Multiscale off-fault brecciation records coseismic energy budget of principal fault zone.

Breccia and pulverized rock are typical textures in off-fault damage adjacent to a main seismogenic zone. Previously, by estimating the energy required to advance the rupture in this zone using particle size distribution at sub-millimeter/micrometer scales, we could constrain the energy budget during coseismic events. However, whether microscopic estimation is sufficient to capture surface energy fragmentation during an earthquake and the effect of measurement scale variation on calculation of co-seismic energy partitioning remained unclear. Here, we investigated the mechanism of coseismic off-fault damage based on field and microstructural observations of a well-exposed breccia body in Ichinokawa, Japan. We used in situ clast measurements coupled with thin-section analysis of breccia clasts to estimate the energy budget of the damage zone adjacent to the principal slip zone of the Median Tectonic Line (MTL). The total surface energy density and corresponding surface energy per unit fault for a width of ~ 500 m of the dynamical damage zone were estimated. The moment magnitude estimated based on surface energy was 5.8-8.3 Mw. In Ichinokawa, off-fault fragmentation is initiated by coseismic activity and is followed by fluid activity. Under dynamic fragmentation conditions, the scale is important to calculate the surface energy.

Upcycling air pollutants to fuels and chemicals via electrochemical reduction technology.

The intensification of fossil fuel usage results in significant air pollution levels. Efforts have been put into developing efficient technologies capable of converting air pollution into valuable products, including fuels and valuable chemicals (e.g., CO2 to hydrocarbon and syngas and NOx to ammonia). Among the strategic efforts to mitigate the excessive concentration of CO2 and NOx pollutants in the atmosphere, the electrochemical reduction technology of CO2 (CO2RR) and NOx (NOxRR) emerges as one of the most promising approaches. It is even more attractive if CO2RR and NOxRR are paired with renewables to store intermittent electricity in the form of chemical feedstocks. This review provides an overview of the electrochemical reduction process to convert CO2 to C1 and/or C2+ chemicals and NOx to ammonia (NH3) with a focus on electrocatalysts, electrolytes, electrolyzer, and catalytic reactor designs toward highly selective electrochemical conversion of the desired products. While the attempts in these aspects are enormous, economic consideration and environmental feasibility for actual implementation are not comprehensively provided. We discuss CO2RR and NOxRR from the life cycle and techno-economic analyses to perceive the feasibility of the current achievements. The remaining challenges associated with the industrial implementation of electrochemical CO2 and NOx reduction are additionally provided.

Agent based simulation with data driven parameterization for evaluation of social acceptance of a geothermal development: a case study in Tsuchiyu, Fukushima, Japan.

Development of geothermal power plants and local geothermal energy initiatives have lagged due to the social problems such as conflicts with stakeholders such as Onsen (Hot Spa) owners, despite the abundant geothermal resources. Study area was Tsuchiyu Onsen in Fukushima prefecture, Tohoku (Northeast) District, Japan, where the Great East Japan Earthquake and Fukushima Nuclear Accident occurred in 2011, and the reconstruction and local initiatives of geothermal energy were still unclear. Agent-based modeling is an effective methodology for modeling and analysis of opinion formation. Parameter estimation method was proposed to extract appropriate parameters from various factors through a Bayesian Network. The characteristics of stakeholders and communities that affected opinion formation in the survey area were successfully extracted. Here we show the sufficient methodology to quantify the characteristics of each person using survey data, and to extract the parameters of the agent by data-driven inverse analysis. By using this methodology, we could reproduce opinion diversity, which is a property of opinion formation in real communities. This result suggests that the model replicates the actual formation of opinion in Tsuchiyu, where the economy was boosted by the construction of a binary cycle power plant.

Volatile-consuming reactions fracture rocks and self-accelerate fluid flow in the lithosphere.

