Structural and functional insights into the conductive pili of Geobacter sulfurreducens revealed in molecular dynamics simulations

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Zuckertransport und Regulation des Hexosestoffwechsels bei Oenococcus oeni

Das Milchsäurebakterium Oenococcus oeni, welches für den biologischen Säureabbau im Wein eingesetzt wird, verstoffwechselt Hexosen über den Phosphoketolaseweg. Dabei können beträchtliche Mengen Acetat entstehen. Die Ursachen dafür wurden untersucht, insbesondere der Fructosestoffwechsel. Außerdem wurde der Hexosetransport untersucht, über den bei O. oeni noch nichts bekannt war. Die Aufnahme von Hexosen in die Zelle erfolgt mit hoher Affinität (KM=10 µM) über einen Symport mit H+, aber mit sehr niedriger spezifischer Aktivität (Vmax=9 U / g TG). Zusätzlich werden Hexosen mit ausreichender Aktivität über (vermutlich erleichterte) Diffusion in die Zelle transportiert, allerdings nur bei hohen Hexosekonzentrationen. Es wurden Gene gefunden, die für ein Hexose- Phosphotransferasesystem kodieren, welches in O. oeni keine bedeutende Rolle beim Transport spielt, aber vermutlich eine regulative Funktion hat. Zur Bildung von Essigsäure tragen verschiedene Faktoren bei: Der Ethanolweg, der in der heterofermentativen Milchsäuregärung die Reoxidation von NAD(P)H bewerkstelligt, ist durch die niedrige spezifische Aktivität der Acetaldehyddehydrogenase limitiert. Diese Limitierung wird noch verstärkt, wenn die zellulären Gehalte von Coenzym A aufgrund von Pantothensäuremangel niedrig sind. O. oeni umgeht durch Bildung von Erythrit die Limitierung, und Acetylphosphat wird nicht zu Ethanol reduziert, sondern als Acetat ausgeschieden. Bei Cofermentation von Hexosen mit externen Elektronenakzeptoren, wie Fructose, Pyruvat oder Sauerstoff, werden letztere zur Reoxidation von NAD(P)H genutzt, und als Folge wird Acetat ausgeschieden. Der Fluss von Fructose in den Phosphoketolaseweg wird durch das Enzym Phosphoglucoseisomerase verhindert, wenn dieses durch 6-Phosphogluconat gehemmt wird. Als Konsequenz wird Fructose im Mannitweg reduziert, was die Bildung von Essigsäure im Phosphoketolaseweg fördert. Bei niedrigen Wachstums- und Stoffwechselraten, z.B. bei C-Limitierung, ist der Ethanolweg nicht limitierend für den Stoffwechsel, und Hexosen werden über heterofermentative Milchsäuregärung umgesetzt, ohne daß Acetat entsteht. Pyruvat kann gleichzeitig als Elektronenakzeptor und als Energiequelle dienen: O. oeni ist in der Lage, Pyruvat mittels Disproportionierung zu Lactat und Acetat+CO2 zu fermentieren, und dabei Energie zu konservieren (0,5 ATP / Pyruvat).

