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Geochemistry and the understanding of ground-water systems
Geochemistry has contributed significantly to the understanding of ground-water systems over the last 50 years. Historic advances include development of the hydrochemical facies concept, application of equilibrium theory, investigation of redox processes, and radiocarbon dating. Other hydrochemical concepts, tools, and techniques have helped elucidate mechanisms of flow and transport in ground-water systems, and have helped unlock an archive of paleoenvironmental information. Hydrochemical and isotopic information can be used to interpret the origin and mode of ground-water recharge, refine estimates of time scales of recharge and ground-water flow, decipher reactive processes, provide paleohydrological information, and calibrate ground-water flow models. Progress needs to be made in obtaining representative samples. Improvements are needed in the interpretation of the information obtained, and in the construction and interpretation of numerical models utilizing hydrochemical data. The best approach will ensure an optimized iterative process between field data collection and analysis, interpretation, and the application of forward, inverse, and statistical modeling tools. Advances are anticipated from microbiological investigations, the characterization of natural organics, isotopic fingerprinting, applications of dissolved gas measurements, and the fields of reaction kinetics and coupled processes. A thermodynamic perspective is offered that could facilitate the comparison and understanding of the multiple physical, chemical, and biological processes affecting ground-water systems.
Contact zone permeability at intrusion boundaries: New results from hydraulic testing and geophysical logging in the Newark Rift Basin, New York, USA
Hydraulic tests and geophysical logging performed in the Palisades sill and the underlying sedimentary rocks in the NE part of the Newark Rift Basin, New York, USA, confirm that the particular transmissive zones are localized within the dolerite-sedimentary rock contact zone and within a narrow interval below this contact zone that is characterized by the occurrence of small layers of chilled dolerite. Transmissivity values determined from fluid injection, aquifer testing, and flowmeter measurements generally fall in the range of 8.1E-08 to 9.95E-06 m 2 /s and correspond to various scales of investigation. The analysis of acoustic and optical BHTV images reveals two primary fracture sets within the dolerite and the sedimentary rocks—subhorizontal fractures, intersected by subvertical ones. Despite being highly fractured either with subhorizontal, subvertical or both fracture populations, the dolerite above and the sedimentary rocks below the contact zone and the zone with the layers of chilled dolerite are significantly less conductive. The distribution of the particular conductive intervals is not a function of the two dominant fracture populations or their density but rather of the intrusion path of the sill. The intrusion caused thermal fracturing and cracking of both formations, resulting in higher permeability along the contact zone.
Mixing of shallow and deep groundwater as indicated by the chemistry and age of karstic springs
Large karstic springs in east-central Florida, USA were studied using multi-tracer and geochemical modeling techniques to better understand groundwater flow paths and mixing of shallow and deep groundwater. Spring water types included Ca-HCO3 (six), Na-Cl (four), and mixed (one). The evolution of water chemistry for Ca-HCO3 spring waters was modeled by reactions of rainwater with soil organic matter, calcite, and dolomite under oxic conditions. The Na-Cl and mixed-type springs were modeled by reactions of either rainwater or Upper Floridan aquifer water with soil organic matter, calcite, and dolomite under oxic conditions and mixed with varying proportions of saline Lower Floridan aquifer water, which represented 4-53% of the total spring discharge. Multiple-tracer data-chlorofluorocarbon CFC-113, tritium (3H), helium-3 (3Hetrit), sulfur hexafluoride (SF6) - for four Ca-HCO3 spring waters were consistent with binary mixing curves representing water recharged during 1980 or 1990 mixing with an older (recharged before 1940) tracer-free component. Young-water mixing fractions ranged from 0.3 to 0.7. Tracer concentration data for two Na-Cl spring waters appear to be consistent with binary mixtures of 1990 water with older water recharged in 1965 or 1975. Nitrate-N concentrations are inversely related to apparent ages of spring waters, which indicated that elevated nitrate-N concentrations were likely contributed from recent recharge. ?? Springer-Verlag 2006.
