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R. O. Rye

Publications and source records attributed to R. O. Rye.

At least 19 recordsLinked to original sources

Climatic/Hydrologic Oscillations since 155,000 yr B.P. at Owens Lake, California, Reflected in Abundance and Stable Isotope Composition of Sediment Carbonate

Sediment grain size, carbonate content, and stable isotopes in 70-cm-long (∼1500-yr) channel samples from Owens Lake core OL-92 record many oscillations representing climate change in the eastern Sierra Nevada region since 155,000 yr B.P. To first order, the records match well the marine δ 18 O record. At Owens Lake, however, the last interglaciation appears to span the entire period from 120,000 to 50,000 yr B.P., according to our chronology, and was punctuated by numerous short periods of wetter conditions during an otherwise dry climate. Sediment proxies reveal that the apparent timing of glacial–interglacial transitions, notably the penultimate one, is proxy-dependent. In the grain-size and carbonate-content records this transition is abrupt and occurs at ∼120,000 yr B.P. In contrast, in the isotopic records the transition is gradual and occurs between 145,000 and 120,000 yr B.P. Differences in timing of the transition are attributed to variable responses by proxies to climate change.

Quaternary Research

Fate of process solution cyanide and nitrate at three Nevada gold mines inferred from stable carbon and nitrogen isotope measurements

Stable isotope methods have been used to identify the mechanisms responsible for cyanide consumption at three heap-leach operations that process Carlin-type gold ores in Nevada, U.S.A. The reagent cyanide had δ 15 N values ranging from -5 to -2‰ and δ 13C values from -60 to -35‰. The wide δ 13 C range reflects the use by different suppliers of isotopically distinct natural-gas feedstocks and indicates that isotopes may be useful in environmental studies where there is a need to trace cyanide sources. In heap-leach circuits displaying from 5 to 98% consumption of cyanide, barren-solution and pregnant-solution cyanide were isotopically indistinguishable. The similarity is inconsistent with cyanide loss predominantly by HCN offgassing (a process that in laboratory experiments caused substantial isotopic changes), but it is consistent with cyanide retention within the heaps as solids, a process that caused minimal isotopic changes in laboratory simulations, or with cyanide oxidation, which also appears to cause minimal changes. In many pregnant solutions cyanide was carried entirely as metal complexes, which is consistent with ferrocyanides having precipitated or cyano-complexes having been adsorbed within the heaps. It is inferred that gaseous cyanide emissions from operations of this type are less important than has generally been thought and that the dissolution or desorption kinetics of solid species is an important control on cyanide elution when the spent heaps undergo rinsing. Nitrate, nitrite and ammonium had δ 15 N values of 1-16‰. The data reflect isotopic fractionation during ammonia offgassing or denitrification of nitrate–particularly in reclaim ponds–but do not indicate the extent to which nitrate is derived from cyanide or from explosive residues.

Nevada

Insights from a synthesis of old and new climate-proxy data from the Pyramid and Winnemucca lake basins for the period 48 to 11.5 cal ka

A synthesis of old and new paleoclimatic data from the Pyramid and Winnemucca lake basins indicates that, between 48.0 and 11.5·10 3 calibrated years BP (hereafter ka), the climate of the western Great Basin was, to a degree, linked with the climate of the North Atlantic. Paleomagnetic secular variation (PSV) records from Pyramid Lake core PLC08-1 were tied to the GISP2 ice-core record via PSV matches to North Atlantic sediment cores whose isotopic and(or) carbonate records could be linked to the GISP2 δ 18 O record. Relatively dry intervals in the western Great Basin were associated with cold Heinrich events and relatively wet intervals were associated with warm Dansgaard-Oeschger (DO) oscillations. The association of western Great Basin dry events with North Atlantic cold events (and vice versa) switched sometime after the Laurentide Ice Sheet (LIS) reached its maximum extent. For example, the Lahontan highstand, which culminated at 15.5 ka, and a period of elevated lake level between 13.1 and 11.7 ka were associated with cold North Atlantic conditions, the latter period with the Youngest Dryas event. Relatively dry periods were associated with the Bølling and Allerød warm events. A large percentage of the LIS may have been lost to the North Atlantic during Heinrich events 1 and 2 and may have resulted in the repositioning of the Polar Jet Stream over North America. The Trego Hot Springs, Wono, Carson Sink, and Marble Bluff tephras found in core PLC08-1 have been assigned GISP2 calendar ages of respectively, 29.9, 33.7, 34.1, and 43.2 ka. Given its unique trace-element chemistry, the Carson Sink Bed is the same as Wilson Creek Ash 15 in the Mono Lake Basin. This implies that the Mono Lake magnetic excursion occurred at approximately 34 ka and it is not the Laschamp magnetic excursion. The entrance of the First Americans into the northern Great Basin is dated to approximately 14.4 ka, a time when the climate was relatively dry. Evidence for human occupation of the Great Basin is lacking for the next 1100 years (y); i.e., the oldest western stemmed point site in the Great Basin dates to 13.3 ka. Two hypotheses are suggested for this cultural hiatus: (1) the climate had deteriorated to the point that people vacated the Great Basin, or (2) people moved to basin-bottom wetlands that persisted during the dry period, and then the subsequent Younger Dryas wet event erased the archaeological evidence deposited around the low-elevation wetland sites.

