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J.K. Böhlke

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

At least 37 records · Page 2Linked to original sources

Limited occurrence of denitrification in four shallow aquifers in agricultural areas of the United States

The ability of natural attenuation to mitigate agricultural nitrate contamination in recharging aquifers was investigated in four important agricultural settings in the United States. The study used laboratory analyses, field measurements, and flow and transport modeling for monitoring well transects (0.5 to 2.5 km in length) in the San Joaquin watershed, California, the Elkhorn watershed, Nebraska, the Yakima watershed, Washington, and the Chester watershed, Maryland. Ground water analyses included major ion chemistry, dissolved gases, nitrogen and oxygen stable isotopes, and estimates of recharge date. Sediment analyses included potential electron donors and stable nitrogen and carbon isotopes. Within each site and among aquifer-based medians, dissolved oxygen decreases with ground water age, and excess N 2 from denitrification increases with age. Stable isotopes and excess N 2 imply minimal denitrifying activity at the Maryland and Washington sites, partial denitrification at the California site, and total denitrification across portions of the Nebraska site. At all sites, recharging electron donor concentrations are not sufficient to account for the losses of dissolved oxygen and nitrate, implying that relict, solid phase electron donors drive redox reactions. Zero-order rates of denitrification range from 0 to 0.14 μmol N L −1 d −1 , comparable to observations of other studies using the same methods. Many values reported in the literature are, however, orders of magnitude higher, which is attributed to a combination of method limitations and bias for selection of sites with rapid denitrification. In the shallow aquifers below these agricultural fields, denitrification is limited in extent and will require residence times of decades or longer to mitigate modern nitrate contamination.

Journal of Environmental Quality↗

Effects of topography and soil properties on recharge at two sites in an agricultural field

Field experiments were conducted from 1992 to 1995 to estimate ground water recharge rates at two sites located within a 2.7-hectare agricultural field. The field lies in a sand plain setting in central Minnesota and is cropped continuously in field corn. The sites are located at a topographically high (upland) site and a topographically low (lowland) site in an effort to quantify the effects of depression focusing of recharge. Three site-specific methods were used to estimate recharge rates: well hydrograph analysis, chlorofluorocarbon age dating, and an unsaturated zone water balance. All three recharge methods indicated that recharge rates at the lowland site (annual average of all methods of 29 cm) exceeded those at the upland site (annual average of 18 cm). On an annual basis, estimates by the individual methods ranged from 12 to 44 percent of precipitation at the upland site and from 21 to 83 percent at the lowland site. The difference in recharge rates between the sites is primarily attributed to depression focusing of surface water runon at the lowland site. However, two other factors were also important: the presence of thin lamellae at the upland site, and coarser textured soils below a depth of 1.5 m at the lowland site.

Minnesota↗

Effects of mother lode-type gold mineralization on 187Os/188Os and platinum group element concentrations in peridotite: Alleghany District, California

Osmium isotope compositions and concentrations of Re, platinum group elements (PGE), and Au were determined for host peridotites (serpentinites and barzburgites) and hydrothermally altered ultramafic wall rocks associated with Mother Lode-type hydrothermal gold-quartz vein mineralization in the Alleghany district, California. The host peridotites have Os isotope compositions and Re, PGE, and Au abundances typical of the upper mantle at their presumed formation age during the late Proterozoic or early Paleozoic. The hydrothermally altered rocks have highly variable initial Os isotope compositions with ??os, values (% deviation of 187OS/188OS from the chondritic average calculated for the approx. 120 Ma time of mineralization) ranging from -1.4 to -8.3. The lowest Os isotope compositions are consistent with Re depletion of a chondritic source (e.g., the upper mantle) at ca. 1.6 Ga. Most of the altered samples are enriched in Au and have depleted and fractionated abundances of Re and PGE relative to their precursor peridotites. Geoehemical characteristics of the altered samples suggest that Re and some PGE were variably removed from the ultramafic rocks during the mineralization event. In addition to Re, the Pt and Pd abundances of the most intensely altered rocks appear to have been most affected by mineralization. The 187Os-depleted isotopic compositions of some altered rocks are interpreted to be a result of preferential 187Os loss via destruction of Re-rich phases during the event. For these rocks, Os evidently is not a useful tracer of the mineralizing fluids. The results do, however, provide evidence for differential mobility of these elements, and mobility of 187Os relative to the initial bulk Os isotope composition during hydrothermal metasomatic alteration of ultramafic rocks. ?? 2007 Society of Economic Geologists, Inc.

