Industrial byproducts for the soil stabilization of trace elements and per- and polyfluorinated alkyl substances (PFASs).

The present work was the first exploration of the use of industrial byproducts from iron and titanium processing as sorbents for the stabilization of soil contamination. The main aim was to test slag waste and iron-rich charred fossil coal ("Fe-char"), as sorbents for per- and polyfluorinated alkyl substances (PFASs), as well as lead (Pb) and antimony (Sb), in four soils from a firefighting training area (PFASs) and a shooting range (Pb and Sb). Adding slag (10-20%) to shooting range soils decreased the leaching of Pb and Sb up to 50-90%. Fe-char amendment to these soils resulted in a moderate reduction in Sb leaching (20-70%) and a slightly stronger effect on Pb (40-50%). The sorption is most likely explained by the presence of Fe oxyhydroxides. These are present in the highest concentrations in the slag, probably resulting in more effective metal binding to the slag than to the Fe-char. Fe-char but not slag proved to be a strong sorbent for PFASs (reducing PFAS leaching from the soil by up to 99.7%) in soil containing low total organic carbon (TOC; 1.2%) but not in high-TOC soil (34%). The sorption coefficient KD for Fe-char was high, in the range of 104.3 to 106.5 L/kg at 1 ng/L in the low-TOC soil. The KD value increased with increasing perfluorocarbon chain length, exceeding PFAS sorption to biochar in the low ng/L concentration range. This result indicates that the mechanism behind the strong PFAS sorption to Fe-char was mainly van der Waals dispersive interactions between the hydrophobic PFAS-chain and the aromatic π-electron systems on nanopore walls within the Fe-char matrix. Overall, this study indicates that industrial byproducts can provide sustainable and cost-effective materials for soil remediation. However, the sorbent needs to be tailored to the type of soil and type of contamination.

Can biochar and designer biochar be used to remediate per- and polyfluorinated alkyl substances (PFAS) and lead and antimony contaminated soils?

Designer biochars can be used to remediate organic and inorganic contaminant polluted soils. Here, a waste timber biochar (BC), a coconut shell activated biochar (aBC) and a wood shrub iron enriched designer biochar (Fe-BC) were investigated. Per- and polyfluorinated alkyl substances (PFAS) contaminated soils with different total organic carbon (TOC) contents (1.6 and 34.2%) were amended with six doses of BC and aBC. Two shooting range soils (TOC 5.2 and 10.2%) contaminated with heavy metals (mainly Pb and Sb) were amended with four doses of BC and Fe-BC. An amendment of 20% BC reduced the PFOS leachate concentration by 86% for the low TOC soil but was not effective for the high TOC soil. An amendment of 1% aBC reduced PFOS leachate concentrations by over >96% for both soils. For the low TOC shooting range soil, a 20% amendment of BC reduced Pb and Sb leaching by 61% and 12%, respectively. An amendment of 20% Fe-BC to soil with low TOC reduced Pb and Sb leaching by 99% and 40%, respectively. The need for "designer" biochars using processes such as iron enrichment or activation should be considered depending on the TOC of the soil, the type of contaminants and remediation goals.

Influence of electrode placement for mobilising and removing metals during electrodialytic remediation of metals from shooting range soil.

Electrodialytic remediation was applied to a shooting range soil to investigate the influence of electrode placement on the removal and binding of metals during the treatment. The set-up was based on a 2-compartment cell, in which the cathode was separated from the soil by a cation exchange membrane and the anode was placed directly in the soil, thereby introducing protons and oxygen directly in the soil. Mobilisation of metals from less available fractions (oxidisable and residual) in the soil occurred, due to oxidation/dissolution of insoluble/soluble organic matter and possibly metal oxides in the residual fraction. The transport via electromigration out of the soil and/or re-precipitation in other fractions of the soil (oxidisable, reducible, exchangeable) depended on the metal. More than 30% of the initial content of Mn, Cd, Cu, Pb and Zn and less than 20% of the initial content of Al, Fe, K, Mg, As, Cr and Ni was transported out of the soil. By decreasing the distance between the electrodes from 3.0 to 1.5 cm, the removal of the targeted metal for remediation, Pb, was improved by more than 200%, from 14 to 31%. A similar removal could be achieved in experiments with long distance between electrodes (3.0 cm) by increasing the current intensity from 4 to 10 mA and/or the remediation time from 7 to 35 d. The experiments showed that the design and optimisation of electrodialytic remediation depends on the targeted metal and metal partitioning.

