Occurrence of heavy metals coupled with elevated levels of essential elements in chocolates: Health risk assessment.

The presence of contaminants in cacao-derived products, especially in chocolates, has raised concerns regarding food safety and human health. The study assessed the concentration variation of 16 elements in 155 chocolate samples from the US market by cacao content and country of geographic origin. The study further examined the potential health risks posed by toxic metals and determined the contribution of essential elements to the Daily Recommended Intake (DRI), estimated based on an ounce (∼28.4 g) of daily chocolate consumption. Dark chocolates with ≥50 % cacao exhibited consecutively increasing mean levels from 1.2 to 391 µg/kg for U, Tl, Th, As, Pb, Se, Cd, and Co. Similarly, Ni, Sr, Cu, Mn, Zn, Fe, Ca, and Mg had mean concentrations from 4.0 to 1890 mg/kg. Dark chocolates sourced from Central and South America exhibited the highest mean levels of Cd, and South America samples also contained elevated Pb, whereas those from West Africa and Asia had low Cd and Pb, respectively. Cacao contents showed increasingly strong association with Cd, Co, Mn, Sr, Ni, Cu, Zn, and Mg (r = 0.60-0.84), and moderately with Se, Fe, As, and Tl (r = 0.35-0.49), indicating these elements are primarily derived from cacao beans. Weak association of cacao contents with Pb, Th, and U levels (r < 0.25), indicates post-harvest contaminations. Hazard Quotient (HQ) > 1 was found only for Cd in 4 dark chocolates, and Hazard Index (HI) > 1 for cumulative risk of Cd, Pb, Ni, As, and U was found in 33 dark chocolates, indicating potential non-carcinogenic risks for 15 kg children but none for 70 kg adults. Dark chocolate also substantially contributed to 47-95 % of the DRI of Cu for children and 50 % for adults. Dark chocolates also provided notable Fe, Mn, Mg, and Zn contributions to the DRI. These essential elements are recognized to reduce the bioavailability of toxic metals such as Cd, Pb, or Ni, thereby potentially lowering associated health risks. This study informs consumers, food industries, and regulatory agencies to target cacao origins or chocolate brands with lower toxic metal contents for food safety and minimizing adverse health effects.

Selenium in drinking water and cereal grains, and biomarkers of Se status in urine and fingernails of the Main Ethiopian Rift Valley population.

BACKGROUND: Selenium (Se) plays an important role in human health, yet Se overexposure or deficiency can lead to deleterious health effects. This study aims to determine the concentration of Se in drinking water and staple cereal grain (maize, wheat, and teff) samples from the Main Ethiopian Rift (MER) Valley, and correspondingly, assesses Se biomarkers and their status as measured in the urine and fingernails of 230 individuals living in 25 MER communities. METHOD: The concentration of Se in drinking water and cereal grain (maize, wheat, and teff) samples, and urine and fingernail samples were measured using Inductively Coupled Plasma Mass Spectrometry (ICP-MS). Demographic, anthropometric, and elemental concentrations were described by their quartiles and mean ± standard deviations. The 5th and 95th percentiles were used to describe the concentrations Se biomarkers ranges. The Se biomarker distributions in different study communities were further characterized according to Se levels found in drinking water, sex, and age using ANOVA, and multivariate regression. We conducted a correlation analysis (with Pearson correlation coefficient) and fitted a regression to evaluate the associations between these variables. RESULTS: The mean concentration of Se in the drinking water samples was 0.66 (range: 0.015-2.64 µg/L; n = 25), and all samples were below the threshold value of 10 µg/L for Se in drinking water set by the World Health Organiation (WHO). In Ethiopia, most rural communities rely on locally produced cereal grains. We found mean Se concentrations (µg/kg) of 357 ± 190 (n = 14), 289 ± 123 (n = 14), and 145 ± 100 (n = 14) in wheat, teff, and maize, respectively. Furthermore, Se concentrations in drinking water showed no significant correlation with biomarker measures, indicating that the primary source of dietary Se is likely from local foods including staple grains. The mean±SD (5th-95th percentiles) of Se concentrations in fingernails and urine among study subjects were 1022 ± 320 (624-1551 µg/kg), and 38 ± 30 (1.9-100 µg/L), respectively. CONCLUSION: A sizeable share of study participants (31%) fell below the lower limits of what is considered the currently accepted Se range of 20-90 µg/L in urine, though relatively few (only 4%) had similarly low fingernail levels. On the other hand, none of the samples reached Se toxicity levels, and the biomarker levels in this study are comparable to results from other studies that find adequate Se. Our results show that Se toxicity or deficiency is unlikely in the study population.

Surface morphology effects on clathrate hydrate wettability.

HYPOTHESIS: Clathrate hydrates preferentially form at interfaces; hence, wetting properties play an important role in their formation, growth, and agglomeration. Experimental evidence suggests that the hydrate preparation process can strongly affect contact angle measurements, leading to the different results reported in the literature. These differences hamper technological progress. We hypothesize that changes in hydrate surface morphologies are responsible for the wide variation of contact angles reported in the literature. EXPERIMENTS: Experimental testing of our hypothesis is problematic due to the preparation history of hydrates on their surface properties, and the difficulties in advanced surface characterization. Thus, we employ molecular dynamics simulations, which allow us to systematically change the interfacial features and the system composition. Implementing advanced algorithms, we quantify fundamental thermodynamic properties to validate our observations. FINDINGS: We achieve excellent agreement with experimental observations for both atomically smooth and rough hydrate surfaces. Our results suggest that contact line pinning forces, enhanced by surface heterogeneity, are accountable for altering water contact angles, thus explaining the differences among reported experimental data. Our analysis and molecular level insights help interpret adhesion force measurements and yield a better understanding of the agglomeration between hydrate particles, providing a microscopic tool for advancing flow assurance applications.

Water Wettability Coupled with Film Growth on Realistic Cyclopentane Hydrate Surfaces.

Although the wettability of hydrate surfaces and hydrate film growth are key to understanding hydrate agglomeration and pipeline plugging, a quantitative understanding of the coupled behavior between both phenomena is lacking. In situ measurements of wettability coupled with film growth were performed for cyclopentane hydrate surfaces in cyclopentane at atmospheric pressure and temperatures between 1.5-6.8 °C. Results were obtained as a function of annealing (conversion) time and subcooling. Hydrate surface wettability decreased as annealing time increased, while hydrate film growth rate was unaffected by annealing time at any subcooling. The results are interpreted as a manifestation of the hydrate surface porosity, which depends on annealing time and controls water spreading on the hydrate surface. The wettability generally decreased as the subcooling increased because higher subcooling yields rougher hydrate surfaces, making it harder for water to spread. However, this effect is balanced by hydrate growth rates, which increase with subcooling. Also affecting the results, surface heating from heat release (from exothermic crystallization) allows excess surface water to promote spreading. The hydrate film growth rate on water droplets increased with subcooling, as expected from a higher driving force. At any subcooling, the instantaneous hydrate growth rate decreased over time, likely from heat transfer limitations. A new phenomenon was observed, where the angle at the three-phase point increases from the initial contact angle upon hydrate film growth, named the crystallization angle. This is attributed to the water droplet trying to spread while the thin film is weak enough to be redirected. Once the hydrate film grows and forms a "wall" around the droplet, it cannot be moved, and further growth yields a crater on the droplet surface, attributed to water penetrating the hydrate surface pore structures. This fundamental behavior has many flow assurance implications since it affects the interactions between the agglomerating hydrate particles and water droplets.