Chemical modification of smectite clays

Today, speciality use organoclays are being developed for an increasingly large number of specific applications. Many of these, including use in cosmetics, polishes, greases and paints, require that the material be free from abrasive impurities so that the product retains a smooth `feel'. The traditional `wet' method preparation of organoclays inherently removes abrasives naturally present in the parent mineral clay, but it is time-consuming and expensive. The primary objective of this thesis was to explore the alternative `dry' method (which is both quicker and cheaper but which provides no refining of the parent clay) as a process, and to examine the nature of the organoclays produced, for the production of a wide range of commercially usable organophilic clays in a facile way. Natural Wyoming bentonite contains two quite different types of silicate surface (that of the clay mineral montmorillonite and that of a quartz impurity) that may interact with the cationic surfactant added in the `dry' process production of organoclays. However, it is oil shale, and not the quartz, that is chiefly responsible for the abrasive nature of the material, although air refinement in combination with the controlled milling of the bentonite as a pretreatment may offer a route to its removal. Ion exchange of Wyoming bentonite with a long chain quaternary ammonium salt using the `dry' process affords a partially exchanged, 69-78%, organoclay, with a monolayer formation of ammonium ions in the interlayer. Excess ion pairs are sorbed on the silicate surfaces of both the clay mineral and the quartz impurity phases. Such surface sorption is enhanced by the presence of very finely divided, super paramagnetic, Fe2O3 or Fe(O)(OH) contaminating the surfaces of the major mineral components. The sorbed material is labile to washing, and induces a measurable shielding of the 29Si nuclei in both clay and quartz phases in the MAS NMR experiment, due to an anisotropic magnetic susceptibility effect. XRD data for humidified samples reveal the interlamellar regions to be strongly hydrophobic, with the by-product sodium chloride being expelled to the external surfaces. Many organic cations will exchange onto a clay. The tetracationic cyclophane, and multipurpose receptor, cyclobis(paraquat-p-phenylene) undergoes ion exchange onto Wyoming bentonite to form a pillared clay with a very regular gallery height. The major plane of the cyclophane is normal to the silicate surfaces, thus allowing the cavity to remain available for complexation. A series of group VI substituted o-dimethoxybenzenes were introduced, and shown to participate in host/guest interactions with the cyclophane. Evidence is given which suggests that the binding of the host structure to a clay substrate offers advantages, not only of transportability and usability but of stability, to the charge-transfer complex which may prove useful in a variety of commercial applications. The fundamental relationship between particle size, cation exchange capacity and chemical composition of clays was also examined. For Wyoming bentonite the extent of isomorphous substitution increases with decreasing particle size, causing the CEC to similarly increase, although the isomorphous substitution site: edge site ratio remains invarient throughout the particle size range studied.

The palynology of the Plenmeller Coalfield and adjacent areas in Northern England

The samples collected in the present investigation from Featherstone, Plenmeller and adjacent areas in the North of England, yielded diverse, well preserved miospore assemblages with marked vertical variation, which compare fairly closely with those previously described from strata of the same age elsewhere. Six major Assemblages are recognised from coal and shale samples collected within Namurian and Westphalian A and B strata which have not previously been dated by miospore evidence. Oetailed comparisons are made with miospore assemblages previously described by several authors from similar stratigraphical horizons in Scotland, North England and. the Central Province. Formal taxonomic description is presented for 206 species belonging to 71 genera.tions 22 new types are described and one new combination is suggested.

Diagenetic processes in ore formation with special reference to the Zambian copperbelt and permian marl slate.

