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USGS2001

Timescales for nitrate contamination of spring waters, northern Florida, USA

Residence times of groundwater, discharging from springs in the middle Suwannee River Basin, were estimated using chlorofluorocarbons (CFCs), tritium ( 3 H), and tritium/helium-3 ( 3 H/ 3 He) age-dating methods to assess the chronology of nitrate contamination of spring waters in northern Florida. During base-flow conditions for the Suwannee River in 1997–1999, 17 water samples were collected from 12 first, second, and third magnitude springs discharging groundwater from the Upper Floridan aquifer. Extending age-dating techniques, using transient tracers to spring waters in complex karst systems, required an assessment of several models [piston-flow (PFM), exponential mixing (EMM), and binary-mixing (BMM)] to account for different distributions of groundwater age. Multi-tracer analyses of four springs yielded generally concordant PFM ages of around 20±2 years from CFC-12, CFC-113, 3 H, and 3 He, with evidence of partial CFC-11 degradation. The EMM gave a reasonable fit to CFC-113, CFC-12, and 3 H data, but did not reproduce the observed 3 He concentrations or 3 H/ 3 He ratios, nor did a combination PFM–EMM. The BMM could reproduce most of the multi-tracer data set only if both endmembers had 3 H concentrations not much different from modern values. CFC analyses of 14 additional springs yielded apparent PFM ages from about 10 to 20 years from CFC-113, with evidence of partial CFC-11 degradation and variable CFC-12 contamination. While it is not conclusive, with respect to the age distribution within each spring, the data indicate that the average residence times were in the order of 10–20 years and were roughly proportional to spring magnitude. Applying similar models to recharge and discharge of nitrate based on historical nitrogen loading data yielded contrasting trends for Suwanee County and Lafayette County. In Suwanee County, spring nitrate trends and nitrogen isotope data were consistent with a peak in fertilizer input in the 1970s and a relatively high overall ratio of artificial fertilizer/manure; whereas in Lafayette County, spring nitrate trends and nitrogen isotope data were consistent with a more monotonic increase in fertilizer input and relatively low overall ratio of artificial fertilizer/manure. The combined results of this study indicate that the nitrate concentrations of springs in the Suwannee River basin have responded to increased nitrogen loads from various sources in the watersheds over the last few decades; however, the responses have been subdued and delayed because the average residence time of groundwater discharging from springs are in the order of decades.

Florida↗

USGS2001

Using multiple geochemical tracers to characterize the hydrogeology of the submarine spring off Crescent Beach, Florida

A spectacular submarine spring is located about 4 km east of Crescent Beach, FL, in the Atlantic Ocean. The single vent feature of Crescent Beach Spring provides a unique opportunity to examine onshore–offshore hydrogeologic processes, as well as point source submarine ground water discharge. The Floridan aquifer system in northeastern Florida consists of Tertiary interspersed limestone and dolomite strata. Impermeable beds confine the water-bearing zones under artesian pressure. Miocene and younger confining strata have been eroded away at the vent feature, enabling direct hydrologic communication of Eocene ground water with coastal bottom waters. The spring water had a salinity of 6.02, which was immediately diluted by ambient seawater during advection/mixing. The concentration of major solutes in spring water and onshore well waters confirm a generalized easterly flow direction of artesian ground water. Nutrient concentrations were generally low in the reducing vent samples, and the majority of the total nitrogen species existed as NH 3 . The submarine ground water tracers, Rn-222 (1174 dpm l −1 , dpm), methane (232 nM) and barium (294.5 nM) were all highly enriched in the spring water relative to ambient seawater. The concentrations of the reverse redox elements U, V and Mo were expectedly low in the submarine waters. The strontium isotope ratio of the vent water ( 87 Sr/ 86 Sr=0.70798) suggests that the spring water contain an integrated signature indicative of Floridan aquifer system ground water. Additional Sr isotopic ratios from a series of surficial and Lower Floridan well samples suggest dynamic ground water mixing, and do not provide clear evidence for a single hydrogeologic water source at the spring vent. In this karst-dominated aquifer, such energetic mixing at the vent feature is expected, and would be facilitated by conduit and fractured flow. Radium isotope activities were utilized to estimate flow-path trajectories and to provide information on potential travel times between an onshore well and the spring. Using either 223 Ra and 224 Ra or 228 Ra, and qualifying this approach with several key assumptions, estimates of water mass travel times from an upper Floridan well in Crescent Beach to the submarine vent feature (distance=4050 m) are in the order of ∼0.01–0.1 m min −1 .

