Miocene methane‐derived carbonates from southwestern Washington,USA and a model for silicification at seeps

Kuechler, R.R., Birgel, D, Kiel, S, Freiwald, A, Goedert, J.L., Thiel, V & Peckmann, J. 2011: Miocene methane‐derived carbonates from southwestern Washington, USA and a model for silicification at seeps. Lethaia, Vol. 45, pp. 259–273. Exotic limestone masses with silicified fossils, enclosed within deep‐water marine siliciclastic sediments of the Early to Middle Miocene Astoria Formation, are exposed along the north shore of the Columbia River in southwestern Washington, USA. Samples from four localities were studied to clarify the origin and diagenesis of these limestone deposits. The bioturbated and reworked limestones contain a faunal assemblage resembling that of modern and Cenozoic deep‐water methane‐seeps. Five phases make up the paragenetic sequence: (1) micrite and microspar; (2) fibrous, banded and botryoidal aragonite cement, partially replaced by silica or recrystallized to calcite; (3) yellow calcite; (4) quartz replacing carbonate phases and quartz cement; and (5) equant calcite spar and pseudospar. Layers of pyrite frequently separate different carbonate phases and generations, indicating periods of corrosion. Negative δ¹³C_carbonate values as low as ?37.6‰ V‐PDB reveal an uptake of methane‐derived carbon. In other cases, δ¹³C_carbonate values as high as 7.1‰ point to a residual, ¹³C‐enriched carbon pool affected by methanogenesis. Lipid biomarkers include ¹³C‐depleted, archaeal 2,6,10,15,19‐pentamethylicosane (PMI; δ¹³C: ?128‰), crocetane and phytane, as well as various iso‐ and anteiso‐carbon chains, most likely derived from sulphate‐reducing bacteria. The biomarker inventory proves that the majority of the carbonates formed as a consequence of sulphate‐dependent anaerobic oxidation of methane. Silicification of fossils and early diagenetic carbonate cements as well as the precipitation of quartz cement – also observed in other methane‐seep limestones enclosed in sediments with abundant diatoms or radiolarians – is a consequence of a preceding increase of alkalinity due to anaerobic oxidation of methane, inducing the dissolution of silica skeletons. Once anaerobic oxidation of methane has ceased, the pH drops again and silica phases can precipitate. □Biomarkers, carbonates, isotopes, methane, Miocene, silicification, Washington.     

Spatial variations of methanotrophic consortia at cold methane seeps: implications from a high-resolution molecular and isotopic approach

Anaerobic methane‐oxidizing microbial communities in sediments at cold methane seeps are important factors in controlling methane emission to the ocean and atmosphere. Here, we investigated the distribution and carbon isotopic signature of specific biomarkers derived from anaerobic methanotrophic archaea (ANME groups) and sulphate‐reducing bacteria (SRB) responsible for the anaerobic oxidation of methane (AOM) at different cold seep provinces of Hydrate Ridge, Cascadia margin. The special focus was on their relation to in situ cell abundances and methane turnover. In general, maxima in biomarker abundances and minima in carbon isotope signatures correlated with maxima in AOM and sulphate reduction as well as with consortium biomass. We found ANME‐2a/DSS aggregates associated with high abundances of sn‐2,3‐di‐O‐isoprenoidal glycerol ethers (archaeol, sn‐2‐hydroxyarchaeol) and specific bacterial fatty acids (C_16:1ω5c, cyC_17:0ω5,6) as well as with high methane fluxes (Beggiatoa site). The low to medium flux site (Calyptogena field) was dominated by ANME‐2c/DSS aggregates and contained less of both compound classes but more of AOM‐related glycerol dialkyl glycerol tetraethers (GDGTs). ANME‐1 archaea dominated deeper sediment horizons at the Calyptogena field where sn‐1,2‐di‐O‐alkyl glycerol ethers (DAGEs), archaeol, methyl‐branched fatty acids (ai‐C_15:0, i‐C_16:0, ai‐C_17:0), and diagnostic GDGTs were prevailing. AOM‐specific bacterial and archaeal biomarkers in these sediment strata generally revealed very similar δ¹³C‐values of around ?100. In ANME‐2‐dominated sediment sections, archaeal biomarkers were even more ¹³C‐depleted (down to ?120), whereas bacterial biomarkers were found to be likewise ¹³C‐depleted as in ANME‐1‐dominated sediment layers (δ¹³C: ?100). The zero flux site (Acharax field), containing only a few numbers of ANME‐2/DSS aggregates, however, provided no specific biomarker pattern. Deeper sediment sections (below 20 cm sediment depth) from Beggiatoa covered areas which included solid layers of methane gas hydrates contained ANME‐2/DSS typical biomarkers showing subsurface peaks combined with negative shifts in carbon isotopic compositions. The maxima were detected just above the hydrate layers, indicating that methane stored in the hydrates may be available for the microbial community. The observed variations in biomarker abundances and ¹³C‐depletions are indicative of multiple environmental and physiological factors selecting for different AOM consortia (ANME‐2a/DSS, ANME‐2c/DSS, ANME‐1) along horizontal and vertical gradients of cold seep settings.     

