AN OVERVIEW OF ATMOSPHERIC VERSUS AN OVERVIEW OF ATMOSPHERIC VERSUS PARTICULATE MATTER FLUXES OF MAJOR PARTICULATE MATTER FLUXES OF MAJOR AND TRACE METALS IN THE BLACK SEAAND TRACE METALS IN THE BLACK SEA

Department of Department of ChemistryChemistryUniversity of CreteUniversity of Crete

Theodosi C.Theodosi C.11, Stavrakakis S., Stavrakakis S.22, Koulaki F., Koulaki F.11, Stavrakaki , Stavrakaki I.I.22, Moncheva S., Moncheva S.33, Papathanasiou E., Papathanasiou E.22, Sanchez-Vidal , Sanchez-Vidal

A.A.44, Koçak M., Koçak M.55 and and Mihalopoulos, N.Mihalopoulos, N.11

Environmental Environmental Chemical Processes Chemical Processes

LaboratoryLaboratory

Hellenic Centre for Marine ResearchHellenic Centre for Marine Research

Institute of Oceanology Institute of Oceanology – – BAS, VarnaBAS, Varna

11 Environmental Chemical Processes Laboratory, Department of Chemistry, Environmental Chemical Processes Laboratory, Department of Chemistry, University of Crete, 71003 Voutes, Heraklion, Crete, GreeceUniversity of Crete, 71003 Voutes, Heraklion, Crete, Greece

22 Hellenic Centre for Marine Research, Institute of Oceanography, Hellenic Centre for Marine Research, Institute of Oceanography, Anavyssos, GreeceAnavyssos, Greece

33 Ins Institute of Oceanology, BAS Parvi Mai str. No 40 Varna, 9000 Bulgariatitute of Oceanology, BAS Parvi Mai str. No 40 Varna, 9000 Bulgaria44 GRC Geociències Marines, Universitat de Barcelona, Spain GRC Geociències Marines, Universitat de Barcelona, Spain

55 Institute of Marine Sciences, Middle East Technical University, Erdemli- Institute of Marine Sciences, Middle East Technical University, Erdemli-Mersin, TurkeyMersin, Turkey

Sediment matter

supply of bioavailable nutrients to surface

waters and in marine biological productivityAtmospheric

deposition is of particular

interest for marine

productivity. How much ?

Atmospheric inputsTrace metals, Ν, Ρ, dust ...

especially for oligotrophic

oceanic areas and semi-

enclosed seas, such as the

Mediterranean

Link between atmospheric deposition

and seawater?

AimAim

Establishing a reliable quantitative budget of major Establishing a reliable quantitative budget of major and trace metals in the Black Sea. and trace metals in the Black Sea.

How significant is atmospheric deposition for How significant is atmospheric deposition for seawater productivity in the Black Sea?seawater productivity in the Black Sea?

Is there any link between atmosphere and sea-water?Is there any link between atmosphere and sea-water?

Sediment Traps Sediment Traps Atmospheric Atmospheric DepositionDeposition

Sediment Traps SamplesSediment Traps SamplesIn the Southern Southern Western Black SeaWestern Black Sea, sediment traps were deployed during the period October 2007 to December 2008. The sediment traps samplers were moored in the Southern Western Black Sea at at

two depths (two depths (930m and 1930m930m and 1930m)) using two time-series sediment traps (Technicap PPS3/3)

SAMPLING SITESSAMPLING SITES

Sediment trap sampler 12 cylinders in circular order

(collection surface 0,125m2) The samples were collected on a two – week basis.

Atmospheric deposition samples were collected at the Institute of Oceanology in Varna situated on the northern edge of the on the northern edge of the

Bulgarian side of the Black Sea CoastBulgarian side of the Black Sea Coast. The samples were collected on a monthly sampling interval

from March 2008 to April 2009.

SAMPLING SITESSAMPLING SITES

Atmospheric Deposition Collector

Atmospheric Deposition SamplesAtmospheric Deposition Samples

Technique described by Markaki et al., 2008

A Gent-type PM10 stacked filter unit (SFU) sampler was used to collect atmospheric particles in two size ranges namely, coarse (10 μm>Da>2.5 μm) and fine (Da<2.5 μm) at a rural sampling at a rural sampling site situated at Sinop Universitysite situated at Sinop University. The sampling campaign was

commenced in April 2009 and ended in December 2009.

