Search Results (2,404)

The continuous discharge of pharmaceutical residues into aquatic environments has raised significant environmental concerns due to their persistence and incomplete removal during wastewater treatment. Non-steroidal anti-inflammatory drugs (NSAIDs) are among the most frequently detected pharmaceutical contaminants in industrial effluents. In this study, a sensitive and selective analytical method was developed for the simultaneous determination of ketoprofen (KTP), meloxicam (MEL), and celecoxib (CEL) in pharmaceutical wastewater using micellar electrokinetic chromatography (MEKC) combined with off-line solid-phase extraction (SPE). A high-volume SPE procedure (1000 mL sample) followed by evaporation and reconstitution provided a theoretical enrichment factor of approximately 10,000. Under optimised conditions, complete separation was achieved in less than 10 min. The method exhibited excellent linearity over a range of 0.5–20 µg/mL (r² > 0.999), with limits of detection in wastewater ranging from 14 to 18 ng/L. Accuracy and precision complied with ICH Q2(B) guidelines, and recoveries from spiked wastewater samples ranged from approximately 99% to 101%, indicating efficient extraction and minimal analyte loss. The validated method was successfully applied to real pharmaceutical wastewater samples, demonstrating its suitability for the routine monitoring of trace-level NSAIDs in complex industrial matrices. Full article

Zebrafish, as an emerging model organism, are widely used in in vivo pharmacodynamic and pharmacokinetic studies. Unlike direct chemical analyses that require no sample preparation, most biological samples must undergo preprocessing steps—procedures that profoundly affect analytical outcomes. This paper systematically summarizes the main methods and types of zebrafish sample pretreatment currently in use, aiming to provide a reference for future research in zebrafish sample analysis and preparation. A systematic search was conducted across PubMed, Web of Science, and CNKI for studies published between 2014 and 2024 focusing on liquid–liquid extraction (LLE), solid phase extraction (SPE), and related techniques for zebrafish drug analysis. The results indicate that traditional methods, including LLE and protein precipitation, remain prevalent due to their operational simplicity, but are limited by low enrichment efficiency and pronounced matrix effects (MEs). In contrast, advanced SPE techniques, particularly solid phase microextraction (SPME), are increasingly favored for complex biological sample processing, with key trends including technique hyphenation (e.g., SPME–high-performance liquid chromatography (SPME-HPLC), and micro-SPE–mass spectrometry (µSPE-MS)) and the development of novel sorbents. Despite these advances, current challenges persist, such as immature rapid on-site pretreatment protocols, the difficulty of balancing analytical efficiency with operational simplicity, and the lack of standardized procedures across studies. Overall, zebrafish sample pretreatment techniques are evolving toward higher efficiency, selectivity, and automation. Future research efforts should prioritize the development of intelligent, eco-friendly pretreatment methods and the establishment of unified standards to enhance the reproducibility and comparability of zebrafish-based pharmacological studies. Full article

Interannual variability in climatic conditions represents a major source of uncertainty in cool-climate viticulture, highlighting the need for cultivar-specific assessments of climate–quality relationships. A multi-year on-farm experiment with six monitoring sites has been conducted in vineyards representative of the Tokaj wine region to monitor and assess vintage effect. This study, as the first part of a broader research project evaluating must components, quantifies relationships between climatic indices and key yield- and sugar-related traits (berry weight, total soluble solids, and total dry extract) in Vitis vinifera L. cv. Furmint grown in the Tokaj wine region over three contrasting vintages. Thermal, radiative, and water-availability variables were calculated for discrete phenological phases and statistically analyzed to identify climatic predictors of berry growth and must composition. Berry weight exhibited pronounced vintage sensitivity, showing consistent associations with precipitation-related variables during early developmental stages. In contrast, total soluble solids and total dry extract displayed weaker and less consistent responses to interannual climatic variability. Several widely used heat-accumulation indices showed limited explanatory power, indicating a moderate climatic sensitivity of sugar-related traits in this cultivar. Overall, the results suggest that early-season climatic conditions exert a stronger influence on berry growth than late-season thermal extremes, while compositional parameters related to sugar accumulation remain comparatively stable. These findings highlight the need to incorporate cultivar-specific response functions into statistical models that assess projected climate-change effects on grape quality. Full article

