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Oxygen isotopes in nitrate: New reference materials for 18O:17O:16O measurements and observations on nitrate-water equilibration

Despite a rapidly growing literature on analytical methods and field applications of O isotope-ratio measurements of NO 3 − in environmental studies, there is evidence that the reported data may not be comparable because reference materials with widely varying δ 18 O values have not been readily available. To address this problem, we prepared large quantities of two nitrate salts with contrasting O isotopic compositions for distribution as reference materials for O isotope-ratio measurements: USGS34 (KNO 3 ) with low δ 18 O and USGS35 (NaNO 3 ) with high δ 18 O and ‘mass-independent’ δ 17 O. The procedure used to produce USGS34 involved equilibration of HNO 3 with 18 O-depleted meteoric water. Nitric acid equilibration is proposed as a simple method for producing laboratory NO 3 − reference materials with a range of δ 18 O values and normal (mass-dependent) 18 O: 17 O: 16 O variation. Preliminary data indicate that the equilibrium O isotope-fractionation factor ( α ) between [NO 3 − ] and H 2 O decreases with increasing temperature from 1.0215 at 22°C to 1.0131 at 100°C. USGS35 was purified from the nitrate ore deposits of the Atacama Desert in Chile and has a high 17 O: 18 O ratio owing to its atmospheric origin. These new reference materials, combined with previously distributed NO 3 − isotopic reference materials IAEA-N3 (=IAEA-NO-3) and USGS32, can be used to calibrate local laboratory reference materials for determining offset values, scale factors, and mass-independent effects on N and O isotope-ratio measurements in a wide variety of environmental NO 3 − samples. Preliminary analyses yield the following results (normalized with respect to VSMOW and SLAP, with reproducibilities of ±0.2–0.3‰, 1 σ ): IAEA-N3 has δ 18 O = +25.6‰ and δ 17 O = +13.2‰; USGS32 has δ 18 O = +25.7‰; USGS34 has δ 18 O = −27.9‰ and δ 17 O = −14.8‰; and USGS35 has δ 18 O = +57.5‰ and δ 17 O = +51.5‰.

Rapid Communications in Mass Spectrometry↗

Using dual-bacterial denitrification to improve δ15N determinations of nitrates containing mass-independent 17O

The bacterial denitrification method for isotopic analysis of nitrate using N 2 O generated from Pseudomonas aureofaciens may overestimate δ 15 N values by as much as 1–2‰ for samples containing atmospheric nitrate because of mass-independent 17 O variations in such samples. By analyzing such samples for δ 15 N and δ 18 O using the denitrifier Pseudomonas chlororaphis , one obtains nearly correct δ 15 N values because oxygen in N 2 O generated by P. chlororaphis is primarily derived from H 2 O. The difference between the apparent δ 15 N value determined with P. aureofaciens and that determined with P. chlororaphis , assuming mass-dependent oxygen isotopic fractionation, reflects the amount of mass-independent 17 O in a nitrate sample. By interspersing nitrate isotopic reference materials having substantially different δ 18 O values with samples, one can normalize oxygen isotope ratios and determine the fractions of oxygen in N 2 O derived from the nitrate and from water with each denitrifier. This information can be used to improve δ 15 N values of nitrates having excess 17 O. The same analyses also yield estimates of the magnitude of 17 O excess in the nitrate (expressed as Δ 17 O) that may be useful in some environmental studies. The 1- σ uncertainties of δ 15 N, δ 18 O and Δ 17 O measurements are ±0.2, ±0.3 and ±5‰, respectively.