Hydration and carbonation reactions within the Earth cause an increase in solid volume by up to several tens of vol%, which can induce stress and rock fracture. Observations of naturally hydrated and carbonated peridotite suggest that permeability and fluid flow are enhanced by reaction-induced fracturing. However, permeability enhancement during solid-volume-increasing reactions has not been achieved in the laboratory, and the mechanisms of reaction-accelerated fluid flow remain largely unknown. Here, we present experimental evidence of significant permeability enhancement by volume-increasing reactions under confining pressure. The hydromechanical behavior of hydration of sintered periclase [MgO + H2O → Mg(OH)2] depends mainly on the initial pore-fluid connectivity. Permeability increased by three orders of magnitude for low-connectivity samples, whereas it decreased by two orders of magnitude for high-connectivity samples. Permeability enhancement was caused by hierarchical fracturing of the reacting materials, whereas a decrease was associated with homogeneous pore clogging by the reaction products. These behaviors suggest that the fluid flow rate, relative to reaction rate, is the main control on hydromechanical evolution during volume-increasing reactions. We suggest that an extremely high reaction rate and low pore-fluid connectivity lead to local stress perturbations and are essential for reaction-induced fracturing and accelerated fluid flow during hydration/carbonation.

Machine-learning techniques for quantifying the protolith composition and mass transfer history of metabasalt.

The mass transfer history of rocks provides direct evidence for fluid-rock interaction within the lithosphere and is recorded by compositional changes, especially in trace elements. The general method adopted for mass transfer analysis is to compare the composition of the protolith/precursor with that of metamorphosed/altered rocks; however, in many cases the protolith cannot be sampled. With the aim of reconstructing the mass transfer history of metabasalt, this study developed protolith reconstruction models (PRMs) for metabasalt using machine-learning algorithms. We designed models to estimate basalt trace-element concentrations from the concentrations of a few (1-9) trace elements, trained with a compositional dataset for fresh basalts, including mid-ocean ridge, ocean-island, and volcanic arc basalts. The developed PRMs were able to estimate basalt trace-element compositions (e.g., Rb, Ba, U, K, Pb, Sr, and rare-earth elements) from only four input elements with a reproducibility of ~ 0.1 log10 units (i.e., ± 25%). As a representative example, we present PRMs where the input elements are Th, Nb, Zr, and Ti, which are typically immobile during metamorphism. Case studies demonstrate the applicability of PRMs to seafloor altered basalt and metabasalt. This method enables us to analyze quantitative mass transfer in regional metamorphic rocks or alteration zones where the protolith is heterogeneous or unknown.

Assessment of heavy metal pollution and ecological risk in river water and sediments in a historically metal mined watershed, Northeast Japan.

Mining legacies continue to impact the geochemical cycles in historically mined watersheds after mine closure. The Hokuroku District in Northeast Japan is a famous metal mining area with a long mining history; however, studies on the distribution mechanisms and pollution characteristics of heavy metals in these historically mined watersheds after the boom period of mining activities are lacking. This study aims to provide fundamental insights into the effects of the mining activities and hydrological conditions on heavy metal pollution in the Kosaka watershed, Hokuroku District. Sampling was performed in terms of watershed segmentation, and the outlet of the tributary within each sub-watershed was also sampled to capture the diffusional pollution status. The distributions of Zn, Cu, Cd, Pb and As in river water and sediments, as well as their pollution characteristics and ecological risks, were analysed under different hydrological conditions. Our findings provide evidence of the ecological risk in surface water induced by Zn, Cu and Pb pollution in the Kosaka River system. In a high proportion of the sub-watershed, there was moderate to strong enrichment in Cd, Cu and Zn in the river sediments. The sub-watersheds with high pollution levels and ecological risk were highly consistent with the sub-watersheds encompassing abandoned mine sites. Suspended particles carried large amounts of Pb and Cu, especially on rainy days. The heavy metal contents in river water were very sensitive to occasional rainfall events; rainy days posed the most risk to organisms in the Kosaka River, followed by the low-water-level season and the high-water-level season.

Enhancement of aragonite mineralization with a chelating agent for CO2 storage and utilization at low to moderate temperatures.