Photovoltaics from discotic liquid crystalline HBCs & poly(2,7-carbazole)s

In this study, the use of the discotic liquid crystalline HBCs and conjugated polymers based on 2,7-carbazole were investigated in detail as donor materials in organic bulk-heterojunction solar cells. It has been shown that they perform efficiently in photovoltaic devices in combination with suitable acceptors. The efficiency was found to depend strongly dependent on the morphology of the film. By investigation of a series of donor materials with similar molecular structures based on both discotic molecules and conjugated polymers, a structure-performance relation was established, which is not only instructive for these materials but also serves as a guideline for improved molecular design. For the series of HBCs used in this study, it is found that the device efficiency decreases with increasing length of the alkyl substituents in the HBC. Thus, the derivative with the smallest alkyl mantle, being more crystalline compared to the HBCs with longer alkyl chains, gave the highest EQE of 12%. A large interfacial separation was found in the blend of HBC-C6,2 and PDI, since the crystallization of the acceptor occurred in a solid matrix of HBC. This led to small dispersed organized domains and benefited the charge transport. In contrast, blends of HBC-C10,6/PDI or HBC-C14,10/PDI revealed a rather homogeneous film limiting the percolation pathways due to a mixed phase. For the first time, poly(2,7-carbazole) was incorporated as a donor material in solar cells using PDI as an electron acceptor. The good fit in orbital energy levels and absorption spectra led to high efficiency. This result indicates that conjugated polymers with high band-gap can also be applied as materials to build efficient solar cells if appropriate electron acceptors are chosen. In order to enhance the light absorption ability, new ladder-type polymers based on pentaphenylene and hexaphenylene with one and three nitrogen bridges per repeat unit have been synthesized and characterized. The polymer 2 with three nitrogen bridges showed more red-shifted absorbance and emission and better packing in the solid-state than the analogous polymer 3 with only one nitrogen bridge per monomer unit. An overall efficiency as high as 1.3% under solar light was obtained for the device based on 1 and PDI, compared with 0.7% for the PCz based device. Therefore, the device performance correlates to a large extent with the solar light absorption ability and the lateral distance between conjugated polymer chains. Since the lateral distance is determined by the length and number of attached alkyl side chains, it is possible to assume that these substituents insulate the charge carrier pathways and decrease the device performance. As an additional consequence, the active semiconductor is diluted in the insulating matrix leading to a lower light absorption. This work suggests ways to improve device performance by molecular design, viz. maintaining the HOMO level while bathochromically shifting the absorption by adopting a more rigid ladder-type structure. Also, a high ratio of nitrogen bridges with small alkyl substituents was a desirable feature both in terms of adjusting the absorption and maintaining a low lateral inter-chain separation, which was necessary for obtaining high current and efficiency values.

Charge transport properties of organic conjugated polymers for photovoltaic applications

Charge transport in conjugated polymers as well as in bulk-heterojunction (BHJ) solar cells made of blends between conjugated polymers, as electron-donors (D), and fullerenes, as electron-acceptors (A), has been investigated. It is shown how charge carrier mobility of a series of anthracene-containing poly(p-phenylene-ethynylene)-alt-poly(p-phenylene-vinylene)s (AnE-PVs) is highly dependent on the lateral chain of the polymers, on a moderate variation of the macromolecular parameters (molecular weight and polydispersity), and on the processing conditions of the films. For the first time, the good ambipolar transport properties of this relevant class of conjugated polymers have been demonstrated, consistent with the high delocalization of both the frontier molecular orbitals. Charge transport is one of the key parameters in the operation of BHJ solar cells and depends both on charge carrier mobility in pristine materials and on the nanoscale morphology of the D/A blend, as proved by the results here reported. A straight correlation between hole mobility in pristine AnE-PVs and the fill factor of the related solar cells has been found. The great impact of charge transport for the performance of BHJ solar cells is clearly demonstrated by the results obtained on BHJ solar cells made of neat-C70, instead of the common soluble fullerene derivatives (PCBM or PC70BM). The investigation of neat-C70 solar cells was motivated by the extremely low cost of non-functionalized fullerenes, compared with that of their soluble derivatives (about one-tenth). For these cells, an improper morphology of the blend leads to a deterioration of charge carrier mobility, which, in turn, increases charge carrier recombination. Thanks to the appropriate choice of the donor component, solar cells made of neat-C70 exhibiting an efficiency of 4.22% have been realized, with an efficiency loss of just 12% with respect to the counterpart made with costly PC70BM.