Quantification of karst aquifer discharge components during storm events through end-member mixing analysis using natural chemistry and stable isotopes as tracers
Karst aquifer components that contribute to the discharge of a water supply well in the Classical Karst (Kras) region (Italy/Slovenia) were quantitatively estimated during storm events. Results show that water released from storage within the epikarst may comprise as much as two-thirds of conduit flow in a karst aquifer following rainfall. Principal components analysis (PCA) and end-member mixing analysis (EMMA) were performed using major ion chemistry and the stable isotopes of water (??18O, ??2H) and of dissolved inorganic carbon (??13CDIC) to estimate mixing proportions among three sources: (1) allogenic river recharge, (2) autogenic recharge, and (3) an anthropogenic component stored within the epikarst. The sinking river most influences the chemical composition of the water-supply well under low-flow conditions; however, this proportion changes rapidly during recharge events. Autogenic recharge water, released from shallow storage in the epikarst, displaces the river water and is observed at the well within hours after the onset of precipitation. The autogenic recharge end member is the second largest component of the well chemistry, and its contribution increases with higher flow. An anthropogenic component derived from epikarstic storage also impacts the well under conditions of elevated hydraulic head, accounting for the majority of the chemical response at the well during the wettest conditions. ?? Springer-Verlag 2006.
Relations between climatic variability and hydrologic time series from four alluvial basins across the southwestern United States
Hydrologic time series of groundwater levels, streamflow, precipitation, and tree-ring indices from four alluvial basins in the southwestern United States were spectrally analyzed, and then frequency components were reconstructed to isolate variability due to climatic variations on four time scales. Reconstructed components (RCs), from each time series, were compared to climatic indices like the Pacific Decadal Oscillation (PDO), North American Monsoon (NAM), and El Nin??o-Southern Oscillation (ENSO), to reveal that as much as 80% of RC variation can be correlated with climate variations on corresponding time scales. In most cases, the hydrologic RCs lag behind the climate indices by 1-36 months. In all four basins, PDO-like components were the largest contributors to cyclic hydrologic variability. Generally, California time series have more variation associated with PDO and ENSO than the Arizona series, and Arizona basins have more variation associated with NAM. ENSO cycles were present in all four basins but were the largest relative contributors in southeastern Arizona. Groundwater levels show a wide range of climate responses that can be correlated from well to well in the various basins, with climate responses found in unconfined and confined aquifers from pumping centers to mountain fronts. ?? Springer-Verlag 2006.
Testing of stack-unit/aquifer sensitivity analysis using contaminant plume distribution in the subsurface of Savannah River Site, South Carolina, USA
Published information on the correlation and field-testing of the technique of stack-unit/aquifer sensitivity mapping with documented subsurface contaminant plumes is rare. The inherent characteristic of stack-unit mapping, which makes it a superior technique to other analyses that amalgamate data, is the ability to deconstruct the sensitivity analysis on a unit-by-unit basis. An aquifer sensitivity map, delineating the relative sensitivity of the Crouch Branch aquifer of the Administrative/Manufacturing Area (A/M) at the Savannah River Site (SRS) in South Carolina, USA, incorporates six hydrostratigraphic units, surface soil units, and relevant hydrologic data. When this sensitivity map is compared with the distribution of the contaminant tetrachloroethylene (PCE), PCE is present within the Crouch Branch aquifer within an area classified as highly sensitive, even though the PCE was primarily released on the ground surface within areas classified with low aquifer sensitivity. This phenomenon is explained through analysis of the aquifer sensitivity map, the groundwater potentiometric surface maps, and the plume distributions within the area on a unit-by- unit basis. The results of this correlation show how the paths of the PCE plume are influenced by both the geology and the groundwater flow. ?? Springer-Verlag 2006.
The application of satellite differential SAR interferometry-derived ground displacements in hydrogeology
The application of satellite differential synthetic aperture radar (SAR) interferometry, principally coherent (InSAR) and to a lesser extent, persistent-scatterer (PSI) techniques to hydrogeologic studies has improved capabilities to map, monitor, analyze, and simulate groundwater flow, aquifer-system compaction and land subsidence. A number of investigations over the previous decade show how the spatially detailed images of ground displacements measured with InSAR have advanced hydrogeologic understanding, especially when a time series of images is used in conjunction with histories of changes in water levels and management practices. Important advances include: (1) identifying structural or lithostratigraphic boundaries (e.g. faults or transitional facies) of groundwater flow and deformation; (2) defining the material and hydraulic heterogeneity of deforming aquifer-systems; (3) estimating system properties (e.g. storage coefficients and hydraulic conductivities); and (4) constraining numerical models of groundwater flow, aquifer-system compaction, and land subsidence. As a component of an integrated approach to hydrogeologic monitoring and characterization of unconsolidated alluvial groundwater basins differential SAR interferometry contributes unique information that can facilitate improved management of groundwater resources. Future satellite SAR missions specifically designed for differential interferometry will enhance these contributions. ?? Springer-Verlag 2006.
