Numerical modeling of gas hydrate emplacements in oceanic sediments

We have implemented a 2-dimensional numerical model for simulating gas hydrate and free gas accumulation in marine sediments. The starting equations are those of the conservation of the transport of momentum, energy, and mass, as well as those of the thermodynamics of methane hydrate stability and methane solubility in the pore-fluid. These constitutive equations are then integrated into a finite element in space, finite-difference in time scheme. We are then able to examine the formation and distribution of methane hydrate and free gas in a simple geologic framework, with respect to the geothermal heat flow, fluid flow, the methane in-situ production and basal flux. Three simulations are performed, leading to the build up of hydrate emplacements largely linear through time. Models act primarily as free gas accumulators and are relatively inefficient with respect to hydrate emplacements: 26–33% of formed methane are converted to hydrate. Seepage of methane across the sea-floor is negligible for fluid flow below 2. 10⁻¹¹ kg/m²/s. At 5.625 10⁻¹¹ kg/m²/s however, 9.7% of the formed methane seeps out of the model. Moreover, along strike variation arising in the 2-dimensional model are outlined. In the absence of focused flow, the thermodynamics of hydrate accumulation are primarily one-dimensional. However, changes in free methane compressibility (density) and methane solubility (the intrinsic dissolved methane flux) subtlety impact on the formation of a free gas zone and the distribution of the hydrate emplacements in our 2-dimensional simulations.     

The characteristics of gas hydrates recovered from the Mount Elbert Gas Hydrate Stratigraphic Test Well, Alaska North Slope

Systematic analyses have been carried out on two gas hydrate-bearing sediment core samples, HYPV4, which was preserved by CH₄ gas pressurization, and HYLN7, which was preserved in liquid-nitrogen, recovered from the BPXA-DOE-USGS Mount Elbert Stratigraphic Test Well. Gas hydrate in the studied core samples was found by observation to have developed in sediment pores, and the distribution of hydrate saturation in the cores imply that gas hydrate had experienced stepwise dissociation before it was stabilized by either liquid nitrogen or pressurizing gas. The gas hydrates were determined to be structure Type I hydrate with hydration numbers of approximately 6.1 by instrumentation methods such as powder X-ray diffraction, Raman spectroscopy and solid state ¹³C NMR. The hydrate gas composition was predominantly methane, and isotopic analysis showed that the methane was of thermogenic origin (mean δ¹³C = −48.6‰ and δ_D = −248‰ for sample HYLN7). Isotopic analysis of methane from sample HYPV4 revealed secondary hydrate formation from the pressurizing methane gas during storage.     

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.     

Raman spectroscopic measurements of synthetic gas hydrates in the ocean

A Raman spectrometer extensively modified for deep ocean use was used to measure synthetic hydrates formed in an ocean environment. This was the first time hydrates formed in the ocean have been measured in situ using Raman spectroscopy. Gas hydrates were formed in situ in the Monterey Bay by pressurizing a Pyrex cell with various gas mixtures. Raman spectra were obtained for sI methane hydrate and sII methane + ethane hydrate. Gas occlusion resulting from rapid gas growth of methane hydrate was measured immediately after formation. The Raman shift for methane free gas was coincident with that of methane in the small 5¹² hydrate cage. The methane Raman peak widths were used to discriminate between methane in the free gas and hydrate phase. Methane + ethane sII hydrate was formed for 43 days on the seafloor. In this case, gas occlusion was not measured when the gas hydrates were allowed to form over an extended time period. Equivalent Raman spectra were obtained for the in situ and laboratory-formed sII methane + ethane hydrates, under similar p, T, and x conditions. With the Raman spectrometer operating in the ocean, seawater contributes to the Raman spectra obtained. Both the Raman bands for the sulfate ion and water were used to qualitatively determine the distribution of water phases measured (hydrate, seawater) in the Raman spectra.     