Florida↗

USGS2002

Assessment of hydrocarbon source rock potential of Polish bituminous coals and carbonaceous shales

We analyzed 40 coal samples and 45 carbonaceous shale samples of varying thermal maturity (vitrinite reflectance 0.59% to 4.28%) from the Upper Carboniferous coal-bearing strata of the Upper Silesian, Lower Silesian, and Lublin basins, Poland, to evaluate their potential for generation and expulsion of gaseous and liquid hydrocarbons. We evaluated source rock potential based on Rock-Eval pyrolysis yield, elemental composition (atomic H/C and O/C), and solvent extraction yields of bitumen. An attempt was made to relate maceral composition to these source rock parameters and to composition of the organic matter and likely biological precursors. A few carbonaceous shale samples contain sufficient generation potential (pyrolysis assay and elemental composition) to be considered potential source rocks, although the extractable hydrocarbon and bitumen yields are lower than those reported in previous studies for effective Type III source rocks. Most samples analysed contain insufficient capacity for generation of hydrocarbons to reach thresholds required for expulsion (primary migration) to occur. In view of these findings, it is improbable that any of the coals or carbonaceous shales at the sites sampled in our study would be capable of expelling commercial amounts of oil. Inasmuch as a few samples contained sufficient generation capacity to be considered potential source rocks, it is possible that some locations or stratigraphic zones within the coals and shales could have favourable potential, but could not be clearly delimited with the number of samples analysed in our study. Because of their high heteroatomic content and high amount of asphaltenes, the bitumens contained in the coals are less capable of generating hydrocarbons even under optimal thermal conditions than their counterpart bitumens in the shales which have a lower heteroatomic content. Published by Elsevier Science B.V.

Chemical Geology↗

USGS2002

U-Pb geochronology of zircon and polygenetic titanite from the Glastonbury Complex, Connecticut, USA: An integrated SEM, EMPA, TIMS, and SHRIMP study

U-Pb ages for zircon and titanite from a granodioritic gneiss in the Glastonbury Complex, Connecticut, have been determined using both isotope dilution thermal ionization mass spectrometry (TIMS) and the sensitive high resolution ion microprobe (SHRIMP). Zircons occur in three morphologic populations: (1) equant to stubby, multifaceted, colorless, (2) prismatic, dark brown, with numerous cracks, and (3) elongate, prismatic, light tan to colorless. Cathodoluminescence (CL) imaging of the three populations shows simple concentric oscillatory zoning. The zircon TIMS age [weighted average of 207Pb/206Pb ages from Group 3 grains-450.5 ?? 1.6 Ma (MSWD=1.11)] and SHRIMP age [composite of 206Pb/238 U age data from all three groups-448.2 ?? 2.7 Ma (MSWD = 1.3)], are interpreted to suggest a relatively simple crystallization history. Titanite from the granodioritic gneiss occurs as both brown and colorless varieties. Scanning electron microscope backscatter (BSE) images of brown grains show multiple cross-cutting oscillatory zones of variable brightness and dark overgrowths. Colorless grains are unzoned or contain subtle wispy or very faint oscillatory zoning. Electron microprobe analysis (EMPA) clearly distinguishes the two populations. Brown grains contain relatively high concentrations of Fe2O3, Ce2O3 (up to ~ 1.5 wt.%), Nb2O5, and Zr. Cerium concentration is positively correlated with total REE + Y concentration, which together can exceed 3.5 wt.%. Oscillatory zoning in brown titanite is correlated with variations in REE concentrations. In contrast, colorless titanite (both as discrete grains and overgrowths on brown titanite) contains lower concentrations of Y, REE, Fe2O3, and Zr, but somewhat higher Al2O3 and Nb2O5. Uranium concentrations and Th/U discriminate between brown grains (typically 200-400 ppm U; all analyses but one have Th/U between about 0.8 and 2) and colorless grains (10-60 ppm U; Th/U of 0-0.17). In contrast to the zircon U-Pb age results, SHRIMP U-Pb data from titanite indicate multiple growth episodes. In brown grains, oscillatory zoned cores formed at 443 ?? 6 Ma, whereas white (in BSE) cross-cutting zones are 425 ?? 9 Ma. Colorless grains and overgrowths on brown grains yield an age of 265 ?? 8 Ma (using the Total Pb method) or 265 ?? 5 Ma (using the weighted average of the 206Pb/238U ages). However, EMPA chemical data identify zoning that suggests that this colorless titanite may preserve three growth events. Oscillatory zoned portions of brown titanite grains are igneous in origin; white cross-cutting zones probably formed during a previously unrecognized event that caused partial dissolution of earlier titanite and reprecipitation of a slightly younger generation of brown titanite. Colorless titanite replaced and grew over the magmatic titanite during the Permian Alleghanian orogeny. These isotopic data indicate that titanite, like zircon, can contain multiple age components. Coupling SHRIMP microanalysis with EMPA and SEM results on dated zones as presented in this study is an efficient and effective technique to extract additional chronologic ?? 2002 Elsevier Science B.V. All rights reserved.

