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Geology topics

E. Busenberg

Publications and source records attributed to E. Busenberg.

At least 19 recordsLinked to original sources
USGS2010

Chlorofluorocarbons (CCl3F and CCl2F2) as dating tools and hydrologic tracers in shallow groundwater of the Delmarva Peninsula, Atlantic Coastal Plain, United States

Concentrations of the Chlorofluorocarbons (CFCs) CFC-11 and CFC-12 were determined in groundwater from coastal plain sediments of the Delmarva Peninsula. CFC-modeled ages were calculated independently for CFC-11 and CFC-12, and agreed to within 2–3 years in the majority of the waters. Recharge temperatures, determined from dissolved nitrogen and argon concentrations, varied from 9±2°C over most of the peninsula to 14±2°C at the southernmost tip of the peninsula in Virginia. The CFC-modeled ages were examined in relation to the known hydrogeologic environment, both on regional scales and in more intensively sampled local scale networks. The CFC-modeled recharge years and measured tritium concentrations were used to reconstruct a tritium input function that was compared to the modeled tritium plus 3 He distribution. Most of the present distribution of tritium in Delmarva groundwater is consistent with low dispersivities. The results of the study strongly support the use of CFCs for dating shallow, aerobic groundwater.

Delaware, Maryland↗
USGS2010

Chlorofluorocarbons as tracers of groundwater transport processes in a shallow, silty sand aquifer

Detailed depth profiles of Chlorofluorocarbons CFC-11(CFCl 3 (, CFC-12 (CF 2 Cl 2 ) and CFC-113 (C 2 F 3 Cl 3 ) have been obtained from a well-characterized field site in central Ontario. Aquifer materials comprise predominantly silty sands, with a mean organic carbon content of 0.03%. Nearly one-dimensional flow exists at this site, and the vertical migration of a well-defined 3 H peak has been tracked through time. Detailed vertical sampling has allowed CFC tracer velocities to be estimated to within 10%. Comparison with 3 H profiles enables estimation of chlorofluorocarbon transport parameters. CFC-12 appears to be the most conservative of the CFCs measured. Sorption at this site is low ( K d < 0.03), and degradation does not appear to be important. CFC- 113 is retarded both with respect to CFC-12 and with respect to 3 H ( K d = 0.09−0.14). CFC-11 appears to be degraded both in the highly organic unsaturated zone and below 3.5 m depth in the aquifer, where dissolved oxygen concentrations decrease to below 0.5 mg L −1 . The half-life for CFC-11 degradation below 3.5 m depth is less than 2 years. While apparent CFC-12 ages match hydraulic ages to within 20% (up to 30 years), apparent CFC-11 and CFC-113 ages significantly overestimate hydraulic ages at our field site.

Water Resources Research↗
USGS2010

Inferring shallow groundwater flow in saprolite and fractured rock using environmental tracers

The Ridge and Valley Province of eastern Tennessee is characterized by (1) substantial topographic relief, (2) folded and highly fractured rocks of various lithologies that have low primary permeability and porosity, and (3) a shallow residuum of medium permeability and high total porosity. Conceptual models of shallow groundwater flow and solute transport in this system have been developed but are difficult to evaluate using physical characterization or short‐term tracer methods due to extreme spatial variability in hydraulic properties. In this paper we describe how chlorofluorocarbon 12, 3 H, and 3 He were used to infer groundwater flow and solute transport in saprolite and fractured rock near Oak Ridge, Tennessee. In the shallow residuum, fracture spacings are <0.05 m, suggesting that concentrations of these tracers in fractures and in the matrix have time to diffusionally equilibrate. The relatively smooth nature of tracer concentrations with depth in the residuum is consistent with this model and quantitatively suggests recharge fluxes of 0.2 to 0.4 m yr −1 . In contrast, groundwater flow within the unweathered rock appears to be controlled by fractures with spacings of the order of 2 to 5 m, and diffusional equilibration of fractures and matrix has not occurred. For this reason, vertical fluid fluxes in the unweathered rock cannot be estimated from the tracer data.

