The International Journal of Applied Radiation and Isotopes
Low-level measurement of tritium by hydrogenation of propadiene and gas counting of propane
Abstract
A new method for low-level measurement of tritium (3H) in water is reported. In this method, a 10 or 20 ml water sample is reduced with magnesium turnings in a furnace at 570°C. The resulting hydrogen is reacted with propadiene to propane in the presence of a catalyst. The 3H concentration in the propane is counted in a 2.61 proportional counter at a pressure of 2 or 4 bars, respectively. With total measuring times up to 8500 min per sample, an experimental detection limit down to 1 TU and 3H standard reproducibilities of 1% were attained. After 20-fold electrolytic enrichment of 3H in water, the experimental detection limit can be lowered to ≤ 0.1 TU.
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Cited by (12)
Groundwater in-situ generation of aquatic humic and fulvic acids and the mineralization of sedimentary organic carbon
2000, Applied GeochemistryIn this paper the groundwater in-situ generation of dissolved organic carbon (DOC) is discussed based on the origin of groundwaters, their physico-chemical and isotopic properties, chemical composition and the dissolved inorganic carbon (DIC) concentration and its 13C content. Three aquifer systems are investigated. Two of these have relatively well defined hydrological and geochemical conditions (Fuhrberg and Munich) and are used as reference systems. The third aquifer (Gorleben) is a complex system containing DOC concentrations up to 200 mg C/L in deep groundwaters. From this aquifer system 19 groundwaters from different hydrogeochemical conditions are analyzed. The in-situ generation of DOC is found to occur in conjunction with the microbiologically mediated mineralization of sedimentary organic carbon (SOC). Thereby, SO4 is reduced and phosphate is released into the groundwater. Where SO4 is depleted, the mineralization of SOC occurs via fermentation, resulting in CH4 generation.
<sup>14</sup>C dating of Gorleben groundwater
2000, Applied GeochemistryPrevious attempts to apply 14C for dating of groundwater in the Gorleben aquifer system has given results with conflicting 3H and stable isotope data and hydrological estimates. 14C model ages of 1–10 ka have been found for 3H containing recharge water, up to 31 ka for groundwater with Holocene stable isotope signatures and 6–10 ka for groundwater at 35 m depth. In this paper it is shown, that the reasons are assumption of to high 14C concentration in recharge groundwater and not correcting for the influence of 14C dilution by dissolved inorganic C (DIC) from microbiologically mediated mineralization of organic components in deep sediments. To overcome these difficulties a new approach is applied evaluating the site-specific 14C source term (including the influence of nuclear atmospheric testing), and the already previously used overall dilution of DIC. Closed system conditions are assumed and no isotopic fractionation is considered. For most of the groundwaters, the 14C ages achieved by the present method are in agreement with 3H, stable isotopes and hydrological estimates. It is shown that down to approximately 140 m depth no 14C decay can be detected. Situations are also discussed, either where the 14C method is not applicable (shallow peat-bog like groundwater) or does not yield reliable groundwater ages (brines at <200 m depth).
Erratum: (Applied Geochemistry 12 (831-849))
1998, Applied GeochemistryHighly saline fluids were encountered during the German Continental Deep Drilling Project (KTB) from depths ranging between 2 and 3 km to about 9 km. The most reliable data were obtained from samples extracted during a long-term pumping test in the 4000-m deep KTB pilot hole. Some 460 m3 Ca–Na–Cl brines with about 68 g l−1 total dissolved solids (TDS) and some 270 m3 associated gases, mainly N2 and CH4 were pumped to the surface from the main fracture system situated near the bottom of the pilot hole. Geochemical and isotopic data support the hydraulic tests which suggest the presence of an open and large fluid reservoir at depth. The pumped fluids from this main fracture system were released from a deep reservoir situated at more than 5500 m depth which is hydraulically connected with the 9101 m deep KTB main hole, drilled some 250 m to the northeast of the pilot hole.
While Ca and Sr contents of the extracted brines may be the result of water–rock interaction, Cl is most likely of external origin. The Cl is hypothesized to derive from geotectonic processes rather than to descending infiltration of paleo-seawater (evaporitic brines). The sampled fluids have probably migrated from a deeper reservoir to their present position since the Cretaceous–Tertiary period due to tectonic activity. However, several isotopic studies have identified an admixture of descending paleowaters down to more than 4000 m depth. The high 36Cl/Cl ratio of the fluids sampled during the long-term pumping test point to a host rock highly enriched in U–Th, unlike the sampled KTB country rocks. The fluid reservoir is believed to be in contact with the Falkenberg granite massif situated about 2 km to the E of the KTB holes, capable of supplying sufficient neutron flux for considerable subsurface production of 36Cl. The Na–Cl–(K-, SO4) precursor fluids of the Ca–Na–Cl brines were produced in the course of extensive tectonic processes since the Late Caledonian within the Bohemian Massif.
