Crack Coalescence in Molded Gypsum and Carrara Marble: Part 2—Microscopic Observations and Interpretation

Experimental uniaxial compression loading tests were conducted on molded gypsum and Carrara marble prismatic specimens to study the cracking and coalescence processes between pre-existing artificial flaws. The study showed that material had an influence on the cracking and coalescence processes (see the companion paper in this issue). As reported in the companion paper, one of the pronounced features as observed in the high-speed video recordings was the development of macroscopic white patches prior to the development of observable cracks in marble, but not in gypsum. This paper (part 2) deals with the microscopic aspects of the study. Specifically, the scanning electron microscope (SEM) and the environmental scanning electron microscope (ESEM) imaging techniques were used to study the microscopic development of white patches and their evolution into macroscopic tensile cracks and shear cracks in marble, and the microscopic initiation of hair-line tensile cracks and their evolution into macroscopic tensile cracks in gypsum. The microscopic imaging study in marble showed that the white patches were associated with extensive microcracking zones (process zones), while the extent of process zone development in gypsum was limited. The comparison of the macroscopic and microscopic results indicates that the different extent of microcracking zone development, related to the material textural properties, is a key factor leading to different macroscopic cracking behavior in gypsum and marble.

Zemannite-type Selenites: Crystal structures of K2[CO2(SeO3)3] · 2H2O and K2[Ni2(SeO3)3] · 2H2O

Summary Crystals of K₂[Co₂(SeO₃)₃]-2H₂O and K₂[Ni₂(SeO₃)₃]-2H₂O were synthesized under low-hydrothermal conditions. Their structures were determined using single crystal X-ray data up to sin / = 0.7Å^-1. [Space group P6₃/m; a = 9.091(3),9.016(2)Å; c = 7.562(2), 7.476(2)Å; Z = 2; R_W = 1.6, 2.5%]. The investigations confirmed that K₂[Co₂(SeO₃)₃].2H₂O and K₂[Ni₂(SeO₃)₃]-2H₂O represent the first selenites belonging to the zemannite structure type, a framework structure with wide channels running parallel [0001]. In both compounds four maxima were clearly located in the channel by Fourier summations and attributed to two K atoms and two H₂O molecules, each with an occupancy factor of 1/6; a possible ordering scheme (full occupancy) with local symmetry 1 and [6]-coordinated K atoms could be derived for the channel atoms.Zusammenfassung Kristalle von K₂[Co₂(SeO₃)₃]-2H₂O und K₂[Ni₂(SeO₃)₃]-2H₂O wurden unter niedrig-hydrothermalen Bedingungen synthetisiert. Die Strukturen wurden unter Verwendung von Einkristallröntgendaten bis sin /= 0.7Å^-1 bestimmt. [Raumgruppe P6₃/m; a = 9.091(3), 9.016(2)Å; c = 7.562(2), 7.476(2)Å; Z = 2; R_W = 1.6, 2.5%] Die Untersuchungen bestätigten, daß K2[Co₂(SeO₃)₃] - 2H₂O und K₂ [Ni₂(SeO₃)₃] - 2H₂O als erste Selenite dem Strukturtyp des Zemannits angehören, einer Gerüststruktur mit weiten, parallel [0001] verlaufenden Kanälen. In beiden Verbindungen wurden im Kanal vier Maxima durch Fourier-Summationen eindeutig lokalisiert und zwei Kalium-atomen sowie zwei H₂O Molekülen, jeweils mit einem Besetzungsfaktor von 1/6, zugeschrieben. Für die Kanalatome konnte ein möglicher Ordnungszustand (volle Besetzung) mit lokaler Symmetrie 1 und [6]-koordinierten Kaliumatomen abgeleitet werden.

