Journal of Marine Systems 25 2000.

269286
www.elsevier.nlrlocaterjmarsys

Mass balance of trace metals in the Adriatic Sea

a,),1, N.B. Price b,2 , P.J. Statham a,3
S.P.C. Tankere
a
School of Ocean and Earth Science, Uniersity of Southampton, Southampton Oceanography Centre, Southampton SO14 3ZH, UK
b
Grant Institute, Department of Geology and Geophysics, Uniersity of Edinburgh, Edinburgh EH9 3JW, UK
Received 15 December 1998; accepted 30 April 1999

Abstract

A first order mass balance of six different trace metals Mn, Fe, Pb, Zn, Cu, Ni. was presented for a 1-year period for the
different compartments of the Adriatic Sea: compartment 1 northern Adriatic Sea., compartment 2 central Adriatic Sea and
surface layer of the southern Adriatic Sea. and compartment 3 deep water of the southern Adriatic Sea.. The Adriatic Sea
appeared to be a source of dissolved Cu, Mn and Fe for the Mediterranean Sea through the Strait of Otranto whereas for
dissolved Zn and Pb the Adriatic Sea appeared to be a net sink. For dissolved Ni, inputs and outputs through the Strait of
Otranto balanced each other. The residence times of all metals in compartment 1 were significantly shorter than that of water
indicating significant removal. In compartments 2 and 3, residence times of Mn and Fe were relatively short suggesting
removal from the water column whereas for the other metals their residence times were similar to that of water. Calculations
of turnover times of metals with respect to different processes showed that in compartments 1 and 2, sedimentation was the
main process that affected the content of the reservoirs whereas in compartment 3, the water flux exchanges played an
important role for Zn, Cu and Ni.
Most of the metals clearly undergo a very dynamic cycle of sedimentationrremobilization particularly in the Northern
Adriatic Sea. In the northern Adriatic Sea, most of the Mn and Fe in deposited sediment were remobilized. This was related
to diagenetic processes involving the utilisation and solubilisation of Mn and Fe oxides, which occur in the surface of the
sediment in the northern Adriatic Sea. In the central Adriatic Sea, remobilization of Mn and Fe was less than in the northern
Adriatic Sea, suggesting that diagenesis processes appear deeper in the sediment. Advective transport of sediment was a
major source of metals for the deep basin. As much as 80% of the sediments in the South Adriatic Pit might be advected
from the shelf. Remobilization fluxes in the South Adriatic Pit were significantly less than in the Northern and Central
Adriatic Sea reflecting hemi-pelagic sediments. q 2000 Elsevier Science B.V. All rights reserved.

Keywords: Adriatic Sea; mass balance; trace metals

)
1. Introduction
Corresponding author. Institutt for Mikrobiologi, Jahnebakken
5, Postboks 7800, 5020 Bergen, Norway.
E-mail addresses: sophie.muller@im.uib.no S.P.C. Tankere ., In this paper, cycling of some trace metals Mn,
brian.price@ed.ac.uk N.B. Price., Fe, Pb, Zn, Cu and Ni. have been considered in a
peter.j.statham@soc.soton.ac.uk P.J. Statham..
1
Fax: q47-55589671.
semi-enclosed sea, the Adriatic Sea. Fig. 1 shows the
2
Fax: q44-131-668-3184. different cycling and transport processes, which oc-
3
Fax: q44-2380-593-059. cur in the cycle of trace metals in the Adriatic Sea.

0924-7963r00r$ - see front matter q 2000 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 4 - 7 9 6 3 0 0 . 0 0 0 2 1 - X
270 et al.r Journal of Marine Systems 25 (2000) 269286
S.P.C. Tankere
Fig. 1. Cycling and transport processes that occur in the cycle of trace metals in the Adriatic Sea.
The continental shelf and the margin represent ca.
70% of the Adriatic surface sediments. These areas
receive important amounts of material mainly sup-
plied by rivers. During the period 19561973 the
average total sediment transport of the Po averaged
13.7 = 10 6 tryear Price et al., 1996a.. Shelf waters
also receive dissolved inputs from rivers, in which
trace metal concentrations are generally higher than
in coastal water. The impact on biota, as well as the
actual flux to the open sea of these inputs, will be
controlled by their fate during estuarine mixing.
Other factors such as benthic remobilization and
eolian inputs may also be important in determining
the distribution of trace metals in shelf waters.
Cycling of metals through the coastal zone has a
fundamental impact on the geochemical balance of
the open sea Bethoux et al., 1990.. Consequently, a
thorough understanding of the factors regulating the
transfer of metals between the different compart-
ments water masses, atm osphere, rivers,
sediments . . . etc.. in the Adriatic Sea is therefore
needed. In this paper, we present an attempt at a first
order mass balance of metals Mn, Fe, Pb, Cu, Ni,
Zn. in the semi-enclosed Adriatic Sea following the
study of their distribution during the EURO-
MARGE-AS Project Tankere and Statham, 1996;
Price et al., 1996b..
2. Methods
Samples for dissolved and particulate metals Mn,
Fe, Pb, Zn, Cu and Ni. were collected in JuneJuly
1994, at Stations 1, 2, 3, 4, 5 and 10 on board the
R.V. Urania, and in May 1994, September 1994 and
February 1995, at Stations 1, 2, 3 on board the R.V.
Daphne II. The sampling locations are shown on Fig.
2.
Concentrations of dissolved and particulate metals
were determined in seawater using sampling and
analytical procedures described previously by
and Statham 1996. and Price et al., 1996b..
Tankere
Samples for salinity measurements were collected
into glass bottles. Salinity was determined using a
Guildline Autosal salinometer. Information on salin-
 et al.r Journal of Marine Systems 25 (2000) 269286
S.P.C. Tankere 271

