[PPT] - Atmospheric Nitrogen deposition Tibisay Prez tperez@ivic.gob.ve PowerPoint Presentation

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Atmospheric Nitrogen deposition

Instituto Venezolano de Investigaciones Científicas

Tibisay Pérez tperez@ivic.gob.ve /tibisay.j.perez@gmail.com August 6th, 2016.

School of Advanced Science on nitrogen cycling, environmental sustainability and climate change. 31 July – 10 August 2016, São Pedro, SP – Brazil.

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NO

Lightning

Terrestrial and oceanic surface

Troposphere

Emissions

NH3

OH

Emissionss

NO2

CH4, CO, RO2, HO2 OH, O3

Fotolysis (hυ)

NOX (NO +NO2)

Δ, hυ Δ, hυ

NO3 radical

O3

NO3

H2O

HNO3 N2O5

H2O (l)

surface

NO2 + M Wet and dry deposition

Dry deposition (gases and aerosols)

Wet deposition

Dry deposition (gas and aerosols)

Wet deposition

Wet and dry deposition

NH4

+

H2O

NH4Cl (s) (NH4)2SO4 (s) NH4NO3 (s,l)

N2

N fixation

2 TWSN = WSIN + WSON

(Slide borrowed from Rafael Rasse ‘s PhD thesis defense, Atkinson, 2000; Finlayson-Pitts and Pitts, 2000; Atkinson and Arey, 2003; Seinfeld and Pandis, 2006)

Urea, aminoacids

Stratosphere

N2O

Emsssions

Organic Nitrates

COVs ,radical NO3, O3 (night) COVs,OH, hυ, O3 (day) hυ, Photolysis and photooxidation

NO O3 O2

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Portmann, R. W. et al., (2012) Stratospheric ozone depletion due to nitrous oxide: influences of other gases.

Phil. Trans. R. Soc. B (2012) 367, 1256–1264. doi:10.1098/rstb.2011.0377.

Why N2O is so relevant after Montreal Protocol?

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Natural ecosystems emitted N2O that is enriched in 15N compared to fertilized soils

δ 15N-N2O (‰) vs AIR

60
50
40
30
20
10

10 20 30 40 10 20 30 40 50 60 70

Natural soils Agricultural soils Ocean average Troposphere averg. Stratosphere averg. Stratosphere values

Source: Perez et al., 2000, 2001; Rahn and Wahlen, 2000. Toyoda et al 2001, 2002 and 2011, Yamulki et al., 2001, Bol et al 2003, Park et al., 2004, , 2011, 2012 and references therein)

δ 18O-N2O (‰) vs VSMOW

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Decrease in δ15N

f 0.3 ‰/decade

Fertilizer use

Tropospheric N2O isotope trend inferred from archived air samples from Cape Grim

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18.8.2016 6

Hot spots of N2O found in permafrost peatlands

Peat Circles Diameter 4 to 25 m Areas 10 to 500 m2 Cover ≈ 4% the peat plateau Peat plateau covers ≈ 20% of Arctic and the total land area of the tundra zone (7.34×10 6 km 2)

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18.8.2016 7

(62⁰57'E, 67⁰03'N) Annual precip. ≈ 505 mm Mean annual temp. ≈ -5.8 °C Growing season: Mid Jun-August Discontinuous permafrost Subarctic East European tundra

Would the enhanced emissions from tundra pit circles shift tropospheric N2O isotopic composition?

Study Site

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J. Gil1, T. Perez, K. Boering, P.J. Martikainen, C.

Biasi Academy of Finland, project CryoN 2010-2014 European Union 7th Framework Program under project(DEFROST)-Nordic Centre of Excellence Program

Graduate student Jenie Gil Research Project DEFROST

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We wanted to know also which microbial/chemical processes contribute to the pit circleN2O production

N2O and CO2 Fluxes δ15N2O; δ18O; 15N-SP [NH4] ; [NO3] and δ15N Soil environmental parameters Weather measurements Bare peat soil profile Bare peat soil surface (Static chamber) [N2O]; [CO2] δ15N2O; δ18O; 15N-SP [NH4] ; [NO3] and δ15N Soil T; [O2]; soil moisture 3 soil profile (PC1;PC2;PC3) 3 bare surface (PC1;PC2; PC3; 5 frames)

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Bare peats surface in sub-arctic tundra emit substantial amounts of N2O

2007 (1.9 – 31 mg N2O. m-2. d-1) 2008 (3.7 – 13.9 mg N2O. m-2. d-1) 0.1 to 3.4 mg N2O m-2 d-1

