Ground-based Ground-based spectroscopic studies of spectroscopic studies of

atmospheric gaseous atmospheric gaseous compositioncomposition

Yana Virolainen, Yuriy Timofeyev, Maria Makarova, Dmitry Ionov, Vladimir Kostsov, Alexander Polyakov,

Anatoly Poberovsky, Marina Kshevetskaya, Anton Rakitin, Sergey Osipov, Hamud Imhasin

Department of Physics of Atmosphere, Saint-Petersburg State University, St. Petersburg, Russia

European Geosciences UnionGeneral Assembly 2011

Vienna, Austria03-08 April 2011

Five most important air mass flow sectors for St. Petersburg:

1. Arctic Ocean and North Russia; 2. continental Russia and Eurasia; 3. Europe;

4. Baltic Sea;

5. Arctic Ocean and Scandinavia.

[1], 14%

[2], 11%[3], 16%

[4], 18%

[5], 41%

Air mass origin for St. Petersburg, RussiaAir mass origin for St. Petersburg, Russia

Devices for atmospheric gases Devices for atmospheric gases measurementsmeasurements

Device Start Method Spectral range Measured

gasesComments

Spectrometer SIRS-2

1991 Direct Sun 3 – 5 μmСО, CH4,

H2O Spectral

resolution 0.3 – 0.5 сm-1

Spectrometers:

Visible-IR - KSVU

OCEAN OPTICS HR4000 UV

HR4000 visible

2004

2009

Scattered solar

radiation

420 – 520 nm

290 – 430 nm410 – 630 nm

О3, NO2, O2-O2

Spectral resolution

1.3 nm

0.4 nm 0.6 nm

MW-radiometer 2007MW

atmospheric radiation

110 GHz О3 Vertical profile

(25 – 60 km)

Fourier-spectrometer

Bruker IFS-125 2009 Direct Sun 1 – 16 μm ~20 gases

Spectral resolution –

up to 0.002 см-1

http://troll.phys.spbu.ru

SIRS-2: CHSIRS-2: CH4 4 total column amount (TCA)total column amount (TCA)

In 1991-2009 the CH4 TCA linear trend is non-significant.

Trend index is positive for Jan-Feb and negative for Jul-Aug

zaits@troll.phys.spbu.ru – Maria Makarova

The tendency is the increase of the amplitude of CH4 TCA annual cycle

1992 1994 1996 1998 2000 2002 2004 2006 2008 20101991 1993 1995 1997 1999 2001 2003 2005 2007 2009

year

3

3.5

4

4.5

CH

4 T

CA

, *10

19 m

ol/с

m2

3

3.5

4

4.5

Methane TCA seasonal variabilityMethane TCA seasonal variability

Month

CH

4

TC

A1

019m

ol/c

m2

mean

zaits@troll.phys.spbu.ru – Maria Makarova

Dec-Jan – max values, Jun-Aug – min values. Annual cycle amplitude ~ 3.6%

The annual variations of TCA may differ significantly from the mean annual cycle

SIRS-2: COSIRS-2: CO total column amounttotal column amount

CO

TC

A1

019m

ol/c

m2

zaits@troll.phys.spbu.ru – Maria Makarova

Linear trends for CO TCA are non-significant. The mean annual cycle for 1995-2009 has max values in Feb-Mar and min values in Jul with ~20% amplitude

Stratospheric NOStratospheric NO22: SCIAMACHY and KSVU: SCIAMACHY and KSVU

good agreement: “SCIAMACHY-KSVU” relative difference is +4±52%

ionov@troll.phys.spbu.ru – Dmitry Ionov

Tropospheric NOTropospheric NO22: OMI, KSVU and HYSPLIT: OMI, KSVU and HYSPLIT

relatively reasonable agreement for the period of comparison in January-March 2006

ionov@troll.phys.spbu.ru – Dmitry Ionov

Stratospheric OStratospheric O33: OMI and OceanOptics: OMI and OceanOptics

reasonable agreement: “OMI-OceanOptics” relative difference is +1.1±6.4%

ionov@troll.phys.spbu.ru – Dmitry Ionov

Example of the ozone profile retrieval: November 28, 2010.

1 – retrieved ozone number density,2 -measured spectrum, 3 - simulated spectrum, 4 – discrepancy.

