A 17-Year Record of Environmental Tracers in Spring Discharge,Shenandoah National Park,Virginia, USA: Use of Climatic Data and Environmental Conditions to Interpret Discharge,Dissolved Solutes,and Tracer Concentrations

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.     

Investigation of young water inflow in karst aquifers using SF6–CFC–3H/He–85Kr–39Ar and stable isotope components

Karst aquifers are known for their wide distribution of water transfer velocities. From this observation, a multiple geochemical tracer approach seems to be particularly well suited to provide a significant assessment of groundwater flows, but the choice of adapted tracers is essential. In this study, several common tracers in karst aquifers such as physicochemical parameters, major ions, stable isotopes, and δ¹³C to more specific tracers such as dating tracers – ¹⁴C, ³H, ³H–³He, CFC-12, SF₆ and ⁸⁵Kr, and ³⁹Ar – were used, in a fractured karstic carbonated aquifer located in Burgundy (France). The information carried by each tracer and the best sampling strategy are compared on the basis of geochemical monitoring done during several recharge events and over longer time periods (months to years).This study’s results demonstrate that at the seasonal and recharge event time scale, the variability of concentrations is low for most tracers due to the broad spectrum of groundwater mixings. The tracers used traditionally for the study of karst aquifers, i.e., physicochemical parameters and major ions, efficiently describe hydrological processes such as the direct and differed recharge, but require being monitored at short time steps during recharge events to be maximized. From stable isotopes, tritium, and Cl⁻ contents, the proportion of the fast direct recharge by the largest porosity was estimated using a binary mixing model. The use of tracers such as CFC-12, SF₆, and ⁸⁵Kr in karst aquifers provides additional information, notably an estimation of apparent age, but they require good preliminary knowledge of the karst system to interpret the results suitably. The CFC-12 and SF₆ methods efficiently determine the apparent age of baseflow, but it is preferable to sample the groundwater during the recharge event. Furthermore, these methods are based on different assumptions such as regional enrichment in atmospheric SF₆, excess air, and flow models among others. ⁸⁵Kr and ³⁹Ar concentrations can potentially provide a more direct estimation of groundwater residence time. Conversely, the ³H–³He method is inefficient in the karst aquifer for dating due to ³He degassing.     

Diffuse soil gas emissions of gaseous elemental mercury (GEM) from hydrothermal-volcanic systems: An innovative approach by using the static closed-chamber method

This study was aimed to test a new methodological approach to carry out measurements of gaseous elemental mercury (GEM) diffusively emitted from soils in hydrothermal-volcanic environments. This method was based on the use of a static closed-chamber (SCC) in combination with a Lumex^® RA-915M analyzer that provides GEM measurements in a wide range of concentrations (from 2 to 50,000 ng m⁻³). Gas samples were collected at fixed time intervals from the SCC positioned on the ground (time-series samples). The Lumex^® inlet port was equipped with a three-way Teflon valve allowing the free entrance of air through a carbon trap, in order to: (i) prevent disturbance to the Lumex^® operative flow rate (10 L min⁻¹) during the injection of the gas samples from the SCC and (ii) minimize the instability of the baseline signal induced by possible variations of GEM concentrations in air. In the lab, known amounts of GEM, pipetted from a vessel containing an Hg-saturated air in equilibrium with liquid mercury at 27 °C, were injected in the Lumex^® via the modified inlet port to construct a calibration curve. The latter was used to calculate the amount of GEM in the SCC (K_SCC) from the corresponding GEM concentrations measured by the Lumex^® analyzer. The K_SCC values of the time-series samples were proportionally increasing with the GEM fluxes (ϕGEM), thus ϕGEM values were computed according to the following equation: ϕGEM = (dK_SCC/dt)/A, where A is the basal area of the SCC and dt is the time interval of the time-series sampling. Up to 214 ϕGEM measurements were carried out at Solfatara crater (Campi Flegrei, southern Italy), a hydrothermally altered tuff cone characterized by an anomalous diffuse soil emission of GEM-rich geogenic gases. The measured ϕGEM values varied up to 4 orders of magnitude, from 1,296, corresponding to the sensitivity of the method at the selected sampling time interval (1 min), to 1,957,500 ng m⁻² day⁻¹, and were consistent with those recently measured in this crater using a different method. In the field, 10 replicates were carried out in 5 selected sites, allowing to demonstrate that the proposed method has a high reproducibility (RDS < 4%). The ϕGEM and ϕCO₂ values, the latter being measured in the same 214 sites by using the accumulation chamber method, showed a low correlation, although both gases were originated from the same deep source. This suggests that GEM and CO₂ soil fluxes are differently affected by environmental parameters, such as soil humidity and temperature, which have a strong effect on the release of GEM from the soil, whereas they do not play a significant role in the diffuse degassing of CO₂. The measured fluxes were used to compute the CO₂ and GEM total outputs (402 and 5.41 × 10⁻⁶ t day⁻¹, respectively) from the study area (92,000 m²) and to construct contour maps showing the spatial distribution of the ϕCO₂ and ϕGEM values. By modifying the geometry of SCC and the time interval of the sampling series, the proposed method can be applied to the measurements of GEM soil fluxes in other geological systems and man-made environments.     