Chemical Geology↗

USGS2002

Determining mineral weathering rates based on solid and solute weathering gradients and velocities: Application to biotite weathering in saprolites

Chemical weathering gradients are defined by the changes in the measured elemental concentrations in solids and pore waters with depth in soils and regoliths. An increase in the mineral weathering rate increases the change in these concentrations with depth while increases in the weathering velocity decrease the change. The solid-state weathering velocity is the rate at which the weathering front propagates through the regolith and the solute weathering velocity is equivalent to the rate of pore water infiltration. These relationships provide a unifying approach to calculating both solid and solute weathering rates from the respective ratios of the weathering velocities and gradients. Contemporary weathering rates based on solute residence times can be directly compared to long-term past weathering based on changes in regolith composition. Both rates incorporate identical parameters describing mineral abundance, stoichiometry, and surface area. Weathering gradients were used to calculate biotite weathering rates in saprolitic regoliths in the Piedmont of Northern Georgia, USA and in Luquillo Mountains of Puerto Rico. Solid-state weathering gradients for Mg and K at Panola produced reaction rates of 3 to 6 x 10-17 mol m-2 s-1 for biotite. Faster weathering rates of 1.8 to 3.6 ?? 10-16 mol m-2 s-1 are calculated based on Mg and K pore water gradients in the Rio Icacos regolith. The relative rates are in agreement with a warmer and wetter tropical climate in Puerto Rico. Both natural rates are three to six orders of magnitude slower than reported experimental rates of biotite weathering. ?? 2002 Elsevier Science B.V. All rights reserved.

Chemical Geology↗

USGS2003

Stable carbon isotope fractionation of trans-1,2-dichloroethylene during co-metabolic degradation by methanotrophic bacteria

Changes in the carbon isotope ratio (δ 13 C) of trans-1,2-dichloroethylene (t-DCE) were measured during its co-metabolic degradation by Methylomonas methanica, a type I methanotroph, and Methylosinus trichosporium OB3b, a type II methanotroph. In closed-vessel incubation experiments with each bacterium, the residual t-DCE became progressively enriched in 13 C, indicating isotopic fractionation. From these experiments, the biological fractionation during t-DCE co-metabolism, expressed as ε, was measured to be -3.5 0 / 00 for the type I culture and -6.7 0 / 00 for the type II culture. This fractionation effect and subsequent enrichment in the δ 13 C of the residual t-DCE can thus be applied to determine the extent of biodegradation of DCE by these organisms. Based on these results, isotopic fractionation clearly warrants further study, as measured changes in the δ 13 C values of chlorinated solvents could ultimately be used to monitor the extent of biodegradation in laboratory or field settings where co-metabolism by methanotrophs occurs.

