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USGS1983

Uptake and transport of heavy metals by heated seawater: A summary of the experimental results

In general, the chemistry of seawater experimentally reacted with basalt is in accord with the observed chemistry of the 350°C vent waters from 21°N on the East Pacific Rise. Experiments at 350°C, 500 bar, and a water/rock ratio of ≤10 reproduce most of the major components in the vent waters, in particular the low Mg and SO 4 and high Si0 2 , Ca, and K. In comparison with the vent waters however the experimental fluids are deficient in H + and heavy metals. Experiments with natural and evolved seawater (Mg and SO 4 depleted) at ≥400 C and 500 bars or 375°C and ~375 bars under rock-dominated conditions more closely reproduce the vent-water chemistry.

Book chapter↗

USGS1975

Experimental results of atomic absorption analyses for indium and thallium in 803 nonmagnetic concentrates from Alaska

The development in the U.S. Geological Survey of rapid methods for the determination by atomic absorption spectrophotometry of indium and thallium at limits of detection as low as 0.2 ppm each in geologic materials affords great advantages over spectrographic methods in studies concerned with values at or near the crustal abundances of these elements. Experimental application of the technique to the analysis of 803 nonmagnetic concentrates from Alaska showed specific disadvantages owing to the insolubility of cassiterite--one of the major sources for indium in concentrates--under the conditions of dissolution used in the preparation of samples for analysis by atomic absorption. Where nonmagnetic concentrates are used as a geochemical sample medium, and an exploration program is based on the interpretation of multi-element data, little purpose is served by independent analyses for indium and thallium.

Alaska↗

USGS2012

Modeling of rock friction 1. Experimental results and constitutive equations

Direct shear experiments on ground surfaces of a granodiorite from Raymond, California, at normal stresses of ??6 MPa demonstrate that competing time, displacement, and velocity effects control rock friction. It is proposed that the strength of the population of points of contacts between sliding surfaces determines frictional strength and that the population of contacts changes continuously with displacements. Previous experiments demonstrate that the strength of the contacts increases with the age of the contacts. The present experiments establish that a characteristic displacement, proportional to surface roughness, is required to change the population of contacts. Hence during slip the average age of the points of contact and therefore frictional strength decrease as slip velocity increases. Displacement weakening and consequently the potential for unstable slip occur whenever displacement reduces the average age of the contacts. In addition to this velocity dependency, which arises from displacement dependency and time dependency, the experiments also show a competing but transient increase in friction whenever slip velocity increases. Creep of the sliding surface at stresses below that for steady state slip is also observed. Constitutive relationships are developed that permit quantitative simulation of the friction versus displacement data as a function of surface roughness and for different time and velocity histories. Unstable slip in experiments is controlled by these constitutive effects and by the stiffness of the experimental system. It is argued that analogous properties control earthquake instability. Copyright ?? 1979 by the American Geophysical Union.

Conference Paper↗

USGS2012

Carbon sequestration via reaction with basaltic rocks: geochemical modeling and experimental results

Basaltic rocks are potential repositories for sequestering carbon dioxide (CO 2 ) because of their capacity for trapping CO 2 in carbonate minerals. We carried out a series of thermodynamic equilibrium models and high pressure experiments, reacting basalt with CO 2 -charged fluids over a range of conditions from 50 to 200 °C at 300 bar. Results indicate basalt has a high reactivity to CO 2 acidified brine. Carbon dioxide is taken up from solution at all temperatures from 50 to 200 °C, 300 bar, but the maximum extent and rate of reaction occurs at 100 °C, 300 bar. Reaction path simulations utilizing the geochemical modeling program CHILLER predicted an equilibrium carbonate alteration assemblage of calcite, magnesite, and siderite, but the only secondary carbonate identified in the experiments was a ferroan magnesite. The amount of uptake at 100 °C, 300 bar ranged from 8% by weight for a typical tholeite to 26% for a picrite. The actual amount of CO2 uptake and extent of rock alteration coincides directly with the magnesium content of the rock suggesting that overall reaction extent is controlled by bulk basalt Mg content. In terms of sequestering CO 2 , an average basaltic MgO content of 8% is equivalent to 2.6 × 10 8 metric ton CO 2 /km 3 basalt.