An SF<Subscript>6</Subscript> Tracer Study of the Flow Dynamics in the Stockton Deep Water Ship Channel: Implications for Dissolved Oxygen Dynamics

A sulfur hexafluoride (SF₆) tracer release experiment was conducted in the Stockton Deep Water Ship Channel (DWSC) to quantify mixing and transport rates. SF₆ was injected in the San Joaquin River upstream of the DWSC and mapped for 8 days. From the temporal change in SF₆ distributions, the longitudinal dispersion coefficient (K _x ) was determined to be 32.7 ± 3.6 m² s⁻¹ and the net velocity was 1.75 ± 0.03 km day⁻¹. Based on the decrease in SF₆ inventory during the experiment, the pulsed residence time for waters in the DWSC was estimated at ∼17 days. Within the DWSC from Stockton downstream to Turner Cut, dissolved oxygen concentrations maintained a steady state value of 4 mg l⁻¹. These values are below water quality objectives for the time of year. The low flow rates observed in the DWSC and the inability of oxygen-rich waters from downstream to mix into the DWSC upstream of Turner Cut contribute to the low dissolved oxygen concentration.     

Sources of nitrate contamination and age of water in large karstic springs of Florida

In response to concerns about the steady increase in nitrate concentrations over the past several decades in many of Floridas first magnitude spring waters (discharge 2.8 m³/s), multiple isotopic and other chemical tracers were analyzed in water samples from 12 large springs to assess sources and timescales of nitrate contamination. Nitrate-N concentrations in spring waters ranged from 0.50 to 4.2 mg/L, and ¹⁵N values of nitrate in spring waters ranged from 2.6 to 7.9 per mil. Most ¹⁵N values were below 6 per mil indicating that inorganic fertilizers were the dominant source of nitrogen in these waters. Apparent ages of groundwater discharging from springs ranged from 5 to about 35 years, based on multi-tracer analyses (CFC-12, CFC-113, SF₆, ³H/³He) and a piston flow assumption; however, apparent tracer ages generally were not concordant. The most reliable spring-water ages appear to be based on tritium and ³He data, because concentrations of CFCs and SF₆ in several spring waters were much higher than would be expected from equilibration with modern atmospheric concentrations. Data for all tracers were most consistent with output curves for exponential and binary mixing models that represent mixtures of water in the Upper Floridan aquifer recharged since the early 1960s. Given that groundwater transit times are on the order of decades and are related to the prolonged input of nitrogen from multiple sources to the aquifer, nitrate could persist in groundwater that flows toward springs for several decades due to slow transport of solutes through the aquifer matrix.     

