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A 17-year record (1995–2012) of a suite of environmental tracer concentrations in discharge from 34 springs located along the crest of the Blue Ridge Mountains in Shenandoah National Park (SNP), Virginia, USA, reveals patterns and trends that can be related to climatic and environmental conditions. These data include a 12-year time series of monthly sampling at five springs, with measurements of temperature, specific conductance, pH, and discharge recorded at 30-min intervals. The monthly measurements include age tracers (CFC-11, CFC-12, CFC-113, CFC-13, SF6, and SF5CF3), dissolved gases (N2, O2, Ar, CO2, and CH4), stable isotopes of water, and major and trace inorganic constituents. The chlorofluorocarbon (CFC) and sulfur hexafluoride (SF6) concentrations (in pptv) in spring discharge closely follow the concurrent monthly measurements of their atmospheric mixing ratios measured at the Air Monitoring Station at Big Meadows, SNP, indicating waters 0–3 years in age. A 2-year (2001–2003) record of unsaturated zone air displayed seasonal deviations from North American Air of ±10 % for CFC-11 and CFC-113, with excess CFC-11 and CFC-113 in peak summer and depletion in peak winter. The pattern in unsaturated zone soil CFCs is a function of gas solubility in soil water and seasonal unsaturated zone temperatures. Using the increase in the SF6 atmospheric mixing ratio, the apparent (piston flow) SF6 age of the water varied seasonally between about 0 (modern) in January and up to 3 years in July–August. The SF6 concentration and concentrations of dissolved solutes (SiO2, Ca2+, Mg2+, Na+, Cl?, and HCO3 ?) in spring discharge demonstrate a fraction of recent recharge following large precipitation events. The output of solutes in the discharge of springs minus the input from atmospheric deposition per hectare of watershed area (mol ha?1 a?1) were approximately twofold greater in watersheds draining the regolith of Catoctin metabasalts than that of granitic gneisses and granitoid crystalline rocks. The stable isotopic composition of water in spring discharge broadly correlates with the Oceanic Niño Index. Below normal precipitation and enriched stable isotopic composition were observed during El Niño years. 相似文献
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A highly reproducible seeded growth technique was used to study calcite crystallization from calcium bicarbonate solutions at 25°C and fixed carbon dioxide partial pressures between 0.03 and 0.3 atm. The results are not consistent with empirical crystallization models that have successfully described calcite growth at low PCO2 (< 10?3 atm). Good agreement was found between observed crystallization rates and those calculated from the calcite dissolution rate law and mechanism proposed by Plummer et al. (1978). 相似文献
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Influence of fracture anisotropy on ground water ages and chemistry,Valley and Ridge province,Pennsylvania 总被引：5，自引：0，他引：5
Model ground water ages based on chlorofluorocarbons (CFCs) and tritium/helium-3 (3 H/3 He) data were obtained from two arrays of nested piezometers located on the north limb of an anticline in fractured sedimentary rocks in the Valley and Ridge geologic province of Pennsylvania. The fracture geometry of the gently east plunging fold is very regular and consists predominately of south dipping to subhorizontal to north dipping bedding-plane parting and east striking, steeply dipping axial-plane spaced cleavage. In the area of the piezometer arrays, which trend north-south on the north limb of the fold, north dipping bedding-plane parting is a more dominant fracture set than is steeply south dipping axial-plane cleavage. The dating of ground water from the piezometer arrays reveals that ground water traveling along paths parallel to the dip direction of bedding-plane parting has younger 3 H/3 He and CFC model ages, or a greater component of young water, than does ground water traveling along paths opposite to the dip direction. In predominantly unmixed samples there is a strong positive correlation between age of the young fraction of water and dissolved sodium concentration. The travel times inferred from the model ages are significantly longer than those previously calculated by a ground water flow model, which assumed isotropically fractured layers parallel to topography. A revised model factors in the directional anisotropy to produce longer travel times. Ground water travel times in the watershed therefore appear to be more influenced by anisotropic fracture geometry than previously realized. This could have significant implications for ground water models in other areas underlain by similarly tilted or folded sedimentary rock, such as elsewhere in the Valley and Ridge or the early Mesozoic basins. 相似文献
4.
