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J.K. Böhlke

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

At least 55 records · Page 3Linked to original sources

Vertical gradients in water chemistry and age in the southern High Plains Aquifer, Texas, 2002

The southern High Plains aquifer is the primary source of water used for domestic, industrial, and irrigation purposes in parts of New Mexico and Texas. Despite the aquifer's importance to the overall economy of the southern High Plains, fundamental ground-water characteristics, such as vertical gradients in water chemistry and age, remain poorly defined. As part of the U.S. Geological Survey's National Water-Quality Assessment Program, water samples from nested, short-screen monitoring wells installed in the southern High Plains aquifer at two locations (Castro and Hale Counties, Texas) were analyzed for field parameters, major ions, nutrients, trace elements, dissolved organic carbon, pesticides, stable and radioactive isotopes, and dissolved gases to evaluate vertical gradients in water chemistry and age in the aquifer. Tritium measurements indicate that recent (post-1953) recharge was present near the water table and that deeper water was recharged before 1953. Concentrations of dissolved oxygen were largest (2.6 to 5.6 milligrams per liter) at the water table and decreased with depth below the water table. The smallest concentrations were less than 0.5 milligram per liter. The largest major-ion concentrations generally were detected at the water table because of the effects of overlying agricultural activities, as indicated by postbomb tritium concentrations and elevated nitrate and pesticide concentrations at the water table. Below the zone of agricultural influence, major-ion concentrations exhibited small increases with depth and distance along flow paths because of rock/water interactions and mixing with water from the underlying aquifer in rocks of Cretaceous age. The concentration increases primarily were accounted for by dissolved sodium, bicarbonate, chloride, and sulfate. Nitrite plus nitrate concentrations at the water table were 2.0 to 6.1 milligrams per liter as nitrogen, and concentrations substantially decreased with depth in the aquifer to a maximum concentration of 0.55 milligram per liter as nitrogen. Dissolved-gas and nitrogen-isotope data from the deep wells in Castro County indicate that denitrification occurred in the aquifer, removing 74 to more than 97 percent of the nitrate originally present in recharge. There was no evidence of denitrification in the deep part of the aquifer in Hale County. After correcting for denitrification effects, the background concentration of nitrate in water recharged before 1953 ranged from 0.4 to 3.2 milligrams per liter as nitrogen, with an average of 1.6 milligrams per liter as nitrogen. The d15N composition of background nitrate at the time of recharge was estimated to range from 9.6 to 12.3 per mil. Mass-balance models indicate that the decreases in dissolved oxygen and nitrate concentrations and small increases in major-ion concentrations along flow paths can be accounted for by small amounts of silicate-mineral and calcite dissolution; SiO2, goethite, and clay-mineral precipitation; organic-carbon and pyrite oxidation; denitrification; and cation exchange. Mass-balance models for some wells also required mixing with water from the underlying aquifer in rocks of Cretaceous age to achieve mole and isotope balances. Carbon mass transfers identified in the models were used to adjust radiocarbon ages of water samples recharged before 1953. Adjusted radiocarbon ages ranged from less than 1,000 to 9,000 carbon-14 years before present. Radiocarbon ages were more sensitive to uncertainties in the carbon-14 content of recharge than uncertainties in carbon mass transfers, leading to 1-sigma uncertainties of about ?2,000 years in the adjusted ages. Despite these relatively large uncertainties in adjusted radiocarbon ages, it appears that deep water in the aquifer was considerably older (at least 1,000 years) than water near the water table. There was essentially no change in ground-water age with depth in deeper parts of the aquifer, indicating that water in that

Texas↗

Two new organic reference materials for δ13C and δ15N measurements and a new value for the δ13C of NBS 22 oil

