I. Micro-nutrients in the oceans - IMEDEA Divulga...

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1 I. Micro-nutrients in the oceans X. Antón Álvarez Salgado CSIC, Instituto de Investigacións Mariñas C/ Eduardo Cabello 6, 36208 - Vigo http://www.iim.csic.es Impact of global change on ocean biogeochemical cycles (N, P, C and trace elements) Palma de Mallorca, 4 – 8 Nov 2013 outline of this presentation some general concepts … is a medium of high ionic strenght I = 0,5 ·Σ(C i ·Z i 2 ) ~ 19,92·S/(1000-1.005·S) ~ 0.7 mol/kg a C = f c (I)·[C] … that experiences hidrostatic pressures ranging from 1 to 1000 atm Seawater… (ΔP/ Δz ~ 0.1 atm/m) T R V P ln i d K d (P, K cause ions occupy less volume) d k d ln P V RT i (P, k cause ions occupy less volume)

Transcript of I. Micro-nutrients in the oceans - IMEDEA Divulga...

Page 1: I. Micro-nutrients in the oceans - IMEDEA Divulga CSIC-UIBimedea.uib-csic.es/master/cambioglobal/Modulo_II... · I. Micro-nutrients in the oceans X. Antón Álvarez Salgado CSIC,

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I. Micro-nutrients in the oceans

X. Antón Álvarez Salgado

CSIC, Instituto de Investigacións Mariñas

C/ Eduardo Cabello 6, 36208 - Vigo

http://www.iim.csic.es

Impact of global change on ocean biogeochemical cycles (N, P, C and trace elements)Palma de Mallorca, 4 – 8 Nov 2013

outline of this presentationsome general concepts

… is a medium of high ionic strenght

I = 0,5 ·Σ(Ci·Zi2) ~ 19,92·S/(1000-1.005·S) ~ 0.7 mol/kg

aC = fc (I)·[C]

… that experiences hidrostatic pressures ranging from 1 to 1000 atm

Seawater…

(ΔP/ Δz ~ 0.1 atm/m)

TR

VP

ln i

d

Kd (↑P, ↑ K cause ions occupy less volume)

d k

d

ln

P

V

R Ti

(↑P, ↑ k cause ions occupy less volume)

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… is a medium that experiences temperatures ranging from -2ºC to >30ºC

Seawater…

d K

d

ln

T

H

R T

0

2

(Vant Hoff law, free entalpy)

d k

d

ln

T

G

R T

0

2

(Arhenius law, free activation energy > 0, ↑T ↑k)

(ΔH0 > 0, ↑T ↑K; ΔH0 < 0, ↑T ↓K)

outline of this presentationsome general concepts

… is a buffer solution

Seawater…

outline of this presentationsome general concepts

K1(35, 15) = 10-6.04 [CO2 = 13.8 µmol·kg-1 (0.7%)

K2(35,15) = 10-9.23 [HCO3- = 1916.5 µmol·kg-1 (91.3%)

S(35,15) = 10-1.43 [CO32- = 169.6 µmol·kg-1 (8.0%)

STANDARD SEAWATER

(pHsws = 8.0; = 2100 µmol·kg-1) 2CO

K2

HCO3- CO3

2- + H+

K1

CO2 + H2O HCO3- + H+

KB

H3BO3 + H2O B(OH)4- + H+ KB(35, 15) = 10-8.74 [B(OH)4

- = 88.7 µmol·kg-1 (21.3%)

[H3BO3 = 327.7 µmol·kg-1 (78.7%)

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outline of this presentationsome general concepts

global conveyor belt

outline of this presentationC, N P and Si reservoirs in the oceans

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Worsfold et al., Anal. Chim. Acta, 2008

outline of this presentationC, N P and Si reservoirs in the oceans

dissolved inorganic phosphorus in the oceans

dissolved inorganic nitrogen in the oceans

dissolved inorganic compounds in the oceans

dissolved silicon in the oceans

outline of this presentation

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Codispoti, Biogeosciences, 2007

dissolved inorganic nitrogen species

dissolved inorganic nitrogen (DIN)

inorganic micro-nutrients in the oceans

dissolved inorganic nitrogen (DIN)

inorganic micro-nutrients in the oceans

STANDARD SEAWATER

KNO3(35, 15) = 102,3

KNO2(35,15) = 10-3,3

KNH4(35,15) = 10-9,68

pHsws= 8.0

NO3- / NO3H 100% / 0%

NO2- / NO2H 100% / 0%

NH4+ / NH3 98% / 2%

dissolved inorganic nitrogen species

NH4+ NH3 (aq) + H+

kNH4

NO2H NO2- + H+

kNO2

NO3H NO3- + H+

kNO3

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Schmitz, WHOI, 1995

distribution of NO3- in the oceans

Sarmiento & Gruber, 2006 (http://www.up.ethz.ch/people/ngruber/publications/textbook)

dissolved inorganic nitrogen (DIN)

inorganic micro-nutrients in the oceans

Sarmiento & Gruber, 2006 (http://www.up.ethz.ch/people/ngruber/publications/textbook)

dissolved inorganic nitrogen (DIN)

inorganic micro-nutrients in the oceans

distribution of NO3- in the oceans

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Sarmiento & Gruber, 2006 (http://www.up.ethz.ch/people/ngruber/publications/textbook)

dissolved inorganic nitrogen (DIN)

inorganic micro-nutrients in the oceans

distribution of NO3- in the oceans

distribution of NO2- in the oceans: the primary maximum (< 1 μmol/kg)

Lomas & Lipschultz, Limnol. Oceanogr., 2006

dissolved inorganic nitrogen (DIN)

inorganic micro-nutrients in the oceans

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distribution of NO2- in the oceans: the secondary maximum (1-10 μmol/kg)

Codispoti et al., Sci. Mar., 2001

dissolved inorganic nitrogen (DIN)

inorganic micro-nutrients in the oceans

dissolved inorganic nitrogen (DIN)

inorganic micro-nutrients in the oceans

distribution of NH4+ in the oceans

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distribution of N2O in the oceans

ΔN2O (natm) ΔN2O (mg N/m2/y)

Nevison et al., Global Biogeochem. Cycles, 1995

dissolved inorganic nitrogen (DIN)

inorganic micro-nutrients in the oceans

Nevison et al., Global Biogeochem. Cycles, 2003

dissolved inorganic nitrogen (DIN)

inorganic micro-nutrients in the oceans

distribution of N2O in the oceans

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dissolved inorganic phosphorus species

dissolved inorganic phosphorus (DIP)

K1P

H3PO4 H2PO4- + H+

K3P

HPO42- PO4

3- + H+

K2P

H2PO4- HPO4

2- + H+

inorganic micro-nutrients in the oceans

STANDARD SEAWATER

K1P(35, 15) = 10-1.60

K2P(35,15) = 10-6.03

K2P(35,15) = 10-8.99

pHsws= 8.0

H3PO4 0.0%

H2PO4- 0.8%

HPO42- 88.4%

PO43- 10.8%

dissolved inorganic phosphorus species

dissolved inorganic phosphorus (DIP)

inorganic micro-nutrients in the oceans

MgH2PO4+, CaH2PO4

+, MgHPO4, CaHPO4, MgPO4-, CaPO4

-

Kester and . Pytkowicz, Linmol Oceanogr, 1967

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distribution of dissolved inorganic phsophorus in the oceans

Sarmiento & Gruber, 2006 (http://www.up.ethz.ch/people/ngruber/publications/textbook)

dissolved inorganic phosphorus (DIP)

inorganic micro-nutrients in the oceans

dissolved inorganic silicon species

inorganic micro-nutrients in the oceansdissolved silicon (SiO2)