Water Resources Research↗
USGS2008

Dating groundwater with trifluoromethyl sulfurpentafluoride (SF 5CF3), sulfur hexafluoride (SF6), CF 3Cl (CFC-13), and CF2Cl2 (CFC-12)

[1] A new groundwater dating procedure using the transient atmospheric signal of the environmental tracers SF5CF3, CFC-13, SF6, and CFC-12 was developed. The analytical procedure determines concentrations of the four tracers in air and water samples. SF 5CF3 and CFC-13 can be used to date groundwaters in some environments where the CFCs and SF6 have previously failed because these new tracers have increasing atmospheric input functions, no known terrigenic source, and are believed to be stable under reducing conditions. SF5CF3 has a dating range from 1970 to modern; the mixing ratio (mole fraction) in North American air has increased from the detection limit of 0.005 parts per trillion (ppt) to the 2006 mole fraction of about 0.16 ppt. No evidence was found for degradation of SF5CF3 in laboratory anaerobic systems. The solubility of SF5CF3 was measured in water from 1 to 35??C. Groundwater samples that contained large amounts of terrigenic SF6 did not contain terrigenic SF 5CF3. CFC-13 is a trace atmospheric gas with a dating range in groundwater of about 1965 to modem. CFC-13 has been used primarily in very low-temperature refrigeration; thus groundwater environments are less likely to be contaminated with nonatmospheric sources as compared to other widely used CFCs. Because of the low solubility of SF5CF3 and CFC-13 in water, an excess air correction must be applied to the apparent ages. The new dating procedure was tested in water samples from wells and springs from Maryland, Virginia, and West Virginia.

Water Resources Research↗
USGS2008

Low-Level detections of halogenated volatile organic compounds in groundwater: Use in vulnerability assessments

Concentrations of halogenated volatile organic compounds (VOCs) were determined by gas chromatography (GC) with an electron-capture detector (GC-ECD) and by gas chromatography with mass spectrometry (GC-MS) in 109 groundwater samples from five study areas in the United States. In each case, the untreated water sample was used for drinking-water purposes or was from a monitoring well in an area near a drinking-water source. The minimum detection levels (MDLs) for 25 VOCs that were identified in GC-ECD chromatograms, typically, were two to more than four orders of magnitude below the GC-MS MDLs. At least six halogenated VOCs were detected in all of the water samples analyzed by GC-ECD, although one or more VOCs were detected in only 43% of the water samples analyzed by GC-MS. In nearly all of the samples, VOC concentrations were very low and presented no known health risk. Most of the low-level VOC detections indicated post-1940s recharge, or mixtures of recharge that contained a fraction of post-1940s water. Concentrations of selected halogenated VOCs in groundwater from natural and anthropogenic atmospheric sources were estimated and used to recognize water samples that are being impacted by nonatmospheric sources. A classification is presented to perform vulnerability assessments at the scale of individual wells using the number of halogenated VOC detections and total dissolved VOC concentrations in samples of untreated drinking water. The low-level VOC detections are useful in vulnerability assessments, particularly for samples in which no VOCs are detected by GC-MS analysis.

Journal of Hydrologic Engineering↗
USGS2006

Application of environmental tracers to mixing, evolution, and nitrate contamination of ground water in Jeju Island, Korea

Tritium/helium-3 ( 3 H/ 3 He) and chlorofluorocarbons (CFCs) were investigated as environmental tracers in ground water from Jeju Island (Republic of Korea), a basaltic volcanic island. Ground-water mixing was evaluated by comparing 3 H and CFC-12 concentrations with lumped-parameter dispersion models, which distinguished old water recharged before the 1950s with negligible 3 H and CFC-12 from younger water. Low 3 H levels in a considerable number of samples cannot be explained by the mixing models, and were interpreted as binary mixing of old and younger water; a process also identified in alkalinity and pH of ground water. The ground-water CFC-12 age is much older in water from wells completed in confined zones of the hydro-volcanic Seogwipo Formation in coastal areas than in water from the basaltic aquifer. Major cation concentrations are much higher in young water with high nitrate than those in uncontaminated old water. Chemical evolution of ground water resulting from silicate weathering in basaltic rocks reaches the zeolite–smectite phase boundary. The calcite saturation state of ground water increases with the CFC-12 apparent (piston flow) age. In agricultural areas, the temporal trend of nitrate concentration in ground water is consistent with the known history of chemical fertilizer use on the island, but increase of nitrate concentration in ground water is more abrupt after the late 1970s compared with the exponential growth of nitrogen inputs.