Nevada

The rise and fall of Lake Bonneville between 45 and 10.5 ka

A sediment core taken from the western edge of the Bonneville Basin has provided high-resolution proxy records of relative lake-size change for the period 45.1–10.5 calendar ka (hereafter ka). Age control was provided by a paleomagnetic secular variation (PSV)-based age model for Blue Lake core BL04-4. Continuous records of δ18O and total inorganic carbon (TIC) generally match an earlier lake-level envelope based on outcrops and geomorphic features, but with differences in the timing of some hydrologic events/states. The Stansbury Oscillation was found to consist of two oscillations centered on 25 and 24 ka. Lake Bonneville appears to have reached its geomorphic highstand and began spilling at 18.5 ka. The fall from the highstand to the Provo level occurred at 17.0 ka and the lake intermittently overflowed at the Provo level until 15.2 ka, at which time the lake fell again, bottoming out at ∼14.7 ka. The lake also fell briefly below the Provo level at ∼15.9 ka. Carbonate and δ18O data indicate that between 14.7 and 13.1 ka the lake slowly rose to the Gilbert shoreline and remained at about that elevation until 11.6 ka, when it fell again. Chemical and sedimentological data indicate that a marsh formed in the Blue Lake area at 10.5 ka. Relatively dry periods in the BL04-4 records are associated with Heinrich events H1–H4, suggesting that either the warming that closely followed a Heinrich event increased the evaporation rate in the Bonneville Basin and (or) that the core of the polar jet stream (PJS) shifted north of the Bonneville Basin in response to massive losses of ice from the Laurentide Ice Sheet (LIS) during the Heinrich event. The second Stansbury Oscillation occurred during Heinrich event H2, and the Gilbert wet event occurred during the Younger Dryas cold interval. Several relatively wet events in BL04-4 occur during Dansgaard-Oeschger (DO) warm events. The growth of the Bear River glacier between 32 and 17 ka paralleled changes in the values of proxy indicators of Bonneville Basin wetness and terminal moraines on the western side of the Wasatch Mountains have ages ranging from 16.9 to 15.2 ka. This suggests a near synchroneity of change in the hydrologic and cryologic balances occurring in the Bonneville drainage system and that glacial extent was linked to lake size.

Quaternary International

Ultra-deep oxidation and exotic copper formation at the late pliocene boyongan and bayugo porphyry copper-gold deposits, surigao, philippines: Geology, mineralogy, paleoaltimetry, and their implications for Geologic, physiographic, and tectonic controls

The Boyongan and Bayugo porphyry copper-gold deposits are part of an emerging belt of intrusion-centered gold-rich deposits in the Surigao district of northeast Mindanao, Philippines. Exhumation and weathering of these Late Pliocene-age deposits has led to the development of the world's deepest known porphyry oxidation profile at Boyongan (600 m), and yet only a modest (30-70 m) oxidation profile at adjacent Bayugo. Debris flows, volcanic rocks, and fluviolacustrine sediments accumulating in the actively extending Mainit graben subsequently covered the deposits and preserved the supergene profiles. At Boyongan and Bayugo, there is a vertical transition from shallower supergene copper oxide minerals (malachite + azurite + cuprite) to deeper sulfide-stable assemblages (chalcocite ?? hypogene sulfides). This transition provides a time-integrated proxy for the position of the water table at the base of the saturated zone during supergene oxidation. Contours of the elevation of the paleopotentiometric surface based on this min- eralogical transition show that the thickest portions of the unsaturated zone coincided with a silt-sand matrix diatreme breccia complex at Boyongan. Within the breccia complex, the thickness of the unsaturated zone approached 600 in, whereas outside the breccia complex (e.g., at Bayugo), the thickness averaged 50 m. Contours of the paleopotentiometric surface suggest that during weathering, groundwater flowed into the breccia complex from the north, south, and east, and exited along a high permeability zone to the west. The high relief (>550 m) on the elevation of the paleopotentiometric surface is consistent with an environment of high topographic relief, and the outflow zone to the west of the breccia complex probably reflects proximity to a steep scarp intersecting the western breccia complex margin. Stable isotope paleoaltimetry has enabled estimation of the elevation of the land surface, which further constrains the physiographic setting during supergene oxidation. Isotopic measurements of oxygen in supergene kaolinite from Boyongan suggest that local paleometeoric water involved in weathering had a ??180 composition of approximately -5.7 per mil. At the latitude of the southern Philippines, this value corresponds to Pleistocene rain water condensing at elevations between 750 and 1,050 m above contemporary sea level, providing a maximum estimate for the surface elevation during weathering of the porphyry systems. Physiographic reconstuctions suggest that the deep oxidation profile at Boyongan formed in an environment of high topographic relief immediately east of a prominent (>550 m) escarpment. The high permeability contrast between the breccia complex and the surrounding wall rocks, coupled with the proximity of the breccia complex to the escarpment, led to a depressed groundwater table and a vertically extensive unsaturated zone in the immediate vicinity of Boyongan. This thick vadose zone and the low hypogene pyrite/copper sulfide ratios (0.6) at Boyongan promoted in situ oxidation of copper sulfides with only modest (<200 m) supergene remobilization of copper. In contrast, higher hypogene pyrite/chalcopyrite ratios (2.3) at Bayugo led to greater acid production during weathering and more complete leaching of copper above the base of oxidation. This process promoted significant (600 m) lateral dispersion of copper down the paleohydraulic gradient into the diatreme breccia comple, ultimately leading to the formation of an exotic copper deposit. ?? 2009 Society of Economices Geologists, Inc.

