parabens and pharmaceuticals in sludge are scarce and focused on the parent compounds in spite that metabolites can be more toxic and concentrated. This fact is of special relevance when sewage sludge is applied as soil fertiliser what is a common practise in many European countries. In that way, they could affect soils and plants and could even enter into the food chain. In this work, to cover the lack of methodologies for the determination of metabolites of parabens and pharmaceuticals in sludge, two analytical methods have been developed. Proposed analytical methods are based on low-cost and easy-to-perform techniques (ultrasonic-assisted extraction (UAE) and QuEChERS) to make them affordable for routinely control laboratories. The methods have been optimised and validated for the determination of 12 relevant metabolites of parabens and pharmaceuticals and their 7 parent compounds. Proposed methods have been compared with a previously reported method based on selective pressurised liquid extraction (SPLE). UAE method provided higher recoveries, lower MQL, higher precision and higher accuracy than QuEChERS method. Nevertheless, both QuEChERS and UAE methods, in spite of being more time-consuming and difficult to automatise, have been demonstrated to be suitable low-cost alternatives to SPLE. To the best of our knowledge, UAE, QuEChERS and SPLE proposed methods constitute the first multiresidue methods for the simultaneous determination of metabolites of parabens and pharmaceuticals in sewage sludge.
Multisampling Strategies for Determining Contaminants of Emerging Concern (CECs) in the Marine Environment
(MDPI, 2025-09-15) Díaz Montaña, Enrique Jacobo; Domínguez-Gil, Sofía; Química Analítica
The determination of contaminants of emerging concern (CECs) in the marine environment is performed through many different sampling approaches. Therefore, the main objective of this study was to compare different existing sampling strategies: biofilm mesocosms, considering micro- and macrofouling; passive sampling; and grab marine water. The sampling of grab water was performed considering spatial and time-line variations. The spatial analysis of CECs showed that three sun agents and caffeine represent the biggest proportion of CECs in the Malaga Mediterranean coastal area, ranging from 0.391 to 0.495 ng/L. The time-line analysis did not show any upward or downward trend in CEC concentration. The mesocosm study comprised a separate evaluation of micro- and macrofouling that showed similar profiles, in which the sun agents presented the highest concentrations. While certain compounds were detected at comparable levels in both fouling types, such as clotrimazole around 0.001 ng/L, others exhibited significant differences in concentration, like caffeine. The passive sampling was also performed, obtaining similar results to those observed in the biofilm mesocosm macrofouling. Finally, all the obtained results from the different samplings were statistically compared, showing that passive sampling presented greater similarities with macrofouling and that there are significant differences between the sampling approach employed.
Influence of the type of treated sludge on LAS degradation after soil application: Risk assessment and considerations under the EU Directive 86/278/EEC
(Elsevier, 2025-12-11) Martín Bueno, Julia; Mejías Padilla, Carmen; García-Criado, Noelia; Arenas Molina, Marina; Santos Morcillo, Juan Luis; Aparicio Gómez, Irene; Alonso Álvarez, Esteban; Heinze, John; Química Analítica
In 2000, the European Commission issued a draft document to regulate the application of sludges from wastewater treatment plants to soil, proposing concentration limits for certain organic compounds, including Linear Alkylbenzene Sulfonates (LAS). A concentration limit of 2600 mg/kg dry matter (dm) for LAS was set, although requirements vary across EU Member States. The aim of this work was to assess the influence of different types of treated sludge (anaerobically-digested, aerobically-digested, dehydrated, lagoon, and compost) on LAS degradation after soil application and to conduct an environmental risk assessment, considering the provisions of EU Directive 86/278/EEC. Laboratory experiments showed LAS concentrations in treated sludges ranged from 236 mg/kg dm in compost to 11,302 mg/kg dm in lagoon sludge. After soil amendment, LAS concentrations in soil ranged from less than 1.5 mg/kg to 66 mg/kg dm, and after three weeks, they ranged from 0.7 to 19 mg/kg dm. LAS degraded rapidly, with half-lives (DT50) from 2 days (dehydrated sludge) to 13 days (anaerobically-digested sludge and compost). Degradation followed a double-exponential decay model, with faster degradation in the solution phase compared to the sorbed phase. DT50 values for LAS increased with chain length for anaerobically- and aerobically-digested sludges but decreased for dehydrated sludge. The type of sludge influenced LAS degradation due to microbial populations and LAS sorption. LAS posed no ecological risk when applied via treated sludge, except for lagoon sludge, which posed a risk for up to seven days. Composting was the most recommended treatment for sludge prior to land application.
