Mechanisms of arsenite (As(III)) fixation regulated by jarosite biomineralization induced by Acidithiobacillus ferrooxidans

Abstract

Jarosite, a common mineral in acid mine drainage (AMD), influences arsenic mobility, yet its role in arsenite (As(III)) transport remains unclear. This study investigated biogenic jarosite formation and intermediate-phase transformation in an Fe(II)-As(III)-SO₄²⁻ environment using Acidithiobacillus ferrooxidans (Fe(II), 160 mmol/L; As(III), 10 − 200 mg/L). The results show that the bacteria first facilitated the crystallization of an As-rich schwertmannite precursor by oxidizing Fe(II) to Fe(III), and then drove its transformation into jarosite as pH declined. Combined analysis of XRD, FTIR, SEM, and elemental composition showed that Fe(III) and As(III) coprecipitated into biogenic jarosite with substituted arsenic. After 72 h, the highest arsenic fixed efficiency, about 60%, was achieved at initial pH 3.0. XPS results showed that As(III) was the main arsenic species on the surface of the intermediate schwertmannite phase. A threestage mechanism governed the process: microbial Fe(II) oxidation initiated As-rich schwertmannite formation, enabling rapid As(III) sequestration at pH>2.5; declining pH triggered jarosite nucleation on schwertmannite surfaces (transitional phase); and sustained acidity completed transformation to jarosite, partially remobilizing As(III) via schwertmannite dissolution. Regulation of pH and competing anions (e.g., phosphate, nitrate) is essential to optimize sequestration and stability during mineral transformation.

Keywords

biogenic jarosite / coprecipitation / arsenite / acid mine drainage / migration

References

[1] Asta M P, Ayora C, Román-ross G, et al. Natural attenuation of arsenic in the Tinto Santa Rosa acid stream (Iberian Pyritic Belt, SW Spain): The role of iron precipitates [J]. Chemical Geology, 2010, 2711–2112.

[2] Chen G, Ye Y, Yao N, et al. A critical review of prevention, treatment, reuse, and resource recovery from acid mine drainage [J]. Journal of Cleaner Production, 2021, 329: 129666.

[3] Sun J, Tang C, Wu P, et al. Migration of Cu, Zn, Cd and as in epikarst water affected by acid mine drainage at a coalfield basin, Xingren, Southwest China [J]. Environmental Earth Sciences, 2013, 69826232632.

[4] Paikaray S. Arsenic Geochemistry of acid mine drainage [J]. Mine Water Environ., 2015, 34: 181-196.

[5] Maillot F, Morin G, Juillot F, et al. Structure and reactivity of As(III)-and As(V)-rich schwertmannites and amorphous ferric arsenate sulfate from the Carnoulès acid mine drainage, France: Comparison with biotic and abiotic model compounds and implications for as remediation [J]. Geochimica et Cosmochimica Acta, 2013, 104: 310-329.

[6] Garelick H, Jones H, Dybowska A, et al. Arsenic pollution sources [M]. Reviews of Environmental Contamination Volume 197, 2008, New York, NY: Springer New York, 17-60

[7] Li X, Wu P. Geochemical characteristics of dissolved rare earth elements in acid mine drainage from abandoned high-As coal mining area, southwestern China [J]. Environmental Science and Pollution Research, 2017, 24252054020555.

[8] Gemici Ü. Evaluation of the water quality related to the acid mine drainage of an abandoned mercury mine (Alaşehir, Turkey) [J]. Environmental Monitoring and Assessment, 2008, 147193106.

[9] Casiot C, Morin G, Juillot F, et al. Bacterial immobilization and oxidation of arsenic in acid mine drainage (Carnoulès creek, France) [J]. Water Research, 2003, 371229292936.

[10] Shi M, Min X, Ke Y, et al. Recent progress in understanding the mechanism of heavy metals retention by iron (oxyhydr)oxides [J]. Science of the Total Environment, 2021, 752: 141930.

[11] Halder D, Lin J, Essilfie-Dughan J, et al. Implications of the iron(II/III)-arsenic ratio on the precipitation of iron-arsenic minerals from pH 2.5 to 10.5 [J]. Applied Geochemistry, 2018, 98: 367-376.

[12] Nishimura T, Robins R G. Confirmation that tooeleite is a ferric arsenite sulfate hydrate, and is relevant to arsenic stabilisation [J]. Minerals Engineering, 2008, 214246251.

