Hydrogen production and consumption of organic acids by a phototrophic microbial consortium

Alternative fuel sources have been extensively studied. Hydrogen gas has gained attention because its combustion releases only water, and it can be produced by microorganisms using organic acids as substrates. The aim of this study was to enrich a microbial consortium of photosynthetic purple non-sulfur bacteria from an Upflow Anaerobic Sludge Blanket reactor (UASB) using malate as carbon source. After the enrichment phase, other carbon sources were tested, such as acetate (30 mmol l(-1)), butyrate (17 mmol l(-1)), citrate (11 mmol l(-1)), lactate (23 mmol l(-1)) and malate (14.5 mmol l(-1)). The reactors were incubated at 30 degrees C under constant illumination by 3 fluorescent lamps (81 mu mol m(-2) s(-1)). The cumulative hydrogen production was 7.8, 9.0, 7.9, 5.6 and 13.9 mmol H-2 l(-1) culture for acetate, butyrate, citrate, lactate and malate, respectively. The maximum hydrogen yield was 0.6, 1.4, 0.7, 0.5 and 0.9 mmol H-2 mmol(-1) substrate for acetate, butyrate, citrate, lactate and malate, respectively. The consumption of substrates was 43% for acetate, 37% for butyrate, 100% for citrate, 49% for lactate and 100% for malate. Approximately 26% of the clones obtained from the Phototrophic Hydrogen-Producing Bacterial Consortium (PHPBC) were similar to Rhodobacter, Rhodospirillum and Rhodopseudomonas, which have been widely cited in studies of photobiological hydrogen production. Clones similar to the genus Sulfurospirillum (29% of the total) were also found in the microbial consortium. Copyright (C) 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

Assessment of a UASB reactor for the removal of sulfate from acid mine water

A bench-scale Upflow Anaerobic Sludge Blanket (UASB) reactor was used to study the treatment of acid mine drainage through the biological reduction of sulfate. The reactor was fed with acid mine drainage collected at the Osamu Utsumi uranium mine (Caldas, MG, Brazil) and supplemented with ethanol as an external carbon source. Anaerobic granular sludge originating from a reactor treating poultry slaughterhouse wastewater was used as the inoculum. The reactor's performance was studied according to variations in the chemical oxygen demand (COD)/SO42- ratio, influent dilution and liquid-phase recirculation. The digestion of a dilution of the acid mine drainage resulted in a 46.3% removal of the sulfate and an increase in the effluent pH (COD/SO42- = 0.67). An increase in the COD/SO42- ratio to 1.0 resulted in an 85.6% sulfate reduction. The reduction of sulfate through complete oxidation of the ethanol was the predominant path in the reactor, although the removal of COD was not greater than 68% in any of the operational stages. The replenishment of the liquid phase with tap water positively affected the reactor, whereas the recirculation of treated effluent caused disequilibrium and decreased efficiency. (C) 2012 Elsevier Ltd. All rights reserved.

A potential application of sludge-based catalysts for the anaerobic bio-decolorization of tartrazine dye.

Two highly efficient (K2CO3/sludge carbon and ZnCl2/sludge carbon) solids were prepared by chemical addition following carbonization at 800 °C and were tested for anaerobic reduction of tartrazine dye in a continuous upflow packed-bed biological reactor, and their performance was compared to that of commercial activated carbon (CAC). The chemical and structural information of the solids was subjected to various characterizations in order to understand the mechanism for anaerobic decolorization, and efficiency for SBCZN800 and SBCPC800 materials was 87% and 74%, respectively, at a short space time (τ) of 2.0 min. A first-order kinetic model fitted the experimental points and kinetic constants of 0.40, 0.92 and 1.46 min(-1) were obtained for SBCZN800, SBCPC800 and CAC, respectively. The experimental results revealed that performance of solids in the anaerobic reduction of tartrazine dye can depend on several factors including chemical agents, carbonization, microbial population, chemical groups and surface chemistry. The Langmuir and Freundlich models are successfully described in the batch adsorption data. Based on these observations, a cost-effective sludge-based catalyst can be produced from harmful sewage sludge for the treatment of industrial effluents.