Rapid Communications in Mass Spectrometry↗

Novel silver tubing method for quantitative introduction of water into high temperature conversion systems for stable hydrogen and oxygen isotopic measurements

A new method to seal water in silver tubes for use in a TC/EA reduction unit using a semi-automated sealing apparatus can yield reproducibilities (1 standard deviation) of δ 2 H and &delta 18 O measurements of 1.0 ‰ and 0.06 ‰, respectively. These silver tubes containing reference waters may be preferred for calibration of H- and O-bearing materials analyzed with a TC/EA reduction unit. The new sealing apparatus employs a computer controlled stepping motor to produce silver tubes identical in length. The reproducibility of mass of water sealed in tubes (in a range of 200 to 400 µg) can be as good as 1 percent. Although silver tubes sealed with reference waters are robust and can be shaken or heated to 110 °C with no loss of integrity, they should not be frozen because the expansion during the phase transition of water to ice will break the cold seals and all water will be lost. They should be shipped in insulated containers. This new method eliminates air inclusions and isotopic fractionation of water associated with the loading of water into capsules using a syringe. The method is also more than an order of magnitude faster than preparing water samples in ordinary Ag capsules. Nevertheless, some laboratories may prefer loading water into silver capsules because expensive equipment is not needed, but they are cautioned to apply the necessary corrections for evaporation, back exchange with laboratory atmospheric moisture, and blank.

Rapid Communications in Mass Spectrometry↗

Stable isotope analyses of oxygen (18O:17O:16O) and chlorine (37Cl:35Cl) in perchlorate: reference materials, calibrations, methods, and interferences

Rationale Perchlorate (ClO 4 − ) is a common trace constituent of water, soils, and plants; it has both natural and synthetic sources and is subject to biodegradation. The stable isotope ratios of Cl and O provide three independent quantities for ClO 4 − source attribution and natural attenuation studies: δ 37 Cl, δ 18 O, and δ 17 O (or Δ 17 O or 17 Δ) values. Documented reference materials, calibration schemes, methods, and interferences will improve the reliability of such studies. Methods Three large batches of KClO 4 with contrasting isotopic compositions were synthesized and analyzed against VSMOW-SLAP, atmospheric O 2 , and international nitrate and chloride reference materials. Three analytical methods were tested for O isotopes: conversion of ClO 4 − to CO for continuous-flow IRMS (CO-CFIRMS), decomposition to O 2 for dual-inlet IRMS (O2-DIIRMS), and decomposition to O 2 with molecular-sieve trap (O2-DIIRMS+T). For Cl isotopes, KCl produced by thermal decomposition of KClO 4 was reprecipitated as AgCl and converted into CH 3 Cl for DIIRMS. Results KClO 4 isotopic reference materials (USGS37, USGS38, USGS39) represent a wide range of Cl and O isotopic compositions, including non-mass-dependent O isotopic variation. Isotopic fractionation and exchange can affect O isotope analyses of ClO 4 − depending on the decomposition method. Routine analyses can be adjusted for such effects by normalization, using reference materials prepared and analyzed as samples. Analytical errors caused by SO 4 2 − , NO 3 − , ReO 4 2 − , and C-bearing contaminants include isotope mixing and fractionation effects on CO and O 2 , plus direct interference from CO 2 in the mass spectrometer. The results highlight the importance of effective purification of ClO 4 − from environmental samples. Conclusions KClO 4 reference materials are available for testing methods and calibrating isotopic data for ClO 4 − and other substances with widely varying Cl or O isotopic compositions. Current ClO 4 − extraction, purification, and analysis techniques provide relative isotope-ratio measurements with uncertainties much smaller than the range of values in environmental ClO 4 − , permitting isotopic evaluation of environmental ClO 4 − sources and natural attenuation.

Rapid Communications in Mass Spectrometry↗

USGS44, a new high-purity calcium carbonate reference material for δ13C measurements

