Novel Electron Donors for Anaerobic Remediation of Acid Rock Drainage

Abstract

We initially studied the treatment of acid rock drainage using a sulfate-reducing bioreactor with zero-valent iron as the electron donor. The results demonstrate that this electron donor can serve as the sole exogenous slow-release electron donor to drive sulfate reduction over 400 operational days at short HRTs (1-3 days). The synthetic acid rock drainage contained high heavy metal concentrations (up to 50 mg/L of copper) and pH values ranging from 3.0 to 7.0. Treatment of this acid rock drainage efficiently removed Cu, Cd and Pb (>99.7%) and increased pH to circumneutral values (7.3-7.7). Elemental analysis indicated that formation of insoluble metal sulfides was responsible for the effective metal removal in the zero valent iron columns. In the second study, three inoculated columns containing anaerobic granular sludge were fed a synthetic medium containing H₂SO₄ and Cu²⁺ during the experimental period of 4 months. Algae biomass promoted 80% of sulfate removal (12.7 mg SO₄²⁻ d-1), enabling near complete Cu removal (>99.5 %), and alkalinity generation, raising the effluent pH to 6.5. In the algae amended columns Cu²⁺ was precipitated with biogenic H2S produced by sulfate reduction. Whole cell algae and lipid extracted algae biomasses were both shown to be effective e-donors in driving sulfate reduction of ARD, thus enabling the precipitation and removal of Cu²⁺. The precipitate retained in the columns was composed mostly of insoluble copper sulfide formed from the biogenic sulfide, as shown by sequential extraction and X-ray diffraction. In the third study, several pretreatments, i.e., thermal, chemical, sonication and combinations thereof, that enhance anaerobic biodegradability of Chlorella protothecoides biomass were evaluated. The results demonstrate that anaerobic digestion of pretreated Chlorella protothecoides biomass generates energy-rich methane and recovers nitrogen nutrients. Sonication of algal biomass under optimized conditions provided a significant increase in the methane yield (327 mL STP CH₄ g⁻¹ VS) compared to untreated algae (146 mL STP CH₄ g⁻¹ VS), as demonstrated in anaerobic digestion experiments incubated for 41 days. In contrast, thermal pretreatment provided only a moderate increase of the methane yield and alkaline treatment led to a decrease of the methane yield compared to the untreated algal biomass. Additionally, sonication treatment provided a 4.1-fold increase in the release of ammonia nitrogen during anaerobic digestion of the algal biomass. In the fourth study, the nutrient recovery and biogas generation from the anaerobic digestion of waste biomass from algal biofuel production was investigated. Anaerobic digestion of whole cell and lipid extracted Chlorella sorokiniana-1412 released 48.1 and 61.5% of the total algal nitrogen as NH₄⁺-N, and 87.7 and 93.6% of the total algal P as soluble P, respectively. The biochemical methane potential, quantified through the methane yield of whole cell algae and lipid extracted algae, was 0.298 and 0.253 L methane/g algal volatile solids, respectively. The conversion of lipid extracted algae and whole cell algae biomasses to methane was very similar (38 and 41% on a COD basis, respectively), indicating that the energy yield was not significantly lowered by extraction of the lipid fraction (which accounted for 9% of algal dry weight). Sonication improved the access of hydrolytic enzymes to algal biopolymers, compensating in part for the energy lost due to lipid extraction. The above results demonstrate that algal waste from the biodiesel industry has the potential to be recycled through anaerobic digestion into valuable nutrients and energy. These studies indicate that zero valent iron and algae biomass are promising reactive materials for the treatment of acid rock drainage in sulfate-reducing permeable reactive barrier systems. Additionally, to promote algae cultivation for the biodiesel industry, the anaerobic digestion of algae residues can generate nutrients and energy, making algae cultivation more fiscally attractive.