Constraining the formation of authigenic carbonates in a seepage‐affected cold‐water coral mound by lipid biomarkers

Cold‐water coral (CWC) mounds are build‐ups comprised of coral‐dominated intervals alternating with a mixed carbonate‐siliciclastic matrix. At some locations, CWC mounds are influenced by methane seepage, but the impact of methane on CWC mounds is poorly understood. To constrain the potential impact of methane on CWC mound growth, lipid biomarker investigations were combined with mineralogical and petrographic analyses to investigate the anaerobic oxidation of methane (AOM) and authigenic carbonate formation in sediment from a seep‐affected CWC mound in the Gulf of Cadiz. The occurrence of AOM was confirmed by characteristic lipids found within a semi‐lithified zone (SLZ) consisting of authigenic aragonite, high‐magnesium calcite and calcium‐excess dolomite. The formation of high‐Mg calcite is attributed to AOM, acting as a lithifying agent. Aragonite is only a minor phase. Ca‐excess dolomite in the SLZ and upper parts may be formed by organoclastic sulphate reduction, favouring precipitation by increased alkalinity. The AOM biomarkers in the SLZ include isoprenoid‐based archaeal membrane lipids, such as abundant glycerol dibiphytanyl glycerol tetraethers (GDGTs) dominated by GDGT‐2. The δ¹³C values of GDGT‐2, measured as ether‐cleaved monocyclic biphytanes, are as low as ?100‰ versus V‐PDB. Further, bacterial dialkyl glycerol diethers with two anteiso‐C₁₅ alkyl chains and δ¹³C values of ?81‰ are interpreted as biomarkers of sulphate‐reducing bacteria. The lipid biomarker signatures and mineralogical patterns suggest that anaerobic methane‐oxidizing archaea of the ANME‐1 group thrived in the subsurface at times of slow and diffusive methane seepage. Petrographic analyses revealed that the SLZ was exhumed at some point (e.g. signs of bioerosion of the semi‐lithified sediment), providing a hard substrate for CWC larval settlement. In addition, this work reveals that AOM‐induced semi‐lithification likely played a role in mound stabilization. Lipid biomarker analysis proves to be a powerful tool to disentangle early diagenetic processes induced by microbial metabolisms.     

Bioturbation and directionality in Earth's carbon isotope record across the Neoproterozoic–Cambrian transition

Mixing of sediments by moving animals becomes apparent in the trace fossil record from about 550 million years ago (Ma), loosely overlapping with the tail end of the extreme carbonate carbon isotope δ¹³C_carbonate fluctuations that qualitatively distinguish the Proterozoic geochemical record from that of the Phanerozoic. These Precambrian‐scale fluctuations in δ¹³C_carbonate (PSF‐δ¹³C_carbonate) remain enigmatic, due to their high amplitude and inclusion of global‐scale negative δ¹³C_carbonate values, below anything attributable to mantle input. Here, we note that different biogeochemical‐model scenarios plausibly explaining globally synchronous PSF‐δ¹³C_carbonate converge: via mechanistic requirements for extensive anoxia in marine sediments to support sedimentary build‐up of ¹³C‐depleted carbon. We hypothesize that bioturbation qualitatively reduced marine sediment anoxia by exposing sediments to oxygenated overlying waters, which ultimately contributed to decreasing the carbon cycle's subsequent susceptibility to PSF‐ δ¹³C_carbonate. Bioturbation may also have reduced the quantity of (isotopically light) organic‐derived carbon available to contribute to PSF‐ δ¹³C_carbonate via ocean crust carbonatization at depth. We conduct a comparative modelling exercise in which we introduce bioturbation to existing model scenarios for PSF‐ δ¹³C_carbonate: expressing both the anoxic proportion of marine sediments, and the global organic carbon burial efficiency, as a decreasing function of bioturbation. We find that bioturbation's oxygenating impact on sediments has the capacity to prevent PSF‐ δ¹³C_carbonate caused by authigenic carbonate precipitation or methanogenesis. Bioturbation's impact on the f‐ratio via remineralization is partially offset by liberation of organic phosphate, some of which feeds back into new production. We emphasize that this study is semiquantitative, exploratory and intended merely to provide a qualitative theoretical framework within which bioturbation's impact on long‐term, first‐order δ¹³C_carbonate can be assessed (and it is hoped quantified in more detail by future work). With this proviso, we conclude that it is entirely plausible that bioturbation made a decisive contribution to the enigmatic directionality in the δ¹³C_carbonate record, from the Neoproterozoic–Cambrian boundary onwards.     