Ullucus tuberosus is an underutilized Andean tuber of South America, representing a highly nutritious food source valuable in bioactive compounds and used in traditional medicine by the local population. Despite its potential as a functional food, limited information is available regarding the phenolic composition of its diverse varieties, hindering its revalorization and potential biotechnological applications. In this study, the total phenolic content (TPC), antioxidant activity (AA), and thirteen individual phenolic compounds were investigated in five ulluco varieties using UV-Vis spectrophotometry and ultra-high-performance liquid chromatography, coupled with electrospray ionization and a triple quadrupole mass spectrometer (UHPLC-ESI-MS/MS). Statistical analyses revealed significant differences (p < 0.05) among the varieties in TPC, AA, and the concentration of the four quantified flavonoids. The major flavonoids found were rutin, quercetin-3-glucoside, kaempferol-3-rutinoside, and isorhamnetin-3-rutinoside, using solid-phase extraction (SPE-C8) as a cleanup step for ultrasound-assisted extracts, achieving satisfactory precision and recovery. Principal Component Analysis (PCA) effectively discriminated the samples based on their phenolic profiles, AA, and TPC. These findings contribute to the revalorization of ulluco varieties by providing new insights into their phenolic composition and demonstrating their potential as a source of health-promoting bioactive compounds. Full article

Cyanotoxins, prevalent in eutrophic aquatic ecosystems, pose significant health risks via contaminated food, yet analytical methods for detecting multiple toxin classes in foodstuffs remain limited. In the current study, a method based on dispersive solid-phase extraction (dSPE) coupled with ultra-high-performance liquid chromatography–tandem mass spectrometry (UHPLC-MS/MS) was developed to simultaneously determine four common classes of cyanotoxins (i.e., microcystins, cylindrospermopsins, nodularins, and anatoxins) in aquatic products, vegetables and algal dietary supplements. Following initial extraction with 80% aqueous methanol, sample purification was performed using anhydrous sodium sulfate (400 mg) and C₁₈ sorbent (50 mg). For plant-based foods, additional graphitized carbon black (GCB, 15 mg) was also included. The method was successfully validated in eight different food matrices, demonstrating recoveries of 65–122% and relative standard deviations below 19%. The limits of detection and quantification across all matrices ranged from 0.1 to 3.4 μg/kg dry weight (dw) and 0.4 to 11.4 μg/kg dw, respectively. When applied to 96 food samples, this method detected multiple cyanotoxins in Tilapia and Spirulina-based dietary supplements. The proposed method provides a rapid, cost-effective, high-throughput, and sensitive analytical tool suitable for monitoring multiple cyanotoxins in various foodstuffs. Full article

One of the major current societal challenges concerns the reuse of waste materials and valuable substances to mitigate the environmental impact of human activities, which has led to the increasing release of pollutants, from plastics to pharmaceuticals. In this study, we report a simple recycling strategy for surgical masks to obtain an activated carbon-like material, suitable for the solid-phase extraction (SPE) of Phthalic acid esters (PAEss) from plastic bottled water. The sorbent was produced by high-temperature calcination after sulfuric acid treatment to enhance the thermal stability of polypropylene. The sorbent was characterized by thermal analysis, Raman spectroscopy, FTIR and scanning electron microscopy. SPE was used to preconcentrate the analytes, and the main parameters affecting the extraction, such as pH, sorbent amount, organic modifier percentage, ionic strength and elution volume, were optimized. PAEs were determined by UHPLC-PDA under gradient elution. The developed method was linear in the range 0.25–1000 ng/mL, with LOQs between 0.25 and 0.10 ng/mL and LODs between 0.008 and 0.003 ng/mL. Recovery ranged from 95.9 to 104.7%, the precision expressed as RSD% was below 7.32, and the accuracy expressed as BIAS% ranged from −5.75 to 5.93. The proposed approach provides a simple and low-cost valorization route for PPE waste, while enabling reliable PAEs analysis in drinking water. Full article

