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At least 343 records · Page 19Linked to original sources
USGS2023

High-precision ID-TIMS U-Pb geochronology of perovskite (CaTiO3) from the Ice River Complex, southeastern British Columbia

Uranium‑lead perovskite in situ geochronology has become a cornerstone technique for determining the emplacement timing of alkaline, ultrapotassic, and silica-undersaturated igneous rocks, kimberlites, and carbonatites. Accurate in situ dates are dependent on the availability of matrix matched mineral reference materials which themselves are chemically well characterized and dated accurately to the highest possible precision. When dating perovskite to high precision, such as by isotope dilution thermal ionization mass spectrometry (ID-TIMS), appropriately accounting and correcting for the quantity and isotopic composition of Pb incorporated into the crystal upon crystallization (Pb i ) is a large source of uncertainty and potential inaccuracy. Unfortunately, although ultra-high precision perovskite dates are attainable with modern mass spectrometry techniques, the accuracy of applied Pb i compositions, which can be a considerable percentage of total Pb in a crystal, has not kept pace, resulting in percent level inaccuracy on precisely measured isotopic ratios. In an effort to characterize the age and initial Pb isotopic composition of a readily available, relatively pure perovskite endmember (93–98%) which will be useful as a matrix matched age reference material for in situ U-Pb geochronology, we date crystals isolated from three samples from the Ice River Complex (samples 81IR6, I90.3, and I92.30) by ID-TIMS and evaluate their suitability as known-age reference materials. We directly determine the isotopic composition of Pb i in each sample by ID-TIMS measurement of cogenetic low 238 U/ 204 Pb (μ < 500) phlogopite, apatite, and/or clinopyroxene. Using these initial common Pb isotopic compositions, which are significantly more radiogenic than those predicted by age appropriate Pb evolution models, we obtain ultra-precise weighted-mean 206 Pb/ 238 U perovskite dates of 355.83 ± 0.14, 355.04 ± 0.15, and 357.34 ± 0.12 Ma on the three Ice River samples, respectively. These dates are consistent with the relative emplacement ages previously established for units in the Ice River layered ultramafic series based on field relationships. They also demonstrate the feasibility of attaining accurate perovskite dates in instances when maximum precision is critical by utilizing ID-TIMS analysis of cogenetic low uranium phases for direct measurement of Pb i .

British Columbia↗
USGS2025

Characterizing sedimentary organic carbon in a hydrothermal spreading center, the Escanaba Trough

Sediments in critical marine mineral environments are of wide importance due to their preservation of both marine minerals and organic carbon (OC) stocks. However, OC storage and cycling is often overlooked in mineral system studies. This work characterizes sedimentary OC within the Escanaba Trough, a hydrothermal sulfide system off the coast of northern California. By utilizing ROV-based push coring, we collected sediments near and far from high temperature, low temperature, and inactive vents. We applied a multipronged organic geochemical approach, measuring bulk sediment, OC fractions of varying labilities, and biomarkers to tease apart the storage, source, and cycling of OC within this complex system. In contrast to past work indicating a primarily terrestrial source to deeper, Pleistocene sediments, our results suggest a primarily marine source in surface sediments at least 50 m away from active venting. Near active venting, we see evidence of locally produced chemosynthetic OC in addition to the background marine source. This chemosynthetic OC appears to be rapidly remineralized and supports more complex deep-sea food webs compared to hemipelagic sites. Still, the greatest contribution of labile OC was observed at inactive vent sites, which we suggest is due to hydrothermal fluid alteration of more labile OC at actively venting sites. Depending on fluid temperature, hydrothermally altered OC is either preserved in the sediments as petroleum or migrated with fluid flow. Considering inactive sites are those most likely to be targeted by potential mining, we suggest additional studies could verify if these results apply at other sedimented seafloor massive sulfide systems.

