Geology topics

T.D. Bullen

Publications and source records attributed to T.D. Bullen.

At least 19 recordsLinked to original sources

USGS2012

Late Cenozoic volcanism, subduction, and extension in the Lassen region of California, southern Cascade Range

Some 537 volcanic vents younger than 7 Ma are identified and these are classified into five age intervals and five compositional categories based on SiO2 content. Maps of vents by age and composition illustrate regionally representative volcanic trends. By 2 Ma, the eastern limit of volcanism had contracted westward toward the late Quaternary arc. Late Quaternary volcanism is concentrated around and north of the silicic Lassen volcanic center. The belt of most recent volcanism (25-0 ka) has been active since at least 2 Ma. Most mafic volcanism is calcalkaline basalt and basaltic andesite. Normal faults and linear groups of vents are evidence of widespread crustal extension throughout most of the Lassen region. NNW orientation of maximum horizontal stress is indicated. The Lassen volcanic region is thought to occur above the subducting Gorda North plate but also within a broad zone of distributed extension that occurs in the North American lithosphere east and southeast of the present Cascadia subduction zone. The scarcity of volcanic rocks older than 7 Ma suggests that a more compressive lithospheric stress regime prior to the late Miocene extensional episode may have suppressed volcanism. -from Authors

Journal of Geophysical Research Solid Earth↗

USGS2012

Trace element and isotopic constraints on magmatic evolution at Lassen volcanic center

Magmatic evolution at the Lassen volcanic center (LVC) is characterized by a transition from predominantly andesitic to predominantly silicic volcanism with time. Magmas of the andesitic, or “Brokeoff phase” of volcanism range in composition from basaltic andesite io dacite, whereas those of silicic, or “Lassen phase” range in composition from basaltic andesite to rhyolite. The compositions of magmas from each phase define well organized but distinct variation trends. Compared with Brokeoff-phase magmas of similar SiO 2 content, most Lassen-phase magmas contain lower concentrations of most incompatible minor and trace elements. Based on the behavior of both incompatible and compatible trace elements, the geochemical trends defined by the Brokeoff-phase magmas cannot be ascribed merely to fractional crystallization from a single or multiple mafic parental magmas, Moreover, the Lassen-phase magmas cannot be derived from the Brokeoff-phase magmas by fractional crystallization. Rather, the geochemical trends that characterize each volcanic phase define arrays that primarily indicate mixing between well-homogenized silicic and heterogeneous mafic magmas. The distinctive mixing-dominated arrays for each volcanic phase manifest the generation and evolution of two physically distinct, but genetically related magma systems. The LVC magmas have Sr, Nd, and Pb isotopic characteristics that approximate two-component mixing arrays. One isotopic component is similar in composition to that of NE Pacific Ocean ridge and seamount basalts (“MORB” component), the other to mafic Mesozoic granitoids sampled from the neighboring KSamath and Sierra Nevada provinces (“KSN” component). The isotopic compositions of the most silicic LVC magmas lie within the ranges defined by the more mafic LVC magmas, which in turn lie within broad ranges defined by primitive mafic lavas sampled from the Lassen region. The lack of a correlation between the major element and isotopic compositions of LVC magmas seriously limits any model for magmatic evolution that relies on assimilation of old middle to upper crust by isotopically homogeneous mafic magmas during their ascent through the crust. Alternatively, the isotopic and geochemical uniformity of the most silicic magmas of the Brokeoff and Lassen phases suggests that they are well-homogenized partial melts. The likely source region for these silicic melts is the lower crust, which we envision to consist primarily of mafic igneous rocks that are similar in geochemical and isotopic diversity to the regional mafic lavas. Magmatic evolution at LVC can be viewed in terms of a series of mantle melting events that subsequently stimulated meiting in a progressively increasing volume of the lower crust. In general, the LVC magmas represent slightly fractionated mixtures of the mantle-derived mafic magmas and silicic partial melts of the lower crust, the latter melts increasing in relative proportion over the history of the volcanic center. The voluminous rhyolitic lavas and pyroclastic materials erupted during the early Lassen phase represent lower crustal melts thai pooled into sufficient volumes to avoid significant blending and dilution with intruding mafic magmas. The geochemical and isotopic heterogeneity of both Brokeoff-phase andésites and mafic magmatic inclusions in the silicic Lassen-phase magmas must in part record the corresponding diversity of the mantle-derived contributions to arc magmagenesis in this region.

