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Among wildlife species, roe deer stands out as a valuable indicator of environmental pollution due to its ecological significance and role as a game animal. The assessment of poly- and perfluoro substances (PFASs) bioaccumulation is of the utmost importance, relying on the liver and muscles as the main organs of interest. The study concerned the identification of 60 PFAS through a non-target workflow analysis based on HPLC Q-Exactive Orbitrap High-Resolution Mass Spectrometry in a homogeneous group of 18 female roe deer species. The developed strategy allowed us to individuate the 60 PFAS compounds with different levels of confirmation. Apart from seven PFASs identified via analytical standards, the remaining fifty-three features were identified with CL 2 or 3. Moreover, by applying a differential statistic approach, it was possible to distinguish the bioaccumulation patterns in the liver and muscle, identifying 12 PFAS upregulated in the muscle and 20 in the liver. The analysis reveals that specific PFAS compounds present exclusively in either the muscle or in the liver. The study emphasises the specificity of the liver and muscle as significant bioaccumulation sites for PFAS, raising questions about the underlying mechanisms of this process. In conclusion, the presented non-targeted PFAS analysis workflow evidenced promising and reliable results, successfully demonstrating its feasibility in the field of environmental research.
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Ciervos , Fluorocarburos , Animales , Femenino , Animales Salvajes , Contaminación Ambiental , Espectrometría de MasasRESUMEN
The objective of the current research was to develop a liquid chromatography-MSn (LC-MSn) methodology for the determination of free cortisol and its 15 endogenous metabolites (6ß-hydroxycortisol, 20α-dihydrocortisol, 20α-dihydrocortisone, 20-ß-dihydrocortisol, 20ß-dihydrocortisone, prednisolone, cortisone, α-cortolone, ß-cortolone, allotetrahydrocortisol, 5α-dihydrocortisol, tetrahydrocortisol, allotetrahydrocortisone, 5ß-dihydrocortisol, tetrahydrocortisone) in human urine. Due to its optimal performance, a linear ion trap operating in ESI negative ion mode was chosen for the spectrometric analysis, performing MS3 and MS4 experiments. The method was validated for limit of detection (LOD) and limit of quantification (LOQ) (0.01 ng mL-1 and 0.05 ng mL-1, for all compounds, respectively), intra- and inter-day precision (CV = 1.4-9.2% and CV = 3.6-10.4%, respectively), intra- and inter-day accuracy (95-110%), extraction recovery (65-95%), linearity (R2 > 0.995), and matrix effect that was absent for all molecules. Additionally, for each compound, the percentage of glucuronated conjugates was estimated. The method was successfully applied to the urine (2 mL) of 50 healthy subjects (25 males, 25 females). It was also successfully employed on urine samples of two patients with Cushing syndrome and one with Addison's disease. This analytical approach could be more appropriate than commonly used determination of urinary free cortisol collected in 24-h urine. The possibility of considering the differences and relationship between cortisol and its metabolites allows analytical problems related to quantitative analysis of cortisol alone to be overcome. Furthermore, the developed method has been demonstrated as efficient for antidoping control regarding the potential abuse of corticosteroids, which could interfere with the cortisol metabolism, due to negative feedback on the hypothalamus-hypophysis-adrenal axis. Lastly, this method was found to be suitable for the follow-up of prednisolone that was particularly important considering its pseudo-endogenous origin and correlation with cortisol metabolism.
