Search Results (119)

Pyrolysis liquid (PL) derived from biomass pyrolysis exhibits biopesticidal properties and represents a promising value-added product within the sustainable circular economy framework. However, knowledge about the antimicrobial potential of PLs produced from walnut residue at different pyrolysis temperatures remains limited. We investigated the chemical composition and antimicrobial activity of PLs obtained from agricultural walnut residue (Juglans regia L.) against selected plant pathogenic bacteria and fungi. PLs were produced at four temperature ranges: 200–300 °C (W-1), 300–400 °C (W-2), 400–500 °C (W-3), and 500–600 °C (W-4). Chemical characterization was performed using Gas chromatography–mass spectrometry (GC-MS), High-performance liquid chromatography (HPLC), and Inductively coupled plasma optical emission spectrometry (ICP-OES), with determination of total phenolic and flavonoid contents. Pyrolysis temperature significantly influenced the chemical profile and bioactive compound content of the PLs, with W-4 showing the highest total phenolic and flavonoid levels. Heavy metal analysis indicated minimal contamination in all samples. Antibacterial activity was observed in stock solutions, whereas diluted applications showed limited effects. The W-4 fraction showed the strongest antibacterial activity and exhibited MIC values of 12.50 µL/mL against Clavibacter michiganensis subsp. michiganensis, Xanthomonas euvesicatoria, and Pseudomonas syringae pv. syringae, and 25.00 µL/mL against Erwinia amylovora. Antifungal activity differed markedly across temperature ranges, with W-3 and W-4 displaying superior activity against Fusarium oxysporum and Verticillium dahliae, achieving complete mycelial growth inhibition at 5%, compared to 10% for W-2 and 20% for W-1. Positive controls confirmed assay validity (ciprofloxacin for antibacterial assays and cycloheximide for antifungal assays), whereas negative controls showed no inhibitory effect. Overall, higher pyrolysis temperatures, particularly 400–600 °C, enhanced the antimicrobial potential of walnut residue-derived PLs, supporting their possible use as bio-based antifungal agents for sustainable crop protection. Full article

The purpose of this work is to investigate the binding state of inorganic elements to flavonoid components in aqueous extract of Silybum marianum (SM) seeds, as well as the antioxidant activity of the extract. This study employed reversed-phase high-performance liquid chromatography (RP-HPLC) to separate silymarin flavonoids in boiling water decoction of SM seeds, and collected the post-column effluent in the segments according to the retention time of seven main silymarin flavonoid components. Inductively coupled plasma mass spectrometry (ICP-MS) was subsequently utilized to quantify nine inorganic elements (As, Cd, Co, Cr, Cu, Fe, Mn, Mo, Zn) in the collected HPLC fractions of the decoction. Meanwhile, electron paramagnetic resonance spectroscopy (EPR) was employed to assess the free radical scavenging activity of aqueous extract of SM seeds, using the signal intensity changes of 2,2-diphenyl-1-picrylhydrazyl (DPPH) and DMPO-OH• adducts as quantitative metrics. The results showed that essential trace elements (Cu, Fe, Mn, Zn) mainly existed as inorganic ions or strong polar forms in the tea-like infusion, with weak binding to flavonoid compounds. On the other hand, the aqueous extract exhibited significant •OH scavenging capacity, with a scavenging rate of 95% against •OH generated by continuous 5 min ultraviolet irradiation of H₂O₂ aqueous solution. This study provides experimental evidence for the development of SM as a food–medicine dual-purpose resource, proposing that consumption of SM seed tea represents a facile and effective approach to supplement trace elements and intake silymarin for enhancing endogenous antioxidant defense. Full article

Mercury (Hg) is of significant concern due to its toxicity, which strongly depends on its chemical forms, and organic mercury compounds, particularly methylmercury (MeHg), are considered the most toxic species. Therefore, mercury speciation analysis is essential for accurate exposure and risk assessment. The primary dietary source of mercury exposure for humans is food consumption, particularly seafood. Consequently, numerous studies have focused on developing analytical techniques for the identification, characterization, and quantification of Hg species in seafood. This review evaluates and compares recent developments (2014–2025) in analytical techniques for the identification and quantification of Hg species in seafood, focusing on both traditional chromatographic methods and emerging methodologies based on biosensors. Hyphenated techniques such as HPLC–ICP-MS and GC–ICP-MS have enabled significant advancements in mercury speciation analysis. Although chromatographic methods are highly effective and widely accepted due to their accuracy and sensitivity, they often require costly instrumentation, skilled operators, and lengthy analysis times. Biosensors are increasingly proposed as alternatives; however, their applicability to seafood analysis remains limited despite advantages such as portability, simplicity, and rapid response. They are still under development and face challenges in selectivity, stability, and standardization. This review provides an overview of existing methodologies, comparing their advantages and limitations, aiming to guide improvements toward optimal methods incorporating all advantageous features. Full article

