Robert L. Michel

Effect of groundwater springs on NO3− concentrations during summer in Catskill Mountain streams

Groundwater and stream water data collected at three headwater catchments in the Neversink River watershed indicate that base flow is sustained by groundwater from two sources: a shallow flow system within the till and soil and a deep flow system within bedrock fractures and bedding planes that discharges as perennial springs. Data from eight wells finished near the till/bedrock interface indicate that saturated conditions are not maintained in the shallow flow system during most summers. In contrast, the discharge of a perennial spring remained constant during two summer rainstorms, providing evidence that the deep flow system is disconnected from the shallow flow system in summer. Discharge from perennial springs was the principal source of streamflow in a headwater reach during low flow. Mean NO3− concentrations were 20–25 μmol L−1 in five perennial springs during the summer but only 5–10 μmol L−1 in shallow groundwater. Thus the deep flow system does not reflect typical NO3− concentrations in the soil during summer. A hydrologic budget at a headwater drainage reveals that March and late fall are the principal groundwater recharge periods. Residence time modeling based on analyses of 18O and 35S indicates that groundwater in the deep flow system is 6–22 months old. These data indicate that summer base flow largely originates from previous dormant seasons when available soil NO3− is greater. In these Catskill watersheds, high base flow concentrations of NO3− during summer do not provide sufficient evidence that the atmospheric N deposition rate exceeds the demand of terrestrial vegetation.

Dating of shallow groundwater: Comparison of the transient tracers 3H/3He, chlorofluorocarbons, and 85Kr

This paper describes a direct comparison of apparent ages derived from 3H/3He, chlorofluorocarbons (CCl3F and CCl2F2), and 85Kr measurements in shallow groundwater. Wells chosen for this study are completed in the unconfined surficial aquifers in late Cenozoic Atlantic Coastal Plain sediments of the Delmarva Peninsula, on the east coast of the United States. Most of the apparent tracer ages agree within 2 years of each other for recharge dates between 1965 and 1990. Discrepancies in apparent tracer ages usually can be explained by hydrological processes such as mixing in a discharge area. Recharge rate calculations based on apparent tracer age gradients at multilevel well locations agree with previous recharge estimates. High recharge rates on the Delmarva Peninsula result in nearly complete dissolved-gas confinement in the groundwater. The remarkable agreement between the different tracer ages indicates negligible mixing of waters of different ages, insignificant dispersion, minimal gas loss to the atmosphere, and insignificant sorption-desorption processes at this location.

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 + or - 2 degrees C over most of the peninsula to 14 + or - 2 degrees 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 [sup 3]He distribution. Most of the present distribution of tritium in Delmarva groundwater is consistent with low dispersivities. The results of this study strongly support the use of CFCs for dating shallow, aerobic groundwater.

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 (3H/3He), chlorofluorocarbons (CFCs), sulfur hexafluoride (SF6), sulfur-35 (35S), and stable isotopes (δ18O and δ2H) 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 SF6 and 3H/3He, 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 35S (>1.5 years) and seasonal variation of δ18O (mean residence time of 5 years) for spring discharge. The higher ages indicated by the 35S and δ18O data reflect travel times through the unsaturated zone and, in the case of 35S, possible sorption and exchange of S with soils or biomass. In springs sampled in April, 1996, apparent ages derived from the 3H/3He data (median age of 0.2 years) are lower than those obtained from SF6 (median age of 4.3 years), and in contrast to median ages from 3H/3He (0.3 years) and SF6 (0.7 years) obtained during the late summer dry season of 1997. Monthly samples from 1999 at four springs in SNP had SF6 apparent ages of only 1.2 to 2.5±0.8 years, and were consistent with the 1997 SF6 data. Water from springs has low excess air (0–1 cm3 kg−1) and N2–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 N2–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 cm3 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.

