Impact of Acid–Base Stimulation Sequence on Mineral Stability for Tight/Impermeable Unconventional Carbonate-Rich Rocks: A Delaware Basin Case Study

Mineral precipitation due to reactions with injected fluids during unconventional fracture stimulation is a well-recognized problem. The goal of this study is to evaluate secondary mineral precipitation and permeability attenuation under chemical injection scenarios specific to the Delaware basin. Whole cylindrical cores (2.54 cm diameter and 2.54 cm height) and ground shale (150–250 μm) from the carbonate-rich Bone Spring Formation, Delaware Basin TX (Leonardian), were reacted at 80 °C and 85 bar using a hydraulic fracturing fluid (HFF) recipe and an injection sequence typical of the Delaware Basin. The reacted shales and solutions were analyzed using a variety of laboratory- and synchrotron-based techniques to characterize both the chemical and spatial distributions of secondary mineral precipitation and identify changes in permeability and mineralogy. This carbonate-rich shale (>84% calcite) rapidly neutralized the acidic HFF. Synchrotron-based X-ray fluorescence mapping coupled with X-ray absorption spectroscopy (both bulk and micro) showed that most of the iron was in an oxidized form prior to exposure to HFF and that almost all iron­(II) became fully oxidized after the reaction. Scanning electron microscopy images of the ground shale samples primarily identified iron­(oxyhydr)­oxide microcrystals on grain surfaces. A few small isolated iron-rich areas also contained sulfur, suggesting that some pyrite was preserved when isolated within a calcite crystal but that most was oxidized. The rapid neutralization of the acid spearhead in these carbonate-rich samples demonstrates that the acid spearhead is useful for initiating fractures in extremely calcite-rich rocks but does little to enhance rock permeability. This suggests that the impact of the acid spearhead is significantly smaller for carbonate-rich shales compared to clay-rich shales, which has broad implications for acidizing in carbonate-rich shale formations and iron transformations within these shales

New Technique for Quantification of Elemental Hg in Mine Wastes and Its Implications for Mercury Evasion Into the Atmosphere

Mercury in the environment is of prime concern to both ecosystem and human health. Determination of the molecular-level speciation of Hg in soils and mine wastes is important for understanding its sequestration, mobility, and availability for methylation. Extended X-ray absorption fine structure (EXAFS) spectroscopy carried out under ambient P-T conditions has been used in a number of past studies to determine Hg speciation in complex mine wastes and associated soils. However, this approach cannot detect elemental (liquid) mercury in Hg-polluted soils and sediments due to the significant structural disorder of liquid Hg at ambient-temperature. A new sample preparation protocol involving slow cooling through the crystallization temperature of Hg(0) (234 K) results in its transformation to crystalline α-Hg(0). The presence and proportion of Hg(0), relative to other crystalline Hg-bearing phases, in samples prepared in this way can be quantified by low-temperature (77 K) EXAFS spectroscopy. Using this approach, we have determined the relative concentrations of liquid Hg(0) in Hg mine wastes from several sites in the California Coast Range and have found that they correlate well with measured fluxes of gaseous Hg released during light and dark exposure of the same samples, with higher evasion ratios from samples containing higher concentrations of liquid Hg(0). Two different linear relationships are observed in plots of the ratio of Hg emission under light and dark conditions vs % Hg(0), corresponding to silica−carbonate- and hot springs-type Hg deposits, with the hot springs-type samples exhibiting higher evasion fluxes than silica−carbonate type samples at similar Hg(0) concentrations. Our findings help explain significant differences in Hg evasion data for different mine sites in the California Coast Range

Thicknesses of Chemically Altered Zones in Shale Matrices Resulting from Interactions with Hydraulic Fracturing Fluid

Hydraulic fracturing of unconventional shale reservoirs increases the fracture network surface area to access hydrocarbons from the low permeability rock matrix. Porosity and permeability of the matrix, through which hydrocarbons migrate to fractures, are important for determining production efficiency and can be altered by chemical interactions between shale and hydraulic fracturing fluids (HFFs). Here, we present results from an experimental study that characterizes the thickness of the alteration zone in the shale matrix after shale–HFF interactions. Experiments were conducted with whole cores submerged in HFF both with and without added barium and sulfate to promote barite scale formation. After 3 weeks of reaction at 77 bar and 80 °C, the cores were characterized using X-ray microtomography, synchrotron X-ray fluorescence microprobe imaging, and synchrotron X-ray absorption spectroscopy. Our results show that the thickness of the altered zone depends on shale mineralogical composition and varies for different chemical reactions. For reactions between the low-carbonate Marcellus shale and HFF, pyrite (FeS2) oxidation manifests as both a thick zone of sulfur oxidation (>0.5 cm) and a thinner zone of iron oxidation (100–150 μm). Carbonate dissolution extended 100–200 μm into the matrix, with the resulting observable secondary porosity localized at the shale–fluid interface where mineral grains were removed by either dissolution or mechanical erosion. In solutions oversaturated with respect to barite, barite precipitates were observed in the reaction fluid and at the shal–HFF interface. In contrast, the carbonate dissolution zone in the high-carbonate Eagle Ford was only 30–40 μm thick, within which a uniform texture of increased porosity was observed. Pyrite oxidation in the Eagle Ford was evident from an iron oxidation zone (150–200 μm thick), while sulfur oxidation was minor and hard to observe. Barite precipitation extended 1–2 mm into the matrix when the initial HFF was oversaturated with respect to barite, filling shale microcracks down to the submicrometer length scale. Our findings provide a scientific basis to predict the extent of chemical alteration in shale reservoirs during hydraulic fracturing and its impacts on hydrocarbon production