Journal of Geophysical Research Solid Earth↗

USGS2012

The impact of biotic/abiotic interfaces in mineral nutrient cycling: A study of soils of the Santa Cruz chronosequence, California

Biotic/abiotic interactions between soil mineral nutrients and annual grassland vegetation are characterized for five soils in a marine terrace chronosequence near Santa Cruz, California. A Mediterranean climate, with wet winters and dry summers, controls the annual cycle of plant growth and litter decomposition, resulting in net above-ground productivities of 280–600 g m −2 yr −1 . The biotic/abiotic (A/B) interface separates seasonally reversible nutrient gradients, reflecting biological cycling in the shallower soils, from downward chemical weathering gradients in the deeper soils. The A/B interface is pedologically defined by argillic clay horizons centered at soil depths of about one meter which intensify with soil age. Below these horizons, elevated solute Na/Ca, Mg/Ca and Sr/Ca ratios reflect plagioclase and smectite weathering along pore water flow paths. Above the A/B interface, lower cation ratios denote temporal variability due to seasonal plant nutrient uptake and litter leaching. Potassium and Ca exhibit no seasonal variability beneath the A/B interface, indicating closed nutrient cycling within the root zone, whereas Mg variability below the A/B interface denotes downward leakage resulting from higher inputs of marine aerosols and lower plant nutrient requirements. The fraction of a mineral nutrient annually cycled through the plants, compared to that lost from pore water discharge, is defined their respective fluxes F j,plants = q j,plants /( q j,plants + q j,discharge ) with average values for K and Ca ( F K,plants = 0.99; F Ca,plants = 0.93) much higher than for Mg and Na ( F Mg,plants 0.64; F Na,plants = 0.28). The discrimination against Rb and Sr by plants is described by fractionation factors ( K Sr/Ca = 0.86; K Rb/K = 0.83) which are used in Rayleigh fractionation-mixing calculations to fit seasonal patterns in solute K and Ca cycling. K Rb/K and K 24 Mg / 22 Mg "> K24Mg/22Mg values (derived from isotope data in the literature) fall within fractionation envelopes bounded by inputs from rainfall and mineral weathering. K Sr/Ca and K 44 Ca / 40 Ca "> K44Ca/40Ca fractionation factors fall outside these envelopes indicating that Ca nutrient cycling is closed to these external inputs. Small net positive K and Ca fluxes (6–14 mol m −2 yr −1 ), based on annual mass balances, indicate that the soils are accumulating mineral nutrients, probably as a result of long-term environmental disequilibrium.

California↗

USGS2011

High-precision measurement of variations in calcium isotope ratios in urine by multiple collector inductively coupled plasma mass spectrometry

We describe a new chemical separation method to isolate Ca from other matrix elements in biological samples, developed with the long-term goal of making high-precision measurement of natural stable Ca isotope variations a clinically applicable tool to assess bone mineral balance. A new two-column procedure utilizing HBr achieves the purity required to accurately and precisely measure two Ca isotope ratios ( 44 Ca/ 42 Ca and 44 Ca/ 43 Ca) on a Neptune multiple collector inductively coupled plasma mass spectrometer (MC-ICPMS) in urine. Purification requirements for Sr, Ti, and K (Ca/Sr > 10000; Ca/Ti > 10000000; and Ca/K > 10) were determined by addition of these elements to Ca standards of known isotopic composition. Accuracy was determined by (1) comparing Ca isotope results for samples and standards to published data obtained using thermal ionization mass spectrometry (TIMS), (2) adding a Ca standard of known isotopic composition to a urine sample purified of Ca, and (3) analyzing mixtures of urine samples and standards in varying proportions. The accuracy and precision of δ 44/42 Ca measurements of purified samples containing 25 μg of Ca can be determined with typical errors less than ±0.2&permil; (2σ).

