Laurence N. Warr

Nanocoatings of clay and creep of the San Andreas fault at Parkfield, California

Mudrock samples were investigated from two fault zones at ∼3066 m and ∼3296 m measured depth (MD) located outside and within the main damage zone of the San Andreas Fault Observatory at Depth (SAFOD) drillhole at Parkfield, California. All studied fault rocks show features typical of those reported across creep zones with variably spaced and interconnected networks of polished displacement surfaces coated by abundant polished films and occasional striations. Electron microscopy and X-ray diffraction study of the surfaces reveal the occurrence of neocrystallized thin film clay coatings containing illite-smectite (I-S) and chlorite-smectite (C-S) minerals. 40 Ar/ 39 Ar dating of the illitic mix-layered coatings demonstrated Miocene to Pliocene crystallization and revealed an older fault strand (8 ± 1.3 Ma) at 3066 m MD, and a probably younger fault strand (4 ± 4.9 Ma) at 3296 m MD. Today, the younger strand is the site of active creep behavior, reflecting a possible (re)activation of these clay-weakened zones. We propose that the majority of slow fault creep is controlled by the high density of thin (

Chlorite-smectite clay minerals and fault behavior: New evidence from the San Andreas Fault Observatory at Depth (SAFOD) core

Segments of the modern San Andreas fault experience creep behavior, which is attributed to various factors, including (1) low values of effective normal stress, (2) elevated pore-fluid pressure, and (3) low frictional strength. The San Andreas Fault Observatory at Depth (SAFOD) drill hole in Parkfield, California, provides new insights into frictional properties by recognizing the importance of smectitic clay minerals, as demonstrated by analysis of mudrock and fault gouge samples from zones between 3186 and 3199 m and 3295 and 3313 m measured depths. X-ray diffraction (XRD) results show illite, chlorite, and mixed-layered illite-smectite and chlorite-smectite minerals in the faulted mudrock, whereas serpentine, Mg-rich smectite, and chlorite-smectite minerals are concentrated in the southwest deformation zone and the central deformation zone of the two actively creeping sections in the San Andreas fault. These rocks are abundantly coated by shiny clay mineral layers in some cases, reflecting mineral formation during creep. Secondary- and transmission-electron microscopy (SEM/TEM) and XRD studies of these slip surface coatings reveal thin films of neoformed chlorite-smectite phases, similar to previously described illite-smectite microscale precipitations. The abundance of chlorite-smectite minerals within fault rock of the SAFOD borehole significantly extends the potential role of mineralogic processes to depths up to 10 km, with cataclasis and fluid infiltration creating nucleation sites for neomineralization on displacement surfaces. We propose that localization of illitic to chloritic smectite clay minerals on slip surfaces from near the surface to the brittle-ductile transition promotes creep behavior of faults.

Frictional melt pulses during a ∼1.1 Ma earthquake along the Alpine Fault, New Zealand

Our understanding of frictional melting that occurs during large earthquake slip events has been hampered by the extremely fine-grain size of frictionally fused rock, and the lack of detailed high-resolution microscopy studies that describe features at the crystal lattice scale. In such a study, we here report the complex nature of melting and crystallization in a symmetrically layered, pseudotachylyte vein from the Alpine Fault, New Zealand. Two melt pulses are recognized, attributed to successive, but rapid, injections of frictionally generated material. The initial injection, preserved at the vein margins, was proximally derived and contains a high concentration of clasts and a Si-rich glass. This was quickly followed by a second generation of a more distally derived, melt-dominated fraction, which was injected into the weak vein center. Whereas fragments of wall-rock biotite are preserved in the marginal zones, neocrystallized microlitic biotite characterizes both margins and center. The vein biotite is different in composition, microstructure and polytypism from the metamorphic biotite of the wall rock. In all melt layers, newly formed biotite shows notable signs of syn-flow crystallization, strain features and erosion at crystal^glass contacts, with breakdown of neocrystallized microlites along both crystal edges and faces. These characteristics imply cyclic pulses of heating, melting and crystallization occurred during a single, large earthquake episode, and probably reflects the stick-slip propagation properties of coseismic faulting. 40 Ar/ 39 Ar total gas ages from the vein center give a 1.11 ; 0.04 Ma date for cyclic melting which, based on current exhumation rates, occurred at a crustal of depth V11 km. < 2003 Elsevier Science B.V. All rights reserved.

