The behaviour of metals in deep fluids of NE Iceland.

In this contribution, we present some of the first data on the elemental signature of deep crustal fluids in a basalt-hosted, low-chloride magmatic-hydrothermal system. Down-hole fluid samples (850-1600 m) from wells in the Theistareykir and Krafla geothermal fields in the Northern Volcanic Zone of Iceland were combined with well-head samples of condensed vapor, cuttings of altered rock, and fresh basalt (being some of the first concentration data for volatile and semi-volatile elements (Sb, Tl, Bi, Cd and As) for this area of Iceland). Results show that the deep fluids are relatively enriched in base metals and (semi)-volatile metals (in particular Te, Hg, Re and Tl) compared to local basalt. We interpret this enrichment in volatile metals to reflect a significant element input from magma degassing. Boiling of this deep fluid results in a well-head fluid composition that is significantly depleted in most elements. This well-head fluid has a distinct elemental signature, including a depletion in Sb that is mirrored in the altered rocks, and a depletion in the base metals that shows their selective sequestration in scale minerals, likely sulphides. As expected, the element content and patterns in surface fluids can thus not be interpreted to directly reflect that of the deep reservoir fluid. The behaviour of elements in Theistareykir and Krafla fluids is consistent, and largely agrees with similar data obtained for the Reykjanes geothermal system in SW Iceland. We therefore posit that our results are representative for this geological setting and indicate a significant magmatic degassing cation input to deep fluids, variably modified by water-rock interaction.

Seasonal variations of geofluids from mud volcano systems in the Southern Junggar Basin, NW China.

Variations in the chemical composition of geofluids and of gas fluxes are significant parameters for understanding mud volcanism and correctly estimate their emissions in carbon species, particularly greenhouse gas, methane. In this study, muddy water and gas samples were collected from the Anjihai, Dushanzi, Aiqigou, and Baiyanggou mud volcanoes in the southern Junggar Basin during the four seasons, around a year. This region hosts the most active mud volcanism throughout China. Gas and water were analyzed for major molecular compositions, carbon and hydrogen isotopes of the gas phase, as well as cations and anions, hydrogen and oxygen isotopes of water. The emitted gases are dominated by CH4 with some C2H6, CO2, and N2. The seasonal changes in the chemical composition and carbon isotopes of emitted gases are not significant, whereas clear variations in the amounts of cations and anions dissolved in the water are reported. These are higher in spring and summer than autumn and winter. The CH4, CO2, and C2H6 fluxes are 157.3-1108 kg/a, 1.8-390.1 kg/a, and 10.2-118.7 kg/a, respectively, and a clear seasonal trend of the gas seepage flux has been observed. In January, the macro-seepage flux of open vents is ≥65 % higher than in April, whereas the micro-seepage flux significantly decreased, probably due to the frozen shallow ground and blockage of soil fractures around the vents by heavy snow and ice during January. This probably causes an extra gas pressure transferred to the major vents, resulting in higher flux of the macro-seepage in the cold season. However, the total flux of the whole mud volcano system is generally consistent around a year.

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.

The growth of lithospheric diamonds.

Natural diamonds contain mineral and fluid inclusions that record diamond growth conditions. Replicating the growth of inclusion-bearing diamonds in a laboratory is therefore a novel diagnostic tool to constrain the conditions of diamond formation in Earth's lithosphere. By determining the carbon isotopic fractionation during diamond growth in fluids or melts, our laboratory experiments revealed that lithospheric monocrystalline and fibrous and coated diamonds grow similarly from redox reactions at isotopic equilibrium in water and carbonate-rich fluids or melts, and not from native carbon. These new results explain why most of the lithospheric diamonds are characterized by a common carbon isotopic fingerprint, inherited from their common parent fluids and not from the mantle assemblage.

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.

Origin of methane-rich natural gas at the West Pacific convergent plate boundary.

