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J.K. Bohlke

Publications and source records attributed to J.K. Bohlke.

At least 73 records · Page 4Linked to original sources

Effects of nitrate and water on the oxygen isotopic analysis of barium sulfate precipitated from water samples

BaSO 4 precipitated from mixed salt solutions by common techniques for SO isotopic analysis may contain quantities of H 2 O and NO that introduce errors in O isotope measurements. Experiments with synthetic solutions indicate that δ 18 O values of CO produced by decomposition of precipitated BaSO 4 in a carbon reactor may be either too low or too high, depending on the relative concentrations of SO and NO and the δ 18 O values of the H 2 O, NO , and SO . Typical δ 18 O errors are of the order of 0.5 to 1‰ in many sample types, and can be larger in samples containing atmospheric NO , which can cause similar errors in δ 17 O and Δ 17 O. These errors can be reduced by (1) ion chromatographic separation of SO from NO , (2) increasing the salinity of the solutions before precipitating BaSO 4 to minimize incorporation of H 2 O, (3) heating BaSO 4 under vacuum to remove H 2 O, (4) preparing isotopic reference materials as aqueous samples to mimic the conditions of the samples, and (5) adjusting measured δ 18 O values based on amounts and isotopic compositions of coexisting H 2 O and NO . These procedures are demonstrated for SO isotopic reference materials, synthetic solutions with isotopically known reagents, atmospheric deposition from Shenandoah National Park, Virginia, USA, and sulfate salt deposits from the Atacama Desert, Chile, and Mojave Desert, California, USA. These results have implications for the calibration and use of O isotope data in studies of SO sources and reaction mechanisms.

Rapid Communications in Mass Spectrometry↗

New reference materials for nitrogen-isotope-ratio measurements

Three new reference materials were manufactured for calibration of relative stable nitrogen‐isotope‐ratio measurements: USGS25 (ammonium sulfate) δ615″=−30 per mil USGS26 (ammonium sulfate) δ615″=+54 per mil USGS32 (potassium nitrate) δ615″=+180 per mil where δN′, relative to atmospheric nitrogen, is an approximate value subject to change following interlaboratory comparisons. These materials are isotopically homogeneous in aliquots at least as small as 10 pot N, (or about 1‐2 mg of salt). The new reference materials greatly extend the range of δ15N values of internationally distributed standards, and they allow normalization of δ15N measurements over almost the full range of known natural isotope variation on Earth. The methods used to produce these materials may be adapted to produce homogeneous local laboratory standards for routine use.

Geostandards Newsletter↗

Tracermodel1- Excel workbook for calculation and presentation of environmental tracer data for simple groundwater mixtures: Use of chlorofluorocarbons in hydrology - a guidebook; Section III.10.3

Atmospheric environmental tracers commonly used to date groundwater on timescales of years to decades include CFC-11, CFC-12, CFC-113, SF6, 85Kr, 3 H and 3 H/3 H0 , where 3 H0 refers to initial tritium (3 H + tritiogenic 3 He) (Cook and Herczeg, 2000). Interpretation of age from environmental tracer data may be relatively simple for a water sample with a single age, but the interpretation is more complex for a sample that is a mixture of waters of varying ages. A mixture can be a natural result of convergence of flow lines to a discharge area such as a spring or stream, or it can be an artefact of sampling a long-screen well. TRACERMODEL1 contains a worksheet that can be used to determine hypothetical concentrations of atmospheric environmental tracers in water samples with several different age distributions. It is designed to permit plotting of ages and tracer concentrations in a variety of different combinations to facilitate interpretation of measurements. TRACERMODEL1 includes several different types of graphs that are linked to the calculations. The spreadsheet and accompanying graphs can be modified for specific applications. For example, the selection of atmospheric environmental tracers can be changed to reflect analytes of interest, the input tracer data can be modified to reflect local conditions or different timescales, and the analytes of interest can include other types of non-point-source contaminants, such as nitrate (Böhlke, 2002). Previous versions of this workbook have been used to evaluate field data in studies of groundwater residence time and agricultural contamination (Böhlke and Denver, 1995; Focazio et al., 1998; Katz et al., 1999; Katz et al., 2001; Plummer et al., 2001; Böhlke and Krantz, 2003; Lindsey et al., 2003).