This thesis is concerned with the role of diagenesis in forming ore deposits. Two sedimentary 'ore-types' have been examined; the Proterozoic copper-cobalt orebodies of the Konkola Basin on the Zambian Copperbelt, and the Permian Marl Slate of North East England. Facies analysis of the Konkola Basin shows the Ore-Shale to have formed in a subtidal to intertidal environment. A sequence of diagenetic events is outlined from which it is concluded that the sulphide ores are an integral part of the diagenetic process. Sulphur isotope data establish that the sulphides formed as a consequence of the bacterial reduction of sulphate, while the isotopic and geochemical composition of carbonates is shown to reflect changes in the compositions of diagenetic pore fluids. Geochemical studies indicate that the copper and cobalt bearing mineralising fluids probably had different sources. Veins which crosscut the orebodies contain hydrocarbon inclusions, and are shown to be of late diagenetic lateral secretion origin. RbiSr dating indicates that the Ore-Shale was subject to metamorphism at 529 A- 20 myrs. The sedimentology and petrology of the Marl Slate are described. Textural and geochemical studies suggest that much of the pyrite (framboidal) in the Marl Slate formed in an anoxic water column, while euhedral pyrite and base metal sulphides formed within the sediment during early diagenesis. Sulphur isotope data confirm that conditions were almost "ideal" for sulphide formation during Marl Slate deposition, the limiting factors in ore formation being the restricted supply of chalcophile elements. Carbon and oxygen isotope data, along with petrographic observations, indicate that much of the calcite and dolomite occurring in the Marl Slate is primary, and probably formed in isotopic equilibrium. A depositional model is proposed which explains all of the data presented and links the lithological variations with fluctuations in the anoxicioxic boundary layer of the water column.

Ammonite biostratigraphy, lithofacies variations, and paleoceanographic implications for Barremian-Aptian sequences of northeastern Mexico

Two Barremian-Aptian sequences studied in Durango and Nuevo Leon States, northeastern Mexico include three lithic units which have been described as the Cupido Formation of Barremian-early Early Aptian age, its lateral equivalent, the Lower Tamaulipas Formation, and the La Peña Formation extending through the early Albian. ^ The present work improves the existing ammonite Aptian biozonation by considering constraints associated with a discontinuous spatial and temporal record of the different taxa within the La Peña Formation. ^ Four ammonite biozones are established: (1) The Dufrenoyia justinae Zone for the late Early Aptian, (2) The Burckhardtites nazasensis/Rhytidoplites robertsi Zone for the middle Aptian, (3) The Cheloniceras inconstans Zone for the early Late Aptian, and (4) The Hypacanthoplites cf. leanzae Zone for the late late Aptian. ^ Also, a detailed sedimentological analysis of the sections shed further light on the possible causes that controlled intermittent occurrences of the ammonites in relation to the prevailing paleoceanographic and paleoecologic conditions in northeastern Mexico during the late Barremian-Aptian. ^ Microfacies analyses show that the upper part of the Cupido facies are represented by biocalcirudite with rudists, biocalcarenites with oolites and algae, and rich benthonic foraminifera assemblages with ostracods. These facies are related to paleoceanographic conditions of sedimentation within a shallow-marine carbonate platform. Its lateral equivalent, deep-water facies extended to the southeast and it is represented by the Lower Tamaulipas Formation, which includes planktonic foraminifera, ostracods, and mollusk and echinoid fragments. The beginning of deposition of the La Peña Formation in the late Early Aptian is characterized by an increase in terrigenous materials and significant decrease in the abundance of benthic fauna. The La Peña Formation is recognized by an alternation of marls and shale limestones containing ammonites, planktonic foraminifera, ostracods, and radiolaria toward the top. Accumulation of the La Peña continued throughout the end of the Aptian and records changes in conditions of sedimentation and productivity in the water column, which abruptly terminated the carbonate deposition in the Cupido Platform. ^ Results of carbon/carbonate content analyses show that changes from the Cupido to the La Peña facies are also characterized by an increase of organic carbon, which indicate the onset of enhanced dysoxic/anoxic conditions in the lower water column. ^

The Current State of Argentina's Oil Industry

An oil wealthy country, Argentina has repeatedly tried and failed to capitalize on its potential. The unfortunate energy policies of subsequent Argentinean government and a lack of investment capital have been two of the main reasons that have significantly limited the production of export oil in the recent past. Yet, with recent discoveries and changes to the country’s hydrocarbon laws, there may be a new dawn for Argentina’s oil industry. Since 1999 when Argentina’s oil production peaked at approximately 800,000 barrels per day, there has been a 24 percent decrease in its oil output. The country’s oil reserves have also been in steady decline. Yet, the recently enacted reforms by Argentina’s government to incentivize foreign investment in the oil industry seem to be working, allowing investors to negotiate the terms of exploration directly with local governments. As a result, foreign investment is increasing, as well as new willingness to finance exploration of untapped reserves. Also, the discovery of shale oil in Argentina may provide the potential to become a key exporter in the region. Nonetheless, there are challenges that need to be overcome and it may be years before the various oil projects underway become profitable. The success of current oil projects, coupled with the potential of shale oil, new discoveries and the sustainability of the current energy policy reforms will likely determine if Argentina is finally able to fulfill its potential and exert itself as an oil exporter country in Latin America.