Economic Geology

Sulfur- and oxygen-isotopes in sediment-hosted stratiform barite deposits

Sulfur- and oxygen-isotope analyses have been obtained for sediment-hosted stratiform barite deposits in Alaska, Nevada, Mexico, and China to examine the environment of formation of this deposit type. The barite is contained in sedimentary sequences as old as Late Neoproterozoic and as young as Mississippian. If previously published data for other localities are considered, sulfur- and oxygen-isotope data are now available for deposits spanning a host-rock age range of Late Neoproterozoic to Triassic. On a ??34S versus ??18O diagram, many deposits show linear or concave-upward trends that project down toward the isotopic composition of seawater sulfate. The trends suggest that barite formed from seawater sulfate that had been isotopically modified to varying degrees. The ??34S versus ??18O patterns resemble patterns that have been observed in the modern oceans in pore water sulfate and water column sulfate in some anoxic basins. However, the closest isotopic analog is barite mineralization that occurs at fluid seeps on modern continental margins. Thus the data favor genetic models for the deposits in which barium was delivered by seafloor seeps over models in which barium was delivered by sedimentation of pelagic organisms. The isotopic variations within the deposits appear to reflect bacterial sulfate reduction operating at different rates and possibly with different electron donors, oxygen isotope exchange between reduction intermediates and H2O, and sulfate availability. Because they are isotopically heterogeneous, sediment-hosted stratiform barite deposits are of limited value in reconstructing the isotopic composition of ancient seawater sulfate.

Geochimica et Cosmochimica Acta

Population variation in isotopic composition of shorebird feathers: Implications for determining molting grounds

Stable isotope analyses have revolutionized the study of migratory connectivity. However, as with all tools, their limitations must be understood in order to derive the maximum benefit of a particular application. The goal of this study was to evaluate the efficacy of stable isotopes of C, N, H, O and S for assigning known-origin feathers to the molting sites of migrant shorebird species wintering and breeding in Argentina. Specific objectives were to: 1) compare the efficacy of the technique for studying shorebird species with different migration patterns, life histories and habitat-use patterns; 2) evaluate the grouping of species with similar migration and habitat use patterns in a single analysis to potentially improve prediction accuracy; and 3) evaluate the potential gains in prediction accuracy that might be achieved from using multiple stable isotopes. The efficacy of stable isotope ratios to determine origin was found to vary with species. While one species (White-rumped Sandpiper, Calidris fuscicollis) had high levels of accuracy assigning samples to known origin (91% of samples correctly assigned), another (Collared Plover, Charadrius collaris) showed low levels of accuracy (52% of samples correctly assigned). Intra-individual variability may account for this difference in efficacy. The prediction model for three species with similar migration and habitat-use patterns performed poorly compared with the model for just one of the species (71% versus 91% of samples correctly assigned). Thus, combining multiple sympatric species may not improve model prediction accuracy. Increasing the number of stable isotopes in the analyses increased the accuracy of assigning shorebirds to their molting origin, but the best combination - involving a subset of all the isotopes analyzed - varied among species.

Waterbirds

Characteristics, extent and origin of hydrothermal alteration at Mount Rainier Volcano, Cascades Arc, USA: Implications for debris-flow hazards and mineral deposits