Potential value of phosphate compounds in enhancing immobilization and reducing bioavailability of mixed heavy metal contaminants in shooting range soil.

Shooting range soils contain mixed heavy metal contaminants including lead (Pb), cadmium (Cd), and zinc (Zn). Phosphate (P) compounds have been used to immobilize these metals, particularly Pb, thereby reducing their bioavailability. However, research on immobilization of Pb's co-contaminants showed the relative importance of soluble and insoluble P compounds, which is critical in evaluating the overall success of in situ stabilization practice in the sustainable remediation of mixed heavy metal contaminated soils. Soluble synthetic P fertilizer (diammonium phosphate; DAP) and reactive (Sechura; SPR) and unreactive (Christmas Island; CPR) natural phosphate rocks (PR) were tested for Cd, Pb and Zn immobilization and later their mobility and bioavailability in a shooting range soil. The addition of P compounds resulted in the immobilization of Cd, Pb and Zn by 1.56-76.2%, 3.21-83.56%, and 2.31-74.6%, respectively. The reactive SPR significantly reduced Cd, Pb and Zn leaching while soluble DAP increased their leachate concentrations. The SPR reduced the bioaccumulation of Cd, Pb and Zn in earthworms by 7.13-23.4% and 14.3-54.6% in comparison with earthworms in the DAP and control treatment, respectively. Bioaccessible Cd, Pb and Zn concentrations as determined using a simplified bioaccessibility extraction test showed higher long-term stability of P-immobilized Pb and Zn than Cd. The differential effect of P-induced immobilization between P compounds and metals is due to the variation in the solubility characteristics of P compounds and nature of metal phosphate compounds formed. Therefore, Pb and Zn immobilization by P compounds is an effective long-term remediation strategy for mixed heavy metal contaminated soils.

Effects of lead mineralogy on soil washing enhanced by ferric salts as extracting and oxidizing agents.

In this study, we evaluated the feasibility of using ferric salts including FeCl3 and Fe(NO3)3 as extracting and oxidizing agents for a soil washing process to remediate Pb-contaminated soils. We treated various Pb minerals including PbO, PbCO3, Pb3(CO3)2(OH)2, PbSO4, PbS, and Pb5(PO4)3(OH) using ferric salts, and compared our results with those obtained using common washing agents of HCl, HNO3, disodium-ethylenediaminetetra-acetic acid (Na2-EDTA), and citric acid. The use of 50 mM Fe(NO3)3 extracted significantly more Pb (above 96% extraction) from Pb minerals except PbSO4 (below 55% extraction) compared to the other washing agents. In contrast, washing processes using FeCl3 and HCl were not effective for extraction from Pb minerals because of PbCl2 precipitation. Yet, the newly formed PbCl2 could be dissolved by subsequent wash with distilled water under acidic conditions. When applying our washing method to remediate field-contaminated soil from a shooting range that had high concentrations of Pb3(CO3)2(OH)2 and PbCO3, we extracted more Pb (approximately 99% extraction) from the soil using 100 mM Fe(NO3)3 than other washing agents at the same process conditions. Our results show that ferric salts can be alternative washing agents for Pb-contaminated soils in view of their extracting and oxidizing abilities.

Utilization of phosphorus loaded alkaline residue to immobilize lead in a shooting range soil.