THE RATE AND MECHANISM OF DEEP-SEA GLAUCONITE FORMATION AT THE IVORY COAST–GHANA MARGINAL RIDGE

The environmental conditions and reaction paths of shallow-water glauconitization (<500 m water depth, ~15°C) close to the sediment-seawater interface are generally considered to be well understood. In contrast, the key factors controlling deep-sea glauconite formation are still poorly constrained. In the present study, green grains formed in the recent deep-sea environment of the ODP Site 959, Ivory Coast-Ghana Marginal Ridge, (~2100 m water depth, 3-6°C) were investigated by X-ray diffraction and electron microscopic methods in order to determine the rate and mechanism of glauconitization.Green clay authigenesis at Hole 959C occurred mainly in the tests of calcareous foraminifera which provided post-depositional conditions ideal for glauconitization. Within this organic-rich microenvironment, Fe-smectite developed <10 ky after deposition of the sediments by precipitation from precursor gels containing Fe, Mg, Al, and silica. This gel formation was supported by microbial activity and cation supply from the interstitial solution by diffusion. At a later stage of early marine diagenesis (900 ky), the Fe-smectites reacted to form mixed-layer glauconite-smectite. Further down (~2500 ky), almost pure glauconite with no compositional gaps between the Fe-smectite and glauconite end members formed. This burial-related Fe-smectite-to-glauconite reaction indicates that the glauconitization process was controlled mainly by the chemistry of the interstitial solutions. The composition of the interstitial solution depends heavily on micro-environmental changes related to early diagenetic oxidation of biodegradable (marine) organic matter, microbial sulfate reduction, silicate mineral alteration, carbonate dissolution, and Fe redox reactions. The availability of Fe is suggested as the probable limiting factor for glauconitization, explaining the various states of green-grain maturity within the samples, and this cation may be the most important rate-determining element.The rate of glauconite formation at ODP Site 959 is given by %GlSed = 22.6·log(ageSed) + 1.6 (R2 = 0.97) where %GlSed is the state of glauconitization in the sediment and ageSed is the sediment age (in ky). This glauconitization rate depends mainly on continuous cation supply (in particular Fe) and is about five times less than that in shallow-shelf regions, suggesting significantly slower reaction at the lower temperature of deep-sea environments.

Bioremediating Oil Spills in Nutrient Poor Ocean Waters Using Fertilized Clay Mineral Flakes: Some Experimental Constraints

Much oil spill research has focused on fertilizing hydrocarbon oxidising bacteria, but a primary limitation is the rapid dilution of additives in open waters. A new technique is presented for bioremediation by adding nutrient amendments to the oil spill using thin filmed minerals comprised largely of Fullers Earth clay. Together with adsorbed N and P fertilizers, filming additives, and organoclay, clay flakes can be engineered to float on seawater, attach to the oil, and slowly release contained nutrients. Our laboratory experiments of microbial activity on weathered source oil from the Deepwater Horizon spill in the Gulf of Mexico show fertilized clay treatment significantly enhanced bacterial respiration and consumption of alkanes compared to untreated oil-in-water conditions and reacted faster than straight fertilization. Whereas a major portion (up to 98%) of the alkane content was removed during the 1 month period of experimentation by fertilized clay flake interaction; the reduced concentration of polyaromatic hydrocarbons was not significantly different from the non-clay bearing samples. Such clay flake treatment could offer a way to more effectively apply the fertilizer to the spill in open nutrient poor waters and thus significantly reduce the extent and duration of marine oil spills, but this method is not expected to impact hydrocarbon toxicity.

Experimental study of clay-hydrocarbon interactions relevant to the biodegradation of the Deepwater Horizon oil from the Gulf of Mexico

Adding clay to marine oil pollution represents a promising approach to enhance bacterial hydrocarbon degradation in nutrient poor waters. In this study, three types of regionally available clays (Ca-bentonite, Fullers Earth and kaolin) were tested to stimulate the biodegradation of source and weathered oil collected from the Deepwater Horizon spill. The weathered oil showed little biodegradation prior to experimentation and was extensively degraded by bacteria in the laboratory in a similar way as the alkane-rich source oil. For both oils, the addition of natural clay-flakes showed minor enhancement of oil biodegradation compared to the non-clay bearing control, but the clay-oil films did limit evaporation. Only alkanes of a molecular weight (MW)xa0>xa0420 showed significant reduction by enhanced biodegradation following natural clay treatment. In contrast, all fertilized clay flakes showed major bacterial degradation of the oil, with a 6-10 times reduction in alkane content, and an up to 8 fold increase in the rate of O2 consumption. Compared to the control, such treatment showed particular reduction of longer chained alkanes (MWxa0>xa0226). The application of natural and fertilized clay flakes also showed selective reduction of PAHs, mainly in the MW range of 200-300, but without significant change in the toxicity indices measured. These results imply that a large variety of clays may be used to boost oil biodegradation by aiding attachment of fertilizing nutrients to the oil.