California↗
USGS2025

The impact of burial diagenesis on soil-formed minerals in paleosols using stable isotopes of phyllosilicates and carbonate clumped isotopes

To understand the effects of burial diagenesis on the stable isotope geochemistry of soil-formed clay and carbonate minerals in paleosols, samples were collected from seven cores, spanning middle- to upper-Pennsylvanian strata of the Illinois Basin, with varied maximum burial depths of 1–3 km. Mixed-layer illite-smectite and kaolinite mixtures give δ 2 H and δ 18 O values of −83 ‰ to −36 ‰ and 11.9 ‰ to 21.1 ‰ (VSMOW), respectively. After carbonates were screened petrographically for diagenetic textures using transmitted light and cathodoluminescence, measured clumped isotope Δ 47 values range from 0.504 to 0.563 ‰ (I-CDES). Resulting mineral formation temperatures for phyllosilicate mineral mixtures are 28 to 66 °C (mean = 47 °C), whereas T(Δ 47 ) estimates for calcites are 36 to 61 °C (mean = 45 °C). Calculated δ 18 O water values from which phyllosilicate minerals and calcites precipitated under isotopic equilibrium ranges from −7.1 to −1.2 ‰ and − 1.4 to +4.9 ‰, respectively. Closed and open-system phyllosilicate-fluid exchange modeling indicates that phyllosilicate alteration occurred in the presence of a low temperature brine or meteoric water and is interpreted to occur in a layer-by-layer illitization transformation. Due to the lack of diagenetic textures and positively correlated T(Δ 47 ) and δ 18 O water , calcites are interpreted to have undergone solid-state bond reordering. Despite low to moderate temperatures (<125 °C) and varying depths of shallow burial (1–3 km), solid-state transformation of phyllosilicates and calcites indicates paleosols had prolonged exposure to burial conditions which has implications for the use of paleosol minerals for paleoenvironmental reconstructions.

Illinois, Indiana, Kentucky↗
USGS2026

Prolonged cooling of andesitic-dacitic lava flows produces optimal groundmass material for 40Ar/39Ar dating

Organizing the eruptive histories and petrogenetic models that underpin hazard assessments at active volcanoes typically requires high-precision ages for late Pleistocene to Holocene lava flows. In this study, features of an existing 40Ar/39Ar dataset for andesitic-dacitic rocks from Ruapehu volcano, Aotearoa New Zealand, were interrogated with new microanalytical data to identify the optimal groundmass material for age determination. To understand the behavior of K and Ar within the cooling melt of lavas during their emplacement, we examined and compared the petrological features of samples from the ice-chilled margin and interior of a lava flow. The groundmass of the rapidly cooled sample comprises non-vesicular rhyolitic glass and microlites of plagioclase, orthopyroxene, and magnetite. The sample from the flow interior has minimal amounts of groundmass glass, and interstices are instead occupied by sanidine and tridymite. Modelling supports the interpretation that sanidine crystallized as a stable groundmass phase during slow cooling of degassed melt in the interior zones of lavas that were insulated behind their glassy margins. Our evaluation of the age data shows that sanidine contributed high yields of radiogenic argon during step-heating experiments for samples collected from lava interiors, which enabled high-precision 40Ar/39Ar ages to be determined. Using Ruapehu as an example of an arc volcano affected by lava-ice interaction, we provide a basic field guide for identifying lava flows that contain groundmass sanidine at the expense of glass. Target outcrops also offer opportunities for reconstructing geomagnetic dynamics and volcano–climate relationships during the Pleistocene and Holocene.

Ruapehu volcano↗
USGS2026

Utilization of multiple geochronology techniques to constrain the age of laterization and mineralization of the world-class Mount Weld rare earth element deposit, Western Australia

