Combined Еffects of Heavy Metal Ions (Fe3+-Cu2+, Fe3+-Zn2+, Fe3+-Cr3+, Cu2+-Zn2+, Cu2+-Cr3+ and Zn2+-Cr3+) on the Productivity of Biogas and Biomethane Production

Authors

DOI:

https://doi.org/10.20535/ibb.2026.10.1.354790

Keywords:

heavy metal, Iron, Zinc, Copper, Сhromium, biogas, biomethane

Abstract

Abstract. Background. Determining the effect of combined metal action on the anaerobic microbial association during the fermentation process and methane production.

Objective. To investigate the effect of the simultaneous interaction of heavy metal ions (Zn–Fe, Zn–Cu, Zn–Cr, Fe–Cu, Fe–Cr, Cu–Cr) on the process of biogas production and methane formation in it.

Methods. A laboratory study performed under conditions approximating industrial biogas production, involving the application of heavy-metal-ion salts and the measurement of the quantitative and qualitative composition of the final product.

Results. The combined effect of two heavy-metal ions on biogas production by an anaerobic microbial association is specific: the synergy of certain metal ions may stimulate the biosynthesis of biomethane while simultaneously inhibit-ing biogas production. In particular, Fe (20 mg/dm³) – Cu (40 mg/dm³) and Fe (20 mg/dm³) – Cr (10 mg/dm³) exhibit a slight positive effect on biogas yield compared to the control, whereas the interaction of these metal ions with Zn (5 mg/dm³) reduces the biogas yield but improves its qualitative composition — the methane content increases.

Conclusions. The combined effect of two heavy-metal ions generally reduces biogas production compared to the con-trol; however, it stimulates the production of a higher methane content in the biogas. Compared with the effect of a sin-gle heavy metal, the combined exposure does not have a positive impact on biogas production, which is attributed to the elevated concentrations of metal ions used in the experiment.

References

Datsko O, Zakharchenko E, Butenko Y, Melnyk O, Kovalenko I, Onychko V, et al. Ecological Assessment of Heavy Metal Content in Ukrainian Soils. Journal of Ecological Engineering. 2024;25(11):100-8. DOI: 10.12911/22998993/192669.

Martynova N, Kolombar T. Phytoremediation technologies promising for the restoration of agricultural lands damaged by military actions. Regulatory Mechanisms in Biosystems. 2025;16(3):e25155. DOI: 10.15421/0225155

Wall DM, O’Shea R. Biogas Systems in Industry: An analysis of sectoral usage, sustainability, logistics and technology development. IEA Bioenergy: Task 37, 2025.

Darmey J, Narra S, Achaw O-W, Stinner W, Ahiekpor JC, Ansah HF, et al. A Review of Pretreatment Strategies for Anaerobic Digestion: Unlocking the Biogas Generation Potential of Wastes in Ghana. Waste. 2025;3(3):24. DOI: 10.3390/waste3030024

Ayantokun AS, Matambo TS, Rashama C, Van der Merwe I, Van Niekerk JA. A critical review of food waste and poultry manure anaerobic co-digestion: an eco-friendly valorization for sustainable waste management and biogas production. Frontiers in Sustainable Food Systems. 2025;9:1695945. DOI: 10.3389/fsufs.2025.1695945

Neri A, Bernardi B, Zimbalatti G, Benalia S. An Overview of Anaerobic Digestion of Agricultural By-Products and Food Waste for Biomethane Production. Energies. 2023;16(19):6851. DOI: 10.3390/en16196851

Razanov S, Alieksieiev O, Alieksieieva O, Vradii O, Mazur K, Puyu V, et al. The Content of Heavy Metals and Trace Elements in Different Soils Used under the Conditions of Homestead Plots and Field Agricultural Lands of Ukraine. Journal of Ecological Engineering. 2024;25(6):42-50. DOI: 10.12911/22998993/186820

Kadam R, Jo S, Lee J, Khanthong K, Jang H, Park J. A Review on the Anaerobic Co-Digestion of Livestock Manures in the Context of Sustainable Waste Management. Energies. 2024;17(3):546. DOI: 10.3390/en17030546

Wang K, Yun S, Xing T, Li B, Abbas Y, Liu X. Binary and ternary trace elements to enhance anaerobic digestion of cattle manure: Focusing on kinetic models for biogas production and digestate utilization. Bioresource Technology. 2021;323:124571. DOI: 10.1016/j.biortech.2020.124571

