Metal(loid) speciation in dermal bioaccessibility extracts from contaminated soils and permeation through synthetic skin.

Dermal exposure to metal(loid)s from contaminated soils can contribute to health risk. Metal(loid) speciation will influence their bioaccessibility in sweat and subsequent permeation across the skin. Therefore, the speciation of the bioaccessible fraction of metal(loid)s in two synthetic sweat formulations (sweat A (pH 6.5) and B (pH 4.7)) was assessed using chemical equilibrium modelling (Visual MINTEQ). Permeation through synthetic skin and the influence of sebum in the permeation of As, Cr, Cu, Ni, Pb, and Zn were also investigated using Franz cells. Following dermal bioaccessibility tests for five Chromated Copper Arsenate (CCA)-contaminated soils and one certified soil (SQC001), mean metal(loid) bioaccessibility (%) was higher in sweat B (2.33-18.8) compared to sweat A (0.12-7.53). Arsenic was almost entirely found as As(V) in both sweats. In sweat A, comparable concentrations of Cr(III) and Cr(VI) were found whereas in sweat B, Cr was primarily present as Cr(III). Copper was primarily found as Cu2+. Bioaccessible Cr extracted from nearly all soils permeated through the Strat-M membrane when it was coated with sebum. The Cr permeation coefficient (Kp) ranged between 0.004 and 0.13 cm/h and the Kp for Cu was higher (0.024-0.52 cm/h). As, Ni, Pb, and Zn did not permeate the synthetic skin.

Incorporating oral, inhalation and dermal bioaccessibility into human health risk characterization following exposure to Chromated Copper Arsenate (CCA)-contaminated soils.

Exposure to potentially toxic metal(loid)s (PTMs) in soil may happen via ingestion, inhalation, and dermal pathway. A more accurate risk characterization should consider PTM bioavailability. Using ten soil samples collected in the Montreal area (Canada) near CCA-treated utility poles, this study aims to characterize non-carcinogenic and carcinogenic human health risks associated with As, Cr, Cu, Pb, and Zn through a multi-pathway exposure approach. This innovative study incorporates, for the first time, the bioaccessible fraction of the metal(loid)s for three exposure routes and two different scenarios. For the residential and industrial scenarios, the oral and dermal pathways yielded a hazard index (HI) much higher than 1 with and without bioaccessibility considerations (range 1.7 - 349 without bioaccessibility and 0.8-134 with bioaccessibility), whereas the inhalation pathway caused a lower hazard (HI < 1). For the dermal pathway, the hazard quotient was higher when bioaccessibility of field-collected samples was considered due to inherent assumptions from the US EPA soil approach to calculate the dermal dose. For carcinogenic risk, As and Pb were the most significant contributors to risk for the oral pathway, followed by the same elements for the dermal pathway. The overall carcinogenic risk was higher than the acceptable risk ( > 10-4) with and without bioaccessibility considerations (range 1.9E-4 - 9.6E-3 without bioaccessibility and 6.8E-5 - 3.8E-3 with bioaccessibility). Bioaccessibility tests provide a more accurate assessment of exposure to PTMs compared to total concentrations in soils.

Comparison of Synthetic Sweat and Influence of Sebum in the Permeation of Bioaccessible Metal(loid)s from Contaminated Soils through a Synthetic Skin Membrane.

Dermal exposure to metal(loid)s from contaminated soils has received less attention than oral and inhalation exposure. Still, it can be a relevant pathway for some contaminants. Comparison of synthetic sweats (donor solutions), the influence of sebum, and the characterization of diffusion parameters through a synthetic membrane (acting as skin surrogate) in the permeation of metal(loid)s (As, Cr, Cu, Ni, Pb, and, Zn) from polluted soils is missing. The dermal bioaccessibility tests were performed using two sweat compositions [EN 1811, pH 6.5 (sweat A) and NIHS 96-10, pH 4.7 (sweat B)]. Diffusion parameters of soluble metal(loid)s using the Franz cell methodology were calculated using the Strat-M membrane. The influence of synthetic sebum in the permeation of metal(loid)s was also investigated. The metal(loid) bioaccessibility percentage was higher for sweat B (pH 4.7) compared to sweat A (pH 6.5), attributed to lower pH of sweat B. Among the six elements tested, only chromium and copper permeated the membrane. Permeation coefficient (Kp) was higher for chromium in sweat A (0.05-0.11 cm h-1) than sweat B (0.0007-0.0037 cm h-1) likely due to a higher pH and thus more permeable Cr species. The presence of sebum increased lag times for copper permeation. Additional studies regarding speciation of metal(loid)s following extractions in synthetic sweat and comparison of synthetic membrane Strat-M and human skin in the permeation of metal(loid)s are recommended.

Comparison of five artificial skin surface film liquids for assessing dermal bioaccessibility of metals in certified reference soils.

Dermal exposure to metals has previously received less attention than oral/inhalation exposure. Nonetheless, human health risk is significant for certain contaminants and exposure scenarios. The present study aims to (1) characterize two certified reference soils (SQC001, BGS 102); and (2) assess Cr, Ni, Pb, and Zn dermal bioaccessibility via in vitro assays using three synthetic sweat formulations (EN 1811, pH 6.5 (Sweat A), NIHS 96-10, pH 4.7 (Sweat B), and a more complex pH 5.5 formulation containing amino acids (Sweat C)) and two sebum formulations. Metals bioaccessibility in sweat followed Sweat B > Sweat C > Sweat A, attributed to sweat B lower pH. Dermal bioaccessibility in both sebum formulations was lower than 1% for Ni and Pb and below 9% for Cr and Zn, possibly due to low affinity of metals for non-polar lipids. It must be noted that bioaccessible Zn in BGS 102 was higher when extracted with synthetic sebum compared to any of the synthetic sweat formulations. Metal bioaccessibility in sweat was considerably higher for SQC001 (up to 76.6% for Zn using Sweat B) than for BGS 102 (ranging between 0.02 and 1.3% for all elements and all sweat formulations), attributed to higher pH, higher organic carbon, and higher cation exchange capacity of reference soil BGS 102. Sebum formulations spiked with metals generally entailed low metal recovery (except for Zn), which may explain overall low bioaccessibility values for sebum. Sebum and sweat formulation, and soil properties seem to control in vitro dermal bioaccessibility of metals.