Sulphur and iron species in Dvurechenskii mud volcano sediments

The deep Black Sea is known to be depleted in electron-acceptors for sulphide oxidation. This study on depth distributions of sulphur species (S(II), S(0),S(n)**2-,S2O3**2-,SO3**2-,SO4**2-) in the Dvurechenskii mud volcano, a cold seep situated in the permanently anoxic eastern Black Sea basin (Sorokin Trough, 2060 m water depth), showed remarkable concentrations of sulphide oxidation products. Sulphite concentrations of up to 11 µmol L**1-, thiosulphate concentrations of up to 22 µmol L**1-, zero-valent sulphur concentrations of up to 150 µmol L**1- and up to five polysulphide species were measured in the upper 20 cm of the sediment. Electron-acceptors found to be available in the Dvurechenskii mud volcano (DMV) for the oxidation of hydrogen sulphide to sulphide oxidation intermediates are iron-minerals, and probably also reactive manganese phases. Up to 60 µmol g**1- of reactive iron-minerals and up to 170 µmol L**1- dissolved iron was present in the central summit with the highest fluid upflow and fresh mud outflow. Thus, the source for the oxidative power in the DMV are reactive iron phases extruded with the mud from an ancient source in the deeply buried sediments, leading to the formation of various sulphur intermediates in comparably high concentrations. Another possible source of sulphide oxidation intermediates in DMV sediments could be the formation of zero-valent sulphur by sulphate dependent anaerobic microbial oxidation of methane followed by disproportionation of zero-valent sulphur. Sulphide oxidation intermediates, which are produced by these processes, do not reach thermodynamic equilibrium with rhombic sulphur, especially close to the active center of the DMV due to a short equilibration time. Thus, mud volcano sediments, such as in the DMV, can provide oxidizing niches even in a highly reduced environment like the abyssal part of the Black Sea.

Major oxides, trace elements and rare earth elements of selected basalt samples at DSDP Hole 83-504B

DSDP Hole 504B is the deepest section drilled into oceanic basement, penetrating through a 571.5-m lava pile and a 209-m transition zone of lavas and dikes into 295 m of a sheeted dike complex. To define the basement composition 194 samples of least altered basalts, representing all lithologic units, were analyzed for their major and 26 trace elements. As is evident from the alteration-sensitive indicators H2O+, CO2, S, K, Mn, Zn, Cu, and the iron oxidation ratio, all rocks recovered are chemically altered to some extent. Downhole variation in these parameters enables us to distinguish five depth-related alteration zones that closely correlate with changes in alteration mineralogy. Alteration in the uppermost basement portion is characterized by pronounced K-uptake, sulfur loss, and iron oxidation and clearly demonstrates low-temperature seawater interaction. A very spectacular type of alteration is confined to the depth range from 910 to 1059 m below seafloor (BSF). Rocks from this basement portion exhibit the lowest iron oxidation, the highest H2O+ contents, and a considerable enrichment in Mn, S, Zn, and Cu. At the top of this zone a stockwork-like sulfide mineralization occurs. The chemical data suggest that this basement portion was at one time within a hydrothermal upflow zone. The steep gradient in alteration chemistry above this zone and the ore precipitation are interpreted as the result of mixing of the upflowing hydrothermal fluids with lower-temperature solutions circulating in the lava pile. Despite the chemical alteration the primary composition and variation of the rocks can be reliably established. All data demonstrate that the pillow lavas and the dikes are remarkably uniform and display almost the same range of variation. A general characteristic of the rocks that classify as olivine tholeiites is their high MgO contents (up to 10.5 wt.%) and their low K abundances (-200 ppm). According to their mg-values, which range from 0.60 to 0.74, most basalts appear to have undergone some high-level crystal fractionation. Despite the overall similarity in composition, there are two major basalt groups that have significantly different abundances and ratios of incompatible elements at similar mg-values. The majority of the basalts from the pillow lava and dike sections are chemically closely related, and most probably represent differentiation products of a common parental magma. They are low in Na2O, TiO2, and P2O5, and very low in the more hygromagmaphile elements. Interdigitated with this basalt group is a very rarely occurring basalt that is higher in Na2O, TiO2, P2O5, much less depleted in hygromagmaphile elements, and similar to normal mid-ocean ridge basalt (MORB). The latter is restricted to Lithologic Units 5 and 36 of the pillow lava section and Lithologic Unit 83 of the dike section. The two basalt groups cannot be related by differentiation processes but have to be regarded as products of two different parental magmas. The compositional uniformity of the majority of the basalts suggests that the magma chamber beneath the Costa Rica Rift reached nearly steady-state conditions. However, the presence of lavas and dikes that crystallized from a different parental magma requires the existence of a separate conduit-magma chamber system for these melts. Occasionally mixing between the two magma types appears to have occurred. The chemical characteristics of the two magma types imply some heterogeneity in the mantle source underlying the Costa Rica Rift. The predominant magma type represents an extremely depleted source, whereas the rare magma type presumably originated from regions of less depleted mantle material (relict or affected by metasomatism).