Residence times in river basins as determined by analysis of long-term tritium records

The US Geological Survey has maintained a network of stations to collect samples for the measurement of tritium concentrations in precipitation and streamflow since the early 1960s. Tritium data from outflow waters of river basins draining 4500–75000 km2 are used to determine average residence times of water within the basins. The basins studied are the Colorado River above Cisco, Utah; the Kissimmee River above Lake Okeechobee, Florida; the Mississippi River above Anoka, Minnesota; the Neuse River above Streets Ferry Bridge near Vanceboro, North Carolina; the Potomac River above Point of Rocks, Maryland; the Sacramento River above Sacramento, California; the Susquehanna River above Harrisburg, Pennsylvania. The basins are modeled with the assumption that the outflow in the river comes from two sources—prompt (within-year) runoff from precipitation, and flow from the long-term reservoirs of the basin. Tritium concentration in the outflow water of the basin is dependent on three factors: (1) tritium concentration in runoff from the long-term reservoir, which depends on the residence time for the reservoir and historical tritium concentrations in precipitation; (2) tritium concentrations in precipitation (the within-year runoff component); (3) relative contributions of flow from the long-term and within-year components. Predicted tritium concentrations for the outflow water in the river basins were calculated for different residence times and for different relative contributions from the two reservoirs. A box model was used to calculate tritium concentrations in the long-term reservoir. Calculated values of outflow tritium concentrations for the basin were regressed against the measured data to obtain a slope as close as possible to 1. These regressions assumed an intercept of zero and were carried out for different values of residence time and reservoir contribution to maximize the fit of modeled versus actual data for all the above rivers. The final slopes of the fitted regression lines ranged from 0.95 to 1.01 (correlation coefficient > 0.96) for the basins studied. Values for the residence time of waters within the basins and average relative contributions of the within-year and long-term reservoirs to outflow were obtained. Values for river basin residence times ranged from 2 years for the Kissimmee River basin to 20 years for the Potomac River basin. The residence times indicate the time scale in which the basin responds to anthropogenic inputs. The modeled tritium concentrations for the basins also furnish input data for urban and agricultural settings where these river waters are used.

Timescales for migration of atmospherically derived sulphate through an alpine/subalpine watershed, Loch Vale Colorado

Sulphur 35, a cosmogenically produced radioisotope with a short half-life (87 days), was measured in snowpack during 1993–1997 and at four locations within the Loch Vale watershed during 1995–1997. The four sites include the two main drainages in the watershed, Andrews Creek and Icy Brook, a small south facing catchment flowing into Andrews Creek (Andrews Spring 1), and a similar north facing catchment flowing out of a scree field into Icy Brook (Spring 19). Concentrations ranged from a high of almost 50 mBq/L for a sample from Spring 19 in June 1996 to a concentration near the detection limit for a sample from Andrews Creek in April 1997. Sulphur 35 concentrations were normalized to sulphate (as mBq/mg SO4−2) and were decay-corrected to a Julian day of 90 (April 1) for each year. Snowpack had the highest 35S concentration with an average concentration of 53 mBq/mg SO4−2. Concentrations in the streams were much lower, even when corrected for decay relative to JD 90. The large 35S concentrations found in Spring 19 were the result of increases in concentration due to sublimation and/or evapotranspiration and were lower than snowpack when normalized to sulphate. Using 35S concentrations found in snowpack as of JD 90 as a beginning concentration, the fraction of sulphate in streamflow that was derived from atmospheric deposition within the prior water year was estimated. For Icy Brook and Andrews Creek the fraction of the sulphate in streamflow derived from that years snowpack and precipitation was low prior to the beginning of the main spring melt, reached a maximum during the period of maximum flow, and decreased as the summer progressed. A calculation of the seasonal flux indicated that about 40% of the sulphate that flowed out of the watershed was derived from atmospheric sulphate deposited during the previous year. This suggests that more than half of the sulphate deposited in the watershed by atmospheric processes during the previous year was removed during the following summer. Thus sulphate retention in alpine watersheds like Loch Vale is very limited, and changes in sulphate deposition should be quickly reflected in stream chemistry.

Use of isotopic data to estimate water residence times of the Finger Lakes, New York