Tracing groundwater with low-level detections of halogenated VOCs in a fractured carbonate-rock aquifer,Leetown Science Center,West Virginia,USA

Measurements of low-level concentrations of halogenated volatile organic compounds (VOCs) and estimates of groundwater age interpreted from ³H/³He and SF₆ data have led to an improved understanding of groundwater flow, water sources, and transit times in a karstic, fractured, carbonate-rock aquifer at the Leetown Science Center (LSC), West Virginia. The sum of the concentrations of a set of 16 predominant halogenated VOCs (TDVOC) determined by gas chromatography with electron-capture detector (GC–ECD) exceeded that possible for air–water equilibrium in 34 of the 47 samples (median TDVOC of 24,800 pg kg⁻¹), indicating that nearly all the water sampled in the vicinity of the LSC has been affected by addition of halogenated VOCs from non-atmospheric source(s). Leakage from a landfill that was closed and sealed nearly 20 a prior to sampling was recognized and traced to areas east of the LSC using low-level detection of tetrachloroethene (PCE), methyl chloride (MeCl), methyl chloroform (MC), dichlorodifluoromethane (CFC-12), and cis-1,2-dichloroethene (cis-1,2-DCE). Chloroform (CHLF) was the predominant VOC in water from domestic wells surrounding the LSC, and was elevated in groundwater in and near the Fish Health Laboratory at the LSC, where a leak of chlorinated water occurred prior to 2006. The low-level concentrations of halogenated VOCs did not exceed human or aquatic-life health criteria, and were useful in providing an awareness of the intrinsic susceptibility of the fractured karstic groundwater system at the LSC to non-atmospheric anthropogenic inputs. The ³H/³He groundwater ages of spring discharge from the carbonate rocks showed transient behavior, with ages averaging about 2 a in 2004 following a wet climatic period (2003–2004), and ages in the range of 4–7 a in periods of more average precipitation (2008–2009). The SF₆ and CFC-12 data indicate older water (model ages of 10s of years or more) in the low-permeability shale of the Martinsburg Formation located to the west of the LSC. A two-a record of specific conductance, water temperature, and discharge recorded at 30-min intervals demonstrated an approximately 3-month lag in discharge at Gray Spring. The low groundwater ages of waters from the carbonate rocks support rapid advective transport of contaminants from the LSC vicinity, yet the nearly ubiquitous occurrence of low-level concentrations of halogenated VOCs at the LSC suggests the presence of long-term persistent sources, such as seepage from the closed and sealed landfill, infiltration of VOCs that may persist locally in the epikarst, exchange with low-permeability zones in fractured rock, and upward leakage of older water that may contain elevated concentrations of halogenated VOCs from earlier land use activities.     

Evidence for crustal degassing of CF4 and SF6 in Mojave Desert groundwaters

Dissolved tetrafluoromethane (CF₄) and sulfur hexafluoride (SF₆) concentrations were measured in groundwater samples from the Eastern Morongo Basin (EMB) and Mojave River Basin (MRB) located in the southern Mojave Desert, California. Both CF₄ and SF₆ are supersaturated with respect to equilibrium with the preindustrial atmosphere at the recharge temperatures and elevations of the Mojave Desert. These observations provide the first in situ evidence for a flux of CF₄ from the lithosphere. A gradual basin-wide enhancement in dissolved CF₄ and SF₆ concentrations with groundwater age is consistent with release of these gases during weathering of the surrounding granitic alluvium. Dissolved CF₄ and SF₆ concentrations in these groundwaters also contain a deeper crustal component associated with a lithospheric flux entering the EMB and MRB through the underlying basement. The crustal flux of CF₄, but not of SF₆, is enhanced in the vicinity of local active fault systems due to release of crustal fluids during episodic fracture events driven by local tectonic activity. When fluxes of CF₄ and SF₆ into Mojave Desert groundwaters are extrapolated to the global scale they are consistent, within large uncertainties, with the fluxes required to sustain the preindustrial atmospheric abundances of CF₄ and SF₆.     

