Reconstructing Past Depositional and Diagenetic Processes through Quantitative Stratigraphic Analysis of the Martian Sedimentary Rock Record

High-resolution orbital and in situ observations acquired of the Martian surface during the past two decades provide the opportunity to study the rock record of Mars at an unprecedented level of detail. This dissertation consists of four studies whose common goal is to establish new standards for the quantitative analysis of visible and near-infrared data from the surface of Mars. Through the compilation of global image inventories, application of stratigraphic and sedimentologic statistical methods, and use of laboratory analogs, this dissertation provides insight into the history of past depositional and diagenetic processes on Mars. The first study presents a global inventory of stratified deposits observed in images from the High Resolution Image Science Experiment (HiRISE) camera on-board the Mars Reconnaissance Orbiter. This work uses the widespread coverage of high-resolution orbital images to make global-scale observations about the processes controlling sediment transport and deposition on Mars. The next chapter presents a study of bed thickness distributions in Martian sedimentary deposits, showing how statistical methods can be used to establish quantitative criteria for evaluating the depositional history of stratified deposits observed in orbital images. The third study tests the ability of spectral mixing models to obtain quantitative mineral abundances from near-infrared reflectance spectra of clay and sulfate mixtures in the laboratory for application to the analysis of orbital spectra of sedimentary deposits on Mars. The final study employs a statistical analysis of the size, shape, and distribution of nodules observed by the Mars Science Laboratory Curiosity rover team in the Sheepbed mudstone at Yellowknife Bay in Gale crater. This analysis is used to evaluate hypotheses for nodule formation and to gain insight into the diagenetic history of an ancient habitable environment on Mars.

A mathematical study of finite-amplitude rock-folding

The problem of the finite-amplitude folding of an isolated, linearly viscous layer under compression and imbedded in a medium of lower viscosity is treated theoretically by using a variational method to derive finite difference equations which are solved on a digital computer. The problem depends on a single physical parameter, the ratio of the fold wavelength, L, to the "dominant wavelength" of the infinitesimal-amplitude treatment, L_d. Therefore, the natural range of physical parameters is covered by the computation of three folds, with L/L_d = 0, 1, and 4.6, up to a maximum dip of 90°.

Significant differences in fold shape are found among the three folds; folds with higher L/L_d have sharper crests. Folds with L/L_d = 0 and L/L_d = 1 become fan folds at high amplitude. A description of the shape in terms of a harmonic analysis of inclination as a function of arc length shows this systematic variation with L/L_d and is relatively insensitive to the initial shape of the layer. This method of shape description is proposed as a convenient way of measuring the shape of natural folds.

The infinitesimal-amplitude treatment does not predict fold-shape development satisfactorily beyond a limb-dip of 5°. A proposed extension of the treatment continues the wavelength-selection mechanism of the infinitesimal treatment up to a limb-dip of 15°; after this stage the wavelength-selection mechanism no longer operates and fold shape is mainly determined by L/L_d and limb-dip.

Strain-rates and finite strains in the medium are calculated f or all stages of the L/L_d = 1 and L/L_d = 4.6 folds. At limb-dips greater than 45° the planes of maximum flattening and maximum flattening rat e show the characteristic orientation and fanning of axial-plane cleavage.

Identifying and interpreting stratification in sedimentary rocks on Mars : insight from Rover and orbital observations and terrestrial field analogs

Sedimentary rocks on Mars provide insight into past aqueous and atmospheric processes, climate regimes, and potential habitability. The stratigraphic architecture of sedimentary rocks on Mars is similar to that of Earth, indicating that the processes that govern deposition and erosion on Mars can be reasonably inferred through reference to analogous terrestrial systems. This dissertation aims to understand Martian surface processes through the use of (1) ground-based observations from the Mars Exploration Rovers, (2) orbital data from the High Resolution Imaging Science Experiment onboard the Mars Reconnaissance Orbiter, and (3) the use of terrestrial field analogs to understand bedforms and sediment transport on Mars. Chapters 1 and 2 trace the history of aqueous activity at Meridiani Planum, through the reconstruction of eolian bedforms at Victoria crater, and the identification of a potential mudstone facies at Santa Maria crater. Chapter 3 uses Terrestrial Laser Scanning to study cross-bedding in pyroclastic surge deposits on Earth in order to understand sediment transport in these events and to establish criteria for their identification on Mars. The final chapter analyzes stratal geometries in the Martian North Polar Layered Deposits using tools for sequence stratigraphic analysis, to better constrain past surface processes and past climate conditions on Mars.

