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Peatlands, known for their ability to retain and immobilize heavy metals due to unique waterlogged conditions and organic matter, face challenges when subjected to disturbances such as land use changes. These disruptions alter the organic matter, redox potential, and pH of the peatsoil, potentially influencing the migration, mobilization, and increased availability of stored heavy metals. Peatsoil samples from various peatland use types (improved and semi-natural grassland, forest, industrial cutaway bog) were collected to assess the human health and ecological risk associated with heavy metals (Cd, Cu, Hg, Pb, and Zn) in Co-Offaly, Ireland. Results reveal variations in heavy metal concentrations across peatland use types, with Cd, Hg, and Pb in improved and semi-natural grassland peatsoils exceeding the World Health Organization (WHO) permissible safety limits. Contamination factors (CF) were higher in improved grassland, especially for Cd and Pb, exceeding one. Hakanson potential ecological risk assessment indicates acceptable overall risk levels, though variations exist between improved grassland, unimproved grassland, forest, and industrial cutaway bog. Combined exposure routes (dermal, ingestion and inhalation routes) to all heavy metals do not exceed safe exposure levels (indicating low non-carcinogenic risks. However, the cancer risk (CR) exceeds acceptable thresholds across all use types, with higher CR in improved grassland, especially for children. Overall, the findings emphasize the need for careful consideration of heavy metal risks associated with land use changes in peatlands, particularly in the improved grassland areas.
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Two new analytical methods, applying absolute 1H qNMR, were developed to monitor product yield and quantify unreacted carbohydrate and fatty acid reactants, in the synthesis of carbohydrate fatty acid esters (CFAE). These methods provide a mass balance of the crude reaction mixtures and diversify the analytical screening and quantitation approaches available within the synthesis of these molecules. Both methods were validated for the model reaction of methyl α-d-glucopyranoside (MAG) and lauric acid (LA) to form the mono ester product, methyl 6-O-dodecanoyl-α-d-glucopyranoside. Analysis in CD3OD by 1H qNMR, with fumaric acid (FA) as an internal standard (IS), allowed monitoring of all reaction components. Alternatively, using CDCl3 and (E)-stilbene as IS enabled the analysis of CFAE and fatty acid. Parameters calculated for method validation included specificity and selectivity, linearity, accuracy, intermediate precision, limit of detection (LOD), limit of quantification (LOQ) and robustness. Both methods provided excellent linearity with R2 > 0.997. The accuracy, precision, and robustness of the method in CD3OD was <2 % uncertainty making it suitable for complete reaction analysis. The method completed in CDCl3 resulted in accuracy, intermediate precision, and robustness of <5 %, except for accuracy in the lowest levels of concentration (>5 %). For all related analytes in the CD3OD and CDCl3 methods, the LOD and LOQ were determined to ensure applicability for the intended use in the assessment of reaction crude composition. Finally, the system suitability was assessed in a scaled lipase catalysed CFAE synthetic reaction. The determined qNMR product yields were verified against isolated purified product yields with <5 % uncertainty.
Assuntos
Ésteres , Ácidos Graxos , Ésteres/química , Ácidos Graxos/química , Ácidos Graxos/análise , Espectroscopia de Ressonância Magnética , Carboidratos/química , Carboidratos/análiseRESUMO
OBJECTIVE: The aim of this study was to quantify relationships among symptoms, interoceptive sensibility (i.e. the conscious level of sensing, interpreting and integrating signals from the body), and self-care management behaviors (i.e. the response to symptoms when they occur) among adults with cardiovascular disease. We hypothesized that better interoceptive sensibility would increase the positive behavior-driving effects of symptoms on self-care management. METHODS: Adult patients with cardiovascular disease who experienced recent symptoms were recruited to participate in this cross-sectional correlational descriptive study. Patient-Reported Outcomes Measurement Information System measures were used to capture dyspnea, pain interference, fatigue, sleep disturbances, nausea and vomiting, anxiety and depressive symptoms. Interoceptive sensibility was measured using the Multidimensional Assessment of Interoceptive Awareness Version 2. The Self-Care of Chronic Illness Inventory was used to measure self-care management. Network analysis was used to identify domains of interoceptive sensibility that were most central. Linear regression with interaction terms was used to test the moderating effect of interoceptive sensibility on the relationship between symptoms and self-care management. RESULTS: The age of participants in the sample (nâ¯=â¯387) ranged from 18 to 88â¯years, a slight majority (53.5â¯%) were female, and a majority were Caucasian (66.4â¯%) or African American (32.0â¯%). Hypertension was the most common disorder (nâ¯=â¯238 (61.5â¯%)), followed by rhythm disorders (nâ¯=â¯124 (32.0â¯%)), coronary artery disease (nâ¯=â¯94 (24.3â¯%)), heart failure (nâ¯=â¯89 (23.0â¯%)), valve disease (nâ¯=â¯69 (17.8â¯%)), stroke (nâ¯=â¯62 (16.0â¯%)) and peripheral vascular disease (nâ¯=â¯49 (12.7â¯%)). Based on network analysis, body listening (i.e. active listening to the body for insights) was the most central interoceptive domain, and distracting (i.e. tendency to ignore or distract oneself from sensations of discomfort) was the least central. Noticing (i.e. greater awareness of body sensations), distracting, and body listening were significant in moderating relationships between dyspnea, sleep disturbances and anxiety and the outcome of self-care management behaviors (all pâ¯<â¯0.001). Better noticing and body listening were associated with better self-care management across symptoms, whereas ignoring or distracting oneself from discomfort was associated with worse self-care management behaviors. CONCLUSION: Among adults with cardiovascular disease, interventions designed to augment the identified interoceptive sensibility domains like body listening, and mitigate the tendency to ignore or distract oneself from discomfort may support adults with cardiovascular disease through the development of future interventions that optimize patient behaviors in response to symptoms when they occur.