| 1. |
- Drake, Henrik, et al.
(författare)
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Extreme fractionation and micro-scale variation of sulphur isotopes during bacterial sulphate reduction in deep groundwater systems
- 2015
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Ingår i: Geochimica Et Cosmochimica Acta. - : Elsevier BV. - 0016-7037 .- 1872-9533. ; 161, s. 1-18
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Tidskriftsartikel (refereegranskat)abstract
- This study conducted at the Aspo Hard Rock Laboratory, SE Sweden, determines the extent and mechanisms of sulphur-isotope fractionation in permanently reducing groundwater in fractured crystalline rock. Two boreholes > 400 m below the ground surface were investigated. In the 17-year-old boreholes, the Al instrumentation pipes had corroded locally (i.e., Al[oxy] hydroxides had formed) and minerals (i.e., pyrite, iron monosulphide, and calcite) had precipitated on various parts on the equipment. By chemically and isotopically comparing the precipitates on the withdrawn instrumentation and the borehole waters, we gained new insight into the dynamics of sulphate reduction, sulphide precipitation, and sulphur-isotope fractionation in deep-seated crystalline-rock settings. An astonishing feature of the pyrite is its huge variability in delta S-34, which can exceed 100 parts per thousand in total (i.e., -47.2 to +53.3 parts per thousand) and 60 parts per thousand over 50 mu m of growth in a single crystal. The values at the low end of the range are up to 71 parts per thousand lower than measured in the dissolved sulphate in the water (20-30 parts per thousand), which is larger than the maximum difference reported between sulphate and sulphide in pure-culture experiments (66 parts per thousand) but within the range reported from natural sedimentary settings. Although single-step reduction seems likely, further studies are needed to rule out the effects of possible S disproportionation. The values at the high end of the range (i.e., high delta S-34(py)) are much higher than could be produced from the measured sulphate under any biogeochemical conditions. This strongly suggests the development of closed-system conditions near the growing pyrite, i.e., the rate of sulphate reduction exceeds the rate of sulphate diffusion in the local fluid near the pyrite, causing the local aqueous phase (and thus the forming pyrite) to become successively enriched in heavy S (S-34). Consequently, the delta S-34 values of the forming pyrite become exceptionally high and strongly decoupled from the delta S-34 values of the sulphate in the bulk fluid. The Al-(oxy) hydroxide and calcite precipitates are explained by a combination of deposit and galvanic corrosion initiated by Al corrosion by H2S produced by sulphate-reducing microorganisms. (C) 2015 Elsevier Ltd. All rights reserved.
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| 2. |
- Drake, Henrik, 1979, et al.
(författare)
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Distinguished multiple events of fracture mineralisation related to far-field orogenic effects in Paleoproterozoic crystalline rocks, Simpevarp area, SE Sweden
- 2009
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Ingår i: Lithos. - : Elsevier BV. - 0024-4937. ; 110:1-4, s. 37-49
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Tidskriftsartikel (refereegranskat)abstract
- Detailed investigations of fracture minerals have been carried out in the Simpevarp area, SE Sweden. in order to reveal the low-temperature evolution of the site and to discern different events of deformation, especially in the brittle regime. The study is part of the site characterisation programme for a potential deep-seated repository for spent nuclear fuel. The bedrock in the area is composed of generally un-metamorphosed 1.8 Ga crystalline rocks. Detailed SEM investigations of cross-cutting fracture mineralisations have revealed several generations of fillings formed at gradually lower temperatures during repeated events of fracturing and reactivation from the Paleoproterozoic until the Quaternary. Ar-40/Ar-39 geochronology, and fracture orientation analyses have been used to relate each fracture filling generation to geological events, such as far-field effects from orogenies, as well as more local effects related to intrusions. Fracturing and formation of different fracture mineral parageneses during at least four different orogenies have been indicated: the waning stages of the Svecokarelian orogeny (> 1.75 Ga), the Danopolonian orogeny (similar to 1.47-1.44 Ga), the Sveconorwegian orogeny (similar to 1.1-0.9 Ga) and the Caledonian orogeny (similar to 0.5-0.4 Ga). The fracture minerals and greisen related to the Danopolonian orogeny mainly formed in relation to the intrusion of two indicatively Danopolonian-related granites nearby. Furthermore, periods of extension are indicated in the area by the presence of late-Sveconorwegian dolerites. Fractures filled with lower Cambrian sandstone are plausibly formed in relation to far-field extensional effects of the opening of the Iapetus Ocean. Fracture minerals of Paleozoic age or younger show influence of loading and unloading cycles. The youngest fracture minerals identified indicate precipitation from waters of similar composition as the present groundwater. (C) 2008 Elsevier B.V. All rights reserved.
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| 3. |
- Sandström, Björn, 1976, et al.
