Systematics of the spinel structure type

Systematic trends in the geometry of 149 oxide and 80 sulfide binary and ternary spinels have been examined from the standpoint of ionic radius and electronegativity. The mean ionic radii of the octahedral and tetrahedral cations, taken together, account for 96.9 and 90.5% of the variation in the unit cell parameter, a, of the oxides and sulfides, respectively, with the octahedral cation exerting by far the dominant influence in sulfides. The mean electronegativity of the octahedral cation exerts an additional, but small, influence on the cell edge of the sulfides. The equation a=(8/3√d)d _tet+(8/3)d _oct, where d _tet and d _oct are the tetrahedral and octahedral bond lengths obained from the sum of the ionic radii, accounts for 96.7 and 83.2% of the variation in a in the oxides and sulfides, respectively, again testifying to the applicability of the hard-sphere ionic model in the case of the spinel structure. Comparison of observed and calculated u values for 94 spinels indicates that up to 40% of the experimentally measured anion coordinates may be significantly in error. In addition to these compounds, u values are given for 52 spinels for which no data have previously been determined. Diagrams are presented for the rapid interpretation of the internal consistency of published data and the prediction of the structural parameters of hypothetical or partially studied spinels.     

Sulfate reduction and the nature of organic matter in estuarine sediments

The reduction of sulfate by sulfate reducing bacteria in the anoxic zone is an extremely important process during early diagenesis of marine sediments. Our data from Great Bay, NH reinforce the proposal that the rate of sulfate reduction is directly proportional to the reactivity of the organic matter or the amount of readily metabolizable organic matter present in the sediment and, hence, the source of the organic material in the anoxic zone. It appears that organic matter rich in marine organic remains is more easily degraded in the anoxic zone and that sulfate reduction rates can vary considerably in an estuarine system where many types of organic material may be deposited.     

A method of searching for radial velocity anomalies in the lower mantle using interfering signals

Radial velocity anomalies in the lower mantle that give rise to triplications in the travel-time curve for short-periodP waves will produce arrivals havingdT/d values that differe by roughly 0.2–0.5 s/deg. The first two arrivals associated with such triplications will be separated by less than one second over a distance range of 4°–10° they may not, therefore, be separable visually on single seismograms, so that their presence can only be inferred from some measurable property that depends on their mutual interference. If there are lateral variations in the regions of anomalous velocity gradients, the interfering signals will also have different azimuths of arrival. Using two synthetic wavelets we have investigated the effect of interference on bothdT/d and azimuth measurements at the Yellowknife Array. We found that if the interfering pulses have a dominant frequencyv, there is a range of time separations (0.30/v0.55/v) over which the measureddT/d and azimuth values may fluctuate by much more than the differences indT/d and azimuth between the interfering signals. We have evaluated the following empirically defined functions for three different primary signals, and for three different relative amplitudes of the interfering signals:f (t), the drift function, which expresses how the measured slownesses,p, and azimuths, , differ from the slownesses and azimuths of the primary wavelets; f(), the range function, which describes the behaviour of the upper and lower bounds ofp and as a function of the difference in arrival times of the signals, andf , studied the properties of these functions, and have outlined how these properties provide criteria based on the numerical and statistical characteristics of the arrival vectors, and on the waveform of the signal that will enable small radial velocity anomalies to be more clearly delineated.Contribution No. 863 from the Earth Physics Branch.     