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Hidrocortisona , Espectrometría de Masas en Tándem , Cromatografía Liquida/métodos , Femenino , Humanos , Masculino , Prednisolona , Espectrometría de Masas en Tándem/métodos , Tetrahidrocortisona/química , Tetrahidrocortisona/orinaRESUMEN
The monitoring of contaminants represents a priority to preserve the integrity of marine ecosystems, as well as to plan and to manage restoration activities in order to protect environmental and human health. In the present study, a 6-months active biomonitoring was performed to explore the levels of eighteen trace and toxic elements, including heavy metals (TEs; i.e. Al, As, Ca, Cd, Cr, Cu, Fe, Hg, K, Mg, Mn, Na, Ni, P, Pb, Sr, Ti, and Zn), accumulated in soft tissues of blue mussel (Mytilus edulis Linnaeus, 1758) individuals transplanted at different depths (5- and 15-m depth) in five locations within the Flekkefjord fjord (Southern Norway). As this area suffered a long-lasting contamination due to both organic and inorganic contaminants, a series of restoration activities were activated to tackle and to prevent potential risks for ecosystem and local population. Our results demonstrated that the levels of TEs accumulated in edible tissues of transplanted mussels in the Flekkefjord fjord were generally low before the beginning of the restoration activities. However, location- and time-specific differences in the accumulation of TEs were noted after the implementation of such activities. Interestingly, the levels of Fe and Mn significantly increased after the beginning of the restoration activities, likely because the release of these TEs from the slag used in such operations and/or resuspension of contaminated sediments. However, assuming that native mussels can accumulate the same TEs at levels measured in transplanted individuals, our results suggest a substantial safety for human consumption of native mussels from the Flekkefjord fjord, regardless of restoration activities.
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Metales Pesados , Mytilus edulis , Oligoelementos , Contaminantes Químicos del Agua , Animales , Ecosistema , Monitoreo del Ambiente/métodos , Estuarios , Humanos , Metales Pesados/análisis , Oligoelementos/análisis , Contaminantes Químicos del Agua/análisisRESUMEN
Cerebral amyloid angiopathy (CAA), one of the main types of cerebral small vessel disease, is a major cause of spontaneous intracerebral haemorrhage and an important contributor to cognitive decline in elderly patients. Despite the number of experimental in vitro studies and animal models, the pathophysiology of CAA is still largely unknown. Although several pathogenic mechanisms including an unbalance between production and clearance of amyloid beta (Aß) protein as well as 'the prion hypothesis' have been invoked as possible disease triggers, they do not explain completely the disease pathogenesis. This incomplete disease knowledge limits the implementation of treatments able to prevent or halt the clinical progression. The continuous increase of CAA patients makes imperative the development of suitable experimental in vitro or animal models to identify disease biomarkers and new pharmacological treatments that could be administered in the early disease stages to prevent irreversible changes and disease progression.
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Péptidos beta-Amiloides/genética , Angiopatía Amiloide Cerebral/genética , Enfermedades de los Pequeños Vasos Cerebrales/genética , Disfunción Cognitiva/genética , Animales , Biomarcadores/sangre , Angiopatía Amiloide Cerebral/sangre , Angiopatía Amiloide Cerebral/patología , Hemorragia Cerebral/genética , Hemorragia Cerebral/patología , Enfermedades de los Pequeños Vasos Cerebrales/sangre , Enfermedades de los Pequeños Vasos Cerebrales/patología , Disfunción Cognitiva/sangre , Disfunción Cognitiva/patología , Progresión de la Enfermedad , Humanos , Modelos Animales , Proteínas Priónicas/genéticaRESUMEN
The pathophysiological mechanisms of Moyamoya angiopathy (MA), which is a rare cerebrovascular condition characterized by recurrent ischemic/hemorrhagic strokes, are still largely unknown. An imbalance of vasculogenic/angiogenic mechanisms has been proposed as one possible disease aspect. Circulating endothelial progenitor cells (cEPCs) have been hypothesized to contribute to vascular remodeling of MA, but it remains unclear whether they might be considered a disease effect or have a role in disease pathogenesis. The aim of the present study was to provide a morphological, phenotypical, and functional characterization of the cEPCs from MA patients to uncover their role in the disease pathophysiology. cEPCs were identified from whole blood as CD45dimCD34+CD133+ mononuclear cells. Morphological, biochemical, and functional assays were performed to characterize cEPCs. A significant reduced level of cEPCs was found in blood samples collected from a homogeneous group of adult (mean age 46.86 ± 11.7; 86.36% females), Caucasian, non-operated MA patients with respect to healthy donors (HD; p = 0.032). Since no difference in cEPC characteristics and functionality was observed between MA patients and HD, a defective recruitment mechanism could be involved in the disease pathophysiology. Collectively, our results suggest that cEPC level more than endothelial progenitor cell (EPC) functionality seems to be a potential marker of MA. The validation of our results on a larger population and the correlation with clinical data as well as the use of more complex cellular model could help our understanding of EPC role in MA pathophysiology.
