The contribution of cacao consumption to the bioaccessible dietary cadmium exposure in the Belgian population.

Since 2019, EU limits apply to cadmium (Cd) concentrations in cacao-derived food products. The dietary risk assessment leading to that regulation used consumption surveys aggregated to a limited number of chocolate product categories and did not consider differences in Cd bioaccessibility. Here, the cacao-related dietary Cd exposure in the Belgian population was estimated with higher resolution and accounting for bioaccessibility. A food frequency questionnaire and a 24-h recall (N = 2055) were set up for the Belgian population, in combination with ICP-MS analysis of a large subset of cacao-containing products (N = 349). Both the average chocolate consumption (28 g day-1) and the relative contribution of chocolate to the total dietary Cd exposure (7-9%) were higher than previously estimated for the Belgian population, probably because of some selection bias towards chocolate consumers in the cohort. The Cd bioaccessibility in chocolate products was a factor 5 (cacao powder) and 2 (dark chocolate) lower compared to wheat flour, suggesting lower bioavailability in chocolate than in wheat, which is a main contributor to dietary Cd. This study suggests that Cd intake from cacao consumption has been underestimated because of hidden cacao in non-chocolate food categories but, in contrast, may have overestimated the true exposure because of lower bioavailability compared to the main foodstuffs contributing to Cd exposure.

Titanium dioxide particles frequently present in face masks intended for general use require regulatory control.

Although titanium dioxide (TiO2) is a suspected human carcinogen when inhaled, fiber-grade TiO2 (nano)particles were demonstrated in synthetic textile fibers of face masks intended for the general public. STEM-EDX analysis on sections of a variety of single use and reusable face masks visualized agglomerated near-spherical TiO2 particles in non-woven fabrics, polyester, polyamide and bi-component fibers. Median sizes of constituent particles ranged from 89 to 184 nm, implying an important fraction of nano-sized particles (< 100 nm). The total TiO2 mass determined by ICP-OES ranged from 791 to 152,345 µg per mask. The estimated TiO2 mass at the fiber surface ranged from 17 to 4394 µg, and systematically exceeded the acceptable exposure level to TiO2 by inhalation (3.6 µg), determined based on a scenario where face masks are worn intensively. No assumptions were made about the likelihood of the release of TiO2 particles itself, since direct measurement of release and inhalation uptake when face masks are worn could not be assessed. The importance of wearing face masks against COVID-19 is unquestionable. Even so, these results urge for in depth research of (nano)technology applications in textiles to avoid possible future consequences caused by a poorly regulated use and to implement regulatory standards phasing out or limiting the amount of TiO2 particles, following the safe-by-design principle.

Intake of food supplements based on algae or cyanobacteria may pose a health risk due to elevated concentrations of arsenic species.

Despite the health benefits of food supplements (FS) based on algae or cyanobacteria, the elevated arsenic (As) concentrations in these FS may raise a health concern. In the present study 33 FS containing algae or cyanobacteria were collected and As (species) were analysed to estimate consumer exposure. Based on hazard and exposure data, potential risks were evaluated using inorganic arsenic (Asi) and the potentially toxic As fraction (Astot minus arsenobetaine (AB)). Astot concentrations were in the range 0.053-57 mg/kg with highest concentrations in FS containing brown algae. Asi concentrations were in the range <0.02-4.7 mg kg-1. A large part of As in FS containing algae or cyanobacteria was identified as potentially toxic AsSugars species. Negligible amounts of AB were detected. According to a tentative risk evaluation, the intake of Asi related to all FS collected was of no health concern for the general population. In 8 out of 33 of the analysed FS, however, the Asi concentration was of concern for population groups with increased cancer risks. If all As species except the non-toxic AB were taken into consideration, only 26 out of 33 of the FS showed 'no concern' for the general population, while for the other 7 FS a potential health risk was identified. This study indicates the need to obtain more data on toxicity of AsSugars and to develop limits for As (species) in FS.

Physico-chemical characterisation of the fraction of silver (nano)particles in pristine food additive E174 and in E174-containing confectionery.

Silver (E174) is authorised as a food additive in the EU. The unknown particle size distribution of E174 is a specific concern for the E174 risk assessment. This study characterised the fraction of silver (nano)particles in 10 commercially available pristine E174 food additives and 10 E174-containing products by transmission electron microscopy (TEM) and single-particle inductively coupled plasma-mass spectrometry (spICP-MS). TEM analysis showed that all samples contained micrometre-sized flakes and also a fraction of (nano)particles. Energy-dispersive X-ray spectroscopy (EDX) and electron diffraction confirmed that the (nano)particles and micrometre-sized flakes consisted of silver. A higher amount of (nano)particles was observed in the products than in the food additives. In addition, the surface of the micrometre-sized flakes was rougher in products. The median of the minimum external dimension, assessed as minimal Feret diameter, of the fraction of (nano)particles determined by quantitative TEM analysis was 11 ± 4 nm and 18 ± 7 nm (overall mean ± standard deviation), for food additives and products, respectively. Similar size distributions were obtained by spICP-MS and TEM, considering the limit of detection of spICP-MS. The median of the equivalent spherical diameter of the fraction of (nano)particles determined by spICP-MS was 19 ± 4 nm and 21 ± 2 nm (overall mean ± standard deviation), for food additives and products, respectively. In all samples, independent of the choice of technique, the nano-sized particles represented more than 97% (by number) of the silver particles, even though the largest mass of silver was present as flakes.

