Brian G. Katz

Timescales for nitrate contamination of spring waters, northern Florida, USA

Residence times of groundwater, discharging from springs in the middle Suwannee River Basin, were estimated using chlorofluorocarbons (CFCs), tritium (3H), and tritium/helium-3 (3H/3He) age-dating methods to assess the chronology of nitrate contamination of spring waters in northern Florida. During base-flow conditions for the Suwannee River in 1997–1999, 17 water samples were collected from 12 first, second, and third magnitude springs discharging groundwater from the Upper Floridan aquifer. Extending age-dating techniques, using transient tracers to spring waters in complex karst systems, required an assessment of several models [piston-flow (PFM), exponential mixing (EMM), and binary-mixing (BMM)] to account for different distributions of groundwater age. Multi-tracer analyses of four springs yielded generally concordant PFM ages of around 20±2 years from CFC-12, CFC-113, 3H, and 3He, with evidence of partial CFC-11 degradation. The EMM gave a reasonable fit to CFC-113, CFC-12, and 3H data, but did not reproduce the observed 3He concentrations or 3H/3He ratios, nor did a combination PFM–EMM. The BMM could reproduce most of the multi-tracer data set only if both endmembers had 3H concentrations not much different from modern values. CFC analyses of 14 additional springs yielded apparent PFM ages from about 10 to 20 years from CFC-113, with evidence of partial CFC-11 degradation and variable CFC-12 contamination. While it is not conclusive, with respect to the age distribution within each spring, the data indicate that the average residence times were in the order of 10–20 years and were roughly proportional to spring magnitude. Applying similar models to recharge and discharge of nitrate based on historical nitrogen loading data yielded contrasting trends for Suwanee County and Lafayette County. In Suwanee County, spring nitrate trends and nitrogen isotope data were consistent with a peak in fertilizer input in the 1970s and a relatively high overall ratio of artificial fertilizer/manure; whereas in Lafayette County, spring nitrate trends and nitrogen isotope data were consistent with a more monotonic increase in fertilizer input and relatively low overall ratio of artificial fertilizer/manure. The combined results of this study indicate that the nitrate concentrations of springs in the Suwannee River basin have responded to increased nitrogen loads from various sources in the watersheds over the last few decades; however, the responses have been subdued and delayed because the average residence time of groundwater discharging from springs are in the order of decades.

Chemical Evolution of Groundwater Near a Sinkhole Lake, Northern Florida: 1. Flow Patterns, Age of Groundwater, and Influence of Lake Water Leakage

Leakage from sinkhole lakes significantly influences recharge to the Upper Floridan aquifer in poorly confined sediments in northern Florida. Environmental isotopes (oxygen 18, deuterium, and tritium), chlorofluorocarbons (CFCs: CFC-11, CCl3F; CFC-12, CCl2F2; and CFC-113, C2Cl3F3), and solute tracers were used to investigate groundwater flow patterns near Lake Barco, a seepage lake in a mantled karst setting in northern Florida. Stable isotope data indicated that the groundwater downgradient from the lake contained 11–67% lake water leakage, with a limit of detection of lake water in groundwater of 4.3%. The mixing fractions of lake water leakage, which passed through organic-rich sediments in the lake bottom, were directly proportional to the observed methane concentrations and increased with depth in the groundwater flow system. In aerobic groundwater upgradient from Lake Barco, CFC-modeled recharge dates ranged from 1987 near the water table to the mid 1970s for water collected at a depth of 30 m below the water table. CFC-modeled recharge dates (based on CFC-12) for anaerobic groundwater downgradient from the lake ranged from the late 1950s to the mid 1970s and were consistent with tritium data. CFC-modeled recharge dates based on CFC-11 indicated preferential microbial degradation in anoxic waters. Vertical hydraulic conductivities, calculated using CFC-12 modeled recharge dates and Darcys law, were 0.17, 0.033, and 0.019 m/d for the surficial aquifer, intermediate confining unit, and lake sediments, respectively. These conductivities agreed closely with those used in the calibration of a three-dimensional groundwater flow model for transient and steady state flow conditions.

Groundwater quality impacts from the land application of treated municipal wastewater in a large karstic spring basin: chemical and microbiological indicators.