Jeju Island↗
USGS2005

Influence of fracture anisotropy on ground water ages and chemistry, Valley and Ridge province, Pennsylvania

Model ground water ages based on chlorofluorocarbons (CFCs) and tritium/helium-3 (3H/3He) 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 3H/3He 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.

Pennsylvania↗
USGS2005

Age of irrigation water in ground water from the Eastern Snake River Plain Aquifer, south-central Idaho

Stable isotope data ( 2 H and 18 O) were used in conjunction with chlorofluorocarbon (CFC) and tritium/helium-3 ( 3 H/ 3 He) data to determine the fraction and age of irrigation water in ground water mixtures from farmed parts of the Eastern Snake River Plain (ESRP) Aquifer in south-central Idaho. Two groups of waters were recognized: (1) regional background water, unaffected by irrigation and fertilizer application, and (2) mixtures of irrigation water from the Snake River with regional background water. New data are presented comparing CFC and 3 H/ 3 He dating of water recharged through deep fractured basalt, and dating of young fractions in ground water mixtures. The 3 H/ 3 He ages of irrigation water in most mixtures ranged from about zero to eight years. The CFC ages of irrigation water in mixtures ranged from values near those based on 3 H/ 3 He dating to values biased older than the 3 H/ 3 He ages by as much as eight to 10 years. Unsaturated zone air had CFC-12 and CFC-113 concentrations that were 60% to 95%, and 50% to 90%, respectively, of modern air concentrations and were consistently contaminated with CFC-11. Irrigation water diverted from the Snake River was contaminated with CFC-11 but near solubility equilibrium with CFC-12 and CFC-113. The dating indicates ground water velocities of 5 to 8 m/d for water along the top of the ESRP Aquifer near the southwestern boundary of the Idaho National Engineering and Environmental Laboratory (INEEL). Many of the regional background waters contain excess terrigenic helium with a 3 He/ 4 He isotope ratio of 7 x 10-6 to 11 x 10-6 (R/R a = 5 to 8) and could not be dated. Ratios of CFC data indicate that some rangeland water may contain as much as 5% to 30% young water (ages of less than or equal to two to 11.5 years) mixed with old regional background water. The relatively low residence times of ground water in irrigated parts of the ESRP Aquifer and the dilution with low-NO 3 irrigation water from the Snake River lower the potential for NO 3 contamination in agricultural areas.

Ground Water↗
USGS2004

Hydrochemical tracers in the middle Rio Grande Basin, USA: 1. Conceptualization of groundwater flow

Chemical and isotopic data for groundwater from throughout the Middle Rio Grande Basin, central New Mexico, USA, were used to identify and map groundwater flow from 12 sources of water to the basin, evaluate radiocarbon ages, and refine the conceptual model of the Santa Fe Group aquifer system. Hydrochemical zones, representing groundwater flow over thousands to tens of thousands of years, can be traced over large distances through the primarily siliciclastic aquifer system. The locations of the hydrochemical zones mostly reflect the “modern” predevelopment hydraulic-head distribution, but are inconsistent with a trough in predevelopment water levels in the west-central part of the basin, indicating that this trough is a transient rather than a long-term feature of the aquifer system. Radiocarbon ages adjusted for geochemical reactions, mixing, and evapotranspiration/dilution processes in the aquifer system were nearly identical to the unadjusted radiocarbon ages, and ranged from modern to more than 30 ka. Age gradients from piezometer nests ranged from 0.1 to 2 year cm –1 and indicate a recharge rate of about 3 cm year –1 for recharge along the eastern mountain front and infiltration from the Rio Grande near Albuquerque. There has been appreciably less recharge along the eastern mountain front north and south of Albuquerque.

