Trace gasesTrace gasesOct 28:Oct 28:
Long lived species (CH4, N2O, CFCs, and CO2)
Material can be partly found in :Material can be partly found in : Emissions and concentrations chap 4Radiative effects (chap 3 and 7)
Johan Mellqvist , Earth and Space tel 4855, mail [email protected]
MethaneMethane
Methane from GAW network
Methane emissions by microbiological activity
Methanogens produce CH4 using 4-5 organic species (CO2+H2, Acetate, methanol etc) which can work as electro acceptors under anaeroboc conditions, 20 40oC ( t 25 oC ) d H 6 8 Th b t i hi hl d th i20-40oC (opt 25 oC ) and pH 6-8. The bacteria are highly dep on other microorganisms to produce the right species. Methanotrops oxidizes CH4 to CO2 under aerobic conditions using several enzymes (methane monooxygenase) and the cofactor NADH (nicotinamide adeninedinucleoide) and PQQ (pyrro-quiniline quinone) used as electron carriers. The) QQ (py q q )bacteria also convert NH3 to N2O. The reactions have little temp dependence but prefer fairly neutral pH 6-8.
CH4 emission (WMO 95) (Total emissions 515 Mton/year
Rice paddies
Biomassburning8%
Landfills6%Ruminants
16%
Rice paddies12% Sewage treatment
5%
Animal waste5%
Energy related21% Termites
Other14%
Wetlands23%
21% Termites4%
CH4 sinks (WMO 95)
S ilStratosphere8%
Soil6%
CH4+OH-> CH3+H2O
86%
CH4 Sources Mt/year• CH4 Sources Mt/year• Natural Wetlands 115• Rice Paddies 110Rice Paddies 110• Enteric Fermentation 80• Biomass burning 55 But recent findings by Keppler
h th t bi i i• Gas Drilling 45• Termites 40• Landfills 40
shows that aerobic emissions from forest may correspond to 30% of toal emissions ?• Landfills 40
• Coal Mining 35• Oceans/Lakes 15
30% of toal emissions ?
Read in Nature: Oceans/Lakes 15
• Methane Hydrate ?• TOTAL 535
Keppler 2006, Bousquet 2006 ,Lelieveld 2006 and F k bFrankenberg
JS1
Slide 10
JS1 Very inhomogeneous emissions require a technique that integrates over the landfill surface.
Conditions vary between landfill to landfill, and historically not well known the amounts and types of waste , why uncertainties in landfill emissions have been and are large so far, also for models ...
The figure shows the Helsingborg landfill - the largest in Sweden. A typical landfill with some finalized soil covered areas and some areas stillopen for landfilling. Yellow pipes are gas utilization pipes.Jerker Samuelsson, 2007-09-04
On site leak search with mobile FTIR at Helsingborg landfill
Active biocell
JM2
Slide 11
JM2 Läcksökning på befintliga vägar och övriga körbara delar. Visar på var ev åtgärder ska sättas in, var spårgasen bör placeras osv. Upprepade undersökningar kan användas för att följa upp om det ser bättre ut på olika delar efterhand som åtgärder satts in.
Söder om själva tippen finns en stor kompostplan där ett litet område ger lite metan, men försvinnande liten volym jmf med deponins bidrag.
Emissioner från slänten ses, biocell innehåller gasdränering, ej lera på toppen, men jord
De gamla delarna sluttäcks med lera (Bentonit)+ 1 m jordlager Rör under finnes. Johan Mellqvist, 2007-09-04
Polarstern
Photo: C. Weinzierl
FTS: Oct/Nov 1994, Oct/Nov 1996, Dec 99/Jan 00, Jun/Jul 00,
Surface flasks: Oct/Nov 2005Dec 99/Jan 00, Jun/Jul 00, Oct/Nov 2002, Jan/Feb 2003, Oct/Nov 2003, Oct/Nov 2005
Comparison model and FTSModel by P. Bergamaschi, European Commission Joint Research Centre, Ispra, ItalyJan/Feb 20031820
1840pb
v)
1760
1780
1800
rage
d C
H4 (
pp
1720
1740
1760
colu
mn
aver
FTS
TM5
Oct/Nov 20031820
pbv)
1700-40 -30 -20 -10 0 10 20 30 40 50
Oct/Nov 2003
1760
1780
1800
aged
CH
4 (pp
1720
1740
1760
colu
mn
aver
a
FTS
TM5
latitude
1700-40 -30 -20 -10 0 10 20 30 40 50
Warneke et al, GRL 2006
TM3 ModellTM3 Modell
Difference toDifference to SCIA
(SCIA TM3)(SCIA-TM3)Plants?