Report↗

Assessing denitrification in groundwater using natural gradient tracer tests with 15N: In situ measurement of a sequential multistep reaction

Denitrification was measured within a nitrate‐contaminated aquifer on Cape Cod, Massachusetts, using natural gradient tracer tests with 15 N nitrate. The aquifer contained zones of relatively high concentrations of nitrite (up to 77 μM) and nitrous oxide (up to 143 μM) and has been the site of previous studies examining ground water denitrification using the acetylene block technique. Small‐scale (15–24 m travel distance) tracer tests were conducted by injecting 15 N nitrate and bromide as tracers into a depth interval that contained nitrate, nitrite, nitrous oxide, and excess nitrogen gas. The timing of the bromide breakthrough curves at down‐gradient wells matched peaks in 15 N abundance above background for nitrate, nitrite, nitrous oxide, and nitrogen gas after more than 40 days of travel. Results were simulated with a one‐dimensional transport model using linked reaction kinetics for the individual steps of the denitrification reaction pathway. It was necessary to include within the model spatial variations in background concentrations of all nitrogen oxide species. The model indicated that nitrite production (0.036–0.047 μmol N (L aquifer) −1 d −1 ) was faster than the subsequent denitrification steps (0.013–0.016 μmol N (L aquifer) −1 d −1 for nitrous oxide and 0.013–0.020 μmol N (L aquifer) −1 d −1 for nitrogen gas) and that the total rate of reaction was slower than indicated by both acetylene block tracer tests and laboratory incubations. The rate of nitrate removal by denitrification was much slower than the rate of transport, indicating that nitrate would migrate several kilometers down‐gradient before being completely consumed.

Water Resources Research↗

Using dual-bacterial denitrification to improve δ15N determinations of nitrates containing mass-independent 17O

The bacterial denitrification method for isotopic analysis of nitrate using N 2 O generated from Pseudomonas aureofaciens may overestimate δ 15 N values by as much as 1–2‰ for samples containing atmospheric nitrate because of mass-independent 17 O variations in such samples. By analyzing such samples for δ 15 N and δ 18 O using the denitrifier Pseudomonas chlororaphis , one obtains nearly correct δ 15 N values because oxygen in N 2 O generated by P. chlororaphis is primarily derived from H 2 O. The difference between the apparent δ 15 N value determined with P. aureofaciens and that determined with P. chlororaphis , assuming mass-dependent oxygen isotopic fractionation, reflects the amount of mass-independent 17 O in a nitrate sample. By interspersing nitrate isotopic reference materials having substantially different δ 18 O values with samples, one can normalize oxygen isotope ratios and determine the fractions of oxygen in N 2 O derived from the nitrate and from water with each denitrifier. This information can be used to improve δ 15 N values of nitrates having excess 17 O. The same analyses also yield estimates of the magnitude of 17 O excess in the nitrate (expressed as Δ 17 O) that may be useful in some environmental studies. The 1- σ uncertainties of δ 15 N, δ 18 O and Δ 17 O measurements are ±0.2, ±0.3 and ±5‰, respectively.

Rapid Communications in Mass Spectrometry↗

Use of environmental tracers and isotopes to evaluate sources of water, nitrate, and uranium in an irrigated alluvial valley, Nebraska

The effects of irrigation canals and the North Platte River on ground-water movement and quality in an irrigated alluvial valley, western Nebraska, were evaluated using environmental tracers. The results indicated that most of the ground water in the alluvium was derived from the North Platte River and generally was less than 30 years old. Ground-water-recharge rates varied substantially from about 0.6 to 9 feet per year with the larger recharge rates reflecting localized canal seepage. Younger water had higher nitrate concentrations than older water. Increases in nitrate concentrations in recharging ground water over time may be associated with an increase in nitrogen fertilizer use over time. Denitrification was limited in the ground water in the alluvium. Uranium concentrations in ground water resulted from dissolution of volcanic ash or other sediments in the underlying bedrock or incorporated in the alluvium. High uranium concentrations in the North Platte River during the winter months were a result of the addition of uranium-rich water from local tributaries and seepage of uranium-rich ground water.

Nebraska↗

Hydrogeologic framework, ground-water geochemistry, and assessment of nitrogen yield from base flow in two agricultural watersheds, Kent County, Maryland