Post-drilling destabilization of temperature profile in borehole Yaxcopoil-1, Mexico

As part of the International Continental Scientific Drilling Program (ICDP), the 1.5-km-deep borehole Yaxcopoil-1, located in the Chixculub meteor impact structure in Mexico, has undergone further study after drilling operations ceased. Temperature logs were repeated ten times at intervals 0.3–0.8, 15, 24 and 34 months after borehole shut-in. The logs bear a distinct signature of transient heat transfer by groundwater flow manifested by a gradual distortion of the linear temperature profile when a cold wave of 0.8–1.6°C amplitude was detected propagating downward from 145 to 312 m at a rate of 4–6 m/month. To understand the nature of this moving anomaly, a 20-day monitoring of the cold wave was carried out at a depth of 307 m that showed further cooling of 0.6°C during the first 16 days of the passage followed by temperature stabilisation. As an explanation of this unusual phenomenon, a theory is proposed, whereby the drilling mud has accumulated within the overlying and cooler highly porous and permeable karstic rocks during the drilling and migrates downward. The observed migration rate suggests a permeability higher than 10^?11 m². This indicates a high vulnerability to contamination of the only freshwater aquifer in the Yucatan region.     

Use and application of CFC-11,CFC-12,CFC-113 and SF_6 as environmental tracers of groundwater residence time:A review

Groundwater residence time is a fundamental property of groundwater to understand important hydrogeological issues,such as deriving sustainable abstraction volumes,or,the evolution of groundwater quality.The anthropogenic trace gases chlorofluorocarbons(CFC-11,CFC-12 and CFC-113)and sulphur hexafluoride(SF_6)are ideal in this regard because they have been released globally at known rates and become dissolved in groundwater following Henry's Law,integrating over large spatial(global)and temporal(decades)scales.The CFCs and SF_6 are able to date groundwater up to～100 years old with the caveat of certain simplifying assumptions.However,the inversion of environmental tracer concentrations(CFCs and SF_6)to derive groundwater age rests on the accurate determination of groundwater recharge parameters,namely temperature,elevation,salinity and excess air,in addition to resolving the potential for contamination,degradation and unsaturated zone effects.This review explores the fundamentals of CFC-11,CFC-12,CFC-113 and SF_6 as environmental tracers of groundwater age and recommends complementary techniques throughout.Once this relatively simple and inexpensive technique has been used to determine initial concentrations at the recharge zone,setting the groundwater dating'clock' to zero,this review then explores the meaning of groundwater'age' in relation to measured environmental tracer concentrations.It is shown that the CFCs and SF_6 may be applied to a wide-range of hydrogeological problems and suggests that environmental tracers are particularly powerful tools when integrated with numerical flow and transport models.     

Do we have enough pieces of the jigsaw to integrate CO2 fluxes in the coastal ocean?

Annually integrated air-water CO₂ flux data in 44 coastal environments were compiled from literature. Data were gathered in 8 major ecosystems (inner estuaries, outer estuaries, whole estuarine systems, mangroves, salt marshes, coral reefs, upwelling systems, and open continental shelves), and up-scaled in the first attempt to integrate air-water CO₂ fluxes over the coastal ocean (26×10⁶ km²), taking into account its geographical and ecological diversity. Air-water CO₂ fluxes were then up-scaled in global ocean (362×10⁶ km²) using the present estimates for the coastal ocean and those from Takahashi et al. (2002) for the open ocean (336×10⁶ km²). If estuaries and salt marshes are not taken into consideration in the up-scaling, the coastal ocean behaves as a sink for atmospheric CO₂(−1.17 mol C m⁻² yr⁻¹) and the uptake of atmospheric CO₂ by the global ocean increases by 24% (−1.93 versus −1.56 Pg C yr⁻¹). The inclusion of the coastal ocean increases the estimates of CO₂ uptake by the global ocean by 57% for high latitude areas (−0.44 versus −0.28 Pg C yr⁻¹) and by 15% for temperate latitude areas (−2.36 versus −2.06 Pg C yr⁻¹) At subtropical and tropical latitudes, the contribution from the coastal ocean increases the CO₂ emission to the atmosphere from the global oceam by 13% (0.87 versus 0.77 Pg C yr⁻¹). If estuaries and salt marshes are taken into consideration in the upscaling, the coastal ocean behaves as a source for atmospheric CO₂ (0.38 mol C m⁻² yr⁻¹) and the uptake of atmospheric CO₂ from the global ocean decreases by 12% (−1.44 versus −1.56 Pg C yr⁻¹) At high and subtropical and tropical latitudes, the coastal ocean behaves as a source for atmospheric CO₂ but at temperate latitudes, it still behaves as a moderate CO₂ sink. A rigorous up-scaling of air-water CO₂ fluxes in the coastal ocean is hampered by the poorly constrained estimate of the surface area of inner estuaries. The present estimates clearly indicate the significance of this biogeochemically, highly active region of the biosphere in the global CO₂ cycle.     

