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At least 1,279 records · Page 71Linked to original sources
USGS2023

Geographic and taxonomic variation in adaptive capacity among mountain-dwelling small mammals: implications for conservation status and actions

Contemporary climate change is modifying the distribution, morphology, phenology, physiology, evolution, and interspecific interactions of species. Effects of climate change are mediated not only through the magnitude of change experienced (exposure) and an animal's sensitivity to such changes, but also through the ability of the population or species to adjust to climatic variability and change genetically, behaviorally, or spatially (via its distribution) (i.e., adaptive capacity; AC). Here, we used an attribute-based framework to systematically evaluate and compare the AC of American pikas ( Ochotona princeps ) against four other mountain-dwelling small mammals of North America to determine whether pikas are disproportionately vulnerable to climate change, as has been postulated. Unlike previous analyses, we also compared AC across O. princeps lineages and across three taxonomic (and thus, spatial) scales. Our results indicate that pikas have markedly lower adaptive capacity than all compared species except bushy-tailed woodrats ( Neotoma cinerea ), and that our assessments of species generally align with earlier characterizations of climate-change vulnerability based on life-history characteristics. Although AC did not differ dramatically among pika lineages, some attributes are likely constraining AC differently in various parts of the geographic range. Comparisons across taxonomic levels of pikas illustrated that, although AC levels were comparable in pika lineages versus range-wide, AC was assessed as lower in interior-Great-Basin pikas than across the entire O.p. schisticeps lineage. We conclude that the comparatively lower AC of pikas results in particularly high susceptibility to anthropogenic climate change, corroborating results from numerous other recent investigations of pikas' climate-responsiveness. Adaptive-capacity evaluations appear useful as a consistent way to identify sentinel species or populations and for conservation prioritization.

Biological Conservation↗
USGS2005

Major and trace element composition of copiapite-group minerals and coexisting water from the Richmond mine, Iron Mountain, California

Copiapite-group minerals of the general formula AR 4 (SO 4 ) 6 (OH) 2 · n H 2 O, where A is predominantly Mg, Fe 2+ , or 0.67Al 3+ , R is predominantly Fe 3+ , and n is typically 20, are among several secondary hydrous Fe sulfates occurring in the inactive mine workings of the massive sulfide deposit at Iron Mountain, CA, a USEPA Superfund site that produces extremely acidic drainage. Samples of copiapite-group minerals, some with coexisting water, were collected from the Richmond mine. Approximately 200 mL of brownish pore water with a pH of −0.9 were extracted through centrifugation from a 10-L sample of moist copiapite-group minerals taken from pyritic muck piles. The pore water is extremely rich in ferric iron (Fe 3+ =149 g L −1 , Fe T =162 g L −1 ) and has a density of 1.52 g mL −1 . The composition of the pore water is interpreted in the context of published phase relations in the Fe 2 O 3 –SO 3 –H 2 O system and previous work on the chemistry of extremely acid mine waters and associated minerals in the Richmond mine. Two distinct members of the copiapite mineral group were identified in the samples with coexisting water: (1) abundant magnesiocopiapite consisting of platy crystals 10 to 50 μm and (2) minor aluminocopiapite present as smaller platy crystals that form spheroidal aggregates. The average composition ( n =5) of the magnesiocopiapite is (Mg 0.90 Fe 2+ 0.17 Zn 0.02 Cu 0.01 ) ∑1.10 (Fe 3+ 3.83 Al 0.09 ) ∑3.92 (SO 4 ) 6.00 (OH) 1.96 ·20H 2 O. Bulk compositions determined by digestion and wet-chemical analysis are consistent with the microanalytical results. These results suggest that magnesiocopiapite is the least soluble member of the copiapite group under the prevailing conditions. Micro-PIXE analysis indicates that the copiapite-group minerals in this sample sequester Zn (average 1420 ppm), with lesser amounts of Cu (average 270 ppm) and As (average 64 ppm).