Analytical grade L-glutamic acid is chemically stable and has a C/N mole ratio of 5, which is close to that of many of natural biological materials, such as blood and animal tissue. Two L-glutamic acid reference materials with substantially different 13 C and 15 N abundances have been prepared for use as organic reference materials for C and N isotopic measurements. USGS40 is analytical grade L-glutamic acid and has a δ 13 C value of −26.24‰ relative to VPDB and a δ 15 N value of −4.52‰ relative to N 2 in air. USGS41 was prepared by dissolving analytical grade L-glutamic acid with L-glutamic acid enriched in 13 C and 15 N. USGS41 has a δ 13 C value of +37.76‰ and a δ 15 N value of +47.57‰. The δ 13 C and δ 15 N values of both materials were measured against the international reference materials NBS 19 calcium carbonate ( δ 13 C = +1.95‰), L-SVEC lithium carbonate ( δ 13 C = −46.48‰), IAEA-N-1 ammonium sulfate ( δ 15 N = 0.43‰), and USGS32 potassium nitrate ( δ 15 N = 180‰) by on-line combustion continuous-flow and off-line dual-inlet isotope-ratio mass spectrometry. Both USGS40 and USGS41 are isotopically homogeneous; reproducibility of δ 13 C is better than 0.13‰, and that of δ 15 N is better than 0.13‰ in 100-μg amounts. These two isotopic reference materials can be used for (i) calibrating local laboratory reference materials, and (ii) quantifying drift with time, mass-dependent fractionations, and isotope-ratio-scale contraction in the isotopic analysis of various biological materials. Isotopic results presented in this paper yield a δ 13 C value for NBS 22 oil of −29.91‰, in contrast to the commonly accepted value of −29.78‰ for which off-line blank corrections probably have not been quantified satisfactorily.

Rapid Communications in Mass Spectrometry↗

Oxygen isotopes in nitrate: New reference materials for 18O:17O:16O measurements and observations on nitrate-water equilibration

Despite a rapidly growing literature on analytical methods and field applications of O isotope-ratio measurements of NO 3 − in environmental studies, there is evidence that the reported data may not be comparable because reference materials with widely varying δ 18 O values have not been readily available. To address this problem, we prepared large quantities of two nitrate salts with contrasting O isotopic compositions for distribution as reference materials for O isotope-ratio measurements: USGS34 (KNO 3 ) with low δ 18 O and USGS35 (NaNO 3 ) with high δ 18 O and ‘mass-independent’ δ 17 O. The procedure used to produce USGS34 involved equilibration of HNO 3 with 18 O-depleted meteoric water. Nitric acid equilibration is proposed as a simple method for producing laboratory NO 3 − reference materials with a range of δ 18 O values and normal (mass-dependent) 18 O: 17 O: 16 O variation. Preliminary data indicate that the equilibrium O isotope-fractionation factor ( α ) between [NO 3 − ] and H 2 O decreases with increasing temperature from 1.0215 at 22°C to 1.0131 at 100°C. USGS35 was purified from the nitrate ore deposits of the Atacama Desert in Chile and has a high 17 O: 18 O ratio owing to its atmospheric origin. These new reference materials, combined with previously distributed NO 3 − isotopic reference materials IAEA-N3 (=IAEA-NO-3) and USGS32, can be used to calibrate local laboratory reference materials for determining offset values, scale factors, and mass-independent effects on N and O isotope-ratio measurements in a wide variety of environmental NO 3 − samples. Preliminary analyses yield the following results (normalized with respect to VSMOW and SLAP, with reproducibilities of ±0.2–0.3‰, 1 σ ): IAEA-N3 has δ 18 O = +25.6‰ and δ 17 O = +13.2‰; USGS32 has δ 18 O = +25.7‰; USGS34 has δ 18 O = −27.9‰ and δ 17 O = −14.8‰; and USGS35 has δ 18 O = +57.5‰ and δ 17 O = +51.5‰.

Rapid Communications in Mass Spectrometry↗

The fate of wastewater-derived nitrate in the subsurface of the Florida Keys: Key Colony Beach, Florida