Rio Grande Basin↗
USGS2004

Historical trends in occurrence and atmospheric inputs of halogenated volatile organic compounds in untreated ground water used as a source of drinking water

Analyses of samples of untreated ground water from 413 community-, non-community- (such as restaurants), and domestic-supply wells throughout the US were used to determine the frequency of detection of halogenated volatile organic compounds (VOCs) in drinking-water sources. The VOC data were compiled from archived chromatograms of samples analyzed originally for chlorofluorocarbons (CFCs) by purge-and-trap gas chromatography with an electron-capture detector (GC-ECD). Concentrations of the VOCs could not be ascertained because standards were not routinely analyzed for VOCs other than trichloromonofluoromethane (CFC-11), dichlorodifluoromethane (CFC-12) and 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113). Nevertheless, the peak areas associated with the elution times of other VOCs on the chromatograms can be classified qualitatively to assess concentrations at a detection limit on the order of parts per quadrillion. Three or more VOCs were detected in 100% (percent) of the chromatograms, and 77.2% of the samples contained 10 or more VOCs. The maximum number of VOCs detected in any sample was 24. Modeled ground-water residence times, determined from concentrations of CFC-12, were used to assess historical trends in the cumulative occurrence of all VOCs detected in this analysis, as well as the occurrence of individual VOCs, such as CFC-11, carbon tetrachloride (CCl 4 ), chloroform and tetrachloroethene (PCE). The detection frequency for all of the VOCs detected has remained relatively constant from approximately 1940 to 2000; however, the magnitude of the peak areas on the chromatograms for the VOCs in the water samples has increased from 1940 to 2000. For CFC-11, CCl 4 , chloroform and PCE, small peaks decrease from 1940 to 2000, and large peaks increase from 1940 to 2000. The increase in peak areas on the chromatograms from analyses of more recently recharged water is consistent with reported increases in atmospheric concentrations of the VOCs. Approximately 44% and 6.7% of the CCl 4 and PCE detections, respectively, in pre-1940 water, and 68% and 62% of the CCl 4 and PCE detections, respectively, in water recharged in 2000 exceed solubility equilibrium with average atmospheric concentrations. These exceedences can be attributed to local atmospheric enrichment or direct contaminant input to ground-water flow systems. The detection of VOCs at concentrations indicative of atmospheric sources in 100% of the samples indicates that untreated drinking water from ground-water sources in the US recharged within the past 60 years has been affected by anthropogenic activity. Additional inputs from a variety of sources such as spills, underground injections and leaking landfills or storage tanks increasingly are providing additional sources of contamination to ground water used as drinking-water sources.

Science of the Total Environment↗
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↗
USGS1998

Flow of river water into a Karstic limestone aquifer. 1. Tracing the young fraction in groundwater mixtures in the Upper Floridan Aquifer near Valdosta, Georgia

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 − , 3 H, tritiogenic helium-3 ( 3 He), chlorofluorocarbons (CFC-11, CFC-12, CFC-113), organic C (DOC), O 2 (DO), H 2 S, CH 4 , δ 18 O, δD, and 14 C 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 − , δ 18 O, δD, CFC-12, and the quantity ( 3 H+ 3 He) are stable in water from the Upper Floridan aquifer, whereas DOC, DO, H 2 S, CH 4 , 14 C, 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 δ 18 O data, recognizing 3 end-member water types in the groundwater mixtures: (1) Withlacoochee River water (δ 18 O=−2.5±0.3‰, Cl − =12.2±2 mg/l), (2) regional infiltration water (δ 18 O=−4.2±0.1‰, Cl − =2.3±0.1 mg/l), and (3) regional paleowater resident in the Upper Floridan aquifer (δ 18 O=−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.

Georgia↗
USGS1998

Flow of river water into a karstic limestone aquifer: 2. Dating the young fraction in groundwater mixtures in the Upper Floridan aquifer near Valdosta, Georgia

Tritium/helium-3 ( 3 H/ 3 He) 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 3 H/ 3 He age is independent of the extent of dilution with older ( 3 H-free and 3 He trit -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 δ 18 O 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 SO 4 -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 3 H concentration of the groundwater. Because of uncertainties associated with very low 3 H and 3 He content in dilute mixtures, 3 H/ 3 He 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 3 H/ 3 He dating, dilution of 3 H and low 3 He concentration limited 3 H/ 3 He dating to 16 mixtures in which 3 H/ 3 He 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 3 H/ 3 He 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 3 H/ 3 He 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.

