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Stanley J. Mroczkowski

Publications and source records attributed to Stanley J. Mroczkowski.

16 recordsLinked to original sources

Reaffirming the consistency of the original stock of NBS 19 limestone and its byproduct with finer grain size for δ13C and δ18O calibrations—Both distributed internationally

Rationale Approximately 3–4 kg of NBS 19 limestone, prepared in 1982 by the U.S. Geological Survey (USGS), serves as a primary reference for the carbon isotope scales VPDB and VPDB-LSVEC and the oxygen isotope scale VPDB. Its consensus values are +1.95‰ for δ 13 C and −2.2‰ for δ 18 O measurements. After more than three decades of distribution, the number of units labeled “NBS 19” shrunk substantially, and the remaining material was quarantined, with a small fraction retained at the USGS and a larger fraction entrusted to the International Atomic Energy Agency (IAEA) for secure storage. Given the critical role of NBS 19, verifying the integrity of its δ 13 C and δ 18 O values across these storage locations is essential. Method Samples from IAEA and USGS stock materials were selected to ensure traceability of carbon and oxygen isotopes to NBS 19 distribution units from various storage locations. To achieve this, distribution units labeled as NBS 19 from both the IAEA and the National Institute of Standards and Technology (NIST) were included. During evaluation, two distinct grain sizes were identified within these units. Grain size was assessed using sieves on five selected samples. The δ 13 C and δ 18 O values of finer and coarser fractions (both labeled NBS 19) were measured at USGS using continuous-flow isotope-ratio mass spectrometry on 100- and 200-μg samples. Results Expanded 95% measurement uncertainties ( k = 2) for δ 13 C and δ 18 O determinations are 0.027‰ and 0.038‰ or better, respectively, for quarantined NBS 19 stocks and finer byproduct calcite, which we term “NBS-19 byproduct,” regardless of storage location. Between the 1990s and circa 2011, NBS-19 byproduct labeled “NBS 19,” distributed by NIST and the IAEA, shows these findings. Conclusions NBS 19 primary isotopic reference material should be used for calibration of new isotopic reference materials rather than NBS-19 byproduct secondary isotopic reference material.

Rapid Communications in Mass Spectrometry

Spatial, seasonal, and diel controls of nitrogen-carbon-oxygen cycling during lake-water infiltration to an aquifer

Many freshwater lakes are groundwater flow-through systems. Although lakes commonly are considered to be sinks for nitrogen inputs, relatively little is known about carbon and nitrogen export from lakes to groundwater. The current study focused on lake-bottom biogeochemical processes accompanying the transport of nitrogen, dissolved oxygen (O 2 ), and dissolved organic carbon (DOC) during lake-water recharge from a groundwater flow-through lake. Lake-water and porewater (15–100 cm below lakebed) samples were collected along transects within the lake downwelling zone. Infiltrating porewater O 2 and DOC concentrations decreased with depth while nitrate (NO 3 − ) concentrations increased, indicating nitrification of organic matter within the profiles. The depth of NO 3 − production and transport was seasonally dependent. In winter, NO 3 − and O 2 were exported beyond 100-cm depth; whereas in summer, shallow nitrification zones were underlain by deeper NO 3 − reduction zones, and diel patterns of O 2 and NO 3 − penetration depths were observed. Microbial community compositions and stable isotope profiles (δ 15 N[NO 3 − ], δ 18 O[NO 3 − ], δ 18 O[O 2 ]) were consistent with apparent C–N–O reaction stoichiometries indicating O 2 reduction and nitrification in shallower porewater, followed by varying NO 3 − reduction at depth. Maximum porewater NO 3 − concentrations (∼10–20 μM) were limited by infiltrating O 2 concentrations and C/N ratios of reacting organic matter. Lake-water level variations caused changes in shoreline position and porewater velocities, while variations in lake-water temperature, DOC, and O 2 contributed to changes in reaction rates and depth of O 2 and NO 3 − penetration into the lakebed. The quality of groundwater recharged by lake water reflected temporally and spatially varying physical and biogeochemical processes in the sediment porewater.