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Selenite des Zemannittyps: Kristallstrukturen von K₂[Co₂(SeO₃)₃] - 2H₂O und K₂[Ni₂(SeO₃)₃]-2H₂O

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Dedicated to Prof. Dr. Josef Zemann at the occasion of his 70^th birthday

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With 2 Figures     

The solubility of [4H]Si defects in α-quartz and their role in the formation of molecular water and related weakening on heating

The nature of the solubility of water as [4H]_Si defects in quartz, and their role in providing a source of molecular water on heating, is investigated. Existing ab inito energy calculations on the incorporation of water in quartz are used to show that energetically 4H for Si substitution is likely to constitute the most prevalent mode of water uptake on the atomic scale in quartz under equilibrium conditions, and that the planar defects previously observed by a number of different authors by electron microscopy in wet quartz are likely to be planar rafts of aggregated [4H]_Si defects which are formed on supersaturation. These new conclusions call into question the previous identification of the planar defects as high pressure water clusters and require that their role in the production of molecular water in the context of recent theories of hydrolytic weakening be re-assessed. Accordingly the existing ab initio results have been used to establish the characteristics of the phase diagram for the system quartz-water in the temperature and pressure range of interest in hydrolytic weakening. Additional electron-optical experiments on wet quartz show that, on annealing at temperature in the electron microscope, similar planar defects develop in wet quartz by a diffusion process. In the context of existing theories of hydrolytic weakening it is now proposed that the conversion of [4H]_Si defects to molecular water, where this is dictated by the equilibrium phase diagram, leads to a relatively large increase in volume and to the appearance of the bubbles of free water and the nucleation of associated prismatic dislocation loops of Burgers vector b=1/3 a $\langle 11\bar 20\rangle $ as previously observed. Ultimately the development of these loops leads to dislocation-induced plasticity.     

BaMn[CO3]2 – a previously unrecognized double carbonate in low-temperature environments: Structural,spectroscopic, and textural tools for future identification

Following a tentative evidence for the occurrence of low-temperature barium manganese(II) carbonates in brackish sediments of the Baltic Sea, a stoichiometric double carbonate, BaMn[CO₃]₂, was synthesized from aqueous solutions at ambient temperature for the first time. Here we report the results of a multi-method approach, including scanning electron microscopy (SEM–EDX) investigations, the chemical composition, and, in particular, the diagnostic powder X-ray diffraction pattern, as well as diagnostic parts of the FT infrared absorption and Raman spectra for future identification of this new carbonate in low-temperature environments, like brackish sediments.     

Single-crystal EPR study of three radiation-induced defects (Al–O2 3?, Ti3+ and W5+) in stishovite

Single-crystal electron paramagnetic resonance spectra of electron-irradiated stishovite, measured at temperatures from 3.5 to 294?K, reveal three S?=?1/2 radiation-induced defects: an aluminum-associated oxygen hole center and two nd ¹ centers (Ti³⁺ and W⁵⁺). The aluminum-associated oxygen hole center, characterized by an orthorhombic site symmetry, coaxial matrices of the electronic Zeeman g, nuclear hyperfine A(²⁷Al) and nuclear quadrupole P(²⁷Al), and the orientation of the g-minimum axis along an O–O direction and those of the unique A(²⁷Al) and P(²⁷Al) axes perpendicular to the O–O direction, is an Al–O₂ ^3? center, with the unpaired electron equally distributed on two equatorial oxygen atoms of a substitutional Al³⁺ ion at the octahedral Si site. Fully optimized Al-doped structure, theoretical ²⁷Al nuclear hyperfine and quadrupole coupling constants and directions, and 3D spin densities from periodic hybrid density functional theory calculations provide further support for this structural model. Spin Hamiltonian parameters of the Ti³⁺ and W⁵⁺ centers, which are confirmed by their diagnostic ⁴⁷Ti, ⁴⁹Ti and ¹⁸³W hyperfine structures, arise from electron trapping on substitutional Ti⁴⁺ and W⁶⁺ ions at the octahedral Si site.     