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Células Endoteliales/patología , Leucocitos Mononucleares/patología , Enfermedad de Moyamoya/fisiopatología , Remodelación Vascular , Adulto , Biomarcadores/sangre , Recuento de Células , Niño , Citocinas/metabolismo , Femenino , Regulación de la Expresión Génica , Células Endoteliales de la Vena Umbilical Humana/metabolismo , Humanos , Masculino , Enfermedad de Moyamoya/sangre , Enfermedad de Moyamoya/genética , Neovascularización Fisiológica , Comunicación Paracrina , ARN Mensajero/genética , ARN Mensajero/metabolismo , Remodelación Vascular/genéticaRESUMEN
AIMS: To evaluate the safety and the efficacy of fluoroscopy-guided only (Fluo-G) and of echocardiography-guided (Echo-G; trans-esophageal echocardiography-TEE-or intracardiac echocardiography-ICE) percutaneous closure of patent foramen ovale (PFO). METHODS AND RESULTS: Single center retrospective registry enrolling 368 consecutive patients (mean age 50.5 years) who underwent PFO closure between June 2004 and December 2011. Most patients had prior cryptogenic stroke (n = 126; 34.2%), TIA (n = 218; 51.1%); some of these had recurrent neurological events [multiple strokes n = 28 (7.8%); multiple TIAs n = 72 (18.6%)]. All the patients underwent a preprocedure TEE. PFO closure was performed with Echo-G in 187 patients (50.8%) (TEE n = 69, 36.8% and ICE n = 124, 66.3%). In Fluo-G cases, PFO with atrial septal aneurysm (ASA) was significantly less present (P < 0.005) and smaller devices (<25 mm) were implanted more frequently (P < 0.001). Both fluoroscopy and total procedural time were lower in the Fluo-G group (P < 0.0001). No differences were found in terms of successful device deployment (98.3% Fluo-G vs. 98.3% Echo-G) and RtL-shunt at follow-up (11.7% Fluo-G vs. 7.6% Echo-G). The rate of conversion from Fluoro-G to Echo-G procedure was 4.4% (n = 8). At a median follow-up of 4 years, freedom from recurrent embolic events rate was similar between the two groups (Echo-G 94.5 vs. Fluo-G 95.7%). CONCLUSIONS: In our experience Fluoro-G PFO closure was performed mainly in cases of simple anatomy, with similar results in terms of safety and efficacy compared to Echo-G cases. Both fluoroscopy and total procedural times were lower in the Fluo-G cases.
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Cateterismo Cardíaco , Procedimientos Quirúrgicos Cardíacos/métodos , Fluoroscopía/métodos , Foramen Oval Permeable/cirugía , Cirugía Asistida por Computador/métodos , Ecocardiografía Transesofágica , Femenino , Estudios de Seguimiento , Foramen Oval Permeable/diagnóstico , Humanos , Imagen por Resonancia Cinemagnética , Masculino , Persona de Mediana Edad , Estudios Retrospectivos , Factores de Tiempo , Tomografía Computarizada por Rayos X , Resultado del TratamientoRESUMEN
BACKGROUND: Percutaneous coronary interventions (PCI) in patients with ischemic systolic left ventricular dysfunction (SLVD) are routinely performed although their impact on prognosis remains unclear. METHODS: We retrospectively evaluated 385 consecutive patients (76 % male, 66 ± 9 years) with SLVD (left ventricular ejection fraction [LVEF] ≤40 %) due to chronic coronary artery disease, who underwent PCI between 1999 and 2009, and explored clinical factors associated with higher risk of death or of a composite of death and hospitalization for acute decompensated heart failure (ADHF). RESULTS: The median follow-up was 28 months (inter-quartile range 14-46 months). Death and the composite outcome of death and hospitalization for ADHF occurred in 80 (21 %) and 109 (28 %) patients respectively (8.4 and 11.5 per 100 patient-years of follow-up). Insulin-dependent diabetes mellitus (IDDM), multivessel disease, LVEF < 35 %, symptoms of heart failure (HF) emerged both as independent predictors of death (adjusted hazard ratios [HR] 2.64; 1.92, 1.88 and 1.67 respectively) and composite outcome of death and hospitalization for ADHF (adjusted HR 2.22, 1.92, 1.79 and 1.94 respectively). Furthermore advanced age (HR = 1.03) emerged as independent predictors of death and having performed a stress test before PCI correlated with reduced number of deaths and ADHF hospitalizations (HR = 0.60). Of note, PCI significantly reduced the symptom of angina from 63.2 % at baseline to 16.3 % at the last follow up (p < 0.0001). CONCLUSIONS: IDDM, symptoms of HF, multivessel disease and LVEF < 35 % appear to be associated with worse outcome patients with ischemic SLVD undergoing PCI, and may be taken into account for optimal risk stratification. On the other hand, performing a stress testing before PCI seems to be associated with a more favorable outcome.
