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Geology topics

T.D. Bullen

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

At least 19 recordsLinked to original sources
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‰ (2σ).

Analytical Chemistry↗
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

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

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

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

New isotopic evidence for the origin of groundwater from the Nubian Sandstone Aquifer in the Negev, Israel

The geochemistry and isotopic composition (H, O, S, O sulfate , C, Sr) of groundwater from the Nubian Sandstone (Kurnub Group) aquifer in the Negev, Israel, were investigated in an attempt to reconstruct the origin of the water and solutes, evaluate modes of water–rock interactions, and determine mean residence times of the water. The results indicate multiple recharge events into the Nubian sandstone aquifer characterized by distinctive isotope signatures and deuterium excess values. In the northeastern Negev, groundwater was identified with deuterium excess values of ∼16‰, which suggests local recharge via unconfined areas of the aquifer in the Negev anticline systems. The δ 18 O H2O and δ 2 H values (−6.5‰ and −35.4‰) of this groundwater are higher than those of groundwater in the Sinai Peninsula and southern Arava valley (−7.5‰ and −48.3‰) that likewise have lower deuterium excess values of ∼10‰. Based on the geochemical differences between groundwater in the unconfined and confined zones of the aquifer, a conceptual geochemical model for the evolution of the groundwater in the Nubian sandstone aquifer has been reconstructed. The isotopic composition of shallow groundwater from the unconfined zone indicates that during recharge oxidation of pyrite to SO 4 ( δ 34 S SO4 ∼−13‰; δ 18 O SO4 ∼+7.7‰) and dissolution of CaCO 3 ( 87 Sr/ 86 Sr ∼0.70787; δ 13 C DIC = −3.7‰) occur. In the confined zone of the aquifer, bacterial SO 4 reduction removes a significant part of dissolved SO 4 2 - "> SO42- , thereby modifying its isotopic composition ( δ 34 S SO4 ∼−2‰; δ 18 O SO4 ∼+8.5‰) and liberating dissolved inorganic C that contains little or no radiocarbon ( 14 C-free) with low δ 13 C DIC values (<−12‰). In addition to local recharge, the Sr and S isotopic data revealed contribution of external groundwater sources to the Nubian Sandstone aquifer, resulting in further modifications of the groundwater chemical and isotopic signatures. In the northeastern Negev, it is shown that SO 4 -rich groundwater from the underlying Jurassic aquifer contributes significantly to the salt budget of the Nubian Sandstone aquifer. The unique chemical and isotopic composition of the Jurassic groundwater ( δ 34 S SO4 ∼ +14‰; δ 18 O SO4 ∼ 14‰; 87 Sr/ 86 Sr ∼0.70764) is interpreted as reflecting dissolution of Late Triassic marine gypsum deposits. In the southern Arava Valley the authors postulate that SO 4 -rich groundwater with distinctively high Br/Cl (3 × 10 −3 ) low 87 Sr/ 86 Sr (0.70734), and high δ 34 S SO4 values (+15‰) is derived from mixing with underlying brines from the Paleozoic units. The radiocarbon measurements reveal low 14 C activities (0.2–5.8 pmc) in both the northeastern Negev and southern Arava Valley. Taking into account dissolution of carbonate rocks and bacterial SO 4 reduction in the unconfined area, estimated mean residence times of groundwater in the confined zone in the northeastern Negev are on the order of 21–38 ka, which suggests recharge predominantly during the last glacial period. The 14 C signal in groundwater from the southern Arava Valley is equally low but due to evidence for mixing with external water sources the residence time estimates are questionable.

Applied Geochemistry↗
USGS2007

Developing a new method of measuring dissolution rates of silicate minerals using changes in the isotopic ratio of a spiked solution

Weathering in the field tends to be incongruent due to the precipitation of secondary phases. However, most laboratory experiments are designed to avoid such precipitation, as it complicates the interpretation of the experimental results. Here we report on a new method that eliminates the effect of secondary phase precipitation on the determination of the dissolution rate of a primary mineral. The dissolution rate determination in the newmethod is based on measured changes in Si isotopic composition of a spiked solution.The newmethod significantly improves the accuracy in calculating near-equilibrium dissolution rates. Moreover, combining this method with measured Al concentration enables the determination of precipitation rate of secondary minerals. © 2007 Taylor & Francis Group, London.

