Dark carbon fixation in the Arabian Sea oxygen minimum zone contributes to sedimentary organic carbon (SOM)

In response to rising CO2concentrations and increasing global sea surface temperatures,oxygen minimum zones (OMZ), or“dead zones”, are expected to expand. OMZs are fueled by highprimary productivity, resulting in enhanced biological oxygen demand at depth, subsequent oxygen depletion, and attenuation of remineralization. This results in the deposition of organic carbon‐rich sediments. Carbon drawdown is estimated by biogeochemical models; however, a major process is ignored: carbon fixation in the mid‐and lower water column. Here, we show that chemoautotrophic carbon fixation is important in the Arabian Sea OMZ; and manifests in a13C‐depleted signature of sedimentary organic carbon. We determined theδ13C values of Corg deposited in close spatial proximity but over a steepbottom‐water oxygen gradient, and theδ13C composition of biomarkers of chemoautotrophic bacteriacapable of anaerobic ammonia oxidation (anammox). Isotope mixing models show that detritus fromanammox bacteria or other chemoautotrophs likely forms a substantial part of the organic matter depositedwithin the Arabian Sea OMZ (~17%), implying that the contribution of chemoautotrophs to settling organicmatter is exported to the sediment. This has implications for the evaluation of past, and future, OMZs:biogeochemical models that operate on the assumption that all sinking organic matter is photosynthetically derived, without new addition of carbon, could significantly underestimate the extent of remineralization. Oxygen demand in oxygen minimum zones could thus be higher than projections suggest, leading to a more intense expansion of OMZs than expected

The tryptophan aminotransferase Tam1 catalyses the single biosynthetic step for tryptophan-dependent pigment synthesis in Ustilago maydis.

Tryptophan is a precursor for many biologically active secondary metabolites. We have investigated the origin of indole pigments first described in the pityriasis versicolor-associated fungus Malassezia furfur. Some of the identified indole pigments have properties potentially explaining characteristics of the disease. As M. furfur is not amenable to genetic manipulation, we used Ustilago maydis to investigate the pathway leading to pigment production from tryptophan. We show by high-performance liquid chromatography, mass spectrometry and nuclear magnetic resonance analysis that the compounds produced by U. maydis include those putatively involved in the etiology of pityriasis versicolor. Using a reverse genetics approach, we demonstrate that the tryptophan aminotransferase Tam1 catalyses pigment biosynthesis by conversion of tryptophan into indolepyruvate. A forward genetics approach led to the identification of mutants incapable of producing the pigments. These mutants were affected in the sir1 gene, presumably encoding a sulphite reductase. In vitro experiments with purified Tam1 showed that 2-oxo 4-methylthio butanoate serves as a substrate linking tryptophan deamination to sulphur metabolism. We provide the first direct evidence that these indole pigments form spontaneously from indolepyruvate and tryptophan without any enzymatic activity. This suggests that compounds with a proposed function in M. furfur-associated disease consist of indolepyruvate-derived spontaneously generated metabolic by-products

Precession driven changes in terrestrial organic matter input to the Eastern Mediterranean leading up to the Messinian Salinity Crisis

