Acetyl Phosphate as a Primordial Energy Currency at the Origin of Life

Metabolism is primed through the formation of thioesters via acetyl CoA and the phosphorylation of substrates by ATP. Prebiotic equivalents such as methyl thioacetate and acetyl phosphate have been proposed to catalyse analogous reactions at the origin of life, but their propensity to hydrolyse challenges this view. Here we show that acetyl phosphate (AcP) can be synthesised in water within minutes from thioacetate (but not methyl thioacetate) under ambient conditions. AcP is stable over hours, depending on temperature, pH and cation content, giving it an ideal poise between stability and reactivity. We show that AcP can phosphorylate nucleotide precursors such as ribose to ribose-5-phosphate and adenosine to adenosine monophosphate, at modest (~2%) yield in water, and at a range of pH. AcP can also phosphorylate ADP to ATP in water over several hours at 50 °C. But AcP did not promote polymerization of either glycine or AMP. The amino group of glycine was preferentially acetylated by AcP, especially at alkaline pH, hindering the formation of polypeptides. AMP formed small stacks of up to 7 monomers, but these did not polymerise in the presence of AcP in aqueous solution. We conclude that AcP can phosphorylate biologically meaningful substrates in a manner analogous to ATP, promoting the origins of metabolism, but is unlikely to have driven polymerization of macromolecules such as polypeptides or RNA in free solution. This is consistent with the idea that a period of monomer (cofactor) catalysis preceded the emergence of polymeric enzymes or ribozymes at the origin of life

An Origin-of-Life Reactor to Simulate Alkaline Hydrothermal Vents

Chemiosmotic coupling is universal: practically all cells harness electrochemical proton gradients across membranes to drive ATP synthesis, powering biochemistry. Autotrophic cells, including phototrophs and chemolithotrophs, also use proton gradients to power carbon fixation directly. The universality of chemiosmotic coupling suggests that it arose very early in evolution, but its origins are obscure. Alkaline hydrothermal systems sustain natural proton gradients across the thin inorganic barriers of interconnected micropores within deep-sea vents. In Hadean oceans, these inorganic barriers should have contained catalytic Fe(Ni)S minerals similar in structure to cofactors in modern metabolic enzymes, suggesting a possible abiotic origin of chemiosmotic coupling. The continuous supply of H2 and CO2 from vent fluids and early oceans, respectively, offers further parallels with the biochemistry of ancient autotrophic cells, notably the acetyl CoA pathway in archaea and bacteria. However, the precise mechanisms by which natural proton gradients, H2, CO2 and metal sulphides could have driven organic synthesis are uncertain, and theoretical ideas lack empirical support. We have built a simple electrochemical reactor to simulate conditions in alkaline hydrothermal vents, allowing investigation of the possibility that abiotic vent chemistry could prefigure the origins of biochemistry. We discuss the construction and testing of the reactor, describing the precipitation of thin-walled, inorganic structures containing nickel-doped mackinawite, a catalytic Fe(Ni)S mineral, under prebiotic ocean conditions. These simulated vent structures appear to generate low yields of simple organics. Synthetic microporous matrices can concentrate organics by thermophoresis over several orders of magnitude under continuous open-flow vent conditions

Ship in a bottle: confinement-promoted self-assembly

Understanding self-assembly in confined spaces is essential to fully understand molecular processes in confined cell compartments and will offer clues on the behaviour of simple confined systems, such as protocells and lipid-vesicle based devices. Using a model system composed of lipid vesicles, a membrane impermeable receptor and a membrane-permeable ligand, we have studied in detail how compartmentalization modulates the interaction between the confined receptor and its ligand. We demonstrate that confinement of one of the building blocks stabilizes complex self-assembled structures to the extent that dilution leads, counterintuitively, to the formation of long range assemblies. The behaviour of the system can be explained by considering a confinement factor that is analogous, although not identical, to the effective molarity for intramolecular binding events. The confinement effect renders complex self-assembled species robust and persistent under conditions where they do not form in bulk solution. Moreover, we show that the formation of stable complex assemblies in systems compartmentalized by semi-permeable membranes does not require the prior confinement of all components, but only that of key membrane impermeable building blocks. To use a macroscopic analogy, lipid vesicles are like ship-in-a bottle constructs that are capable of directing the assembly of the confined ship following the confinement of a few key wooden planks. Therefore, we believe that the confinement effect described here would have played an important role in shaping the increase of chemical complexity within protocells during the first stages of abiogenesis. Additionally, we argue that this effect can be exploited to design increasingly efficient functional devices based on comparatively simple vesicles for applications in biosensing, nanoreactors and drug delivery vehicles

