Diffusional losses of amended anaerobic electron acceptors in sediment field microcosms

Hudson River sediment microcosms from Piles Creek (PC), Piermont Marsh (PM), and Iona Island (II) were amended with ∼100 mM nitrate or sulfate to stimulate anaerobic bioremediation. Nitrate and sulfate decreased over two years of field incubation and the fraction of these losses due to diffusion to the water column was predicted using Fick’s law. Apparent diffusion (D_app) values of 1-4 × 10⁻¹⁰ m² s⁻¹ predicted the majority of loss/gain from/to the sediments by 700 d, but not at all times. Effective diffusion (D_eff) values predicted by the porosity function (D_eff = D_mol ε^4/3) were larger than those observed in the field, and field data indicates a cube power relationship: D_eff = D_mol ε³. D_app greatly increased in surficial layers at PM and PC in year two, suggesting that bioadvection caused by bioturbating organisms had occurred. The effects of bioturbation on transport to/from the sediments are modeled, and results can be applied to various sediment treatment scenarios such as capping.     

Bacterial biogas production in coastal systems affected by freshwater inputs

The concentrations of two greenhouse gases, nitrous oxide (N₂O) and methane (CH₄), and the bacterial processes involved in their production (nitrification and denitrification for N₂O, and methanogenesis for CH₄), were determined in surface waters of two coastal areas under the influence of freshwater inputs, on one part in the Gulf of Lions and the Rhone River plume, in northwestern Mediterranean Sea, and on the other part in the inner Thermaikos Gulf, in Aegean Sea, eastern Mediterranean Sea. High concentrations of dissolved CH₄ and N₂O were recorded in the surface waters of Gulf of Lions and Gulf of Thermaikos, up to 1300 nM for CH₄, and 40 nM for N₂O. No direct relationship could be found between the concentration and production of the biogases, as they may also be produced in deep water or bottom sediment in shallow areas, or derived from anthropogenic activity or ship contamination in polluted areas. Irrespective of the origin of CH₄ and N₂O, the presence of extremely high concentrations of these two gases in superficial seawater implies that they can easily escape to the atmosphere; consequently, these nearshore waters enriched in greenhouse gases may play an important role in the increase in atmospheric concentration of both CH₄ and N₂O.     

Authigenic minerals from the Paola Ridge (southern Tyrrhenian Sea): Evidences of episodic methane seepage

Paola Ridge, along the NW Calabrian margin (southern Tyrrhenian Sea), is one of the few reported deep sea sites of precipitation of authigenic carbonates in the Tyrrhenian Sea. Here, the changing composition of the seeping fluids and the dynamic nature of the seepage induced the precipitation of pyrite, siderite and other carbonate phases. The occurrence of this array of authigenic precipitates is thought to be related to fluctuation of the sulfate-methane transition zone (SMTZ).Concretions of authigenic minerals formed in the near sub-bottom sediments of the Paola Ridge were investigated for their geochemical and isotopic composition. These concretions were collected in an area characterized by the presence of two alleged mud volcanoes and three mud diapirs. The mud diapirs are dotted by pockmarks and dissected by normal faults, and are known for having been a site of fluid seepage for at least the past 40 kyrs. Present-day venting activity occurs alongside the two alleged mud volcanoes and is dominated by CO₂-rich discharging fluids. This discover led us to question the hypothesis of the mud volcanoes and investigate the origin of the fluids in each different domed structure of the study area.In this study, we used stable isotopes (carbon and oxygen) of carbonates coupled with rare earth element (REE) composition of different carbonate and non-carbonate phases for tracing fluid composition and early diagenesis of authigenic precipitates. The analyses on authigenic precipitates were coupled with chemical investigation of venting gas and sea-water.Authigenic calcite/aragonite concretions, from surficial sediments on diapiric structures, have depleted ¹³C isotopic composition and slightly positive δ¹⁸O values. By contrast, siderite concretions, generally found within the first 6 m of sediments on the alleged mud volcanoes, yielded positive δ¹³C and δ¹⁸O values. The siderite REE pattern shows consistent LREE (light REE) fractionation, MREE (medium REE) enrichment and positive Gd and La anomalies. As shown by the REE distribution, the ¹³C-depleted composition and their association with chemosymbiotic fauna, calcite/aragonite precipitated at time of moderate to high methane flux close to the seafloor, under the influence of bottom seawater. Authigenic siderite, on the other hand, formed in the subseafloor, during periods of lower gas discharges under prolonged anoxic conditions within sediments in equilibrium with ¹³C-rich dissolved inorganic carbon (DIC) and ¹⁸O-rich water, likely related to methanogenesis and intermittent venting of deep-sourced CO₂.     

A large epeiric methanogenic Bambuí sea in the core of Gondwana supercontinent?

