Publisher Correction: No detection of methane on Mars from early ExoMars Trace Gas Orbiter observations.

The surname of author Cathy Quantin-Nataf was misspelled 'Quantin-Nata', authors Ehouarn Millour and Roland Young were missing from the ACS and NOMAD Science Teams list, and minor changes have been made to the author and affiliation lists; see accompanying Amendment. These errors have been corrected online.

No detection of methane on Mars from early ExoMars Trace Gas Orbiter observations.

The detection of methane on Mars has been interpreted as indicating that geochemical or biotic activities could persist on Mars today1. A number of different measurements of methane show evidence of transient, locally elevated methane concentrations and seasonal variations in background methane concentrations2-5. These measurements, however, are difficult to reconcile with our current understanding of the chemistry and physics of the Martian atmosphere6,7, which-given methane's lifetime of several centuries-predicts an even, well mixed distribution of methane1,6,8. Here we report highly sensitive measurements of the atmosphere of Mars in an attempt to detect methane, using the ACS and NOMAD instruments onboard the ESA-Roscosmos ExoMars Trace Gas Orbiter from April to August 2018. We did not detect any methane over a range of latitudes in both hemispheres, obtaining an upper limit for methane of about 0.05 parts per billion by volume, which is 10 to 100 times lower than previously reported positive detections2,4. We suggest that reconciliation between the present findings and the background methane concentrations found in the Gale crater4 would require an unknown process that can rapidly remove or sequester methane from the lower atmosphere before it spreads globally.

Evidence for massive emission of methane from a deep-water gas field during the Pliocene.

Geologic hydrocarbon seepage is considered to be the dominant natural source of atmospheric methane in terrestrial and shallow-water areas; in deep-water areas, in contrast, hydrocarbon seepage is expected to have no atmospheric impact because the gas is typically consumed throughout the water column. Here, we present evidence for a sudden expulsion of a reservoir-size quantity of methane from a deep-water seep during the Pliocene, resulting from natural reservoir overpressure. Combining three-dimensional seismic data, borehole data and fluid-flow modeling, we estimate that 18-27 of the 23-31 Tg of methane released at the seafloor could have reached the atmosphere over 39-241 days. This emission is ∼10% and ∼28% of present-day, annual natural and petroleum-industry methane emissions, respectively. While no such ultraseepage events have been documented in modern times and their frequency is unknown, seismic data suggest they were not rare in the past and may potentially occur at present in critically pressurized reservoirs. This neglected phenomenon can influence decadal changes in atmospheric methane.

Upward revision of global fossil fuel methane emissions based on isotope database.

Methane has the second-largest global radiative forcing impact of anthropogenic greenhouse gases after carbon dioxide, but our understanding of the global atmospheric methane budget is incomplete. The global fossil fuel industry (production and usage of natural gas, oil and coal) is thought to contribute 15 to 22 per cent of methane emissions to the total atmospheric methane budget. However, questions remain regarding methane emission trends as a result of fossil fuel industrial activity and the contribution to total methane emissions of sources from the fossil fuel industry and from natural geological seepage, which are often co-located. Here we re-evaluate the global methane budget and the contribution of the fossil fuel industry to methane emissions based on long-term global methane and methane carbon isotope records. We compile the largest isotopic methane source signature database so far, including fossil fuel, microbial and biomass-burning methane emission sources. We find that total fossil fuel methane emissions (fossil fuel industry plus natural geological seepage) are not increasing over time, but are 60 to 110 per cent greater than current estimates owing to large revisions in isotope source signatures. We show that this is consistent with the observed global latitudinal methane gradient. After accounting for natural geological methane seepage, we find that methane emissions from natural gas, oil and coal production and their usage are 20 to 60 per cent greater than inventories. Our findings imply a greater potential for the fossil fuel industry to mitigate anthropogenic climate forcing, but we also find that methane emissions from natural gas as a fraction of production have declined from approximately 8 per cent to approximately 2 per cent over the past three decades.

Relevant methane emission to the atmosphere from a geological gas manifestation.

