Hostname: page-component-78c5997874-lj6df Total loading time: 0 Render date: 2024-11-17T17:12:01.406Z Has data issue: false hasContentIssue false

UV Photochemical Oxidation and Extraction of Marine Dissolved Organic Carbon at UC Irvine: Status, Surprises, and Methodological Recommendations

Published online by Cambridge University Press:  15 April 2019

Brett D Walker*
Affiliation:
Department of Earth and Environmental Sciences, University of Ottawa, Ottawa, ON K1N 6N5, Canada Department of Earth System Science, University of California Irvine, CA 92697-3100, USA
Steven R Beaupré
Affiliation:
School of Marine and Atmospheric Sciences, Stony Brook University, Stony Brook, NY 11794-5000, USA
Sheila Griffin
Affiliation:
Department of Earth System Science, University of California Irvine, CA 92697-3100, USA
Ellen R M Druffel
Affiliation:
Department of Earth System Science, University of California Irvine, CA 92697-3100, USA
*
*Corresponding author. Email: [email protected].

Abstract

The first ultraviolet photochemical oxidation (UVox) extraction method for marine dissolved organic carbon (DOC) as CO2 gas was established by Armstrong and co-workers in 1966. Subsequent refinement of the UVox technique has co-evolved with the need for high-precision isotopic (Δ14C, δ13C) analysis and smaller sample size requirements for accelerator mass spectrometry radiocarbon (AMS 14C) measurements. The UVox line at UC Irvine was established in 2004 and the system reaction kinetics and efficiency for isolating seawater DOC rigorously tested for quantitative isolation of ∼1 mg C for AMS 14C measurements. Since then, improvements have been made to sampling, storage, and UVox methods to increase overall efficiency. We discuss our progress, and key UVox system parameters for optimizing precision, accuracy, and efficiency, including (1) ocean to reactor: filtration, storage and preparation of DOC samples, (2) cryogenic trap design, efficiency and quantification of CO2 break through, and (3) use of isotopic standards, blanks and small sample graphitization techniques for the correction of DOC concentrations and Fm values with propagated uncertainties. New DOC UVox systems are in use at many institutions. However, rigorous assessment of quantitative UVox DOC yields and blank contributions, DOC concentrations and carbon isotopic values need to be made. We highlight the need for a community-wide inter-comparison study.

Type
Conference Paper
Copyright
© 2019 by the Arizona Board of Regents on behalf of the University of Arizona 

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

Footnotes

Selected Papers from the 23rd International Radiocarbon Conference, Trondheim, Norway, 17–22 June, 2018

References

REFERENCES

Armstrong, FA, Williams, PM, Strickland, JD. 1966. Photo-oxidation of organic matter in sea water by ultra-violet radiation analytical and other applications. Nature 211(5048):481483.CrossRefGoogle Scholar
Beaupré, SR, Druffel, ERM. 2009. Constraining the propagation of bomb-radiocarbon through the dissolved organic carbon (DOC) pool in the northeast Pacific Ocean. Deep Sea Research Part I: Oceanographic Research Papers 56:17171726.CrossRefGoogle Scholar
Beaupré, SR, Druffel, ERM. 2012. Photochemical reactivity of ancient marine dissolved organic carbon. Geophysical Research Letters 39(18):L18602.CrossRefGoogle Scholar
Beaupré, SR, Druffel, ERM, Griffin, S. 2007. A low-blank photochemical extraction system for concentration and isotopic analyses of marine dissolved organic carbon. Limnology and Oceanography-Methods 5(6):174184.CrossRefGoogle Scholar
Broek, TAB, Walker, BD, Guilderson, TP, McCarthy, MD. 2017. Coupled ultrafiltration and solid phase extraction approach for the targeted study of semi-labile high molecular weight and refractory low molecular weight dissolved organic matter. Marine Chemistry 194:146157.CrossRefGoogle Scholar
Druffel, E, Griffin, S, Walker, BD. 2013. Total uncertainty of radiocarbon measurements of marine dissolved organic carbon and methodological recommendations. Radiocarbon 55(3):11351141.CrossRefGoogle Scholar
Griffin, S, Beaupré, SR, Druffel, ERM. 2010. An alternate method of diluting dissolved organic carbon seawater samples for 14C analysis. Radiocarbon 52(3):12241229.CrossRefGoogle Scholar
Lide, DR. 2005. CRC handbook of chemistry and physics, internet version 2005. Boca Raton: CRC Press.Google Scholar
Oppenländer, T. 2007. Photochemical purification of water and air: advanced oxidation processes (AOPs)-principles, reaction mechanisms, reactor concepts. Weinheim: Wiley-VCH.Google Scholar
Santos, GM, Southon, JR, Griffin, S, Beaupré, SR, Druffel, ERM. 2007. Ultra small-mass AMS C-14 sample preparation and analyses at KCCAMS/UCI facility. Nuclear Instruments & Methods in Physics Research B 259(1):293302.CrossRefGoogle Scholar
Walker, BD, Druffel, ERM, Kolasinski, J, Roberts, BJ, Xu, X, Rosenheim, BE. 2017. Stable and radiocarbon isotopic composition of dissolved organic matter in the Gulf of Mexico. Geophysical Research Letters 44(16):84248434.CrossRefGoogle Scholar
Walker, BD, Griffin, S, Druffel, ERM. 2016. Effect of acidified versus frozen storage on marine dissolved organic carbon concentration and isotopic composition. Radiocarbon 59(3):843857.CrossRefGoogle Scholar
Walker, BD, Xu, X. 2019. An improved method for the sealed-tube zinc graphitization of microgram carbon samples and 14C AMS measurement. Nuclear Instruments & Methods in Physics Research B 438:5865.CrossRefGoogle Scholar
Williams, PM. 1968. Stable carbon isotopes in the dissolved organic matter of the sea. Nature 219(5150):152.CrossRefGoogle Scholar
Williams, PM, Oeschger, H, Kinney, P. 1969. Natural radiocarbon activity of dissolved organic carbon in north-east pacific ocean. Nature 224(5216):256.CrossRefGoogle Scholar
Xu, X, Trumbore, SE, Zheng, S, Southon, JR, McDuffee, KE, Luttgen, M, Liu, JC. 2007. Modifying a sealed tube zinc reduction method for preparation of AMS graphite targets: reducing background and attaining high precision. Nuclear Instruments & Methods in Physics Research B 259(1):320329.CrossRefGoogle Scholar
Xue, Y, Ge, T, Wang, X. 2015. An effective method of UV-oxidation of dissolved organic carbon in natural waters for radiocarbon analysis by accelerator mass spectrometry. Journal of Ocean University of China 14(6):989993.CrossRefGoogle Scholar
Zigah, PK, McNichol, AP, Xu, L, Johnson, C, Santinelli, C, Karl, DM, Repeta, DJ. 2017. Allochthonous sources and dynamic cycling of ocean dissolved organic carbon revealed by carbon isotopes. Geophysical Research Letters 44(5):24072415.CrossRefGoogle Scholar