Ksi

H4SiO4 Si(OH)3O- + H+

STANDARD SEAWATER

KSi(35,15)= 10-9.52

pHsws = 8.0

H4SiO4 96.7%

Si(OH)3O- 4.2%

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distribution of Si(OH)4 in the oceans

Sarmiento & Gruber, 2006 (http://www.up.ethz.ch/people/ngruber/publications/textbook)

dissolved silicon (SiO2)

inorganic micro-nutrients in the oceans

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II. Biogenic materials in the oceans

X. Antón Álvarez Salgado

CSIC, Instituto de Investigacións Mariñas

C/ Eduardo Cabello 6, 36208 - Vigo

http://www.iim.csic.es

Impact of global change on ocean biogeochemical cycles (N, P, C and trace elements)Palma de Mallorca, 4 – 8 Nov 2013

outline of this presentation

Biogenic inorganic compounds: silica and calcium carbonate

Biogenic organic compounds: dissolved organic matter

Biogenic organic compounds: particulate organic matter

organic and inorganic biogenic compounds in the oceans

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microorganisms with biogenic silica structures

biogenic inorganic compoundsSiO2 · n H2O

diatom silicoflagelate radiolaria

polimerization of silicic acid

SiO2 · n H2O

Coradin et al., Chem. Biochem., 2003

2 Si(OH)4 →

→ (OH)3Si-O-Si(OH)3++ H2O

SiO2 · n H2O (~10% H2O)

biogenic inorganic compounds

Insat. : 0.1% - 10%

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Hecky et al., 1973

SiO2 · n H2O

biogenic inorganic compounds

Bopp et al., Geophys. Res. Lett., 2005

distribution of biogenic silica in the oceans

SiO2 · n H2O

biogenic inorganic compounds

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Helhen et al., Biogeosciences, 2008

distribution of biogenic silica in marine sediments

BSi

(% w

/w

)

SiO2 · n H2O

biogenic inorganic compounds

microorganisms with calcium carbonate structures

CaCO3

coccolithophores foraminiphers

biogenic inorganic compounds

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Langer, PhD Thesis, 2005

structure of a calcium carbonate cocolite

A) Sketch of a three dimensional arrayof a very small portion of CaCO3atoms in their spatial arrangementin calcite; reproduced from Younget al. (1999).

B) Drawing of a coccolith of Emilianiahuxleyi; reproduced from Young etal. (1999)

C) Schematic cross-section through anE. huxleyi crystal showing itscrystallographic relation to thecalcite rhomb (grey); reproducedfrom Henriksen et al. (2004a).

D) SEM image of inorganicallyprecipitated calcite (courtesy ofGernot Nehrke, AWIBremerhaven)

E) SEM image of E. huxleyi

Sobresat.: 250-400%

CaCO3

biogenic inorganic compounds

distribution of CaCO3 in the oceans

CaCO3

biogenic inorganic compounds

Balch & Utgoff, Oceanography, 2009

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distribution of CaCO3 in the oceans

CaCO3

biogenic inorganic compounds

Balch et al., Global Bigeochem. Cy., 2005

distribution of CaCO3 in marine sediments

Helhen et al., Biogeosciences, 2008

CaC

O3 (%

w/

w)

CaCO3

biogenic inorganic compounds

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Gould & Mantoura (1990)

partition of organic matter in the oceans

biogenic organic compounds

0.00010.0010.010.11101001000

ZOOPLANKTON

PHYTOPLANKTON

BACTERIA

DETRITUS

VIRUSES

SIZE, µm

dissolved

sinking suspended colloidal-HMW

filter

particulate

LMW

0.7-0.2µm

500-1000 Da

particulate organic matter (POM)

DOM 662 GtC

detritus 20 GtC

phytoplankton 13 GtC

zooplankton 0.1 GtC

bacteria 0.1 GtC

Fraga & Álvarez-Salgado, Ciencias Marina, 2006

POM composition and contribution to alkalinity

fórmula m.w % (w/w)

Carbohydrates C6H10O5 456,4 24,4

Lipids C53H89O6 822,3 16,5

Pigments C46H52O5N4Mg 764,3 2,0

Proteins C139H217O45N39S 3171,0 45,1

Phosphorus comp. C45H76O31N12P5 1436,0 12,0

Avg. composition C106H171O44N16PS0.3 100,0

biogenic organic compoundsparticulate organic matter (POM)

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distribution of POM in the oceans

biogenic organic compoundsparticulate organic matter (POM)

distribution of POM in the oceans

biogenic organic compoundsparticulate organic matter (POM)

Duforet-Gaurnier et al., Deep Sea Res., 2010

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distribution of POM in marine sediments

Helhen et al., Biogeosciences, 2008

PO

C (

% w

/w

)

biogenic organic compoundsparticulate organic matter (POM)

Brook, Nature, 2008

origin of dissolved organic matter: biotic

Mesozoo lysis

nutrients

nutrients

metabolites

POM

OH-

O2l-MOD

r-MODH+

O2

anabolismcatabolism

exudationexcretion

biogenic organic compoundsdissolved organic matter (DOM)

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melanoidins poly-insaturate fattly acids

H2O

R NH2C

O

R NH2C

Oaminoacid

O C R’

H

O C R’

Hmonosacharide

R NC

O

C R’

H

R NC

O

C R’

H

Schift base

biogenic organic compoundsdissolved organic matter (DOM)

origin of dissolved organic matter: abiotic

Jickells et al., 1991

molecular weight and reactivity (biological)

biogenic organic compoundsdissolved organic matter (DOM)

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biogenic organic compoundsdissolved organic matter (DOM)

molecular weight and reactivity (biological)

LMWMOD HMWMOD

mol. weight < 1 kDa > 1 kDa

contribution ~70% ~30%

lDOM monosacharides, aminoacids, urea, fattly acids, glicolate

(~ hoursdays)

sugar polymers, amides, peptides, phosphoric esters, phosphonates

(~ daysweeks)

rDOM ?

(~40006000 years)

humic susbtances

( ~ 150200 years)

biogenic organic compoundsdissolved organic matter (DOM)

molecular weight and reactivity (biological)

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humic acid

fulvic acid

Ritchie & Perdue, Geochim. Cosmochim. Acta, 2003

biogenic organic compoundsdissolved organic matter (DOM)

humic substances

lightyellow

darkyellow brown dark

grey black

fulvic acid humic acid humins

color

polymerization degree

Molecular weight

Carbon content

Oxygen content

insolubility in water

2000

45%

48%

300.000

62%

30%

Stevenson, 1982

biogenic organic compoundsdissolved organic matter (DOM)

humic substances

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distribution of DOM in the oceans

Hansell et al., Oceanography, 2009

biogenic organic compoundsdissolved organic matter (DOM)

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III. Metabolism of the oceans: synthesis and mineralization processes

X. Antón Álvarez Salgado

CSIC, Instituto de Investigacións Mariñas

C/ Eduardo Cabello 6, 36208 - Vigo

http://www.iim.csic.es

Impact of global change on ocean biogeochemical cycles (N, P, C and trace elements)Palma de Mallorca, 4– 8 Nov 2013

outline of this presentation

synthesis of biogenic materials

anaerobic mineralisation of biogenic materials

aerobic mineralisation of biogenic materials

anabolism and catabolism of the microbial communities

stoichiometry of metabolic processes in the microbial food web

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global distribution of primary production

synthesis of biogenic materialssynthesis of organic matter by marine phytoplankton

marine ecosystemsC106H171O44N16P

0.6-3.0 Gt C1-3 weeks

50 Gt C a-1 (375 mg C m–2 d-1 )

terrestrial ecosystem

560 Gt C

10 years

60 Gt C a-1 (1150 mg C m–2 d-1 )

C830H1230O604N9P

limiting elements of marine primary production

synthesis of biogenic materials

Bernard et al., Biogeosciences disc., 2009

synthesis of organic matter by marine phytoplankton

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Longhurst, Progr. Oceanogr., 1995

synthesis of biogenic materials

biogeographic provinces in the oceans

synthesis of organic matter by marine phytoplankton

composition of phytoplanktonic organic matter

Fraga & Álvarez-Salgado, Cienc. Mar., 2005

synthesis of biogenic materials

formula % (w/w)