Hydrothermal alteration at Mount Rainier waxed and waned over the 500,000-year episodic growth of the edifice. Hydrothermal minerals and their stable-isotope compositions in samples collected from outcrop and as clasts from Holocene debris-flow deposits identify three distinct hypogene argillic/advanced argillic hydrothermal environments: magmatic-hydrothermal, steam-heated, and magmatic steam (fumarolic), with minor superimposed supergene alteration. The 3.8 km 3 Osceola Mudflow (5600 y BP) and coeval phreatomagmatic F tephra contain the highest temperature and most deeply formed hydrothermal minerals. Relatively deeply formed magmatic-hydrothermal alteration minerals and associations in clasts include quartz (residual silica), quartz–alunite, quartz–topaz, quartz–pyrophyllite, quartz–dickite/kaolinite, and quartz–illite (all with pyrite). Clasts of smectite–pyrite and steam-heated opal–alunite–kaolinite are also common in the Osceola Mudflow. In contrast, the Paradise lahar, formed by collapse of the summit or near-summit of the edifice at about the same time, contains only smectite–pyrite and near-surface steam-heated and fumarolic alteration minerals. Younger debris-flow deposits on the west side of the volcano (Round Pass and distal Electron Mudflows) contain only low-temperature smectite–pyrite assemblages, whereas the proximal Electron Mudflow and a < 100 y BP rock avalanche on Tahoma Glacier also contain magmatic-hydrothermal alteration minerals that are exposed in the avalanche headwall of Sunset Amphitheater, reflecting progressive incision into deeper near-conduit alteration products that formed at higher temperatures. The pre-Osceola Mudflow alteration geometry is inferred to have consisted of a narrow feeder zone of intense magmatic-hydrothermal alteration limited to near the conduit of the volcano, which graded outward to more widely distributed, but weak, smectite–pyrite alteration within 1 km of the edifice axis, developed chiefly in porous breccias. The edifice was capped by a steam-heated alteration zone, most of which resulted from condensation of fumarolic vapor and oxidation of H 2 S in the unsaturated zone above the water table. Weakly developed smectite–pyrite alteration extended into the west and east flanks of the edifice, spatially associated with dikes that are localized in those sectors; other edifice flanks lack dikes and associated alteration. The Osceola collapse removed most of the altered core and upper east flank of the volcano, but intensely altered rocks remain on the uppermost west flank. Major conclusions of this study are that: (1) Hydrothermal–mineral assemblages and distributions at Mount Rainier can be understood in the framework of hydrothermal processes and environments developed from studies of ore deposits formed in analogous settings. (2) Frequent eruptions supplied sufficient hot magmatic fluid to alter the upper interior of the volcano hydrothermally, despite the consistently deep (≥ 8 km) magma reservoir which may have precluded formation of economic mineral deposits within or at shallow depths beneath Mount Rainier. The absence of indicator equilibrium alteration-mineral assemblages in the debris flows that effectively expose the volcano to a depth of 1–1.5 km also suggests a low potential for significant high-sulfidation epithermal or porphyry-type mineral deposits at depth. (3) Despite the long and complex history of the volcano, intensely altered collapse-prone rocks were spatially restricted to near the volcano's conduit system and summit, and short distances onto the upper east and west flanks, due to the necessary supply of reactive components carried by ascending magmatic fluids. (4) Intensely altered rocks were removed from the summit, east flank, and edifice interior by the Osceola collapse, but remain on the upper west flank in the Sunset Amphitheater area and present a continuing collapse hazard. (5) Visually conspicuous rocks on the lower east and mid-to-lower west flanks are not intensely altered and probably have not significantly weakened the rock, and thus do not present significant collapse hazards. (6) Alteration developed most intensely within breccia units, because of their high permeability and porosity. Volcanoes with abundant near-conduit upper-edifice breccias are prone to alteration increasing the possibility of collapse, whereas those that are breccia-poor (e.g., massive domes) are less prone to alteration.

Journal of Volcanology and Geothermal Research

Discrimination of carbon and nitrogen isotopes from milk to serum and vibrissae in Alaska Steller sea lions (Eumetopias jubatus)

Knowledge of diet-tissue stable isotope discrimination is required to properly interpret stable isotope values and to identify possible diet shifts, such as might be expected from nursing through weaning. This study compared ??13C and ??15N of paired serum and vibrissal roots with those of ingested milk (n = 52) from free-ranging Steller sea lion (Eumetopias jubatus (Schreber, 1776)) pups (1-11 months) and juveniles (14-27 months) to estimate diet-tissue discrimination. Mean 15N enrichment from ingested milk to serum was 2.1??? ?? 0.6%??? and ??15N at the root of the vibrissae (representing current growth) were not significantly different from serum values. Milk was enriched for mean 13C by 5.0??? ?? 1.0%??? and 7.3??? ?? 1.2??? relative to serum and vibrissal roots, respectively, which was due to the presence of 13C-depleted lipids in milk. This was confirmed by lipid extraction from a subset of milk and serum samples, resulting in a 5.8??? ?? 1.0??? change only in milk. This study established that vibrissal roots and serum are reflective of a milk diet with approximately 2.0??? 15N enrichment, and vibrissal roots reflect serum and lipid-extracted milk values with approximately 2.0??? 13C enrichment. These discrimination factors are important to establish for stable isotope studies assessing diet shifts. ?? 2008 NRC.