Excited-state dynamics in donor-acceptor systems for energy conversion

In dieser Arbeit werden die Dynamiken angeregter Zustände in Donor-Akzeptorsystemen für Energieumwandlungsprozesse mit ultraschneller zeitaufgelöster optischer Spektroskopie behandelt. Der Hauptteil dieser Arbeit legt den Fokus auf die Erforschung der Photophysik organischer Solarzellen, deren aktive Schichten aus diketopyrrolopyrrole (DPP) basierten Polymeren mit kleiner Bandlücke als Elektronendonatoren und Fullerenen als Elektronenakzeptoren bestehen. rnEin zweiter Teil widmet sich der Erforschung von künstlichen primären Photosynthesereaktionszentren, basierend auf Porphyrinen, Quinonen und Ferrocenen, die jeweils als Lichtsammeleinheit, Elektronenakzeptor beziehungsweise als Elektronendonatoren eingesetzt werden, um langlebige ladungsgetrennte Zustände zu erzeugen.rnrnZeitaufgelöste Photolumineszenzspektroskopie und transiente Absorptionsspektroskopie haben gezeigt, dass Singulettexzitonenlebenszeiten in den Polymeren PTDPP-TT und PFDPP-TT Polymeren kurz sind (< 20 ps) und dass in Mischungen der Polymere mit PC71BM geminale Rekombination von gebundenen Ladungstransferzuständen ein Hauptverlustkanal ist. Zudem wurde in beiden Systemen schnelle nichtgeminale Rekombination freier Ladungen zu Triplettzuständen auf dem Polymer beobachtet. Für das Donor-Akzeptor System PDPP5T:PC71BM wurde nachgewiesen, dass die Zugabe eines Lösungsmittels mit hohem Siedepunkt, und zwar ortho-Dichlorbenzol, die Morphologie der aktiven Schicht stark beeinflusst und die Solarzelleneffizienz verbessert. Der Grund hierfür ist, dass die Donator- und Akzeptormaterialien besser durchmischt sind und sich Perkolationswege zu den Elektroden ausgebildet haben, was zu einer verbesserten Ladungsträgergeneration und Extraktion führt. Schnelle Bildung des Triplettzustands wurde in beiden PDPP5T:PC71BM Systemen beobachtet, da der Triplettzustand des Polymers über Laungstransferzustände mit Triplettcharakter populiert werden kann. "Multivariate curve resolution" (MCR) Analyse hat eine starke Intensitätsabhängigkeit gezeigt, was auf nichtgeminale Ladungsträgerrekombination in den Triplettzustand hinweist.rnrnIn den künstlichen primären Photosynthesereaktionszentren hat transiente Absorptionsspektroskopie bestätigt, dass photoinduzierter Ladungstransfer in Quinon-Porphyrin (Q-P) und Porphyrin-Ferrocen (P-Fc) Diaden sowie in Quinon-Porphyrin-Ferrocen (Q-P-Fc) Triaden effizient ist. Es wurde jedoch auch gezeigt, dass in den P-Fc unf Q-P-Fc Systemen die ladungsgetrennten Zustände in den Triplettzustand der jeweiligen Porphyrine rekombinieren. Der ladungsgetrennte Zustand konnte in der Q-P Diade durch Zugabe einer Lewissäure signifikant stabilisiert werden.

DRUG METABOLISM IN LIVER TUMORS: PURIFICATION AND CHARACTERIZATION OF NADPH-CYTOCHROME-P450 REDUCTASE AND THE RESOLUTION OF MULTIPLE FORMS OF CYTOCHROME P-450

The hydroxylation of N- and O-methyl drugs and a polycyclic hydrocarbon has been demonstrated in microsomes prepared from two transplantable Morris hepatomas (i.e., 7288C. t.c. and 5123 t.c.(H). The hydroxylation rates of the drug benzphetamine and the polycyclic hydrocarbon benzo {(alpha)} pyrene by tumor microsomes were inducible 2 to 3-fold and 2-fold, respectively by pretreatment of rats with phenobarbital/hydrocortisone. Hepatoma 5123t.c.(h) microsomal hydroxylation activities were more inducible after these pretreatments than hepatoma 7288C.t.c. Two chemotherapeutic drugs (cyclophosphamide and isophosphamide) were shown to be mutagenic after activation by the tumor hemogenate with the TA100 strain of Salmonella typhimurium bacteria. NADPH-cytochrome P-450 was purified from phenobarbital/hydrocortisone treated rat hepatoma 5123t.c.(H) microsomes 353-fold with a specific activity 63.6 nmol of cytochrome c reduced per min per mg of protein. The purified enzyme, has an apparent molecular weight of 79,500 daltons, and contained an equal molar ratio of FMN and FAD, with a total flavin content of 16.4 nmol per mg of protein. The purified enzyme also catalyzed electron transfer to artificial electron acceptors with the K(,m) values of the hepatoma reductase similar to those of purified liver reductase. The K(,m) value of the hepatoma reductase (13 uM) for NADPH was similar to that of purified liver reductase (5.0 uM). In addition the purified hepatoma reductase was immunochemically similar to the liver reductase.^ Hepatoma cytochrome P-450, the hemeprotein component of the hepatoma microsomes of rats pretreated with phenobarbital/hydrocortisone. The resolution of the six forms was achieved by the DE-53 ion-exchange chromatography, and further purified by hydroxyapatite. The six different fractions that contained P-450 activity, had specific contents from 0.47 to 1.75 nmol of cytochrome P-450 per mg of protein, and indicated a 2 to 9-fold purification as compared to the original microsomes. In addition, difference spectra, molecular weights and immunological results suggest there are at least six different forms of cytochrome P-450 in hepatoma 5123 t.c.(H). ^

