Hydrate Stability Research Articles

Slow Dynamics of Hydrate Systems Revealed by a Double BSR

AbstractDetermining how gas hydrate distribution evolved along continental margins in the past is essential to understanding its evolution in the future. Moreover, hydrate decomposition has been linked to several catastrophic events, including some of the largest submarine landslides on Earth and the massive release of greenhouse gases into the ocean. Offshore Romania, the presence of a second bottom‐simulating reflector (BSR) provides an opportunity to gain valuable insights into hydrate dynamics since the Last Glacial Period (LGP). We conducted transient modeling of hydrate thermodynamic stability by merging in‐situ observations with indirect assessments of sea‐bottom temperature, thermal conductivity, salinity, sedimentation rate, and sea‐level variations. We reveal a strong correlation between the BSRs and the base of the Gas Hydrate Stability Zone (GHSZ) during both the present and LGP periods. The gradual evolution of the GHSZ over the past 34 ka presented here supports a conceptual model that excludes catastrophic environmental scenarios.

Pozzolanic potential of sustainable precursors for engineered geopolymer composites (EGC)

Confirming the pozzolanic activity is crucial to ensure their compatibility and performance in geopolymer composite (GC) applications, as it improves the geopolymerization process and optimizes the strength characteristics of GCs. This work evaluates the pozzolanic properties of Fly ash (FA), Basic Oxygen Furnace (BOF) slag, and Iron Ore Tailings (IOT) for their potential use in the development of Engineered Geopolymer Composites (EGC). IOT partially substitutes fine aggregate, while FA and BOF slag are the major precursors. Pozzolanic properties of the aforementioned materials were assessed through the Frattini, saturated lime test (SLT), and strength activity index (SAI). The Frattini test values recorded were 90, 47, and 30% of CaO removal, denoting their degree of pozzolanicity respectively for BOF Slag, FA, and IOT. In the SLT, the formation of stable calcium silicate hydrates and aluminates are verified by the reaction of the test pozzolans with lime, thereby conforming their pozzolanicity. The results from the Frattini and SAI tests showed a significant correlation, indicating an effective pozzolanicity measure of the test materials. However, the results from the SLT did not align with the outcomes from the Frattini and SAI tests. This contradiction suggests that the SLT is ineffective compared to the other two test methods in measuring the pozzolanic activity of the test materials. The research findings provide valuable insights into the potential usage of these materials (pozzolans) as sustainable building materials in the construction industry.

Spatial Variability of the Methane Hydrate Stability Zone’s Upper Boundary Parameters in the Water Column of the Sea of Okhotsk

Spatial Variability of the Methane Hydrate Stability Zone’s Upper Boundary Parameters in the Water Column of the Sea of Okhotsk

In-silico investigation of mechanical behavior of hydrated Na-montmorillonite tactoid

Swelling clay minerals, exemplified by Na-montmorillonite (Na-Mt), are vital constituents in expansive soils and hold significant relevance in geotechnical engineering. Comprehending their distinctive swelling behavior upon hydration is imperative for managing potential damage to civil infrastructure. Conversely, this swelling property gives rise to numerous advantageous applications, including using these clays in barrier materials and nanocomposites. The hierarchical structure of montmorillonite, consisting of clay mineral layers, tactoids, aggregates, and assemblies of aggregates, plays a pivotal role in the swelling behavior of expansive clays. This investigation employs molecular dynamics (MD) and steered molecular dynamic (SMD) simulations to explore the nanomechanical properties of hydrated Na-Mt tactoids at various hydration levels. It provides insights into their responses to compression, tensile, and shear deformation. This study reveals increased hydration levels increase interlayer spacing in clay structures, resulting in higher average d‐values. Water molecules drive attractive electrostatic interactions with clay mineral layers, predominantly mediated by sodium ions, highlighting the complex interplay between interlayer hydration and tactoid stability. Higher hydration enhances tactoid compressibility, reducing the stress required for deformation by compressing water molecules and clay mineral layers in the interlayer space. The study also demonstrates a notable reduction in tensile modulus with increasing hydration, signifying the significant impact of even minimal hydration on interlayer cation-clay layer interactions. Hydrated tactoids exhibit altered mechanical responses in shear deformation compared to dry ones, requiring lower shear stress to detach the top clay layer from the tactoid. The presence of water molecules impedes the locking of clay mineral layers, further influencing mechanical properties. The results and insight provided by this work will contribute to a better understanding of the impact of interlayer hydration on the stability and response of swelling clay minerals.