A margin-wide BSR gas hydrate assessment: Canada’s Atlantic margin

It is the intent of this paper to explore a significant extent of an entire passive continental margin for hydrate occurrence to understand hydrate modes of occurrence, preferred geologic settings and estimate potential volumes of methane. The presence of gas hydrates offshore of eastern Canada has long been inferred from estimated stability zone calculations, but little physical evidence has been offered. An extensive set of 2-D and 3-D, single and multi-channel seismic reflection data comprising in excess of 140,000 line-km was analyzed. Bottom simulating reflections (BSR) were unequivocally identified at seven sites, ranging between 250 and 445 m below the seafloor and in water depths of 620-2850 m. The combined area of the BSRs is 9311 km², which comprises a small proportion of the entire theoretical stability zone along the Canadian Atlantic margin (∼715,165 km²). The BSR within at least six of these sites lies in a sedimentary drift deposit or sediment wave field, indicating the likelihood of grain sorting and potential porosity and permeability (reservoir) development. Although there are a variety of conditions required to generate and recognize a BSR, one might assume that these sites offer the most potential for highest hydrate concentration and exploitation. Total hydrate in formation at the sites of recognized BSR’s is estimated at 17 to 190 × 10⁹ m³ or 0.28 to 3.12 × 10¹³ m³ of methane gas at STP. Although it has been shown that hydrate can exist without a BSR, the results from this regional study argue that conservative estimates of the global reserve of hydrate along continental margins are necessary.     

In situ hydrocarbon concentrations from pressurized cores in surface sediments, Northern Gulf of Mexico

Two newly developed coring devices, the Multi-Autoclave-Corer and the Dynamic Autoclave Piston Corer were deployed in shallow gas hydrate-bearing sediments in the northern Gulf of Mexico during research cruise SO174 (Oct–Nov 2003). For the first time, they enable the retrieval of near-surface sediment cores under ambient pressure. This enables the determination of in situ methane concentrations and amounts of gas hydrate in sediment depths where bottom water temperature and pressure changes most strongly influence gas/hydrate relationships. At seep sites of GC185 (Bush Hill) and the newly discovered sites at GC415, we determined the volume of low-weight hydrocarbons (C₁ through C₅) from nine pressurized cores via controlled degassing. The resulting in situ methane concentrations vary by two orders of magnitudes between 0.031 and 0.985 mol kg^− 1 pore water below the zone of sulfate depletion. This includes dissolved, free, and hydrate-bound CH₄. Combined with results from conventional cores, this establishes a variability of methane concentrations in close proximity to seep sites of five orders of magnitude. In total four out of nine pressure cores had CH₄ concentrations above equilibrium with gas hydrates. Two of them contain gas hydrate volumes of 15% (GC185) and 18% (GC415) of pore space. The measurements prove that the highest methane concentrations are not necessarily related to the highest advection rates. Brine advection inhibits gas hydrate stability a few centimeters below the sediment surface at the depth of anaerobic oxidation of methane and thus inhibits the storage of enhanced methane volumes. Here, computerized tomography (CT) of the pressure cores detected small amounts of free gas. This finding has major implications for methane distribution, possible consumption, and escape into the bottom water in fluid flow systems related to halokinesis.     

Inferred gas hydrate on the Barents Sea shelf — a model for its formation and a volume estimate

 On the southwestern Barents Sea shelf, sediments containing gas hydrates that overlie free gas have been inferred from multichannel seismic data. The volume of suspected gas hydrate is tentatively estimated to about 1.9×10⁸ m³. The gas hydrate zone probably formed from thermogenic gas leaking from a deeper source. The hydrate zone may have thickened during the Neogene by including gas originally trapped as free gas below the hydrate following a significant downward migration of the isotherms caused by erosion and/or subsidence. Within the present oceanographic conditions, gas hydrate is suspected to be stable or slowly decomposing. Received: 20 December 1996 / Revision received: 20 August 1997     

Laboratory experiment and numerical simulation on authigenic mineral formation induced by seabed methane seeps