Hydrostratigraphic and geochemical data collected in two adjacent watersheds on the Delmarva Peninsula, in Kent County, Maryland, indicate that shallow subsurface stratigraphy is an important factor that affects the concentrations of nitrogen in ground water discharging as stream base flow. The flux of nitrogen from shallow aquifers can contribute substantially to the eutrophication of streams and estuaries, degrading water quality and aquatic habitats. The information presented in this report includes a hydrostratigraphic framework for the Locust Grove study area, analyses and interpretation of ground-water chemistry, and an analysis of nutrient yields from stream base flow. An understanding of the processes by which ground-water nitrogen discharges to streams is important for optimal management of nutrients in watersheds in which ground-water discharge is an appreciable percentage of total streamflow. The U.S. Geological Survey, in cooperation with the U.S. Environmental Protection Agency (USEPA), collected and analyzed hydrostratigraphic and geochemical data in support of ground-water flow modeling by the USEPA. The adjacent watersheds of Morgan Creek and Chesterville Branch have similar topography and land use; however, reported nitrogen concentrations are generally 6 to 10 milligrams per liter in Chesterville Branch but only 2 to 4 milligrams per liter in Morgan Creek. Ground water in the surficial aquifer in the recharge areas of both streams has high concentrations of nitrate (greater than 10 milligrams per liter as N) and dissolved oxygen. One component of the ground water discharging to Morgan Creek typically is anoxic and contains virtually no dissolved nitrate; most of the ground water discharging to Chesterville Branch is oxygenated and contains moderately high concentrations of nitrate. The surficial aquifer in the study area is composed of the deeply weathered sands and gravels of the Pensauken Formation (the Columbia aquifer) and the underlying glauconitic sands of the upper Aquia Formation (the Aquia aquifer). The lower 6 to 9 meters of the Aquia Formation is a low-permeability silt-clay with abundant glauconite. The Aquia confining layer underlies the Columbia-Aquia surficial aquifer throughout the study area. The sediment redox transition, identified in cores, that occurs in the upper 0.5 to 1 meter of the Aquia confining layer is thought to be a site for subsurface denitrification of ground water. The first confined aquifer is composed of the glauconitic sands in the upper 9 to 11 meters of the Hornerstown Formation. The Hornerstown aquifer is underlain by 10 to 15 meters of glauconitic silt-clay at the base of the Hornerstown Formation (the Hornerstown confining layer), and 5 meters of low-permeability clay in the underlying Severn Formation. The Aquia and Hornerstown Formations dip and thicken to the southeast, and the Aquia confining layer subcrops shallowly (within 5 meters of the land surface) in a band that strikes southwest to northeast across the northern edge of the study area. The surficial aquifer is very thin (generally less than 5 meters) north of Morgan Creek, and the alluvial valley of Morgan Creek has incised into the top of the Aquia confining layer. In contrast, the Aquia confining layer lies 22 meters below Chesterville Branch, and the surficial aquifer approaches 30 meters in thickness (away from the creek). Chemically reduced iron sulfides and glauconite in the Aquia confining layer are likely substrates for denitrification of nitrate in ground water. Evidence from the dissolved concentrations of nitrate, sulfate, iron, argon, and nitrogen gas, and stable nitrogen isotopes support the interpretation that ground water flowing near the top of the Aquia confining layer, or through the confined Hornerstown aquifer, has undergone denitrification. This process appears to have the greatest effect on ground-water chemistry north of Morgan Creek, where the surficial aquifer is thin and a greater percentage of the ground water contacts the Aquia confining layer. The base-flow discharges of total nitrogen from the two watersheds are of similar magnitude, although Chesterville Branch has somewhat higher loads (29,000 kilograms of nitrogen per year) than Morgan Creek (20,000 kilograms of nitrogen per year), although Morgan Creek has a larger drainage area and a greater discharge of water. The base-flow yield of nitrogen (load per unit area) in Chesterville Branch (median of 0.058 grams per second per square kilometer at the outlet) is more than twice that of Morgan Creek (median of 0.022 grams per second per square kilometer at the outlet), reflecting the higher concentration of nitrate in ground water discharging to Chesterville Branch. Total nitrogen concentrations tend to decrease downstream in Chesterville Branch and increase downstream in Morgan Creek. The downstream trend in Chesterville Branch may be affected by instream nitrogen uptake and denitrification, and an increasing proportion of older, denitrified ground water in downstream discharge. The downstream trends in Morgan Creek may be affected by inflow from tributaries, downstream changes in the source of discharge water, and downstream changes in the riparian zone, which could affect the processes and degree of denitrification. Although these two watersheds appear to have landscape features (such as topography, land use, and soils) that would produce similar nitrogen discharges, a more detailed examination of landscape features indicates that Chesterville Branch has soils that are slightly better drained, tributary stream outlets at higher altitudes, and a slightly higher percentage of agricultural land. All of these factors have been related to higher nitrogen yields. Nonetheless, most of the data support the interpretation that hydrostratigraphy has the greatest effect in producing the difference in nitrogen yields between the two watersheds.