Evaluation of Jordanian zeolite tuff as a controlled slow-release fertilizer for NH4 +

 The exchange and release properties of the natural phillipsite tuff from the Aritain area in Jordan were evaluated by studying the exchange properties of this natural zeolite in the NH₄ ⁺–Na⁺ system. Exchange isotherms at 18, 35, and 50  °C showed that phillipsite exchanged NH₄ ⁺ preferably over Na⁺ at all temperatures. However, the selectivity coefficient for NH₄ ⁺ decreased with decreasing temperature. The release of NH₄ ⁺ from phillipsite saturated with ammonium sulfate took place in two stages characterized by different SO₄ ^2– : NH₄ ⁺ ratios. Aritain phillipsite from NE Jordan could be processed and used as NH₄ ⁺ slow-release fertilizers. The use of NH₄ ⁺-phillipsite tuff offers an option to the widely used soluble NH₄-fertilizers in agciculture to avoid environmental problems associated with nitrogen contamination of surface water and groundwater. Received: 19 December 1996 · Accepted: 13 May 1997     

The practicalities of using CFCs and SF6 for groundwater dating and tracing

Knowledge of groundwater residence time is important in understanding key issues in the evolution of water quality, whether this occurs due to water–rock interaction or simply by mixing or contamination. The build-up in the atmosphere of the trace gases chlorofluorocarbons (CFCs) and sulphur hexafluoride (SF₆) from the middle of the last century offers a convenient way of dating waters up to ∼60 a old. The gases are well-mixed in the atmosphere so their input functions are not area-specific as is the case with ³H. While any one of these trace gases can in principle provide a groundwater age, when two or more are measured on water samples the potential exists to distinguish between different modes of flow including piston flow, exponential flow and simple end-member mixing. As with all groundwater dating methods, caveats apply. Factors such as recharge temperature and elevation must be reasonably well-constrained. Primarily for SF₆, the phenomenon of ‘excess air’ also requires consideration. Primarily for the CFCs, local sources of contamination need to be considered, as do redox conditions. For both SF₆ and the CFCs, the nature and thickness of the unsaturated zone need to be factored into residence time calculations. However, as an inexpensive dating method, the trace gases can be applied to a wide range of groundwater problems where traditional age indicators might once have been used more sparingly. Examples include tracing flowlines, detecting small modern inputs in ‘old’ waters, and pollution risk assessment. In the future, with the main CFCs already declining in the atmosphere, new anthropogenic trace gases are likely to take their place.     

High precision analysis of all four stable isotopes of sulfur (32S, 33S, 34S and 36S) at nanomole levels using a laser fluorination isotope-ratio-monitoring gas chromatography–mass spectrometry

The discovery of mass-independent isotope effects observed in Archean rocks, certain classes of meteorites, and atmospheric aerosols has had profound implications to our understanding of ancient and present atmospheric sulfur chemistry. We present a new technique that takes advantage of continuous He flow isotope-ratio-monitoring gas chromatography–mass spectrometry to achieve precise analysis of all four stable sulfur isotopes (³²S, ³³S, ³⁴S, and ³⁶S) at nanomole level samples. The technique involves fluorination of sulfide (silver sulfide or pyrite), and separation of product gas by gas chromatography and the removal of mass-131 interference by a liquid-nitrogen ethanol slush at − 110 °C. This technique works with an optimum sample size of 100 to 200 nmol with precision for Δ³³S and Δ³⁶S at 0.1 and 0.5‰ (2σ). Samples, as small as tens of nanomole, can be analyzed using this new method. One of the major sources of error in irm-GCMS is found to be tailing of the major ion beam (³²SF₅⁺) onto minor beams (³³SF₅⁺ and ³⁶SF₅⁺), which results in contraction of the measured δ³³S and δ³⁶S scales. This effect is corrected by measuring a series of reference sulfide samples with mass-dependent sulfur isotope compositions. This methodology increases the spatial resolution of the laser ablation in situ analysis and considerably reduces the analysis time as compared with conventional dual inlet methods.     