DOY

190 200 210 220 230 240

0,8

0,0 0,8 1,6 2,4 3,2

(mg N2O. m-2.d-1)

Tropical forests (0.09 – 2.5 mg N2O m-2 . d-1) Drained boreal peatlands/agriculture (0.1 – 15.1 mg N2O. m-2 . d-1)

PC1 PC2 PC3

Mean =1.2 ± 0.8

Gil J., et al, Global Biogeochemical Cycles under final revisions

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δ15Nbulk ( -17‰ to -8‰)

DOY

190 200 210 220 230 240

20
15
10
5

5 10

13.0 ± 2.0‰

δ 15N-N2O (‰) vs AIR δ18O (-6‰ to 30‰)

DOY

190 200 210 220 230 240

10

10 20 30 40 50

12 ± 3‰

δ 18O-N2O (‰) vs VSMOW

The first data for δ15Nbulk of N2O emitted from Arctic tundra so far…

(A) (B) 5.66 ± 0.01‰ 44.2 ± 0.4‰

PC1 PC2 PC3 Gil J., et al, Global Biogeochemical Cycles under final revisions

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12

Natural ecosystems emitted N2O that is enriched in 15N compared to fertilized soils

δ 15N-N2O (‰) vs AIR

60
50
40
30
20
10

10 20 30 40 10 20 30 40 50 60 70

Tundra Pit Circles Natural soils Agricultural soils Ocean average Troposphere averg. Stratosphere averg. Stratosphere values

Source: Perez et al., 2000, 2001; Rahn and Wahlen, 2000. Toyoda et al 2001, 2002 and 2011, Yamulki et al., 2001, Bol et al 2003, Park et al., 2004, , 2011, 2012 and references therein)

δ 18O-N2O (‰) vs VSMOW

Gil J., et al, Global Biogeochemical Cycles under final revisions

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Decrease in δ15N

f 0.3 ‰/decade

Fertilizer use

N2O isotope trend might slow down due to global warming of artic tundra

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Ecosystem relevant nitrogen species 14 Inorganic

Reactive nitrogen (Nr-trace levels)

Organic NH3 NH4

+

NOx(NO+NO2) HNO3 N2O Radical NO3 Urea Aminoacids Proteins Nucleic acids Organic nitrates Plant derived part

(Neff et al., 2002. Biogeochemistry 57/58; Galloway et al., Biogeochemistry.2004. 70)

WSIN (NH4

++NO3

+NO2
):

Water soluble inorganic nitrogen WSON: Water soluble organic nitrogen TOTAL DISSOLVED NITROGEN (TDN)=WSIN + WSON

Reactive Nitrogen (Nr) in the troposphere

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Nr

CO2 GPP Net sink of CO2 NEGATIVE RADIATIVE FORCING

FLUXNET temperate evergreen needleleaf forest sites. NPP ↑ with ↑ nitrogen deposition (up to 8Kg N/ha yr). Tropical forest (not N limited) sites need more information particularly systematic Nr atmospheric deposition network More comprehensive measurements of nitrogen stocks and cycling at the global network of carbon monitoring sites are required

Why Nr matters on an global perspective

Fleischer et al., 2013, GBC 27 (1), 187–199.

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Neff, J. et al (2002). The origin, composition and rates of organic nitrogen deposition: A missing piece of the nitrogen cycle? Biogeochemistry 57/58: 99–136, 2002

All the Nr species have been considered?

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Relative contribution of WSON to Nr in wet deposition

(32 ± 11)% (32 ± 11)%

WSON WSIN

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Global reactive nitrogen (Nr) change through time

50 100 150 200 250 1 2 3 Tg-N/año Emisiones a la atmósfera Deposición atmosférica

1860 1990 2050

Nr emissions

WSON is not included

(Galloway et al., 2004. Biogeochemitsry. 70)

Nr atmospheric deposition Tg-N/yr

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19

Bioavailability of DON DON bioavailability

f DON (%)

Time of uptake References Estuarines 40-72 10-15 days Seitzinger and Sanders 1999 Aquatic Systems 12-72 Days –weeks Bronk 2002 Marine ecosystem 20-30

Violaki et al., 2009

Marine ecosystem 46-80

Wedyan et al., 2007

Marine ecosystem 20-30 hours –few days Peierls and Paerl, 1997

Plants Ocean Soils Soil microbial decomposition

f bioavailable organic

nitrogen

Bioavailability of WSON

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Kanakidou, M., S. et al 2016: Past, Present and Future Atmospheric Nitrogen Deposition. J. Atmos. Sci. doi:10.1175/JAS-D-15-0278.1, in press.