Analytical Chemistry↗

USGS2009

Metal stable isotopes in low-temperature systems: A primer

Recent advances in mass spectrometry have allowed isotope scientists to precisely determine stable isotope variations in the metallic elements. Biologically infl uenced and truly inorganic isotope fractionation processes have been demonstrated over the mass range of metals. This Elements issue provides an overview of the application of metal stable isotopes to low-temperature systems, which extend across the borders of several science disciplines: geology, hydrology, biology, environmental science, and biomedicine. Information on instrumentation, fractionation processes, data-reporting terminology, and reference materials presented here will help the reader to better understand this rapidly evolving field.

Elements↗

USGS2009

Fractionation of metal stable isotopes by higher plants

Higher plants induce chemical reactions in the rhizosphere, facilitating metal uptake by roots. Fractionation of the isotopes in nutrients such as calcium, iron, magnesium, and zinc produces a stable isotope composition in the plants that generally differs from that of the growth medium. Isotope fractionation also occurs during transport of the metals within most plants, but its extent depends on plant species and on the metal, in particular, on the metal's redox state and what ligand it is bound to. The metal stable isotope variations observed in plants create an isotope signature of life at the Earth's surface, contributing substantially to our understanding of metal cycling processes in the environment and in individual organisms.

Elements↗

USGS2009

Environmental and biomedical applications of natural metal stable isotope variations

etal stable isotopes are now being used to trace metal contaminants in the environment and as indicators of human systemic function where metals play a role. Stable isotope abundance variations provide information about metal sources and the processes affecting metals in complex natural systems, complementing information gained from surrogate tracers, such as metal abundance ratios or biochemical markers of metal metabolism. The science is still in its infancy, but the results of initial studies confirm that metal stable isotopes can provide a powerful tool for forensic and biomedical investigations.

Elements↗

USGS2009

Essentials of iron, chromium, and calcium isotope analysis of natural materials by thermal ionization mass spectrometry

The use of isotopes to understand the behavior of metals in geological, hydrological, and biological systems has rapidly expanded in recent years. One of the mass spectrometric techniques used to analyze metal isotopes is thermal ionization mass spectrometry, or TIMS. While TIMS has been a useful analytical technique for the measurement of isotopic composition for decades and TIMS instruments are widely distributed, there are significant difficulties associated with using TIMS to analyze isotopes of the lighter alkaline earth elements and transition metals. Overcoming these difficulties to produce relatively long-lived and stable ion beams from microgram-sized samples is a non-trivial task. We focus here on TIMS analysis of three geologically and environmentally important elements (Fe, Cr, and Ca) and present an in-depth look at several key aspects that we feel have the greatest potential to trouble new users. Our discussion includes accessible descriptions of different analytical approaches and issues, including filament loading procedures, collector cup configurations, peak shapes and interferences, and the use of isotopic double spikes and related error estimation. Building on previous work, we present quantitative simulations, applied specifically in this study to Fe and Ca, that explore the effects of (1) time-variable evaporation of isotopically homogeneous spots from a filament and (2) interferences on the isotope ratios derived from a double spike subtraction routine. We discuss how and to what extent interferences at spike masses, as well as at other measured masses, affect the double spike-subtracted isotope ratio of interest (44Ca/40Ca in the case presented, though a similar analysis can be used to evaluate 56Fe/54Fe and 53Cr/52Cr). The conclusions of these simulations are neither intuitive nor immediately obvious, making this examination useful for those who are developing new methodologies. While all simulations are carried out in the context of a specific isotope system, it should be noted that the same methods can be used to evaluate any isotope system of interest. ?? 2008 Elsevier B.V.

Chemical Geology↗

USGS2009

Strontium isotope record of seasonal scale variations in sediment sources and accumulation in low-energy, subtidal areas of the lower Hudson River estuary

