Shale adhesion force measurements via atomic force microscopy

Wettability of sedimentary rock surface is an essential parameter that defines oil recovery and production rates of a reservoir. The discovery of wettability alteration in reservoirs, as well as complications that occur in analysis of heterogeneous sample, such as shale, for instance, have prompted scientists to look for the methods of wettability assessment at nanoscale. At the same time, bulk techniques, which are commonly applied, such as USBM (United States Bureau of Mines) or Amott tests, are not sensitive enough in cases with mixed wettability of rocks as they provide average wettability values of a core plug. Atomic Force Microscopy (AFM) has been identified as one of the methods that allow for measurement of adhesion forces between cantilever and sample surface in an exact location at nanoscale. These adhesion forces can be used to estimate wettability locally. Current research, however, shows that the correlation is not trivial. Moreover, adhesion force measurement via AFM has not been used extensively in studies with geological samples yet. In this study, the adhesion force values of the cantilever tip interaction with quartz inclusion on the shale sample surface, have been measured using the AFM technique. The adhesion force measured in this particular case was equal to the capillary force of water meniscus, formed between the sample surface and the cantilever tip. Experiments were conducted with a SiconG cantilever with (tip radius of 5 nm). The adhesion forces between quartz grain and cantilever tip were equal to 56.5 ± 5 nN. Assuming the surface of interaction to be half spherical, the adhesion force per area was 0.36 ± 0.03 nN/nm2. These measurements and results acquired at nano-scale will thus create a path towards much higher accuracy-wettability measurements and consequently better reservoir-scale predictions and improved underground operations

The origin and fate of C during alteration of the oceanic crust

The contents and isotope compositions of water and carbon, including total, reduced, and inorganic (carbonate) C, were studied in 170 My altered oceanic basalts from Ocean Drilling Program Hole 801C in the western Pacific Ocean. Reduced C contents of 0.12–0.29 wt% CO2 and $\delta ^{13}$C values of $-22.6$ to $-27.8‰$ occur throughout the basement section. High total C concentrations in the upper volcanic section (UVS), above 300 m sub-basement, are dominated by inorganic C, and concentrations of both decrease with depth, from 1.92 to 0.57 wt% CO2 and 1.76 wt% CO2 to 0.66 wt% CO2, respectively. The $\delta ^{13}$C of inorganic C in the UVS ($-$0.4 to ${+}1.5{‰}$) indicates precipitation of seawater dissolved inorganic carbon (DIC) through the intensive circulation of seawater. $\delta$D values of $-$59.8 to ${-}17.6{‰}$ in the UVS also result from seawater interaction. In contrast, total C contents in the lower volcanic section (LVS) are low (0.22–0.39 wt% CO2) and dominated by reduced C, resulting in negative $\delta ^{13}$C values for total C ($-$18.7 to ${-}23.5{‰}$). We propose that a proportion of this reduced C could have formed through abiotic reduction of magmatic CO2 at the ridge axis. The contents and $\delta ^{13}$C values of inorganic carbon in the LVS (0.05–0.09 wt% CO2 and $-$10.7 to ${-}9.5{‰}$, respectively) fall in the range characteristic of C in mid-ocean ridge basalt glasses, also suggesting a magmatic origin. $\delta$D values in the LVS (weighted average $= {-}69.3{‰}$) are consistent with magmatic water. Reduced C in the basalts may also have formed through microbial activity at low temperatures, as indicated by previous work showing negative $\delta ^{34}$S values in the basalts.Our results show: (1) that magmatic C can be stored in altered oceanic basalts both as reduced and inorganic C resulting from high-temperature processes at mid-ocean ridges; (2) that microbial activity may add reduced C to the basalts during low-temperature alteration on ridge flanks; and (3) that circulation of cold seawater in the uppermost few hundred meters of basement adds seawater DIC as carbonate to the basalts and filling fractures in the basement. We estimate the content of magmatic C stored in the altered basaltic crust to be 0.126 wt% CO2. Compared with previous estimates, this concentration probably represents an upper limit for magmatic C. This resultant magmatic C flux into the crust, ranging from $1.5\times 10^{12}$–$2\times 10^{12}$ molC${\cdot }$y$^{-1}$ is similar to the outgassing CO2 flux [${\sim }1.32\pm 0.8$–$2.0 \times 10^{12}$ molC${\cdot }$y$^{-1}$, Le Voyer et al., 2019 and Cartigny et al., 2018, respectively]. Further data are needed to better constrain the fraction of magmatic CO2 that does not escape the oceanic lithosphere but remains stored as reduced and inorganic carbon

