Preface 1 Carbon, the Earth and life: 11 Carbon and the basic requirements of life12 Chemical elements, simple compounds and their origins13 The origin of life14 Evolution of life and the atmosphere15 Major contributors to sedimentary organic matter 2 Chemical composition of biogenic matter: 21 Structure of natural products22 Carbohydrates23 Amino acids and proteins24 Lipids25 Lignins, tannins and related compounds26 Nucleotides and nucleic acids27 Geochemical implicatiions of compositional variation 3 Production, preservation and degradation of organic matter: 31 How and why organic-rich deposits form32 Controls on primary production33 Preservation and degradation of organic matter34 Depositional environments associated with accumulation of organic matter 4 Long-term fate of organic matter in the geosphere: 41 Diagenesis42 Humic material43 Coal44 Kerogen45 Catagenesis and metagenesis46 Temporal and geographical distribution of fossil organic carbon 5 Chemical stratigraphy 51 Biologically mediated transformations52 Examples of source indicators in recent sediments53 Diagenesis at the molecular level54 Source and environment indicators in ancient sediments and oil55 Thermal maturity and molecular transformations56 Palaeotemperature and age measurement57 Maturity of ancient sedimentary organic matter58 Isotopic palaeontology 6 The carbon cycle and climate 61 Global carbon cycle62 Changes in carbon reservoirs over geological time63 Palaeoclimatic variations64 Isotopic excursions at period boundaries65 Human influence on the carbon cycle 7 Anthropogenic carbon and the environment 71 Introduction72 Halocarbons73 Hydrocarbon pollution in aquatic environments74 Endocrine disrupting chemicals75 Environmental behaviour of selected xenobiotic compounds76 Factors affecting the rate of anthropogenic components Appendix 1: SI units usedAppendix 2: SI unit prefixesAppendix 3: Geological timescaleReferencesIndex

An introduction to organic geochemistry

The maturation of organic material in hydrocarbon source rocks and inorganic diagenetic reactions in reservoir sandstones are a natural consequence when a prism of sedimentary rocks is buried. We can predict the distribution of porosity and permeability enhancement in potential hydrocarbon reservoirs by integrating the reaction processes characterizing the progressive diagenesis of a reservoir/source rock system. A variety of observations suggests that the organic solvents needed to increase aluminosilicate and carbonate solubilities in sandstones can be generated either by thermal or oxidative cracking of carbonylic or phenolic groups from kerogen in adjacent source rocks. For example, nuclear magnetic resonance (NMR) spectra of kerogen show that peripheral carbonylic and phenolic groups are released from the kerogen molecule before liquid hydrocarbons are generated. Experimental data indicate these water-soluble organic species can significantly affect the stability of both carbonates and aluminosilicates. Water-soluble organic acid anions (carboxylic) have been observed in oil-field waters in concentrations up to 10,000 ppm, and they commonly dominate the alkalinity in the fluid phase from 80° to 120°C. We can model the integration of organic and inorganic diagenetic reactions by constructing a series of potential reaction pathways with increasing temperature for a system that includes aluminosilicates, carbonates, organic chelate species (carboxylic and phenolic), and CO2. The important chemical divides in these diagenetic flow diagrams are dependent on temperature, the nature of the pH buffer (carbonate species or organic acid anion species), and the relationship between organic acid anions and PCO2 (P = partial pressure). Forward predictive capabilities result when this general diagenetic model is placed in a time-temperature framework. The detailed organic and inorganic geochemistry and the general thermal scenario used in the time-temperature ana ysis must be basin specific. Casting the diagenetic history of a sandstone into this type of process-oriented model helps us move from a descriptive mode to a predictive mode of analysis. Two types of information result: (1) general optimum conditions for porosity and permeability enhancement in sandstones are delineated and (2) specifically, the degree and potential for porosity and permeability enhancement are determined. Predictive models have been developed for several tectonic settings, including rift or pull-apart basins and intermontane or Laramide basins. From these reconstructions, we can forward-predict the porosity-enhancing potential of a diagenetic system based on an understanding of the reaction process in a time-temperature framework.

