Sulfur from biogas desulfurization: Fate of S during storage in manure and after application to plants

Abstract

Residues from hydrogen sulfide (H2S) removal in biogas filters contain sulfur (S) in various forms (sulfate, sulfide, elemental S) that, if properly stored, is potentially valuable as crop fertilizer. We investigated 1) the turnover of the S compounds from filter materials during storage in untreated and digested cattle manure (CM), and 2) the S fertilizer replacement value (SFRV) of the filter materials applied in pure form or mixed manure with and without storage. The S filter materials from four H2S removal processes (biological and physical-chemical) containing mostly sulfate and/or elemental S were added to untreated CM or digested CM and stored at 10 °C for six months. Afterwards, a pot experiment was established to assess the S availability in an oil-seed rape (Brassica napus) crop. Microbial reduction of sulfate into sulfide took place rapidly after 69 days storage of untreated CM. A lower reduction rate was observed in digested CM mixtures. After six months, 68% and 32% of the initial sulfate content were still present in mixtures containing the S filter materials from biological desulfurization with digested CM and untreated CM, respectively. Sulfate reduction was inhibited for 120 days when digested CM was mixed with S saturated solution from an ash filter, probably due to high pH (≥8.2) and redox potential (>−100 mV) levels. Oppositely, elemental S was immediately and simultaneously both reduced and oxidized. Relatively low losses of total S were observed during the present storage conditions. Despite S turnover, the SFRV of CM and digested CM significantly increased from 15–19% (of total S applied) to 56–90% when S filter materials were added. The storage of S filter materials in digested manure reduced the risk of sulfide production and potential S volatilization. The S filter materials were a valuable source of plant-available S.