Rationale The stable carbon isotopic ( δ 13 C) reference material (RM) LSVEC Li 2 CO 3 has been found to be unsuitable for δ 13 C standardization work because its δ 13 C value increases with exposure to atmospheric CO 2 . A new CaCO 3 RM, USGS44, has been prepared to alleviate this situation. Methods USGS44 was prepared from 8 kg of Merck high-purity CaCO 3 . Two sets of δ 13 C values of USGS44 were determined. The first set of values was determined by online combustion, continuous-flow (CF) isotope-ratio mass spectrometry (IRMS) of NBS 19 CaCO 3 ( δ 13 C VPDB = +1.95 milliurey (mUr) exactly, where mUr = 0.001 = 1‰), and LSVEC Li 2 CO 3 ( δ 13 C VPDB = −46.6 mUr exactly), and normalized to the two-anchor δ 13 C VPDB-LSVEC isotope-delta scale. The second set of values was obtained by dual-inlet (DI)-IRMS of CO 2 evolved by reaction of H 3 PO 4 with carbonates, corrected for cross contamination, and normalized to the single-anchor δ 13 C VPDB scale. Results USGS44 is stable and isotopically homogeneous to within 0.02 mUr in 100-μg amounts. It has a δ 13 C VPDB-LSVEC value of −42.21 ± 0.05 mUr. Single-anchor δ 13 C VPDB values of −42.08 ± 0.01 and −41.99 ± 0.02 mUr were determined by DI-IRMS with corrections for cross contamination. Conclusions The new high-purity, well-homogenized calcium carbonate isotopic reference material USGS44 is stable and has a δ 13 C VPDB-LSVEC value of −42.21 ± 0.05 mUr for both EA/IRMS and DI-IRMS measurements. As a carbonate relatively depleted in 13 C, it is intended for daily use as a secondary isotopic reference material to normalize stable carbon isotope delta measurements to the δ 13 C VPDB-LSVEC scale. It is useful in quantifying drift with time, determining mass-dependent isotopic fractionation (linearity correction), and adjusting isotope-ratio-scale contraction. Due to its fine grain size (smaller than 63 μm), it is not suitable as a δ 18 O reference material. A δ 13 C VPDB-LSVEC value of −29.99 ± 0.05 mUr was determined for NBS 22 oil.

Rapid Communications in Mass Spectrometry↗

Perils of categorical thinking: "Oxic/anoxic" conceptual model in environmental remediation

Given ambient atmospheric oxygen concentrations of about 21 percent (by volume), the lower limit for reliable quantitation of dissolved oxygen concentrations in groundwater samples is in the range of 0.1–0.5 mg/L. Frameworks for assessing in situ redox condition are often applied using a simple two-category (oxic/anoxic) model of oxygen condition. The "oxic" category defines the environmental range in which dissolved oxygen concentrations are clearly expected to impact contaminant biodegradation, either by supporting aerobic biodegradation of electron-donor contaminants like petroleum hydrocarbons or by inhibiting anaerobic biodegradation of electron-acceptor contaminants like chloroethenes. The tendency to label the second category "anoxic" leads to an invalid assumption that oxygen is insignificant when, in fact, the dissolved oxygen concentration is less than detection but otherwise unknown. Expressing dissolved oxygen concentrations as numbers of molecules per volume, dissolved oxygen concentrations that fall below the 0.1 mg/L field detection limit range from 1 to 1017 molecules/L. In light of recent demonstrations of substantial oxygen-linked biodegradation of chloroethene contaminants at dissolved oxygen concentrations well below the 0.1–0.5 mg/L field detection limit, characterizing "less than detection" oxygen concentrations as "insignificant" is invalid.

Remediation Journal↗

Water-quality assessment of the Lower Grand River Basin, Missouri and Iowa, USA, in support of integrated conservation practices

