Different controls on the Hg spikes linked the two pulses of the Late Ordovician mass extinction in South China.

The Late Ordovician mass extinction (LOME, ca. 445 Ma; Hirnantian stage) is the second most severe biological crisis of the entire Phanerozoic. The LOME has been subdivided into two pulses (intervals), at the beginning and the ending of the Hirnantian glaciation, the LOMEI-1 and LOMEI-2, respectively. Although most studies suggest a rapid cooling and/or oceanic euxinia as major causes for this mass extinction, the driver of these environmental changes is still debated. As other Phanerozoic's mass extinctions, extensive volcanism may have been the potential trigger of the Hirnantian glaciation. Indirect evidence of intense volcanism comes from Hg geochemistry: peaks of Hg concentrations have been found before and during the LOME, and have all been attributed to global volcanism in origin. Here, we present high-resolution mercury (Hg) profiles in three study sections, from a shelf to slope transect, on the Yangtze Shelf Sea (South China) to address the origin of Hg anomalies across the Ordovician-Silurian (O-S) boundary. The results show Hg anomaly enrichments in the middle Katian, late Katian, the LOMEI-1 at the beginning of the Hirnantian glaciation, the LOMEI-2 in the late Hirnantian glaciation, and late Rhuddanian. The Hg anomaly enrichments during the middle-late Katian and late Rhuddanian would probably reflect a volcanic origin. We find two different controls on the recorded Hg anomalies during the extinction time: i.e., primarily volcanism for the Hg anomaly at the LOMEI-1 and euxinia for the Hg anomaly at the LOMEI-2. Expansion of euxinia at the LOMEI-1 would have been probably enhanced by volcanic fertilization via weathering of volcanic deposits during the Middle and late Katian, and combined with euxinia at the LOMEI-2 to finally be responsible for the two pulses of the LOME.

Hydrochemistry of flowback water from Changning shale gas field and associated shallow groundwater in Southern Sichuan Basin, China: Implications for the possible impact of shale gas development on groundwater quality.

The worldwide expansion of shale gas production and increased use of hydraulic fracturing have raised public concerns about safety and risks of groundwater resources in shale gas extraction areas. China has the largest shale gas resources in the world, most of which are located in the Sichuan Basin. Shale gas extraction in the Sichuan Basin has been increasing rapidly in recent years. However, the potential impact on shallow groundwater quality has not yet been systematically investigated. In order to evaluate the possible impact of shale gas extraction on groundwater quality, we present, for the first time, the hydrochemistry and Sr isotopic data of shallow groundwater, as well as flowback and produced water (FP water) in the Changning shale gas field in Sichuan Basin, one of the major shale gas fields in China. The Changning FP water is characterized by high salinity (TDS of 13,100-53,500 mg/L), Br/Cl (2.76 × 10-3) and 87Sr/86Sr (0.71849), which are distinguished from the produced waters from nearby conventional gas fields with higher Br/Cl (4.5 × 10-3) and lower 87Sr/86Sr (0.70830-0.71235). The shallow groundwater samples were collected from a Triassic karst aquifer in both active and nonactive shale gas extraction areas. They are dominated by low salinity (TDS of 145-1100 mg/L), Ca-HCO3 and Ca-Mg-HCO3 types water, which are common in carbonate karst aquifers. No statistical difference of the groundwater quality was observed between samples collected in active versus nonactive shale gas extraction areas. Out of 66 analyzed groundwater, three groundwater samples showed relatively higher salinity above the background level, with low 87Sr/86Sr (0.70824-0.7110) and Br/Cl (0.5-1.8 × 10-3) ratios relatively to FP water, excluding the possibility of contamination from FP water. None of the groundwater samples had detected volatile organic compounds (VOCs). The integration of geochemical and statistical analysis shows no direct evidence of groundwater contamination caused by shale gas development.

Origin of Flowback and Produced Waters from Sichuan Basin, China.

Shale gas extraction through hydraulic fracturing and horizontal drilling is increasing in China, particularly in Sichuan Basin. Production of unconventional shale gas with minimal environmental effects requires adequate management of wastewater from flowback and produced water (FP water) that is coextracted with natural gas. Here we present, for the first time, inorganic chemistry and multiple isotope (oxygen, hydrogen, boron, strontium, radium) data for FP water from 13 shale gas wells from the Lower Silurian Longmaxi Formation in the Weiyuan gas field, as well as produced waters from 35 conventional gas wells from underlying (Sinian, Cambrian) and overlying (Permian, Triassic) formations in Sichuan Basin. The chemical and isotope data indicate that the formation waters in Sichuan Basin originated from relics of different stages of evaporated seawater modified by water-rock interactions. The FP water from shale gas wells derives from blending of injected hydraulic fracturing water and entrapped saline (Cl ∼ 50,000 mg/L) formation water. Variations in the chemistry, δ18O, δ11B, and 87Sr/86Sr of FP water over time indicate that the mixing between the two sources varies with time, with a contribution of 75% (first 6 months) to 20% (>year) of the injected hydraulic fracturing water in the blend that compose the FP water. Mass-balance calculation suggests that the returned hydraulic fracturing water consisted of 28-49% of the volume of the injected hydraulic fracturing water, about a year after the initial hydraulic fracturing. We show differential mobilization of Na, B, Sr, and Li from the shale rocks during early stages of operation, which resulted in higher Na/Cl, B/Cl, Li/Cl, and 87Sr/86Sr and lower δ11B of the FP water during early stages of FP water formation relative to the original saline formation water recorded in late stages FP water. This study provides a geochemical framework for characterization of formation waters from different geological strata, and thus the ability to distinguish between different sources of oil and gas wastewater in Sichuan Basin.

