FORMATION, TRANSPORT, PARTITIONING AND FATE OF ORGANOHALOGENS IN - - PowerPoint PPT Presentation

FORMATION, TRANSPORT, PARTITIONING AND FATE OF ORGANOHALOGENS IN ANTARCTICA ANTARCTICA

Vladim ir Bogillo g Dep a rtm ent of Anta rctic Geology a nd Geoecology gy

Institute of Geological Sciences, National Academy of Sciences, Kiev, Ukraine e-mail: vbog@carrier.kiev.ua

This study is a part of project “Past and future of Antarctic atmosphere”

• Antarctica is the highest (mean elevation = 2.300 m),

coldest (minimum temperature = -89.6°C), geographically most isolated land mass on Earth most isolated land mass on Earth

• By virtue of its geographical isolation and unique

meteorological conditions this most southerly of continents meteorological conditions, this most southerly of continents provides unparalleled opportunities for monitoring globally integrated geophysical and ecological processes

• The key atmospheric issues in the Antarctica are the

depletion of the stratospheric ozone layer, the long-range transport of air pollutants and warming associated with global climate change. These problems are mainly due to anthropogenic activities in other parts of the world anthropogenic activities in other parts of the world.

Role of Antarctic snowpack and ice sheet in formation partitioning and fate of volatile organic formation, partitioning and fate of volatile organic pollutants

• Accumulation of anthropogenic persistent organic

pollutants (pesticides, PAHs, PCB/Ns, PCDD/Fs, PBDEs) E i h t f th i l til f h l th i

• Enrichment of anthropogenic volatile freons, halons, their

substitutes and chloro-containing solvents

• Formation of volatile halogen and sulfur containing
• Formation of volatile halogen- and sulfur-containing

compounds in biochemical processes of ice microalgaes, coastal macroalgaes and phytoplankton g p y p

• Formation of alkenes, halocarbons, aldehydes, ketones,

carboxylic acids, alkyl nitrates, hydroperoxides in y y y p photochemical and redox reactions of organic matter in snowpack

Transport of OCs to Antarctica

T d i d d l Trade winds and cyclones directions

Galindez island Galindez island 65o 15’ S, 64o 16’ W 65 15 S, 64 16 W

Greenhouse gases: CO N O propene 0-70 years CO2, N2O, propene Sulfur-containing gases: COS, CS2, CH3SCH3, CH3SSCH3 470 years Natural halocarbons: СF4, CH3Cl, C2H5Cl, CH2=CHCl, CH3Br, CH2Br2, CHBr CH I CH =CHI C H I 1110 years 1860 years CHBr3, CH3I, CH2=CHI, C2H5I Anthropogenic halocarbons: CHCl3, CH2Cl2, CCl4, CH3CCl3, Cl2C=CCl2 30 m 2780 years 3685 years Chlorofluorocarbons and their replacements: СF2Cl2 (CFC-12), CFCl3 (CFC-11), CCl FCClF (CFC 113) CClF CClF (CFC 114) 3685 years

4220 years 4760 years

CCl2FCClF2 (CFC-113), CClF2CClF2 (CFC-114), CHClF2 (HCFC-22)

4760 years

GC-MS analysis of volatile compounds in ice layers

• f coastal glacier, Galindez Island (1998-2003)
• More than 200 organic compounds have been identified in young layer
• e

a 00 o ga c co pou ds a e ee de ed you g aye

• 13 industrial HFCs, CFCs, HCFCs and halons
• 63 natural and anthropogenic F, Cl, Br and I -halocarbons
• 13 S- and Se-containing compounds
• 13 S and Se containing compounds
• 26 acyclic and cyclic alkanes
• 35 acyclic and cyclic alkenes
• 6 alkynes and halogenated acetylenes
• 6 alkynes and halogenated acetylenes
• 19 substituted benzenes
• 5 carboxylic acids

28 li h ti d ti ld h d d k t

• 28 aliphatic and aromatic aldehydes and ketones
• 13 alcohols, phenols, ethers and esters
• 25 O-, S- and N-containing heterocyclic compounds

They are characterized by very large enrichment factors in comparison with their atmospheric mixture ratio in air comparison with their atmospheric mixture ratio in air (from 4 to 50000)

Wet extraction, cryofocusing, thermal desorption and GC-MS analysis and GC MS analysis

• f the volatile impurities in the ice blocks

2 6 5 8 1 9 1 2 10 6 3 4 7 6 13 14 15 11 12 13

Atmospheric mixing ratio of the impurities p g p

CO2 (ppm) 10850 2600 375 CF (ppt) 35 75 35 70

Compound Xfresh Xold Xair ∆Xcorr

CF4 (ppt) 35 75 35-70 C3H6 55300 0-1740 CHClF2 170 5 120-170 1-30 CF Cl 1000 40 520-560 10-535 CF2Cl2 1000 40 520-560 10-535 CFCl3 380 70 250-340 10-170 CCl2FCClF2 125 40 80-90 5-120 CClF2CClF2 10 10-15 0-2 CClF2CClF2 10 10 15 0 2 CH3Cl 4430 7930 550 100-730 C2H5Cl 450 200 2 CH3CCl3 1000 60-90 0-15

3 3

CH2=CHCl 180 2350 50 170-990 CH3Br 100 150 10 1-20 CH3I 130 600 0-1 1-80

3

C2H5I 1000 480 0.2 4-70 COS 5800 74800 500 3500-50500 CS2 16800 6700 2-20 140-1900 CH3SCH3 12000 10-600 CH3SSCH3 44000 2-300

Change of concentrations for volatile atmospheric impurities after their deposition on snow surface and during snow metamorphism their deposition on snow surface and during snow metamorphism

Сатм, глоб Сатм, лок С

Возраст (лет) Плотность (кг/м )

3

0,6 1 20 600 200 400

Сснег С

100 120 840 800

Сфирн След

• Snowpack includes three phases: solid ice, water and airs
• Three main parameters determine behavior of chemical in snowpack:

ee a pa a ete s dete e be av o o c e ca s owpac : vapor pressure, water/air partition coefficient (Henry law constant) and ice surface/air partition coefficient

• One of possible reason of the enrichment in the warm glacier may be
• One of possible reason of the enrichment in the warm glacier may be

dissolution of the gases in meltwater percolating through the underlying firn layers, subsequent refreezing of the enriched solution during cold season and repeating of the melt freeze cycles season and repeating of the melt-freeze cycles

