Geology topics

Craig R. Tobias

Publications and source records attributed to Craig R. Tobias.

10 recordsLinked to original sources

USGS2020

The influence of sample matrix on the accuracy of nitrite N and O isotope ratio analyses with the azide method

Rationale The isotope ratios of nitrogen ( 15 N/ 14 N) and oxygen ( 18 O/ 16 O) in nitrite (NO 2 − ) can be measured by conversion of the nitrite into nitrous oxide (N 2 O) with azide, followed by mass spectrometric analysis of N 2 O by gas chromatography isotope ratio mass spectrometry (GC/IRMS). While applying this method to brackish samples, we noticed that the N and O isotope ratio measurements of NO 2 − are highly sensitive to sample salinity and to the pH at which samples are preserved. Methods We investigated the influence of sample salinity and sample preservation pH on the N and O isotope ratios of the N 2 O produced from the reaction of NO 2 − with azide. The N 2 O isotope ratios were measured by GC/IRMS. Results Under the experimental reaction conditions, the conversion of NO 2 − into N 2 O was less complete in lower salinity solutions, resulting in respective N and O isotopic offsets of +2.5‰ and −14.0‰ compared with seawater solutions. Differences in salinity were also associated with differences in the fraction of O atoms exchanged between NO 2 − and water during the reaction. Similarly, aqueous NO 2 − samples preserved at elevated pH values resulted in the incomplete conversion of NO 2 − into N 2 O by azide, and consequent pH‐dependent isotopic offsets, as well as differences in the fraction of O atoms exchanged with water. The addition of sodium chloride to the reaction matrix of samples and standards largely mitigated salinity‐dependent isotopic offsets in the N 2 O product, and nearly homogenized the fraction of O atom exchange among samples of different salinity. A test of the hypobromite–azide method to measure N isotope ratios of ammonium by conversion into NO 2 − then N 2 O revealed no influence of sample salinity on the N isotope ratios of the N 2 O product. Conclusions We outline recommendations to mitigate potential matrix effects among samples and standards, to improve the accuracy of N and O isotope ratios in NO 2 − measured with the azide method.

Rapid Communications in Mass Spectrometry↗

USGS2020

Degradation of RDX (Hexahydro-1,3,5-trinitro-1,3,5-triazine) in contrasting coastal marine habitats: Subtidal non-vegetated (sand), subtidal vegetated (silt/eel grass), and intertidal marsh

Hundreds of explosive-contaminated marine sites exist globally, many of which contain the common munitions constituent hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX). Quantitative information about RDX transformation in coastal ecosystems is essential for management of many of these sites. Isotopically labelled RDX containing 15 N in all 3 nitro groups was used to track the fate of RDX in three coastal ecosystem types. Flow-through mesocosms representing subtidal vegetated (silt/eel grass), subtidal non-vegetated (sand) and intertidal marsh ecosystems were continuously loaded with isotopically labelled RDX for 16–17 days. Sediment, pore-water and overlying surface water were analyzed to determine the distribution of RDX, nitroso-triazine transformation products (NXs) and nitrogen containing complete mineralization products, including ammonium, nitrate+nitrite, nitrous oxide and nitrogen gas. The marsh, silt, and sand ecotypes transformed 94%, 90% and 76% of supplied RDX, respectively. Total dissolved NXs accounted for 2%–4% of the transformed 15 N-RDX. The majority of RDX transformation in the water column was by mineralization to inorganic N (dissolved and evaded; 64%–78% of transformed 15 N-RDX). RDX was mineralized primarily to N 2 O (62–74% of transformed 15 N-RDX) and secondarily to N 2 (1–2% of transformed 15 N-RDX) which exchanged with the atmosphere. Transformation of RDX was favored in carbon-rich lower redox potential sediments of the silt and marsh mesocosms where anaerobic processes of iron and sulfate reduction were most prevalent. RDX was most persistent in the carbon-poor sand mesocosm. Partitioning of 15 N derived from RDX onto sediment and suspended particulates was negligible in the overall mass balance of RDX transformation (2%–3% of transformed 15 N-RDX). The fraction of 15 N derived from RDX that was sorbed or assimilated in sediment was largest in the marsh mesocosm (most organic carbon), and smallest in the sand mesocosm (largest grain size and least organic carbon). Sediment redox conditions and available organic carbon stores affect the fate of RDX in different coastal marine habitats.