SAMPLING SITESSAMPLING SITES

Genk type filter unit

Atmospheric Deposition SamplesAtmospheric Deposition Samples

During this period, a total of 516 aerosol filters (256 daily coarse and fine samples) were collected with a

temporal resolution of 24 h.

What is the role of atmospheric deposition

in the surface waters and the water column?

?

By comparing By comparing Varna deposition data Varna deposition data with results from with results from aerosol aerosol observations at Sinop observations at Sinop Varna is representativeVarna is representative

A covariation between all the measured species is clearly A covariation between all the measured species is clearly evidentevident

Significant correlations (p <0.01)Significant correlations (p <0.01) : crustal (Al, Fe, Ca, Mn), : crustal (Al, Fe, Ca, Mn), anthropogenic (Pb, Cr, V, Ni) or even mixed (Cu, Zn) anthropogenic (Pb, Cr, V, Ni) or even mixed (Cu, Zn) similar similar

seasonal variabilityseasonal variability common mechanism of transport common mechanism of transport

Atmospheric fluxes for the atmospheric mass and the studied

elements in Varna and Sinop

ATMOSPHERE: ATMOSPHERE: METALSMETALS

Mass/10

00Al/

50Ca

/20 V*10 Cr Mn

Fe/20 Ni Cu

Zn/10

Cd*20 Pb

0.000

0.005

0.010

0.015

0.020

Flux

(mg

m-2 d

-1)

Sinop Varna

a

0.0

0.3

0.6

0.9

1.2

1.5

1.8

Al,

Pb*1

00 (

mg

m-2 d

-1)

Atm

osph

eric

Mas

s Fl

ux (

mg

m-2

d-1) Al

b Atmospheric Mass Flux

0

10

20

30

40

50

60 Pb *100

Seasonal variations of Al, Pb and atmospheric mass in Varna

SEAWATERSEAWATER

0

50

100

150

200

250

300

350

400

CC (m

g m

-2 d-1

)

Parti

cula

te M

atte

r Flu

x 93

0m (m

g m

-2 d-1

)

Particulate Matter Flux (930m) CC (930m)

a

0

25

50

75

100

125

150

175

200

0

50

100

150

200

250

300

350

400

CC (m

g m

-2 d-1

)

Parti

cula

te M

atte

r Flu

x 19

30m

(mg

m-2

d-1)

Particulate Matter Flux (1930m)b CC (1930m)

0

25

50

75

100

125

150

175

200

Time series of particulate matter flux and at both depths (930 and 1930m) in mg m-2 d-1

Seasonal patternSeasonal pattern: : Lower fluxesLower fluxes occurred from occurred from January January to Marchto March

Both depthsBoth depths

% OC :% OC : 10% 10%% Carbonates :% Carbonates : 21% of the total mass 21% of the total mass% Lithogenic Matter:% Lithogenic Matter: 31-34%, using Al, Fe as a crustal 31-34%, using Al, Fe as a crustal tracertracer

Higher fluxesHigher fluxes from from October to November October to November and Mayand May

0

10

20

30

40

50

V (m

g m

-2 d-1

)

OC

, EC

(m

g m

-2 d-1

)

OC (930m) EC (930m) V (930m)

0.000

0.003

0.006

0.009

0.012

0.015

0.018

a

SEAWATER: PARTICULATE MATTER - SEAWATER: PARTICULATE MATTER - CARBONCARBON

0

50

100

150

200

250

300

350

400

CC (m

g m

-2 d-1

)

Parti

cula

te M

atte

r Flu

x 93

0m (m

g m

-2 d-1

)

Particulate Matter Flux (930m) CC (930m)

a

0

25

50

75

100

125

150

175

200

OC – Particulate matter same maxima (3) OC – Particulate matter same maxima (3) connection connection between particulate matter max and phytoplankton blooms between particulate matter max and phytoplankton blooms produces aggregates and sweeps from the surface both produces aggregates and sweeps from the surface both lithogenic and anthropogenic elements transported rapidly to lithogenic and anthropogenic elements transported rapidly to the deepthe deep

OC, CC max May coccoliths coccoliths bloombloom

OC max Autumn dinoflagellates bloom dinoflagellates bloom low low

contribution in CCcontribution in CC

CC, consisting of coccoliths within fecal pellets, are the CC, consisting of coccoliths within fecal pellets, are the dominant component almost 75% of the particulate matter dominant component almost 75% of the particulate matter fluxes as also observed by Hay et al. (1990). fluxes as also observed by Hay et al. (1990).