[13] Egal M, Casiot C, Morin G, et al. Kinetic control on the formation of tooeleite, schwertmannite and jarosite by Acidithiobacillus ferrooxidans strains in an As(III)-rich acid mine water [J]. Chemical Geology, 2009, 2653–4432441.

[14] Tanaka M, Sasaki K, Okibe N. Behavior of sulfate ions during biogenic scorodite crystallization from dilute As (III)-bearing acidic waters [J]. Hydrometallurgy, 2018, 180: 144-152.

[15] Song Y, Luo H, Yang J, et al. Effects of pH on coprecipitation of As(III) with biogenic synthesized schwertmannite and jarosite [J]. Environmental Technology, 2025, 461016001611.

[16] Ahoranta S H, Kokko M E, Papirio S, et al. Arsenic removal from acidic solutions with biogenic ferric precipitates [J]. Journal of Hazardous Materials, 2016, 306: 124-132.

[17] Sánchez-españa J, Yusta I, López G A. Schwertmannite to jarosite conversion in the water column of an acidic mine pit lake [J]. Mineralogical Magazine, 2012, 76726592682.

[18] Chen H, Zhang D, Li Q, et al. Release and fate of as mobilized via bio-oxidation of arsenopyrite in acid mine drainage: Importance of As/Fe/S speciation and As (III) immobilization [J]. Water Research, 2022, 223: 118957.

[19] Cheng H, Hu Y, Luo J, et al. Geochemical processes controlling fate and transport of arsenic in acid mine drainage (AMD) and natural systems [J]. Journal of Hazardous Materials, 2009, 1651–31326.

[20] Wang X, Li Q, Liao Q, et al. Arsenic(III) biotransformation to tooeleite associated with the oxidation of Fe(II) via Acidithiobacillus ferrooxidans [J]. Chemosphere, 2020, 248: 126080.

[21] Burton E D, Karimian N, Johnston S G, et al. Arsenic-imposed effects on schwertmannite and jarosite formation in acid mine drainage and coupled impacts on arsenic mobility [J]. ACS Earth and Space Chemistry, 2021, 5614181435.

[22] Cruz-hernández P, Carrero S, Pérez-lópez R, et al. Influence of As(V) on precipitation and transformation of schwertmannite in acid mine drainage-impacted waters [J]. European Journal of Mineralogy, 2019, 312237245.

[23] Fukushi K, Sasaki M, Sato T, et al. A natural attenuation of arsenic in drainage from an abandoned arsenic mine dump [J]. Applied Geochemistry, 2003, 18812671278.

[24] Regenspurg S, Peiffer S. Arsenate and chromate incorporation in schwertmannite [J]. Applied Geochemistry, 2005, 20612261239.

[25] Wang Y, Gao M, Huang W, et al. Effects of extreme pH conditions on the stability of As(V)-bearing schwertmannite [J]. Chemosphere, 2020, 251: 126427.

[26] Song J, Jia S Y, Ren H T, et al. Application of a high-surface-area schwertmannite in the removal of arsenate and arsenite [J]. International Journal of Environmental Science and Technology, 2015, 12515591568.

[27] Paikaray S, Göttlicher J, Peiffer S. Removal of As(III) from acidic waters using schwertmannite: Surface speciation and effect of synthesis pathway [J]. Chemical Geology, 2011, 2833–4134142.

[28] Song Y, Zhang J, Wang H. Initial pH and K⁺ concentrations jointly determine the types of biogenic ferric hydroxysulfate minerals and their effect on adsorption removal of Cr(VI) in simulated acid mine drainage [J]. Water Science and Technology, 2018, 781021832192.

[29] Karimian N, Johnston S G, Burton E D. Antimony and arsenic partitioning during Fe²⁺-induced transformation of jarosite under acidic conditions [J]. Chemosphere, 2018, 195: 515-523.

[30] Kumar S V, Manna S, Kumar B J, et al. Recovery of residual metals from jarosite waste using chemical and biochemical processes to achieve sustainability: A state-of-the-art review [J]. Journal of Environmental Management, 2023, 343: 118221.

[31] Li H, Wang N, Xiao T, et al. Sorption of arsenate(V) to naturally occurring secondary iron minerals formed at different conditions: The relationship between sorption behavior and surface structure [J]. Chemosphere, 2021, 285: 131525.