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Enfermedad Coronaria/complicaciones , Enfermedad Coronaria/cirugía , Isquemia Miocárdica/complicaciones , Intervención Coronaria Percutánea , Disfunción Ventricular Izquierda/complicaciones , Anciano , Enfermedad Coronaria/fisiopatología , Diabetes Mellitus Tipo 1/complicaciones , Angiopatías Diabéticas/complicaciones , Femenino , Insuficiencia Cardíaca/complicaciones , Mortalidad Hospitalaria , Hospitalización , Humanos , Masculino , Persona de Mediana Edad , Pronóstico , Estudios Retrospectivos , Factores de RiesgoRESUMEN
BACKGROUND: According to European Union legislation, prednisolone, a steroid that belongs to the glucocorticosteroid group, is banned as a growth promoter in cattle husbandry and therefore should not be present in bovine feedstuffs. As our preliminary investigations detected prednisolone in this matrix, we performed a study on different commercially available complementary feedstuffs, stored at the farm and/or in the laboratory, in order to verify whether its presence was due to neo-formation during storage. RESULTS: Prednisolone was detected in almost all (95%) feedstuffs collected at the farm.When the feedstuffs were stored at the laboratory, the frequency (31%) and the concentration of prednisolone-positives were lower. This difference, which is likely due to different environmental conditions, implies the possibility of its neo-formation. CONCLUSION: Our data indicate that the neo-formation of prednisolone can occur in feedstuff, and that the frequency and concentration could be related to the storage conditions. The individuation of an objective parameter that is useful for the identification of the compliance of feed is therefore essential.
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Alimentación Animal/análisis , Contaminación de Alimentos/análisis , Almacenamiento de Alimentos , Prednisolona/análisis , Crianza de Animales Domésticos , Animales , Bovinos , Dieta , Unión Europea , Prednisolona/metabolismoRESUMEN
Meat is a highly nutritious food but there is a lot of significant evidence of negative health outcomes related to its excessive consumption, especially for processed one. Among the variety of emerging contaminants of concern for human health, a key role is played by poly- and per-fluoroalkyl substances (PFASs), which show adverse effects in humans who are exposed to them through diet. In the present study, for the first time, 70 paired batches of pre-cooked and canned bovine meat were analysed by Liquid Chromatography coupled to High Resolution Mass Spectrometry to evaluate the presence and concentration of 18 PFASs. These data were used to assess Italian consumers' health risks by performing the PFAS intake evaluation. PFBA and PFOS were detected in the precooked and canned meat samples, with PFBA mean concentration of 0.22 ± 0.36 ng g-1, and
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Due to their physicochemical properties, per- and polyfluorinated alkyl substances (PFASs) persist and bioaccumulate in living organisms, causing adverse health effects. Since exposure to xenobiotics is influenced by factors related to both the living organism and the considered compounds, biomonitoring PFASs' presence in the environment is of crucial importance. This study aimed to detect and quantify 15 PFASs in the muscle and liver of 40 roe deer from a specific area in Northern Italy by UPLC-HRMS. In the roe deer, liver PFAS concentrations were higher than those seen in muscle (p < 0.05). Although PFAS content in animals from urbanized areas was higher than those found in deer from rural areas, this difference was not statistically significant. In female roe deer, the concentration was higher than in males (p < 0.05); moreover, older animals showed higher concentrations of PFASs in the liver than younger animals (p < 0.05). In conclusion, the amount of PFASs was higher in tissues from roe deer belonging to urbanized areas, showing that this species might serve as a good bioindicator due to its territorial behavior. PFAS content was significantly higher in female roe deer, although the reason is not fully known. Finally, PFAS concentration was higher in the liver of older animals, probably due to compromised hepatic function.
