Factors Controlling Sulfide Geochemistry in Sub-tropical Estuarine and Bay Sediments

The primary factors that control the concentration of total reduced (inorganic) sulfide in coastal sediments are believed to be the availability of reactive iron, dissolved sulfate and metabolizable organic carbon. We selected nine sites in shallow (<3 m), close to sub-tropical, estuaries and bays along the central Texas coast that represented a range in sediment grain size (a proxy for reactive iron), salinity (a proxy for dissolved sulfate), and total organic carbon (a proxy for metabolizable organic carbon). Based on these parameters a prediction was made of which factor was likely to control total reduced sulfide at each site and what the relative total reduced sulfide concentration was likely to be. To test the prediction, the sediments were analyzed for total reduced sulfide, acid volatile sulfide, and citrate dithionate-extractable, HCl-extractable and total Fe in the solid phase. Using solid-state gold–mercury amalgam microelectrodes and voltammetry, we determined pore water depth profiles of Fe(II) and ΣH₂S and presence or absence of FeS_(aq). At five of the nine sites the calculated degree of sufildization of citrate dithionite-reactive-iron was close to or greater than 1 indicating that rapidly reactive iron was probably the limiting factor for iron sulfide mineral formation. At one site (salinity = 0.9) dissolved Fe(II) was high, ΣH₂S was undetectable and the total reduced sulfide concentration was low indicating sulfate limitation. At the last three sites a low degree of sulfidization and modest total reduced (inorganic) sulfide concentrations appeared to be the result of a limited supply of metabolizable organic carbon. Fe(II)–S(-II) clusters (FeS_(aq)) were undetectable in 10 out of 12 bay sediment profiles where ΣH₂S was close to or below detection limits, but was observed in all other porewater profiles. Acid volatile sulfide, but not total reduced sulfide, was well correlated with total organic carbon and ranged from being undetectable in some cores to representing a major portion of total reduced sulfide in other cores. Although predicted controls on total reduced sulfide were good for very low salinity water or sandy sediments, they were only right about half the time for the other sediments. The likely reasons for the wrong predictions are the poor correlation of total organic carbon with grain size and differing fractions of metabolizable organic carbon in different sedimentary environments. Differences in sediment accumulation rates may also play a role, but these are difficult to determine in this region where hurricanes often resuspend and move sediments. This study demonstrates the need to examine more complex and often difficult to determine parameters in anoxic “normal marine” sediments if we are to understand what controls the concentration and distribution of sulfides.     

Compaction localization in the Earth and the laboratory: state of the research and research directions

Localized compaction in porous rocks is a recently recognized phenomenon that has been shown to reduce permeability dramatically. Consequently, the phenomenon is relevant to a variety of technologies involving fluid injection or withdrawal. This article summarizes current understanding of localized compaction and impediments to further progress. The article is based on discussions at a small workshop on localized compaction sponsored by the Office of Science, U. S. Department of Energy.     

Ethanol Production: Energy and Economic Issues Related to U.S. and Brazilian Sugarcane

For a thorough and up-to-date evaluation of all the fossil energy costs of ethanol production from sugarcane in both the U.S. and Brazil, every energy input in the biomass production and ultimate conversion process must be included. In this study, more than 12 energy inputs in average U.S. and Brazilian sugarcane production are evaluated. Then in the fermentation/distillation operation, nine more fossil fuel inputs are identified and included. Some energy and economic credits are given for the bagasse to reduce the energy inputs required for steam and electricity. Based on all the fossil energy inputs in U.S. sugarcane conversion process, a total of 1.12 kcal of ethanol is produced per 1 kcal of fossil energy expended. In Brazil a total of 1.38 kcal of ethanol is produced per 1 kcal of fossil energy expended. Some pro-ethanol investigators have overlooked various energy inputs in U.S. and Brazilian sugarcane production, including farm labor, farm machinery, processing machinery, and others. In other studies, unrealistic low energy costs were attributed to such energy inputs, as nitrogen fertilizer, insecticides, and herbicides. Both the U.S. and Brazil heavily subsidize ethanol production. Thus billions of dollars are invested in subsidies and this significantly increases the costs to the consumers. The environmental costs associated with producing ethanol in the U.S. and Brazil are significant but have been generally overlooked. The negative environmental impacts on the availability of cropland and freshwater, as well as on air pollution and public health, have yet to be carefully assessed. These environmental costs in terms of energy and economics should be calculated and included in future ethanol analyses so that sound assessments can be made. In addition, the production of ethanol in the U.S. and Brazil further confirms that the mission of converting biomass into ethanol will not replace oil. This mission is impossible. General concern has been expressed about taking food crops to produce ethanol for burning in automobiles instead of using these crops as food for the many malnourished people in the world. The World Health Organization reports that more than 3.7 billion humans are currently malnourished in the world—the largest number of malnourished ever in history.     