The effectiveness of agricultural conservation programmes to adequately reduce nutrient exports to receiving streams and to help limit downstream hypoxia issues remains a concern. Quantifying programme success can be difficult given that short-term basin changes may be masked by long-term water-quality shifts. We evaluated nutrient export at stream sites in the 44 months that followed a period of increased, integrated conservation implementation within the Lower Grand River Basin. These short-term responses were then compared with export that occurred in the main stem and adjacent rivers in northern Missouri over a 22-year period to better contextualize any recent changes. Results indicate that short-term (October 2010 through May 2014) total nitrogen (TN) concentrations in the Grand River were 20% less than the long-term average, and total phosphorus (TP) concentrations were 23% less. Nutrient reductions in the short term were primarily the result of the less-than-average precipitation and, consequently, streamflow that was 36% below normal. Therefore, nutrient concentrations measured in tributary streams were likely less than normal during the implementation period. Northern Missouri streamflow-normalized TN concentrations remained relatively flat or declined over the period 1991 through 2013 likely because available sources of nitrogen, determined as the sum of commercial fertilizers, available animal manures and atmospheric inputs, were typically less than crop requirement for much of that time frame. Conversely, flow-normalized stream TP concentrations increased over the past 22 years in northern Missouri streams, likely in response to many years of phosphorus inputs in excess of crop requirements. Stream nutrient changes were most pronounced during periods that coincided with the major tillage, planting and growth phases of row crops and increased streamflow. Nutrient reduction strategies targeted at the period February through June would likely have the greatest impact on reducing nutrient export from the basin. Published 2015. This article is a U.S. Government work and is in the public domain in the USA.

River Research and Applications↗

Weather radar data correlate to hail-induced mortality in grassland birds

Small-bodied terrestrial animals such as songbirds (Order Passeriformes) are especially vulnerable to hail-induced mortality; yet, hail events are challenging to predict, and they often occur in locations where populations are not being studied. Focusing on nesting grassland songbirds, we demonstrate a novel approach to estimate hail-induced mortality. We quantify the relationship between the probability of nests destroyed by hail and measured Level-III Next Generation Radar (NEXRAD) data, including atmospheric base reflectivity, maximum estimated size of hail and maximum estimated azimuthal wind shear. On 22 June 2014, a hailstorm in northern Colorado destroyed 102 out of 203 known nests within our research site. Lark bunting ( Calamospiza melanocorys ) nests comprised most of the sample ( n = 186). Destroyed nests were more likely to be found in areas of higher storm intensity, and distributions of NEXRAD variables differed between failed and surviving nests. For 133 ground nests where nest-site vegetation was measured, we examined the ameliorative influence of woody vegetation, nest cover and vegetation density by comparing results for 13 different logistic regression models incorporating the independent and additive effects of weather and vegetation variables. The most parsimonious model used only the interactive effect of hail size and wind shear to predict the probability of nest survival, and the data provided no support for any of the models without this predictor. We conclude that vegetation structure may not mitigate mortality from severe hailstorms and that weather radar products can be used remotely to estimate potential for hail mortality of nesting grassland birds. These insights will improve the efficacy of grassland bird population models under predicted climate change scenarios.

Remote Sensing in Ecology and Conservation↗

Aquatic ecosystem metabolism as a tool in environmental management

Recent advances in high-frequency environmental sensing and statistical approaches have greatly expanded the breadth of knowledge regarding aquatic ecosystem metabolism - the measurement and interpretation of gross primary productivity (GPP) and ecosystem respiration (ER). Aquatic scientists are poised to take advantage of widely available datasets and freely-available modeling tools to apply functional information gained through ecosystem metabolism to better environmental management. Historically, several logistical and conceptual factors have limited the widespread application of metabolism in management settings. Benefitting from new instrumental and modeling tools, it is now relatively straightforward to extend routine monitoring of dissolved oxygen (DO) to dynamic measures of aquatic ecosystem function (GPP & ER) and key physical processes such as gas exchange with the atmosphere (G). We review the current approaches for using DO data in environmental management with a focus on the United States, but briefly describe management frameworks in Europe and Canada. We highlight new applications of diel DO data and metabolism in regulatory settings and explore how they can be applied to managing and monitoring ecosystems. We then review existing data types and provide a short guide for implementing field measurements and modeling of ecosystem metabolic processes using currently available tools. Finally, we discuss research needed to overcome current conceptual limitations of applying metabolism in management settings. Despite challenges associated with modeling metabolism in rivers and lakes, rapid developments in this field have moved us closer to utilizing real-time estimates of GPP, ER and G to improve the assessment and management of environmental change.

