Dataset: Concentrations of dissolved organic carbon and phenols from Polarstern cruise PS 94-ARK-XXIX/3 from August to October 2015

ValidatedFinal no updates expectedDOI: 10.1575/1912/bco-dmo.767285.1Version 1 (2019-05-10)Dataset Type:Cruise Results

Principal Investigator: Karl Kaiser (Texas A&M, Galveston)

BCO-DMO Data Manager: Shannon Rauch (Woods Hole Oceanographic Institution)


Project: Development and application of a high sensitivity, ultra low volume method to measure biomarkers of terrigenous organic matter in the open ocean (Lignin phenol method development)


Abstract

Concentrations of dissolved organic carbon and phenols from Polarstern cruise PS 94-ARK-XXIX/3 from August to October 2015.

Samples were filtered straight from Niskin bottles following established protocols for trace-metal clean sampling (Sample handling protocols for GEOTRACES cruises).

Samples for DOC concentration were acidified to pH 2.5 and analyzed by high-temperature combustion on a Shimadzu TOC-L. DOC was calculated as the mean of between three and five injections using a six-point standard curve.

Lignin-derived phenols were determined following Yan and Kaiser (2018; Anal. Chem), and Yan and Kaiser (2018; Analytica Chimica Acta). Briefly, C18 extracts were redissolved in 200 μL of 1.1 mol L−1 argon- sparged (10 min) NaOH in a 400 uL Teflon vial (Savillex Corp) and amended with containing 500 mg CuO, and amended with 10μL of10 mmolL−1 CuSO4 and 10μ L of 0.2 molL−1 ascorbic acid. Oxidation was at 150 C for 120 minutes. Following oxidation, the samples were spiked with with a surrogate standard mixture of p- hydroxybenzoic acid-13C7, vanillin-13C6, and syringaldehyde-13C6 and acidified to pH ≈ 2.5 with 6 mol L−1 sulfuric acid in the reaction vials.  Clean-up of samples was performed with Waters HLB cartrides and final sample eluates were dried under ultra-high purity argon. Phenols were quantified by liquid chromatography/electrospray ionization-tandem mass spectrometry using a five-point calibration curve bracketing the concentration range. Quantified phenols (TDLP included vanillin, acetovanillone, vanillic acid, syringaldehyde, acetosyringone, syringic acid, coumaric acid, ferulic acid, p-hydroxy-benzaldehyde, p-hydroxy-acetophenone, and p-hydroxy-benzoic acid.

Samples were filtered straight from Niskin bottles following established protocols for trace-metal clean sampling (Sample handling protocols for GEOTRACES cruises)

Samples for DOC concentration were acidified to pH 2.5 and analyzed by high-temperature combustion on a Shimadzu TOC-L. DOC was calculated as the mean of between three and five injections using a six-point standard curve.

Lignin-derived phenols were determined following Yan and Kaiser (2018; Anal. Chem), and Yan and Kaiser (2018; Analytica Chimica Acta). Briefly, C18 extracts were redissolved in 200 μL of 1.1 mol L−1 argon- sparged (10 min) NaOH in a 400 uL Teflon vial (Savillex Corp) and amended with containing 500 mg CuO, and amended with 10μL of10 mmolL−1 CuSO4 and 10μ L of 0.2 molL−1 ascorbic acid. Oxidation was at 150 C for 120 minutes. Following oxidation, the samples were spiked with with a surrogate standard mixture of p- hydroxybenzoic acid-13C7, vanillin-13C6, and syringaldehyde-13C6 and acidified to pH ≈ 2.5 with 6 mol L−1 sulfuric acid in the reaction vials.  Clean-up of samples was performed with Waters HLB cartrides and final sample eluates were dried under ultra-high purity argon. Phenols were quantified by liquid chromatography/electrospray ionization-tandem mass spectrometry using a five-point calibration curve bracketing the concentration range. Quantified phenols: TDLP included vanillin, acetovanillone, vanillic acid, syringaldehyde, acetosyringone, syringic acid, coumaric acid, ferulic acid, p-hydroxy-benzaldehyde, p-hydroxy-acetophenone, and p-hydroxy-benzoic acid.


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Methods

Cutter, G., Andersson, P., Codispoti, L., Croot, P., François, R., Lohan, M. C., Obata, H. and Rutgers v. d. Loeff, M. (2010). Sampling and Sample-handling Protocols for GEOTRACES Cruises, [Miscellaneous] Version 1.
Methods

Yan, G., & Kaiser, K. (2018). A rapid and sensitive method for the analysis of lignin phenols in environmental samples using ultra-high performance liquid chromatography-electrospray ionization-tandem mass spectrometry with multiple reaction monitoring. Analytica Chimica Acta, 1023, 74–80. doi:10.1016/j.aca.2018.03.054
Methods

Yan, G., & Kaiser, K. (2018). Ultralow Sample Volume Cupric Sulfate Oxidation Method for the Analysis of Dissolved Lignin. Analytical Chemistry, 90(15), 9289–9295. doi:10.1021/acs.analchem.8b01867