In natural gas hydrate marine settings, cold seepage of methane fluid is a widely observed phenomenon, where authigenic minerals serve as an indication of potential gas hydrate-bearing reservoirs at depth. In this study, based on the data from the site HD196 near Dongsha Island, northern continental slope of South China Sea, laboratory experiments and numerical simulation studies were conducted to investigate the biogeochemical processes of authigenic mineral formation induced by methane seepage. The bioreactor experimental results show that in response to methane flux, pH increased to 8.5 after 20 days of reaction, and Eh declined rapidly first and then remained unchanged at about 100 mV. The decrease in SO₄²⁻, HS⁻ and HCO₃⁻ concentrations indicated the occurrence of anaerobic oxidation of methane coupled with sulfate reduction (AOM-SR). The depletion of Fe²⁺ implied the formation of iron-bearing minerals, e.g., iron sulfides. Carbonate minerals were also identified in the experimental phase of this study. Most iron sulfides existed as massive pieces, and in some cases as spherical or rod-shape pieces. The calcium carbonates were observed as blocky pieces. Numerical simulations were also performed to reproduce the biogeochemical reactions that occurred in the reactor experiments. Based on experimental data, kinetic parameters associated with the observed reactions were calibrated. The model simulated results are general consistent with those obtained by the experiments conducted in this study. The combination of simulation and experimental studies provided a powerful tool to investigate the biogeochemical processes in the methane leakage environment at different temporal and spatial scales. This study gave a new perspective to understand the formation of cold seep authigenic minerals in marine sediments, and was significant for future investigations on the effects of hydrate decomposition.     

Gas geochemistry of the Mount Elbert Gas Hydrate Stratigraphic Test Well, Alaska North Slope: Implications for gas hydrate exploration in the Arctic

Gases were analyzed from well cuttings, core, gas hydrate, and formation tests at the BPXA-DOE-USGS Mount Elbert Gas Hydrate Stratigraphic Test Well, drilled within the Milne Point Unit, Alaska North Slope. The well penetrated a portion of the Eileen gas hydrate deposit, which overlies the more deeply buried Prudhoe Bay, Milne Point, West Sak, and Kuparuk River oil fields. Gas sources in the upper 200 m are predominantly from microbial sources (C₁ isotopic compositions ranging from −86.4 to −80.6‰). The C₁ isotopic composition becomes progressively enriched from 200 m to the top of the gas hydrate-bearing sands at 600 m. The tested gas hydrates occur in two primary intervals, units D and C, between 614.0 m and 664.7 m, containing a total of 29.3 m of gas hydrate-bearing sands. The hydrocarbon gases in cuttings and core samples from 604 to 914 m are composed of methane with very little ethane. The isotopic composition of the methane carbon ranges from −50.1 to −43.9‰ with several outliers, generally decreasing with depth. Gas samples collected by the Modular Formation Dynamics Testing (MDT) tool in the hydrate-bearing units were similarly composed mainly of methane, with up to 284 ppm ethane. The methane isotopic composition ranged from −48.2 to −48.0‰ in the C sand and from −48.4 to −46.6‰ in the D sand. Methane hydrogen isotopic composition ranged from −238 to −230‰, with slightly more depleted values in the deeper C sand. These results are consistent with the concept that the Eileen gas hydrates contain a mixture of deep-sourced, microbially biodegraded thermogenic gas, with lesser amounts of thermogenic oil-associated gas, and coal gas. Thermal gases are likely sourced from existing oil and gas accumulations that have migrated up-dip and/or up-fault and formed gas hydrate in response to climate cooling with permafrost formation.     

Vodyanitskii mud volcano,Sorokin trough,Black Sea: Geological characterization and quantification of gas bubble streams