ima at 150-m depth at Stations 5 and 10 in winter

also suggest a greater importation of Mixed Levan-
tine Intermediate Water through the Strait of Otranto
in winter than in summer.
The Adriatic Sea can be represented by a three-
compartment box model Fig. 4.. Compartment 1
represents the continental margin of the northern
Adriatic Sea from the Gulf of Trieste to the Jabuka
Pit. Two compartments represent the southern Adri-
atic Sea: One for the surface layer 0100 m. com-
partment 2. and one for the deep water 1001100
m. compartment 3.. The central Adriatic Sea was
included in compartment 2 as the hydrographic prop-
erties were similar to the southern Adriatic surface
water Fig. 3.. Compartments were defined by physi-
cal and hydrographic characteristics, so that each
compartment can be considered as reasonably ho-
mogenous. For the purpose of modelling the bio-
Fig. 2. Topography of the Adriatic Sea and sampling locations.

ity, temperature, dissolved oxygen, pH and Chl a

was also obtained using a CTD system at each
station.

2.1. A simple box model for the Adriatic Sea

Fig. 3 presents some interesting hydrographic data

in the different parts of the Adriatic Sea in winter
and summer seasons. Temperature and salinity distri-
bution patterns below the Po river outflow were
affected by the freshwater inputs to a decreasing
extent southwards and vertically towards the bottom
Stations 1, 2 and 3; Fig. 3.. During summer period,
the water column was strongly stratified due to
atmospheric heating: thermoclines and haloclines
were well defined. The Northern Adriatic basin
showed typical shallow water mass characteristics
which could be considered independent of the Mid-
dle and Southern basins as they were more affected
by seasonal temperature and salinity variability. At
Stations 4, 10 and 5, salinity in surface waters was
significantly lower in summer than in winter suggest-
ing a prevailing influence of freshwater inputs com-
Fig. 3. CTD data for temperature and salinity in the Adriatic Sea
ing from the northern part in summer and a prevail- in winter and summer seasons; data for Stations 1, 2 and 3 have
ing influence of Surface Ionian Water through the been collected in June 1994 and February 1995; data for Stations
Strait of Otranto in winter. The higher salinity max- 4, 5 and 10 have been collected in February 1994 and June 1994.
272 et al.r Journal of Marine Systems 25 (2000) 269286
S.P.C. Tankere
Fig. 4. A simple box model for the Adriatic Sea.
chemical cycle of trace metals, the euphotic zone
was defined as the upper 100-m layer.
Compartments receive and lose trace metals in
different ways listed below; Fig. 4..
- Atmospheric inputs At 1 and At 2 .: there is dry
deposition elements are associated to aerosols. and
there is wet deposition trace metals are in dissolved
or particulate phases..
- Riverine inputs Rv1 and Rv2 . are in dissolved
and particulate phases.
- Dissolved and particulate trace metals are trans-
ported with water mass exchanges between the dif-
ferent compartments. Water mass exchanges take
place between compartment 1 and compartment 2
due to horizontal advection. There is a general clock-
wise circulation; along the east coast, the surface
water from compartment 2 is entering compartment
1 water flux V1 .; along the west coast, the water
from compartment 1, is entering compartment 2
V2 .. In the Strait of Otranto, exchanges take place
in the surface layer between the Ionian Sea and
compartment 2. On the east side of the Strait, surface
water from the Ionian Sea enters the Adriatic Sea
V3 .; on the west side of the Strait, surface water
hugging the Italian coast exits the Adriatic Sea V4 ..
Deeper in the water column compartment 3. there is
exchange of water masses and associated trace met-
als with the Ionian Sea. An ingress of Mixed Levan-
tine Intermediate Water V5 . and Ionian Intermediate
Water V6 . into the Adriatic Sea is counterbalanced
by an export of South Adriatic Water V7 . leaving
the Adriatric Sea along the bottom and an export of
Intermediate Adriatic Water V8 .. There are also
exchanges between the surface layer compartment
2. and the deep layer compartment 3.; further,
dynamic processes such as upwelling V10 . and
downwelling V9 . also result in transport of trace
metals between the 2 compartments. During the win-
ter period, the formation of dense water along the
West Coast produces downwellings Lascaratos,
1993..
- There is a downward flux of particles P X .
between compartments 2 and 3, which result from
sedimentation. These particles may be detrital or
biogenic in origin. There are sedimentation fluxes in
each compartment representing settling of particles
on the bottom.
- In each compartment there is, additionally, a
remobilization flux, which is due to the diffusion of
trace metals from the pore waters into the bottom
layer.
- Advective transport of sediments Adv1 and
Adv2 . can be a major source of metals for compart-
ments 2 and 3, respectively.
 et al.r Journal of Marine Systems 25 (2000) 269286
S.P.C. Tankere 273