[32] Asta M P, Cama J, Martínez M, et al. Arsenic removal by goethite and jarosite in acidic conditions and its environmental implications [J]. Journal of Hazardous Materials, 2009, 1711–3965972.

[33] Jhariya U, Chien M, Umetsu M, et al. Effective selenate removal using pH modulated synthesis of biogenic jarosite: Comparative insight with non-biogenic jarosite and biogenic schwertmannite [J]. Journal of Hazardous Materials, 2024, 480: 136256.

[34] Duquesne K, Lebrun S, Casiot C, et al. Immobilization of arsenite and ferric iron by Acidithiobacillus ferrooxidans and its relevance to acid mine drainage [J]. Applied and Environmental Microbiology, 2003, 691061656173.

[35] Kim Y. Effects of different oxyanions in solution on the precipitation of jarosite at room temperature [J]. Journal of Hazardous Materials, 2018, 353: 118-126.

[36] Kamde K, Pandey R A, Thul S T, et al. Microbially assisted arsenic removal using Acidithiobacillus ferrooxidans mediated by iron oxidation [J]. Environmental Technology & Innovation, 2018, 10: 78-90.

[37] Piervandi Z, Khodadadi D A, Mousavi S M, et al. Effect of biogenic jarosite on the bio-immobilization of toxic elements from sulfide tailings [J]. Chemosphere, 2020, 258: 127288.

[38] Feng K, Wang X, Ding B, et al. Acidithiobacillus ferrooxidans mediates morphology evolution of schwertmannite in the presence of Fe²⁺ [J]. Chemical Geology, 2022, 598: 120828.

[39] Yu S, Yang B, Fang C, et al. Dissolution mechanism of the oxidation process of covellite by ferric and ferrous ions [J]. Hydrometallurgy, 2021, 201: 105585.

[40] Bai S, Xu Z, Wang M, et al. Both initial concentrations of Fe(II) and monovalent cations jointly determine the formation of biogenic iron hydroxysulfate precipitates in acidic sulfate-rich environments [J]. Materials Science and Engineering: C, 2012, 32823232329.

[41] Mukherjee C, Jones F S, Bigham J M, et al. Synthesis of argentojarosite with simulated bioleaching solutions produced by Acidithiobacillus ferrooxidans [J]. Materials Science & Engineering C, Materials for Biological Applications, 2016, 66: 164-169.

[42] Yan S, Zheng G, Meng X, et al. Assessment of catalytic activities of selected iron hydroxysulphates biosynthesized using Acidithiobacillus ferrooxidans for the degradation of phenol in heterogeneous Fenton-like reactions [J]. Separation and Purification Technology, 2017, 185: 83-93.

[43] Deng Y, Zhang Q, Zhang Q, et al. Arsenate removal from underground water by polystyrene-confined hydrated ferric oxide (HFO) nanoparticles: Effect of humic acid [J]. Environmental Science and Pollution Research, 2020, 27768616871.

[44] Chang C, Wei C C, Lin L H, et al. Humic acids enhance the microbially mediated release of sedimentary ferrous iron [J]. Environmental Science and Pollution Research, 2016, 23541764184.

[45] Dou X, Mohan D, Pittman C U. Arsenate adsorption on three types of granular schwertmannite [J]. Water Research, 2013, 47929382948.

[46] Jeong Y, Fan M, Van L J, et al. Effect of competing solutes on arsenic(V) adsorption using iron and aluminum oxides [J]. Journal of Environmental Sciences, 2007, 198910919.

[47] Zhou S, Gan M, Wang X, et al. ROS formation driven by pyrite-mediated arsenopyrite oxidation and its potential role on arsenic transformation [J]. Journal of Hazardous Materials, 2023, 443: 130151. Pt A

[48] Tamura H, Goto K, Yotsuyanagi T, et al. Spectrophotometric determination of iron(II) with 1, 10-phenanthroline in the presence of large amounts of iron(III) [J]. Talanta, 1974, 214314318.

[49] Uddin A H, Khalid R S, Alaama M, et al. Comparative study of three digestion methods for elemental analysis in traditional medicine products using atomic absorption spectrometry [J]. Journal of Analytical Science and Technology, 2016, 716.

[50] Shirley D A. High-resolution X-ray photoemission spectrum of the valence bands of gold [J]. Physical Review B, 1972, 51247094714.