Song Y, Qiao W, Westerholm M, Huang G, Taherzadeh MJ, Dong R. Microbiological and Technological Insights on Anaerobic Digestion of Animal Manure: A Review. Fermentation. 2023;9(5):436. DOI: 10.3390/fermentation9050436

Sarode SD, Kumar D, Mathias D, McNeill D, Kaparaju P. Anaerobic Digestion of Spoiled Maize, Lucerne and Barley Silage Mixture with and without Cow Manure: Methane Yields and Kinetic Studies. Energies. 2023;16(17):6179. DOI: 10.3390/en16176179

Guo Q, Majeed S, Xu R, Zhang K, Kakade A, Khan A, et al. Heavy metals interact with the microbial community and affect biogas production in anaerobic digestion: A review. Journal of Environmental Management. 2019;240:266-72. DOI: 10.1016/j.jenvman.2019.03.104

Golub NB, Shynkarchuk AV, Kozlovets OA, Kozlovets MV. Effects of Heavy Metal Ions (Fe3+, Cu2+, Zn2+ and Cr3+) on the Productivity of Biogas and Biomethane Production. Advances in Bioscience and Biotechnology. 2022;13(1):1-14. DOI: 10.4236/abb.2022.131001

Dincă M, Moiceanu G, Paraschiv G, Voicu G, Ungureanu N, Toma L, Ionescu M. The influence of heavy metals on biogas production during the anaerobic digestion process. In: Proceedings of the 3rd International Conference of Thermal Equipment, Renewable Energy and Rural Development (TE-RE-RD 2014), Mamaia, Romania. 2014, pp. 219-24.

González-Suárez A, Pereda-Reyes I, Oliva-Merencio D, Suárez-Quiñones T, José da Silva A, Zaiat M. Bioavailability and dosing strategies of mineral in anaerobic mono-digestion of maize straw. Engineering in Life Sciences. 2018;18(8):562-9. DOI: 10.1002/elsc.201700018

Zayed G, Winter J. Inhibition of methane production from whey by heavy metals - protective effect of sulfide. Applied Microbiology and Biotechnology. 2000;53(6):726-31. DOI: 10.1007/s002530000336

Tian Y, Zhang H, Sanganyado E. Biodegradability during Anaerobic Fermentation Process Impacted by Heavy Metals. In: New Advances on Fermentation Processes. IntechOpen; 2020. DOI: 10.5772/intechopen.87161

Wang Z, Wang R, Yuan H, Zhu N. A novel strategy for high efficiency of anaerobic digestion of waste activated sludge by using a Fe-Cu microelectrolysis method: performance, electron transfer, key enzymes and microbial community. Water Research. 2025;287(Part A):124322. DOI: 10.1016/j.watres.2025.124322

Cai Y, Cheng M, Liu X, Qu G, Zou H, Li H, et al. Effects of copper and zinc on three stages-anaerobic fermentation of organic wastes. Environmental Research. 2025;284:122216. DOI: 10.1016/j.envres.2025.122216

Wongsaroj L, Chanabun R, Tunsakul N, Prombutara P, Panha S, Somboonna N. First reported quantitative microbiota in different livestock manures used as organic fertilizers in the Northeast of Thailand. Scientific Reports. 2021;11:102. DOI: 10.1038/s41598-020-80543-3

Shynkarchuk M. Biotechnology of biogas production from fat-containing raw materials: PhD thesis. National Technical University of Ukraine “Igor Sikorsky Kyiv Polytechnic Institute”, 2020. Available from: https://ela.kpi.ua/handle/123456789/35946

Baird RB, Eaton AD, Rice EW (eds.). Standard Methods for the Examination of Water and Wastewater, 23rd edition. American Public Health Association, American Water Works Association, Water Environment Federation; 2017.

VDI 4630. Vergärung organischer Stoffe - Substratcharakterisierung, Probenahme, Stoffdatenerhebung, Gärversuche. Verein Deutscher Ingenieure; 2016.