Description and crystal structure of albrechtschraufite, MgCa4F2[UO2(CO3)3]2⋅17-18H2O

Albrechtschraufite, MgCa₄F₂[UO₂(CO₃)₃]₂?17-18H₂O, triclinic, space group Pī, a?=?13.569(2), b?=?13.419(2), c?=?11.622(2) Å, α?=?115.82(1), β?=?107.61(1), γ?=?92.84(1)° (structural unit cell, not reduced), V?=?1774.6(5) ų, Z?=?2, D _c?=?2.69 g/cm³ (for 17.5 H₂O), is a mineral that was found in small amounts with schröckingerite, NaCa₃F[UO₂(CO₃)₃](SO₄)?10H₂O, on a museum specimen of uranium ore from Joachimsthal (Jáchymov), Czech Republic. The mineral forms small grain-like subhedral crystals (≤ 0.2 mm) that resemble in appearance liebigite, Ca₂[UO₂(CO₃)₃]??~?11H₂O. Colour pale yellow-green, luster vitreous, transparent, pale bluish green fluorescence under ultraviolet light. Optical data: Biaxial negative, nX?=?1.511(2), nY?=?1.550(2), nZ?=?1.566(2), 2?V?=?65(1)° (λ?=?589 nm), r < v weak. After qualitative tests had shown the presence of Ca, U, Mg, CO₂ and H₂O, the chemical formula was determined by a crystal structure analysis based on X-ray four-circle diffractometer data. The structure was later on refined with data from a CCD diffractometer to R1?=?0.0206 and wR2?=?0.0429 for 9,236 independent observed reflections. The crystal structure contains two independent [UO₂(CO₃)₃]^4? anions of which one is bonded to two Mg and six Ca while the second is bonded to only one Mg and three Ca. Magnesium forms a MgF₂(O_carbonate)₃(H₂O) octahedron that is linked via the F atoms with three Ca atoms so as to provide each F atom with a flat pyramidal coordination by one Mg and two Ca. Calcium is 7- and 8-coordinate forming CaFO₆, CaF₂O₂(H₂O)₄, CaFO₃(H₂O)₄ and CaO₂(H₂O)₆ coordination polyhedra. The crystal structure is built up from MgCa₃F₂[UO₂(CO₃)₃]?8H₂O layers parallel to (001) which are linked by Ca[UO₂(CO₃)₃]?5H₂O moieties into a framework of the composition MgCa₄F₂[UO₂(CO₃)₃]?13H₂O. Five additional water molecules are located in voids of the framework and show large displacement parameters. One of the water positions is partly vacant, leading to a total water content of 17-18H₂O per formula unit. The MgCa₃F₂[UO₂(CO₃)₃]?8H₂O layers are pseudosymmetric according to plane group symmetry cmm. The remaining constituents do not sustain this pseudosymmetry and make the entire structure truly triclinic. A characteristic paddle-wheel motif Ca[UO₂(CO₃)₃]₄Ca relates the structure of albrechtschraufite partly to that of andersonite and two synthetic alkali calcium uranyl tricarbonates.     

Dauphiné twinning and texture memory in polycrystalline quartz. Part 3: texture memory during phase transformation

Samples of quartz-bearing rocks were heated above the α (trigonal)–β (hexagonal) phase transformation of quartz (625–950°C) to explore changes in preferred orientation patterns. Textures were measured both in situ and ex situ with neutron, synchrotron X-ray and electron backscatter diffraction. The trigonal–hexagonal phase transformation does not change the orientation of c- and a-axes, but positive and negative rhombs become equal in the hexagonal β-phase. In naturally deformed quartzites measured by neutron diffraction a perfect texture memory was observed, i.e. crystals returned to the same trigonal orientation they started from, with no evidence of twin boundaries. Samples measured by electron back-scattered diffraction on surfaces show considerable twinning and memory loss after the phase transformation. In experimentally deformed quartz rocks, where twinning was induced mechanically before heating, the orientation memory is lost. A mechanical model can explain the memory loss but so far it does not account for the persistence of the memory in quartzites. Stresses imposed by neighboring grains remain a likely cause of texture memory in this mineral with a very high elastic anisotropy. If stresses are imposed experimentally the internal stresses are released during the phase transformation and the material returns to its original state prior to deformation. Similarly, on surfaces there are no tractions and thus texture memory is partially lost.     