Georgia↗
USGS1997

Groundwater record of halocarbon transport by the Danube River

Groundwater dating studies have supported the concept that aquifers with low coefficients of dispersion may contain coherent records of past conditions in recharge areas. Groundwater records can provide unique information about natural or anthropogenic changes in the atmosphere and hydrosphere where long-term monitoring data are not available. Here we describe a 40-year record of halocarbon contamination in the Danube River that was retrieved from a shallow aquifer in northwest Hungary. The time scale is based on 3H and He isotope dating of groundwaters that were recharged by the Danube River and moved horizontally away from the river in a surficial gravel aquifer with minor dispersion at a maximum rate of at least 500 m/yr. Analyses of dated groundwaters along a flow path indicate that the river loads of selected compounds (including CFC-12, CFC-113, and trichloroethane) were negligible before about 1950, rose rapidly to peak values in the 1960s and 1970s, and then decreased by varying degrees to the present. Peak concentrations are tentatively attributed to point sources in upstream urban-industrial centers; while recent decreases presumably resulted from declining manufacturing rates and(or) improvements in control of urban- industrial runoff and sewage effluent entering the river in upstream areas.

Danube River↗
USGS1996

Age dating of shallow groundwater with chlorofluorocarbons, tritium/helium: 3, and flow path analysis, southern New Jersey coastal plain

Groundwater age dating through the combination of transient tracer methods (chlorofluorocarbons (CFCs) and tritium/helium 3 ( 3 H/ 3 He)) and groundwater flow path analysis is useful for investigating groundwater travel times, flow patterns, and recharge rates, as demonstrated by this study of the homogeneous shallow, unconfined Kirkwood-Cohansey aquifer system in the southern New Jersey coastal plain. Water samples for age dating were collected from three sets of nested observation wells (10 wells) with 1.5-m-long screens located near groundwater divides. Three steady state finite difference groundwater flow models were calibrated by adjusting horizontal and vertical hydraulic conductivities to match measured heads and head differences (range, 0.002–0.23 m) among the nested wells, with a uniform recharge rate of 0.46 m per year and porosities of 0.35 (sand) and 0.45 (silt) that were assumed constant for all model simulations and travel time calculations. The simulated groundwater travel times increase with depth in the aquifer, ranging from about 1.5 to 6.5 years for the shallow wells (screen bottoms 3–4 m below the water table), from about 10 to 25 years for the medium-depth wells (screen bottoms 8–19 m below the water table), and from about 30 to more than 40 years for the deep wells (screen bottoms 24–26 m below the water table). Apparent groundwater ages based on CFC- and 3 H/ 3 He-dating techniques and model-based travel times could not be statistically differentiated, and all were strongly correlated with depth. Confinement of 3He was high because of the rapid vertical flow velocity (of the order of 1 m/yr), resulting in clear delineation of groundwater travel times based on the 3 H/ 3 He-dating technique. The correspondence between the 3 H/ 3 He and CFC ages indicates that dispersion has had a minimal effect on the tracer-based ages of water in this aquifer. Differences between the tracer-based apparent ages for seven of the 10 samples were smaller than the error values. A slight bias toward older apparent ages, found not to be statistically significant, was noted for the 3 H/ 3 He-dating technique relative to the CFC-dating technique. This result may be caused by enrichment of local air in CFC-Il and CFC-12 from urban and industrial sources in the northeastern United States and minor contamination from sampling equipment. The demonstrated validity of the combined tracer-dating techniques to determine the age of water in the Kirkwood-Cohansey aquifer system indicates that groundwater flow models can be refined when apparent ages based on 3 H/ 3 He- and CFC- dating are used as calibration targets.

New Jersey↗
USGS1992

Dissolution of aragonite-strontianite solid solutions in nonstoichiometric Sr (HCO3)2-Ca (HCO3)2-CO2-H2O solutions