Carbohydrates C6H10O5 24,4

Lipids C53H89O6 16,5

Chlorophyll a, b, c1 y c2 C46H52O5N4Mg 2,0

Proteins C139H217O45N39S 45,1

Phosphorus compounds C45H76O31N12P5 12,0

Average composition C106H171O44N16PS0.3 100,0

synthesis of organic matter by marine phytoplankton

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ΣCO2 sources and buffering capacity of seawater

synthesis of biogenic materials

K2

HCO3- CO3

2- + H+

STANDARD SEAWATER

(pHsws = 8.0; = 2100 µmol·kg-1) 2CO

K1

CO2 + H2O HCO3- + H+

KB

H3BO3 + H2O B(OH)4- + H+

K1(35, 15) = 10-6.04 [CO2 = 13.8 µmol·kg-1 (0.7%)

K2(35,15) = 10-9.23 [HCO3- = 1916.5 µmol·kg-1 (91.3%)

S(35,15) = 10-1.43 [CO32- = 169.6 µmol·kg-1 (8.0%)

KB(35, 15) = 10-8.74 [B(OH)4- = 88.7 µmol·kg-1 (21.3%)

[H3BO3 = 327.7 µmol·kg-1 (78.7%)

synthesis of organic matter by marine phytoplankton

ΣCO2 sources of marine phytoplankton photosynthesis

mechanisms of incorporation of CO2 y HCO3-

CO2HCO3

- CO32-

CO2

HCO3-

OH-

OH-POM

14 μM 1917 μM 170 μM

CO2

Anhidrasacarbónica

lentolento

CO2HCO3

- CO32-

CO2

HCO3-

OH-

OH-POM

14 μM 1917 μM 170 μM

CO2

Anhidrasacarbónica

lentolento

De Baar, Prog. Oceanogr., 1994

synthesis of biogenic materials

CO2HCO3

- CO32-

CO2

HCO3-

POM

14 μM 1917 μM 170 μM

CO2

lentolento

CaCO3

Ca2+

10.3 mM

CO2HCO3

- CO32-

CO2

HCO3-

POM

14 μM 1917 μM 170 μM

CO2

lentolento

CaCO3

Ca2+

10.3 mM2

OH-

OH-

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using NH4+ as nitrogen source

stoichiometry of the synthesis of biogenic materials

106 HCO3- + 16 NH4

+ + HPO42- + 46 H2O C106H171O44N16P + 116 O2 + 92 OH-

synthesis of biogenic materials

assuming no buffering capacity

initial Corg = 106 final

pH 8.00 +1.40 9.40

initial Corg= 106 final

pH 8.00 +0.23 8.23

synthesis of biogenic materialsusing NH4

+ as nitrogen source

assuming HCO3-/ CO3

2- buffer only:

HCO3- + OH- CO3

2- + H2O

106 HCO3- + 16 NH4

+ + HPO42- + 46 H2O C106H171O44N16P + 116 O2 + 92 OH-

buffering capacity of seawater

3

23

10H10 HCO

COlogfKlogpH 2

198 HCO3- + 16 NH4

+ + HPO42- C106H171O44N16P + 116 O2 + 92 CO3

2- + 46 H2O

+

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seawater pH buffer:

variable initial Corg= 106 final

(µmol·kg-1) 2100 -106 1994

A (µmol·kg-1) 2348 -16 2332

pH 8.00 +0.16 8.16

[CO2 (µmol·kg-1) 13.8 -5.0 8.8

[HCO3- (µmol·kg-1) 1917 -157 1760

[CO32- (µmol·kg-1) 170 +55 225

ARG 2.6 3.5

CAL 4.1 5.3

pCO2(g) (µatm) 370 -135 235

[O2 (µmol·kg-1) 248 +116 364

2CO

synthesis of biogenic materialsusing NH4

+ as nitrogen source

stoichimetry and buffering capacity

using NO3- as nitrogen source

NO3- NO2

- + 1/2 O2 (nitrate reductase)

NO2- + 3 H2O NH4

+ + 3/2 O2 +2 OH- (nitrite reductase)assimilative reduction

synthesis of biogenic materials

stoichiometry of the synthesis of biogenic materials

106 HCO3- + 16 NH4

+ + HPO42- + 46 H2O C106H171O44N16P + 116 O2 + 92 OH-

HCO3- + OH- CO3

2- + H2O

106 HCO3- + 16 NO3

- + HPO42- + 94 H2O C106H171O44N16P + 148 O2 + 124 OH-

+

+230 HCO3

- + 16 NO3- + HPO4

2- C106H171O44N16P + 148 O2 + 124 CO32- + 30 H2O

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variable initial Corg= 106 final

(µmol·kg-1) 2100 +106 1994

A (µmol·kg-1) 2348 +16 2364

pH 8.00 +0.21 8.21

[CO2 (µmol·kg-1) 13.8 -6.1 7.7

[HCO3- (µmol·kg-1) 1917 -180 1734

[CO32- (µmol·kg-1) 170 +80 249

ARG 2.6 3.8

CAL 4.1 6.0

pCO2(g) (µatm) 370 -163 207

[O2 (µmol·kg-1) 248 +148 396

2CO

synthesis of biogenic materialsusing NO3

- as nitrogen source

stoichiometry and buffering capacity

using N2 as nitrogen source

global distribution of N2 fixation in the oceans

Deutsch et al., Nature, 2007

synthesis of biogenic materials

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N2+ 5 H2O 2 NH4+ + 3/2 O2 + 2 OH- (nitrogenase) – Trichodesmiun & cianobacteria

synthesis of biogenic materialsusing N2 as nitrogen source

106 HCO3- + 16 NH4

+ + HPO42- + 46 H2O C106H171O44N16P + 116 O2 + 92 OH-

106 HCO3- + 8 N2 + HPO4

2- + 86 H2O C106H171O44N16P + 128 O2 + 108 OH-

+

HCO3- + OH- CO3

2- + H2O

214 HCO3- + 8 N2 + HPO4

2- C106H171O44N16P + 128 O2 + 108 CO32- + 22 H2O

+

stoichiometry of the synthesis of biogenic materials

variable initial Corg= 106 final

(µmol·kg-1) 2100 -106 1994

A (µmol·kg-1) 2348 +0 2348

pH 8.00 +0.18 8.18

[CO2 (µmol·kg-1) 13.8 -5.5 8.3

[HCO3- (µmol·kg-1) 1917 -167 1750

[CO32- (µmol·kg-1) 170 +66 236

ARG 2.6 3.6

CAL 4.1 5.7

pCO2(g) (µatm) 370 -149 221

[O2 (µmol·kg-1) 248 +128 376

2CO

synthesis of biogenic materialsusing N2 as nitrogen source

stoichimetry and buffering capacity

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using multiple nitrogen sources