A simple, rapid, and cost-effective method for the determination of benzo[a]pyrene (BaP) in edible oil was developed and validated. Nickel oxide-deposited silica (SiO₂@NiO) was employed as a solid-phase extraction (SPE) adsorbent for the extraction of BaP from edible oil, followed by high-performance liquid chromatography–diode array detector (HPLC-DAD) analysis of BaP. The edible oil was diluted with n-hexane and directly loaded to SiO₂@NiO for SPE. The n-hexane was also used to clean the fat-soluble interference substance in the edible oil, and BaP was selectively captured using SiO₂@NiO through the electron donor–acceptor interaction. The SPE conditions, including the amount of adsorbent, volume of washing solvent, and type and volume of desorption solvent, were optimized. This SiO₂@NiO-based SPE coupled with the HPLC-DAD method demonstrated good linearity within a BaP concentration range of 6–1875 ng/g in edible oils, with a limit of detection of 1.3 ng/g, spiked recovery of 97.4–105.1%, and relative standard deviation (RSD) of <3.0%. The method was applied to the analysis of BaP in 11 real oil samples (soybean oil, olive oil, corn germ oil, flaxseed oil, walnut oil, sunflower kernel oil, peanut oil, unrefined oil, and high-temperature frying oil), and the results show that the unrefined oil and high-temperature frying oil were at risk of BaP exceeding acceptable level. Full article

In vitro fecal inoculation coupled with gas chromatography–mass spectrometry (GC-MS) has been used for evaluating fecal deodorants. However, high cost and complex data interpretation limit its routine application. An electronic nose (eNose) offers a rapid, cost-effective alternative. This study aimed to evaluate the eNose as a screening tool for fecal odor compared with solid-phase microextraction gas chromatography–mass spectrometry (SPME GC-MS) and to examine the in vitro effects of fecal deodorant supplements on fecal odor profiles. Feces from ten healthy cats were serially diluted (1:1 to 1:8) and analyzed using both instruments. Four dietary supplements—Yucca schidigera extract (YSE), Quillaja saponaria extract (QSE), fructooligosaccharides (FOS), and oat beta-glucans (OBG)—were tested at concentrations of 0.0, 0.2, 0.4, and 0.8 g/100 mL. The eNose showed comparable performance to GC-MS in discriminating among sample dilutions. In vitro fermentation showed that FOS and OBG significantly increased volatile fatty acid (VFA)-related sensor responses while signals linked to ammonia and sulfur compounds were reduced. QSE had minimal effect, whereas YSE produced moderate changes. The total sensor response intensities did not differ between treatments. These findings indicate that prebiotic supplements exert stronger effects than saponin-based supplements and highlight the potential of eNoses with in vitro fermentation for rapid screening of fecal deodorants. Full article

The manuscript describes an optical sensing microplate for the high-throughput screening of imidazolinone herbicides in soil extracts. As far as we know, imprinted proteins (IPs) specific to imidazolinone herbicides have not been synthesized and used as a recognition element for their solid-phase extraction before. Imprinted bovine serum albumin (BSA) and glucose oxidase (GOx) were synthesized in the presence of imazamox as a template and then these IPs were immobilized at the bottom of microplate wells. The sorption capacity (Q) of aminated silica nanoparticles modified by IPs (IP–BIS) was 6.38 mg g⁻¹ while the imprinting factor ($IF$) equaled 2.6. The concentration of imazamox was determined by a “turn-off” solid-phase assay using alloyed CdZnSeS/ZnS quantum dots (QDs) as a component of fluorescent substrate. Alloyed CdZnSeS/ZnS QDs were stabilized in an aqueous phase by positively charged cysteamine that, as far we know, had not been used as this type of ligand before. Our method allows for determining the concentration of imazamox in the range of 0.5–9.2 μg mL⁻¹, with a limit of quantification limit of quantitation (LOQ) equal to 0.45 μg mL⁻¹ The sensing microplate enables parallel detection of up to 96 samples containing herbicides using standard fluorescence microplate readers or smartphones. The paper describes how such sensing microplates can be used for the analysis of artificially contaminated soil samples. The proposed approach combines pre-concentration of analyte at the IPs with its subsequent determination on a single analytical platform, thus allowing for both highly sensitive determination in laboratory conditions and mass screening in the field. Full article