Vodyanitskii mud volcano is located at a depth of about 2070 m in the Sorokin Trough, Black sea. It is a 500-m wide and 20-m high cone surrounded by a depression, which is typical of many mud volcanoes in the Black Sea. 75 kHz sidescan sonar show different generations of mud flows that include mud breccia, authigenic carbonates, and gas hydrates that were sampled by gravity coring. The fluids that flow through or erupt with the mud are enriched in chloride (up to ∼650 mmol L⁻¹ at ∼150-cm sediment depth) suggesting a deep source, which is similar to the fluids of the close-by Dvurechenskii mud volcano. Direct observation with the remotely operated vehicle Quest revealed gas bubbles emanating at two distinct sites at the crest of the mud volcano, which confirms earlier observations of bubble-induced hydroacoustic anomalies in echosounder records. The sediments at the main bubble emission site show a thermal anomaly with temperatures at ∼60 cm sediment depth that were 0.9 °C warmer than the bottom water. Chemical and isotopic analyses of the emanated gas revealed that it consisted primarily of methane (99.8%) and was of microbial origin (δD-CH₄ = −170.8‰ (SMOW), δ¹³C-CH₄ = −61.0‰ (V-PDB), δ¹³C-C₂H₆ = −44.0‰ (V-PDB)). The gas flux was estimated using the video observations of the ROV. Assuming that the flux is constant with time, about 0.9 ± 0.5 × 10⁶ mol of methane is released every year. This value is of the same order-of-magnitude as reported fluxes of dissolved methane released with pore water at other mud volcanoes. This suggests that bubble emanation is a significant pathway transporting methane from the sediments into the water column.     

A comparative study between present and palaeo-heat flow in the Qiangtang Basin,northern Tibet,China

The Qiangtang Basin is a significant prospective area for hydrocarbon and gas hydrate resources in the Tibetan Plateau, China. However, relatively little work has been performed to characterise heat flow in this basin, which has restricted petroleum and gas hydrate exploration. In this study, we compare present and palaeo-heat flow in the Qiangtang Basin to provide information on geothermal regime, hydrocarbon generation and permafrost that is necessary for further petroleum and gas hydrate exploration. We base our study on temperature data from a thermometer well, thermal conductivity tests, vitrinite reflectance data, homogenisation temperature data from fluid inclusions, stratigraphic information and a time-independent modelling approach. Our results indicate that in the central Qiangtang Basin, the present thermal gradient is approximately 15.5 °C/km, and heat flow is approximately 46.69 mW/m². Heat flow in the Qiangtang Basin is not relatively stable since the Early Jurassic, as previous research has suggested, and it is generally decreasing with time. Additionally, there is a clear difference between the hottest thermal regime of the southern and northern Qiangtang Depressions during Cretaceous to Pleistocene time. In the southern Qiangtang Depression, the palaeogeothermal gradient is approximately 32.0 °C/km, and palaeo-heat flow is approximately 70 mW/m². However, in the northern Qiangtang Depression, the palaeogeothermal gradient exceeds 81.8 °C/km, and palaeo-heat flow is greater than 172.09 mW/m². The high thermal regime in the northern Qiangtang Depression is driven mainly by hydrothermal convection. Gas reservoirs are possible targets for hydrocarbon exploration in this depression. Currently, the northwestern part of the northern Qiangtang Depression is the most favourable area for gas hydrate exploration in the Qiangtang Basin.     

Heat flow and quantity of methane deduced from a gas hydrate field in the vicinity of the Dnieper Canyon,northwestern Black Sea

Seismic reflection data document for the first time the existence of a BSR in a limited area west of the Dnieper Canyon in the northwestern Black Sea. Seismic wide-angle data suggest that gas hydrates occupy in average 15±2% of the pore space in a zone of 100 m in thickness. A conservative quantification of the amount of methane associated with this gas hydrate occurrence is about 12±3×10¹¹ m³ (0.6±0.2 Gt of methane carbon). Conductive heat flow deduced from the BSR depth is in the range of 21±6 to 55±15 mW m^–2.     

Methane hydrate dissolution rates in undersaturated seawater under controlled hydrodynamic forcing

The dissolution of in-situ generated methane hydrate in undersaturated, synthetic seawater (S = 35) was investigated in a series of laboratory-based experiments at P-/T-conditions within the hydrate stability field. A controlled flow field was generated across the smooth hydrate surface to test if, in addition to thermodynamic variables, the dissolution rate is influenced by changing hydrodynamic conditions. The dissolution rate was found to be strongly dependent on the friction velocity, showing that hydrate dissolution in undersaturated seawater is a diffusion-controlled process. The experimental data was used to obtain diffusional mass transfer coefficients k_d, which were found to correlate linearly with the friction velocity, u. The resulting k_d/u-correlation allows predicting the flux of methane from natural gas hydrate exposures at the sediment/seawater interface into the bulk water for a variety of natural P, T and flow conditions. It also is a tool for estimating the rate of hydrate regrowth at locations where natural hydrate outcrops at the seafloor persist in contact with undersaturated seawater.     

