Mineralogy, Fluid Inclusions, and Oxygen Isotope Geochemistry Signature of Wolframite to Scheelite and Fe,Mn Chlorite Veins from the W, (Cu,Mo) Ore Deposit of Borralha, Portugal

Scheelitization of Mn-bearing wolframite, scheelite, quartz, and Fe,Mn-chlorite veins was identified in the W, (Cu,Mo) ore deposits of Borralha, by optical microscopy, electron-microprobe analysis, and stable isotope geochemistry. Fluid inclusions derived scheelite crystallization temperature was compared with the oxygen isotope temperature estimated. Scheelite was formed mainly during stage I from a low salinity aqueous-carbonic fluid dominated by CO2, where the homogenization temperature (Th) decreased from 380 °C to 200 °C (average of 284 °C). As temperature decreased further, the aqueous-carbonic fluid became dominated by CH4 (Stage II; (average Th = 262 °C)). The final stage III corresponds to lower temperature mineralizing aqueous fluid (average Th = 218 °C). In addition, salinity gradually decreased from 4.8 wt.% to 1.12 wt.%. The δ18OFluid values calculated for quartz-water and wolframite-water fractionation fall within the calculated magmatic water range. The ∆quartz-scheelite fractionation occurred at about 350–400 °C. The ∆chlorite-water fractionation factor calculated is about +0.05‰ for 330 °C, dropping to −0.68‰ and −1.26‰ at 380 °C and 450 °C, respectively. Estimated crystallizing temperatures based on semi-empirical chlorite geothermometers range from 373 °C to 458 °C and 435 °C to 519 °C. A narrower temperature range of 375 °C to 410 °C was estimated for Fe,Mn-chlorite crystallization.

Retaining Geochemical Signatures During Aragonite-Calcite Transformation at Hydrothermal Conditions

Transformation of aragonite, a mineral phase metastable at Earth’s surface, to calcite widely occurs in both sedimentary and metamorphic systems with the presence of an aqueous phase. The transformation process can affect geochemical signatures of aragonite (a protolith). This study focused on quantification of the retention of Mg/Ca and Sr/Ca ratios, and d18O during the transformation process as well as evaluation of the transformation rate. To investigate the effect of transformation from aragonite to calcite on elemental and stable isotope ratios, we conducted a series of experiments in NaCl solutions at temperatures between 120 and 184 °C. Two additional experiments at 250 °C were conducted to estimate the transformation rate of aragonite to calcite. Protolith materials consist of (1) synthetic (Mg; Sr-bearing or non-Mg; Sr bearing) needle-shaped microcrystals of aragonite (<5 µm in size) and (2) larger chips (>100 µm in size) of natural aragonite. X-ray diffraction (XRD) showed that microcrystals successfully transformed to calcite within 30 h and scanning electron microscopy (SEM) yielded a change in the crystal size to >10 µm in rhombohedral shape. Electron backscatter diffraction (EBSD) of the larger aragonite chips showed that transformation to randomly oriented calcite occurred at the rims and along the cracks while the core retained an aragonite crystal structure. Isotope-ratio mass spectrometry (IRMS) analyses showed that calcite δ18O was controlled by temperature and δ18O of the solution. The obtained calibration curve of isotope fractionation factor versus temperature is consistent with other studies. Inductively coupled plasma optical emission spectroscopy (ICP-OES) analyses showed that calcite partially or completely retained Mg/Ca and Sr/Ca ratios through the transformation.

Carbon isotope excursions during the late Miocene recorded by lipids of marine Thaumarchaeota, Piedmont Basin, Mediterranean Sea

