Synthesis of mesoporous silica from geothermal water.

Mesoporous silica was successfully synthesized for the first time using geothermal water from the Onuma Geothermal Power Plant, Akita Prefecture, Japan. Cetyltrimethylammonium bromide (CTAB) was used as an organic template for the synthesis. CTAB with a concentration of 2.4 × 10-4 mol/L was reacted for 30 min with geothermal water at a temperature of 90 °C, which had a total silicic acid concentration of 475 mg/L (SiO2), at pH 7.0, pH 8.2 (raw water) and pH 9.0. By calcination of the resulting precipitate at 550 °C, mesoporous silica with a pore size of about 2.8 nm and a specific surface area of > 800 m2/g was formed. The total silicic acid concentration in the solution after formation of the mesoporous precipitates was reduced to < 280 mg/L, indicating efficient recovery of supersaturated silicic acid from geothermal water. The monosilicic acid in geothermal water plays an important role in the formation of mesoporous silica. Production of mesoporous silica by our method will contribute not only to prevention of silica scale formation in the piping systems of geothermal power plants but also to its use as an industrial resource.

Groundwater oxygen anomaly related to the 2016 Kumamoto earthquake in Southwest Japan.

Here, we report the groundwater oxygen isotope anomalies caused by the 2016 Kumamoto earthquake (MJMA7.3) that occurred in Southwest Japan on April 16, 2016. One hundred and seventeen groundwater samples were collected from a deep well located 3 km to the southeast of the epicenter in Mifune Town, Kumamoto Prefecture; they were drinking water packed in PET bottles and distributed in the area between April 2015 and March 2018. Further, the oxygen and hydrogen isotopes were evaluated via cavity ring-down spectroscopy without performing any pretreatment. An anomalous increase was observed with respect to the δ18O value (up to 0.51‰) soon after the earthquake along with a precursory increase of 0.38‰ in January 2016 before the earthquake. During these periods, there was no noticeable change in the hydrogen isotopic ratios. Rapid crustal deformation related to the earthquake may have enhanced the microfracturing of the aquifer rocks and the production of new surfaces, inducing δ18O enrichment via oxygen isotopic exchange between rock and porewater without changing δ2H.

An automated laser fluorination technique for high-precision analysis of three oxygen isotopes in silicates.

RATIONALE: The three oxygen isotopes in terrestrial/extraterrestrial silicates can provide geochemical and cosmochemical information about their origin and secondary processes that result from isotopic exchange. A laser fluorination technique has been widely used to extract oxygen from silicates for δ17 O and δ18 O measurements by isotope ratio mass spectrometry. Continued improvement of the techniques is still important for high-precision measurement of oxygen-isotopic ratios. METHODS: We adopted an automated lasing technique to obtain reproducible fluorination of silicates using a CO2 laser-BrF5 fluorination system connected online to an isotope ratio mass spectrometer. The automated lasing technique enables us to perform high-precision analysis of the three oxygen isotopes of typical reference materials (e.g., UWG2 garnet, NBS28 quartz and San Carlos olivine) and in-house references (mid-ocean ridge basalt glass and obsidian). The technique uses a built-in application of laser control with which the laser power can be varied in a programmed manner with a defocused beam which is in a fixed position. RESULTS: The oxygen isotope ratios of some international reference materials analyzed by the manual lasing technique were found to be isotopically lighter with wider variations in δ18 O values, whereas those measured by the automated lasing technique gave better reproducibility (less than 0.2‰, 2SD). The Δ17 O values, an excess of the δ17 O value relative to the fractionation line, also showed high reproducibility (±0.02‰, 2SD). CONCLUSIONS: The system described herein provides high-precision δ17 O and δ18 O measurements of silicate materials. The use of the automated lasing technique followed by careful and controlled purification procedures is preferred to achieve satisfactory isotopic ratio results.

Groundwater oxygen isotope anomaly before the M6.6 Tottori earthquake in Southwest Japan.

Geochemical monitoring of groundwater in seismically-active regions has been carried out since 1970s. Precursors were well documented, but often criticized for anecdotal or fragmentary signals, and for lacking a clear physico-chemical explanation for these anomalies. Here we report - as potential seismic precursor - oxygen isotopic ratio anomalies of +0.24‰ relative to the local background measured in groundwater, a few months before the Tottori earthquake (M 6.6) in Southwest Japan. Samples were deep groundwater located 5 km west of the epicenter, packed in bottles and distributed as drinking water between September 2015 and July 2017, a time frame which covers the pre- and post-event. Small but substantial increase of 0.07‰ was observed soon after the earthquake. Laboratory crushing experiments of aquifer rock aimed to simulating rock deformation under strain and tensile stresses were carried out. Measured helium degassing from the rock and 18O-shift suggest that the co-seismic oxygen anomalies are directly related to volumetric strain changes. The findings provide a plausible physico-chemical basis to explain geochemical anomalies in water and may be useful in future earthquake prediction research.

Hydrogeochemistry and quality of surface water and groundwater in the vicinity of Lake Monoun, West Cameroon: approach from multivariate statistical analysis and stable isotopic characterization.