Scientific concern regarding the widespread occurrence of micropollutants (MPs) in aquatic environments has been growing. Background/Objectives: Since conventional wastewater and drinking water (DW) treatment plants are generally unable to completely remove MPs, their presence in DW may occur, potentially posing adverse effects on public health. Highly sensitive analytical methods are crucial, as MPs may occur at very low concentrations in DW, usually at ng L⁻¹ levels. Methods: An offline solid-phase extraction ultra-high performance liquid-chromatography coupled to tandem mass-spectrometry (SPE-UHPLC-MS/MS) method was optimized and validated for the determination of 23 MPs in DW, including 12 pharmaceuticals, 9 pesticides, and 2 UV-filters, listed in the 2 most recent European Union (EU) Decisions (2022/1307 and 2025/439) for surface water monitoring, and in the revised EU Urban Wastewater Treatment Directive (2024/3019). The validated method was applied to 50 DW samples collected across Portugal. Results: The optimized SPE-UHPLC-MS/MS method showed high analytical sensitivity, achieving method detection limits below 1.50 ng L⁻¹. Up to 3 MPs were detected per sample, with quantifiable concentrations of each ranging from 0.28 to 98.8 ng L⁻¹. However, benzotriazole and dimoxystrobin exceeded the upper limits of their calibration curves (i.e., concentrations higher than 133 and 117 ng L⁻¹, respectively) in one and 3 of the collected samples, respectively. Considering all analyzed samples, 4 (fluconazole, irbesartan, dimoxystrobin, and benzotriazole) of the 23 target compounds were detected. Hazard quotient values for all detected MPs were below 0.2. Conclusions: The validated SPE-UHPLC-MS/MS method is suitable for the sensitive determination of MPs in DW. Some MPs were detected, with concentrations indicating no expected human health risks under the conditions evaluated. Further monitoring campaigns should be conducted in the future, with compounds exceeding the limits of the calibration curves requiring special attention. Full article

Given the increasing hepatotoxicity risk associated with pyrrolizidine alkaloids (PAs) in Emilia sonchifolia (L.) DC., this study aimed to systematically characterize its PA components and identify the material basis responsible for liver injury. Using solid-phase extraction (SPE) enrichment coupled with ultra-high-performance liquid chromatography–quadrupole/orbitrap high-resolution mass spectrometry (UHPLC-HRMS), efficient annotation of PAs was achieved through building-block-based molecular network (BBMN) cluster analysis. A total of 76 PAs were identified (66 otonecine-type and 10 retronecine-type PAs), including 35 known compounds (e.g., senkirkine and petasitenine) and 41 potentially novel compounds. Semi-quantitative analysis revealed that senkirkine accounted for 86% of the total PAs. As an otonecine-type diester alkaloid, it serves as the core toxic substance triggering hepatic sinusoidal obstruction syndrome (HSOS). Network toxicology analysis identified 52 intersecting targets between senkirkine and hepatotoxicity. A protein–protein interaction (PPI) network was constructed, revealing 44 connected nodes with MAPK1, AKT1, and PIK3CA as key hub targets. Enrichment analysis indicated that these targets are primarily involved in the PI3K-Akt signaling pathway and focal adhesion. Molecular docking further validated that senkirkine exhibits strong binding affinities with these core targets, with binding energies ranging from −26.33 to −51.50 kcal/mol, stabilized by robust hydrogen-bonding networks. Consequently, senkirkine was identified as the critical safety indicator for quality control, and processing techniques were applied to reduce its content, balancing efficacy and toxicity risks. Full article

Red mud, a strongly alkaline solid waste generated during alumina production, contains valuable metals including aluminum, iron, titanium, and others. Efficient extraction of these metals is of great significance for promoting circular economy development and regional ecological conservation. This paper proposes a stepwise extraction process involving alkali roasting-water leaching to separate Al from Fe and Ti, hydrochloric acid leaching to separate Fe from Ti, and sulfuric acid leaching to extract Ti. Bayer red mud from Guangxi, China was used as the raw material, and the effects of process parameters on the stepwise leaching of Al, Fe, and Ti were systematically investigated. The overall leaching results indicated that the total leaching rates of Al, Fe, and Ti were 99.61%, 99.02%, and 92.75%, respectively. Through comparative analysis of the chemical composition, phase composition, and micromorphology of the raw red mud, roasted clinker, and leaching residues, the stepwise leaching mechanisms of Al, Fe, and Ti were elucidated. Furthermore, the second-stage acid leachate was hydrolyzed, and the H₂TiO₃ content in the obtained hydrolyzate reached 89.43%, approximately 12 times that of the titanium component in the raw red mud. The Ti hydrolysis recovery rate was 90.41%, and the total Ti recovery rate was 78.65%. Overall, the process enables stepwise extraction of Al, Fe, and Ti, along with the enrichment and recovery of titanium resources, providing an effective reference route for the technical chain of resource utilization of valuable components in red mud. Full article

