Modeling phytoremediation of aged soil Ni from anthropogenic deposition using Alyssum murale.

Several field-scale phytoextraction scenarios were created in a greenhouse study to investigate the feasibility of using Alyssum murale, to remediate three types of industrially Ni-contaminated soil (heavy clay, sand, organic muck) from Port Colborne, Ontario. The observed distribution of Ni mass between soil and aboveground vegetation was used in STELLA modeling software to predict timelines for the target soil Ni concentration, namely 1200 mg Ni/kg. Alyssum murale grown in sand would have a relatively constant pool of Ni available for plant uptake, which would not be the case for plants grown in organic muck and heavy clay. The maximum Ni extraction (%, plant Ni mass/soil Ni mass) was achieved in A. murale grown in unfertilized clay soil at the higher irrigation rate. Using these data, the STELLA model predicted that 246 years would be required to reduce soil Ni concentration in the most efficient combination of treatments to the remediation target. In addition, hypothetical A. murale Ni extraction in plant-soil systems optimized by manipulating soil chemistry and physical attributes, were modeled. The most optimized A. murale plant-soil systems for Ni extraction would require 9 years to achieve the same reduction, and it is not clear that this optimization can be achieved in the field. This study showed that phytoremediation using A. murale is not likely a time-sensitive approach for these soils.

Towards an exposure narrative for metals and arsenic in historically contaminated Ni refinery soils: Relationships between speciation, bioavailability, and bioaccessibility.

Archived soils contaminated with Ni, Cu, Co, and As from legacy operations of a nickel refinery at Port Colborne, Ontario, Canada were speciated using mineral liberation analysis. Four Ni minerals were identified as fingerprint compounds of the historical refinery emissions. Cu and Co were present in solid solution in these minerals due to their presence in the refinery's feed. The highest concentrations of Ni, Cu, Co, and As in these soils were 18,553, 1915, 196, and 79mg/kg, respectively, these elevated contaminant concentrations attesting to the importance of incidental soil ingestion to the oral exposure pathway in Port Colborne. The in vitro gastric bioaccessibility (BAc) was determined for these contaminants, as was in vivo oral bioavailability (BAv), using a mass balance approach in male Sprague-Dawley rats. In spite of the elevated soil concentrations of Cu, the BAv of this physiologically important metal could not be distinguished from that in commercial rat chow, suggesting low potential for exposure. Co and As also had low apparent BAv (<2%). For Ni, baseline oral BAv of naturally sourced dietary Ni was found to be approximately 2%, as was the oral BAv of Ni from nickel sulfate hexahydrate. The mass balances of NiSO4·6H2O were fully accounted-for in urine and feces after a single gavage dose, indicating little to no organ incorporation from this highly soluble salt. Therefore, the urinary estimates of Ni BAv for these soils were assumed to represent true BAv despite variable fecal recoveries. The high Ni concentrations enabled BAc-BAv relationships to be developed for these contaminated soils. For absolute bioavailability (ABA) and relative bioavailability (RBA) the relationships were: ABA=0.0116(BAc)-0.0479 and RBA=0.5542(BAc)-2.2817. These findings will advance the development of robust exposure narratives for soil metal contamination in Port Colborne and elsewhere.