Abstract Water retention times in the Finger Lakes, a group of 11 lakes in central New York with similar hydrologic and climatic characteristics, were estimated by use of a tritium-balance model. During July 1991, samples were collected from the 11 lakes and selected tributary streams and were analyzed for tritium, deuterium, and oxygen-18. Additional samples from some of the sites were collected in 1990, 1992 and 1993. Tritium concentration in lake water ranged from 24.6 Tritium Units (TU) (Otisco Lake) to 43.2 TU (Seneca Lake).The parameters in the model used to obtain water retention time (WRT) included relative humidity, evaporation rate, tritium concentrations of inflowing water and lake water, and WRT of the lake. A historical record of tritium concentrations in precipitation and runoff was obtained from rainfall data at Ottawa, Canada, analyses of local wines produced during 1977–1991, and streamflow samples collected in 1990–1991. The model was simulated in yearly steps for 1953–1991, and the WRT was varied to reproduce tritium concentrations measured in each lake in 1991. Water retention times obtained from model simulations ranged from 1 year for Otisco Lake to 12 years for Seneca Lake, and with the exception of Seneca Lake and Skaneateles Lake, were in agreement with earlier estimates obtained from runoff estimates and chloride balances. The sensitivity of the model to parameter changes was tested to determine possible reasons for the differences calculated for WRTs for Seneca Lake and Skaneateles Lake. The shorter WRT obtained from tritium data for Lake Seneca (12 years as compared to 18 years) can be explained by a yearly addition of less than 3% by lake volume of ground water to the lake, the exact percentage depending on tritium concentration in the ground water.

Use of Natural 35S to Trace Sulphate Cycling in Small Lakes, Flattops Wilderness Area, Colorado, U.S.A.

Measurements of the cosmogenically-produced 35S, a radioisotope of sulphur (t1/2 = 87 days), are reported for the Ned Wilson Lake watershed in Colorado. The watershed contains two small lakes and a flowing spring presumed to be representative of local ground water. The watershed is located in the Flattops Wilderness Area and the waters in the system have low alkalinity, making them sensitive to increases in acid and sulphate deposition. Time series of 35S measurements were made during the summers of 1995 and 1996 (July–September) at all three sites. The system is dominated by melting snow and an initial concentration of 16–20 mBq L-1 was estimated for snowmelt based on a series of snow samples collected in the Rocky Mountains. The two lakes had large initial 35S concentrations in July, indicating that a large fraction of the lake water and sulphate was introduced by meltwater from that years snowpack. In 1995 and 1996, 35S concentrations decreased more rapidly than could be accounted for by decay, indicating that other processes were affecting 35S concentrations. The most likely explanation is that exchange with sediments or the biota was removing 35S from the lake and replacing it with older sulphate devoid of 35S. In September of 1995 and 1996, 35S concentrations increased, suggesting that atmospheric deposition is important in the sulphate flux of these lakes in late summer. Sulphur-35 concentrations in the spring water were highly variable but never higher than 3.6 mBq L-1 and averaged 2 mBq L-1. Using a simple mixing model, it was estimated that 75% of the spring water was derived from precipitation of previous years.

Interface dissolution control of the 14C profile in marine sediment

Abstract The process of carbonate dissolution at the sediment-water interface has two possible endmember boundary conditions. Either the carbonate particles dissolve mostly before they are incorporated into the sediment by bioturbation (interface dissolution), or the vertical mixing is rapid relative to their extermination rate (homogeneous dissolution). In this study, a detailed radiocarbon profile was determined in deep equatorial Pacific sediment that receives a high rate of carbonate supply. In addition, a box model of sediment mixing was used to simulate radiocarbon, carbonate content and excess thorium profiles that result from either boundary process following a dissolution increase. Results from homogeneous dissolution imply a strong, very recent erosional event, while interface dissolution suggests that moderately increased dissolution began about 10,000 years ago. In order to achieve the observed mixed layer radiocarbon age, increased homogeneous dissolution would concentrate a greater amount of clay and 230Th than is observed, while for interface dissolution the predicted concentrations are too small. These results together with small discontinuities beneath the mixed layer in 230Th profiles suggest a two-stage increase in interface dissolution in the deep Pacific, the first occurring near the beginning of the Holocene and the second more recently, roughly 5000 years ago.

Isotopes as Indicators of Environmental Change

Publisher Summary In addition to providing an understanding of processes within a catchment system, isotopic techniques have been instrumental in providing reconstructions of catchment climate and other environmental indicators at various time scales. Many recent changes are a direct consequence of anthropogenic activities. Isotopic analysis serves as a valuable tool for distinguishing between natural variations in long-term climatic patterns and anthropogenic effects, yielding improved understanding of natural feedback mechanisms and the development of realistic remediation strategies. This chapter discusses the examples of isotopic techniques that have been applied to understand several types of ongoing and recent environmental changes, and in paleo-environmental studies. It discusses isotope geochemistry, hydrology, and climatology to look at new ways of applying isotopic tracing techniques to provide information on environmental change. It also gives an overview on how isotopic indicators are being applied in investigations of environmental change in continental settings.