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D.Z. Piper

Publications and source records attributed to D.Z. Piper.

At least 19 recordsLinked to original sources

Trace-element budgets in the Ohio/Sunbury shales of Kentucky: Constraints on ocean circulation and primary productivity in the Devonian-Mississippian Appalachian Basin

The hydrography of the Appalachian Basin in late Devonian-early Mississippian time is modeled based on the geochemistry of black shales and constrained by others' paleogeographic reconstructions. The model supports a robust exchange of basin bottom water with the open ocean, with residence times of less than forty years during deposition of the Cleveland Shale Member of the Ohio Shale. This is counter to previous interpretations of these carbon-rich units having accumulated under a stratified and stagnant water column, i.e., with a strongly restricted bottom bottom-water circulation. A robust circulation of bottom waters is further consistent with the palaeoclimatology, whereby eastern trade-winds drove upwelling and arid conditions limited terrestrial inputs of siliciclastic sediment, fresh waters, and riverine nutrients. The model suggests that primary productivity was high (~ 2??g C m- 2 d- 1), although no higher than in select locations in the ocean today. The flux of organic carbon settling through the water column and its deposition on the sea floor was similar to fluxes found in modern marine environments. Calculations based on the average accumulation rate of the marine fraction of Ni suggest the flux of organic carbon settling out of the water column was approximately 9% of primary productivity, versus an accumulation rate (burial) of organic carbon of 0.5% of primary productivity. Trace-element ratios of V:Mo and Cr:Mo in the marine sediment fraction indicate that bottom waters shifted from predominantly anoxic (sulfate reducing) during deposition of the Huron Shale Member of the Ohio Shale to predominantly suboxic (nitrate reducing) during deposition of the Cleveland Shale Member and the Sunbury Shale, but with anoxic conditions occurring intermittently throughout this period. ?? 2008 Elsevier B.V.

Palaeogeography, Palaeoclimatology, Palaeoecology

Geochemistry of bed and suspended sediment in the Mississippi river system: Provenance versus weathering and winnowing

Stream-bed sediment for the size fraction less than 150 μm, examined in 14,000 samples collected mostly from minor tributaries to the major rivers throughout the Mississippi River drainage system, is composed of 5 mineral fractions identified by factor analysis—Al-silicate minerals, quartz, calcite and dolomite, heavy minerals, and an Fe–Mn fraction. The Al-silicate fraction parallels its distribution in the regolith, emphasizing the local sediment source as a primary control to its distribution. Quartz and the heavy-mineral fraction, and associated trace elements, exhibit a complementary distribution to that of the Al-silicate fraction, with a level of enrichment in the bed sediment that is achieved through winnowing and sorting. The carbonate fraction has a distribution suggesting its dissolution during transport. Trace elements partitioned onto the Fe–Mn, possibly amorphous oxyhydride, fraction are introduced to the streams, in part, through human activity. Except for the heavy-mineral fraction, these fractions are identified in suspended sediment from the Mississippi River itself. Although comparison of the tributary bed sediment with the riverine suspended sediment is problematic, the geochemistry of the suspended sediment seems to corroborate the interpretation of the geochemistry of the bed sediment.

Arkansas basin, Ohio basin Tennessee basin, Lower

An upwelling model for the Phosphoria sea: A Permian, ocean-margin sea in the northwest United States

The Permian Phosphoria Formation, a petroleum source rock and world-class phosphate deposit, was deposited in an epicratonic successor basin on the western margin of North America. We calculate the seawater circulation in the basin during deposition of the lower ore zone in the Meade Peak Member from the accumulation rates of carbonate fluorapatite and trace elements. The model gives the exchange rate of water between the Phosphoria sea and the open ocean to the west in terms of an upwelling rate (84 m yr-1) and residence time (4.2 yr) of seawater in the basin. These hydrographic properties supported a mean rate of primary productivity of 0.87 g m-2 d-1 of carbon in the uppermost few tens of meters of the water column (the photic zone) and denitrifying redox conditions in the bottom water (below approximately 150 m depth). High rain rates, onto the sea floor, of the organic matter that hosted the phosphate and several trace elements contributed to the accumulation of phosphorite, chert, and black shales and mudstones. Evaporation in the Goose Egg basin to the east of the Phosphoria basin ensured the import of surface seawater from the Phosphoria sea. Budgets of water, salt, phosphate, and oxygen, plus the minor accumulation of the biomarker gammacerane, show that exchange of water between the two basins was limited, possibly by the shallow carbonate platform that separated the two basins.