Evaluation of sheep exposure to poly- and perfluoroalkyl substances through hair sample analysis
(Sciendo, 2025-04-04) Gonkowski, SŁawomir; Martín Bueno, Julia; Kadyralieva, Nariste; Aparicio Gómez, Irene; Santos Morcillo, Juan Luis; Alonso Álvarez, Esteban; Química Analítica; FQM344: Análisis Químico Industrial y Medioambiental
Introduction: Poly- and perfluoroalkyl substances (PFASs) are a numerous group of synthetic organic compounds used in various industries. They pollute the natural environment and negatively affect humans and animals. The aim of the present investigation was to assess the exposure of sheep bred in the Kyrgyz Republic to six selected PFASs. Material and Methods: Six selected PFASs were assessed in 50 sheep (39 females and 11 males) of Kyrgyz and Arashan breeds ranging in age from 1 to 8 years (mean 2.1 ± 1.1), recruited equally from the Alamedin and Sokuluk regions. The substances were five perfluoroalkyl carboxylic acids (perfluorobutanoic acid – PFBuA, perfluoropentanoic acid – PFPeA, perfluorohexanoic acid – PFHxA, perfluoroheptanoic acid – PFHpA and perfluorooctanoic acid – PFOA) and perfluorooctane sulphonic acid (PFOS), and were determined through the liquid chromatography–tandem mass spectrometry of hair samples. Results: All the listed PFASs were found in the studied hair samples. The highest concentrations were noted for PFPeA and PFBuA. The concentration of PFPeA ranged from 0.99 ng/g to 27.90 ng/g (mean 5.55 ± 4.54 ng/g) and that of PFBuA from 0.95ng/g to 14.18 ng/g (mean 2.24 ± 2.34 ng/g). The mean concentration levels of other PFASs were as follows: 1.06 ± 0.78 ng/g for PFHxA, 1.02 ± 0.76 ng/g for PFHpA, 0.87 ± 0.68 ng/g for PFOA and below the method quantification limit for PFOS. Clear differences in PFASs levels were noted between the two regions. Conclusion: Sheep are exposed to various PFASs, and sheep wool and items made of it may be the source of human exposure to these compounds. Hair samples may be used for biomonitoring of sheep exposure to PFASs.
Multisampling Strategies for Determining Contaminants of Emerging Concern (CECs) in the Marine Environment
(MDPI, 2025-09-10) Díaz Montaña, Enrique Jacobo; Domínguez-Gil, Sofía; Química Analítica; AGR104: Proyecto Sexia
The determination of contaminants of emerging concern (CECs) in the marine environment is performed through many different sampling approaches. Therefore, the main objective of this study was to compare different existing sampling strategies: biofilm mesocosms, considering micro- and macrofouling; passive sampling; and grab marine water. The sampling of grab water was performed considering spatial and time-line variations. The spatial analysis of CECs showed that three sun agents and caffeine represent the biggest proportion of CECs in the Malaga Mediterranean coastal area, ranging from 0.391 to 0.495 ng/L. The time-line analysis did not show any upward or downward trend in CEC concentration. The mesocosm study comprised a separate evaluation of micro- and macrofouling that showed similar profiles, in which the sun agents presented the highest concentrations. While certain compounds were detected at comparable levels in both fouling types, such as clotrimazole around 0.001 ng/L, others exhibited significant differences in concentration, like caffeine. The passive sampling was also performed, obtaining similar results to those observed in the biofilm mesocosm macrofouling. Finally, all the obtained results from the different samplings were statistically compared, showing that passive sampling presented greater similarities with macrofouling and that there are significant differences between the sampling approach employed.
Efficient one-pot synthesis of ruthenium catalysts and their role in optimizing sugar alcohol production: Investigating structural sensitivity
(Elsevier, 2024-11-30) Santos Morcillo, Juan Luis; Murzin, Dmitry Y.; Centeno Gallego, Miguel Ángel; Química Analítica; Ministerio de Ciencia e Innovación (MICIN). España; European Commission (EC). Fondo Europeo de Desarrollo Regional (FEDER); Junta de Andalucía; FQM344: Análisis Químico Industrial y Medioambiental
The study explores the feasibility of producing ruthenium catalysts supported on char through a one-pot synthesis, an original approach for the preparation of noble metal-based catalysts in this field. This method combines high-temperature stages, such as catalytic support carburization and catalyst activation, in a single step. The innovation represents a significant advancement in utilizing cellulose as a model of waste biomass, enhancing its value, and reducing catalyst production costs. The one-pot catalysts were successfully tested in the hydrogenation reaction of sugar mixtures (L-Arabinose and D-Galactose) under mild conditions, achieving full selectivities. The research also introduces for the first time in that reaction a structural sensitivity analysis of the reaction, comparing experimental results with a theoretical model. The findings reveal a direct correlation between catalytic activity and the {0001} exposed face of hcp ruthenium nanoclusters. This discovery opens new avenues for industrial-scale catalyst development, promising substantial reductions in energy and production costs, and emphasizing the economic appeal of the process.