WIREs Water↗

Evidence, Age, and Thickness of a Frozen Paleolake in Utopia Planitia, Mars

Recent mapping studies west of Elysium Mons, Mars, have pinpointed subice features that suggest the existence of a frozen paleolake in Utopia Planitia as recently as 1.8 billion years ago. The subice features are interpreted to be hyaloclastic ridges and hills, table mountains, associated jo??kulhlaup deposits, and fluvial channels. Photoclinometric studies of these features and of a basal scarp around the northwest flank of Elysium Mons interpreted to have been an ice-sheet boundary indicate that the maximum thickness of ice within the basin may have been about 180 m. This thickness of ice during a relatively late stage of Martian geologic history would have important implications concerning the atmospheric, the climatic, and possibly the exobiologic history of the planet. ?? 1994 Academic Press. All rights reserved.

Icarus↗

Carbonate-Sulfate Volcanism on Venus?

Venusian canali, outflow channels, and associated volcanic deposits resemble fluvial landforms more than they resemble volcanic features on Earth and Mars. Some canali have meandering habits and features indicative of channel migration that are very similar to meandering river channels and flood plains on Earth, venusian outflow channels closely resemble water-carved outflow channels on Mars and the Channeled Scabland in Washington, collapsed terrains at the sources of some venusian channels resemble chaotic terrains at the sources of martian outflow channels, venusian lava deltas are similar to bird's-foot deltas such as the Mississippi delta, and venusian valley networks indicate sapping. The depositional fluvial-type features (deltas, braided bars, and channeled plains) are generally among the smoothest terrains at the Magellan radar wavelength (12.6 cm) on Venus. These features suggest the involvement of an unusual lava, unexpected processes, and/or extraordinary eruption conditions. Possibly the lava was an ordinary silicate lava such as basalt or a less common type of silicate lava, and conditions unique to Venus or to those particular eruptions may have caused an unusual volcanological behavior. We have developed the alternative possibility that the lava had a water-like rheology and a melting point slightly greater than Venus' surface temperature, thus accounting for the unusual behavior of the lava. Unlike silicate lavas, some carbonatites (including carbonate-sulfate-rich liquids) have these properties; thus they can flow great distances while retaining a high fluidity, significant mechanical erosiveness, and substantial capacity to transport and deposit sediment. Venusian geochemistry and petrology are consistent with extensive eruptions of carbonatite lavas, which could have crustal and/or mantle origins. Venus' atmosphere (especially CO2, HCl, and HF abundances) and rocks may be in local chemical equilibrium, which suggests that the upper crust contains large amounts of calcite, anhydrite, and other salts. Chemical analyses indicate, according to some models, that Venusian rocks may contain 4-19% calcite and anhydrite. Mixtures of crustal salts could melt at temperatures a few tens to a few hundred Kelvins higher than Venus' surface temperature; hence, melting may be induced by modest endogenetic or impact heating. Salts may have many of the same geologic roles on Venus as water and ice have on Mars. A molten salt (carbonatite) "aquifer" may exist beneath a few hundred meters to several kilometers of solidified salt-rich "permafrost." Many geologic features can be explained by carbonatite magmatism: (1) impact melting of crustal salts can explain crater outflows, (2) small, sustained eruptions from molten salt aquifers can explain sapping valleys, (3) large, sustained eruptions may explain canali and their flood plans, and (4) catastrophic outbursts may have formed outflow channels and chaotic terrain. Landforms created by carbonate-rich lavas would be thermally stable on Venus' surface, though some minerals may weather to other solid substances.