Within trophic level shifts in collagen–carbonate stable carbon isotope spacing are propagated by diet and digestive physiology in large mammal herbivores

Stable carbon isotope analyses of vertebrate hard tissues such as bones, teeth, and tusks provide information about animal diets in ecological, archeological, and paleontological contexts. There is debate about how carbon isotope compositions of collagen and apatite carbonate differ in terms of their relationship to diet, and to each other. We evaluated relationships between δ¹³C_collagen and δ¹³C_carbonate among free‐ranging southern African mammals to test predictions about the influences of dietary and physiological differences between species. Whereas the slopes of δ¹³C_collagen–δ¹³C_carbonate relationships among carnivores are ≤1, herbivore δ¹³C_collagen increases with increasing dietary δ¹³C at a slower rate than does δ¹³C_carbonate, resulting in regression slopes >1. This outcome is consistent with predictions that herbivore δ¹³C_collagen is biased against low protein diet components (¹³C‐enriched C₄ grasses in these environments), and δ¹³C_carbonate is ¹³C‐enriched due to release of ¹³C‐depleted methane as a by‐product of microbial fermentation in the digestive tract. As methane emission is constrained by plant secondary metabolites in browse, the latter effect becomes more pronounced with higher levels of C₄ grass in the diet. Increases in δ¹³C_carbonate are also larger in ruminants than nonruminants. Accordingly, we show that Δ¹³C_collagen‐_carbonate spacing is not constant within herbivores, but increases by up to 5 ‰ across species with different diets and physiologies. Such large variation, often assumed to be negligible within trophic levels, clearly cannot be ignored in carbon isotope‐based diet reconstructions.     

The Late Eocene ‘Whiskey Creek’ methane-seep deposit (western Washington State)

The Late Eocene ‘Whiskey Creek’ deposit (Pysht Formation, Olympic Penisula, Washington State) formed at a methane-seep. Early diagenetic micrites and aragonite cement have δ¹³C values as low as −36‰ indicating that the seepage fluids contained methane. With respect to micrite samples, low δ¹³C values correlate with relatively high δ¹³O values andvice versa. Ongoing micrite formation after the cessation of the seepage during increased burial might have altered the isotopic composition of the microcrystalline carbonates toward lower δ¹³O values and higher δ¹³C values. Alternatively, the trend in isotope values may reflect a change in the composition of seepage fluids. The principal difference between these scenarios is the duration of seepage with respect to micrite formation. Two petrographically similar varieties of blocky calcite spar are related to different carbonate sources. The δ¹³C values range from −32 to −29‰ for one type of blocky spar and are either the result of methane oxidation or indicate thermal decarboxylation of organic matter. Low δ¹⁸O values are in favour of the latter. For the other type of spar, δ¹³C values as high as +6‰ indicate carbonate formation within the zone of methanogensis. The ‘Whiskey Creek’ limestone exhibits a chaotic fabric produced by a variety of processes, including bioturbation, concretionary carbonate formation, earlyin situ brecciation, carbonate corrosion, and late fracturing of the rock. Two varieties of micrite aggregates are responsible for the nodular fabric of the limestone. Smoothly-shaped pyritiferous micrite nodules are of diagenetic origin and formed in a manner similar to that which produces carbonate concretions. Apart from being induced by anaerobic oxidation of methane, their formation is proposed to be linked to iron reduction and sulphide formation. The second, dominant variety is represented by irregularly-shaped, nodular to angular micrite aggregates surrounded by massive rims of pyrite, resulting from carbonate corrosion. A pure, fluorescent seam-micrite, constructive in origin, lines cavities or surrounds micritic aggregates.     