Economic Geology↗

Vertical gradients in water chemistry and age in the Northern High Plains Aquifer, Nebraska, 2003

The northern High Plains aquifer is the primary source of water used for domestic, industrial, and irrigation purposes in parts of Colorado, Kansas, Nebraska, South Dakota, and Wyoming. Despite the aquifer’s importance to the regional economy, 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 northern High Plains aquifer were analyzed for major ions, nutrients, trace elements, dissolved organic carbon, pesticides, stable and radioactive isotopes, dissolved gases, and other parameters to evaluate vertical gradients in water chemistry and age in the aquifer. Chemical data and tritium and radiocarbon ages show that water in the aquifer was chemically and temporally stratified in the study area, with a relatively thin zone of recently recharged water (less than 50 years) near the water table overlying a thicker zone of older water (1,800 to 15,600 radiocarbon years). In areas where irrigated agriculture was an important land use, the recently recharged ground water was characterized by elevated concentrations of major ions and nitrate and the detection of pesticide compounds. Below the zone of agricultural influence, major-ion concentrations exhibited small increases with depth and distance along flow paths because of rock/water interactions. The concentration increases were accounted for primarily by dissolved calcium, sodium, bicarbonate, sulfate, and silica. In general, the chemistry of ground water throughout the aquifer was of high quality. None of the approximately 90 chemical constituents analyzed in each sample exceeded primary drinking-water standards. Mass-balance models indicate that changes in groundwater chemistry along flow paths in the aquifer can be accounted for by small amounts of feldspar and calcite dissolution; goethite and clay-mineral precipitation; organic-carbon and pyrite oxidation; oxygen reduction and denitrification; and cation exchange. Mixing with surface water affected the chemistry of ground water in alluvial sediments of the Platte River Valley. Radiocarbon ages in the aquifer, adjusted for carbon mass transfers, ranged from 1,800 to 15,600 14C years before present. These results have important implications with respect to development of ground-water resources in the Sand Hills. Most of the water in the aquifer predates modern anthropogenic activity so excessive removal of water by pumping is not likely to be replenished by natural recharge in a meaningful timeframe. Vertical gradients in ground-water age were used to estimate long-term average recharge rates in the aquifer. In most areas, the recharge rates ranged from 0.02 to 0.05 foot per year. The recharge rate was 0.2 foot per year in one part of the aquifer characterized by large downward hydraulic gradients. Nitrite plus nitrate concentrations at the water table were 0.13 to 3.13 milligrams per liter as nitrogen, and concentrations substantially decreased with depth in the aquifer. Dissolved-gas and nitrogen-isotope data indicate that denitrification in the aquifer removed 0 to 97 percent (average = 50 percent) of the nitrate originally present in recharge. The average amount of nitrate removed by denitrification in the aquifer north of the Platte River (Sand Hills) was substantially greater than the amount removed south of the river (66 as opposed to 0 percent), and the extent of nitrate removal appears to be related to the presence of thick deposits of sediment on top of the Ogallala Group in the Sand Hills that contained electron donors, such as organic carbon and pyrite, to support denitrification. Apparent rates of dissolved-oxygen reduction and denitrification were estimated on the basis of decreases in dissolved-oxygen concentrations and increases in concentrations of excess nitrogen gas and ground-water ages along flow paths from the water table to deeper wells. Median rates of dissolved-oxygen reduction and denitrification south of the Platte River were at least 10 times smaller than the median rates north of the river in the Sand Hills. The relatively large denitrification rates in the Sand Hills indicate that the aquifer in that area may have a greater capacity to attenuate nitrate contamination than the aquifer south of the river, depending on rates of ground-water movement in the two areas. Small denitrification rates south of the river indicate that nitrate contamination in that part of the aquifer would likely persist for a longer period of time.