Chemical Geology↗
USGS2005

Eolian deposits in the Neoproterozoic Big Bear Group, San Bernardino Mountains, California, USA

Strata interpreted to be eolian are recognized in the Neoproterozoic Big Bear Group in the San Bernardino Mountains of southern California, USA. The strata consist of medium- to large-scale (30 cm to > 6 m) cross-stratified quartzite considered to be eolian dune deposits and interstratified thinly laminated quartzite that are problematically interpreted as either eolian translatent climbing ripple laminae, or as tidal-flat deposits. High index ripples and adhesion structures considered to be eolian are associated with the thinly laminated and cross-stratified strata. The eolian strata are in a succession that is characterized by flaser bedding, aqueous ripple marks, mudcracks, and interstratified small-scale cross-strata that are suggestive of a tidal environment containing local fluvial deposits. The eolian strata may have formed in a near-shore environment inland of a tidal flat. The Neoproterozoic Big Bear Group is unusual in the western United States and may represent a remnant of strata that were originally more widespread and part of the hypothetical Neoproterozoic supercontinent of Rodinia. The Big Bear Group perhaps is preserved only in blocks that were downdropped along Neoproterozoic extensional faults. The eolian deposits of the Big Bear Group may have been deposited during arid conditions that preceded worldwide glacial events in the late Neoproterozoic. Possibly similar pre-glacial arid events are recognized in northern Mexico, northeast Washington, Australia, and northwest Canada.

California↗
USGS2008

Changes in stream chemistry and biology in response to reduced levels of acid deposition during 1987-2003 in the Neversink River Basin, Catskill Mountains

Atmospheric acid deposition has decreased in the northeastern United States since the 1970s, resulting in modest increases in pH, acid-neutralizing capacity (ANC), and decreases in inorganic monomeric aluminum (AlIM) concentrations since stream chemistry monitoring began in the 1980s in the acid-sensitive upper Neversink River basin in the Catskill Mountains of New York. Stream pH has increased by 0.01 units/year during 1987-2003 at three sites in the Neversink basin as determined by Seasonal Kendall trend analysis. In light of this observed decrease in stream acidity, we sampled 12 stream sites within the Neversink River watershed for water chemistry, macroinvertebrates, fish, and periphytic diatoms in 2003 to compare with a similar data set collected in 1987. Metrics and indices that reflect sensitivity to stream acidity were developed with these biological data to determine whether changes in stream biota over the intervening 16 years parallel those of stream chemistry. Statistical comparisons of data on stream chemistry and an acid biological assessment profile (Acid BAP) derived from invertebrate data showed no significant differences between the two years. For pH and ANC, however, values in 2003 were generally lower than those in 1987; this difference likely resulted from higher streamflow in summer 2003. Despite these likely flow-induced changes in summer 2003, an ordination and cluster analysis of macroinvertebrate taxa based on the Acid BAP indicated that the most acidic sites in the upstream half of the East Branch Neversink River form a statistically significant separate cluster consistent with less acidic stream conditions. This analysis is consistent with limited recovery of invertebrate species in the most acidic reaches of the river, but will require additional improvement in stream chemistry before a stronger conclusion can be drawn. Data on the fish and periphytic diatom communities in 2003 indicate that slimy sculpin had not extended their habitat to upstream reaches that previously were devoid of this acid-intolerant species in 1987; a diatom acid-tolerance index indicates continued high-acid impact throughout most of the East Branch and headwaters of the West Branch Neversink River. ?? 2007 Elsevier Ltd. All rights reserved.

Ecological Indicators↗
USGS2009

Impacts of acidification on macroinvertebrate communities in streams of the western Adirondack Mountains, New York, USA

Limited stream chemistry and macroinvertebrate data indicate that acidic deposition has adversely affected benthic macroinvertebrate assemblages in numerous headwater streams of the western Adirondack Mountains of New York. No studies, however, have quantified the effects that acidic deposition and acidification may have had on resident fish and macroinvertebrate communities in streams of the region. As part of the Western Adirondack Stream Survey, water chemistry from 200 streams was sampled five times and macroinvertebrate communities were surveyed once from a subset of 36 streams in the Oswegatchie and Black River Basins during 2003-2005 and evaluated to: (a) document the effects that chronic and episodic acidification have on macroinvertebrate communities across the region, (b) define the relations between acidification and the health of affected species assemblages, and (c) assess indicators and thresholds of biological effects. Concentrations of inorganic Al in 66% of the 200 streams periodically reached concentrations toxic to acid-tolerant biota. A new acid biological assessment profile (acidBAP) index for macroinvertebrates, derived from percent mayfly richness and percent acid-tolerant taxa, was strongly correlated (R2 values range from 0.58 to 0.76) with concentrations of inorganic Al, pH, ANC, and base cation surplus (BCS). The BCS and acidBAP index helped remove confounding influences of natural organic acidity and to redefine acidification-effect thresholds and biological-impact categories. AcidBAP scores indicated that macroinvertebrate communities were moderately or severely impacted by acidification in 44-56% of 36 study streams, however, additional data from randomly selected streams is needed to accurately estimate the true percentage of streams in which macroinvertebrate communities are adversely affected in this, or other, regions. As biologically relevant measures of impacts caused by acidification, both BCS and acidBAP may be useful indicators of ecosystem effects and potential recovery at the local and regional scale.