Pervasive chemical weathering on stable cratons may form thick regoliths and elemental enrichment, but constraining the age of regolith formation is challenging. In this study we utilize multiple geochronological techniques on different minerals from the world-class Mount Weld rare earth element (REE) deposit, formed by lateritic weathering of a carbonatite, to constrain the age of formation and provide insight into landscape evolution. The oldest dates, ca. 100 to 38 Ma, are from Lu-Hf dating of churchite [HREE(PO 4 )·2(H 2 O)], a heavy REE phosphate mineral. Growth bands on individual minerals show a younging outwards. 40 Ar/ 39 Ar geochronology of cryptomelane [K(Mn 4+ ,Mn 2+ )₈O₁₆] yielded dates from ca. 40 to 27 Ma. Similarly, (U-Th)/He geochronology of goethite [FeO(OH)] yielded dates ranging from ca. 45 to 19 Ma. Integrating results into regional constraints, suggests 1) churchite formed by mineral saturation in a karst-like setting below the water table from ca. 100 to 40 Ma, 2) with minor uplift and erosion, cryptomelane and goethite formed at or near the water table between ca. 45 and 19 Ma, 3) after ca. 15 to 10 Ma chemical weathering within the profile had ended. Other studies document that the region experienced minimal uplift and a wet, warm climate from ca. 100 Ma to 15 Ma. These conditions and the high carbonate content of the carbonatite promote extensive chemical weathering, a deep weathering profile, and the preservation of the weathered section. This study highlights the use of multiple geochronological techniques utilizing different minerals to provide insight into how laterites form and to constrain the timing and history of the formation of this important mineral deposit.

Western Australia↗
USGS2026

Osmium isotope constraints on Mauna Loa–Kilauea magmatic connectivity, Island of Hawai‘i

The Hawaiian volcanic chain exhibits a long-recognized double track of volcanism defined by the Loa and Kea trends, which erupt chemically and isotopically distinct lavas. Mauna Loa and Kīlauea, the two most frequently active volcanoes of the Loa and Kea trends, produce distinct endmember compositions. However, historical periods of compositional convergence have prompted debate regarding a potential magmatic connection between the two adjacent volcanoes. Proposed links include a shallow edifice-level plumbing system, a common magma source at ∼40 km depth, or a deeper asthenospheric source. In the latter scenario, based on correlated Sr–Nd–Pb isotopes and trace-element systematics, a “shared” mantle source supplies melt alternately to both volcanoes on multi-decadal timescales. Here, we use Os isotopes to evaluate the proposed connections. We measured Os isotopes in eight historical Mauna Loa tholeiites along with three Kīlauea tholeiites (1832 summit eruption; Uēkahuna Bluff; 2000 Pu‘u‘ō‘ō eruption) previously identified as isotopically intermediate between Mauna Loa and Kīlauea endmembers. We found that the acidic bromide leachates of all samples yield more radiogenic 187 Os/ 188 Os than corresponding bulk residues, with the labile Os-bearing phase comprising ∼0.4–27% of bulk Os. Mauna Loa tholeiites display nearly constant 187 Os/ 188 Os over the past ∼200 years (0.134–0.136; mean = 0.1357 ± 0.0013, n = 8, 2SD), despite large variations in total [Os] ranging from ∼30 pg/g (2022 tholeiite) to ∼966 pg/g (1868 picrite). The Kīlauea 1832 sample has 187 Os/ 188 Os = 0.1302 ± 0.0008, slightly higher than the Kīlauea endmember (0.1285 ± 0.0008), whereas the Uēkahuna Bluff and Pu‘u‘ō‘ō samples exhibit more elevated ratios (0.1314 ± 0.0008 and 0.1327 ± 0.0008, respectively). We conclude that the “shared” mantle source exerts negligible control on Mauna Loa Os isotope systematics. In contrast, the Kīlauea mantle source is more heterogeneous, with contributions from small-scale recycled domains with variable time-integrated Re/Os ratios.

Hawaii↗
USGS2026

Trace element heterogeneity and crystallization history of the Plesovice zircon: Implications for its use as a U–Pb LA-ICP-MS reference material