Geochimica et Cosmochimica Acta↗

USGS2021

Origin of the isotopic composition of natural perchlorate: Experimental results for the impact of reaction pathway and initial ClOx reactant

Natural perchlorate (ClO 4 − ) exists in many places on Earth, in lunar regolith, meteorites, and on the surface of Mars. Terrestrial natural ClO 4 − has widely variable Cl and O stable isotopic compositions (δ 37 Cl, δ 18 O, Δ 17 O). The δ 18 O and Δ 17 O values of ClO 4 − from the most hyper-arid locations co-vary. ClO 4 − from less arid areas has relatively little 17 O excess and poor Δ 17 O-δ 18 O correlation. ClO 4 − from the Atacama Desert has unusually low δ 37 Cl (<−10‰) and exhibits a positive correlation between δ 37 Cl and δ 18 O, while the δ 37 Cl of ClO 4 − from all other locations varies between −5 and +7‰ with no δ 37 Cl-δ 18 O covariation. To evaluate the impact of different precursors (ClO x ) and reaction pathways on the isotopic composition of ClO 4 − , we measured the isotopic composition of ClO 4 − produced in the laboratory by UV or O 3 mediated aqueous oxidation of Cl − , OCl − , ClO 2 − , and ClO 2 ° as well as O 3 mediated oxidation of dry NaCl. ClO x oxidation in aqueous or dry systems enriched in O 3 produced ClO 4 − with Δ 17 O values that generally increased with the number of O atoms required and included evidence that the site-specific 17 O anomaly in O 3 was preferentially transferred to ClO 4 − . Based on the inferred number of O atoms sourced from O 3 , and known Cl and O reaction pathways, it appears that ClO 2 ° and ClO 3 * were required intermediates in the production of ClO 4 − in the O 3 experiments. ClO x aqueous oxidation by UV irradiation produced ClO 4 − with a large range of δ 18 O values and little or no 17 O anomaly. ClO 3 − was produced to a much greater extent than ClO 4 − in all experiments except dry oxidation of NaCl by O 3 . The isotopic composition of ClO 3 − was distinct from that of ClO 4 − produced from the same initial reactants. Combined results of O 3 and UV mediated reactions largely bracketed the range of natural ClO 4 − δ 18 O and Δ 17 O values as well as δ 37 Cl values of non-Atacama natural samples, but no conditions produced the low δ 37 Cl values of Atacama ClO 4 − . Our results indicate that variation in production mechanisms, possibly combined with isotopically variable precursors, could be responsible for much of the observed isotopic variation in natural ClO 4 − and ClO 3 − .

Geochimica et Cosmochimica Acta↗

USGS1989

Responses to human intruders by birds nesting in colonies: Experimental results and management guidelines

Colonies of nesting wading birds and seabirds were studied at coastal sites in Virginia and North Carolina to determine distances at which birds flushed in response to human intrusion. There were few statistically significant relationships between flushing distances and colony size. Similarly, there were few differences between responses during incubation compared to post-hatching periods.

Colonial Waterbirds↗

USGS1988

Sex specificity of behavioral dominance and fasting endurance in wintering canvasbacks: Experimental results

Hand-reared canvasbacks (Aythya valisineria) of varying sex ratios were maintained in pens during winter 1980-81 (3M-3F, 6M-0F, 0M-6F) and winter 1981-82 (4M-2F, 2M-4F) and fed two diets (control and stress). They were observed during feeding trials to determine intrasexual and intersexual aggressive activity. There was little evidence that either diet or sex ratio affected the total number of aggressive encounters. Females fed both control and stress diets were more aggressive and spent more time in the small feeding areas than males in pens with 3M-3F, 4M-2F, and 2M-4F sex ratios. Stressed ducks tended to weigh less than controls throughout the study. Females in the 3M-3F and 4M-2F pens weighed less than those in the 0M-6F and 2M-4F pens, respectively. However, relative weight changes throughout the winter were similar for males and females. Thus, results of these experiments do not lead to conclusive rejection of either the behavioral dominance hypothesis or the fasting endurance hypothesis.