Quantifying natural geological sources of methane (CH4) allows to improve the assessment of anthropogenic emissions to the atmosphere from fossil fuel industries. The global CH4 flux of geological gas is, however, an object of debate. Recent fossil (14C-free) CH4 measurements in preindustrial-era ice cores suggest very low global geological emissions (~ 1.6 Tg year-1), implying a larger fossil fuel industry source. This is however in contrast with previously published bottom-up and top-down geo-emission estimates (~ 45 Tg year-1) and even regional-scale emissions of ~ 1-2 Tg year-1. Here we report on significant geological CH4 emissions from the Lusi hydrothermal system (Indonesia), measured by ground-based and satellite (TROPOMI) techniques. Both techniques indicate a total CH4 output of ~ 0.1 Tg year-1, equivalent to the minimum value of global geo-emission derived by ice core 14CH4 estimates. Our results are consistent with the order of magnitude of the emission factors of large seeps used in global bottom-up estimates, and endorse a substantial contribution from natural Earth's CH4 degassing. The preindustrial ice core assessments of geological CH4 release may be underestimated and require further study. Satellite measurements can help to test geological CH4 emission factors and explain the gap between the contrasting estimates.

Overlapping redox zones control arsenic pollution in Pleistocene multi-layer aquifers, the Po Plain (Italy).

Understanding the factors that control As concentrations in groundwater is vital for supplying safe groundwater in regions with As-polluted aquifers. Despite much research, mainly addressing Holocene aquifers hosting young (<100 yrs) groundwater, the source, transport, and fate of As in Pleistocene aquifers with fossil (>12,000 yrs) groundwaters are not yet fully understood and so are assessed here through an evaluation of the redox properties of the system in a type locality, the Po Plain (Italy). Analyses of redox-sensitive species and major ions on 22 groundwater samples from the Pleistocene arsenic-affected aquifer in the Po Plain shows that groundwater concentrations of As are controlled by the simultaneous operation of several terminal electron accepters. Organic matter, present as peat, is abundant in the aquifer, allowing groundwater to reach a quasi-steady-state of highly reducing conditions close to thermodynamic equilibrium. In this system, simultaneous reduction of Fe-oxide and sulfate results in low concentrations of As (median 7 µg/L) whereas As reaches higher concentrations (median of 82 µg/L) during simultaneous methanogenesis and Fe-reduction. The position of well-screens is an additional controlling factor on groundwater As: short screens that overlap confining aquitards generate higher As concentrations than long screens placed away from them. A conceptual model for groundwater As, applicable worldwide in other Pleistocene aquifers with reducible Fe-oxides and abundant organic matter is proposed: As may have two concentration peaks, the first after prolonged Fe-oxide reduction and until sulfate reduction takes place, the second during simultaneous Fe-reduction and methanogenesis.

Influence of tectonics on global scale distribution of geological methane emissions.

Earth's hydrocarbon degassing through gas-oil seeps, mud volcanoes and diffuse microseepage is a major natural source of methane (CH4) to the atmosphere. While carbon dioxide degassing is typically associated with extensional tectonics, volcanoes, and geothermal areas, CH4 seepage mostly occurs in petroleum-bearing sedimentary basins, but the role of tectonics in degassing is known only for some case studies at local scale. Here, we perform a global scale geospatial analysis to assess how the presence of hydrocarbon fields, basin geodynamics and the type of faults control CH4 seepage. Combining georeferenced data of global inventories of onshore seeps, faults, sedimentary basins, petroleum fields and heat flow, we find that hydrocarbon seeps prevail in petroleum fields within convergent basins with heat flow ≤ 98 mW m-2, and along any type of brittle tectonic structure, mostly in reverse fault settings. Areas potentially hosting additional seeps and microseepage are identified through a global seepage favourability model.

Using global isotopic data to constrain the role of shale gas production in recent increases in atmospheric methane.