[51] Morin G, Juillot F, Casiot C, et al. Bacterial formation of tooeleite and mixed arsenic(III) or arsenic(V)-iron(III) gels in the carnoulès acid mine drainage, France. a XANES, XRD, and SEM study [J]. Environmental Science & Technology, 2003, 37917051712.

[52] Liu H, Lu X, Zhang L, et al. Collaborative effects of Acidithiobacillus ferrooxidans and ferrous ions on the oxidation of chalcopyrite [J]. Chemical Geology, 2018, 493: 109-120.

[53] Jönsson J, Persson P, Sjöberg S, et al. Schwertmannite precipitated from acid mine drainage: Phase transformation, sulphate release and surface properties [J]. Applied Geochemistry, 2005, 201179191.

[54] Paikaray S, Göttlicher J, Peiffer S. As(III) retention kinetics, equilibrium and redox stability on biosynthesized schwertmannite and its fate and control on schwertmannite stability on acidic (pH 3.0) aqueous exposure [J]. Chemosphere, 2012, 866557564.

[55] Tabelin C B, Corpuz R D, Igarashi T, et al. Hematite-catalysed scorodite formation as a novel arsenic immobilisation strategy under ambient conditions [J]. Chemosphere, 2019, 233: 946-953.

[56] Di I E, Cho H G, Liu Y, et al. Arsenate retention mechanisms on hematite with different morphologies evaluated using AFM, TEM measurements and vibrational spectroscopy [J]. Geochimica et Cosmochimica Acta, 2018, 237: 155-170.

[57] Savage K S, Bird D K, O’day P A. Arsenic speciation in synthetic jarosite [J]. Chemical Geology, 2005, 2151–4473498.

[58] Zhu J, Gan M, Zhang D, et al. The nature of Schwertmannite and Jarosite mediated by two strains of Acidithiobacillus ferrooxidans with different ferrous oxidation ability [J]. Materials Science and Engineering: C, 2013, 33526792685.

[59] Johnston S G, Burton E D, Keene A F, et al. Arsenic mobilization and iron transformations during sulfidization of As(V)-bearing jarosite [J]. Chemical Geology, 2012, 334: 9-24.

[60] Bigham J M, Schwertmann U, Traina S J, et al. Schwertmannite and the chemical modeling of iron in acid sulfate waters [J]. Geochimica et Cosmochimica Acta, 1996, 601221112121.

[61] Liao Y, Liang J, Zhou L. Adsorptive removal of As(III) by biogenic schwertmannite from simulated As-contaminated groundwater [J]. Chemosphere, 2011, 833295301.

[62] Sharma P, Ofner J, Kappler A. Formation of binary and ternary colloids and dissolved complexes of organic matter, Fe and as [J]. Environmental Science & Technology, 2010, 441244794485.

[63] Liu G, Fernandez A, Cai Y. Complexation of arsenite with humic acid in the presence of ferric iron [J]. Environmental Science & Technology, 2011, 45832103216.

[64] Kim E J, Hwang B R, Baek K. Effects of natural organic matter on the coprecipitation of arsenic with iron [J]. Environmental Geochemistry and Health, 2015, 37610291039.

[65] Xue Q, Ran Y, Tan Y, et al. Arsenite and arsenate binding to ferrihydrite organo-mineral coprecipitate: Implications for arsenic mobility and fate in natural environments [J]. Chemosphere, 2019, 224: 103-110.

[66] Vithana C L, Sullivan L A, Burton E D, et al. Liberation of acidity and arsenic from schwertmannite: Effect of fulvic acid [J]. Chemical Geology, 2014, 372: 1-11.

[67] Kong Y, Kang J, Shen J, et al. Influence of humic acid on the removal of arsenate and arsenic by ferric chloride: Effects of pH, As/Fe ratio, initial as concentration, and co-existing solutes [J]. Environmental Science and Pollution Research, 2017, 24323812393.

[68] Eftekhari N, Kargar M, Zamin F, et al. A review on various aspects of jarosite and its utilization potentials [J]. Annales de Chimie-Science des Matériaux, 2020, 4414352.

[69] Burton E D, Bush R T, Johnston S G, et al. Sorption of arsenic(V) and arsenic(III) to schwertmannite [J]. Environmental Science & Technology, 2009, 432492029207.

Rights & permissions

Central South University