On the origin of saline fluids in the KTB (Continental Deep Drilling Project of Germany)
1997, Applied GeochemistryHighly saline fluids were encountered during the German Continental Deep Drilling Project (KTB) from depths ranging between 2 and 3 km to about 9 km. The most reliable data were obtained from samples extracted during a long-term pumping test in the 4000-m deep KTB pilot hole. Some 460 m3 CaNaCl brines with about 68 g l−1 total dissolved solids (TDS) and some 270 m3 associated gases, mainly N2 and CH4 were pumped to the surface from the main fracture system situated near the bottom of the pilot hole. Geochemical and isotopic data support the hydraulic tests which suggest the presence of an open and large fluid reservoir at depth. The pumped fluids from this main fracture system were released from a deep reservoir situated at more than 5500 m depth which is hydraulically connected with the 9101 m deep KTB main hole, drilled some 250 m to the northeast of the pilot hole.
While Ca and Sr contents of the extracted brines may be the result of water-rock interaction, Cl is most likely of external origin. The Cl is hypothesized to derive from geotectonic processes rather than to descending infiltration of paleo-seawater (evaporitic brines). The sampled fluids have probably migrated from a deeper reservoir to their present position since the Cretaceous-Tertiary period due to tectonic activity. However, several isotopic studies have identified an admixture of descending paleowaters down to more than 4000 m depth. The high 36ClCl ratio of the fluids sampled during the long-term pumping test point to a host rock highly enriched in UTh, unlike the sampled KTB country rocks. The fluid reservoir is believed to be in contact with the Falkenberg granite massif situated about 2 km to the E of the KTB holes capable of supplying sufficient neutron flux for considerable subsurface production of 36C1. The NaCl(K, SO4) precursor fluids of the CaNaCI brines were produced in the course of extensive tectonic processes since the Late Caledonian within the Bohemian Massif.
Ground water chemistry and geochemical modeling of water-rock interactions at the Osamu Utsumi mine and the Morro do Ferro analogue study sites, Poços de Caldas, Minas Gerais, Brazil
1992, Journal of Geochemical ExplorationSurface and ground waters, collected over a period of three years from the Osamu Utsumi uranium mine and the Morro do Ferro thorium/rare-earth element (Th/REE) deposits, were analyzed and interpreted to identify the major hydrogeochemical processes. These results provided information on the current geochemical evolution of ground waters for two study sites within the Poços de Caldas Natural Analogue Project.
The ground waters are a KFeSO4F type, a highly unusual composition related to intense weathering of a hydrothermally altered and mineralized complex of phonolites. Tritium and stable isotope data indicate that ground waters are of meteoric origin and are not affected significantly by evaporation or water-rock interactions. Recharging ground waters at both study sites demonstrate water of less than about 35 years in age, whereas deeper, more evolved ground waters are below 1 TU but still contain in most cases detectable tritium. These deeper ground waters may be interpreted as being of 35 to 60 or more years in age, resulting mainly from an admixture of younger with older ground waters and/or indicating the influence of subsurface produced tritium.
Geochemical processes involving water-rock-gas interactions have been modeled using ground water compositions, mineralogic data, ion plots and computations of speciation, non-thermodynamic mass balance and thermodynamic mass transfer. The geochemical reaction models can reproduce the water chemistry and mineral occurrences and they were validated by comparing the results of thermodynamic mass transfer calculations (using the PHREEQE program, Parkhurst et al., 1980). The results from the geochemical reaction models reveal that the dominant processes are production of CO2 in the soil zone through aerobic decay of organic matter, dissolution of fluorite, calcite, K-feldspar, albite, chlorite and manganese oxides, oxidation of pyrite and sphalerite, and precipitation of ferric oxides, silica and kaolinite. Gibbsite precipitation can be modeled for the shallow (recharge) water chemistry at Morro do Ferro, consistent with known mineralogy. Recharge waters are undersaturated with respect to barite and discharging waters and deeper ground waters are saturated to supersaturated with respect to barite demonstrating a strong solubility control. Strontium isotope data demonstrate that sources other than calcium-bearing minerals are required to account for the dissolved strontium in the ground waters. These may include K-feldspar, smectite-chlorite mixed-layer clays and goyazite [SrAl3(PO4)2(OH)5·H2O].
Measurements and interpretations of <sup>36</sup>Cl in groundwater, Milk River aquifer, Alberta, Canada
1991, Applied GeochemistryThe36Cl/Cl ratios of 12 groundwater samples from the Milk River aquifer were determined by accelerator mass spectrometry. Using known Cl concentrations,36Cl concentrations were deduced. Approximately linear relations were observed between the logarithm of the36Cl concentration, the Cl concentration, and the distance from the recharge area along two flow paths. The results are discussed in two approaches:
- (1)
in an interpretation of the linear relation between logarithm of the36Cl concentration and Cl concentration excluding and includingin situ production of36Cl;
- (2)
in a diffusion model. The increase of the Cl concentration with the distance from the recharge area is considered to be due to diffusion of Cl from the underlying confining Colorado shale to the aquifer.
Flow velocities ranging between 0.04 and 0.14 m/a, and ages of the groundwater between 0.6 and 2 Ma are obtained at a distance of 80 km from the recharge area.
- (1)