Using oral bioaccessibility measurements to refine risk assessment of potentially toxic elements in topsoils across an urban area.

Elevated concentrations of As, Cr, Cu, Ni, Pb, V and Zn in topsoils in Belfast, Northern Ireland have been found to exceed assessment criteria in the city and therefore may pose a risk to human health. Most generic assessment criteria (GAC) for potentially toxic elements (PTEs) in soils assume PTEs are 100% bioavailable to humans. Here we use in-vitro oral bioaccessibility testing using the Unified BARGE method (UBM) to measure what proportion of soil contamination dissolves in the digestive tract and therefore is available for absorption by the body. This study considers how PTE bioaccessibility in soils varies spatially across urban areas and refines human health risk assessment for these PTEs using site specific oral bioaccessibility results to present the first regional assessment of risk that incorporates bioaccessibility testing. A total of 103 urban soil samples were selected for UBM testing. Results showed low bioaccessible fraction (BAF) for the PTEs from geogenic sources: Cr (0.45-5.9%), Ni (1.1-46.3%) and V (2.2-23.9%). Higher BAF values were registered for PTEs from anthropogenic sources: As (8.0-86.9%), Cu (3.4-67.8%), Pb (9.1-106.2%) and Zn (2.4-77.5%). Graphs of bioaccessibility adjusted assessment criteria (BAAC) were derived for each urban land use type and PTE. These provide a visual representation of the significance of oral bioaccessibility when deriving BAAC and how this is affected by 1) dominant exposure pathways for each land use and 2) relative harm posed from exposure to PTEs via each pathway, allowing oral bioaccessibility research to be targeted to contaminants and pathways that most significantly impact risk assessment. Pb was the most widespread contaminant with 16.5% of sites exceeding the Pb GAC. Applying BAAC did not significantly change risk evaluation for these samples as many had Pb BAF>50%. In contrast, all samples that exceeded the As GAC were found to no longer exceed a minimal level of risk when oral bioaccessibility was considered. Oral bioaccessibility testing resulted in a 45% reduction in the number of sites identified as posing a potential risk to human health.

Incorporating oral bioaccessibility into human health risk assessment due to potentially toxic elements in extractive waste and contaminated soils from an abandoned mine site.

The waste rock, tailings and soil around an abandoned mine site in Gorno (northwest Italy) contain elevated concentrations of potentially toxic elements (PTE) exceeding the permissible limits for residential uses. Specifically, the maximum concentrations of As, Cd, Pb, and Zn were 107 mg/kg, 340 mg/kg, 1064 mg/kg, and 148 433 mg/kg, respectively. A site-specific human health risk assessment (HHRA) was conducted for residential and recreational exposure scenarios, using an approach based on Risk Based Corrective Action (RBCA) method, refined by incorporating oral bioaccessibility data. Oral bioaccessibility analyses were performed by simulating the human digestion process in vitro (Unified BARGE Method). Detailed analysis of oral bioaccessible fraction (BAF i.e. ratio of bioaccessible concentrations to total concentrations on <250 µm fraction) indicated BAF of As (5-33%), Cd (72-98%), Co (24-42%), Cr (3-11%), Cu (25-90%), Ni (17-60%), Pb (16-88%) and Zn (73-94%). The solid phase distribution and mineralogical analyses showed that the variation of BAF is attributed to presence of alkaline calcareous rocks and association of PTE with a variety of minerals. The HHRA for ingestion pathway, suggested that bioaccessibility-corrected cancer risk reached up to 2.7 × 10-5 and 0.55 × 10-5 for residential and recreational senarios respectively (acceptable level is 1 × 10-5). The hazard index (HI) recalculated after incorporation of oral bioaccessible concentrations for a residential scenario ranged from 0.02 to 17.9. This was above the acceptable level (>1) for 50% of the samples, indicating potential human health risks. This study provides information for site-specific risk assessments and planning future research.

Linking oral bioaccessibility and solid phase distribution of potentially toxic elements in extractive waste and soil from an abandoned mine site: Case study in Campello Monti, NW Italy.

