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This is an Open Access book chapter distributed under the terms of the Creative Commons Attribution Licence (CC BY 4.0), which permits copying, adaptation and redistribution, provided the original work is properly cited (http://creativecommons.org/licenses/by/4.0/). The chapter is from the book Trace Elements in Anaerobic Biotechnologies, Fernando G. Fermoso, Eric van Hullebusch, Gavin Collins, Jimmy Roussel, Ana Paula Mucha and Giovanni Esposito (Eds.).

Essential trace elements (TE) are a prerequisite that ensures optimal performance of the anaerobic digestion (AD) process. However, finding the proper way to deliver these micronutrients to microbial communities is not an easy task. The chemical speciation of TE and the complex environment characterizing AD play a critical role in their mobility, bioavailability, and toxicity. These aspects are particularly critical when establishing the total versus bioavailable concentration of TE, by properly balancing the two sides of the same coin, namely essentiality and toxicity. Both non-redox sensitive (e.g. Co, Cu, Ni, Zn) and redox-sensitive (e.g. Fe, Mn, Mo, Se, W) elements engage in a complex interplay with the mineral and organic phases present in AD. In addition, TE can also interact with each other, thus further complicating our current understanding. All these ‘parasitic’ reactions may render a large fraction of supplemented TE non-bioavailable for the efficient degradation of organic matter by microbial consortia, therefore limiting the biomethane yield. Current analytical limitations related to sampling and assessing the speciation, bioavailability, and matrix (liquid/solid) analysis add to the difficulty of understanding the bigger picture. This chapter reviews and discusses at length all these aspects, providing an up-to-date presentation of the biogeochemistry of TE in AD.

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