•Elemental, GC–MS and GC-IRMS analysis of organic matter (OM) from a coastal peat bog.•Changes in climate over a ca. 3400 yr period during the mid-Holocene.•Evidence of the 4.2 ka event and Subboreal-Subatlantic transition in Ireland.•Implications for environmental conditions resulting in formation of a ‘drowned’ forest landscape.Following a period of unusually strong winds and high seas in the spring of 2014, a blanket peat bog formerly covered by a beach comprised of fine sand and large rocks was uncovered at a coastal site in Spiddal, Co. Galway, Ireland. The surface of the bog was littered with standing tree stumps, the remnants of a Holocene forest that had succumbed to a relatively sudden drowning. A combination of inorganic and organic geochemical techniques was applied to determine the cause of this rapid submersion and to glean palaeoclimatic information from the preserved record within the peat. The study represents the first use of a multiproxy lipid biomarker approach to investigate palaeoclimate conditions from a peat bog in Ireland. The results provide evidence of climatic variation throughout a ca. 3400 yr timeframe during the mid-Holocene. Biomarker proxies displaying the relative contribution of Sphagnum spp. vs. higher plants were used to show changes in precipitation and temperature during peat formation. The data correlate with described events, including the 4.2 ka event and the Subboreal-Subatlantic transition and show the benefit of a lipid biomarker method for investigating Ireland’s peatland resources. In particular, the indication of colder/wetter conditions coinciding with the 4.2 ka event implies the possibility that its effects were felt in Ireland, contrary to some reports. The results suggest that a combination of warm and dry conditions followed by a rapid rise in sea level led to the growth and subsequent drowning of the ancient forest landscape.

Previous evidence for fragments of a cosmic airburst in the Western Alps has been shown to reside in weathering rinds in surface clasts of Late Glacial (LG) (mid-LG-post Allerød) deposits and in Ah horizons of several associated paleosols. In contrast to outlying strata, Younger Dryas (YD) paleosol horizons contain minor reworked airburst evidence that includes melted quartz/pyroxene grains, carbon spherules, glass-like carbon, and with minor differences in microbial populations. New data from LG paleosol profiles show REEs elevated above crustal abundance in several profiles of mid-Late Glacial age, along with elevated Pt concentrations, similar to those found at the YD Boundary in the Greenland Ice Sheet. Pt/Pd ratios that are elevated above background suggest an exogenic influx of Pt from meteoritic ablation and/or airbursts. An increasing number of localities with sedimentary time lines coeval with an airburst (12.8 ka) indicate the event was intercontinental, producing widespread conflagrations archived in local sediment sequences. This is the first instance worldwide in which evidence of the black mat event has been found both in weathering rinds and in paleosols in the Alps, with such information being applicable to reconnaissance beyond Earth such as in the case of Mars.

The microbial contribution to soil organic matter (SOM) has recently been shown to be much larger than previously thought and thus its role in carbon sequestration may also be underestimated. In this study we employ 13C (13CO2) to assess the potential CO2 sequestration capacity of soil chemoautotrophic bacteria and combine nuclear magnetic resonance (NMR) with stable isotope probing (SIP), techniques that independently make use of the isotopic enrichment of soil microbial biomass. In this way molecular information generated from NMR is linked with identification of microbes responsible for carbon capture. A mathematical model is developed to determine real-time CO2 flux so that net sequestration can be calculated. Twenty-eight groups of bacteria showing close homologies with existing species were identified. Surprisingly, Ralstonia eutropha was the dominant group. Through NMR we observed the formation of lipids, carbohydrates, and proteins produced directly from CO2 utilized by microbial biomass. The component of SOM directly associated with CO2 capture was calculated at 2.86 mg C (89.21 mg kg–1) after 48 h. This approach can differentiate between SOM derived through microbial uptake of CO2 and other SOM constituents and represents a first step in tracking the fate and dynamics of microbial biomass in soil.

Sediments recovered from 0 to 27 + meters below the seafloor (mbsf) of a gas-hydrate and gas-venting active area in the Gulf of Mexico were added to a hydrate growth test cell to determine the influence of the organic and inorganic sedimentary components on hydrate induction times and formation rates. Induction times were sixteen times shorter in the presence of sediment from approximately 18 mbsf (relative to sediment from 1 mbsf), and remained stable in the presence of sediment from 18 to 27 mbsf. Formation rates increased by a factor of 2.5 in the presence of sediments from approximately 18 mbsf and decreased somewhat in the presence of sediment from 18 to 27 mbsf. Selected samples (surface, 18 and 27 mbsf) were density fractionated and subjected to bulk elemental and X-ray photoelectron spectroscopy (XPS) analysis. XPS revealed the presence of iron in various chemical environments at depths of 18 and 27 mbsf. High Resolution Magic Angle Spinning Nuclear Magnetic Resonance (HR-MAS NMR) was used to characterize the organic component of sediments from selected depths. The discovery of intact proteinaceous material in the surface sediment was surprising due to the labile nature of these biopolymers, and potentially reflects microbial activity in these surface layers. This material was less abundant in sediment from increasing depths, where more lipid-like compounds were prominent. The results suggest that hydrate growth is inhibited by the presence of proteinaceous material but enhanced by lipid-like compounds associated with iron-bearing mineral surfaces.