Journal of Geophysical Research: Biogeosciences

Isotopic discrimination of natural and anthropogenic perchlorate sources in groundwater in a semi-arid region of northeastern Oregon (USA)

Perchlorate (ClO4−) has synthetic and natural sources. Synthetic ClO4− is released to the environment from its use as an oxidant in military and aerospace applications, and from its presence in a variety of common commercial products, such as safety flares, chlorate herbicides, and fireworks. Natural sources of ClO4− in the environment include imported nitrate fertilizers derived from salt deposits in the Atacama Desert of Chile and indigenous natural ClO4− that accumulates in unsaturated soils and groundwaters in other arid and semi-arid environments, largely from atmospheric deposition. The stable isotope ratios of chlorine (37Cl/35Cl) and oxygen (18O/16O, 17O/16O) and the isotopic abundance of radioactive 36Cl in ClO4− can be used to discriminate these different sources. Perchlorate was previously detected at relatively high concentrations (3.8–34.7 μg/L) in groundwater from many wells in the Boardman-Umatilla area near the Columbia River in northeastern Oregon, which is a semi-arid, highly agricultural, heavily irrigated area that includes several past and current military installations. Eight representative groundwater wells were sampled throughout this region and isotopic characteristics of ClO4− collected from each well were measured along with other chemical and isotopic parameters including tritium and other groundwater age indicators. Isotopic data indicate that indigenous natural ClO4− was present in groundwater from all sampled wells and was the predominant source in five of the wells. Synthetic ClO4− was present in the three remaining wells with natural ClO4−, and a minor fraction of Atacama-fertilizer-derived ClO4− was indicated in one of the wells. Data from this study expand the geographic area of the USA in which indigenous natural ClO4− has been detected to include the semi-arid northwest. This study also illustrates the role of irrigation recharge as a mechanism for producing relatively high concentrations of indigenous natural ClO4− in groundwater by flushing accumulated salts from the unsaturated zone.

Oregon

Exploring the potential of electrospray-Orbitrap for stable isotope analysis using nitrate as a model

Widely used isotope ratio mass spectrometers have limited capabilities to measure metabolites, drugs, or small polyatomic ions without the loss of structural isotopic information. A new approach has recently been introduced that uses electrospray ionization Orbitrap to measure multidimensional isotope signatures of intact polar compounds. Using nitrate as a model compound, this study aims to establish performance metrics for comparisons with conventional IRMS at the natural abundance level. We present a framework on how to convert isotopolog intensities to δ values that are commonly used in the isotope geochemistry community. The quantification of seven nitrate isotopologs provides multiple pathways for obtaining the primary N and O δ values including non-mass-dependent O isotope variations, as well as opportunities to explore nonrandom isotopic distributions (i.e., clumping effects) within molecular nitrate. Using automation and the adaptation of measurement principles that are specific to isotope ratio analysis, nitrate δ15NAIR, δ18OVSMOW, and δ17OVSMOW were measured with a long-term precision of 0.4‰ or better for isotopic reference materials and purified nitrate from environmental samples. In addition, we demonstrate promising results for unpurified environmental samples in liquid form. With these new developments, this study connects the two largely disparate mass spectrometry fields of bioanalytical MS and isotope ratio MS, thus providing a route to measure new isotopic signatures in diverse organic and inorganic solutes.

Analytical Chemistry

Isotopic composition of natural and synthetic chlorate (δ18O, Δ17O, δ37Cl, 36Cl/Cl): Methods and initial results