The water footprint of hydraulic fracturing in Sichuan Basin, China.

Shale gas is likely to play a major role in China's transition away from coal. In addition to technological and infrastructural constraints, the main challenges to China's sustainable shale gas development are sufficient shale gas production, water availability, and adequate wastewater management. Here we present, for the first time, actual data of shale gas production and its water footprint from the Weiyuan gas field, one of the major gas fields in Sichuan Basin. We show that shale gas production rates during the first 12 months (24 million m3 per well) are similar to gas production rates in U.S. shale basins. The amount of water used for hydraulic fracturing (34,000 m3 per well) and the volume of flowback and produced (FP) water in the first 12 months (19,800 m3 per well) in Sichuan Basin are also similar to the current water footprints of hydraulic fracturing in U.S. basins. We present salinity data of the FP water (5000 to 40,000 mgCl/L) in Sichuan Basin and the treatment operations, which include sedimentation, dilution with fresh water, and recycling of the FP water for hydraulic fracturing. We utilize the water use data, empirical decline rates of shale gas and FP water productions in Sichuan Basin to generate two prediction models for water use for hydraulic fracturing and FP water production upon achieving China's goals to generate 100 billion m3 of shale gas by 2030. The first model utilizes the current water use and FP production data, and the second assumes a yearly 5% intensification of the hydraulic fracturing process. The predicted water use for hydraulic fracturing in 2030 (50-65 million m3 per year), FP water production (50-55 million m3 per year), and fresh water dilution of FP water (25 million m3 per year) constitute a water footprint that is much smaller than current water consumption and wastewater generation for coal mining, but higher than those of conventional gas production in China. Given estimates for water availability in Sichuan Basin, our predictions suggest that water might not be a limiting factor for future large-scale shale gas development in Sichuan Basin.

Water Availability for Shale Gas Development in Sichuan Basin, China.

Unconventional shale gas development holds promise for reducing the predominant consumption of coal and increasing the utilization of natural gas in China. While China possesses some of the most abundant technically recoverable shale gas resources in the world, water availability could still be a limiting factor for hydraulic fracturing operations, in addition to geological, infrastructural, and technological barriers. Here, we project the baseline water availability for the next 15 years in Sichuan Basin, one of the most promising shale gas basins in China. Our projection shows that continued water demand for the domestic sector in Sichuan Basin could result in high to extremely high water stress in certain areas. By simulating shale gas development and using information from current water use for hydraulic fracturing in Sichuan Basin (20,000-30,000 m(3) per well), we project that during the next decade water use for shale gas development could reach 20-30 million m(3)/year, when shale gas well development is projected to be most active. While this volume is negligible relative to the projected overall domestic water use of ∼36 billion m(3)/year, we posit that intensification of hydraulic fracturing and water use might compete with other water utilization in local water-stress areas in Sichuan Basin.

Applications of Micro-Fourier Transform Infrared Spectroscopy (FTIR) in the Geological Sciences--A Review.

Fourier transform infrared spectroscopy (FTIR) can provide crucial information on the molecular structure of organic and inorganic components and has been used extensively for chemical characterization of geological samples in the past few decades. In this paper, recent applications of FTIR in the geological sciences are reviewed. Particularly, its use in the characterization of geochemistry and thermal maturation of organic matter in coal and shale is addressed. These investigations demonstrate that the employment of high-resolution micro-FTIR imaging enables visualization and mapping of the distributions of organic matter and minerals on a micrometer scale in geological samples, and promotes an advanced understanding of heterogeneity of organic rich coal and shale. Additionally, micro-FTIR is particularly suitable for in situ, non-destructive characterization of minute microfossils, small fluid and melt inclusions within crystals, and volatiles in glasses and minerals. This technique can also assist in the chemotaxonomic classification of macrofossils such as plant fossils. These features, barely accessible with other analytical techniques, may provide fundamental information on paleoclimate, depositional environment, and the evolution of geological (e.g., volcanic and magmatic) systems.

Do Shale Pore Throats Have a Threshold Diameter for Oil Storage?

In this work, a nanoporous template with a controllable channel diameter was used to simulate the oil storage ability of shale pore throats. On the basis of the wetting behaviours at the nanoscale solid-liquid interfaces, the seepage of oil in nano-channels of different diameters was examined to accurately and systematically determine the effect of the pore diameter on the oil storage capacity. The results indicated that the lower threshold for oil storage was a pore throat of 20 nm, under certain conditions. This proposed pore size threshold provides novel, evidence-based criteria for estimating the geological reserves, recoverable reserves and economically recoverable reserves of shale oil. This new understanding of shale oil processes could revolutionize the related industries.

Lattice Boltzmann modeling of permeability in porous materials with partially percolating voxels.

A partial-bounce-back lattice Boltzmann model has been used to simulate flow on a lattice consisting of cubic voxels with a locally varying effective percolating fraction. The effective percolating fraction of a voxel is the total response to the partial-bounce-back techniques for porous media flow due to subvoxel fine structures. The model has been verified against known analytic solutions on two- and three-dimensional regular geometries, and has been applied to simulate flow and permeabilities of two real-world rock samples. This enables quantitative determination of permeability for problems where voxels cannot be adequately segmented as discrete compositions. The voxel compositions are represented as volume fractions of various material phases and void. The numerical results have shown that, for the tight-sandstone sample, the bulk permeability is sensitive to the effective percolating fraction of calcite. That is, the subvoxel flow paths in the calcite phase are important for bulk permeability. On the other hand, flow in the calcite phase in the sandstone sample makes an insignificant contribution to the bulk permeability. The calculated permeability value for the sandstone sample is up to two orders of magnitude greater than the tight sandstone. This model is generic and could be applied to other oil and gas reservoir media or to material samples.