Ecological Indicators↗
USGS2018

Relationships between indicators of acid-base chemistry and fish assemblages in streams of the Great Smoky Mountains National Park

The acidity of many streams in the Great Smoky Mountains National Park (GRSM) has increased significantly since pre-industrial (∼1850) times due to the effects of highly acidic atmospheric deposition in poorly buffered watersheds. Extensive stream-monitoring programs since 1993 have shown that fish and macroinvertebrate assemblages have been adversely affected in many streams across the GRSM. Matching chemistry and fishery information collected from 389 surveys performed at 52 stream sites over a 22-year period were assessed using logistic regression analysis to help inform the U.S. Environmental Protection Agency’s assessment of the environmental impacts of emissions of oxides of nitrogen (NO x ) and sulfur (SO x ). Numerous logistic equations and associated curves were derived that defined the relations between acid neutralizing capacity (ANC) or pH and different levels of community richness, density, and biomass; and density and biomass of brook trout, rainbow trout, and small prey (minnow) populations in streams of the GRSM. The equations and curves describe the status of fish assemblages in the GRSM under contemporary emission levels and deposition loads of nitrogen (N) and sulfur (S) and provide a means to estimate how newly proposed (and various alternative) target deposition loads, which strongly influence stream ANC, might affect key ecological indicators. Several examples using ANC, community richness, and brook trout density are presented to illustrate the steps needed to predict how future changes in stream chemistry (resulting from different target deposition loads of N and S) will affect the probabilities of observing specific levels of selected biological indicators in GRSM streams. The implications of this study to the regulation of NO x and SO x emissions, water quality, and fisheries management in streams of the GRSM are discussed, but also qualified by the fact that specific examples provided need to be further explored before recommendations concerning their use as ecological indicators could be proposed.

North Carolina, Tennessee↗
USGS2021

Monitoring long-term riparian vegetation trends to inform local habitat management in a mountainous environment

Riparian ecosystems provide critical habitat for many species, yet assessment of vegetation condition at local scales is difficult to measure when considering large areas over long time periods. We present a framework to map and monitor two deciduous cover types, upland and riparian, occupying a small fraction of an expansive, mountainous landscape in north-central Wyoming. Initially, we developed broad-scale predictions of predominant woody vegetation types by integrating Landsat data into species distribution models and combining subsequent outputs into a synthesis map. Then, we evaluated a 35-year Landsat time series (1985–2019) using the Mann-Kendall test to identify significant trends in the condition of upland and riparian deciduous vegetation and assessed the rate and direction of change using the Theil-Sen estimator. Finally, we used plot level data to assess the utility of the framework to detect bottom-up controls (ungulate browse pressure and management actions) on vegetation condition. The synthesis map had an overall correct classification rate of 87% and field data indicated deciduous vegetation within 45 m of coniferous forest faces increased pressure of conifer expansion. The trend assessment identified consistent patterns operating at the landscape scale across both upland and riparian deciduous vegetation; a predominant greening trend was observed for 12 years followed by a 9-year browning trend, before switching back to a greening trend for the last 13 years of the study. Our results indicate trends are driven by the climate of the measurement period at the landscape scale. Although we did not find conclusive evidence to establish a strong link between browse pressure and satellite data, we highlight examples where prevailing trends can be overridden by local disturbance or management intervention. This framework is transferable to other understudied riparian environments throughout western North America to provide insight on ecohydrological processes and assess global and local stressors across broad spatiotemporal scales.