Idaho, Montana, Utah, Wyoming

Molybdenum accumulation in Cariaco basin sediment over the past 24 k.y.: A record of water-column anoxia and climate

Molybdenum (Mo) concentrations in a sediment core from the Cariaco basin on the Venezuelan continental shelf can be partitioned between a marine fraction and a terrigenous fraction. The accumulation rate of the marine fraction of Mo increased abruptly 15 000 calendar years ago (15 ka), from <0.5 μgṁcm −2 ṁyr −1 to >4 μgṁcm −2 ṁyr −1 , and then decreased abruptly at 9 ka. The accumulation rate remained high throughout this 6 k.y. period, but exhibited maxima at 15–14 and 12.5 ka, corresponding in time to meltwater pulse IA into the Gulf of Mexico and the onset of the Younger Dryas cold event, respectively. The marine fraction of Mo is interpreted in terms of redox conditions of bottom water, as dictated by both the flux of settling organic matter and bottom-water residence time. Correspondence between geochemical extremes in this core with changes in sea level and global climate demonstrates the high degree to which this ocean-margin basin has responded to the paleoceanographic regime throughout the past 24 k.y.

Geology

Phosphovanadylite: a new vanadium phosphate mineral with a zeolite-type structure

Phosphovanadylite, whose simplified formula is (Ba,Ca,K,Na)x([(Va,Al)4P2(P,OH)16].12H2), is a new vanadium phosphate zeolite mineral found in the Phosphoria Formation at Monsanto's Enoch Valley Mine, Soda Springs, Idaho. Its formula in more detail is (Ba0.38Ca0.20K0.006Na0.02)??0.66 [P2(V3.44Al0.046)??3.90O10.34(OH)5.66] .12H2O. The drusy mineral occurs as pale greenish-blue euhedral cubes (20-50 ??m edge) coating phosphatic, organic-rich mudstone. The chemical composition determined by electron microprobe is (in weight percent) V-28.02, P-9.91, Al-1.97, Ca-1.31, Ba-8.28, Cd-0.09, Zn-0.34, Na-0.15, K-0.73, O-46.57, and F-0.03. The index of refraction is nD = 1.566 (4) and specific gravity is 2.16 (3). The X-ray powder pattern shows strong reflections at 3.16 A (422), 2.58 (600), 2.44 (620), and 7.73 (200), which are indexed on the basis of a cubic body-centered unit cell with a = 15.470 (4) A. From the single-crystal structure analysis, its space group was determined to be I43m, Z = 6, and its structure consists of V4O18 16 octahedral clusters linked to each other by P atoms to form a cubic lattice, creating cavities 7.0 and 5.5 A in diameter where mainly H2O resides. Final residual indexes are R = 0.066, Rw = 0.061, goodness-of-fit = 0.75, and 93 observations and 24 parameters.

American Mineralogist

Fe-Ca-phosphate, Fe-silicate, and Mn-oxide minerals in concretions from the Monterey Formation

Concentrically zoned phosphatic-enriched concretions were collected at three sites from the Monterey Formation. The following minerals were identified: vivianite, lipscombite, rockbridgeite, leucophosphite, mitridatite, carbonate fluorapatite, nontronite, todorokite, and barite. The mineralogy of the concretions was slightly different at each of the three collection sites. None of the concretions contains all of the minerals, but the spatial distribution of minerals in individual concretions, overlapping mineralogies between different concretions, and the geochemical properties of the separate minerals suggest a paragenesis represented by the above order. Eh increased from the precipitation of vivianite to that of rockbridgeite/lipscombite. The precipitation of leucophosphite, then mitridatite, carbonate fluorapatite and todorokite/Fe-oxide indicates increasing pH. Concretion growth culminated with the precipitation of todorokite, a Mn oxide, and minor amounts of barite along microfractures. Conspicuously absent are Fe-sulfide and Mn-phosphate minerals. The concretions are hosted by finely laminated diatomite. The laminations exhibit little to no deformation around the concretions, requiring that the concretions formed after compaction. We interpret this sediment feature and the paragenesis as recording the evolving pore-water chemistry as the formation was uplifted into the fresh-ground-water zone.

Chemical Geology

Instability of bottom-water redox conditions during accumulation of Quaternary sediment in the Japan Sea