Oral bioaccessibility and solid phase distribution of potentially toxic elements (PTE) from extractive waste streams were investigated to assess the potential human health risk posed by abandoned mines. The solid phase distribution along with micro-X-ray fluorescence (micro-XRF) and scanning electron microscopy (SEM) analysis were also performed. The results showed that the total concentrations of PTE were higher in <250 µm size fractions of waste rock and soil samples in comparison to the <2 mm size fractions. Mean value of total concentrations of chromium(Cr), copper (Cu), and nickel (Ni) in waste rocks (size fractions <250 µm) were found to be 1299, 1570, and 4010 mg/kg respectively due to the parent material. However, only 11% of Ni in this sample was orally bioaccessible. Detailed analysis of the oral bioaccessible fraction (BAF, reported as the ratio of highest bioaccessible concentration compared with the total concentration from the 250 µm fraction) across all samples showed that Cr, Cu, and Ni varied from 1 to 6%, 14 to 47%, and 5 to 21%, respectively. The variation can be attributed to the difference in pH, organic matter content and mineralogical composition of the samples. Non-specific sequential extraction showed that the non-mobile forms of PTE were associated with the clay and Fe oxide components of the environmental matrices. The present study demonstrates how oral bioaccessibility, solid phase distribution and mineralogical analysis can provide insights into the distribution, fate and behaviour of PTE in waste streams from abandoned mine sites and inform human health risk posed by such sites .

Evidence for co-selection of antibiotic resistance genes and mobile genetic elements in metal polluted urban soils.

Antibiotic resistance genes (ARGs) constitute emerging environmental pollutants and pose risks to public health. Toxic metals are known to select for metal-resistant bacteria in metal-contaminated soils, but there is growing concern that metal contaminants can also act as co-selective agents thereby causing environmental proliferation of antibiotic resistance. In this study, we quantified ARGs and selected mobile genetic elements (MGEs) known to constitute potential ARG hosts in 50 archived urban and suburban soils from the Belfast metropolitan area using a high-throughput qPCR ARG chip. ARG prevalence was linked to concentrations of individual metals and a soil metal toxicity index calculated based on the relative toxicity of different metals to soil microbial processes. A total of 164 ARGs were detected across the 50 soils analyzed with an average absolute abundance of 3.4 × 107 ARG gene copies per gram of soil. A significant correlation between abundance of ARGs and MGEs was observed, suggesting the importance of horizontal gene transfer for ARG dissemination. Network analysis revealed significant co-occurrence patterns between specific metals (As, Cd, Co, Cr, Cu. Hg, Ni and Zn) and associated ARGs. Path analysis further indicated that the soil metal toxicity index significantly affected the number of detected ARGs (λ = 0.32, P < 0.001) and the abundance of metal co-occurring ARGs (λ = 0.612, P < 0.001) via effects on MGEs. Collectively, our results indicate a role of soil metals in co-selection of ARGs and MGEs in urban and semi-urban soils and suggest a risk for environmental ARG dissemination via horizontal gene transfer.

Bioelectro-Fenton: A sustainable integrated process for removal of organic pollutants from water: Application to mineralization of metoprolol.

The relevant environmental hazard related to the presence of pharmaceuticals in water sources requires the development of high effective and suitable wastewater treatment technologies. In the present work, a hybrid process coupling electro-Fenton (EF) process and aerobic biological treatment (Bio-EF process) was implemented for the efficient and cost-effective mineralization of beta-blocker metoprolol (MPTL) aqueous solutions. Firstly, operating factors influencing EF process were assessed. MTPL solutions were completely mineralized after 4h-electrolysis under optimal operating conditions and BDD anode demonstrated its oxidation superiority. The absolute rate constant of MTPL oxidation byOH (kMTPL) was determined by the competition kinetics method and found to be (1.72±0.04)×10(9)M(-1)s(-1). A reaction pathway for the mineralization of the drug was proposed based on the identification of oxidation by-products. Secondly, EF process was used as pre-treatment. An increase of BOD5/COD ratio from 0.012 to 0.44 was obtained after 1h EF treatment, along with 47% TOC removal and a significant decrease of toxicity, demonstrating the feasibility of a post-biological treatment. Finally, biological treatment successfully oxidized 43% of the total TOC content. An overall 90% mineralization of MPTL solutions was achieved by the Bio-EF process, demonstrating its potentiality for treating wastewater containing pharmaceutical residues.