In this empirically-driven research, multibeam backscatter angular response analysis is presented, together with shallow electromagnetic data and groundtruthing, to examine its suitability as a proxy for sediment characterisation. Backscatter angular curves extracted from Kongsberg EM1002 sonar (95–98 kHz), acquired in the Malin Basin to the northwest of Ireland, have been selected as a case study. Standard angular backscatter features and newly derived curvature features are examined and cross compared. Exhaustive statistical analysis has been performed on the data to elucidate the complex relationship between multibeam backscatter and sediment properties. Subtle subsurface sediment property gradients across the basin identified by the conductivity system are also captured by the newly derived backscatter features. The results reveal that Near-range backscatter is better suited for subsurface sediment characterisation in soft, fine-grained sediments than far-range. Furthermore, the analysis has constrained the optimum interval for such characterisation to in-between 4° and 16° for the parameters of this study. A number of shape features (slope, first derivative, second derivative and Fourier-smoothed least-squares-fitted curvature) have been examined, and their suitability discussed, in terms of sediment characterisation and, in particular, as potential proxies for delineating the boundary between sand- or silt-dominated sediment facies. Nonetheless, curvature features are found to be independent from average angular backscatter response, but outperform both first and second derivatives when correlating with conductivity in the central part of this case-study with fine-grained homogeneous sediments.

Sequestration of CO2 via biological sinks is a matter of great scientific importance due to the potential lowering of atmospheric CO2. In this study, a custom built incubation chamber was used to cultivate a soil microbial community to instigate chemoautotrophy of a temperate soil. Real-time atmospheric CO2 concentrations were monitored and estimations of total CO2 uptake were made. After careful background flux corrections, 4.52 ± 0.05 g CO2 kg−1 dry soil was sequestered from the chamber atmosphere over 40 h. Using isotopically labelled 13CO2 and GCMS–IRMS, labelled fatty acids were identified after only a short incubation, hence confirming CO2 sequestration for soil. The results of this in vivo study provide the ground work for future studies intending to mimic the in situ environment by providing a reliable method for investigating CO2 uptake by soil microorganisms.Highlights► 13CO2 was sequestered by a soil chemoautotrophic microcosm incubated with an electron donor. ► Labelled fatty acids were identified confirming CO2 sequestration in a soil slurry. ► After careful background flux corrections, 4.52 ± 0.05 g CO2 kg−1 dry soil was removed over 40 h. ► The results of this in vivo study provide the ground work for future in situ studies.

•PLFA biomarkers indicate that microbial populations are impacted by the type anthropogenic pollution.•Sterol biomarkers reveal the ‘fingerprint’ of historical sewage discharge from point sources.•PAH accumulation is dictated by depositional processes in the bay.•10 stations exceed the suggested effect range low (ERL) for PAHs.The source, concentration, and potential impact of sewage discharge and incomplete organic matter (OM) combustion on sedimentary microbial populations were assessed in Dublin Bay, Ireland. Polycyclic aromatic hydrocarbons (PAHs) and faecal steroids were investigated in 30 surface sediment stations in the bay. Phospholipid fatty acid (PLFA) content at each station was used to identify and quantify the broad microbial groups present and the impact of particle size, total organic carbon (%TOC), total hydrogen (%H) and total nitrogen (%N) was also considered. Faecal sterols were found to be highest in areas with historical point sources of sewage discharge. PAH distribution was more strongly associated with areas of deposition containing high %silt and %clay content, suggesting that PAHs are from diffuse sources such as rainwater run-off and atmospheric deposition. The PAHs ranged from 12 to 3072 ng/g, with 10 stations exceeding the suggested effect range low (ERL) for PAHs in marine sediments. PAH isomer pair ratios and sterol ratios were used to determine the source and extent of pollution. PLFAs were not impacted by sediment type or water depth but were strongly correlated to, and influenced by PAH and sewage levels. Certain biomarkers such as 10Me16:0, i17:0 and a17:0 were closely associated with PAH polluted sediments, while 16:1ω9, 16:1ω7c, Cy17:0, 18:1ω6, i16:0 and 15:0 all have strong positive correlations with faecal sterols. Overall, the results show that sedimentary microbial communities are impacted by anthropogenic pollution.