(författare)
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Brittle tectonothermal evolution in the Forsmark area, central Fennoscandian Shield, recorded by paragenesis, orientation and Ar-40/Ar-39 geochronology of fracture minerals
- 2009
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Ingår i: Tectonophysics. - : Elsevier BV. - 0040-1951. ; 478:3-4, s. 158-174
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Forskningsöversikt (refereegranskat)abstract
- In this paper, we show how studies of fracture mineral paragenesis, their orientation and Ar-40/Ar-39 geochronology can be applied in order to recognise the brittle tectonothermal evolution in an area. Samples were selected from nearly 18 km of drill cores from the upper I km of the Fennoscandian Shield obtained during the site investigation for a repository of spent nuclear fuel in Forsmark, central Sweden. Four major events of fracturing and/or reactivation of fractures associated with fracture mineralisation have been distinguished. The first event was characterised by precipitation of epidote, quartz and chlorite, along preferably sub-horizontal and gently-dipping fractures or steep, WNW-ESE to NW-SE fractures. Precipitation occurred between 1.8 and 1.1 Ga, possibly during the late stage of the Svecokarelian orogeny close to 1.8-1.7 Ga. The second event is associated with precipitation of hematite-stained adularia and albite, prehnite, laumontite, calcite and chlorite, preferably along steep, ENE-WSW to NNE-SSW and NNW-SSE fractures. Precipitation occurred around 1107 +/- 7 to 1034 +/- 3 Ma, probably due to effects from the Sveconorwegian orogeny. This event was followed by a period with dissolution of fracture minerals and subsequent precipitation of mainly calcite, quartz, pyrite and asphaltite during the Palaeozoic. The formation fluid emanated from an overlying organic-rich sedimentary cover. Precipitation occurred during reactivation of Proterozoic fractures, but formation of new fractures is also inferred, possibly due to far-field effects of the Caledonian orogeny, or elevated hydrostatic pressure due to its foreland basin. The latest event is dominated by clay minerals, chlorite and calcite along hydraulically conductive fractures. These minerals are prominent along sub-horizontal and gently-dipping fractures, but also occur in sets of steeply-dipping fractures. It is inferred that the hydraulically conductive fractures are Proterozoic structures in which mineral precipitation has occurred during a long period. However, some of the near-surface, sub-horizontal fractures may be Quaternary in age. (C) 2009 Elsevier B.V. All rights reserved.
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| 4. |
- Sandström, Björn, 1976, et al.
(författare)
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Episodic fluid migration in the Fennoscandian Shield recorded by stable isotopes, rare earth elements and fluid inclusions in fracture minerals at Forsmark, Sweden
- 2009
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Ingår i: Chemical Geology. - : Elsevier BV. - 0009-2541. ; 266, s. 135-151
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Tidskriftsartikel (refereegranskat)abstract
- Drilling through the Palaeoproterozoic bedrock at Forsmark, central Sweden, during the site investigation for a potential geological repository of highly radioactive nuclear waste has provided high quality drill-core material from the upper 1 km of the Fennoscandian Shield. Analyses of stable isotopes (δ13C, δ18O, δ34S, 87Sr/86Sr), rare earth elements and fluid inclusions in fracture filling calcite and pyrite from these drill cores have resulted in the discrimination of several episodes of fracture mineralisations. These events represent migration of fluids during a wide range of conditions, ranging from high-temperature hydrothermal to present-day groundwater circulation. Four major events have been distinguished: 1) Precipitation of epidote, chlorite and quartz under hydrothermal conditions (T >200°C) during the Proterozoic, sometime between 1.8 and 1.1 Ga. 2) Hydrothermal circulation at temperatures between 150 and 280°C with precipitation of adularia, albite, prehnite, laumontite, calcite and chlorite. Most of these minerals precipitated during a tectonothermal event between 1.1 and 1.0 Ga, possibly in response to far-field effects of the Sveconorwegian orogeny. 3) Precipitation of mainly quartz, calcite, pyrite and asphaltite occurred during the Palaeozoic, at temperatures between 60 and 190°C (mainly at <100°C). Mixing of a fluid emanating from an organic rich overlying sedimentary cover and a deep basinal fluid from the crystalline bedrock is suggested to have caused this precipitation, possibly as a far-field response to the Caledonian orogeny and/or the development of the Caledonian foreland basin. 4) The youngest generation of fracture minerals is associated with precipitation of clay minerals and calcite with minor occurrences of pyrite and goethite. These minerals have probably precipitated episodically during a long time period (possibly from the Late Palaeozoic to the present) from various fluids at low temperature conditions (< 50°C). Few calcites in equilibrium with the present groundwater suggest that the ongoing precipitation of calcite is very limited.
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| 5. |
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| 6. |
- Sandström, Björn, 1976, et al.