Book chapter↗

USGS2023

Intramolecular carbon isotope geochemistry of butane isomers from laboratory maturation and Monte-Carlo simulations of kerogen types I, II, and III

Position-specific (PS) carbon isotope compositions of light hydrocarbons such as propane and butane isomers (n-butane and i-butane) can provide a wealth of information on the history of natural gases in the subsurface reservoirs and other environments. For PS carbon isotope analysis of butane isomers, we have established a GC-pyrolysis-GC-isotope ratio mass spectrometry method with demonstrated accuracy. With this method, we analyzed PS δ 13 C values of butane isomers generated from the systematic laboratory pyrolysis experiments of three different kerogen types (I, II, and III) at temperatures of 310–430 °C with corresponding thermal maturity (Easy %R o ) ranging from 0.7 to 3.3. The observed evolution in the abundances of butane isomers can be interpreted and semi-quantitatively modeled based on the abundances of different C C bonds within the kerogens at low maturity and thermal degradation of butane isomers at high maturity. The δ 13 C values at the central sites of both nC 4 and iC 4 were heavier than those at the terminal positions, similar to our previous observations of propane. Their isotopic evolution with the maturity were controlled largely by kinetic isotope effects associated with breaking of different C C bonds during the generation and degradation of butane isomers. Kinetic Monte Carlo (kMC) simulations of n-butane generated from thermal cracking of model kerogens (I, II, and III) and an oil with a series of reactions (homolytic cleavage, β-scission, radical isomerization, H-abstraction, and termination by radical recombination) provided generally consistent results with the experimental observations, although the difference in PS δ 13 C values between the central and terminal positions are somewhat overestimated. On the other hand, the kMC simulation with homolytic cleavage and capping reactions alone produced significant deviations from the experimental results. Re-assessment of very limited data of PS δ 13 C values of natural butanes with our experimental and simulation results show that biodegradation significantly increased δ 13 C values at the central positions, not only of propane, but also of both butane isomers. This study lays a foundation and demonstrates the potential of PS isotope geochemistry of butane isomers to further improve our understanding of the sources, and geochemical and microbial processes of light hydrocarbons in the subsurface and other natural environments.

Geochimica et Cosmochimica Acta↗

USGS2021

Active neutron interrogation experiments and simulation verification using the SIngle-scintillator Neutron and Gamma-Ray spectrometer (SINGR) for geosciences

We present a new SIngle-scintillator Neutron and Gamma Ray spectrometer (SINGR) instrument for use with both passive and active measurement techniques. Here we discuss the application of SINGR for planetary exploration missions, however, hydrology, nuclear non-proliferation, and resource prospecting are all potential areas where the instrument could be applied. SINGR uses an elpasolite scintillator, Cs 2 YLiCl 6 :Ce (CLYC), that has been shown to have high neutron efficiency even at small volumes, with a gamma-ray energy resolution of approximately 4% full-width-at-half-maximum at 662 keV. Active gamma-ray and neutron (GRNS) measurements were performed with SINGR at the NASA Goddard Space Flight Center (GSFC) Goddard Geophysical and Astronomical Observatory (GGAO) outdoor test site using a pulsed neutron generator (PNG) to interrogate geologically relevant materials (basalt and granite monuments). These experimental results, combined with simulations, demonstrate that SINGR is capable of generating neutron die-away curves that can be used to reconstruct the bulk hydrogen abundance and the depth distribution of hydrogen within the monuments. We compare our experimental results with Monte Carlo N-Particle (MCNP) 6.1 transport simulations to constrain the uncertainties in depth and hydrogen abundance from the neutron die-away data generated by SINGR. For future planetary exploration missions, SINGR provides a single detector system for interrogating the shallow subsurface to characterize the presence and abundance of hydrated phases and to provide bulk elemental analysis.