Molecular insight into the decomposition mechanism and stability of CO2 hydrate in the symmetric non-flat double-plate porous media system

Unveiling the decomposition mechanism and stability of hydrate in porous media sediments is the fundamental issue related to hydrate-based CO2 capture and sequestration. In this work, Molecular Dynamics (MD) simulations were performed to study the decomposition mechanism and stability of CO2 hydrate in the porous media of symmetric non-flat double-plate system and explore its mass transfer process. The model of CO2 hydrate in porous media possessing symmetric non-flat double-plate structure was constructed using square quartz (SiO2) as the single crystal material of porous media, illustrating the decomposition mechanism and stability law of CO2 hydrate in such media system. Simulation results indicate that there exists no pretty noteworthy discrepancy between CO2 hydrate in the symmetric non-flat double-plate porous media system and pure CO2 hydrate at the aspect of the decomposition process and sequence. The decomposition process can be divided into two stages: initial cage destruction and CO2 bubble evolution. The decomposition order proceeds in an outside to inside manner generally, with CO2 hydrate decomposition in the middle layer and diagonal region taking priority. Furthermore, the distance between media layers exerts a prominent influence on CO2 hydrate decomposition, which larger distance motivates the decomposition of CO2 hydrate easier. The results also indicated that, compared with pure water system, the stability of CO2 hydrate is greater in the symmetric non-flat double-plate porous media system, with the extreme values of DC reaching 0.64 times only than pure water system. Additionally, CO2 hydrate displayed a stronger stability in the confined space. These findings are beneficial for understanding the decomposition mechanism and stability of CO2 hydrate and provide an interesting insight into geological CO2 sequestration in sediments.

Bottom simulating reflections across the northern Gulf of Mexico slope

Bottom simulating reflections (BSRs) are widely used indicators for natural gas hydrate in reflection seismic data. BSRs, however, are typically studied on a local scale at a single site and less frequently on a large, regional scale. Herein, we map and describe BSRs over a 68,000 km2 area across the northern Gulf of Mexico slope, using publicly released industry-acquired 3D seismic data. We map 74 BSR zones that cover a total area of 2060 km2. To understand the characteristics of these BSR zones, we classify them based on their BSR characteristics in the seismic data (continuous, discontinuous, and clustered) and the geological settings in which they appear (structural, stratigraphic, and venting). The most common type of BSRs are discontinuous BSRs; such BSRs were mapped over ∼60% of the total BSR area. Discontinuous BSRs occur most commonly in structural or stratigraphic settings. Discontinuous BSRs indicate that gas and hydrate are likely concentrated in discrete layers crossing the base of the hydrate stability zone (HSZ). Continuous BSRs occur in 27% of the total BSR area and they primarily occur in venting and stratigraphic settings. At vent sites, hydrate formation likely reduces sediment permeability and focuses fluid flow laterally underneath the base of the HSZ, likely resulting in a continuous BSR along the area of lateral gas flow. Clustered BSRs, chaotic sequences of high amplitude reflections, occur in only 13% of the total BSR area and are only found within structural settings. In addition, the majority of clustered BSR zones are close to paleochannels, suggesting that clustered BSRs may be more common where coarser-grained sediments exist.