Synthetic strontianite-aragonite solid-solution minerals were dissolved in CO 2 -saturated non-stoichiometric solutions of Sr(HCO 3 ) 2 and Ca(HCO 3 ) 2 at 25°C. The results show that none of the dissolution reactions reach thermodynamic equilibrium. Congruent dissolution in Ca(HCO 3 ) 2 solutions either attains or closely approaches stoichiometric saturation with respect to the dissolving solid. In Sr(HCO 3 ) 2 solutions the reactions usually become incongruent, precipitating a Sr-rich phase before reaching stoichiometric saturation. Dissolution of mechanical mixtures of solids approaches stoichiometric saturation with respect to the least stable solid in the mixture. Surface uptake from subsaturated bulk solutions was observed in the initial minutes of dissolution. This surficial phase is 0–10 atomic layers thick in Sr(HCO 3 ) 2 solutions and 0–4 layers thick in Ca(HCO 3 ) 2 solutions, and subsequently dissolves and/or recrystallizes, usually within 6 min of reaction. The initial transient surface precipitation (recrystallization) process is followed by congruent dissolution of the original solid which proceeds to stoichiometric saturation, or until the precipitation of a more stable Sr-rich solid. The compositions of secondary precipitates do not correspond to thermodynamic equilibrium or stoichiometric saturation states. X-ray photoelectron spectroscopy (XPS) measurements indicate the formation of solid solutions on surfaces of aragonite and strontianite single crystals immersed in Sr(HCO 3 ) 2 and Ca(HCO 3 ) 2 solutions, respectively. In Sr(HCO 3 ) 2 solutions, the XPS signal from the outer ~ 60 Å on aragonite indicates a composition of 16 mol% SrCO 3 after only 2 min of contact, and 14–18 mol% SrCO 3 after 3 weeks of contact. The strontianite surface averages approximately 22 mol% CaCO 3 after 2 min of contact with Ca(HCO 3 ) 2 solution, and is 34–39 mol% CaCO 3 after 3 weeks of contact. XPS analysis suggests the surface composition is zoned with somewhat greater enrichment in the outer ~25 Å (as much as 26 mol% SrCO 3 on aragonite and 44 mol% CaCO 3 on strontianite). The results indicate rapid formation of a solid-solution surface phase from subsaturated aqueous solutions. The surface phase continually adjusts in composition in response to changes in composition of the bulk fluid as net dissolution proceeds. Dissolution rates of the endmembers are greatly reduced in nonstoichiometric solutions relative to dissolution rates observed in stoichiometric solutions. All solids dissolve more slowly in solutions spiked with the least soluble component ((Sr(HCO 3 ) 2 )) than in solutions spiked with the more soluble component (Ca(HCO 3 ) 2 ), an effect that becomes increasingly significant as stoichiometric saturation is approached. It is proposed that the formation of a non-stoichiometric surface reactive zone significantly decreases dissolution rates.

Geochimica et Cosmochimica Acta↗
USGS1990

Reaction paths and equilibrium end-points in solid-solution aqueous-solution systems

Equations are presented describing equilibrium in binary solid-solution aqueous-solution (SSAS) systems after a dissolution, precipitation, or recrystallization process, as a function of the composition and relative proportion of the initial phases. Equilibrium phase diagrams incorporating the concept of stoichiometric saturation are used to interpret possible reaction paths and to demonstrate relations between stoichiometric saturation, primary saturation, and thermodynamic equilibrium states. The concept of stoichiometric saturation is found useful in interpreting and putting limits on dissolution pathways, but there currently is no basis for possible application of this concept to the prediction and/ or understanding of precipitation processes. Previously published dissolution experiments for (Ba, Sr)SO 4 and (Sr, Ca)C̈O 3orth. solids are interpreted using equilibrium phase diagrams. These studies show that stoichiometric saturation can control, or at least influence, initial congruent dissolution pathways. The results for (Sr, Ca)CO 3orth. solids reveal that stoichiometric saturation can also control the initial stages of incongruent dissolution, despite the intrinsic instability of some of the initial solids. In contrast, recrystallisation experiments in the highly soluble KCl-KBr-H 2 O system demonstrate equilibrium. The excess free energy of mixing calculated for K(Cl, Br) solids is closely modeled by the relation G E = χ KBr χ KCl RT [ a 0 + a 1 (2 χ KBr −1)], where a 0 is 1.40 ± 0.02, a 1 , is −0.08 ± 0.03 at 25°C, and χ KBr and χ KCl are the mole fractions of KBr and KCl in the solids. The phase diagram constructed using this fit reveals an alyotropic maximum located at χ KBr = 0.676 and at a total solubility product, ΣΠ = [ K + ]([ Cl − ] + [ Br − ]) = 15.35.

Geochimica et Cosmochimica Acta↗