Designing and Implementing a Network for Sensing Water Quality and Hydrology across Mountain to Urban Transitions

Water resources are increasingly impacted by growing human populations, land use, and climate changes, and complex interactions among biophysical processes. In an effort to better understand these factors in semiarid northern Utah, United States, we created a real-time observatory consisting of sensors deployed at aquatic and terrestrial stations to monitor water quality, water inputs, and outputs along mountain to urban gradients. The Gradients Along Mountain to Urban Transitions (GAMUT) monitoring network spans three watersheds with similar climates and streams fed by mountain winter-derived precipitation, but that differ in urbanization level, land use, and biophysical characteristics. The aquatic monitoring stations in the GAMUT network include sensors to measure chemical (dissolved oxygen, specific conductance, pH, nitrate, and dissolved organic matter), physical (stage, temperature, and turbidity), and biological components (chlorophyll-a and phycocyanin). We present the logistics of designing, implementing, and maintaining the network; quality assurance and control of numerous, large datasets; and data acquisition, dissemination, and visualization. Data from GAMUT reveal spatial differences in water quality due to urbanization and built infrastructure; capture rapid temporal changes in water quality due to anthropogenic activity; and identify changes in biological structure, each of which are demonstrated via case study datasets

Reconstruction of a flash flood with large wood transport and its influence on hazard patterns in an ungauged mountain basin

The reconstruction of past flash floods in ungauged basins leads to a high level of uncertainty, which increases if other processes are involved such as the transport of large wood material. An important flash flood occurred in 1997 in Venero Claro (Central Spain), causing significant economic losses. The wood material clogged bridge sections, raising the water level upstream. The aim of this study was to reconstruct this event, analysing the influence of woody debris transport on the flood hazard pattern. Because the reach in question was affected by backwater effects due to bridge clogging, using only high water mark or palaeostage indicators may overestimate discharges, and so other methods are required to estimate peak flows. Therefore, the peak discharge was estimated (123±18 m3 s–1) using indirect methods, but one-dimensional hydraulic simulation was also used to validate these indirect estimates through an iterative process (127± 33 m3 s–1) and reconstruct the bridge obstruction to obtain the blockage ratio during the 1997 event (~48%) and the bridge clogging curves. Rainfall–Runoff modelling with stochastic simulation of different rainfall field configurations also helped to confirm that a peak discharge greater than 150 m3 s–1 is very unlikely to occur and that the estimated discharge range is consistent with the estimated rainfall amount (233± 27 mm). It was observed that the backwater effect due to the obstruction (water level ~7 m) made the 1997 flood (~35-year return period) equivalent to the 50-year flood. This allowed the equivalent return period to be defined as the recurrence interval of an event of specified magnitude, which, where large woody debris is present, is equivalent in water depth and extent of flooded area to a more extreme event of greater magnitude. These results highlight the need to include obstruction phenomena in flood hazard analysis. Copyright © 2012 John Wiley & Sons, LtdWe express our gratitude to the Spanish Ministry of Science and Innovation for financial support. This work was funded by the MAS Dendro-Avenidas project (CGL2010-19274) and the Geological Survey of Spain (IGME). We are grateful to the Tagus Water Authority, Environment Department of Castilla y Leon in avila, Caja avila, Asocio de avila and Navaluenga Council for their collaboration. Our special thanks to forester Jose Luis Galan for his assistance in the field. We would also like to mention Juan Ballesteros, Ignacio Gutierrez, Tasio Fernandez, Leticia Salas, Carolina Guardiola and angel Prieto for contributing suggestions and interesting discussions that significantly improved this paper. Thanks to the contribution of two anonymous reviewers, which improved the quality of the early version of this manuscript.Ruiz-Villanueva, V.; Bodoque, J.; Díez-Herrero, A.; Eguíbar Galán, MÁ.; Pardo-Igúzquiza, E. (2012). Reconstruction of a flash flood with large wood transport and its influence on hazard patterns in an ungauged mountain basin. Hydrological Processes. (9433):1-14. https://doi.org/10.1002/hyp.9433S114943