Canadian Journal of Zoology

Isotope and Chemical Methods in Support of the U.S. Geological Survey Science Strategy, 2003-2008

Principal functions of the Mineral Resources Program are providing information to decision-makers related to mineral deposits on federal lands and predicting the environmental consequences of the mining or natural weathering of those deposits. Performing these functions requires that predictions be made of the likelihood of undiscovered deposits. The predictions are based on geologic and geoenvironmental models that are constructed for the various types of mineral deposits from detailed descriptions of actual deposits and detailed understanding of the processes that formed them. Over the past three decades the understanding of ore-forming processes has benefitted greatly from the integration of laboratory-based geochemical tools with field observations and other data sources. Under the aegis of the Evolution of Ore Deposits and Technology Transfer Project (EODTTP), a five-year effort that terminated in 2008, the Mineral Resources Program provided state-of-the-art analytical capabilities to support applications of several related geochemical tools.

Fact Sheet

Microbial sulfate reduction and metal attenuation in pH 4 acid mine water

Sediments recovered from the flooded mine workings of the Penn Mine, a Cu-Zn mine abandoned since the early 1960s, were cultured for anaerobic bacteria over a range of pH (4.0 to 7.5). The molecular biology of sediments and cultures was studied to determine whether sulfate-reducing bacteria (SRB) were active in moderately acidic conditions present in the underground mine workings. Here we document multiple, independent analyses and show evidence that sulfate reduction and associated metal attenuation are occurring in the pH-4 mine environment. Water-chemistry analyses of the mine water reveal: (1) preferential complexation and precipitation by H2S of Cu and Cd, relative to Zn; (2) stable isotope ratios of 34S/32S and 18O/16O in dissolved SO4 that are 2-3 ??? heavier in the mine water, relative to those in surface waters; (3) reduction/oxidation conditions and dissolved gas concentrations consistent with conditions to support anaerobic processes such as sulfate reduction. Scanning electron microscope (SEM) analyses of sediment show 1.5-micrometer, spherical ZnS precipitates. Phospholipid fatty acid (PLFA) and denaturing gradient gel electrophoresis (DGGE) analyses of Penn Mine sediment show a high biomass level with a moderately diverse community structure composed primarily of iron- and sulfate-reducing bacteria. Cultures of sediment from the mine produced dissolved sulfide at pH values near 7 and near 4, forming precipitates of either iron sulfide or elemental sulfur. DGGE coupled with sequence and phylogenetic analysis of 16S rDNA gene segments showed populations of Desulfosporosinus and Desulfitobacterium in Penn Mine sediment and laboratory cultures. ?? 2007 Church et al; licensee BioMed Central Ltd.

Geochemical Transactions

Geology and reconnaissance stable isotope study of the Oyu Tolgoi porphyry Cu-Au system, South Gobi, Mongolia

The Oyu Tolgoi porphyry Cu-Au system in the South Gobi desert, Mongolia, comprises five deposits that extend over 6 km in a north-northeast-oriented zone. They occur in a middle to late Paleozoic are terrane and are related to Late Devonian quartz monzodiorite intrusions. The Hugo Dummett deposits are the northernmost and deepest, with up to 1,000 m of premineral sedimentary and volcanic cover rock remaining. They are the largest deposits discovered to date and characterized by high-grade copper (>2.5% Cu) and gold (0.5-2 g/t) mineralization associated with intense quartz veining and several phases of quartz monzodiorite intruded into basaltic volcanic host rocks. Sulfide minerals in these deposits are zoned outward from a bornite-dominated core to chalcopyrite, upward to pyrite ?? enargite and covellite at shallower depth. The latter high-sulfidation-state sulfides are hosted by advanced argillic alteration mineral associations. This alteration is restricted mainly to dacitic ash-flow tuff that overlies the basaltic volcanic rock and includes ubiquitous quartz and pyrophyllite, kaolinite, plus late dickite veins, as well as K alunite, Al phosphate-sulfate minerals, zunyite, diaspore, topaz, corundum, and andalusite. A reconnaissance oxygen-hydrogen and sulfur isotope study was undertaken to investigate the origin of several characteristic alteration minerals in the Oyu Tolgoi system, with particular emphasis on the Hugo Dummett deposits. Based on the isotopic composition of O, H, and S (??18O(SO4) = 8.8-20.1???, ??D = -73 to -43???, ??34S = 9.8-17.9???), the alunite formed from condensation of magmatic vapor that ascended to the upper parts of the porphyry hydrothermal system, without involvement of significant amounts of meteoric water. The isotopic data indicate that pyrophyllite (??18O = 6.5-10.9???, ??D = -90 to -106???) formed from a magmatic fluid with a component of meteoric water. Muscovite associated with quartz monzodiorite intrusions occurs in the core of the Hugo Dummett deposits, and isotopic data (??18O = 3.0-9.0???, ??D = -101 to -116%o) show it formed from a magmatic fluid with water similar in composition to that which formed the pyrophyllite. Mg chlorite (??18O = 5.5???, ??D = -126???) is a widespread mineral retrograde after hydrothermal biotite and may have formed from fluids similar to those related to the muscovite during cooling of the porphyry system. By contrast, paragenetically later and postmineralization alteration fluid, which produced dickite (??18O = -4.1 to +3.3???, ??D = -130 to -140???), shows clear evidence for mixing with substantial amounts of meteoric water. Relatively low ??D values (-140???) for this meteoric water component may indicate that its source was at high elevations. The geologic structure, nature of alteration, styles of mineralization, and stable isotope data indicate that the Oyu Tolgoi deposits constitute a typical porphyry system formed in an island-arc setting. The outward zonation of sulfide minerals for the Hugo Dummett deposits, from a bornite-dominated core to chalcopyrite and pyrite-enargite, can be interpreted to be related to a cooling magmatic hydrothermal system which transgressed outward over enclosing advanced argillic alteration. This resulted in some unusual alteration and sulfide parageneses, such as topaz, or pyrite, enargite, and tennantite, entrained by high-grade bornite. ?? 2006 by Economic Geology.