IASI instrument
Nadir looking FTS12 km pixel x 4 @ nadir + scanning = ~ 48.3°
Spectral coverage = 645-2760 cm-1
Spectral resolution = 0.5 cm-1
Radiometric noise ~ 0.25-0.5 K
5 CO2
• Study of important species for climate or tropospheric chemistry 1.0x10-5
1.2x10-5
1.4x10-5
O3
HNO3CFC11, CFC12
CO
2 sr m
-1)
2
chemistry
• 2 spectral regions possible for methane retrievals 6.0x10-6
8.0x10-6
1.0x10
N2O, CH4
CO2, N2Onc
e (W
/ m
2
2.0x10-6
4.0x10-6
CH4
HDOH2
16O
H218O
H216O, HDO
Rad
ian
800 1000 1200 1400 1600 1800 2000 2200 2400 26000.0
Wavenumber (cm-1)
CH4 trends from solar FTIRCH4 trends from solar FTIR3.6
x 1019
-2)
Harestua
measuredfitted model
3 4
3.5
mn
(mol
ecul
es*c
m- fitted model
trendtrend + season
1996 1998 2000 2002 2004 2006 2008 2010
3.3
3.4
Tota
l Col
um
1996 1998 2000 2002 2004 2006 2008 2010
Year
x 1019 Jungfraujoch
-2)
2 3
2.35
2.4
mn
(mol
ecul
es*c
m-
1996 1998 2000 2002 2004 2006 2008 2010
2.25
2.3
Tota
l Col
um
1996 1998 2000 2002 2004 2006 2008 2010Year
Species Time period Jungfraujoch
(47,8,3600)Zugspitze
(47 11 300)
Harestua
(60 11 600)
Kiruna
(68 20 400)(47,11,300) (60,11,600) (68,20,400)
CH4 1996-1999 Molecules* 90.0±9.22 102±22.8 208±35.3 178±32.74
cm-2*1015
%*yr-1 0.38±0.04 0.4±0.09 0.61±0.10 0.51±0.09
1999-2007 Molecules*
cm-2*1015
15.7±19.7 17.3±46.8 73.9±75.4 38.8±69.9
%* yr-1 0.07±0.08 0.07±0.18 0.22±0.22 0.11±0.20
2007-2009 Molecules*
-2*1015
211±17.9 169±31.8 197±75.4 435±72.9
cm-2*1015
%*yr-1 0.90±0.08 0.66±0.13 0.57±0.22 1.24±0.21
N2O 1996-2007 Molecules* 85.5±2.61 85.0±5.60 240±13.6 172±14.4N2O 1996 2007 Molecules
cm-2*1014
85.5±2.61 85.0±5.60 240±13.6 172±14.4
% *yr-1 0.21±0.01 0.19±0.01 0.41±0.02 0.29±0.02
CH4 trends possible explainationsCH4 trends possible explainations Time period Growth rate Possible reasonp
Part of the interannual variability controlled by QBO modulating the t t t h & t t strat-trop exchange & strat ozone
1980- 1991 Decrease Increase in OH98 99 Decrease ncrease n OH
1991 Maximum Less UV due to Pinatubo
1992 Mi i L t d t Pi t b d 1992 Mimimum Lower temp due to Pinatubo and increasing UV due to strat O3 depl.
1992 1997 Still l L i i d t bi 1992-1997 Still low Lower emission due to biomass burning/smaller Russian natural gas
leaks97-06 Decrease in
growthLower wasteland emissions(dry) , but
higher anthropogenic?
Variability in global OH concentration contributes to methane inter-annual variability.
Tropical methane Tropical methane sources contribute the most to the inter-annual variabilityvariability.