Maryland↗

Determining timescales for groundwater flow and solute transport

One of the principal uses of environmental tracers is for determining the ages of soil waters and groundwaters. (We may refer to this as ‘hydrochronology’by analogy with the dating of solid materials known as geochronology.) Information on soil water and groundwater age enables timescales for a range of subsurface processes to be determined. For example, ‘groundwater stratigraphy’is used increasingly to decipher past recharge rates and conditions in unconfined aquifers, in much the same way that sedimentary stratigraphy yields information about past depositional environments. The use of environmental tracers to determine water ages allows groundwater recharge rates and flow velocities to be determined independently, and commonly more accurately, than with traditional hydraulic methods where hydraulic properties of aquifers are poorly known or spatially variable. Studies of groundwater residence times in association with groundwater contamination studies can enable historic release rates of contaminants and contaminant transport rates to be determined. Where input rates are known, measurements of groundwater contaminant concentrations, together with groundwater dating, can sometimes be used for estimating chemical reaction rates. The combination of these dating methods with stable isotope measurements has sometimes allowed changes in contaminant sources over time to be determined.

Book chapter↗

Sources of nitrate in water from springs and the Upper Floridan aquifer, Suwannee River basin, Florida

In the Suwannee River basin of northern Florida, nitrate-N concentrations are 1.5 to 20 mg 1-1 in waters of the karstic Upper Floridan aquifer and in springs that discharge into the middle reach of the Suwannee River. During 1996-1997, fertilizers and animal wastes from farming operations in Suwannee County contributed approximately 49% and 45% of the total N input, respectively. Values of ??15N-NO3 in spring waters range from 3.9??? to 5.8???, indicating that nitrate most likely originates from a mixture of inorganic (fertilizers) and organic (animal waste) sources. In Lafayette County, animal wastes from farming operations and fertilizers contributed approximately 53% and 39% of the total N input, respectively, but groundwater near dairy and poultry farms has ??15N-NO3 values of 11.0-12.1???, indicative of an organic source of nitrate. Spring waters that discharge to the Suwannee River from Lafayette County have ??15N-NO3 values of 5.4-8.39???, which are indicative of both organic and inorganic sources. Based on analyses of CFCs, the mean residence time of shallow groundwater and spring water ranges between 8-12 years and 12-25 years, respectively.

IAHS-AISH Publication↗

Use of nitrogen isotopes to determine sources of nitrate contamination in two desert basins in California

Nitrogen-15/14 isotope ratios (δ 15 N) were measured in groundwater, infiltrating wastewater, and natural uncontaminated soil to determine the source of high NO 3 - concentrations in two desert basins at Fort Irwin National Training Center in the Mojave Desert. The abundance and isotopic composition of dissolved nitrogen gas were measured in some of the groundwater samples to determine the effects of denitrification on the abundance and isotopic composition of the NO 3 - . Delta 15 N-NO 3 values in groundwaters most likely to include sewage effluent ranged from about 11 to 23‰. Delta 15 N values in groundwater not near sources of sewage effluent ranged from 6 to 11‰, a range similar to that found in the overlying soils, which contain large concentrations of leachable NO 3 - presumed to be of natural origin. Some of the samples with relatively low NO 3 - concentrations and high δ 15 N values contained excess non-atmospheric nitrogen gas attributed to denitrification. These data indicate that high NO 3 - concentrations in groundwater unaffected by sewage effluent may result from leaching of naturally occurring nitrogen in desert soils, and that some of the NO 3 - may be removed by denitrification at the water table. Nitrogen-15/14 isotope ratios (δ 15 N) were measured in groundwater, infiltrating wastewater, and natural uncontaminated soil to determine the source of high NO 3 - concentrations in two desert basins at Fort Irwin National Training Center in the Mojave Desert. The abundance and isotopic composition of dissolved nitrogen gas were measured in some of the groundwater samples to determine the effects of denitrification on the abundance and isotopic composition of the NO 3 - . Delta 15 N-NO 3 values in groundwaters most likely to include sewage effluent ranged from about 11 to 23 per mil. Delta 15 N values in groundwater not near sources of sewage effluent ranged from 6 to 11 per mil, a range similar to that found in the overlying soils, which contain large concentrations of leachable NO 3 - presumed to be of natural origin. Some of the samples with relatively low NO 3 - concentrations and high δ 15 N values contained excess non-atmospheric nitrogen gas attributed to denitrification. These data indicate that high NO 3 - concentrations in groundwater unaffected by sewage effluent may result from leaching of naturally occurring nitrogen in desert soils, and that some of the NO 3 - may be removed by denitrification at the water table.

California↗