Zircon crystals from Plešovice hyperpotassic granulite (HPG) have been widely used as a reference material for LA-ICP-MS dating. Detailed cathodoluminescence (CL) imaging and trace element analysis reveal a complex internal structure of Plešovice zircon linked to extreme chemical heterogeneity, which allows us to distinguish different zircon domains formed during its crystallization: (i) rare low-CL cores enriched in U, Nb, HREE and Y; (ii) dominant sector-zoned to oscillatory-zoned domains, and (iii) CL-bright rims poor in trace elements. Relic fine oscillatory zoned areas are chemically homogeneous, whereas coarsened and blurred areas, and CL-dark replacement domains, are heterogeneous. Based on these data we suggest a complex and protracted zircon evolution: (i) crystallization of metamorphic zircon in anatectic calc-alkaline granulite; (ii) magmatic zircon crystallization at high temperature and pressure in a dry ultrapotassic melt at presence of peritectic garnet; (iii) coupled zircon dissolution-precipitation processes triggered by percolating hydrous residual melt; and (iv) coarsening and replacement of the pre-existing zircon due to prolonged exposure to a reactive fluid/hydrous melt. New CA-ID-TIMS U Pb dates between 337.167 ± 0.080 and 337.840 ± 0.080 Ma confirm crystallization age for HPG zircon at around 337.4 Ma and suggest that previously published dates of 336.37 Ma were biased by non-mitigated lead loss. We thus confirm the U/Pb homogeneity of Plešovice reference zircon despite its chemical heterogeneity. We further discuss the implications of using the chemically extremely heterogeneous Plešovice reference zircon as primary or secondary standard for in-situ LA-ICP-MS geochronology, in particular for quantification of the chemical matrix-dependence of the relative sensitivity factor ( β ) of laser ablation.

Plešovice quarry↗
USGS2026

Release and recapture: Limited carbon mobilization in sediment adjacent to Central Atlantic Magmatic Province sills, Florida, USA

Large Igneous Provinces (LIPs) are associated with dramatic changes to the Earth system; their rapid release of carbon may initiate catastrophic climatic changes causing mass extinction. This carbon release is often associated with volcanic emissions, yet metamorphic carbon production is poorly constrained. Metamorphic carbon devolatilization occurs as intrusions interact with host sediment, potentially releasing substantial sedimentary carbon. While this process has been modeled, few studies use an observational approach. Here, we apply geochemical analysis, petrographic analysis, Raman spectroscopy, vitrinite reflectance, and thermodynamic modeling to understand carbon devolatilization in sediment adjacent to Central Atlantic Magmatic Province basaltic intrusions using two boreholes that penetrate the Florida basement. We find geochemical and petrographic evidence for CO 2 release from carbonates below a 10 m thick sill, with upward fluid transport and recapture of mobilized CO 2 at the top of the sill. Ultimately, we estimate 220 mols/m 2 to 9900 mols/m 2 of carbon were mobilized from sedimentary carbonate. Uncertainties in the extent of re‑carbonation suggest that anywhere from 0 mols/m 2 to 7100 mols/m 2 may have escaped to the surface. We find little evidence of organic carbon mobility, due partly to the increased activity of CO 2 from carbonate devolatilization. Discrepancies between measured temperatures and 1D thermal models suggest complexities in heat transport through aqueous pore fluid flow and short (hundred to thousand year) heating timescales. These results highlight that further field-based study can help clarify the roles that heating timescales, fluid flow, sediment chemistry, and other factors play in releasing and capturing carbon during LIP emplacement.

Florida↗
USGS2000

Ion exchange separation of chromium from natural water matrix for stable isotope mass spectrometric analysis

A method has been developed for separating the Cr dissolved in natural water from matrix elements and determination of its stable isotope ratios using solid-source thermal-ionization mass spectrometry (TIMS). The separation method takes advantage of the existence of the oxidized form of Cr as an oxyanion to separate it from interfering cations using anion-exchange chromatography, and of the reduced form of Cr as a positively charged ion to separate it from interfering anions such as sulfate. Subsequent processing of the separated sample eliminates residual organic material for application to a solid source filament. Ratios for 53Cr/52Cr for National Institute of Standards and Technology Standard Reference Material 979 can be measured using the silica gel-boric acid technique with a filament-to-filament standard deviation in the mean 53Cr/52Cr ratio for 50 replicates of 0.00005 or less.