Northern hemisphere sources contribute the sources contribute the most to long-term methane variability.
Bousquet et al., Nature, 2006
N2ON2O
N2O Emission sources Mton N/year (Prather 95)(Total 2.9-8.6 Mton N/year)
Cattle and feed lots6%
Industrial Sources22%
6%
22%
Cultivated soils62%
Biomass burning10%
N O b d t (P th t l IPCC 1994) N2O budget (Prather et al. IPCC 1994) Source Range Mton
N/year Likely
l Natural Oceans 1-5 3 tropical soils wet forests 2.2-3.7 3 dry savannas 0 5-2 1 dry savannas 0.5 2 1 temperate soils forests 0.1-2 1 grasslands 0.5-2 1
Sum natural 6-12 9 Anthropogenic Cultivates soils 1.8-5.3 3.5
biomass burning 0.2-1 0.5 industrial sources 0 7-1 8 1 3 industrial sources 0.7-1.8 1.3 cattle and feed lots 0.2-0.5 0.4
SUM Anth 3.7-7.7 5.7 TOTAL 10-17 60% of emissions NH
60% of emissions NH
Industrial sourcesIndustrial sources
• Nylon production• Nitric acid productionNitric acid production• Fossil fuel fired power plants• Vehicle emissions
N2O mixing ratio profileN2O mixing ratio profile60
50
30
40
tude
20
30
Alti
t
10
00.0E+00 5.0E-08 1.0E-07 1.5E-07 2.0E-07 2.5E-07 3.0E-07 3.5E-07
Mixing ratio
SinkSink
• Photolytic destruction 90%• Reaction with O1D 10%Reaction with O D 10%
(6 years feedback on its own lifetime114 insread of 120 years)114 insread of 120 years)
N2O from soilsN2O from soilsNit id (N2O) i d d b d t• Nitrous oxide (N2O) is produced as a by-product during nitrification and occurs as an intermediate during denitrificationduring denitrification .
• Microbial processes in soils contribute about 70% of the atmospheric budget of N2O70% of the atmospheric budget of N2O
• N2O emissions from soils have greatly increased with increasing N inputs by fertilizationincreased with increasing N inputs by fertilization of agricultural soils).
• In Phosphorous limited ecosystems (tropics) N• In Phosphorous limited ecosystems (tropics) N fertilization greatly increases N2O emissions
25 field chamber (Keron)25 field chamber (Keron)
N2O
Correlation between ammonia input p
(fertilization) and N2O emissions
FIG. 1. Effect of incubation at low, mediumFIG. 1. Effect of incubation at low, medium and high ammonia concentrations (LA, MA, and HA) on ammonium transformation. The stacked bars indicate percent contributions pof nitrification (open) and denitrification (shaded) to total N2O emission, and the small squares indicate the rates of total N2O 2emission. Means ± standard errors are shown (n = 3).
CHANGES IN TRENDS OF N2O
Time period Growth rate Possible reason
1980- 1992 1 ppb/year Gen. Increase in emissions 1980 1992 1 ppb/year Gen. Increase in emissions
1992-1995 0.5 ppb/year 1. Reduction in nitrogen fertilizers.
2. post-Pinatubo temp-reductions p pyielding lower soil emissions.
3. Reduced trop oceanic upwelling
4. Stratospheric circulation changes due to Pinatubo
1995 1997 0 6 b/ 1995-1997 0.6 ppb/year
I t f N2O h d• In recent years, no new sources of N2O have appeared,• Emission factors for mobile combustion need to be
revisited; ;• Agricultural emissions need to be re-evaluated; • More experimental data in terrestrial and aquatic
systems particularly long term measurementssystems, particularly long term measurements. – 50% uncertainty in estimates of N2O emissions from terrestrial
systems 50% t i t f i i f ti t– >50% uncertainty for emissions from aquatic systems
• Global nitrogen fixation, conversion of dinitrogen into reactive forms through combustion, fertilizer production g pand biological sources, continues to parallel or exceed the rate of growth of human population.
• During the past two decades the global distribution ofDuring the past two decades the global distribution of fixed nitrogen production and consumption has continued to shift from economically developed regions to economies in transition and developing regionsto economies in transition and developing regions.