Among the CaCO3 polymorphs, aragonite demonstrates a better performance as a filler material in the paper and plastic industries. Despite being ideal from the environmental protection perspective, the production of aragonite particles via CO2 mineralization of rocks is hindered by the difficulty in achieving high production efficiencies and purities, which, however, can be mitigated by exploiting the potential ability of chelating agents on metal ions extraction and carbonation controlling. Herein, chelating agent N,N-dicarboxymethyl glutamic acid (GLDA) was used to enhance the extraction of Ca from calcium silicate and facilitate the production of aragonite particles during the subsequent Ca carbonation. CO2 mineralization was promoted in the presence of 0.01-0.1 M GLDA at ≤ 80 °C, with the maximal CaCO3 production efficiency reached 308 g/kg of calcium silicate in 60 min using 0.03 M GLDA, which is 15.5 times higher than that without GLDA. In addition, GLDA showed excellent effects on promoting aragonite precipitation, e.g., the content of aragonite was only 5.1% in the absence of GLDA at 50 °C, whereas highly pure (> 90%, increased by a factor of 18) and morphologically uniform aragonite was obtained using ≥ 0.05 M GLDA under identical conditions. Aragonite particle morphologies could also be controlled by varying the GLDA concentration and carbonation temperature. This study proposed a carbon-negative aragonite production method, demonstrated the possibility of enhanced and controlled aragonite particle production during the CO2 mineralization of calcium silicates in the presence of chelating agents.

Hydrotransport-Oriented Zn, Cu, and Pb Behavior Assessment and Source Identification in the River Network of a Historically Mined Area in the Hokuroku Basin, Northeast Japan.

Aquatic ecosystems continuously receive potentially hazardous heavy metals from natural and anthropogenic sources. Focusing on the origin of heavy metals, this study aims to estimate the load contribution of tributaries from individual watershed and human drainage and to dissect the source of heavy metals, as commonly required for environmental impact assessment. Using integrated water dynamics, Geographic Information System (GIS), and chemical analysis, we identified and evaluated the heavy metal sources of the Kosaka river system in Hokuroku basin, which is a historically mined area in Northeast Japan, both in the high-water and low-water seasons. The migration and diffusion behaviors of heavy metals along with hydro-transport were analyzed, and the effects of mining activities on regional water quality both in the high-water and low-water seasons were clarified. The results indicate that Zn pollution was obvious in the Kosaka River network, especially in the downstream area. The spatial heterogeneity of heavy metal outflows from tributary watersheds was obvious, and the variations had strong correlations with mine site locations. The heavy metal flows in the mainstream increased sharply in the vicinity downstream of the Kosaka refinery drainage outlets. Compared to the low-water season, the influences of human drainage were slighter in high-water season, with lower contribution rates due to the dilution effect of the greater water discharge. Downscale sampling is effective to identify pollutant sources in regional basins.

Silica nanoparticles produced by explosive flash vaporization during earthquakes.

Hydrothermal activity in the crust results in the precipitation of large volumes of silica and often involves the formation of ore deposits, the shaping of geothermal systems, and recurring earthquakes. Pore fluid pressures fluctuate between lithostatic and hydrostatic, depending on seismic activity, and some models suggest the possibility of flash vaporization, given that fluid pressures can drop to the level of vapour at fault jogs during seismic slip. The phase changes of water could create extremely high supersaturations of silica, but the mechanisms of quartz vein formation under such extreme conditions remain unclear. Here we describe flash experiments conducted with silica-saturated solutions under conditions ranging from subcritical to supercritical. We found that amorphous silica is produced instantaneously as spherical nano- to micron-scale particles via nucleation and aggregation during the evaporation of water droplets. The nanoparticles are transformed to microcrystalline quartz very rapidly by dissolution and precipitation in hydrothermal solutions, with this process requiring less than one day under supercritical conditions because of the huge surface areas involved. We suggest that such short-lived silica nanoparticles have significant impacts on the dynamic changes in mechanical behaviour and hydrology of hydrothermal systems in volcanic areas.

Cloud-fracture networks as a means of accessing superhot geothermal energy.