Supraglacial ponds regulate runoff from Himalayan debris-covered glaciers

Meltwater and runoff from glaciers in High Mountain Asia is a vital freshwater resource for one fifth of the Earth's population. Between 13% and 36% of the region's glacierized areas exhibit surface debris cover and associated supraglacial ponds whose hydrological buffering roles remain unconstrained. We present a high-resolution meltwater hydrograph from the extensively debris-covered Khumbu Glacier, Nepal, spanning a seven-month period in 2014. Supraglacial ponds and accompanying debris cover modulate proglacial discharge by acting as transient and evolving reservoirs. Diurnally, the supraglacial pond system may store >23% of observed mean daily discharge, with mean recession constants ranging from 31 to 108 hours. Given projections of increased debris-cover and supraglacial pond extent across High Mountain Asia, we conclude that runoff regimes may become progressively buffered by the presence of supraglacial reservoirs. Incorporation of these processes is critical to improve predictions of the region's freshwater resource availability and cascading environmental effects downstream

Groundwater–surface water interactions in an ephemeral savanna catchment, Kruger National Park

The semi-arid conditions in savanna landscapes ensure that ephemeral drainage dominates the hydrological network in these dryland systems. Quantification of their hydrological processes is important to inform ecosystem understanding and future conservation efforts under a changing climate, and to provide guidance for restoration. By combining in situ hydrometric observations, hydrochemistry, remote sensing and a soil water balance model, we characterise the groundwater–surface water interactions in ephemeral low-order catchments of the granitoid regions of the southern Kruger National Park (KNP). Streams at the lowest orders are augmented by lateral interflows from the catena, although the second-and third-order stream reaches are conduits for groundwater recharge to the fractured rock aquifer; the soils of the crests and foot-slopes also show preferential flow, and are truly recharge soils, whilst the duplex soils of the midslopes clearly show their responsive nature to a low soil moisture deficit in the shallow horizons. Actual evaporation (aET) differed between catena elements with surprisingly little variation at third-order hillslopes, with the greatest overall aET at the first order. Meanwhile, soil water balances demonstrated a significant variation in storage of the riparian zones as a result of interflow from upslope and aET losses. Furthermore, data support broader-scale observations that groundwater recharge through the vadose zone to the fractured rock aquifer is dependent upon threshold antecedent precipitation conditions. Moderate precipitation events (5 mm/day – 35 mm/day) over a 2–3 week period initiate groundwater responses with a 2–3 month lag, whilst intense precipitation events (>100 mm/day) are expressed within 2–3 weeks

Glaciovolcanic hydrothermal environments in Iceland and implications for their detection on Mars

Volcanism has been a dominant process on Mars, along with a pervasive global cryosphere. Therefore, the interaction between these two is considered likely. Terrestrial glaciovolcanism produces distinctive lithologies and alteration terrains, as well as hydrothermal environments that can be inhabited by microorganisms. Here, we provide a framework for identifying evidence of such glaciovolcanic environments during future Mars exploration, and provide a descriptive reference for active hydrothermal environments to be utilised for future astrobiological studies. Remote sensing data were combined with field observations and sample analysis that included X-ray diffraction, Raman spectroscopy, thin section petrography, scanning electron microscopy, electron dispersive spectrometer analysis, and dissolved water chemistry to characterise samples from two areas of basaltic glaciovolcanism: Askja and Kverkfjöll volcanoes in Iceland. The glaciovolcanic terrain between these volcanoes is characterised by subglacially-erupted fissure swarm ridges, which have since been modified by multiple glacial outburst floods. Active hydrothermal environments at Kverkfjöll include hot springs, anoxic pools, glacial meltwater lakes, and sulfur- and iron- depositing fumaroles, all situated within ice-bound geothermal fields. Temperatures range from 0 °C - 94.4 °C, and aqueous environments are acidic - neutral (pH 2 - 7.5) and sulfate-dominated. Mineralogy of sediments, mineral crusts, and secondary deposits within basalts suggest two types of hydrothermal alteration: a low-temperature ( 120 °C) assemblage signified by zeolite (heulandite) and quartz. These mineral assemblages are consistent with those identified at the Martian surface. In-situ and laboratory VNIR (440 – 1000 nm) reflectance spectra representative of Mars rover multispectral imaging show sediment spectral profiles to be influenced by Fe2 +/3 + - bearing minerals, regardless of their dominant bulk mineralogy. Characterising these terrestrial glaciovolcanic deposits can help identify similar processes on Mars, as well as identifying palaeoenvironments that may once have supported and preserved life