Methane emission from the geosphere is generally characterized by a radiocarbon-free signature and might preserve information on the deep carbon cycle on Earth. Here we report a clear relationship between the origin of methane-rich natural gases and the geodynamic setting of the West Pacific convergent plate boundary. Natural gases in the frontal arc basin (South Kanto gas fields, Northeast Japan) show a typical microbial signature with light carbon isotopes, high CH4/C2H6 and CH4/3He ratios. In the Akita-Niigata region - which corresponds to the slope stretching from the volcanic-arc to the back-arc -a thermogenic signature characterize the gases, with prevalence of heavy carbon isotopes, low CH4/C2H6 and CH4/3He ratios. Natural gases from mud volcanoes in South Taiwan at the collision zone show heavy carbon isotopes, middle CH4/C2H6 ratios and low CH4/3He ratios. On the other hand, those from the Tokara Islands situated on the volcanic front of Southwest Japan show the heaviest carbon isotopes, middle CH4/C2H6 ratios and the lowest CH4/3He ratios. The observed geochemical signatures of natural gases are clearly explained by a mixing of microbial, thermogenic and abiotic methane. An increasing contribution of abiotic methane towards more tectonically active regions of the plate boundary is suggested.

Characterizing the Noble Gas Isotopic Composition of the Barnett Shale and Strawn Group and Constraining the Source of Stray Gas in the Trinity Aquifer, North-Central Texas.

This study presents the complete set of stable noble gases for Barnett Shale and Strawn Group production gas together with stray flowing gas in the Trinity Aquifer, Texas. It places new constraints on the source of this stray gas and further shows that Barnett and Strawn gas have distinct crustal and atmospheric noble gas signatures, allowing clear identification of these two sources. Like stray gas, Strawn gas is significantly more enriched in crustal 4He*, 21Ne*, and 40Ar* than Barnett gas. The similarity of Strawn and stray gas crustal noble gas signatures suggests that the Strawn is the source of stray gas in the Trinity Aquifer. Atmospheric 22Ne/36Ar ratios of stray gas mimic also that of Strawn, further reinforcing the notion that the source of stray gas in this aquifer is the Strawn. While noble gas signatures of Strawn and stray gas are consistent with a single-stage water degassing model, a two-stage oil modified groundwater exsolution fractionation model is required to explain the light atmospheric noble gas signature of Barnett Shale production gas. These distinct Strawn and Barnett noble gas signatures are likely the reflection of distinct evolution histories with Strawn gas being possibly older than that of Barnett Shale.

Regional assessment of concentrations and sources of pharmaceutically active compounds, pesticides, nitrate, and E. coli in post-glacial aquifer environments (Canada).

There is growing concern worldwide about the exposure of groundwater resources to pharmaceutically active compounds (PhACs) and agricultural contaminants, such as pesticides, nitrate, and Escherichia coli. For regions with a low population density and an abundance of water, regional contamination assessments are not carried out systematically due to the typically low concentrations and high costs of analyses. The objectives of this study were to evaluate regional-scale contaminant distributions in untreated groundwater in a rural region of Quebec (Canada). The geological and hydrogeological settings of this region are typical of post-glacial regions around the world, where groundwater flow can be complex due to heterogeneous geological conditions. A new spatially distributed Anthropogenic Footprint Index (AFI), based on land use data, was developed to assess surface pollution risks. The Hydrogeochemical Vulnerability Index (HVI) was computed to estimate aquifer vulnerability. Nine wells had detectable concentrations of one to four of the 13 tested PhACs, with a maximum concentration of 116ng·L-1 for benzafibrate. A total of 34 of the 47 tested pesticides were detected in concentrations equal to or greater than the detection limit, with a maximum total pesticide concentration of 692ng·L-1. Nitrate concentrations exceeded 1mg·L-1 N-NO3 in 15.3% of the wells, and the Canadian drinking water standard was exceeded in one well. Overall, 13.5% of the samples had detectable E. coli. Including regional-scale sources of pollutants to the assessment of aquifer vulnerability with the AFI did not lead to the identification of contaminated wells, due to the short groundwater flow paths between recharge and the sampled wells. Given the occurrence of contaminants, the public health concerns stemming from these new data on regional-scale PhAC and pesticide concentrations, and the local flow conditions observed in post-glacial terrains, there is a clear need to investigate the sources and behaviours of local-scale pollutants.