Heat flow derived from BSR and its implications for gas hydrate stability zone in Shenhu Area of northern South China Sea

Bottom simulating reflectors (BSRs), known as the base of gas hydrate stability zone, have been recognized and mapped using good quality three-dimensional (3D) pre-stack migration seismic data in Shenhu Area of northern South China Sea. Additionally, seismic attribute technique has been applied to better constrain on the distribution of gas hydrate. The results demonstrate that gas hydrate is characterized by “blank” zone (low amplitude) in instantaneous amplitude attribute. The thickness of gas hydrate stability zone inferred from BSR ranges from 125 to 355 m with an average of 240 m at sea water depth from 950 to 1,600 m in this new gas hydrate province. The volume of gas in-place bound in hydrate is estimated from 1.7 × 10⁹ to 4.8 × 10⁹ m³, with the most likely value of around 3.3 × 10⁹ m³, using Monte Carlo simulation. Furthermore, geothermal gradient and heat flow are derived from the depths of BSRs using a conductive heat transfer model. The geothermal gradient varies from 35 to 95°C km⁻¹ with an average of 54°C km⁻¹. Corresponding heat flow values range from 43 to 105 mW m⁻² with an average of 64 mW m⁻². By comparison with geological characteristics, we suggest that the distribution of gas hydrate and heat flow are largely associated with gas chimneys and faults, which are extensively distributed in Shenhu Area, providing easy pathways for fluids migrating into the gas hydrate stability zone for the formation of gas hydrate. This study can place useful constraints for modeling gas hydrate stability zone from measured heat flow data and understanding the mechanism of gas hydrate formation in Shenhu Area.     

A method for the calculation of anaerobic oxidation of methane rates across regional scales: an example from the Belt Seas and The Sound (North Sea–Baltic Sea transition)

Estimating the amount of methane in the seafloor globally as well as the flux of methane from sediments toward the ocean–atmosphere system are important considerations in both geological and climate sciences. Nevertheless, global estimates of methane inventories and rates of methane production and consumption through anaerobic oxidation in marine sediments are very poorly constrained. Tools for regionally assessing methane formation and consumption rates would greatly increase our understanding of the spatial heterogeneity of the methane cycle as well as help constrain the global methane budget. In this article, an algorithm for calculating methane consumption rates in the inner shelf is applied to the gas-rich sediments of the Belt Seas and The Sound (North Sea–Baltic Sea transition). It is based on the depth of free gas determined by hydroacoustic techniques and the local methane solubility concentration. Due to the continuous nature of shipboard hydroacoustic measurements, this algorithm captures spatial heterogeneities in methane fluxes better than geochemical analyses of point sources such as observational/sampling stations. The sensibility of the algorithm with respect to the resolution of the free gas depth measurements (2 m vs. 50 cm) is proven of minor importance (a discrepancy of <10%) for a small part of the study area. The algorithm-derived anaerobic methane oxidation rates compare well with previous measured and modeling studies. Finally, regional results reveal that contemporary anaerobic methane oxidation in worldwide inner-shelf sediments may be an order of magnitude lower (ca. 0.24 Tmol year^–1) than previous estimates (4.6 Tmol year^–1). These algorithms ultimately help improve regional estimates of anaerobic oxidation of methane rates.     