Nebraska↗

Nitrogen saturation in the Rocky Mountains: Linking emissions, deposition, and ecosystem effects using stable isotopes of nitrogen compounds

Elevated levels of atmospheric N deposition are affecting terrestrial and aquatic ecosystems at high elevations in Rocky Mountain National Park and adjacent areas of the Front Range of Colorado. Federal and state agencies are now working together to develop cost-effective means for reducing atmospheric N deposition. A discussion on N saturation covers the need for better understanding of N emission source areas and source types that contribute to N deposition in the Rocky Mountains Front Range of Colorado; reductions in NO emissions that resulted from Clean Air Act Amendments, which caused NO3 deposition to decrease between 1984 and 2003; factors contributing to N deposition, e.g., rapid population growth and energy development; origins of NO3, e.g., as NO emissions from fossil fuel combustion, including stationary sources (e.g. emission from coal combustion in electric generating units), and mobile sources (vehicle emissions); disperse stationary sources from energy resource development, e.g., natural gas production; and the importance of incorporating local source characterization and finer spatial and temporal sampling into future studies, which could provide additional insight into N deposition source attribution. This is an abstract of a paper presented at the 100th Annual Conference and Exhibition of the Air and Waste Management Association (Pittsburgh, PA 6/26-29/2007).

Conference Paper↗

Ammonium transport and reaction in contaminated groundwater: Application of isotope tracers and isotope fractionation studies

Ammonium (NH 4 + ) is a major constituent of many contaminated groundwaters, but its movement through aquifers is complex and poorly documented. In this study, processes affecting NH 4 + movement in a treated wastewater plume were studied by a combination of techniques including large‐scale monitoring of NH 4 + distribution; isotopic analyses of coexisting aqueous NH 4 + , NO 3 − , N 2 , and sorbed NH 4 + ; and in situ natural gradient 15 NH 4 + tracer tests with numerical simulations of 15 NH 4 + , 15 NO 3 − , and 15 N 2 breakthrough data. Combined results indicate that the main mass of NH 4 + was moving downgradient at a rate about 0.25 times the groundwater velocity. Retardation factors and groundwater ages indicate that much of the NH 4 + in the plume was recharged early in the history of the wastewater disposal. NO 3 − and excess N 2 gas, which were related to each other by denitrification near the plume source, were moving downgradient more rapidly and were largely unrelated to coexisting NH 4 + . The δ 15 N data indicate areas of the plume affected by nitrification (substantial isotope fractionation) and sorption (no isotope fractionation). There was no conclusive evidence for NH 4 + ‐consuming reactions (nitrification or anammox) in the anoxic core of the plume. Nitrification occurred along the upper boundary of the plume but was limited by a low rate of transverse dispersive mixing of wastewater NH 4 + and O 2 from overlying uncontaminated groundwater. Without induced vertical mixing or displacement of plume water with oxic groundwater from upgradient sources, the main mass of NH 4 + could reach a discharge area without substantial reaction long after the more mobile wastewater constituents are gone. Multiple approaches including in situ isotopic tracers and fractionation studies provided critical information about processes affecting NH 4 + movement and N speciation.

Water Resources Research↗

Regional patterns in the isotopic composition of natural and anthropogenic nitrate in groundwater, High Plains, U.S.A.