Selenium (Se) biofortification of vegetables can improve dietary Se intake; however, the dose-dependent balance between inorganic Se retention and organic Se assimilation following foliar selenate application remains insufficiently resolved across species. Five leafy vegetable species (garden rocket, wild rocket, dandelion, and two chicory cultivars) were grown under controlled greenhouse conditions and treated twice with foliar sodium selenate at increasing application rates (1 + 1, 2 + 2, 5 + 5, 10 + 0, 10 + 10, and 10 + 50 mg Se L⁻¹) across two experiments. Total Se and Se species were determined by HPLC-UV-HG-AFS following enzymatic extraction and cross-checked on selected extracts by HPLC-ICP-MS. Foliar selenate induced substantial Se accumulation in all species, reaching up to 102 µg g⁻¹ DW in garden rocket. At moderate application rates (notably 2 + 2 and 5 + 5 mg Se L⁻¹), a considerable proportion of extracted Se was converted into organic forms, with selenomethionine (SeMet) accounting for up to ~40% of total extracted Se. In contrast, at the highest application rate (10 + 50 mg Se L⁻¹), inorganic Se(VI) became predominant (often >40%), while SeMet proportion declined sharply to ~2–4%, indicating a saturation of metabolic assimilation capacity under high Se exposure. Leaf biomass was promoted at intermediate treatments (e.g., 5 + 5 and 10 + 0/10 + 10 mg Se L⁻¹), whereas the highest rate reduced growth. Overall, foliar selenate effectively biofortifies chicory, rocket, and dandelion leaves, but excessive application rates shift Se speciation toward inorganic storage and markedly suppress SeMet formation. These findings highlight the importance of dose optimization to maximize nutritional quality while avoiding metabolic overload. Full article

Arsenic occurs in food in both inorganic (iAs) and organic (oAs) forms. Inorganic arsenic is highly toxic and classified as carcinogenic to humans, whereas oAs species, such as arsenobetaine (AB), monomethylarsonic acid (MMA), and dimethylarsinic acid (DMA), generally exhibit lower toxicity. Rice and rice-based products represent major contributors to dietary iAs exposure. Within this context, the present study provides an updated assessment of the occurrence of iAs and oAs in rice-based beverages available on the Italian market. A method for the simultaneous determination of iAs, AB, DMA, and MMA was developed and validated, and it exhibits adequate sensitivity to ensure robust occurrence data, eliminating left-censoring for iAs. A comprehensive analysis of twenty-five representative rice-based beverages was conducted, revealing that the contamination profiles exhibited a high degree of homogeneity, with iAs as the predominant species. All samples complied with the European maximum level for iAs in non-alcoholic rice-based beverages. When combined with recent Italian consumption data, these results enabled age-specific dietary exposure assessment. Although rice drinks contribute marginally to overall population exposure, estimated intakes for regular consumers in early childhood are associated with a small margin of exposure, raising potential concern for vulnerable subgroups. The increasing diversification of dietary habits and the rising consumption of plant-based beverages point to the necessity of continuous monitoring of iAs. Ongoing efforts in monitoring studies, updated food consumption surveys, and effective risk communication are essential to refine exposure assessment and thereby enhance public health protection. Full article

Detecting and quantifying disinfection by-products (DBPs), especially brominated species (Br-DBPs), is analytically challenging, often necessitating multiple techniques and specific standards for each target. This complexity hinders comprehensive assessment. To overcome these limitations, we present a powerful, integrated approach combining liquid chromatography with inductively coupled plasma mass spectrometry (LC-ICP-MS) and high-resolution mass spectrometry (LC-HRMS). This method enables rapid, non-targeted group screening of Br-DBPs: LC-ICP-MS selectively identifies bromine-containing compounds, while LC-HRMS provides tentative structural identification. Crucially, this synergistic combination allows for the quantification of any Br-DBP without requiring individual reference standards. This study successfully demonstrates the application of this combined LC-ICP-MS and LC-HRMS strategy for the non-targeted detection, identification, and subsequent quantification of Br-DBPs in real drinking water samples, offering a significant advancement for DBP monitoring and risk assessment. Full article