Exploring 222Rn as a tool for tracing groundwater inflows from eskers and moraines into slope peatlands of the Amos region of Quebec, Canada.

Peatlands can play an important role in the hydrological dynamics of a watershed. However, interactions between groundwater and peat water remain poorly understood. Here, we present results of an exploratory study destined to test radon (222Rn) as a potential tracer of groundwater inflows from fluvioglacial landform aquifers to slope peatlands in the Amos region of Quebec, Canada. 222Rn occurs in groundwater but is expected to be absent from peat water because of its rapid degassing to the atmosphere. Any 222Rn activity detected in peat water should therefore derive from groundwater inflow. 222Rn activity was measured in groundwater from municipal, domestic wells and newly drilled and instrumented piezometers from the Saint-Mathieu-Berry and Barraute eskers (n = 9), from the Harricana Moraine (n = 4), and from the fractured bedrock (n = 3). Forty measurements of 222Rn activity were made from piezometers installed in five slope peatlands, along six transects oriented perpendicular to the fluvioglacial deposits. The relationship between 222Rn and total dissolved solids (TDS) measured in water from the mineral deposits underlying the peat layer suggests that 222Rn is introduced by lateral inflow from eskers and moraine together with salinity. This input is then diluted by peat water, depleted in both TDS and 222Rn. The fact that a relationship between TDS and 222Rn is visible calls for a continuous inflow of groundwater from lateral eskers/moraines, being 222Rn rapidly removed from the system by radioactive decay. Although more research is required to improve the sampling and tracing techniques, this work shows the potential of 222Rn tracer to identify groundwater inflow areas from granular aquifers found in eskers and moraines to slope peatlands.

Anthropogenic and natural methane emissions from a shale gas exploration area of Quebec, Canada.

The increasing number of studies on the determination of natural methane in groundwater of shale gas prospection areas offers a unique opportunity for refining the quantification of natural methane emissions. Here methane emissions, computed from four potential sources, are reported for an area of ca. 16,500km(2) of the St. Lawrence Lowlands, Quebec (Canada), where Utica shales are targeted by the petroleum industry. Methane emissions can be caused by 1) groundwater degassing as a result of groundwater abstraction for domestic and municipal uses; 2) groundwater discharge along rivers; 3) migration to the surface by (macro- and micro-) diffuse seepage; 4) degassing of hydraulic fracturing fluids during first phases of drilling. Methane emissions related to groundwater discharge to rivers (2.47×10(-4) to 9.35×10(-3)Tgyr(-1)) surpass those of diffuse seepage (4.13×10(-6) to 7.14×10(-5)Tgyr(-1)) and groundwater abstraction (6.35×10(-6) to 2.49×10(-4)Tgyr(-1)). The methane emission from the degassing of flowback waters during drilling of the Utica shale over a 10- to 20-year horizon is estimated from 2.55×10(-3) to 1.62×10(-2)Tgyr(-1). These emissions are from one third to sixty-six times the methane emissions from groundwater discharge to rivers. This study shows that different methane emission sources need to be considered in environmental assessments of methane exploitation projects to better understand their impacts.

Ten-year helium anomaly prior to the 2014 Mt Ontake eruption.