Sulfur bacteria promote dissolution of authigenic carbonates at marine methane seeps

Carbonate rocks at marine methane seeps are commonly colonized by sulfur-oxidizing bacteria that co-occur with etch pits that suggest active dissolution. We show that sulfur-oxidizing bacteria are abundant on the surface of an exemplar seep carbonate collected from Del Mar East Methane Seep Field, USA. We then used bioreactors containing aragonite mineral coupons that simulate certain seep conditions to investigate plausible in situ rates of carbonate dissolution associated with sulfur-oxidizing bacteria. Bioreactors inoculated with a sulfur-oxidizing bacterial strain, Celeribacter baekdonensis LH4, growing on aragonite coupons induced dissolution rates in sulfidic, heterotrophic, and abiotic conditions of 1773.97 (±324.35), 152.81 (±123.27), and 272.99 (±249.96) μmol CaCO₃ • cm⁻² • yr⁻¹, respectively. Steep gradients in pH were also measured within carbonate-attached biofilms using pH-sensitive fluorophores. Together, these results show that the production of acidic microenvironments in biofilms of sulfur-oxidizing bacteria are capable of dissolving carbonate rocks, even under well-buffered marine conditions. Our results support the hypothesis that authigenic carbonate rock dissolution driven by lithotrophic sulfur-oxidation constitutes a previously unknown carbon flux from the rock reservoir to the ocean and atmosphere.Subject terms: Microbial ecology, Water microbiology, Biogeochemistry, Biogeochemistry, Biofilms     

The variable roads to sacrifice: Isotopic investigations of human remains from Chotuna‐Huaca de los Sacrificios,Lambayeque, Peru

This study investigates two key variables—residential context and subsistence—among sacrificial victims dating to the Late Horizon (A.D. 1450–1532) in the Huaca de los Sacrificios at the Chotuna‐Chornancap Archaeological Complex in north coastal Peru. We investigate whether aspects of sacrifice in this distant coastal province mirrored that found in Inca heartland contexts such as the capacocha, or remained more typical of coastal sacrificial traditions. Stable carbon, nitrogen, and oxygen isotope values were characterized in bone carbonate, bone collagen, and hair keratin to estimate geographic residence during the decade before death and diet in the decade, versus months, before death. Bone δ¹⁸O_carbonate values have a mean (±SD) of 26.8 ± 1.1%, bone δ¹³C_carbonate values ?6.7 ± 1.7%, and bone δ¹³C_collagen values 11.8 ± 1.3%; bone δ¹⁵N_collagen values have a mean of 11.5 ± 1.3%. Combined hair δ¹³C_keratin values have a mean of ?12.8 ± 1.6%, and hair δ¹⁵N_keratin values 10.8 ± 1.3%. In contrast to contemporaneous coastal and highland contexts, we are unable to identify immigrants among the sacrificed individuals or changes in diet that indicate provisioning with a standardized diet leading up to death. Instead, results suggest that victims were local to the area, but consumed moderately variable diets consistent with local subsistence patterns. These findings suggest a distinct pattern of human sacrifice in the Late Horizon and underscore the regional and temporal variation in sacrificial practices in the central Andes. Am J Phys Anthropol 151:22–37, 2013. © 2013 Wiley Periodicals, Inc.     

Methanogenic capabilities of ANME‐archaea deduced from 13C‐labelling approaches

Anaerobic methanotrophic archaea (ANME) are ubiquitous in marine sediments where sulfate dependent anaerobic oxidation of methane (AOM) occurs. Despite considerable progress in the understanding of AOM, physiological details are still widely unresolved. We investigated two distinct microbial mat samples from the Black Sea that were dominated by either ANME‐1 or ANME‐2. The ¹³C lipid stable isotope probing (SIP) method using labelled substances, namely methane, bicarbonate, acetate, and methanol, was applied, and the substrate‐dependent methanogenic capabilities were tested. Our data provide strong evidence for a versatile physiology of both, ANME‐1 and ANME‐2. Considerable methane production rates (MPRs) from CO₂‐reduction were observed, particularly from ANME‐2 dominated samples and in the presence of methane, which supports the hypothesis of a co‐occurrence of methanotrophy and methanogenesis in the AOM systems (AOM/MPR up to 2:1). The experiments also revealed strong methylotrophic capabilities through ¹³C‐assimilation from labelled methanol, which was independent of the presence of methane. Additionally, high MPRs from methanol were detected in both of the mat samples. As demonstrated by the ¹³C‐uptake into lipids, ANME‐1 was found to thrive also under methane free conditions. Finally, C₃₅‐isoprenoid hydrocarbons were identified as new lipid biomarkers for ANME‐1, most likely functioning as a hydrogen sink during methanogenesis.     

