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Geology topics

Thomas D. Bullen

Publications and source records attributed to Thomas D. Bullen.

At least 19 recordsLinked to original sources
USGS2017

Ca isotopic geochemistry of an Antarctic aquatic system

The McMurdo Dry Valleys, Antarctica, are a polar desert ecosystem. The hydrologic system of the dry valleys is linked to climate with ephemeral streams that flow from glacial melt during the austral summer. Past climate variations have strongly influenced the closed-basin, chemically stratified lakes on the valley floor. Results of previous work point to important roles for both in-stream processes (e.g., mineral weathering, precipitation and dissolution of salts) and in-lake processes (e.g., mixing with paleo-seawater and calcite precipitation) in determining the geochemistry of these lakes. These processes have a significant influence on calcium (Ca) biogeochemistry in this aquatic ecosystem, and thus variations in Ca stable isotope compositions of the waters can aid in validating the importance of these processes. We have analyzed the Ca stable isotope compositions of streams and lakes in the McMurdo Dry Valleys. The results validate the important roles of weathering of aluminosilicate minerals and/or CaCO 3 in the hyporheic zone of the streams, and mixing of lake surface water with paleo-seawater and precipitation of Ca-salts during cryo-concentration events to form the deep lake waters. The lakes in the McMurdo Dry Valleys evolved following different geochemical pathways, evidenced by their unique, nonsystematic Ca isotope signatures.

Geophysical Research Letters↗
USGS2016

Structured heterogeneity in a marine terrace chronosequence: Upland mottling

Soil mottles generally are interpreted as a product of reducing conditions during periods of water saturation. The upland soils of the Santa Cruz, CA, marine terrace chronosequence display an evolving sequence of reticulate mottling from the youngest soil (65 ka) without mottles to the oldest soil (225 ka) with well-developed mottles. The mottles consist of an interconnected network of clay and C-enriched regions (gray, 2.5Y 6/1) bordered by leached parent material (white, 2.5Y 8/1) within a diminishing matrix of oxidized parent material (orange, 7.5YR 5/8). The mottles develop in soils that formed from relatively uniform nearshore sediments and occur below the depth of soil bioturbation. To explore how a presumably wetland feature occurs in an unsaturated upland soil, physical and chemical characteristics of mottle separates (orange, gray, and white) were compared through the deep time represented by the soil chronosequence. Mineralogical, isotopic, and surface-area differences among mottle separates indicate that rhizogenic centimeter-scale mass transfer acting across millennia is an integral part of weathering, pedogenesis, and C and nutrient transfer. Elemental analysis, electron microscopy, and Fe-isotope systematics indicate that mottle development is driven by deep roots together with their fungal and microbial symbionts. Taken together, these data suggest that deep soil horizons on old stable landforms can develop reticulate mottling as the long-term imprint of rhizospheric processes. The processes of rhizogenic mottle formation appear to regulate pedogenesis, nutrients, and C sequestration at depth in unsaturated zones.

California↗
USGS2016

Ca, Sr and Ba stable isotopes reveal the fate of soil nutrients along a tropical climosequence

Nutrient biolifting is an important pedogenic process in which plant roots obtain inorganic nutrients such as phosphorus (P) and calcium (Ca) from minerals at depth and concentrate those nutrients at the surface. Here we use soil chemistry and stable isotopes of the alkaline earth elements Ca, strontium (Sr) and barium (Ba) to test the hypothesis that biolifting of P has been an important pedogenic process across a soil climosequence developed on volcanic deposits at Kohala Mountain, Hawaii. The geochemical linkage between these elements is revealed as generally positive site-specific relationships in soil mass gains and losses, particularly for P, Ba and Ca, using the ratio of immobile elements titanium and niobium (Ti/Nb) to link individual soil samples to a restricted compositional range of the chemically and isotopically diverse volcanic parent materials. At sites where P is enriched in surface soils relative to abundances in deeper soils, the isotope compositions of exchangeable Ca, Sr and Ba in the shallowest soil horizons (< 10 cm depth) are lighter than those of the volcanic parent materials and trend toward those of plants growing on fresh volcanic deposits. In contrast the isotope composition of exchangeable Ba in deeper soil horizons (> 10 cm depth) at those sites is consistently heavier than the volcanic parent materials. The isotope compositions of exchangeable Ca and Sr trend toward heavier compositions with depth more gradually, reflecting increasing leakiness from these soils in the order Ba < Sr < Ca and downward transfer of light biocycled Ca and Sr to deeper exchange sites. Given the long-term stability of ecosystem properties at the sites where P is enriched in surface soils, a simple box model demonstrates that persistence of isotopically light exchangeable Ca, Sr and Ba in the shallowest soil horizons requires that the uptake flux to plants from those near-surface layers is less than the recycling flux returned to the surface as litterfall. This observation implicates an uptake flux from an additional source which we attribute to biolifting. We view the heavy exchangeable Ba relative to soil parent values in deeper soils at sites where P is enriched in surface soils, and indeed at all but the wettest site across the climosequence, to represent the complement of an isotopically light Ba fraction removed from these soils by plant roots consistent with the biolifting hypothesis. We further suggest that decreasing heaviness of depth-integrated exchangeable Ba in deeper soils with increasing median annual precipitation across the climosequence reflects greater reliance on shallow nutrient sources as site water balance increases. While the Ca, Sr and Ba isotopes considered together were useful in confirming an important role for nutrient biolifting across the climosequence, the Ba isotopes provided the most robust tracer of biolifting and have the greatest potential to find application as an isotopic proxy for P dynamics in soils.