Chemical Geology↗
USGS2000

Temporal variations in parameters reflecting terminal-electron-accepting processes in an aquifer contaminated with waste fuel and chlorinated solvents

A fundamental issue in aquifer biogeochemistry is the means by which solute transport, geochemical processes, and microbiological activity combine to produce spatial and temporal variations in redox zonation. In this paper, we describe the temporal variability of TEAP conditions in shallow groundwater contaminated with both waste fuel and chlorinated solvents. TEAP parameters (including methane, dissolved iron, and dissolved hydrogen) were measured to characterize the contaminant plume over a 3-year period. We observed that concentrations of TEAP parameters changed on different time scales and appear to be related, in part, to recharge events. Changes in all TEAP parameters were observed on short time scales (months), and over a longer 3-year period. The results indicate that (1) interpretations of TEAP conditions in aquifers contaminated with a variety of organic chemicals, such as those with petroleum hydrocarbons and chlorinated solvents, must consider additional hydrogen-consuming reactions (e.g., dehalogenation); (2) interpretations must consider the roles of both in situ (at the sampling point) biogeochemical and solute transport processes; and (3) determinations of microbial communities are often necessary to confirm the interpretations made from geochemical and hydrogeological measurements on these processes.

Michigan↗
USGS2001

Precise K-Ar, 40Ar/39Ar, Rb-Sr and U/Pb mineral ages from the 27.5 Ma fish canyon tuff reference standard

The accuracy of ages measured using the 40Ar/39Ar technique is affected by uncertainties in the age of radiation fluence-monitor minerals. At present, there is lack of agreement about the ages of certain minerals used as fluence monitors. The accuracy of the age of a standard may be improved if the age can be measured using different decay schemes. This has been done by measuring ages on minerals from the Oligocene Fish Canyon Tuff (FCT) using the K-Ar, 40Ar/39Ar. Rb-Sr and U/Pb methods. K-Ar and 40Ar/39Ar total fusion ages of sanidine, biotite and hornblende yielded a mean age of 27.57 ?? 0.36 Ma. The weighted mean 40Ar/39Ar plateau age of sanidine and biotite is 27.57 ?? 0.18 Ma. A biotite-feldspar Rb-Sr isochron yielded an age of 27.44 ?? 0.16 Ma. The U-Pb data for zircon are complex because of the presence of Precambrian zircons and inheritance of radiogenic Pb. Zircons with 207Pb/235U < 0.4 yielded a discordia line with a lower concordia intercept of 27.52 ?? 0.09 Ma. Evaluation of the combined data suggests that the best age for FCT is 27.51 Ma. Published by Elsevier Science B.V.

Chemical Geology↗
USGS2001

Eddy covariance measurement of CO2 flux to the atmosphere from a area of high volcanogenic emissions, Mammoth Mountain, California

Three pilot studies were performed to assess application of the eddy covariance micrometeorological method in the measurement of carbon dioxide (CO 2 ) flux of volcanic origin. The selected study area is one of high diffuse CO 2 emission on Mammoth Mountain, CA. Because terrain and source characteristics make this a complex setting for this type of measurement, added consideration was given to source area and upwind fetch. Footprint analysis suggests that the eddy covariance measurements were representative of an upwind elliptical source area (3.8×10 3 m 2 ) which can vary with mean wind direction, surface roughness, and atmospheric stability. CO 2 flux averaged 8–16 mg m −2 s −1 (0.7–1.4 kg m −2 day −1 ). Eddy covariance measurements of flux were compared with surface chamber measurements made in separate studies [Geophys. Res. Lett. 25 (1998a) 1947; EOS Trans. 79 (1998) F941.] and were found to be similar.

Chemical Geology↗
USGS2001

Elevated carbon dioxide flux at the Dixie Valley geothermal field, Nevada; relations between surface phenomena and the geothermal reservoir