Seismic reflection experiments imaging the physical nature of crustal structures in southern California

Seismic reflection methods have been extensively used to probe the Earth's crust and suggest the nature of its formative processes. The analysis of multi-offset seismic reflection data extends the technique from a reconnaissance method to a powerful scientific tool that can be applied to test specific hypotheses. The treatment of reflections at multiple offsets becomes tractable if the assumptions of high-frequency rays are valid for the problem being considered. Their validity can be tested by applying the methods of analysis to full wave synthetics.

Three studies illustrate the application of these principles to investigations of the nature of the crust in southern California. A survey shot by the COCORP consortium in 1977 across the San Andreas fault near Parkfield revealed events in the record sections whose arrival time decreased with offset. The reflectors generating these events are imaged using a multi-offset three-dimensional Kirchhoff migration. Migrations of full wave acoustic synthetics having the same limitations in geometric coverage as the field survey demonstrate the utility of this back projection process for imaging. The migrated depth sections show the locations of the major physical boundaries of the San Andreas fault zone. The zone is bounded on the southwest by a near-vertical fault juxtaposing a Tertiary sedimentary section against uplifted crystalline rocks of the fault zone block. On the northeast, the fault zone is bounded by a fault dipping into the San Andreas, which includes slices of serpentinized ultramafics, intersecting it at 3 km depth. These interpretations can be made despite complications introduced by lateral heterogeneities.

In 1985 the Calcrust consortium designed a survey in the eastern Mojave desert to image structures in both the shallow and the deep crust. Preliminary field experiments showed that the major geophysical acquisition problem to be solved was the poor penetration of seismic energy through a low-velocity surface layer. Its effects could be mitigated through special acquisition and processing techniques. Data obtained from industry showed that quality data could be obtained from areas having a deeper, older sedimentary cover, causing a re-definition of the geologic objectives. Long offset stationary arrays were designed to provide reversed, wider angle coverage of the deep crust over parts of the survey. The preliminary field tests and constant monitoring of data quality and parameter adjustment allowed 108 km of excellent crustal data to be obtained.

This dataset, along with two others from the central and western Mojave, was used to constrain rock properties and the physical condition of the crust. The multi-offset analysis proceeded in two steps. First, an increase in reflection peak frequency with offset is indicative of a thinly layered reflector. The thickness and velocity contrast of the layering can be calculated from the spectral dispersion, to discriminate between structures resulting from broad scale or local effects. Second, the amplitude effects at different offsets of P-P scattering from weak elastic heterogeneities indicate whether the signs of the changes in density, rigidity, and Lame's parameter at the reflector agree or are opposed. The effects of reflection generation and propagation in a heterogeneous, anisotropic crust were contained by the design of the experiment and the simplicity of the observed amplitude and frequency trends. Multi-offset spectra and amplitude trend stacks of the three Mojave Desert datasets suggest that the most reflective structures in the middle crust are strong Poisson's ratio (σ) contrasts. Porous zones or the juxtaposition of units of mutually distant origin are indicated. Heterogeneities in σ increase towards the top of a basal crustal zone at ~22 km depth. The transition to the basal zone and to the mantle include increases in σ. The Moho itself includes ~400 m layering having a velocity higher than that of the uppermost mantle. The Moho maintains the same configuration across the Mojave despite 5 km of crustal thinning near the Colorado River. This indicates that Miocene extension there either thinned just the basal zone, or that the basal zone developed regionally after the extensional event.

Oxygen, carbon and hydrogen isotope studies of contact metamorphism

The O¹⁸/O¹⁶, C¹³/C¹², and D/H ratios have been determined for rocks and coexisting minerals from several granitic plutons and their contact metamorphic aureoles in northern Nevada, eastern California, central Colorado, and Texas, with emphasis on oxygen isotopes. A consistent order of O¹⁸/O¹⁶, C¹³/C¹², and D/H enrichment in coexisting minerals, and a correlation between isotopic fractionations among coexisting mineral pairs are in general observed, suggesting that mineral assemblages tend to approach isotopic equilibrium during contact metamorphism. In certain cases, a correlation is observed between oxygen isotopic fractionations of a mineral pair and sample distance from intrusive contacts. Isotopic temperatures generally show good agreement with heat flow considerations. Based on the experimentally determined quartz-muscovite O¹⁸/O¹⁶ fractionation calibration curve, temperatures are estimated to be 525 to 625°C at the contacts of the granitic stocks studied.