CFCsCFCs
Important CFCsImportant CFCsCFC 11 (CCl3F t i hl fl th ) i• CFC-11 (CCl3F, trichlorofluoromethane) is now used primarily within rigid plastic insulating foams ("closed cell foams").foams ( closed cell foams ).
• CFC-12 (CCl2F2, dichlorodifluoromethane) isCFC 12 (CCl2F2, dichlorodifluoromethane) is now used primarily within refrigeration and air conditioning systems as the working fluid
• HCFC-22 (CHClF2, chlorodifluoromethane) is used primarily within refrigeration and airused primarily within refrigeration and air conditioning systems as the working fluid.
450000
500000
CFC11 Mg/year
350000
400000CFC11 Mg/yearCFC-12 Mg/yearHCFC-22 Mg/year
250000
300000
150000
200000
250000
100000
150000
0
50000
1940 1950 1960 1970 1980 1990 2000 2010
CFC12
CFC11CFC11
CO2CO2
• CO2: 280 ppm interglacial, 180 ppm glacialCO2: 280 ppm interglacial, 180 ppm glacial• Why? Probably ocean uptake and several
mechamisms such as the following hypothesis:mechamisms, such as the following hypothesis: – CO2 solubility increase at low T, but reduces at hi
salinity nut these effcts almost cancelssalinity, nut these effcts almost cancels– Extended sea ice prevents outgassing of upwelled CO2
rich water around antartica. Also in summer a melt water c ate a ou d a ta t ca so su e a e t atecap may have restricted the emissions
– Increasesd utlisation of surface nutrients by marine yecosystems in hi lat, leading to stronger vertical gradients of DIC and thus reduced atmospheric CO2 during glacial titimes.
Prehistoric CO2, geochemically infered from from rocksinfered from from rocks, sediments, fossiles etc. ,
High CO2 occurs during El Nino events since d d h di i d h bdry and hot conditions reduce the carbon uptake from the biosphere
CO2 emissions ⇔ CO2 concentrations• Recent increases far exceed the natural variability during
700 000 yearsy• 280+-10 ppm the last 1000 years• The rate of increase in concentration has increased in
step with the emissions, and is unprecedented in history• The increase in CO2 is faster in the NH than in SH,
consistent with sourcesconsistent with sources• Atmospheric O2 declines at a rate consistent with fossil
fuel burningfuel burning• 14C/12C and 13C/12C have declined during the past
two centuries, consistent with recent fossil fuel emissions• Evidence that the terrestrial biosphere and oceans have
been sinks rather than sources
Feedbacks in the carbon cycle due to climate change
• Warming reduces the solubility of CO2 and therefore reduces uptake of CO2 by the oceans
• Increased vertical stratification in the ocean due to increasing global temperatureg g
• On short time scales, warming increases the rate of heterotrophic respiration on land, butrate of heterotrophic respiration on land, but extent is not clear because it also changes the geographic distributiongeographic distribution.
Budget of atmospheric CO
Changement climatique
Budget of atmospheric CO2
Source from land seland use change
Source from fossil-fuel emissions
Ocean sink
1960-2005: 45% of total emissions
Land sink
remain in atmosphereAtmospheric accumulation =
FFoss + FLUC + FLandAir + FOceanAir
Raupach, PNAS, 2007
Land sinkFFoss FLUC FLandAir FOceanAir
CO2 fluxes from inversions of atmospheric concentrations (ICOS network)
Carbon (Pg)Carbon (Pg)
Atmosphere 730
Soil (1500) plants 50090
Ocean 38000Soil (1500) plants 500
Geological reserv 5000-10000Geological reserv. 5000 10000
The human perturbation (3.3) Pg C/year
Atmosphere 730
Soil (1500) plants 500
1.9
Ocean 38000Soil (1500) plants 500
Fossil fuel burning 5.3
CO2 prod 0 1
Geological reserv 5000-10000
CO2 prod 0.10.4
Geological reserv. 5000 10000
Ocean uptakeOcean uptake• Because of solubility and chemical reactivity CO2 is taken up by the
ocean much more efficently than other anthropogenic gases.