Mobilization of natural nitrate (NO 3 - ) deposits in the subsoil by irrigation water in arid and semiarid regions has the potential to produce large groundwater NO 3 - concentrations. The use of isotopes to distinguish between natural and anthropogenic NO 3 - sources in these settings could be complicated by the wide range in δ 15 N values of natural NO 3 - . An ∼10 000 year record of paleorecharge from the regionally extensive High Plains aquifer indicates that δ 15 N values for NO 3 - derived from natural sources ranged from 1.3 to 12.3‰ and increased systematically from the northern to the southern High Plains. This collective range in δ 15 N values spans the range that might be interpreted as evidence for fertilizer and animal-waste sources of NO 3 - ; however, the δ 15 N values for NO 3 - in modern recharge ( less than 50 years) under irrigated fields were, for the most part, distinctly different from those of paleorecharge when viewed in the overall regional context. An inverse relation was observed between the δ 15 N[NO 3 - ] values and the NO 3 - /Cl - ratios in paleorecharge that is qualitatively consistent with fractionating losses of N increasing from north to south in the High Plains. N and O isotope data for NO 3 - are consistent with both NH 3 volatilization and denitrification, having contributed to fractionating losses of N prior to recharge. The relative importance of different isotope fractionating processes may be influenced by regional climate patterns as well as by local variation in soils, vegetation, topography, and moisture conditions.

Environmental Science & Technology↗

Storage and transit time of chemicals in thick unsaturated zones under rangeland and irrigated cropland, High Plains, United States

In 2000-2002, three rangeland and six irrigated sites were instrumented to assess the storage and transit time of chemicals in thick (15 to 50 m) unsaturated zones (UZ) in the High Plains. These processes are likely to influence relations between land use and groundwater quality, yet they have not been documented systematically in the High Plains. Land use and climate were important controls on the size of subsoil chloride, nitrate, and pesticide compound reservoirs. The reservoirs under irrigated cropland generally were larger than those under rangeland because more chemicals were applied to cropland than to rangeland. In some cases, chloride and nitrate reservoirs under rangeland were larger than those under cropland, presumably because of long‐term evaporative concentration near the base of the root zone. Natural salts mobilized by irrigation return flow accounted for as much as 60 and 80% of the nitrate and chloride reservoirs, respectively, under some cropland, as indicated by detailed chemical profiles and isotopic tracers ( 15 N, 18 O in nitrate and 2 H, 3 H, 18 O in water). Advective chemical transit times in the UZ under cropland ranged from about 50 to 375 years, longer than any of the instrumented fields had been irrigated, yet agrichemicals were detected at the water table at four of the six sites. The data provide evidence for the existence of slow and fast paths for water movement in the UZ, with larger subsoil chemical reservoirs occurring in areas dominated by slow paths. Implications of these findings with respect to water quality in the aquifer are significant because they indicate that the amount of chemical mass reaching the aquifer could increase with time as chemicals that still reside under irrigated fields reach the water table.

Water Resources Research↗

Perchlorate in pleistocene and holocene groundwater in North-Central New Mexico

Groundwater from remote parts of the Middle Rio Grande Basin in north-central New Mexico has perchlorate (ClO 4 - ) concentrations of 0.12−1.8 μg/L. Because the water samples are mostly preanthropogenic in age (0−28 000 years) and there are no industrial sources in the study area, a natural source of the ClO 4 - is likely. Most of the samples have Br - , Cl - , and SO 4 2 - concentrations that are similar to those of modern bulk atmospheric deposition with evapotranspiration (ET) factors of about 7−40. Most of the ET values for Pleistocene recharge were nearly twice that for Holocene recharge. The NO 3 - /Cl - and ClO 4 - /Cl - ratios are more variable than those of Br - /Cl - or SO 4 2 - /Cl - . Samples thought to have recharged under the most arid conditions in the Holocene have relatively high NO 3 - /Cl - ratios and low δ 15 N values (+1 per mil (‰)) similar to those of modern bulk atmospheric N deposition. The δ 18 O values of the NO 3 - (−4 to 0 ‰) indicate that atmospheric NO 3 - was not transmitted directly to the groundwater but may have been cycled in the soils before infiltrating. Samples with nearly atmospheric NO 3 - /Cl - ratios have relatively high ClO 4 - concentrations (1.0−1.8 μg/L) with a nearly constant ClO 4 - /Cl - mole ratio of (1.4 ± 0.1) × 10 - 4 , which would be consistent with an average ClO 4 - concentration of 0.093 ± 0.005 μg/L in bulk atmospheric deposition during the late Holocene in north-central NM. Samples thought to have recharged under wetter conditions have higher δ 15 N values (+3 to +8 ‰), lower NO 3 - /Cl - ratios, and lower ClO 4 - /Cl - ratios than the ones most likely to preserve an atmospheric signal. Processes in the soils that may have depleted atmospherically derived NO 3 - also may have depleted ClO 4 - to varying degrees prior to recharge. If these interpretations are correct, then ClO 4 - concentrations of atmospheric origin as high as 4 μg/L are possible in preanthropogenic groundwater in parts of the Southwest where ET approaches a factor of 40. Higher ClO 4 - concentrations in uncontaminated groundwater could occur in recharge beneath arid areas where ET is greater than 40, where long-term accumulations of atmospheric salts are leached suddenly from dry soils, or where other (nonatmospheric) natural sources of ClO 4 - exist.