(författare)
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Fracture-related hydrothermal alteration of metagranitic rock and associated changes in mineralogy, geochemistry and degree of oxidation: a case study at Forsmark, central Sweden
- 2010
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Ingår i: International Journal of Earth Sciences. - 1437-3254 .- 1437-3262. ; 99:1, s. 1-25
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Tidskriftsartikel (refereegranskat)abstract
- Red-staining of rocks due to fluid–rock interaction during hydrothermal circulation in fractures is a common feature in crystalline sequences. In this study, redstained metagranitic rock adjacent to fractures in Forsmark, central Sweden, has been studied with emphasis on the mineral reactions and associated element mobility occurring during the alteration. The main mineral reactions associated with the hydrothermal alteration are an almost complete saussuritization of plagioclase accompanied by total chloritization of biotite. Magnetite has been partly replaced by hematite whereas quartz and K-feldspar were relatively unaffected by the hydrothermal alteration. We show that redistribution of elements on the whole rock scale was very limited and is mainly manifested by enrichment of Na2O and volatiles and depletion of CaO, FeO and SiO2 in the red-stained rock. However, on the microscale, element redistribution was more extensive, with both intragranular and intergranular migration of e.g. Ca, K, Na, Al, Si, Fe, Ba, Cs, Rb, Sr, Ti and REEs. The altered rock shows a shift towards higher total oxidation factors, but the change is smaller than 1r and the redstaining of the rock is due to hematite dissemination rather than a significant oxidation of the rock. An increase in the connected porosity is also observed in the altered rock.
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| 7. |
- Sandström, Björn, 1976, et al.
(författare)
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Mineral i sprickor
- 2009
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Ingår i: Geologiskt Forum. - 1104-4721. ; 63:3, s. 17-19
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Tidskriftsartikel (övrigt vetenskapligt/konstnärligt)
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| 8. |
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| 9. |
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| 10. |
- Drake, Henrik, et al.
(författare)
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Variability of sulphur isotope ratios in pyrite and dissolved sulphate in granitoid fractures down to 1km depth - Evidence for widespread activity of sulphur reducing bacteria
- 2013
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Ingår i: Geochimica et Cosmochimica Acta. - : Elsevier BV. - 0016-7037 .- 1872-9533. ; 102, s. 143-161
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Tidskriftsartikel (refereegranskat)abstract
- Euhedral pyrite crystals in 46 open bedrock (granitoid) fractures at depths down to nearly 1 km were analysed for sulphur isotope ratios (delta S-34) by the in situ secondary ion mass spectrometry (SIMS) technique and by conventional bulk-grain analysis, and were compared with groundwater data. Twenty nine of the fractures sampled for pyrite had corresponding data for groundwater, including chemistry and isotopic ratios of sulphate, which provided a unique opportunity to compare the sulphur-isotopic ratios of pyrite and dissolved sulphate both at site and fracture-specific scales. Assessment of pyrite age and formation conditions were based on the geological evolution of the area (Laxemar, SE Sweden), and on data on co-genetic calcite as follows: (1) the isotopic ratios of the calcite crystals (delta O-18, delta C-13, Sr-87/Sr-86) were compared with previously defined isotopic features of fracture mineral assemblages precipitated during various geological periods, and (2) the delta O-18 of the calcites were compared with the delta O-18 of groundwater in fractures corresponding to those where the calcite/pyrite assemblages were sampled. Taken together, the data show that all the sampled fractures carried pyrite/calcite that are low-temperature and precipitated from the current groundwater or similar pre-existing groundwater, except at depths of -300 to -600 m where water with a glacial component dominates and the crystals are from pre-modern fluids. An age of <10 Ma are anticipated for the pre-modern fluids. The delta S-34(pyr) showed huge variations across individual crystals (such as -32 to +73 parts per thousand) and extreme minimum (-50 parts per thousand) and maximum (+91 parts per thousand) values. For this kind of extreme S-isotopic variation at earth-surface conditions there is no other explanation than activity of sulphur reducing bacteria coupled with sulphate-limited conditions. Indeed, the most common subgrain feature was an increase in delta S-34(pyr) values from interior to rim of the crystal, which we interpret are related to successively higher delta S-34 values of the dissolved source SO42- caused by ongoing bacterial sulphate reduction in fractures with low-flow or stagnant waters. The measured groundwater had delta S-34(SO4) values of +9 parts per thousand to +37 parts per thousand, with the highest values associated with low sulphate concentrations. These values are overall, and especially in the sulphate-poor waters down to -400 m, somewhat higher than the anticipated initial values, and can thus, like for the S-34-enriched pyrites, be explained by a Rayleigh distillation process driven by microbial sulphate reduction. An intriguing feature was that the delta S-34(SO4) values of the groundwater were in no case reaching up to the values required to produce biogenic pyrite with delta S-34 values of +40 parts per thousand to +91 parts per thousand. To explain this feature, we suggest that groundwater in low-flow fractures with near-stagnant water (carrying sulphate and pyrite with high delta S-34) is masked by high-flow parts of the fracture system carrying groundwater that often contains sulphate in abundance and considerably less fractionated with respect to S-34 and S-32. In order to gain detailed knowledge of chemical processes and patterns in groundwater in fractured rock, fracture-mineral investigations are a powerful tool, as we have shown here for the sulphur system. (C) 2012 Elsevier Ltd. All rights reserved.
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