Iron sulphides mediated autotrophic denitrification: An emerging bioprocess for nitrate pollution mitigation and sustainable wastewater treatment.

Iron sulphides, mainly in the form of mackinawite (FeS), pyrrhotite (Fe1-xS, x = 0-0.125) and pyrite (FeS2), are the most abundant sulphide minerals and can be oxidized under anoxic and circumneutral pH conditions by chemoautotrophic denitrifying bacteria to reduce nitrate to N2. Iron sulphides mediated autotrophic denitrification (ISAD) represents an important natural attenuation process of nitrate pollution and plays a pivotal role in linking nitrogen, sulphur and iron cycles in a variety of anoxic environments. Recently, it has emerged as a promising bioprocess for nutrient removal from various organic-deficient water and wastewater, due to its specific advantages including high denitrification capacity, simultaneous nitrogen and phosphorus removal, self-buffering properties, and fewer by-products generation (sulphate, waste sludge, N2O, NH4+, etc.). This paper provides a critical overview of fundamental and engineering aspects of ISAD, including the theoretical knowledge (biochemistry, and microbial diversity), its natural occurrence and engineering applications. Its potential and limitations are elucidated by summarizing the key influencing factors including availability of iron sulphides, low denitrification rates, sulphate emission and leaching heavy metals. This review also put forward two key questions in the mechanism of anoxic iron sulphides oxidation, i.e. dissolution of iron sulphides and direct substrates for denitrifiers. Finally, its prospects for future sustainable wastewater treatment are highlighted. An iron sulphides-based biotechnology towards next-generation wastewater treatment (NEO-GREEN) is proposed, which can potentially harness bioenergy in wastewater, incorporate resources (P and Fe) recovery, achieve simultaneous nutrient and emerging contaminants removal, and minimize waste sludge production.