Superhot geothermal environments (above ca. 400 °C) represent a new geothermal energy frontier. However, the networks of permeable fractures capable of storing and transmitting fluids are likely to be absent in the continental granitic crust. Here we report the first-ever experimental results for well stimulation involving the application of low-viscosity water to granite at temperatures ≥400 °C under true triaxial stress. This work demonstrates the formation of a network of permeable microfractures densely distributed throughout the entire rock body, representing a so-called cloud-fracture network. Fracturing was found to be initiated at a relatively low injection pressure between the intermediate and minimum principal stresses and propagated in accordance with the distribution of preexisting microfractures, independent of the directions of the principal stresses. This study confirms the possibility of well stimulation to create excellent fracture patterns that should allow the effective extraction of thermal energy.

Effects of soil erosion and anoxic-euxinic ocean in the Permian-Triassic marine crisis.

The largest mass extinction of biota in the Earth's history occurred during the Permian-Triassic transition and included two extinctions, one each at the latest Permian (first phase) and earliest Triassic (second phase). High seawater temperature in the surface water accompanied by euxinic deep-intermediate water, intrusion of the euxinic water to the surface water, a decrease in pH, and hypercapnia have been proposed as direct causes of the marine crisis. For the first-phase extinction, we here add a causal mechanism beginning from massive soil and rock erosion and leading to algal blooms, release of toxic components, asphyxiation, and oxygen-depleted nearshore bottom water that created environmental stress for nearshore marine animals. For the second-phase extinction, we show that a soil and rock erosion/algal bloom event did not occur, but culmination of anoxia-euxinia in intermediate waters did occur, spanning the second-phase extinction. We investigated sedimentary organic molecules, and the results indicated a peak of a massive soil erosion proxy followed by peaks of marine productivity proxy. Anoxic proxies of surface sediments and water occurred in the shallow nearshore sea at the eastern and western margins of the Paleotethys at the first-phase extinction horizon, but not at the second-phase extinction horizon. Our reconstruction of ocean redox structure at low latitudes indicates that a gradual increase in temperature spanning the two extinctions could have induced a gradual change from a well-mixed oxic to a stratified euxinic ocean beginning immediately prior to the first-phase extinction, followed by culmination of anoxia in nearshore surface waters and of anoxia and euxinia in the shallow-intermediate waters at the second-phase extinction over a period of approximately one million years or more. Enhanced global warming, ocean acidification, and hypercapnia could have caused the second-phase extinction approximately 60 kyr after the first-phase extinction. The causes of the first-phase extinction were not only those environmental stresses but also environmental stresses caused by the soil and rock erosion/algal bloom event.

Machine-learning techniques for geochemical discrimination of 2011 Tohoku tsunami deposits.

Geochemical discrimination has recently been recognised as a potentially useful proxy for identifying tsunami deposits in addition to classical proxies such as sedimentological and micropalaeontological evidence. However, difficulties remain because it is unclear which elements best discriminate between tsunami and non-tsunami deposits. Herein, we propose a mathematical methodology for the geochemical discrimination of tsunami deposits using machine-learning techniques. The proposed method can determine the appropriate combinations of elements and the precise discrimination plane that best discerns tsunami deposits from non-tsunami deposits in high-dimensional compositional space through the use of data sets of bulk composition that have been categorised as tsunami or non-tsunami sediments. We applied this method to the 2011 Tohoku tsunami and to background marine sedimentary rocks. After an exhaustive search of all 262,144 (= 2(18)) combinations of the 18 analysed elements, we observed several tens of combinations with discrimination rates higher than 99.0%. The analytical results show that elements such as Ca and several heavy-metal elements are important for discriminating tsunami deposits from marine sedimentary rocks. These elements are considered to reflect the formation mechanism and origin of the tsunami deposits. The proposed methodology has the potential to aid in the identification of past tsunamis by using other tsunami proxies.

The fate of arsenic in a river acidified by volcanic activity and an acid thermal water and sedimentation mechanism.

