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UK GEOTRACES: Characterizing nitrate isotopes in South Atlantic water masses (40°S). Oxford 10th-11th September 2012 Robyn Tuerena, Raja Ganeshram, Anthony Fallick, Andrew Tait, Julie Dougans, Malcolm Woodward. Marine Nitrogen cycle • N Limits on biological production Sigman et al., 2000; Difiore et al.,2008 • Trace N fluxes Brandes and Devol, 2002; Codispoti et al., 2001 • Changing productivity patterns Duce et al., 2008; Falkowski et al., 1998 Characterizing nitrate isotopes in South Atlantic water masses (40°S) Robyn Tuerena, Raja Ganeshram, Anthony Fallick, Andrew Tait, Julie Dougans, Malcolm Woodward. Study area D357, RRS Discovery JC068, RRS James Cook Brazil SACW AAIW Agulhas NADW AABW Characterizing nitrate isotopes in South Atlantic water masses (40°S) Robyn Tuerena, Raja Ganeshram, Anthony Fallick, Andrew Tait, Julie Dougans, Malcolm Woodward. Stable isotope biogeochemistry δ15N (‰ vs. air) = 𝟏𝟓/𝟏𝟒 (𝐬𝐚𝐦𝐩𝐥𝐞) 𝟏𝟓/𝟏𝟒(𝐫𝐞𝐟𝐞𝐫𝐞𝐧𝐜𝐞) − 𝟏 x 1000 Spatially and temporally integrated value! Sigman et al., 2009 Characterizing nitrate isotopes in South Atlantic water masses (40°S) Robyn Tuerena, Raja Ganeshram, Anthony Fallick, Andrew Tait, Julie Dougans, Malcolm Woodward. Nitrate isotope cycling 1. N2 fixation 2. Remineralization 3. Nitrate utilization 4. Denitrification N2 ε ~ 25 ‰ 4. ~ -1 ‰ 1. NO 3 5‰ 4. ε ~0 ‰ 3. ε ~5 ‰ PP 2. ε ~≤ 3 ‰ Characterizing nitrate isotopes in South Atlantic water masses (40°S) Robyn Tuerena, Raja Ganeshram, Anthony Fallick, Andrew Tait, Julie Dougans, Malcolm Woodward. Characterizing water masses SURFACE Isotope fractionation Nitrate utilization, indicator of productivity Spatial pattern of δ15NNO3 and δ18ONO3 DEEP Tracer for N2 fixation, denitrification and partially utilized nitrate Characterizing nitrate isotopes in South Atlantic water masses (40°S) Robyn Tuerena, Raja Ganeshram, Anthony Fallick, Andrew Tait, Julie Dougans, Malcolm Woodward. Methods Denitrifier method (Sigman et al., 2001, Casciotti et al., 2002) NO3- converted to N2O Isotope ratio mass spectrometry Characterizing nitrate isotopes in South Atlantic water masses (40°S) Robyn Tuerena, Raja Ganeshram, Anthony Fallick, Andrew Tait, Julie Dougans, Malcolm Woodward. Deep water masses Station 3 Station 6 Station 10 0 δ15N 0.2 ‰ -1000 δ18O 0.5 ‰ Y Data Depth (m) -2000 -3000 d15N d18O -4000 -5000 0 2 4 6 8 10 12 -15 14 -10 -5 0 5 Per mil (‰) -2 0 10 15 2 4 6 8 10 12 Characterizing nitrate isotopes in South Atlantic water masses (40°S) Robyn Tuerena, Raja Ganeshram, Anthony Fallick, Andrew Tait, Julie Dougans, Malcolm Woodward. Deep water masses Characterizing nitrate isotopes in South Atlantic water masses (40°S) Robyn Tuerena, Raja Ganeshram, Anthony Fallick, Andrew Tait, Julie Dougans, Malcolm Woodward. Deep water masses AAIW AABW 4.9 ± 0.1 ‰ NADW 4.5 ± 0.2 ‰ AAIW 5.4 ± 0.4 ‰ AABW NADW AAIW NADW AABW Characterizing nitrate isotopes in South Atlantic water masses (40°S) Robyn Tuerena, Raja Ganeshram, Anthony Fallick, Andrew Tait, Julie Dougans, Malcolm Woodward. Deep water masses AAIW Incorporation of NO3- that has been partially consumed in Antarctic surface waters NADW Release of lighter N through sinking particles? Depleted source values? AABW Formed on shelf, Weddell sea and entrainment of CDW (~ 4.8 ‰, Sigman 1999) Characterizing nitrate isotopes in South Atlantic water masses (40°S) Robyn Tuerena, Raja Ganeshram, Anthony Fallick, Andrew Tait, Julie Dougans, Malcolm Woodward. Surface water masses Nitrate utilization enriches δ15N up to 13 ‰ at surface SAMW Characterizing nitrate isotopes in South