Eastern Mediterranean sediments over the past 12 Myr commonly show strongly developed precessional cyclicity, thought to be a biogeochemical response to insolation-driven freshwater input from run-off. The Mediterranean's dominant freshwater source today and in the past, is the Nile, which is fed by North African monsoon rain; other, smaller, circum-Mediterranean rivers also contribute to Mediterranean hydrology. Crucially, run-off through all of these systems appears to vary with precession, but there is no direct evidence linking individual water sources to the biogeochemical response recorded in Mediterranean sediments. Consequently, it is not clear whether the North African monsoon is entirely responsible for the Mediterranean's sedimentary cyclicity, or whether other, precessional signals, such as Atlantic storm precipitation, drive it. Organic matter in sediments derives from both marine and terrestrial sources and biomarker analysis can be used to discriminate between the two, thereby providing insight into sedimentary and ecological processes. We analysed a wide range of lipids from the Late Miocene (6.6–5.9 Ma) Pissouri section, southern Cyprus, and reconstructed the vegetation supplied to this region by measuring the carbon isotopes of the terrestrial component to identify its geographic source. BIT (Branched-Isoprenoidal-Tetraether) indices reflect changes in the relative abundance of marine vs terrestrial (soil) organic matter inputs, and with the exception of records from the last deglaciation, this work is the first application of the BIT approach to the reconstruction of orbital impacts on sedimentological processes. BIT indices show that the organic matter supplied to Cyprus changed over the course of each precession cycle and was dominantly terrestrial during insolation maxima when North African run-off was enhanced. The δ13C values from these intervals are compatible with tropical North African vegetation. However, the δ13C record indicates that during insolation minima, organic material supplied to southern Cyprus derives from a more arid source region. This is likely to have been aeolian-transported organic matter from the Anatolian Plateau demonstrating that even in Mediterranean sedimentary systems influenced by Nile run-off, there is more than one independent precessional organic matter contribution to the sedimentary cyclicity. Pissouri's organic geochemistry also illustrates a long-term trend towards more saline Mediterranean conditions during the 600 kyr leading up to the Messinian Salinity Crisis

Precession driven changes in terrestrial organic matter input to the Eastern Mediterranean leading up to the Messinian Salinity Crisis

Eastern Mediterranean sediments over the past 12 Myr commonly show strongly developed precessional cyclicity, thought to be a biogeochemical response to insolation-driven freshwater input from run-off. The Mediterranean's dominant freshwater source today and in the past, is the Nile, which is fed by North African monsoon rain; other, smaller, circum-Mediterranean rivers also contribute to Mediterranean hydrology. Crucially, run-off through all of these systems appears to vary with precession, but there is no direct evidence linking individual water sources to the biogeochemical response recorded in Mediterranean sediments. Consequently, it is not clear whether the North African monsoon is entirely responsible for the Mediterranean's sedimentary cyclicity, or whether other, precessional signals, such as Atlantic storm precipitation, drive it. Organic matter in sediments derives from both marine and terrestrial sources and biomarker analysis can be used to discriminate between the two, thereby providing insight into sedimentary and ecological processes. We analysed a wide range of lipids from the Late Miocene (6.6–5.9 Ma) Pissouri section, southern Cyprus, and reconstructed the vegetation supplied to this region by measuring the carbon isotopes of the terrestrial component to identify its geographic source. BIT (Branched-Isoprenoidal-Tetraether) indices reflect changes in the relative abundance of marine vs terrestrial (soil) organic matter inputs, and with the exception of records from the last deglaciation, this work is the first application of the BIT approach to the reconstruction of orbital impacts on sedimentological processes. BIT indices show that the organic matter supplied to Cyprus changed over the course of each precession cycle and was dominantly terrestrial during insolation maxima when North African run-off was enhanced. The δ13C values from these intervals are compatible with tropical North African vegetation. However, the δ13C record indicates that during insolation minima, organic material supplied to southern Cyprus derives from a more arid source region. This is likely to have been aeolian-transported organic matter from the Anatolian Plateau demonstrating that even in Mediterranean sedimentary systems influenced by Nile run-off, there is more than one independent precessional organic matter contribution to the sedimentary cyclicity. Pissouri's organic geochemistry also illustrates a long-term trend towards more saline Mediterranean conditions during the 600 kyr leading up to the Messinian Salinity Crisis

Determination of the δ 2H Values of High Molecular Weight Lipids by High Temperature GC Coupled to Isotope Ratio Mass Spectrometry