Propolis is an apicultural product known for its antioxidant, antimicrobial and anti-inflammatory properties. However, its composition varies with botanical sources, geography, season and bee species, complicating quality control and creating opportunities for adulteration, such as the addition of poplar bud extracts or non-propolis resins. This review synthesizes the latest primary studies and reviews addressing chemical markers identified through analytical platforms, such as TLC, HPTLC, HPLC, LC-MS, GC-MS, NMR, FTIR and ICP, often integrated with chemometrics and machine learning for authentication and standardization. Marker panels are linked to regional chemotypes, including poplar-type, Brazilian green, red and brown, Cuban variants, and stingless bee propolis. Fraud detection strategies using marker-based screening and spectral pattern recognition are also summarized. Multi-marker and chemometric approaches consistently differentiate botanical types, origins and commercial extracts. Common marker families include flavonoids (pinocembrin, chrysin, galangin), phenolic esters (CAPE, benzyl/allyl caffeates), prenylated cinnamates like artepillin C, lignans, and volatile terpenoids or benzenoids. Rapid screening by ATR-FTIR and NMR is often complemented with LC-MS for confirmatory quantitation. Propolis quality control is moving toward harmonized workflows combining FTIR/NMR/HPTLC screening with LC-MS verification and optional elemental or volatile profiling, paving the way for shared marker sets and international standards similar to those for honey. Full article

Occupational exposure to soil-borne pesticides remains a critical safety and process-management challenge in industrial and agro-industrial settings. This work proposes a process-integrated analytical workflow that couples comparative instrumental identification of soil xenobiotics with an occupational risk assessment framework. We comparatively evaluate GC-MS (gas chromatography–mass spectrometry), HPLC (high performance liquid chromatography), FTIR (Fourier-Transform Infrared Spectroscopy), LC-MS/MS (Liquid Chromatography coupled with tandem Mass Spectrometry), and ICP-MS (Inductively Coupled Plasma Mass Spectrometry) against matrix complexity, sensitivity, cost, and throughput, and implement the Quick, easy, cheap, effective, rugged, safe (QuEChERS) method-based sample preparation followed by GC-MS and LC-MS/MS to demonstrate applicability on representative soil and food-chain samples. Complementary risk tools (toxicity–probability matrices, exposure pathway diagrams) and an integrated monitoring scheme that combines environmental data with biomonitoring are used to link concentrations to exposure potential and control priorities. In a soil case sample, low-level organochlorines were detected with total DDT at 0.010 mg/kg and total HCH at 0.003 mg/kg, illustrating how analytical outputs feed decision matrices for prioritizing interventions. Case analyses from agricultural and industrial contexts indicate that targeted substitution, optimized application, ventilation and dust control, PPE (personal protective equipment) adherence, and worker training can measurably reduce symptoms and biomarkers of exposure. Overall, a complementary, process-analytical approach—integrating sensitive multi-technique detection with exposure assessment and continuous monitoring—supports proactive risk management and aligns with process systems and monitoring themes. Recommendations include standardizing workflows, coupling routine environmental monitoring with biomonitoring where feasible, and embedding preventive policies and training into industrial management systems. Full article

The residual cake obtained after extracting oil from Moringa oleifera seeds is a promising source of plant-based proteins due to its high content of proteins, dietary fibre and essential minerals. However, its food applications are limited by a strong bitter taste that affects consumer acceptance and antinutritional compounds that reduce mineral bioavailability such as phytates. This study aimed to evaluate the effect of saline and ethanol treatments of moringa cake—reported in the literature as improving its sensory properties—on its nutritional profile. Proximal composition was determined by gravimetry for moisture, muffle incineration for ash, and solvent extraction with the Randall method for lipids. Protein content was analyzed using the Dumas combustion method. Mineral elements (calcium, iron, zinc, sodium) were quantified by Inductively Coupled Plasma Mass Spectrometry (ICP-MS) and phytates by High-Performance Liquid Chromatography (HPLC). The untreated cake revealed a favourable nutritional profile, mainly due to its protein content, but also contained high phytate levels. Both treatments slightly reduced phytates (5–12%), with saline extraction proving more effective. Nevertheless, mineral loss was observed, while there was a notable increase in sodium in the saline-treated samples. Ethanol treatment, in contrast, led to a statistically marked reduction in residual lipids. Importantly, both treatments diminished the bitter taste, improving sensory acceptability. Although neither method completely eliminated phytates, the overall improvements in protein quality, mineral profile, and sensory properties highlight the potential of moringa residual cake as a valuable ingredient. Thus, it emerges as a sustainable, high-nutritional-value source of plant proteins for the development of innovative food products. Full article

