Description: Microbial degradation of substrates to terminal products is commonly understood as a unidirectional process. In individual enzymatic reactions, however, reversibility (reverse reaction and product back flux) is common. Hence, it is possible that entire pathways of microbial degradation are associated with back flux from the accumulating product pool through intracellular intermediates into the substrate pool. We investigated carbon and sulfur back flux during the anaerobic oxidation of methane (AOM) with sulfate, one of the least exergonic microbial catabolic processes known. The involved enzymes must operate not far from the thermodynamic equilibrium. Such an energetic situation is likely to favor product back flux. Indeed, cultures of highly enriched archaeal–bacterial consortia, performing net AOM with unlabeled methane and sulfate, converted label from 14C-bicarbonate and 35S-sulfide to 14C-methane and 35S-sulfate, respectively. Back fluxes reached 5% and 13%, respectively, of the net AOM rate. The existence of catabolic back fluxes in the reverse direction of net reactions has implications for biogeochemical isotope studies. In environments where biochemical processes are close to thermodynamic equilibrium, measured fluxes of labeled substrates to products are not equal to microbial net rates. Detection of a reaction in situ by labeling may not even indicate a net reaction occurring in the direction of label conversion but may reflect the reverse component of a so far unrecognized net reaction. Furthermore, the natural isotopic composition of the substrate and product pool will be determined by both the forward and back flux. This finding may have to be considered in the interpretation of stable isotope records.

Description: Highlights • Naturally enriched AOM biomass was studied in high-pressure continuous incubation. • We report the first S- and O-isotope fractionation values by sulfate reduction coupled to AOM from culture studies. • There is a tight link between methane concentration and S- and O-isotope fractionation. • S- and O-isotope fractionation values indicate reversibility of energy limited microbial processes. • The wide range of environmental S- and O-isotope signatures can be explained. Abstract Isotope signatures of sulfur compounds are key tools for studying sulfur cycling in the modern environment and throughout earth's history. However, for meaningful interpretations, the isotope effects of the processes involved must be known. Sulfate reduction coupled to the anaerobic oxidation of methane (AOM-SR) plays a pivotal role in sedimentary sulfur cycling and is the main process responsible for the consumption of methane in marine sediments − thereby efficiently limiting the escape of this potent greenhouse gas from the seabed to the overlying water column and atmosphere. In contrast to classical dissimilatory sulfate reduction (DSR), where sulfur and oxygen isotope effects have been measured in culture studies and a wide range of isotope effects has been observed, the sulfur and oxygen isotope effects by AOM-SR are unknown. This gap in knowledge severely hampers the interpretation of sulfur cycling in methane-bearing sediments, especially because, unlike DSR which is carried out by a single organism, AOM-SR is presumably catalyzed by consortia of archaea and bacteria that both contribute to the reduction of sulfate to sulfide. We studied sulfur and oxygen isotope effects by AOM-SR at various aqueous methane concentrations from 1.4±0.6 mM1.4±0.6 mM up to 58.8±10.5 mM58.8±10.5 mM in continuous incubation at steady state. Changes in the concentration of methane induced strong changes in sulfur isotope enrichment (View the MathML sourceεS34) and oxygen isotope exchange between water and sulfate relative to sulfate reduction (θOθO), as well as sulfate reduction rates (SRR). Smallest View the MathML sourceεS34 (21.9±1.9‰21.9±1.9‰) and θOθO (0.5±0.20.5±0.2) as well as highest SRR were observed for the highest methane concentration, whereas highest View the MathML sourceεS34 (67.3±26.1‰67.3±26.1‰) and θOθO (2.5±1.52.5±1.5) and lowest SRR were reached at low methane concentration. Our results show that View the MathML sourceεS34, θOθO and SRR during AOM-SR are very sensitive to methane concentration and thus also correlate with energy yield. In sulfate–methane transition zones, AOM-SR is likely to induce very large sulfur isotope fractionation between sulfate and sulfide (i.e. 〉60‰〉60‰) and will drive the oxygen isotope composition of sulfate towards the sulfate–water oxygen isotope equilibrium value. Sulfur isotope fractionation by AOM-SR at gas seeps, where methane fluxes are high, will be much smaller (i.e. 20 to 40‰).