Multiple-method estimation of recharge rates at diverse locations in the North Carolina Coastal Plain, USA
Recharge rates determined at diverse study sites in a shallow, unconfined aquifer differed from one another depending on the analytical method used and on each method's applicability and limitations. Total recharge was quantified with saturated-zone methods using water-table fluctuations at seven sites in North Carolina, USA and using groundwater-age dating at three of the seven sites; at two of the sites, potential recharge was quantified with an unsaturated-zone method using Darcy's law; and at five of the sites, net recharge was quantified with a stream hydrograph-separation method using streamflow-recession curves. Historical mean net recharge was 25 to 69% of the historical total recharge rates. The large disparity is attributed to groundwater losses between recharge and discharge areas, primarily by evapotranspiration and seepage to underlying aquifers. The spatial distribution of historical mean annual total recharge did not vary between landscape units, as suggested in a previous study. Similarly, total recharge did not correlate significantly with mean annual rainfall, mean annual water table depth, or the surficial soil properties of percent clay and bulk density. Total recharge did correlate significantly with the surficial soil properties of percent sand and percent silt. ?? Springer-Verlag 2007.
Effects of intraborehole flow on groundwater age distribution
Environmental tracers are used to estimate groundwater ages and travel times, but the strongly heterogeneous nature of many subsurface environments can cause mixing between waters of highly disparate ages, adding additional complexity to the age-estimation process. Mixing may be exacerbated by the presence of wells because long open intervals or long screens with openings at multiple depths can transport water and solutes rapidly over a large vertical distance. The effect of intraborehole flow on groundwater age was examined numerically using direct age transport simulation coupled with the Multi-Node Well Package of MODFLOW. Ages in a homogeneous, anisotropic aquifer reached a predevelopment steady state possessing strong depth dependence. A nonpumping multi-node well was then introduced in one of three locations within the system. In all three cases, vertical transport along the well resulted in substantial changes in age distributions within the system. After a pumping well was added near the nonpumping multi-node well, ages were further perturbed by a flow reversal in the nonpumping multi-node well. Results indicated that intraborehole flow can substantially alter groundwater ages, but the effects are highly dependent on local or regional flow conditions and may change with time.
Temporal trends in concentrations of DBCP and nitrate in groundwater in the eastern San Joaquin Valley, California, USA
Temporal monitoring of the pesticide 1,2-dibromo-3-chloropropane (DBCP) and nitrate and indicators of mean groundwater age were used to evaluate the transport and fate of agricultural chemicals in groundwater and to predict the long-term effects in the regional aquifer system in the eastern San Joaquin Valley, California. Twenty monitoring wells were installed on a transect along an approximate groundwater flow path. Concentrations of DBCP and nitrate in the wells were compared to concentrations in regional areal monitoring networks. DBCP persists at concentrations above the US Environmental Protection Agency's maximum contaminant level (MCL) at depths of nearly 40 m below the water table, more than 25 years after it was banned. Nitrate concentrations above the MCL reached depths of more than 20 m below the water table. Because of the intensive pumping and irrigation recharge, vertical flow paths are dominant. High concentrations (above MCLs) in the shallow part of the regional aquifer system will likely move deeper in the system, affecting both domestic and public-supply wells. The large fraction of old water (unaffected by agricultural chemicals) in deep monitoring wells suggests that it could take decades for concentrations to reach MCLs in deep, long-screened public-supply wells, however. ?? Springer-Verlag 2007.
