Barium isotope (re-)equilibration in the barite-fluid system and its implications for marine barite archives

Variations in the Ba isotopic composition of seawater are largely driven by the extent of barite precipitation in the marine photic zone and replenishment of Ba by upwelling and/or continental inputs. Pelagic barites offer a robust tool for tracing sources and sinks of Ba in the (paleo)ocean as they record these isotopic variations. Knowledge of the Ba isotope fractionation between barite and ambient waters is therefore imperative. Here, the Ba isotope fractionation between barite and Ba2+ (aq) under equilibrium conditions has been estimated by the three-isotope method with a 135Ba-enriched reactive fluid. The estimated Ba isotope fractionation was Δ137/134BaBarite-Ba2+ = −0.07 ± 0.08‰. Textural observations of barite crystals recovered up to 756 days of reaction reveal smoothing of solid surfaces but also typical dissolution features such as development of pits and cracks. Thus, dissolution/re-precipitation is likely the mechanism controlling the observed isotope exchange that is facilitated by the further development of porosity in the crystals. Additionally, the isotope exchange in the experimental runs fits a second-order law yielding a surface normalized isotope exchange rate of ∼2.8 × 10−10 mol/m2/s. This exchange rate could theoretically result in complete isotope exchange between pelagic barite with a typical edge size of 1 μm and ambient seawater or pore fluid within years, altering the barite's Ba isotopic composition during settling towards the seafloor and/or after deposition in marine sediments. Although there is considerable uncertainty in extrapolating experimental results to natural conditions and longer time scales, the rapid rates of exchange observed experimentally over short timescales suggest that isotope exchange in pelagic barite should be considered during interpretation of the Ba isotope composition as a paleoarchive.</p

In-situ Raman spectroscopy of amorphous calcium phosphate to crystalline hydroxyapatite transformation

Amorphous calcium phosphate (Ca3(PO4)2xnH2O; n = 3–4.5; ACP) is a precursor phase of the mineral hydroxyapatite (Ca5(PO4)3(OH); HAP) that in natural settings occurs during both authigenic and biogenic mineral formation. In aqueous solutions ACP transforms rapidly to the crystalline phase. The transformation rate is highly dependent on the prevailing physico-chemical conditions, most likely on: Ca & PO4 concentration, pH and temperature. In this study, we conducted a calcium phosphate precipitation experiment at 20 °C and pH 9.2, in order to study the temporal evolution of the phosphate mineralogy. We monitored and assessed the transformation process of ACP to crystalline HAP using highly time-resolved in-situ Raman spectroscopy at 100 spectra per hour, in combination with solution chemistry and XRD data. Transformation of ACP to crystalline HAP occurred within 18 h, as it is illustrated in a clear peak shift in Raman spectra from 950 cm−1 to 960 cm−1 as well as in a sharpening of the 960 cm−1 peak. The advantages of this method are: • In-situ Raman spectroscopy facilitates quasi – continuous monitoring of phase transitions. • It is an easy to handle and non-invasive method. Method name: In-situ Raman monitoring, Keywords: Amorphous calcium phosphate, In-situ monitoring, Raman spectroscopy, Intermediate phase, Apatit

Barium isotope (re-)equilibration in the barite-fluid system and its implications for marine barite archives

Variations in the Ba isotopic composition of seawater are largely driven by the extent of barite precipitation in the marine photic zone and replenishment of Ba by upwelling and/or continental inputs. Pelagic barites offer a robust tool for tracing sources and sinks of Ba in the (paleo)ocean as they record these isotopic variations. Knowledge of the Ba isotope fractionation between barite and ambient waters is therefore imperative. Here, the Ba isotope fractionation between barite and Ba2+ (aq) under equilibrium conditions has been estimated by the three-isotope method with a 135Ba-enriched reactive fluid. The estimated Ba isotope fractionation was BaBarite-Ba2+ = −0.07 ± 0.08‰. Textural observations of barite crystals recovered up to 756 days of reaction reveal smoothing of solid surfaces but also typical dissolution features such as development of pits and cracks. Thus, dissolution/re-precipitation is likely the mechanism controlling the observed isotope exchange that is facilitated by the further development of porosity in the crystals. Additionally, the isotope exchange in the experimental runs fits a second-order law yielding a surface normalized isotope exchange rate of ∼2.8 × 10−10 mol/m2/s. This exchange rate could theoretically result in complete isotope exchange between pelagic barite with a typical edge size of 1 μm and ambient seawater or pore fluid within years, altering the barite's Ba isotopic composition during settling towards the seafloor and/or after deposition in marine sediments. Although there is considerable uncertainty in extrapolating experimental results to natural conditions and longer time scales, the rapid rates of exchange observed experimentally over short timescales suggest that isotope exchange in pelagic barite should be considered during interpretation of the Ba isotope composition as a paleoarchive

Long-Term Evolution of Fracture Permeability in Slate: An Experimental Study with Implications for Enhanced Geothermal Systems (EGS)