• The dependence of CO2 enrichment factor on age of the ice reflects the

number and intensity of repetitive melt-freeze cycles, the enrichment has i i i i i i i i f maximum in young ice and this correlates well with climatic history of coastal Western Antarctica

• However, the enrichment for most other species decreases as this value

grows for CO2. Even corrected on the solubility in meltwater, the content

• f the species is in large excess in comparison with their atmospheric level

Influence of the solubility in water and adsorption on ice/air interface in ice samples on enrichment coefficients interface in ice samples on enrichment coefficients

• f the impurities

2,5 3,0

dard]

4

dard]

70 years 4000 years

1,0 1,5 2,0 2,5

ent factor, Xe is stand

1 2 3

ent factor, Xe is stan

• 1,0
• 0,5

0,0 0,5

g [Relative enrichme

2

• 1

g [Relative enrichme

• 5
• 4
• 3
• 2
• 1

Log Log [ice/air partition constant at 273 K], cm

• 1,5
• 1,0
• 0,5

0,0 0,5 1,0 1,5 2,0 2,5

• 2

Log Log [Henry's law constant at 273K]

ln F = 0.5×ln H + 0.3×ln KIA + 4.2 ln F = 0.9×ln H + 0.4×ln KIA + 4.9 (R 0 699) (R = 0.639) (R = 0.699)

Simulation of enrichment for soluble impurities in snowpack

5

t=16 days mg l

• 1

Depth: 80 cm

3 4

t=12 days

• ncentration m

Diameter of grains: 5 mm Snow density: 0.275 g/cm3 Snow porosity: 0.70 S t t 272 K

2 3

t=8 days Co

Snow temperature: 272 K Co = 0.2 mg/l dл = 0.917 g/cm3 S C0

20 40 60 80 1

t=4 days t=0

S0 = 0 pc = -400 N/m2 g = 10 m/s2, d = 1.0 g/cm3 σ = 0 0075 N/m

20 40 60 80

Depth from Snow Surface (cm)

σ0 = 0.0075 N/m

Calculation of enrichment for water-soluble impurity in snowpack due to repetitive melting- impurity in snowpack due to repetitive melting freezing cycles during 20 days of warm season

Annual Temperature, C

TREND OF ANNUAL AIR TEMPERATURE (GALINDEZ, 1947 – 1997)

• 2
• 1

Annual Temperature, C

• 4
• 3
• 6
• 5
• 9
• 8
• 7

1940 1950 1960 1970 1980 1990 2000 9

Year

) 6 . 25 6 . 107 ( ] [ ) 013 . 052 . ( ] , [ ± − × ± = Years C e Temperatur

• 000191

. ; 51 ; 36651 . 1 ; 4993 . ) ( ] [ ) ( ] , [ = = = = P N sd R p

] [ ) 25 . 1 01 . 6 ( ) 3 . 6 8 . 85 ( ] [ × ± + ± = TEMP RAIN 71 ; 74125 . 39 ; 50047 . ] [ ) 25 . 1 01 . 6 ( ) 3 . 6 8 . 85 ( ] [ = = = × ± + ± N sd R TEMP RAIN

Dependence of СО2 enrichment coefficient on age of the ice

30 35

я СО

2

p

2

g

25 30

огащени

15 20

циент об

5 10

Коэффиц

1000 2000 3000 4000

Возраст воздуха в блоке льда, лет р у

Taking into account the effect for solubility of the impurities In infiltration water on calculated atmospheric mixing ratio (СО2 - standard)

[ ] [ ]

[ ]

1 ] [ + × +

H

K X X X

[ ] [ ] [ ]

[ ] [ ]

1 ] [ 1 ] [ ] [

2 2 2 2

+ × + × = + + =

H CO X g g w X

K CO K X CO CO X X χ

[ ]

[ ]

1 ] [ ] [

2 2 2 2

+ × +

CO g g w

K CO CO CO

[ ] [ ] [ ]

1 1 ] [ ] [

2 2

+ × × =

H H CO g X g

K K CO X χ

[ ]

1 +

H X g

K

High enrichment in firn and snowpack interstitial air was discovered during 1998-2008 years for many inorganic and organic compounds NO NO HONO (C1 C4) RONO CH C(O)OONO

• NO, NO2, HONO, (C1-C4)-RONO2, CH3C(O)OONO2
• O3, OH, HO2, H2O2
• CO HCHO CH CHO (CH ) C O C H C(O)CH
• CO, HCHO, CH3CHO, (CH3)2C=O, C2H5C(O)CH3,

HCOOH, CH3COOH

• CH2=CH2, CH3CH=CH2, CH3CH2CH=CH2

CH2 CH2, CH3CH CH2, CH3CH2CH CH2

• BrO, CH3Br, C2H5Br, CH2Br2, CHBr3, CHBrCl2,

CHBr2Cl, CH3I, C2H5I, CH2ClI

Most of processes for the products formation are photochemically driven

• F. Domine, P. Shepson,

Nature, 2002, v. 297, p. 1506

Reactants in firn and snowpack

• Inorganic aerosols (terrigenous, sea salts)→ NO3
• , S2-, Cl-, Br-, I-; Fen+,

Mnn+, Cun+, Con+

• Organic aerosols from surface oceanic layer → phenols
• Organic aerosols from surface oceanic layer → phenols,

hydroxyacetophenones, hydroxybenzaldehydes, carbohydrates, C8 – C18 – monoacids, C5 – C11 – diacids, amino acids, proteins

• Phytoplancton, ice microalgae, microbes
• O2, O3, OH, HO2, HOCl, HOBr, HOI, ClO, BrO, IO, Cl, Br, I

Pathways for the products formation:

i i i i

• Direct and indirect photolysis
• Radical reactions
• Ionic reactions

Ionic reactions

• Biochemical reactions
• Redox-reactions

Phenomena occur in freezing of aqueous solutions and in snowpack: in snowpack:

• freeze – concentration (segregation of reactants)
• freezing potential (up to 100 V)
• freezing potential (up to 100 V)
• pH change (up to 4 pH units)
• concentration diffusion
• concentration diffusion
• cage effect in recombination of ions and radicals

f ti f H b d l ti d f ti f i i

• formation of H-bonds, solvation and formation of ion pairs
• temperature and matrix effects (restricted diffusion and

conformational mobility) conformational mobility)

• high photochemically active medium → low activation

barriers for photochemical formation of reactive species barriers for photochemical formation of reactive species

• dispersion kinetics

Acceleration of chemical reaction by freeze- concentration in polycrystalline ice

