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John Karl Bohlke

Publications and source records attributed to John Karl Bohlke.

At least 19 recordsLinked to original sources

Brackish groundwater in the United States

For some parts of the Nation, large-scale development of groundwater has caused decreases in the amount of groundwater that is present in aquifer storage and that discharges to surface-water bodies. Water supply in some areas, particularly in arid and semiarid regions, is not adequate to meet demand, and severe drought is affecting large parts of the United States. Future water demand is projected to heighten the current stress on groundwater resources. This combination of factors has led to concerns about the availability of freshwater to meet domestic, agricultural, industrial, mining, and environmental needs. To ensure the water security of the Nation, currently [2016] untapped water sources may need to be developed. Brackish groundwater is an unconventional water source that may offer a partial solution to current and future water demands. In support of the national census of water resources, the U.S. Geological Survey completed the national brackish groundwater assessment to better understand the occurrence and characteristics of brackish groundwater in the United States as a potential water resource. Analyses completed as part of this assessment relied on previously collected data from multiple sources; no new data were collected. Compiled data included readily available information about groundwater chemistry, horizontal and vertical extents and hydrogeologic characteristics of principal aquifers (regionally extensive aquifers or aquifer systems that have the potential to be used as a source of potable water), and groundwater use. Although these data were obtained from a wide variety of sources, the compiled data are biased toward shallow and fresh groundwater resources; data representing groundwater that is at great depths and is saline were not as readily available. One of the most important contributions of this assessment is the creation of a database containing chemical characteristics and aquifer information for the known areas with brackish groundwater in the United States. Previously published digital data relating to brackish groundwater resources were limited to a small number of State- and regional-level studies. Data sources for this assessment ranged from single publications to large datasets and from local studies to national assessments. Geochemical data included concentrations of dissolved solids, major ions, trace elements, nutrients, and radionuclides as well as physical properties of the water (pH, temperature, and specific conductance). Additionally, the database provides selected well information (location, yield, depth, and contributing aquifer) necessary for evaluating the water resource. The assessment was divided into national-, regional-, and aquifer-scale analyses. National-scale analyses included evaluation of the three-dimensional distribution of observed dissolved-solids concentrations in groundwater, the three-dimensional probability of brackish groundwater occurrence, and the geochemical characteristics of saline (greater than or equal to 1,000 mg/L of dissolved solids) groundwater resources. Regional-scale analyses included a summary of the percentage of observed grid cell volume in the region that was occupied by brackish groundwater within the mixture of air, water, and rock for multiple depth intervals. Aquifer-scale analyses focused primarily on four regions that contained the largest amounts of observed brackish groundwater and included a generalized description of hydrogeologic characteristics from previously published work; the distribution of dissolved-solids concentrations; considerations for developing brackish groundwater resources, including a summary of other chemical characteristics that may limit the use of brackish groundwater and the ability of sampled wells producing brackish groundwater to yield useful amounts of water; and the amount of saline groundwater being used in 2010.

Professional Paper

A partial exponential lumped parameter model to evaluate groundwater age distributions and nitrate trends in long-screened wells

A partial exponential lumped parameter model (PEM) was derived to determine age distributions and nitrate trends in long-screened production wells. The PEM can simulate age distributions for wells screened over any finite interval of an aquifer that has an exponential distribution of age with depth. The PEM has 3 parameters – the ratio of saturated thickness to the top and bottom of the screen and mean age, but these can be reduced to 1 parameter (mean age) by using well construction information and estimates of the saturated thickness. The PEM was tested with data from 30 production wells in a heterogeneous alluvial fan aquifer in California, USA. Well construction data were used to guide parameterization of a PEM for each well and mean age was calibrated to measured environmental tracer data ( 3 H, 3 He, CFC-113, and 14 C). Results were compared to age distributions generated for individual wells using advective particle tracking models (PTMs). Age distributions from PTMs were more complex than PEM distributions, but PEMs provided better fits to tracer data, partly because the PTMs did not simulate 14 C accurately in wells that captured varying amounts of old groundwater recharged at lower rates prior to groundwater development and irrigation. Nitrate trends were simulated independently of the calibration process and the PEM provided good fits for at least 11 of 24 wells. This work shows that the PEM, and lumped parameter models (LPMs) in general, can often identify critical features of the age distributions in wells that are needed to explain observed tracer data and nonpoint source contaminant trends, even in systems where aquifer heterogeneity and water-use complicate distributions of age. While accurate PTMs are preferable for understanding and predicting aquifer-scale responses to water use and contaminant transport, LPMs can be sensitive to local conditions near individual wells that may be inaccurately represented or missing in an aquifer-scale flow model.

