Mabel Mora

Cross effect of temperature, pH and free ammonia on autotrophic denitrification process with sulphide as electron donor

Autotrophic denitrification is a suitable technology to simultaneously remove oxidised nitrogen compounds and reduced sulphur compounds yielding nitrogen gas, sulphur and sulphate as the main products. In this work, several batch tests were conducted to investigate the cross effect of temperature, pH and free ammonia on the autotrophic denitrification. Denitrification efficiencies above 95% were achieved at 35°C and pH 7.5-8.0 with maximum specific autotrophic denitrifying activities up to 188mgN2g(-1)VSSd(-1). Free ammonia did not show any effect on denitrification at concentrations up to 53mg NH3-NL(-1). Different sulphide concentrations were also tested with stoichiometric nitrite and nitrate concentrations. Sulphide inhibited denitrification at concentrations higher than 200mgS(2-)L(-1). A 50% inhibition was also found at nitrite concentrations above 48mg NO2(-)-NL(-1). The maximum specific activity decreased until a value of 25mgN2g(-1) VSSd(-1) at 232mg NO2(-)-NL(-1). The Haldane model was used to describe denitrification inhibition caused by nitrite. Kinetic parameters determined from the fitting of experimental data were rmax=176mgN2g(-1)VSSd(-1), Ks=10.7mg NO2(-)-NL(-1) and Ki=34.7mg NO2(-)-NL(-1). The obtained model allowed optimising an autotrophic denitrification process by avoiding situations of inhibition and thus obtaining higher denitrification efficiencies.

Aerobic desulfurization of biogas by acidic biotrickling filtration in a randomly packed reactor

Biotrickling filters for biogas desulfurization still must prove their stability and robustness in the long run under extreme conditions. Long-term desulfurization of high loads of H2S under acidic pH was studied in a lab-scale aerobic biotrickling filter packed with metallic Pall rings. Reference operating conditions at steady-state corresponded to an empty bed residence time (EBRT) of 130s, H2S loading rate of 52gS-H2Sm(-3)h(-1) and pH 2.50-2.75. The EBRT reduction showed that the critical EBRT was 75s and the maximum EC 100gS-H2Sm(-3)h(-1). Stepwise increases of the inlet H2S concentration up to 10,000 ppmv lead to a maximum EC of 220gS-H2Sm(-3)h(-1). The H2S removal profile along the filter bed indicated that the first third of the filter bed was responsible for 70-80% of the total H2S removal. The oxidation rate of solid sulfur accumulated inside the bioreactor during periodical H2S starvation episodes was verified under acidic operating conditions. The performance under acidic pH was comparable to that under neutral pH in terms of H2S removal capacity. However, bioleaching of the metallic packing used as support and chemical precipitation of sulfide/sulfur salts occurred.

Examining thiosulfate-driven autotrophic denitrification through respirometry

Anoxic respirometry was applied to characterize a sulfide-oxidizing nitrate-reducing (SO-NR) culture obtained from an anoxic biogas desulfurizing biotrickling filter treating high loads of H2S. Immobilized biomass extracted from the biotrickling filter was grown in a suspended culture with thiosulfate as electron donor to obtain the biomass growth yield and the S2O3(2)(-)/NO3(-) consumed ratio. Afterward, respirometry was applied to describe thiosulfate oxidation under anoxic conditions. A pure culture of Thiobacillus denitrificans was also used as a control culture in order to validate the procedure proposed in this work to characterize the SO-NR biomass. Respirometric profiles obtained with this microbial culture showed that nitrite was formed as intermediate during nitrate reduction and revealed that no competitive inhibition appeared when both electron acceptors were present in the medium. Although final bioreaction products depended on the initial S2O3(2)(-)/NO3(-) ratio, such ratio did not affect thiosulfate oxidation or denitrification rates. Moreover, respirometric profiles showed that the specific nitrite uptake rate depended on the biomass characteristics being that of a SO-NR mixed culture (39.8mgNg(-1) VSSh(-1)) higher than that obtained from a pure culture of T. denitrificans (19.7mgNg(-1) VSSh(-1)). For the first time, the stoichiometry of the two-step denitrification mechanism with thiosulfate oxidation and biomass growth associated was solved for both reactions.

Respirometric characterization of aerobic sulfide, thiosulfate and elemental sulfur oxidation by S-oxidizing biomass

Respirometry was used to reveal the mechanisms involved in aerobic biological sulfide oxidation and to characterize the kinetics and stoichiometry of a microbial culture obtained from a desulfurizing biotrickling filter. Physical-chemical processes such as stripping and chemical oxidation of hydrogen sulfide were characterized since they contributed significantly to the conversions observed in respirometric tests. Mass transfer coefficient for hydrogen sulfide and the kinetic parameters for chemical oxidation of sulfide with oxygen were estimated. The stoichiometry of the process was determined and the different steps in the sulfide oxidation process were identified. The conversion scheme proposed includes intermediate production of elemental sulfur and thiosulfate and the subsequent oxidation of both compounds to sulfate. A kinetic model describing each of the reactions observed during sulfide oxidation was calibrated and validated. The product selectivity was found to be independent of the dissolved oxygen to hydrogen sulfide concentration ratio in the medium at sulfide concentrations ranging from 3 to 30 mg S L(-1). Sulfide was preferentially consumed (SOURmax = 49.2 mg DO g(-1) VSS min(-1)) and oxidized to elemental sulfur at dissolved oxygen concentrations above 0.8 mg DO L(-1). Substrate inhibition of sulfide oxidation was observed (K(i,S(2-))= 42.4 mg S L(-1)). Intracellular sulfur accumulation also affected negatively the sulfide oxidation rate. The maximum fraction of elemental sulfur accumulated inside cells was estimated (25.6% w/w) and a shrinking particle equation was included in the kinetic model to describe elemental sulfur oxidation. The microbial diversity obtained through pyrosequencing analysis revealed that Thiothrix sp. was the main species present in the culture (>95%).

Screening of biological sulfate reduction conditions for sulfidogenesis promotion using a methanogenic granular sludge

Effluents containing great amounts of oxidized sulfur compounds, such as sulfate or sulfite, can be valorized as elemental sulfur from a sequential reduction-oxidation biological process. However, the most important, challenging step to be optimized is the reduction of sulfate. The present study aimed at seeking out the optimal conditions to promote sulfidogenesis instead of methanogenesis using waste carbon sources and a methanogenic granular sludge. Crude glycerol showed better results in terms of the consumed COD/S-Sulfate ratio compared with acetate, cheese whey, pig slurry, and vinasse. Then, the screening of several conditions (T, pH, and COD/S-Sulfate ratio) and the effects of air presence and dissolved sulfide inhibition on sulfate reduction was carried out. Sulfidogenesis was promoted at 35 °C, pH = 8.5, COD/S-Sulfate ratio above 7.0 g O2 g-1 S, microaerophilic conditions, and dissolved sulfide concentrations below 250 mg S2- L-1. These conditions were tested for nearly 3 months in the startup and operation of a 2 L UASB reactor. An inlet sulfate concentration of 220 mg S L-1 and an HRT of 2 h were set. Removal efficiencies of approximately 90% were obtained with less than 20% of organic matter destined for biogas production.