Very concentrated solution

I

Unfrozen solution freezing y

I I I I I I I I I I I R R

Processes in snowpack

Direct and indirect photolysis, radical reactions

R(C O)CH CH CH + λ RC O + CH CH CH

• R(C=O)CH2CH2CH3+ λν → RC=O. + .CH2CH2CH3
• RC=O. + .CH2CH2CH3 → R(C=O)H + CH2=CHCH3
• R(C=O)R’ + λν → [RC=O. + .R’]
• [RC=O. + .R’] + R”SH → R”S. + RC=O. + .R’H
• R”S. + RC=O. → RC=O-SR”
• RC=O-SR” + λν → R-R” + COS
• CH3SCH2CH2CH(NH2)COOH + λν → CH3SCH2CH2CHO + NH3 +

CO2

• CH3SCH2CH2CHO + OH → CH2=CH2 + CH3S. + HCOOH

3 2 2 2 2 3

• CH3S. + CH3S. + M → CH3SH + CH2S + M
• CH2S + λν → HCS. + H
• CH2S + OH. → HCS. + H2O

CH2S OH HCS H2O

• HCS. + O2 → COS + OH.
• HSCH2CH(NH2)C(=O)OH + O2 + hv→ HSCH2CHO +

NH + CO NH3 + CO2

• HSCH2CHO + OH → HCS + CO2
• 2HCS → CS2 + CH2:

2

• HCS + O2 → COS + OH

Direct and indirect photolysis, radical reactions

• CH3SCH3 + OH. → CH3SCH2

. + H2O

• CH3SCH2

. + O2 + M → CH3SCH2O2 . + M

• CH3SCH2O2

. + NO → CH3SCH2O. + NO2

CH3SCH2O2 + NO → CH3SCH2O + NO2

• CH3SCH2O. → CH3S. + CH2O
• CH3S. + CH3S. → CH3SSCH3
• CH SCH O. + O → CH SCHO + HO
• CH3SCH2O. + O2 → CH3SCHO + HO2
• CH3SCHO + OH. → COS + CH3. + H2O
• CS2 + OH. → COS + HS.

N O + N Cl N NO + ClNO

• N2O5 + NaCl → NaNO3 + ClNO2
• ClNO2 + NaCl → NaNO2 + Cl2
• NO3 + NaCl → NaNO3 + Cl.
• ClNO2 + hv → Cl + NO2
• Cl2 + hv → 2Cl.
• R. + Cl. → RCl (R = CH3, C2H5, CH=CH2)

(

3, 2 5, 2)

• R’(C=O)CH3 + λν → R’C=O. + CH3.
• OH. (RO., ROO.) + Br- → OH- (RO-, ROO-) + Br.
• CH3

. + Br. → CH3Br

CH3 Br CH3Br

• CH3SCHO + OH. → CH3S(OH)CHO.
• CH3S(OH)CHO. + Br. → COS + CH3Br + H2O

Ionic and biochemical reactions

• (CH3)2S+CH2CH2COO- + enzyme → (CH3)2S + CH2=CH-CHO
• (CH3)2S+CH2CH2COO- + OH-→ CH3SCH2CH2COO- + CH3OH
• CH SCH CH COO- + H+ → CH SH + CH CH COOH
• CH3SCH2CH2COO + H → CH3SH + CH3CH2COOH
• (CH3)2S + (H+,OH-) → CH3SH + CH3OH
• 2 CH3SH + OH- → CH3SSCH3 + H2O
• (CH3)2S+CH2CH2COO- + Cl- → CH3Cl + CH3SCH2CH2COO-
• HOOCCH(NH2)CH2CH2S+(CH3) -adenosine + Cl- → CH3Cl +

HOOCCH(NH2)CH2CH2S-adenosine (

2) 2 2

• NH2C(COOH)CH2CH2S+(CH3)2 + Cl- → CH3Cl +

NH2C(COOH)CH2CH2SCH3

• H2O2 + Cl- + chloroperoxidase → H2O + OCl-

H2O2 + Cl + chloroperoxidase → H2O + OCl

• OCl- + H+→ HOCl → HO- + (Cl+)
• R’(CO)RH + (Cl+) → RCl + R’(CO)H + (R = CH3, C2H5, CH2=CH)
• R-C(=O) + enzyme + Br- + H2O2 → R-COOH + CHBr3
• R-S(O2)CH3 + Br(δ+) → R-S(O2)CBr3
• R-S(O2)CBr3 + OH- → RS(=O)OOH + CHBr3

R S(O2)CBr3 OH RS( O)OOH CHBr3

Redox reactions

Organic matter + Men+ + X- → R-X + M(n-1)+ (Me = Fe Co Mn Cu; X = Cl Br I; R = CH C H CH =CH) (Me = Fe, Co, Mn, Cu; X = Cl, Br, I; R = CH3, C2H5, CH2=CH)

Sources of the impurities in ice samples of coastal glacier Sources of the impurities in ice samples of coastal glacier

Chl fl b d th i l t hl t i i l t

• Chlorofluorocarbons and their replacements, chloro-containing solvents

Anthropogenic origin

• Tetrafluorocarbon: anthropogenic (50%) + emission from granites (50%)

p g ( ) g ( )

• Propene: photochemical decomposition of dissolved organic matter from

micro/macroalgaes R(C=O)CH2CH2CH3+ λν → RC=O. + .CH2CH2CH3 R(C O)CH2CH2CH3+ λν → RC O + CH2CH2CH3 RC=O. + .CH2CH2CH3 → R(C=O)H + CH2=CHCH3

• Dimethyl sulfide and dimethyl disulfide: biosynthesis from algaes

(CH3)2S+CH2CH2COO- → (CH3)2S + CH2=CH-CHO 2 CH3SH + OH- → CH3SSCH3 + H2O

• Carbonyl sulfide and carbon disulfide: photolysis of organic matter

Carbonyl sulfide and carbon disulfide: photolysis of organic matter R(C=O)R’ + λν → RC=O-SR” + λν → R-R” + COS HSCH2CH(NH2)C(=O)OH ” + λν → CS2 + CH2:

Sources of the impurities in ice samples of coastal glacier

CH Cl C H Cl CH CHCl bi h i f l d h l k di l b i i

• CH3Cl, C2H5Cl, CH2=CHCl: biosynthesis from algaes and phytoplankton, radical substitution

in organic matter chlorroperoxydase + Cl- + H2O2 + R’(CO)RH → R-Cl SO (NO OH) + Cl + R M R Cl SO4