The three compartments of the Adriatic were If we apply this concept to the Adriatic Sea model
assumed to be in steady state and coupled, conse- Fig. 4., the dynamic behaviour of the system is
quently remobilization fluxes from sediments can be governed by the three differential equations:
calculated by difference when all other fluxes have
been estimated. The parameters used were the dis- d M1
s yV2 C1 q C1X . q V1 C2 q C2X .
solved and particulate metal concentrations in the dt
different reservoirs, the fluxes of water between the
q At 1 q Rv1 q R 1 y Sd 1
reservoirs and the input and output fluxes of the
elements at the boundaries. d M2
This type of model provides a steady-state de- s V2 C1 q C1X . y V1 C2 q C2X . q V10 C3
dt
scription of fluxes, reservoir contents and turnover
times. It gives a basis for quantitative modelling and y V9 C2 y P X C2X q V3 C Is q CXIs .
it helps to estimate the relative magnitudes of fluxes.
y V4 C2X q C2 . q At 2

2.2. Equations q Rv2 q R 2 q Adv1 y Sd 2

d M3
The equation describing the rate of change of s V9 C2 q P X C2X y V10 C3 q V5 C Lv q CXLv .
dt
mass within a reservoir can be written as:
q V6 C Id q CXId . y V8 C3 q C3X .
dM
sQyS y V7 C3 q C3X . q R 3 q Adv2 y Sd 3
dt
d Mrdt is the variation of mass of metal within of
the reservoir; Q represents the sources flux of metal
C1 , C2 , C3 , C Is , C Lv , C Id are the dissolved trace
into the reservoir.; S represents the sinks flux of
metal concentrations for compartments 1, 2 and 3,
metal out of the reservoir..
for the Ionian Sea surface layer, the Levantine
The working assumption is that the three compart-
Intermediate water and for the Ionian Sea deep
ments are coupled and are in a steady state, that is to
water.
say: d Mrdt s 0. Consequently sources Q . and sinks
C1X , C2X , C3X , CXIs , CXLv , CXId are the particulate trace
S . must balance in out each compartment. Metal
metal concentrations for compartments 1, 2 and 3,
fluxes between compartments are proportional to
for the Ionian Sea surface layer, the Levantine
chemical concentrations in the compartment where
Intermediate water and for the Ionian Sea deep
they originate. The flux Fi j from reservoir i to
water.
reservoir j is given by:
Vi is a water flux i s 1,10., see Section 2.1 for
Fi j s Vi j Ci description
P X is the mass flux of particles between compart-
where Vi j represents the water flux from reservoir i ments 2 and 3
to reservoir j and Ci represents the metal concentra- At 1 and At 2 : atmospheric inputs in compartments
tion in the reservoir i. 1 and 2
The rate of change of the mass of metal Mi . in Rv1 and Rv2 : riverine inputs in compartments 1
the reservoir i is thus: and 2
R 1 , R 2 and R 3 : remobilization in compartments
d Mi 1, 2 and 3, respectively
s Vi j CM j y CM i Vi j for i / j
dt js1, n js1, n Sd 1 , Sd 2 and Sd 3 : sedimentation in compartments
1, 2 and 3, respectively
where n is the total number of reservoirs in the Adv1 and Adv2 : advective transport of sediments
system. from compartments 1 and 2, respectively.
274 et al.r Journal of Marine Systems 25 (2000) 269286
S.P.C. Tankere
3. Estimation of water fluxes
A quantitative estimation of the mean water fluxes
in the Adriatic Sea is proposed, on the basis of the
water and salt mass balances for each compartment
Bethoux, 1980..
On the basis of the water and salt mass balances,
it is possible to write the following equations:
Water mass balance for compartment 1:
V1 y V2 y EP . 1 s 0
Salt mass balance for compartment 1:
r 2 S2 V2 s r 1 S1V1
Water mass balance for compartment 2:
V2 y V1 q V3 y V4 q V10 y V9 y E y P . 2 s 0
Salt mass balance for compartment 2:
r 3 S3V3 y r4 S4 V4 q r 10 S10 V10 y r 9 S9V9
q r 2 S2 V2 y r 1 S1V1 s 0
Water mass balance for compartment 3:
V5 q V6 y V7 y V8 q V9 y V10 s 0
Salt mass balance for compartment 3:
r 9 S9V9 y r 10 S10 V10 q r 5 S5V5 q r6 S6 V6
y r 7 S 7 V 7 y r 8 S8 V8 s 0
Water mass balance for the entire Adriatic Sea:
V4 q V7 q V8 s To total outflow.
V3 q V5 q V6 s Ti total inflow.
Ti y To y EP . 1 y EP . 2 s 0
In order to determine the fluxes, observed salinity
Si , i s 1,10. and density r i , i s 1,10. values have
been introduced into the mass balance equations.
Bethoux 1980. also estimated the water deficits
EP . where E s evaporation and P s precipita-
tion and runoff. in the different surface compart-
ments of the Adriatic Sea. The northern part of the
Adriatic Sea compartment 1. had a positive water
budget EP .1 s y3 km3ryear., loss by evapora-
tion E . being slightly less than river influx and
precipitation P . whereas the southern part of the
Adriatic compartment 2. had a negative budget
EP . 2 s 21 km3ryear..
The value of V2 was obtained from Mosetti et al.
1996., while V3 , V5 , V7 , Ti and To were obtained
from Poulain et al. 1996.. However, the results
given by Poulain et al. 1996. for total outflow and
total inflow in the Strait of Otranto did not fit the
1. water budget for the entire Adriatic Sea Eq. 9., total
outflow being significantly different from total in-
flow. This difference might have been due to low
2. spatial resolution of current meters and consequently
some recirculation due to mesoscale eddies, occur-
ring especially in the shear zone between inflow and
outflow, might have been missed. To satisfy Eq. 9,
the net water flux through the Strait of Otranto was
3. taken equal to the water deficit EP . for the entire
Adriatic Sea, using the highest values between total
outflow and total inflow in the data given by Poulain
et al. 1996..
Once Ti and To had been estimated, their values
4. were used to calculate V4 , V6 , V8 , V9 , V10 and V1
using Eqs. 1. 8.. Results are shown in Fig. 5.
The calculated results for water fluxes required