The accelerated increase in global methane (CH4) in the atmosphere, accompanied by a decrease in its 13C/12C isotopic ratio (δ13CCH4) from -47.1‰ to -47.3‰ observed since 2008, has been attributed to increased emissions from wetlands and cattle, as well as from shale gas and shale oil developments. To date both explanations have relied on poorly constrained δ13CCH4 source signatures. We use a dataset of δ13CCH4 from >1600 produced shale gas samples from regions that account for >97% of global shale gas production to constrain the contribution of shale gas emissions to observed atmospheric increases in the global methane burden. We find that US shale gas extracted since 2008 has volume-weighted-average δ13CCH4 of -39.6‰. The average δ13CCH4 weighted by US basin-level measured emissions in 2015 was -41.8‰. Therefore, emission increases from shale gas would contribute to an opposite atmospheric δ13CCH4 signal in the observed decrease since 2008 (while noting that the global isotopic trend is the net of all dynamic source and sink processes). This observation strongly suggests that changing emissions of other (isotopically-lighter) CH4 source terms is dominating the increase in global CH4 emissions. Although production of shale gas has increased rapidly since 2008, and CH4 emissions associated with this increased production are expected to have increased overall in that timeframe, the simultaneously-observed increase in global atmospheric CH4 is not dominated by emissions from shale gas and shale oil developments.

Natural geological seepage of hydrocarbon gas in the Appalachian Basin and Midwest USA in relation to shale tectonic fracturing and past industrial hydrocarbon production.

Geological hydrocarbon gas seepage is a major global source of atmospheric methane, ethane and propane as greenhouse gases and photochemical pollutants. Natural gas seepage is generally related to faults and associated fracture intensification domains that provide conduits for natural gas from reservoir rocks to migrate upward and enter the atmosphere. In this study, we compare the case of intense gas seepage stemming directly from source rocks, mostly organic-rich fractured black shales in western New York State (NYS) versus areas with rare seepage in the more southern regions of the Appalachian Basin and the Midwest USA. In addition to thermogenic methane, western NYS shale gas seeps emit ethane and propane with C2+3 gas concentrations reaching up to 35 vol%. Fractures in NYS developed, reactivated and maintained permeability for gas as a result of Quaternary glaciation and post-glacial basin uplift. In contrast, the Appalachian regions farther south and the southern Midwest regions experienced less glacial loading and unloading than in NYS, resulting in less recent natural fracturing, as witnessed by the rarity of seepage on surface outcrops and in caves overlying gas-bearing shales and coals. The historical literature suggests that early western NYS drilling and production of oil and gas diminished shale gas pressure and resulted in declining gas seepage rates. Our survey documented 12 active western NYS natural gas seeps, whereas >32 seeps have been reported or documented since the 17th century. Preliminary tests showed that SCIAMACHY satellite data did not detect atmospheric methane anomalies over western NYS seeps.

Methane on Mars and Habitability: Challenges and Responses.

Recent measurements of methane (CH4) by the Mars Science Laboratory (MSL) now confront us with robust data that demand interpretation. Thus far, the MSL data have revealed a baseline level of CH4 (∼0.4 parts per billion by volume [ppbv]), with seasonal variations, as well as greatly enhanced spikes of CH4 with peak abundances of ∼7 ppbv. What do these CH4 revelations with drastically different abundances and temporal signatures represent in terms of interior geochemical processes, or is martian CH4 a biosignature? Discerning how CH4 generation occurs on Mars may shed light on the potential habitability of Mars. There is no evidence of life on the surface of Mars today, but microbes might reside beneath the surface. In this case, the carbon flux represented by CH4 would serve as a link between a putative subterranean biosphere on Mars and what we can measure above the surface. Alternatively, CH4 records modern geochemical activity. Here we ask the fundamental question: how active is Mars, geochemically and/or biologically? In this article, we examine geological, geochemical, and biogeochemical processes related to our overarching question. The martian atmosphere and surface are an overwhelmingly oxidizing environment, and life requires pairing of electron donors and electron acceptors, that is, redox gradients, as an essential source of energy. Therefore, a fundamental and critical question regarding the possibility of life on Mars is, "Where can we find redox gradients as energy sources for life on Mars?" Hence, regardless of the pathway that generates CH4 on Mars, the presence of CH4, a reduced species in an oxidant-rich environment, suggests the possibility of redox gradients supporting life and habitability on Mars. Recent missions such as ExoMars Trace Gas Orbiter may provide mapping of the global distribution of CH4. To discriminate between abiotic and biotic sources of CH4 on Mars, future studies should use a series of diagnostic geochemical analyses, preferably performed below the ground or at the ground/atmosphere interface, including measurements of CH4 isotopes, methane/ethane ratios, H2 gas concentration, and species such as acetic acid. Advances in the fields of Mars exploration and instrumentation will be driven, augmented, and supported by an improved understanding of atmospheric chemistry and dynamics, deep subsurface biogeochemistry, astrobiology, planetary geology, and geophysics. Future Mars exploration programs will have to expand the integration of complementary areas of expertise to generate synergistic and innovative ideas to realize breakthroughs in advancing our understanding of the potential of life and habitable conditions having existed on Mars. In this spirit, we conducted a set of interdisciplinary workshops. From this series has emerged a vision of technological, theoretical, and methodological innovations to explore the martian subsurface and to enhance spatial tracking of key volatiles, such as CH4.