Ammonite biostratigraphy, lithofacies variations, and paleoceanographic implications for barremian-aptian sequences of northeastern Mexico

Two Barremian-Aptian sequences studied in Durango and Nuevo Leon States, northeastern Mexico include three lithic units which have been described as the Cupido Formation of Barremian-early Early Aptian age, its lateral equivalent, the Lower Tamaulipas Formation, and the La Pena Formation extending through the early Albian. The present work improves the existing ammonite Aptian biozonation by considering constraints associated with a discontinuous spatial and temporal record of the different taxa within the La Pena Formation. Four ammonite biozones are established: 1) The Dufrenoyia justinae Zone for the late Early Aptian, 2) The Burckhardtites nazasensis/Rhytidoplites robertsi Zone for the middle Aptian, 3) The Cheloniceras inconstans Zone for the early Late Aptian, and 4) The Hypacanthoplites cf. leanzae Zone for the late late Aptian. Also, a detailed sedimentological analysis of the sections shed further light on the possible causes that controlled intermittent occurrences of the ammonites in relation to the prevailing paleoceanographic and paleoecologic conditions in northeastern Mexico during the late Barremian-Aptian. Microfacies analyses show that the upper part of the Cupido facies are represented by biocalcirudite with rudists, biocalcarenites with oolites and algae, and rich benthonic foraminifera assemblages with ostracods. These facies are related to paleoceanographic conditions of sedimentation within a shallow-marine carbonate platform. Its lateral equivalent, deep-water facies extended to the southeast and it is represented by the Lower Tamaulipas Formation, which includes planktonic foraminifera, ostracods, and mollusk and echinoid fragments. The beginning of deposition of the La Pena Formation in the late Early Aptian is characterized by an increase in terrigenous materials and significant decrease in the abundance of benthic fauna. The La Pena Formation is recognized by an alternation of marls and shale limestones containing ammonites, planktonic foraminifera, ostracods, and radiolaria toward the top. Accumulation of the La Pena continued throughout the end of the Aptian and records changes in conditions of sedimentation and productivity in the water column, which abruptly terminated the carbonate deposition in the Cupido Platform. Results of carbon/carbonate content analyses show that changes from the Cupido to the La Pena facies are also characterized by an increase of organic carbon, which indicate the onset of enhanced dysoxic/anoxic conditions in the lower water column.

(Tables 4-5, page 160) REE contents in ferromanganese concretions from the Gulf of Bothnia and the Barents Sea

Ferromanganese concretions from the Svalbard shelf in the Barents Sea show slightly convex shale-normalized REE patterns with no Eu anomalies. Concretions from the Gulf of Bothnia, northern part of the Baltic Sea, exhibit an enrichment of light REE and negative Eu anomalies. This difference is interpreted as a consequence of different conveyor mechanisms of the REE to the sediment. It is suggested that dissolving biogenic debris contributes to the convex pattern obtained in the Barents Sea, whereas an inorganic suspended fraction with scavenged REE is the main carrier in the Gulf of Bothnia. During oxic diagenesis in the sediment, the scavenged REE are set free into the porewater and contribute to the distribution pattern in concretions found in the Gulf of Bothnia. Small Mn-rich spheroidal concretions are enriched two to five times in REE compared to average shale, whereas Mn-poor flat concretions are low in REE. Specific surface area of the concretion and the depth of burial in the oxidized surface sediment are two factors that strongly affect the enrichment of the REE. Weak Ce anomalies are present in the analysed concretions and a redox level dependence is seen.