Small-scale oxygen isotope exchange effects between intrusive and country rock are observed over distances of 0.5 to 3 feet on both sides of the contacts; the isotopic gradients are typically 2 to 3 per mil per foot. The degree of oxygen isotopic exchange is essentially identical for different coexisting minerals. This presumably occurred through a diffusion-controlled recrystallization process. The size of the oxygen isotope equilibrium systems in the small-scale exchanged zones vary from about 1.5 cm to 30 cm. A xenolith and a re-entrant of country rock projecting into on intrusive hove both undergone much more extensive isotopic exchange (to hundreds of feet); they also show abnormally high isotopic temperatures. The marginal portions of most plutons have unusually high O¹⁸/O¹⁶ ratios compared to "normal" igneous rocks, presumably due to large-scale isotopic exchange with meta-sedimentary country rocks when the igneous rocks were essentially in a molten state. The isotopic data suggest that outward horizontal movement of H₂O into the contact metamorphic aureoles is almost negligible, but upward movement of H₂O may be important. Also, direct influx and absorption of water from the country rock may be significant in certain intrusive stocks.

Except in the exchanged zones, the O¹⁸/O¹⁶ ratios of pelitic rocks do not change appreciably during contact metamorphism, even in the cordierite and sillimanite grades; this is in contrast to regional metamorphic rocks which commonly decrease in O¹⁸ with increasing grade. Low O¹⁸/O¹⁶ and C¹³/C¹² ratios of the contact metamorphic marbles generally correlate well with the presence of calc-silicate minerals, indicating that the CO₂ liberated during metamorphic decarbonation reactions is enriched in both O¹⁸ and C¹³ relative to the carbonates.

The D/H ratios of biotites in the contact metamorphic rocks and their associated intrusions show a geographic correlation that is similar to that shown by the D/H ratios of meteoric surface waters, perhaps indicating that meteoric waters were present in the rocks during crystallization of the biotites.

Interaction of aqueous inorganic orthophosphate and phosphate rock

An experimental study was made of the interaction of phosphate rock and aqueous inorganic orthophosphate, calcium, and hydroxyl ions. A model of the reaction was developed by observing electron diffraction patterns in conjunction with concentration changes of chemical components. The model was applied in explaining the performance of batch suspensions of powdered phosphate rock and packed columns of granular phosphate rock. In both cases the reaction consisted initially of a rapid nucleation phase that occurred in a time period of minutes. In the batch system the calcium phosphate nuclei then ripened into larger micro-crystals of hydroxyapatite, which eventually became indistinguishable from the original phosphate rock surface. During column operation the high supersaturation ratio that existed after the rapid nucleation phase resulted in a layer of small nuclei that covered a slowly growing hydroxyapatite crystal.

The column steady-state rate constant was found to increase with increasing temperature, pH, and fluoride concentration, and to decrease with increasing concentrations of magnesium sulfate, ammonium chloride, and bicarbonate ion.

An engineering feasibility study indicated that, based on economic considerations, nucleation of apatite on phosphate rock ore has a potential use as a wastewater phosphate removal treatment process.

The structure and petrology of the Johnny Lyon Hills area, Cochise County, Arizona

The Johnny Lyon Hills area is located in Cochise County in southeastern Arizona. The rocks of the area include a central core of Lower pre-Cambrian igneous and metamorphic rocks surrounded by a complexly faulted and tilted section of Upper pre-Cambrian and Paleozoic strata. Limited exposures of Mesozoic and Tertiary sedimentary and volcanic rocks are present at the north end of the map area. Late Tertiary and Quaternary alluvium almost completely surrounds and overlaps upon the older rocks.

The older pre-Cambrian rocks include a section of more than 9000 feet of generally moderately metamorphosed graywackes, slates and conglomerates of the Pinal schist injected in zones by somewhat younger rnyolite sheets. The original sediments were deposited in a geosyncline whose extent probably included large parts of Arizona, New Mexico and west Texas. During the Mazatzal Revolution the Pinal schist was deformed into northeast-trending, steeply dipping and plunging structures and the entire local section was overturned steeply toward the northwest. The pre-Cambrian Johnny Lyon granodiorite was emplaced as a large epi-tectonic pluton which modified the metamorphic character of part of the Pinal schist. Larsen method determinations indicate an age of about 715 million years for this rock, which is about the minimum age compatible with the geologic relations.

The Laramide orogeny produced numerous major thrust faults in the area involving all rocks older than and including the Lower Cretaceous Bisbee group. Major compression from the southwest and subsequent superimposed thrusting from the southeast and east are indicated. Minimum thrust displacements of more than a mile are clear and the probable displacements are of much greater magnitude. The crystalline core behaved as a single structural unit and probably caused important local divergences from the regional pattern of northeast-trending compressive forces. The massif was rotated as a unit 40 degrees or more about a northwest-trending axis overturning the pre-Cambrian fold axes in the Pinal schist.