β-agonists are prohibited antibiotics that have raised concerns due to their illegal use in the livestock industry, posing potential toxicity risks to human health. For ultra-performance liquid chromatography–tandem mass spectrometry (UPLC-MS/MS) analysis of β-agonists, effective sample pretreatment is a crucial and challenging process that dictates the overall reliability and sensitivity of the method. Thus, this study developed a reliable method utilizing dispersive solid-phase extraction (d-SPE) with NH₂-UiO-66 as a superior adsorbent, coupled with UPLC-MS/MS, to extract and quantify β-agonists in environmental water, swine urine, and milk. The synthesized NH₂-UiO-66 exhibited outstanding adsorption capacities (146.06–358.00 mg/g) towards the target analytes. The optimized method demonstrated excellent performance: low matrix effects (−13.10–15.30%), wide linearity (0.1–50 μg/L), low limits of detection (0.04–0.09 μg/L), and satisfactory recoveries (81.48–106.67%) with good precision (intra-day RSDs 1.51–6.24%; inter-day RSDs 2.06–10.96%). Adsorption mechanism studies revealed that the extraction process, which followed the Langmuir isotherm and pseudo-second-order kinetic models, was driven primarily by electrostatic interactions, π-π stacking, and hydrogen bonding. Moreover, the material could be reused up to 10 times, with satisfactory recoveries of 81.30% to 116.10%. The proposed NH₂-UiO-66-d-SPE-UPLC-MS/MS protocol is generic and provides a robust and practical solution for monitoring trace β-agonists in animal-derived foods and environmental samples, ensuring food safety and environmental health. Full article

The generation of Ge-containing dust (GCD) during Zn hydrometallurgy raises considerable toxicity concerns; however, GCD contains useful metals, such as Zn, Ge, and Pb. The unique characteristics of Ge often result in the formation of specific Ge compounds within GCD, which manifest as either independent insoluble phases or inclusions, which complicates their separation and recovery. To address the challenges associated with the traditional recovery methods, this study proposes a novel process that utilizes SO₂ reduction in conjunction with H₂SO₄ to extract Zn and Ge from GCD. The introduction of SO₂ facilitates the conversion of insoluble materials through reduction reactions. A high SO₂ flow rate enhances its interaction with the solid surface, thereby promoting continuous peeling and improving the reaction efficiency. The key parameters influencing the leaching rate of Zn and Ge, and the toxicity of the resulting reaction residue, include the initial acidity, liquid–solid ratio, duration of SO₂ exposure, reaction temperature, and reaction time. Experimental findings indicate that SO₂-promoted H₂SO₄ leaching outperforms the conventional methods, achieving increases of 3% and 12% in the leaching rates of Zn and Ge, respectively. Furthermore, the concentration of toxic metals in the residue is reduced to suitable levels post-reaction. The resultant Pb residue can be reintegrated into the Pb-recovery process for further utilization. In conclusion, the SO₂-promoted H₂SO₄-leaching method represents a promising and environmentally sustainable approach for the recovery of useful metals from GCD. Full article

Elderberry (Sambucus nigra L.) and linden (Tilia cordata Mill.) flower extracts are known for their pro-healthy properties. Various extraction methods, both conventional (Soxhlet) and advanced (ultrasound assisted extraction, UAE, accelerated solvent extraction, ASE, and matrix solid phase dispersion, MSPD), were applied to obtain ethanol–water extracts from the plants. The biological profiles, the total polyphenol content (TPC) and total flavonoid content (TFC) in the extracts were determined spectrophotometrically. Almost 40 compounds were identified in extracts by means of HPLC-MS/MS. The contents of the chosen phenolic acids (chlorogenic, p-coumaric, protocatechuic, and gallic) and flavonoids (rutin, catechin, quercetin, kaempferol, apigenin, and naringenin) were determined by HPLC-DAD. It was observed that the elderflower extracts contained higher levels of the compounds investigated than did the linden extracts. Chlorogenic acid was the main phenolic acid in the majority of extracts form the elderberry flower, whereas in the linden extracts, it was protocatechuic acid. Nevertheless, rutin was the main component of both plant extracts. The cytotoxicity of the elderberry and linden flower extracts against VERO, FaDu, H1HeLa, and RKO cell lines were subsequently examined. The elderflower extracts exerted no cytotoxicity, whereas linden extracts showed selective cytotoxicity against FaDu and RKO cells with CC₅₀ of 54.35 and 46.27 µg/mL, respectively. The antiviral potential of the extracts against HHV-1, CVB3, and HRV14 were also examined. The results demonstrate antiviral activity against HHV-1, particularly for linden flower extract in concentration of 62.5 µg/mL. Full article