Soil microbial biomass is a primary source of soil organic carbon (SOC) and therefore plays a fundamental role in carbon and nitrogen cycling. However, little is known about the fate and transformations of microbial biomass in soil. Here we employ HR-MAS NMR spectroscopy to monitor 13C and 15N labeled soil microbial biomass and leachate degradation over time. As expected, there is a rapid loss of carbohydrate structures. However, diffusion edited HR-MAS NMR data reveals that macromolecular carbohydrates are more resistant to degradation and are found in the leachate. Aromatic components survive as dissolved species in the leachate while aliphatic components persist in both the biomass and leachate. Dissolved protein and peptidoglycan accumulate in the leachate and recalcitrant amide nitrogen and lipoprotein persists in both the degraded biomass and leachate. Cross-peaks that appear in 1H–15N HR-MAS NMR spectra after degradation suggest that specific peptides are either selectively preserved or used for the synthesis of unknown structures. The overall degradation pathways reported here are similar to that of decomposing plant material degraded under similar conditions suggesting that the difference between recalcitrant carbon from different sources is negligible after decomposition.

Pyrophosphate-extractable Al has been used to establish the presence of organically-complexed compounds in middle latitude and tropical soils and paleosols on Earth. As proxy data used to establish the presence of organic molecules and trace movement within profiles, it has proved an accurate indicator of downward translocation in Spodosols (podzols). Antarctic paleosols, dating from Middle to Early Miocene age (15–20 Ma), are mineralic weathering profiles lacking A and B horizons. These profiles exhibit pavement/Cox/Cz/Cu horizons, largely with sandy silt textures, little clay, and exceedingly low concentrations of organic matter. Recent chemical investigations of 33 soil samples from the New Mountain and Aztec Mountain areas near the Inland Ice, adjacent to the Taylor Glacier, show that pyrophosphate-extractable Al concentrations vary in phase with organic carbon as determined by loss-on-ignition. While Al-extract concentrations in selected samples are low (< 0.15%), increasing values above nil approximately correlate positively with increases in bacterial populations of several common phylum, the extreme high numbers with more advanced biota including fossil Coleoptera. Available data suggest Alp extracts may target samples which may have undergone minor chelation, and which over long periods of time might have a cumulative weathering effect resulting in the accumulation of small concentrations of organic matter.As such, Alp extracts may prove useful in targeting the presence of life once in situ investigations of paleosols begin on Mars.

Fired glaciofluvial beds in outwash considered to date from the onset of the Younger Dryas Event (~ 12.9 ka) in the northwestern Venezuelan Andes are considered equivalent to the Black Mat deposits described in other areas of North and South America and Europe. It may be equivalent to sediment recovered from other sites containing beds with spikes of cosmic nuclides and charcoal indicating the presence of widespread fire, one of the signatures of the Black Mat conflagration that followed the proposed breakup of Comet Encke or an unknown asteroid over the Laurentide Icesheet at 12.9 ka. In the northern Andes at Site MUM7B, sediment considered coeval with the Black Mat contains glassy carbon spherules, tri-coatings of C welded onto quartz and feldspar covered with Fe and Mn. Monazite with excessive concentrations of REEs, platinum metals including Ru and Rh, possible pdf's, and disrupted/brecciated and microfractured quartz and feldspar from impacting ejecta and excessive heating summarize the data obtained so far. The purpose of this paper is to document the physical character, mineralogy and biotic composition of the Black Mat.

•Carbonate mounds at the Codling Fault Zone in the western Irish Sea were investigated.•Isotopically depleted carbonate and the presence of framboidal pyrite confirm AOM.•Isotopic values suggests biogenic source, but thermogenic gas cannot be ruled out.•Ongoing seepage and mounds composed of stacked MDAC pavements.•Significant dilution of the AOM biomarker evidence by organic matter from photosynthesis.Methane-derived authigenic carbonate (MDAC) mound features at the Codling Fault Zone (CFZ), located in shallow waters (50–120 m) of the western Irish Sea were investigated and provide a comparison to deep sea MDAC settings. Carbonates consisted of aragonite as the major mineral phase, with δ13C depletion to − 50‰ and δ18O enrichment to ~ 2‰. These isotope signatures, together with the co-precipitation of framboidal pyrite confirm that anaerobic oxidation of methane (AOM) is an important process mediating methane release to the water column and the atmosphere in this region. 18O-enrichment could be a result of MDAC precipitation with seawater in colder than present day conditions, or precipitation with 18O-enriched water transported from deep petroleum sources. The 13C depletion of bulk carbonate and sampled gas (− 70‰) suggests a biogenic source, but significant mixing of thermogenic gas and depletion of the original isotope signature cannot be ruled out. Active seepage was recorded from one mound and together with extensive areas of reduced sediment, confirms that seepage is ongoing. The mounds appear to be composed of stacked pavements that are largely covered by sand and extensively eroded. The CFZ mounds are colonized by abundant Sabellaria polychaetes and possible Nemertesia hydroids, which benefit indirectly from available hard substrate. In contrast to deep sea MDAC settings where seep-related macrofauna are commonly reported, seep-specialist fauna appear to be lacking at the CFZ. In addition, unlike MDAC in deep waters where organic carbon input from photosynthesis is limited, lipid biomarkers and isotope signatures related to marine planktonic production (e.g. sterols, alkanols) were most abundant. Evidence for microbes involved in AOM was limited from samples taken; possibly due to this dilution effect from organic matter derived from the photic zone, and will require further investigation.