Wyoming↗
USGS2007

Application of a coupled ecosystem-chemical equilibrium model, DayCent-Chem, to stream and soil chemistry in a Rocky Mountain watershed

Atmospheric deposition of sulfur and nitrogen species have the potential to acidify terrestrial and aquatic ecosystems, but nitrate and ammonium are also critical nutrients for plant and microbial productivity. Both the ecological response and the hydrochemical response to atmospheric deposition are of interest to regulatory and land management agencies. We developed a non-spatial biogeochemical model to simulate soil and surface water chemistry by linking the daily version of the CENTURY ecosystem model (DayCent) with a low temperature aqueous geochemical model, PHREEQC. The coupled model, DayCent-Chem, simulates the daily dynamics of plant production, soil organic matter, cation exchange, mineral weathering, elution, stream discharge, and solute concentrations in soil water and stream flow. By aerially weighting the contributions of separate bedrock/talus and tundra simulations, the model was able to replicate the measured seasonal and annual stream chemistry for most solutes for Andrews Creek in Loch Vale watershed, Rocky Mountain National Park. Simulated soil chemistry, net primary production, live biomass, and soil organic matter for forest and tundra matched well with measurements. This model is appropriate for accurately describing ecosystem and surface water chemical response to atmospheric deposition and climate change. ?? 2006 Elsevier B.V. All rights reserved.

Ecological Modelling↗
USGS2010

Limited hydrologic response to Pleistocene climate change in deep vadose zones - Yucca Mountain, Nevada

Understanding the movement of water through thick vadose zones, especially on time scales encompassing long-term climate change, is increasingly important as societies utilize semi-arid environments for both water resources and sites viewed as favorable for long-term disposal or storage of hazardous waste. Hydrologic responses to Pleistocene climate change within a deep vadose zone in the eastern Mojave Desert at Yucca Mountain, Nevada, were evaluated by uranium-series dating of finely layered hyalitic opal using secondary ion mass spectrometry. Opal is present within cm-thick secondary hydrogenic mineral crusts coating floors of lithophysal cavities in fractured volcanic rocks at depths of 200 to 300 m below land surface. Uranium concentrations in opal fluctuate systematically between 5 and 550 μg/g. Age-calibrated profiles of uranium concentration correlate with regional climate records over the last 300,000 years and produce time-series spectral peaks that have distinct periodicities of 100- and 41-ka, consistent with planetary orbital parameters. These results indicate that the chemical compositions of percolating solutions varied in response to near-surface, climate-driven processes. However, slow (micrometers per thousand years), relatively uniform growth rates of secondary opal and calcite deposition spanning several glacial–interglacial climate cycles imply that water fluxes in the deep vadose zone remained low and generally buffered from the large fluctuations in available surface moisture during different climates.

Nevada↗
USGS2006

Changes in stream chemistry and nutrient export following a partial harvest in the Catskill Mountains, New York, USA

Clearcut forest harvesting typically results in large changes in stream water chemistry in northeastern North America. The effects of partial forest harvests on stream chemistry have not received as much attention, even though partial cutting is a more common forestry practice than clearcutting in this region. Changes in stream water chemistry following a partial cut are reported here from a 10 ha study catchment in a northern hardwood forest in the Catskill Mountains of southern New York, and are compared to those of a nearby 48 ha reference catchment. The lower two thirds of the treatment catchment was harvested in February-April 2002 by a shelterwood method, such that 33% of the basal area of the catchment was removed. Stream NO3-, NH4+, Ca2+, K+, and total dissolved aluminum (Alto) concentrations increased significantly after the harvest. Stream Ca2+, Mg2+ and NH4+ concentrations peaked 5 months after the initiation of the harvest, NO 3- and K+ concentrations peaked 6 months after cutting, and Alto concentrations peaked 1 year after cutting. Streamflow was not significantly affected by the harvest when compared to the flow of three nearby streams. Export of NO3- in stream water increased five-fold the year after the cut, and briefly exceeded atmospheric inputs of inorganic nitrogen during 4 months in the fall of 2002. Changes in stream NO3- and K+ concentrations were less than predicted by the relative basal area removed compared with those of a recent nearby clearcut. In contrast, changes in Ca2+, Mg 2+ and Alto concentrations were approximately proportional to basal area removal in these two cuts. Stream chemistry returned to values close to those of the pre-cut period and to reference values by early spring of 2003, just over a year after the initiation of the harvest, except for NO 3- concentrations, which remained elevated above background 18-20 months after completion of the cut.