Carbonate facies‐specific stable isotope data record climate,hydrology, and microbial communities in Great Salt Lake,UT

Organic and inorganic stable isotopes of lacustrine carbonate sediments are commonly used in reconstructions of ancient terrestrial ecosystems and environments. Microbial activity and local hydrological inputs can alter porewater chemistry (e.g., pH, alkalinity) and isotopic composition (e.g., δ¹⁸O_water, δ¹³C_DIC), which in turn has the potential to impact the stable isotopic compositions recorded and preserved in lithified carbonate. The fingerprint these syngenetic processes have on lacustrine carbonate facies is yet unknown, however, and thus, reconstructions based on stable isotopes may misinterpret diagenetic records as broader climate signals. Here, we characterize geochemical and stable isotopic variability of carbonate minerals, organic matter, and water within one modern lake that has known microbial influences (e.g., microbial mats and microbialite carbonate) and combine these data with the context provided by 16S rRNA amplicon sequencing community profiles. Specifically, we measure oxygen, carbon, and clumped isotopic compositions of carbonate sediments (δ¹⁸O_carb, δ¹³C_carb, ?₄₇), as well as carbon isotopic compositions of bulk organic matter (δ¹³C_org) and dissolved inorganic carbon (DIC; δ¹³C_DIC) of lake and porewater in Great Salt Lake, Utah from five sites and three seasons. We find that facies equivalent to ooid grainstones provide time‐averaged records of lake chemistry that reflect minimal alteration by microbial activity, whereas microbialite, intraclasts, and carbonate mud show greater alteration by local microbial influence and hydrology. Further, we find at least one occurrence of ?₄₇ isotopic disequilibrium likely driven by local microbial metabolism during authigenic carbonate precipitation. The remainder of the carbonate materials (primarily ooids, grain coatings, mud, and intraclasts) yield clumped isotope temperatures (T(?₄₇)), δ¹⁸O_carb, and calculated δ¹⁸O_water in isotopic equilibrium with ambient water and temperature at the time and site of carbonate precipitation. Our findings suggest that it is possible and necessary to leverage diverse carbonate facies across one sedimentary horizon to reconstruct regional hydroclimate and evaporation–precipitation balance, as well as identify microbially mediated carbonate formation.     

Aragonite infill in overgrown conceptacles of coralline Lithothamnion spp. (Hapalidiaceae,Hapalidiales, Rhodophyta): new insights in biomineralization and phylomineralogy

New empirical and quantitative data in the study of calcium carbonate biomineralization and an expanded coralline psbA framework for phylomineralogy are provided for crustose coralline red algae. Scanning electron microscopy (SEM) and energy dispersive spectrometry (SEM‐EDS) pinpointed the exact location of calcium carbonate crystals within overgrown reproductive conceptacles in rhodolith‐forming Lithothamnion species from the Gulf of Mexico and Pacific Panama. SEM‐EDS and X‐ray diffraction (XRD) analysis confirmed the elemental composition of these calcium carbonate crystals to be aragonite. After spore release, reproductive conceptacles apparently became overgrown by new vegetative growth, a strategy that may aid in sealing the empty conceptacle chamber, hence influencing the chemistry of the microenvironment and in turn promoting aragonite crystal growth. The possible relevance of various types of calcium carbonate polymorphs present in the complex internal structure and skeleton of crustose corallines is discussed. This is the first study to link SEM, SEM‐EDS, XRD, Microtomography and X‐ray microscopy data of aragonite infill in coralline algae with phylomineralogy. The study contributes to the growing body of literature characterizing and speculating about how the relative abundances of carbonate biominerals in corallines may vary in response to changes in atmospheric pCO₂, ocean acidification, and global warming.     

Paleoecology of Neoproterozoic hypersaline environments: Biomarker evidence for haloarchaea,methanogens, and cyanobacteria