5. data from independent measurements, each of which
was subject to a random uncertainty and each of
which contributed to the net random error of the
result. For the purpose of showing how such random
uncertainties affected the outcome of the results, the
6. sources of error affecting the individual fluxes were
assumed to be independent from each other. Calcu-
7.
8.
9.
Fig. 5. Water fluxes for AutumnrWinter and SpringrSummer
periods.
 et al.r Journal of Marine Systems 25 (2000) 269286
S.P.C. Tankere
lated standard deviations s V4 , s V 8 , s V 6 turned out to
be relatively small compared to the calculated fluxes
V4 , V8 and V6 and consequently these fluxes can be
considered as reliable. By contrast, standard devia-
tions s 10 and sv 9 were respectively exceeding V10
and V9 by several order of magnitude suggesting a
large uncertainty on the calculated fluxes V10 and V9 .
According to Lascaratos 1993., the water mass for-
mation which occurs in the Southern Adriatic Sea
during winter is 10,722 km3ryear. This number is
much higher than the value V9 . presented in Fig. 5.
Poulain et al. 1996. found that the outflow of ADW
in the deepest central portion of the Strait and on the
western continental margin was not continuous, and
appeared as a series of bursts of southward flows
lasting for about a week. They found also that these
bursts corresponded to a bottom intensified pulsation
of the entire water column. The value for water
formation V9 . represents a mean for 6 months and
consequently is compatible with the value given by
Lascaratos 1993. which is representative of a short
period of time.
4. Estimation of annual metal fluxes
4.1. Rierine inputs
4.1.1. The Rier Po
The Po River accounts for 49% of the total river-
ine inputs to the Adriatic Sea. Details about the flow
rate variations are described in Price et al. 1996a..
The Po delta is a micro-tidal estuary, which is strati-
fied. Consequently there is a short residence time of
the fresh water inputs in the mixing zone; the fresh
water being rapidly transported southward.
Dissolved and particulate metal concentrations
Mn, Co, Fe, Cu, Ni, Zn, Cd, Pb. for the river Po
have been reported in Table 1. These values repre-
sent a mean of data collected monthly during the
EUROMARGE-AS Project. Dissolved Cu, Ni and
Pb have shown conservative behaviour during mix-
ing between River Po water and Adriatic Sea water
suggesting that only dilution influences the distribu-
tion of these trace metals in the mixing between the
two end members Tankere and Statham, 1996;
1998.. Other metals Mn, Fe, Co and Zn.
Tankere,
are affected by removal processes Tankere and
275
1998.. Dissolved riverine
Statham, 1996; Tankere,
inputs have been calculated by multiplying concen-
trations in the upper reaches of the river at Ponte-
lagoscuro. by the river flow. Particulate concentra-
tions are positively correlated with the river flow
Price et al., 1996a. and consequently particulate
fluxes have been calculated by multiplying particu-
late trace metals concentrations by the river flow.
4.1.2. Total rierine inputs for the Adriatic
Such estimation was difficult because of the large
number of rivers with unknown inputs into the Adri-
atic Sea. The Po river represents 49% of the total
river inputs, with a runoff of 67.7 km3ryear Price et
al., 1996a.. The other rivers in the Northern Adriatic
Sea have an estimated runoff of 35.4 km3ryear
Zore-Armanda, 1969; Pettine et al., 1985.. Conse-
quently, the total riverine input for compartment 1
was estimated at 103.1 km3ryear. The river inputs
for compartment 2 was estimated at 36.3 km3ryear
Pettine et al., 1985..
Fluxes of trace metals for compartments 1 and 2
are reported in Table 1. To determine these fluxes
several assumptions were made: 1. Dissolved and
particulate trace metal concentrations from the Po
river were extrapolated to the other rivers. 2. Sea-
sonal variations for river flow and trace metal con-
centrations were observed Price et al., 1996a.. In
the light of these observations, two periods were
differentiated: autumnwinter and springsummer.
Trace metal concentrations were estimated for these
two periods Table 1.. The river flow was estimated
as 60% of the annual flow for the autumnwinter
period and as 40% for the springsummer period.
3. The behaviour of dissolved trace elements in the
mixing zone was taken as conservative.
4.2. Atmospheric inputs
The estimation of trace metal atmospheric fluxes
is difficult because of the variability of meteorologi-
cal conditions. The Adriatic Sea is situated between
the subtropical high-pressure zone and the mid-lati-
tude or westerlies belt, in which atmospheric distur-
bances generally move from west to east. These
zones shift throughout the year causing sharp sea-
sonal differences.
 276
S.P.C. Tankere
et al.r Journal of Marine Systems 25 (2000) 269286
Table 1
Dissolved and particulate trace metal concentrations in the river Po and estimations of total riverine fluxes for compartments 1 and 2 and for the entire Adriatic Sea AS.
Dissolved trace metals Particulate trace metals
Conc. mgrl., Conc. mgrl., Flux tryear., Flux tryear., Conc. mgrl., Conc. mgrl., Flux tryear., Flux tryear., Flux
summer winter comp 1. comp 2. summer winter comp 1. comp 2. tryear.
Mn 1.41"1.28 2.75"1.84 229 80 78.7"43.0 68.7"32.0 7500 2640 10,400
Fe 2.10"1.04 2.34"0.81 232 82 2160"2000 2330"1090 233,000 82,000 316,000
Pb 0.24"0.19 0.32"0.10 30 11 8.75"6.74 5.97"4.00 730 257 1030
Zn 4.18"3.66 6.15"1.18 553 195 23.6"16.82 21.9"12.6 2330 818 3890
Cu 2.63"1.28 3.65"1.13 334 118 4.78"4.04 5.15"2.17 516 181 1150
Ni 2.80"0.66 3.06"0.52 305 107 17.1"10.2 18.6"8.1 1860 654 2920
 et al.r Journal of Marine Systems 25 (2000) 269286
S.P.C. Tankere 277