Methane Seepage on Mars: Where to Look and Why.

Methane on Mars is a topic of special interest because of its potential association with microbial life. The variable detections of methane by the Curiosity rover, orbiters, and terrestrial telescopes, coupled with methane's short lifetime in the martian atmosphere, may imply an active gas source in the planet's subsurface, with migration and surface emission processes similar to those known on Earth as "gas seepage." Here, we review the variety of subsurface processes that could result in methane seepage on Mars. Such methane could originate from abiotic chemical reactions, thermogenic alteration of abiotic or biotic organic matter, and ancient or extant microbial metabolism. These processes can occur over a wide range of temperatures, in both sedimentary and igneous rocks, and together they enhance the possibility that significant amounts of methane could have formed on early Mars. Methane seepage to the surface would occur preferentially along faults and fractures, through focused macro-seeps and/or diffuse microseepage exhalations. Our work highlights the types of features on Mars that could be associated with methane release, including mud-volcano-like mounds in Acidalia or Utopia; proposed ancient springs in Gusev Crater, Arabia Terra, and Valles Marineris; and rims of large impact craters. These could have been locations of past macro-seeps and may still emit methane today. Microseepage could occur through faults along the dichotomy or fractures such as those at Nili Fossae, Cerberus Fossae, the Argyre impact, and those produced in serpentinized rocks. Martian microseepage would be extremely difficult to detect remotely yet could constitute a significant gas source. We emphasize that the most definitive detection of methane seepage from different release candidates would be best provided by measurements performed in the ground or at the ground-atmosphere interface by landers or rovers and that the technology for such detection is currently available. Key Words: Mars-Methane-Seepage-Clathrate-Fischer-Tropsch-Serpentinization. Astrobiology 17, 1233-1264.

Contrasting taxonomic stratification of microbial communities in two hypersaline meromictic lakes.

Hypersaline meromictic lakes are extreme environments in which water stratification is associated with powerful physicochemical gradients and high salt concentrations. Furthermore, their physical stability coupled with vertical water column partitioning makes them important research model systems in microbial niche differentiation and biogeochemical cycling. Here, we compare the prokaryotic assemblages from Ursu and Fara Fund hypersaline meromictic lakes (Transylvanian Basin, Romania) in relation to their limnological factors and infer their role in elemental cycling by matching taxa to known taxon-specific biogeochemical functions. To assess the composition and structure of prokaryotic communities and the environmental factors that structure them, deep-coverage small subunit (SSU) ribosomal RNA (rDNA) amplicon sequencing, community domain-specific quantitative PCR and physicochemical analyses were performed on samples collected along depth profiles. The analyses showed that the lakes harbored multiple and diverse prokaryotic communities whose distribution mirrored the water stratification patterns. Ursu Lake was found to be dominated by Bacteria and to have a greater prokaryotic diversity than Fara Fund Lake that harbored an increased cell density and was populated mostly by Archaea within oxic strata. In spite of their contrasting diversity, the microbial populations indigenous to each lake pointed to similar physiological functions within carbon degradation and sulfate reduction. Furthermore, the taxonomy results coupled with methane detection and its stable C isotope composition indicated the presence of a yet-undescribed methanogenic group in the lakes' hypersaline monimolimnion. In addition, ultrasmall uncultivated archaeal lineages were detected in the chemocline of Fara Fund Lake, where the recently proposed Nanohaloarchaeota phylum was found to thrive.