synthesis of biogenic materials

stoichiometry of the synthesis of biogenic materials

198 HCO3- + 16 NH4

+ + HPO42- C106H171O44N16P + 116 O2 + 92 CO3

2- + 46 H2O

230 HCO3- + 16 NO3

- + HPO42- C106H171O44N16P + 148 O2 + 124 CO3

2- + 30 H2O

214 HCO3- + 8 N2 + HPO4

2- C106H171O44N16P + 128 O2 + 108 CO32- + 22 H2O

NH4+

NO2-

NO3-

(NH2)2CO

N2

N2

OH-

O2

MOP

(NH2)2CO NH4+

NO3-

N2

nitrogenasa

ureasa

Nitrito reductasa

Nitrato reductasa

tranpsorte

exudación

incorporación

NH4+

NO2-

NO3-

(NH2)2CO

N2

N2

OH-

O2

MOP

(NH2)2CO NH4+

NO3-

N2

nitrogenasa

ureasa

Nitrito reductasa

Nitrato reductasa

tranpsorte

exudación

incorporación

synthesis of biogenic materialsusing multiple nitrogen sources

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Lee, 2001

global distribution of calcification in the oceans: 1,1 ± 0,3 × 1015 g C/yr

synthesis of calcium carbonate in the oceans

synthesis of biogenic materials

CO32- + Ca2+ CaCO3 (s)

synthesis of biogenic materialssynthesis of calcium carbonate in the oceans

stoichiometry of the synthesis of biogenic materials

230 HCO3- + 16 NO3

- + HPO42- + 106 Ca2+

(C106H171O44N16P)(CaCO3)106 + 148 O2 + 18 CO32- + 30 H2O

+50%

50%230 HCO3- + 16 NO3

- + HPO42- C106H171O44N16P + 148 O2 + 124 CO3

2- + 30 H2O

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Variable inicial Corg= 106 final

(µmol·kg-1) 2100 -212 1888

A (µmol·kg-1) 2348 -196 2152

pH 8.00 +0.06 8.06

[CO2 (µmol·kg-1) 13.8 -3.1 10.7

[HCO3- (µmol·kg-1) 1917 -212 1704

[CO32- (µmol·kg-1) 170 4 173

ARG 2.6 2.7

CAL 4.1 4.2

pCO2(g) (µatm) 370 -84 286

[O2 (µmol·kg-1) 248 +148 396

2CO

ΔCorg = Δ CaCO3, ΔNT = Δ [NO3-] (cocolitofores using nitrate as nitrogen source)

synthesis of biogenic materialssynthesis of calcium carbonate in the oceans

stoichimetry and buffering capacity

global distribution of silification in the oceans: 6,85 1015 g /yr

synthesis of biogenic silica in the oceans

Table 7.2.1 Estimates of opal production in the world ocean.

Production rate (mmol m-2 d-1 of Si) Region Number of profiles Low Mean High

Coastal Upwelling 77 2.3 90 1140 Other Coastal 55 0.2 15 131 Deep Ocean 84 0.2 2.3 12 Southern Ocean 74 0.9 15 93

Bopp et al., Geophys. Res. Lett., 2005

synthesis of biogenic materials

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12

H4SiO4 + (n-2) H2O SiO2·nH2O(s)

synthesis of biogenic materialssynthesis of biogenic silica in the oceans

stoichiometry of the synthesis of biogenic materials

230 HCO3- + 16 NO3

- + HPO42- + 16 H4SiO4

(C106H171O44N16P)(SiO2· nH2O)16 + 148 O2 + 18 CO32- + 30 H2O

+230 HCO3

- + 16 NO3- + HPO4

2- C106H171O44N16P + 148 O2 + 124 CO32- + 30 H2O

variable initial Corg= 106 final

(µmol·kg-1) 2100 +106 1994

A (µmol·kg-1) 2348 +16 2364

pH 8.00 +0.21 8.21

[CO2 (µmol·kg-1) 13.8 -6.1 7.7

[HCO3- (µmol·kg-1) 1917 -180 1734

[CO32- (µmol·kg-1) 170 +80 249

ARG 2.6 3.8

CAL 4.1 6.0

pCO2(g) (µatm) 370 -163 207

[O2 (µmol·kg-1) 248 +148 396

2CO

synthesis of biogenic materials

stoichiometry and buffering capacity

synthesis of biogenic silica in the oceans

ΔNorg = ΔSiO2·nH2O, ΔNT = Δ [NO3-] (disatoms using nitrate as nitrogen source)

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aerobic mineralization of biogenic materialsammonification

stoichiometry of the mineralization of biogenic materials

CO32- + H+ HCO3

-

C106H171O44N16P + 116 O2 + 46 H2O 106 HCO3- + 16 NH4+ + HPO4

2- + 92 H+

C106H171O44N16P + 116 O2 + 92 CO32- + 46 H2O 198 HCO3- + 16 NH4

+ + HPO42-

+

variable initial Corg=-106 final

(µmol·kg-1) 2100 +106 2206

A (µmol·kg-1) 2348 +16 2364

pH 8.00 -0.19 7.81

[CO2 (µmol·kg-1) 13.8 +9.4 23.3

[HCO3- (µmol·kg-1) 1917 +149 2065

[CO32- (µmol·kg-1) 170 -52 117

ARG 2.6 1.8

CAL 4.1 2.8

pCO2(g) (µatm) 370 +252 621

[O2 (µmol·kg-1) 248 -116 132

2CO

aerobic mineralization of biogenic materialsammonification

stoichiometry and buffering capacity

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nitrification

NH4+ + 3/2 O2 NO2

+ H2O + 2H+ NH4+ + 1/2 O2 NH2OH + H+

NH2OH + O2 NO2 + H2O + H+

2 NH2OH + O2 N2O + 3H2O

nitrification, phase I(nitrosomonas)

nitrification, phase II(nitrosococcus)

NO2 + 1/2 O2 NO3

C106H171O44N16P + 148 O2 + 124 CO32- + 30 H2O 106 HCO3

- + 16 NO3- + HPO4

2-

aerobic mineralization of biogenic materials

C106H171O44N16P + 116 O2 + 92 CO32- + 46 H2O 198 HCO3

- + 16 NH4+ + HPO4

2-

stoichiometry of the mineralization of biogenic materials

variable initial Corg=-106 final

(µmol·kg-1) 2100 +106 2206

A (µmol·kg-1) 2348 -16 2232

pH 8.00 -0.27 7.73

[CO2 (µmol·kg-1) 13.8 +14.1 28.0

[HCO3- (µmol·kg-1) 1917 +163 2079

[CO32- (µmol·kg-1) 170 -71 99

ARG 2.6 1.5

CAL 4.1 2.4

pCO2(g) (µatm) 370 +377 747

[O2 (µmol·kg-1) 248 -148 100

2CO

aerobic mineralization of biogenic materialsnitrification

stoichiometry and buffering capacity

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distribution in the oceans

Sarmiento & Gruber, 2006 (http://www.up.ethz.ch/people/ngruber/publications/textbook)

aerobic mineralization of biogenic materialsnitrification

C106H171O44N16P + 102,4 NO3- 106 HCO3

- + 59,2 N2 + HPO42- + 29,2 H2O + 5,6 H+

NO3- is consumedquickly!

anaerobic mineralization of biogenic materialsdenitrification

stoichiometry of the mineralization of biogenic materials

CO32- + H+ HCO3

-

C106H171O44N16P + 102,4 NO3-+ 5,6 CO3

2- 111,6 HCO3- +59,2 N2 + HPO4

2- + 29,2 H2O

+

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variable initial Corg= -21 final

(µmol·kg-1) 2279 +21 2300

A (µmol·kg-1) 2321 +20 2341

pH 7.69 -0.04 7.65

[CO2 (µmol·kg-1) 50.7 +0.4 51.1

[HCO3- (µmol·kg-1) 2169 +19 2188

[CO32- (µmol·kg-1) 59.3 +0.5 59.8

ARG 0.91 0.92

CAL 1.43 1.44

pCO2(g) (µatm) 1353 12 1365

[O2 (µmol·kg-1) 0 0 0

2CO

anaerobic mineralization of biogenic materialsdenitrification

stoichiometry and buffering capacity

global distribution in the oceans

oxígeno disuelto a 200 m de profundidad (ref. 1994)

anaerobic mineralization of biogenic materialsdenitrification

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denitrification

anaerobic mineralization of biogenic materials

global distribution in the oceans

anaerobic ammonium oxidation

Ward et al., Oceanography, 2007

the new route: anammox

NH4+ + NO2

-→ N2 + 2 H2O

i) NO2- + 2 NH4

+ + H2O → 3 NH2OH + H+

(hidoxilamina)