Development and application of low-melting-point microencapsulated phase change materials for enhanced thermal stability in cementing natural gas hydrate layers

In the exploration of deep-water oil and gas resources, encountering natural gas hydrate (NGH) layers poses significant challenges, particularly during cementing operations critical for wellbore stabilization. This study proposes a strategy employing cement slurries integrated with micro-encapsulated phase change materials (MPCMs) to address the destabilization of NGH layers, a key obstacle in deep-water cementing. MPCMs containing BaCO3 shell and low-melting binary PCMs in the core were synthesized by the self-assembly method. The structure and thermal properties of MPCMs were thoroughly characterized. MPCMs exhibited a distinct core-shell structure with a hydrophilic and well-sealed shell. Their phase change temperatures were in closely matched the temperatures found in NGH formations, at 3.5 °C and 13.9 °C. A comprehensive evaluation of the fundamental properties of cement slurries containing MPCMs (CSM) was conducted, including thermal stability, setting time, pore structure, and mechanical strength. Additionally, a laboratory device was employed to simulate cementing operations, allowing for intuitive analysis of the impact of hydration heat evolution on NGH stability—a notably underexplored aspect in related literature. The results demonstrated that MPCMs effectively reduced the hydration heat generated by cement slurry within the initial 36 h. Specifically, at a 9% MPCMs dosage, the hydration heat of CSM decreased by 19.0%, resulting in the sustained stability of NGH. In contrast, the control group's cementing process directly led to the complete decomposition of NGH. Even at lower MPCMs concentrations, the decomposed NGH was more likely to recrystallize and return to a stable state due to the slower hydration heat release rate of CSM. This study not only provides evidence of the effectiveness of MPCMs as heat inhibitors in reducing the disruption of hydrate stability during well cementing but also provides theoretical guidance for the design and application of cement slurries for NGH reservoirs. By enhancing the stability of NGH layers, this work supports the safe and efficient exploitation of undersea hydrocarbon resources, contributing to shaping future global energy strategies.

Seep carbonate clumped isotopes revealing ocean warming-induced gas hydrate dissociation

The dissociation of marine methane hydrates due to the increased ocean temperature may be widespread in the context of global warming. However, direct evidence for this phenomenon is limited. Here, we reported the carbon and oxygen isotopes, mineralogy, elements, and clumped isotopes (Δ47) of coring seep carbonates (MIS5e) to explore the influence of temperature changes on gas hydrate stability. The extremely low δ13C and high δ18O values of bulk carbonates (average, −48.1‰ and 4.4‰, respectively) indicated the authigenic carbonates formed from the anaerobic oxidation of methane and gas hydrate dissociation. An anaerobic environmental condition with intense methane seepages was confirmed by the dominant aragonite, Mo enrichment (MoEF averaged as 312), and positive Ce anomalies (averaged as −0.03). The Δ47 values ranged from 0.714 to 0.745, indicating a higher bottom-water temperature (averaged at 7.5 °C) during MIS5e compared with the current seafloor temperature (5.4 °C). This study provides direct evidence for the dissociation of gas hydrate triggered by ocean warming, presenting new insights into potential temperature-induced gas hydrate instability due to global climate warming.

Study on the Mechanism of Natural Gas Hydrate Decomposition and Seabed Seepage Triggered by Mass Transport Deposits

Previous studies indicate that mass transport deposits are related to the dynamic accumulation of natural gas hydrates and gas leakage. This research aims to elucidate the causal mechanism of seabed seepage in the western region of the southeastern Qiongdongnan Basin through the application of seismic interpretation and attribute fusion techniques. The mass transport deposits, bottom simulating reflector, submarine mounds, and other phenomena were identified through seismic interpretation techniques. Faults and fractures were identified by utilizing variance attribute analysis. Gas chimneys were identified using instantaneous frequency attribute analysis. Free gas and paleo-seepage points were identified using sweetness attributes, enabling the analysis of fluid seepage pathways and the establishment of a seepage evolution model. Research has shown that in areas where the mass transport deposits develop thicker layers, there is a greater uplift of the bottom boundary of the gas hydrate stability zone, which can significantly alter the seafloor topography. Conversely, the opposite is true. The research indicates that the upward migration of the gas hydrate stability zone, induced by the mass transport deposits in the study area, can result in the rapid decomposition of gas hydrates. The gas generated from the decomposition of gas hydrates is identified as the principal factor responsible for inducing seabed seepage. Moderate- and low-speed natural gas seepage can create spiny seamounts and domed seamounts, respectively.

