John Karl Böhlke

METHODS FOR MEASURING DENITRIFICATION: DIVERSE APPROACHES TO A DIFFICULT PROBLEM

Denitrification, the reduction of the nitrogen (N) oxides, nitrate (NO3-) and nitrite (NO2-), to the gases nitric oxide (NO), nitrous oxide (N2O), and dinitrogen (N2), 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) 15N tracers, (3) direct N2 quantification, (4) N2: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.

Combined Use of Groundwater Dating, Chemical, and Isotopic Analyses to Resolve the History and Fate of Nitrate Contamination in Two Agricultural Watersheds, Atlantic Coastal Plain, Maryland

The history and fate of groundwater nitrate (NO3−) contamination were compared in 2 small adjacent agricultural watersheds in the Atlantic coastal plain by combined use of chronologic (CCl2F2, 3H), chemical (dissolved solids, gases), and isotopic (δ15N,δ13C, δ34S) analyses of recharging groundwaters, discharging groundwaters, and surface waters. The results demonstrate the interactive effects of changing agricultural practices, groundwater residence times, and local geologic features on the transfer of NO3− through local flow systems. Recharge dates of groundwaters taken in 1990–1992 from the surficial aquifer in the Chesterville Branch and Morgan Creek watersheds near Locust Grove, Maryland, ranged from pre-1940 to the late 1980’s. When corrected for localized denitrification by use of dissolved gas concentrations, the dated waters provide a 40-year record of the recharge rate of NO3−, which increased in both watersheds by a factor of 3–6, most rapidly in the 1970s. The increase in groundwater NO3− over time was approximately proportional to the documented increase in regional N fertilizer use, and could be accounted for by oxidation and leaching of about 20–35% of the fertilizer N. Groundwaters discharging upward beneath streams in both watersheds had measured recharge dates from pre-1940 to 1975, while chemical data for second-order reaches of the streams indicated average groundwater residence times in the order of 20+ years. At the time of the study, NO3− discharge rates were less than NO3− recharge rates for at least two reasons: (1) discharge of relatively old waters with low initial NO3− concentrations, and (2) local denitrification. In the Chesterville Branch watershed, groundwaters remained oxic throughout much of the surficial aquifer and discharged relatively unaltered to the stream, which had a relatively high NO3− concentration (9–10 mg/L as N). In the Morgan Creek watershed, groundwaters were largely reduced and denitrified before discharging to the stream, which had a relatively low NO3− concentration (2–3 mg/L as N). Chemical and isotopic data indicate that quantitative denitrification occurred within buried calcareous glauconitic marine sediments that are present at relatively shallow depths beneath the Morgan Creek watershed. NO3− removal by forests, wetlands, and shallow organic-rich soils in near-stream environments was largely avoided by groundwaters that followed relatively deep flow paths before converging and discharging rapidly upward to the streams.

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 Ar(E) and its uncertainty U[Ar(E)] recommended by CAWIA in 2001.

Isotope-abundance variations of selected elements (IUPAC Technical Report)

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 variations in materials of natural ter- restrial 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.

Methane-hydrogen gas seeps, Zambales Ophiolite, Philippines: deep or shallow origin?

Abstract Isotopically anomalous CH4-rich gas escapes at low flow rate and ambient temperature from seeps in serpentinized ultramafic rock in the Zambales Ophiolite, Philippines. The major components of the gas are CH4 (55 mole%) and H2 (42 mole%); the CH 4 CO 2 ratio is > 1800 and the CH 4 He ratio is 9.2·104. The δ13C-value of the CH4 is −7.0±0.4‰ (PDB), ∼8‰ higher than the highest published values for CH4 in other natural gases and hot springs, but similar to values commonly attributed to mantle carbon. The 3 He 4 He ratio is 5.70·10−6, 4.1 times the atmospheric ratio, indicative of a substantial mantle He component. The δD-values of CH4 and H2 are −136 and −590‰, respectively, consistent with equilibration temperatures of 110–125°C. Carbon and He isotopic data could be consistent with derivation of the Zambales gas directly from a reduced mantle. However, phase equilibria and H isotope data indicate that the gas also could have been produced by reduction of water and carbon during low-temperature serpentinization of the ophiolite.