While numerous studies have examined modern hypersaline ecosystems, their equivalents in the geologic past, particularly in the Precambrian, are poorly understood. In this study, biomarkers from ~820 million year (Ma)‐old evaporites from the Gillen Formation of the mid‐Neoproterozoic Bitter Springs Group, central Australia, are investigated to elucidate the antiquity and paleoecology of halophiles. The sediments were composed of alternating laminae of dolomitized microbial mats and up to 90% anhydrite. Solvent extraction of these samples yielded thermally well‐preserved hydrocarbon biomarkers. The regularly branched C₂₅ isoprenoid 2,6,10,14,18‐pentamethylicosane, the tail‐to‐tail linked C₃₀ isoprenoid squalane, and breakdown products of the head‐to‐head linked C₄₀ isoprenoid biphytane, were particularly abundant in the most anhydrite‐rich sediments and mark the oldest current evidence for halophilic archaea. Linear correlations between isoprenoid concentrations (normalized to n‐alkanes) and the anhydrite/dolomite ratio reveal microbial consortia that fluctuated with changing salinity levels. Halophilic archaea were the dominant organisms during periods of high salinity and gypsum precipitation, while bacteria were prevalent during stages of carbonate formation. The irregularly branched C₂₅ isoprenoid 2,6,10,15,19‐pentamethylicosane (PMI), with a central tail‐to‐tail link, was also abundant during periods of elevated salinity, highlighting the activity of methanogens. By contrast, the irregularly branched C₂₀ isoprenoid 2,6,11,15‐tetramethylhexadecane (crocetane) was more common in dolomite‐rich facies, revealing that an alternate group of archaea was active during less saline periods. Elevated concentrations of isotopically depleted heptadecane (n‐C₁₇) revealed the presence of cyanobacteria under all salinity regimes. The combination of biomarkers in the mid‐Neoproterozoic Gillen Formation resembles lipid compositions from modern hypersaline cyanobacterial mats, pointing to a community composition that remained broadly constant since at least the Neoproterozoic. However, as a major contrast to most modern hypersaline environments, the Gillen evaporites did not yield any evidence for algae or other eukaryotes.     

Anaerobic and Aerobic Oxidation of Methane at Late Cretaceous Seeps in the Western Interior Seaway,USA

The Late Cretaceous (Campanian) Tepee Buttes represent a series of conical, fossiliferous limestone deposits embedded in marine shales that deposited in the Western Interior Seaway. The previously suggested origin of the Tepee Buttes at methane-seeps was confirmed by this study. δ¹³C values as low as ?50‰ of early diagenetic carbonate phases of two Tepee Buttes near Pueblo (Colorado) reveal that methane was the major carbon source. Molecular fossils released from a methane-seep limestone contain abundant ¹³C-depleted archaeal lipids (PMI, biphytane; δ ¹³C: ?118 and ?102‰), derived from anaerobic methanotrophs. A suite of ¹³C-depleted bacterial biomarkers (branched fatty acids; ?73 to ?51‰) reflects the former presence of sulfate-reducing bacteria, corroborating that a syntrophic consortium of archaea and bacteria mediating anaerobic oxidation of methane already existed in Cretaceous times. Molecular fossils also suggest that methane was not exclusively oxidized in an anaerobic process. A series of unusual C₃₄/C₃₅-8,14-secohexahydrobenzohopanes with low δ¹³C values (?110 and ?107‰) points to the presence of aerobic methanotrophic bacteria at the ancient seep site.     

The prominent role of bacterial sulfate reduction in the formation of glendonite: a case study from Paleogene marine strata of western Washington State

Ikaite (CaCO₃·6H₂O) forms at near-freezing temperatures and its precipitation is favored by high alkalinity and high concentrations of dissolved phosphate. With increasing temperatures during early burial, ikaite transforms into its calcite pseudomorph referred to as glendonite. To further constrain the biogeochemical processes that impact the transformation of ikaite to glendonite, glendonites from Cenozoic strata of western Washington State, USA, were analyzed for their petrographic characteristics, stable isotope (C, O, S) patterns, and lipid biomarker inventories. Glendonites from the Humptulips, Pysht, Lincoln Creek, and Astoria Formations occur in strata that enclose abundant methane-seep deposits. Despite robust evidence for the anaerobic oxidation of methane (AOM) at these ancient seep sites, molecular signatures of this biogeochemical process were not found within glendonite. Glendonite was found to contain abundant, moderately ¹³C-depleted iso- and anteiso-fatty acids, compounds interpreted as biomarkers of sulfate-reducing bacteria in marine settings. The ³⁴S-enrichment in carbonate-associated sulfate (δ³⁴S_CAS = 54.1 ‰) and the ³⁴S-depletion of pyrite (δ³⁴S_CRS = 6.8–12.5 ‰) in glendonite samples confirm that bacterial sulfate reduction was a prominent process in the sedimentary environment during the transformation of ikaite to glendonite. Low δ¹³C_glendonite values, such as those of the Washington State glendonites (as low as ?21‰), have previously been interpreted as signatures of methane-derived carbon; however, the admittedly small data set obtained from the Washington State glendonites is best explained with organoclastic sulfate reduction as the alkalinity engine driving carbonate precipitation. This surprising finding reveals that more comprehensive work is needed to decipher the biogeochemical processes that governed the transformation of ikaite to glendonite in ancient marine settings, including the relative contribution of organoclastic sulfate reduction and AOM.     