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This study aimed to investigate the exposure of wild boars and swine from semi-extensive farms in the same area to essential and non-essential elements, measuring their concentration in liver and muscle. Furthermore, the study explored the influence of factors such as sex, age, and the sampling location on wild boars. Higher liver element concentrations were observed in both wild boars and swine. Geographical comparisons revealed minor differences. Young wild boars showed significantly higher Cu, Se, Cd, and Cr levels, while older subjects exhibited elevated Mn levels, reflecting age-related element absorption variations. No significant sex-based variations were noted. Comparing wild boars to swine, wild boars had more non-essential elements due to their foraging behavior and a larger home range. Conversely, swine exhibited a greater prevalence of essential elements, potentially resulting from dietary supplementation.
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In a balanced diet, regular fish consumption provides positive outcomes for human health. On the other hand, the seafood supply chain faces a significant food safety risk due to the presence of potentially toxic elements (PTEs). In the present study, to assess the risk for Italian consumers, the concentrations of five PTEs, namely lead, chromium, cadmium, mercury, nickel, and aluminum, were determined in the three most consumed preserved fish in Italy: tuna (Thunnus albacares, Katsuwonus pelamis), mackerel (Scomber scombrus) and anchovy (Engraulis encrasicolus). Samples were collected from the national market, and the instrumental analysis was performed by inductively coupled plasma mass spectrometry (ICP-MS). The analyzed PTEs were found in all the species that were investigated. However, after considering the target hazard quotient (THQ) and the hazard index (HI), it was observed that the three fish preserves did not pose any risk of chronic toxicity for the average consumer, even at the highest concentrations detected. However, for significant consumers, mercury detected in tuna samples represented almost 90% of the tolerable weekly intake (TWI) reported by the European Food Safety Authority (EFSA), representing a matter of concern for consumers, particularly regarding developmental neurotoxicity, whose HI exceeded 111%. The acute toxicity of nickel was also considered for significant consumers at the highest concentration detected, and the margin of exposure (MOE) calculated was above 7000, much higher than the value of 30 indicated by EFSA. Due to the lack of data on non-professional carcinogenicity or human intake through foods with low cancer risk, this toxicity was not considered in the analysis of PTEs.
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Fish plays a key role in a healthy and balanced Italian diet, but it is also subject to the bioaccumulation of different contaminants depending on the geographical or anthropogenic context from which it is derived. In recent years, the European Food Safety Authority (EFSA) has been focusing its attention on consumer toxicological risk, considering emerging contaminants such as perfluoroalkyl substances (PFASs) and potentially toxic elements (PTEs). Regarding fish, anchovies are among the five small pelagic main commercial species in the European Union and the top five fresh species consumed by households in Italy. Considering the lack of data on PFASs and PTEs in this species, our aim was to investigate the mentioned contaminants in salted and canned anchovies collected over 10 months from different fishing areas, even those far apart, to verify possible variations in bioaccumulation and to consider the risk for the consumer. According to our results, the assessed risk was very reassuring also for large consumers. The only concern, related to Ni acute toxicity, also dependent on the different consumers' sensitivity, was related to only one sample.