Atlantic water masses (40°S) Robyn Tuerena, Raja Ganeshram, Anthony Fallick, Andrew Tait, Julie Dougans, Malcolm Woodward. Surface water masses D357 Characterizing nitrate isotopes in South Atlantic water masses (40°S) Robyn Tuerena, Raja Ganeshram, Anthony Fallick, Andrew Tait, Julie Dougans, Malcolm Woodward. Surface water masses Mixing dilutes δ15N values: Agulhas 6-8 ‰ SACW 5-7‰ Characterizing nitrate isotopes in South Atlantic water masses (40°S) Robyn Tuerena, Raja Ganeshram, Anthony Fallick, Andrew Tait, Julie Dougans, Malcolm Woodward. Nitrate Utilization 2 1 19 16 5 µM 12 ‰ 7 30 µM 5‰ 17.5 µM 6‰ Characterizing nitrate isotopes in South Atlantic water masses (40°S) Robyn Tuerena, Raja Ganeshram, Anthony Fallick, Andrew Tait, Julie Dougans, Malcolm Woodward. Mixing 0 0 200 200 400 Agulhas 400 Depth (m) Depth (m) δ15Nnr: 600 Indicates deviations from 800 related expected enrichment to NO3- concentrations 600 800 1000 1000 1200 1200 1400 Station 2 Station 6 -12 -10 -8 -6 -4 -2 0 15Nnr SACW Station 16 Station 19 1400 2 -8 -6 -4 -2 15Nnr Characterizing nitrate isotopes in South Atlantic water masses (40°S) Robyn Tuerena, Raja Ganeshram, Anthony Fallick, Andrew Tait, Julie Dougans, Malcolm Woodward. 0 2 Surface water masses Δ15,18 = (δ15N -δ15Nm) -(15ε/18ε)x(δ18O-δ18Om) Sigman et al., (2005) Deviations from δ15N:δ18O stoichiometry Characterizing nitrate isotopes in South Atlantic water masses (40°S) Robyn Tuerena, Raja Ganeshram, Anthony Fallick, Andrew Tait, Julie Dougans, Malcolm Woodward. Conclusions High resolution deep ocean transect Deep AAIW: partially utilized NO3- in surface waters 15N and δ18O measurements of NO - give an δ 3 NADW: Lighter values may indicate sinking of newly fixed OM integrated signal of N cycling processes over Surface space and time Water mass mixing dilutes δ15N enrichment in surface waters δ13C and δ15N of particulates can further Future constrainwork N cycling Finish analysis of surface and Western basin samples Finish particulate analyses Arctic and Southern Ocean samples Characterizing nitrate isotopes in South Atlantic water masses (40°S) Robyn Tuerena, Raja Ganeshram, Anthony Fallick, Andrew Tait, Julie Dougans, Malcolm Woodward. Collaborations • Aerosol data - Rosie Chance and Alex Baker • Mixing fluxes • Biological productivity in surface waters Acknowledgements Sample collection UK GEOTRACES team, Crew of the RRS Discovery and RRS James Cook, Sue Reynolds, Amandine Sabadel Method development Sian Henley, Jan Kaiser, Laura Campisi, Karen Casciotti, Matt McIlvin R.Schlitzer, Ocean Data View, http://www.awi-bremerhaven.de/GEO/ODV, 2012 Particulates d15 PN 1.0 Below 500 m 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 PN (uM) 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 0 Station 3 δ15PN increases to ~ 5 ‰ below 1000 m 1000 Depth (m) δ15NO3- source waters ~ 6 ‰ 500 1500 2000 d15N PN (uM) d15PON Nitrate [uM/L] 2500 4 6 8 10 12 14 d15 NO3 (per mil) 0 5 10 15 20 25 30 NO3 (uM) Characterizing nitrate isotopes in South Atlantic water masses (40°S) Robyn Tuerena, Raja Ganeshram, Anthony Fallick, Andrew Tait, Julie Dougans, Malcolm Woodward. 35 40 2D Graph 3 Particulates Particulates… POC (uM) 0 Surface 1 2 3 4 5 d13C (per mil) -24.5 -24.0 -23.5 -23.0 -22.5 -22.0 -21.5 -21.0 -20.5 0 Station 9 or 1.5 Enrichment in C-13 and N-15 at POC max 100 Depth (m) Enrichment with depth 50 150 200 d15PN d13POC POC (uM) 250 0 1 2 3 4 d15N PN (per mil) Characterizing nitrate isotopes in South Atlantic water masses (40°S) Robyn Tuerena, Raja Ganeshram, Anthony Fallick, Andrew Tait, Julie Dougans, Malcolm Woodward. 5 6