Hawaii↗
USGS2014

Metal stable isotopes in weathering and hydrology

This chapter highlights some of the major developments in the understanding of the causes of metal stable isotope compositional variability in and isotope fractionation between natural materials and provides numerous examples of how that understanding is providing new insights into weathering and hydrology. At this stage, our knowledge of causes of stable isotope compositional variability among natural materials is greatest for the metals lithium, magnesium, calcium, and iron, the isotopes of which have already provided important information on weathering and hydrological processes. Stable isotope compositional variability for other metals such as strontium, copper, zinc, chromium, barium, molybdenum, mercury, cadmium, and nickel has been demonstrated but is only beginning to be applied to questions related to weathering and hydrology, and several research groups are currently exploring the potential. And then there are other metals such as titanium, vanadium, rhenium, and tungsten that have yet to be explored for variability of stable isotope composition in natural materials, but which may hold untold surprises in their utility. This impressive list of metals having either demonstrated or potential stable isotope signals that could be used to address important unsolved questions related to weathering and hydrology, constitutes a powerful toolbox that will be increasingly utilized in the coming decades.

Book chapter↗
USGS2014

Alpha-emitting isotopes and chromium in a coastal California aquifer

The unadjusted 72-h gross alpha activities in water from two wells completed in marine and alluvial deposits in a coastal southern California aquifer 40 km north of San Diego were 15 and 25 picoCuries per liter (pCi/L). Although activities were below the Maximum Contaminant Level (MCL) of 15 pCi/L, when adjusted for uranium activity; there is concern that new wells in the area may exceed MCLs, or that future regulations may limit water use from the wells. Coupled well-bore flow and depth-dependent water-quality data collected from the wells in 2011 (with analyses for isotopes within the uranium, actinium, and thorium decay-chains) show gross alpha activity in marine deposits is associated with decay of naturally-occurring 238 U and its daughter 234 U. Radon activities in marine deposits were as high as 2230 pCi/L. In contrast, gross alpha activities in overlying alluvium within the Piedra de Lumbre watershed, eroded from the nearby San Onofre Hills, were associated with decay of 232 Th, including its daughter 224 Ra. Radon activities in alluvium from Piedra de Lumbre of 450 pCi/L were lower than in marine deposits. Chromium VI concentrations in marine deposits were less than the California MCL of 10 &mu;g/L (effective July 1, 2014) but &delta; 53 Cr compositions were near zero and within reported ranges for anthropogenic chromium. Alluvial deposits from the nearby Las Flores watershed, which drains a larger area having diverse geology, has low alpha activities and chromium as a result of geologic and geochemical conditions and may be more promising for future water-supply development.