南海台西南盆地天然气水合物区沉积物的地球化学和微生物特征分析

The Taixinan Basin is one of the most potential gas hydrate bearing areas in the South China Sea and abundant gas hydrates have been discovered during expedition in 2013. In this study, geochemical and microbial methods are combinedly used to characterize the sediments from a shallow piston Core DH_CL_11(gas hydrate free) and a gas hydrate-bearing drilling Core GMGS2-16 in this basin. Geochemical analyses indicate that anaerobic oxidation of methane(AOM) which is speculated to be linked to the ongoing gas hydrate dissociation is taking place in Core DH_CL_11 at deep. For Core GMGS2-16, AOM related to past episodes of methane seepage are suggested to dominate during its diagenetic process; while the relatively enriched δ18O bulk-sediment values indicate that methane involved in AOM might be released from the "episodic dissociation" of gas hydrate.Microbial analyses indicate that the predominant phyla in the bacterial communities are Firmicutes and Proteobacteria(Gammaproteobacteria and Epsilonproteobacteria), while the dominant taxa in the archaeal communities are Marine_Benthic_Group_B(MBGB), Halobacteria, Thermoplasmata, Methanobacteria,Methanomicrobia, Group C3 and MCG. Under parallel experimental operations, comparable dominant members(Firmicutes and MBGB) are found in the piston Core DH_CL_11 and the near surface layer of the long drilling Core GMGS2-16. Moreover, these members have been found predominant in other known gas hydrate bearing cores, and the dominant of MBGB has even been found significantly related to gas hydrate occurrence. Therefore,a high possibility for the existing of gas hydrate underlying Core DH_CL_11 is inferred, which is consistent with the geochemical analyses. In all, combined geochemical and microbiological analyses are more informative in characterizing sediments from gas hydrate-associated areas in the South China Sea.     

Modeling of rising methane bubbles during production leaks from the gas hydrate sites of India

Natural gas hydrates is considered as a strategic unconventional clean hydrocarbon resource in the energy sector. Understanding the behavior of the rising methane gas bubbles during production leaks from the deep marine gas hydrate reservoirs well head is essential for environmental impact studies and to design environmental monitoring systems. Numerical model for quantitatively characterizing the vertical dissolution pattern of the wellhead released methane gas bubbles is analyzed for three potential gas hydrate locations in India. Simulation results indicate that the methane bubbles with diameter of 10?mm can transport methane gas till 650, 800, and 750?m from the seabed in the Krishna–Godavari(KG), Mahanadi and Andaman basins respectively. Results brought out that potential well head damage during methane hydrate production at 1050?m water depth could release up to 28?m³ of methane gas, in which 50% of the molar mass shall get dissolved within 40?m of water column from the seafloor.     

Simultaneous solution for water,heat and salt balances in a Mediterranean coastal lagoon (Mar Menor,Spain)

A modelling approach is proposed to evaluate the environmental dynamics of coastal lagoons. The water, heat and salt balances are addressed simultaneously, providing a better estimation of evaporation and water exchanges. Compared to traditional approaches, the model presented accounts for the effects of water salinity, heat storage and net energy advected in the water body. The model was applied daily to the Mar Menor coastal lagoon (SE Spain) from 2003 through 2006. Water exchanges with the Mediterranean Sea were estimated based on the monthly trend of the lagoon salinity and were correlated with monthly averages of wind speed. The mean daily water exchange with the sea was 1.77 hm³ d⁻¹. This exchange accounted for only 1% of the heat losses in the lagoon heat balance, and it is the most important flow in the water balance. The mean annual evaporation flux amounted to 101.3 W m⁻² (3.55 mm d⁻¹), while the sensible heat flux amounted to 19.7 W m⁻², leading to an annual Bowen ratio on the order of 0.19. To validate the model, daily water temperatures were predicted based on the daily heat balance of the water body and were compared with remote sensing data from water surface standard products.     

Molecular and isotopic signatures in sediments and gas hydrate of the central/southwestern Ulleung Basin: high alkalinity escape fuelled by biogenically sourced methane