In the later part of the 1990s, a large die-off of desert shrubs occurred over an approximately 1 km2 area in the northwestern section of the Dixie Valley (DV) geothermal field. This paper reports results from accumulation-chamber measurements of soil CO2 flux from locations in the dead zone and stable isotope and chemical data on fluids from fumaroles, shallow wells, and geothermal production wells within and adjacent to the dead zone. A cumulative probability plot shows three types of flux sites within the dead zone: Locations with a normal background CO2 flux (7 g m-2 day-1); moderate flux sites displaying "excess" geothermal flux; and high flux sites near young vents and fumaroles. A maximum CO2 flux of 570 g m-2 day-1 was measured at a location adjacent to a fumarole. Using statistical methods appropriate for lognormally distributed populations of data, estimates of the geothermal flux range from 7.5 t day-1 from a 0.14-km2 site near the Stillwater Fault to 0.1 t day-1 from a 0.01 -km2 location of steaming ground on the valley floor. Anomalous CO2 flux is positively correlated with shallow temperature anomalies. The anomalous flux associated with the entire dead zone area declined about 35% over a 6-month period. The decline was most notable at a hot zone located on an alluvial fan and in the SG located on the valley floor. Gas geochemistry indicates that older established fumaroles along the Stillwater Fault and a 2-year-old vent in the lower section of the dead zone discharge a mixture of geothermal gases and air or gases from air-saturated meteoric water (ASMW). Stable isotope data indicate that steam from the smaller fumaroles is produced by ??? 100??C boiling of these mixed fluids and reservoir fluid. Steam from the Senator fumarole (SF) and from shallow wells penetrating the dead zone are probably derived by 140??C to 160??C boiling of reservoir fluid. Carbon-13 isotope data suggest that the reservoir CO2 is produced mainly by thermal decarbonation of hydrothermal calcite in veins that cut reservoir rocks. Formation of the dead zone is linked to the reservoir pressure decline caused by continuous reservoir drawdown from 1986 to present. These reservoir changes have restricted flow and induced boiling in a subsurface hydrothermal outflow plume extending from the Stillwater Fault southeast toward the DV floor. We estimate that maximum CO2 flux in the upflow zone along the Stillwater Fault in 1998 was roughly seven to eight times greater than the pre-production flux in 1986. The eventual decline in CO2 flux reflects the drying out of the outflow plume. Published by Elsevier Science B.V.

Chemical Geology↗
USGS2001

Soil efflux and total emission rates of magmatic CO2 at the horseshoe lake tree kill, mammoth mountain, California, 1995-1999

We report the results of eight soil CO2 efflux surveys by the closed circulation chamber method at the Horseshoe Lake tree kill (HLTK) - the largest tree kill on Mammoth Mountain. The surveys were undertaken from 1995 to 1999 to constrain total HLTK CO2 emissions and to evaluate occasional efflux surveys as a surveillance tool for the tree kills. HLTK effluxes range from 1 to > 10,000 g m -2 day -1 (grams CO2 per square meter per day); they are not normally distributed. Station efflux rates can vary by 7-35% during the course of the 8- to 16-h surveys. Disturbance of the upper 2 cm of ground surface causes effluxes to almost double. Semivariograms of efflux spatial covariance fit exponential or spherical models; they lack nugget effects. Efflux contour maps and total CO2 emission rates based on exponential, spherical, and linear kriging models of survey data are nearly identical; similar results are also obtained with triangulation models, suggesting that the kriging models are not seriously distorted by the lack of normal efflux distributions. In addition, model estimates of total CO2 emission rates are relatively insensitive to the measurement precision of the efflux rates and to the efflux value used to separate magmatic from forest soil sources of CO2. Surveys since 1997 indicate that, contrary to earlier speculations, a termination of elevated CO2 emissions at the HLTK is unlikely anytime soon. The HLTK CO2 efflux anomaly fluctuated greatly in size and intensity throughout the 1995-1999 surveys but maintained a N-S elongation, presumably reflecting fault control of CO2 transport from depth. Total CO2 emission rates also fluctuated greatly, ranging from 46 to 136 t day-1 (metric tons CO2 per day) and averaging 93 t day-1. The large inter-survey variations are caused primarily by external (meteorological) processes operating on time scales of hours to days. The externally caused variations can mask significant changes occurring at depth; a striking example is the masking of a degassing event generated at depth and detected by a soil gas sensor network in September 1997 while an efflux survey was in progress. Thus, occasional efflux surveys are not an altogether effective surveillance tool for the HLTK, and making them effective by greatly increasing their frequency may not be practical. Published by Elsevier Science B.V.