SEAWATER: PARTICULATE MATTER - SEAWATER: PARTICULATE MATTER - CARBONCARBON

Cross Correlation Factor (CCF) between particulate matter flux Cross Correlation Factor (CCF) between particulate matter flux at both traps shows the highest correlation coefficient at lag 1 at both traps shows the highest correlation coefficient at lag 1 transport time from surface down to the first sediment trap transport time from surface down to the first sediment trap

within 2 weekswithin 2 weeks good correspondence between atmospheric deposition and good correspondence between atmospheric deposition and

sediment traps materialsediment traps material

0

10

20

30

40

50

V (m

g m

-2 d-1

)

OC

, EC

(m

g m

-2 d-1

)

OC (930m) EC (930m) V (930m)

0.000

0.003

0.006

0.009

0.012

0.015

0.018

a

EC maxEC max during during latelate spring and spring and autumn autumn

Biomass burning Biomass burning events occur events occur around Black Sea region around Black Sea region in in

spring and summerspring and summer

By using as tracers By using as tracers V/ECV/EC biomass biomass

burningburning

The association of EC with combustion material such as V The association of EC with combustion material such as V indicates also significant contribution from burning indicates also significant contribution from burning

activitiesactivities

Seasonal Seasonal variation of variation of

biomass burning biomass burning sources around E. sources around E.

MediterraneanMediterranean

Bio

mas

s bu

rnin

g ae

roso

lB

iom

ass

burn

ing

aero

sol

SEAWATER: METALSSEAWATER: METALS

Removal occurs largely by Removal occurs largely by incorporation into larger incorporation into larger sinking “marine snow” sinking “marine snow”

aggregates and fecal pellets aggregates and fecal pellets during sporadic intense during sporadic intense

plankton bloomsplankton blooms

All maxima of major and trace metals fluxes were All maxima of major and trace metals fluxes were associated to OC and particulate matter fluxes associated to OC and particulate matter fluxes

corroborating the above hypothesiscorroborating the above hypothesis

Lithogenic material contributes 31-34% of the Lithogenic material contributes 31-34% of the particulate matter flux at both depthsparticulate matter flux at both depths

0

50

100

150

200

Pb 9

30m

(mg

m-2 d

-1)

Lith

ogen

ic M

atte

r 930

m (m

g m

-2 d

-1) Lithogenic Matter (930m)

Pb (930m)

0.00

0.02

0.04

0.06

0.08

0.10

b

Chemical composition measurements revealed that Chemical composition measurements revealed that these these mass peaks at 930mass peaks at 930 mm are due to are due to both

lithogeniclithogenic and and anthropogenic influenceanthropogenic influence

SEAWATER: METALSSEAWATER: METALS

two in spring two in spring (63% March 2008, 51% (63% March 2008, 51%

May 2008) May 2008)

Lithogenic material at the shallow trap presents 3 Lithogenic material at the shallow trap presents 3 maxima if the mass ratio is consideredmaxima if the mass ratio is considered

These maxima occur simultaneously with the These maxima occur simultaneously with the phytoplanktonic bloom, phytoplanktonic bloom, spring and autumn spring and autumn is the is the typical season for typical season for Sahara dust outbreaksSahara dust outbreaks, which , which

reached the Black Seareached the Black SeaLithogenic contribution Lithogenic contribution min during summer (12-min during summer (12-

22%) 22%) during the coccoliths bloomduring the coccoliths bloom

0

50

100

150

200

Lith

ogen

ic 9

30m

(m

g g-1

)

Lith

ogen

ic 9

30m

(m

g m

-2 d-1

)

mg m-2 d-1 mg g-1

d

0

100

200

300

400

500

600

700

one in autumn one in autumn (62% September 2008)(62% September 2008)

ATMOSPHERIC VERSUS VERTICAL ATMOSPHERIC VERSUS VERTICAL FLUXESFLUXESLithogenic matter major component of particle fluxesLithogenic matter major component of particle fluxes

For For Al, V, Cr, Fe, Mn, Cu, Pb Al, V, Cr, Fe, Mn, Cu, Pb atmospheric deposition provides atmospheric deposition provides quantitatively quantitatively > ¼ > ¼ amount of metals collected by the sediment amount of metals collected by the sediment