Stable isotope evidence for an atmospheric origin of desert nitrate deposits in northern Chile and southern California, U.S.A.

Natural surficial accumulations of nitrate-rich salts in the Atacama Desert, northern Chile, and in the Death Valley region of the Mojave Desert, southern California, are well known, but despite many geologic and geochemical studies, the origins of the nitrates have remained controversial. N and O isotopes in nitrate, and S isotopes in coexisting soluble sulfate, were measured to determine if some proposed N sources could be supported or rejected, and to determine if the isotopic signature of these natural deposits could be used to distinguish them from various types of anthropogenic nitrate contamination that might be found in desert groundwaters. High-grade calich-a-type nitrate deposits from both localities have δ15N values that range from −5 to +5‰, but are mostly near 0‰. Values of δ15N near 0‰ are consistent with either bulk atmospheric N deposition or microbial N fixation as major sources of the N in the deposits. δ18O values of those desert nitrates with δ15N near 0‰ range from about +31 to +50‰ (V-SMOW), significantly higher than that of atmospheric O2 (+23.5‰). Such high values of δ18O are considered unlikely to result entirely from nitrification of reduced N, but rather resemble those of modern atmospheric nitrate in precipitation from some other localities. Assuming that limited modern atmospheric isotope data are applicable to the deposits, and allowing for nitrification of co-deposited ammonium, it is estimated that the fraction of the nitrate in the deposits that could be, accounted for isotopically by atmospheric N deposition may be at least 20% and possibly as much as 100%. δ34S values are less diagnostic but could also be consistent with atmospheric components in some of the soluble sulfates associated with the deposits. The stable isotope data support the hypothesis that some high-grade caliche-type nitrate-rich salt deposits in some of the Earths hyperarid deserts represent long-term accumulations of atmospheric deposition (possibly in the order of 104 yr for the Death Valley region, 107 yr for the Atacama Desert) in the relative absence of soil leaching or biologic cycling. The combined N and O isotope signature of the nitrate in these deposits is significantly different from those of many other natural and anthropogenic sources of nitrate.

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 (3H/3He), chlorofluorocarbons (CFCs), sulfur hexafluoride (SF6), sulfur-35 (35S), and stable isotopes (δ18O and δ2H) 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 SF6 and 3H/3He, 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 35S (>1.5 years) and seasonal variation of δ18O (mean residence time of 5 years) for spring discharge. The higher ages indicated by the 35S and δ18O data reflect travel times through the unsaturated zone and, in the case of 35S, possible sorption and exchange of S with soils or biomass. In springs sampled in April, 1996, apparent ages derived from the 3H/3He data (median age of 0.2 years) are lower than those obtained from SF6 (median age of 4.3 years), and in contrast to median ages from 3H/3He (0.3 years) and SF6 (0.7 years) obtained during the late summer dry season of 1997. Monthly samples from 1999 at four springs in SNP had SF6 apparent ages of only 1.2 to 2.5±0.8 years, and were consistent with the 1997 SF6 data. Water from springs has low excess air (0–1 cm3 kg−1) and N2–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 N2–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 cm3 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.