Chemical Geology↗
USGS2001

Radiocarbon studies of plant leaves and rings from mammoth mountain, CA: A long-term record of magmatic CO2 release

Evaluation of 14C in tree rings provides a measure of the flux of magmatic CO2 from Mammoth Mountain both before and after 1994 when copious diffuse emissions were first discovered and linked to tree kill. We analyzed the annual rings of trees with two main purposes: (1) to track changes in the magnitude of magmatic CO2 emission over time, and (2) to determine the onset of magmatic CO2 emission at numerous sites on Mammoth Mountain. The onset of CO2 emission at different areas of tree kill was determined to be in 1990, closely following the seismic events of 1989. At Horseshoe Lake (HSL), CO2 emission was found to have peaked in 1991 and to have subsequently declined by a factor of two through 1998. The tree-ring data also show that emissions of magmatic carbon from cold springs below the tree-kill areas occurred well before 1989. Trees located on the margins of the kill areas or otherwise away from zones of maximum gas discharge were found to be better integrators of magmatic CO2 emission than those located in the center of tree kills. Although quantitative extrapolations from our data to a flux history will require that a relationship be established between 14C depletion in tree rings and average annual magmatic CO2 flux, the pattern of 14C depletion in tree rings is likely to be the most reliable indicator of the long-term changes in the magnitude of CO2 release from Mammoth Mountain. ?? 2001 Elsevier Science B.V. All rights reserved.

Chemical Geology↗
USGS2001

Chlorine-36, bromide, and the origin of spring water

Natural ratios of chlorine-36 (36Cl) to stable chlorine (i.e., 36Cl/Cl ?? 10-15) vary in shallow groundwater of the United States from about 50 in coastal areas to about 1400 in the northern Rocky Mountains. Ratios lower than these indicate the presence of chloride (Cl-) that has been isolated from the atmosphere for hundreds of thousands of years, if not longer. Higher ratios, which can exceed 5000, usually originate from fallout from testing thermonuclear devices in the western Pacific in the 1950s. Natural mass ratios of chloride to bromide (Cl-/Br-) in precipitation vary in the United States from about 250 in coastal areas to about 50 in the north-central states. Lower ratios may suggest contamination from human sources. Higher ratios, which may exceed 2000, commonly reflect the dissolution of halite. Seawater has a Cl-/Br- ratio of 290. Both 36Cl and Cl-/Br- ratios have been measured in 21 samples of spring water collected from springs in 10 different states. Brackish water from Saratoga Springs area in New York has low values for both 36Cl and Cl-/Br- ratios. This indicates that a large component of the water has a very deep origin. Brackish water from Alexander Springs in Florida has a low 36Cl ratio but a high Cl-/Br- ratio similar to seawater. This suggests the addition of ancient seawater that may be trapped in the aquifer. Big Spring in Iowa discharges water with a very high Cl-/Br- ratio but a moderate 36Cl ratio. The high ratio of Cl-/Br- may be produced by dissolution of road salt or agricultural chemicals. Of the 21 springs sampled, only 10 appeared to have potable water not significantly affected by human activity. Chlorine-36 from testing of nuclear devices is still being flushed out of four of the spring systems that were sampled. Thus, more than 45 years have passed since 36Cl was introduced into the aquifers feeding the springs and the systems, as yet, have not been purged. Published by Elsevier Science B.V.

Chemical Geology↗
USGS2001

Groundwater residence times in Shenandoah National Park, Blue Ridge Mountains, Virginia, USA: A multi-tracer approach