Icarus↗

Topography of closed depressions, scarps, and grabens in the North Tharsis region of Mars: implications for shallow crustal discontinuities and graben formation

Using Viking Orbiter images, detailed photoclinometric profiles were obtained across 10 irregular depressions, 32 fretted fractures, 49 troughs and pits, 124 solitary scarps, and 370 simple grabens in the north Tharsis region of Mars. These data allow inferences to be made on the shallow crustal structure of this region. The frequency modes of measured scarp heights correspond with previous general thickness estimates of the heavily cratered and ridged plains units. The depths of the flat-floored irregular depressions (55-175 m), fretted fractures (85-890 m), and troughs and pits (60-1620 m) are also similar to scarp heights (thicknesses) of the geologic units in which these depressions occur, which suggests that the depths of these flat-floored features were controlled by erosional base levels created by lithologic contacts. Although the features have a similar age, both their depths and their observed local structural control increase in the order listed above, which suggests that the more advanced stages of associated fracturing facilitated the development of these depressions by increasing permeability. If a ground-ice zone is a factor in development of these features, as has been suggested, our observation that the depths of these features decrease with increasing latitude suggests that either the thickness of the ground-ice zone does not increase poleward or the depths of the depressions were controlled by the top of the ground-ice zone whose depth may decrease with latitude. Deeper discontinuities are inferred from fault-intersection depths of 370 simple grabens (assuming 60° dipping faults that initiate at a mechanical discontinuity) in Tempe Terra and Alba Patera and from the depths of the large, flat-floored troughs in Tempe Terra. The frequency distributions of these fault-intersection and large trough depths show a concentration at 1.0-1.6 km depth, similar to data obtained for Syria, Sinai, and Lunae Plana. The consistency of these depth data over such a large region of western Mars suggests that a discontinuity or a process that transcends local and regional geology is responsible for the formation of these features. If this discontinuity is represented by the base of the cryosphere, its uniform depth over 55° of latitude suggests that the cryosphere did not thicken poleward. Alternatively, the concentration of depths at 1.0-1.6 km may represent the upper level of noneruptive dike ascent (lateral dike propagation) of Mars, which is controlled by gravity and atmospheric pressure and magma and country-rock characteristics, and was probably controlled, in part, by ground ice. Fault-intersection depths in the north Tharsis region locally extend down to a depth of 5-7 km. The depth data between 2 and 3 km are attributed to the discontinuity at the interface of megaregolith and basement or to the upper limit of noneruptive dike ascent of magma with a high volatile content. Intersection depths greater than 3 km, which were found at Alba Patera, may be due to the megaregolith-basement discontinuity, which was buried and depressed by volcanic loading, or to the upper level of noneruptive dike ascent of magma with a low volatile content. The near absence of narrow simple grabens with fault-initiation depths less than 0.6-1.0 km in this study area, as well as in most of western Mars, suggests that this depth represents the minimum depth that normal faults can initiate; at shallower depths tension cracks or joints would form instead. This hypothesis is supported by the application of the Griffith failure criterion to this minimum depth of normal fault initiation, which suggests that shallow crustal materials have a tensile strength of 2-4 MPa throughout most of western Mars, in close agreement with previous estimates of tensile strength of martian basaltic rock.

