Geology topics

Geoffrey S Ellis

Publications and source records attributed to Geoffrey S Ellis.

5 recordsLinked to original sources

USGS2015

The modern muds of Laguna Mar Chiquita (Argentina): Particle size and geochemical trends from a large saline lake in the "thick-skinned" Andean foreland

Laguna Mar Chiquita (central Argentina; ~latitude 31°S, longitude 63°W) provides an outstanding opportunity to examine organic facies development and petroleum source-rock potential in a modern thick-skinned foreland basin lake. In this case study, we define profundal, paleodelta, and lake-margin depositional environments based on trends in bathymetry and lake-floor sediment particle size. Sedimentary geochemical analyses indicate that organic carbon–rich muds accumulate in profundal environments during the extant lake-level highstand. The lateral variability of organic facies is minimal. The quality of organic facies is controlled by lake level and depositional environment, both of which dictate patterns of algal productivity, siliciclastic dilution, and early diagenesis. We present conceptual models of lacustrine source rocks in both thick-skinned and thin-skinned foreland basins based on modern analog data from both Laguna Mar Chiquita and other lakes in the central Andean foreland. Over relatively short time intervals (10 2 –10 4 yr), climatically driven water-level fluctuations influence the source-rock potential of these basins. Over time intervals >10 5 yr, contraction and lateral migration of the basin flexural profile control stratal stacking patterns and the potential for hydrocarbon play development.

Laguna Mar Chiquita↗

USGS2011

Playa-lake sedimentation and organic matter accumulation in an Andean piggyback basin: The recent record from the Cuenca de Pozuelos, NW Argentina

Expansive playa‐lake systems situated in high‐altitude piggyback basins are important and conspicuous components of both modern and ancient cordilleran orogenic systems. Extant playa lakes provide vital habitat for numerous endemic species, whereas sediments from these deposystems may record signals of climate change or develop natural resources over geological time. Laguna de los Pozuelos (North‐west Argentina) provides the opportunity for an actualistic sedimentological and geochemical assessment of a piggyback basin playa lake in an area of critical interest for understanding Quaternary palaeoclimate dynamics. Silty clays and diatom ooze are the dominant playa‐lake centre microfacies, with concentrations of total organic carbon and biogenic silica commonly exceeding 1·5 wt% in this sub‐environment. Elemental and stable isotopic analyses point to a mixed organic matter composition in the playa‐lake centre, with substantial contributions from algae and transported aquatic macrophytes. Bulk sediment and organic mass accumulation rates in the southern playa‐lake centre approach 0.22g cm −2 year −1 and 2.89 mg cm −2 year −1 , respectively, indicating moderately rapid deposition with negligible deflation over historic time. Playa margin facies contain higher percentages of fragmented biogenic carbonate (ostracods and charophytes) and inorganically precipitated aragonite crusts due to seasonal pumping and evaporation of ground water. Organic matter accumulation is limited along these heavily bioturbated wet and dry mud flats. Fluvial–lacustrine transitional environments, which are key waterbird habitats, are either silty terminal splay (northern axis) or sandy deltas (southern axis) containing highly oxidized and partially allochthonous organic matter. Modern analogue data from Laguna de los Pozuelos provide key insights for: (i) environmental reconstructions of ancient lake sequences; and (ii) improving facies models for piggyback basins.

Cuenca de Pozuelos↗

USGS2008

The role of labile sulfur compounds in thermal chemical sulfate reduction

The reduction of sulfate to sulfide coupled with the oxidation of hydrocarbons to carbon dioxide, commonly referred to as thermochemical sulfate reduction (TSR), is an important abiotic alteration process that most commonly occurs in hot carbonate petroleum reservoirs. In the present study we focus on the role that organic labile sulfur compounds play in increasing the rate of TSR. A series of gold-tube hydrous pyrolysis experiments were conducted with n -octane and CaSO 4 in the presence of reduced sulfur (e.g. H 2 S, S°, organic S) at temperatures of 330 and 356 °C under a constant confining pressure. The in-situ pH was buffered to 3.5 (∼6.3 at room temperature) with talc and silica. For comparison, three types of oil with different total S and labile S contents were reacted under similar conditions. The results show that the initial presence of organic or inorganic sulfur compounds increases the rate of TSR. However, organic sulfur compounds, such as 1-pentanethiol or diethyldisulfide, were significantly more effective in increasing the rate of TSR than H 2 S or elemental sulfur (on a mole S basis). The increase in rate is achieved at relatively low concentrations of 1-pentanethiol, less than 1 wt% of the total n -octane, which is comparable to the concentration of organic S that is common in many oils (∼0.3 wt%). We examined several potential reaction mechanisms to explain the observed reactivity of organic LSC. First, the release of H 2 S from the thermal degradation of thiols was discounted as an important mechanism due to the significantly greater reactivity of thiol compared to an equivalent amount of H 2 S. Second, we considered the generation of olefines in association with the elimination of H 2 S during thermal degradation of thiols because olefines are much more reactive than n -alkanes during TSR. In our experiments, olefines increased the rate of TSR, but were less effective than 1-pentanethiol and other organic LSC. Third, the thermal decomposition of organic LSC creates free-radicals that in turn might initiate a radical chain-reaction that creates more reactive species. Experiments involving radical initiators, such as diethyldisulfide and benzyldisulfide, did not show an increase in reactivity compared to 1-pentanethiol. Therefore, we conclude that none of these can sufficiently explain our observations of the initial stages of TSR; they may, however, be important in the later stages. In order to gain greater insight into the potential mechanism for the observed reactivity of these organic sulfur compounds during TSR, we applied density functional theory-based molecular modeling techniques to our system. The results of these calculations indicate that 1-pentanethiol or its thermal degradation products may directly react with sulfate and reduce the activation energy required to rupture the first S–O bond through the formation of a sulfate ester. This study demonstrates the importance of labile sulfur compounds in reducing the onset timing and temperature of TSR. It is therefore essential that labile sulfur concentrations are taken into consideration when trying to make accurate predictions of TSR kinetics and the potential for H 2 S accumulation in petroleum reservoirs.