Group I mesophilic Thaumarchaeota fix dissolved inorganic carbon (DIC), accompanied by a biosynthetic fractionation factor of ~20‰. Accordingly, the δ13C signature of their diagnostic biomarker crenarchaeol was suggested as a potential δ13CDIC proxy in marine basins if input from nonmarine Thaumarchaeota is negligible. Semi-enclosed basins are sensitive to carbon-cycle perturbations, because they tend to develop thermohaline stratification. Water column stratification typified the semi-enclosed basins of the Mediterranean Sea during the late Miocene (Messinian) salinity crisis (5.97–5.33 Ma). To assess how the advent of the crisis affected the carbon cycle, we studied sediments of the Piedmont Basin (northwestern Italy), the northernmost Mediterranean subbasin. A potential bias of our δ13CDIC reconstructions from the input of soil Thaumarchaeota is discarded, since high and increasing branched and isoprenoid tetraether (BIT) index values do not correspond to low and decreasing δ13C values for thaumarchaeal lipids, which would be expected in case of high input from soil Thaumarchaeota. Before the onset of the crisis, the permanently stratified distal part of the basin hosted a water mass below the chemocline with a δ13CDIC value of approximately –3.5‰, while the well-mixed proximal part had a δ13CDIC value of approximately –0.8‰. The advent of the crisis was marked by 13C enrichment of the DIC pool, with positive δ13CDIC excursions up to +5‰ in the upper water column. Export of 12C to the seafloor after phytoplankton blooms and limited replenishment of remineralized carbon due to the stabilization of thermohaline stratification primarily caused such 13C enrichment of the DIC pool.

Investigating chromium cycling in global oxygen deficient zones with chromium isotopes

Chromium (Cr) isotopes have shown great potential as a paleo-redox proxy to trace the redox conditions of ancient oceans and atmosphere. However, its cycling in modern environments is poorly constrained. In my thesis, I attempt to fill in the gap of our understanding of chromium cycling in the modern ocean, with a focus on the redox processes in global oxygen deficient zones (ODZs). Firstly, we developed a method to analyze Cr isotopes of different Cr redox species. Tests on processing conditions demonstrated its robustness in obtaining accurate Cr isotope data. It is applicable to both frozen and fresh samples. This method allows us to investigate the redox cycling of Cr that is hard to unravel by existing total Cr methods. Secondly, in the Eastern Tropical North Pacific (ETNP), Eastern Tropical South Pacific (ETSP) and Arabian Sea ODZs, their total dissolved Cr profiles show preferential reduction of isotopically light Cr(VI) to Cr(III), which is scavenged and exported to deeper oceans. Applying our new method to ETNP and ETSP ODZ seawater samples, we observed Cr(VI) reduction in both ODZs with a similar fractionation factor. This indicates similar mechanisms may be controlling Cr(VI) reduction in the two ODZs. Cr(III) maximum coincides with Fe(II) and secondary nitrite maximums in the upper core of both ODZs. Shipboard incubations with spiked Fe(II) showed fast Cr(VI) reduction occurring in the ETNP ODZ. But neither Fe(II) nor microbes were reducing Cr(VI) directly. Thirdly, we calculated the isotope effects of Cr scavenging in the ETNP and ETSP ODZs. Thetwo ODZs show a similar isotope partitioning during Cr scavenging. And spatial variability is observed in the ETNP ODZ. Our calculated scavenged Cr isotope ratio is lighter than that of the total dissolved Cr from the same depth. It is also comparable to that of reducing or anoxic sediments, which implies that Cr isotopes can be used as an archive for local redox conditions.

Silicon Isotope Signatures of Radiolaria Reveal Taxon-Specific Differences in Isotope Fractionation