Atmospheric chemistry- transport model (TM4- ECPL)

Organic nitrogen 60%

anthropogenic.

Total N deposition

estimate increases by about 20% relative to simulations without ON.

About 20-25% of total

deposited N is ON.

About 10% of the emitted

nitrogen oxides are deposited as ON instead of inorganic nitrogen(IN) as is considered in most global models.

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Kanakidou, M., S. et al 2016: Past, Present and Future Atmospheric Nitrogen Deposition. J. Atmos. Sci. doi:10.1175/JAS-D-15-0278.1, in press.

Almost a 3-fold increase
ver land (2-fold over the
cean) of TN from 1850

to present.

Significant changes in

the regional distribution

f N deposition and

chemical composition, with reduced compounds gaining importance relative to oxidized ones, but very small changes in the global total flux.

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Luo, M. et al., 2015. Satellite observations of tropospheric ammonia and carbon monoxide: Global distributions, regional correlations and comparisons to model simulations. Atmospheric Environment 106 (2015) 262-277.

Satelite information a valuable tool for global Nr estimates

NH3 DJF MAM JJA SON

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Luo, M. et al., 2015. Satellite observations of tropospheric ammonia and carbon monoxide: Global distributions, regional correlations and comparisons to model simulations. Atmospheric Environment 106 (2015) 262-277.

Satelite information a valuable tool for global Nr estimates

CO DJF MAM JJA SON

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Luo, M. et al., 2015. Satellite observations of tropospheric ammonia and carbon monoxide: Global distributions, regional correlations and comparisons to model simulations. Atmospheric Environment 106 (2015) 262-277.

NH3/CO

Partitioning NH3 sources

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P=Power plant T=Transport I=Industry D=Domestic F=Fertilizer use L=Livestock H=Human waste N=Natural emissions

Zhao, Y. et al., 2015.Atmospheric nitrogen deposition to the northwestern Pacific: seasonal variation and source attribution. Atmos. Chem. Phys., 15, 10905–10924.

Partitioning Nr sources

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Vet, R. et al (2014). A global assessment of precipitation chemistry and deposition of sulfur, nitrogen, sea salt, base cations, organic acids, acidity and pH, and

phosphorus. Atmospheric Environment 93. 3-100.

Ground based Nr monitoring

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Vet, R. et al (2014). A global assessment

f precipitation chemistry and

deposition of sulfur, nitrogen, sea salt, base cations, organic acids, acidity and pH, and phosphorus. Atmospheric Environment 93. 3-100.

Kanakidou, M., S. et al 2016: Past, Present and Future Atmospheric Nitrogen Deposition. J. Atmos. Sci. doi:10.1175/JAS-D-15-0278.1, in press.

Comparison between estimates

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Kanakidou, M., S. et al 2016: Past, Present and Future Atmospheric Nitrogen Deposition. J. Atmos. Sci. doi:10.1175/JAS-D-15-0278.1, in press.

Inclusion of WSON in new estimates!

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How to assess N deposition in Latin Ameria and the Caribbean?

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Coordinator: Jean Pierre Ometto INPE. (jean.ometto@inpe.br)

Nitrogen Cycling in Latin America: Drivers, Impacts and Vulnerabilities (Nnet)

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N atmospheric deposition and BNFcomponents

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Nreduced becoming important

Vet, R. et al (2014). A global assessment of precipitation chemistry and deposition of sulfur, nitrogen, sea salt, base cations, organic acids, acidity and pH, and

phosphorus. Atmospheric Environment 93. 3-100.

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N atmospheric deposition from Venezuela

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WSON concentrations in total suspended particles (TSP) and wet deposition

Concentration (µg-N m3 aire) WSON/TN (%) Venezuela 0,07-1,3 35-72% Other studies 0,01-2,1 10-64% Concentration (µg-N/L) WSON/TN (%) Venezuela 0,34-0,96 51-92%* Other studies 0,04-0,31 5-84%

* Maracaibo excluded

Wet deposition Total Suspended Particles

Venezuela → ↑ [NOS] %

[NOS] ↑ Canaima National Park (30.000 km²)

Morales et al., .2001. Water, Air, and Soil Pollution 128, 207-221; Pacheco et al., 2004. Tellus 56B; Canelón et al., 2007 Eos Trans. AGU, 88(52).