Geochimica et Cosmochimica Acta↗

USGS2008

Experimental investigation on thermochemical sulfate reduction by H2S initiation

Hydrogen sulfide (H 2 S) is known to catalyze thermochemical sulfate reduction (TSR) by hydrocarbons (HC), but the reaction mechanism remains unclear. To understand the mechanism of this catalytic reaction, a series of isothermal gold-tube hydrous pyrolysis experiments were conducted at 330 °C for 24 h under a constant confining pressure of 24.1 MPa. The reactants used were saturated HC (sulfur-free) and CaSO 4 in the presence of variable H 2 S partial pressures at three different pH conditions. The experimental results showed that the in - situ pH of the aqueous solution (herein, in - situ pH refers to the calculated pH of aqueous solution under the experimental conditions) can significantly affect the rate of the TSR reaction. A substantial increase in the TSR reaction rate was recorded with a decrease in the in - situ pH value of the aqueous solution involved. A positive correlation between the rate of TSR and the initial partial pressure of H 2 S occurred under acidic conditions (at pH ∼3–3.5). However, sulfate reduction at pH ∼5.0 was undetectable even at high initial H 2 S concentrations. To investigate whether the reaction of H 2 S (aq) and HSO 4 - "> HSO4- occurs at pH ∼3, an additional series of isothermal hydrous pyrolysis experiments was conducted with CaSO 4 and variable H 2 S partial pressures in the absence of HC at the same experimental temperature and pressure conditions. CaSO 4 reduction was not measurable in the absence of paraffin even with high H 2 S pressure and acidic conditions. These experimental observations indicate that the formation of organosulfur intermediates from H 2 S reacting with hydrocarbons may play a significant role in sulfate reduction under our experimental conditions rather than the formation of elemental sulfur from H 2 S reacting with sulfate as has been suggested previously (Toland W. G. (1960) Oxidation of organic compounds with aqueous sulphate. J. Am. Chem. Soc. 82 , 1911–1916). Quantification of labile organosulfur compounds (LSC), such as thiols and sulfides, was performed on the products of the reaction of H 2 S and HC from a series of gold-tube non-isothermal hydrous pyrolysis experiments conducted at about pH 3 from 300 to 370 °C and a 0.1-°C/h heating rate. Incorporation of sulfur into HC resulted in an appreciable amount of thiol and sulfide formation. The rate of LSC formation positively correlated with the initial H 2 S pressure. Thus, we propose that the LSC produced from H 2 S reaction with HC are most likely the reactive intermediates for H 2 S initiation of sulfate reduction. We further propose a three-step reaction scheme of sulfate reduction by HC under reservoir conditions, and discuss the geological implications of our experimental findings with regard to the effect of formation water and oil chemistry, in particular LSC content.

Geochimica et Cosmochimica Acta↗

USGS2008

Theoretical study on the reactivity of sulfate species with hydrocarbons

The abiotic, thermochemically controlled reduction of sulfate to hydrogen sulfide coupled with the oxidation of hydrocarbons, is termed thermochemical sulfate reduction (TSR), and is an important alteration process that affects petroleum accumulations in nature. Although TSR is commonly observed in high-temperature carbonate reservoirs, it has proven difficult to simulate in the laboratory under conditions resembling nature. The present study was designed to evaluate the relative reactivities of various sulfate species in order to provide greater insight into the mechanism of TSR and potentially to fill the gap between laboratory experimental data and geological observations. Accordingly, quantum mechanics density functional theory (DFT) was used to determine the activation energy required to reach a potential transition state for various aqueous systems involving simple hydrocarbons and different sulfate species. The entire reaction process that results in the reduction of sulfate to sulfide is far too complex to be modeled entirely; therefore, we examined what is believed to be the rate limiting step, namely, the reduction of sulfate S(VI) to sulfite S(IV). The results of the study show that water-solvated sulfate anions SO 4 2- are very stable due to their symmetrical molecular structure and spherical electronic distributions. Consequently, in the absence of catalysis, the reactivity of SO 4 2- is expected to be extremely low. However, both the protonation of sulfate to form bisulfate anions ( HSO 4 - ) and the formation of metal-sulfate contact ion-pairs could effectively destabilize the sulfate molecular structure, thereby making it more reactive. Previous reports of experimental simulations of TSR generally have involved the use of acidic solutions that contain elevated concentrations of " HSO 4 - relative to SO 4 2- . However, in formation waters typically encountered in petroleum reservoirs, the concentration of HSO 4 - is likely to be significantly lower than the levels used in the laboratory, with most of the dissolved sulfate occurring as SO 4 2- , aqueous calcium sulfate ([CaSO 4 ] (aq) ), and aqueous magnesium sulfate ([MgSO 4 ] (aq) ). Our calculations indicate that TSR reactions that occur in natural environments are most likely to involve bisulfate ions ( HSO 4 - ) and/or magnesium sulfate contact ion-pairs ([MgSO 4 ] CIP ) rather than ‘free’ sulfate ions ( SO 4 2- ) or solvated sulfate ion-pairs, and that water chemistry likely plays a significant role in controlling the rate of TSR.

Geochimica et Cosmochimica Acta↗