A systematic evaluation of Flow Field Flow Fractionation and single-particle ICP-MS to obtain the size distribution of organo-mineral iron oxyhydroxide colloids.

Colloidal iron(III) oxyhydroxides (FeOx) are important reactive adsorbents in nature. This study was set up to determine the size of environmentally relevant FeOx colloids with new methods, i.e. Flow Field Flow Fractionation (FlFFF-UV-ICP-MS) and single-particle ICP-MS/MS (sp-ICP-MS) and to compare these with standard approaches, i.e. dynamic light scattering (DLS), nanoparticle tracking analysis (NTA), microscopy (TEM), membrane filtration, centrifugation and dialysis. Seven synthetic nano- and submicron FeOx with different mineralogy and coating were prepared and two soil solutions were included. The FlFFF was optimized for Fe recovery, yielding 70-90%. The FlFFF determines particle size with high resolution in a 1 mM NH4HCO3 (pH 8.3) background and can detect Fe-NOM complexes <5 nm and organo-mineral FeOx particles ranging 5-300 nm. The sp-ICP-MS method had a size detection limit for FeOx of about 32-47 nm. The distribution of hydrodynamic diameters of goethite particles detected with FlFFF, NTA and DLS were similar but the values were twice as large as the Fe cores of particles detected with sp-ICP-MS and TEM. Conventional fractionation by centrifugation and dialysis generally yielded similar fractions as FlFFF but membrane filtration overestimated the large size fractions. Particles formed from Fe(II) oxidation in the presence of NOM showed strikingly smaller organo-mineral Fe-Ox colloids as the NOM/Fe ratio increased. The soil solution obtained with centrifugation of an acid peat was dominated by small (<30 nm) Fe-OM complexes and organo-mineral FeOx colloids whereas that of a mineral pH neutral soil mainly contains larger (30-200 nm) Fe-rich particles. The FlFFF-UV-ICP-MS is recommended for environmental studies of colloidal FeOx since it has a wide size detection range, it fractionates in an environmentally relevant background (1 mM NH4HCO3) and it has acceptable element recoveries.

Polyphosphates and Fulvates Enhance Environmental Stability of PO4-Bearing Colloidal Iron Oxyhydroxides.

Iron oxyhydroxide nanoparticles (Fe-NPs) are natural vectors of phosphate (PO4) in the environment. Their mobility is determined by colloidal stability, which is affected by surface composition. This might be manipulated in engineered NPs for environmental or agricultural applications. Here, the stability of PO4-Fe-NPs (HFO/goethite) was determined across contrasting environmental conditions (pH, Ca concentration) and by using fulvates (FA) and polyphosphates (poly-P's) as coatings. The PO4-Fe-NPs are unstable at Ca concentrations above 0.1 mM. Addition of FA and some poly-P's significantly improved stability. Zeta potential explained colloidal stability across treatments; surface charge was calculated with surface complexation models and explained for phytic acid (PA) and hexametaphosphate (HMP) by a partial (1-4 of the 6 PO4 units) adsorption to the surface, while the remaining PO4 units stayed in solution. This study suggests that Ca concentration mainly affects the mobility of natural or engineered PO4-Fe-NPs and that HMP is a promising agent for increasing colloidal stability.

A dynamic model to calculate cadmium concentrations in bovine tissues from basic soil characteristics.

A chain model was developed to calculate the flow of cadmium from soil, drinking water and feed towards bovine tissues. The data used for model development were tissue Cd concentrations of 57 bovines and Cd concentrations in soil, feed and drinking water, sampled at the farms were the bovines were reared. Validation of the model occurred with a second set of measured tissue Cd concentrations of 93 bovines of which age and farm location were known. The exposure part of the chain model consists of two parts: (1) a soil-plant transfer model, deriving cadmium concentrations in feed from basic soil characteristics (pH and organic matter content) and soil Cd concentrations, and (2) bovine intake calculations, based on typical feed and water consumption patterns for cattle and Cd concentrations in feed and drinking water. The output of the exposure model is an animal-specific average daily Cd intake, which is then taken forward to a kinetic uptake model in which time-dependent Cd concentrations in bovine tissues are calculated. The chain model was able to account for 65%, 42% and 32% of the variation in observed kidney, liver and meat Cd concentrations in the validation study.