0 5 10 15 20 25 30December 2007 [days]

80

120

160

200

To

tal

ozo

ne

22

-60

km

[DU

]

ground-basedMLS

110.7 110.8 110.9 111f [GHz]

-0.4-0.2

00.2

[K

]

144

148

152

156

160

Tb

[K]2

3

4

0 2E+012 4E+012O3, cm-3

20

30

40

50

60z

[km

]

1

vlad@troll.phys.spbu.ru – Vladimir Kostsov

Ozone sounding by microwave radiometerOzone sounding by microwave radiometer

Comparison with MLS AURA satellite data

Measured Measured gasesgases

Spectral Spectral windowswindows, с, сmm-1-1

Random error Random error for one for one

measurementmeasurement, , %%

Influenced Influenced gasesgases

H2O 2898 – 2905 1.5 CH4, HCl, HDO

CH4 2898 – 2905 0.8 H2O, HCl, HDO

N2O 2156 – 2164 1.0 CO, H2O, O3

CO 2156 – 2164 1.5 N2O, H2O, O3

CO2 2626.3 – 2627.0 1.8 CH4

C2H6 2976.6 – 2977.1 2.0 O3, H2O, CH4

HCl 2925.75 – 2926.0

1.7 CH4,H2O,

HF 4038.85 – 4039.05

2 H2O, HDO

CCl3F

(CFC-11)

830 – 870 13 H2O, HNO3, O3

Errors of Bruker spectrometer TCA Errors of Bruker spectrometer TCA retrievalsretrievals

kit@troll.phys.spbu.ru – Anton Rakitin

2009 2010 20111.2

1.6

2

2.4

2.8

CO

TC

A, 1

018 m

ol/c

m2

J F M A M J J A S O N D J F M A M J J A S O N D

2009 2010 20113.5

3.6

3.7

3.8

3.9

4

CH

4 T

CA

, 101

9 m

ol/c

m2

Bruker IFS125SIRS (grating spectrom eter)

J F M A M J J A S O N D J F M A M J J A S O N D

CHCH44 and CO TCA retrievals and CO TCA retrievals (Bruker)(Bruker)

zaits@troll.phys.spbu.ru – Maria Makarova

Average values of CH4 TCA for Mar-Jun 2009 obtained by two instruments are agree within 0.5%.

NN22O TCA retrievals (Bruker/NDACC stations)O TCA retrievals (Bruker/NDACC stations)

kshevetskaya.marina@gmail.com – Marina Kshevetskaya

Annual means of N2O TCA for local measurements are in good coincidence with annual means for NDACC stations

Mar Apr May Jun Jul Aug Sep Oct Nov Dec Jan Feb Mar Apr 2009 2010

PeterhoffACE-FTS 500km

0

1

2

3

Max values – Feb-Mar, min values – summer-fall. Good agreement with measurements on NDACC stations.

Good coincidence with satellite ACE-FTS measurements.

Seasonal cycle of HF TCASeasonal cycle of HF TCA

polyakov@troll.phys.spbu.ru – Alexander Polyakov

Brem en, 53.1 NHartestua, 60.2 NEureka, 80.1 NPeterhoff, 59.9 N

Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec

0

1

2

3

HF

T

CA

, 10

15

cm

-2

Bruker ozone TCA measurementsBruker ozone TCA measurements

Yana.Virolainen@JV14952.spb.edu – Yana Virolainen

TCA ozone measurements near St. Petersburg made by different instrumentation

Dobson and M-124 – ground-based instruments located ~ 50 km NE of PeterhofOMI – satellite instrument, temporal-space coincidence ~ 100 km

Yana.Virolainen@JV14952.spb.edu – Yana Virolainen

The example of ozone TCA diurnal variations measured by Bruker spectrometer (noise component of ~ 3 D.U.)

Correlation between ozone TCA obtained from different devices (mean – 0.3-1.7%, RMS – 3-4%)

Bruker ozone TCA measurementsBruker ozone TCA measurements

Combined method (IR+MW) for ozone: Combined method (IR+MW) for ozone: errorserrors

Yana.Virolainen@JV14952.spb.edu – Yana Virolainen

Main characteristics:

S – measurement error matrix (1)A– averaging kernel matrix (2)

S=(Sa-1+KTSε

-1K)-1 (1)

A =(Sa-1+KTSε

-1K)-1 KTS ε-1K =

SKTSε-1K (2)

Sa – a priori variability matrix for sought vector of atmospheric state

K – the matrix of variational derivates of the radiation with respect atmospheric parameters

Sε – the matrix of non-correlated measurement errors

Errors of retrieving the ozone mixing ratio profile for different measurement scenarios

Yana.Virolainen@JV14952.spb.edu – Yana Virolainen

Combined method (IR+MW): ozone Combined method (IR+MW): ozone profileprofile

Averaging kernels for ozone measurements by interferometer and microwave radiometer

Layer, km 0-10 10-1515-20

20-25 25-30 30-40 40-50

UO3, DU 34.4 38.2 62.2 100.7 86.1 82.2 14.2

σ apriori, % 30 33 32 32 32 30 31

σ aposteriori, % 3.7 6.4 5.6 3.8 4.0 3.6 5.9

Potential error of ozone retrieval in thick atmospheric layers

Main results and conclusionsMain results and conclusions

http://troll.phys.spbu.ru

• A large number of atmospheric trace gases (TG) are retrieved by different ground-based instrumentation • Temporal variations (from diurnal cycles to long-term trends) of TG are studied on the basis of experimental data

•The TG measurements are used for numerical modeling and for validation of satellite data

•Further development of techniques for TG profiles retrieving and expanding the list of TG are planned