(Appendix) Petrographic information, trace element and Sr isotope ratios of Pito Deep samples

Fluid flow through the axial hydrothermal system at fast spreading ridges is investigated using the Sr-isotopic composition of upper crustal samples recovered from a tectonic window at Pito Deep (NE Easter microplate). Samples from the sheeted dike complex collected away from macroscopic evidence of channelized fluid flow, such as faults and centimeter-scale hydrothermal veins, show a range of 87Sr/86Sr from 0.7025 to 0.7030 averaging 0.70276 relative to a protolith with 87Sr/86Sr of ~0.7024. There is no systematic variation in 87Sr/86Sr with depth in the sheeted dike complex. Comparison of these new data with the two other localities that similar data sets exist for (ODP Hole 504B and the Hess Deep tectonic window) reveals that the extent of Sr-isotope exchange is similar in all of these locations. Models that assume that fluid-rock reaction occurs during one-dimensional (recharge) flow lead to significant decreases in the predicted extent of isotopic modification of the rock with depth in the crust. These model results show systematic misfits when compared with the data that can only be avoided if the fluid flow is assumed to be focused in isolated channels with very slow fluid-rock exchange. In this scenario the fluid at the base of the crust is little modified in 87Sr/86Sr from seawater and thus unlike vent fluids. Additionally, this model predicts that some rocks should show no change from the fresh-rock 87Sr/86Sr, but this is not observed. Alternatively, models in which fluid-rock reaction occurs during upflow (discharge) as well as downflow, or in which fluids are recirculated within the hydrothermal system, can reproduce the observed lack of variation in 87Sr/86Sr with depth in the crust. Minimum time-integrated fluid fluxes, calculated from mass balance, are between 1.5 and 2.6 * 10**6 kg/m**2 for all areas studied to date. However, new evidence from both the rocks and a compilation of vent fluid compositions demonstrates that some Sr is leached from the crust. Because this leaching lowers the fluid 87Sr/86Sr without changing the rock 87Sr/86Sr, these mass balance models must underestimate the time-integrated fluid flux. Additionally, these values do not account for fluid flow that is channelized within the crust.

Geochemistry and fluxes at DSDP Hole 83-504B

This chapter documents the chemical changes produced by hydrothermal alteration of basalts drilled on Leg 83, in Hole 504B. It interprets these chemical changes in terms of mineralogical changes and alteration processes and discusses implications for geochemical cycling. Alteration of Leg 83 basalts is characterized by nonequilibrium and is heterogeneous on a scale of centimeters to tens or hundreds of meters. The basalts exhibit trends toward losses of SiO2, CaO, TiO2; decreases in density; gains of MnO, Na2O, CO2, H2O+ , S; slight gains of MgO; increased oxidation of Fe; and variable changes in A12O3. Some mobility of rare earth elements (REE) also occurred, especially the light REE and Eu. The basalts have lost Ca in excess of Mg + Na gains. Variations in chemical trends are due to differing water/rock ratios, substrate control of secondary mineralogy, and superimposition of greenschist and zeolite facies mineralogies. Zeolitization resulted in uptake of Ca and H2O and losses of Si, Al, and Na. These effects are different from the Na uptake observed in other altered basalts from the seafloor attributed to the zeolite facies and are probably due to higher temperatures of alteration of Leg 83 basalts. Basalts from the transition zone are enriched in Mn, S, and CO2 relative to the pillow and dike sections and contain a metal-sulfide-rich stockwork zone, suggesting that they once were located within or near a hydrothermal upflow zone. Samples from the bottom of the dike section are extensively fractured and recrystallized indicating that alteration was significantly affected by local variations in permeability.