Connecticut, New York↗

USGS2019

Constraining the oxygen isotopic composition of nitrate produced by nitrification

Measurements of the stable isotope ratios of nitrogen ( 15 N/ 14 N) and oxygen ( 18 O/ 16 O) in nitrate (NO 3 – ) enable identification of sources, dispersal, and fate of natural and contaminant NO 3 – in aquatic environments. The 18 O/ 16 O of NO 3 – produced by nitrification is often assumed to reflect the proportional contribution of oxygen atom sources, water, and molecular oxygen, in a 2:1 ratio. Culture and seawater incubations, however, indicate oxygen isotopic equilibration between nitrite (NO 2 – ) and water, and kinetic isotope effects for oxygen atom incorporation, which modulate the NO 3 – 18 O/ 16 O produced during nitrification. To investigate the influence of kinetic and equilibrium effects on the isotopic composition of NO 3 – produced from the nitrification of ammonia (NH 3 ), we incubated streamwater supplemented with ammonium (NH 4 + ) and increments of 18 O-enriched water. Resulting NO 3 – 18 O/ 16 O ratios showed (1) a disproportionate sensitivity to the 18 O/ 16 O ratio of water, mediated by isotopic equilibration between water and NO 2 – , as well as (2) kinetic isotope discrimination during O atom incorporation from molecular oxygen and water. Empirically, the NO 3 – 18 O/ 16 O ratios thus produced fortuitously converge near the 18 O/ 16 O ratio of water. More elevated NO 3 – 18 O/ 16 O values commonly reported in soils and oxic groundwater may thus derive from processes additional to nitrification, including NO 3 – reduction.

Environmental Science & Technology↗

USGS2019

Tracing the cycling and fate of the munition, Hexahydro-1,3,5-trinitro-1,3,5-triazine in a simulated sandy coastal marine habitat with a stable isotopic tracer, 15N-[RDX]

Coastal marine habitats become contaminated with the munitions constituent, Hexahydro-1,3,5-trinitro-1,3,5-trazine (RDX), via military training, weapon testing and leakage of unexploded ordnance. This study used 15 N labeled RDX in simulated aquarium-scale coastal marine habitat containing seawater, sediment, and biota to track removal pathways from surface water including sorption onto particulates, degradation to nitroso-triazines and mineralization to dissolved inorganic nitrogen (DIN). The two aquaria received continuous RDX inputs to maintain a steady state concentration (0.4 mg L −1 ) over 21 days. Time series RDX and nitroso-triazine concentrations in dissolved (surface and porewater) and sorbed phases (sediment and suspended particulates) were analyzed. Distributions of DIN species (ammonium, nitrate + nitrite and dissolved N 2 ) in sediments and overlying water were also measured along with geochemical variables in the aquaria. Partitioning of RDX and RDX-derived breakdown products onto surface sediment represented 13% of the total added 15 N as RDX ( 15 N-[RDX]) equivalents after 21 days. Measured nitroso-triazines in the aquaria accounted for 6–13% of total added 15 N-[RDX]. 15 N-labeled DIN was found both in the oxic surface water and hypoxic porewaters, showing that RDX mineralization accounted for 34% of the 15 N-[RDX] added to the aquaria over 21 days. Labeled ammonium ( 15 NH 4 + , found in sediment and overlying water) and nitrate + nitrite ( 15 NO X , found in overlying water only) together represented 10% of the total added 15 N-[RDX]. The production of 15 N labeled N 2 ( 15 N 2 ), accounted for the largest individual sink during the transformation of the total added 15 N-[RDX] (25%). Hypoxic sediment was the most favorable zone for production of N 2 , most of which diffused through porous sediments into the water column and escaped to the atmosphere.

Science of the Total Environment↗

USGS2017

Tracking the fate of nitrate through pulse-flow wetlands: A mesocosm scale 15N enrichment tracer study

Quantitative information about the fate of applied nitrate (NO 3 -N) in pulse-flow constructed wetlands is essential for designing wetland treatment systems and assessing their nitrogen removal services for agricultural and stormwater applications. Although many studies have documented NO 3 -N losses in wetlands, controlled experiments indicating the relative importance of different processes and N sinks are scarce. In the current study, 15 NO 3 -N isotope enrichment tracer experiments were conducted in wetland mesocosms of two different wetland soil types at two realistic agricultural NO 3 -N source loads. The 15 N label was traced from the source NO 3 -N into plant biomass, soil (including organic matter and ammonium), and N-gas constituents over 7–10 day study periods. All sinks responded positively to higher NO 3 -N loading. Plant uptake exceeded denitrification 2–3 fold in the low NO 3 -N loading experiments, while both fates were nearly equivalent in the high loading experiments. One to two years later, soils largely retained the assimilated tracer N, whereas plants had lost much of it. Results demonstrated that plant and microbial assimilation in the soil (temporary N sinks) can exceed denitrification (permanent N loss) in pulse-flow environments and must be considered by wetland designers and managers for optimizing nitrogen removal potential.