Chemical Geology↗

USGS2003

Stable isotope fractionation of selenium by natural microbial consortia

The mobility and bioavailability of Se depend on its redox state, and reduction of Se oxyanions to less mobile, reduced species controls transport of this potentially toxic element in the environment. Stable isotope fractionation of Se is currently being developed as an indicator of Se immobilization through reduction. In this study, Se isotope fractionation resulting from reduction of Se(VI) and Se(IV) oxyanions by natural microbial consortia was measured in sediment slurry experiments under nearly natural conditions, with no substrate added. Experiments were conducted with a wide range of initial Se concentrations and with sediment and water from three locations with contrasting environmental settings. The products of Se(VI) and Se(IV) reduction were enriched in the lighter isotopes relative to the reactants. Shifts of -2.6 0 / 00 to -3.1 0 / 00 and -5.5 0 / 00 to -5.7 0 / 00 , respectively, were observed in the 80 Se/ 76 Se ratio. These isotopic fractionations did not depend significantly on initial Se concentrations, which were varied from 22 μg/l to 8 mg/l, or on geochemical differences among the sediments. These results provide estimates of Se isotope fractionation in organic-rich wetland environments but may not be appropriate for substrate-poor aquifers and marine sediments.

Chemical Geology↗

USGS2003

Highly siderophile elements in chondrites

The abundances of the highly siderophile elements (HSE), Re, Os, Ir, Ru, Pt and Pd, were determined by isotope dilution mass spectrometry for bulk samples of 13 carbonaceous chondrites, 13 ordinary chondrites and 9 enstatite chondrites. These data are coupled with corresponding 187Re-187Os isotopic data reported by Walker et al. [Geochim. Cosmochim. Acta, 2002] in order to constrain the nature and timing of chemical fractionation relating to these elements in the early solar system. The suite of chondrites examined displays considerable variations in absolute abundances of the HSE, and in the ratios of certain HSE. Absolute abundances of the HSE vary by nearly a factor of 80 among the chondrite groups, although most vary within a factor of only 2. Variations in concentration largely reflect heterogeneities in the sample aliquants. Different aliquants of the same chondrite may contain variable proportions of metal and/or refractory inclusions that are HSE-rich, and sulfides that are HSE-poor. The relatively low concentrations of the HSE in CI1 chondrites likely reflect dilution by the presence of volatile components. Carbonaceous chondrites have Re/Os ratios that are, on average, approximately 8% lower than ratios for ordinary and enstatite chondrites. This is also reflected in 187Os/188Os ratios that are approximately 3% lower for carbonaceous chondrites than for ordinary and enstatite chondrites. Given the similarly refractory natures of Re and Os, this fractionation may have occurred within a narrow range of high temperatures, during condensation of these elements from the solar nebula. Superimposed on this major fractionation are more modest movements of Re or Os that occurred within the last 0-2 Ga, as indicated by minor open-system behavior of the Re-Os isotope systematics of some chondrites. The relative abundances of other HSE can also be used to discriminate among the major classes of chondrites. For example, in comparison to the enstatite chondrites, carbonaceous and ordinary chondrites have distinctly lower ratios of Pd to the more refractory HSE (Re, Os, Ir, Ru and Pt). Differences are particularly well resolved for the EH chondrites that have Pd/Ir ratios that average more than 40% higher than for carbonaceous and ordinary chondrite classes. This fractionation probably occurred at lower temperatures, and may be associated with fractionation processes that also affected the major refractory lithophile elements. Combined, 187Os/188Os ratios and HSE ratios reflect unique early solar system processing of HSE for each major chondrite class. ?? 2002 Elsevier Science B.V. All rights reserved.

Chemical Geology↗

USGS2003

Evaluation of the 34S/32S ratio of Soufre de Lacq elemental sulfur isotopic reference material by continuous flow isotope-ratio mass spectrometry

Soufre de Lacq elemental sulfur reference material (IAEA-S-4) isotopically is homogeneous in amounts as small as 41 ??g as determined by continuous flow isotope-ratio mass spectrometry. The ??34S value for this reference material is +16.90 ?? 0.12??? (1??) on a scale (Vienna Can??on Diablo troilite, VCDT) where IAEA-S-1 Ag2S is -0.3??? and IAEA-S-2 Ag2S is +22.67???. Published by Elsevier Science B.V.