Guieu et al. 1991, 1997., Guerzoni et al. 1991.,

Nicolas et al. 1995. and Chester et al. 1993. stud-
ied total atmospheric trace metal deposition in the
Western Mediterranean Sea. To estimate atmospheric
inputs of the Adriatic Sea, data from Guieu et al.
1997. were used since these include information for
all the trace metals studied in the Adriatic Sea. Total
atmospheric inputs were partitioned in proportion to
the relative surface areas of compartment 1 45% of
the whole of the Adriatic. and compartment 2 55%..
Results in tryear for the Adriatic atmospheric inputs
Fig. 6. Fluxes of dissolved and particulate metals In and Out of
are presented in Table 2.
compartment 1.
These estimates were based on data collected in
the Northern Western Mediterranean Sea and on the
hypothesis that fluxes were uniform throughout the
entire Adriatic Sea. However, Guerzoni et al. 1995. mainly transported in the particulate phase whereas
demonstrated that Saharan aerosol fluxes decrease Ni and Cu were primarily transported in the dis-
exponentially with latitude. Consequently, the esti- solved phase.
mated values may represent upper limits for trace
metals with a Saharan origin. 4.4. Trace metal fluxes through the Strait of Otranto

4.3. Trace metal fluxes between compartments 1 and First estimates of dissolved metal fluxes were
2 generated by multiplying the metal concentrations by
the appropriate water mass inflow and outflow data
Water fluxes between compartments 1 and 2 were for the Adriatic Sea in winter and summer. Since
combined with dissolved and particulate trace metal particulate trace metal data were not available for the
data obtained during the EUROMARGE-AS Project. Strait of Otranto, particulate trace metals were not
Seasonal variations were taken into account for the included in the mass balance for the Strait. However,
calculation of fluxes out of compartment 1 since a SPM was very low in this area consequently particu-
high variability in trace metal concentrations was late trace metals can be considered as a negligible
observed in the North Adriatic Sea. Fig. 6 gives fraction of the total Civitarese et al., 1998..
results for trace metal fluxes in and out of compart- For dissolved Fe and Ni, inflows and outflows
ment 1. Trace metals were exported from compart- cancel out to within 10% Fig. 7.. There is net export
ment 1 to compartment 2. Fe, Mn, Pb and Zn were of dissolved Mn and Cu out of the Adriatic Sea. For
dissolved Zn and Pb the Adriatic Sea appears to be a
net sink. This is particularly so for dissolved Zn
where the concentrations tend to be lower in the
Table 2 Adriatic Sea than in the Ionian Sea Tankere and
Atmospheric inputs for the Adriatic Sea; data extrapolated from Statham, 1996.. Dissolved Zn is probably imported
the North-Western Mediterranean Sea Guieu et al., 1997. into the system through the Strait of Otranto and is
Compartment 1 Compartment 2 Adriatic Sea trapped in the sediment. Zn is a biological reactive
tryear. tryear. tryear. element. It is taken up by phytoplankton during
Mn 1368 484 1852 blooms and transported to the sediment when the
Fe 5256 792 6048 phytoplankton dies. The trapping efficiency of the
Pb 288 220 508 Adriatic Sea towards Pb is comparable to that for Zn,
Zn 130 194 324
Cu 144 53 197
though probably not for the same reasons: Pb has no
Ni 29 44 73 known biological function but tends to adhere
strongly to the surface of particles.
278 et al.r Journal of Marine Systems 25 (2000) 269286
S.P.C. Tankere