Natural chlorate (ClO 3 − ) is widely distributed in terrestrial and extraterrestrial environments. To improve understanding of the origins and distribution of ClO 3 − , we developed and tested methods to determine the multi-dimensional isotopic compositions (δ 18 O, Δ 17 O, δ 37 Cl, 36 Cl/Cl) of ClO 3 − and then applied the methods to samples of natural nitrate-rich caliche-type salt deposits in the Atacama Desert, Chile, and Death Valley, USA. Tests with reagents and artificial mixed samples indicate stable-isotope ratios were minimally affected by the purification processes. Chlorate extracted from Atacama samples had δ 18 O = +7.0 to +11.1‰, Δ 17 O = +5.7 to +6.4‰, δ 37 Cl = −1.4 to +1.3‰, and 36 Cl/Cl = 48 × 10 −15 to 104 × 10 −15 . Chlorate from Death Valley samples had δ 18 O = −6.9 to +1.6‰, Δ 17 O = +0.4 to +2.6‰, δ 37 Cl = +0.8 to +1.0‰, and 36 Cl/Cl = 14 × 10 −15 to 44 × 10 −15 . Positive Δ 17 O values of natural ClO 3 − indicate that its production involved reaction with O 3 , while its Cl isotopic composition is consistent with a tropospheric or near-surface source of Cl. The Δ 17 O and δ 18 O values of natural ClO 3 − are positively correlated, as are those of ClO 4 − and NO 3 − from the same localities, possibly indicating variation in the relative contributions of O 3 as a source of O in the formation of the oxyanions. Additional isotopic analyses of ClO 3 − could provide stronger constraints on its production mechanisms and/or post-formational alterations, with applications for environmental forensics, global biogeochemical cycling of Cl, and the origins of oxyanions detected on Mars.

Chemosphere

Origin of the isotopic composition of natural perchlorate: Experimental results for the impact of reaction pathway and initial ClOx reactant

Natural perchlorate (ClO 4 − ) exists in many places on Earth, in lunar regolith, meteorites, and on the surface of Mars. Terrestrial natural ClO 4 − has widely variable Cl and O stable isotopic compositions (δ 37 Cl, δ 18 O, Δ 17 O). The δ 18 O and Δ 17 O values of ClO 4 − from the most hyper-arid locations co-vary. ClO 4 − from less arid areas has relatively little 17 O excess and poor Δ 17 O-δ 18 O correlation. ClO 4 − from the Atacama Desert has unusually low δ 37 Cl (<−10‰) and exhibits a positive correlation between δ 37 Cl and δ 18 O, while the δ 37 Cl of ClO 4 − from all other locations varies between −5 and +7‰ with no δ 37 Cl-δ 18 O covariation. To evaluate the impact of different precursors (ClO x ) and reaction pathways on the isotopic composition of ClO 4 − , we measured the isotopic composition of ClO 4 − produced in the laboratory by UV or O 3 mediated aqueous oxidation of Cl − , OCl − , ClO 2 − , and ClO 2 ° as well as O 3 mediated oxidation of dry NaCl. ClO x oxidation in aqueous or dry systems enriched in O 3 produced ClO 4 − with Δ 17 O values that generally increased with the number of O atoms required and included evidence that the site-specific 17 O anomaly in O 3 was preferentially transferred to ClO 4 − . Based on the inferred number of O atoms sourced from O 3 , and known Cl and O reaction pathways, it appears that ClO 2 ° and ClO 3 * were required intermediates in the production of ClO 4 − in the O 3 experiments. ClO x aqueous oxidation by UV irradiation produced ClO 4 − with a large range of δ 18 O values and little or no 17 O anomaly. ClO 3 − was produced to a much greater extent than ClO 4 − in all experiments except dry oxidation of NaCl by O 3 . The isotopic composition of ClO 3 − was distinct from that of ClO 4 − produced from the same initial reactants. Combined results of O 3 and UV mediated reactions largely bracketed the range of natural ClO 4 − δ 18 O and Δ 17 O values as well as δ 37 Cl values of non-Atacama natural samples, but no conditions produced the low δ 37 Cl values of Atacama ClO 4 − . Our results indicate that variation in production mechanisms, possibly combined with isotopically variable precursors, could be responsible for much of the observed isotopic variation in natural ClO 4 − and ClO 3 − .