Chemical Geology↗

USGS2003

TEMORA 1: A new zircon standard for Phanerozoic U-Pb geochronology

The role of the standard is critical to the derivation of reliable U-Pb zircon ages by micro-beam analysis. For maximum reliability, it is critically important that the utilised standard be homogeneous at all scales of analysis. It is equally important that the standard has been precisely and accurately dated by an independent technique. This study reports the emergence of a new zircon standard that meets those criteria, as demonstrated by Sensitive High Resolution Ion MicroProbe (SHRIMP), isotope dilution thermal ionisation mass-spectrometry (IDTIMS) and excimer laser ablation- inductively coupled plasma-mass-spectrometry (ELA-ICP-MS) documentation. The TEMORA 1 zircon standard derives from the Middledale Gabbroic Diorite, a high-level mafic stock within the Palaeozoic Lachlan Orogen of eastern Australia. Its 206Pb/238U IDTIMS age has been determined to be 416.75??0.24 Ma (95% confidence limits), based on measurement errors alone. Spike-calibration uncertainty limits the accuracy to 416.8??1.1 Ma for U-Pb intercomparisons between different laboratories that do not use a common spike. ?? 2003 Published by Elsevier Science B.V. All rights reserved.

Chemical Geology↗

USGS1983

Harding Iceland spar: A new δ18O−δ13C carbonate standard for hydrothermal minerals

An isotopically homogeneous calcite, Harding Iceland Spar (HIS), having 6180 = +11.78 ± 0.07‰ (= +22.15‰ for CO 2 ) and δ 13 C = −4.80 ± 0.02‰, has been prepared in quantities suitable for use as a working standard in mass spectrometric analysis. The isotopic values are well-suited for analysis of minerals of hydrothermal origin.

Chemical Geology↗

USGS1997

Early diagenetic partial oxidation of organic matter and sulfides in the Middle Pennsylvanian (Desmoinesian) Excello Shale Member of the Fort Scott Limestone and equivalents, northern Midcontinent region, USA

A process of early diagenetic partial oxidation of organic matter and sulfides has altered the chemical composition of the Middle Pennsylvanian Excello Shale Member of the Fort Scott Limestone and equivalents in the northern Midcontinent region. This process was identified by comparison of organic carbon contents, Rock-Eval hydrogen indices, organic carbon ??13C and element compositions of core and surface mine samples of the Excello Shale Member with analyses of three other underlying and overlying organic-matter-rich marine shales (offshore shale lithofacies) from southern Iowa, northern Missouri, eastern Kansas and northeastern Oklahoma. The end product of the partial oxidation process is shale with relatively low contents of hydrogen-poor, C13-enriched organic matter, lower contents of sulfur and sulfide-forming elements, and relatively unchanged contents of phosphorus and many trace elements (e.g. Cr, Ni, and V). However, because of lower organic carbon contents, element/organic carbon ratios are greatly increased. The partial oxidation process apparently took place during subaerial exposure of the overlying marine carbonate member (Blackjack Creek Member of the Fort Scott Limestone) following a marine regression when meteoric waters percolated down to the level of the Excello muds allowing oxidation of organic matter and sulfides. This hypothesis is supported by earlier workers, who have identified meteoric carbonate cements within, and soil horizons at the top of the Blackjack Creek Member. The period of oxidation is constrained in that organic matter and sulfides in the Little Osage Shale Member of the Fort Scott Limestone and equivalents (immediately overlying the Blackjack Creek Member) appear unaltered. Similar alteration of other shales in the Middle and Upper Pennsylvanian sections may be local to regional in extent and would depend on the extent and duration of the marine regression and be influenced by local variations in permeability and topography. The partial oxidation process has likely led to a redistribution of sulfur and sulfide-forming elements into other organic-rich lithologies in the section. The altered/oxidized shales are nongenerative with respect to hydrocarbon generation.

Chemical Geology↗

USGS1996

Mechanisms for chelator stimulation of microbial Fe(III) -oxide reduction

The mechanisms by which nitrilotriacetic acid (NTA) stimulated Fe(III) reduction in sediments from a petroleum-contaminated aquifer were investigated in order to gain insight into how added Fe(III) chelators stimulate the activity of hydrocarbon-degrading, Fe(III)-reducing microorganisms in these sediments, and how naturally occurring Fe(III) chelators might promote Fe(III) reduction in aquatic sediments. NTA solubilized Fe(III) from the aquifer sediments. NTA stimulation of microbial Fe(III) reduction did not appear to be the result of making calcium, magnesium, potassium, or trace metals more available to the microorganisms. Stimulation of Fe(III) reduction could not be attributed to NTA serving as a source of carbon or fixed nitrogen for Fe(III)-reducing bacteria as NTA was not degraded in the sediments. Studies with the Fe(III)-reducing microorganism, Geobacter metallireducens, and pure Fe(III)-oxide forms, demonstrated that NTA stimulated the reduction of a variety of Fe(III) forms, including highly crystalline Fe(III)-oxides such as goethite and hematite. The results suggest that NTA solubilization of insoluble Fe(III)-oxide is an important mechanism for the stimulation of Fe(III) reduction by NTA in aquifer sediments.