Extreme carbon monoxide pollution of the atmospheric boundary layer in Moscow region in the summer of 2010

Using data of spectroscopic measurements in Moscow and Moscow region and data of ecological monitoring from Ostankino TV Tower, it has been found that, in the period of intense smoke blanketing of the atmosphere in summer 2010 due to large-scale forest-peat fires on the territory of the European part of the Russian Federation, the carbon monoxide content in the boundary layer and in the atmospheric depth of Moscow region reached the extremely high level of 8 g/m², or 17 ×10¹⁸ mol/cm², and the carbon monoxide concentration in the near-ground atmospheric layer increased to 37.5 mg/m³, i.e., an unprecedentedly large value for Moscow and more than a factor of 7 larger than the one-time maximum permissible concentration for carbon monoxide MPC_ot = 5 mg/m³. In the first decade of August, when intense smoke blanketing of the Moscow region was observed, the average carbon monoxide concentrations varied in the range from approximately 3 to 7 m/g³, i.e., an order of magnitude larger than the annual average concentrations calculated according to data of measurements in 2009. The probabilities of exceeding MPC_ot and multiples of MPC_ot are calculated. Analysis of data of thermal sensing showed that an important feature of the atmospheric boundary layer over the city was a high stability of the lower atmospheric layer with the thickness of 150–200 m, and also long-term nighttime and morning inversions of the air temperature in this layer.     

Synthesis of analcime from volcanic sediments in sodium silicate solution

Analcime has been synthesized from natural rhyolitic tuff and green tuff (Miocene age) at 200° C and 20 kg/cm² with solution of Na₂SiO₃ (12%) in 50- to 260-hr runs. From the diffraction intensities, it was found that the alteration products of green tuff contained more analcime than those of rhyolitic tuff. It has been concluded that the lithological character of starting materials and the chemical behavior of reaction products are important controlling factors in analcimization.     

Saturated permeability measurements on pumice and welded-tuffaceous materials

Fluid flows in consolidated porous media of volcanic origin are being investigated to support such diverse efforts as the modeling of thermal/outgassing phenomena at Mount St. Helens and the hydrological modeling of tuffaceous rocks in support of the Department of Energy’s (DOE) Nevada Nuclear Waste Storage Investigations Project An experimental apparatus was designed and built to allow water-saturated permeabilities as low as 10⁻¹⁸ m² to be measured on cores of diameter 5 cm and length 10 cm under steady-state flow conditions. This same apparatus can also be utilized in a transient (pressure-decay) mode in order to measure permeabilities several orders of magnitude lower than the steady-state limit. Tests were conducted on samples of pumice, fractured welded tuff, and welded tuff, representing a permeability range of seven orders of magnitude Pumice was found to have a permeability of ∼3×10⁻¹² m², sufficiently high to allow the complete Darcy-to-Ergun regime to be investigated Welded (unfractured) tuff was tested in the transient mode, yielding a permeability of ∼5×10⁻¹⁹ m². Two, long-time-scale, steady-flow experiments were conducted on a core of welded tuff containing a single, through-going fracture. For the first experiment, the core was an integral cylinder containing a naturally occurring fracture. For the second experiment, the core was separated into two pieces along the existing fracture plane, then rejoined. Effects of essentially constant, as well as rapidly varied, circumferential stress were studied in both tests. Results showed core permeability to decay to 2×10⁻¹⁸ m² in both cases, independent of the initial fracture state (closed versus open). With a naturally occurring fracture, core permeability decreased by a factor of 2 over a 200-h test period. With an initially open fracture, core permeability decreased by a factor of 4 under the influence of a comparable 200-h load-time history, after 700 h of testing, core permeability was reduced by an order of magnitude from its initial level. Final effective hydraulic fracture aperture was calculated to be 10⁻⁶ m, corresponding to a calculated effective fracture permeability of 10⁻¹³ m² Fracture flow was thus estimated to account for 80% of the total flow rate through this core under final test conditions.     