Strontium isotope ( 87 Sr/ 86 Sr) profiles in sediment cores collected from two subtidal harbor slips in the lower Hudson River estuary in October 2001 exhibit regular patterns of variability with depth. Using additional evidence from sediment Ca/Sr ratios, 137 Cs activity and Al, carbonate (CaCO 3 ), and organic carbon (OC sed ) concentration profiles, it can be shown that the observed variability reflects differences in the relative input and trapping of fine-grained sediment from seaward sources vs. landward sources linked to seasonal-scale changes in freshwater flow. During high flow conditions, the geochemical data indicate that most of the fine-grained sediments trapped in the estuary are newly eroded basin materials. During lower (base) flow conditions, a higher fraction of mature materials from seaward sources with higher carbonate content is trapped in the lower estuary. Results show that high-resolution, multi-geochemical tracer approaches utilizing strontium isotope ratios ( 87 Sr/ 86 Sr) can distinguish sediment sources and constrain seasonal scale variations in sediment trapping and accumulation in dynamic estuarine environments. Low-energy, subtidal areas such as those in this study are important sinks for metastable, short-to-medium time scale sediment accumulation. These results also show that these same areas can serve as natural recorders of physical, chemical, and biological processes that affect particle and particle-associated material dynamics over seasonal-to-yearly time scales. ?? 2009.

Chemical Geology↗

USGS2009

Chemical weathering of a marine terrace chronosequence, Santa Cruz, California. Part II: Solute profiles, gradients and the comparisons of contemporary and long-term weathering rates

The spatial and temporal changes in hydrology and pore water elemental and 87 Sr/ 86 Sr compositions are used to determine contemporary weathering rates in a 65- to 226-kyr-old soil chronosequence formed from granitic sediments deposited on marine terraces along coastal California. Soil moisture, tension and saturation exhibit large seasonal variations in shallow soils in response to a Mediterranean climate. These climate effects are dampened in underlying argillic horizons that progressively developed in older soils, and reached steady-state conditions in unsaturated horizons extending to depths in excess of 15 m. Hydraulic fluxes (q h ), based on Cl mass balances, vary from 0.06 to 0.22 m yr -1 , resulting in fluid residence times in the terraces of 10-24 yrs. As expected for a coastal environment, the order of cation abundances in soil pore waters is comparable to sea water, i.e., Na > Mg > Ca > K > Sr, while the anion sequence Cl > NO 3 > HCO 3 > SO 4 reflects modifying effects of nutrient cycling in the grassland vegetation. Net Cl-corrected solute Na, K and Si increase with depth, denoting inputs from feldspar weathering. Solute 87 Sr/ 86 Sr ratios exhibit progressive mixing of sea water-dominated precipitation with inputs from less radiogenic plagioclase. While net Sr and Ca concentrations are anomalously high in shallow soils due to biological cycling, they decline with depth to low and/or negative net concentrations. Ca/Mg, Sr/Mg and 87 Sr/ 86 Sr solute and exchange ratios are similar in all the terraces, denoting active exchange equilibration with selectivities close to unity for both detrital smectite and secondary kaolinite. Large differences in the magnitudes of the pore waters and exchange reservoirs result in short-term buffering of the solute Ca, Sr, and Mg. Such buffering over geologic time scales can not be sustained due to declining inputs from residual plagioclase and smectite, implying periodic resetting of the exchange reservoir such as by past vegetational changes and/or climate. Pore waters approach thermodynamic saturation with respect to albite at depth in the younger terraces, indicating that weathering rates ultimately become transport-limited and dependent on hydrologic flux. Contemporary rates R solute are estimated from linear Na and Si pore weathering gradients b solute such that R solute = frac(q h , b solute ?? S v ) where S v is the volumetric surface area and ?? is the stoichiometric coefficient. Plagioclase weathering rates (0.38-2.8 ?? 10 -15 mol m -2 s -1 ) are comparable to those based on 87 Sr/ 86 Sr mass balances and solid-state Na and Ca gradients using analogous gradient approximations. In addition, contemporary solute gradients, under transport-limited conditions, approximate long-term solid-state gradients when normalized against the mass of protolith plagioclase and its corresponding aqueous solubility. The multi-faceted weathering analysis presented in this paper is perhaps the most comprehensive yet applied to a single field study. Within uncertainties of the methods used, present day weathering rates, based on solute characterizations, are comparable to average long-term past rates as evidenced by soil profiles.