Multiple-methods investigation of recharge at a humid-region fractured rock site, Pennsylvania, USA
Lysimeter-percolate and well-hydrograph analyses were combined to evaluate recharge for the Masser Recharge Site (central Pennsylvania, USA). In humid regions, aquifer recharge through an unconfined low-porosity fractured-rock aquifer can cause large magnitude water-table fluctuations over short time scales. The unsaturated hydraulic characteristics of the subsurface porous media control the magnitude and timing of these fluctuations. Data from multiple sets of lysimeters at the site show a highly seasonal pattern of percolate and exhibit variability due to both installation factors and hydraulic property heterogeneity. Individual event analysis of well hydrograph data reveals the primary influences on water-table response, namely rainfall depth, rainfall intensity, and initial water-table depth. Spatial and seasonal variability in well response is also evident. A new approach for calculating recharge from continuous water-table elevation records using a master recession curve (MRC) is demonstrated. The recharge estimated by the MRC approach when assuming a constant specific yield is seasonal to a lesser degree than the recharge estimate resulting from the lysimeter analysis. Partial reconciliation of the two recharge estimates is achieved by considering a conceptual model of flow processes in the highly-heterogeneous underlying fractured porous medium.
A simple daily soil-water balance model for estimating the spatial and temporal distribution of groundwater recharge in temperate humid areas
Quantifying the spatial and temporal distribution of natural groundwater recharge is usually a prerequisite for effective groundwater modeling and management. As flow models become increasingly utilized for management decisions, there is an increased need for simple, practical methods to delineate recharge zones and quantify recharge rates. Existing models for estimating recharge distributions are data intensive, require extensive parameterization, and take a significant investment of time in order to establish. The Wisconsin Geological and Natural History Survey (WGNHS) has developed a simple daily soil-water balance (SWB) model that uses readily available soil, land cover, topographic, and climatic data in conjunction with a geographic information system (GIS) to estimate the temporal and spatial distribution of groundwater recharge at the watershed scale for temperate humid areas. To demonstrate the methodology and the applicability and performance of the model, two case studies are presented: one for the forested Trout Lake watershed of north central Wisconsin, USA and the other for the urban-agricultural Pheasant Branch Creek watershed of south central Wisconsin, USA. Overall, the SWB model performs well and presents modelers and planners with a practical tool for providing recharge estimates for modeling and water resource planning purposes in humid areas. ?? Springer-Verlag 2007.
Origin of halite brine in the Onondaga Trough near Syracuse, New York State, USA: Modeling geochemistry and variable-density flow
Halite brine (saturation ranging from 45 to 80%) lies within glacial sediments that fill the Onondaga Trough, a bedrock valley deepened by Pleistocene glaciation near Syracuse, New York State, USA. The most concentrated brine occupies the northern end of the trough, about 10 km downgradient of the northern limit of halite beds in the Silurian Salina Group, the assumed source of salt. The chemical composition of the brine and its radiocarbon age suggest that the brine originally formed about 16,700 years ago through dissolution of halite by glacial melt water and later mixed with saline bedrock water. Two hypotheses regarding the formation of the brine pool were tested through variable-density flow simulations using SEAWAT. Simulation results supported the first hypothesis that the brine pool was derived from a source in the glacial sediments and then migrated to its current position, where it has persisted for over 16,000 years. A second hypothesis that the brine pool formed through steady accumulation of brine from upward flow of a source in the underlying bedrock was not supported by simulation results, because the simulated age distribution was much younger than the age estimated from geochemical modeling.
Characterization of the shallow groundwater system in an alpine watershed: Handcart Gulch, Colorado, USA
Water-table elevation measurements and aquifer parameter estimates are rare in alpine settings because few wells exist in these environments. Alpine groundwater systems may be a primary source of recharge to regional groundwater flow systems. Handcart Gulch is an alpine watershed in Colorado, USA comprised of highly fractured Proterozoic metamorphic and igneous rocks with wells completed to various depths. Primary study objectives include determining hydrologic properties of shallow bedrock and surficial materials, developing a watershed water budget, and testing the consistency of measured hydrologic properties and water budget by constructing a simple model incorporating groundwater and surface water for water year 2005. Water enters the study area as precipitation and exits as discharge in the trunk stream or potential recharge for the deeper aquifer. Surficial infiltration rates ranged from 0.1-6.2??0-5 m/s. Discharge was estimated at 1.28??10-3 km3. Numerical modeling analysis of single-well aquifer tests predicted lower specific storage in crystalline bedrock than in ferricrete and colluvial material (6.7??10-5-2.10??0-3 l/m). Hydraulic conductivity in crystalline bedrock was significantly lower than in colluvial and alluvial material (4.3??10-9 -2.0??10-4 m/s). Water budget results suggest that during normal precipitation and temperatures water is available to recharge the deeper groundwater flow system. ?? Springer-Verlag 2007.