Geochemical and microbiological techniques were used to assess water-quality impacts from the land application of treated municipal wastewater in the karstic Wakulla Springs basin in northern Florida. Nitrate-N concentrations have increased from about 0.2 to as high as 1.1 mg/L (milligrams per liter) during the past 30 years in Wakulla Springs, a regional discharge point for groundwater (mean flow about 11.3 m(3)/s) from the Upper Floridan aquifer (UFA). A major source of nitrate to the UFA is the approximately 64 million L/d (liters per day) of treated municipal wastewater applied at a 774 ha (hectare) sprayfield farming operation. About 260 chemical and microbiological indicators were analyzed in water samples from the sprayfield effluent reservoir, wells upgradient from the sprayfield, and from 21 downgradient wells and springs to assess the movement of contaminants into the UFA. Concentrations of nitrate-N, boron, chloride, were elevated in water samples from the sprayfield effluent reservoir and in monitoring wells at the sprayfield boundary. Mixing of sprayfield effluent water was indicated by a systematic decrease in concentrations of these constituents with distance downgradient from the sprayfield, with about a 10-fold dilution at Wakulla Springs, about 15 km (kilometers) downgradient from the sprayfield. Groundwater with elevated chloride and boron concentrations in wells downgradient from the sprayfield and in Wakulla Springs had similar nitrate isotopic signatures, whereas the nitrate isotopic composition of water from other sites was consistent with inorganic fertilizers or denitrification. The sprayfield operation was highly effective in removing most studied organic wastewater and pharmaceutical compounds and microbial indicators. Carbamazepine (an anti-convulsant drug) was the only pharmaceutical compound detected in groundwater from two sprayfield monitoring wells (1-2 ppt). One other detection of carbamazepine was found in a distant well water sample where enteroviruses also were detected, indicating a likely influence from a nearby septic tank.

The combined use of 87Sr/86Sr and carbon and water isotopes to study the hydrochemical interaction between groundwater and lakewater in mantled karst

Abstract The hydrochemical interaction between groundwater and lakewater influences the composition of water that percolates downward from the surficial aquifer system through the underlying intermediate confining unit and recharges the Upper Floridan aquifer along highlands in Florida. The 87Sr/86Sr ratio along with the stable isotopes, D, 18O, and 13C were used as tracers to study the interaction between groundwater, lakewater, and aquifer minerals near Lake Barco, a seepage lake in the mantled karst terrane of northern Florida. Upgradient from the lake, the 87Sr/86Sr ratio of groundwater decreases with depth (mean values of 0.71004, 0.70890, and 0.70852 for water from the surficial aquifer system, intermediate confining unit, and Upper Floridan aquifer, respectively), resulting from the interaction of dilute oxygenated recharge water with aquifer minerals that are less radiogenic with depth. The concentrations of Sr2+ generally increase with depth, and higher concentrations of Sr2+ in water from the Upper Floridan aquifer (20–35 μg/L), relative to water from the surficial aquifer system and the intermediate confining unit, result from the dissolution of Sr-bearing calcite and dolomite in the Eocene limestone. Dissolution of calcite [δ13C= −1.6permil(‰)] is also indicated by an enriched δ13CDIC(-8.8 to -11.4 ‰) in water from the Upper Floridan aquifer, relative to the overlying hydrogeologic units (δ13CDIC Groundwater downgradient from Lake Barco was enriched in18O and D relative to groundwater upgradient from the lake, indicating mixing of lakewater leakage and groundwater. Downgradient from the lake, the 87Sr/86Sr ratio of groundwater and aquifer material become less radiogenic and the Sr2+ concentrations generally increase with depth. However, Sr2+ concentrations are substantially less than in upgradient groundwaters at similar depths. The lower Sr2+ concentrations result from the influence of anoxic lakewater leakage on the mobility of Sr2+ from clays. Based on results from mass-balance modeling, it is probable that cation exchange plays the dominant role in controlling the 87Sr/86Sr ratio of groundwater, both upgradient and downgradient from Lake Barco. Even though groundwater from the three distinct hydrogeologic units displays considerable variability in Sr concentration and isotopic composition, the dominant processes associated with the mixing of lakewater leakage with groundwater, as well as the effects of mineral-water interaction, can be ascertained by integrating the use of stable and radiogenic isotopic measurements of groundwater, lakewater, and aquifer minerals.

Sources and chronology of nitrate contamination in spring waters, Suwannee River basin, Florida

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Chemical Evolution of Groundwater Near a Sinkhole Lake, Northern Florida: 2. Chemical Patterns, Mass Transfer Modeling, and Rates of Mass Transfer Reactions

Chemical patterns along evolutionary groundwater flow paths in silicate and carbonate aquifers were interpreted using solute tracers, carbon and sulfur isotopes, and mass balance reaction modeling for a complex hydrologic system involving groundwater inflow to and outflow from a sinkhole lake in northern Florida. Rates of dominant reactions along defined flow paths were estimated from modeled mass transfer and ages obtained from CFC-modeled recharge dates. Groundwater upgradient from Lake Barco remains oxic as it moves downward, reacting with silicate minerals in a system open to carbon dioxide (CO2), producing only small increases in dissolved species. Beneath and downgradient of Lake Barco the oxic groundwater mixes with lake water leakage in a highly reducing, silicate-carbonate mineral environment. A mixing model, developed for anoxic groundwater downgradient from the lake, accounted for the observed chemical and isotopic composition by combining different proportions of lake water leakage and infiltrating meteoric water. The evolution of major ion chemistry and the 13C isotopic composition of dissolved carbon species in groundwater downgradient from the lake can be explained by the aerobic oxidation of organic matter in the lake, anaerobic microbial oxidation of organic carbon, and incongruent dissolution of smectite minerals to kaolinite. The dominant process for the generation of methane was by the CO2 reduction pathway based on the isotopic composition of hydrogen (δ2H(CH4) = −186 to −234‰) and carbon (δ13C(CH4) = −65.7 to −72.3‰). Rates of microbial metabolism of organic matter, estimated from the mass transfer reaction models, ranged from 0.0047 to 0.039 mmol L−1 yr−1 for groundwater downgradient from the lake.