Forest Ecology and Management↗
USGS2011

The relation of harvesting intensity to changes in soil, soil water, and stream chemistry in a northern hardwood forest, Catskill Mountains, USA

Previous studies have shown that clearcutting of northern hardwood forests mobilizes base cations, inorganic monomeric aluminum (Al im ), and nitrate (NO 3 - - N) from soils to surface waters, but the effects of partial harvests on NO 3 - - N have been less frequently studied. In this study we describe the effects of a series of partial harvests of varying proportions of basal area removal (22%, 28% and 68%) on Al im , calcium (Ca 2+ ), and NO 3 - - N concentrations in soil extracts, soil water, and surface water in the Catskill Mountains of New York, USA. Increases in NO 3 - - N concentrations relative to pre-harvest values were observed within a few months after harvest in soils, soil water, and stream water for all three harvests. Increases in Al im and Ca 2+ concentrations were also evident in soil water and stream water over the same time period for all three harvests. The increases in Al im , Ca 2+ , and NO 3 - - N concentrations in the 68% harvest were statistically significant as measured by comparing the 18-month pre-harvest period with the 18-month post-harvest period, with fewer significant responses in the two harvests of lowest intensity. All three solutes returned to pre-harvest concentrations in soil water and stream water in the two lowest intensity harvests in 2–3 years compared to a full 3 years in the 68% harvest. When the results of this study were combined with those of a previous nearby clearcut and 40% harvest, the post-harvest increases in NO 3 - - N concentrations in stream water and soil water suggest a harvesting level above which the relation between concentration and harvest intensity changes; there was a greater change in concentration per unit change in harvest intensity when basal area removal was greater than 40%. These results indicate that the deleterious effects on aquatic ecosystems previously demonstrated for intensive harvests in northern hardwood forests of northeastern North America that receive high levels of atmospheric N deposition can be greatly diminished as harvesting intensity decreases below 40?8%. These results await confirmation through additional incremental forest harvest studies at other locations throughout the world that receive high levels of atmospheric N deposition.

New York↗
USGS2013

Fire regimes of quaking aspen in the Mountain West

Quaking aspen (Populus tremuloides Michx.) is the most widespread tree species in North America, and it is found throughout much of the Mountain West (MW) across a broad range of bioclimatic regions. Aspen typically regenerates asexually and prolifically after fire, and due to its seral status in many western conifer forests, aspen is often considered dependent upon disturbance for persistence. In many landscapes, historical evidence for post-fire aspen establishment is clear, and following extended fire-free periods senescing or declining aspen overstories sometimes lack adequate regeneration and are succeeding to conifers. However, aspen also forms relatively stable stands that contain little or no evidence of historical fire. In fact, aspen woodlands range from highly fire-dependent, seral communities to relatively stable, self-replacing, non-seral communities that do not require fire for persistence. Given the broad geographic distribution of aspen, fire regimes in these forests likely co-vary spatially with changing community composition, landscape setting, and climate, and temporally with land use and climate – but relatively few studies have explicitly focused on these important spatiotemporal variations. Here we reviewed the literature to summarize aspen fire regimes in the western US and highlight knowledge gaps. We found that only about one-fourth of the 46 research papers assessed for this review could be considered fire history studies (in which mean fire intervals were calculated), and all but one of these were based primarily on data from fire-scarred conifers. Nearly half of the studies reported at least some evidence of persistent aspen in the absence of fire. We also found that large portions of the MW have had little or no aspen fire history research. As a result of this review, we put forth a classification framework for aspen that is defined by key fire regime parameters (fire severity and probability), and that reflects underlying biophysical settings and correlated aspen functional types. We propose the following aspen fire regime types: (1) fire-independent, stable aspen; (2) fire-influenced, stable aspen; (3) fire-dependent, seral, conifer-aspen mix; (4) fire-dependent, seral, montane aspen-conifer; and (5) fire-dependent, seral, subalpine aspen-conifer. Closing research gaps and validating our proposed aspen fire regime classification will likely require additional site-specific research, enhanced dendrochronology techniques, charcoal and pollen record analysis, spatially-explicit modeling, and other techniques. We hope to encourage development of site-appropriate disturbance ecology characterizations, in order to aid efforts to manage and restore aspen communities and to diagnose key factors contributing to changes in aspen.