Crystal structure of KMn3+ [SeO4]2 — a triclinic distorted member of the Yavapaiite family

Summary The crystal structure of synthetic KMn[SeO₄]₂ was determined by single crystal X-ray diffraction methods in space group , a = 4.827(2) Å, b = 4.988(2) Å, c = 7.981(3) Å, = 83.18(1)°, = 85.32(2)°, = 67.92(1)°, V = 176.66 ų, Z = 1; 1564 unique data, measured up to 2 = 70° (MoK-radiation); R, R(I)_w = 0.034, 0.074.KMn[SeO₄]₂ is closely related to monoclinic yavapaiite, KFe[SO₄]₂, and isotypic compounds. Jahn-Teller distorted MnO₆ octahedra are alternately linked with KO₁₀ polyhedra along [001]. The mean values of the Mn-O and Se-O distances are 2.007 Å and 1.637 Å, respectively.

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Die Kristallstruktur vonKMn ³⁺[SeO₄]-einem triklin verzerrten Vertreter der Yavapaiite-Familie

Zusammenfassung Die Kristallstruktur von synthetisch dargestelltem KMn[SeO₄]₂ wurde mittels Einkristallröntgenmethoden in der Raumgruppe bestimmt: a = 4.827(2) Å, b = 4.988(2) Å, c = 7.981(3) Å, = 83.18(1)°, = 85.32(2)°, = 67.92(1)°, V = 176.66 ų, Z = 1; 1564 unabhängige Daten bis 2 = 70° (MoK-Strahlung); R, R(I)_w = 0.034, 0.074.KMn[SeO₄]₂ ist eng mit dem monoklinen Mineral Yavapaiit, KFe[SO₄]₂ und einer Reihe damit isotyper Verbindungen verwandt. Jahn-Teller verzerrte MnO₆ Oktaeder sind alternierend mit KO₁₀ Polyedern parallel [001] verbunden. Die Mittelwerte der Mn-O und Se-O Abstände sind 2.007 Å bzw. 1.637 Å.

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With 1 Figure     

1—（2—羟基—3,5—二硝基苯基）—3—[4—（苯基偶氮）苯基]—三氮烯与铜的显色反应

研究了新合成的１－（２－羟基－３,５－二硝基苯基）－３－「４－（苯基偶氮）苯基」－三氮烯（ＨＤＮＰＡＰＴ）试剂与铜的显色反应。在乳化剂ＯＰ存在下,ＰＨ１１．０的Ｎａ２Ｂ４Ｏ７－ＮａＯＨ介质中,铜与ＨＤＮＰＡＰＴ形成的红色配合物,其组成比为１：２,λｍａｘ＝５４０ｎｍ,表观摩尔吸光系数ε５４０＝１．７３×１０＾５Ｌ·ｍｏｌ＾－１·ｃｍ＾－１,铜的质量浓度在０￣３６０μｇ／Ｌ符合比尔定律。方法应用于大     

Interactions in the system [basalt-SO2-O2 ± S2]: A thermodynamic model

A thermodynamic model for gas-rock interactions in the system [basalt-SO₂-O₂±S₂] is suggested. Calculations are performed for a wide range of temperatures (100–850°C) and pressures (1–1000 bars). The high-temperature part of this model was verified by experimental research, which was carried out at 850, 650 and 450°C. The modeling prediction of interactions in the system [(alumino)silicates SO₂-O₂±S₂] at relatively low temperatures (100–300°C) gives steady mineral associations that are typical for natural secondary quartzites: quartz-pyrite-hematite-Al-silicates-metal sulfates (Ca, Mg, Na, K, Al, and Fe). The formation of sulfates stabilizes the level of SO₂ concentration in the gas phase; this level falls with a temperature decrease.     

Modeling CO2 chemistry, δC, and oxidation of organic carbon and methane in sediment porewater: Implications for paleo-proxies in benthic foraminifera