Shallow injection is the predominant mode of wastewater disposal for most tourist-oriented facilities and some residential communities in the US Florida Keys National Marine Sanctuary. Concern has been expressed that wastewater nutrients may be escaping from the saline groundwater system into canals and surrounding coastal waters and perhaps to the reef tract 10 km offshore, promoting unwanted algal growth and degradation of water quality. We performed a field study of the fate of wastewater-derived nitrate in the subsurface of a Florida Keys residential community (Key Colony Beach, FL) that uses this disposal method, analyzing samples from 21 monitoring wells and two canal sites. The results indicate that wastewater injection at 18–27 m depth into saline groundwater creates a large buoyant plume that flows quickly (within days) upward to a confining layer 6 m below the surface, and then in a fast flow path toward a canal 200 m to the east within a period of weeks to months. Low-salinity groundwaters along the fast flow path have nitrate concentrations that are not significantly reduced from that of the injected wastewaters (ranging from 400 to 600 μmol kg −1 ). Portions of the low-salinity plume off the main axis of flow have relatively long residence times (>2 months) and have had their nitrate concentrations strongly reduced by a combination of mixing and denitrification. These waters have dissolved N 2 concentrations up to 1.6 times air-saturation values with δ 15 N[N 2 ]=0.5-5‰, δ 15 N[NO 3 - ]=16-26‰, and calculated isotope fractionation factors of about −12±4‰, consistent with denitrification as the predominant nitrate reduction reaction. Estimated rates of denitrification of wastewater in the aquifer are of the order of 4 μmol kg -1 N day -1 or 0.008 day -1 . The data indicate that denitrification reduces the nitrate load of the injected wastewater substantially, but not completely, before it discharges to nearby canals.

Florida↗

Determination of the total oxygen isotopic composition of nitrate and the calibration of a Δ17Ο nitrate reference material

A thermal decomposition method was developed and tested for the simultaneous determination of δ 18 O and δ 17 Ο in nitrate. The thermal decomposition of AgNO 3 allows for the rapid and accurate determination of 18 O/ 16 O and 17 O/ 16 O isotopic ratios with a precision of ±1.5‰ for δ 18 O and ±0.11‰ for Δ 17 Ο (Δ 17 Ο = δ 17 Ο − 0.52 × δ 18 O). The international nitrate isotope reference material IAEA-NO3 yielded a δ 18 O value of +23.6‰ and Δ 17 Ο of −0.2‰, consistent with normal terrestrial mass-dependent isotopic ratios. In contrast, a large sample of NaNO 3 from the Atacama Desert, Chile, was found to have Δ 17 Ο = 21.56 ± 0.11‰ and δ 18 O = 54.9 ± 1.5‰, demonstrating a substantial mass-independent isotopic composition consistent with the proposed atmospheric origin of the desert nitrate. It is suggested that this sample (designated USGS-35) can be used to generate other gases (CO 2 , CO, N 2 O, O 2 ) with the same Δ 17 Ο to serve as measurement references for a variety of applications involving mass-independent isotopic compositions in environmental studies.

Analytical Chemistry↗

Denitrification in the recharge area and discharge area of a transient agricultural nitrate plume in a glacial outwash sand aquifer, Minnesota

Recharge rates of nitrate (NO 3 − ) to groundwater beneath agricultural land commonly are greater than discharge rates of NO 3 − in nearby streams, but local controls of NO 3 − distribution in the subsurface generally are poorly known. Groundwater dating (CFC, 3 H) was combined with chemical (ions and gases) and stable isotope (N, S, and C) analyses to resolve the effects of land use changes, flow patterns, and water‐aquifer reactions on the distributions of O 2 , NO 3 − , SO 4 = , and other constituents in a two‐dimensional vertical section leading from upland cultivated fields to a riparian wetland and stream in a glacial outwash sand aquifer near Princeton, Minnesota. Within this section a “plume” of oxic NO 3 − ‐rich groundwater was present at shallow depths beneath the fields and part of the wetland but terminated before reaching the stream or the wetland surface. Groundwater dating and hydraulic measurements indicate travel times in the local flow system of 0 to >40 years, with stratified recharge beneath the fields, downward diversion of the shallow NO 3 − ‐bearing plume by semiconfining organic‐rich valley‐filling sediments under the wetland and upward discharge across the valley and stream bottom. The concentrations and δ 15 N values of NO 3 − and N 2 indicate that the NO 3 − plume section was bounded in three directions by a curvilinear zone of active denitrification that limited its progress; however, when recalculated to remove the effects of denitrification, the data also indicate changes in both the concentrations and δ 15 N values of NO 3 − that was recharged in the past. Isotope data and mass balance calculations indicate that FeS 2 and other ferrous Fe phases were the major electron donors for denitrification in at least two settings: (1) within the glacial‐fluvial aquifer sediments beneath the recharge and discharge areas and (2) along the bottom of the valley‐filling sediments in the discharge area. Combined results indicate that the shape and progress of the oxic NO 3 − plume termination were controlled by a combination of (1) historical and spatial variations in land use practices, (2) contrast in groundwater flow patterns between the agricultural recharge area and riparian wetland discharge area, and (3) distribution and abundance of electron donors in both the sand aquifer and valley‐filling sediments. The data are consistent with slow migration of redox zones through the aquifer in response to recharging oxic groundwater during Holocene time, then an order‐of‐magnitude increase in the flux of electron acceptors as a result of agricultural NO 3 − contamination in the late twentieth century, to which the redox zone configuration still may be adjusting. The importance of denitrification for NO 3 − movement through formerly glaciated terrains should depend on the source areas and depositional environments of the glacial sediments, as well as geomorphology and recent stream‐valley sediment history.