California

Identification of groundwater nitrate contamination from explosives used in road construction: Isotopic, chemical, and hydrologic evidence

Explosives used in construction have been implicated as sources of NO 3 – contamination in groundwater, but direct forensic evidence is limited. Identification of blasting-related NO 3 – can be complicated by other NO 3 – sources, including agriculture and wastewater disposal, and by hydrogeologic factors affecting NO 3 – transport and stability. Here we describe a study that used hydrogeology, chemistry, stable isotopes, and mass balance calculations to evaluate groundwater NO 3 – sources and transport in areas surrounding a highway construction site with documented blasting in New Hampshire. Results indicate various groundwater responses to contamination: (1) rapid breakthrough and flushing of synthetic NO 3 – (low δ 15 N, high δ 18 O) from dissolution of unexploded NH 4 NO 3 blasting agents in oxic groundwater; (2) delayed and reduced breakthrough of synthetic NO 3 – subjected to partial denitrification (high δ 15 N, high δ 18 O); (3) relatively persistent concentrations of blasting-related biogenic NO 3 – derived from nitrification of NH 4 + (low δ 15 N, low δ 18 O); and (4) stable but spatially variable biogenic NO 3 – concentrations, consistent with recharge from septic systems (high δ 15 N, low δ 18 O), variably affected by denitrification. Source characteristics of denitrified samples were reconstructed from dissolved-gas data (Ar, N 2 ) and isotopic fractionation trends associated with denitrification (Δδ 15 N/Δδ 18 O ≈ 1.31). Methods and data from this study are expected to be applicable in studies of other aquifers affected by explosives used in construction.

Environmental Science & Technology

Role of anaerobic ammonium oxidation (anammox) in nitrogen removal from a freshwater aquifer

Anaerobic ammonium oxidation (anammox) couples the oxidation of ammonium with the reduction of nitrite, producing N 2 . The presence and activity of anammox bacteria in groundwater were investigated at multiple locations in an aquifer variably affected by a large, wastewater-derived contaminant plume. Anammox bacteria were detected at all locations tested using 16S rRNA gene sequencing and quantification of hydrazine oxidoreductase ( hzo ) gene transcripts. Anammox and denitrification activities were quantified by in situ 15 NO 2 – tracer tests along anoxic flow paths in areas of varying ammonium, nitrate, and organic carbon abundances. Rates of denitrification and anammox were determined by quantifying changes in 28 N 2 , 29 N 2 , 30 N 2 , 15 NO 3 – , 15 NO 2 – , and 15 NH 4 + with groundwater travel time. Anammox was present and active in all areas tested, including where ammonium and dissolved organic carbon concentrations were low, but decreased in proportion to denitrification when acetate was added to increase available electron supply. Anammox contributed 39–90% of potential N 2 production in this aquifer, with rates on the order of 10 nmol N 2 –N L –1 day –1 . Although rates of both anammox and denitrification during the tracer tests were low, they were sufficient to reduce inorganic nitrogen concentrations substantially during the overall groundwater residence times in the aquifer. These results demonstrate that anammox activity in groundwater can rival that of denitrification and may need to be considered when assessing nitrogen mass transport and permanent loss of fixed nitrogen in aquifers.