Chemical and isotopic properties of water discharging from springs and wells in Shenandoah National Park (SNP), near the crest of the Blue Ridge Mountains, VA, USA were monitored to obtain information on groundwater residence times. Investigated time scales included seasonal (wet season, April, 1996; dry season, August–September, 1997), monthly (March through September, 1999) and hourly (30-min interval recording of specific conductance and temperature, March, 1999 through February, 2000). Multiple environmental tracers, including tritium/helium-3 ( 3 H/ 3 He), chlorofluorocarbons (CFCs), sulfur hexafluoride (SF 6 ), sulfur-35 ( 35 S), and stable isotopes ( δ 18 O and δ 2 H) of water, were used to estimate the residence times of shallow groundwater discharging from 34 springs and 15 wells. The most reliable ages of water from springs appear to be based on SF 6 and 3 H/ 3 He, with most ages in the range of 0–3 years. This range is consistent with apparent ages estimated from concentrations of CFCs; however, CFC-based ages have large uncertainties owing to the post-1995 leveling-off of the CFC atmospheric growth curves. Somewhat higher apparent ages are indicated by 35 S (>1.5 years) and seasonal variation of δ 18 O (mean residence time of 5 years) for spring discharge. The higher ages indicated by the 35 S and δ 18 O data reflect travel times through the unsaturated zone and, in the case of 35 S, possible sorption and exchange of S with soils or biomass. In springs sampled in April, 1996, apparent ages derived from the 3 H/ 3 He data (median age of 0.2 years) are lower than those obtained from SF 6 (median age of 4.3 years), and in contrast to median ages from 3 H/ 3 He (0.3 years) and SF 6 (0.7 years) obtained during the late summer dry season of 1997. Monthly samples from 1999 at four springs in SNP had SF 6 apparent ages of only 1.2 to 2.5±0.8 years, and were consistent with the 1997 SF 6 data. Water from springs has low excess air (0–1 cm 3 kg −1 ) and N 2 –Ar temperatures that vary seasonally. Concentrations of He and Ne in excess of solubility equilibrium indicate that the dissolved gases are not fractionated. The seasonal variations in N 2 –Ar temperatures suggest shallow, seasonal recharge, and the excess He and Ne data suggest waters mostly confined to gas exchange in the shallow, mountain-slope, water-table spring systems. Water from wells in the fractured rock contains up to 8 cm 3 kg −1 of excess air with ages in the range of 0–25 years. Transient responses in specific conductance and temperature were observed in spring discharge within several hours of large precipitation events in September, 1999; both parameters increased initially, then decreased to values below pre-storm base-flow values. The groundwater residence times indicate that flushing rates of mobile atmospheric constituents through groundwater to streams draining the higher elevations in SNP average less than 3 years in base-flow conditions.

Virginia↗
USGS2001

Determination of the sources of nitrate contamination in karst springs using isotopic and chemical indicators

The sources of nitrate (NO-3) in groundwater of the shallow karst aquifer in southwestern Illinois' sinkhole plain were investigated using chemical and isotopic techniques. The groundwater in this aquifer is an important source of potable water for about half of the residents of the sinkhole plain area. Previous work has shown that groundwater from approximately 18% of the wells in the sinkhole plain has NO-3 concentrations in excess of the USEPA's drinking water standard of 10 mg N/1. Relative to background levels, the NO-3 concentrations in water from 52% of the wells, and probably all of the springs in the study area, are anomalously high, suggesting that sources other than naturally occurring soil organic matter have contributed additional NO-3 to groundwater in the shallow karst aquifer. This information, and the dominance of agriculture in the study area, suggest that agrichemical contributions may be significant. To test this hypothesis, water samples from 10 relatively large karst springs were collected during four different seasons and analyzed for inorganic constituents, dissolved organic carbon, atrazine, and ??15N and ??18O of the NO-3 ions. The isotopic data were most definitive and suggested that the sources of NO-3 in spring water are dominated by N-fertilizer with some possible influence of atmospheric NO-3 and, to a much lesser extent, human and/or animal waste. Differences in the isotopic composition of NO-3 and some of the chemical characteristics were observed during the four consecutive seasons in which spring water samples were collected. Isotopic values for ??15N and ??18O of the NO-3 ranged from 3.2??? to 19.1??? and from 7.2??? to 18.7???, respectively. The trend of ??15N and ??18O data for NO-3 also indicated that a significant degree of denitrification is occurring in the shallow karst hydrologic system (within the soil zone, the epikarst and the shallow karst aquifer) prior to discharging to springs. ?? 2001 Elsevier Science B.V. All rights reserved.

Chemical Geology↗