Water Resources Research↗

Groundwater recharge and agricultural contamination

Agriculture has had direct and indirect effects on the rates and compositions of groundwater recharge and aquifer biogeochemistry. Direct effects include dissolution and transport of excess quantities of fertilizers and associated materials and hydrologic alterations related to irrigation and drainage. Some indirect effects include changes in water–rock reactions in soils and aquifers caused by increased concentrations of dissolved oxidants, protons, and major ions. Agricultural activities have directly or indirectly affected the concentrations of a large number of inorganic chemicals in groundwater, for example NO 3 – , N 2 , Cl, SO 4 2– , H + , P, C, K, Mg, Ca, Sr, Ba, Ra, and As, as well as a wide variety of pesticides and other organic compounds. For reactive contaminants like NO 3 – , a combination of chemical, isotopic, and environmental-tracer analytical approaches might be required to resolve changing inputs from subsequent alterations as causes of concentration gradients in groundwater. Groundwater records derived from multi-component hydrostratigraphic data can be used to quantify recharge rates and residence times of water and dissolved contaminants, document past variations in recharging contaminant loads, and identify natural contaminant-remediation processes. These data indicate that many of the world's surficial aquifers contain transient records of changing agricultural contamination from the last half of the 20th century. The transient agricultural groundwater signal has important implications for long-term trends and spatial heterogeneity in discharge.

Hydrogeology Journal↗

Compilation of minimum and maximum isotope ratios of selected elements in naturally occurring terrestrial materials and reagents

Documented variations in the isotopic compositions of some chemical elements are responsible for expanded uncertainties in the standard atomic weights published by the Commission on Atomic Weights and Isotopic Abundances of the International Union of Pure and Applied Chemistry. This report summarizes reported variations in the isotopic compositions of 20 elements that are due to physical and chemical fractionation processes (not due to radioactive decay) and their effects on the standard atomic weight uncertainties. For 11 of those elements (hydrogen, lithium, boron, carbon, nitrogen, oxygen, silicon, sulfur, chlorine, copper, and selenium), standard atomic weight uncertainties have been assigned values that are substantially larger than analytical uncertainties because of common isotope abundance variations in materials of natural terrestrial origin. For 2 elements (chromium and thallium), recently reported isotope abundance variations potentially are large enough to result in future expansion of their atomic weight uncertainties. For 7 elements (magnesium, calcium, iron, zinc, molybdenum, palladium, and tellurium), documented isotope-abundance variations in materials of natural terrestrial origin are too small to have a significant effect on their standard atomic weight uncertainties. This compilation indicates the extent to which the atomic weight of an element in a given material may differ from the standard atomic weight of the element. For most elements given above, data are graphically illustrated by a diagram in which the materials are specified in the ordinate and the compositional ranges are plotted along the abscissa in scales of (1) atomic weight, (2) mole fraction of a selected isotope, and (3) delta value of a selected isotope ratio. There are no internationally distributed isotopic reference materials for the elements zinc, selenium, molybdenum, palladium, and tellurium. Preparation of such materials will help to make isotope ratio measurements among laboratories comparable. The minimum and maximum concentrations of a selected isotope in naturally occurring terrestrial materials for selected chemical elements reviewed in this report are given below: Isotope Minimum mole fraction Maximum mole fraction -------------------------------------------------------------------------------- 2H 0 .000 0255 0 .000 1838 7Li 0 .9227 0 .9278 11B 0 .7961 0 .8107 13C 0 .009 629 0 .011 466 15N 0 .003 462 0 .004 210 18O 0 .001 875 0 .002 218 26Mg 0 .1099 0 .1103 30Si 0 .030 816 0 .031 023 34S 0 .0398 0 .0473 37Cl 0 .240 77 0 .243 56 44Ca 0 .020 82 0 .020 92 53Cr 0 .095 01 0 .095 53 56Fe 0 .917 42 0 .917 60 65Cu 0 .3066 0 .3102 205Tl 0 .704 72 0 .705 06 The numerical values above have uncertainties that depend upon the uncertainties of the determinations of the absolute isotope-abundance variations of reference materials of the elements. Because reference materials used for absolute isotope-abundance measurements have not been included in relative isotope abundance investigations of zinc, selenium, molybdenum, palladium, and tellurium, ranges in isotopic composition are not listed for these elements, although such ranges may be measurable with state-of-the-art mass spectrometry. This report is available at the url: http://pubs.water.usgs.gov/wri014222.