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34

R2 = 0.69, n=24

3
2
1

1

1

1 2 3

Ln(nss-SO4

2)

Ln(WSON)

R2 = 0.73, n=25

3
2
1

1 0,2 0,4 0,6 0,8 1 1,2

WSIN Ln(WSON)

SOA derived:

Remote continental sites: biomass burning
Remote coastal and oceanic sites: Long range transport and tropospheric
xidation of VOCs including DMS

p<0..0 1 p<0..0 1

Canelón et al., 2007 Eos Trans. AGU, 88(52).

WSON and WSIN from TSP in remote continental and oceanic sites

N atmospheric deposition from Venezuela

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N atmospheric deposition from Venezuela

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Mar Caribe Noreste del Océano Atlántico

Fosa de Cariaco Isla de Margarita

Faro de Punta Ballena

El Piache

Isla de Margarita

Margarita Island

Venezuelan Navy Hidrography Division (DHN)

Pampatar-Margarita

Rainy season and dry season collection

Cariaco oceanic time series: http://imars.marine.usf.edu/CAR/

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36

0.4 0.8 1.2 1.6 2

(µg-N/m3 aire)

WSIN WSON

Nr in TSP

36

Bermuda Irlanda Tenerife Barbados Isla de Aves Margarita Catia la mar Atlántico Norte Margarita Costa Irlanda Isla de Aves Osma Miami Barbados Atlántico Este Mar de China Mediterraneo (Grecia) Mediterráneo (Turquía) Pacifico Isla Tasmania Hawái

Oceánicas-Costeras Lugar de Muestreo Costera-Influencia continental 2 1,6 1,2 0,8 0,4

Concentration (µg-N/m3 air)

Canelón 2007; Chen and Chen 2010; Lesworth et al. 2010; Mace et al. 2003a; Mace et al. 2003b; Miyazaki et al. 2011; Nakamura et al. 2006; Spokes et al. 2000; Violaki and Mihalopoulos 2008; Violaki et al. 2010; Zamora et al. 2011

Ocean Margarita Island Coastal urban-influenced

N atmospheric deposition from Venezuela

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1 2 3 4 0.1 0.3 0.5

Rainy season Dry season 0,5 0,3 0,1 WSIN WSON WSIN WSON

Concentration (µg-N/m3 aie) [WSIN] and [WSON] rainy season> dry season (ρ<0,01;N=28)

WSON/WSIN ratio ~ 1:1 possible similar sources

TSP WSIN and WSON seasonal variability

N atmospheric deposition from Venezuela

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Mean concentration values

WSIN and WSON in TSP

0.2 0.4 0.6

NOS-(µg-N/m3 aire)

0.2 0.4 0.6

NIS-(µg-N/m3 aire)

0,6

PTS-E. Lluvia SIC-E. Lluvia PTS-E.Seca SIC-E. Seac

Y=1,01X + 0,001 R2=0,94 N=26

WSIN (µg-N/m3 air) 0,5 0,4 0,3 0,2 0,1 0,2 0,4 0,6 WSON (µg-N/m3 air) 0,1

Rainy season Dry season

[WSIN] and [WSON] rainy season> dry season (ρ<0,01;N=28)

N atmospheric deposition from Venezuela

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Back trajectories and meteorological data

Rainy season

39

Continental air masses

Dry season

N atmospheric deposition from Venezuela

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Concentration of Non Sea Salt Sulfate 40

[WSIN] Vs [NSS-SO4

2-] (R2=0,423; ρ<0,05;N=28)

[WSON] Vs [NSS-SO4

2-] (R2=0,480; ρ <0,05;N=28)

1 2 0.0 1.0 2.0 3.0

NSS-SO4

2-

NSS-SO4

2-

3,0 2,0 1,0 0,0

Concentration (µg/m3 air)

Rainy season Dry season Back trajectories, meteorological data, [CO] and [ NSS-SO4

2]

Fossil fuel combustion and/or Biomass Burning during rainy season [NSS-SO4

2-] Rainy season > dry season

(ρ<0,01;N=28)

N atmospheric deposition from Venezuela

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1 2 3 4 5 6 0.00 0.10 0.20

>7.20 3.0-7,20 1,50-3.0 0,95-1,50 0,49-0,95 <0,49 Concentración NOS (µg-N/m3)

41

WSON (g-N/m3) 0,2 0,1 Fine (<1,5 µm ) Coarse (>1,5 µm ) (29±12)% (71-±12)%

1 2 3 4 5 6 0.00 0.10 0.20

Fine (<1,5 µm ) Coarse (>1,5 µm )

mass median aerodynamic diameter (µm)