Environmental Science & Technology↗

Assessment of nitrification potential in ground water using short term, single-well injection experiments

Nitrification was measured within a sand and gravel aquifer on Cape Cod, MA, using a series of single-well injection tests. The aquifer contained a wastewater-derived contaminant plume, the core of which was anoxic and contained ammonium. The study was conducted near the downgradient end of the ammonium zone, which was characterized by inversely trending vertical gradients of oxygen (270 to 0 μM) and ammonium (19 to 625 μM) and appeared to be a potentially active zone for nitrification. The tests were conducted by injecting a tracer solution (ambient ground water + added constituents) into selected locations within the gradients using multilevel samplers. After injection, the tracers moved by natural ground water flow and were sampled with time from the injection port. Rates of nitrification were determined from changes in nitrate and nitrite concentration relative to bromide. Initial tests were conducted with 15 N-enriched ammonium; subsequent tests examined the effect of adding ammonium, nitrite, or oxygen above background concentrations and of adding difluoromethane, a nitrification inhibitor. In situ net nitrate production exceeded net nitrite production by 3- to 6- fold and production rates of both decreased in the presence of difluoromethane. Nitrification rates were 0.02–0.28 μmol (L aquifer) −1 h −1 with in situ oxygen concentrations and up to 0.81 μmol (L aquifer) −1 h −1 with non-limiting substrate concentrations. Geochemical considerations indicate that the rates derived from single-well injection tests yielded overestimates of in situ rates, possibly because the injections promoted small-scale mixing within a transport-limited reaction zone. Nonetheless, these tests were useful for characterizing ground water nitrification in situ and for comparing potential rates of activity when the tracer cloud included non-limiting ammonium and oxygen concentrations.

Microbial Ecology↗

Denitrification across landscapes and waterscapes: A synthesis

Denitrification is a critical process regulating the removal of bioavailable nitrogen (N) from natural and human-altered systems. While it has been extensively studied in terrestrial, freshwater, and marine systems, there has been limited communication among denitrification scientists working in these individual systems. Here, we compare rates of denitrification and controlling factors across a range of ecosystem types. We suggest that terrestrial, freshwater, and marine systems in which denitrification occurs can be organized along a continuum ranging from (1) those in which nitrification and denitrification are tightly coupled in space and time to (2) those in which nitrate production and denitrification are relatively decoupled. In aquatic ecosystems, N inputs influence denitrification rates whereas hydrology and geomorphology influence the proportion of N inputs that are denitrified. Relationships between denitrification and water residence time and N load are remarkably similar across lakes, river reaches, estuaries, and continental shelves. Spatially distributed global models of denitrification suggest that continental shelf sediments account for the largest portion (44%) of total global denitrification, followed by terrestrial soils (22%) and oceanic oxygen minimum zones (OMZs; 14%). Freshwater systems (groundwater, lakes, rivers) account for about 20% and estuaries 1% of total global denitrification. Denitrification of land-based N sources is distributed somewhat differently. Within watersheds, the amount of land-based N denitrified is generally highest in terrestrial soils, with progressively smaller amounts denitrified in groundwater, rivers, lakes and reservoirs, and estuaries. A number of regional exceptions to this general trend of decreasing denitrification in a downstream direction exist, including significant denitrification in continental shelves of N from terrestrial sources. Though terrestrial soils and groundwater are responsible for much denitrification at the watershed scale, per-area denitrification rates in soils and groundwater (kg N·km −2 ·yr −1 ) are, on average, approximately one-tenth the per-area rates of denitrification in lakes, rivers, estuaries, continental shelves, or OMZs. A number of potential approaches to increase denitrification on the landscape, and thus decrease N export to sensitive coastal systems exist. However, these have not generally been widely tested for their effectiveness at scales required to significantly reduce N export at the whole watershed scale.