Environmental Science & Technology

Chemical considerations for an updated National assessment of brackish groundwater resources

Brackish groundwater (BGW) is increasingly used for water supplies where fresh water is scarce, but the distribution and availability of such resources have not been characterized at the national scale in the United States since the 1960s. Apart from its distribution and accessibility, BGW usability is a function of the chemical requirements of the intended use, chemical characteristics of the resource, and treatment options to make the resource compatible with the use. Here, we discuss relations between these three chemical factors using national-scale examples and local case studies. In a preliminary compilation of BGW data in the United States, five water types accounted for the major-ion composition of 70% of samples. PHREEQC calculations indicate that 57–77% of samples were oversaturated with respect to barite, calcite, or chalcedony. In the study, 5–14% of samples had concentrations of arsenic, fluoride, nitrate, or uranium that exceeded drinking-water standards. In case studies of the potential use of BGW for drinking water, irrigation, and hydraulic fracturing, PHREEQC simulations of a hypothetical treatment process resembling reverse osmosis (RO) showed that BGW had the potential to form various assemblages of mineral deposits (scale) during treatment that could adversely affect RO membranes. Speciation calculations showed that most boron in the irrigation example occurred as boric acid, which has relatively low removal efficiency by RO. Results of this preliminary study indicate that effective national or regional assessments of BGW resources should include geochemical characterizations that are guided in part by specific use and treatment requirements.

Groundwater

Groundwater movement, recharge, and perchlorate occurrence in a faulted alluvial aquifer in California (USA)

Perchlorate from military, industrial, and legacy agricultural sources is present within an alluvial aquifer in the Rialto-Colton groundwater subbasin, 80 km east of Los Angeles, California (USA). The area is extensively faulted, with water-level differences exceeding 60 m across parts of the Rialto-Colton Fault separating the Rialto-Colton and Chino groundwater subbasins. Coupled well-bore flow and depth-dependent water-quality data show decreases in well yield and changes in water chemistry and isotopic composition, reflecting changing aquifer properties and groundwater recharge sources with depth. Perchlorate movement through some wells under unpumped conditions from shallower to deeper layers underlying mapped plumes was as high as 13 kg/year. Water-level maps suggest potential groundwater movement across the Rialto-Colton Fault through an overlying perched aquifer. Upward flow through a well in the Chino subbasin near the Rialto-Colton Fault suggests potential groundwater movement across the fault through permeable layers within partly consolidated deposits at depth. Although potentially important locally, movement of groundwater from the Rialto-Colton subbasin has not resulted in widespread occurrence of perchlorate within the Chino subbasin. Nitrate and perchlorate concentrations at the water table, associated with legacy agricultural fertilizer use, may be underestimated by data from long-screened wells that mix water from different depths within the aquifer.

California

Transport of nitrate in the Mississippi river in July-August 1999

Lagrangian sampling was conducted on the Mississippi River in late July through early August 1999 to test the hypothesis that nitrate (NO 3 - ) is transported conservatively in the Mississippi River. Three different approaches were pursued to test the hypothesis: (1) a mass balance for NO 3 - was evaluated for evidence of net gains and losses, (2) stable isotopes of NO 3 - were measured (δ 15 N and δ 18 O) to determine if fractionation occurred, and (3) the concentrations of dissolved gases (N 2 O, N 2 and Ar) in river water were measured and compared to theoretical equilibrium concentrations. Integrated water samples and flow measurements were obtained at 10 sites on the Mississippi River and 7 sites near the mouths of major tributaries from northern Iowa to southern Louisiana, a distance of about 2,250 river kilometers. Mass balance calculations indicate that more than 80 percent of the NO 3 - mass discharged from the Mississippi River (1,930 metric tons/day) during the study period originated in the first 500 river kilometers of the study reach. The mass balance calculations also indicate that NO 3 - was not lost from the water column upstream of Vicksburg, MS, but that there might have been some loss of NO 3 - in the lower 700 kilometers of the study reach. The stable isotope ratios of N and O (δ 15 N and δ 18 O) of NO 3 - were consistent with mixing and transport in the absence of fractionating gains or losses. The concentrations of nitrogen (N 2 ) and argon (Ar) dissolved in river water decreased in the downstream direction, approximately in equilibrium with air at increasing temperatures, giving no evidence of gains or losses of N 2 by nitrogen fixation or denitrification. Nitrous oxide (N 2 O) concentrations in the Mississippi River were approximately 26 to 200 percent of air saturation, indicating relatively low net production by combination of nitrification and denitrification. Results from this study indicate that most (>90%) of the NO 3 - that entered the Mississippi River during July-August 1999 was transported to the Gulf of Mexico.