The origin and fate of C during alteration of the oceanic crust

The contents and isotope compositions of water and carbon, including total, reduced, and inorganic (carbonate) C, were studied in 170 My altered oceanic basalts from Ocean Drilling Program Hole 801C in the western Pacific Ocean. Reduced C contents of 0.12–0.29 wt% CO2 and $\delta ^{13}$C values of $-22.6$ to $-27.8‰$ occur throughout the basement section. High total C concentrations in the upper volcanic section (UVS), above 300 m sub-basement, are dominated by inorganic C, and concentrations of both decrease with depth, from 1.92 to 0.57 wt% CO2 and 1.76 wt% CO2 to 0.66 wt% CO2, respectively. The $\delta ^{13}$C of inorganic C in the UVS ($-$0.4 to ${+}1.5{‰}$) indicates precipitation of seawater dissolved inorganic carbon (DIC) through the intensive circulation of seawater. $\delta$D values of $-$59.8 to ${-}17.6{‰}$ in the UVS also result from seawater interaction. In contrast, total C contents in the lower volcanic section (LVS) are low (0.22–0.39 wt% CO2) and dominated by reduced C, resulting in negative $\delta ^{13}$C values for total C ($-$18.7 to ${-}23.5{‰}$). We propose that a proportion of this reduced C could have formed through abiotic reduction of magmatic CO2 at the ridge axis. The contents and $\delta ^{13}$C values of inorganic carbon in the LVS (0.05–0.09 wt% CO2 and $-$10.7 to ${-}9.5{‰}$, respectively) fall in the range characteristic of C in mid-ocean ridge basalt glasses, also suggesting a magmatic origin. $\delta$D values in the LVS (weighted average $= {-}69.3{‰}$) are consistent with magmatic water. Reduced C in the basalts may also have formed through microbial activity at low temperatures, as indicated by previous work showing negative $\delta ^{34}$S values in the basalts.Our results show: (1) that magmatic C can be stored in altered oceanic basalts both as reduced and inorganic C resulting from high-temperature processes at mid-ocean ridges; (2) that microbial activity may add reduced C to the basalts during low-temperature alteration on ridge flanks; and (3) that circulation of cold seawater in the uppermost few hundred meters of basement adds seawater DIC as carbonate to the basalts and filling fractures in the basement. We estimate the content of magmatic C stored in the altered basaltic crust to be 0.126 wt% CO2. Compared with previous estimates, this concentration probably represents an upper limit for magmatic C. This resultant magmatic C flux into the crust, ranging from $1.5\times 10^{12}$–$2\times 10^{12}$ molC${\cdot }$y$^{-1}$ is similar to the outgassing CO2 flux [${\sim }1.32\pm 0.8$–$2.0 \times 10^{12}$ molC${\cdot }$y$^{-1}$, Le Voyer et al., 2019 and Cartigny et al., 2018, respectively]. Further data are needed to better constrain the fraction of magmatic CO2 that does not escape the oceanic lithosphere but remains stored as reduced and inorganic carbon

Slab melting as a barrier to deep carbon subduction

Interactions between crustal and mantle reservoirs dominate the surface inventory of volatile elements over geological time, moderating atmospheric composition and maintaining a lifesupporting planet1. While volcanoes expel volatile components into surface reservoirs, subduction of oceanic crust is responsible for replenishment of mantle reservoirs2,3. Many natural, ‘superdeep’ diamonds originating in the deep upper mantle and transition zone host mineral inclusions, indicating an affinity to subducted oceanic crust4–7. Here we show that the majority of slab geotherms will intersect a deep depression along the melting curve of carbonated oceanic crust at depths of approximately 300 to 700 kilometres, creating a barrier to direct carbonate recycling into the deep mantle. Low-degree partial melts are alkaline carbonatites that are highly reactive with reduced ambient mantle, producing diamond. Many inclusions in superdeep diamonds are best explained by carbonate melt–peridotite reaction. A deep carbon barrier may dominate the recycling of carbon in the mantle and contribute to chemical and isotopic heterogeneity of the mantle reservoir

Mineralogical and geochemical analysis of Fe-phases in drill-cores from the Triassic Stuttgart Formation at Ketzin CO₂ storage site before CO₂ arrival