Análise estratigráfica da sequência mesodevoniana-eocarbonífera da Bacia do Parnaíba, nordeste do Brasil

The Middle Devonian-Early Carboniferous sequence of the Parnaíba Basin, lithostratigraphically defined as Canindé Group, has been reinterpreted using the basic model of sequence stratigraphy. Therefore, lithology and gamma ray well-logs and seismic lines of central portion of the basin were analyzed, producing up from there diagrams 1D, isochore maps and stratigraphic sections. As results of this study, were defined two depositional cycles of second order, referred as Depositional Sequence 1 (SEQ1) and the Depositional Sequence 2 (SEQ2). The SEQ1, with interval about 37 Ma, is limited below by Early Devonian Unconformity and is equivalent to the formations Itaim, Pimenteiras and Cabeças. The SEQ2, which follows, comprises a range of about 15 Ma and is equivalent to the Longá Formation The SEQ1 starts with the lowstand systems tract, consisting of progradational parasequence set in the basal part, predominantly pelitic, deposited on a prodelta under influence of storms and the upper part consists in sandstones of deltaic front, with the maximum regressive surface on the upper limit. The transgressive systems tract, deposited above, is characterized by retrogradacional parasequence set composed of shallow shelf mudstones, deposited under storm conditions. The maximum flooding surface, upper limit of this tract, is positioned in a shale level whose radioactivity in gammaray well-log is close to 150 API. The highstand systems tract presents progradational parasequence set, comprising mudstones and sandstones deposited in shelf, fluvial-estuarine or deltaic and periglacial environments, with the upper limit the Late Devonian Unconformity. The SEQ2 was deposited in shelf environment, starting with the lowstand systems tract, that is characterized by a progradational parasequence set, followed by the transgressive systems tract, with retrogradational character. The upper limit of the tract corresponding to the fusion between maximum flooding surface with the upper limit of this sequence, which is the Early Carboniferous Unconformity, where the overlapping section was eroded. This section, which corresponds the highstand systems tract is restricted to portions at which the erosion that generate the Early-Carboniferous Unconformity was less effective, preserving the records of this unit.

Análise estratigráfica da sequência mesodevoniana-eocarbonífera da Bacia do Parnaíba, nordeste do Brasil

The Middle Devonian-Early Carboniferous sequence of the Parnaíba Basin, lithostratigraphically defined as Canindé Group, has been reinterpreted using the basic model of sequence stratigraphy. Therefore, lithology and gamma ray well-logs and seismic lines of central portion of the basin were analyzed, producing up from there diagrams 1D, isochore maps and stratigraphic sections. As results of this study, were defined two depositional cycles of second order, referred as Depositional Sequence 1 (SEQ1) and the Depositional Sequence 2 (SEQ2). The SEQ1, with interval about 37 Ma, is limited below by Early Devonian Unconformity and is equivalent to the formations Itaim, Pimenteiras and Cabeças. The SEQ2, which follows, comprises a range of about 15 Ma and is equivalent to the Longá Formation The SEQ1 starts with the lowstand systems tract, consisting of progradational parasequence set in the basal part, predominantly pelitic, deposited on a prodelta under influence of storms and the upper part consists in sandstones of deltaic front, with the maximum regressive surface on the upper limit. The transgressive systems tract, deposited above, is characterized by retrogradacional parasequence set composed of shallow shelf mudstones, deposited under storm conditions. The maximum flooding surface, upper limit of this tract, is positioned in a shale level whose radioactivity in gammaray well-log is close to 150 API. The highstand systems tract presents progradational parasequence set, comprising mudstones and sandstones deposited in shelf, fluvial-estuarine or deltaic and periglacial environments, with the upper limit the Late Devonian Unconformity. The SEQ2 was deposited in shelf environment, starting with the lowstand systems tract, that is characterized by a progradational parasequence set, followed by the transgressive systems tract, with retrogradational character. The upper limit of the tract corresponding to the fusion between maximum flooding surface with the upper limit of this sequence, which is the Early Carboniferous Unconformity, where the overlapping section was eroded. This section, which corresponds the highstand systems tract is restricted to portions at which the erosion that generate the Early-Carboniferous Unconformity was less effective, preserving the records of this unit.