Chemical Geology↗

USGS1996

Weathering rates as a function of flow through an alpine soil

The effect of flow on release rates of solutes from soil in a 39-m2 alpine catchment in the Colorado Rockies was measured during the summers of 1990-1994. Flow rates through the soil were varied by augmenting natural rainfall with deionized irrigation water. Daily water inputs averaged between 96 and 216 1 day-1 during the five field seasons, and mean discharge (inputs minus evapotranspiration) varied from 35 to 175 1 day-1. Volume-weighted mean concentrations of base cations and silica decreased only moderately in response to the increased water inputs. Input fluxes of solutes in precipitation were similar in each of the study seasons, but output fluxes of base cations and silica in surface outflow increased substantially in conjunction with the average water input rate for the season. Weathering rates calculated from the chemical fluxes increased substantially in response to increases in water input rates. The increases appear to be largely attributable to enhanced transport of solutes from the soil matrix under high flow conditions. At high flow, physical flushing of micropores presumably occurs to a greater extent than during low-flow periods because of greater soil wetness and higher hydrologic head. Increased flushing would also cause an increased rate of diffusion of solutes from microcracks in mineral surfaces and constricted pore spaces in response to an increased concentration gradient between those regions and adjacent areas in the soil matrix. Another consequence of the increased flushing that occurs during periods of high flow is that concentrations throughout the soil matrix tend to be lower, which might increase chemical weathering rates of some silicate minerals such as microcline, which are relatively close to saturation. Decreased Si concentrations under high-flow conditions appear to promote dissolution of amorphous aluminosilicates or desorption of Si from mineral surfaces, buffering Si concentrations in the soil solutions. Thus, both physical transport of solutes and subsequent chemical effects appear to be responsible for the positive relation observed between fluxes of weathering products and water input rates.

Chemical Geology↗

USGS1996

The effect of iron content and dissolved O 2 on dissolution rates of clinopyroxene at pH 5.8 and 25°C: Preliminary results

Dissolution experiments using augite (Mg 0.87 Ca 0.85 Fe 0.19 Na 0.09 Al 0.03 Si 2 O 6 ) and diopside (Mg 0.91 Ca 0.93 Fe 0.07 Na 0.03 Al 0.03 Si 2 O 6 ) were conducted in flow-through reactors (5-ml/h flow rate). A pH of 5.8 was maintained by bubbling pure CO 2 through a solution of 0.01 M KHCO 3 at 25°C. Two experiments were run for each pyroxene type. In one experiment dissolved O 2 concentration in reactors was 0.6 (±0.1) ppm and in the second dissolved O 2 was 1.5 (±0.1) ppm. After 60 days, augite dissolution rates (based on Si release) were approximately three times greater in the 1.5 ppm. dissolved O 2 experiments than in the sealed experiments. In contrast, diopside dissolution rates were independent of dissolved O 2 concentrations. Preliminary results from the augite experiments suggest that dissolution rate is directly related to oxidation of iron. This effect was not observed in experiments performed on iron-poor diopside. Additionally, dissolution rates of diopside were much slower than those of augite, again suggesting a relationship between Fe content, Fe oxidation and dissolution rates.

Chemical Geology↗

USGS1997

Fe-Ca-phosphate, Fe-silicate, and Mn-oxide minerals in concretions from the Monterey Formation

Concentrically zoned phosphatic-enriched concretions were collected at three sites from the Monterey Formation. The following minerals were identified: vivianite, lipscombite, rockbridgeite, leucophosphite, mitridatite, carbonate fluorapatite, nontronite, todorokite, and barite. The mineralogy of the concretions was slightly different at each of the three collection sites. None of the concretions contains all of the minerals, but the spatial distribution of minerals in individual concretions, overlapping mineralogies between different concretions, and the geochemical properties of the separate minerals suggest a paragenesis represented by the above order. Eh increased from the precipitation of vivianite to that of rockbridgeite/lipscombite. The precipitation of leucophosphite, then mitridatite, carbonate fluorapatite and todorokite/Fe-oxide indicates increasing pH. Concretion growth culminated with the precipitation of todorokite, a Mn oxide, and minor amounts of barite along microfractures. Conspicuously absent are Fe-sulfide and Mn-phosphate minerals. The concretions are hosted by finely laminated diatomite. The laminations exhibit little to no deformation around the concretions, requiring that the concretions formed after compaction. We interpret this sediment feature and the paragenesis as recording the evolving pore-water chemistry as the formation was uplifted into the fresh-ground-water zone.