Geochimica et Cosmochimica Acta

Stable isotope analyses of oxygen (18O:17O:16O) and chlorine (37Cl:35Cl) in perchlorate: reference materials, calibrations, methods, and interferences

Rationale Perchlorate (ClO 4 − ) is a common trace constituent of water, soils, and plants; it has both natural and synthetic sources and is subject to biodegradation. The stable isotope ratios of Cl and O provide three independent quantities for ClO 4 − source attribution and natural attenuation studies: δ 37 Cl, δ 18 O, and δ 17 O (or Δ 17 O or 17 Δ) values. Documented reference materials, calibration schemes, methods, and interferences will improve the reliability of such studies. Methods Three large batches of KClO 4 with contrasting isotopic compositions were synthesized and analyzed against VSMOW-SLAP, atmospheric O 2 , and international nitrate and chloride reference materials. Three analytical methods were tested for O isotopes: conversion of ClO 4 − to CO for continuous-flow IRMS (CO-CFIRMS), decomposition to O 2 for dual-inlet IRMS (O2-DIIRMS), and decomposition to O 2 with molecular-sieve trap (O2-DIIRMS+T). For Cl isotopes, KCl produced by thermal decomposition of KClO 4 was reprecipitated as AgCl and converted into CH 3 Cl for DIIRMS. Results KClO 4 isotopic reference materials (USGS37, USGS38, USGS39) represent a wide range of Cl and O isotopic compositions, including non-mass-dependent O isotopic variation. Isotopic fractionation and exchange can affect O isotope analyses of ClO 4 − depending on the decomposition method. Routine analyses can be adjusted for such effects by normalization, using reference materials prepared and analyzed as samples. Analytical errors caused by SO 4 2 − , NO 3 − , ReO 4 2 − , and C-bearing contaminants include isotope mixing and fractionation effects on CO and O 2 , plus direct interference from CO 2 in the mass spectrometer. The results highlight the importance of effective purification of ClO 4 − from environmental samples. Conclusions KClO 4 reference materials are available for testing methods and calibrating isotopic data for ClO 4 − and other substances with widely varying Cl or O isotopic compositions. Current ClO 4 − extraction, purification, and analysis techniques provide relative isotope-ratio measurements with uncertainties much smaller than the range of values in environmental ClO 4 − , permitting isotopic evaluation of environmental ClO 4 − sources and natural attenuation.

Rapid Communications in Mass Spectrometry

A new organic reference material, L-glutamic acid, USGS41a, for δ 13 C and δ 15 N measurements − a replacement for USGS41

Rationale The widely used l -glutamic acid isotopic reference material USGS41, enriched in both 13 C and 15 N, is nearly exhausted. A new material, USGS41a, has been prepared as a replacement for USGS41. Methods USGS41a was prepared by dissolving analytical grade l -glutamic acid enriched in 13 C and 15 N together with l -glutamic acid of normal isotopic composition. The δ 13 C and δ 15 N values of USGS41a were directly or indirectly normalized with the international reference materials NBS 19 calcium carbonate ( δ 13 C VPDB = +1.95 mUr, where milliurey = 0.001 = 1 ‰), LSVEC lithium carbonate ( δ 13 C VPDB = −46.6 mUr), and IAEA-N-1 ammonium sulfate ( δ 15 N Air = +0.43 mUr) and USGS32 potassium nitrate ( δ 15 N = +180 mUr exactly) by on-line combustion, continuous-flow isotope-ratio mass spectrometry, and off-line dual-inlet isotope-ratio mass spectrometry. Results USGS41a is isotopically homogeneous; the reproducibility of δ 13 C and δ 15 N is better than 0.07 mUr and 0.09 mUr, respectively, in 200-μg amounts. It has a δ 13 C value of +36.55 mUr relative to VPDB and a δ 15 N value of +47.55 mUr relative to N 2 in air. USGS41 was found to be hydroscopic, probably due to the presence of pyroglutamic acid. Experimental results indicate that the chemical purity of USGS41a is substantially better than that of USGS41. Conclusions The new isotopic reference material USGS41a can be used with USGS40 (having a δ 13 C VPDB value of −26.39 mUr and a δ 15 N Air value of −4.52 mUr) for (i) analyzing local laboratory isotopic reference materials, and (ii) quantifying drift with time, mass-dependent isotopic fractionation, and isotope-ratio-scale contraction for isotopic analysis of biological and organic materials. Published in 2016. This article is a U.S. Government work and is in the public domain in the USA.