Diet, residential origin, and pathology at Machu Picchu, Peru

Pathological conditions in human skeletal remains provide a wealth of information about archaeological populations, but many are limited in their interpretive significance by their nonspecific etiologies. This study analyzes three common pathological conditions known to manifest in infancy and childhood in the skeletal population from Machu Picchu, Peru (N = 74) with published carbon, nitrogen, oxygen, strontium, and lead isotopic data (Turner et al.: J Archaeol Sci 36 (2009) 317–332; Turner et al.: Chungara: Revista de Antropología Chilena 42 (2010) 515–524) to distinguish early‐life diet from residential origins as significantly associated with pathologies among the site's inhabitants. Analyses of variance indicate highly significant variation between enamel δ¹⁸O values, which serve as a rough proxy of local environment, and both cribra orbitalia (CO) and porotic hyperostosis (PH), generally understood to be markers of anemia. Results tentatively suggest that individuals manifesting these lesions may have lived closer to the arid coasts; however, no significant variation was found in parameters of diet (enamel δ¹³C_carbonate, dentin δ¹³C_collagen, dentin δ¹⁵N) by either CO or PH, suggesting that the primary factors causing anemia may have been more significantly related to residential origin rather than diet. Linear enamel hypoplasia (LEH) frequency significantly varied by both dietary and residential parameters, supporting models of LEH formation from a synergy of dietary and environmental factors. These results support previous research on the etiology of PH in the Andes; they also represent a useful approach to refining site‐specific interpretations of pathological conditions in archaeological populations, and exploring etiological variation between populations. Am J Phys Anthropol, 2012. © 2012 Wiley Periodicals, Inc.     

Analysis of archaeal core ether lipids using Time of Flight–Secondary Ion Mass Spectrometry (ToF-SIMS): Exploring a new prospect for the study of biomarkers in geobiology

The capability of Time of Flight–Secondary Ion Mass Spectrometry (ToF‐SIMS) of analysing molecular archaeal biomarkers in geobiological samples was tested and demonstrated. Using a bismuth cluster primary ion source, isopranyl glycerol di‐ and tetraether core lipids were detected in small amounts of total organic extracts from methanotrophic microbial mats, simultaneously and without further chemical treatment and chromatographic separation. ToF‐SIMS was also employed to track the distribution of fossilized ether lipids in a massive carbonate (aragonite) microbialite that precipitated as a result of the microbial anaerobic oxidation of methane. An unambiguous signal was obtained when analysing a freshly broken rock surface (base of a microdrill core). Though some limitation occurred due to µm‐topographical effects (sample roughness), it was possible to display the abundance of high molecular weight (C₈₆) of tetraethers exposed in particular regions of the rock surface. ‘Molecular mapping’ revealed that a part of these molecules was encased within the rock fabric in a cluster‐like distribution that might trace the arrangement of the calcifying microbial colonies in the once active mat system. The results reveal promising perspectives of ToF‐SIMS for (i) the quasi‐nondestructive analysis of lipids in extremely small geobiological samples at low concentrations; (ii) resolving the spatial distribution of these compounds on a µm²‐ to cm²‐scale; and (iii) the more exact assignment of lipid biomarkers to their biological source.     

Microbial diversity and community structure of a highly active anaerobic methane‐oxidizing sulfate‐reducing enrichment

Anaerobic oxidation of methane (AOM) is an important methane sink in the ocean but the microbes responsible for AOM are as yet resilient to cultivation. Here we describe the microbial analysis of an enrichment obtained in a novel submerged‐membrane bioreactor system and capable of high‐rate AOM (286 μmol g_{dry weight}^?1 day^?1) coupled to sulfate reduction. By constructing a clone library with subsequent sequencing and fluorescent in situ hybridization, we showed that the responsible methanotrophs belong to the ANME‐2a subgroup of anaerobic methanotrophic archaea, and that sulfate reduction is most likely performed by sulfate‐reducing bacteria commonly found in association with other ANME‐related archaea in marine sediments. Another relevant portion of the bacterial sequences can be clustered within the order of Flavobacteriales but their role remains to be elucidated. Fluorescent in situ hybridization analyses showed that the ANME‐2a cells occur as single cells without close contact to the bacterial syntrophic partner. Incubation with ¹³C‐labelled methane showed substantial incorporation of ¹³C label in the bacterial C₁₆ fatty acids (bacterial; 20%, 44% and 49%) and in archaeal lipids, archaeol and hydroxyl‐archaeol (21% and 20% respectively). The obtained data confirm that both archaea and bacteria are responsible for the anaerobic methane oxidation in a bioreactor enrichment inoculated with Eckernförde bay sediment.     