Uranium-series disequilibrium in tuffs from Yucca Mountain,Nevada, as evidence of pore-fluid flow over the last million years

Samples of tuff from boreholes drilled into fault zones in the Exploratory Studies Facility (ESF) and relatively unfractured rock of the Cross Drift tunnels, at Yucca Mountain, Nevada, have been analysed by U-series methods. This work is part of a project to verify the finding of fast flow-paths through the tuff to ESF level, indicated by the presence of ‘bomb’ ³⁶Cl in pore fluids. Secular radioactive equilibrium in the U decay series, (i.e. when the radioactivity ratios ²³⁴U/²³⁸U, ²³⁰Th /²³⁴U and ²²⁶Ra/²³⁰Th all equal 1.00) might be expected if the tuff samples have not experienced radionuclide loss due to rock-water interaction occurring within the last million years. However, most fractured and unfractured samples were found to have a small deficiency of ²³⁴U (weighted mean ²³⁴U/²³⁸U=0.95±0.01) and a small excess of ²³⁰Th (weighted mean ²³⁰Th/²³⁴U 1.10±0.02). The ²²⁶Ra/²³⁰Th ratios are close to secular equilibrium (weighted mean=0.94±0.07). These data indicate that ²³⁴U has been removed from the rock samples in the last ∼350 ka, probably by pore fluids. Within the precision of the measurement, it would appear that ²²⁶Ra has not been mobilized and removed from the tuff, although there may be some localised ²²⁶Ra redistribution as suggested by a few ratio values that are significantly different from 1.0. Because both fractured and unfractured tuffs show approximately the same deficiency of ²³⁴U, this indicates that pore fluids are moving equally through fractured and unfractured rock. More importantly, fractured rock appears not to be a dominant pathway for groundwater flow (otherwise the ratio would be more strongly affected and the Th and Ra isotopic ratios would likely also show disequilibrium). Application of a simple mass-balance model suggests that surface infiltration rate is over an order of magnitude greater than the rate indicated by other infiltration models and that residence time of pore fluids at ESF level is about 400 a. Processes of U sorption, precipitation and re-solution are believed to be occurring and would account for these anomalous results but have not been included in the model. Despite the difficulties, the U-series data suggest that fractured rock, specifically the Sundance and Drill Hole Wash faults, are not preferred flow paths for groundwater flowing through the Topopah Spring tuff and, by implication, rapid-flow, within 50 a, from the surface to the level of the ESF is improbable.     

Groundwater age,mixing and flow rates in the vicinity of large open pit mines,Pilbara region,northwestern Australia

Determining groundwater ages from environmental tracer concentrations measured on samples obtained from open bores or long-screened intervals is fraught with difficulty because the sampled water represents a variety of ages. A multi-tracer technique (Cl, ¹⁴C, ³H, CFC-11, CFC-12, CFC-113 and SF₆) was used to decipher the groundwater ages sampled from long-screened production bores in a regional aquifer around an open pit mine in the Pilbara region of northwest Australia. The changes in tracer concentrations due to continuous dewatering over 7 years (2008–2014) were examined, and the tracer methods were compared. Tracer concentrations suggest that groundwater samples are a mixture of young and old water; the former is inferred to represent localised recharge from an adjacent creek, and the latter to be diffuse recharge. An increase in ¹⁴C activity with time in wells closest to the creek suggests that dewatering of the open pit to achieve dry mining conditions has resulted in change in flow direction, so that localised recharge from the creek now forms a larger proportion of the pumped groundwater. The recharge rate prior to development, calculated from a steady-state Cl mass balance, is 6 mm/y, and is consistent with calculations based on the ¹⁴C activity. Changes in CFC-12 concentrations with time may be related to the change in water-table position relative to the depth of the well screen.     