California↗
USGS2013

Evidence for high salinity of Early Cretaceous sea water from the Chesapeake Bay crater

High salinity groundwater more than 1000 metres deep in the Atlantic Coastal Plain of the United States has been documented in several locations1,2, most recently within the 35 million-year-old Chesapeake Bay impact crater3,4,5. Suggestions for the origin of increased salinity in the crater have included evaporite dissolution6, osmosis6, and evaporation from heating7 associated with the bolide impact. Here we present chemical, isotopic and physical evidence that together indicate that groundwater in the Chesapeake crater is remnant Early Cretaceous North Atlantic (ECNA) seawater. We find that the seawater is likely 100-145 million years old and that it has an average salinity of about 70 per mil, which is twice that of modern seawater and consistent with the nearly closed ECNA basin8. Previous evidence for temperature and salinity levels of ancient oceans have been estimated indirectly from geochemical, isotopic and paleontological analyses of solid materials in deep sediment cores. In contrast, our study identifies ancient seawater in situ and provides a direct estimate of its age and salinity. Moreover, we suggest that it is likely that remnants of ECNA seawater persist in deep sediments at many locations along the Atlantic margin.

Maryl;Virginia↗
USGS2013

234U/238U and δ87Sr in peat as tracers of paleosalinity in the Sacramento-San Joaquin Delta of California, USA

The purpose of this study was to determine the history of paleosalinity over the past 6000+ years in the Sacramento-San Joaquin Delta (the Delta), which is the innermost part of the San Francisco Estuary. We used a combination of Sr and U concentrations, d87Sr values, and 234U/238U activity ratios (AR) in peat as proxies for tracking paleosalinity. Peat cores were collected in marshes on Browns Island, Franks Wetland, and Bacon Channel Island in the Delta. Cores were dated using 137Cs, the onset of Pb and Hg contamination from hydraulic gold mining, and 14C. A proof of concept study showed that the dominant emergent macrophyte and major component of peat in the Delta, Schoenoplectus spp., incorporates Sr and U and that the isotopic composition of these elements tracks the ambient water salinity across the Estuary. Concentrations and isotopic compositions of Sr and U in the three main water sources contributing to the Delta (seawater, Sacramento River water, and San Joaquin River water) were used to construct a three-end-member mixing model. Delta paleosalinity was determined by examining variations in the distribution of peat samples through time within the area delineated by the mixing model. The Delta has long been considered a tidal freshwater marsh region, but only peat samples from Franks Wetland and Bacon Channel Island have shown a consistently fresh signal (<0.5 ppt) through time. Therefore, the eastern Delta, which occurs upstream from Bacon Channel Island along the San Joaquin River and its tributaries, has also been fresh for this time period. Over the past 6000+ years, the salinity regime at the western boundary of the Delta (Browns Island) has alternated between fresh and oligohaline (0.5-5 ppt).

California↗
USGS2013

Forest calcium depletion and biotic retention along a soil nitrogen gradient

High nitrogen (N) accumulation in terrestrial ecosystems can shift patterns of nutrient limitation and deficiency beyond N toward other nutrients, most notably phosphorus (P) and base cations (calcium [Ca], magnesium [Mg], and potassium [K]). We examined how naturally high N accumulation from a legacy of symbiotic N fixation shaped P and base cation cycling across a gradient of nine temperate conifer forests in the Oregon Coast Range. We were particularly interested in whether long-term legacies of symbiotic N fixation promoted coupled N and organic P accumulation in soils, and whether biotic demands by non-fixing vegetation could conserve ecosystem base cations as N accumulated. Total soil N (0–100 cm) pools increased nearly threefold across the N gradient, leading to increased nitrate leaching, declines in soil pH from 5.8 to 4.2, 10-fold declines in soil exchangeable Ca, Mg, and K, and increased mobilization of aluminum. These results suggest that long-term N enrichment had acidified soils and depleted much of the readily weatherable base cation pool. Soil organic P increased with both soil N and C across the gradient, but soil inorganic P, biomass P, and P leaching loss did not vary with N, implying that historic symbiotic N fixation promoted soil organic P accumulation and P sufficiency for non-fixers. Even though soil pools of Ca, Mg, and K all declined as soil N increased, only Ca declined in biomass pools, suggesting the emergence of Ca deficiency at high N. Biotic conservation and tight recycling of Ca increased in response to whole-ecosystem Ca depletion, as indicated by preferential accumulation of Ca in biomass and surface soil. Our findings support a hierarchical model of coupled N–Ca cycling under long-term soil N enrichment, whereby ecosystem-level N saturation and nitrate leaching deplete readily available soil Ca, stimulating biotic Ca conservation as overall supply diminishes. We conclude that a legacy of biological N fixation can increase N and P accumulation in soil organic matter to the point that neither nutrient is limiting to subsequent non-fixers, while also resulting in natural N saturation that intensifies base cation depletion and deficiency.

