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BACKGROUND: Metal sulfide recovery in sulfate reducing bioreactors is a challenge due to the formation of small precipitates with poor settling properties. The size of the metal sulfide precipitates with the change in operational parameters such as pH, sulfide concentration and reactor configuration has been previously studied. The effect of the hydraulic retention time (HRT) on the metal precipitate characteristics such as particle size for settling has not yet been addressed. RESULTS:The change in size of the metal (Cu, Zn, Pb and Cd) sulfide precipitates as a function of the HRT was studied in two sulfate reducing inversed fluidized bed (IFB) reactors operating at different chemical oxygen demand concentrations to produce high and low sulfide concentrations. The decrease of the HRT from 24 to 9 h in both IFB reactors affected the contact time of the precipitates formed, thus making differences in aggregation and particle growth regardless of the differences in sulfide concentration. Further HRT decrease to 4.5 h affected the sulfate reducing activity for sulfide production and hence, the supersaturation level and solid phase speciation. Metal sulfide precipitates affected the sulfate reducing activity and community in the biofilm, probably because of the stronger local supersaturation causing metal sulfides accumulation in the biofilm.CONCLUSIONS: This study shows that the HRT is an important factor determining the size and thus the settling rate of the metal sulfides formed in bioreactors.

The morphology, mineralogy, and solid-liquid phase separation of the Cu and Zn precipitates formed with sulfide produced in a sulfate-reducing bioreactor were studied at pH 3, 5, and 7. The precipitates formed at pH 7 display faster settling rates, better dewaterability, and higher concentrations of settleable solids as compared to the precipitates formed at pH 3 and 5. These differences were linked to the agglomeration of the sulfidic precipitates and coprecipitation of the phosphate added to the bioreactor influent. The Cu and Zn quenched the intensity of the dissolved organic matter peaks identified by fluorescence-excitation emission matrix spectroscopy, suggesting a binding mechanism that decreases supersaturation, especially at pH 5. X-ray absorption fine structure spectroscopy analyses confirmed the precipitation of Zn-S as sphalerite and Cu-S as covellite in all samples, but also revealed the presence of Zn sorbed on hydroxyapatite. These analyses further showed that CuS structures remained amorphous regardless of the pH, whereas the ZnS structure was more organized at pH 5 as compared to the ZnS formed at pH 3 and 7, in agreement with the cubic sphalerite-type structures observed through scanning electron microscopy at pH 5.