Geochimica et Cosmochimica Acta↗

USGS2008

Influences of calcium availability and tree species on Ca isotope fractionation in soil and vegetation

The calcium (Ca) isotope system is potentially of great use for understanding biogeochemical processes at multiple scales in forest ecosystems, yet remains largely unexplored for this purpose. In order to further our understanding of Ca behavior in forests, we examined two nearly adjacent hardwood-dominated catchments with differing soil Ca concentrations, developed from crystalline bedrock, to determine the variability of 44Ca/ 40Ca ratios (expressed as ??44Ca) within soil and vegetation pools. For both sugar maple and American beech, the Ca isotope compositions of the measured roots and calculated bulk trees were considerably lighter than those of soil pools at these sites, suggesting that the trees were able to preferentially take up light Ca at the root-soil interface. The Ca isotope compositions of three of four root samples were among the lightest values yet reported for terrestrial materials (??44Ca ???-3.95???). Our results further indicate that Ca isotopes were fractionated along the transpiration streams of both tree species with roots having the least ??44Ca values and leaf litter the greatest. An approximately 2??? difference in ??44Ca values between roots and leaf litter of both tree species suggests a persistent fractionation mechanism along the transpiration stream, likely related to Ca binding in wood tissue coupled with internal ion exchange. Finally, our data indicate that differing tree species demand for Ca and soil Ca concentrations together may influence Ca isotope distribution within the trees. Inter-catchment differences in Ca isotope distributions in soils and trees were minor, indicating that the results of our study may have broad transferability to studies of forest ecosystems in catchments developed on crystalline substrates elsewhere. ?? 2008 Springer Science+Business Media B.V.

Biogeochemistry↗

USGS2008

Chromium, chromium isotopes and selected trace elements, western Mojave Desert, USA

Chromium(VI) concentrations in excess of the California Maximum Contaminant Level (MCL) of 50 μg/L occur naturally in alkaline, oxic ground-water in alluvial aquifers in the western Mojave Desert, southern California. The highest concentrations were measured in aquifers eroded from mafic rock, but Cr(VI) as high as 27 μg/L was measured in aquifers eroded from granitic rock. Chromium(VI) concentrations did not exceed 5 μg/L at pH < 7.5 regardless of geology. δ 53 Cr values in native ground-water ranged from 0.7 to 5.1‰ and values were fractionated relative to the average δ 53 Cr composition of 0‰ in the earth’s crust. Positive δ 53 Cr values of 1.2 and 2.3‰ were measured in ground-water recharge areas having low Cr concentrations, consistent with the addition of Cr(VI) that was fractionated on mineral surfaces prior to entering solution. δ 53 Cr values, although variable, did not consistently increase or decrease with increasing Cr concentrations as ground-water flowed down gradient through more oxic portions of the aquifer. However, increasing δ 53 Cr values were observed as dissolved O 2 concentrations decreased, and Cr(VI) was reduced to Cr(III), and subsequently removed from solution. As a result, the highest δ 53 Cr values were measured in water from deep wells, and wells in discharge areas near dry lakes at the downgradient end of long flow paths through alluvial aquifers. δ 53 Cr values at an industrial site overlying mafic alluvium having high natural background Cr(VI) concentrations ranged from −0.1 to 3.2‰. Near zero δ 53 Cr values at the site were the result of anthropogenic Cr. However, mixing with native ground-water and fractionation of Cr within the plume increased δ 53 Cr values at the site. Although δ 53 Cr was not necessarily diagnostic of anthropogenic Cr, it was possible to identify the extent of anthropogenic Cr at the site on the basis of the δ 53 Cr values in conjunction with major-ion data, and the δ 18 O and δD composition of water from wells.

Applied Geochemistry↗

USGS2008

Microbial mass-dependent fractionation of chromium isotopes

Mass-dependent fractionation of Cr isotopes occurs during dissimilatory Cr(VI) reduction by Shewanella oneidensis strain MR-1. Cells suspended in a simple buffer solution, with various concentrations of lactate or formate added as electron donor, reduced 5 or 10 ??M Cr(VI) to Cr(III) over days to weeks. In all nine batch experiments, 53Cr/52Cr ratios of the unreacted Cr(VI) increased as reduction proceeded. In eight experiments covering a range of added donor concentrations up to 100 ??M, isotopic fractionation factors were nearly invariant, ranging from 1.0040 to 1.0045, with a mean value somewhat larger than that previously reported for abiotic Cr(VI) reduction (1.0034). One experiment containing much greater donor concentration (10 mM lactate) reduced Cr(VI) much faster and exhibited a lesser fractionation factor (1.0018). These results indicate that 53Cr/52Cr measurements should be effective as indicators of Cr(VI) reduction, either bacterial or abiotic. However, variability in the fractionation factor is poorly constrained and should be studied for a variety of microbial and abiotic reduction pathways. ?? 2008 Elsevier Ltd.