Mississippi River

Comprehensive inter-laboratory calibration of reference materials for δ18O versus VSMOW using various on-line high-temperature conversion techniques

Internationally distributed organic and inorganic oxygen isotopic reference materials have been calibrated by six laboratories carrying out more than 5300 measurements using a variety of high-temperature conversion techniques (HTC) in an evaluation sponsored by the International Union of Pure and Applied Chemistry (IUPAC). To aid in the calibration of these reference materials, which span more than 125‰, an artificially enriched reference water ( δ 18 O of +78.91‰) and two barium sulfates (one depleted and one enriched in 18 O) were prepared and calibrated relative to VSMOW2 and SLAP reference waters. These materials were used to calibrate the other isotopic reference materials in this study, which yielded: Reference material δ 18 O and estimated combined uncertainty IAEA-602 benzoic acid +71.28 ± 0.36‰ USGS35 sodium nitrate +56.81 ± 0.31‰ IAEA-NO-3 potassium nitrate +25.32 ± 0.29‰ IAEA-601 benzoic acid +23.14 ± 0.19‰ IAEA-SO-5 barium sulfate +12.13 ± 0.33‰ NBS 127 barium sulfate +8.59 ± 0.26‰ VSMOW2 water 0‰ IAEA-600 caffeine −3.48 ± 0.53‰ IAEA-SO-6 barium sulfate −11.35 ± 0.31‰ USGS34 potassium nitrate −27.78 ± 0.37‰ SLAP water −55.5‰ The seemingly large estimated combined uncertainties arise from differences in instrumentation and methodology and difficulty in accounting for all measurement bias. They are composed of the 3-fold standard errors directly calculated from the measurements and provision for systematic errors discussed in this paper. A primary conclusion of this study is that nitrate samples analyzed for δ 18 O should be analyzed with internationally distributed isotopic nitrates, and likewise for sulfates and organics. Authors reporting relative differences of oxygen-isotope ratios ( δ 18 O) of nitrates, sulfates, or organic material should explicitly state in their reports the δ 18 O values of two or more internationally distributed nitrates (USGS34, IAEA-NO-3, and USGS35), sulfates (IAEA-SO-5, IAEA-SO-6, and NBS 127), or organic material (IAEA-601 benzoic acid, IAEA-602 benzoic acid, and IAEA-600 caffeine), as appropriate to the material being analyzed, had these reference materials been analyzed with unknowns. This procedure ensures that readers will be able to normalize the δ 18 O values at a later time should it become necessary. The high-temperature reduction technique for analyzing δ 18 O and δ 2 H is not as widely applicable as the well-established combustion technique for carbon and nitrogen stable isotope determination. To obtain the most reliable stable isotope data, materials should be treated in an identical fashion; within the same sequence of analyses, samples should be compared with working reference materials that are as similar in nature and in isotopic composition as feasible.