Carbon isotope compositions of both sedimentary carbonate and organic matter can be used as key proxies of the global carbon cycle and of its evolution through time,as long as they are acquired from waters where the dissolved inorganic carbon(DIC)is in isotope equilibrium with the atmospheric CO2.However,in shallow water platforms and epeiric settings,the influence of local to regional parameters on carbon cycling may lead to DIG isotope variations unrelated to the global carbon cycle.This may be especially true for the terminal Neoproterozoic,when Gondwana assembly isolated waters masses from the global ocean,and extreme positive and negative carbon isotope excursions are recorded,potentially decoupled from global signals.To improve our understanding on the type of information recorded by these excursions,we investigate the pairedδ^13Ccarb andδ^13Corg evolution for an increasingly restricted late Ediacaran-Cambrian foreland system in the West Gondwana interior:the basal Bambui Group.This succession represents a 1~(st)-order sedimentary sequence and records two majorδ^13Ccarb excursions in its two lowermost lower-rank sequences.The basal cap carbonate interval at the base of the first sequence,deposited when the basin was connected to the ocean,hosts antithetical negative and positive excursions forδ^13Ccarb andδ^13Corg,respectively,resulting inΔ^13C values lower than 25‰.From the top of the basal sequence upwards,an extremely positiveδ^13Ccarb excursion is coupled toδ^13Corg,reaching values of+14‰and-14‰,respectively.This positive excursion represents a remarkable basin-wide carbon isotope feature of the Bambui Group that occurs with only minor changes inΔ^13C values,suggesting change in the DIC isotope composition.We argue that this regional isotopic excursion is related to a disconnection between the intrabasinal and the global carbon cycles.This extreme carbon isotope excursion may have been a product of a disequilibria between the basin DIC and atmospheric CO2 induced by an active methanogenesis,favored by the basin restriction.The drawdown of sulfate reservoir by microbial sulfate reduction in a poorly ventilated and dominantly anoxic basin would have triggered methanogenesis and ultimately methane escape to the atmosphere,resulting in a^13C-enriched DIC influenced by methanogenic CO2.Isolated basins in the interior of the Gondwana supercontinent may have represented a significant source of methane inputs to the atmosphere,potentially affecting both the global carbon cycle and the climate.     

Deep pore water profiles reflect enhanced microbial activity towards tidal flat margins

Microbial activity in permeable tidal flat margin sediments is enhanced by two main processes. First, organic matter is supplied by rapid sedimentation at prograding tidal flat margins. Second, surface and deep pore water advection lead to a replenishment of the dissolved organic matter and sulfate pools. Increasing microbial activity towards the low water line is reflected in sulfate and methane profiles as well as in total cell numbers, sulfate reduction rates, and remineralization products. The impact of high sedimentation rates on pore water biogeochemistry is confirmed by inverse modeling reproducing the depth profiles obtained by measurements. In central parts of the tidal flats, low sedimentation rates and pore water flow velocities limit microbial activity despite the high availability of electron acceptors for microbial respiration such as sulfate. Therefore, tidal flat margins with high microbial activity are of special importance for budgeting biogeochemical cycling in tidal flat areas.     

Bacterial methane in the Atzbach-Schwanenstadt gas field (Upper Austrian Molasse Basin), Part I: Geology

Bacterial methane gas accumulations occur in Upper Oligocene to Early Miocene clastic deepwater sediments in the Austrian Molasse Basin. Methane gas is produced from the Upper Puchkirchen Fm. (Aquitanian) in the Atzbach-Schwanenstadt gas field which is one of the largest gas fields in this basin.     

Stable isotope geochemistry of ground and surface waters associated with undisturbed massive sulfide deposits; constraints on origin of waters and water-rock reactions

Stable isotopes (H, O, C) were determined for ground and surface waters collected from two relatively undisturbed massive sulfide deposits (Halfmile Lake and Restigouche) in the Bathurst Mining Camp (BMC), New Brunswick, Canada. Additional waters from active and inactive mines in the BMC were also collected. Oxygen and hydrogen isotopes of surface and shallow groundwaters from both the Halfmile Lake and Restigouche deposits are remarkably uniform (− 13 to − 14‰ and − 85 to − 95‰ for δ¹⁸O_VSMOW and δ²H_VSMOW, respectively). These values are lighter than predicted for northern New Brunswick and, combined with elevated deuterium excess values, suggest that recharge waters are dominated by winter precipitation, recharged during spring melting. Deeper groundwaters from the Restigouche deposit, and from active and inactive mines have heavier δ¹⁸O_VSMOW ratios (up to − 10.8‰) than shallow groundwaters suggesting recharge under warmer climate or mixing with Shield-type brines. Some of the co-variation in Cl concentrations and δ¹⁸O_VSMOW ratios can be explained by mixing between saline and shallow recharge water end-members. Carbon isotopic compositions of dissolved inorganic carbon (DIC) are variable, ranging from − 15 to − 5‰ δ¹³C_VPDB for most ground and surface waters. Much of the variation in the carbon isotopes is consistent with closed system groundwater evolution involving soil zone CO₂ and fracture zone carbonate minerals (calcite, dolomite and siderite; average = − 6.5‰ δ¹³C_VPDB). The DIC of saline Restigouche deposit groundwater is isotopically heavy (∼+ 12‰ δ¹³C_VPDB), indicating carbon isotopic fractionation from methanogenesis via CO₂ reduction, consistent with the lack of dissolved sulfate in these waters and the observation of CH₄-degassing during sampling.     