The long-term sustainability of fractures within rocks determines whether it is reasonable to utilize such formations as potential EGS reservoirs. Representative for reservoirs in Variscan metamorphic rocks, three long-term (one month each) fracture permeability experiments on saw-cut slate core samples from the Hahnenklee well (Harz Mountains, Germany) were performed. The purpose was to investigate fracture permeability evolution at temperatures up to 90 °C using both deionized water (DI) and a 0.5 M NaCl solution as the pore fluid. Flow with DI resulted in a fracture permeability decline that is more pronounced at 90 °C, but permeability slightly increased with the NaCl fluid. Microstructural observations and analyses of the effluent composition suggest that fracture permeability evolution is governed by an interplay of free-face dissolution and pressure solution. It is concluded that newly introduced fractures may be subject to a certain permeability reduction due to pressure solution that is unlikely to be mitigated. However, long-term fracture permeability may be sustainable or even increase by free-face dissolution when the injection fluid possesses a certain (NaCl) salinity

Suitability of calibrated X-ray fluorescence core scanning for environmental geochemical characterisation of heterogeneous sediment cores

Multi-element analysis of discrete samples via X-Ray fluorescence or inductively coupled plasma spectrometry is commonly used to characterise the composition of solid geo-materials for environmental geochemical characterisation. Conventional geochemical analysis of individual samples is time consuming and costly, which often results in low-resolution sampling with the danger of missing crucial information. X-ray fluorescence Core Scanning (XCS) provides an alternative method to obtain elemental information, which can be potentially used quantitatively when combined with the Multivariate Log-ratio Calibration (MLC) approach. The suitability of the XCS-MLC method was tested for environmental geochemical characterisation on four terrestrial Holocene-Pleistocene sediment cores that have a variable lithology (clay, sand, peat, with variable calcareous content), were stored at ambient room conditions and scanned post sampling. Element contents based on XCS-MLC and conventional geochemical analysis proved to be comparable (R2 > 0.5) for Al, Ca, Cr, Fe, K, Sr, Mn, Ni, Pb, Rb, S, Si, Ti, Zn, Zr, and also for Br as proxy for organic matter. For As, Cu and Ba the correlations were less satisfactory (R2

Iron isotope variability in ocean floor lavas and mantle sources in the Lau back-arc basin

Iron isotopes in ocean floor basalts (OFB) away from convergent margins comprising mid-ocean-ridge and ocean island lavas show significant variation of >0.4‰ (expressed in the delta notation δ57Fe relative to IRMM-014), but processes responsible for this variation remain elusive. Bond-valence theory predicts that valence states (Fe3+ vs. Fe2+) control Fe isotopes during partial melting and crystal fractionation along the liquid line of descent and thus contribute substantially to this variation. Memory of past melt extraction or metasomatic re-enrichment in the source of OFB may further add to the observed variability, but systematic investigations to elucidate the respective contributions of these effects have been lacking. Submarine ridges and rifts in the Lau back-arc basin offer a unique opportunity to compare Fe isotopes in OFB from different melting regimes and variably depleted mantle sources. New Fe isotope data is presented for submarine lavas from the Rochambeau Ridges (RR) and the Northwest Lau Spreading Centre (NWLSC), and is compared with published data from the Central Lau Spreading Centre (CLSC). In line with first principle calculations and observations from a range of natural systems, crystal fractionation is identified as the dominant, controlling process for elevating δ57Fe in the lavas with olivine tentatively identified as the key driver. To compensate for the effect of crystal fractionation, olivine is mathematically added towards calculated primitive melt compositions (δ57Feprim). For this, we used a constant Ol-melt isotope fractionation factor based on published equilibrium partition functions adapted to decreasing temperature in a cooling melt. The degree of calculated Fe isotope fractionation through olivine crystal fractionation (monitored as Δ57Fe = δ57Femeasured − δ57Feprim) is positively correlated with increasing S and decreasing Ni content in the cooling lavas, fortifying the validity of the approach. Primitive lavas from individual Lau spreading centres and ridges vary to 0.1‰ in δ57Feprim, similar to primitive open-ocean MORB. However, the entire spread in Fe isotope variability in the primitive melts remains at 0.3‰, which we propose to be the extent of isotope heterogeneity in Earth’s upper mantle, with few extreme exceptions. The largest variability in δ57Feprim is observed for RR intra-plate lavas, which have been associated with the Samoan mantle plume and melting in an edge-driven convection scenario. Low, mid-ocean ridge-like 87Sr/86Sr in RR lavas excludes significant influence of isotopically heavy Samoan EM2-type components. However, co-variations with rare earth element pattern in some RR intra-plate lavas indicate garnet plays a role in elevating δ57Feprim during deeper melting. Excluding these deep-seated melts uncovers systematically decreasing δ57Feprim coupled to the degree of mantle source depletion, as recorded in Lu/Hf and Sm/Nd, in the back-arc basin basalts. This, however, holds only true for a comparison between sources of individual ridges, whereas no co-variation is observed within ridge segment data. This suggests that a process other than source depletion and crystal fractionation further adds to Fe isotope variability in the order of 0.1‰ on scales of individual ridge segments. This either marks the degree of Fe isotope variability below ridge segments, or is caused by secondary processes, such as melt-wallrock interaction or RTX (recharge and crystal fractionation) magma chambers.ON thanks M. Dietzel & D. Hippler for access to the Nu Plasma in Graz. This study is supported by ARC grant FT140101062 to O