Methane seeps on the U.S. Atlantic margin: An updated inventory and interpretative framework

Since the discovery of >570 methane flares on the northern U.S. Atlantic margin between Cape Hatteras and Georges Bank in the last decade, the acquisition of thousands of kilometers of additional water column imaging data has provided greater coverage at water depths between the outer continental shelf and the lower continental slope. The additional high-resolution data reveal >1400 gas flares, but the removal of probable duplicates from the combined database of new flares and those recognized in 2014 yields ∼1139 unique sites. Most of these sites occur in clusters of 5 or more seeps, leaving about 275 unique locations (including 47 clusters) for seepage along the margin. As a function of depth, seep distribution is heavily skewed toward the upper continental slope at water depths shallower than 400 m on the southern New England margin and ∼ 550 m in the Mid-Atlantic Bight, with additional seeps clustered at ∼1100 m and just deeper than ∼1400 m in both sectors. Despite little ongoing tectonic deformation or active faulting on this passive margin, a variety of processes driven from below the seafloor (e.g., migration of fluids along faults or through permeable strata, seepage above diapirs or other pre-existing structures) and from above (e.g., erosion, sapping, unroofing) contribute to the development of seeps in different settings along the margin. In addition, the prevalence of seeps on promontories overlooking shelf-breaking canyons may be directly related to the three-dimensional nature of the hydrate stability zone in these locations. As a function of depth, the parts of the slope at the contemporary landward limit of gas hydrate stability are devoid of seeps, and the upper slope zones with the most concentrated seepage were not within the gas hydrate stability zone even during the Last Glacial Maximum. Thus, if the large number of upper slope seeps is at least partially sourced in gas hydrate degradation, the gas emitted at these seeps must have migrated there from greater depths on the continental slope.

Modeling oceanic sedimentary methane hydrate growth through molecular dynamics simulation.

The crystallization process of methane hydrates in a confined geometry resembling seabed porous silica sedimentary conditions has been studied using molecular dynamics simulations. With this objective in mind, a fully atomistic quartz silica slit pore has been designed, and the temperature stability of a methane hydrate crystalline seed in the presence of water and guest molecule methane has been analyzed. NaCl ion pairs have been added in different concentrations, simulating salinity conditions up to values higher than average oceanic conditions. The structure obtained when the hydrate crystallizes inside the pore is discussed, paying special attention to the presence of ionic doping inside the hydrate and the subsequent induced structural distortion. The shift in the hydrate stability conditions due to the increasing water salinity is discussed and compared with the case of unconfined hydrate, concluding that the influence of the confinement geometry and pore hydrophilicity produces a larger deviation in the confined hydrate phase equilibria.

Preference of curing regimes based on fire resistance of ultra-high performance cementitious materials (UHPCM) mixed with fly ash

The cement-fly ash (FA) binary system was prepared as the ultra-high performance cementitious materials (UHPCM), and the effect of curing regimes on the evolution of microstructure and compressive strength of UHPCM at elevated temperatures was investigated. The results showed that multi-stage combined curing (MC) could remarkably improve the compressive strength of UHPCM at ambient temperature, which attributed to the further hydration of cement and the pozzolanic reaction of FA to produce more stable hydrates. However, steam curing (90 °C for 7 d) was more conducive to the residual compressive strength growth and retention of UHPCM exposed to elevated temperatures. The mechanism of this phenomenon was revealed by XRD and SEM analysis. The further hydration and conversion reactions occurred mainly inside the steam cured specimens when exposed to fire temperature, and a large number of C–S–H gels were gradually transformed into crystalline hydrates with high strength, excellent thermal stability and different forms, which made the microstructure denser and thus had better fire resistance. Comparatively, a large number of crystalline hydrates were generated prematurely in dry-hot air cured specimens, which made the decomposition reactions dominate under fire, resulting in coarsening of microstructure and reduction of macroscopic mechanical strength of UHPCM continuously.