Cadmium (Cd) is a recognized environmental contaminant, present in soil, water, and food, which has been reported to cause male reproductive damage in vivo and vitro. Selenium-enriched rapeseed flowering stalks exhibit protective effects against Cd-induced reproductive damage, yet the bioactive components and underlying mechanisms remain unclear. We optimized the process of obtaining the crude extract (CE) via single-factor experiments. Subsequent bioassay-guided fractionation identified the water extract (WE) as significantly more effective in alleviating Cd-induced cytotoxicity compared to the petroleum ether extract, ethyl acetate extract, and n-butanol extract. High-performance liquid chromatography–inductively coupled plasma mass spectrometry (HPLC-ICP-MS) analysis revealed that WE contained the highest contents of methylselenocysteine (MeSeCys) and selenocystine (SeCys₂) among four fractions. Both MeSeCys and SeCys₂ exhibited protective effects against Cd-induced cytotoxicity. To further elucidate the underlying mechanisms, network pharmacology, RNA-Seq, qPCR, and Western blotting analysis were employed. The results revealed that WE exhibited good free radical scavenging capabilities, and the protective mechanisms of WE, MeSeCys, and SeCys₂ against Cd-induced cytotoxicity were related to a reduction in oxidative damage, the inhibition of the ERK/p38 MAPK signaling pathway, and the suppression of cell cycle arrest, inflammation, and apoptosis triggered by Cd exposure. Collectively, these findings suggest that selenium-enriched rapeseed flowering stalks may serve as a promising dietary supplement in the prevention of Cd-induced reproductive toxicity. Full article

Porphyrins are intermediates in heme biosynthesis and have been proposed as biomarkers of metabolic dysfunction and environmental exposure in autism spectrum disorder (ASD). This study aimed to evaluate urinary porphyrin fractions and trace element ratios in children with ASD compared to neurotypical controls. Urinary porphyrins were quantified using high-performance liquid chromatography (HPLC), and trace elements were measured via inductively coupled plasma mass spectrometry (ICP-MS) normalized to urinary creatinine. Trace element ratios (e.g., Zn/Cu, Se/Pb) were calculated. Statistical comparisons were made using the Mann–Whitney U-test. Children with ASD showed significantly elevated urinary levels of coproporphyrin (median: 1.94 µg/g creatinine vs. 1.32 in controls; p = 0.02) and pentacarboxyporphyrin (0.86 vs. 0.57; p = 0.01), and reduced hexacarboxyporphyrin (0.12 vs. 0.23; p = 0.03). Lead (Pb) levels were significantly higher in ASD (median: 1.96 µg/g creatinine vs. 0.82; p = 0.004), while mercury (Hg) was not significantly different. Several trace element ratios differed significantly: Zn/Cu (ASD 41.9 vs. controls 49.1; p = 0.021), Se/Pb (12.9 vs. 25.7; p = 0.002), Cu/Se (0.49 vs. 0.38; p = 0.008), and Zn/Pb (19.5 vs. 44.8; p = 0.002). The Hg/Se ratio did not differ significantly.: Children with ASD demonstrate altered porphyrin profiles and trace element imbalances, including increased Pb and disrupted Zn/Cu and Se/Pb ratios, indicating oxidative stress and impaired detoxification. Combined assessment of porphyrins and trace element ratios may provide valuable non-invasive biomarkers for environmental and metabolic disturbances in ASD. Full article