CHARACTERIZATION OF CYTOCHROME P-450 MIXED FUNCTION OXIDASE OF RAT COLON MUCOSA

Non-pregnant, female adult rats pretreated with either phenobarbital (PB) or (beta)-naphthoflavone ((beta)NF) through short-course intraperitoneal injections were shown by sodium dithionite-reduced carbon monoxide difference spectroscopy and NADPH-cytochrome c in vitro assay to contain cytochrome P-450 and NADPH-dependent reductase associated with the microsomal fraction of colon mucosa. These two protein components of the mixed function oxidase system were released from the microsomal membrane, resolved from each other, and partially purified by using a combination of techniques including solubilization in nonionic detergent followed by ultracentrifugation, anion exchange and adsorption column chromatographies, native gel electrophoresis, polyethylene glycol fractionation and ultrafiltration.^ In vitro reconstitution assays demonstrated the cytochrome P-450 fraction as the site of substrate and molecular oxygen binding. By the use of immunochemical techniques including radial immunodiffusion, Ouchterlony double diffusion and protein electroblotting, the cytochrome P-450 fraction was shown to contain at least 5 forms of the protein, having molecular weights as determined by SDS gel electrophoresis identical to the corresponding hepatic cytochrome P-450. Estimation of total cytochrome P-450 content confirmed the preferential induction of particular forms in response to the appropriate drug pretreatment.^ The colonic NADPH-dependent reductase was isolated from native gel electrophoresis and second dimensional SDS gel electrophoresis was performed in parallel to that for purified reductase from liver. Comparative electrophoretic mobilities together with immunochemical analysis, as with the cytochrome P-450s, reconstitution assays, and kinetic characterization using artificial electron acceptors, gave conclusive proof of the structural and functional homology between the colon and liver sources of the enzyme.^ Drug metabolism was performed in the reconstituted mixed function oxidase system containing a particular purified liver cytochrome P-450 form or partially pure colon cytochrome P-450 fraction plus colon or liver reductase and synthetic lipid vesicles. The two drugs, benzo{(alpha)}pyrene and benzphetamine, which are most representative of the action of system in liver, lung and kidney, were tested to determine the specificity of the reconstituted system. The kinetics of benzo{(alpha)}pyrene hydroxylation were followed fluorimetrically for 3-hydroxybenzo{(alpha)}pyrene production. . . . (Author's abstract exceeds stipulated maximum length. Discontinued here with permission of author.) UMI ^

Comparison of TEX86 and UK'37 temperature proxies in sinking particles in the Cariaco Basin

The Cariaco Basin, a silled, permanently anoxic basin on the continental shelf of Venezuela with a dynamic chemocline (-240-350 m), has been subject of > 20 years of oceanographic observation and sediment trap studies. We evaluated UK'37 and the TEX86 temperature proxies using sinking particles collected in shallow sediment trap samples at 275 m (Trap A) and 455 m (Trap B) (within and below the chemocline). The organic geochemical temperature proxies, UK'37. (based on coccolithophorid alkenone lipids) and TEX86 (based on archaeal glycerol dialkyl glycerol tetraether (GDGT) lipids), use observed relationships between the ratio of specific lipids and measured sea surface temperature to hindcast past sea surface temperatures. In this study, both UK'37 and TEX86 temperature proxies record seasonal temperature variations, including the cooling associated with upwelling events. UK'37-based temperatures are colder than measured sea surface temperatures, and better correlated temperature at the chlorophyll maximum. In sediment trap material collected below the chemocline (Trap B), UK'37 values are higher than those in Trap A. Warmer subchemocline UK'37 based temperatures may be related to autooxidation of sinking particles, either by small amounts of available oxygen or by alternate electron acceptors concentrated in the biologically dynamic chemocline (e.g. intermediate sulfur compounds). The absolute flux weighted TEX86 temperature values measured in sinking particles from Trap A match the measured SST well. The differences in the TEX86 values between Traps A and B are small and reflect less impact of degradation. Overall, the TEX86 temperatures in sinking particles in the Cariaco Basin reflect annual SST.

