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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.
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
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
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