Economic Geology

A test of geographic assignment using isotope tracers in feathers of known origin

We used feathers of known origin collected from across the breeding range of a migratory shorebird to test the use of isotope tracers for assigning breeding origins. We analyzed δD, δ 13 C, and δ 15 N in feathers from 75 mountain plover ( Charadrius montanus ) chicks sampled in 2001 and from 119 chicks sampled in 2002. We estimated parameters for continuous-response inverse regression models and for discrete-response Bayesian probability models from data for each year independently. We evaluated model predictions with both the training data and by using the alternate year as an independent test dataset. Our results provide weak support for modeling latitude and isotope values as monotonic functions of one another, especially when data are pooled over known sources of variation such as sample year or location. We were unable to make even qualitative statements, such as north versus south, about the likely origin of birds using both δD and δ 13 C in inverse regression models; results were no better than random assignment. Probability models provided better results and a more natural framework for the problem. Correct assignment rates were highest when considering all three isotopes in the probability framework, but the use of even a single isotope was better than random assignment. The method appears relatively robust to temporal effects and is most sensitive to the isotope discrimination gradients over which samples are taken. We offer that the problem of using isotope tracers to infer geographic origin is best framed as one of assignment, rather than prediction.

Oecologia

Evolution of the magmatic-hydrothermal acid-sulfate system at Summitville, Colorado: Integration of geological, stable-isotope, and fluid-inclusion evidence

The Summitville Au-Ag-Cu deposit is a classic volcanic dome-hosted high-sulfidation deposit. It occurs in the Quartz Latite of South Mountain, a composite volcanic dome that was emplaced along the coincident margins of the Platoro and Summitville calderas at 22.5??0.5 Ma, penecontemporaneous with alteration and mineralization. A penecontemporaneous quartz monzonite porphyry intrusion underlies the district and is cut and overlain by pyrite-quartz stockwork veins with traces of chalcopyrite and molybdenite. Alteration and mineralization proceeded through three hypogene stages and a supergene stage, punctuated by at least three periods of hydrothermal brecciation. Intense acid leaching along fractures in the quartz latite produced irregular pipes and lenticular pods of vuggy silica enclosed sequentially by alteration zones of quartz-alunite, quartz-kaolinite, and clay. The acid-sulfate-altered rocks host subsequent covellite+enargite/luzonite+chalcopyrite mineralization accompanied by kaolinite, and later barite-base-metal veins, some containing high Au values and kaolinite. The presence of both liquid- and vapor-rich fluid inclusions indicates the episodic presence of a low-density fluid at all levels of the system. In the mineralized zone, liquid-rich fluid inclusions in healed fractures in quartz phenocrysts and in quartz associated with mineralization homogenize to temperatures between 160 and 390 ??C (90% between 190 and 310 ??C), consistent with the range (200-250 ??C) estimated from the fractionation of sulfur isotopes between coexisting alunite and pyrite. A deep alunite-pyrite pair yielded a sulfur-isotope temperature of 390 ??C, marking a transition from hydrostatic to lithostatic pressure at a depth of about 1.5 km. Two salinity populations dominate the liquid-rich fluid inclusions. One has salinities between 0 and 5 wt.% NaCl equivalent; the other has salinities of up to 43 wt.% NaCl equivalent. The occurrence of high-salinity fluid inclusions in vein quartz associated with mineralization, as well as in the deep stockwork veins, suggests that brines originating deep in the system transported the metals. The ??34S values of sulfides in magnetite (-2.3???) and of sulfate in apatite (5.4???) in unaltered quartz latite indicate that ??34S???S was near 0???. The ??34S values of coexisting alteration alunite and pyrite are 18.2??? to 24.5??? and -8.1??? to -2.2???, respectively. Deep in the system, most of the change in ??34S values occurs in the sulfates, indicating that the fluids were initially H2S-dominant, their redox state buffered at depth by equilibration with igneous rocks. However, in the main alteration zone, most of the change in ??34S values occurs in pyrite, indicating that the fluids moved off the rock buffer and became SO42- -dominant as pyrite precipitated and SO2 disproportionation produced the sulfuric acid requisite for acid leaching. The ??34S values of the late-stage barite and sulfides indicate that the system returned to high H2S/SO42- ratios typical of the original rock-buffered fluid. The ??DH2O of alunite parent fluids was near -45??? and their ??18O ranged from 7??? to -1???, depending on the degree of exchange in the alteration zone at low water-rock ratio, or mixing with unexchanged meteoric water. The low ??D values of some alunite samples are interpreted to result from postdepositional exchange with later ore fluids. Fluid exsolved fr om the magma at depth had ??DH2O and ??18OH2O values near -70??? and 10???, respectively. During and following migration to the top of the magma chamber, the fluid underwent isotopic exchange with the partially crystallized magma and its solid and cooler, but still plastic, carapace just below the transition from a lithostatic to hydrostatic pressure regime. These evolved magmatic fluids had ??DH2O and ??18OH2O values close to -40??? and 5???, respectively, prior to release into the superjacent hydrostatically pressured fracture zone, wherein the fluids separat