The concentrations of Cd, Cr, Cu, Mo, Ni, Sb, U, V, and Zn were measured in early Quaternary sediment (1.32 to 1.08 Ma) from the Oki Ridge in the Japan Sea. The elements were partitioned between a detrital fraction, composed of terrigenous and volcaniclastic aluminosilicate debris, and a marine fraction, composed of biogenic and hydrogenous debris derived from seawater. The most important factors controlling minor-element accumulation rates in the marine fraction were (1) primary productivity in the photic zone, which largely controlled the flux of particulate organic-matter-bound minor elements settling through the water column and onto the seafloor, and (2) bottom-water redox, which determined the suite of elements that accumulated directly from seawater. This marine fraction of minor elements on Oki Ridge recorded six periods of high minor-element abundance. Assuming a constant bulk sediment accumulation rate, each period lasted roughly 5,000 to 10,000 years with a 41,000-year cycle. Accumulation rates of individual elements such as Cd, Mo, and U suggest sulfate-reducing conditions were established in the bottom water during the 10,000-year periods; accumulation rates of Cr and V during the intervening periods are indicative of less reducing, denitrifying conditions. Interelement ratios, for example, Cu:Mo, V:Cr, and Sb:Mo, further reflect bottom-water instability, such that bottom-water redox actually varied from sulfate reducing to denitrifying during the periods of highest minor-element accumulation rates; it varied from denitrifying to oxidizing during the intervening periods. Sediment lithology supports these interpretations of the minor-element distributions; the sediment is finely laminated for several of the periods represented by Cd, Mo, and U maxima and weakly laminated to bioturbated for the intervening periods. The geochemistry of this sediment demonstrates the unambiguous signal of Mo, principally, but of several other minor elements as well in recording sulfate-reducing conditions in bottom water. The forcing function that altered their accumulation, that is, that altered primary productivity and bottom water redox conditions, is problematic. Currently held opinion suggests that O 2 depletion was most strongly developed during glacial advances. Low sea level during such times is interpreted to have enhanced primary productivity and restricted bottom-water advection.

Paleoceanography and Paleoclimatology

Minor elements in Quaternary sediment from the Sea of Japan: A record of surface-water productivity and intermediate-water redox conditions

Sediment of Quaternary age from Oki Ridge (903 m depth) in the Sea of Japan (∼3500 m deep) records six episodes of high accumulation rates of Cd, Cr, Cu, Mo, Ni, U, V, and Zn. The high rates correspond to periods of sulfate reduction in the water column at the intermediate depth of Oki Ridge; the intervening low values correspond to periods of denitrification and oxygen respiration. The maxima have a period of 41 k.y., the youngest having an age of 1.10 Ma. The 41 k.y. cycle is similar to the cycle of δ 18 O values of open-ocean plankton of the same age. The similarity between the cycles of minor-element accumulation in Sea of Japan sediment and δ 18 O values of Atlantic Ocean foraminifera indicates that redox changes in the water column of the Sea of Japan during the Quaternary, forced by major shifts in water-column advection and minor shifts in photic-zone productivity, reflect global events.

Geological Society of America Bulletin

Seawater as the source of minor elements in black shales, phosphorites and other sedimentary rocks

Many of the minor elements in seawater today have a concentration-depth profile similar to that of the biologically essential nutrients, NO-3 and PO3-4. They show a relative depletion in the photic zone and enrichment in the deep ocean. The difference between their surface- and deep-ocean values, normalized to the change in PO3-4, approaches the average of measured minor-element: P ratios in marine plankton, although individual analyses of the latter show extreme scatter for a variety of reasons. Despite this scatter in the minor-element analyses of plankton, agreement between the two sets of data shows unequivocally that an important marine flux of many minor elements through the ocean is in the form of biogenic matter, with a composition approaching that of plankton. This interpretation is further supported by sediment studies, particularly of sediments which accumulate in shelf-slope environments where biological productivity in the photic zone is exceptionally high and organic carbon contents of the underlying sediment elevated. The interelement relations observed for some of these sediments approach the average values of plankton. These same interelement relations are observed in many marine sedimentary rocks such as metalliferous black shales and phosphorites, rocks which have a high content of marine fractions (e.g., organic matter, apatite, biogenic silica and carbonates). Many previous studies of the geochemistry of these rocks have concluded that local hydrothermal activity, and/or seawater with an elemental content different from that of the modern ocean, was required to account for their minor-element contents. However, the similarity in several of the minor-element ratios in many of these formations to minor-element ratios in modern plankton demonstrates that these sedimentary rocks accumulated in environments whose marine chemistry was virtually identical to that seen on continental shelf-slopes, or in marginal seas, of the ocean today. The accumulation of the marine fraction of minor elements on these ancient sea floors was determined largely by the accumulation of organic matter, settling from the photic zone and with a composition of average plankton. A second marine fraction of minor elements in these rocks accumulated through precipitation and adsorption from seawater. The suite of elements in this fraction reflects redox conditions in the bottom water, as determined by bacterial respiration. For example, high Mn, high Cr+V and high Mo concentrations, above those which can be attributed to the accumulation of planktonic matter, characterize accumulation under bottom-water oxidizing, denitrifying and sulfate-reducing conditions, respectively. ?? 1994.