For For Cd, Ni and partly Zn Cd, Ni and partly Zn atmospheric deposition is also a atmospheric deposition is also a significant external source contributing significant external source contributing at least 10 and 40%at least 10 and 40%

Hence, atmospheric deposition provides a sufficient amount of Hence, atmospheric deposition provides a sufficient amount of metals to the seawater of the Black Seametals to the seawater of the Black Sea

Dust from atmospheric deposition Dust from atmospheric deposition 25-77% 25-77% of dust in the of dust in the water water

column column of the Black Seaof the Black Sea

Atmospheric inputs of mass 19-Atmospheric inputs of mass 19-29% 29% of the particulate matter of the particulate matter in in sediment traps sediment traps in the Black Seain the Black Sea

0

20

40

60

80

100 177%

%

930m 1930m 144%

CONCLUSIONCONCLUSIONBLACK SEABLACK SEA

• Seawater:Seawater: Significant correlation between Significant correlation between particulate matter, OC and lithogenic material particulate matter, OC and lithogenic material

removal occurs largely by incorporation into removal occurs largely by incorporation into larger sinking “marine snow” aggregates and larger sinking “marine snow” aggregates and fecal pellets during sporadic intense plankton fecal pellets during sporadic intense plankton

bloombloom

• Atmosphere:Atmosphere: Atmospheric deposition Atmospheric deposition presents an important seasonal variability presents an important seasonal variability

driven by meteorology, especially air masses driven by meteorology, especially air masses origin and precipitationorigin and precipitation

This study reports on the chemical This study reports on the chemical composition of atmospheric deposition and composition of atmospheric deposition and

sediment trap samples collected in the Black sediment trap samples collected in the Black SeaSea

CONCLUSIONCONCLUSIONBLACK SEABLACK SEA

• By comparing atmospheric deposition fluxes of By comparing atmospheric deposition fluxes of metals with data from sediment trapsmetals with data from sediment traps

the significant role of the atmosphere as an the significant role of the atmosphere as an external source external source of major and trace metals to the of major and trace metals to the

Black Sea has Black Sea has been demonstrated been demonstrated

•Thus atmospheric deposition should be thus Thus atmospheric deposition should be thus taken into account in biogeochemical modelstaken into account in biogeochemical models

Thank you for your attentionThank you for your attention

Inductively Coupled Plasma Mass Spectrometry (X-Series)

ANALYSISANALYSIS

Atmospheric Deposition Samples and Sediment trap filters

were analyzed for major and trace metals major and trace metals

Al, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Cd and PbAl, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Cd and Pbusing acid microwave digestion procedure followed by ICP-MS (Theodosi et al., 2010)

ANALYSISANALYSIS All filters were pre- and post-weighed using a 5-

digit microbalance (KERN ABT 120-5DM)

Sediment trap filtersSediment trap filters from the South Western Black Sea

were analyzed for Organic and Elemental Carbon (OC and EC)Organic and Elemental Carbon (OC and EC)

using Sunset Laboratory OC/EC Analyzer and the Thermal-Optical Transmission technique (Koulouri

et al., 2008)

Thermal/Optical Carbon analyser

SEAWATER: PARTICULATE MATTER - SEAWATER: PARTICULATE MATTER - CARBONCARBON

Particulate matter flux : Particulate matter flux : a minimum peak during a minimum peak during winterwinter and

0

50

100

150

200

250

300

350

400

CC (m

g m

-2 d-1

)

Parti

cula

te M

atte

r Flu

x 93

0m (m

g m

-2 d-1

)

Particulate Matter Flux (930m) CC (930m)

a

0

25

50

75

100

125

150

175

200

0

50

100

150

200

250

300

350

400

CC (m

g m

-2 d-1

)

Parti

cula

te M

atte

r Flu

x 19

30m

(mg

m-2

d-1)

Particulate Matter Flux (1930m)b CC (1930m)

0

25

50

75

100

125

150

175

200

Time series of particulate matter flux and at both depths (930 and 1930m) in mg m-2 d-1

Both observed levels and the seasonal variation are in Both observed levels and the seasonal variation are in agreement with previous studies in the area (Hay et agreement with previous studies in the area (Hay et al., 1990; Muramoto et al., 1991; Osawa et al., 2005)al., 1990; Muramoto et al., 1991; Osawa et al., 2005)

3 maxima3 maxima,, two in two in autumn autumn (October and November) and (October and November) and one in one in springspring