The global silicon (Si) cycle plays a critical role in regulating the biological pump and the carbon cycle in the oceans. A promising tool to reconstruct past dissolved silicic acid (DSi) concentrations is the silicon isotope signature of radiolaria (δ30Sirad), siliceous zooplankton that dwells at subsurface and intermediate water depths. However, to date, only a few studies on sediment δ30Sirad records are available. To investigate its applicability as a paleo proxy, we compare the δ30Sirad of different radiolarian taxa and mixed radiolarian samples from surface sediments off Peru to the DSi distribution and its δ30Si signatures (δ30SiDSi) along the coast between the equator and 15°S. Three different radiolarian taxa were selected according to their specific habitat depths of 0–50 m (Acrosphaera murrayana), 50–100 m (Dictyocoryne profunda/truncatum), and 200–400 m (Stylochlamydium venustum). Additionally, samples containing a mix of species from the bulk assemblage covering habitat depths of 0 to 400 m have been analyzed for comparison. We find distinct δ30Sirad mean values of +0.70 ± 0.17‰ (Acro; 2 SD), +1.61 ± 0.20 ‰ (Dictyo), +1.19 ± 0.31 ‰ (Stylo) and +1.04 ± 0.19 ‰ (mixed radiolaria). The δ30Si values of all individual taxa and the mixed radiolarian samples indicate a significant (p &lt; 0.05) inverse relationship with DSi concentrations of their corresponding habitat depths. However, only δ30Si of A. murrayana are correlated to DSi concentrations under normally prevailing upwelling conditions. The δ30Si of Dictyocoryne sp., Stylochlamydium sp., and mixed radiolaria are significantly correlated to the lower DSi concentrations either associated with nutrient depletion or shallower habitat depths. Furthermore, we calculated the apparent Si isotope fractionation between radiolaria and DSi (Δ30Si ∼ 30ε = δ 30Sirad − δ 30SiDSi) and obtained values of −1.18 ± 0.17 ‰ (Acro), −0.05 ± 0.25 ‰ (Dictyo), −0.34 ± 0.27 ‰ (Stylo), and −0.62 ± 0.26 ‰ (mixed radiolaria). The significant differences in Δ30Si between the order of Nassellaria (A. murrayana) and Spumellaria (Dictyocoryne sp. and Stylochlamydium sp.) may be explained by order-specific Si isotope fractionation during DSi uptake, similar to species-specific fractionation observed for diatoms. Overall, our study provides information on the taxon-specific fractionation factor between radiolaria and seawater and highlights the importance of taxonomic identification and separation to interpret down-core records.

Bromine Isotope Variations in Magmatic and Hydrothermal Sodalite and Tugtupite and the Estimation of Br Isotope Fractionation between Melt and Sodalite

We determined the bromine isotope compositions of magmatic and hydrothermal sodalite (Na8Al6Si6O24Cl2) and tugtupite (Na8Al2Be2Si8O24Cl2) from the Ilímaussaq intrusion in South Greenland, in order to constrain the Br isotope composition of the melt and hydrothermal fluids from which these minerals were formed. Early formed magmatic sodalite has high Br contents (138 ± 10 µg/g, n = 5) and low δ81Br values (+0.23 ± 0.07‰). Late stage hydrothermal sodalite has lower Br contents (53±10 µg/g, n = 5) and higher δ81Br values (+0.36 ± 0.08‰). Tugtupite that forms at even later stages shows the lowest Br contents (26 ± 2 µg/g, n = 2) and the highest δ81Br values (+0.71 ± 0.17‰). One hydrothermal sodalite has a Br concentration of 48 ± 9 µg/g and an exceptionally high δ81Br of 0.82 ± 0.12‰, very similar to the δ81Br of tugtupites. We suggest that this may be a very late stage sodalite that possibly formed under Be deficient conditions. The data set suggests that sodalite crystallises with a negative Br isotope fractionation factor, which means that the sodalite has a more negative δ81Br than the melt, of −0.3 to −0.4‰ from the melt. This leads to a value of +0.5 to +0.6‰ relative to SMOB for the melt from which sodalite crystallises. This value is similar to a recently published δ81Br value of +0.7‰ for very deep geothermal fluids with very high R/Ra He isotope ratios, presumably derived from the mantle. During crystallisation of later stage hydrothermal sodalite and the Be mineral tugtupite, δ81Br of the residual fluids (both melt and hydrothermal fluid) increases as light 79Br crystallises in the sodalite and tugtupite. This results in increasing δ81Br values of later stage minerals that crystallise with comparable fractionation factors from a fluid with increasingly higher δ81Br values.

Ge/Si and Ge Isotope Fractionation During Glacial and Non-glacial Weathering: Field and Experimental Data From West Greenland