I present a numerical diffusion-advection-reaction model to simulate CO₂ chemistry, δ¹³C, and oxidation of organic carbon and methane in sediment porewater. The model takes into account detailed reaction kinetics of dissolved CO₂ compounds, H₂O, H⁺, OH⁻, boron and sulfide compounds. These reactions are usually assumed to be in local equilibrium, which is shown to be a good approximation in most cases. The model also includes a diffusive boundary layer across which chemical species are transported between bottom water and the sediment-water interface. While chemical concentrations and δ¹³C_TCO2 at these locations are frequently assumed equal, I demonstrate that they can be quite different. In this case, shells of benthic foraminifera do not reflect the desired properties of bottom water, even for species living at the sediment-water interface (z = 0 cm). Environmental conditions recorded in their shells are strongly influenced by processes occurring within the sediment. The model is then applied to settings in the Santa Barbara Basin and at Hydrate Ridge (Cascadia Margin), locations of strong organic carbon and methane oxidation. In contrast to earlier studies, I show that a limited contribution of methane-derived carbon to porewater TCO₂ in the Santa Barbara Basin cannot be ruled out. Simulation of methane venting shows that at oxidation rates greater than , the δ¹³C of porewater TCO₂ at z > 1 cm is depleted by more than 15‰ relative to bottom water. Depletions of this magnitude have not been observed in living benthic foraminifera, even at methane vents with much higher oxidation rates. This suggests that foraminifera at these sites either calcify at very shallow sediment depth or during times when oxidation rates are much lower than ∼50 μmol cm⁻² y⁻¹.     

Dissolution kinetics of selected natural minerals relevant to potential CO2-injection sites – Part 2: Dissolution and alteration of carbonates and feldspars in CO2-bearing brines

Chemical interaction processes among injected CO₂, saline fluids and potential reservoir materials are experimentally simulated to derive dissolution rates of natural materials (minerals) that can be used as input parameters for modeling of CO₂ storage in deep saline formations and risk analyses. In order to study dissolution processes, mineral aliquots were exposed to CO₂-bearing brines at elevated temperature (60, 100, 150 °C) and pressure (85 bar) and at various run durations. Several potential reservoir rocks include carbonates as cement. Calcite and dolomite grains were therefore mainly used as solid starting material. Experiments with the two feldspar varieties alkali feldspar and almost pure anorthite were performed in addition. Grain sizes of the mineral starting materials varied between <63 μm and 500 μm with most experiments performed at grain size fractions of 160 – 250 μm and 250 – 500 μm. All experiments run with a complex synthetic brine (total dissolved solids: ∼156 g/l) according to a natural upper cretaceous formation water. Dry ice was used as CO₂-source. All experiments were done in closed batch reactors. These reactors allow mimicking reservoir conditions far from the injection site as well as reservoir conditions after finishing the CO₂ injection. The concentration changes during the experiment were monitored by ICP-OES measurements of the initial and the post-run fluids. Dissolution rates were derived based on the concentration changes of the brine.Most of the studied experimental variables and parameters (temperature, run duration, grain size, brine composition – expressed as pH-value and ionic strength) impact alteration of the reacting agents, i.e. they change the chemical composition of the brine, change the surfaces of the mineral aliquots exposed to the CO₂-bearing brine, and induce formation of secondary minerals. Hence, all influencing parameters on dissolution processes have to be considered and time-resolved changes of the dissolution behavior have to be implemented in numerical simulations of processes at CO₂ injection sites and CO₂ storage reservoirs.     

Re-equilibration of natural H2O–CO2–salt-rich fluid inclusions in quartz—Part 1: experiments in pure water at constant pressures and differential pressures at 600 °C

Re-equilibration processes of natural H₂O–CO₂–NaCl-rich fluid inclusions quartz are experimentally studied by exposing the samples to a pure H₂O external fluid at 600 °C. Experimental conditions are selected at nearly constant pressure conditions (309 MPa) between fluid inclusions and pore fluid, with only fugacity gradients in H₂O and CO₂, and at differential pressure conditions (394–398 MPa, corresponding to an internal under-pressure) in addition to similar CO₂ fugacity gradients and larger H₂O fugacity gradients. Modifications of fluid inclusion composition and density are monitored with changes in ice dissolution temperature, clathrate dissolution temperature and volume fraction of the vapour phase at room temperature. Specific modification of these parameters can be assigned to specific processes, such as preferential loss/gain of H₂O and CO₂, or changes in total volume. A combination of these parameters can clearly distinguish between modifications according to bulk diffusion or deformation processes. Bulk diffusion of CO₂ according to fugacity gradients is demonstrated at constant pressure conditions. The estimated preferential loss of H₂O is not in accordance with those gradients in both constant pressure and differential pressure experiments. The development of deformation halos in quartz around fluid inclusions that are either under-pressurized or over-pressurized promotes absorption of H₂O from the inclusions and inhibits bulk diffusion according to the applied fugacity gradients.     