• CO2 that dissolves in sewater (DIC) is found in 3 forms:– Dissolved CO2 (non-ionoc 1%) taken up until partical pressure in water
and atmosphere are equaland atmosphere are equal– Bicarbonate ion (HCO3-) 91%, CO2+H20+CO32->2HCO3-– Carbonate ion 8% (CO32-
• Increased atmospheric CO2 leads to larger uptake, ending up as p g p , g pHCO3, but the availability of CO32- will decrease causing a larger proportion to remain in its dissolved form, hence restricting further uptake. (The present 100 ppm increase in CO2 has caused that the DIC concentration is already 40% less relative to preindustrial levels.concentration is already 40% less relative to preindustrial levels.
• The uptake varies also with seawater temperature (neg corr) salinity (positive corr) and alkalinity
• Another neg corr is Increased vertical stratification in the ocean due to increasing global temperature, leading to less uptake
Global CO2 emissions (Oak Ridge Lab.)
6000
7000
1.4
1.5Total CO2 fossil-fuels
5000
6000
n/ye
ar
1 2
1.3
year
Per capita CO2 emissions(metric tons of carbon)
4000
issi
ons
Mto
n
1.1
1.2
r cap
ita a
nd y
2000
3000
Tota
l CO
2 em
0.9
1
ton
CO
2 pe
r
1000
T
0.7
0.8
01950 1955 1960 1965 1970 1975 1980 1985 1990 1995 2000
Time
0.6
Istopic fractionation of O2 versus CO2 concentration
O2 versus CO2 concentration
CO2 emission sources (Marland 1998, Schimel 1996)(Tot emission 7-9 Gt C) ( )
Cement manufactue
Coal30%
Land use changes22%
Flaring1%
manufactue2%
30%
Gas14% Petrol
31%
8000
Total CO2 emiss ions from foss il-fuels (mil l ion metric tons of C)
6000
7000 CO2 emiss ions from gas fuel consumption
CO2 emiss ions from liquid fuel consumption
CO2 emiss ions from solid fuel consumption
5000
p
CO2 emiss ions from cement production
CO2 emiss ions from gas flaring
3000
4000
2000
0
1000
1850 1870 1890 1910 1930 1950 1970 1990 2010 2030
-1000
1850 1870 1890 1910 1930 1950 1970 1990 2010 2030
If all land use changes could be restored, the CO2 would go d b 40 70 (10 20%)down by 40-70 ppm (10-20%)
CO2
RANK NATION CO2_CAP
1 U.S. VIRGIN ISLANDS 33.87
CO2 per capita 2003
1 U.S. VIRGIN ISLANDS 33.87
2 QATAR 20.33
3 UNITED ARAB EMIRATES 11.81
4 KUWAIT 8.81 capita 20035 BAHRAIN 8.67
6 GUAM 6.83
7 NETHERLAND ANTILLES 6.18
8 ARUBA 6.12
9 LUXEMBOURG 6.05
10 TRINIDAD AND TOBAGO 5.98
11 UNITED STATES OF AMERICA 5.43
13 CANADA 4.88
14 AUSTRALIA 4.85
16 FAEROE ISLANDS 3.91
17 ESTONIA 3.67
18 SAUDI ARABIA 3.64
20 FINLAND 3.56
64 FRANCE (INCLUDING MONACO) 1.70
66 SWEDEN 1.61
101 CHINA (MAINLAND) 0 86101 CHINA (MAINLAND) 0.86
131 INDONESIA 0.36
136 INDIA 0.33
CO2 RANK NATION CO2_TOT
1 UNITED STATES OF AMERICA 1580175
emissions2 CHINA (MAINLAND) 1131175
3 RUSSIAN FEDERATION 407593
4 INDIA 347577
5 JAPAN 336142
6 GERMANY 219776
7 CANADA 154392
8 UNITED KINGDOM 152460
http://cdiac.ornl.gov/trends/emis/tre_coun.htm
8 UNITED KINGDOM 152460
9 REPUBLIC OF KOREA 124455
10 ITALY (INCLUDING SAN MARINO) 121608
11 MEXICO 11354211 MEXICO 113542
12 ISLAMIC REPUBLIC OF IRAN 104112
13 FRANCE (INCLUDING MONACO) 102065
14 SOUTH AFRICA 9941514 SOUTH AFRICA 99415
15 AUSTRALIA 96657
16 UKRAINE 85836
17 SPAIN 84401
18 POLAND 83121
19 SAUDI ARABIA 82530
21 INDONESIA 80544
53 SWEDEN 14378
Swedish CO2 emissions (Oak Ridge lab)
30000
9
10
20000
25000
106 to
ns
7
8
9
s C
/yea
r
Total Gas
petrol coal
15000
O2 e
mis
sion
1C
/yea
r
4
5
6
r cap
ita t
ons
Cement Per cap
5000
10000
Tota
l CO
1
2
3
CO
2 per
01820 1840 1860 1880 1900 1920 1940 1960 1980 2000
Time
0
1
Robust findings IPCC 07Robust findings IPCC 07Current atmospheric concentrations of CO2 and CH4, and their associated
positive radiative forcing,far exced those determined from ice core p g,measurements spanning the last 650,000 years. {6.4}
Fossil fuel use, agriculture and land use have been the dominant cause of increases in greenhouse gases over the last 250 yearsincreases in greenhouse gases over the last 250 years.