Oregon↗
USGS2012

Delta Chromium-53/52 isotopic composition of native and contaminated groundwater, Mojave Desert, USA

Chromium(VI) concentrations in groundwater sampled from three contaminant plumes in aquifers in the Mojave Desert near Hinkley, Topock and El Mirage, California, USA, were as high as 2600, 5800 and 330 μg/L, respectively. δ 53/52 Cr compositions from more than 50 samples collected within these plumes ranged from near 0‰ to almost 4‰ near the plume margins. Assuming only reductive fractionation of Cr(VI) to Cr(III) within the plume, apparent fractionation factors for δ 53/52 Cr isotopes ranged from ε app = 0.3 to 0.4 within the Hinkley and Topock plumes, respectively, and only the El Mirage plume had a fractionation factor similar to the laboratory derived value of ε = 3.5. One possible explanation for the difference between field and laboratory fractionation factors at the Hinkley and Topock sites is localized reductive fractionation of Cr(VI) to Cr(III), with subsequent advective mixing of native and contaminated water near the plume margin. Chromium(VI) concentrations and δ 53/52 Cr isotopic compositions did not uniquely define the source of Cr near the plume margin, or the extent of reductive fractionation within the plume. However, Cr(VI) and δ 53/52 Cr data contribute to understanding of the interaction between reductive and mixing processes that occur within and near the margins of Cr contamination plumes. Reductive fractionation of Cr(VI) predominates in plumes having higher ε app , these plumes may be suitable for monitored natural attenuation. In contrast, advective mixing predominates in plumes having lower ε app , the highly dispersed margins of these plumes may be difficult to define and manage.

California↗
USGS2010

Tertiary volcanic rocks from the southern Pannonian Basin, Croatia

The Tertiary volcanic rocks of the southern part of the Pannonian Basin are related to a sequence of tectonic events that occurred along the northern margin of the Dinarides when subduction ceased and after uplift of the region in middle Eocene time. The oldest rocks are andesites and dacites erupted during an Egerian to Eggenburgian marine transpression phase. In early Miocene time (about 17 Ma), rifting started, probably caused by the rise of the mantle, resulting in E-W extension and strike-slip faulting leading to formation of the Pannonian Basin. The initial rifting was accompanied by trachyandesitic volcanism of Karpathian age, followed by Badenian-age (15 to 13 Ma) volcanic activity producing basalts, andesites, and dacites. During these volcanic phases the Pannonian Basin, or the Paratethys, probably was periodically connected with the Mediterranean Sea. The final period of volcanism (about 9 to 7 Ma) produced alkalic basalts and basalts and occurred in fresh-water environments. These volcanic rocks have had a complex petrological evolution, related to an active continental margin. Egerian-Eggenburgian andesites and dacites can be explained by upper crustal assimilation with fractional crystallization (ACF) of primary basalt magma. The three younger associations originated by partial melting of rocks from both the upper mantle and the lower crust. Their evolution was accompanied by crustal contamination.

Carpathian Basin, Pannonian Basin↗
USGS2007

Formation of tellurium nanocrystals during anaerobic growth of bacteria that use Te oxyanions as respiratory electron acceptors

Certain toxic elements support the metabolism of diverse prokaryotes by serving as respiratory electron acceptors for growth. Here, we demonstrate that two anaerobes previously shown to be capable of respiring oxyanions of selenium also achieve growth by reduction of either tellurate [Te(VI)] or tellurite [Te(IV)] to elemental tellurium [Te(0)]. This reduction achieves a sizeable stable-Te-isotopic fractionation (isotopic enrichment factor [ε] = −0.4 to −1.0 per ml per atomic mass unit) and results in the formation of unique crystalline Te(0) nanoarchitectures as end products. The Te(0) crystals occur internally within but mainly externally from the cells, and each microorganism forms a distinctly different structure. Those formed by Bacillus selenitireducens initially are nanorods (∼10-nm diameter by 200-nm length), which cluster together, forming larger (∼1,000-nm) rosettes composed of numerous individual shards (∼100-nm width by 1,000-nm length). In contrast, Sulfurospirillum barnesii forms extremely small, irregularly shaped nanospheres (diameter < 50 nm) that coalesce into larger composite aggregates. Energy-dispersive X-ray spectroscopy and selected area electron diffraction indicate that both biominerals are composed entirely of Te and are crystalline, while Raman spectroscopy confirms that they are in the elemental state. These Te biominerals have specific spectral signatures (UV-visible light, Raman) that also provide clues to their internal structures. The use of microorganisms to generate Te nanomaterials may be an alternative for bench-scale syntheses. Additionally, they may also generate products with unique properties unattainable by conventional physical/chemical methods.