Hao H, Tian Y, Zhang H, Chai Y. Copper stressed anaerobic fermentation: biogas properties, process stability, biodegradation and enzyme responses. Biodegradation. 2017;28(5-6):369-81. DOI: 10.1007/s10532-017-9802-0

Erşan M, Şenol H. Anaerobik Sindirimdeki Demir, Nikel ve Krom İz Elementlerin En İyi Konsantrasyonunun Cevap Yüzey Yöntemi ile Belirlenmesi. Karadeniz Fen Bilimleri Dergisi. 2024;14(1):281-94. DOI: 10.31466/kfbd.1402300

Lu T, Zhang J, Wei Y, Shen P. Effects of ferric oxide on the microbial community and functioning during anaerobic digestion of swine manure. Bioresource Technology. 2019;287:121393. DOI: 10.1016/j.biortech.2019.121393

Xing B-S, Su Y-M, Fu Y-L, Wu Y-F, Yan C-H, Wang XC, et al. Comparison of the short- and long-term effects of zinc ions on the anaerobic mesophilic co-digestion of food waste and waste activated sludge: Digester performance, antibiotic resistance gene reduction and the microbial community. Journal of Hazardous Materials. 2024;480:136119. DOI: 10.1016/j.jhazmat.2024.136119

Casals E, Barrena R, García A, González E, Delgado L, Busquets-Fité M, et al. Programmed Iron Oxide Nanoparticles Disintegration in Anaerobic Digesters Boosts Biogas Production. Small. 2014;10(14):2801-8. DOI: 10.1002/smll.201303703

Fermoso FG, Collins G, Bartacek J, Lens PNL. Zinc deprivation of methanol fed anaerobic granular sludge bioreactors. Journal of Industrial Microbiology and Biotechnology. 2008;35(6):543-57. DOI: 10.1007/s10295-008-0315-z

Tian Y, Zhang H, Zheng L, Li S, Hao H, Huang H. Effect of Zn Addition on the Cd-Containing Anaerobic Fermentation Process: Biodegradation and Microbial Communities. International Journal of Environmental Research and Public Health. 2019;16(16):2998. DOI: 10.3390/ijerph16162998

Verma VK, Singh YP, Rai JPN. Biogas production from plant biomass used for phytoremediation of industrial wastes. Bioresource Technology. 2007;98(8):1664-9. DOI: 10.1016/j.biortech.2006.05.038

Alrawashdeh KA, Gul E, Yang Q, Yang H, Bartocci P, Fantozzi F. Effect of Heavy Metals in the Performance of Anaerobic Digestion of Olive Mill Waste. Processes. 2020;8(9):1146. DOI: 10.3390/pr8091146

Luna-delRisco M, Orupõld K, Dubourguier H-C. Particle-size effect of CuO and ZnO on biogas and methane production during anaerobic digestion. Journal of Hazardous Materials. 2011;189(1–2):603-8. DOI: 10.1016/j.jhazmat.2011.02.085

Ganzoury MA, Allam NK. Impact of nanotechnology on biogas production: A mini-review. Renewable and Sustainable Energy Reviews. 2015;50:1392-404. DOI: 10.1016/j.rser.2015.05.073

Chen Y, Cheng JJ, Creamer KS. Inhibition of anaerobic digestion process: A review. Bioresource Technology. 2008;99(10):4044-64. DOI: 10.1016/j.biortech.2007.01.057

Glass JB, Orphan VJ. Trace Metal Requirements for Microbial Enzymes Involved in the Production and Consumption of Methane and Nitrous Oxide. Frontiers in Microbiology. 2012;3:61. DOI: 10.3389/fmicb.2012.00061

Cruz VA, Marques RS, Kvamme K, Limede AC, Cidrini FAA, Cidrini IA, et al. Effects of maternal Cu, Mn, and Zn supplementation from different sources on physiological and productive responses of cows and their offspring. Journal of Animal Science. 2025;103:skae391. DOI: 10.1093/jas/skae391

Golub N, Shinkarchuk A. Influence of heavy metal ions on the process of biogas production. In: Materials of the XXIII International Scientific and Practical Conference "Renewable energy and energy efficiency in the 21st century", Kyiv, Ukraine. 2022, pp. 275-7.

Downloads

Published

2026-03-26

How to Cite

1.
Shynkarchuk A, Golub N, Kozlovets M, Kozlovets O, Dombrovskis M. Combined Еffects of Heavy Metal Ions (Fe3+-Cu2+, Fe3+-Zn2+, Fe3+-Cr3+, Cu2+-Zn2+, Cu2+-Cr3+ and Zn2+-Cr3+) on the Productivity of Biogas and Biomethane Production. Innov Biosyst Bioeng [Internet]. 2026Mar.26 [cited 2026Apr.18];10(1):15-26. Available from: https://ibb.kpi.ua/article/view/354790