Nuclear Instruments and Methods in Physics Researc↗

USGS2014

Sulfur isotope fractionation between fluid and andesitic melt: An experimental study

Glasses produced from decompression experiments conducted by Fiege et al. (2014a) were used to investigate the fractionation of sulfur isotopes between fluid and andesitic melt upon magma degassing. Starting materials were synthetic glasses with a composition close to a Krakatau dacitic andesite. The glasses contained 4.55–7.95 wt% H 2 O, ∼140 to 2700 ppm sulfur (S), and 0–1000 ppm chlorine (Cl). The experiments were carried out in internally heated pressure vessels (IHPV) at 1030 °C and oxygen fugacities ( f O 2 ) ranging from QFM+0.8 log units up to QFM+4.2 log units (QFM: quartz–fayalite–magnetite buffer). The decompression experiments were conducted by releasing pressure ( P ) continuously from ∼400 MPa to final P of 150, 100, 70 and 30 MPa. The decompression rate ( r ) ranged from 0.01 to 0.17 MPa/s. The samples were annealed for 0–72 h (annealing time, t A ) at the final P and quenched rapidly from 1030 °C to room temperature ( T ). The decompression led to the formation of a S-bearing aqueous fluid phase due to the relatively large fluid–melt partitioning coefficients of S. Secondary ion mass spectrometry (SIMS) was used to determine the isotopic composition of the glasses before and after decompression. Mass balance calculations were applied to estimate the gas–melt S isotope fractionation factor α g-m . No detectable effect of r and t A on α g-m was observed. However, SIMS data revealed a remarkable increase of α g-m from ∼0.9985 ± 0.0007 at >QFM+3 to ∼1.0042 ± 0.0042 at ∼QFM+1. Noteworthy, the isotopic fractionation at reducing conditions was about an order of magnitude larger than predicted by previous works. Based on our experimental results and on previous findings for S speciation in fluid and silicate melt a new model predicting the effect of f O 2 on α g-m (or Δ 34 S g–m ) in andesitic systems at 1030 °C is proposed. Our experimental results as well as our modeling are of high importance for the interpretation of S isotope signatures in natural samples (e.g., melt inclusions or volcanic gases).

Geochimica et Cosmochimica Acta↗

USGS1981

The partitioning of copper among selected phases of geologic media of two porphyry copper districts, Puerto Rico

In experiments designed to determine the manner in which copper is partitioned among selected phases that constitute geologic media, we have applied the five-step sequential extraction procedure of Chao and Theobald to the analysis of drill core, soils, and stream sediments of the Rio Vivi and Rio Tanama porphyry copper districts of Puerto Rico. The extraction procedure affords a convenient means of determining the trace-metal content of the following fractions: (1) Mn oxides and “reactive” Fe oxides; (2) “amorphous” Fe oxides; (3) “crystalline” Fe oxides; (4) sulfides and magnetite; and (5) silicates. An additional extraction between steps (1) and (2) was performed to determine organic-related copper in stream sediments. The experimental results indicate that apportionment of copper among phases constituting geologic media is a function of geochemical environment. Distinctive partitioning patterns were derived from the analysis of drill core from each of three geochemical zones: (a) the supergene zone of oxidation; (b) the supergene zone of enrichment; and (c) the hypogene zone; and similarly, from the analysis of; (d) soils on a weakly leached capping; (e) soils on a strongly leached capping; and (f) active stream sediment. The experimental results also show that geochemical contrasts (anomaly-to-background ratios) vary widely among the five fractions of each sampling medium investigated, and that at least one fraction of each medium provides substantially stronger contrast than does the bulk medium. Fraction (1) provides optimal contrast for stream sediments of the district; fraction (2) provides optimal contrast for soils on a weakly leached capping; fraction (3) provides optimal contrast for soils on a strongly leached capping. Selective extraction procedures appear to have important applications to the orientation and interpretive stages of geochemical exploration. Further investigation and testing of a similar nature are recommended.

Puerto Rico↗

USGS2005

Evaluation of ground-penetrating radar to detect free-phase hydrocarbons in fractured rocks: Results of numerical modeling and physical experiments