• (NO3, OH) + Cl- + R~M→ R-Cl
• CH3Br: biosynthesis from algaes, photolysis and redox – reactions of organic matter in

presence of Br- ions bromoperoxidase + Cl- + H O + R’(CO)HCH → CH Br bromoperoxidase + Cl + H2O2 + R’(CO)HCH3 → CH3Br R’(C=O)CH3 + λν + Br- → CH3Br + R’C=O PhOCH3 + Fe3+ + Br- → CH3Br + Fe2+ + Ph=O CH Br CHBr : biosynthesis from algaes

• CH2Br2, CHBr3: biosynthesis from algaes

R-C(=O) + Br- + H2O2 + enzyme → CH2Br2(CHBr3) + R-COOH

• CH3I, C2H5I, CH2=CHI: biosynthesis from algaes, photolysis and redox – reactions of

i tt i f I i

• rganic matter in presence of I- ions

Relationships between impurity concentrations in the glacier and their temporal dependencies

300 6000

1

C H Cl vs CH Cl CH3Cl vs COS CH =CHCl vs CH Cl

200 250 300

[C2H5Cl], трлн

• 1

3000 4000 5000 6000

[CH2=CHCl], трлн

• 1

20000 30000

[CH3Cl], трлн

• 1

C2H5Cl vs CH3Cl CH3Cl vs COS CH2=CHCl vs CH3Cl

50 100 150 1000 2000

[

10000 20000 4000 5000 6000 7000 8000 50

[CH3Cl], трлн

• 1

4000 4500 5000 5500 6000 6500 7000 7500

[CH3Cl], трлн

• 1

100000 200000 300000 400000

[COS], трлн

• 1

180 200

r], трлн

• 1

800

трлн

• 1

CH3I vs CO2 CH3Br vs CO2

140 160

[CH3Br

400 600

[CH3I],

CH3I vs CO2

2000 4000 6000 8000 10000 12000 80 100 120 200 2000 4000 6000 8000 10000 12000

[CO2], млн

• 1

4000 8000 12000

[CO2], млн

• 1

Concentration and temporal trends for the impurities in the glacier

[CH3CH=CH2] = 32140±18160 – (29±17)×[Age] + (0,006±0,003)×[Age]2; r=0,495 [CS ] 13074±2106 (2 3±0 8)×[A ] 0 774 [CS2] = 13074±2106 - (2,3±0,8)×[Age]; r=0,774 [COS] = 24393±16739 + (8,4±6,1)×[Age]; r=0,490 [CH B ] 112±37 + (0 015±0 012)×[A ] 0 428 [CH3Br] = 112±37 + (0,015±0,012)×[Age]; r=0,428 [CH3Br] = 121±33 + (0 005±0 003)×[CH3Cl]; r=0 617 [CH3Br] = 121±33 + (0,005±0,003)×[CH3Cl]; r=0,617 [CH3Br] = 105±28 + (0,09±0,06)×[CH3I]; r=0,493 [CH3Br] = 122±25 + (0,0006±0,0002)×[COS]; r=0,745 [ C 2 [C2H5I] = 34±214 + (0,8±0,6)×[CH3I]; r = 0,600 [CH3Cl] = 1846±859 + (0,080±0,006)×[COS]; r=0,973 H 5 I ] =

Sources and fate of volatile impurities in Antarctic

• xidation, radical

Biosynthesis by ice

• xidation, radical

reactions (ОН, NO3, RO, О3), photolysis y y microalgae and microbes, Photolysis and redox- reactions of organic matter

emission from k

3), p

y in presence of halide ions in snowpack and firn

rocks

biosynthesis from macroalgaes and phytoplankton dry and wet d iti p y p photolysis and redox-reactions of

• rganic matter in surface layers
• f the ocean

deposition advective transport with photolysis, hydrolysis, nucleophylic transport with aerosols p y substitution,

• xidation

microbial decomposition hydrolysis microbial decomposition, hydrolysis,

• xidation

Interface Processes between the Ocean, Atmosphere,

• In the near future climate change is predicted to be at a significantly

Sea Ice, and Snow in Antarctica

faster rate in Western coastal Antarctic than for the planet as a whole, due to the influence of feedbacks related to the changing surfaces of glaciers and Southern Ocean g

• Numerous recent observations indicate that the exchange of

atmospherically important chemical species with this surface is driven by physical and photochemical processes occurring on the surface of by physical and photochemical processes occurring on the surface of the snowpack and sea ice, and that this exchange significantly impacts the concentrations of chemical species such as ozone and mercury

• Biologically-mediated processes have also been observed to impact the

interactions between ocean, ice, and/or snow and the atmosphere

• Both dynamic (movement) and thermodynamic (temperature)

Both dynamic (movement) and thermodynamic (temperature) processes in the marine cryosphere affect the exchange process of mass and energy, and the latter are being affected by global scale climate variability and change variability and change

Interface processes between the Ocean, Atmosphere Sea Ice and Snow in Polar Atmosphere, Sea Ice, and Snow in Polar Regions

H th l t h i th P l i How the lower atmosphere in the Polar regions will change as climate and the nature of the ice volume change? ice volume change?

International programs (IPY2007-2008) OASIS (Ocean Atmosphere Sea Ice and Sno e change

• OASIS (Ocean-Atmosphere-Sea Ice and Snow exchange

processes)

• AICI (Atmosphere-Ice Chemical Interactions),

ASCOS (Arctic Summer Cloud Ocean Study)

• ASCOS (Arctic Summer Cloud Ocean Study)
• POLARCAT (Polar Study using Aircraft, Remote Sensing,

Surface Measurements and Models, of Climate, Chemistry, Aerosols and Transport) Aerosols, and Transport)

Future effects of snowpack reactions on lower atmosphere stratosphere and climate o er Antarctic atmosphere, stratosphere and climate over Antarctic

Rise of surface Depletion of stratospheric ozone

Rise of UV-B irradiation

Increase of rate and yield for direct and indirect surface

• zone

Gl b l i

irradiation

direct and indirect photochemical reactions Global warming I f t Enhanced fluxes

• f volatile

Increase of rate

• f ionic and

biochemical

• f volatile

products into atmosphere Emission of reactions Enhanced fluxes i Formation

• f CNN

Emission of ODP- compounds i t into hydrosphere into stratosphere

Increase of air temperature and UV-B radiation leads to:

• Acceleration of photochemical, thermal and biochemical

processes of the impurities formation in snowpack, firn and

• ceanic surface layer
• ceanic surface layer
• Acceleration of the impurities evaporation from snow surface
• Growth of water content in the snow and increase of water
• Growth of water content in the snow and increase of water-

soluble impurities content in the snowpack and firn

• Acceleration of the glaciers ablation melting of the snowpack
• Acceleration of the glaciers ablation, melting of the snowpack

and washing of the impurities with snow melt water in ocean and their evaporation in atmosphere p p

• Growth of icebergs amount and their melting

Annual emission of the impurities due to glaciers melting and calving of the icebergs in coastal Antarctic

COS 840 t

and calving of the icebergs in coastal Antarctic

COS 840 t CS2 54 t CH Cl CH3Cl 50 t CHBr3 25 t CH2=CHCl 21 t CF Cl 15 t CF2Cl2 15 t CFCl3 10 t CH3I 6 t Cl2C=CCl2 3 t

2 2

CH3Br 2 t

Influence of the impurities on stratospheric and tropospheric

• zone and radiation balance of Antarctic atmosphere

CH Cl 13% f i Cl i t t h

• CH3Cl – 13% of organic Cl in stratosphere
• С2H5Cl + CH2=CHCl - > 1% Cl in stratosphere
• Br atoms are more effective catalysts in depletion of ozone layers (50-60 times)

i i ith Cl t in comparison with Cl atoms

• CH3Br, CH2Br2 and CHBr3 – 80% of organic Br in stratosphere
• Obtained Cl- and Br-containing hydrocarbons are responsible for 40%

d l ti f th l i th h l t l ti l depletion of the ozone layer in the halogen catalytic cycles

• CH3I, C2H5I и CH2=CHI - are responsible for depletion of ozone in oceanic

boundary layer Prod cts of o idation and photol sis of CH I C H I CH CHI COS CS

• Products of oxidation and photolysis of CH3I, C2H5I, CH2=CHI, COS, CS2,

CH3SCH3 and CH3SSCH3 are effective clouds condensation nuclei over Southern Ocean and their content affects on meteorological conditions over

• cean.

• Since 1960s, persistent semi- or low-volatile organochlorine

compounds (OC), such as pesticides (aldrin, dieldrin, compounds (OC), such as pesticides (aldrin, dieldrin, endrin, chlordane (CHL), heptachlor, DDT and its metabolites (DDE and DDD), toxaphenes, mirex, h hl b (HCB) d h hl l h hexachlorobenzene (HCB) and hexachlorocyclohexanes (HCH)), polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs) and p y p ( ) polychlorinated dibenzofurans (PCDFs) were found in abiotic compartments of Antarctica and its biota. Th A t ti i t f f h i l i k f

• The Antarctic region acts as a form of chemical sink for

these contaminants.

• The strong temperature dependence of gas

The strong temperature dependence of gas phase/condensed phase partitioning together with the spatial temperature gradients on a global scale can lead to l ti i h t f hi hl i t t OC i A t ti relative enrichment of highly persistent OCs in Antarctica by “cold condensation” (CC hypothesis).

• The other mechanism is the high persistence of OCs in cold

The other mechanism is the high persistence of OCs in cold Antarctic environment.

Aims of the study Aims of the study

• Transport pathways for OCs to Antarctica
• Latitudinal seasonal and spatial variations of OCs
• Latitudinal, seasonal and spatial variations of OCs

levels in air – agreement with CC hypothesis

• Temporal variations of OCs in air, seawater, snow

p , , and sea ice – agreement with CC hypothesis

• Influence of temperature on partition coefficients

and distribution of OCs between abiotic compartments of Antarctic environment

• Direction and strength of OCs fluxes between the
• Direction and strength of OCs fluxes between the

compartments

• Impact of current and future climate changes on

Impact of current and future climate changes on transport and re-emission of the contaminants in Antarctica

Transport of OCs to Antarctica

T d i d d l Trade winds and cyclones directions

Transport of OCs to Antarctica

• Comparable levels of OCs in seawater and its biota from

north and south of the Antarctic Convergence, which g , separates sharply defined and distinct water masses, indicated that the atmosphere, not the water, was the dominant pathway for the transport of the OCs to the Antarctica T (bl k b i l d t) t t th

• Tracer (black carbon, mineral dust) transport over the
• cean is fastest in the mid-troposphere. The typical age is

about 5.5 d for tracers from Patagonia to Central about 5.5 d for tracers from Patagonia to Central Antarctica, 6.5 d for Australian tracers and about 8.5 d for advection from Southern Africa

Scenarios for “global fractionation” of OCs in the environment

• “Primary source”: After release from a primary source,

th t i t i d it d d b tl t d the contaminant is deposited and subsequently prevented from volatilizing through permanent retention in environmental reservoirs. The different long-range i i i i i i potential of OCs in air would result in fractionation of a contaminants mixture away from the primary source. Absolute amounts would therefore be expected to decrease with latitude/distance from the source.

• “Secondary source”: Emission of OCs from the

environmental reservoirs would control levels in the environmental reservoirs would control levels in the

• atmosphere. Repeated air-surface exchange would see the

OCs move in a series of “hops” (“grasshopper effect”). This would also result in fractionation becoming more This would also result in fractionation, becoming more pronounced over time, absolute concentrations of some contaminants may became higher at higher latitudes, and more volatile OCs becoming more abundant over time in more volatile OCs becoming more abundant over time in higher latitudes.

Major modes of OCs transport in range 25 - 0

• C

2

multiple hoppers single hoppers

HCB PCB180 PCB101 PCB52 PCB8

(F. Wania, 2006)

• 3
• 2

mers

PCB15 PCB194 PCB153 PCB101 PCB28

KAW

• 4
• 3

swimm

PCB15

α-HCH

OCDD TCDD DDT

log K

• 5

4 PBDE47

γ-HCH

• 6

CHL 7 8 9 10 11 12 13

log KOA g

OA

Latitudinal variations

50 s Σ Tri-CB 90

3

Σ Tri-CB

(Data from Montone et al, 2005 and Lohmann et al, 2001)

30 40 50 B congeners Σ Tetra-CB Σ Penta-CB Σ Hexa-CB Σ Hepta-CB 50 60 70 80 CA, pg m

• 3

Σ Tetra-CB Σ Penta-CB Σ Hexa-CB Σ Hepta-CB 10 20 30 ercent of PC 20 30 40 50 25 30 35 40 45 50 55 60 65 10 Pe L tit d