Geochimica et Cosmochimica Acta↗

USGS2008

Characterization of calcium isotopes in natural and synthetic barite

The mineral barite (BaSO4) accommodates calcium in its crystal lattice, providing an archive of Ca-isotopes in the highly stable sulfate mineral. Holocene marine (pelagic) barite samples from the major ocean basins are isotopically indistinguishable from each other (??44/40Ca = -2.01 ?? 0.15???) but are different from hydrothermal and cold seep barite samples (??44/40Ca = -4.13 to -2.72???). Laboratory precipitated (synthetic) barite samples are more depleted in the heavy Ca-isotopes than pelagic marine barite and span a range of Ca-isotope compositions, ??44/40Ca = -3.42 to -2.40???. Temperature, saturation state, a Ba2 + / a SO42 -, and aCa2+/aBa2+ each influence the fractionation of Ca-isotopes in synthetic barite; however, the fractionation in marine barite samples is not strongly related to any measured environmental parameter. First-principles lattice dynamical modeling predicts that at equilibrium Ca-substituted barite will have much lower 44Ca/40Ca than calcite, by -9??? at 0 ??C and -8??? at 25 ??C. Based on this model, none of the measured barite samples appear to be in isotopic equilibrium with their parent solutions, although as predicted they do record lower ??44/40Ca values than seawater and calcite. Kinetic fractionation processes therefore most likely control the extent of isotopic fractionation exhibited in barite. Potential fractionation mechanisms include factors influencing Ca2+ substitution for Ba2+ in barite (e.g. ionic strength and trace element concentration of the solution, competing complexation reactions, precipitation or growth rate, temperature, pressure, and saturation state) as well as nucleation and crystal growth rates. These factors should be considered when investigating controls on isotopic fractionation of Ca2+ and other elements in inorganic and biogenic minerals. ?? 2008 Elsevier Ltd.

Geochimica et Cosmochimica Acta↗

USGS2008

Application of multiple isotopic and geochemical tracers for investigation of recharge, salinization, and residence time of water in the Souss-Massa aquifer, southwest of Morocco

Groundwater and surface water in Souss-Massa basin in the west-southern part of Morocco is characterized by a large variation in salinity, up to levels of 37 g L-1. The high salinity coupled with groundwater level decline pose serious problems for current irrigation and domestic water supplies as well as future exploitation. A combined hydrogeologic and isotopic investigation using several chemical and isotopic tracers such as Br/Cl, ??18O, ??2H, 3H, 87Sr/86Sr, ??11B, and 14C was carried out in order to determine the sources of water recharge to the aquifer, the origin of salinity, and the residence time of water. Stable isotope, 3H and 14C data indicate that the high Atlas mountains in the northern margin of the Souss-Massa basin with high rainfall and low ??18O and ??2H values (-6 to -8??? and -36 to -50???) is currently constitute the major source of recharge to the Souss-Massa shallow aquifer, particularly along the eastern part of the basin. Localized stable isotope enrichments offset meteoric isotopic signature and are associated with high nitrate concentrations, which infer water recycling via water agricultural return flows. The 3H and 14C data suggest that the residence time of water in the western part of the basin is in the order of several thousands of years; hence old water is mined, particularly in the coastal areas. The multiple isotope analyses and chemical tracing of groundwater from the basin reveal that seawater intrusion is just one of multiple salinity sources that affect the quality of groundwater in the Souss-Massa aquifer. We differentiate between modern seawater intrusion, salinization by remnants of seawater entrapped in the middle Souss plains, recharge of nitrate-rich agricultural return flow, and dissolution of evaporate rocks (gypsum and halite minerals) along the outcrops of the high Atlas mountains. The data generated in this study provide the framework for a comprehensive management plan in which water exploitation should shift toward the eastern part of the basin where current recharge occurs with young and high quality groundwater. In contrast, we argued that the heavily exploited aquifer along the coastal areas is more vulnerable given the relatively longer residence time of the water and salinization processes in this part of the aquifer. ?? 2008 Elsevier B.V. All rights reserved.

