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Offshore hydrocarbon accumulations in the Gulf of Mexico (GoM) are often accompanied by natural seepage of oil and gas from subsurface reservoirs into shallow sediments and the water column. This study investigated the temporal patterns and carbon-sulfur (C-S) coupling associated with authigenic carbonate samples recovered from surface sediments of a crude oil seepage site in southern GoM (Chapopote asphalt volcano, Bay of Campeche) using radioactive U-Th dates, and stable C, O, and S isotopes. The results were compared with data from multiple seep sites in the northern GoM where methane seepage is dominant along with non-methane hydrocarbons (ethane , propane, crude oil, etc.). U-Th age-dating of Chapopote seep carbonate samples yielded ages of 13.5 ka to 4.6 ka before present (BP), suggesting that Chapopote asphalt seepage has been ongoing for thousands of years. The results are also consistent with previous studies from the northern GoM that hypothesize that seeps along the GoM continental slope were active during the last deglaciation. δ13CCaCO3 and δ18OCaCO3 values from authigenic carbonates at Chapopote indicated a mixed contribution of methane and non-methane hydrocarbons to the dissolved inorganic carbon (DIC) pool, consistent with previous results. Comparison of δ13CCaCO3 vs. δ34SCRS (CRS = chromium reducible sulfur) from carbonate samples showed noticeable differences at the Chapopote seep site (average δ13CCaCO3 -25‰ VDPB, δ34SCRS -27‰ VCDT) relative to the methane seep-dominated samples from the northern GoM (average δ13CCaCO3 0‰ VCDT). Our results point toward distinguishable differences in the paired δ13CDIC and δ34Ssulfide signatures produced via the diagenetic processes of sulfate-driven anaerobic oxidation of methane versus non-methane hydrocarbons. These results potentially provide an important proxy for identification of such diagenetic processes within the sedimentary records.

The Campeche Knolls in the Bay of Campeche, southern Gulf of Mexico, were investigated through detailed seafloor mapping, ROV surveys, and sediment and pore water sampling. The knolls are elongated, submarine hills created by salt tectonics with a positive relief of up to 800 m above the surrounding seafloor. Several of the knolls are associated with sea-surface oil slicks identified from satellite data, indicating the presence of hydrocarbon seeps on the seafloor. One of the knolls, named “Chapopote”, was studied in detail during two international research expeditions (SO174/2 and M67/2) and is characterized by extensive hydrocarbon seepage including large asphalt flows, oil and gas seeps, and seafloor gas hydrate deposits. Chemosymbiotic biological communities and authigenic carbonate deposits are associated with the seeps and are the result of both biogeochemical turnover and the interaction between downward-diffusing seawater and hydrocarbon-rich pore fluids at shallow sediment depth. Authigenic carbonates are characterized by aragonite, exhibit a porous texture, and are cemented by a matrix of microsparitic to sparitic aragonite. Macropores of the carbonates were completely filled with liquid oil. Carbonate microfabrics include peloidal or clotted fabrics that may indicate the existence of microenvironments resulting from microbial metabolism. Banded/botryoidal aragonite cements line the intra- and bioclasts and incompletely fill the pore spaces. The stable carbon isotopic composition of authigenic aragonite varies between − 28.6‰ and − 17.9‰ (PDB), identifying oil oxidation as the primary source of carbon to the DIC pool, while lipid biomarker data demonstrate the concurrent existence of microbial communities responsible for anaerobic oxidation of methane (AOM). These observations indicate the presence of additional, AOM-independent reactions responsible for carbon sequestration at hydrocarbon seeps and demonstrate the complexity of biogeochemical processes at seep sites in the Gulf of Mexico basin. Oxygen isotope data of authigenic aragonite vary from + 2.5‰ to + 3.8‰ (PDB), indicating carbonate precipitation in slight disequilibrium with the surrounding pore fluids.

Authigenic carbonates from five continental margin locations, the Eel River Basin, Monterey Bay, Santa Barbara Basin, the Sea of Okhotsk, and the North Sea, exhibit a wide range of mineralogical and stable isotopic compositions. These precipitates include aragonite, low- and high-Mg calcite, and dolomite. The carbon isotopic composition of carbonates varies widely, ranging from −60‰ to +26‰, indicating complex carbon sources that include ^(13)C-depleted microbial and thermogenic methane and residual, 13C-enriched, bicarbonate. A similarly large variability of δ^(18)O values (−5.5‰ to +8.9‰) demonstrates the geochemical complexity of these sites, with some samples pointing toward an ^(18)O-enriched oxygen source possibly related to advection of ^(18)O-enriched formation water or to the decomposition of gas hydrate. Samples depleted in ^(18)O are consistent with formation deeper in the sediment or mixing of pore fluids with meteoric water during carbonate precipitation. A wide range of isotopic and mineralogical variation in authigenic carbonate composition within individual study areas but common trends across multiple geographic areas suggest that these parameters alone are not indicative for certain tectonic or geochemical settings. Rather, the observed variations probably reflect local controls on the flux of carbon and other reduced ions, such as faults, fluid conduits, the presence or absence of gas hydrate in the sediment, and the temporal evolution of the local carbon reservoir. Areas with seafloor carbonates that indicate formation at greater depth below the sediment–water interface must have undergone uplift and erosion in the past or are still being uplifted. Consequently, the occurrence of carbonate slabs on the seafloor in areas of active hydrocarbon seepage is commonly an indicator of exhumation following carbonate precipitation in the shallow subsurface. Therefore, careful petrographic and geochemical analyses are critical components necessary for the correct interpretation of processes related to hydrocarbon seepage in continental margin environments and elsewhere.