The suitability of common-offset ground-penetrating radar (GPR) to detect free-phase hydrocarbons in bedrock fractures was evaluated using numerical modeling and physical experiments. The results of one- and two-dimensional numerical modeling at 100 megahertz indicate that GPR reflection amplitudes are relatively insensitive to fracture apertures ranging from 1 to 4 mm. The numerical modeling and physical experiments indicate that differences in the fluids that fill fractures significantly affect the amplitude and the polarity of electromagnetic waves reflected by subhorizontal fractures. Air-filled and hydrocarbon-filled fractures generate low-amplitude reflections that are in-phase with the transmitted pulse. Water-filled fractures create reflections with greater amplitude and opposite polarity than those reflections created by air-filled or hydrocarbon-filled fractures. The results from the numerical modeling and physical experiments demonstrate it is possible to distinguish water-filled fracture reflections from air- or hydrocarbon-filled fracture reflections, nevertheless subsurface heterogeneity, antenna coupling changes, and other sources of noise will likely make it difficult to observe these changes in GPR field data. This indicates that the routine application of common-offset GPR reflection methods for detection of hydrocarbon-filled fractures will be problematic. Ideal cases will require appropriately processed, high-quality GPR data, ground-truth information, and detailed knowledge of subsurface physical properties. Conversely, the sensitivity of GPR methods to changes in subsurface physical properties as demonstrated by the numerical and experimental results suggests the potential of using GPR methods as a monitoring tool. GPR methods may be suited for monitoring pumping and tracer tests, changes in site hydrologic conditions, and remediation activities.The suitability of common-offset ground-penetrating radar (GPR) to detect free-phase hydrocarbons in bedrock fractures was evaluated using numerical modeling and physical experiments. The results of one- and two-dimensional numerical modeling at 100 megahertz indicate that GPR reflection amplitudes are relatively insensitive to fracture apertures ranging from 1 to 4 mm. The numerical modeling and physical experiments indicate that differences in the fluids that fill fractures significantly affect the amplitude and the polarity of electromagnetic waves reflected by subhorizontal fractures. Air-filled and hydrocarbon-filled fractures generate low-amplitude reflections that are in-phase with the transmitted pulse. Water-filled fractures create reflections with greater amplitude and opposite polarity than those reflections created by air-filled or hydrocarbon-filled fractures. The results from the numerical modeling and physical experiments demonstrate it is possible to distinguish water-filled fracture reflections from air- or hydrocarbon-filled fracture reflections, nevertheless subsurface heterogeneity, antenna coupling changes, and other sources of noise will likely make it difficult to observe these changes in GPR field data. This indicates that the routine application of common-offset GPR reflection methods for detection of hydrocarbon-filled fractures will be problematic. Ideal cases will require appropriately processed, high-quality GPR data, ground-truth information, and detailed knowledge of subsurface physical properties. Conversely, the sensitivity of GPR methods to changes in subsurface physical properties as demonstrated by the numerical and experimental results suggests the potential of using GPR methods as a monitoring tool. GPR methods may be suited for monitoring pumping and tracer tests, changes in site hydrologic conditions, and remediation activities.

Ground Water↗

USGS1985

Salt-water-freshwater transient upconing - An implicit boundary-element solution

The boundary-element method is used to solve the set of partial differential equations describing the flow of salt water and fresh water separated by a sharp interface in the vertical plane. In order to improve the accuracy and stability of the numerical solution, a new implicit scheme was developed for calculating the motion of the interface. The performance of this scheme was tested by means of numerical simulation. The numerical results are compared to experimental results for a salt-water upconing under a drain problem.

Journal of Hydrology↗

USGS2010

Segregating gas from melt: an experimental study of the Ostwald ripening of vapor bubbles in magmas

Diffusive coarsening (Ostwald ripening) of H 2 O and H 2 O-CO 2 bubbles in rhyolite and basaltic andesite melts was studied with elevated temperature–pressure experiments to investigate the rates and time spans over which vapor bubbles may enlarge and attain sufficient buoyancy to segregate in magmatic systems. Bubble growth and segregation are also considered in terms of classical steady-state and transient (non-steady-state) ripening theory. Experimental results are consistent with diffusive coarsening as the dominant mechanism of bubble growth. Ripening is faster in experiments saturated with pure H 2 O than in those with a CO 2 -rich mixed vapor probably due to faster diffusion of H 2 O than CO 2 through the melt. None of the experimental series followed the time 1/3 increase in mean bubble radius and time -1 decrease in bubble number density predicted by classical steady-state ripening theory. Instead, products are interpreted as resulting from transient regime ripening. Application of transient regime theory suggests that bubbly magmas may require from days to 100 years to reach steady-state ripening conditions. Experimental results, as well as theory for steady-state ripening of bubbles that are immobile or undergoing buoyant ascent, indicate that diffusive coarsening efficiently eliminates micron-sized bubbles and would produce mm-sized bubbles in 10 2 –10 4 years in crustal magma bodies. Once bubbles attain mm-sizes, their calculated ascent rates are sufficient that they could transit multiple kilometers over hundreds to thousands of years through mafic and silicic melt, respectively. These results show that diffusive coarsening can facilitate transfer of volatiles through, and from, magmatic systems by creating bubbles sufficiently large for rapid ascent.