L. N. Plummer E. Busenberg S. Drenkard P. Schlosser B. Ekwurzel R. Weppernig J. B. McConnell R. L. Michel 《Applied Geochemistry》1998,13(8):1017-1043
Tritium/helium-3 (3H/3He) and chlorofluorocarbon (CFCs, CFC–11, CFC–12, CFC–113) data are used to date the young fraction in groundwater mixtures from a karstic limestone aquifer near Valdosta, Georgia, where regional paleowater in the Upper Floridan aquifer receives recharge from two young sources—the flow of Withlacoochee River water through sinkholes in the river bed, and leakage of infiltration water through post-Eocene semi-confining beds above the Upper Floridan aquifer. In dating the young fraction of mixtures using CFCs, it is necessary to reconstruct the CFC concentration that was in the young fraction prior to mixing. The 3H/3He age is independent of the extent of dilution with older (3H-free and 3Hetrit-free) water. The groundwater mixtures are designated as Type-1 for mixtures of regional paleowater and regional infiltration water and Type-2 for mixtures containing more than approximately 4% of river water. The fractions of regional paleowater, regional infiltration water, and Withlacoochee River water in the groundwater mixtures were determined from Cl− and δ18O data for water from the Upper Floridan aquifer at Valdosta, Georgia.The chlorofluorocarbons CFC–11 and CFC–113 are removed by microbial degradation and/or sorption processes in most anaerobic (Type-2) groundwater at Valdosta, but are present in some aerobic Type-1 water. CFC–12 persists in both SO4-reducing and methanogenic water. The very low detection limits for CFCs (approximately 0.3 pg kg−1) permitted CFC–11 and CFC–12 dating of the fraction of regional infiltration water in Type-1 mixtures, and CFC-12 dating of the river-water fraction in Type-2 mixtures. Overall, approximately 50% of the 85 water samples obtained from the Upper Floridan aquifer have CFC–12-based ages of the young fraction that are consistent with the 3H concentration of the groundwater. Because of uncertainties associated with very low 3H and 3He content in dilute mixtures, 3H/3He dating is limited to the river-water fraction in Type-2 mixtures containing more than about 10% river water. Of the 41 water samples measured for 3H/3He dating, dilution of 3H and low 3He concentration limited 3H/3He dating to 16 mixtures in which 3H/3He ages are defined with errors ranging from ±2 to ±7.5 a (1 σ). After correction for dilution with (assumed) CFC-free regional infiltration water and regional paleowater in the Upper Floridan aquifer, adjusted CFC–12 ages agree with 3H/3He ages within 5 a or less in 7 of the 9 co-dated Type-2 mixtures.Tritium data and dating based on both CFC–11 and CFC–12 in Type-1 mixtures indicate that travel times of infiltration water through the overlying Post-Eocene semi-confining beds exceed 35 a. The CFC and 3H/3He dating indicate that the river fraction in most groundwater entered the groundwater reservoir in the past 20 to 30 a. Few domestic and municipal supply wells sampled intercept water younger than 5 a. Calculated velocities of river water in the Upper Floridan aquifer downgradient of the sinkhole area range from 0.4 to 8.2 m/d. Radiocarbon data indicate that ages of the regional paleowater are on the 10 000-a time scale. An average lag time of approximately 10 to 25 a is determined for discharge of groundwater from the surficial and intermediate aquifers above the Upper Floridan aquifer to the Withlacoochee River. 相似文献
5.
Significant amounts of SO42?, Na+, and OH? are incorporated in marine biogenic calcites. Biogenic high Mg-calcites average about 1 mole percent SO42?. Aragonites and most biogenic low Mg-calcites contain significant amounts of Na+, but very low concentrations of SO42?. The SO42? content of non-biogenic calcites and aragonites investigated was below 100 ppm. The presence of Na+ and SO42? increases the unit cell size of calcites. The solid-solutions show a solubility minimum at about 0.5 mole percent SO42? beyond which the solubility rapidly increases. The solubility product of calcites containing 3 mole percent SO42? is the same as that of aragonite. Na+ appears to have very little effect on the solubility product of calcites. The amounts of Na+ and SO42? incorporated in calcites vary as a function of the rate of crystal growth. The variation of the distribution coefficient () of SO42? in calcite at 25.0°C and 0.50 molal NaCl is described by the equation where and are constants equal to and , respectively, and is the rate of crystal growth of calcite in mg·min?1·g?1 of seed. The data on Na+ are consistent with the hypothesis that a significant amount of Na+ occupies interstitial positions in the calcite structure. The distribution of Na+ follows a Freundlich isotherm and not the Berthelot-Nernst distribution law. The numerical value of the Na+ distribution coefficient in calcite is probably dependent on the number of defects in the calcite structure. The Na+ contents of calcites are not very accurate indicators of environmental salinities. 相似文献
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Calcite grew continuously for 500,000 years on the submerged walls of an open fault plane (Devils Hole) in southern Nevada, U.S.A. at rates of 0.3 to 1.3 mm/ka, but ceased growing approximately 60,000 years ago, even though the fault plane remained open and was continuously submerged. The maximum initial in-situ growth rate on pre-weighed crystals of Iceland spar placed in Devils Hole (calcite saturation index, SI, is 0.16 to 0.21 at 33.7 °C) for growth periods of 0.75 to 4.5 years was 0.22 mm/ka. Calcite growth on seed crystals slowed or ceased following initial contact with Devils Hole groundwater. Growth rates measured in synthetic Ca-HCO3 solutions at 34 °C, CO2 partial pressures of 0.101, 0.0156 (similar to Devils Hole groundwater) and 0.00102 atm, and SI values of 0.2 to 1.9 were nearly independent of PCO
2, decreased with decreasing saturation state, and extrapolated through the historical Devils Hole rate. The results show that calcite growth rate is highly sensitive to saturation state near equilibrium. A calcite crystal retrieved from Devils Hole, and used without further treatment of its surface, grew in synthetic Devils Hole groundwater when the saturation index was raised nearly 10-fold that of Devils Hole water, but the rate was only 1/4 that of fresh laboratory crystals that had not contacted Devils Hole water. Apparently, inhibiting processes that halted calcite growth in Devils Hole 60,000 years ago continue today. 相似文献
8.