The emerging terrestrial record of Aptian-Albian global change

The integration of terrestrial carbonate δ¹³C chemostratigraphy and radiometric dates is opening a new window into the continental paleoclimate dynamics of the major carbon cycle perturbations of the Aptian-Albian interval. Results published to date by many researchers clearly show that there was a tight temporal coupling between Aptian-Albian marine, atmospheric, and terrestrial carbon pools that now permits refined global chemostratigraphic and chronostratigraphic correlations on time scales of 10⁶ years or less. This development opens new opportunities to explore the Aptian-Albian Earth system by incorporating continental climate change dynamics in a developing global synthesis. In this paper, we present new U–Pb and U–Th/He age dates on a late Albian volcanic ash deposit in a stratigraphic section that fills a previous gap in in the terrestrial δ¹³C record. Here we also present, for the first time, coordinated δ¹³C_carbonate, δ¹⁸O_carbonate, and δ¹³C_organic data from stacked successions of paleosols in Aptian-Albian terrestrial strata of the Cedar Mountain Formation of Utah, USA. From the whole of this record, the late Aptian C10 C-isotope feature is especially noteworthy as an interval of major global change. Coordinated carbonate and organic carbon isotope data from this interval suggest that this positive carbon isotope excursion (CIE) was related to a buildup of atmospheric pCO₂ to a peak level of about 1200 ppmV over a period of several million years duration, above earlier Aptian baseline levels of about 1000 ppmV. The C10 interval was immediately preceded and followed by drawdowns in pCO₂ to levels of about 800 ppmV, and the entirety of the Aptian-Albian record from the Cedar Mountain Formation suggests a long-term fall of pCO₂ levels from about 1000 down to 600 ppmV. We suggest that the late Aptian buildup likely is related to submarine volcanic activity in the Kerguelen Large Igneous Province in the southern Indian Ocean. Strata of the C-10 C-isotope feature are also associated with sedimentary evidence for an aridification event in the leeward rain shadow of the Sevier Mountains. On the basis of diagenetic studies of dolomitized calcretes in this C10 interval, we calculate that the precipitation-evaporation deficit intensified to the extent that 35–50% of the shallow groundwater system was lost to the atmosphere through evaporation.     

Groundwater exploration and drilling problems encountered in basaltic and granitic terrain of Nanded district,Maharashtra

The Central Ground Water Board (CGWB) constructed 72 bore wells down to a targeted depth of 208 m in Nanded district, Maharashtra which is mainly underlain by hard rocks, namely basalts and granites. The yield of these bore wells varies from 0.10 litres/second (l/s) to 25 l/s and depth of weathering varies from less than 1 m to 24 meters below ground level (m bgl). The shallowest and the deepest aquifer zones are encountered at 7 and 172 m bgl respectively and majority of the productive aquifer zones are encountered within 100 meter (m) depth. Most productive zones are fractured basalts, fractured and weathered granites and 31 % of the zones are encountered within 25 m, 36 % within 25–50 m, 24 % within 50–100 m, 8 % within 100–150 m and less than 1 % within 150–173 m depth ranges. Out of the three major sets of lineaments, the NE-SW trending lineaments are more productive, and a maximum of five fracture zones are encountered in all. Surface geophysical studies (profiling) reveal that wherever the ratio between high resistivity and low resistivity is high, the discharge is high, and where the ratio is low the discharge is low. The depth to water level in these bore wells are in the range of 1.5–47.5 m bgl (below ground level). The transmissivity (T) and Storativity (S) values of 21 wells range from 3 to 593 m²/day and 6.5 × 10^?6 to 7.32 × 10^?2 respectively. The groundwater from the area is mostly of Ca-Na-HCO₃-Cl, Ca-Na-HCO₃, Ca-HCO₃-Cl, Na-HCO₃, Na-HCO₃-Cl, Na-Cl, Ca-HCO₃ types in the descending order of dominance and a few are found to be unsuitable for drinking. At a few sites, drilling down to the targeted depth of 200 m couldn’t be completed due to highly fractured nature of formations, hydraulic backpressure, occurrences of saturated intertrappean beds and high magnetic nature of formations.