Contributions to Mineralogy and Petrology↗

USGS2007

A critical review of three methods used for the measurement of mercury (Hg2+)-dissolved organic matter stability constants

Three experimental techniques - ion exchange, liquid-liquid extraction with competitive ligand exchange, and solid-phase extraction with competitive ligand exchange (CLE-SPE) - were evaluated as methods for determining conditional stability constants (K) for the binding of mercury (Hg2+) to dissolved organic matter (DOM). To determine the utility of a given method to measure stability constants at environmentally relevant experimental conditions, experimental results should meet three criteria: (1) the data must be experimentally valid, in that they were acquired under conditions that meet all the requirements of the experimental method, (2) the Hg:DOM ratio should be determined and it should fall within levels that are consistent with environmental conditions, and (3) the stability constants must fall within the detection window of the method. The ion exchange method was found to be limited by its detection window, which constrains the method to stability constants with log K values less than about 14. The liquid-liquid extraction method was found to be complicated by the ability of Hg-DOM complexes to partition into the organic phase. The CLE-SPE method was found to be the most suitable of these methods for the measurement of Hg-DOM stability constants. Stability constants for DOM isolates measured using the CLE-SPE method at environmentally relevant Hg:DOM ratios were log K = 25-30 (M-1). These values are consistent with the strong Hg2+ binding expected for reduced S-containing binding sites.

Applied Geochemistry↗

USGS2014

Pollen dispersal by catapult: Experiments of Lyman J. Briggs on the flower of mountain laurel

The flower of Kalmia latifolia L. employs a catapult mechanism that flings its pollen to considerable distances. Physicist Lyman J. Briggs investigated this phenomenon in the 1950s after retiring as longtime director of the National Bureau of Standards, attempting to explain how hydromechanical effects inside the flower’s stamen could make it possible. Briggs’s unfinished manuscript implies that liquid under negative pressure generates stress, which, superimposed on the stress generated from the flower’s growth habit, results in force adequate to propel the pollen as observed. With new data and biophysical understanding to supplement Briggs’s experimental results and research notes, we show that his postulated negative-pressure mechanism did not play the exclusive and crucial role that he credited to it, though his revisited investigation sheds light on various related processes. Important issues concerning the development and reproductive function of Kalmia flowers remain unresolved, highlighting the need for further biophysical advances.

Physics in Perspective↗

USGS2009

Marine electrical resistivity imaging of submarine groundwater discharge: Sensitivity analysis and application in Waquoit Bay, Massachusetts, USA

Electrical resistivity imaging has been used in coastal settings to characterize fresh submarine groundwater discharge and the position of the freshwater/salt-water interface because of the relation of bulk electrical conductivity to pore-fluid conductivity, which in turn is a function of salinity. Interpretation of tomograms for hydrologic processes is complicated by inversion artifacts, uncertainty associated with survey geometry limitations, measurement errors, and choice of regularization method. Variation of seawater over tidal cycles poses unique challenges for inversion. The capabilities and limitations of resistivity imaging are presented for characterizing the distribution of freshwater and saltwater beneath a beach. The experimental results provide new insight into fresh submarine groundwater discharge at Waquoit Bay National Estuarine Research Reserve, East Falmouth, Massachusetts (USA). Tomograms from the experimental data indicate that fresh submarine groundwater discharge may shut down at high tide, whereas temperature data indicate that the discharge continues throughout the tidal cycle. Sensitivity analysis and synthetic modeling provide insight into resolving power in the presence of a time-varying saline water layer. In general, vertical electrodes and cross-hole measurements improve the inversion results regardless of the tidal level, whereas the resolution of surface arrays is more sensitive to time-varying saline water layer.

Massachusetts↗

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↗