Environmental tracers as indicators of karst conduits in groundwater in South Dakota, USA
Environmental tracers sampled from the carbonate Madison aquifer on the eastern flank of the Black Hills, South Dakota, USA indicated the approximate locations of four major karst conduits. Contamination issues are a major concern because these conduits are characterized by direct connections to sinking streams, high groundwater velocities, and proximity to public water supplies. Objectives of the study were to estimate approximate conduit locations and assess possible anthropogenic influences associated with conduits. Anomalies of young groundwater based on chlorofluorocarbons (CFCs), tritium, and electrical conductivity (EC) indicated fast moving, focused flow and thus the likely presence of conduits. ??18O was useful for determining sources of recharge for each conduit, and nitrate was a useful tracer for assessing flow paths for anthropogenic influences. Two of the four conduits terminate at or near a large spring complex. CFC apparent ages ranged from 15 years near conduits to >50 years in other areas. Nitrate-N concentrations >0.4 mg/L in groundwater were associated with each of the four conduits compared with concentrations ranging from <0.1 to 0.4 mg/L in other areas. These higher nitrate-N concentrations probably do not result from sinking streams but rather from other areas of infiltration. ?? Springer-Verlag 2007.
Application of environmental groundwater tracers at the Sulphur Bank Mercury Mine, California, USA
Boron, chloride, sulfate, ??D, ??18O, and 3H concentrations in surface water and groundwater samples from the Sulphur Bank Mercury Mine (SBMM), California, USA were used to examine geochemical processes and provide constraints on evaporation and groundwater flow. SBMM is an abandoned sulfur and mercury mine with an underlying hydrothermal system, adjacent to Clear Lake, California. Results for non-3H tracers (i.e., boron, chloride, sulfate, ??D, and ??18O) identify contributions from six water types at SBMM. Processes including evaporation, mixing, hydrothermal water input and possible isotopic exchange with hydrothermal gases are also discerned. Tritium data indicate that hydrothermal waters and other deep groundwaters are likely pre-bomb (before ???1952) in age while most other waters were recharged after ???1990. A boron-based steady-state reservoir model of the Herman Impoundment pit lake indicates that 71-79% of its input is from meteoric water with the remainder from hydrothermal contributions. Results for groundwater samples from six shallow wells over a 6-month period for ??D and ??18O suggests that water from Herman Impoundment is diluted another 3% to more than 40% by infiltrating meteoric water, as it leaves the site. Results for this investigation show that environmental tracers are an effective tool to understand the SBMM hydrogeologic regime. ?? Springer-Verlag 2007.
In situ estimation of the effective chemical diffusion coefficient of a rock matrix in a fractured aquifer
An in situ method of estimating the effective diffusion coefficient for a chemical constituent that diffuses into the primary porosity of a rock is developed by abruptly changing the concentration of the dissolved constituent in a borehole in contact with the rock matrix and monitoring the time-varying concentration. The experiment was conducted in a borehole completed in mudstone on the campus of the University of the Free State in Bloemfontein, South Africa. Numerous tracer tests were conducted at this site, which left a residual concentration of sodium chloride in boreholes that diffused into the rock matrix over a period of years. Fresh water was introduced into a borehole in contact with the mudstone, and the time-varying increase of chloride was observed by monitoring the electrical conductivity (EC) at various depths in the borehole. Estimates of the effective diffusion coefficient were obtained by interpreting measurements of EC over 34 d. The effective diffusion coefficient at a depth of 36 m was approximately 7.8×10 −6 m 2 /d, but was sensitive to the assumed matrix porosity. The formation factor and mass flux for the mudstone were also estimated from the experiment.