2 NH2OH + O2 → N2O + 3H2O

NH2OH

N2O

ii) NH2OH + NH4+ → N2H4+ H2O + H+

(hidrazina)

iii) 3 N2H4+ 4 H+ → N2 + 4 NH4+

anaerobic mineralization of biogenic materials

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sulphate-reduction

C106H171O44N16P + 58 SO42- + 46 H2O 106 HCO3

- + 16 NH4+ + HPO4

2- + 58 HS- + 34 H+

anaerobic mineralization of biogenic materials

stoichiometry of the mineralization of biogenic materials

CO32- + H+ HCO3

-

C106H171O44N16P + 58 SO42- + 34 CO3

2- + 46 H2O 140 HCO3- +16 NH4

+ + HPO42- + 58 HS-

+

distribution in the oceans

sulphate-reduction

anaerobic mineralization of biogenic materials

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fermentation

C106H171O44N16P + 104 H2O 58 CH4+ 48 HCO3- + 16 NH4

+ + HPO42- + 34 H+

anaerobic mineralization of biogenic materials

stoichiometry of the mineralization of biogenic materials

CO32- + H+ HCO3

-

C106H171O44N16P + 34 CO32- + 104 H2O 58 CH4+ 82 HCO3

- +16 NH4+ + HPO4

2-

+

distribution in the oceans

Reeburgh, Chem. Rev., 2007

fermentation

anaerobic mineralization of biogenic materials

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sediments

aerobic

anaerobic

Norg

Norg

Norg

N residual

geo-polymers

NH4+ NO2

- NO3-

N2NO3-NH4

+

NH4+ NO3

- NO2- N2

NH4+·clay/humins

ionic exchange

denitrification

nitrificationammonification

reactionssedimentation diffusion

Klump & Martens, 1983

procceses in the sediments

anaerobic mineralization of biogenic materials

Amonificación

C106H171O44N16P + 116 O2+ 46 H2O 106 HCO3-+ 16 NH4

+ + HPO42- + 92 H+

Nitrificación

C106H171O44N16P+ 148 O2+ 30 H2O 106 HCO3-+16 NO3

- + HPO42- + 124 H+

desnitrificación 2 NO3- + 6 H20 + 10 e- N2 + 12 OH-

Mn(IV) MnO2 + 4 H+ + 2 e- Mn2+ + 2 H2O (birnesita, nsutita ó pirolusita)

NO3- NH4

+ NO3- + 7 H2O + 8 e- NH4

+ + 10 OH-

Fe(III) Fe2O3 + 6 H+ + 2 e- 2 Fe+2 + 3 H2O (hematita)FeOOH + 3 H+ + 1e- Fe2+ + 2 H2O (geotita)

sulfato reducción SO42- + 5 H2O + 8 e- HS- + 9 OH-

fermentación CO2 + 8 H+ + 8 e- CH4 +2 H2O

Semi-par reductor (donante de e-)

C106H171O44N16P+278 H2O 106 HCO3-+16 NH4+ + HPO4

2- + 556 H+ + 464 e-

Semi-par oxidante (aceptor de e-)

aero

bia

anae

rob

ia

pro

fun

did

ad

+0,20 /+0,80

+0,05 /+0,75

+0,10 /+0,60

-0,65 /-0,20

-0,20 /+0,40

-0,50 /+0,05

Eh (Volts)

procceses in the sediments

anaerobic mineralization of biogenic materials

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methane in coastal sediments

Kaudla & Sandler, Energy & Fuel, 2005

procceses in the sediments

anaerobic mineralization of biogenic materials

mineralization of inorganic biogenic materialsmineralization of biogenic silica

stoichiometry of the mineralization of biogenic materials

SiO2·nH2O(s) H4SiO4 + (n-2) H2O

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global distribution of BSi disolution in the oceans

mineralization of inorganic biogenic materialsmineralization of biogenic silica

mineralization of calcareous structures

CaCO3 (s) CO32- + Ca2+

mineralization of inorganic biogenic materials

stoichiometry of the mineralization of biogenic materials

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Sarmiento & Gruber, 2006 (http://www.up.ethz.ch/people/ngruber/publications/textbook)

mineralization of inorganic biogenic materialsmineralization of calcareous structures

global distribution of CaCO3 dissolution in the oceans

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1

IV. Ocean biogeochemical cycles

X. Antón Álvarez Salgado

CSIC, Instituto de Investigacións Mariñas

C/ Eduardo Cabello 6, 36208 - Vigo

http://www.iim.csic.es

Impact of global change on ocean biogeochemical cycles (N, P, C and trace elements)Palma de Mallorca, 4 – 8 Nov 2013

outline of this presentation

the biological pump: before (1980’s) and after (1990’s)

cycling of biogenic inorganic matter: silicon and calcium carbonate

cycling of biogenic organic matter: nitrogen and phosphorus in the oceans

ocean biogeochemical cycles

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Eppley & Petersen (1979) model

the biological pump in the oceansthe biological pump in the 1980’s

1%

NO3-NO3-

NO3-NO3-

NH4+NH4+

NOP

PRPN

new or exportable production estimates

sediment traps

M.O.

geochemical budgets

Z

NT

1%

VZ KZ

NT

1%

PRPN

NO3-

NO3- NOS

NH4+

15NO3 , 15NH4

-

+

the biological pump in the oceansthe biological pump in the 1980’s

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Sarmiento & Gruber, 2006 (http://www.up.ethz.ch/people/ngruber/publications/textbook)

the biological pump in the oceansthe biological pump in the 1980’s

new or exportable production estimates

Sarmiento & Gruber, 2006 (http://www.up.ethz.ch/people/ngruber/publications/textbook)

sediment traps

the biological pump in the oceansthe biological pump in the 1980’s

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Sarmiento & Gruber, 2006 (http://www.up.ethz.ch/people/ngruber/publications/textbook)

the biological pump in the oceansthe biological pump in the 1980’s

sediment traps

sediment traps: fluxes at the epi-mesopelagic interface (150 m)

Sarmiento & Gruber, 2006 (http://www.up.ethz.ch/people/ngruber/publications/textbook)

the biological pump in the oceansthe biological pump in the 1980’s

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Sarmiento & Gruber, 2006 (http://www.up.ethz.ch/people/ngruber/publications/textbook)

the biological pump in the oceansthe biological pump in the 1980’s

sediment traps: fluxes at the epi-mesopelagic interface (150 m)

Sarmiento & Gruber, 2006 (http://www.up.ethz.ch/people/ngruber/publications/textbook)

the biological pump in the oceansthe biological pump in the 1980’s

sediment traps: fluxes at the epi-mesopelagic interface (150 m)

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Honjo et al.., Prog. Oceanogr., 2008

the biological pump in the oceansthe biological pump in the 1980’s

sediment traps: fluxes at the meso-batipelagic interface (2 Km)

Honjo et al.., Prog. Oceanogr., 2008

the biological pump in the oceansthe biological pump in the 1980’s

sediment traps: fluxes at the meso-batipelagic interface (2 Km)

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Honjo et al.., Prog. Oceanogr., 2008

the biological pump in the oceansthe biological pump in the 1980’s

sediment traps: fluxes at the meso-batipelagic interface (2 Km)

Dunne et al.., Global Biogeochem. Cy., 2007

sediment traps: summary of organic carbon fluxes (Pg C/a)

Near-shore (<50m) Shelf (50-200m) Slope (200-2000m) Rise/Plain (>2000m)

