2016
DOI: 10.1002/rcm.7570
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Updates to instrumentation and protocols for isotopic analysis of nitrate by the denitrifier method

Abstract: RATIONALE:The denitrifier method allows for highly sensitive measurement of the 15 N/ 14 N (δ 15 N value) and 18 O/ 16 O (δ 18 O value) of nitrate dissolved in natural waters and for highly sensitive δ 15 N measurement of other N forms (e.g., organic N) that can be converted into nitrate. Here, updates to instrumentation and protocols are described, and improvements in data quality are demonstrated. METHODS: A 'heart cut' of the N 2 O was implemented in the extraction system to (1) minimize introduction of con… Show more

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Cited by 171 publications
(184 citation statements)
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“…Individual analyses were referenced to injections from a laboratory standard N 2 O tank and calibrated using the NO 3 − reference materials IAEA ‐ N3 (4.7‰ vs. N 2 and 25.6‰ vs. VSMOW; Böhlke et al, ; Gonfiantini et al, ) and U.S. Geological Survey ‐ 34 (−1.8‰ vs. N 2 ; −27.9‰ vs. VSMOW; Böhlke et al, ), with monitoring of reproducibility by analysis of an internal seawater NO 3 − standard from the deep North Atlantic. NO 3 − standards in individual runs were diluted in nutrient‐free seawater to concentrations equivalent to those of samples to account for potential matrix effects on δ 18 O NO3 measurements (Weigand et al, ). In order to ensure measurement accuracy, samples were analyzed in duplicate within runs, for a minimum of three discrete runs, yielding average standard deviations of 0.2‰ for N and 0.3‰ for O, although with a lower precision averaging 0.4‰ for δ 18 O NO3 at lower NO 3 − concentrations (<10 μM).…”
Section: Methodsmentioning
confidence: 99%
“…Individual analyses were referenced to injections from a laboratory standard N 2 O tank and calibrated using the NO 3 − reference materials IAEA ‐ N3 (4.7‰ vs. N 2 and 25.6‰ vs. VSMOW; Böhlke et al, ; Gonfiantini et al, ) and U.S. Geological Survey ‐ 34 (−1.8‰ vs. N 2 ; −27.9‰ vs. VSMOW; Böhlke et al, ), with monitoring of reproducibility by analysis of an internal seawater NO 3 − standard from the deep North Atlantic. NO 3 − standards in individual runs were diluted in nutrient‐free seawater to concentrations equivalent to those of samples to account for potential matrix effects on δ 18 O NO3 measurements (Weigand et al, ). In order to ensure measurement accuracy, samples were analyzed in duplicate within runs, for a minimum of three discrete runs, yielding average standard deviations of 0.2‰ for N and 0.3‰ for O, although with a lower precision averaging 0.4‰ for δ 18 O NO3 at lower NO 3 − concentrations (<10 μM).…”
Section: Methodsmentioning
confidence: 99%
“…Each batch of samples intended for mass spectrometric analysis included NO3 reference materials that was also amended with sulfamic acid to ensure that no contamination originates from this treatment. As a concentration effect is reported for measurements of NO3 δ 18 O, nitrate reference materials were diluted with low‐nutrient Sargasso Sea surface water to generate concentrations that bracket the concentrations of the samples in each batch (Weigand et al ). We use any trends between the measured δ 18 O of the two references concentrations bracketing of the sample concentrations to generate a linear correction for this trend (Marconi et al ; Weigand et al ).…”
Section: Methodsmentioning
confidence: 99%
“…Then, the skeleton powder was dissolved with HCl, and the released OM was oxidized into nitrate with alkaline persulfate oxidizing reagent. The concentration of the nitrate in the examined sample was analyzed by chemiluminescence ( 41 ), whereas δ 15 N of nitrate was measured by conversion into nitrous dioxide with the “denitrifier method” ( 42 ), followed by automated extraction, purification, and isotopic analysis of the N 2 O product ( 43 ). Two amino acid reference materials (USGS40 and USGS41) were included in each batch of analyses to correct for the reagent blank of the protocol and to reference the data to atmospheric N 2 , the universal reference.…”
Section: Methodsmentioning
confidence: 99%