Conference Paper↗
USGS2005

Using stable isotopes of water and strontium to investigate the hydrology of a natural and a constructed wetland

Wetlands cannot exist without water, but wetland hydrology is difficult to characterize. As a result, compensatory wetland mitigation often only assumes the proper hydrology has been created. In this study, water sources and mass transfer processes in a natural and constructed wetland complex were investigated using isotopes of water and strontium. Water isotope profiles in the saturated zone revealed that the natural wetland and one site in the constructed wetland were primarily fed by ground water; profiles in another constructed wetland site showed recent rain was the predominant source of water in the root zone. Water isotopes in the capillary fringe indicated that the residence time for rain is less in the natural wetland than in the constructed wetland, thus transpiration (an important water sink) was greater in the natural wetland. Strontium isotopes showed a systematic difference between the natural and constructed wetlands that we attribute to the presence or absence of peat. In the peat‐rich natural wetland, δ 87 Sr in the pore water increased along the flowline due to preferential weathering of minerals containing radiogenic Sr in response to elevated Fe concentrations in the water. In the constructed wetland, where peat thickness was thin and Fe concentrations in water were negligible, δ 87 Sr did not increase along the flowline. The source of the peat (on‐site or off‐site derived) applied in the constructed wetland controlled the δ 87 Sr at the top of the profile, but the effects were restricted by strong cation exchange in the underlying fluvial sediments. Based on the results of this study, neither constructed wetland site duplicated the water source and weathering environment of the adjoining natural wetland. Moreover, stable isotopes were shown to be effective tools for investigating wetlands and gaining insight not easily obtained using non‐isotopic techniques. These tools have potential widespread application to wetlands that have distinct isotopic endmember sources.

Ground Water↗
USGS2005

Use of chemical and isotopic tracers to characterize the interactions between ground water and surface water in mantled karst

In the mantled karst terrane of northern Florida, the water quality of the Upper Floridan aquifer is influenced by the degree of connectivity between the aquifer and the surface. Chemical and isotopic analyses [ 18 O/ 16 O (δ 18 O), 2 H/ 1 H (δD), 13 C/ 12 C (δ 13 C), tritium ( 3 H), and strontium‐87/strontium‐86 ( 87 Sr/ 86 Sr)] along with geochemical mass‐balance modeling were used to identify the dominant hydrochemical processes that control the composition of ground water as it evolves downgradient in two systems. In one system, surface water enters the Upper Floridan aquifer through a sinkhole located in the Northern Highlands physiographic unit. In the other system, surface water enters the aquifer through a sinkhole lake (Lake Bradford) in the Woodville Karst Plain. Differences in the composition of water isotopes (δ 18 O and <δD) in rainfall, ground water, and surface water were used to develop mixing models of surface water (leakage of water to the Upper Floridan aquifer from a sinkhole lake and a sinkhole) and ground water. Using mass‐balance calculations, based on differences in δ 18 O and δD, the proportion of lake water that mixed with meteoric water ranged from 7 to 86% in water from wells located in close proximity to Lake Bradford. In deeper parts of the Upper Floridan aquifer, water enriched in 18 O and D from five of 12 sampled municipal wells indicated that recharge from a sinkhole (1 to 24%) and surface water with an evaporated isotopic signature (2 to 32%) was mixing with ground water. The solute isotopes, δ 13 C and 87 Sr/ 86 Sr, were used to test the sensitivity of binary and ternary mixing models, and to estimate the amount of mass transfer of carbon and other dissolved species in geochemical reactions. In ground water downgradient from Lake Bradford, the dominant processes controlling carbon cycling in ground water were dissolution of carbonate minerals, aerobic degradation of organic matter, and hydrolysis of silicate minerals. In the deeper parts of the Upper Floridan aquifer, the major processes controlling the concentrations of major dissolved species included dissolution of calcite and dolomite, and degradation of organic matter under oxic conditions. The Upper Floridan aquifer is highly susceptible to contamination from activities at the land surface in the Tallahassee area. The presence of post‐ 1950s concentrations of 3 H in ground water from depths greater than 100 m below land surface indicates that water throughout much of the Upper Floridan aquifer has been recharged during the last 40 years. Even though mixing is likely between ground water and surface water in many parts of the study area, the Upper Floridan aquifer produces good quality water, which due to dilution effects shows little if any impact from trace elements or nutrients that are present in surface waters.