Correlated δ18O and [Ti] in lunar zircons: a terrestrial perspective for magma temperatures and water content on the Moon

Zircon grains were separated from lunar regolith and rocks returned from four Apollo landing sites, and analyzed in situ by secondary ion mass spectrometry. Many regolith zircons preserve magmatic δ¹⁸O and trace element compositions and, although out of petrologic context, represent a relatively unexplored resource for study of the Moon and possibly other bodies in the solar system. The combination of oxygen isotope ratios and [Ti] provides a unique geochemical signature that identifies zircons from the Moon. The oxygen isotope ratios of lunar zircons are remarkably constant and unexpectedly higher in δ¹⁸O (5.61 ± 0.07 ‰ VSMOW) than zircons from Earth’s oceanic crust (5.20 ± 0.03 ‰) even though mare basalt whole-rock samples are nearly the same in δ¹⁸O as oceanic basalts on Earth (~5.6 ‰). Thus, the average fractionation of oxygen isotopes between primitive basalt and zircon is smaller on the Moon [Δ¹⁸O(WR-Zrc) = 0.08 ± 0.09 ‰] than on Earth (0.37 ± 0.04 ‰). The smaller fractionations on the Moon suggest higher temperatures of zircon crystallization in lunar magmas and are consistent with higher [Ti] in lunar zircons. Phase equilibria estimates also indicate high temperatures for lunar magmas, but not specifically for evolved zircon-forming melts. If the solidus temperature of a given magma is a function of its water content, then so is the crystallization temperature of any zircon forming in that melt. The systematic nature of O and Ti data for lunar zircons suggests a model based on the following observations. Many of the analyzed lunar zircons are likely from K, rare earth elements, P (KREEP)-Zr-rich magmas. Zircon does not saturate in normal mafic magmas; igneous zircons in mafic rocks are typically late and formed in the last most evolved portion of melts. Even if initial bulk water content is moderately low, the late zircon-forming melt can concentrate water locally. In general, water lowers crystallization temperatures, in which case late igneous zircon can form at significantly lower temperatures than the solidus inferred for a bulk-rock composition. Although lunar basalts could readily lose H₂ to space during eruption, lowering water fugacity; the morphology, large size, and presence in plutonic rocks suggest that many zircons crystallized at depths that retarded degassing. In this case, the crystallization temperatures of zircons are a sensitive monitor of the water content of the parental magma as well as the evolved zircon-forming melt. If the smaller Δ¹⁸O(zircon–mare basalt) values reported here are characteristic of the Moon, then that would suggest that even highly evolved zircon-forming magmas on the Moon crystallized at higher temperature than similar magmas on Earth and that magmas, though not necessarily water-free, were generally drier on the Moon.     

Chemical and physical studies of type 3 chondrites—VIII: Thermoluminescence and metamorphism in the CO chondrites

The thermoluminescence properties of nine CO chondrites have been measured. With the exception of Colony and Allan Hills A77307 (ALHA 77307), whose maximum induced TL emission is at approximately 350°C, CO chondrites exhibit two TL peaks, one at 124 ± 7°C (130°C peak) and one at 252 ± 7°C (250°C peak). The 130°C peak shows a 100-fold range in TL sensitivity (0.99 ± 0.21 for Isna to 0.010 ± 0.004 for Colony), and correlates with various metamorphism-related phenomena, such as silicate heterogeneity, metal composition and McSween's metamorphic subtypes. The peak at 250°C does not show these correlations and, Colony excepted, varies little throughout the class (0.3 to 0.07, Colony 0.018 ± 0.004). Mineral separation experiments, and a series of annealing experiments on Isna, suggest that the TL properties for CO chondrites reflect the presence of feldspar in two forms, (1) a form produced during metamorphism, and analogous to the dominant form of feldspar in type 3 ordinary chondrites, and (2) a primary, metamorphism-independent form, perhaps associated with the amoeboid inclusions. If this interpretation is correct, then the CO chondrites have not experienced temperatures above the order/disorder temperature for feldspar (500–600°C) and they cooled more slowly than comparable (i.e. type <3.5) type 3 ordinary chondrites. Colony and ALHA 77307 have atypical TL properties, including very low TL sensitivity, suggesting that phosphors other than feldspar are important. They have apparently experienced less metamorphism than the others, and may have also been aqueously altered.     