Geologic emissions of methane to the atmosphere.

The atmospheric methane budget is commonly defined assuming that major sources derive from the biosphere (wetlands, rice paddies, animals, termites) and that fossil, radiocarbon-free CH4 emission is due to and mediated by anthropogenic activity (natural gas production and distribution, and coal mining). However, the amount of radiocarbon-free CH4 in the atmosphere, estimated at approximately 20% of atmospheric CH4, is higher than the estimates from statistical data of CH4 emission from fossil fuel related anthropogenic sources. This work documents that significant amounts of "old" methane, produced within the Earth crust, can be released naturally into the atmosphere through gas permeable faults and fractured rocks. Major geologic emissions of methane are related to hydrocarbon production in sedimentary basins (biogenic and thermogenic methane) and, subordinately, to inorganic reactions (Fischer-Tropsch type) in geothermal systems. Geologic CH4 emissions include diffuse fluxes over wide areas, or microseepage, on the order of 10(0)-10(2) mg m(-2) day(-1), and localised flows and gas vents, on the order of 10(2) t y(-1), both on land and on the seafloor. Mud volcanoes producing flows of up to 10(3) t y(-1) represent the largest visible expression of geologic methane emission. Several studies have indicated that methanotrophic consumption in soil may be insufficient to consume all leaking geologic CH4 and positive fluxes into the atmosphere can take place in dry or seasonally cold environments. Unsaturated soils have generally been considered a major sink for atmospheric methane, and never a continuous, intermittent, or localised source to the atmosphere. Although geologic CH4 sources need to be quantified more accurately, a preliminary global estimate indicates that there are likely more than enough sources to provide the amount of methane required to account for the suspected missing source of fossil CH4.

Earth's degassing: a missing ethane and propane source.

Current emission inventories require an additional "unknown" source to balance the global atmospheric budgets of ethane (C2H6). Here, we provide evidence that a substantial part of the missing source can be attributed to natural gas seepage from petroliferous, geothermal, and volcanic areas. Such geologic sources also inject propane (C3H8) into the atmosphere. The analysis of a large data set of methane (CH4), ethane, and propane concentrations in surface gas emissions of 238 sites from different geographic and geologic areas, coupled with published estimates of geomethane emissions, suggests that Earth's degassing accounts for at least 17% and 10% of total ethane and propane emissions, respectively.

Acoustic scattering from mud volcanoes and carbonate mounds.

Submarine mud volcanoes occur in many parts of the world's oceans and form an aperture for gas and fluidized mud emission from within the earth's crust. Their characteristics are of considerable interest to the geology, geophysics, geochemistry, and underwater acoustics communities. For the latter, mud volcanoes are of interest in part because they pose a potential source of clutter for active sonar. Close-range (single-interaction) scattering measurements from a mud volcano in the Straits of Sicily show scattering 10-15 dB above the background. Three hypotheses were examined concerning the scattering mechanism: (1) gas entrained in sediment at/near mud volcano, (2) gas bubbles and/or particulates (emitted) in the water column, (3) the carbonate bio-construction covering the mud volcano edifice. The experimental evidence, including visual, acoustic, and nonacoustic sensors, rules out the second hypothesis (at least during the observation time) and suggests that, for this particular mud volcano the dominant mechanism is associated with carbonate chimneys on the mud volcano. In terms of scattering levels, target strengths of 4-14 dB were observed from 800 to 3600 Hz for a monostatic geometry with grazing angles of 3-5 degrees. Similar target strengths were measured for vertically bistatic paths with incident and scattered grazing angles of 3-5 degrees and 33-50 degrees, respectively.