Swarms of Late Cretaceous(?) or Early Tertiary(?) lamprophyric dikes cross the Laramide structures and are probably related to the large Texas Canyon stock several miles southeast of the map area. Intermittent high angle faulting, both older and younger than the dikes, has continued since the Laramide orogeny and has been superimposed on the older structures. This steep faulting combined with the fundamental northwesterly Laramide structural grain to produce the northwesterly trends characteristic of the mountain ridges and valleys of the area.

Manganese: Minerals, Microbes, and the Evolution of Oxygenic Photosynthesis

Oxygenic photosynthesis fundamentally transformed our planet by releasing molecular oxygen and altering major biogeochemical cycles, and this exceptional metabolism relies on a redox-active cubane cluster of four manganese atoms. Not only is manganese essential for producing oxygen, but manganese is also only oxidized by oxygen and oxygen-derived species. Thus the history of manganese oxidation provides a valuable perspective on our planet’s environmental past, the ancient availability of oxygen, and the evolution of oxygenic photosynthesis. Broadly, the general trends of the geologic record of manganese deposition is a chronicle of ancient manganese oxidation: manganese is introduced into the fluid Earth as Mn(II) and it will remain only a trace component in sedimentary rocks until it is oxidized, forming Mn(III,IV) insoluble precipitates that are concentrated in the rock record. Because these manganese oxides are highly favorable electron acceptors, they often undergo reduction in sediments through anaerobic respiration and abiotic reaction pathways.

The following dissertation presents five chapters investigating manganese cycling both by examining ancient examples of manganese enrichments in the geologic record and exploring the mineralogical products of various pathways of manganese oxide reduction that may occur in sediments. The first chapter explores the mineralogical record of manganese and reports abundant manganese reduction recorded in six representative manganese-enriched sedimentary sequences. This is followed by a second chapter that further analyzes the earliest significant manganese deposit 2.4 billon years ago, and determines that it predated the origin of oxygenic photosynthesis and thus is supporting evidence for manganese-oxidizing photosynthesis as an evolutionary precursor prior to oxygenic photosynthesis. The lack of oxygen during this early manganese deposition was partially established using oxygen-sensitive detrital grains, and so a third chapter delves into what these grains mean for oxygen constraints using a mathematical model. The fourth chapter returns to processes affecting manganese post-deposition, and explores the relationships between manganese mineral products and (bio)geochemical reduction processes to understand how various manganese minerals can reveal ancient environmental conditions and biological metabolisms. Finally, a fifth chapter considers whether manganese can be mobilized and enriched in sedimentary rocks and determines that manganese was concentrated secondarily in a 2.5 billion-year-old example from South Africa. Overall, this thesis demonstrates how microbial processes, namely photosynthesis and metal oxide-reducing metabolisms, are linked to and recorded in the rich complexity of the manganese mineralogical record.

Geomorphology of a Portion of the Easternmost Ventura Basin

The Humphreys Quadrangle is a portion of the easternmost Ventura Basin underlain by a thick series of Tertiary sedimentary rocks. On these rocks a great variety of geomorphic forms have been molded by the processes of running water typical of a semi-arid climate and by several types of mass movement. Among the different categories of mass movement present, a new type, the siltflow, was observed.

The geomorphic forms of special interest present in the quadrangle are rock cones, open canyonheads, asymmetric canyons, and stream terraces and straths. The author urges the adoption of the definition of strath as that part of an old dissected valley floor, including the floors of tributary valleys, which was not part of the floodplain of the main valley stream.

An old erosion surface, the Puckett Mesa Surface, is present in the Humphreys Quadrangle which is correlative with certain of the older stream terraces. By correlating the variation of gradient and of fill of the stream terraces with post –Wisconsin climatic fluctuations the age of the Puckett Mesa Surface is set at approximately 6000 B.C. This correlation sets the probable age of the older Rancho La Brea deposits at 6000 to 8000 B. C. and the probable age of the Carpenteria brea deposits at 1000 to 1 B. C.

Hydrothermal experiments on the thermal stability of amino substances in sediments

Aspartic acid, threonine, serine and other thermally unstable amino acids have been found in fine-grained elastic sediments of advanced geologic age. The presence of these compounds in ancient sediments conflicts with experimental data determined for their simple thermal decomposition.

Recent and Late Miocene sediments and their humic acid extracts, known to contain essentially complete suites of amino acids, were heated with H₂O in a bomb at temperatures up to 500°C in order to compare the thermal decomposition characteristics of the sedimentary amino compounds.

Most of the amino acids found in protein hydrolyzates are obtained from the Miocene rock in amounts 10 to 100 times less than from the Recent sediment. The two unheated humic acids are rather similar despite their great age difference. The Miocene rock appears uncontaminated by Recent carbon.