Water-Resources Investigations Report↗

A bacterial method for the nitrogen isotopic analysis of nitrate in seawater and freshwater

We report a new method for measurement of the isotopic composition of nitrate (NO 3 - ) at the natural-abundance level in both seawater and freshwater. The method is based on the isotopic analysis of nitrous oxide (N 2 O) generated from nitrate by denitrifying bacteria that lack N 2 O-reductase activity. The isotopic composition of both nitrogen and oxygen from nitrate are accessible in this way. In this first of two companion manuscripts, we describe the basic protocol and results for the nitrogen isotopes. The precision of the method is better than 0.2‰ (1 SD) at concentrations of nitrate down to 1 μM, and the nitrogen isotopic differences among various standards and samples are accurately reproduced. For samples with 1 μM nitrate or more, the blank of the method is less than 10% of the signal size, and various approaches may reduce it further.

Analytical Chemistry↗

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↗

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 ( 3 H), and tritium/helium-3 ( 3 H/ 3 He) 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, 3 H, and 3 He, with evidence of partial CFC-11 degradation. The EMM gave a reasonable fit to CFC-113, CFC-12, and 3 H data, but did not reproduce the observed 3 He concentrations or 3 H/ 3 He ratios, nor did a combination PFM–EMM. The BMM could reproduce most of the multi-tracer data set only if both endmembers had 3 H 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.

Florida↗

Strontium isotope geochemistry of groundwaters and streams affected by agriculture, Locust Grove, MD

The effects of agriculture on the isotope geochemistry of Sr were investigated in two small watersheds in the Atlantic coastal plain of Maryland. Stratified shallow oxic groundwaters in both watersheds contained a retrievable record of increasing recharge rates of chemicals including NO 3 − , Cl, Mg, Ca and Sr that were correlated with increasing fertilizer use between about 1940 and 1990. The component of Sr associated with recent agricultural recharge was relatively radiogenic ( 87 Sr/ 86 Sr=0.715) and it was overwhelming with respect to Sr acquired naturally by water–rock interactions in the oxidized, non-calcareous portion of the saturated zone. Agricultural groundwaters that penetrated relatively unoxidized calcareous glauconitic sediments at depth acquired an additional component of Sr from dissolution of early Tertiary marine CaCO 3 ( 87 Sr/ 86 Sr=0.708) while undergoing O 2 reduction and denitrification. Ground-water discharge contained mixtures of waters of various ages and redox states. Two streams draining the area are considered to have higher 87 Sr/ 86 Sr ratios and NO 3 − concentrations than they would in the absence of agriculture; however, the streams have consistently different 87 Sr/ 86 Sr ratios and NO 3 − concentrations because the average depth to calcareous reducing (denitrifying) sediments in the local groundwater flow system was different in the two watersheds. The results of this study indicate that agriculture can alter significantly the isotope geochemistry of Sr in aquifers and streams and that the effects could vary depending on the types, sources and amounts of fertilizers added, the history of fertilizer use and groundwater residence times.