Levels of linear alkylbenzene sulfonates and nonylphenol in wild bat guano samples
(Frontiers Media, 2025-08-15) Gonkowski, SŁawomir; Martín Bueno, Julia; Aparicio Gómez, Irene; Santos Morcillo, Juan Luis; Alonso Álvarez, Esteban; Sowinska, Wioleta; Rytel, Liliana; Química Analítica; Minister of Science in Poland; FQM344: Análisis Químico Industrial y Medioambiental
Introduction: Surfactants are substances that are commonly used in the industry, and they pollute the environment and negatively affect living organisms. In this article, we describe, for the first time, the exposure of wild bats to selected surfactants: nonylphenol (NP) and linear alkylbenzene sulfonates (LASs), including LAS C10, LAS C11, LAS C12, and LAS C13 (where “C” with a number indicates the length of the alkyl carbon chain). Methods: The levels of the abovementioned compounds were evaluated in guano samples collected from various colonies of the greater mouse-eared bat (Myotis myotis) using liquid chromatography coupled with mass spectrometry (LC-MS/MS).Results: All surfactants studied were found in the guano samples. Mean levels of LASs (±SD) ranged from 87 ± 28.5 ng/g (median 75.1 ng/g) in the case of LAS C10 to 662 ± 227.2 ng/g (median 560.5 ng/g) in the case of LAS C12. The mean concentration of NP was 65.2 ± 74.9 ng/g (median 23.5 ng/g). Moreover, significant differences in surfactant levels were noted between particular bat colonies. Discussion: The results showed that wild bats are highly exposed to LASs and NP, and the degree of this exposure shows clear intraregional differences. Moreover, the study demonstrated that guano samples serve as a valuable tool to assess bat exposure to these surfactants.
Hydrothermal Synthesis of ZnO@MnO₂-Montmorillonite Nanocomposites: Influence of Molarity on Structural, Optical, and Photocatalytic Performance toward Ciprofloxacin Degradation under Variable Conditions
(American Chemical Society, 2025-09-18) Bezerra, Elisabethe; Alburquerque, William A. Santos; Filho, Adilson J. Neres; Lins, Alexsandro; Barbosa, Ricardo; Almeida, Luciano C.; Medina-Carrasco, Santiago; Orta Cuevas, María del Mar; Osajima, Josy A.; Trigueiro, Pollyana; Peña Garcia, Ramón R.; Química Analítica; Coordenação de Aperfeiçoamento de Pessoal de Nível Superior; Conselho Nacional de Desenvolvimento Científico e Tecnológico. Brasil; Fundação de Amparo à Ciência e Tecnologia de Pernambuco; FQM410: Análisis Estructural y Composicional Aplicado
In this work, a series of ZnO@MnO₂-montmorillonite nanocomposites was successfully synthesized via a hydrothermal route using NaOH solutions at varying molarities (3−9 M) and evaluated for their structural, optical, morphological, and photocatalytic properties, with specific application in ciprofloxacin degradation. Structural investigation confirmed the coexistence of pure ZnO (hexagonal), MnO₂ (tetragonal), and montmorillonite phases and showed molarity-dependent variations in crystallite size, from 34 nm (ZMM5) to 7 nm (ZMM9), and dislocation density, which ranged from 0.0009 to 0.0180 nm⁻² . Fourier-transform infrared spectroscopy (FTIR) spectra evidenced the progressive occupation of montmorillonite OH sites by metal oxides. At the same time, photoluminescence deconvolution revealed a shift in dominant intrinsic defects: ZMM3 exhibited 49% Zn vacancies (VZn), whereas ZMM7 and ZMM9 showed higher concentrations of oxygen vacancies (VO⁺ up to 40.7%). The band gap narrowed from 3.294 eV (ZMM3) to 2.945 eV (ZMM9), indicating an increase in defect states and enhanced light absorption. Textural analysis revealed that ZMM3 had the highest surface area (35.1 m² g⁻¹) and microporosity, whereas samples synthesized at higher molarities exhibited mesoporous structures with reduced surface areas (∼18−22 m² g⁻¹). Photocatalytic tests under ultraviolet (UV) irradiation for 120 min showed excellent degradation performance for all nanocomposites: ZMM3 (60.1%), ZMM5 (61.0%), ZMM7 (59.7%), and ZMM9 (59.5%), indicating robust activity independent of structural variations. Operational parameter studies confirmed that ZMM5 maintained high activity across different catalyst dosages (25−100 mg (47−61%)), pollutant concentrations (10−30 mg L⁻¹ (45−61%)), and pH levels (3−9 (48−61%)), achieving degradation rates between 45 and 61%. Scavenger tests confirmed hydroxyl radicals (•OH) and holes (h⁺) as the main active species. Reusability tests revealed a 28% drop after three cycles (from 59 to 31%), while X-ray diffraction (XRD) confirmed structural stability with no formation of secondary phases. These results demonstrate the robustness, tunability, and applicability of the ZnO@MnO₂-montmorillonite system for real-world water treatment under variable conditions.