Pore-water chemistry of ODP sites 111-677 and 111-678

Sites 677 and 678 were drilled on ODP Leg 111 to test hypotheses about the nature and pattern of hydrothermal circulation on a mid-ocean ridge flank. Together with earlier results from DSDP Site 501/504 and several heatflow and piston coring surveys covering a 100-km**2 area surrounding the three drill sites, they confirm that hydrothermal circulation persists in this 5.9-m.y.-old crust, both in basement and through the overlying sediments (Langseth et al., 1988, doi:10.2973/odp.proc.ir.111.102.1988). Profiles of sediment pore-water composition with depth at the three drill sites show both vertical and horizontal gradients. The shapes of the profiles and their variation from one site to another result from a combination of vertical and horizontal diffusion, convection, and reaction in the sediments and basement. Chemical species that are highly reactive in the siliceous-calcareous biogenic sediments include bicarbonate (alkalinity), ammonium, sulfate, manganese, calcium, strontium, lithium, silica, and possibly potassium. Reactions include bacterial sulfate reduction, mobilization of Mn2+, precipitation of CaCO3, and recrystallization of calcareous and siliceous oozes to chalk, limestone, and chert. Species with profiles more affected by reaction in basaltic basement than in the sediments include Mg, Ca, Na, K, and oxygen isotopes. Reaction in basement at 60?C and at higher temperatures has produced a highly altered basement formation water that is uniform in composition over distances of several kilometers. As inferred from the composition of the basal sediment pore water at the three sites, this uniformity extends from up flow zone to downflow zone in basement and the sediments. It exists in spite of large variations in heat flow and depth to basement, apparently as a result of homogenization by hydrothermal circulation in basement. Profiles for chlorinity, Na, Mg, and other species in the sediment pore waters confirm that Site 678, drilled on a localized heatflow high identified by Langseth et al. (1988), is a site of long-lived upwelling of warm water from basement through the sediments at velocities of 1 to 2 mm/yr. The upflow through the anomalously thin sediments is apparently localized above an uplifted fault block in basement. This site and other similar sites in the survey area give rise to lateral diffusion and possibly flow through the sediments, which produces lateral gradients in sediment pore-water composition at sites such as 501/504. The complementary pore-water profiles at the low-heatflow Site 677 2 km to the south indicate that downflow is occurring through the sediments there, at comparable rates of 1 to 2 mm/yr.

Aplicación de un tratamiento biológico a las aguas residuales provenientes de una destilería de alcohol de caña, utilizando un reactor UASB