Chemical Geology

"Sour gas" hydrothermal jarosite: Ancient to modern acid-sulfate mineralization in the southern Rio Grande Rift

As many as 29 mining districts along the Rio Grande Rift in southern New Mexico contain Rio Grande Rift-type (RGR) deposits consisting of fluorite-barite??sulfide-jarosite, and additional RGR deposits occur to the south in the Basin and Range province near Chihuahua, Mexico. Jarosite occurs in many of these deposits as a late-stage hydrothermal mineral coprecipitated with fluorite, or in veinlets that crosscut barite. In these deposits, many of which are limestone-hosted, jarosite is followed by natrojarosite and is nested within silicified or argillized wallrock and a sequence of fluorite-barite??sulfide and late hematite-gypsum. These deposits range in age from ???10 to 0.4 Ma on the basis of 40Ar/39Ar dating of jarosite. There is a crude north-south distribution of ages, with older deposits concentrated toward the south. Recent deposits also occur in the south, but are confined to the central axis of the rift and are associated with modern geothermal systems. The duration of hydrothermal jarosite mineralization in one of the deposits was approximately 1.0 my. Most ??18OSO4-OH values indicate that jarosite precipitated between 80 and 240 ??C, which is consistent with the range of filling temperatures of fluid inclusions in late fluorite throughout the rift, and in jarosite (180 ??C) from Pen??a Blanca, Chihuahua, Mexico. These temperatures, along with mineral occurrence, require that the jarosite have had a hydrothermal origin in a shallow steam-heated environment wherein the low pH necessary for the precipitation of jarosite was achieved by the oxidation of H2S derived from deeper hydrothermal fluids. The jarosite also has high trace-element contents (notably As and F), and the jarosite parental fluids have calculated isotopic signatures similar to those of modern geothermal waters along the southern rift; isotopic values range from those typical of meteoric water to those of deep brine that has been shown to form from the dissolution of Permian evaporite by deeply circulating meteoric water. Jarosite ??34S values range from -24??? to 5???, overlapping the values for barite and gypsum at the high end of the range and for sulfides at the low end. Most ??34S values for barite are 10.6??? to 13.1???, and many ??34S values for gypsum range from 13.1??? to 13.9??? indicating that a component of aqueous sulfate was derived from Permian evaporites (??34 S=12??2???). The requisite H2SO4 for jarosite formation was derived from oxidation of H2S which was likely largely sour gas derived from the thermochemical reduction of Permian sulfate. The low ??34S values for the precursor H2S probably resulted from exchange deeper in the basin with the more abundant Permian SO42- at ???150 to 200 ??C. Jarosite formed at shallow levels after the pH buffering capacity of the host rock (typically limestone) was neutralized by precipitation of earlier minerals. Some limestone-hosted deposits contain caves that may have been caused by the low pH of the deep basin fluids due to the addition of deep-seated HF and other magmatic gases during periods of renewed rifting. Caves in other deposits may be due to sulfuric acid speleogenesis as a result of H2S incursion into oxygenated groundwaters. The isotopic data in these "sour gas" jarosite occurrences encode a record of episodic tectonic or hydrologic processes that have operated in the rift over the last 10 my. ?? 2004 Elsevier B.V. All rights reserved.