With the use of conventional hydrogeochemical techniques, multivariate statistical analysis, and stable isotope approaches, this paper investigates for the first time surface water and groundwater from the surrounding areas of Lake Monoun (LM), West Cameroon. The results reveal that waters are generally slightly acidic to neutral. The relative abundance of major dissolved species are Ca(2+) > Mg(2+) > Na(+) > K(+) for cations and HCO3 (-) â‰« NO3 (-) > Cl(-) > SO4 (2-) for anions. The main water type is Ca-Mg-HCO3. Observed salinity is related to water-rock interaction, ion exchange process, and anthropogenic activities. Nitrate and chloride have been identified as the most common pollutants. These pollutants are attributed to the chlorination of wells and leaching from pit latrines and refuse dumps. The stable isotopic compositions in the investigated water sources suggest evidence of evaporation before recharge. Four major groups of waters were identified by salinity and NO3 concentrations using the Q-mode hierarchical cluster analysis (HCA). Consistent with the isotopic results, group 1 represents fresh unpolluted water occurring near the recharge zone in the general flow regime; groups 2 and 3 are mixed water whose composition is controlled by both weathering of rock-forming minerals and anthropogenic activities; group 4 represents water under high vulnerability of anthropogenic pollution. Moreover, the isotopic results and the HCA showed that the CO2-rich bottom water of LM belongs to an isolated hydrological system within the Foumbot plain. Except for some springs, groundwater water in the area is inappropriate for drinking and domestic purposes but good to excellent for irrigation.

Bacterial and archaeal communities in Lake Nyos (Cameroon, Central Africa).

The aim of this study was to assess the microbial diversity associated with Lake Nyos, a lake with an unusual chemistry in Cameroon. Water samples were collected during the dry season on March 2013. Bacterial and archaeal communities were profiled using Polymerase Chain Reaction-Denaturing Gradient Gel Electrophoresis (PCR-DGGE) approach of the 16S rRNA gene. The results indicate a stratification of both communities along the water column. Altogether, the physico-chemical data and microbial sequences suggest a close correspondence of the potential microbial functions to the physico-chemical pattern of the lake. We also obtained evidence of a rich microbial diversity likely to include several novel microorganisms of environmental importance in the large unexplored microbial reservoir of Lake Nyos.

Oxygen isotopic fractionation of O2 during adsorption and desorption processes using molecular sieve at low temperatures.

RATIONALE: Cryogenic trapping using molecular sieves is commonly used to collect O2 extracted from silicates for (17)O/(16)O and (18)O/(16)O analyses. However, gases which interfere with (17)O/(16)O analysis, notably NF3, are also trapped and their removal is essential for accurate direct measurement of the (17)O/(16)O ratio. It is also necessary to identify and quantify any isotopic fractionation associated with the use of cryogenic trapping using molecular sieves. METHODS: The oxygen isotopic compositions of O2 before and after desorption from, and adsorption onto, 13X and 5A molecular sieves (MS13X and MS5A) at 0°C, -78°C, -114°C, and -130°C were measured in order to determine the oxygen isotopic fractionation at these temperatures. We also investigated whether isotopic fractionation occurred when O2 gas was transferred sequentially into a second cold finger, also containing molecular sieve. RESULTS: It was confirmed that significant oxygen isotopic fractionation occurs between the gaseous O2 and that adsorbed onto molecular sieve, if desorption and adsorption are incomplete. As the fraction of released or untrapped O2 becomes smaller with decreasing trapping temperature (from 0 to -130°C), the isotopic fractionation becomes larger. Approximately half of the total adsorbed O2 is released from the molecular sieve during desorption at -114°C, which is the temperature recommended for separation from NF3 (retained on the molecular sieve), and this will interfere with (17)O/(16)O measurements. CONCLUSIONS: The use of a single cold finger should be avoided, because partial desorption is accompanied by oxygen isotopic fractionation, thereby resulting in inaccurate isotopic data. The use of a dual cold finger arrangement is recommended because, as we have confirmed, the transfer of O2 from the first trap to the second is almost 100%. However, even under these conditions, a small isotopic fractionation (0.18 ± 0.05‰ in δ(17)O values and 0.26 ± 0.06‰ in δ(18)O values) occurred, with O2 in the second trap being isotopically enriched in the heavier isotopes.

Degassing Lakes Nyos and Monoun: defusing certain disaster.

Since the catastrophic releases of CO(2) in the 1980s, Lakes Nyos and Monoun in Cameroon experienced CO(2) recharge at alarming rates of up to 80 mol/m(2) per yr. Total gas pressures reached 8.3 and 15.6 bar in Monoun (2003) and Nyos (2001), respectively, resulting in gas saturation levels up to 97%. These natural hazards are distinguished by the potential for mitigation to prevent future disasters. Controlled degassing was initiated at Nyos (2001) and Monoun (2003) amid speculation it could inadvertently destabilize the lakes and trigger another gas burst. Our measurements indicate that water column structure has not been compromised by the degassing and local stability is increasing in the zones of degassing. Furthermore, gas content has been reduced in the lakes approximately 12-14%. However, as gas is removed, the pressure at pipe inlets is reduced, and the removal rate will decrease over time. Based on 12 years of limnological measurements we developed a model of future removal rates and gas inventory, which predicts that in Monoun the current pipe will remove approximately 30% of the gas remaining before the natural gas recharge balances the removal rate. In Nyos the single pipe will remove approximately 25% of the gas remaining by 2015; this slow removal extends the present risk to local populations. More pipes and continued vigilance are required to reduce the risk of repeat disasters. Our model indicates that 75-99% of the gas remaining would be removed by 2010 with two pipes in Monoun and five pipes in Nyos, substantially reducing the risks.