Progress in isotope paleohydrology using lake sediment cellulose

Recent advances in sample preparation techniques and mass spectrometry have fostered more routine oxygen isotope analysis of aquatic cellulose in lake sediment cores, a proxy for lake water oxygen isotope history. These methodological developments have significantly increased the feasibility of incorporating this approach into high-resolution, multi-site, and multi-proxy studies, which are frequently necessary to answer complex hydrological, hydroecological and hydroclimatic questions requiring a paleoenvironmental perspective. Direct translation of lake sediment aquatic cellulose oxygen isotope composition into lake water oxygen isotope composition offers appreciable opportunity for quantitative paleohydrological reconstructions, as evidenced by studies conducted over the past 15 years that span Holocene and pre-historical timescales.     

Slowness-backazimuth weighted migration: A new array approach to a high-resolution image

We have developed a new array method combining conventional migration with a slowness-backazimuth deviation weighting scheme. All seismic traces are shifted based on the theoretical traveltime of the scattered wave from specific gridpoints in a 3-D volume. Observed slowness and backazimuth are calculated for each raypath and compared with theoretical values in order to estimate slowness and backazimuth deviations. Subsequently, stacked energy calculated by a conventional migration method is weighted by the slowness and backazimuth deviations to suppress any arrival energy whose slowness and backazimuth are inconsistent with the expected theoretical values. This new method was applied to two P- wave data sets which comprise (1) underside reflections at the 410 and 660 km mantle discontinuities and (2) D" reflections as well as their corresponding synthetic data sets. The results show that the weighting scheme dramatically increases the resolution of the migrated images and enables us to obtain well-constrained, focused images, making upper-mantle discontinuities and D" reflections more distinct by reducing their surrounding energy.     

Monitoring overburden layer changes and fault movements from time-lapse seismic data on the Valhall Field

A method developed by Røste et al. , which discriminates between layer thickness and velocity changes, is tested on pre-stack time-lapse seismic ocean bottom cable (OBC) data from the Valhall Field. A key parameter in this discrimination process is the dilation factor, α, which is the relative velocity change divided by the relative thickness change within a given layer. The high quality and good repeatability of the OBC data enables us to estimate α with a reasonable accuracy for α-values between 0 and −5. For α-values below −5, complementary information, like for instance geomechanics is required. For the top reservoir horizon we estimate a maximum subsidence of 0.50 m ± 0.29 m and a corresponding velocity decrease for the sequence from the seabed to the top reservoir of 2.0 m s⁻¹± 0.40 m s⁻¹.
Time-lapse distortion patterns with characteristic time-shift versus offset signatures are observed. The positions and vertical extents of the distortion zones are determined from ray path considerations and modelling. The distortion zones correlate with buried faults, indicating that a (time-lapse) distortion zone might be produced by a localized slip in a fault zone. We present an extended method which allows for vertical (in addition to lateral) variations in the relative thickness and velocity changes. This method can be viewed as a simplified version of time-lapse tomography, but involving fewer unknown parameters, giving more stability to the estimated changes in thickness and velocity. Using this technique, we are able to estimate α for positions with localized time-lapse distortions.     

New insights into the P- and S-wave velocity structure of the D" discontinuity beneath the Cocos plate

Broad-band P - and S -waves from earthquakes in South America recorded at Californian network stations are analysed to image lateral variations of the D"-discontinuity beneath the Cocos plate. We apply two array processing methods to the data set: a simplified migration method to the P -wave data set and a double-array method to both the P - and S -wave data sets, allowing us to compare results from the two methods. The double-array method images a dipping reflector at a depth range from 2650 to 2700 km in the southern part of the study area. We observe a step-like topography of 100 km to a shallower reflector at about 2600 km depth to the north, as well as evidence for a second (deeper) reflector at a depth range from 2700 to 2750 km in the north. Results from the simplified migration agree well with those from the double-array method, similarly locating a large step in reflector depth in a similar location (about 2650 km depth in the south and about 2550 km in the north) as well as the additional deeper reflector at the depth of about 2750 km in the north. Waveform modelling of the reflected waves from both methods suggests a positive velocity contrast for S waves, but a negative velocity contrast for P waves for the upper reflector in agreement with predictions from mineral physical calculations for a post-perovskite phase transition. The data also show some evidence for the existence of another deeper reflector that could indicate a double intersection of the geotherm with the post-perovskite stability field, that is, the back-transformation of post-perovskite to perovskite close to the core–mantle boundary.