Chemical Geology

Origin of secondary sulfate minerals on active andesitic stratovolcanoes

Sulfate minerals in altered rocks on the upper flanks and summits of active andesitic stratovolcanoes result from multiple processes. The origin of these sulfates at five active volcanoes, Citlalte??petl (Mexico), and Mount Adams, Hood, Rainier, and Shasta (Cascade Range, USA), was investigated using field observations, petrography, mineralogy, chemical modeling, and stable-isotope data. The four general groups of sulfate minerals identified are: (1) alunite group, (2) jarosite group, (3) readily soluble Fe- and Al-hydroxysulfates, and (4) simple alkaline-earth sulfates such as anhydrite, gypsum, and barite. Generalized assemblages of spatially associated secondary minerals were recognized: (1) alunite+silica??pyrite??kaolinite?? gypsum??sulfur, (2) jarosite+alunite+silica; (3) jarosite+smectite+silica??pyrite, (4) Fe- and Al-hydroxysulfates+silica, and (5) simple sulfates+silica??Al-hydroxysulfates??alunite. Isotopic data verify that all sulfate and sulfide minerals and their associated alteration assemblages result largely from the introduction of sulfur-bearing magmatic gases into meteoric water in the upper levels of the volcanoes. The sulfur and oxygen isotopic data for all minerals indicate the general mixing of aqueous sulfate derived from deep (largely disproportionation of SO2 in magmatic vapor) and shallow (oxidation of pyrite or H2S) sources. The hydrogen and oxygen isotopic data of alunite indicate the mixing of magmatic and meteoric fluids. Some alunite-group minerals, along with kaolinite, formed from sulfuric acid created by the disproportionation of SO2 in a condensing magmatic vapor. Such alunite, observed only in those volcanoes whose interiors are exposed by erosion or edifice collapse, may have ??34S values that reflect equilibrium (350??50 ??C) between aqueous sulfate and H2S. Alunite with ??34S values indicating disequilibrium between parent aqueous sulfate and H2S may form from aqueous sulfate created in higher level low-temperature environments in which SO2 is scrubbed out by groundwater or where H2S is oxidized. Jarosite-group minerals associated with smectite in only slightly altered volcanic rock are formed largely from aqueous sulfate derived from supergene oxidation of hydrothermal pyrite above the water table. Soluble Al- and Fehydroxysulfates form in low-pH surface environments, especially around fumaroles, and from the oxidation of hydrothermal pyrite. Anhydrite/gypsum, often associated with native sulfur and occasionally with small amounts of barite, also commonly form around fumaroles. Some occurrences of anhydrite/gypsum may be secondary, derived from the dissolution and reprecipitation of soluble sulfate. Edifice collapse may also reveal deep veins of anhydrite/gypsum??barite that formed from the mixing of saline fluids with magmatic sulfate and dilute meteoric water. Alteration along structures associated with both hydrothermal and supergene sulfates, as well as the position of paleo-water tables, may be important factors in edifice collapse and resulting debris flows at some volcanoes. ?? 2004 Elsevier B.V. All rights reserved.

Chemical Geology

Use of naturally occurring mercury to determine the importance of cutthroat trout to Yellowstone grizzly bears

Spawning cutthroat trout ( Oncorhynchus clarki (Richardson, 1836)) are a potentially important food resource for grizzly bears ( Ursus arctos horribilis Ord, 1815) in the Greater Yellowstone Ecosystem. We developed a method to estimate the amount of cutthroat trout ingested by grizzly bears living in the Yellowstone Lake area. The method utilized ( i ) the relatively high, naturally occurring concentration of mercury in Yellowstone Lake cutthroat trout (508 &plusmn; 93 ppb) and its virtual absence in all other bear foods ( 6 ppb), ( ii ) hair snares to remotely collect hair from bears visiting spawning cutthroat trout streams between 1997 and 2000, ( iii ) DNA analyses to identify the individual and sex of grizzly bears leaving a hair sample, ( iv ) feeding trials with captive bears to develop relationships between fish and mercury intake and hair mercury concentrations, and ( v ) mercury analyses of hair collected from wild bears to estimate the amount of trout consumed by each bear. Male grizzly bears consumed an average of 5 times more trout/kg bear than did female grizzly bears. Estimated cutthroat trout intake per year by the grizzly bear population was only a small fraction of that estimated by previous investigators, and males consumed 92% of all trout ingested by grizzly bears.

Wyoming, Montana, Idaho

Stable hydrogen isotope analysis of bat hair as evidence for seasonal molt and long-distance migration

Although hoary bats ( Lasiurus cinereus ) are presumed to be migratory and capable of long-distance dispersal, traditional marking techniques have failed to provide direct evidence of migratory movements by individuals. We measured the stable hydrogen isotope ratios of bat hair (δD h ) and determined how these values relate to stable hydrogen isotope ratios of precipitation (δD p ). Our results indicate that the major assumptions of stable isotope migration studies hold true for hoary bats and that the methodology provides a viable means of determining their migratory movements. We present evidence that a single annual molt occurs in L. cinereus prior to migration and that there is a strong relationship between δD h and δD p during the molt period. This presumably reflects the incorporation of local δD p into newly grown hair. Furthermore, we present evidence that individual hoary bats are capable of traveling distances in excess of 2,000 km and that hair is grown at a wide range of latitudes and elevations. Stable hydrogen isotope analysis offers a promising new tool for the study of bat migration.

Journal of Mammalogy