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Eggs play an important role in a balanced diet; however, the European Food Safety Authority (EFSA) recognizes eggs as a major source of poly and per-fluoroalkyl substances (PFASs). In this study, the presence of PFASs was analysed in eggs produced by hens from Northern Italian regions, a PFASs-contaminated area. Sixty-five samples were analysed by high-performance liquid chromatography coupled with high-resolution mass spectrometry. The greatest presence of PFASs was found in eggs from Veneto and Emilia Romagna, and the most detected PFASs were perfluorobutanoic acid (PFBA) and perfluorooctanesulfonic acid (PFOS) (mean concentrations 0.30 ± 0.15 and 0.05 ± 0.00 ng g-1). Considering the most recent updates for the sum of the main four PFASs, the highest concentration found in the analysed samples was 0.05 ng g-1, well below the maximum limit set by the European Union. The PFAS intake evaluation confirmed that egg consumption does not represent a risk for Italian consumers.
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The definition of new reliable markers for neonatal maturity evaluation is crucial in canine clinical practice. Concerns about the safety of amniotic sampling in pregnant dogs have prevented its collection for diagnostic purposes. Moreover, amniotic fluid had been considered waste material until the latest studies reported amniocentesis as a reliable and safe procedure, even in the canine species. In our study, amniotic fluid (n = 63) collected at birth from ten dogs undergoing elective Caesarean sections at term was analysed to discover new potential indices of canine neonatal maturity. Based on gestational age, mothers and puppies were divided into two groups: the early group (≤65 days from luteinizing hormone (LH) surge, n = 5) and the late group (>65 days from LH surge, n = 5). Amniotic parameters of the lightest and heaviest puppy in individual/each litter, with a birth weight difference of at least 20% among littermates, were also compared. In particular, the content of lecithin, sphingomyelin, surfactant protein A (SP-A), cortisol, and pentraxin 3 (PTX3) in amniotic fluid, which is considered predictive of foetal development in humans, were investigated. Maternal serum SP-A and cortisol were also measured simultaneously. All amniotic parameters were detectable in canine amniotic fluid. Interestingly, the concentrations of different amniotic parameters correlated with each other. Lecithin was positively correlated with sphingomyelin (p < 0.0001), maternal SP-A (p < 0.0005), and the ratio of amniotic and maternal cortisol (p < 0.004). Amniotic SP-A was inversely correlated to maternal SP-A (p < 0.05), lecithin (p < 0.005), and lecithin-sphingomyelin ratio (p < 0.05). A positive correlation was also recorded between amniotic and maternal cortisol (p < 0.008). Considering that all puppies were born alive and mature, these data could provide a potential range of expected amniotic values in full-term new-born dogs. Furthermore, since gestational age was positively correlated with both maternal and amniotic cortisol (p < 0.0001) and amniotic PTX3 (p < 0.05), amniotic fluid seems to be an attractive, innovative, and minimally invasive matrix with potential diagnostic and prognostic utility for the investigation of canine maturity.
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Líquido Amniótico , Lecitinas , Animales , Perros , Femenino , Embarazo , Líquido Amniótico/metabolismo , Edad Gestacional , Hidrocortisona/metabolismo , Parto , Esfingomielinas/análisis , Esfingomielinas/metabolismoRESUMEN
Bovine milk is a pillar of the human diet and plays a key role in the nutrition of infants. Perfluoroalkyl substances (PFASs) are well-recognized highly stable organic compounds that are able to pollute ecosystems persistently and threaten both human and animal health. The study aimed to analyze the distribution of 14 PFASs within the milk matrix by comparing their content in whole milk, and its skimmed and creamed fractions. Raw milk samples were individually collected from 23 healthy cows (10 primiparous and 13 multiparous) reared on a farm in Northern Italy not surrounded by known point sources of PFASs. Each sample was fractioned in whole, skim, and cream components to undergo PFAS analysis using liquid chromatography-high-resolution mass spectrometry. All samples contained at least one PFAS, with perfluorobutanoic acid (PFBA) being the primary contaminant in all three fractions, followed by perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA). PFOS was shown to be significantly (p < 0.001) more concentrated in cream than in raw and skimmed milk. Multiparous cows showed a higher frequency of positive samples in all analyzed fractions. Further research is necessary to assess the risk of dairy diets and high-fat dairy products and to investigate the toxicological effects of PFASs on cattle, even in environments without known PFAS sources.