0.71x1013 m2 31.07x1013 m22.24x1013 m20.95x1013 m2

3.61±0.45

2.47±0.54

1.14±0.41

0.04±0.47

1.10±0.39

0.09±0.060.53±0.38

0.48±0.32

2.87±0.26

2.01±0.37

0.86±0.31

0.34±0.22

0.52±0.20

0.05±0.030.29±0.10

0.19±0.13

4.06±0.51

3.56±0.57

1.00±0.36

0.64±0.19

0.36±0.18

0.036±0.0300.22±0.12

0.10±0.08

43.1±8.4

36.5±7.7

6.55±2.55

6.24±0.94

0.31±0.30

0.107±0.1200.19±0.19

0.012±0.020

the biological pump in the oceansthe biological pump in the 1980’s

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atmospheric inputs

1%

NO3-NO3-

NO3-NO3-

NH4+NH4+

NOP

PRPN

the biological pump in the oceansthe biological pump in the 1980’s

1%

NO3-NO3-

NO3-NO3-

NH4+NH4+

NOP

PRPN

NH4+NH4+NO3

-NO3-

NH4+NH4+ N2

N2

the biological pump in the oceansthe biological pump in the 1980’s

atmospheric inputs

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l-DOM: recycled in hours-days

1%

NO3-NO3-

NO3-NO3-

LNOD

NH4+NH4+

NOP

PRPN

NH4+NH4+NO3

-NO3-

NH4+NH4+ N2

N2

the biological pump in the oceansthe biological pump in the 1990’s

phytoplankton< 5 µm

0.1 - 2 µmbacteria

2 - 30 µmflagellates

8 - 100 µmciliates

DOM&

POM

met

azoa

phytoplankton> 5 µm

Sherr & Sherr, Limnol. Oceanogr., 1989

the biological pump in the oceansthe biological pump in the 1990’s

l-DOM: recycled in hours-days

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the biological pump in the oceansthe biological pump in the 1990’s

l-DOM: recycled in hours-days

Steinberg et al., Limnol. Oceanogr., 2008

Leboulanger et al., Deep-Sea Res., 1995

the biological pump in the oceansthe biological pump in the 1990’s

l-DOM: recycled in hours-days

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11

s-DOM: recycling in weeks-months

1%

NO3-NO3-

NO3-NO3-

LNOD

NH4+NH4+

NOP

PRPN

NH4+NH4+NO3

-NO3-

NH4+NH4+ N2

N2

the biological pump in the oceansthe biological pump in the 1990’s

1%

NO3-

NO3-

LNOD

NH4+

NOP

SNOD

SNOD

PRPN

NH4+NO3

-

NH4+ N2

N2

1%

NO3-

NO3-

LNOD

NH4+

NOP

SNOD

SNOD

PRPN

NH4+NO3

-

NH4+ N2

N2

1%

NO3-NO3-

NO3-NO3-

LNOD

NH4+NH4+

NOP

SNOD

SNOD

PRPN

NH4+NH4+NO3

-NO3-

NH4+NH4+ N2

N2

the biological pump in the oceansthe biological pump in the 1990’s

s-DOM: recycling in weeks-months

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12

Carlson et al., Nature, 1994

COD (µM-C)

50 60 70 80 90

pro

fun

did

ad

(m

)0

50

100

150

200

250

temperatura (°C)

18 20 22 24 26 28

primavera

verano

otoño

invierno

(adaptado de Carlson et al., 1994)

the biological pump in the oceansthe biological pump in the 1990’s

s-DOM: recycling in weeks-months

the biological pump in the oceansthe biological pump in the 1990’s

s-DOM: recycling in weeks-months

Lefevre et al., J. Mar. Sys., 1996

150 m

200 m

1000 m

respiración total13.8 g C m-2 a-1

1.4 g C m-2 a-1

4.0 g C m-2 a-1

M.O.P

M.O.D.

18.4 g C m-2 a-1

Trampas de sedimento ETS HTCO

primavera invierno

150 m

200 m

1000 m

respiración total13.8 g C m-2 a-1

1.4 g C m-2 a-1

4.0 g C m-2 a-1

M.O.P

M.O.D.

18.4 g C m-2 a-1

Trampas de sedimento ETS HTCO

primavera invierno

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13

the biological pump in the oceansthe biological pump in the 1990’s

s-DOM: recycling in weeks-months

Álvarez-Salgado et al., Limnol. Oceanogr., 2007

Álvarez-Salgado et al., Limnol. Oceanogr., 2007

plataformataludocéano abierto plataformataludocéano abierto

MOPsusp+MOD

MOPsink

afloramiento

the biological pump in the oceansthe biological pump in the 1990’s

s-DOM: recycling in weeks-months

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14

Álvarez-Salgado et al., Limnol. Oceanogr., 2007

the biological pump in the oceansthe biological pump in the 1990’s

s-DOM: recycling in weeks-months

r-DOM: recycling in years-millennia

1%

NO3-

NO3-

LNOD

NH4+

NOP

SNOD

SNOD

PRPN

NH4+NO3

-

NH4+ N2

N2

1%

NO3-

NO3-

LNOD

NH4+

NOP

SNOD

SNOD

PRPN

NH4+NO3

-

NH4+ N2

N2

1%

NO3-NO3-

NO3-NO3-

LNOD

NH4+NH4+

NOP

SNOD

SNOD

PRPN

NH4+NH4+NO3

-NO3-

NH4+NH4+ N2

N2

the biological pump in the oceansthe biological pump in the 1990’s

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15

1%

NO3-NO3-

NO3-NO3-

LDON

RDONNH4

+NH4+

PON

SDON

SDON

RPNP

NH4+NH4+NO3

-NO3-

NH4+NH4+ N2

N2

RDON

the biological pump in the oceansthe biological pump in the 1990’s

r-DOM: recycling in years-millennia

Kieber et al.L Limnol. Oceanogr. 1997

r-DOM: recycling in years-millennia: abiotic processes

the biological pump in the oceansthe biological pump in the 1990’s

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16

Nieto-Cid et al., Limnol. Oceanogr., 2006

R (µmol kg-1 d-1)

0 4 8 12 16

FMO

DM

(d

ark)

(ppm

QSU

d-1

)

-0.4

-0.2

0.0

0.2

0.4

0.6

0.8

FMODM = -0.05(±0.01)+0.027(±0.003) R

r = 0.73, p< 0.01

the biological pump in the oceansthe biological pump in the 1990’s

r-DOM: recycling in years-millennia: biotic processes

1%

NO3-NO3-

NO3-NO3-

LDON

RDONNH4

+NH4+

PON

SDON

SDON

RPNP

NH4+NH4+NO3

-NO3-

NH4+NH4+ N2

N2

RDON

the biological pump in the oceansthe biological pump in the 1990’s

r-DOM: recycling in years-millennia

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17

1%

NO3-NO3-

NO3-NO3-

LDON

RDONNH4

+NH4+

PON

SDON

RDON

SDON

RPNP

NH4+NH4+NO3

-NO3-

NH4+NH4+ N2

N2

RDON

the biological pump in the oceansthe biological pump in the 1990’s

r-DOM: recycling in years-millennia

Hansell et al., Oceanography, 2009

the biological pump in the oceansthe biological pump in the 1990’s

r-DOM: recycling in years-millennia

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18

Jiao et al., Nature Rev. Microb., 2010

the biological pump in the oceansthe biological pump in the 1990’s

r-DOM: recycling in years-millennia

CMOD CO2biótico

CO

bacterias

COS

COS

SO4H2 = 280315nm

CO2

CO2

abiótico

CO

RCR’

O

CO2

?