Icarus↗

Active Volcanism on Io as Seen by Galileo SSI

Active volcanism on Io has been monitored during the nominal Galileo satellite tour from mid 1996 through late 1997. The Solid State Imaging (SSI) experiment was able to observe many manifestations of this active volcanism, including (1) changes in the color and albedo of the surface, (2) active airborne plumes, and (3) glowing vents seen in eclipse. About 30 large-scale (tens of kilometers) surface changes are obvious from comparison of the SSI images to those acquired by Voyager in 1979. These include new pyroclastic deposits of several colors, bright and dark flows, and caldera-floor materials. There have also been significant surface changes on Io during the Galileo mission itself, such as a new 400-km-diameter dark pyroclastic deposit around Pillan Patera. While these surface changes are impressive, the number of large-scale changes observed in the four months between the Voyager 1 and Voyager 2 flybys in 1979 suggested that over 17 years the cumulative changes would have been much more impressive. There are two reasons why this was not actually the case. First, it appears that the most widespread plume deposits are ephemeral and seem to disappear within a few years. Second, it appears that a large fraction of the volcanic activity is confined to repeated resurfacing of dark calderas and flow fields that cover only a few percent of Io's surface. The plume monitoring has revealed 10 active plumes, comparable to the 9 plumes observed by Voyager. One of these plumes was visible only in the first orbit and three became active in the later orbits. Only the Prometheus plume has been consistently active and easy to detect. Observations of the Pele plume have been particularly intriguing since it was detected only once by SSI, despite repeated attempts, but has been detected several times by the Hubble Space Telescope at 255 nm. Pele's plume is much taller (460 km) than during Voyager 1 (300 km) and much fainter at visible wavelengths. Prometheus-type plumes (50-150 km high, long-lived, associated with high-temperature hot spots) may result from silicate lava flows or shallow intrusions interacting with near-surface SO2. A major and surprising result is that ~30 of Io's volcanic vents glow in the dark at the short wavelengths of SSI. These are probably due to thermal emission from surfaces hotter than 700 K (with most hotter than 1000 K), well above the temperature of pure sulfur volcanism. Active silicate volcanism appears ubiquitous. There are also widespread diffuse glows seen in eclipse, related to the interaction of energetic particles with the atmosphere. These diffuse glows are closely associated with the most active volcanic vents, supporting suggestions that Io's atmopshere is dominated by volcanic outgassing. Globally, volcanic centers are rather evenly distributed. However, 14 of the 15 active plumes seen by Voyager and/or Galileo are within 30?? of the equator, and there are concentrations of glows seen in eclipse at both the sub- and antijovian points. These patterns might be related to asthenospheric tidal heating or tidal stresses. Io will continue to be observed during the Galileo Europa Mission, which will climax with two close flybys of Io in late 1999. ?? 1998 Academic Press.

Icarus↗

Tectonic Speleogenesis of Devils Hole, Nevada, and Implications for Hydrogeology and the Development of Long, Continuous Paleoenvironmental Records

Devils Hole, in southern Nevada, is a surface collapse into a deep, planar, steeply dipping fault-controlled fissure in Cambrian limestone and dolostone. The collapse intersects the water table about 15 m below land surface and the fissure extends at least 130 m deeper. Below water, most of the fissure is lined with a >30-cm-thick layer of dense maxillary calcite that precipitated continuously from groundwater for >500,000 yr. The thick mammillary calcite coat implies a long history of calcite-supersaturated groundwaters, which, combined with the absence of dissolutional morphologies, suggests that Devils Hole was not formed by karst processes. Devils Hole is located in a region of active extension; its tectonic origin is shown by evidence of spreading of its planar opening along a fault and by the orientation of its opening and others nearby, perpendicular to the northwest-southeast minimum principal stress direction of the region. Most Quaternary tectonic activity in the area, including seismicity and Quaternary faults and fractures, occurs on or parallel to northeast-striking structures. The hydrogeologic implications of this primarily structural origin are that fracture networks and caves opened by extensional tectonism can act as groundwater flowpaths functionally similar to those developed by karst processes and that, during active extension, transmissivity can be maintained despite infilling by mineral precipitation. Such extensional environments can provide conditions favorable for accumulation of deposits preserving long, continuous paleoenvironmental records. The precipitates in Devils Hole store chronologies of flow system water-level fluctuations, hydrochemistry, a half-million-yr proxy paleoclimate record, evidence of Devils Hole's tectonic origin, and probably atmospheric circulation.

Quaternary Research↗

Evidence from Lake Baikal for Siberian glaciation during oxygen-isotope substage 5d

The paleoclimatic record from bottom sediments of Lake Baikal (eastern Siberia) reveals new evidence for an abrupt and intense glaciation during the initial part of the last interglacial period (isotope substage 5d). This glaciation lasted about 12 000 yr from 117 000 to 105 000 yr BP according to correlation with the SPEC-MAP isotope chronology. Lithological and biogeochemical evidence of glaciation from Lake Baikal agrees with evidence for the advance of ice sheet in northwestern Siberia during this time period and also with cryogenic features within the strata of Kazantzevo soils in Southern Siberia. The severe 5d glaciation in Siberia was caused by dramatic cooling due to the decrease in solar insolation (as predicted by the model of insulation changes for northern Asia according to Milankovich theory) coupled with western atmospheric transport of moisture from the opea areas of Northern Atlantic and Arctic seas (which became ice-free due to the intense warming during preceeding isotope substage 5e). Other marine and continental records show evidence for cooling during 5d, but not for intense glaciation. Late Pleistocene glaciations in the Northern Hemisphere may have begun in northwestern Siberia.