Rank of coal beds of the Narragansett basin,Massachusetts and Rhode Island

Coal of the Narragansett basin generally has been considered to be anthracite and/or meta-anthracite. However, no single reliable method has been used to distinguish these two ranks in this basin. Three methods — chemical, X-ray, and petrographic — have been used with some degree of success on coal of the Narragansett basin, but too often the results are in conflict. Chemical methods have been limited by inadequate sampling on a coal-bed-by-coal-bed basis and by a lack of analyses made according to (American Society for Testing and Materials, 1974) standard specifications.In addition, when corrections are made by using the Parr formulas, as required by the ASTM (1974) procedures, the generally high to very high ash content of coal from the Narragansett basin causes the fixed-carbon content to appear higher than it actually is. X-ray methods using the degree of graphitization as a measure of rank are not reliable because some of the graphite is related to shearing and brecciation associated with folding and faulting. Petrographic methods using reflectance on vitrinite give results that are generally consistent with results from chemical determinations. However, it is not clear whether the mean maximum reflectance or mean bireflectance is a better indicator of similar rank of such high-rank coals that have been structurally deformed.Coal from the Cranston Mine, RI, is probably meta-anthracite and coal from the Portsmouth Mine is probably anthracite. These ranks are based on chemical,X-ray, and petrographic data and are supported by associated metamorphic mineral assemblages that indicate that the Cranston Mine is in a higher metamorphic zone than the zone containing the Porthmouth Mine. Interpretation of the rank of Mansfield, MA, coal on the basis of extant chemical data is difficult because it is an impure coal with an ash content of 33 to 50%. Reflectance data indicate that the Mansfield, Foxborough, and Plainville coals in the northern part of the Narragansett basin are meta-anthracite but this is in disagreement with the rank suggested by the low degree of metamorphism of the associated rocks.     

Measurement of the effect of particle size variation on the detrital remanent magnetization to anhysteretic remanent magnetization ratio in some abyssal sediments

Deposition experiments have been carried out to measure the effect of particle size variation on the relationship between detrital remanent magnetization (DRM), anhysteretic remanent magnetization (ARM), and geomagnetic field intensity in sediments.Foraminiferal ooze from a box core taken in the Columbian Basin south of Jamaica was separated into several particle size ranges and redeposited in the laboratory in known magnetic fields. The intensity and alternating field (AF) demagnetization characteristics of the DRM and a subsequently applied ARM were compared for the various particle size ranges.The results show a variation of DRM/ARM ratios with particle size. The DRM intensities and directions indicate that particle sizes greater than 38 μm do not contribute significantly to the DRM of the total sediment. ARM intensities for larger particle sizes and particle size analysis of the whole sediment indicate that the fraction greater than 38 μm does make a significant contribution to the total ARM of a sample. Use of the DRM/ARM ratio in experimental measurements of magnetic paleointensity indicates that the method is unsatisfactory for sediments having a significant fraction of magnetic particles larger than 38 μm. It is also shown that, for sediments having a significant fraction of high-coercivity magnetic grains, the relative orientation of the ARM and DRM will affect ARM intensities, making necessary the use of corrected ARM and DRM intensities for ratio calculations.     

Biogeochemical and hydrographic controls on chromophoric dissolved organic matter distribution in the Pacific Ocean

Recent in situ observations of chromophoric dissolved organic material (CDOM) in the Pacific Ocean reveal the biogeochemical controls on CDOM and indicate predictive potential for open-ocean CDOM in diagnosing particulate organic matter (POM) remineralization rates within ocean basins. Relationships between CDOM and concentrations of dissolved oxygen, nutrients and inorganic carbon in the subthermocline waters of the Pacific reflect the relative influences of water mass ventilation and water-column oxidative remineralization. Apparent in situ oxygen utilization (AOU) accounts for 86% and 61% of variance in CDOM abundance, respectively, in Antarctic Intermediate Water and North Pacific Intermediate Water. In the deep waters of the Pacific below the zone of remineralization, AOU explains 26% of CDOM variability. The AOU–CDOM relationship results from competing biogeochemical and advective processes within the ocean interior. Dissolved organic carbon (DOC) is not statistically linked to the CDOM or AOU distributions, indicating that the majority of CDOM production occurs during the remineralization of sinking POM and thus potentially provides key information about carbon export. Once formed in the ocean interior, CDOM is relatively stable until it reaches the surface ocean where it is destroyed by solar bleaching. Susceptibility to bleaching confers an additional tracer-like quality for CDOM in water masses with active convection, such as mode waters that appear as subsurface CDOM minima. In the surface ocean, atypically low CDOM abundance highlights a region of unusually extreme oligotrophy: the subtropical South Pacific gyre. For these hyper-oligotrophic waters, the present CDOM observations are consistent with analysis of in situ radiometric observations of light attenuation and reflectance, demonstrating the accuracy of the CDOM spectrophotometric observations. Overall, we illustrate how CDOM abundance in the ocean interior can potentially diagnose rates of thermohaline overturning as they affect regional biogeochemistry and export. We further show how relative surface ocean CDOM abundances are driven in large part by processes occurring in the deep layers of the ocean. This is particularly significant for the interpretation of the global surface distribution of CDOM using satellite remote sensing.