Annual emissions of CO2 from fossil fuel burning, cement production and gas flaring increased from a mean of 6.4 ± 0.4 GtC yr–1 in the 1990s to 7.2 ±flaring increased from a mean of 6.4 ± 0.4 GtC yr 1 in the 1990s to 7.2 ±0.3 GtC yr–1 for 2000 to 2005. {7.3}
The sustained rate of increase in radiative forcing from CO2, CH4 and N2O th t 40 i l th t ti d i t l t th tover the past 40 years is larger than at any time during at least the past
2000 years.
Natural processes of CO2 uptake by the oceans and terrestrial biosphereNatural processes of CO2 uptake by the oceans and terrestrial biosphere remove about 50 to 60% of anthropogenic emissions (i.e., fossil CO2 emissions andland use change fl ux). Uptake by the oceans and the terrestrial biosphere are similar in magnitude over recent decades but that by the terrestrial biosphere is more variable {7 3}by the terrestrial biosphere is more variable. {7.3}
Robust findings IPCC 07Robust findings IPCC 07It is virtually certain that anthropogenic aerosols produceIt is virtually certain that anthropogenic aerosols producea net negative radiative forcing (cooling infl uence) with agreater magnitude in the NH than in the SH.
From new estimates of the combined anthropogenicforcing due to greenhouse gases, aerosols and land surfacechanges it is extremely likely that human activities havechanges, it is extremely likely that human activities haveexerted a substantial net warming infl uence on climatesince 1750.
Solar irradiance contributions to global average radiativeforcing are considerably smaller than the contribution ofincreases in greenhouse gases over the industrial period.g g p
Key uncertainties IPCC07Key uncertainties IPCC07Th f ll f l di t difi ti f l dThe full range of processes leading to modification of cloud
properties by aerosols is not well understood and the magnitudes of associated indirect radiative effects are gpoorly determined.
The causes of, and radiative forcing due to stratospheric t h t ll tifi dwater vapour changes are not well quantified.
The geographical distribution and time evolution of the radiative forcing due to changes in aerosols during theradiative forcing due to changes in aerosols during the 20th century are not well characterised.
The causes of recent changes in the growth rate of g gatmospheric CH4 are not well understood.
Key uncertainties IPCC07Key uncertainties IPCC07Th l f diff t f t i i t h iThe roles of different factors increasing troposphericozone concentrations since pre-industrial times are notwell characterisedwell characterised.
Land surface properties and land-atmosphere interactionsLand surface properties and land-atmosphere interactions that lead to radiative forcing are not well quantified.
Knowledge of the contribution of past solar changes to radiative forcing on the time scale of centuries is not b d di t t d i h t lbased upon direct measurements and is hence strongly dependent upon physical understanding.
1100 ppm
?Contexte :Contexte : Le Changement Climatique550 ppm
?g q
pCO2atmosphérique
+6,0 oC
atmosphérique
370 ppm
21001750
280 ppm
?2000
Températurede surface +1,5 oC
+0,6 oC
1750 1900 21002000