Iron isotope variability in ocean floor lavas and mantle sources in the Lau back-arc basin

International audienceIron isotopes in ocean floor basalts (OFB) away from convergent margins comprising mid-ocean-ridge and ocean island lavas show significant variation of >0.4‰ (expressed in the delta notation δ57Fe relative to IRMM-014), but processes responsible for this variation remain elusive. Bond-valence theory predicts that valence states (Fe3+ vs. Fe2+) control Fe isotopes during partial melting and crystal fractionation along the liquid line of descent and thus contribute substantially to this variation. Memory of past melt extraction or metasomatic re-enrichment in the source of OFB may further add to the observed variability, but systematic investigations to elucidate the respective contributions of these effects have been lacking. Submarine ridges and rifts in the Lau back-arc basin offer a unique opportunity to compare Fe isotopes in OFB from different melting regimes and variably depleted mantle sources. New Fe isotope data is presented for submarine lavas from the Rochambeau Ridges (RR) and the Northwest Lau Spreading Centre (NWLSC), and is compared with published data from the Central Lau Spreading Centre (CLSC). In line with first principle calculations and observations from a range of natural systems, crystal fractionation is identified as the dominant, controlling process for elevating δ57Fe in the lavas with olivine tentatively identified as the key driver. To compensate for the effect of crystal fractionation, olivine is mathematically added towards calculated primitive melt compositions (δ57Feprim). For this, we used a constant Ol-melt isotope fractionation factor based on published equilibrium partition functions adapted to decreasing temperature in a cooling melt. The degree of calculated Fe isotope fractionation through olivine crystal fractionation (monitored as Δ57Fe = δ57Femeasured - δ57Feprim) is positively correlated with increasing S and decreasing Ni content in the cooling lavas, fortifying the validity of the approach. Primitive lavas from individual Lau spreading centres and ridges vary to 0.1‰ in δ57Feprim, similar to primitive open-ocean MORB. However, the entire spread in Fe isotope variability in the primitive melts remains at 0.3‰, which we propose to be the extent of isotope heterogeneity in Earth's upper mantle, with few extreme exceptions. The largest variability in δ57Feprim is observed for RR intra-plate lavas, which have been associated with the Samoan mantle plume and melting in an edge-driven convection scenario. Low, mid-ocean ridge-like 87Sr/86Sr in RR lavas excludes significant influence of isotopically heavy Samoan EM2-type components. However, co-variations with rare earth element pattern in some RR intra-plate lavas indicate garnet plays a role in elevating δ57Feprim during deeper melting. Excluding these deep-seated melts uncovers systematically decreasing δ57Feprim coupled to the degree of mantle source depletion, as recorded in Lu/Hf and Sm/Nd, in the back-arc basin basalts. This, however, holds only true for a comparison between sources of individual ridges, whereas no co-variation is observed within ridge segment data. This suggests that a process other than source depletion and crystal fractionation further adds to Fe isotope variability in the order of 0.1‰ on scales of individual ridge segments. This either marks the degree of Fe isotope variability below ridge segments, or is caused by secondary processes, such as melt-wallrock interaction or RTX (recharge and crystal fractionation) magma chambers

Effect of Pressure Perturbations on CO₂ Degassing in a Mofette System: The Case of Hartoušov, Czech Republic

Mofettes are gas emission sites where high concentrations of CO2 ascend through conduits from as deep as the mantle to the Earth’s surface and as such provide direct windows to processes at depth. The Hartoušov mofette, located at the western margin of the Eger Graben, is a key site to study interactions between fluids and swarm earthquakes. The mofette field (10 mofettes within an area of 100 m × 500 m and three wells of 28, 108, and 239 m depth) is characterized by high CO2 emission rates (up to 100 t/d) and helium signatures with (3He/4He)c up to 5.8 Ra, indicating mantle origin. We compiled geological, geophysical, geochemical, and isotopic data to describe the mofette system. Fluids in the Cheb basin are mixtures between shallow groundwater and brine (>40 g/L at a depth of 235 m) located at the deepest parts of the basin fillings. Overpressured CO2-rich mineral waters are trapped below the mudstones and clays of the sealing Cypris formation. Drilling through this sealing layer led to blow-outs in different compartments of the basin. Pressure transients were observed related to natural disturbances as well as human activities. External (rain) and internal (earthquakes) events can cause pressure transients in the fluid system within hours or several days, lasting from days to years and leading to changes in gas flux rates. The 2014 earthquake swarm triggered an estimated excess release of 175,000 tons of CO2 during the following four years. Pressure oscillations were observed at a wellhead lasting 24 h with increasing amplitudes (from 10 to 40 kPa) and increasing frequencies reaching five cycles per hour. These oscillations are described for the first time as a potential natural analog to a two-phase pipe–relief valve system known from industrial applications