Rapid Communications in Mass Spectrometry

A simple technique for continuous measurement of time-variable gas transfer in surface waters

Mass balance models of dissolved gases in streams, lakes, and rivers serve as the basis for estimating wholeecosystem rates for various biogeochemical processes. Rates of gas exchange between water and the atmosphere are important and error-prone components of these models. Here we present a simple and efficient modification of the SF6 gas tracer approach that can be used concurrently while collecting other dissolved gas samples for dissolved gas mass balance studies in streams. It consists of continuously metering SF6-saturated water directly into the stream at a low rate of flow. This approach has advantages over pulse injection of aqueous solutions or bubbling large amounts of SF6 into the stream. By adding the SF6 as a saturated solution, we minimize the possibility that other dissolved gas measurements are affected by sparging and/or bubble injecta. Because the SF6 is added continuously we have a record of changing gas transfer velocity (GTV) that is contemporaneous with the sampling of other nonconservative ambient dissolved gases. Over a single diel period, a 30% variation in GTV was observed in a second-order stream (Sugar Creek, Indiana, USA). The changing GTV could be attributed in part to changes in temperature and windspeed that occurred on hourly to diel timescales.

Limnology and Oceanography: Methods

Fractionation of stable isotopes in perchlorate and nitrate during in situ biodegradation in a sandy aquifer

An in situ experiment was performed in a shallow alluvial aquifer in Maryland to quantify the fractionation of stable isotopes in perchlorate (Cl and O) and nitrate (N and O) during biodegradation. An emulsified soybean oil substrate that was previously injected into this aquifer provided the electron donor necessary for biological perchlorate reduction and denitrification. During the field experiment, groundwater extracted from an upgradient well was pumped into an injection well located within the in situ oil barrier, and then groundwater samples were withdrawn for the next 30 h. After correction for dilution (using Br– as a conservative tracer of the injectate), perchlorate concentrations decreased by 78% and nitrate concentrations decreased by 82% during the initial 8.6 h after the injection. The observed ratio of fractionation effects of O and Cl isotopes in perchlorate (e18O/e37Cl) was 2.6, which is similar to that observed in the laboratory using pure cultures (2.5). Denitrification by indigenous bacteria fractionated O and N isotopes in nitrate at a ratio of ~0.8 (e18O/e15N), which is within the range of values reported previously for denitrification. However, the magnitudes of the individual apparent in situ isotope fractionation effects for perchlorate and nitrate were appreciably smaller than those reported in homogeneous closed systems (0.2 to 0.6 times), even after adjustment for dilution. These results indicate that (1) isotope fractionation factor ratios (e18O/e37Cl, e18O/e15N) derived from homogeneous laboratory systems (e.g. pure culture studies) can be used qualitatively to confirm the occurrence of in situ biodegradation of both perchlorate and nitrate, but (2) the magnitudes of the individual apparent e values cannot be used quantitatively to estimate the in situ extent of biodegradation of either anion.

Environmental Chemistry

The oxygen-18 isotope approach for measuring aquatic metabolism in high-productivity waters

We examined the utility of δ 18 O 2 measurements in estimating gross primary production (P), community respiration (R), and net metabolism (P : R) through diel cycles in a productive agricultural stream located in the midwestern U.S.A. Large diel swings in O 2 (±200 µmol L −1 ) were accompanied by large diel variation in δ 18 O 2 (±10‰). Simultaneous gas transfer measurements and laboratory‐derived isotopic fractionation factors for O 2 during respiration (α r ) were used in conjunction with the diel monitoring of O 2 and δ 18 O 2 to calculate P, R, and P :R using three independent isotope‐based methods. These estimates were compared to each other and against the traditional “open‐channel diel O 2 ‐change” technique that lacked δ 18 O 2 . A principal advantage of the δ 18 O 2 measurements was quantification of diel variation in R, which increased by up to 30% during the day, and the diel pattern in R was variable and not necessarily predictable from assumed temperature effects on R. The P, R, and P :R estimates calculated using the isotope‐based approaches showed high sensitivity to the assumed system fractionation factor (α r ). The optimum modeled ar values (0.986‐0.989) were roughly consistent with the laboratory‐derived values, but larger (i.e., less fractionation) than α r values typically reported for enzyme‐limited respiration in open water environments. Because of large diel variation in O 2 , P :R could not be estimated by directly applying the typical steady‐state solution to the O 2 and 18 O‐O 2 mass balance equations in the absence of gas transfer data. Instead, our results indicate that a modified steady‐state solution (the daily mean value approach) could be used with time‐averaged O 2 and δ 18 O 2 measurements to calculate P :R independent of gas transfer. This approach was applicable under specifically defined, net heterotrophic conditions. The diel cycle of increasing daytime R and decreasing nighttime R was only partially explained by temperature variation, but could be consistent with the diel production/consumption of labile dissolved organic carbon from photosynthesis.