Denitrification and mixing in a stream—aquifer system: effects on nitrate loading to surface water

Ground water in terrace deposits of the South Platte River alluvial aquifer near Greeley, Colorado, USA, had a median nitrate concentration of 1857 μmol l−1. Median nitrate concentrations in ground water from adjacent floodplain deposits (468 μmol l−1) and riverbed sediments (461 μmol l−1), both of which are downgradient from the terrace deposits, were lower than the median concentration in the terrace deposits. The concentrations and δ15N values of nitrate and N2 in ground water indicated that denitrifying activity in the floodplain deposits and riverbed sediments accounted for 15–30% of the difference in nitrate concentrations. Concentrations of Cl− and SiO2 indicated that mixing between river water and ground water in the floodplain deposits and riverbed sediments accounted for the remainder of the difference in nitrate concentrations. River flux measurements indicated that ground-water discharge in a 7.5 km segment of river had a nitrate load of 1718 kg N day− and accounted for about 18% of the total nitrate load in the river at the downstream end of that segment. This nitrate load was 70% less than the load predicted on the basis of the median nitrate concentration in the terrace deposits and assuming no denitrification or mixing in the aquifer. Water exchange between the river and aquifer caused ground water that originally discharged to the river to reenter denitrifying sediments in the riverbed and floodplain, thereby further decreasing the nitrate load in this stream—aquifer system. Results from this study indicated that denitrification and mixing within akluvial aquifer sediments may substantially decrease the nitrate load added to rivers by discharging ground water.

Laser microprobe analyses of Cl, Br, I, and K in fluid inclusions: Implications for sources of salinity in some ancient hydrothermal fluids

The relative concentrations of Cl, Br, I, and K in fluid inclusions in hydrothermal minerals were measured by laser microprobe noble gas mass spectrometry on irradiated samples containing 10−10 to 10−8 L of fluid. Distinctive halogen signatures indicate contrasting sources of fluid salinity in fluid inclusions from representative “magmatic” (St. Austell), “metamorphic” (Alleghany), and “geothermal” (Creede, Salton Sea) aqueous systems. Br/Cl mol ratios are lowest at Salton Sea (0.27–0.33 × 10−3), where high salinities are largely due to halite dissolution; intermediate at St. Austell (0.85 × 10−3), possibly representative of magmatic volatiles; and highest (near that of seawater) at Creede (1.5–2.1 × 10−3) and Alleghany (1.2–2.4 × 10−3), where dissolved halogens probably were leached from volcanic and (or) nonevaporitic sedimentary rocks. IC1 mol ratios are lowest (near that of seawater) at Creede (1–14 × 10−6), possibly because organisms scavenged I during low temperature recharge; intermediate at Salton Sea (24–26 × 10−6) and St. Austell (81× 10−6); and highest at Alleghany (320–940 × 10−6), probably because the fluids interacted with organic-rich sediments at high temperatures before being trapped. KCl mol ratios indicate disequilibrium with respect to hypothetical feldspathic alkali-Al-silicate mineral buffers at fluid inclusion trapping temperatures at Creede, and large contributions of (Na, K)-bicarbonate to total fluid ionic strength at Alleghany. Significant variations in Cl/Br/I/K ratios among different fluid inclusion types are correlated with previously documented mineralization stages at Creede, and with the apparent oxidation state of dissolved carbon at Alleghany. The new data indicate that Cl/ Br/I ratios in hydrothermal fluid inclusions vary by several orders of magnitude, as they do in modern surface and ground waters. This study demonstrates that halogen signatures of fluid inclusions determined by microanalysis yield important information about sources of fluid salinity and provide excellent definition of fluid reservoirs and tracers of flow and interaction in ancient hydrothermal systems.

Geochemistry of reduced gas related to serpentinization of the Zambales ophiolite, Philippines

Abstract Methane-hydrogen gas seeps with mantle-like C and noble gas isotopic characteristics issue from partially serpentinized ultramafic rocks in the Zambales ophiolite, Philippines. New measurements of noble gas and 14C isotope abundances, rock/mixed-volatile equilibrium calculations, and previous chemical and isotopic data suggest that these reduced gases are products of periodotite hydration. The gas seeps are produced in rock-dominated zones of serpentinization, and similar gases may be ubiquitous in ultramafic terranes undergoing serpentinization.