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Explore the fascinating world of nitrogen cycling in the ocean, from N2 fixation to denitrification. Learn about the Redfield Ratio, types of nitrogen, and the importance of this essential element in marine ecosystems. Discover how research methods like isotopic tracing shed light on nitrogen dynamics.
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Nitrogen cycling in the ocean Deborah Bronk Department of Physical Sciences
Nitrogen Revolution mid-1990s-present • Nitrification • Denitrification/anammox • N2 fixation • Anthropogenic N inputs N N N
Why nitrogen is so cool! SEAWIFs chl a image
Outline: 1. Types & distribution 2. The Redfield Ratio 3. The nitrogen cycle 4. Liebig’s Law of the Minimum 5. New & regenerated production 6. Is the N cycle in steady state?
Types: Gaseous – N2 gas Dissolved Inorganic: ammonium – NH4+ nitrite – NO2- nitrate – NO3- Organic – DON Particulate – PN (cells & detritus)
Types: Gaseous – N2 gas Dissolved Inorganic: ammonium – NH4+ nitrite – NO2- nitrate – NO3- Organic – DON Particulate – PN (cells & detritus)
Southern California Bight Nitracline Bronk & Ward 2005 DSRI
The Ocean Euphotic zone light - ~little N Aphotic zone no light - lots N
Southern California Bight Nitracline Bronk & Ward 2005 DSRI
TDN - DIN = DON TDN - (NO3- + NO2- + NH4+ )
North Pacific Gyre – Particulate Nitrogen (mM) Mahaffey et al. 2008 DSRII
The Redfield Ratio C:N:P = 106: 16: 1 106CO2 + 122H2O + 16HNO3 + H3PO4 (CH2O)106(NH3)16(H3PO4) detritus vs. phyto vs. bacteria?
The Nitrogen Cycle Love, Mulholland, & Bronk 2011
Nitrogen fixation N2 + 8H+ + 8e- + 16 ATP 2 NH3 + H2 + 16 ADP + 16Pi Nitrogenase • “Fixing” broken N2 • Energetically very expensive – N2 has triple bond • Nitrogenase is irreversibly inactivated by oxygen • Most N2 fixers form heterocysts • Requires P, Fe, and trace metals (Mo, Co, V)
N2 fixation N2 N2 Trichodesmium • Two morphological forms • Colonial – 100s cells/trichome and 100s trichomes/colony • Traditionally considered the dominant N fixer in the ocean • Found in tropical and subtropical waters (NOT!)
How do we study the nitrogen cycle? [target] 15N Target Pool Source pool atom % of target Rate = atom % Time of source
[ ] PN 15N cell 15N2 N2 atom% PN Fixation = Rate atom % N2 Time
Trichodesmiummystery Non-heterocystous Photosynthesis CO2 O2 N2 fixation N2 NH4+ nitrogenase Temporal or spatial segregation?
cyanophycin granules High resolution-secondary ion mass spectrometry (Nano SIMS) Supports temporal segregation! Finzi-Hart et al. 2009 PNAS
N2 fixation N2 N2 Zehr et al. 2001 Nature Unicellular cyanobacteria that expressed nitrogenase at HOT Montoya et al. 2004 Nature Rates of N fixation by the single cell forms can equal or exceed rates by Trichodemsium
Ammonification N2 * N2 DON NH4+ Phytoplankton * Glibert & Bronk 1994
Ammonification - the conversion of DON or PON to NH4+ Two types: Bacterial - a. Traditional view of bacterial decomposition b. Was considered primary source of NH4+ (Now primary source if believed to be grazers) Photochemical (abiotic!) a. More recently recognized source b. Importance of process is still debated
Nitrification NH4+ ----------------->NO2- -----------------> NO3 Ammonium oxidizers: Nitrite oxidizers: very slow growing faster growing sensitive to light more sensitive to light • Nitrifiers are chemolithoautotrophs. • Maximum rates occur near the base of the • euphotic zone.
Nitrification PN or DON NO2- NH4+ dead cells/detritus ammonification NO3- Nitrifying bacteria - or is it??
Karner et al. 2001 Nature 39% of the picoplankton in the mesopelagic at HOT are archaea.
Könneke et al. 2005 Nature Isolated a marine crenarchaeota that can grow by aerobically oxidizing NH4+ to NO2-. Ingalls et al. 2006 PNAS An isotopic mass balance of radiocarbon signatures of archaeal membrane lipids indicates that 83% of their carbon is obtained autotrophically at depth.
Lost to system Denitrification N2 NO3- NO2- NO N2O nitrate reductase nitrite reductase nitric ox. reductase nitrous oxide reductase • N is used as an electron acceptor, not as a N source • Lots of organisms can reduce NO3- • Fewer can reduce NO2- • All the enzymes are induced by anoxia • NO is very labile and does not accumulate
Denitrification NO2- N2 NO N2O Canonical denitrification (- O2) N2 PN or DON NO3- NO2- NH4+
ANAMMOX ANaerobic AMMonium OXidation + NO2- NH4+ N2 • First described in a wastewater treatment plant in the • Netherlands in 1995. • Oxygen inhibition is reversible. • Thandrup & Dalsgaard (2002) published the first marine • data (sediment study)
N2 ANNAMOX N2 N2 PN NO3- NO2- NH4+ NO2- N2 NO N2O
+ NO2- NH4+ N2 N2 NO3- NO2- NO N2O Canonical denitrification? OR Anammox?? obligate anaerobic autotrophs facultative anaerobic heterotrophs
What’s the best way to make a living in a given place? Reaction Energy yield (kcal) Aerobic respiration 686 Denitrification 545 (-O2) Nitrification NH4+ oxidation 66 NO2- oxidation 17 N2 fixation -147
BREAK You see nitrite (NO2-) produced in the water. Design a tracer experiment to determine which process is producing it.
Uptake and regeneration in the surface ocean
Liebig’s Law of the Minimum (1840) - the resource in smallest supply relative to what the organism needs is the limiting factor. Growth versus biomass
Factor limiting growth rates during summer Moore et al. 2004 GBC