Contribution of anaerobic microbial activity to natural attenuation of benzene in groundwater

Anaerobic biodegradation of hydrocarbons, using a variety of terminal electron acceptors (TEAs), is increasingly being reported both in laboratory studies and in the field. Of all the petroleum hydrocarbons, benzene is considered the most problematical due to its high toxicity and relatively high aqueous solubility. These, combined with its peculiarly stable structure, mean that it has long been considered recalcitrant in all but aerobic conditions. There is now a small, but growing, literature to suggest that this may not in fact be the case. We present an assessment of the field, encompassing reviews up to 1997 and original papers published since then. It appears that benzene is indeed degraded anaerobically, but that organisms capable of doing so are not ubiquitous. In addition, benzene degradation may be competitively inhibited by the presence of more readily degraded compounds such as toluene. Certainly, the occurrence and rate of benzene attenuation under anaerobic conditions is far more site-specific than for other benzene, toluene, ethylbenzene and xylenes (BTEX) compounds. We discuss a mathematical method for modelling redox-dependent, differential degradation rates.     

Methane sources in gas hydrate-bearing cold seeps: Evidence from radiocarbon and stable isotopes

Fossil methane from the large and dynamic marine gas hydrate reservoir has the potential to influence oceanic and atmospheric carbon pools. However, natural radiocarbon (¹⁴C) measurements of gas hydrate methane have been extremely limited, and their use as a source and process indicator has not yet been systematically established. In this study, gas hydrate-bound and dissolved methane recovered from six geologically and geographically distinct high-gas-flux cold seeps was found to be 98 to 100% fossil based on its ¹⁴C content. Given this prevalence of fossil methane and the small contribution of gas hydrate (≤ 1%) to the present-day atmospheric methane flux, non-fossil contributions of gas hydrate methane to the atmosphere are not likely to be quantitatively significant. This conclusion is consistent with contemporary atmospheric methane budget calculations.In combination with δ¹³C- and δD-methane measurements, we also determine the extent to which the low, but detectable, amounts of ¹⁴C (~ 1–2% modern carbon, pMC) in methane from two cold seeps might reflect in situ production from near-seafloor sediment organic carbon (SOC). A ¹⁴C mass balance approach using fossil methane and ¹⁴C-enriched SOC suggests that as much as 8 to 29% of hydrate-associated methane carbon may originate from SOC contained within the upper 6 m of sediment. These findings validate the assumption of a predominantly fossil carbon source for marine gas hydrate, but also indicate that structural gas hydrate from at least certain cold seeps contains a component of methane produced during decomposition of non-fossil organic matter in near-surface sediment.     

Recognising biodegradation in gas/oil accumulations through the δC compositions of gas components

A large suite of natural gases (93) from the North West Shelf and Gippsland and Otway Basins in Australia have been characterised chemically and isotopically resulting in the elucidation of two types of gases. About 26% of these gases have anomalous stable carbon isotope compositions in the C₁–C₄ hydrocarbons and CO₂ components, and are interpreted to have a secondary biogenic history. The characteristics include unusually large isotopic separations between successive n-alkane homologues (up to +29‰ PDB) and isotopically heavy CO₂ (up to +19.5‰ PDB). Irrespective of geographic location, these anomalous gases are from the shallower accumulations (600–1700 m) where temperatures are lower than 75°C. The secondary biogenic gases are readily distinguishable from thermogenic gases (74% of this sample suite), which should assist in the appraisal of hydrocarbons during exploration where hydrocarbon accumulations are under 2000 m. While dissolution effects may have contributed to the high ¹³C enrichment of the CO₂ component in the secondary biogenic gases, the primary signature of this CO₂ is attributed to biochemical fractionation associated with anaerobic degradation and methanogenesis. Correlation between biodegraded oils and biodegraded “dry” gas supports the concept that gas is formed from the bacterial destruction of oil, resulting in “secondary biogenic gas”. Furthermore, the prominence of methanogenic CO₂ in these types of accumulations along with some isotopically-depleted methane provides evidence that the processes of methanogenesis and oil biodegradation are linked. It is further proposed that biodegradation of oil proceeds via a complex anaerobic coupling that is integral to and supports methanogenesis.