land, 1983.. The distribution of scavenged elements

Fig. 7. Trace metal mass balance for the Adriatic Sea across the
Strait of Otranto.
4.5. Trace metal fluxes associated with upwelling
and downwelling
Vertical water fluxes were estimated in Section 3.
The winter fluxes took into accounts the water mass
formation that occurs in the Southern Adriatic Pit.
The amounts of dissolved trace metals transported by
upwelling and downwelling, expressed as yearly
fluxes, are reported in Table 3.
4.6. Down column fluxes of particulate trace metals
Trace metals are transferred from the dissolved
phase to the particulate phase through adsorption or
biological uptake depending on the type of element
and particle. Two major types of trace metals have
been defined: the nutrient type Ni, Cu, Zn and Cd.
and the scavenged type Pb, Mn, Co and Fe. Bru-
reflects boundary inputs and interactions with the
particulate phase in suspension in the water column.
In contrast, the nutrient-type distribution reflects the
involvement of the trace metals in the major biologi-
cal cycles which, in the open ocean, results in sur-
face depletion and subsurface enrichment in their
dissolved concentrations.
Heussner et al. 1995. reported some data on
downward fluxes of particles in the Southern part of
the Adriatic Station 5. obtained by a sediment trap
technique. They reported a mass flux of 0.12 kg my2
yeary1 . Particulate metal data for Mn, Fe, Cu and Ni
were available for the Southern Adriatic Sea Price
et al., 1996b.. Some data from the wider Mediter-
ranean Sea Tankere et al., 1995. were used for Pb
and Zn. These data were combined with the particle
flux data of Heussner et al. 1995. to give an esti-
mate of particulate trace metal fluxes between com-
partments 2 and 3 see Table 4..
4.7. Sedimentation
The assessment of sediment accumulation rates is
crucial to understand the role played by the sedi-
ments as marine sinks for components that have
flowed through the seawater reservoirs. Frignani and
Langone 1991. and Frignani et al. 1996. discussed
apparent accumulation rates from a series of sedi-
ment cores collected in the Po delta, in the western
side of the Adriatic continental shelf and in the
Southern Adriatic Basin Table 5a.. The sediment
accumulation rate studies were conducted using 210 Pb
and 137Cs measurements. Generally, there was a
good agreement between the accumulation rates de-
rived by the different techniques.

Table 3
Vertical exchanges of dissolved trace metals
Mn Fe Pb Zn Cu Ni
Concentrations mgrl. 0.243 0.158 0.029 0.192 0.168 0.204
in compartment 2.
Downwelling tryear. 739 480 88 584 509 620
Concentrations mgrl. 0.062 0.064 0.019 0.200 0.103 0.244
in compartment 3.
Upwelling tryear. 61 64 3 241 7 198
 et al.r Journal of Marine Systems 25 (2000) 269286
S.P.C. Tankere 279

Table 4 around 2.6 kg my2 yeary1 . In the Southern Adriatic

Estimation of particulate trace metal fluxes from compartment 2
to compartment 3 in the southern Adriatic Sea Flux of particles is
0.12 kg my2 yeary1 ; Heussner et al., 1995.
Mn Fe Pb Zn
Concentrations 180 6158 4.4 41
mgrg.
Flux try. 950 32,514 23 214
The highest accumulation rates occur near the Po
delta where the supply of sedimentary material from
the land is greatest. There the accumulation rates lie
in the range 18.0 " 2.9 to 5.3 " 0.4 kg my2 yeary1 .
A mean value 7.7 kg my2 yeary1 for the Po delta
area 10% of the total surface area. has been calcu-
lated. Accumulation rates south of the delta are
lower and fairly constant 2.9 kg my2 yeary1 .. At
Station 3, the 210 Pb and 137Cs measurements give
respectively mass accumulations of 1.2 and 1.4 kg
my2 yeary1. In the central Adriatic Sea Station 4.,
accumulation rates vary with time Frignani et al.,
1996.. The core collected at Station 4 shows a
sediment accumulation rate of 3.1 kg my2 yeary1
until 1945; after this date and up to 1965, the
accumulation rate reduces to 1.2 kg my2 yeary1 and
since this date the accumulation rate appears to be
Basin, a sediment accumulation rate of 0.6 kg my2
yeary1 has been measured using 210 Pb measure-
ments.
Cu Ni
During the previous phase of the EUROMARGE
84 31
project, a large number of cores were collected and
444 164 analysed for trace metals in the northern and central
parts of the Adriatic Sea Price et al., 1995.. The
results for surficial sediments are presented in Table
5b. Sedimentation fluxes in the different parts of the
Adriatic Sea were calculated using the metal concen-
trations in surficial sediments and sedimentation rates
described above. The results are presented in Table
6. The effects of diagenetic reactions Chester, 1990.
on surficial sediment composition were assumed to
be negligible.
4.8. Adectie transport of sediments from the shelf
Advective transport of sediments from compart-
ment 1 to compartment 2 was evident from sedimen-
tation rate measurements: sedimentation in compart-
ment 2 2.6 kg my2 yeary1 . was exceeding in situ
production and sedimentation in compartment 1 1.2
kg my2 yeary1 .. The Marine snow produced in
the Northern Adriatic waters is composed of aggre-

Table 5
a. Sedimentation rates in different parts of the Adriatic Sea; the locations of sampling are shown on Fig. 2
Station % of total Sedimentation rate
surface area kg my2 yeary1 .
1A 10 7.7
2 10 3
3 25 1.3
4 27.5 1.2
5 27.5 0.6

b. Trace metal compositions of cores total values for the first 2 mm. in different parts of the Adriatic Sea; the locations of sampling are
shown in Fig. 2
Station Mn %. Fe %. Pb mgrg. Zn mgrg. Cu mgrg. Ni mgrg.
1A 0.103 3.64 50.2 146 31.3 70.1
2A 0.087 3.84 21.8 102 30.4 81.1
6 0.131 3.61 25.5 105 21.1 62.1
8 0.087 3.65 29.3 105 26.5 63.5
10 0.327 3.19 22.6 89.1 20.2 122
5 0.158 3.71 27.7 99.6 49.4 153
280 et al.r Journal of Marine Systems 25 (2000) 269286
S.P.C. Tankere