Yields of amino acids generally decline in the heated Recent sediment. Some amino compounds apparently increase with heating time in the Miocene rock.

Relative thermal stabilities of the amino acids in sediments are generally similar to those determined using pure aqueous solutions. The relative thermal stabilities of glutamic acid, glycine, and phenylalanine vary in the Recent sediment but are uniform in the Miocene rock.

Amino acids may occur in both proteins and humic complexes in the Recent sediment, while they are probably only present in stabilized organic substances in the Miocene rock. Thermal decomposition of protein amino acids may be affected by surface catalysis in the Recent sediment. The apparent activation energy for the decomposition of alanine in this sediment is 8400 calories per mole. Yields of amino compounds from the heated sediments are not affected by thermal decomposition only.

Amino acids in sediments may only be useful for geothermometry in a very general way.

A better picture of the amino acid content of older sedimentary rocks may be obtained if these sediments are heated in a bomb with H₂O at temperatures around 150°C prior to HCl hydrolysis.

Leucine-isoleucine ratios may prove to be useful as indicators of amino acid sources or for evaluating the fractionation of these substances during diagenesis. Leucine-isoleucine ratios of the Recent and Miocene sediments and humic acids are identical. The humic acids may have a continental source.

The carbon-nitrogen and carbon-hydrogen ratios of sediments and humic acids increase with heating time and temperature. Ratios comparable to those in some kerogens are found in the severely heated Miocene sediment and humic acid.

The geochronology of the plutonic and metamorphic rocks of New Zealand

Extensive Rubidium-Strontium age determinations on both mineral and total rock samples of the crystalline rocks of New Zealand, which almost solely crop out in the South Island, indicate widespread plutonic and metamorphic activity occurred during two periods, one about 100-118 million years ago and the other about 340-370 million years ago. The former results date the Rangitata Orogeny as Cretaceous. They associate extensive plutonic activity with this orogeny which uplifted and metamorphosed the rocks of the New Zealand Geosyncline, although no field association between the metamorphosed geosynclinal rocks and plutonic rocks has been found. The Cretaceous plutonic rocks occur to the west in the Foreland Province in Fiordland, Nelson, and Westland, geographically separated from the Geosynclinal Province. Because of this synchronous timing of plutonic and high pressure metamorphic activity in spatially separated belts, the Rangitata Orogeny in New Zealand is very similar to late Mesozoic orogenic activity in many other areas of the circum-Pacific margin (Miyashiro, 1961).

The 340-370 million year rocks, both plutonic and metamorphic, have been found only in that part of the Foreland Province north of the Alpine Fault. There, they are concentrated along the west coast over a distance of 500 km, and appear scattered inland from the coast. Probably this activity marks the outstanding Phanerozoic stratigraphic gap in New Zealand which occurred after the Lower Devonian.

A few crystalline rocks in the Foreland Province north of the Alpine Fault with measured ages intermediate between 340 and 120 million years have been found. Of these, those with more than one mineral examined give discordant results. All of these rocks are tentatively regarded as 340-370 million year old rocks that have been variously disturbed during the Rangitata Orogeny, 100-120 million years ago.

In addition to these two periods, plutonic activity, dominantly basic and ultrabasic, but including the development of some rocks of intermediate and acidic composition, occurred along the margin of the Geosynclinal Province at its border with the Foreland Province during Permian times about 245 million years ago, and this activity possibly extended into the Mesozoic.

Evidence from rubidium-strontium analyses of minerals and a total rock, and from uranium, thorium, and lead analyses of uniform euhedral zircons from a meta-igneous portion of the Charleston Gneiss, previously mapped as Precambrian, indicate that this rock is a 350-370 million year old plutonic rock metamorphosed 100 million yea rs ago during the Rangitata Orogeny. No crystalline rocks with primary Precambrian ages have been found in New Zealand. However, Pb²⁰⁷/Pb₂₀₆ ages of 1360 million years and 1370 million years have been determined for rounded detrital zircons separated from each of two hornfels samples of one of New Zealand's olde st sedimentary units, the Greenland Series. These two samples were metamorphosed 345- 370 million years ago. They occur along the west coast, north of the Alpine Fault, at Waitaha River and Moeraki River, separated by 135 km. The Precambrian measured ages are most likely minimum ages for the oldest source area which provided the detrital zircons because the uranium, thorium and lead data are highly discordant. These results are of fundamental importance for the tectonic picture of the Southwest Pacific margin and demonstrate the existence of relatively old continental crust of some lateral extent in the neighborhood of New Zealand.