Forest Ecology and Management↗
USGS2017

Landscape-scale quantification of fire-induced change in canopy cover following mountain pine beetle outbreak and timber harvest

Across the western United States, the three primary drivers of tree mortality and carbon balance are bark beetles, timber harvest, and wildfire. While these agents of forest change frequently overlap, uncertainty remains regarding their interactions and influence on specific subsequent fire effects such as change in canopy cover. Acquisition of pre- and post-fire Light Detection and Ranging (LiDAR) data on the 2012 Pole Creek Fire in central Oregon provided an opportunity to isolate and quantify fire effects coincident with specific agents of change. This study characterizes the influence of pre-fire mountain pine beetle (MPB; Dendroctonus ponderosae ) and timber harvest disturbances on LiDAR-estimated change in canopy cover. Observed canopy loss from fire was greater (higher severity) in areas experiencing pre-fire MPB (Δ 18.8%CC) than fire-only (Δ 11.1%CC). Additionally, increasing MPB intensity was directly related to greater canopy loss. Canopy loss was lower for all areas of pre-fire timber harvest (Δ 3.9%CC) than for fire-only, but among harvested areas, the greatest change was observed in the oldest treatments and the most intensive treatments [i.e., stand clearcut (Δ 5.0%CC) and combination of shelterwood establishment cuts and shelterwood removal cuts (Δ 7.7%CC)]. These results highlight the importance of accounting for and understanding the impact of pre-fire agents of change such as MPB and timber harvest on subsequent fire effects in land management planning. This work also demonstrates the utility of multi-temporal LiDAR as a tool for quantifying these landscape-scale interactions.

Oregon↗
USGS2023

Masting is shaped by tree-level attributes and stand structure, more than climate, in a Rocky Mountain conifer species

Masting describes the spatiotemporal variability in seed production by a population of plants. Both abiotic and biotic factors drive masting, but the importance of these factors can vary among individuals and populations. To better understand how a changing climate, altered disturbance regimes, or novel management strategies might affect future seed production, we quantified the joint influence of multiple factors on annual cone production in a widespread conifer species, Rocky Mountain ponderosa pine ( Pinus ponderosa var . scopulorum ). We reconstructed individual-level annual cone production across climatic gradients using the cone abscission scar method, and explored the causes and drivers of masting in this species. Site-level responses between weather and masting were highly variable, notably differing in the strength of their response to either summer or spring weather. In addition, the relationship to summer precipitation during cone initiation, a primary driver of annual seed production in this species, was strongest at hotter and drier sites. Additionally, we found that masting was strongly influenced by tree- and stand-level factors such as diameter, age, and local neighborhood density, all of which were associated with the mean, interannual variability, and between-tree synchrony of cone production at the individual-level. Larger and older trees produced more cones, more frequently, and with less synchrony than smaller and younger trees. Open grown trees experiencing lower levels of neighborhood competition also produced more cones with less interannual variability, but with higher between-tree synchrony. Because tree- and stand-level traits appear to regulate seed production more strongly than climate or weather in this species, management interventions targeting these factors could be powerful tools to manage future tree recruitment. Thus, current efforts to reduce stand density and conserve large trees in some ponderosa pine forests may enhance tree-level seed production and reduce variability in seed crops among years.

Arizona, Colorado, New Mexico, South Dakota, Wyomi↗
USGS2005

Diel behavior of iron and other heavy metals in a mountain stream with acidic to neutral pH: Fisher Creek, Montana, USA