Enigmatic structures within salt walls of the Santos Basin—Part 1: Geometry and kinematics from 3D seismic reflection and well data

Understanding intrasalt structure may elucidate the fundamental kinematics and, ultimately, the mechanics of diapir growth. However, there have been relatively few studies of the internal structure of salt diapirs outside the mining industry because their cores are only partly exposed in the field and poorly imaged on seismic reflection data. This study uses 3D seismic reflection and borehole data from the São Paulo Plateau, Santos Basin, offshore Brazil to document the variability in intrasalt structural style in natural salt diapirs. We document a range of intrasalt structures that record: (i) initial diapir rise; (ii) rise of lower mobile halite through an arched and thinned roof of denser, layered evaporites, and emplacement of an intrasalt sheet or canopy; (iii) formation of synclinal flaps kinematically linked to emplacement of the intrasalt allochthonous bodies; and (iv) diapir squeezing. Most salt walls contain simple internal anticlines. Only a few salt walls contain allochthonous bodies and breakout-related flaps. The latter occur in an area having a density inversion within the autochthonous salt layer, such that upper, anhydrite-rich, layered evaporites are denser than lower, more halite-rich evaporites. We thus interpret that most diapirs rose through simple fold amplification of internal salt stratigraphy but that locally, where a density inversion existed in the autochthonous salt, Rayleigh–Taylor overturn within the growing diapir resulted in the ascent of less dense evaporites into the diapir crest by breaching of the internal anticline. This resulted in the formation of steep salt-ascension zones or feeders and the emplacement of high-level intrasalt allocthonous sheets underlain by breakout-related flaps. Although regional shortening undoubtedly occurred on the São Paulo Plateau during the Late Cretaceous, we suggest this was only partly responsible for the complex intrasalt deformation. We suggest that, although based on the Santos Basin, our kinematic model may be more generally applicable to other salt-bearing sedimentary basins.     

Modeling the Population Effects of Hypoxia on Atlantic Croaker (<Emphasis Type="Italic">Micropogonias undulatus</Emphasis>) in the Northwestern Gulf of Mexico: Part 2—Realistic Hypoxia and Eutrophication

Quantifying the population-level effects of hypoxia on coastal fish species has been challenging. In the companion paper (part 1), we described an individual-based population model (IBM) for Atlantic croaker in the northwestern Gulf of Mexico (NWGOM) designed to quantify the long-term population responses to low dissolved oxygen (DO) concentrations during the summer. Here in part 2, we replace the idealized hypoxia conditions with realistic DO concentrations generated from a 3-dimensional water quality model. Three years were used and randomly arranged into a time series based on the historical occurrence of mild, intermediate, and severe hypoxia year types. We also used another water quality model to generate multipliers of the chlorophyll concentrations to reflect that croaker food can be correlated to the severity of hypoxia. Simulations used 100 years under normoxia and hypoxia conditions to examine croaker population responses to the following: (1) hypoxia with food uncoupled and coupled to the severity of hypoxia, (2) hypoxia reducing benthos due to direct mortality, (3) how much hypoxia would need to be reduced to offset decreased croaker food expected under 25 and 50% reduction in nutrient loadings, and (4) key assumptions about avoidance movement. Direct mortality on benthos had no effect on long-term simulated croaker abundance, and the effect of hypoxia (about a 25% reduction in abundance) was consistent whether chlorophyll (food) varied with hypoxia or not. Reductions in hypoxia needed with a 25% reduction in nutrient loadings to result in minimal loss of croaker is feasible, and the croaker population will likely do as well as possible (approach abundance under normoxia) under the 50% reduction in nutrient loadings. We conclude with a discussion of why we consider our simulation-based estimates of hypoxia causing a 25% reduction the long-term population abundance of croaker in the NWGOM to be realistic and robust.