• S

25 30 35 40 45 50 55 60 65 10 Latitude,

• S

10*(PCB-77)-94% Latitude, S Latitude, S 2000 2500 fg m

• 3

PCB-77 10*PCB-126 100*PCB-169 50 60 70

• ngener

10 (PCB-77)-94% 10*PCB-126 100*PCB-169 500 1000 1500 CA, f 20 30 40 nt of PCB c 10 20 30 40 50 60 70 80 500 Southern Latitude 10 20 30 40 50 60 70 80 10 Percen S i

Latitudinal variations

• Marked decrease along north to south was established for PCBs,

DDTs, HCHs, PCDDs and PCDFs levels in air (Tanabe et al, , , ( , 1982,1983; Iwata et al, 1993; Bidleman et al, 1993; Lohmann et al, 2001; Ockenden et al, 2001; Montone et al, 2005)

• In contrast to other OCs, concentration of HCB increased towards the

A t ti I HCB d i “ ld d ti ” ? I f t thi

• Antarctica. Is HCB undergoing “cold condensation” ? In fact, this was

explained by better retention of HCB in the adsorption column of polyurethane foam of the colder sampling stations (Bidleman et al, 1993; Montone et al, 2005; Dickhut et al, 2005). 1993; Montone et al, 2005; Dickhut et al, 2005).

• The relative contribution of light PCB congeners increases or it is

steady with latitude, while the contribution of heavy congeners drops with latitude. These trends are consistent with the global fractionation theory.

• The strong latitudinal gradients for the OCs in air toward the

Antarctic coast are comparable with similar gradients for such t f t h i l ti l t i tt components of atmospheric aerosols as particulate organic matter, elemental carbon and sea salts

Seasonal variations

120

γ-HCH in air

m

• 3

60

Σ DDT in air

60 90 CA, pg m 45 CA, pg m

• 3

30 60 15 30

• 30
• 25
• 20
• 15
• 10
• 5

5 t,

• C
• 21
• 18
• 15
• 12
• 9
• 6
• 3

t,

• C

Data from Larsson et al, 1992 Data from Tanabe et al, 1983

Seasonal variations

• High OCs concentrations were generally obtained during the austral

summer than during the austral winter

• Significant correlation is observed between concentration of OCs and

g mean daily temperature of air

• The relative contribution of light PCB congeners increases or it is

steady with temperature, while the contribution of heavy congeners d ith t t b t i ifi t l ti hi f d drops with temperature, but no significant relationships were found between levels of DDTs and PCBs in the air and temperature

• This seasonal difference was explained by removing of OCs by

snowfall in winter with intensive snowfalls more intensive application snowfall in winter with intensive snowfalls, more intensive application

• f the pesticides on lands in summer and active evaporation of the

POPs into atmosphere from their various sources on lands in summer

• These variations coincide with a summer maximum and winter

These variations coincide with a summer maximum and winter minimum for concentrations of black carbon in air measured at Halley station and at South Pole (Wilff et al, 1998).

• Additional reason to the variations may be break down of the

y Antarctic circumpolar vortex and weakness of surface inversion during the summer months

Spatial variations

M i t ti f th ti id d PCB i

• Maximum concentrations for the pesticides and PCBs in

air were observed near Western Antarctica Peninsula, King George Island, 61.16 oS, 55.7 oW and Signy Island, 60o 72’ S 45o 60’ W )] i i ith t 60o, 72’ S, 45o 60’ W )] in comparison with more eastern locations (Halley Station, 75o 35’ S, 26o 30’ W; Neumayer Station, 70o38’ S, 8o16’ W; Terra Nova Buy, 75o S, 164o 06’ E d R I l d 77 38 1’S 166 24 6’ E) E; and Ross Island, 77o 38.1’S, 166o 24.6’ E)

• By analogy with atmospheric tracers, this west-east

gradient may be explained by prevailing northwest winds g y p y p g and west-east direction of cyclones in coastal Antarctica, more short time for transport of OCs from South America in comparison with that from South Africa or in comparison with that from South Africa or Australia/New Zealand, and gradual decrease for level of OCs from the west coastal area to east of inland area

Temporal variations in air

HCB in air 150 200 250 DT, pg m

• 3

Σ DDTs in air

120 160 CA, pg m

• 3

Σ HCHs in air 60 80 CA, pg m

• 3

HCB in air 50 100 150

Σ DD

40 80 C 20 40 C 1980 1984 1988 1992 1996 Year 1980 1990 2000 Year 1986 1992 1998 Year g m

• 3

Σ chlordane in air

120 160 200

CA, pg m

• 3

Σ PCB in air

6 CA, p

3

• DDT in air

p,p'-DDE/p,p'-DDT in air

40 80 120

C

3

1 2

p'-DDE/p,p'-

1980 1990 2000

Year

1984 1988 1992 1996 Year 1980 1984 1988 1992 1996 Year p,p

Temporal variations in seawater

40 60 CW, pg L

• 1

Σ DDTs in sea water

300 400 CW, pg L

• 3

Σ PCB in sea water

20 C 100 200 1980 1983 1986 1989Year 1980 1990 2000 Year 800 CW, pg L

• 1

Σ HCHs in seawater

8

α-HCH/γ-HCH in seawater γ-HCH

400 4 6

α-HCH/γ

1980 1990 2000 Year 1992 1996 2000 2 Year

Temporal variations in snow and sea ice

4000 5000

Σ DDTs in snow

2 E/DDT DDE/DDT ratio in snow 1000 2000 3000 1 DDE 1960 1970 1980 1000 Year CS, pg L

• 1

1968 1976 1984 Year 5000 CS, pg L

• 1

Σ HCHs in snow

CI, pg L

• 1

Σ HCHs in sea ice

2000 3000 4000 2000 3000 1960 1980 2000 1000 2000 Year 1980 1990 2000 1000 Year Year Year

Temporal variations

Distinct declines are observed for ΣDDT and ΣHCH in air, seawater and snow, HCB, ΣPCB and ΣCHL in air, ΣHCH in sea ice, DDT/DDE ratio in air and snow, and α-HCH/γ-HCH ratio in seawater. These trends were treated assuming first-order kinetics: ln Ci = A – kap(Year)

p

and first-order half-lives for OCs in different mobile mediums were estimated: tap1/2 = (ln 2)/kap