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.

Vulnerability of a Public Supply Well in a Karstic Aquifer to Contamination

To assess the vulnerability of ground water to contamination in the karstic Upper Floridan aquifer (UFA), age-dating tracers and selected anthropogenic and naturally occurring compounds were analyzed in multiple water samples from a public supply well (PSW) near Tampa, Florida. Samples also were collected from 28 monitoring wells in the UFA and the overlying surficial aquifer system (SAS) and intermediate confining unit located within the contributing recharge area to the PSW. Age tracer and geochemical data from the earlier stage of the study (2003 through 2005) were combined with new data (2006) on concentrations of sulfur hexafluoride (SF(6)), tritium ((3)H), and helium-3, which were consistent with binary mixtures of water for the PSW dominated by young water (less than 7 years). Water samples from the SAS also indicated mostly young water (less than 7 years); however, most water samples from monitoring wells in the UFA had lower SF(6) and (3)H concentrations than the PSW and SAS, indicating mixtures containing high proportions of older water (more than 60 years). Vulnerability of the PSW to contamination was indicated by predominantly young water and elevated nitrate-N and volatile organic compound concentrations that were similar to those in the SAS. Elevated arsenic (As) concentrations (3 to 19 microg/L) and higher As(V)/As(III) ratios in the PSW than in water from UFA monitoring wells indicate that oxic water from the SAS likely mobilizes As from pyrite in the UFA matrix. Young water found in the PSW also was present in UFA monitoring wells that tap a highly transmissive zone (43- to 53-m depth) in the UFA.

Using Multiple Chemical Indicators to Assess Sources of Nitrate and Age of Groundwater in a Karstic Spring Basin

Human health and ecological concerns have arisen due to a steady increase in nitrate-N concentrations during the past 40 years in Fannin Springs (0.3–4.7 mg/L), a regional discharge point with an average flow of >2.8 m3/second (>100 ft3/second) for water from the karstic Upper Floridan aquifer (UFA). Multiple chemical indicators (major dissolved species, 15N and 18O of nitrate, dissolved gases, 78 pesticides and degradates, and 67 organic compounds typically found in domestic and industrial wastewater) and transient tracers (3H/3He, chlorofluorocarbons [CFCs], sulfur hexafluoride [SF6]) were analyzed in water samples from nine wells along three transects and in spring water to assess groundwater age and potential contaminant sources. Land use is predominantly agricultural (52 percent) and forest (31 percent) in the 320 km2 (124 mi2) spring basin, which was delineated from a potentiometric-surface map of the UFA using high-resolution water-level data. Nitrate-N concentrations were highly variable in the oxic UFA and ranged from <0.02 to 4.7 mg/L. δ15N-NO3 values (3.4–9.9 per mil) indicated that nitrate contamination originated from inorganic sources (synthetic fertilizer) and organic sources (manure spreading or waste disposal). Higher nitrate concentrations and the younger age of spring water relative to water from upgradient wells indicate better communication with N sources at the surface. Apparent ages of groundwater correlated positively with well depth (P < 0.05) and were younger in water from wells nearer to the spring (<8 years) compared with other wells (10–50 years). Most transient tracer concentrations were consistent with binary mixing curves representing mixtures of water recharged during the past 10 years and older water (recharged before 1940). Young water mixing fractions ranged from 0.07 to 0.90. Trace levels of herbicides found in groundwater and spring water were indicative of applications for vegetative control in agricultural and other land-use types.

Factors Affecting Public-Supply Well Vulnerability in Two Karst Aquifers

Karst aquifers occur in a range of climatic and geologic settings. Nonetheless, they are commonly characterized by their vulnerability to water-quality impairment. Two karst aquifers, the Edwards aquifer in south-central Texas and the Upper Floridan aquifer in western Florida, were investigated to assess factors that control the movement of contaminants to public-supply wells (PSWs). The geochemistry of samples from a selected PSW or wellfield in each aquifer was compared with that from nearby monitoring wells and regional PSWs. Geochemistry results were integrated with age tracers, flow modeling, and depth-dependent data to refine aquifer conceptual models and to identify factors that affect contaminant movement to PSWs. The oxic Edwards aquifer is vertically well mixed at the selected PSW/wellfield, although regionally the aquifer is geochemically variable downdip. The mostly anoxic Upper Floridan aquifer is affected by denitrification and also is geochemically variable with depth. In spite of considerable differences in geology and hydrogeology, the two aquifers are similarly vulnerable to anthropogenic contamination. Vulnerability in studied PSWs in both aquifers is strongly influenced by rapid karst flowpaths and the dominance of young (<10 years) groundwater. Vulnerability was demonstrated by the frequent detection of similar constituents of concern in both aquifers (nitrate, atrazine, deethylatrazine, tetrachloroethene, and chloroform). Specific consideration of water-quality protection efforts, well construction and placement, and aquifer response times to land-use changes and contaminant loading are discussed, with implications for karst groundwater management.