Lake Baikal↗

Late Pleistocene C4 plant dominance and summer rainfall in the southwestern United States from isotopic study of herbivore teeth

Patterns of climate and C4 plant abundance in the southwestern United States during the last glaciation were evaluated from isotopic study of herbivore tooth enamel. Enamel ??13C values revealed a substantial eastward increase in C4 plant consumption for Mammuthus spp., Bison spp., Equus spp., and Camelops spp. The ??13C values were greatest in Bison spp. (-6.9 to + 1.7???) and Mammuthus spp. (-9.0 to +0.3???), and in some locales indicated C4-dominated grazing. The ??13C values of Antilocaprids were lowest among taxa (-12.5 to -7.9???) and indicated C3 feeding at all sites. On the basis of modern correlations between climate and C4 grass abundance, the enamel data imply significant summer rain in parts of southern Arizona and New Mexico throughout the last glaciation. Enamel ??18O values range from +19.0 to +31.0??? and generally increase to the east. This pattern could point to a tropical or subtropical source of summer rainfall. At a synoptic scale, the isotope data indicate that interactions of seasonal moisture, temperature, and lowered atmospheric pCO2 determined glacial-age C4 abundance patterns.

Quaternary Research↗

Geochemical variations in Peoria Loess of western Iowa indicate paleowinds of midcontinental North America during last glaciation

Peoria Loess deposited in western Iowa during the last glacial maximum (LGM) shows distinct geochemical and particle-size variations as a function of both depth and distance east of the Missouri River. Geochemical and particle-size data indicate that Peoria Loess in western Iowa probably had two sources: the Missouri River valley, and a source that lay to the west of the Missouri River. Both sources indicate that LGM paleowinds in western Iowa had a strong westerly component, similar to interpretations of previous workers. A compilation of loess studies in Iowa and elsewhere indicates that westerly winds were dominant during loess transport over much of the midcontinent south of the Laurentide ice sheet, which is not in agreement with paleowinds simulated by atmospheric general circulation models (AGCMs). AGCMs consistently generate a glacial anticyclone with easterly or northeasterly winds over the Laurentide ice sheet and the area to the south of it. Loess deposition in the midcontinent during the LGM may be a function of infrequent northwesterly winds that were unrelated to the presence of the glacial anticyclone.

Quaternary Research↗

Comparison of conventional K-Ar and 40Ar/39Ar dating of young mafic volcanic rocks

K-Ar and 40Ar/39Ar ages have been measured on nine mafic volcanic rocks younger than 1 myr from the Snake River Plain (Idaho), Mount Adams (Washington), and Crater Lake (Oregon). The K-Ar ages were calculated from Ar measurements made by isotope dilution and K2O measurements by flame photometry. The 40Ar/39Ar ages are incremental-heating experiments using a low-blank resistance-heated furnace. The results indicate that high-quality ages can be measured on young, mafic volcanic rocks using either the K-Ar or the 40Ar/39Ar technique. The precision of an 40Ar/39Ar plateau age generally is better than the precision of a K-Ar age because the plateau age is calculated by pooling the ages of several gas increments. The precision of a plateau age generally is better than the precision of an isotope correlation (isochron) age for the same sample. For one sample the intercept of the isochron yielded an 40Ar/36Ar value significantly different from the atmospheric value of 295.5. Recalculation of increment ages using the isochron intercept for the composition of nonradiogenic Ar in the sample resulted in much better agreement of ages for this sample. The results of this study also indicate that, given suitable material and modern equipment, precise K-Ar and 40Ar/39Ar ages can be measured on volcanic rocks as young as the latest Pleistocene, and perhaps even the Holocene.

Quaternary Research↗