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The return to pasture use as an alternative to intensive livestock farming implies some risks with the lack or the excessive presence of potentially toxic elements; in this regard, wild animals have been used as bioindicators for decades. Thus, the purpose of this study is quantifying Cu, Cr, Mn, Zn, Se, As, Cd, Ni, Pb, Al, Fe, and Mg in fur from roe deer and understanding if it is a valid bioindicator tool. Hair was collected from 39 hunted roe deer and divided by age (<36 months old/≥36 months old), sex (male/female), and area of origin (urbanized/rural area). The mean concentrations of Fe, Mg, Mn, Al, Cr, and Pb were higher (p < 0.05) in the urbanized group; the mean levels of Mg and Cr were higher (p < 0.05) in older animals; and Cu, Fe, Mg, Cd, and Cr showed a higher accumulation in females. Our findings showed an age-related variation of elements, with higher concentrations in adult animals and females. In conclusion, our findings prove that hair is a valid matrix for this type of survey, and wild animals are good bioindicators for monitoring the presence of trace elements in pastures.
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RATIONALE: After the detection of low concentrations of prednisolone in racehorse urine samples collected at Italian racetracks, a study was initiated to investigate the accuracy of the analytical protocol used and the possible endogenous origin of detected prednisolone. METHODS: Multiple reaction monitoring (MRM) MS(2) acquisition with a triple quadrupole (n = 780) and full scan MS(2) and MS(3) (n = 180) acquisition with a linear ion trap were checked. As a further confirmation, ten urine samples were analysed by high-resolution mass spectrometry (HRMS). RESULTS: The study showed the difficulty of identifying prednisolone, probably due to interfering compounds with the same molecular weight (360 Da) present in the matrix. The characteristic transitions for prednisolone were identified, both in MS(2) and MS(3), as the ions 187 and 280; the ion 295 was also used for identification. The concentrations detected with the triple quadrupole and the linear ion trap were not statistically different. The exact mass of prednisolone formiate (the adduct acting as a molecular ion) was identified by HRMS. CONCLUSIONS: The very high frequency of prednisolone detection in the samples (78.5%), the low concentration of this steroid and, importantly, the narrow range of the 95% confidence limits (0.97-1.05 in MS(2) mode and 0.88-1.04 in MS(3) mode), could represent evidence that its presence is endogenous. In the light of these results, this hypothesis seems the most probable, even if further studies are required to confirm it. Furthermore, a microbiological origin (i.e. fermentation of cortisol after sample collection) could not be disregarded.
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Cromatografía Líquida de Alta Presión/métodos , Sustancias para Mejorar el Rendimiento/orina , Prednisolona/orina , Espectrometría de Masa por Ionización de Electrospray/métodos , Animales , Cromatografía Líquida de Alta Presión/veterinaria , Doping en los Deportes/prevención & control , Caballos , Espectrometría de Masa por Ionización de Electrospray/veterinariaRESUMEN
Chlorates and perchlorates are endocrine disruptors and emerging environmental contaminants found in various types of foods, including milk and dairy products. The presence of chlorate has been associated with the use of chlorine-based sanitizers to disinfect equipment and water used in food processing. Perchlorate, on the other hand, occurs naturally in the environment but is also released from anthropogenic sources. To protect consumers, the EU set an MRL for chlorate in milk but not for perchlorate. Considering that data on chlorates and perchlorates in this field are limited, the objective of this study was to assess the presence of these two anions in 148 samples of raw bovine milk collected from different farms of Lombardy and grouped in three different geographical zones. Chlorate was detected in 73% of the samples analyzed, at concentrations ranging from
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The primary source of persistent organic pollutant (POP) exposure is food, especially fish. European seabass (Dicentrarchus labrax) and gilthead seabream (Sparus aurata) are among the most eaten sea fish in Italy. Fish from lakes in Northern Italy, such as agone (Alosa agone), represent niche consumption for most people, but possibly constitute a much larger percentage of overall consumption volume for local residents. This study dealt with the presence of POPs in the above-mentioned fish species via GC-MS/MS analysis. None of the analytes for which maximum limits are in place showed concentrations above those limits. Moreover, none of the substances without maximum limits exceeded the provisional tolerable daily intake (PTDI) when given, nor did they exceed the more general values considered safe, even for 99th percentile consumers.