L.N. Plummer E. Busenberg J.B. McConnell S. Drenkard P. Schlosser R.L. Michel 《Applied Geochemistry》1998,13(8):995-1015
The quality of water in the Upper Floridan aquifer near Valdosta, Georgia is affected locally by discharge of Withlacoochee River water through sinkholes in the river bed. Data on transient tracers and other dissolved substances, including Cl−, 3H, tritiogenic helium-3 (3He), chlorofluorocarbons (CFC-11, CFC-12, CFC-113), organic C (DOC), O2 (DO), H2S, CH4, δ18O, δD, and 14C were investigated as tracers of Withlacoochee River water in the Upper Floridan aquifer. The concentrations of all tracers were affected by dilution and mixing. Dissolved Cl−, δ18O, δD, CFC-12, and the quantity (3H+3He) are stable in water from the Upper Floridan aquifer, whereas DOC, DO, H2S, CH4, 14C, CFC-11, and CFC-113 are affected by microbial degradation and other geochemical processes occurring within the aquifer. Groundwater mixing fractions were determined by using dissolved Cl− and δ18O data, recognizing 3 end-member water types in the groundwater mixtures: (1) Withlacoochee River water (δ18O=−2.5±0.3‰, Cl−=12.2±2 mg/l), (2) regional infiltration water (δ18O=−4.2±0.1‰, Cl−=2.3±0.1 mg/l), and (3) regional paleowater resident in the Upper Floridan aquifer (δ18O=−3.4±0.1‰, Cl−=2.6±0.1 mg/l) (uncertainties are ±1σ). Error simulation procedures were used to define uncertainties in mixing fractions. Fractions of river water in groundwater range from 0 to 72% and average 10%. The influence of river-water discharge on the quality of water in the Upper Floridan aquifer was traced from the sinkhole area on the Withlacoochee River 25 km SE in the direction of regional groundwater flow. Infiltration of water is most significant to the N and NW of Valdosta, but becomes negligible to the S and SE in the direction of general thickening of post-Eocene confining beds overlying the Upper Floridan aquifer. 相似文献
9.
Eurybiades Busenberg 《Geochimica et cosmochimica acta》1978,42(11):1679-1686
Chemical analyses of 300 solutions produced by the artificial weathering of eight different feldspars in fourteen experiments of up to 1200hr duration were used to study the evolution of water during weathering. The range of pH was between 4 and 5·5. Within 4 hr of dissolution, the activity of Al was controlled by the pH and the solubility of microcrystalline gibbsite. After 100 hr of dissolution, the pH and microcrystalline halloysite controlled the activities of Al and silicic acid in all of the solutions.Microcrystalline halloysite was the only phase identified in the weathering of plagioclases in distilled water and 1 atm CO2 partial pressure. Montmorillonites, halloysite and other clay minerals were produced from oligoclase in aqueous solutions containing high initial concentrations of Ca. Mg, K and SiO2.The experimentally determined log solubility product of microcrystalline gibbsite was ?32·78 ± 0·04 and log for the hydrolysis of microcrystalline halloysite was 11.58 ± 0·05. The results suggest that very poorly crystalline metastable phases may control the initial compositions of some waters in contact with rocks containing feldspar minerals. 相似文献
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