Temporal variations

ΣDDT i i t 2 9±0 7 (1980 1995) (3 3 0 4

)

emission t1/2

ΣDDT in air: tap1/2 = 2.9±0.7 yr (1980 – 1995) (3.3±0.4 yr) ΣDDT in seawater: tap1/2 = 3.0±1.4 yr (1980 – 1990) ΣDDT in snow: tap1/2 = 5.4±3.8 yr (1960 – 1982) ΣHCH in air: tap1/2 = 3.2±0.3 yr (1980 – 2002) ΣHCH in seawater: tap1/2 = 3.2±0.3 yr (1981 – 2002) ΣHCH in snow: tap1/2 = 3.3±0.5 yr (1981 – 2002) ΣHCH in sea ice: tap1/2 = 3.2±0.3 yr (1981 – 2002) HCB in air: tap1/2 = 9.1±3.1 yr (1983 – 2001) (7.0±1.1 yr)

p

ΣPCB in air: tap1/2 = 4.6±1.3 yr (1981 – 2004) (5 – 15 yr) ΣCHL in air: tap1/2 = 2.8±1.3 yr (1983 – 1995)

ap1/2

y ( ) DDT/DDE in air: tap1/2 = 5.4±2.2 yr (1981 – 1995) DDT/DDE in snow: t

1/2 = 11.7±10.7 yr (1975 – 1981)

DDT/DDE in snow: tap1/2 11.7±10.7 yr (1975 1981) αHCH/γHCH in seawater: tap1/2 = 7.7±3.4 yr (1981 – 2002)

Temporal variations

• The half-lives for ΣDDT and ΣHCH are close with each
• ther in air, seawater and snow
• The half live for ΣPCB in the Antarctic air (4 6 yr) is
• The half-live for ΣPCB in the Antarctic air (4.6 yr) is

comparable with half-lives for the PCBs congeners in Norwegian, UK and Great Lakes background air (1.7 – 6 r) yr)

• The half-lives for the OCs are not related to their

decomposition half-lives in air, water and sediments as a p result of their OH radical degradation in air, hydrolysis and microbial decomposition in water and sediments

• The temporal declines in OCs level in the mobile

The temporal declines in OCs level in the mobile compartments of Antarctic environment reflect the global declines in use and emission of the OCs in Southern Hemisphere Hemisphere

• The observed declines for the OCs (HCB, HCHs, DDTs,

PCBs, CHLs) in Antarctic environment conflict with “ d ” i f l b l f ti ti f “secondary source” scenario for global fractionation of OCs

Partitioning of the OCs between abiotic compartments compartments

• All from the OCs show a strong tendency to partition between the

f A i i Thi i i i i compartments of Antarctic environment. This partitioning is controlled by their physico-chemical properties, the characteristics of the compartments as well as temperature.

• The partition coefficients (octanol/air (KOA), octanol/water (KOW),

water/air (KWA), air-water interface/air (KIA)) are used to estimate the water/air, snow/air, soil/air and sediment/water partitioning of the OCS ll th i / i i ti d t h i OCS as well as their snow/air scavenging ratio and atmospheric particle-bound fractions.

• Generally, air temperature is varied in Antarctica from – 70 oC to
• 20 oC (Central Plateau) and from – 30 oC to 0 oC (Coastal areas).

Seawater temperature is near 0 oC. The partition coefficients for OCs at these temperatures were estimated using the relationships between logarithms of partition coefficients and corresponding partition enthalpies for PCB congeners.

Partitioning of the OCs between abiotic compartments

Plot ∆HOA versus log KOA at 298.15 K

5

Plot ∆HOW versus log KOW(298.15 K)

• 76
• 72

OA

g

OA

PCB101 PCB28 PCB15

A, kJ mole

• 1
• 15
• 10
• 5

OW

g

OW(

) PCB180 PCB101

W, kJ mole

• 1

88

• 84
• 80

PCB138 PCB180 PCB101

∆HOA

• 25
• 20

PCB138 PCB28 PCB15

α-HCH ∆HOW

7 8 9 10 11

• 92
• 88

PCB118 log KOA

3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5

• 30

log KOW

100 70 80 90

kJ mole

• 1

50 60 70

HAW(EXPERIM), k

40 50 60 70 80 90 100 40

∆H ∆HAW (ESTIMATED), kJ mole

• 1

Influence of temperature

Particle-bound fraction Snow/air scavenging ratio

1.0

ΦP

CHL DDT

30000000

WSA DDT

0.6 0.8

DDT PCB-31 PCB-180 TCDD

α-HCH

15000000 20000000 25000000

DDT PCB-31 PCB-180 TCDD

α-HCH

0 0 0.2 0.4

α-HCH

γ-HCH HCB

5000000 10000000

α HCH

γ-HCH HCB

Mean atmospheric half-live

• 40
• 20

20 0.0

t,

• C
• 40
• 30
• 20
• 10

t,

• C

t (A) days

60000 80000

t1/2(A), days DDT DDT + part PCB-180 PCB 180 + part

T

decrease of reactivity of OH radical decrease of concentration

20000 40000

PCB-180 + part γ-HCH γ-HCH + part HCB HCB + part

T

decrease of concentration

• f OH radical

Increase of inert particle bound

• 20

20 20000

t,

• C

HCB + part

Increase of inert particle-bound fraction

Air-seawater exchange

Fluxes of HCHs by gas exchange between air and water

2 s

• 1

Air/water exchange of HCHs along the Western Antarctic Peninsula

10 20 30 40 50 60

• 0 10
• 0.05

0.00

A/W, pg m

• 2

Southern Latitude

• 0.004

0.000

2 s

• 2

α-HCH

• 0.20
• 0.15
• 0.10

FA α-HCH γ-HCH

• 0.012
• 0.008

FS, pg m

• 2

γ-HCH

• 0.30
• 0.25
• 0.016

CA and CW values from Lakaschus et al, 2002

CA and CW values from Dickhut et al, 2005

,

,

These fluxes indicate on net deposition of HCHs in seawater near to equilibrium

Air-snow exchange

Fl f OC f i k

80

Lake Nurume

• 20

Fluxes of OCs from air to snowpack

ΣDDT ΣHCH

g m

2s

• 1

40

Tottuki Point Mizuho Station g m

• 2 s
• 1
• 60
• 40

ΣPCB ΣDDT

C

• w flux, pg
• 120
• 80
• 40

FA, p HCHs DDTs

100

• 80

60

Air/sno Lakaschus, 2000 Dickhut, 2001 Tanabe 1981

• 160

PCBs

CA and CS values from Tanabe et al 1981

1 2 3

• 100

Tanabe, 1981

from Tanabe et al, 1981

1 2 3 4 5

Dickhut, 2001 Lakaschus, 2000

Th fl i di t t d iti

1 2 3 4 5

• 1

g m

• 2 s
• 1

These fluxes indicate on net deposition

• f OCs into snowpack in 1980s and

they are close to equilibrium in 2000s

• 3
• 2

Flux, pg

α-HCH

α HCH γ-HCH

Air-soil exchange

A plot of log CS versus log [OM] will have a slope of 1 at equilibrium between soil and air (Gouin et al, 2004) Soil-air equilibrium is indicated by fugacity fraction = 0.5. Net volatilization and deposition of gas-phase OCs are indicated by fugacity fractions > 0 5 and <0 5 (Harner et al indicated by fugacity fractions > 0.5 and <0.5 (Harner et al, 2001) For 11 soils from East Antarctica (Negoita et al, 2003)