Journal of Hydrology↗

USGS2008

Utilizing geochemical, hydrologic, and boron isotopic data to assess the success of a salinity and selenium remediation project, Upper Colorado River Basin, Utah

Stream discharge and geochemical data were collected at two sites along lower Ashley Creek, Utah, from 1999 to 2003, to assess the success of a site specific salinity and Se remediation project. The remediation project involved the replacement of a leaking sewage lagoon system that was interacting with Mancos Shale and increasing the dissolved salinity and Se load in Ashley Creek. Regression modeling successfully simulated the mean daily dissolved salinity and Se loads (R2 values ranging from 0.82 to 0.97) at both the upstream (AC1) and downstream (AC2/AC2A) sites during the study period. Prior to lagoon closure, net gain in dissolved-salinity load exceeded 2177??metric tons/month and decreased after remediation to less than 590??metric tons/month. The net gain in dissolved Se load during the same pre-closure period exceeded 120??kg/month and decreased to less than 18??kg/month. Sen's slope estimator verified the statistical significance of the modeled reduction in monthly salinity and Se loads. Measured gain in dissolved constituent loads during seepage tests conducted during September and November 2003 ranged from 0.334 to 0.362??kg/day for dissolved Se and 16.9 to 26.1??metric tons/day for dissolved salinity. Stream discharge and changes in the isotopic values of delta boron-11 (??11B) were used in a mixing model to differentiate between constituent loadings contributed by residual sewage effluent and naturally occurring ground-water seepage entering Ashley Creek. The majority of the modeled ??11B values of ground-water seepage were positive, indicative of minimal seepage contributions from sewage effluent. The stream reach between sites S3 and AC2A contained a modeled ground-water seepage ??11B value of - 2.4???, indicative of ground-water seepage composed of remnant water still draining from the abandoned sewage lagoons.

Science of the Total Environment↗

USGS2008

A dynamic marine calcium cycle during the past 28 million years

Multiple lines of evidence have shown that the isotopic composition and concentration of calcium in seawater have changed over the past 28 million years. A high-resolution, continuous seawater calcium isotope ratio curve from marine (pelagic) barite reveals distinct features in the evolution of the seawater calcium isotopic ratio suggesting changes in seawater calcium concentrations. The most pronounced increase in the ??44/40Ca value of seawater (of 0.3 per mil) occurred over roughly 4 million years following a period of low values around 13 million years ago. The major change in marine calcium corresponds to a climatic transition and global change in the carbon cycle and suggests a reorganization of the global biogeochemical system.

Science↗

USGS2007

The geochemistry of groundwater resources in the Jordan Valley: The impact of the Rift Valley brines

The chemical composition of groundwater in the Jordan Valley, along the section between the Sea of Galilee and the Dead Sea, is investigated in order to evaluate the origin of the groundwater resources and, in particular, to elucidate the role of deep brines on the chemical composition of the regional groundwater resources in the Jordan Valley. Samples were collected from shallow groundwater in research boreholes on two sites in the northern and southern parts of the Jordan Valley, adjacent to the Jordan River. Data is also compiled from previous published studies. Geochemical data (e.g., Br/Cl, Na/Cl and SO 4 /Cl ratios) and B, O, Sr and S isotopic compositions are used to define groundwater groups, to map their distribution in the Jordan valley, and to evaluate their origin. The combined geochemical tools enabled the delineation of three major sources of solutes that differentially affect the quality of groundwater in the Jordan Valley: (1) flow and mixing with hypersaline brines with high Br/Cl (>2 × 10 −3 ) and low Na/Cl (<0.8) ratios; (2) dissolution of highly soluble salts (e.g., halite, gypsum) in the host sediments resulting in typically lower Br/Cl signal (<2 × 10 −3 ); and (3) recharge of anthropogenic effluents, primarily derived from evaporated agricultural return flow that has interacted (e.g., base-exchange reactions) with the overlying soil. It is shown that shallow saline groundwaters influenced by brine mixing exhibit a north–south variation in their Br/Cl and Na/Cl ratios. This chemical trend was observed also in hypersaline brines in the Jordan valley, which suggests a local mixing process between the water bodies.

Applied Geochemistry↗