Matrix solid-phase dispersion, combined with online SPE-LC-MS/MS, for the determination of tetracyclines and their main transformation products in sludge and agricultural soils
(Elsevier, 2025-12-15) García-Criado, Noelia; Martín Bueno, Julia; Santos Morcillo, Juan Luis; Aparicio Gómez, Irene; Alonso Álvarez, Esteban; Química Analítica; Ministerio de Ciencia e Innovación; Ministerio de Ciencia, Innovación y Universidades (MICIU). España; FQM344: Análisis Químico Industrial y Medioambiental
Background Tetracyclines are frequently detected in the environment due to their persistence and extensive use as antibiotics in human and veterinary medicine. They can accumulate in sludge and in agricultural soils fertilised with treated sludge or manure. This behaviour may lead to ecological risk, propagation of antibiotic resistance and can affect crops and human health through the consumption of vegetables and fruits. Analytical methods for the determination of tetracyclines and their transformation products (TPs) in sludge and agricultural soils are scarce, include a small number of tetracyclines, do not include their TPs and are not specifically developed for their determination. Results A matrix solid-phase dispersion (MSPD) method has been optimised for the simultaneous determination of six tetracyclines and six of their main TPs in the types of sludge applied as soil fertiliser (digested sludge and composted sludge) and in agricultural soil. Analytical determination by online SPE-LC-MS/MS has also been optimised. The method was validated for each of the above-mentioned matrices, with good linearity (R2 ≥ 0.98), precision (RSD ≤12.3 %), accuracy (64–117 %) and method quantification limits (below 10 ng g⁻¹ dry weight (dw) for most compounds). Application of the method to digested sludge, composted sludge and agricultural soils revealed high concentrations not only of the parent compounds (tetracycline and doxycycline, up to 353 ng g⁻¹ dw and 1069 ng g⁻¹ dw, respectively, in digested sludge) but also of their TPs (epitetracycline, anhydrotetracycline and 4-epioxytetracycline up to 327 ng g⁻¹ dw, 117 ng g−1 dw and 10.2 ng g⁻¹ dw, respectively, in digested sludge).
Distribution and fate of antibiotics and their main metabolites in sludge stabilization technologies
(Elsevier, 2025-09) Mejías Padilla, Carmen; Santos Morcillo, Juan Luis; Martín Bueno, Julia; Aparicio Gómez, Irene; Alonso Álvarez, Esteban; Química Analítica; Ministerio de Ciencia, Innovación y Universidades (MICIU). España
Sewage sludge tends to accumulate emerging contaminants during wastewater treatment, with many pollutants persisting even after undergoing sludge stabilization treatments, posing potential environmental risks. Antibiotic contamination is of particular concern due to their high persistence and ability to promote the development of resistance genes. However, limited information is available regarding the behavior of antibiotic metabolites. In this study, seventeen antibiotics and metabolites of five therapeutic groups of critically and highly important antibiotics were monitored in wastewater and sludges from fifteen wastewater treatment plants (WWTPs) with five different sludge stabilization treatments: anaerobic digestion, aerobic digestion, dehydration, composting, and lagooning. Results demonstrated that the distribution ratio of metabolites and parent compounds in influent wastewater was correlated with their excretion rates, reflecting pharmaceutical consumption as their primary source to WWTPs. Fluoroquinolone and sulfonamide antibiotics were predominant in influent wastewater, while macrolide antibiotics were more prevalent in primary sludge, likely due to their higher hydrophobicity, which results in greater retention in sludge. Parent compounds dominated over metabolites in sewage sludge, with composting plants showing the highest removal efficiency and highest metabolization among all sludge stabilization technologies studied. Tetracyclines were not detected in any of the sludge samples analyzed and macrolides resulted in the most persistent antibiotics in treated sludges. Results showed low environmental risks associated with the reuse of treated sludge as an organic amendment in agriculture.

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