um DDTs HCHs HCB

0.8 1.0

• n

equilibriu HeptaCB Octa-CB

ΣPCBs

DDTs

0 4 0.6

city fractio ΣDDT ΣHCH HCB PCB Tri-CB Tetra-CB Penta-CB Hexa-CB

0 0 0.2 0.4

Fugac

ΣPCB

0.0 0.2 0.4 0.6 0.8 1.0

Tri-CB Slope

1 2 3 4 0.0

% organic carbon in soil

Air-soil exchange S l th f il t i ti ith OC i Several pathways of soils contamination with OCs in Antarctica are suggested (Negoita et al, 2003): (a) Long-range transport by air from the continents of ( ) g g p y South Hemisphere, where OCs were extensively used in the past. (b) Local contamination by PCBs (area of few hundreds of (b) Local contamination by PCBs (area of few hundreds of meters) due to human activities on scientific stations (c) Local focusing of OCs, due to biotic activities (excrement, eggs, carcasses). These activities are responsible for the transport of OCs to the Antarctic environment via migratory birds birds Different directions of air-soil fluxes for the OCs confirm those suggestions. It is shown that soils are far from the equilibrium with the atmosphere They have been equilibrium with the atmosphere. They have been “oversupplied” with the chemicals and have lost considerable quantities by evaporation. q y p

Seawater-sediment exchange By analogy with soil-air equilibrium, seawater-sediment equilibrium is indicated by fugacity fraction = 0.5. Net desorption from sediments and deposition of dissolved OCs are indicated by fugacity fractions > 0.5 d <0 5 and <0.5

Data from Montone et al, 2001 Data from Bondar et al, 2000

PCB-138 PCB-153 PCB-110

γ-HCH

HCB PCB 110 PCB-101 PCB-44 p,p'-DDE

γ HCH

0 0 0 5 1 0

PCB-52 PCB-18

0.0 0.5 1.0

p,p'-DDT

0.0 0.5 1.0

Fugacity fraction Fugicity fraction

Final sinks for OCs in Antarctic environment

• Soil, snow-firn-ice cover, shelf sediments and burial in

deep ocean waters are possible main final sinks for OCs in Antarctic environment. Antarctic environment.

• The amounts of OCs deposited on Antarctic continent

during 1980 – 2006 (4.2 t DDTs, 14.5 t HCHs) were estimated using above CS - year relationships and mean annually snow accumulation (2.01015 kg yr-1), or using last value, their levels in air and the snow/air partition last value, their levels in air and the snow/air partition coefficients (7.3 t DDTs, 87 t HCHs, 6 t PCBs and 54 kg HCB).

• The Weddell and Ross Seas in Southern Ocean represent

main deep-water formation sites of the world ocean. Estimated mean OCs total fluxes associated with the Estimated mean OCs total fluxes associated with the formation of deep oceanic waters in the seas are: 1.5 t yr-1 DDTs, 74 t yr-1 HCHs, 21 t yr-1 HCB, 3 t yr-1 CHLs and 7 t yr-1 PCBs.

Relation of climate change in Western Antarctic Peninsula to the release of OCs from retreated glaciers the release of OCs from retreated glaciers

• Weather records in the Antarctic Peninsula indicate a 2.5
• C warming trend in mean annual air temperature over

g p the last 50 years. For example, on Faraday (Vernadsky) station this warming record is + 5.7±2.0 oC 100 a-1, mainly due to winter warming (+ 11±9.0 oC 100 a-1). Each degree g ( ) g

• f warming will result in a snow-accumulation rate of 12.5

mm year-1. One expected effect of global warming is therefore increased atmospheric cycling of OCs. therefore increased atmospheric cycling of OCs.

• Melting of glaciers under current global warming is to be

essential source of OCs secondary emission into the aquatic ecosystems aquatic ecosystems.

• Upper limits for total amounts of the POPs released from

glaciers into coastal waters of Antarctic Peninsula during 1980 2030 0 8 DDT 0 3 PCB d 4 5 1980 – 2030 years are: 0.8 t DDTs, 0.3 t PCBs and 4.5 t HCHs.

Conclusions

• The temporal variations of OCs in Antarctica are

inconsistent with “second sources” scenario for global fractionation of OCs fractionation of OCs

• The air/seawater and air/snow fluxes indicate on net

deposition of OCs from air to these mediums near the eq ilibri m at present equilibrium at present

• The fugacity fractions for air/soil and seawater/sediment

exchanges of OCs testify that most soils and sediments are g y contaminated from local sources of OCs due to human activities and biotic activities of seabirds, or this is consequence of the “global distillation” for OCs in q g Antarctica

• The firn-ice cover in Antarctica and burial in deep waters of

Ross and Weddell Seas are to be important final sinks for Ross and Weddell Seas are to be important final sinks for OCs

• Melting of glaciers of Antarctic Peninsula under current and

f t l b l i i t b ti l f OC future global warming is to be essential source of OCs secondary emission into the aquatic ecosystems

My acknowledgments: My acknowledgments:

S i d T h l C t i Uk i ( j t #2196)

• Science and Technology Center in Ukraine (project #2196)
• Ukrainian Antarctic Center of MES
• US National Science Foundation Office (COBASE programs)

( p g )

• Max-Planck Institute for Aeronomy, Germany
• Kent State University, OH, US
• CNRS Laboratoire de Glaciologie et Geophysique de
• CNRS, Laboratoire de Glaciologie et Geophysique de

l’Environnement, France

• Center for Atmospheric Sciences, Cambridge University, UK
• Robert Scott Polar Institute, Cambridge University, UK