The Shozu-gawa river, located in the Aomori Prefecture, northern Japan, is affected by volcanic activities and acid thermal waters. The river is unique because both solid arsenic (As; as orpiment, As2S3) and dissolved As are supplied to the river from the uppermost caldera lake (Usori-ko Lake) and thermal ponds. The watershed is an excellent site for investigating the fate of different As species in a fluvial system. Upstream sediments near the caldera lake and geothermal ponds are highly contaminated by orpiment. This solid phase is transported as far as the mouth of the river. On the other hand, dissolved As is removed from the river system by hydrous ferric oxides (HFOs); however, HFO formation and removal of dissolved As do not occur in the uppermost area of the watershed, resulting in further downstream transport of dissolved As. Consequently, upstream river sediments are enriched in orpiment, whereas As(v), which is associated with HFOs in river sediments, increases downstream. Furthermore, orpiment particles are larger, and possibly heavier, than those of HFO with sorbed As. Fractionation between different chemical states of As during transport in the Shozu-gawa river is facilitated not only by chemical processes (i.e., sorption of dissolved As by HFOs), but also by physical factors (i.e., gravity). In contrast to acid mine drainage (AMD), in some areas of the Shozu-gawa river, both solid forms of As (as sulfide minerals) and dissolved As are introduced into the aquatic system. Considering that the stabilities of sulfide minerals are rather different from those of oxides and hydroxides, river sediments contacted with thermal waters possibly act as sources of As under both aerobic and anaerobic conditions.

Distribution coefficients (K(d)) of stable iodine in estuarine and coastal regions, Japan, and their relationship to salinity and organic carbon in sediments.

The sediment-water distribution coefficient, (K(d)), is one of the most important parameters in radionuclide assessment models. In this study, we determined K ds of stable iodine (I) in estuarine and coastal regions. We studied 16 estuarine and coastal regions of Japan and obtained I data on water and sediments. Data on salinity, pH, dissolved organic carbon and dissolved oxygen in water, and organic carbon (OC) in sediments were also obtained as estuarine variables. Determined (K(d))S of I in the Sagami River estuary decreased along the salinity gradient (salinity range, 0.1-33.8), indicating that salinity is one of the important factors controlling the (K(d)) values; however, when the (K(d)) values were compared among all the estuaries, the difference between minimum and maximum (K(d)) values varied by about two orders of magnitude in a narrow salinity range of 30.0-34.4. A significant correlation between (K(d)) value and OC content in sediments was observed in all the stations with a salinity of ≥ 30 except for stations in the Ishikari and Onga River estuaries. The exceptions are probably due to different sources of the sediments, which are explained by the results of relatively low I/OC ratios in sediments in those two estuaries, compared to the other estuaries. Thus, OC in sediments as well as salinity may be responsible for the variation of (K(d))S of I in the estuarine and coastal regions.

Application of a dynamic reaction cell (DRC) ICP-MS in chromium and iron determinations in rock, soil and terrestrial water samples.

Despite environmental and geochemical interests, Cr and Fe have been left beyond the reach of determinations by ICP-MS due to severe interferences originating from Ar. The applicability of a dynamic reaction cell (DRC)-ICP-MS has been examined for determinations in environmental and geochemical samples. The reaction with NH(3) in the DRC system provides an eligible technique to determine Cr, because of a greater improvement in the signal/noise (S/N) ratio due to an effective elimination of interferences arising from Ar (ArC, ArN and ArO), and makes it possible to analyze Cr even at sub-microg L(-1) levels. As compared to non-DRC mode analyses, the DRC technique using m/z 56 appeared to be preferable for Fe determination in most terrestrial waters because of effective suppression of (40)Ar(16)O(+). In addition, the effects of cluster ions, such as (39)K(14)N(1)H(3)(+) and (40)Ca(14)N(1)H(2)(+), on Fe determination were also negligibly small. Measurements using (54)Fe by the DRC mode are also advantageous for Ca-rich samples, such as limestone and dolomite.

Application of TL as a geochemical sensor.

Two-dimensional thermoluminescence (TL) and spectroscopy of rock samples were measured to identify a mass transport front in rock matrix. Samples were selected from the Kamaishi Mine including the hydrothermal mineral veins and the surrounding altered zone. Results showed some different distribution of TL intensity between the altered and unaltered zones. Minerals in the altered zone showed stronger TL than those in the unaltered zone, and different phenomena for wavelength could be observed between them. Therefore, it could possibly be shown that TL can be used as a chemical sensor, which identifies mass change (transport front in rocks), by using these TL methods.