Rapid Communications in Mass Spectrometry

Novel silver tubing method for quantitative introduction of water into high temperature conversion systems for stable hydrogen and oxygen isotopic measurements

A new method to seal water in silver tubes for use in a TC/EA reduction unit using a semi-automated sealing apparatus can yield reproducibilities (1 standard deviation) of &delta; 2 H and &delta 18 O measurements of 1.0 ‰ and 0.06 ‰, respectively. These silver tubes containing reference waters may be preferred for calibration of H- and O-bearing materials analyzed with a TC/EA reduction unit. The new sealing apparatus employs a computer controlled stepping motor to produce silver tubes identical in length. The reproducibility of mass of water sealed in tubes (in a range of 200 to 400 µg) can be as good as 1 percent. Although silver tubes sealed with reference waters are robust and can be shaken or heated to 110 °C with no loss of integrity, they should not be frozen because the expansion during the phase transition of water to ice will break the cold seals and all water will be lost. They should be shipped in insulated containers. This new method eliminates air inclusions and isotopic fractionation of water associated with the loading of water into capsules using a syringe. The method is also more than an order of magnitude faster than preparing water samples in ordinary Ag capsules. Nevertheless, some laboratories may prefer loading water into silver capsules because expensive equipment is not needed, but they are cautioned to apply the necessary corrections for evaporation, back exchange with laboratory atmospheric moisture, and blank.

Rapid Communications in Mass Spectrometry

Comprehensive inter-laboratory calibration of reference materials for δ18O versus VSMOW using various on-line high-temperature conversion techniques

Internationally distributed organic and inorganic oxygen isotopic reference materials have been calibrated by six laboratories carrying out more than 5300 measurements using a variety of high-temperature conversion techniques (HTC) in an evaluation sponsored by the International Union of Pure and Applied Chemistry (IUPAC). To aid in the calibration of these reference materials, which span more than 125‰, an artificially enriched reference water ( δ 18 O of +78.91‰) and two barium sulfates (one depleted and one enriched in 18 O) were prepared and calibrated relative to VSMOW2 and SLAP reference waters. These materials were used to calibrate the other isotopic reference materials in this study, which yielded: Reference material δ 18 O and estimated combined uncertainty IAEA-602 benzoic acid +71.28 ± 0.36‰ USGS35 sodium nitrate +56.81 ± 0.31‰ IAEA-NO-3 potassium nitrate +25.32 ± 0.29‰ IAEA-601 benzoic acid +23.14 ± 0.19‰ IAEA-SO-5 barium sulfate +12.13 ± 0.33‰ NBS 127 barium sulfate +8.59 ± 0.26‰ VSMOW2 water 0‰ IAEA-600 caffeine −3.48 ± 0.53‰ IAEA-SO-6 barium sulfate −11.35 ± 0.31‰ USGS34 potassium nitrate −27.78 ± 0.37‰ SLAP water −55.5‰ The seemingly large estimated combined uncertainties arise from differences in instrumentation and methodology and difficulty in accounting for all measurement bias. They are composed of the 3-fold standard errors directly calculated from the measurements and provision for systematic errors discussed in this paper. A primary conclusion of this study is that nitrate samples analyzed for δ 18 O should be analyzed with internationally distributed isotopic nitrates, and likewise for sulfates and organics. Authors reporting relative differences of oxygen-isotope ratios ( δ 18 O) of nitrates, sulfates, or organic material should explicitly state in their reports the δ 18 O values of two or more internationally distributed nitrates (USGS34, IAEA-NO-3, and USGS35), sulfates (IAEA-SO-5, IAEA-SO-6, and NBS 127), or organic material (IAEA-601 benzoic acid, IAEA-602 benzoic acid, and IAEA-600 caffeine), as appropriate to the material being analyzed, had these reference materials been analyzed with unknowns. This procedure ensures that readers will be able to normalize the δ 18 O values at a later time should it become necessary. The high-temperature reduction technique for analyzing δ 18 O and δ 2 H is not as widely applicable as the well-established combustion technique for carbon and nitrogen stable isotope determination. To obtain the most reliable stable isotope data, materials should be treated in an identical fashion; within the same sequence of analyses, samples should be compared with working reference materials that are as similar in nature and in isotopic composition as feasible.