Organic-Inorganic Interactions and Sandstone Diagenesis

Empirical relationships between clay mineral transformations and temperature provide a basis for the use of clay minerals as geothermometers. Clay-mineral geothermometry has been applied mainly to diagenetic, hydrothermal, and contact- and burial-metamorphic settings to better understand the thermal histories of migrating fluids, hydrocarbon source beds, and ore and mineral formation. Quantitatively, the most important diagenetic clay mineral reaction in sedimentary rocks is the pro- gressive transformation of smectite to illite via mixed-layer illite/smectite (I/S). Changes in both the illite/ smeetite ratio and ordering of t/S, as determined from X-ray powder diffraction profiles, correlate with changes in temperature due to burial depth. Although the smectite-to-illite reaction may be influenced by several factors, reaction progress appears to be strongly controlled by temperature. Studies show that the model proposed by Hoffman and Hower in 1979 is applicable in burial diagenetic settings from about 5 to 330 Ma, and includes most rocks about Miocene to Mississippian in age. Reliability of the I/S geothermometer is, however, dependent upon a good understanding of the rock's original clay-mineral composition. Changes in the ordering of I/S are particularly useful in the exploration for hydrocarbons because of the common coincidence between the temperatures for the conversion from random-to-ordered I/S and those for the onset of peak, or main phase, oil generation. Here, the utility of the I/S geothermometer is reviewed in hydrocarbon-bearing rocks of Miocene to Mississippian age. Using three common applica- tions, the I/S geothermometer is compared to other mineral geothermometers, organic maturation indices, and grades of indigenous hydrocarbons. Good agreement between changes in ordering of I/S and calculated maximum burial temperatures or hydrocarbon maturity suggests that I/S is a reliable semiquantitative geothermometer and an excellent measures of thermal maturity.

Considerations and applications of the illite/smectite geothermometer in hydrocarbon-bearing rocks of Miocene to Mississippian age

We have generated ∼300 Kyr records of biogenic opal, calcite, and organic carbon (Corg) for three cores in the eastern and central equatorial Pacific Ocean and have compared the records to determine whether common periods of biogenic sedimentation have occurred throughout the region. We find that Corg has been deposited in common pulses throughout the area, while opal has a much more local pattern of variation. Calcite varies regionally, but the record is shaped by superimposed dissolution and productivity processes. The most intense Corg peak occurs at 18 ka and can have greater than 2 times the Holocene Corg content. Other major Corg peaks occur 150 ka and perhaps at 280 ka. We have compared the Corg record in one of the cores, V19–28, to a model deepwater oxygen record developed from ∂13C data in the nearby V19–30 to test whether the Corg record has been mostly shaped by degradation or by the rain of organic matter from the euphotic zone. We found no coherence between the two records, implying that the Corg record is primarily a measure of productivity. By comparing the opal, calcite, and Corg records in V19–28, a core which is at or above the lysocline, we found that both increased calcite and opal deposition matches high Corg accumulation. We also found, however, that the calcite and opal records were uncorrelated, so that episodes of high opal deposition do not necessarily accumulate calcite rapidly. We hypothesize that at least two different plankton communities have been dominant in the waters above this site, one rich in opal-secreting plankton and one more dominated by calcite producers. The opal-rich plankton community was dominant during the intervals 10–15 ka and 35–60 ka.

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The record of Late Pleistocene biogenic sedimentation in the eastern tropical Pacific Ocean

The smectite to illite reaction was studied by transmission and analytical electron microscopy (TEM/AEM) in argillaceous sediments from depths of 1750, 2450, and 5500 m in a Gulf Coast well. Smectite was texturally characterized as having wavy 10- to 13-A layers with a high density of edge-dislocations, and illite, as having relatively defect-free straight 10-A layers. The structures of smectite and illite were not continuous parallel to (001) at smectite-illite interfaces. AEM data showed that the smectite and illite were chemically distinct although smectite had a more variable composition. Mite formation appeared to have initiated with the growth of small packets of illite layers within subparallel layers of smectite matrix. With increasing depth, ubiquitous thin packets of illite layers increased in size until they coalesced. A model for the transition requires that the structure of smectite was largely disrupted at the illite-smectite interface and reconstituted as illite, with concomitant changes in the chemistry of octahedral and tetrahedral sites. At least partial Na-K exchange of smectite preceded illite formation. Transport of reactants (K, Al) and products (Na, Si, Fe, Mg, H20) through the surrounding smectite matrix may have taken place along dislocations. The smectite-to-illite conversion process for the studied samples does not necessarily appear to have required mixed-layer illite/smectite as an intermediate phase, and TEM and AEM data from unexpanded samples were found to be incompatible with the existence of mixed-layer illite/smectite in specimens whose XRD patterns indicated its presence.

Transmission and Analytical Electron Microscopy of the Smectite-To-Illite Transition

Clay Mineral Assemblages as Low Grade Metamorphic Geothermometers: Application to the Thrust Faulted Disturbed Belt Of Montana, U.S.A

Mesozoic sedimentary rocks overridden by thrust plates in the disturbed belt of northwestern Montana have been metamorphosed by burial beneath these plates. Bentonite in the Cretaceous section has been converted to potash bentonite by this metamorphism, allowing radiometric dating of the emplacement of the thrust plates by the K-Ar method. Ages determined thus far range from 72 to 56 m.y. B.P. The oldest ages coincide with estimates for the beginning of thrusting from stratigraphic and structural evidence. Field evidence does not allow a reliable estimate for the end of thrusting. Thus, the younger ages, which indicate completion of thrusting at the end of Paleocene time, represent additional data of interest to the structural history of the disturbed belt.

Janet Hoffman

Papers

Clay Mineral Assemblages as Low Grade Metamorphic Geothermometers: Application to the Thrust Faulted Disturbed Belt Of Montana, U.S.A

Radiometric dating of time of thrusting in the disturbed belt of Montana