Table 6
Fluxes of trace metals into sediments
Mn Fe Pb Zn Cu Ni
tryear. tryear. tryear. tryear. tryear. tryear.
Compartment 1 237,000 8,205,000 8560 28,300 6410 15,800
Compartment 2 99,500 4,176,000 3350 12,000 3030 7260
Compartment 3 41,700 979,000 731 2630 1300 4040
Adriatic Sea 378,000 13,360,000 12,600 43,000 10,700 27,100

gated biogenic and inorganic particles which floccu-
late and are easily resuspended when reaching the
sediment floor. The transport of this material in
deeper water is facilitated by resuspension and is
topography driven: it is transported along the Italian
coast in a southward direction. A first estimate of
this transport shows that 54% of the sediment in
compartment 2 may originate from compartment 1.
Advective transport of sediment from the shelf could
also be a major source of metals for compartment 3
since sedimentation rates obtained by 210 Pb and 137Cs
measurements in sediments were significantly higher
than the sedimentation rate obtained by sediment
trap technique. As much as 80% of the sediments in
compartment 3 may be advected from the shelf.
However, a more detailed study of the particle trans-
fer from the Northern Adriatic Sea to the South
Adriatic Pit needs to be done with sediment traps
which would allow to identify and measure the
influence of the general and local factors controlling
the particle transfer.
5. Results and discussion
A first order mass balance of 6 different trace
elements Mn, Fe, Pb, Zn, Cu and Ni. in the Adriatic
Sea is presented for a 1-year period for the different
compartments Tables 79.. Remobilization from
sediments was calculated by difference, when all
other fluxes had been estimated. Remobilization
fluxes were high in the Northern and Central Adri-
atic Sea. Although remobilization was not quantified
directly, the results of the mass balance suggest that
the process is potentially important and needs to be
assessed.
5.1. Mass balance in compartment 1
In compartment 1, trace metal inputs were from
rivers, the atmosphere and remobilization. Riverine
inputs tended to be higher than atmospheric inputs
for all metals Mn, Fe, Pb, Zn, Cu and Ni. and were
mainly associated with particles. A fraction of these

Table 7
Mass balance of trace metals in compartment 1
Phase Mn Fe Pb Zn Cu Ni
tryear. tryear. tryear. tryear. tryear. tryear.
Riverine inputs Dissolved 229 232 30 553 334 305
Particulate 7500 233,000 730 2330 516 1858
Atmospheric inputs Total 1368 5256 288 130 144 29
Exchanges between Dissolved y1193 y180 y31 y250 y155 y121
compartments 1 and 2
Particulate y1974 y58,300 y343 y686 y173 y148
Sedimentation Particulate y237,000 y8,205,000 y8560 y28,300 y6410 y15,800
Remobilization Dissolved 231,000 8,025,000 7880 26,300 5750 13,800
% Remobilization 97 98 92 93 90 88

q s source of metal; - s sink or export of metal.

 et al.r Journal of Marine Systems 25 (2000) 269286
S.P.C. Tankere 281

Table 8
Mass balance of trace metals in compartment 2
Phase Mn Fe Pb Zn Cu Ni
tryear. tryear. tryear. tryear. tryear. tryear.
Riverine inputs Dissolved 80 82 11 194 118 107
Particulate 2638 82,043 257 818 181 654
Atmospheric inputs Total 484 792 220 194 53 44
Exchanges between Dissolved 1193 180 31 250 155 121
compartments 1 and 2
Particulate 1974 58,312 343 686 173 148
Exchanges with the Strait of Otranto Dissolved y693 y122 220 995 y966 612
Upwelling Dissolved 61 64 18 198 102 241
Downwelling Dissolved y739 y480 y88 y584 y509 y620
Particulate flux Particulate y950 y32,514 y23 y214 y444 y164
Sedimentation Particulate y99,500 y4,176,000 y3350 y12,000 y3032 y7260
Advective transport of sediments Particulate 53,500 2,250,000 1800 6460 1631 3910
Remobilization Dissolved 41,900 1,821,000 560 3010 2540 2210
% Remobilization 42 44 17 25 84 31

q s source of metal; - s sink or export of metal.

inputs was likely to be carried southward into com-
partment 2 via water fluxes. However, the contribu-
tion of the Northern Adriatic to the rest of the
Adriatic Sea was relatively small because of the
restricted water exchange and the losses due to burial
in the sediment. Only 35% Mn., 25% Fe., 36%
Pb., 34% Zn., 37% Cu. and 13% Ni. of total
riverine and atmospheric inputs in compartment 1
may possibly be transported to the Central Adriatic
Sea.
In the northern Adriatic Sea regeneration of Mn,
Fe, Pb, Zn, Cu, Ni from deposited sediment repre-
sented most of the sedimentary flux. The remobiliza-
tion and recycling of trace elements in the sediment
y interstitial water y seawater complex is intimately
related to the diagenetic environment under which
the sediment is deposited. This suggests that diage-
netic reactions occur in the sediment surface in the
northern Adriatic Sea. The organic carbon that
reaches the sea floor is oxidised successively by O 2 ,
nitrate, MnO 2 and Fe 2 O 3 and remobilization of Mn
and Fe occurs in the sediment Sundby et al., 1986..
Metals like Pb, Zn, Cu, Ni which can be adsorbed
onto Mn y and Fe y oxides, can simultaneously be
released during dissolution of Mn and Fe solid phases
Sawlan and Murray, 1983.. The recycled elements
Cu, Ni, and Zn. may also be released during the
decomposition of organic debris Sawlan and Mur-