Geochemical environments of continental shelf-upper slope sediments in the northern Gulf of Mexico

Geochemical environments were characterized for 14 sites along the northern Gulf of Mexico continental shelf and upper slope, in an effort to examine the relationship between sediment geochemistry and carbonate shell taphonomy in a long-term study—Shelf and Slope Experimental Taphonomy Initiative (SSETI). Three groups of environments of preservation (seep, near-seep, and shelf-and-slope) were identified based on their geochemical characteristics (i.e., oxygen uptake rate and penetration depth, pore-water saturation states, and carbonate dissolution fluxes). Diffusive oxygen uptake rate increased in the order of shelf-and-slope, near-seep, and seep, although carbonate dissolution flux did not show significant correlation with O₂ flux, presumably due to non-diffusive behavior at some sites. Using pore-water saturation indices with respect to aragonite and calcite and sedimentation rates, we defined a semi-quantitative parameter, carbonate dissolution index (CDI), to predict carbonate preservation potential during the taphonomic processes. Our limited database suggests that both the seep and the shelf-and-slope sediments may have higher carbonate preservation potential than the near-seep sediments.     

Methane-flux-dependent lateral faunal changes in a Late Cretaceous chemosymbiotic assemblage from the Nakagawa area of Hokkaido, Japan

A Late Cretaceous carbonate body (2 m in maximum diameter) surrounded by clastic rocks, recently discovered in the Nakagawa area (Hokkaido, Japan), is interpreted as a methane‐seep deposit, on the basis of negative carbon isotopic composition (as low as ?43.5‰), variable sulphide sulphur isotopic composition, high carbonate content, and in situ fractures. It most likely formed owing to methane‐bearing pore‐water diffusion. We estimate that the concentration of methane decreased toward the margin of the carbonate body, and that only small carbonate concretions were precipitated at a certain distance from the methane‐seep centre. These spatial characteristics coincide well with the observed pattern of faunal distribution. The gastropod‐dominated association (indeterminate abyssochrysids and ataphrids and the acmaeid limpet Serradonta sp. are most common) co‐occurs with lucinid and thyasirid bivalves (Thyasira sp., Myrtea sp., and Miltha sp.), and was found within and just above the methane‐derived carbonate body. Acharax and Nucinella (solemyoid bivalves) are more typical of the peripheral part of the methane‐influenced sediments. We suggest that this pattern of faunal distribution reflects the decreasing concentration of methane and apparently also hydrogen sulphide when moving from the centre of discharge toward the periphery of the methane seep.     

The formation of giant tubular concretions triggered by anaerobic oxidation of methane as revealed by archaeal molecular fossils (Lower Eocene, Varna, Bulgaria)

Impressive, several meters high tubular concretions in shallow marine calcareous sands and sandstones represent part of the well-exposed, subsurface plumbing network of an Early Eocene methane seep system in the Balkanides foreland (Pobiti Kamani area, Varna, NE Bulgaria). An integrated approach, including petrography, inorganic geochemistry and lipid biomarker analyses was used to reconstruct the evolution of pore fluids and cementation conditions during tube formation and particularly, the role of methane-related carbonate diagenesis. Host sediment lithification from marine pore waters was perturbed soon after deposition by oxidation of predominantly microbial methane causing pervasive cementation by a ¹³C-poor, homogeneous calcite cement (δ¹³C values as low as − 44.5‰ V-PDB). The importance of microbially mediated anaerobic oxidation of methane (AOM) is confirmed by extremely ¹³C-depleted archaeal biomarkers (δ¹³C values as low as − 123‰ V-PDB). A suite of macrocyclic dialkyl glycerol diethers (MDGD-0 to -2) and sn-3-hydroxyarchaeol comprises a characteristic trait of the Eocene tubular concretions and might represent molecular fossils of so far unknown methane-oxidizing archaea (ANME). Subsurface calcite cementation surrounding the ascending methane plume, resulted from the changing pore water chemistry in response to AOM and could have, on a local scale, been encouraged by the concurrent alteration of detrital feldspar. Fluctuating δ¹³C (up to − 8‰ V-PDB) and δ¹⁸O (− 0.5 to − 9‰ V-PDB) signatures within a single tubular sandstone concretion are at least partly the consequence of isotopic resetting during late meteoric water circulation.