Maryland↗

Monthly variability and possible sources of nitrate in ground water beneath mixed agricultural land use, Suwannee and Lafayette Counties, Florida

In an area of mixed agricultural land use in Suwannee and Lafayette Counties of northern Florida, water samples were collected monthly from 14 wells tapping the Upper Floridan aquifer during July 1998 through June 1999 to assess hydrologic and land-use factors affecting the variability in nitrate concentrations in ground water. Unusually high amounts of rainfall in September and October 1998 (43.5 centimeters total for both months) resulted in an increase in water levels in all wells in October 1998. This was followed by unusually low amounts of rainfall during November 1998 through May 1999, when rainfall was 40.7 centimeters below 30-year mean monthly values. The presence of karst features (sinkholes, springs, solution conduits) and the highly permeable sands that overlie the Upper Floridan aquifer provide for rapid movement of water containing elevated nitrate concentrations to the aquifer. Nitrate was the dominant form of nitrogen in ground water collected at all sites and nitrate concentrations ranged from less than 0.02 to 22 milligrams per liter (mg/L), as nitrogen. Water samples from most wells showed substantial monthly or seasonal fluctuations in nitrate concentrations. Generally, water samples from wells with nitrate concentrations higher than 10 mg/L showed the greatest amount of monthly fluctuation. For example, water samples from six of eight wells had monthly nitrate concentrations that varied by at least 5 mg/L during the study period. Water from most wells with lower nitrate concentrations (less than 6 mg/L) also showed large monthly fluctuations. For instance, nitrate concentrations in water from four sites showed monthly variations of more than 50 percent. Large fluctuations in nitrate concentrations likely result from seasonal agricultural practices (fertilizer application and animal waste spreading) at a particular site. For example, an increase in nitrate concentrations observed in water samples from seven sites in February or March 1999 most likely results from application of synthetic fertilizers during the late winter months. Lower nitrate concentrations were detected in water samples from five of eight wells sampled during high-flow conditions for the Suwannee River in March 1998 compared to low-flow conditions in November 1998. Evidence for reduction of nitrate due to denitrification reactions was observed at one site (AC-1), as indicated by elevated concentrations of nitrogen gas and a corresponding increase in nitrogen isotope (d15N-NO3) values with a decrease in nitrate concentrations. Denitrification is unlikely at other sites based on the presence of dissolved oxygen concentrations greater than 2 mg/L in ground water and no observed trend between nitrate concentrations and values d15N-NO3 values. Nitrate was the dominant nitrogen species in most monthly rainfall samples; however, ammonium concentrations were similar or greater than nitrate during November and December 1998. During February through May 1999, both nitrate and ammonium concentrations were substantially higher in monthly rainfall samples collected at the study area compared to mean monthly concentrations at the Bradford Forest site located east of the study area, which is part of the National Atmospheric Deposition Program/National Trends Network. Also, higher nitrogen deposition rates in the study area compared to those at Bradford Forest could indicate that substantial amounts of ammonia are volatilized from fertilizers and animal wastes, released to the atmosphere, and incorporated as nitrate and ammonium in rainfall deposited in the middle Suwannee River Basin. Ground-water samples from most sites had d15N-NO3 values that indicated a mixture of inorganic and organic sources of nitrogen, which corresponded to multiple land uses where both synthetic fertilizers and manure are used on fields near these sites. Distinct d15N-NO3 signatures, however, were observed at some sites. For example, water samples from areas of row-crop farming as the dominant land use had d15N-NO3 values less than 4 per mil, indicating an inorganic nitrogen source such as synthetic fertilizer. In contrast, d15N-NO3 values greater than 9 per mil were found in water samples from three sites where manure from dairy and or poultry operations is spread on fields throughout the year.

Florida↗

Groundwater/surface-water interactions and sources of nitrogen and uranium in an irrigated area of Nebraska, USA