Three simultaneous 24-h samplings at three sites over a downstream pH gradient were conducted to examine diel fluctuations in heavy metal concentrations in Fisher Creek, a small mountain stream draining abandoned mine lands in Montana. Average pH values at the upstream (F1), middle (F2), and downstream (F3) monitoring stations were 3.31, 5.46, and 6.80, respectively. The downstream increase in pH resulted in precipitation of hydrous ferric oxide (HFO) and hydrous aluminum oxide (HAO) on the streambed. At F1 and F2, Fe showed strong diel cycles in dissolved concentration and Fe(II)/Fe(III) ratio; these cycles were attributed to daytime photoreduction of Fe(III) to Fe(II), reoxidation of Fe(II) to Fe(III), and temperature-dependent hydrolysis and precipitation of HFO. At the near-neutral downstream station, no evidence of Fe(III) photoreduction was observed, and suspended particles of HFO dominated the total Fe load. HFO precipitation rates between F2 and F3 were highest in the afternoon, due in part to reoxidation of a midday pulse of Fe 2+ formed by photoreduction in the upper, acidic portions of the stream. Dissolved concentrations of Fe(II) and Cu decreased tenfold and 2.4-fold, respectively, during the day at F3. These changes were attributed to sorption onto fresh HFO surfaces. Results of surface complexation modeling showed good agreement between observed and predicted Cu concentrations at F3, but only when adsorption enthalpies were added to the thermodynamic database to take into account diel temperature variations. The field and modeling results illustrate that the degree to which trace metals adsorb onto actively forming HFO is strongly temperature dependent. This study is an example of how diel Fe cycles caused by redox and hydrolysis reactions can induce a diel cycle in a trace metal of toxicological importance in downstream waters.

Montana↗
USGS2005

Diel behavior of rare earth elements in a mountain stream with acidic to neutral pH

Diel (24-h) changes in concentrations of rare earth elements (REE) were investigated in Fisher Creek, a mountain stream in Montana that receives acid mine drainage in its headwaters. Three simultaneous 24-h samplings were conducted at an upstream station (pH = 3.3), an intermediate station (pH = 5.5), and a downstream station (pH = 6.8). The REE were found to behave conservatively at the two upstream stations. At the downstream station, REE partitioned into suspended particles to a degree that varied with the time of day, and concentrations of dissolved REE were 2.9- to 9.4-fold (190% to 830%) higher in the early morning vs. the late afternoon. The decrease in dissolved REE concentrations during the day coincided with a corresponding increase in the concentration of REE in suspended particles, such that diel changes in the total REE concentrations were relatively minor (27% to 55% increase at night). Across the lanthanide series, the heavy REE partitioned into the suspended solid phase to a greater extent than the light REE. Filtered samples from the downstream station showed a decrease in shale-normalized REE concentration across the lanthanide series, with positive anomalies at La and Gd, and a negative Eu anomaly. As the temperature of the creek increased in the afternoon, the slope of the REE profile steepened and the magnitude of the anomalies increased. The above observations are explained by cyclic adsorption of REE onto suspended particles of hydrous ferric and aluminum oxides (HFO, HAO). Conditional partition coefficients for each REE between the suspended solids and the aqueous phase reached a maximum at 1700 hours and a minimum at 0700 hours. This pattern is attributed to diel variations in stream temperature, possibly reinforced by kinetic factors (i.e., slower rates of reaction at night than during the day). Estimates of the enthalpy of adsorption of each REE onto suspended particles based on the field results averaged +82 kJ/mol and are similar in magnitude to estimates in the literature for adsorption of divalent metal cations onto clays and hydrous metal oxides. The results of this study have important implications to the use of REE as hydrogeochemical tracers in streams.

Geochimica et Cosmochimica Acta↗
USGS2008

Natural radionuclide mobility and its influence on U-Th-Pb dating of secondary minerals from the unsaturated zone at Yucca Mountain, Nevada