Chemical Geology↗

USGS1997

Beryllium geochemistry in soils: Evaluation of 10Be/9Be ratios in authigenic minerals as a basis for age models

Soils contain a diverse and complex set of chemicals and minerals. Being an 'open system', both in the chemical and nuclear sense, soils have defied quantitative nuclear dating. However, based on the published studies of the cosmogenic atmospheric 10Be in soils, its relatively long half-life (1.5 Ma), and the fact that 10Be gets quickly incorporated in most soil minerals, this radionuclide appears to be potentially the most useful for soil dating. We therefore studied the natural variations in the specific activities of 10Be with respect to the isotope 9Be in mineral phases in eight profiles of diverse soils from temperate to tropical climatic regimes and evaluated the implications of the data for determining the time of formation of soil minerals, following an earlier suggestion [Lal et al., 1991. Development of cosmogenic nuclear methods for the study of soil erosion and formation rates. Current Sci. 61, 636-639.]. We find that the 10Be/9Be ratios in both bulk soils and in the authigenic mineral phases are confined within a narrower range than in 10Be concentrations. Also, the highest 10Be/9Be ratios in authigenic minerals are observed at the soil-rock interface as predicted by the model. We present model 10Be/9Be ages of the B-horizon and the corresponding soil formation rates for several soil profiles. The present study demonstrates that the 10Be/9Be ratios in the authigenic phases, e.g. clay and Fe-hydroxides, can indeed be used for obtaining useful model ages for soils younger than 10-15 Ma. However, the present work has to be pushed considerably further, to take into account more realistic age models in which, for instance, downward transport of 10Be and clays, and in-situ dissolution of clay minerals at depths, altering the 10Be/9Be ratios of the acidic solutions, are included. We show that in the case of younger soils (< 1 Ma) studied here, their 10Be inventories and 10Be/9Be ratios have been significantly disturbed possibly by mixing with transported soils. ?? 1997 Elsevier Science B.V.

Chemical Geology↗

USGS1997

Using δ 87 Sr values to identify sources of salinity to a freshwater aquifer, Greater Aneth Oil Field, Utah, USA

Salinity increases in water from the freshwater Navajo aquifer in the Aneth area have been documented in recent years. Previous studies during the 1980s in the Aneth area suggested that brines associated with oil production and their subsequent re-injection were the probable source of salinity in the Navajo aquifer. Differences in the delta strontium-87 (δ 87 Sr) composition of ground-water samples from southeastern Utah were used to determine if oil-field brine or water from the upper Paleozoic aquifer is a plausible source of salinity to the Navajo aquifer. The δ 87 Sr values of the oil-field brine samples (mean = −0.95%, range = −1.06 to −0.79%, n = 5) are substantially more negative than the values in water samples from wells completed in the Navajo aquifer (mean = 0.73, range = −0.85 to 2.02%, n = 48), indicating that oil-field brine is not a source of salinity. The δ 87 Sr values in water samples from wells completed in the upper Paleozoic aquifer (mean = 0.801% range = 0.34 to 1.10%, n = 4) are similar to the mean isotopic composition of the more saline water from the Navajo aquifer. The δ 87 Sr values in water from the Navajo aquifer confirm that two distinct flow areas are present. Mixing models using the δ 87 Sr values and Sr concentrations of non-saline water from the Navajo aquifer and saline water from the upper Paleozoic aquifer indicate that water from the upper Paleozoic aquifer is a plausible source of saline water to the Navajo aquifer. Most Navajo aquifer wells that contain water with a δ 87 Sr signature similar to water from the upper Paleozoic aquifer are located within or adjacent to an area where the hydraulic gradient is favorable for upward movement of water from the upper Paleozoic aquifer into the Navajo aquifer.

Chemical Geology↗