Ecological Applications↗

Methods for measuring denitrification: Diverse approaches to a difficult problem

Denitrification, the reduction of the nitrogen (N) oxides, nitrate (NO 3 − ) and nitrite (NO 2 − ), to the gases nitric oxide (NO), nitrous oxide (N 2 O), and dinitrogen (N 2 ), is important to primary production, water quality, and the chemistry and physics of the atmosphere at ecosystem, landscape, regional, and global scales. Unfortunately, this process is very difficult to measure, and existing methods are problematic for different reasons in different places at different times. In this paper, we review the major approaches that have been taken to measure denitrification in terrestrial and aquatic environments and discuss the strengths, weaknesses, and future prospects for the different methods. Methodological approaches covered include (1) acetylene-based methods, (2) 15 N tracers, (3) direct N 2 quantification, (4) N 2 :Ar ratio quantification, (5) mass balance approaches, (6) stoichiometric approaches, (7) methods based on stable isotopes, (8) in situ gradients with atmospheric environmental tracers, and (9) molecular approaches. Our review makes it clear that the prospects for improved quantification of denitrification vary greatly in different environments and at different scales. While current methodology allows for the production of accurate estimates of denitrification at scales relevant to water and air quality and ecosystem fertility questions in some systems (e.g., aquatic sediments, well-defined aquifers), methodology for other systems, especially upland terrestrial areas, still needs development. Comparison of mass balance and stoichiometric approaches that constrain estimates of denitrification at large scales with point measurements (made using multiple methods), in multiple systems, is likely to propel more improvement in denitrification methods over the next few years.

Ecological Applications↗

Denitrification in nitrate-rich streams: Application of N2:Ar and 15N-tracer methods in intact cores

Rates of benthic denitrification were measured using two techniques, membrane inlet mass spectrometry (MIMS) and isotope ratio mass spectrometry (IRMS), applied to sediment cores from two NO 3 − ‐rich streams draining agricultural land in the upper Mississippi River Basin. Denitrification was estimated simultaneously from measurements of N 2 :Ar (MIMS) and 15 N[N 2 ] (IRMS) after the addition of low‐level 15 NO 3 − tracer ( 15 N:N = 0.03–0.08) in stream water overlying intact sediment cores. Denitrification rates ranged from about 0 to 4400 μmol N·m −2 ·h −1 in Sugar Creek and from 0 to 1300 μmol N·m −2 ·h −1 in Iroquois River, the latter of which possesses greater streamflow discharge and a more homogeneous streambed and water column. Within the uncertainties of the two techniques, there is good agreement between the MIMS and IRMS results, which indicates that the production of N 2 by the coupled process of nitrification/denitrification was relatively unimportant and surface‐water NO 3 − was the dominant source of NO 3 − for benthic denitrification in these streams. Variation in stream NO 3 − concentration (from about 20 μmol/L during low discharge to 1000 μmol/L during high discharge) was a significant control of benthic denitrification rates, judging from the more abundant MIMS data. The interpretation that NO 3 − concentration directly affects denitrification rate was corroborated by increased rates of denitrification in cores amended with NO 3 − . Denitrification in Sugar Creek removed ≤11% per day of the in‐stream NO 3 − in late spring and removed roughly 15–20% in late summer. The fraction of NO 3 − removed in Iroquois River was less than that of Sugar Creek. Although benthic denitrification rates were relatively high during periods of high stream flow, when NO 3 concentrations were also high, the increase in benthic denitrification could not compensate for the much larger increase in stream NO 3 − fluxes during high flow. Consequently, fractional NO 3 − losses were relatively low during high flow.

