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D.Z. Piper

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

At least 19 recordsLinked to original sources
USGS2008

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↗
USGS2007

Rare-earth elements in the Permian Phosphoria formation: Paleo proxies of ocean geochemistry

The geochemistry of deposition of the Meade Peak Member of the Phosphoria Formation (MPM) in southeast Idaho, USA, a world-class sedimentary phosphate deposit of Permian age that extends over 300,000 km 2 , is ascertained from its rare earth element (REE) composition. Ratios of REE:Al 2 O 3 suggest two sources—seawater and terrigenous debris. The seawater-derived marine fraction identifies bottom water in the Phosphoria Sea as O 2 -depleted, denitrifying (suboxic) most of the time, and seldom sulfate-reducing (anoxic). This interpretation is supported by earlier research that showed progressively greater ratios in the marine sediment fraction of Cr:Ni>V:Ni⪢Mo:Ni, relative to their ratios in seawater; for which marine Cr, V, and Mo can have a dominantly O 2 –depleted bottom-water source and Ni a photic-zone, largely algal, source. The water chemistry was maintained by a balance between bacterial oxidation of organic matter settling through the water column, determined largely by primary productivity in the photic zone, and the flux of oxidants into the bottom water via advection of seawater from the open ocean. Samples strongly enriched in carbonate fluorapatite, the dominant REE host mineral, have variable Er/Sm, Tm/Sm, and Yb/Sm ratios. Their distribution may represent greater advection of seawater between the Phosphoria Sea and open ocean during deposition of two ore zones than a center waste and greater upwelling of nutrient-enriched water into the photic zone. However, the mean rate of deposition of marine Ni, a trace nutrient of algae, and PO 4 3− , a limiting nutrient, indicate that primary productivity was probably high throughout the depositional history. An alternative interpretation of the variable enrichments of Er, Tm, and Yb, relative to Sm, is that they may reflect temporally variable carbonate alkalinity of open-ocean seawater in Permian time. A more strongly negative Ce anomaly for all phosphatic units than the Ce anomaly of modern pelletal phosphate is further indicative of an elevated O 2 concentration in the Permo-Carboniferous open ocean, as proposed by others, in contrast to the depletion of O 2 in the bottom water of the Phosphoria Sea itself. The oceanographic conditions under which the deposit accumulated were likely similar to conditions under which many sedimentary phosphate deposits have accumulated and to conditions under which many black shales that are commonly phosphate poor have accumulated. A shortcoming of several earlier studies of these deposits has resulted from a failure to examine the marine fraction of elements separate from the terrigenous fraction.

Idaho↗
USGS2006

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 ↗
USGS2004

A modern vs. Permian black shale - the hydrography, primary productivity, and water-column chemistry of deposition

The sediment currently accumulating in the Cariaco Basin, on the continental shelf of Venezuela, has an elevated organic-carbon content of approximately 5%; is accumulating under O2-depleted bottom-water conditions (SO42- reduction); is composed dominantly of foraminiferal calcite, diatomaceous silica, clay, and silt; and is dark greenish gray in color. Upon lithification, it will become a black shale. Recent studies have established the hydrography of the basin and the level of primary productivity and bottom-water redox conditions. These properties are used to model accumulation rates of Cd, Cr, Cu, Mo, Ni, V, and Zn on the seafloor. The model rates agree closely with measured rates for the uppermost surface sediment.The model is applied to the Meade Peak Phosphatic Shale Member of the Phosphoria Formation, a phosphate deposit of Permian age in the northwest United States. It too has all of the requisite properties of a black shale. Although the deposit is a world-class phosphorite, it is composed mostly of phosphatic mudstone and siltstone, chert, limestone, and dolomite. It has organic-carbon concentrations of up to 15%, is strongly enriched in several trace elements above a terrigenous contribution and is black. The trace-element accumulation defines a mean primary productivity in the photic zone of the Phosphoria Basin as moderate, at 500 g m-2 year-1 organic carbon, comparable to primary productivity in the Cariaco Basin. The source of nutrient-enriched water that was imported into the Phosphoria Basin, upwelled into the photic zone, and supported primary productivity was an O2 minimum zone of the open ocean. The depth range over which the water was imported would have been between approximately 100 and 600 m. The mean residence time of bottom water in the basin was approximately 4 years vs. 100 years in the Cariaco Basin. The bottom water was O2 depleted, but it was denitrifying, or NO3- reducing, rather than SO42- reducing. Published by Elsevier B.V.