Description: Collectively, marine sediments comprise the largest reservoir of methane on Earth. The flux of methane from the sea bed to the overlying water column is mitigated by the sulphate-dependent anaerobic oxidation of methane by marine microbes within a discrete sedimentary horizon termed the sulphate–methane transition zone. According to conventional isotope systematics, the biological consumption of methane leaves a residue of methane enriched in 13C (refs 1, 2, 3). However, in many instances the methane within sulphate–methane transition zones is depleted in 13C, consistent with the production of methane, and interpreted as evidence for the intertwined anaerobic oxidation and production of methane4, 5, 6. Here, we report results from experiments in which we incubated cultures of microbial methane consumers with methane and low levels of sulphate, and monitored the stable isotope composition of the methane and dissolved inorganic carbon pools over time. Residual methane became progressively enriched in 13C at sulphate concentrations above 0.5 mM, and progressively depleted in 13C below this threshold. We attribute the shift to 13C depletion during the anaerobic oxidation of methane at low sulphate concentrations to the microbially mediated carbon isotope equilibration between methane and carbon dioxide. We suggest that this isotopic effect could help to explain the 13C-depletion of methane in subseafloor sulphate–methane transition zones.

Description: Purpose Sinusoidal gradient oscillations in the kilohertz range are proposed for position tracking of NMR probes and prospective motion correction for arbitrary imaging sequences without any alteration of sequence timing. The method is combined with concurrent field monitoring to robustly perform image reconstruction in the presence of potential dynamic field deviations. Methods Benchmarking experiments were done to assess the accuracy and precision of the method and to compare it with theoretical predictions based on the field probe's time-dependent signal-to-noise ratio. An array of four field probes was used to perform real-time prospective motion correction in vivo. Images were reconstructed based on both predetermined and concurrently measured k-space trajectories. Results For observation windows of 4.8 ms, the precision of probe position determination was found to be 35 to 62 µm, and the maximal measurement error was 595 µm root-mean-square on a single axis. Sequence update per repetition time on this basis yielded images free of conspicuous artifacts despite substantial head motion. Predetermined and concurrently observed k-space trajectories yielded equivalent image quality. Conclusion NMR field probes in conjunction with gradient tones permit the tracking and prospective correction of rigid-body motion. Relying on gradient oscillations in the kilohertz range, the method allows for concurrent motion detection and image encoding. Magn Reson Med, 2014. © 2014 Wiley Periodicals, Inc.

Description: Purpose Zero echo time (ZTE) imaging is a robust and silent 3D radial technique suitable for direct MRI of tissues with very rapid transverse relaxation. Given its successful application on micro- and animal MRI systems, the purpose of this work is to enable and demonstrate ZTE imaging in humans using a whole-body magnet. Methods A commercial 7 T MRI scanner was complemented by rapid high-power transmit-receive switches, a custom-built spectrometer, and a proton-free detector coil. With this setup, transmit-receive switching is achieved within 1 µs, radiofrequency (RF) excitation is performed in 3 µs, and digital bandpass filtering takes 5.3 µs, resulting in an effective dead time of only 5 µs. Results ZTE imaging was performed at 250 and 500 kHz bandwidth with central k-space gaps of 1.2 and 2.5 Nyquist intervals and repetition times of 739 and 471 µs. The technique was applied for silent 3D imaging of the head and joints of human volunteers at an isotropic resolution down to 0.83 mm. A sound pressure level of 41 dB(A) was measured, which is a reduction of more than 40 dB(A) compared to gradient-switched MRI. Conclusion ZTE imaging in humans was demonstrated for the first time, enabled by dedicated, high-performing RF hardware. Magn Reson Med, 2013. © 2013 Wiley Periodicals, Inc.

Description: Purpose Magnetic field fluctuations caused by subject motion, such as breathing or limb motion, can degrade image quality in brain MRI, especially at high field strengths. The purpose of this study was to investigate the feasibility of retrospectively correcting for such physiological field perturbations based on concurrent field monitoring. Theory and Methods High-resolution T2*-weighted gradient-echo images of the brain were acquired at 7T with subjects performing different breathing and hand movement patterns. Field monitoring with a set of 19 F NMR probes distributed around the head was performed in two variants: concurrently with imaging or as a single field measurement per readout. The measured field fluctuations were then accounted for in the image reconstruction. Results Significant field fluctuations due to motion were observed in all subjects, resulting in severe artifacts in uncorrected images. The artifacts were largely removed by reconstruction based on field monitoring. Accounting for field perturbations up to the 1st spatial order was generally sufficient to recover good image quality. Conclusions It has been demonstrated that artifacts due to physiologically induced dynamic field perturbations can be greatly reduced by retrospective image correction based on field monitoring. The necessity to perform such correction is greatest at high fields and for field-sensitive techniques such as T2*-weighted imaging. Magn Reson Med, 2014. © 2014 Wiley Periodicals, Inc.