Changes in oral bioaccessibility of heavy metals in non-digestive sucking habits due to the formation of complexes between digestive fluid components and metals/metalloids.

Humans, especially infants, are exposed to harmful substances through various means, including non-nutritive sucking behaviors. Here, we compared the "one-compartment model" and the "three-compartment model" within the "suck model" to assess the oral bioaccessibility of heavy metals in various products and evaluated whether these models can be employed to assess 12 heavy metals present in consumer products. Several certified reference materials, including plastic, paint, glass, and metals, were employed to ensure sample homogeneity. By comparing the two models, we validated that a considerable amount of complexes were formed between saliva components and the extracted heavy metals and that some of these complexes dissociated during reactions with the gastric/intestinal fluids. Furthermore, we observed that in the cases of Cu and Pb, additional complexes were formed as a result of reactions with gastric/intestinal fluids. We measured the total concentrations of the extracted heavy metals using artificial saliva through acid digestion and found that up to 99.7% of the heavy metals participated in the formation of complexes, depending on the characteristics of the sample (e.g., composition) and the target element. This result indicates that the current suck model may notably underestimate the oral bioaccessibility of heavy metals in products associated with sucking behaviors. Therefore, we propose a more conservative and simpler test method for assessing oral bioaccessibility of heavy metals that involves measuring the total concentrations of heavy metals extracted from consumer products using artificial saliva. By doing so, we can account for potential variations in the digestive milieu (e.g., due to ingested food) and the inconsistency in complex formation-dissociation characteristics.

Effect of aging on polyethylene microfiber surface properties and its consequence on adsorption characteristics of 17alpha-ethynylestradiol.

This study assessed the interactive changes to the endocrine disruptor 17 alpha-ethynylestradiol (EE2) triggered by photoaging onto fibrous microplastics frequently found in the environment. The physicochemical property change of the polyethylene (PE) microfiber according to irradiation (i.e. 14 d UV-C (254 nm)) was studied through Fourier transform infrared spectroscopy, scanning electron microscope, and contact angle analysis. Additionally, the EE2 adsorption kinetics experiment was performed for the PE microfiber before and after UV irradiation to assess the change in adsorption characteristics. After UV irradiation, the PE microfiber surface roughness increased, the oxygen-containing functional group (e.g. carbonyl group) increased, and the contact angle (virgin PE: 80.02°, aged PE: 65.13°) decreased. A decrease in the surface hydrophobicity led to a decrease in the adsorption rate of EE2 (virgin PE: k = 0.0105 h-1, aged PE: not calculated). The hydrophobic interaction significantly affects the adsorption behavior of hydrophobic organic pollutants such as EE2 onto MPs, and continuous photo-aging of MPs may cause a new pattern of ecological risk. Therefore, there is a greater necessity for additional research relevant to this issue.

Adsorption Characteristics of Dimethylated Arsenicals on Iron Oxide-Modified Rice Husk Biochar.

In this study, the adsorption characteristics of dimethylated arsenicals to rice husk biochar (BC) and Fe/biochar composite (FeBC) were assessed through isothermal adsorption experiments and X-ray absorption spectroscopy analysis. The maximal adsorption capacities (qm) of inorganic arsenate, calculated using the Langmuir isotherm equation, were 1.28 and 6.32 mg/g for BC and FeBC, respectively. Moreover, dimethylated arsenicals did not adsorb to BC at all, and in the case of FeBC, qm values of dimethylarsinic acid (DMA(V)), dimethylmonothioarsinic acid (DMMTA(V)), and dimethyldithioarsinic acid (DMDTA(V)) were calculated to be 7.08, 0.43, and 0.28 mg/g, respectively. This was due to the formation of iron oxide (i.e., two-line ferrihydrite) on the surface of BC. Linear combination fitting using As K-edge X-ray absorption near edge structure spectra confirmed that all chemical forms of dimethylated arsenicals adsorbed on the two-line ferrihydrite were DMA(V). Thus, FeBC could retain highly mobile and toxic arsenicals such as DMMTA(V) and DMDTA(V)) in the environment, and transform them into DMA(V) with relatively low toxicity.

Dimethylmonothioarsinic acid and dimethyldithioarsinic acid in the environment: Sorption characteristics on 2-line ferrihydrite and acute toxicity to Daphnia magna.

Dimethylmonothioarsinic acid (DMMTA(V)) and dimethyldithioarsinic acid (DMDTA(V)), which are commonly found in landfill leachate and pore water of rice paddy soil, have attracted considerable attention for their high toxicity. This study aims to evaluate the behavior and potential risks of DMMTA(V) and DMDTA(V) in the environment by conducting an equilibrium sorption test using 2-line ferrihydrite and acute toxicity (immobilization) test using Daphnia magna. The overall maximum sorption capacity (qm) derived by the Langmuir isotherm model showed an increase in the order of inorganic arsenate (As(V)) > dimethylarsinic acid (DMA(V)) > DMMTA(V) > DMDTA(V), which was likely due to steric hindrance due to the presence of methyl and thiol groups. Moreover, DMMTA(V) and DMDTA(V) showed no or negligible change in qm with pH change, while qm decreased rapidly with increasing pH in As(V) and DMA(V). The 50% inhibition concentrations (IC50) for As(V), DMA(V), DMMTA(V), and DMDTA(V), which were measured after 48 h exposure to D. magna, were 9.5, > 30, 1.7, and 6.5 mg/L, respectively. Overall, the results demonstrated that DMMTA(V) and DMDTA(V) have high mobility and eco-toxicity in the environment and that methylated thioarsenicals should be accurately monitored and controlled.