Ecological Engineering↗

USGS2015

Tracing the cycling and fate of the explosive 2,4,6-trinitrotoluene in coastal marine systems with a stable isotopic tracer, 15N-[TNT]

2,4,6-Trinitrotoluene (TNT) has been used as a military explosive for over a hundred years. Contamination concerns have arisen as a result of manufacturing and use on a large scale; however, despite decades of work addressing TNT contamination in the environment, its fate in marine ecosystems is not fully resolved. Here we examine the cycling and fate of TNT in the coastal marine systems by spiking a marine mesocosm containing seawater, sediments, and macrobiota with isotopically labeled TNT ( 15 N-[TNT]), simultaneously monitoring removal, transformation, mineralization, sorption, and biological uptake over a period of 16 days. TNT degradation was rapid, and we observed accumulation of reduced transformation products dissolved in the water column and in pore waters, sorbed to sediments and suspended particulate matter (SPM), and in the tissues of macrobiota. Bulk δ 15 N analysis of sediments, SPM, and tissues revealed large quantities of 15 N beyond that accounted for in identifiable derivatives. TNT-derived N was also found in the dissolved inorganic N (DIN) pool. Using multivariate statistical analysis and a 15 N mass balance approach, we identify the major transformation pathways of TNT, including the deamination of reduced TNT derivatives, potentially promoted by sorption to SPM and oxic surface sediments.

Environmental Science & Technology↗

USGS2013

Hyporheic zone denitrification: controls on effective reaction depth and contribution to whole-stream mass balance

Stream denitrification is thought to be enhanced by hyporheic transport but there is little direct evidence from the field. To demonstrate at a field site, we injected 15 NO 3 − , Br (conservative tracer), and SF 6 (gas exchange tracer) and compared measured whole-stream denitrification with in situ hyporheic denitrification in shallow and deeper flow paths of contrasting geomorphic units. Hyporheic denitrification accounted for between 1 and 200% of whole-stream denitrification. The reaction rate constant was positively related to hyporheic exchange rate (greater substrate delivery), concentrations of substrates DOC and nitrate, microbial denitrifier abundance (nirS), and measures of granular surface area and presence of anoxic microzones. The dimensionless product of the reaction rate constant and hyporheic residence time, λ hz τ hz define a Damköhler number, Da den-hz that was optimal in the subset of hyporheic flow paths where Da den-hz ≈ 1. Optimal conditions exclude inefficient deep pathways transport where substrates are used up and also exclude inefficient shallow pathways that require repeated hyporheic entries and exits to complete the reaction. The whole-stream reaction significance, R s (dimensionless), was quantified by multiplying Da den-hz by the proportion of stream discharge passing through the hyporheic zone. Together these two dimensionless metrics, one flow-path scale and the other reach-scale, quantify the whole-stream significance of hyporheic denitrification. One consequence is that the effective zone of significant denitrification often differs from the full depth of the hyporheic zone, which is one reason why whole-stream denitrification rates have not previously been explained based on total hyporheic-zone metrics such as hyporheic-zone size or residence time.

Indiana↗

USGS2009

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

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

Limnology and Oceanography: Methods↗

USGS2009

Dynamic modeling of nitrogen losses in river networks unravels the coupled effects of hydrological and biogeochemical processes

The importance of lotic systems as sinks for nitrogen inputs is well recognized. A fraction of nitrogen in streamflow is removed to the atmosphere via denitrification with the remainder exported in streamflow as nitrogen loads. At the watershed scale, there is a keen interest in understanding the factors that control the fate of nitrogen throughout the stream channel network, with particular attention to the processes that deliver large nitrogen loads to sensitive coastal ecosystems. We use a dynamic stream transport model to assess biogeochemical (nitrate loadings, concentration, temperature) and hydrological (discharge, depth, velocity) effects on reach-scale denitrification and nitrate removal in the river networks of two watersheds having widely differing levels of nitrate enrichment but nearly identical discharges. Stream denitrification is estimated by regression as a nonlinear function of nitrate concentration, streamflow, and temperature, using more than 300 published measurements from a variety of US streams. These relations are used in the stream transport model to characterize nitrate dynamics related to denitrification at a monthly time scale in the stream reaches of the two watersheds. Results indicate that the nitrate removal efficiency of streams, as measured by the percentage of the stream nitrate flux removed via denitrification per unit length of channel, is appreciably reduced during months with high discharge and nitrate flux and increases during months of low-discharge and flux. Biogeochemical factors, including land use, nitrate inputs, and stream concentrations, are a major control on reach-scale denitrification, evidenced by the disproportionately lower nitrate removal efficiency in streams of the highly nitrate-enriched watershed as compared with that in similarly sized streams in the less nitrate-enriched watershed. Sensitivity analyses reveal that these important biogeochemical factors and physical hydrological factors contribute nearly equally to seasonal and stream-size related variations in the percentage of the stream nitrate flux removed in each watershed.

Biogeochemistry↗

USGS2007

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

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

Limnology and Oceanography↗