Applied and Environmental Microbiology↗
USGS2006

Variability of isotope and major ion chemistry in the Allequash Basin, Wisconsin

As part of ongoing research conducted at one of the U.S. Geological Survey's Water, Energy, and Biogeochem-ical Budgets sites, work was undertaken to describe the spatial and temporal variability of stream and ground water isotopic composition and cation chemistry in the Trout Lake watershed, to relate the variability to the watershed flow system, and to identify the linkages of geochemical evolution and source of water in the watershed. The results are based on periodic sampling of sites at two scales along Allequash Creek, a small headwater stream in northern Wisconsin. Based on this sampling, there are distinct water isotopic and geochemical differences observed at a smaller hillslope scale and the larger Allequash Creek scale. The variability was larger than expected for this simple watershed, and is likely to be seen in more complex basins. Based on evidence from multiple isotopes and stream chemistry, the flow system arises from three main source waters (terrestrial-, lake-, or wetland-derived recharge) that can be identified along any flowpath using water isotopes together with geochemical characteristics such as iron concentrations. The ground water chemistry demonstrates considerable spatial variability that depends mainly on the flow-path length and water mobility through the aquifer. Calcium concentrations increase with increasing flowpath length, whereas strontium isotope ratios increase with increasing extent of stagnation in either the unsaturated or saturated zones as waters move from source to sink. The flowpath distribution we identify provides important constraints on the calibration of ground water flow models such as that undertaken by Pint et al. (this issue).

Wisconsin↗
USGS2004

Use of 87 Sr/ 86 Sr and δ 11 B to Identify Slag-Affected Sediment in Southern Lake Michigan

Slag is a ubiquitous byproduct of the iron-smelting industry and influences geochemistry and water quality in adjacent geologic units, ground and surface water. Despite extensive slag deposition along the Indiana shoreline of Lake Michigan, definitive evidence that slag has affected lakebed sediments has not been established. Concerns for the protection of water and ecosystem resources in the Great Lakes motivated this study to determine if strontium and boron isotopes could be used to identify and delineate slag-affected bed sediment in Lake Michigan. Sixty-five samples of bed sediment were acquired from the southern lobe of Lake Michigan and analyzed for 87Sr/86Sr and ??11B. Samples immediately offshore from Indiana steel mills and slag-disposal sites contained higher median 87Sr/86Sr values (0.70881) than shoreline sediments collected elsewhere in the basin (0.70847) and uniquely decreased with increasing distance from the shoreline. The highest ??11B values occurred in sediments from the Indiana shoreline (+12.9 to 16.4???) but were also elevated in sediments collected offshore from three Lake Michigan cities (+11.7 to 12.7???). Contoured isotope data indicated that 82-154 km2 of bed sediment along the Indiana shoreline had elevated 87Sr/86Sr and ??11B values relative to shoreline sediments elsewhere in southern Lake Michigan.

Environmental Science & Technology↗
USGS2004

Selenium, iron, and chromium stable isotope ratio measurements by the double isotope spike TIMS method

This chapter focuses on the double-spike calibrated thermal ionization mass spectrometry (TIMS) methods for measurement of mass dependent isotope fractionation in Se, Fe, and Cr. Current measurement precision is approximately ± 0.2 per mil on 80 Se / 76 Se, 56 Fe / 54 Fe, and 53 Cr / 52 Cr. Sample size requirements are 500ng, 1μg, and 250ng for Se, Fe, and Cr respectively. These measurements have been developed recently, and further improvements in precision and sample size are likely. The present purification procedures for these elements and the geochemical applications of the measurements are reviewed. TIMS instruments were usually limited to measurement of positive ions. One of the major recent developments in TIMS is the development of methods for measuring negative ions. An important future direction in mass spectrometry of Se, Fe, and Cr, is multi-collector inductively coupled plasma- mass spectrometry (MC-ICP-MS). This recent technique has a number of advantages over TIMS techniques and may eventually dominate. Instrumental discrimination is very large with MC-ICP-MS and must be monitored and modeled correctly.

Book chapter↗