The alkaline residue generated from the production of soda ash using the ammonia-soda method has been successfully used in removing phosphorus (P) from aqueous solution. But the accumulation of P-containing solid after P removal is an undesirable menace to the environment. To achieve the goal of recycling, this study explored the feasibility of reusing the P loaded alkaline residue as an amendment for immobilization of lead (Pb) in a shooting range soil. The main crystalline phase and micromorphology of amendments were determined using X-ray diffraction (XRD) and scanning electron microscopy-electron dispersion spectroscopy (SEM-EDS) methods. The toxicity characteristic leaching procedure (TCLP), sequential extraction procedure, and physiologically based extraction test (PBET) were employed to evaluate the effectiveness of Pb immobilization in soil after 45 d incubation. Treatment with P loaded alkaline residue was significantly effective in reducing the TCLP and PBET extractable Pb concentrations in contrast to the untreated soil. Moreover, a positive change in the distribution of Pb fractions was observed in the treated soil, i.e., more than 60% of soil-Pb was transformed to the residual fraction compared to the original soil. On the other hand, P loaded amendments also resulted in a drastic reduction in phytoavailable Pb to the winter wheat and a mild release of P as a nutrient in treated soil, which also confirmed the improvement of soil quality.

Antimony (Sb) and lead (Pb) in contaminated shooting range soils: Sb and Pb mobility and immobilization by iron based sorbents, a field study.

Small-arm shooting ranges often receive a significant input of lead (Pb), copper (Cu) and antimony (Sb) from ammunition. The goal of the present study was to investigate the mobility, distribution and speciation of Pb and Sb pollution under field conditions in both untreated and sorbent-amended shooting range soil. Elevated Sb (19-349µgL(-1)) and Pb (7-1495µgPbL(-1)) concentrations in the porewater of untreated soil over the four-year test period indicated a long-term Sb and Pb source to the adjacent environment in the absence of remedial measures. Mixing ferric oxyhydroxide powder (CFH-12) (2%) together with limestone (1%) into the soil resulted in an average decrease of Sb and Pb porewater concentrations of 66% and 97%, respectively. A similar reduction was achieved by adding 2% zerovalent iron (Fe°) to the soil. The remediation effect was stable over the four-year experimental period indicating no remobilization. Water- and 1M NH4NO3-extractable levels of Sb and Pb in field soil samples indicated significant immobilization by both treatments (89-90% for Sb and 89-99% for Pb). Results from sequential extraction analysis indicate fixation of Sb and Pb in less accessible fractions like amorphous iron oxides or even more crystalline and residual mineral phases, respectively. This work shows that amendment with Fe-based sorbents can be an effective method to reduce the mobility of metals both in cationic and anionic form in polluted shooting range soil.

Release of antimony from contaminated soil induced by redox changes.

Soil contamination by toxic antimony (Sb) released from corroding ammunition has become an issue of public concern in various countries. Many of these soils are at least occasionally subject to waterlogging; yet mechanisms controlling Sb mobility under anaerobic conditions are still poorly understood. We investigated Sb concentration and speciation dynamics in a calcareous shooting range soil in terms of changing redox conditions using microcosm experiments. The transition to reducing conditions invoked by indigenous microbial activity at first led to the immobilization of Sb, as Sb(V) was converted to Sb(III), which binds more extensively to iron (hydr)oxides. When reducing conditions continued, the previously sorbed Sb(III) was gradually released into solution due to reductive dissolution of the iron (hydr)oxides. Speciation measurements in the solid phase by Sb K-edge XANES spectroscopy and in the soil solution by liquid chromatography ICP-MS provided the first evidence that Sb(III) predominated at low redox conditions (Eh <0.05 V) in both phases. The results show that Sb(V) is less stable in reducing environments than commonly assumed. Given that Sb(III) is generally more toxic than Sb(V), the mobilization of Sb(III) under Fe-reducing conditions may significantly increase (eco)toxicological risks arising from Sb-contaminated soils that are prone to flooding or waterlogging.