Geochemistry of reduction haloes in ODP Holes 135-834A and 135-837A

The sediment column overlying basement in the Lau Basin consists of a sequence of volcaniclastic turbidites interbedded with hemipelagic clayey nannofossil mixed sediments, overlain in turn by a sequence of hemipelagic clayey nannofossil oozes containing sporadic calcareous turbidites. The clayey nannofossil oozes and mixed sediments are pervasively stained by hydrothermally derived iron and manganese oxyhydroxides. Sharply defined, lighter colored bands occur in the hemipelagic sediments, immediately beneath some (but by no means all) volcaniclastic and calcareous turbidites. These are identified as reduction haloes, of a type previously identified in quite different turbidite/pelagic sequences. The haloes are attributed to the burial of labile surficial Corg by turbidites, followed by the remineralization of this Corg with Mn and Fe oxyhydroxides as electron acceptors. The resultant characteristic Mn and Fe concentration/depth profiles are described, and a model is proposed for their development. The color alteration of the halo is ascribed to the removal of Mn oxyhydroxides, because, although the Fe content fluctuates through the haloes, this does not appear to affect their color. Other elements (Co, Cu, and Ni) are also at low concentration levels in the haloes like Mn, consistent with remobilization and migration out of the halo section, although the profile shapes are not identical with those of Mn. The behavior of V is distinctive in that it appears to have migrated into the haloes to be enriched there. Haloes are unlikely to form if turbidite emplacement is erosive and removes the near-surface layer, which generally is the most fluid part of the sediment and contains the highest levels of reactive Corg to drive the reduction process. Conversely, the presence of a halo implies that emplacement of the overlying turbidite did not significantly erode the pre-existing sediment/water interface.

Organic carbon and nitrogen at DSDP Leg 58 Holes

The sediments penetrated on Leg 58 of the Deep Sea Drilling Project in the Philippine Sea represent long periods of geologic time during which depositional conditions apparently remained very constant. Organic carbon and nitrogen contents of the sediments decrease with increasing depth of burial, before leveling off at minimum values of about 0.05 to 0.10 per cent and 0.01 per cent, respectively. The depth at which the minimum values are reached varies from site to site, but ages of sediments corresponding to the minima are all about 5 m.y. We infer that slow bacterial diagenesis is responsible for the gradual depletion of organic carbon and nitrogen. It is likely that the rate of bacterial metabolism is controlled by the rate of diffusion of electron acceptors within the sediments. These results suggest that bacterial ecosystems in deep-water sediments play a much more important role in diagenesis than has previously been thought.

Highly sensitive biological and chemical sensors based on reversible fluorescence quenching in a conjugated polymer

The fluorescence of a polyanionic conjugated polymer can be quenched by extremely low concentrations of cationic electron acceptors in aqueous solutions. We report a greater than million-fold amplification of the sensitivity to fluorescence quenching compared with corresponding “molecular excited states.” Using a combination of steady-state and ultrafast spectroscopy, we have established that the dramatic quenching results from weak complex formation [polymer(−)/quencher(+)], followed by ultrafast electron transfer from excitations on the entire polymer chain to the quencher, with a time constant of 650 fs. Because of the weak complex formation, the quenching can be selectively reversed by using a quencher-recognition diad. We have constructed such a diad and demonstrate that the fluorescence is fully recovered on binding between the recognition site and a specific analyte protein. In both solutions and thin films, this reversible fluorescence quenching provides the basis for a new class of highly sensitive biological and chemical sensors.

Energy Sources for HCO3− and CO2 Transport in Air-Grown Cells of Synechococcus UTEX 6251

Light-dependent inorganic C (Ci) transport and accumulation in air-grown cells of Synechococcus UTEX 625 were examined with a mass spectrometer in the presence of inhibitors or artificial electron acceptors of photosynthesis in an attempt to drive CO2 or HCO3− uptake separately by the cyclic or linear electron transport chains. In the presence of 3-(3,4-dichlorophenyl)-1,1-dimethylurea, the cells were able to accumulate an intracellular Ci pool of 20 mm, even though CO2 fixation was completely inhibited, indicating that cyclic electron flow was involved in the Ci-concentrating mechanism. When 200 μm N,N-dimethyl-p-nitrosoaniline was used to drain electrons from ferredoxin, a similar Ci accumulation was observed, suggesting that linear electron flow could support the transport of Ci. When carbonic anhydrase was not present, initial CO2 uptake was greatly reduced and the extracellular [CO2] eventually increased to a level higher than equilibrium, strongly suggesting that CO2 transport was inhibited and that Ci accumulation was the result of active HCO3− transport. With 3-(3,4-dichlorophenyl)-1,1-dimethylurea-treated cells, Ci transport and accumulation were inhibited by inhibitors of CO2 transport, such as COS and Na2S, whereas Li+, an HCO3−-transport inhibitor, had little effect. In the presence of N,N-dimethyl-p-nitrosoaniline, Ci transport and accumulation were not inhibited by COS and Na2S but were inhibited by Li+. These results suggest that CO2 transport is supported by cyclic electron transport and that HCO3− transport is supported by linear electron transport.