Thermodynamic phase equilibria study of Hythane (methane + hydrogen) gas hydrates for enhanced energy storage applications

Hydrogen blending with natural gas has become an effective technique for incorporating the characteristics of natural gas and facilitating the storage and transportation of hydrogen gas. The transportation of hydrogen and natural gas (methane) blend, also referred to as Hythane, presents numerous challenges, advantages, and disadvantages that differ based on the technology employed. The current research showcased a thorough examination of the thermodynamics involved in studying the three phase equilibrium analysis of gas hydrate technology for storing Hythane gas mixtures. Three different Hythane compositions varying in hydrogen percentage were selected, and the isochoric gas hydrate phase equilibria study was performed. The experimental results of phase equilibria and thermodynamic modelling using CPA EOS in software were compared. A similar study was also conducted in the presence of a 5.56 mol % THF solution to understand the reduction in the pressure requirement for the phase equilibria. Results from the mixed Hythane+THF gas hydrate findings suggested stable gas hydrate formation at much lower pressure requirements, increasing the credibility of storing Hythane mixtures in gas hydrates at moderate conditions. The gas compositions for each experiment were analyzed using gas chromatography to evaluate the presence of the desired gas in the hydrate phase. Heat exchange during the gas hydrate dissociation was analyzed using a high pressure differential scanning calorimeter (DSC). The change in the heat release temperature also indicates the stability of the gas hydrate, and with increasing hydrogen gas in the blend, the gas hydrate stability decreased. The Clausius-Clapeyron equation was employed to compute the heat of gas hydrate dissociation, and a comparison was made with the heat of dissociation obtained from the DSC study. The experimental investigations on Hythane gas hydrates were performed to find the hydrogen storage inside the gas hydrate phase and compare it with the previous studies of pure hydrogen hydrates. To demonstrate the Hythane gas transportation, Hythane gas hydrate pellets were formed, followed by their storage in a controlled environment to observeany changes in pressure and temperature. The Hythane gas hydrate pellets demonstrated exceptional stability of Hythane gas presenting an intriguing prospect for utilizing gas hydrate technology in Hythane gas transportation.

Natural rubber latex as a potential additive for water-based drilling fluids

The environmental hazards and "carbon footprint" of oil and gas drilling can be significantly reduced by replacing traditional petroleum-based chemical additives with natural materials derived from plants and animals. This paper explored for the first time the interaction mechanism between natural rubber latex (NRL) and bentonite suspensions (BTs) through a series of characterization experiments, as well as the potential applications in water-based drilling fluids (WBDF). The gel viscoelasticity experiments showed that NRL could decrease the consistency coefficient (k) and flow index (n) of BTs, and enhance the shear thinning performance of BTs as pseudo-plastic fluids. In addition, 0.5 w/v% NRL not only increased the critical yield stress and strengthened the structural strength between the bentonite particles, but also facilitated the compatibility of pressure loss and flow efficiency. The evaluation of colloidal stability and WBDF performance indicated that NRL particles could promote the hydration and charge stability on the surface of BTs particles, and optimize the particle size distribution and flow resistance of WBDF under the "intercalation-exfoliation-encapsulation" synergistic interaction. Moreover, NRL can improve the rheological properties of WBDF at high temperatures (<150 °C), and form a dense blocking layer by bridging and sealing the pores and cracks of the filter cake, which ultimately reduces the permeability of the cake and the filtration loss of WBDF.