Anaerobic oxidation of methane (AOM) impacts carbon cycling by acting as a methane sink and by sequestering inorganic carbon via AOM-induced carbonate precipitation. These precipitates commonly take the form of carbonate nodules that form within methane seep sediments. The timing and sequence of nodule formation within methane seep sediments are not well understood. Further, the microbial diversity associated with sediment-hosted nodules has not been well characterized and the degree to which nodules reflect the microbial assemblage in surrounding sediments is unknown. Here, we conducted a comparative study of microbial assemblages in methane-derived authigenic carbonate nodules and their host sediments using molecular, mineralogical, and geochemical methods. Analysis of 16S rRNA gene diversity from paired carbonate nodules and sediments revealed that both sample types contained methanotrophic archaea (ANME-1 and ANME-2) and syntrophic sulfate-reducing bacteria (Desulfobacteraceae and Desulfobulbaceae), as well as other microbial community members. The combination of geochemical and molecular data from Eel River Basin and Hydrate Ridge suggested that some nodules formed in situ and captured the local sediment-hosted microbial community, while other nodules may have been translocated or may represent a record of conditions prior to the contemporary environment. Taken together, this comparative analysis offers clues to the formation regimes and mechanisms of sediment-hosted carbonate nodules.

Marine methane vents and cold seeps are common features along continental margins worldwide, serving as localized sites for methane release and colonization by microbial and chemosynthetic megafaunal communities. The Eel River Basin (ERB), located on the continental slope off Northern California, contains active methane vents and seep-associated chemosynthetic biological communities (CBC) on the crests of anticlines in ∼520-m water depth. Seep-related features on the seafloor have a patchy distribution and include active bubbling vents, chemosynthetic clam beds, and sulfide-oxidizing bacterial mats. Methane sources supplying local seeps are heterogeneous on all spatial scales and support a large and diverse microbial assemblage involved in the anaerobic oxidation of methane (AOM). To develop a comprehensive understanding of the complex biological, geochemical and physical processes associated with, and influencing seafloor methane seepage, a multidisciplinary approach is required. Here we present an integrative, multidisciplinary study that illustrates the diverse processes associated with seafloor methane seepage within the Eel River Basin and the complex interactions defining the geochemistry, mineralogy and microbiology within this environment.

Asphalt volcanoes and lava-like flows of solidified asphalt on the seafloor (Figure 1) were first discovered and described by MacDonald et al. [2004]. The flows covered more than one square kilometer of a dissected salt dome at abyssal depths (∼3000 m) in the southern Gulf of Mexico. “Chapopote” (93°26′W, 21°54′N) was one of two asphalt volcanoes they discovered. MacDonald et al. determined that the apparently fresh asphalt must initially have flowed in a hot state, and subsequently chilled, contracted, and solidified, much in the same way as normal lava does on the surface of the Earth. The two asphalt-volcanoes discovered occur at the apex of salt domes that pierce through the seafloor. These “piercement salt domes,” known as the Campeche Knolls, are pertinent features of the deep Campeche Sedimentary Basin, which has a sediment thickness of about 10 km. According to conventional theory [Vendeville and Jackson, 1992], piercement salt domes represent “salt diapirs” that have risen up, due partly to density contrasts between salt and clay/sand from the “mother salt” located between 7 and 10 km below seafloor. A salt diapir is a vertical body of sub-surface salt, which is most often circular in cross section, is one to several kilometers in diameter, and can be 8–10 km high.

Chemosynthetic cold-seep vestimentiferan tubeworms and vesicomyid clams inhabiting oceanic basaltic rock have been discovered on the Gorda Escarpment sector of the Mendocino transform fault 73 km west of Cape Mendocino, northern California. The sparse cold-seep animals are "biomarkers" that identify zones of focused fluid venting from a methane gas horizon seismically imaged as a bottom-simulating reflector (BSR) within sediments on the southern flank of the escarpment. This is the first example of a methane-based cold-seep community on exposed oceanic basement rock within an area dominated by transform tectonics. This discovery extends the range of known environments in which the subsurface flow and venting of methane-rich fluids are linked both with geological activity and chemosynthetic communities. Observations by remotely operated vehicle of the distribution of the animals, sediment, basaltic talus, and basement outcrop delineate a large slump headscarp that channels subsurface fluid. Seismic surveys of the southern flank of the Mendocino transform fault (the Vizcaino block) define a BSR hosted in the thick sedimentary sequence that projects to the wall of the Gorda Escarpment at the same depth as the chemosynthetic community. The well-defined BSR in the marine sediment of the Vizcaino block results from an accumulation of methane gas possibly capped by methane hydrate. The isotopic composition of Mg-calcite found along the headscarp (δ 1 3 C = -65‰; δ 1 8 O = 4.8‰) is consistent with fluids derived from dissociated methane hydrate. We propose that the tectonic uplift along this transform margin has resulted in the lateral, northward movement of methane from the Vizcaino sedimentary sequence to the east-trending wall of the north-facing Gorda Escarpment.