Extreme U and Pb isotope variations produced by disequilibrium in decay chains of 238U and 232Th are found in calcite, opal/chalcedony, and Mn-oxides occurring as secondary mineral coatings in the unsaturated zone at Yucca Mountain, Nevada. These very slowly growing minerals (mm my-1) contain excess 206Pb and 208Pb formed from excesses of intermediate daughter isotopes and cannot be used as reliable 206Pb/238U geochronometers. The presence of excess intermediate daughter isotopes does not appreciably affect 207Pb/235U ages of U-enriched opal/chalcedony, which are interpreted as mineral formation ages. Opal and calcite from outer (younger) portions of coatings have 230Th/U ages from 94.6 ?? 3.7 to 361.3 ?? 9.8 ka and initial 234U/238U activity ratios (AR) from 4.351 ?? 0.070 to 7.02 ?? 0.12, which indicate 234U enrichment from percolating water. Present-day 234U/238U AR is ???1 in opal/chalcedony from older portions of the coatings. The 207Pb/235U ages of opal/chalcedony samples range from 0.1329 ?? 0.0080 to 9.10 ?? 0.21 Ma, increase with microstratigraphic depth, and define slow long-term average growth rates of about 1.2-2.0 mm my-1, in good agreement with previous results. Measured 234U/238U AR in Mn-oxides, which pre-date the oldest calcite and opal/chalcedony, range from 0.939 ?? 0.006 to 2.091 ?? 0.006 and are >1 in most samples. The range of 87Sr/86Sr ratios (0.71156-0.71280) in Mn-oxides overlaps that in the late calcite. These data indicate that Mn-oxides exchange U and Sr with percolating water and cannot be used as a reliable dating tool. In the U-poor calcite samples, measured 206Pb/207Pb ratios have a wide range, do not correlate with Ba concentration as would be expected if excess Ra was present, and reach a value of about 1400, the highest ever reported for natural Pb. Calcite intergrown with opal contains excesses of both 206Pb and 207Pb derived from Rn diffusion and from direct ??-recoil from U-rich opal. Calcite from coatings devoid of opal/chalcedony contains 206Pb and 208Pb excesses, but no appreciable 207Pb excesses. Observed Pb isotope anomalies in calcite are explained by Rn-produced excess Pb. The Rn emanation may strongly affect 206Pb-238U ages of slow-growing U-poor calcite, but should be negligible for dating fast-growing U-enriched speleothem calcite.

Geochimica et Cosmochimica Acta↗
USGS2008

Weathering of the Rio Blanco quartz diorite, Luquillo Mountains, Puerto Rico: Coupling oxidation, dissolution, and fracturing

In the mountainous Rio Icacos watershed in northeastern Puerto Rico, quartz diorite bedrock weathers spheroidally, producing a 0.2-2 m thick zone of partially weathered rock layers (???2.5 cm thickness each) called rindlets, which form concentric layers around corestones. Spheroidal fracturing has been modeled to occur when a weathering reaction with a positive ??V of reaction builds up elastic strain energy. The rates of spheroidal fracturing and saprolite formation are therefore controlled by the rate of the weathering reaction. Chemical, petrographic, and spectroscopic evidence demonstrates that biotite oxidation is the most likely fracture-inducing reaction. This reaction occurs with an expansion in d (0 0 1) from 10.0 to 10.5 A??, forming 'altered biotite'. Progressive biotite oxidation across the rindlet zone was inferred from thin sections and gradients in K and Fe(II). Using the gradient in Fe(II) and constraints based on cosmogenic age dates, we calculated a biotite oxidation reaction rate of 8.2 ?? 10-14 mol biotite m-2 s-1. Biotite oxidation was documented within the bedrock corestone by synchrotron X-ray microprobe fluorescence imaging and XANES. X-ray microprobe images of Fe(II) and Fe(III) at 2 ??m resolution revealed that oxidized zones within individual biotite crystals are the first evidence of alteration of the otherwise unaltered corestone. Fluids entering along fractures lead to the dissolution of plagioclase within the rindlet zone. Within 7 cm surrounding the rindlet-saprolite interface, hornblende dissolves to completion at a rate of 6.3 ?? 10-13 mol hornblende m-2 s-1: the fastest reported rate of hornblende weathering in the field. This rate is consistent with laboratory-derived hornblende dissolution rates. By revealing the coupling of these mineral weathering reactions to fracturing and porosity formation we are able to describe the process by which the quartz diorite bedrock disaggregates and forms saprolite. In the corestone, biotite oxidation induces spheroidal fracturing, facilitating the influx of fluids that react with other minerals, dissolving plagioclase and chlorite, creating additional porosity, and eventually dissolving hornblende and precipitating secondary minerals. The thickness of the resultant saprolite is maintained at steady state by a positive feedback between the denudation rate and the weathering advance rate driven by the concentration of pore water O2 at the bedrock-saprolite interface. ?? 2008 Elsevier Ltd. All rights reserved.

Geochimica et Cosmochimica Acta↗