80%

Yamashita and Tanoue, Nature, 2008

r-DOM: photochemical decomposition in surface waters

1%UVB, 80m

1%PAR, 200m

the biological pump in the oceansthe biological pump in the 1990’s

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19

0 3 6 9 12 15

FMO

DM

(pp

b Q

SU)

0

3

6

9

0 3 6 9 12 15

FMO

DM

(pp

b Q

SU)

0

3

6

9

incubation time (days)

0 3 6 9 12 15

FMO

DM

(ppb

QSU

)

0

3

6

9

incubation time (days)

0 3 6 9 12 15

FMO

DM

(ppb

QSU

)

0

3

6

9

winter

autumnsummer

spring

Nieto-Cid et al., Limnol. Oceanogr., 2005

the biological pump in the oceansthe biological pump in the 1990’s

r-DOM: photochemical decomposition in surface waters

Nieto-Cid et al., Limnol. Oceanogr., 2006

FDOM CO2biotic

CO

bacteria

COS

COS

SO4H2 = 280315nm

CO2

CO2abiotic

CO

RCR’

O

RCR’

O

CO2

FDOM

bacteriabacteria

photochemistry

microbial degradation

COD (µM-C)

40 50 60 70 80 90

pro

fun

did

ad (

m)

0

50

100

150

200

250

COD (µM-C)

40 50 60 70 80 90

r-MOD

COD

r-COD

COD

(a) (b)

the biological pump in the oceansthe biological pump in the 1990’s

r-DOM: photochemical decomposition in surface waters

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20

DOM: summarizing

1%

NO3-NO3-

NO3-NO3-

NH4+NH4+

NOP

PRPN

the biological pump in the oceansthe biological pump in the 1990’s

1%

NO3-NO3-

NO3-NO3-

NH4+NH4+

NOP

PRPN

NH4+NH4+NO3

-NO3-

NH4+NH4+ N2

N2

the biological pump in the oceansthe biological pump in the 1990’s

DOM: summarizing

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21

1%

NO3-NO3-

NO3-NO3-

LNOD

NH4+NH4+

NOP

PRPN

NH4+NH4+NO3

-NO3-

NH4+NH4+ N2

N2

the biological pump in the oceansthe biological pump in the 1990’s

DOM: summarizing

1%

NO3-

NO3-

LNOD

NH4+

NOP

SNOD

SNOD

PRPN

NH4+NO3

-

NH4+ N2

N2

1%

NO3-

NO3-

LNOD

NH4+

NOP

SNOD

SNOD

PRPN

NH4+NO3

-

NH4+ N2

N2

1%

NO3-NO3-

NO3-NO3-

LNOD

NH4+NH4+

NOP

SNOD

SNOD

PRPN

NH4+NH4+NO3

-NO3-

NH4+NH4+ N2

N2

the biological pump in the oceansthe biological pump in the 1990’s

DOM: summarizing

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22

1%

NO3-NO3-

NO3-NO3-

LDON

RDONNH4

+NH4+

PON

SDON

SDON

RPNP

NH4+NH4+NO3

-NO3-

NH4+NH4+ N2

N2

RDON

the biological pump in the oceansthe biological pump in the 1990’s

DOM: summarizing

1%

NO3-NO3-

NO3-NO3-

LDON

RDONNH4

+NH4+

PON

SDON

RDON

SDON

RPNP

NH4+NH4+NO3

-NO3-

NH4+NH4+ N2

N2

RDON

the biological pump in the oceansthe biological pump in the 1990’s

DOM: summarizing

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23

open versus coastal ocean

Laurelle et al, Global Biogeochem. Cy., 2009

organic matter cycling in the oceansnitrogen

20-200m

4000m

0m

nitrogen(x 1012 g N/y)

275

N2 N2O

NO3-

NH4+

PN: 1530

1155101140

Norg

N2 N2O N2 NOX, NH3

30 33(22)

5 49NO3

-

NH4+

Norg

4 1 (0.5)

N2O

N2

N2O

335

NO3-

103

7

1137NO3

-

Wollast, 1993

75(21)

Norg

Galloway et al., Biogeochemistry, 2004

121129 193

PR: 7170

5

4

organic matter cycling in the oceansnitrogen

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24

nitrogen cycle in the coastal zone

precipitación

aguas continentales

océano

sedimentos

efluentes

organic matter cycling in the oceansnitrogen

►represent <10% of the area and <1% of the volume of the oceans

►support between 25% and 50% of the global new production

►receive 80% of the sedimentation of the oceans

►about 90% of the fish resoruces are extracted from the coastal zone

Gattuso et al., 1998

organic matter cycling in the oceansnitrogen

nitrogen cycle in the coastal zone

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25

Wollast, 1993

sedimentsFossil PON

335

325 175

150 125350

390PON 25

continentalwaters

openocean

precipitation denitrificationfixation

10 15 50

atmosphere

N2NO3

NO3-

NH4+

NOD50

190155

Galloway et al., Biogechemistry, 2004

PON NH4

50

Regenerated prod. 350

New prod. 700

10

PON

NO3-

organic matter cycling in the oceansnitrogen

nitrogen cycle in the coastal zone (in 1012 gN/y)

coastal and open ocean phosphorus cycle

Slomp & Van Cappellen, Biogeosciences., 2007

organic matter cycling in the oceansphosphorus

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26

Nelson et al., Global. Biogeochem. Cy, 1995

20-200m

4000m

Bsi production160

atmosphericdeposition

0.5

continentalwaters

Si(OH)4 = 7BSi = 1

hidrolisisof basaltos

0.4

Hydretermal vents0.2

oxidativedissolution

120

upwelling39.5

SiO2(x1012 mol Si/y)

Sedimentation 42

Non oxidativedissolution

22

deposition20

redissolution17

0m

Bsi production60-200

prod. Bsi48

oxidativedissolution

31 dep.13

redis.9

Bsi pres.4

coastalexport

4

Laruelle et al., Global. Biogeochem. Cy, 2009

silicon cycle in the open ocean and the coastal zone

3preservación

organic matter cycling in the oceanssilicon

Milliman et al., Deep. Sea Res., 1999

1000m

4000m

0m

CO32-

79

Hydrothermal vents

3

pelagicdissolution

38

12preservation

sedimentation

27

prod. CaCO365

CaCO3(x1012 mol C/y)

continentalwaters

14

Benthicdissolution

15

prod. CaCO330

coastalexport

14

21preservation

benthicdissolution

9

Wollast, 1994

CaCO3 cycle in the ocean and the coastal zone

organic matter cycling in the oceanscalcium carbonate

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1

V. Impact of global change on ocean biogeochemical cycles

X. Antón Álvarez Salgado

CSIC, Instituto de Investigacións Mariñas

C/ Eduardo Cabello 6, 36208 - Vigo

http://www.iim.csic.es

Impact of global change on ocean biogeochemical cycles (N, P, C and trace elements)Palma de Mallorca, 4– 8 Nov 2013

outline of this presentation

nitrogen

impact of global change on the ocean biogeochemical cycle of …

phosphorus

silicon

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2

global distribution of surface temperature

http://ingrid.ldgo.columbia.edu/SOURCES/LEVITUS94/

mankind: the king of N2 fixation in the bisophere

global change and nitrogen in the oceans

mankind: the king of N2 fixation in the bisophere

global distribution of nitrate

http://ingrid.ldgo.columbia.edu/SOURCES/LEVITUS94/

global change and nitrogen in the oceans

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3

global distribution of chlorophyll

http://marine.rutgers.edu/opp/

mankind: the king of N2 fixation in the bisophere

global change and nitrogen in the oceans

global distribution of primary production

http://marine.rutgers.edu/opp/

mankind: the king of N2 fixation in the bisophere

global change and nitrogen in the oceans

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4

heat content of the oceans (0-700m) 1955-2005

http://www.ipcc-wg2.org

mankind: the king of N2 fixation in the bisophere

global change and nitrogen in the oceans

http://www.ipcc-wg2.org

air temperature increase over the next decade

mankind: the king of N2 fixation in the bisophere

global change and nitrogen in the oceans

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5

Fritz Haber(1868 – 1934)