Natural marine gas hydrate was discovered in Korean territorial waters during a 2007 KIGAM cruise to the central/southwestern Ulleung Basin, East Sea. The first data on the geochemical characterization of hydrate-bound water and gas are presented here for cold seep site 07GHP-10 in the central basin sector, together with analogous data for four sites (07GHP-01, 07GHP-02, 07GHP-03, and 07GHP-14) where no hydrates were detected in other cores from the central/southwestern sectors. Hydrate-bound water displayed very low concentrations of major ions (Cl⁻, SO₄²⁻, Na⁺, Mg²⁺, K⁺, and Ca²⁺), and more positive δD (15.5‰) and δ¹⁸O (2.3‰) signatures compared to seawater. Cl^– freshening and more positive isotopic values were also observed in the pore water at gas hydrate site 07GHP-10. The inferred sulfate–methane interface (SMI) was very shallow (<5 mbsf) at least at four sites, suggesting the widespread occurrence of anaerobic oxidation of methane (AOM) at shallow sediment depths, and possibly high methane flux. Around the SMI, pore water alkalinity was very high (>40 mM), but the carbon isotopic ratios of dissolved inorganic carbon (δ¹³C_DIC) did not show minimum values typical of AOM. Moreover, macroscopic authigenic carbonates were not observed at any of the core sites. This can plausibly be explained by carbon with high δ¹³C values diffusing upward from below the SMI, increasing alkalinity via deep methanogenesis and eventually escaping as alkalinity into the water column, with minor precipitation as solid phase. This contrasts, but is not inconsistent with recent reports of methane-fuelled carbonate formation at other sites in the southwestern basin sector. Methane was the main hydrocarbon component (>99.85%) of headspace, void, and hydrate-bound gases, C₁/C₂₊ ratios were at least 1,000, and δ¹³C_CH4 and δD_CH4 values were in the typical range of methane generated by microbial reduction of CO₂. This is supported by the δ¹³C_C2H6 signatures of void and hydrate-bound gases, and helps clarify some contradictory interpretations existing for the Ulleung Basin as a whole. In combination, these findings suggest that deep biogenic gas and pore waters migrate upward through pathways such as hydrofractures, and measurably influence the shallow carbon cycle. As a result, cation-adjusted alkalinity/removed sulfate diagrams cannot always serve to estimate the degree of alkalinity produced by sulfate reduction and AOM in high methane flux areas.     

Benthic fluxes in a tropical Estuary and their role in the ecosystem

In-situ measurements of benthic fluxes of oxygen and nutrients were made in the subtidal region of the Mandovi estuary during premonsoon and monsoon seasons to understand the role of sediment–water exchange processes in the estuarine ecosystem. The Mandovi estuary is a shallow, highly dynamic, macrotidal estuary which experiences marine condition in the premonsoon season and nearly fresh water condition in the monsoon season. The benthic flux of nutrients exhibited strong seasonality, being higher in the premonsoon compared to the monsoon season which explains the higher ecosystem productivity in the dry season in spite of negligible riverine nutrient input. NH₄⁺ was the major form of released N comprising 70–100% of DIN flux. The benthic respiration rate varied from −98.91 to −35.13 mmol m⁻² d⁻¹, NH₄⁺ flux from 5.15 to 0.836 mmol m⁻² d⁻¹, NO₃⁻ + NO₂⁻ from 0.06 to −1.06 mmol m⁻² d⁻¹, DIP from 0.12 to 0.23 mmol m⁻² d⁻¹ and SiO₄⁴⁻ from 5.78 to 0.41 mmol m⁻² d⁻¹ between premonsoon to monsoon period. The estuarine sediment acted as a net source of DIN in the premonsoon season, but changed to a net sink in the monsoon season. Variation in salinity seemed to control NH₄⁺ flux considerably. Macrofaunal activities, especially bioturbation, enhanced the fluxes 2–25 times. The estuarine sediment was observed to be a huge reservoir of NH₄⁺, PO₄³⁻ and SiO₄⁴⁻ and acted as a net sink of combined N because of the high rate of benthic denitrification as it could remove 22% of riverine DIN influx thereby protecting the eco system from eutrophication and consequent degradation. The estuarine sediment was responsible for ∼30–50% of the total community respiration in the estuary. The benthic supply of DIN, PO₄³⁻ and SiO₄⁴⁻ can potentially meet 49%, 25% and 55% of algal N, P and Si demand, respectively, in the estuary. Based on these observations we hypothesize that it is mainly benthic NH₄⁺ efflux that sustains high estuarine productivity in the NO₃⁻ depleted dry season.