Limnology and Oceanography

Isotopic analysis of N and O in nitrite and nitrate by sequential selective bacterial reduction to N2O

Nitrite is an important intermediate species in the biogeochemical cycling of nitrogen, but its role in natural aquatic systems is poorly understood. Isotopic data can be used to study the sources and transformations of NO 2 - in the environment, but methods for independent isotopic analyses of NO 2 - in the presence of other N species are still new and evolving. This study demonstrates that isotopic analyses of N and O in NO 2 - can be done by treating whole freshwater or saltwater samples with the denitrifying bacterium Stenotrophomonas nitritireducens , which selectively reduces NO 2 - to N 2 O for isotope ratio mass spectrometry. When calibrated with solutions containing NO 2 - with known isotopic compositions determined independently, reproducible δ 15 N and δ 18 O values were obtained at both natural-abundance levels (±0.2−0.5‰ for δ 15 N and ±0.4−1.0‰ for δ 18 O) and moderately enriched 15 N tracer levels (±20−50‰ for δ 15 N near 5000‰) for 5−20 nmol of NO 2 - (1−20 μmol/L in 1−5 mL aliquots). This method is highly selective for NO 2 - and was used for mixed samples containing both NO 2 - and NO 3 - with little or no measurable cross-contamination. In addition, mixed samples that were analyzed with S. nitritireducens were treated subsequently with Pseudomonas aureofaciens to reduce the NO 3 - in the absence of NO 2 - , providing isotopic analyses of NO 2 - and NO 3 - separately in the same aliquot. Sequential bacterial reduction methods like this one should be useful for a variety of isotopic studies aimed at understanding nitrogen cycling in aquatic environments. A test of these methods in an agricultural watershed in Indiana provides isotopic evidence for both nitrification and denitrification as sources of NO 2 - in a small stream.

Indiana

Oxygen isotopes in nitrite: Analysis, calibration, and equilibration

Nitrite is a central intermediate in the nitrogen cycle and can persist in significant concentrations in ocean waters, sediment pore waters, and terrestrial groundwaters. To fully interpret the effect of microbial processes on nitrate (NO 3 - ), nitrite (NO 2 - ), and nitrous oxide (N 2 O) cycling in these systems, the nitrite pool must be accessible to isotopic analysis. Furthermore, because nitrite interferes with most methods of nitrate isotopic analysis, accurate isotopic analysis of nitrite is essential for correct measurement of nitrate isotopes in a sample that contains nitrite. In this study, nitrite salts with varying oxygen isotopic compositions were prepared and calibrated and then used to test the denitrifier method for nitrite oxygen isotopic analysis. The oxygen isotopic fractionation during nitrite reduction to N 2 O by Pseudomonas aureofaciens was lower than for nitrate conversion to N 2 O, while oxygen isotopic exchange between nitrite and water during the reaction was similar. These results enable the extension of the denitrifier method to oxygen isotopic analysis of nitrite (in the absence of nitrate) and correction of nitrate isotopes for the presence of nitrite in “mixed” samples. We tested storage conditions for seawater and freshwater samples that contain nitrite and provide recommendations for accurate oxygen isotopic analysis of nitrite by any method. Finally, we report preliminary results on the equilibrium isotope effect between nitrite and water, which can play an important role in determining the oxygen isotopic value of nitrite where equilibration with water is significant.