Porosity and distribution of water in perlite from the island of Milos, Greece

A perlite sample representative of an operating mine in Milos was investigated with respect to the type and spatial distribution of water. A set of different methods was used which finally provided a consistent view on the water at least in this perlite. Infrared spectroscopy showed the presence of different water species (molecular water and hydroxyl groups / strongly bound water). The presence of more than 0.5 mass% smectite, however, could be excluded considering the cation exchange capacity results. The dehydration measured by thermal analysis occurred over a wide range of temperatures hence confirming the infrared spectroscopical results. Both methods point to the existence of a continuous spectrum of water binding energies. The spatial distribution of water and/or pores was investigated using different methods (CT: computer tomography, FIB: scanning electron microscopy including focused ion beam technology, IRM: infrared microscopy). Computer tomography (CT) showed large macropores (20 – 100xa0μm) and additionally revealed a mottled microstructure of the silicate matrix with low density areas up to a few μm in diameter. Scanning electron microscopy (FIB) confirmed the presence of μm sized pores and IRM showed the filling of these pores with water. In summary, two types of pores were found. Airfilled 20 – 100xa0μm pores and μm-sized pores disseminated in the glass matrix containing at least some water. Porosity measurements indicate a total porosity of 26 Vol%, 11 Vol% corresponding to the μm-sized pores. It remains unsolved wether the water in the μm-sized pores entered after or throughout perlite formation. However, the pores are sealed and no indications of cracks were found which indicated a primary source of the water, i.e. water was probably entrapped by quenching of the lava. The water in these pores may be the main reason for the thermal expandability which results in the extraordinarily porous expanded perlite building materials.

Crystal chemistry of Na-rich rectorite from North Little Rock, Arkansas

Abstract The rectorite, a regular mixed layer mineral consisting of dioctahedral swelling and non-swelling 2:1 layers, from North Little Rock, Arkansas, was studied to define the crystal chemistry and structural parameters (e.g. layer charge of the different layers, presence of cis/trans-vacancies). X-ray diffraction, simultaneous thermal analysis coupled with mass spectrometry, X-ray fluorescence and cation exchange capacity are used to characterize this rectorite. The rectorite has a coefficient of variation (CV) of 0.19 and a cation exchange capacity of 60 cmol(+)/kg, as determined by the ammonium acetate method. The mineral is best described as a regular interstratification of brammallite-like and high-charged beidellite-like layers. Dehydration occurs at ≈118°C with a mass loss of 6.77% and dehydroxylation occurs in two steps at 470°C and 588°C with an overall mass loss of 4.67%. Peak decomposition of the mass spectrometer curve of evolved water shows ≈20% peak area with a maximum higher than 600°C, indicating ≈20% cis-vacant layers.

Constraining the alteration history of a Late Cretaceous Patagonian volcaniclastic bentonite–ash–mudstone sequence using K–Ar and 40Ar/39Ar isotopes

Smectite is typically considered unsuitable for radiometric dating, as argon (40Ar) produced from decay of exchangeable potassium (40K) located in the interlayer sites can be lost during fluid–rock interaction and/or during wet sample preparation in the laboratory. However, age analysis of Late Cretaceous Argentinian bentonites and associated volcaniclastic rocks from Lago Pellegrini, Northern Patagonia, indicates that, in the case of these very low-permeability rocks, the radioactive 40Ar was retained and thus can provide information on smectite age and the timing of rock alteration. This study presents isotopic results that indicate the ash-to-bentonite conversion and alteration of the overlying tuffaceous mudstones in Northern Patagonia was complete ~13–17 my after middle Campanian sedimentation when the system isotopically closed. The general absence of illite in these smectite-rich lithologies reflects the low activity of K and the low temperature (<60xa0°C) of the formation waters that altered the parent ash.