Self-sustaining treatment as a novel alternative for the stabilization of anaerobic digestate.

Self-sustaining smouldering combustion (SSS) is a technology based on the flameless oxidation of an organic substrate and limited by the rate at which oxygen is diffused to the surface of the substrate. This work aims to evaluate the SSS combustion as a treatment process for the stabilization of anaerobic digestate, determining the limits of operational conditions, (moisture content (MC), air flux) that allow for a self-sustaining process. Maximum possible MC was found at 82 wt% with Darcy air flux of 50 cm/s. The digestate destruction rate (kg/(h·m2), and the addition of sand as an inert solid, to enhance the oxygen diffusion, were also investigated. A sand/substrate mass ratio of 1 allowed for SSS at 85 wt% MC, but decreased the digestate destruction rate. The average composition of the emitted gases showed ca. 25% CO and 10% H2, whereas the analysis of the ashes showed almost complete digestate inertization.

Rabbit manure as a potential inoculum for anaerobic digestion.

The potential of using rabbit manure as inoculum for biogas production was evaluated through batch assays using bean straw as substrate. The microbial diversity in the rabbit manure included lignin-degrading bacteria (classes Bacteroidia, Bacilli and Clostridia) as well as key acetoclastic (Matheanosarcina and Methanosaeta), and hydrogenotrophic (Methanobacterium, Methanolinea, and Methanovebribacter) archaea. The effects of particle size, substrate to inoculum ratio (S/X) and pH adjustment were studied to improve the inoculum activity. The adjustment of the pH entailed the highest improvement in methane production (515%) and rate (164%). However, high S/X, (3-4), resulted in the acidification of the processes, denoting an imbalance between hydrolytic bacteria and methanogenic archaea in the rabbit manure. This confirmed that the use of rabbit manure as inoculum could sustain anaerobic digestion from agricultural residues, although a proper enrichment and adaptation is necessary to ensure an appropriate methane production.

Effect of process variables on the sulfate reduction process in bioreactors treating metal-containing wastewaters: factorial design and response surface analyses.

The individual and combined effect of the pH, chemical oxygen demand (COD) and SO4 (2-) concentration, metal to sulfide (M/S(2-)) ratio and hydraulic retention time (HRT) on the biological sulfate reduction (SR) process was evaluated in an inverse fluidized bed reactor by factorial design analysis (FDA) and response surface analysis (RSA). The regression-based model of the FDA described the experimental results well and revealed that the most significant variable affecting the process was the pH. The combined effect of the pH and HRT was barely observable, while the pH and COD concentration positive effect (up to 7 and 3 gCOD/L, respectively) enhanced the SR process. Contrary, the individual COD concentration effect only enhanced the COD removal efficiency, suggesting changes in the microbial pathway. The RSA showed that the M/S(2-) ratio determined whether the inhibition mechanism to the SR process was due to the presence of free metals or precipitated metal sulfides.

Morphology, mineralogy, and solid-liquid phase separation characteristics of Cu and Zn precipitates produced with biogenic sulfide.

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.

Sulfide response analysis for sulfide control using a pS electrode in sulfate reducing bioreactors.

Step changes in the organic loading rate (OLR) through variations in the influent chemical oxygen demand (CODin) concentration or in the hydraulic retention time (HRT) at constant COD/SO4(2-) ratio (0.67) were applied to create sulfide responses for the design of a sulfide control in sulfate reducing bioreactors. The sulfide was measured using a sulfide ion selective electrode (pS) and the values obtained were used to calculate proportional-integral-derivative (PID) controller parameters. The experiments were performed in an inverse fluidized bed bioreactor with automated operation using the LabVIEW software version 2009(®). A rapid response and high sulfide increment was obtained through a stepwise increase in the CODin concentration, while a stepwise decrease to the HRT exhibited a slower response with smaller sulfide increment. Irrespective of the way the OLR was decreased, the pS response showed a time-varying behavior due to sulfide accumulation (HRT change) or utilization of substrate sources that were not accounted for (CODin change). The pS electrode response, however, showed to be informative for applications in sulfate reducing bioreactors. Nevertheless, the recorded pS values need to be corrected for pH variations and high sulfide concentrations (>200 mg/L).

Influence of sulfide concentration and macronutrients on the characteristics of metal precipitates relevant to metal recovery in bioreactors.

Purity and settling properties determine metal sulfide recovery from bioreactors. The influence of macronutrients commonly present in mineral media and wastewaters on Cu, Pb, Cd and Zn depletion kinetics and characteristics was evaluated in batch experiments with chemically produced sulfide at different concentrations. The metal depletion kinetics showed that metals with slower depletion rates (Zn and Cd) are susceptible to other removal mechanisms such as biosorption onto the sulfate reducing biofilm and precipitation with macronutrients when sulfide is below the stoichiometric metal to sulfide ratio. For Zn, the main mechanism of removal is its sorption onto apatite (Ca(5)(PO(4)))(3)(+)(OH(-)), a compound formed due to the presence of CaCl(2)·2H(2)O and KH(2)PO(4) in the mineral medium. All precipitates were 8.1-10.0µm regardless the sulfide concentration demonstrating that this parameter is less relevant for particle growth and settling, compared to the agglomeration of the precipitates.

Effect of sulfide concentration on the location of the metal precipitates in inversed fluidized bed reactors.

The effect of the sulfide concentration on the location of the metal precipitates within sulfate-reducing inversed fluidized bed (IFB) reactors was evaluated. Two mesophilic IFB reactors were operated for over 100 days at the same operational conditions, but with different chemical oxygen demand (COD) to SO(4)(2-) ratio (5 and 1, respectively). After a start up phase, 10mg/L of Cu, Pb, Cd and Zn each were added to the influent. The sulfide concentration in one IFB reactor reached 648 mg/L, while it reached only 59 mg/L in the other one. In the high sulfide IFB reactor, the precipitated metals were mainly located in the bulk liquid (as fines), whereas in the low sulfide IFB reactor the metal preciptiates were mainly present in the biofilm. The latter can be explained by local supersaturation due to sulfide production in the biofilm. This paper demonstrates that the sulfide concentration needs to be controlled in sulfate reducing IFB reactors to steer the location of the metal precipitates for recovery.