Role of metalliferous mudstones and graphitic shales in the location, genesis, and paleoenvironment

The Cambrian Tally Pond volcanic belt in central Newfoundland contains numerous volcanogenic massive sulphide (VMS) deposits, prospects, and showings that are locally associated with metalliferous mudstones and/or graphitic shales. Deposits in the belt are bimodal felsic-type VMS that are both base metal- (e.g., Duck Pond, Boundary) and precious metal-enriched (e.g., Lemarchant). At the Lemarchant deposit metalliferous mudstones are genetically and spatially associated with mineralization, whereas the relationship of other mudstones and shales to massive sulphide mineralization is more intricate and remains not fully understood. Metalliferous mudstones represent a hiatus in the volcanic activity where the deposition of hydrothermal products dominated over the abiogenic background sedimentation and/or dilution by volcaniclastic-epiclastic material. Lithogeochemical signatures allow one to distinguish between predominantly hydrothermally or detritally (i.e., non-hydrothermal) derived material. Metalliferous mudstones with a significant hydrothermal component, like those at Lemarchant, have elevated Fe/Al and base-metal contents, compared to detrital shales, and shale-normalized negative Ce and positive Eu anomalies, indicative of deposition from high temperature (>250°C) hydrothermal fluids within an oxygenated water column. Mudstones and shales sampled from other locations in the Tally Pond volcanic belt have more variable signatures ranging from hydrothermal (signatures as above) to non-hydrothermal (no positive Eu-anomalies, flat REE patterns), with some that have mixed (hydrothermal and detrital) signatures. Both S and Pb isotopic compositions indicate that proximal sulphides hosted in mudstones immediately associated with massive sulphide mineralization within the Lemarchant deposit contain a higher proportion of sulphur derived from hydrothermal sources and processes, and have more juvenile lead contributions, when compared to sulphides distal (not associated with massive sulphides) from mineralization. Lead and Nd isotopic compositions of both whole rock and minerals in the Lemarchant mudstones indicate involvement of underlying crustal basement during massive sulphide formation and throughout the evolution of the Tally Pond belt. Metalliferous mudstones precipitated early in the massive sulphide depositional history, but also have undergone syn- and post-ore-forming processes and have a larger lateral extent than the mineralization. Using lithogeochemistry, whole rock and in situ stable and radiogenic isotopes it is possible to distinguish prospective vent proximal (immediately associated with massive sulphide mineralization) from less prospective distal (not associated with massive sulphides) depositional environments and to reconstruct the paleotectonic setting on a deposit- to regional-scale for the Lemarchant deposit and other mudstone-associated prospects in the Tally Pond volcanic belt.

Colorado's Piceance Basin: Variation in the local public finance effects of oil and gas development

A large increase in natural gas production occurred in western Colorado’s Piceance basin in the mid- to late-2000s, generating a surge in population, economic activity, and heavy truck traffic in this rural region. We describe the fiscal effects related to this development for two county governments: Garfield and Rio Blanco, and two city governments: Grand Junction and Rifle. Counties maintain rural road networks in Colorado, and Garfield County’s ability to fashion agreements with operators to repair roads damaged during operations helped prevent the types of large new costs seen in Rio Blanco County, a neighboring county with less government capacity and where such agreements were not made. Rifle and Grand Junction experienced substantial oil- and gas-driven population growth, with greater challenges in the smaller, more isolated, and less economically diverse city of Rifle. Lessons from this case study include the value of crafting road maintenance agreements, fiscal risks for small and geographically isolated communities experiencing rapid population growth, challenges associated with limited infrastructure, and the desirability of flexibility in the allocation of oil- and gas-related revenue.

Local government revenue from oil and gas production

Oil and gas production generates substantial revenue for state and local governments. This report examines revenue from oil and gas production flowing to local governments through four mechanisms: (i) state taxes or fees on oil and gas production; (ii) local property taxes on oil and gas property; (iii) leasing of state-owned land; and (iv) leasing of federally owned land. We examine every major oil- and gas-producing state and find that the share of oil and gas production value allocated to and collected by local governments ranges widely, from 0.5 percent to more than 9 percent due to numerous policy differences among states. School districts and trust funds endowing future school operations tend to see the highest share of revenue, followed by counties. Municipalities and other local governments with more limited geographic boundaries tend to receive smaller shares of oil and gas driven revenue. Some states utilize grant programs to allocate revenue to where impacts from the industry are greatest. Others send most revenue to state operating or trust funds, with little revenue earmarked specifically for local governments.