The effects of irrigation canals and the North Platte River on groundwater in western Nebraska, USA, were evaluated using chemical and isotopic data. The data indicated that groundwater in the associated alluvium generally is <20 years old with estimated recharge rates from about 10 to >100 cm year -1 . Most groundwater is derived from surface water, as shown by H 2 O and U isotope analyses. Seasonal losses of canal water to the aquifer cause changes in groundwater quality. In the deepest parts of the alluvium, some water quality may reflect precipitation recharge, older river water, or cross-formational flow. The distribution and isotopic composition of NO 3 - are consistent with increased fertilizer use over time. Relatively high U concentrations in groundwater may be attributed to dissolution of volcanic ash or other minerals in underlying bedrocks. The relatively high concentration of U in surface water at times is attributed to seepage from U-rich groundwater and flow of U-rich surface water from a tributary. The effects of irrigation canals and the North Platte River on groundwater in western Nebraska, USA, were evaluated using chemical and isotopic data. The data indicated that groundwater in the associated alluvium generally is <20 years old with estimated recharge rates from about 10 to >100 cm year -1 . Most groundwater is derived from surface water, as shown by H 2 O and U isotope analyses. Seasonal losses of canal water to the aquifer cause changes in groundwater quality. In the deepest parts of the alluvium, some water quality may reflect precipitation recharge, older river water, or cross-formational flow. The distribution and isotopic composition of NO 3 - are consistent with increased fertilizer use over time. Relatively high U concentrations in groundwater may be attributed to dissolution of volcanic ash or other minerals in underlying bedrock. The relatively high concentration of U in surface water at times is attributed to seepage from U-rich groundwater and flow of U-rich surface water from a tributary.

IAHS-AISH Publication↗

Denitrification in marine shales in northeastern Colorado

Parts of the South Platte River alluvial aquifer in northeastern Colorado are underlain by the Pierre Shale, a marine deposit of Late Cretaceous age that is <1000 m thick. Ground water in the aquifer is contaminated with NO 3 ‐ , and the shale contains abundant potential electron donors for denitrification in the forms of organic carbon and sulfide minerals. Nested piezometers were sampled, pore water was squeezed from cores of shale, and an injection test was conducted to determine if denitrification in the shale was a sink for alluvial NO 3 − and to measure denitrification rates in the shale. Measured values of NO 3 − , N 2 , NH 4 + , δ 15 N[NO 3 − ], δ 15 N[N 2 ], and δ 15 N[NH 4 + ] in the alluvial and shale pore water indicated that denitrification in the shale was a sink for alluvial NO 3 − . Chemical gradients, reaction rate constants, and hydraulic head data indicated that denitrification in the shale was limited by the slow rate of NO 3 − transport (possibly by diffusion) into the shale. The apparent in situ first‐order rate constant for denitrification in the shale based on diffusion calculations was of the order of 0.04–0.4 yr −1 , whereas the potential rate constant in the shale based on injection tests was of the order of 60 yr −1 . Chemical data and mass balance calculations indicate that organic carbon was the primary electron donor for denitrification in the shale during the injection test, and ferrous iron was a minor electron donor in the process. Flux calculations for the conditions encountered at the site indicate that denitrification in the shale could remove only a small fraction of the annual agricultural NO 3 ‐ input to the alluvial aquifer. However, the relatively large potential first‐order rate constant for denitrification in the shale indicated that the percentage of NO 3 − uptake by the shale could be considerably larger in areas where NO 3 − advection.

Colorado↗

Determination of δ 18 O and δ 15 N in Nitrate

The analyses of both O and N isotopic compositions of nitrate have many potential applications in studies of nitrate sources and reactions in hydrology, oceanography, and atmospheric chemistry, but simple and precise methods for these analyses have yet to be developed. Testing of a new method involving reaction of potassium nitrate with catalyzed graphite (C + Pd + Au) at 520 °C resulted in quantitative recovery of N and O from nitrate as free CO 2 , K 2 CO 3 , and N 2 . The δ 18 O values of nitrate reference materials were obtained by analyzing both the CO 2 and K 2 CO 3 from catalyzed graphite combustion. Provisional values of δ 18 O VSMOW for the internationally distributed KNO 3 reference materials IAEA-N3 and USGS-32 were both equal to +22.7 ± 0.5‰. Because the fraction of free CO 2 and the isotopic fractionation factor between CO 2 and K 2 CO 3 were constant in the combustion products, the δ 18 O value of KNO 3 could be calculated from measurements of the δ 18 O of free CO 2 . Thus, δ 18 O KNO 3 = a δ 18 O free CO 2 − b , where a and b were equal to 0.9967 and 3.3, respectively, for the specific conditions of the experiments. The catalyzed graphite combustion method can be used to determine δ 18 O of KNO 3 from measurements of δ 18 O of free CO 2 with reproducibility on the order of ±0.2‰ or better if local reference materials are prepared and analyzed with the samples. Reproducibility of δ 15 N was ±0.1‰ after trace amounts of CO were removed.

Analytical Chemistry↗

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↗