Chemical Geology

The metal oxide fraction of pelagic sediment in the equatorial North Pacific Ocean: A source of metals in ferromanganese nodules

Pelagic sediment recovered at DOMES Site A in the equatorial North Pacific (151°W, 9° 15′N) consists of a surface homogeneous layer, approximately 10 cm thick, overlying a strongly mottled layer that is lighter in color. The radiolarian composition of both units is Quaternary. In areas where this sediment was only a few centimeters thick, the underlying sediment was early Tertiary. Clay mineralogy and major oxide composition of the two Quaternary sediments are uniform. Their similarity to continental shale suggests that the sediment has a terrigenous source. Clay mineralogy and major oxide composition of the Tertiary sediment also are uniform, although they differ markedly from the Quarternary sediment. In contrast to the major oxides, concentrations of Mn, Co, Cu, and Ni soluble in hydroxylamine hydrochlorideacetic acid are strongly different in the surface and subsurface Quaternary sediment. Mn and Ni exhibit pronounced depletions in the subsurface sediment, Ni slightly more than Mn. Cu is also depleted in the subsurface sediment, but less than Mn. It is also depleted in the subsurface Tertiary sediment, whereas the Mn concentration remains high. Concentration of Co relative to Mn increases into the subsurface Quaternary sediment to a constant Co:Mn ratio of 3 × 10 −2 . The trivalent REE (the REE exclusive of Ce) and Fe exhibit little down-core variation. Distribution of elements in these sediments is closely related to their concentration in associated surface ferromanganese nodules. The nodules are of two distinct types: those from the area where the Quaternary sediment is relatively thick have δ-MnO 2 as the dominant manganese mineral. The ratios of Ni:Mn, Cu:Mn, and Fe:Mn in these nodules approximate the corresponding ratios of the soluble fraction of surface sediment. Todorokite is the dominant mineral of nodules recovered from areas where the Quaternary sediment is thin. Relatively high Cu/Mn, Ni/Mn, and low Fe/Mn ratios of these nodules mirror differences between the soluble fraction of surface and subsurface Quaternary sediment. These compositional trends of sediment and nodules at DOMES Site A reflect a diagenetic origin for the todorokite nodules and a predominantly hydrogenous origin for the δ-MnO 2 nodules.

Geochimica et Cosmochimica Acta

Rare earth elements in the phosphatic-enriched sediment of the Peru shelf

Apatite-enriched materials from the Peru shelf have been analyzed for their major oxide and rare earth element (REE) concentrations. The samples consist of (1) the fine fraction of sediment, mostly clay material, (2) phosphatic pellets and fish debris, which are dispersed throughout the fine-grained sediment, (3) tabular-shaped phosphatic crusts, which occur within the uppermost few centimeters of sediment, and (4) phosphatic nodules, which occur on the seafloor. The bulk REE concentrations of the concretions suggest that these elements are partitioned between the enclosed detrital material and the apatite fraction. Analysis of the fine-grained sediment with which the samples are associated suggested that this detrital fraction in the concretions should have shale REE values; the analysis of the fish debris suggested that the apatite fraction might have seawater values. The seawater contribution of REE's is negligible in the nodules and crust, in which the apatite occurs as a fine-grained interstitial cement. That is, the concentration of REE's and the REE patterns are predominantly a function of the amount of enclosed fine-grained sediment. By contrast, the REE pattern of the pelletal apatite suggests a seawater source and the absolute REE concentrations are relatively high. The REE P 2 O 5 "> REEP2O5 ratios of the apatite fraction of these samples thus vary from approximately zero (in the case of the crust and nodules) to as much as approximately 1.2 × 10 −3 (in the case of the pellets). The range of this ratio suggests that rather subtle variations in the depositional environment might cause a significant variation in the REE content of this authigenic fraction of the sediment.

Marine Geology

Geochemistry of the rare earth elements in ferromanganese nodules from DOMES Site A, northern equatorial Pacific

The distribution of rare earth elements (REE) in ferromanganese nodules from DOMES Site A has been determined by instrumental neutron activation methods. The concentrations of the REE vary markedly. Low concentrations characterize samples from a depression (the valley), in which Quaternary sediments are thin or absent; high concentrations are found in samples from the surrounding abyssal hills (the highlands) where the Quaternary sediment section is relatively thick. Moreover, the valley nodules are strongly depleted in the light trivalent REE (LREE) and Ce compared with nodules from the highlands, some of the former showing negative Ce anomalies. The REE abundances in the nodules are strongly influenced by the REE abundances in coexisting bottom water. Some controls on the REE chemistry of bottom waters include: a) the more effective removal of the LREE relative to the HREE from seawater because of the greater degree of complexation of the latter elements with seawater ligands, b) the very efficient oxidative scavenging of Ce on particle surfaces in seawater, and c) the strong depletion of both Ce and the LREE in, or a larger benthic flux of the HREE into, the Antarctic Bottom Water (AABW) which flows through the valley. The distinctive REE chemistry of valley nodules is a function of their growth from geochemically evolved AABW. In contrast, the REE chemistry of highland nodules indicates growth from a local, less evolved seawater source.

Geochimica et Cosmochimica Acta