3 CH4 + 6 H2O 3 CO2 + 12 H24 N2 + 12 H2 8 NH3________________________________________________________

3 CH4 + 4N2 + 6 H2O 3 CO2 + 8 NH3

mankind: the king of N2 fixation in the bisophere

global change and nitrogen in the oceans

% cultivo cerelaes % pastizales

Pongratz et al., Global Biogeochem Cy, 2009

mankind: the king of N2 fixation in the bisophere

global change and nitrogen in the oceans

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6

Galloway et al., Biogeochemistry, 2004

balance global del nitrógeno en 1860 (en Tg N a-1)

141

N2

N2

NOY NHX NHX

N2O

continentes costas océanos

tormentas

c. fósiles

C-FBN

N-FBN

Haber Bosch

5.4

0.3

15

0

120

7.46.6

8.96.0 4.8

6.2

2.3

1.4

27

8 0.8

8 0.4 3.5

98 172 129

121

7.1 5.6

sed. sed.

mankind: the king of N2 fixation in the bisophere

global change and nitrogen in the oceans

Galloway et al., Biogeochemistry, 2004

balance global del nitrógeno en 1990 (en Tg N a-1)

8.96.6

8 0.4

98 172

8

27

7.11.44.86.07.424.8

4834.1

16.1 4.6

2.3

6.2

120

0

15

0.324.5

31.5

100

107

21

12.4

258.4

48

15

0.811

115 193

141268

N2

N2

NOY NHX NHX

N2O

continentes costas océanos

tormentas

c. fósiles

C-FBN

N-FBN

Haber Bosch

5.4

0.8

3.5

129

121

5.6

sed. sed.

mankind: the king of N2 fixation in the bisophere

global change and nitrogen in the oceans

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7

Galloway et al., Biogeochemistry, 2004

balance global del nitrógeno en 2050 (en Tg N a-1)

7.11.4 258.417.1 46.76.68.9

4.86.07.424.8

4834.1

16.1 4.642.2109

79.423.9 3.6

NHX

8 0.4

98 172

8

27

2.3

6.2

120

0

15

0.324.5

31.5

100

107

21

12.4

48

15

0.811

115 193

141268

NHX

tormentas

c. fósiles

C-FBN

N-FBN

Haber Bosch

5.4

0.8

3.5

129

121

5.6

sed. sed.

52.5

50

165

98

36.3

27.5

63.2

21

1.613.2

160 210

371

continentes costas océanos

N2O

N2

NOY

N2

mankind: the king of N2 fixation in the bisophere

global change and nitrogen in the oceans

deposition of combined nitrogen in the open ocean

Duce et al, Science, 2008

deposition of NHx + NOy + Norg (in Tg N a-1)

Depo.: 20 Tg N y-1 ( 30%)

Prod.: 34 Tg N y-1 ( 30%)

Depo.: 67 Tg N y-1 ( 80%)

Prod.: 116 Tg N y-1 ( 78%)

Depo.: 77 Tg N y-1 ( 80%)

Prod.: 132 Tg N y-1 ( 86%)

global change and nitrogen in the oceans

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8

consequences of the anthropogenic fertilization of the oceans

Duce et al, Science, 2008

impact on primary production

global change and nitrogen in the oceans

Duce et al, Science, 2008

impact on nitrification

global change and nitrogen in the oceansconsequences of the anthropogenic fertilization of the oceans

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9

impact on nitrification

global change and nitrogen in the oceansconsequences of the anthropogenic fertilization of the oceans

Davidson, Nature Geosciences, 2009

global change and nitrogen in the oceansconsequences of the anthropogenic fertilization of the oceans

Canfiled et al, Science, 2010

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10

Liu, 2006

afloramientotectónico

atmósfera

océanos

sedimentos

aguascontinentales

naturaleza

rocas de fosfato

suelo

erosión

erosión exportación

deposiciónaerosoles

sedimentaciónmeteorización

mineríaalimentación

mineralesde fosfato

fosfato

humanos

ganadería

residuos

antroposfera

fertilizantes

recirculación

alimentaciónaditivos

alimen.deterg.

recicladoreciclado

cosechas

procesado

agricultura

granjas

erosióndeposición

global change and phosphorus in the oceansconsequences of the anthropogenic fertilization of the oceans

humankind is …

► extracting huge amounts of phosphate from the phosphorite reserves toproduce fertilizers

► reducing the phosphate reserves in tropical forests due to deforestation

► adding phosphate to continental and marine aquatic ecosystems

Liu, 2006

global change and phosphorus in the oceansconsequences of the anthropogenic fertilization of the oceans

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global change and phosphorus in the oceansconsequences of the anthropogenic fertilization of the oceans

Harrison et al, Global Biogeochem Cy, 2010

global change and phosphorus in the oceansconsequences of the anthropogenic fertilization of the oceans

Harrison et al, Global Biogeochem Cy, 2010

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global change and phosphorus in the oceansconsequences of the anthropogenic fertilization of the oceans

Harrison et al, Global Biogeochem Cy, 2010

global change and phosphorus in the oceansconsequences of the anthropogenic fertilization of the oceans

Mahowald et al, Global Biogeochem Cy,2008

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Smil, 2002

global change and phosphorus in the oceansconsequences of the anthropogenic fertilization of the oceans

Filippelli, 2008

end of P reserves(1860 Tg)

global change and phosphorus in the oceansconsequences of the anthropogenic fertilization of the oceans

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the decline of diatoms

► building dams → reduction of silicon discharge

► transforming virgin into cultured lands → increase of nitrogen discharge

► warming the Earth → increase of stratification → dinoflagelates dominance

Humankind is …

global change and silicon in the oceans

the decline of diatoms

global change and silicon in the oceans

Beunser et al., Global Biogeochemical Cycles, 2009

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the decline of diatoms

global change and silicon in the oceans

http://www.maweb.org.

Intercepted runoff is 3 to 6 times natural runoff

the decline of diatoms

global change and silicon in the oceans

Beunser et al., Global Biogeochemical Cycles, 2009

River dams retain 20% of the continental dSi that should arrive to the oceans

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the decline of diatoms

global change and silicon in the oceans

Bernard et al., Biogeosciences, 2010

River dams retain 20% of the continental dSi that should arrive to the oceans

impact on diatoms biomass in coastal areas

Edwards et al., L&O, 2006

the decline of diatoms

global change and silicon in the oceans

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renewal time (d)

0 10 20 30 40 50

max

imum

nº o

f day

s cl

osed

0

50

100

150

200

250

300

y = 365*[1-exp(- x/37(±2))]

R2 = 0.79, n = 42, p < 0.001

Álvarez-Salgado et al., Harmful Algae, 2008

the decline of diatoms

global change and silicon in the oceans

Arousa inner

Muros - Noia

Pontevedra

Vigo outerVigo inner

Arousa outer

impact on diatoms biomass in coastal areas

Álvarez-Salgado et al., Harmful Algae, 2011

Qr May (m3 s-1)

0 10 20 30 40 50 60

% d

ays

clos

ed in

sum

mer

0

20

40

60

80

100

EkL August (m2 s-1)

-0.6 -0.4 -0.2 0.0 0.2 0.4 0.6 0.8 1.0

% d

ays

clos

ed in

aut

umn

0

20

40

60

80

100

03

0704

05

01 00

99

00

99

01

02

03

0706

05

02

a) b)

04

06

80%

the decline of diatoms

global change and silicon in the oceans

impact on diatoms biomass in coastal areas