En este trabajo se llevó a cabo el tratamiento de vinazas mediante dos tecnologías anaerobias. Se dividió en cuatro estudios técnicos. El primero fue el arranque y estabilización del reactor UASB (Upflow Anaerobic Sludge Blanket), en dónde se evaluó la estabilización mediante la eficiencia de remoción de DQO y la granulación del lodo. El segundo estudio evaluó el rendimiento del reactor UASB frente a diferentes Cva. El tercer estudio evaluó el efecto del TRH sobre la eficiencia del reactor UASB, y el cuarto de ellos fue evaluar el rendimiento del RABF (Reactor Anaerobio de Biomasa Fija). El reactor UASB de 2,6 L de capacidad, fue arrancado por lotes, con seis ensayos utilizando vinaza como sustrato. Se obtuvieron eficiencias de remoción en DQO en un rango de 79-91%, en los seis lotes. Se obtuvo formación de gránulos con diámetro (Ø) de 0,85-1,15 mm y un coeficiente de esfericidad (Є) de 0,7-0,77. Se logró la granulación de lodos tras 2 meses de operación. Alcanzada la estabilización del reactor UASB, se siguió una operación en flujo continuo. Las Cva probadas de 1, 2, 4 y 6 gDQO/L.d para el reactor UASB dan una respuesta bastante favorable con respecto al rendimiento del reactor, ya que presento eficiencias de remoción de DQOs del 51 hasta el 76%, eficiencias similares a los reportados por la literatura. En el estudio de TRH se operó con Cva de 6 gDQO/L.d y los TRH fueron de 24, 12 ,5 ,3 y 1 día. El % de eliminación de DQO fue de 51, 60, 57, 60 y 63 % remoción en DQOsoluble, respectivamente. Se alcanzó una producción de biogás máximo de 5.283 ml/d, pero al reducir el TRH se observó una reducción proporcional del volumen total de biogás. El %CH4 contenido en el biogás aumento al disminuir el TRH, reflejando valores de 80 al 92 % de CH4. El RABF con un volumen de 8,2 L, utilizo tubos de plástico corrugado como medio de soporte para las bacterias. Se aplicaron las siguientes Cva; 0,5, 1, 3 y 6 gDQO/L.d. El reactor RABF presento una excelente remoción de la materia orgánica (80% DQOs), una producción de biogás estable, y un contenido en CH4 del biogás muy interesante. Sin embargo, para una Cva superior a 3 gDQO/L.d empezó un comportamiento inesperado de reducción de capacidad. Las condiciones hidrodinámicas del reactor UASB son decisivas para la formación de los gránulos, condición previa para iniciar el flujo continuo. Al operar el reactor UASB en modo continuo, se pudo evaluar las mejores condiciones de operación para este tipo de residuo (vinaza). La Cva de 6 gDQO/L.d para el reactor UASB alimentado con vinaza bruta representa el límite de su capacidad. Sin embargo, al aumentar la Cva se genera una mayor producción de biogás y metano. La eficiencia de remoción de la DQO soluble es independiente del TRH, para una Cva de 6 g DQO/L•d y las condiciones de TRH probadas (24, 12, 5, 3 y 1 días). Los valores de remoción de DQO alcanzados son un poco superior a los valores de biodegradabilidad anaerobia de la vinaza observados de 50 %. De manera general, la reducción del TRH o bien la dilución de la vinaza no presenta un efecto significativo sobre la remoción de la materia orgánica soluble, pero si lo presenta en la remoción de sulfatos reduciendo indirectamente su toxicidad. El soporte termoplástico inoculado en el RABF y alimentado con vinaza bruta, actuó como un filtro, además de obtener buenos resultados en eliminación de DQO, pero dada las dimensiones y la altura del relleno se frena la evacuación del metano. This work was carried out by treatment vinasses with two anaerobic technologies. It was divided into four technical studies. The first was the start up and stabilization Upflow Anaerobic Sludge Blanket (UASB) reactor, where the stability was evaluated by the removal efficiency of COD and sludge granulation. The second study evaluated the performance of the UASB reactor against different OLR. The third study evaluated the effect of HRT on the efficiency of the UASB reactor, and the fourth of which was evaluate the performance Fixed Biomass Anaerobic (FBA) reactor. The UASB reactor of 2,6 L capacity, was started in batch, with six assays using vinasse as substrate. Were obtained removal efficiencies of COD in the range of 79- 91% in the six batches. Forming granules were obtained with a diameter (Ø) of 0,85- 1,15 mm and sphericity coefficient (Є) of 0,7 to 0,77. Sludge granulation was achieved after 2 months of operation. Once stabilization is achieved of the UASB reactor, it was followed by a continuous flow operation. The OLR tested 1, 2, 4 and 6 gCOD/L.d for UASB reactor gives a very favorable response regarding the performance of the reactor, as presented COD5 removal efficiencies of 51 to 76%, similar efficiencies those reported in the literature The HRT study was operated with an OLR of 6 gCOD/L.d and HRT were 24, 12, 5, 3 and 1 day. The removal efficiency was 51, 60, 57, 60 and 63% in soluble COD, respectively. It reached a maximum biogas production of 5.283 ml / d, but by reducing the HRT showed a proportional reduction in the total volume of biogas. The %CH4 content in the biogas increased with decreasing TRH, reflecting values of 80 to 92% of CH4. The FBA reactor with a volume of 8,2 L, used corrugated plastic tubes as carrier for bacteria transportation. The following OLR was applied, 0,5, 1, 3 and 6 gCOD/L.d. The FBA reactor showed an excellent removal of organic matter (80% CODS), a stable biogas production, and CH4 content very interesting. However, for more than 3 gCOD/L.d OLR began with unexpected behavior of capacity reduction. The UASB reactor hydrodynamic conditions are decisive for the formation of the granules, precondition to start the continuous flow. By operating the UASB reactor in continuous mode, it was possible to evaluate the best operating conditions for this type of waste (vinasse). The OLR of 6 gCOD/L.d for the UASB reactor fed with raw vinasse represents the limit of its capacity. However, with increasing OLR creates increased biogas production and methane. The removal efficiency of soluble COD is independent of HRT for OLR of 6 gCOD/L.d and HRT conditions tested (24, 12, 5, 3 and 1 day). COD Removal values achieved are slightly higher than the values of the vinasse anaerobic biodegradability of observed at 50%. Generally, reduction of HRT or vinasse dilution does not present a significant effect on the removal of the soluble organic matter; however if it occurs in the removal of sulfate reducing indirectly its toxicity. The thermoplastic support inoculated in FBA reactor and fed with raw vinasse, acted as a filter, in addition to obtaining good results in COD removal, but given the size and height of the filling slows evacuation of methane.