Mt Ontake in central Japan suddenly erupted on 27(th) September 2014, killing 57 people with 6 still missing. It was a hydro-volcanic eruption and new magmatic material was not detected. There were no precursor signals such as seismicity and edifice inflation. It is difficult to predict hydro-volcanic eruptions because they are local phenomena that only affect a limited area surrounding the explosive vent. Here we report a long-term helium anomaly measured in hot springs close to the central cone. Helium-3 is the most sensitive tracer of magmatic volatiles. We have conducted spatial surveys around the volcano at once per few years since November 1981. The (3)He/(4)He ratios of the closest site to the cone stayed constant until June 2000 and increased significantly from June 2003 to November 2014, while those of distant sites showed no valuable change. These observations suggest a recent re-activation of Mt Ontake and that helium-3 enhancement may have been a precursor of the 2014 eruption. We show that the eruption was ultimately caused by the increased input of magmatic volatiles over a ten-year period which resulted in the slow pressurization of the volcanic conduit leading to the hydro-volcanic event in September 2014.

Methane baseline concentrations and sources in shallow aquifers from the shale gas-prone region of the St. Lawrence lowlands (Quebec, Canada).

Hydraulic fracturing is becoming an important technique worldwide to recover hydrocarbons from unconventional sources such as shale gas. In Quebec (Canada), the Utica Shale has been identified as having unconventional gas production potential. However, there has been a moratorium on shale gas exploration since 2010. The work reported here was aimed at defining baseline concentrations of methane in shallow aquifers of the St. Lawrence Lowlands and its sources using δ(13)C methane signatures. Since this study was performed prior to large-scale fracturing activities, it provides background data prior to the eventual exploitation of shale gas through hydraulic fracturing. Groundwater was sampled from private (n = 81), municipal (n = 34), and observation (n = 15) wells between August 2012 and May 2013. Methane was detected in 80% of the wells with an average concentration of 3.8 ± 8.8 mg/L, and a range of <0.0006 to 45.9 mg/L. Methane concentrations were linked to groundwater chemistry and distance to the major faults in the studied area. The methane δ(1)(3)C signature of 19 samples was > -50‰, indicating a potential thermogenic source. Localized areas of high methane concentrations from predominantly biogenic sources were found throughout the study area. In several samples, mixing, migration, and oxidation processes likely affected the chemical and isotopic composition of the gases, making it difficult to pinpoint their origin. Energy companies should respect a safe distance from major natural faults in the bedrock when planning the localization of hydraulic fracturation activities to minimize the risk of contaminating the surrounding groundwater since natural faults are likely to be a preferential migration pathway for methane.

(222)Rn activity in groundwater of the St. Lawrence Lowlands, Quebec, eastern Canada: relation with local geology and health hazard.

One hundred ninety-eight groundwater wells were sampled to measure the (222)Rn activity in the region between Montreal and Quebec City, eastern Canada. The aim of this study was to relate the spatial distribution of (222)Rn activity to the geology and the hydrogeology of the study area and to estimate the potential health risks associated with (222)Rn in the most populated area of the Province of Quebec. Most of the groundwater samples show low (222)Rn activities with a median value of 8.6 Bq/L. Ninety percent of samples show (222)Rn activity lower than 100 Bq/L, the exposure limit in groundwater recommended by the World Health Organization. A few higher (222)Rn activities (up to 310 Bq/L) have been measured in wells from the Appalachian Mountains and from the magmatic intrusion of Mont-Saint-Hilaire, known for its high level of indoor radon. The spatial distribution of (222)Rn activity seems to be related mainly to lithology differences between U-richer metasediments of the Appalachian Mountains and magmatic intrusions and the carbonaceous silty shales of the St. Lawrence Platform. Radon is slightly enriched in sodium-chlorine waters that evolved at contact with clay-rich formations. (226)Ra, the parent element of (222)Rn could be easily adsorbed on clays, creating a favorable environment for the production and release of (222)Rn into groundwater. The contribution of groundwater radon to indoor radon or by ingestion is minimal except for specific areas near Mont-Saint-Hilaire or in the Appalachian Mountains where this contribution could reach 45% of the total radioactive annual dose.