Ecological Applications↗

Perchlorate isotope forensics

Perchlorate has been detected recently in a variety of soils, waters, plants, and food products at levels that may be detrimental to human health. These discoveries have generated considerable interest in perchlorate source identification. In this study, comprehensive stable isotope analyses ( 37 Cl/ 35 Cl and 18 O/ 17 O/ 16 O) of perchlorate from known synthetic and natural sources reveal systematic differences in isotopic characteristics that are related to the formation mechanisms. In addition, isotopic analyses of perchlorate extracted from groundwater and surface water demonstrate the feasibility of identifying perchlorate sources in contaminated environments on the basis of this technique. Both natural and synthetic sources of perchlorate have been identified in water samples from some perchlorate occurrences in the United States by the isotopic method.

Analytical Chemistry↗

Isotopic compositions of the elements, 2001

The Commission on Atomic Weights and Isotopic Abundances of the International Union of Pure and Applied Chemistry completed its last review of the isotopic compositions of the elements as determined by isotope-ratio mass spectrometry in 2001. That review involved a critical evaluation of the published literature, element by element, and forms the basis of the table of the isotopic compositions of the elements (TICE) presented here. For each element, TICE includes evaluated data from the “best measurement” of the isotope abundances in a single sample, along with a set of representative isotope abundances and uncertainties that accommodate known variations in normal terrestrial materials. The representative isotope abundances and uncertainties generally are consistent with the standard atomic weight of the element A r ( E ) "> A r ( E ) Ar(E) and its uncertainty U[A r ( E )] "> U[A r ( E )] U[Ar(E)] recommended by CAWIA in 2001.

Journal of Physical and Chemical Reference Data↗

Reach-scale isotope tracer experiment to quantify denitrification and related processes in a nitrate-rich stream, midcontinent United States

We conducted an in-stream tracer experiment with Br and 15 N-enriched NO 3 - to determine the rates of denitrification and related processes in a gaining NO 3 - -rich stream in an agricultural watershed in the upper Mississippi basin in September 2001. We determined reach-averaged rates of N fluxes and reactions from isotopic analyses of NO 3 - , NO 2 - , N 2 , and suspended particulate N in conjunction with other data in a 1.2-km reach by using a forward time-stepping numerical simulation that included groundwater discharge, denitrification, nitrification, assimilation, and air-water gas exchange with changing temperature. Denitrification was indicated by a systematic downstream increase in the d15N values of dissolved N 2 . The reach-averaged rate of denitrification of surface-water NO 3 - indicated by the isotope tracer was approximately 120 ± 20 µmol m -2 h -1 (corresponding to zero- and first-order rate constants of 0.63 µmol L -1 h -1 and 0.009 h -1 , respectively). The overall rate of NO 3 - loss by processes other than denitrification (between 0 and about 200 µmol m -2 h -1 ) probably was less than the denitrification rate but had a large relative uncertainty because the NO 3 - load was large and was increasing through the reach. The rates of denitrification and other losses would have been sufficient to reduce the stream NO 3 - load substantially in the absence of NO 3 - sources, but the losses were more than offset by nitrification and groundwater NO 3 - inputs at a combined rate of about 500-700 µmol m -2 h -1 . Despite the importance of denitrification, the overall mass fluxes of N 2 were dominated by discharge of denitrified groundwater and air-water gas exchange in response to changing temperature, whereas the flux of N 2 attributed to denitrification was relatively small. The in-stream isotope tracer experiment provided a sensitive direct reach-scale measurement of denitrification and related processes in a NO 3 - -rich stream where other mass-balance methods were not suitable because of insufficient sensitivity or offsetting sources and sinks. Despite the increasing NO 3 - load in the experimental reach, the isotope tracer data indicate that denitrification was a substantial permanent sink for N leaving this agricultural watershed during low-flow conditions.