Ground Water↗
USGS2005

Identifying calcium sources at an acid deposition-impacted spruce forest: A strontium isotope, alkaline earth element multi-tracer approach

Depletion of calcium from forest soils has important implications for forest productivity and health. Ca is available to fine feeder roots from a number of soil organic and mineral sources, but identifying the primary source or changes of sources in response to environmental change is problematic. We used strontium isotope and alkaline earth element concentration ratios of trees and soils to discern the record of Ca sources for red spruce at a base-poor, acid deposition-impacted watershed. We measured 87 Sr/ 86 Sr and chemical compositions of cross-sectional stemwood cores of red spruce, other spruce tissues and sequential extracts of co-located soil samples. 87 Sr/ 86 Sr and Sr/Ba ratios together provide a tracer of alkaline earth element sources that distinguishes the plant-available fraction of the shallow organic soils from those of deeper organic and mineral soils. Ca/Sr ratios proved less diagnostic, due to within-tree processes that fractionate these elements from each other. Over the growth period from 1870 to 1960, 87 Sr/ 86 Sr and Sr/Ba ratios of stemwood samples became progressively more variable and on average trended toward values that considered together are characteristic of the uppermost forest floor. In detail the stemwood chemistry revealed an episode of simultaneous enhanced uptake of all alkaline earth elements during the growth period from 1930 to 1960, coincident with reported local and regional increases in atmospheric inputs of inorganic acidity. We attribute the temporal trends in stemwood chemistry to progressive shallowing of the effective depth of alkaline earth element uptake by fine roots over this growth period, due to preferential concentration of fine roots in the upper forest floor coupled with reduced nutrient uptake by roots in the lower organic and upper mineral soils in response to acid-induced aluminum toxicity. Although both increased atmospheric deposition and selective weathering of Ca-rich minerals such as apatite provide possible alternative explanations of aspects of the observed trends, the chemical buffering capacity of the forest floor-biomass pool limits their effectiveness as causal mechanisms.

Biogeochemistry↗
USGS2005

Management scenarios for the Jordan River salinity crisis

Recent geochemical and hydrological findings show that the water quality of the base flow of the Lower Jordan River, between the Sea of Galilee and the Dead Sea, is dependent upon the ratio between surface water flow and groundwater discharge. Using water quality data, mass-balance calculations, and actual flow-rate measurements, possible management scenarios for the Lower Jordan River and their potential affects on its salinity are investigated. The predicted scenarios reveal that implementation of some elements of the Israel-Jordan peace treaty will have negative effects on the Jordan River water salinity. It is predicted that removal of sewage effluents dumped into the river (???13 MCM/a) will significantly reduce the river water's flow and increase the relative proportion of the saline groundwater flux into the river. Under this scenario, the Cl content of the river at its southern point (Abdalla Bridge) will rise to almost 7000 mg/L during the summer. In contrast, removal of all the saline water (16.5 MCM/a) that is artificially discharged into the Lower Jordan River will significantly reduce its Cl concentration, to levels of 650-2600 and 3000-3500 mg/L in the northern and southern areas of the Lower Jordan River, respectively. However, because the removal of either the sewage effluents or the saline water will decrease the river's discharge to a level that could potentially cause river desiccation during the summer months, other water sources must be allocated to preserve in-stream flow needs and hence the river's ecosystem. ?? 2005 Elsevier Ltd. All rights reserved.

Applied Geochemistry↗
USGS2005

The ubiquitous nature of accessory calcite in granitoid rocks: Implications for weathering, solute evolution, and petrogenesis

Calcite is frequently cited as a source of excess Ca, Sr and alkalinity in solutes discharging from silicate terrains yet, no previous effort has been made to assess systematically the overall abundance, composition and petrogenesis of accessory calcite in granitoid rocks. This study addresses this issue by analyzing a worldwide distribution of more than 100 granitoid rocks. Calcite is found to be universally present in a concentration range between 0.028 to 18.8 g kg −1 (mean = 2.52 g kg −1 ). Calcite occurrences include small to large isolated anhedral grains, fracture and cavity infillings, and sericitized cores of plagioclase. No correlation exists between the amount of calcite present and major rock oxide compositions, including CaO. Ion microprobe analyses of in situ calcite grains indicate relatively low Sr (120 to 660 ppm), negligible Rb and 87 Sr/ 86 Sr ratios equal to or higher than those of coexisting plagioclase. Solutes, including Ca and alkalinity produced by batch leaching of the granitoid rocks (5% CO 2 in DI water for 75 d at 25°C), are dominated by the dissolution of calcite relative to silicate minerals. The correlation of these parameters with higher calcite concentrations decreases as leachates approach thermodynamic saturation. In longer term column experiments (1.5 yr), reactive calcite becomes exhausted, solute Ca and Sr become controlled by feldspar dissolution and 87 Sr/ 86 Sr by biotite oxidation. Some accessory calcite in granitoid rocks is related to intrusion into carbonate wall rock or produced by later hydrothermal alteration. However, the ubiquitous occurrence of calcite also suggests formation during late stage (subsolidus) magmatic processes. This conclusion is supported by petrographic observations and 87 Sr/ 86 Sr analyses. A review of thermodynamic data indicates that at moderate pressures and reasonable CO 2 fugacities, calcite is a stable phase at temperatures of 400 to 700°C.

Geochimica et Cosmochimica Acta↗