Glacial environments offer the opportunity to study the incipient stages of chemical weathering due to the high availability of finely ground sediments, low water temperatures, and typically short rock-water interaction times. In this study we focused on the geochemical behavior of germanium (Ge) in west Greenland, both during subglacial weathering by investigating glacier-fed streams, as well as during a batch reactor experiment by allowing water-sediment interaction for up to 2 years in the laboratory. Sampled in late August 2014, glacial stream Ge and Si concentrations were low, ranging between 12–55 pmol/L and 7–33 µmol/L, respectively (Ge/Si = 0.9–2.2 µmol/mol, similar to parent rock). As reported previously, the dissolved stable Ge isotope ratio (δ74Ge) of the Watson River was 0.86 ± 0.24‰, the lowest among global rivers and streams measured to date. This value was only slightly heavier than the suspended load (0.48 ± 0.23‰), which is likely representative of the bulk parent rock composition. Despite limited Ge/Si and δ74GeGe fractionation, both Ge and Si appear depleted relative to Na during subglacial weathering, which we interpret as the relatively congruent uptake of both phases by amorphous silica (aSi). Continued sediment-water interaction over 470–785 days in the lab produced a large increase in dissolved Si concentrations (up to 130–230 µmol/L), a much smaller increase in dissolved Ge (up to ∼70 pmol/L), resulting in a Ge/Si decrease (to 0.4–0.5 µmol/mol) and a significant increase in δ74Ge (to 1.9–2.2‰). We argue that during the experiment, both Si and Ge are released by the dissolution of previously subglacially formed aSi, and Ge is then incorporated into secondary phases (likely adsorbed to Fe oxyhydroxides), with an associated Δ74Gesecondary−dissolved fractionation factor of −2.15 ± 0.46‰. In summary, we directly demonstrate Ge isotope fractionation during the dissolution-precipitation weathering reactions of natural sediments in the absence of biological Ge and Si uptake, and highlight the significant differences in Ge behavior during subglacial and non-glacial weathering.

Kinetic effects during ocean evaporation: observed relationship with wind speed

&lt;p&gt;Water vapor has a fundamental role in weather and climate, being the strongest natural greenhouse gas in the Earth&amp;#8217;s atmosphere. The main source of water vapor in the atmosphere is ocean evaporation, which transfers a large amount of energy via latent heat fluxes. In the past, evaporation was intensively studied using stable isotopes because of the large fractionation effects involved during water phase changes, providing insights on processes occurring at the air-water interface. Current theories describe evaporation near the air-water interface as a combination of molecular and turbulent diffusion processes into separated sublayers. The importance of those two sublayers, in terms of total resistance to vapor transport in air, is expected to be dependent on parameters such as moisture deficit, temperature and wind speed. Non-equilibrium fractionation effects in isotopic evaporation models are then expected to be related to these physical parameters. In the last 10 years, several water vapor observations from oceanic expeditions were focused on the impact of temperature and wind speed effect, assuming the influence of those parameters on non-equilibrium fractionation in the marine boundary layer. Wind speed effect is expected to be small on total kinetic fractionation and was discussed at length but was not completely ruled out. With a gradient-diffusion approach (2 heights above the ocean surface) and Cavity Ring-Down Spectroscopy we have estimated non-equilibrium fractionation factors for &lt;sup&gt;18&lt;/sup&gt;O/&lt;sup&gt;16&lt;/sup&gt;O during evaporation, showing that the wind speed effect can be detected and has no significant impact on kinetic fractionation. Results obtained for wind speeds between 0 and 10 m s&lt;sup&gt;-1&lt;/sup&gt; in the North Atlantic Ocean are consistent with the Merlivat and Jouzel (1979) parametrization for smooth surfaces (mean &amp;#949;&lt;sub&gt;18&lt;/sub&gt;=6.1&amp;#8240;). A small monotonic decrease of the fractionation parameter is observed as a function of 10 m wind speed (slope&amp;#160; &amp;#8773; 0.15 &amp;#8240; m&lt;sup&gt;-1&lt;/sup&gt; s), without any evident discontinuity. However, depending on the data filtering approach it is possible to highlight a rapid decrease of the kinetic fractionation factor at low wind speed (&amp;#8804; 2.5 m s&lt;sup&gt;-1&lt;/sup&gt;). An evident decrease of fractionation factor is also observed for wind speeds above 10 m s&lt;sup&gt;-1&lt;/sup&gt;, allowing to hypothesize the possible effect of sea spray in net evaporation flux. Considering the average wind speed over the oceans, we conclude that a constant kinetic fractionation factor for evaporation is a more simple and reasonable solution than a wind-speed dependent parametrization.&amp;#160;&lt;/p&gt;&lt;p&gt;&amp;#160;&lt;/p&gt;&lt;p&gt;Merlivat, L., &amp; Jouzel, J. (1979). Global climatic interpretation of the deuterium&amp;#8208;oxygen 18 relationship for precipitation. Journal of Geophysical Research: Oceans, 84(C8), 5029-5033.&lt;/p&gt;