Limnology and Oceanography↗

Geochemistry, radiocarbon ages, and paleorecharge conditions along a transect in the central High Plains aquifer, southwestern Kansas, USA

Water samples from short-screen monitoring wells installed along a 90-km transect in southwestern Kansas were analyzed for major ions, trace elements, isotopes (H, B, C, N, O, S, Sr), and dissolved gases (He, Ne, N 2 , Ar, O 2 , CH 4 ) to evaluate the geochemistry, radiocarbon ages, and paleorecharge conditions in the unconfined central High Plains aquifer. The primary reactions controlling water chemistry were dedolomitization, cation exchange, feldspar weathering, and O 2 reduction and denitrification. Radiocarbon ages adjusted for C mass transfers ranged from <2.6 ka ( 14 C) B.P. near the water table to 12.8 ± 0.9 ka ( 14 C) B.P. at the base of the aquifer, indicating the unconfined central High Plains aquifer contained a stratified sequence of ground water spanning Holocene time. A cross-sectional model of steady-state ground-water flow, calibrated using radiocarbon ages, is consistent with recharge rates ranging from 0.8 mm/a in areas overlain by loess to 8 mm/a in areas overlain by dune sand. Paleorecharge temperatures ranged from an average of 15.2 ± 0.7 °C for the most recently recharged waters to 11.6 ± 0.4 °C for the oldest waters. The temperature difference between Early and Late Holocene recharge was estimated to be 2.4 ± 0.7 °C, after taking into account variable recharge elevations. Nitrogen isotope data indicate NO 3 in paleorecharge (average concentration=193 μM) was derived from a relatively uniform source such as soil N, whereas NO 3 in recent recharge (average concentration=885 μM) contained N from varying proportions of fertilizer, manure, and soil N. Deep water samples contained components of N 2 derived from atmospheric, denitrification, and deep natural gas sources. Denitrification rates in the aquifer were slow (5 ± 2× 10 −3 μmol N L −1 a −1 ), indicating this process would require >10 ka to reduce the average NO 3 concentration in recent recharge to the Holocene background concentration.

Kansas↗

Contamination of groundwater under cultivated fields in an arid environment, central Arava Valley, Israel

The purpose of this study is to obtain a better understanding of groundwater contamination processes in an arid environment (precipitation of 50 mm/year) due to cultivation. Additional aims were to study the fate of N, K, and other ions along the whole hydrological system including the soil and vadose zone, and to compare groundwater in its natural state with contaminated groundwater (through the drilling of several wells). A combination of physical, chemical, and isotopic analyses was used to describe the hydrogeological system and the recharge trends of water and salts to the aquifers. The results indicate that intensive irrigation and fertilization substantially affected the quantity and quality of groundwater recharge. Low irrigation efficiency of about 50% contributes approximately 3.5–4 million m 3 /year to the hydrological system, which corresponds to 0.65 m per year of recharge in the irrigated area, by far the most significant recharge mechanism. Two main contamination processes were identified, both linked to human activity: (1) salinization due to circulation of dissolved salts in the irrigation water itself, mainly chloride, sulfate, sodium and calcium, and (2) direct input of nitrate and potassium mainly from fertilizers. The nitrate concentrations in a local shallow groundwater lens range between 100 and 300 mg/l and in the upper sub-aquifer are over 50 mg/l. A major source of nitrate is fertilizer N in the excess irrigation water. The isotopic compositions of δ 15 N–NO 3 (range of 4.9–14.8‰) imply also possible contributions from nearby sewage ponds and/or manure. Other evidence of contamination of the local groundwater lens includes high concentrations of K (20–120 mg/l) and total organic carbon (about 10 mg/l).

Journal of Hydrology↗