Rationale: The hydrogen isotopic composition of lipids (δ 2Hlipid) is widely used in foodscience and as a proxy for past hydrological conditions. Determining the δ 2H values of large,well-preserved triacylglycerides and other uniquely microbial lipids, such as glycerol dialkylglycerol tetraether (GDGT) lipids, is thus of widespread interest but has so far not been possible due to their size which prohibits analysis by traditional gas chromatographypyrolysis isotope ratio mass spectrometry (GC-P-IRMS).Methods: We determined the δ 2H values of large, polar molecules and applied hightemperature gas chromatography (GC) methods on a modified GC-P-IRMS system. Themethods were validated using authentic standards of large, functionalised molecules(triacylglycerides, TAG), purified reference standards of GDGTs, and compared to δ 2Hvalues determined by elemental analyser pyrolysis isotope ratio mass spectrometry (EA-PIRMS); and subsequently applied to the analysis of GDGTs in a sample from a methaneseep and a Welsh peat.Results: δ 2H values of TAGs agreed within error between different between GC-P-IRMS andEA-P-IRMS, with GC-P-IRMS showing 3-5 ‰ precision for 10 ng H injected. Archaeal lipidGDGTs with up to three cyclisations could be analysed: δ 2H values were not significantlydifferent between methods with standard deviations of 5 to 6 ‰. When environmentalsamples were analysed, δ 38 2H values of isoGDGTs were 50 ‰ more negative than those ofterrestrial brGDGTs.Conclusions: Our results indicate that the high temperature GC-P-IRMS (HTGC-P-IRMS)method developed here is appropriate to determine the δ 2H values of TAGs, GDGT lipidswith up to two cyclisations, and potentially other high molecular weight compounds. Themethodology will widen the current analytical window for biomarker and alimentary lightstable isotope analyses. Moreover, our initial measurements suggest that bacterial andarchaeal GDGT δ 2H values can record environmental and ecological conditions</div

Evolution of the Late Miocene Mediterranean–Atlantic gateways and their impact on regional and global environmental change

Marine gateways play a critical role in the exchange of water, heat, salt and nutrients between oceans and seas. As a result, changes in gateway geometry can significantly alter both the pattern of global ocean circulation and associated heat transport and climate, as well as having a profound impact on local environmental conditions. Mediterranean–Atlantic marine corridors that pre-date the modern Gibraltar Strait, closed during the Late Miocene and are now exposed on land in northern Morocco and southern Spain. The restriction and closure of these Miocene connections resulted in extreme salinity fluctuations in the Mediterranean, leading to the precipitation of thick evaporites. This event is known as the Messinian Salinity Crisis (MSC). The evolution and closure of the Mediterranean–Atlantic gateways are a critical control on the MSC, but at present the location, geometry and age of these gateways are still highly controversial, as is the impact of changing Mediterranean outflow on Northern Hemisphere circulation. Here, we present a comprehensive overview of the evolution of the Late Miocene gateways and the nature of Mediterranean–Atlantic exchange as deduced from published studies focussed both on the sediments preserved within the fossil corridors and inferences that can be derived from data in the adjacent basins. We also consider the possible impact of evolving exchange on both the Mediterranean and global climate and highlight the main enduring challenges for reconstructing past Mediterranean–Atlantic exchange

Evolution of the Late Miocene Mediterranean–Atlantic gateways and their impact on regional and global environmental change

Marine gateways play a critical role in the exchange of water, heat, salt and nutrients between oceans and seas. As a result, changes in gateway geometry can significantly alter both the pattern of global ocean circulation and associated heat transport and climate, as well as having a profound impact on local environmental conditions. Mediterranean–Atlantic marine corridors that pre-date the modern Gibraltar Strait, closed during the Late Miocene and are now exposed on land in northern Morocco and southern Spain. The restriction and closure of these Miocene connections resulted in extreme salinity fluctuations in the Mediterranean, leading to the precipitation of thick evaporites. This event is known as the Messinian Salinity Crisis (MSC). The evolution and closure of the Mediterranean–Atlantic gateways are a critical control on the MSC, but at present the location, geometry and age of these gateways are still highly controversial, as is the impact of changing Mediterranean outflow on Northern Hemisphere circulation. Here, we present a comprehensive overview of the evolution of the Late Miocene gateways and the nature of Mediterranean–Atlantic exchange as deduced from published studies focussed both on the sediments preserved within the fossil corridors and inferences that can be derived from data in the adjacent basins. We also consider the possible impact of evolving exchange on both the Mediterranean and global climate and highlight the main enduring challenges for reconstructing past Mediterranean–Atlantic exchange