Bentonites used for wine clarification vary widely in their ability to remove proteins and alter wine composition, yet the role of their intrinsic properties remains unclear. To address this, eight commercial bentonites with diverse physico-chemical characteristics were analyzed. The doses required for complete protein removal and stabilization were determined and then applied to clarify a Malvazija istarska (Vitis vinifera L.) white wine. Clarified wines were compared with one another and with a non-clarified control using ICP-OES for elemental composition, HPLC-DAD for phenolic compounds, and HS-SPME-GC/MS for volatile compounds. Protein removal efficiency correlated positively with Na/Ca ratio, cation exchange capacity, swelling capacity, negative ζ-potential, and internal specific surface area, and negatively with particle size and external specific surface area. Sodium and calcium showed the greatest increases in wine concentrations. Effects on individual low-molecular-weight phenols were inconsistent, though all bentonites removed a fraction of total phenols. Volatile compounds, particularly esters, were significantly reduced. When compared on a per-gram basis, bentonites that were more efficient in protein removal also showed greater removal of phenols and volatile compounds; however, at full application doses, many of these differences diminished or reversed. Overall, the study advances understanding of bentonite–wine interactions and supports more informed selection of bentonites in oenological practice. Full article

Rice (Oryza sativa L.) is a vital staple food and an important source of energy and macro- and micronutrients for billions of people. However, rice can accumulate undesirable levels of toxic trace elements, especially inorganic arsenic, which may pose a health risk. This study aimed to determine the concentrations of 29 essential and toxic elements and the fractions of four As species in 58 rice samples purchased in Croatian supermarkets. In addition, the influence of rice variety, cultivation methods, and origin on the composition of trace elements was analysed. The elements were quantified using inductively coupled plasma mass spectrometry (ICP-MS), and As species were quantified using high-performance liquid chromatography (HPLC) coupled with ICP-MS. Organic brown rice had higher concentrations of essential trace elements (Se, Zn, Cu, Fe, Mn, Co, Cr) than white rice, with organic brown rice containing more essential elements than conventionally grown rice. The average total arsenic concentration (tAs) across all samples was 142 ± 57 µg/kg, with brown, conventionally grown rice containing a higher amount. Arsenite was the predominant arsenic species. Regional differences in As and Se concentrations were observed. These results emphasize the complex relationship between trace elements in rice and their potential impacts on health. Full article

Three types of solid waste are produced during beer fermentation: spent grain, hot trub, and residual yeast. While the first is used as livestock feed, the seconds has not yet found any real reapplication in the field of circular economy. The aim of this work is to study and characterize these two brewing wastes, i.e., hot trub and residual yeast, to evaluate their potential reuse in the agricultural field. Samples from top-fermented and bottom-fermented beers were chemically investigated. Initially, the safety was assessed via multi-detection analysis of 57 mycotoxins, and all samples were deemed safe. Subsequently, the chemical and elemental composition was examined via ICP-MS and microanalysis, along with phenolic compounds and antioxidant activity via HPLC and spectrophotometric determinations, to achieve a thorough characterization of these waste samples. The C/N ratio of residual yeast from top-fermented beer and hot trub of the bottom-fermented one were near the optimal one (10:1). This research marks an initial step towards repurposing brewery waste materials as fertilizers. The subsequent steps will involve the formulation and field trials. Full article

Objectives: The aim of this study was to provide a comprehensive overview of the nutritional and toxicological aspects of different forms of blueberry products (fresh blueberries, dried blueberries, supplements and herbal teas). Methods: Twelve aglycone and glycoside polyphenolic compounds, such as stilbenoids (resveratrol, astringin), flavonols (quercetin, rutin, isoquercitrin, quercitrin, kaempferol), flavanols (catechin, epicatechin), flavanone (hesperitin), flavone (luteolin), and forty chemical elements were analyzed using high-performance liquid chromatography coupled to a mass spectrometer and inductively coupled plasma mass spectrometry. Total phenolic and flavonoid content and antioxidant activity were also evaluated. Results: Different distributions of polyphenolic compounds were observed in the blueberry samples, with quercetin and its derivatives, as well as catechin and epicatechin, present in all samples. High concentrations of Ca, K, Mg and P (10–5800 mg/kg) were detected, followed by Fe and Mn at levels below the allowable limits in foods (425 and 500 mg/kg, respectively). The daily intake of polyphenols was quantified, and the estimated daily intake (EDI) was calculated for sixteen elements (including As, Cd, Cu, Fe, Ni, Pb, V and Zn). Hazard quotients (HQs), hazard index (HI) and cancer risk (CR) were assessed for carcinogenic and non-carcinogenic risks associated with the EDI of these elements in food products for both adults and young consumers. For all samples, HI values were below 1, and CR values were within acceptable limits. Conclusions: The diversity in polyphenolic profiles and elemental content in blueberry-based products was highlighted by this exploratory study. These findings are valuable for understanding the health benefits and risks of blueberry products. Full article