Oxygen microprofiles and porewater chemistry in sediments of the Skagerrak

Sediment porewater oxygen profiles were measured with micro and needle electrodes in sediment cores of 27 stations in the Skagerrak (northeastern North Sea). Oxygen penetration depth ranged from 3 to 20 mm depth. Fluxes estimated from the oxygen gradients varied from 3 to 18 mmol m**-2 d**-1. Oxygen penetration and flux depend on water depth, but possibly more on the hydrological conditions, related to the import of fresh organic matter by primary production in the water column. Oxygen fluxes were not related to the total organic carbon (TOC) content of the sediments. Stations in the eastern part of the Skagerrak showed high burial rates of TOC. At 6 stations porewater chemistry of Fe, Mn and NO3- was strongly associated with the oxygen distribution. The average relative contribution of terminal electron acceptors to carbon mineralisation was estimated at 85% for O2, 0.5% for Mn, 4.5% for [NO3]3-, 1% for Fe and 9% for [SO4]2-. At one station the occurrence of exceptionally high solid manganese oxyhydroxides was probably related to an active internal manganese cycle.

The Effect of Nutrient-Rich Effluents from Shrimp Farming on Mangrove Soil Carbon Storage and Geochemistry Under Semi-Arid Climate Conditions in Northern Brazil

A semi-arid mangrove estuary system in the northeast Brazilian coast (Ceará state) was selected for this study to (i) evaluate the impact of shrimp farm nutrient-rich wastewater effluents on the soil geochemistry and organic carbon (OC) storage and (ii) estimate the total amount of OC stored in mangrove soils (0–40 cm). Wastewater-affected mangrove forests were referred to as WAM and undisturbed areas as Non-WAM. Redox conditions and OC content were statistically correlated (P < 0.05) with seasonality and type of land use (WAM vs. Non-WAM). Eh values were from anoxic to oxic conditions in the wet season (from − 5 to 68 mV in WAM and from < 40 to > 400 mV in Non-WAM soils) and significantly higher (from 66 to 411 mV) in the dry season (P < 0.01). OC contents (0–40 cm soil depth) were significantly higher (P < 0.01) in the wet season than the dry season, and higher in Non-WAM soils than in WAM soils (values of 8.1 and 6.7 kg m− 2 in the wet and dry seasons, respectively, for Non-WAM, and values of 3.8 and 2.9 kg m− 2 in the wet and dry seasons, respectively, for WAM soils; P < 0.01). Iron partitioning was significantly dependent (P < 0.05) on type of land use, with a smaller degree of pyritization and lower Fe-pyrite presence in WAM soils compared to Non-WAM soils. Basal respiration of soil sediments was significantly influenced (P < 0.01) by type of land use with highest CO2 flux rates measured in the WAM soils (mean values of 0.20 mg CO2 h− 1–g− 1 C vs. 0.04 mg CO2 h− 1–g− 1 C). The OC storage reduction in WAM soils was potentially caused (i) by an increase in microbial activity induced by loading of nutrient-rich effluents and (ii) by an increase of strong electron acceptors [e.g., NO3−] that promote a decrease in pyrite concentration and hence a reduction in soil OC burial. The current estimated OC stored in mangrove soils (0–40 cm) in the state of Ceará is approximately 1 million t.

Methane and sulphate consumption in different habitats of the Håkon Mosby Mud Volcano (HMMV)

The Hakon Mosby Mud Volcano is a highly active methane seep hosting different chemosynthetic communities such as thiotrophic bacterial mats and siboglinid tubeworm assemblages. This study focuses on in situ measurements of methane fluxes to and from these different habitats, in comparison to benthic methane and oxygen consumption rates. By quantifying in situ oxygen, methane, and sulfide fluxes in different habitats, a spatial budget covering areas of 10-1000 -m diameter was established. The range of dissolved methane efflux (770-2 mmol m-2 d-1) from the center to the outer rim was associated with a decrease in temperature gradients from 46°C to < 1°C m-1, indicating that spatial variations in fluid flow control the distribution of benthic habitats and activities. Accordingly, total oxygen uptake (TOU) varied between the different habitats by one order of magnitude from 15 mmol m-2 d-1 to 161 mmol m-2 d-1. High fluid flow rates appeared to suppress benthic activities by limiting the availability of electron acceptors. Accordingly, the highest TOU was associated with the lowest fluid flow and methane efflux. This was most likely due to the aerobic oxidation of methane, which may be more relevant as a sink for methane as previously considered in submarine ecosystems.