INFLUENCE OF PLEISTOCENE GLACIATION ON PETROLEUM SYSTEMS AND GAS HYDRATE STABILITY IN THE OLGA BASIN REGION, BARENTS SEA

This study presents the results of a 2D numerical basin and petroleum systems model of the Olga Basin in the NW Barents Sea offshore northern Norway, a frontier exploration area in which there are abundant seafloor oil and gas seepages. The effects of Pleistocene ice sheet advances on rock properties and subsurface fluid migration in this area, and on seafloor hydrocarbon seepage, are not well understood. The 2D numerical model takes account of recurrent ice advances and retreats, together with related erosional and temperature effects, and investigates the influence of these parameters on fluid migration. Model results show that Pleistocene glaciations reduced the temperature in the sedimentary succession in the Olga Basin by up to 20 °C, for example in the uppermost Cretaceous and Jurassic sediments which underlie the seafloor down to a depth of 0.5 to 1 km. The decrease in temperature was in general predominantly related to the intensity of glacial erosion, which was set in this study to a depth of 600 m based on previous studies. Hydrocarbon fluids expelled from potential thermogenic source rocks of Carboniferous to Triassic ages on the SW margin of the Olga Basin migrated to the seafloor through permeable carrier beds. However, fluid migration to the surface in the NE of the study area took place along fault conduits. In a closed fault model scenario, only 0.3 Mt of hydrocarbons are modelled to have migrated along the 0.5 km wide model section; in a second scenario with partially open faults, about 22 Mt of hydrocarbons, representing about 11% of the total hydrocarbons generated by potential thermogenic source rocks in the study area, were lost to the surface during the Pleistocene. The potential for microbial methane generation in the Olga Basin was limited both during the Pleistocene and at the present day due to the significant reduction in temperature during glacial episodes, and due to the intense glacial‐related erosion of the Mesozoic to Cenozoic stratigraphy. During glacial stages, the gas hydrate stability zone beneath the ice sheet is modelled to have extended to a depth of up to 900 m for a pure methane composition, and to a depth of up to 1100 m for a possible thermogenic‐sourced mixed gas composition of 90% methane, 7% propane and 3% ethane. Gas hydrates with this mixed composition are modelled to have been stable in the Olga Basin during the last three glacial advances and into the present. These modelling results provide an insight into the key factors controlling the migration and surface leakage of hydrocarbon fluids in the Olga Basin region, and into the effects of glaciations on rock properties in a glaciated basin.

Can Glacial Sea‐Level Drop‐Induced Gas Hydrate Dissociation Cause Submarine Landslides?

AbstractWe conducted two‐dimensional numerical simulations to investigate the mechanisms underlying the strong spatiotemporal correlation observed between submarine landslides and gas hydrate dissociation due to glacial sea‐level drops. Our results suggest that potential plastic deformation or slip could occur at localized and small scales in the shallow‐water portion of the gas hydrate stability zone (GHSZ). This shallow‐water portion of the GHSZ typically lies within the area enclosed by three points: the BGHSZ–seafloor intersection, the seafloor at ∼600 m below sea level (mbsl), and the base of the GHSZ (BGHSZ) at ∼1,050 mbsl in low‐latitude regions. The deep BGHSZ (&gt;1,050 mbsl) could not slip; therefore, the entire BGHSZ was not a complete slip surface. Glacial hydrate dissociation alone is unlikely to cause large‐scale submarine landslides. Observed deep‐water (much greater than 600 mbsl) turbidites containing geochemical evidence of glacial hydrate dissociation potentially formed from erosion or detachment in the GHSZ pinch‐out zone.

Effects of differential tectonic activities on overpressure evolution in the deep-water area of the Qiongdongnan Basin: implications for gas hydrate accumulation

The lack of data on the complex tectonics of the Qiongdongnan Basin has thus far restricted our understanding of the overpressure, deep hydrocarbon and shallow gas hydrate distribution. We therefore combined integrated seismic, well and borehole test data with basin models to clarify the relationship between tectonic activity and overpressure evolution, as well as the potential effects of the subsurface pressure on gas hydrate accumulation. The results show differences in tectonic activity and pressure characteristics between the eastern and western basins. Large numbers of faults and magmatic intrusions have developed in the post-rift layer of the eastern basin (the Baodao to Changchang sub-basins) since the Late Miocene ( c. 10.5 Ma), although they seldom formed in the western basin (the Lengdong to Lingshui sub-basins). Correspondingly, the eastern basin was characterized by lower overpressures (up to 40 MPa) and the western basin displayed higher overpressures (up to 110 MPa). The results indicate that tectonic activity since c. 10.5 Ma caused the relief of overpressure in the eastern basin. In stark contrast, the overpressure in the western basin increased significantly due to the lack of structural conduits and rapid sedimentation of the thick Pliocene and Quaternary deposits. Numerical models reveal that the faults and gas chimneys associated with the intrusions constituted shallow plumbing systems through which deep natural gas was able to migrate upwards. The formation of gas hydrates relied on the migration of deep gas to the hydrate stability zone below the seafloor. The relatively lower overpressured zones due to pressure relief in the eastern basin are therefore considered the next areas potentially favourable for the formation of gas hydrates. Thematic collection: This article is part of the Emerging knowledge on the tectonics of the South China Sea collection available at: https://www.lyellcollection.org/topic/collections/south-china-sea