Rapid Communications in Mass Spectrometry

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

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

Rapid Communications in Mass Spectrometry

Oxygen isotopes in nitrite: Analysis, calibration, and equilibration

Nitrite is a central intermediate in the nitrogen cycle and can persist in significant concentrations in ocean waters, sediment pore waters, and terrestrial groundwaters. To fully interpret the effect of microbial processes on nitrate (NO 3 - ), nitrite (NO 2 - ), and nitrous oxide (N 2 O) cycling in these systems, the nitrite pool must be accessible to isotopic analysis. Furthermore, because nitrite interferes with most methods of nitrate isotopic analysis, accurate isotopic analysis of nitrite is essential for correct measurement of nitrate isotopes in a sample that contains nitrite. In this study, nitrite salts with varying oxygen isotopic compositions were prepared and calibrated and then used to test the denitrifier method for nitrite oxygen isotopic analysis. The oxygen isotopic fractionation during nitrite reduction to N 2 O by Pseudomonas aureofaciens was lower than for nitrate conversion to N 2 O, while oxygen isotopic exchange between nitrite and water during the reaction was similar. These results enable the extension of the denitrifier method to oxygen isotopic analysis of nitrite (in the absence of nitrate) and correction of nitrate isotopes for the presence of nitrite in “mixed” samples. We tested storage conditions for seawater and freshwater samples that contain nitrite and provide recommendations for accurate oxygen isotopic analysis of nitrite by any method. Finally, we report preliminary results on the equilibrium isotope effect between nitrite and water, which can play an important role in determining the oxygen isotopic value of nitrite where equilibration with water is significant.

Analytical Chemistry

Chemical analysis and modes of occurrence of selected trace elements in a Powder River basin coal and its corresponding simulated cleaned coal

This report provides semi-quantitative data on modes of occurrence of 19 elements in as-mined Powder River Basin coal and its corresponding simulated cleaned coal. The data are in support of the project "Prediction of Trace Element Removal from Coal" --a Cooperative Research and Development Agreement (CRADA) with CQ Inc. The purpose of this CRADA is to apply modes of occurrence information to coal cleaning procedures. Techniques used in this study include sequential selective leaching procedures, scanning electron microscopy, X-ray diffraction analysis, and electron microprobe analysis. Selective leaching results indicate that greater than 40 percent of the elements Co, U, Be, Ca, Fe, Mn, Ba, Zn, Cd, Pb are associated with HCIsoluble carbonates, iron oxides, or monosulfides, greater than 40 percent of the Al, Cr and Mo are associated with HF-soluble silicates, greater than 40 percent of the Ni, Cu, As and Sb are associated with acid-insoluble phases and/or organic matter, and greater than 50 percent of the Hg is associated with HMDs-soluble pyrite. Thirty percent of the Th was leached by HCI and 30 percent of this element was leached by HF. Scanning electron microscopy indicates that quartz, kaolinite, illite and iron oxide, possibly hematite, are the major minerals present. X-ray diffraction analysis confirmed that quartz, kaolinite and hematite are present, but did not determine illite, indicating that illite in these coals is of low abundance or is poorly crystalline. Electron microprobe data indicate that concentrations of the chalcophile elements As, Se, Cu, Ni, Zn, and Cd in most pyrite grains are at or below the detection limit of about 100-200 ppm in both the as-mined coal and its corresponding simulated cleaned coal product. The results of this project should aid in the development of models for predicting the response of potentially toxic trace elements in commercial coal cleaning procedures.

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