Pumping groundwater from arsenic (As)-contaminated aquifers exposes millions of people, especially those in developing countries, to high doses of the toxic contaminant. Previous studies have investigated cost-effective techniques to remove groundwater arsenic by stimulating sulfate-reducing bacteria (SRB) to form biogenic arsenian pyrite. This study intends to improve upon these past methods to demonstrate the effectiveness of SRB arsenic remediation at an industrial site in Florida. This study developed a ferrous sulfate and molasses mixture to sequester groundwater arsenic in arsenian pyrite over nine months. The optimal dosage of the remediating mixture consisted of 5 kg of ferrous sulfate, ~27 kg (60 lbs) of molasses, and ~1 kg (2 lbs) of fertilizer per 3785.4 L (1000 gallons) of water. The remediating mixture was injected into 11 wells hydrologically upgradient of the arsenic plume in an attempt to obtain full-scale remediation. Groundwater samples and precipitated biominerals were collected from June 2018 to March 2019. X-ray diffraction (XRD), X-ray fluorescence (XRF), electron microprobe (EMP), and scanning electron microscope (SEM) analyses determined that As has been sequestered mainly in the form of arsenian pyrite, which rapidly precipitated as euhedral crystals and spherical aggregates (framboids) 1–30 μm in diameter within two weeks of the injection. The analyses confirmed that the remediating mixture and injection scheme reduced As concentrations to near or below the site’s clean-up standard of 0.05 mg/L over the nine months. Moreover, the arsenian pyrite contained 0.03–0.89 weight percentage (wt%) of sequestered arsenic, with >80% of groundwater arsenic removed by SRB biomineralization. Considering these promising findings, the study is close to optimizing an affordable procedure for sequestrating dissolved As in industry settings.

Naturally occurring biogenic pyrite has been found in Holocene fluvial aquifers in the Uphapee watershed, Macon County, Alabama. The electron microprobe (EMP) analysis showed that the pyrite grains contain 0.20–0.92 weight% of arsenic (As). The scanning electron microscope and energy dispersive spectroscopy (SEM-EDS) analysis confirmed a similar concentration of As in the pyrite that was consistent with the EMP analysis. The SEM analysis also confirmed the presence of additional trace elements such as cobalt (0.19 wt.%), and nickel (0.15 wt.%), indicative of pyrite’s capacity to sequester As and other trace elements. Pyrite grains were naturally formed and developed as large (20–200 μm) euhedral (i.e., cube, octahedron) crystals and non-framboid aggregates. However, the inductively coupled plasma mass spectrometry (ICP-MS) analysis showed that the As concentration in the groundwater was not high, and it was within the EPA drinking water standard for As (10 µg/L). These results indicate that dissolved As is sequestered in naturally formed pyrite found in the fluvial sediments. The groundwater was moderately reducing to slightly oxidizing (Eh = 46 to173 mV), and nearly neutral to slightly acidic (pH = 5.53 to 6.51). Groundwater geochemistry data indicated a redox sequence of oxidation, denitrification, Mn(IV) reduction, Fe(III) reduction, and sulfate reduction along the flow path in the fluvial aquifer. The downgradient increases in dissolved Mn and then Fe concentrations reflect increased Mn(II) and Fe(II) production via microbial competition as the aquifer becomes progressively more reduced. Bacterial sulfate reduction seems to dominate near the end of the groundwater flow path, as the availability of Mn- and Fe-oxyhydroxides becomes limited in sediments rich in lignitic wood where increasing sulfate reduction leads to the formation of biogenic pyrite. The groundwater is a Ca-SO₄ type and is not SO₄ limited; thus, sulfate may serve as an electron acceptor for the bacterial sulfate-reducing reactions that sequester As into pyrite, which in turn results in very low groundwater As concentration (<2 µg/L).