Effects of organic degradation products on the migration behaviour of radionuclides in cementitious materials

The impact of phthalates, which might be present in a cementitious repository as degradation products of superplasticisers or PVC additives, on the migration behaviour of An(III)/Ln(III) was investigated in batch sorption experiments on hardened cement paste. In the absence of organics, An(III)/Ln(III) sorb strongly on HCP with distribution ratios, Rd, of 105 to 106 L kg−1. Above a no-effect level of ~ 10–3 mol L−1 phthalate, a distinct decrease of the An(III)/Ln(III) sorption was observed with sorption reduction factors (i.e., the ratio between the Rd values without and with organic ligand) of 100 to 1000 at phthalate concentrations of 10–1 mol L−1. This sorption reduction is attributed to the effect of Ca complexation with phthalate on the stability of calcium silicate hydrate (C–S–H) phases as main sorbing phase. These results and ongoing diffusion experiments indicate an increase in the mobility of An(III)/Ln(III) in cementitious barriers with increasing phthalate concentrations.Graphical abstract

Gas hydrate in the North Carnarvon Basin, offshore Western Australia

Analysis of hydrate systems across basins is not common, as most studies are focused on smaller sites. Using petroleum industry well and seismic data, we identify natural gas hydrate accumulations across the entire North Carnarvon Basin, offshore Western Australia. Out of 120 wells, 52 wells have evidence for gas hydrate, though hydrate is distributed throughout the hydrate stability zone in low concentrations. In addition, we do not observe a connection between the presence of hydrate in wells and deeper thermogenic gas reservoirs. From 3D seismic data, we observe bottom simulating reflections (BSRs) are very rare. In addition, while faults are common across the basin, shallow bright spots, which indicate shallow free gas, are uncommon. Based on all these observations from well and seismic data, we argue that hydrate across the North Carnarvon Basin formed predominantly from in-situ gas that is microbial in nature.

Experimental measurement and thermodynamic modeling of hydrate stability conditions in the methane + cyclopentane + tetra-n‑butyl ammonium chloride (TBAC) aqueous solution system

The present study investigates hydrate dissociation conditions in methane + cyclopentane (CP) and tetra-n‑butyl ammonium chloride (TBAC) aqueous solution. The experimental work was done using an isochoric vessel with varying compositions of the promoters in the pressure and temperature ranges of (1.42 to 4.90) MPa and (291.2 to 298.9) K, respectively. The methane hydrate dissociation pressure was predicted by the Gibbs minimization method. The findings denote that adding CP to the TBAC-containing system shifts the hydrate dissociation temperature of methane to higher values. The results also show an average increase of 12, 9, 5, and 3 K in hydrate dissociation temperature for 5, 10, 20, and 30 wt% TBAC in aqueous solution within the pressures. These results can be caused by the existence of more dodecahedral cages that are inhabited by methane. Thus, it makes hydrates more stable and increases the temperature of hydrate dissociation. On the other hand, adding TBAC to CP containing system has an inhibitor effect. The methane hydrate dissociation temperature was not changed sensibly when a 5 wt% TBAC was added to CP containing system. When the addition of the TBAC weight percentage to CP containing system is increased to 10, the average hydrate dissociation temperature decreases by 1 K within the pressures. When adding 20 and 30 wt% TBAC to CP containing system an average decrease of 2 K and 3 K in the hydrate dissociation temperature is resulted, respectively, within the pressures. The reduction in the hydrate dissociation temperatures can be attributed to salting-out and ion clustering. The experimental data and modeling results for the hydrate dissociation pressures exhibit an AARD of 2.4 %.