Reactive iron (Fe) oxides and sheet silicate-bound Fe in reservoir rocks may affect the subsurface storage of CO2 through several processes by changing the capacity to buffer the acidification by CO2 and the permeability of the reservoir rock: (1) the reduction of three-valent Fe in anoxic environments can lead to an increase in pH, (2) under sulphidic conditions, Fe may drive sulphur cycling and lead to the formation of pyrite, and (3) the leaching of Fe from sheet silicates may affect silicate diagenesis. In order to evaluate the importance of Fe-reduction on the CO2 reservoir, we analysed the Fe geochemistry in drill-cores from the Triassic Stuttgart Formation (Schilfsandstein) recovered from the monitoring well at the CO2 test injection site near Ketzin, Germany. The reservoir rock is a porous, poorly to moderately cohesive fluvial sandstone containing up to 2–4 wt% reactive Fe. Based on a sequential extraction, most Fe falls into the dithionite-extractable Fe-fraction and Fe bound to sheet silicates, whereby some Fe in the dithionite-extractable Fe-fraction may have been leached from illite and smectite. Illite and smectite were detected in core samples by X-ray diffraction and confirmed as the main Fe-containing mineral phases by X-ray absorption spectroscopy. Chlorite is also present, but likely does not contribute much to the high amount of Fe in the silicate-bound fraction. The organic carbon content of the reservoir rock is extremely low (<0.3 wt%), thus likely limiting microbial Fe-reduction or sulphate reduction despite relatively high concentrations of reactive Fe-mineral phases in the reservoir rock and sulphate in the reservoir fluid. Both processes could, however, be fuelled by organic matter that is mobilized by the flow of supercritical CO2 or introduced with the drilling fluid. Over long time periods, a potential way of liberating additional reactive Fe could occur through weathering of silicates due to acidification by CO2

CO2-water-basalt interactions: Experimental and mineralogical study

International audienc

C and H geochemistry of altered oceanic crus of ODP/IODP Hole 1256D

Carbon and hydrogen concentrations and isotopic compositions were measured in 19 samples from altered oceanic crust cored in ODP/IODP Hole 1256D through lavas, dikes down to the gabbroic rocks. Bulk water content varies from 0.32 to 2.14 wt% with dD values from -64per mil to -25per mil. All samples are enriched in water relative to fresh basalts. The dD values are interpreted in terms of mixing between magmatic water and another source that can be either secondary hydrous minerals and/or H contained in organic compounds such as hydrocarbons. Total CO2, extracted by step-heating technique, ranges between 564 and 2823 ppm with d13C values from -14.9per mil to -26.6per mil. As for water, these altered samples are enriched in carbon relative to fresh basalts. The carbon isotope compositions are interpreted in terms of a mixing between two components: (1) a carbonate with d13C = -4.5per mil and (2) an organic compound with d13C = -26.6per mil. A mixing model calculation indicates that, for most samples (17 of 19), more than 75% of the total C occurs as organic compounds while carbonates represent less than 25%. This result is also supported by independent estimates of carbonate content from CO2 yield after H3PO4 attack. A comparison between the carbon concentration in our samples, seawater DIC (Dissolved Inorganic Carbon) and DOC (Dissolved Organic Carbon), and hydrothermal fluids suggests that CO2 degassed from magmatic reservoirs is the main source of organic C addition to the crust during the alteration process. A reduction step of dissolved CO2 is thus required, and can be either biologically mediated or not. Abiotic processes are necessary for the deeper part of the crust (>1000 mbsf) because alteration temperatures are greater than any hyperthermophilic living organism (i.e. T > 110 °C). Even if not required, we cannot rule out the contribution of microbial activity in the low-temperature alteration zones. We propose a two-step model for carbon cycling during crustal alteration: (1) when "fresh" oceanic crust forms at or close to ridge axis, alteration starts with hot hydrothermal fluids enriched in magmatic CO2, leading to the formation of organic compounds during Fischer-Tropsch-type reactions; (2) when the crust moves away from the ridge axis, these interactions with hot hydrothermal fluids decrease and are replaced by seawater interactions with carbonate precipitation in fractures. Taking into account this organic carbon, we estimate C isotope composition of mean altered oceanic crust at ? -4.7per mil, similar to the d13C of the C degassed from the mantle at ridge axis, and discuss the global carbon budget. The total flux of C stored in the altered oceanic crust, as carbonate and organic compound, is 2.9 ± 0.4 * 10**12 molC/yr