Chemical Geology↗
USGS2002

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↗
USGS2001

Marine chemistry of the permian phosphoria formation and basin, Southeast Idaho

Major components in the Meade Peak Member of the Phosphoria Formation are apatite, dolomite, calcite, organic matter, and biogenic silica-a marine fraction; and aluminosilicate quartz debris-a terrigenous fraction. Samples from Enoch Valley, in southeast Idaho, have major element oxide abundances of Al2O3, Fe2O3, K2O, and TiO2 that closely approach the composition of the world shale average. Factor analysis further identifies the partitioning of several trace elements-Ba, Ga, Li, Sc, and Th and, at other sites in southeast Idaho and western Wyoming, B, Co, Cs, Hf, Rb, and Ta-totally into this fraction. Trace elements that fail to show such correlations or factor loadings include Ag, As, Cd, Cr, Cu, Mo, Ni, Se, the rare earth elements (REE), U, V, and Zn. Their terrigenous contribution is determined from minimum values of trace elements versus the terrigenous fraction. These minima too define trace element concentrations in the terrigenous fraction that approximately equal their concentrations in the world shale average. The marine fraction of trace elements represents the difference between the bulk trace element content of a sample and the terrigenous contribution. Of the trace elements enriched above a terrigenous contribution, Ag, Cr, Cu, Mo, and Se show strong loadings on the factor with an organic matter loading and U and the REE on the factor with a strong apatite loading. Cd, Ni, V, and Zn do not show a strong correlation with any of the marine components but are, nonetheless, strongly enriched above a terrigenous contribution. Interelement relationships between the trace elements identify two seawater sources-planktonic debris and basinal bottom water. Relationships between Cd, Cu, Mo, Zn, and possibly Ni and Se suggest a solely biogenic source. Their accumulation rates, and that of PO3-4, further identify the level of primary productivity as having been moderate and the residence time of water in the basin at 4.5 yr. Enrichments of Cr, U, V, and the REE, above both terrigenous and biogenic contributions, define bottom-water redox conditions as having been oxygen depleted, that is, denitrifying but not sulfate reducing.

Economic Geology↗
USGS1999

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↗
USGS1998

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↗
USGS1997

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↗
USGS1997

Inorganic geochemical indicators of glacial-interglacial changes in productivity and anoxia on the California continental margin

Evidence from sediments in cores collected from within the present oxygen-minimum zone (OMZ; 600–1200 m) on the central and northern California margins record several episodes during the last interstadial (OIS-3, ca. 60-24 ka) of deposition of laminated sediments containing elevated concentrations of several trace elements indicative of anoxic conditions (e.g., Mo, Ni, Zn, and Cu). The presence of abundant well-preserved organic matter, as well as lack of bioturbation and the presence of elevated concentrations of Mo and other trace elements, all support the theory that the OMZ in the northeastern Pacific Ocean was more intense, possibly anoxic, at several times during the late Pleistocene. Sediments of all ages in cores from the southern California margin contain elevated concentrations of Mo, suggesting that this area has always had higher rates of sulfate reduction than either the central or northern California areas. Most of the Ba in sediments in all cores collected on the upper continental slope (200–2700 m) off California and southern Oregon is derived from detrital clastic material, and this source did not change much in time. However, the amount of biogenic Ba did vary with time, and these variations closely follow the temporal variations in organic C (Corg) mass accumulation rate. Using Ba and Corg mass accumulation rates as proxy variables for productivity, all cores show that organic productivity under the California Current upwelling system was highest during OIS-3 and the Holocene, and lowest during the last glacial interval (LGI, ca. 24-10 ka). All paleoproductivity proxy variables indicate that the southern California area has always experienced higher productivity than other areas under the California Current, at least over the last 50 ky.

California↗
USGS1996

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↗
USGS1995

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↗
USGS1995

Geochemistry of minor elements in the Monterey Formation, California; seawater chemistry of deposition

Approximately 24 samples of the Monterey Formation, Southern California, have been analyzed for their major-element oxide and minor-element content. These analyses allow identification of a detrital fraction, composed of terrigenous quartz, clay minerals, and other Al silicate minerals, and a marine fraction, composed of biogenic silica, calcite, dolomite, organic matter, apatite, and minor amounts of pyrite. The minor-element contents in the marine fraction alone are interpreted to have required, at the time of deposition, a high level of primary productivity in the photic zone and denitrifying bacterial respiration in the bottom water.

California↗
USGS1994

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↗