Application of calcite Mg partitioning functions to the reconstruction of paleocean Mg/Ca

Calcite Mg/Ca is usually assumed to vary linearly with solution Mg/Ca, that a constant partition coefficient describes the relationship between these two ratios. Numerous published empirical datasets suggests that this relationship is better described by a power function. We provide a compilation of these literature data for biotic and abiotic calcite in the form of Calcite Mg/Ca = F(Solution Mg/Ca)^H, where F and H are empirically determined fitting parameters describing the slope and deviation from linearity, respectively, of the function. This is equivalent to Freundlich sorption behavior controlling Mg incorporation in calcite. Using a power function, instead of a partition coefficient, lowers Phanerozoic seawater Mg/Ca estimates based on echinoderm skeletal material by, on average, 0.5 mol/mol from previous estimates.These functions can also be used to model the primary skeletal calcite Mg/Ca of numerous calcite phases through geologic time. Such modeling suggests that the Mg/Ca of all calcite precipitated from seawater has varied through the Phanerozoic in response to changing seawater Mg/Ca and that the overall range in Mg/Ca measured among various calcite phases would be greatest when seawater Mg/Ca was also high (e.g., “aragonite seas”) and lowest when seawater Mg/Ca was low (e.g., “calcite seas”). It follows that, during times of “calcite seas” when the seawater Mg/Ca is presumed to have been lower, deposition of calcite with low Mg contents would have resulted in a depressed drive for diagenetic stabilization of shelfal carbonate and, in turn, lead to greater preservation of crystal and skeletal microfabrics and primary chemistries in biotic and abiotic calcites.     

Using Resin‐Based 3D Printing to Build Geometrically Accurate Proxies of Porous Sedimentary Rocks

Three‐dimensional (3D) printing is capable of transforming intricate digital models into tangible objects, allowing geoscientists to replicate the geometry of 3D pore networks of sedimentary rocks. We provide a refined method for building scalable pore‐network models (“proxies”) using stereolithography 3D printing that can be used in repeated flow experiments (e.g., core flooding, permeametry, porosimetry). Typically, this workflow involves two steps, model design and 3D printing. In this study, we explore how the addition of post‐processing and validation can reduce uncertainty in the 3D‐printed proxy accuracy (difference of proxy geometry from the digital model). Post‐processing is a multi‐step cleaning of porous proxies involving pressurized ethanol flushing and oven drying. Proxies are validated by: (1) helium porosimetry and (2) digital measurements of porosity from thin‐section images of 3D‐printed proxies. 3D printer resolution was determined by measuring the smallest open channel in 3D‐printed “gap test” wafers. This resolution (400 µm) was insufficient to build porosity of Fontainebleau sandstone (～13%) from computed tomography data at the sample's natural scale, so proxies were printed at 15‐, 23‐, and 30‐fold magnifications to validate the workflow. Helium porosities of the 3D‐printed proxies differed from digital calculations by up to 7% points. Results improved after pressurized flushing with ethanol (e.g., porosity difference reduced to ～1% point), though uncertainties remain regarding the nature of sub‐micron “artifact” pores imparted by the 3D printing process. This study shows the benefits of including post‐processing and validation in any workflow to produce porous rock proxies.     

Physicochemical structural characterization of ambers from deposits in Poland

The physical and chemical properties of 8 samples of amber from different localities in Poland (Baltic Coast, Bełchatów Tertiary brown coal, and Jaroszów clay mine) were investigated by N₂ sorption at 77 K, positron annihilation spectroscopy for chemical analysis (PASCA) and by organic geochemical methods (FT-IR,¹H and¹³C NMR, GC, and GC-MS). The porosity of the ambers as determined by PASCA consists of narrow micropores with diameters ranging from 0.8 to 0.9 nm and a volume 0.025 cm³ g⁻¹. In the external eroded part of the amber samples (rind) the concentration of pores where positronium atoms can form is lower and consists of approximately12 the concentration as in their interior. Values of pore parameters determined from sorption of N₂ are comparable with those found by the PASCA method. The average diameter of pores ranges from 2 to 12 nm, while their volume varies from 0.018 to 0.048 cm³ g⁻¹.. The chemical character of the ambers is similar based on FT-IR spectroscopy. However, noticeable differences in concentrations of ester and hydroxyl groups are observed in both exterior and interior regions, where the abundances of the ester groups are lower in the exterior rind. The proportion of organic material extractable with chloroform-methanol (1:1, v/v) ranges from 15 to 50% and correlates inversely to the average reflectances (R_r) of polished amber surfaces which range from 1.7 to 0.1 %. These variations are attributed to differing concentrations of oxygenated groups in the respective amber samples. The FT-IR spectra of the non-polar fractions (NP) from the extracts resemble the spectra of the source ambers. However, the intensities of the absorbance for the hdroxyl group are much lower, while absorbances for exomethylene groups are not present. The¹H and¹³C NMR data of NP fractions showed a complex diversity of components in mixtures with different relative concentrations but predominantly aliphatic in character for the respective samples.GC and GC-MS analyses of these fractions revealed that they are comprised of a mixture of compounds typical for Baltic amber but with variable relative concentrations. Two groups of compounds are found to be common to all NP fractions. The first is a minor concentration of homologousn-alkanes with a characteristic Gaussian distribution in the range from C₂₂ to C₃₂ and maximizing at C₂₆–C₂₇. In addition C₂₂ is characteristically slightly higher in concentration compared to C₂₃. The second group of compounds is comprised of succinates with methyl, fenchyl, bomyl and isobornyl alcohols. The composition of these diesters revealed the same equilibrium ratio between compounds with fenchyl, bornyl and isobornyl alcohols in all NP fractions. We suggest an early enzymatically controlled (bacterial) process in the formation of succinates during resin diagenesis from the biotic precursors, yielding the same characteristic ratio of the respective succinates in these ambers. These results show that all the ambers analyzed here fall into a common class of fossil resin, succinite (class Ia) independent of the sample location in Poland.     

Touchable topography: 3D printing elevation data and structural models to overcome the issue of scale

The fundamental problem of geology is scale. Geological length scales range from angstroms for atoms to thousands of kilometres for planets. Geological processes are often very slow (and geological events so very infrequent). Since the beginning of our discipline, it has been the business of geologists to integrate observations at a variety of length and time scales to answer questions about Earth's history and to make predictions about its future. While this may sound like one of the most academic of pursuits, multi‐billion dollar decisions are routinely made by governments and the largest multi‐national corporations on the basis of geological studies that, for example, model groundwater or petroleum occurrence.