Local fiscal effects of oil and gas development in eight states

Oil and gas production in the United States has increased dramatically in the past 10 years. This growth has important implications for local governments, which often see new revenues from a variety of sources: property taxes on oil and gas property, sales taxes driven by the oil and gas workforce, allocations of state revenues from severance taxes or state and federal leases, leases on local government land, and contributions from oil and gas companies to support local services. At the same time, local governments tend to experience a range of new costs such as road damage caused by heavy industry truck traffic, increased demand for emergency services and law enforcement, and challenges with workforce retention. This report examines county and municipal fiscal effects in 14 oil- and gas-producing regions of eight states: AK, CA, KS, OH, OK, NM, UT, and WV. We find that for most local governments, oil and gas development—whether new or longstanding—has a positive effect on local public finances. However, effects can vary substantially due to a variety of local factors and policy issues. For some local governments, particularly those in rural regions experiencing large increases in development, revenues have not kept pace with rapidly increased costs and demand for services, particularly on road repair.

(Table 1) Organic carbon, hydrogen and oxygen index and hydrocarbons at DSDP Hole 93-603B

C2-C8 hydrocarbon concentrations (about 35 compounds identified, including saturated, aromatic, and olefinic compounds) from 27 shipboard-sealed, deep-frozen core samples of DSDP Hole 603B off the east coast of North America were determined by a gas-stripping/thermovaporization method. Total yields representing the hydrocarbons dissolved in the pore water and adsorbed on the mineral surfaces of the sediments vary from 22 to 2400 ng/g of dryweight sediment. Highest yields are measured in the two black shale samples of Core 603B-34 (hydrogen index of 360 and 320 mg/g Corg, respectively). In organic-carbon-normalized units these samples have hydrocarbon contents of 12,700 and 21,500 ng/g Corg, respectively, indicating the immaturity of their kerogens. Unusually high organic-carbonnormalized yields are associated with samples that are extremely lean in organic carbon. It is most likely that they are enriched by small amounts of migrated light hydrocarbons. This applies even to those samples with high organic-carbon contents (1.3-2.2%) of Sections 603B-28-4, 603B-29-1, 603B-49-2, and 603B-49-3, because they have an extremely low hydrocarbon potential (hydrogen index between 40 and 60 mg/g Corg). Nearly all samples were found to be contaminated by varying amounts of acetone that is used routinely in large quantities on board ship during core-cutting procedures. Therefore, 48 samples from the original set of 75 collected had to be excluded from the present study.

Geochemical composition of ODP Site 210-1276 shales

During Ocean Drilling Program Leg 210, a greatly expanded sedimentary sequence of continuous Cretaceous black shales was recovered at Site 1276. This section corresponds to the Hatteras Formation, which has been documented widely in the North Atlantic Ocean. The cored sequence extends from the lowermost Albian, or possibly uppermost Aptian, to the Cenomanian/Turonian boundary and is characterized by numerous gravity-flow deposits and sporadic, finely laminated black shales. The sequence also includes several sedimentary intervals with high total organic carbon (TOC) contents, in several instances of probable marine origin that may record oceanic anoxic events (OAE). These layers might correspond to the Cenomanian-Turonian OAE 2; the mid-Cenomanian event; and OAE 1b, 1c, and 1d in the Albian. In addition, another interval with geochemical characteristics similar to OAE-type layers was recognized in the Albian, although it does not correspond to any of the known OAEs. This study investigates the origin of the organic matter contained within these black shale intervals using TOC and CaCO3 contents, Corg/Ntot ratios, organic carbon and nitrogen isotopes, trace metal composition, and rock-eval analyses. Most of these black shale intervals, especially OAE 2 and 1b, are characterized by low 15N values (<0) commonly observed in mid-Cretaceous black shales, which seem to reflect the presence of an altered nitrogen cycle with rates of nitrogen fixation significantly higher than in the modern ocean.