Analytical Chemistry

Aquifer-scale controls on the distribution of nitrate and ammonium in ground water near La Pine, Oregon, USA

Geochemical and isotopic tools were applied at aquifer, transect, and subtransect scales to provide a framework for understanding sources, transport, and fate of dissolved inorganic N in a sandy aquifer near La Pine, Oregon. NO3 is a common contaminant in shallow ground water in this area, whereas high concentrations of NH4-N (up to 39 mg/L) are present in deep ground water. N concentrations, N/Cl ratios, tracer-based apparent ground-water ages, N isotope data, and hydraulic gradients indicate that septic tank effluent is the primary source of NO3. N isotope data, N/Cl and N/C relations, 3H data, and hydraulic considerations point to a natural, sedimentary organic matter source for the high concentrations of NH4, and are inconsistent with an origin as septic tank N. Low recharge rates and flow velocities have largely restricted anthropogenic NO3 to isolated plumes within several meters of the water table. A variety of geochemical and isotopic data indicate that denitrification also affects NO3 gradients in the aquifer. Ground water in the La Pine aquifer evolves from oxic to increasingly reduced conditions. Suboxic conditions are achieved after about 15-30 y of transport below the water table. NO3 is denitrified near the oxic/suboxic boundary. Denitrification in the La Pine aquifer is characterized well at the aquifer scale with a redox boundary approach that inherently captures spatial variability in the distribution of electron donors.

Oregon

Ground water stratification and delivery of nitrate to an incised stream under varying flow conditions

Ground water processes affecting seasonal variations of surface water nitrate concentrations were investigated in an incised first-order stream in an agricultural watershed with a riparian forest in the coastal plain of Maryland. Aquifer characteristics including sediment stratigraphy, geochemistry, and hydraulic properties were examined in combination with chemical and isotopic analyses of ground water, macropore discharge, and stream water. The ground water flow system exhibits vertical stratification of hydraulic properties and redox conditions, with sub-horizontal boundaries that extend beneath the field and adjacent riparian forest. Below the minimum water table position, ground water age gradients indicate low recharge rates (2-5 cm yr-1) and long residence times (years to decades), whereas the transient ground water wedge between the maximum and minimum water table positions has a relatively short residence time (months to years), partly because of an upward increase in hydraulic conductivity. Oxygen reduction and denitrification in recharging ground waters are coupled with pyrite oxidation near the minimum water table elevation in a mottled weathering zone in Tertiary marine glauconitic sediments. The incised stream had high nitrate concentrations during high flow conditions when much of the ground water was transmitted rapidly across the riparian zone in a shallow oxic aquifer wedge with abundant outflow macropores, and low nitrate concentrations during low flow conditions when the oxic wedge was smaller and stream discharge was dominated by upwelling from the deeper denitrified parts of the aquifer. Results from this and similar studies illustrate the importance of near-stream geomorphology and subsurface geology as controls of riparian zone function and delivery of nitrate to streams in agricultural watersheds.

Maryland

Water-quality data from two agricultural drainage basins in northwestern Indiana and northeastern Illinois: I. Lagrangian and synoptic data, 1999-2002

Methods of data collection and results of analyses are presented for Lagrangian and synoptic water-quality data collected from two agricultural drainages, the Iroquois River in northwestern Indiana and Sugar Creek in northwestern Indiana and northeastern Illinois. During six separate sampling trips, in April, June and September 1999, May 2000, September 2001 and April 2002, 152 discrete water samples were collected to characterize the water chemistry over the course of 2 to 4 days on each of these drainages. Data were collected for nutrients, major inorganic constituents, dissolved organic carbon, trace elements, dissolved gases, total bacterial cell counts, chlorophyll- a concentrations, and suspended sediment concentrations. In addition, field measurements of streamflow, pH, specific conductance, water temperature, and dissolved oxygen concentration were made during all trips except April 1999.

Indiana, Illinois