Stable Hg Isotope Signatures in Creek Sediments Impacted by a Former Hg Mine

The goal of this study was to investigate the Hg stable isotope signatures of sediments in San Carlos Creek downstream of the former Hg mine New Idria, CA, USA and to relate the results to previously studied Hg isotope signatures of unroasted ore waste and calcine materials in the mining area. New Idria unroasted ore waste was reported to have a narrow δ²⁰²Hg range (−0.09 to 0.16‰), while roasted calcine materials exhibited a very large variability in δ²⁰²Hg (−5.96 to 14.5‰). In this study, creek sediment samples were collected in the stream bed from two depths (0–10 and 10–20 cm) at 10 locations between the mine adit and 28 km downstream. The sediment samples were size-fractionated into sand, silt, and (if possible) clay fractions as well as hand-picked calcine pebbles. The sediment samples contained highly elevated Hg concentrations (8.2 to 647 μg g^–1) and displayed relatively narrow mass-dependent fractionation (MDF, δ²⁰²Hg; ± 0.08‰, 2SD) ranges (−0.58 to 0.24‰) and little to no mass-independent fractionation (MIF, Δ¹⁹⁹Hg; ± 0.04‰, 2SD) (0.00 to 0.10‰), similar to what was observed previously for the unroasted ore waste. However, due to the highly variable and overlapping δ²⁰²Hg signatures of the calcines, they could not be ruled out as source of Hg to the creek sediments. Overall, our results suggest that analyzing creek sediments downstream of former Hg mines can provide a more reliable Hg isotope source signature for tracing studies at larger spatial scales, than analyzing the isotopically highly heterogeneous tailing piles typically found at former mining sites. Creek sediments carry an integrated isotope signature of Hg transported away from the mine with runoff into the creek, eventually affecting ecosystems downstream

Geochemical Modeling of Celestite (SrSO₄) Precipitation and Reactive Transport in Shales

Celestite (SrSO4) precipitation is a prevalent example of secondary sulfate mineral scaling issues in hydraulic fracturing systems, particularly in basins where large concentrations of naturally occurring strontium are present. Here, we present a validated and flexible geochemical model capable of predicting celestite formation under such unconventional environments. Simulations were built using CrunchFlow and guided by experimental data derived from batch reactors. These data allowed the constraint of key kinetic and thermodynamic parameters for celestite precipitation under relevant synthetic hydraulic fracturing fluid conditions. Effects of ionic strength, saturation index, and the presence of additives were considered in the combined experimental and modeling construction. This geochemical model was then expanded into a more complex system where interactions between hydraulic fracturing fluids and shale rocks were allowed to occur subject to diffusive transport. We find that the carbonate content of a given shale and the presence of persulfate breaker in the system strongly impact the location and extent of celestite formation. The results of this study provide a novel multicomponent reactive transport model that may be used to guide future experimental design in the pursuit of celestite and other sulfate mineral scale mitigation under extreme conditions typical of hydraulic fracturing in shale formations

Effect of Chloride on the Dissolution Rate of Silver Nanoparticles and Toxicity to <i>E. coli</i>

Pristine silver nanoparticles (AgNPs) are not chemically stable in the environment and react strongly with inorganic ligands such as sulfide and chloride once the silver is oxidized. Understanding the environmental transformations of AgNPs in the presence of specific inorganic ligands is crucial to determining their fate and toxicity in the environment. Chloride (Cl–) is a ubiquitous ligand with a strong affinity for oxidized silver and is often present in natural waters and in bacterial growth media. Though chloride can strongly affect toxicity results for AgNPs, their interaction is rarely considered and is challenging to study because of the numerous soluble and solid Ag–Cl species that can form depending on the Cl/Ag ratio. Consequently, little is known about the stability and dissolution kinetics of AgNPs in the presence of chloride ions. Our study focuses on the dissolution behavior of AgNPs in chloride-containing systems and also investigates the effect of chloride on the growth inhibition of E.coli (ATCC strain 33876) caused by Ag toxicity. Our results suggest that the kinetics of dissolution are strongly dependent on the Cl/Ag ratio and can be interpreted using the thermodynamically expected speciation of Ag in the presence of chloride. We also show that the toxicity of AgNPs to E.coli at various Cl– concentrations is governed by the amount of dissolved AgClx(x–1)– species suggesting an ion effect rather than a nanoparticle effect

Mercury Isotope Signatures as Tracers for Hg Cycling at the New Idria Hg Mine

Mass-dependent fractionation (MDF) and mass-independent fractionation (MIF) of Hg isotopes provides a new tool for tracing Hg in contaminated environments such as mining sites, which represent major point sources of Hg pollution into surrounding ecosystems. Here, we present Hg isotope ratios of unroasted ore waste, calcine (roasted ore), and poplar leaves collected at a closed Hg mine (New Idria, CA, U.S.A.). Unroasted ore waste was isotopically uniform with δ²⁰²Hg values from −0.09 to 0.16‰ (±0.10‰, 2 SD), close to the estimated initial composition of the HgS ore (−0.26‰). In contrast, calcine samples exhibited variable δ²⁰²Hg values ranging from −1.91‰ to +2.10‰. Small MIF signatures in the calcine were consistent with nuclear volume fractionation of Hg isotopes during or after the roasting process. The poplar leaves exhibited negative MDF (−3.18 to −1.22‰) and small positive MIF values (Δ¹⁹⁹Hg of 0.02 to 0.21‰). Sequential extractions combined with Hg isotope analysis revealed higher δ²⁰²Hg values for the more soluble Hg pools in calcines compared with residual HgS phases. Our data provide novel insights into possible in situ transformations of Hg phases and suggest that isotopically heavy secondary Hg phases were formed in the calcine, which will influence the isotope composition of Hg leached from the site