WSIN (µg-N/m3) 0,1 (28±10)% (72±10)% 0,2

N atmospheric deposition from Venezuela

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Nitrogen species nss-SO4

2-

nss-K+ nss-Ca2+ WSON Fine fraction WSIN 0.892** 0.326 0.656** 0.898** WSON 0.836** 0.330 0.659**

Coarse fraction

WSIN

0.203

0.054 0.325 0.898** WSON

0.086

0.092 0.346

**Correlation is significant at the 0.01 level

0.4 0.8 1.2 1.6 2 NOS (µg-N/m3) 0.05 0.1 0.15 0.2 0.25 NSS-SO4

2- (µg/m3)

Época de lluvia Época Seca

0,090X + 0,002 R2=0,83 N=13

0.4 0.8 1.2 1.6 2 NIS (µg-N/m3) 0.04 0.08 0.12 0.16 0.2 NSS-SO4

2- (µg/m3)

Época de lluvia Época Seca 0,078X + 0,004 R2=0,81 N=14

0.20 0.16 0.12 0.08 0.04 0.4 0.8 1.2 1.6 2 WSIN (µg-N/m3) WSON (µg-N/m3) 0.4 0.8 1.2 1.6 2 0.25 0.20 0.15 0.10 0.05

NSS-SO4

2- (µg/m3)

NSS-SO4

2- (µg/m3)

Rainy season Dry season Rainy season Dry season

Y=0,078X + 0,004 R2=0,892 N=14 Y=0,090X + 0,002 R2=0,836 N=13

Identifying sources of WSIN and WSON

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43

Rainy season Dry season

AVOC NOx, SOx, CO, BC Ca+2 BVOC DMS WSON WSIN SO4

2

OH NO3 Sea salt BC NO2 Ca+2 BVOC DMS WSON WSIN SO4

2

OH Sea salt

Chen and Chen, 2010; Rollins et al., 2012; Osthoff et al., 2009; Stark et al., 2007.

Identifying sources of WSIN and WSON

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0.2 0.4 0.6 0.8 1

NOS (µM-N)

Wet deposition: WSON WSON ~ 50% Nr

Mar del Norte Océano Atlántico Océano Pacifico Antártida Sur América Caribe y Centro América Norte América Australia-Nueva Zelanda Europa Caracas (urbana) Valencia (urbana) Altos de Pipe (suburbana) Calabozo (rural) Parupa (remota) Maracaibo (urbana) Barranquitas (rural) Santa Bárbara (rural) La Ceiba (rural) Canal VOC (rural) Margarita (E. seca) Margarita (E. lluvia)

1,0 0,8 0,6 0,4 0,2 WSON (mg-N/L) 100 80 60 40 20 Otros estudios Lugar de estudio

[WSIN] Vs [Vpreci] (R2=-0,587; ρ<0,05;N=12) [WSON] Vs [Vpreci] (R2=-0,440; ρ <0,05;N=12)

Other studies Margarita Island

Partition of WSIN and WSON

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Especies solubles de nitrógeno 1000 2000 3000 500 1500 2500 Deposición húmeda (t-N/tiempo*) NOS NIS NST

Anual E.Lluvia E.Seca

WSIN: (48±5) % WSON: (53±4) % No seasonal variation

3000 2500 2000 1500 1000 500

N wet deposition (t-N/yr) Nitrogen species

Dry Season Wet season Annual

WSON WSIN Nr

NDw: 2,4x103 t-N/año

N annual wet deposition (NDw)

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N dry deposition (NDd) NDd =(Σ Vni x[NS]ni) x Cariaco basin area

Total N atmospheric deposition (NDt) = NDw + NDd

Vni: constant deposition velocity (cm/s) [NS]ni: N concentration (µg-N/m3)

Cariaco trench basin area: 12600 Km2

N annual dry deposition (NDd)

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47 N wet deposjtion= (68 ± 6)% N dry deposition= (31 ± 14)%

Total N atmospheric deposition in the Cariaco Basin

Atmospheric N deposition T-N/year %WSIN %WSON

Dry deposition

1,2x103 47±22 53±24

Wet deposition

2,4x103 48±5 53±4

Total deposition

3,6x103 48±23 53±24

N annual dry deposition (NDd)

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48

Cariaco basin total N deposition (2.85 Kg N ha-1 yr-1)

Vet, R. et al (2014). A global assessment of precipitation chemistry and deposition of sulfur, nitrogen, sea salt, base cations, organic acids, acidity and pH, and

phosphorus. Atmospheric Environment 93. 3-100.