Table 9
Mass balance of trace metals in compartment 3
Phase Mn Fe Pb Zn Cu Ni
tryear. tryear. tryear. tryear. tryear. tryear.
Exchange with the Dissolved y821 y128 36 356 y901 y636
Strait of Otranto
Upwelling Dissolved y61 y64 y18 y198 y102 y241
Downwelling Dissolved 739 480 88 584 509 620
Particulate flux Particulate 950 32,514 23 214 444 164
Advective transport of sediments Particulate 33,400 784,000 585 2100 1042 3231
Sedimentation Particulate y41,700 y979,000 y731 y2630 y1303 y4039
Remobilization Dissolved 7540 163,100 17 y430 311 901
% Remobilization 18 17 2 y16 24 22

q s source of metal; - s sink or export of metal.

282 et al.r Journal of Marine Systems 25 (2000) 269286
S.P.C. Tankere
ray, 1983.. Westerlund et al. 1986. measured fluxes
of trace metals Cd, Cu, Ni, Zn and Pb. across the
sediment-water interface in situ at 6-m depth in
Gullmarsfjorden Sweden., using diver-operated
stirred benthic flux-chambers. The measured release
rate with benthic chamber was high for Cd, Cu, Zn
and Ni and was attributed to breakdown of labile
organic matter during oxidation. Scavenging by par-
ticles, in particular by Fe and Mn oxide coatings was
an important process in maintaining the low trace
metal concentrations for Cu and Zn observed in pore
waters in the surface of the core. Remobilization
fluxes for trace elements, estimated with the mass
balance, were consistent with the high concentrations
of dissolved metals observed in bottom waters of the
northern Adriatic Sea, particularly during the sum-
mer period Tankere, 1998..
5.2. Mass balance in compartment 2
Though a lesser factor in the Southern Adriatic
Sea than in the Northern part, riverine inputs still
represented a major contribution to the mass balance
of compartment 2. Most of the metals were associ-
ated with the particulate phase. Compartment 2 re-
ceived metals from compartment 1 via water fluxes
because of a net export of metals from the Northern
Adriatic Sea to the Southern Adriatic Sea. In the
Strait of Otranto Pb, Zn and Ni tended to be im-
ported into compartment 2 from the Ionian Sea
whereas Mn, Fe and Cu were exported towards the
Ionian Sea. Upwelling and downwelling tended to
mix the water column and, consequently, metals
which had higher concentrations in the surface layer
due to riverine and atmospheric inputs Mn, Fe, Pb,
Zn and Cu. were transported from the surface layer
to the underlying layers. Downward fluxes of parti-
cles through the water column represented a major
transport for Mn and Fe. In general, advective trans-
port of sediment from compartment 1 and sedimenta-
tion fluxes in the coastal zone exceeded by several
orders of magnitude the other fluxes, as did remobi-
lization fluxes which were calculated by difference
Table 8.. In the central Adriatic Sea, the remobiliza-
tion fluxes of Mn and Fe accounted for 42% and
44%, respectively, of their deposition fluxes, as com-
pared with 97% and 98% in compartment 1, suggest-
ing that diagenetic processes appear deeper in the
sediment in the central Adriatic Sea. In the central
Adriatic Sea, the dissolved Mn and Fe concentrations
in the interstitial waters were low in the surface of
the core and increase below 2 and 4 cm, respectively
1998.. This is characteristic of sub-oxic
Tankere,
pore waters and results from the utilisation and
solubilisation of Mn- and Fe- oxides in the diage-
netic sequence. There was less remobilization of Pb
in compartment 2 17% of deposited sediments.. A
similar observation was made in Gullmarsfjorden
Sweden. by Westerlund et al., 1986. who argued
that most Pb in these sediments was present in a
non-mobile form. Remobilization of Zn and Ni ac-
counted for 25% and 31%, respectively, of their
deposition fluxes. This was possibly due to oxidation
of their organic carrier phases in the sediment col-
umn via oxidants such as O 2 , NO 3 and Mn oxides
Sawlan and Murray, 1983.. Remobilization of Cu
84%. was relatively high compared to that of Zn
and Ni. Two factors may conspire to produce the
high values of % remineralization of Cu observed.
Firstly, the affinity of Cu with surface active organic
substances, which is well documented in the Adri-
atic, will result in a proportionally higher than Ni or
Zn. percentage of Cu being remineralized during
partial oxidation of organic matter. Secondly, much
of Cu thus remineralized is likely to be kept in
solution and not re-adsorbed like Zn. through com-
plexation with strong organic complexing agents.
5.3. Mass balance in compartment 3
All metals but Pb and Zn were exported from the
Adriatic to the Ionian Sea across the Strait of Otranto.
Advective transport of sediments from compartment
2 constituted a major input of metals for compart-
ment 3. Remobilization fluxes were significantly less
in compartment 3 than in compartments 2 and 1.
This was consistent with the fact that the southern
Adriatic sea floor is made of hemi-pelagic sediments
where dissolved Mn concentrations in interstitial wa-
1998.. Remobi-
ters increase below 17 cm Tankere,
lization fluxes for Mn, Fe, Cu and Ni accounted for
18%, 17%, 24% and 22%, respectively, of deposited
sediments. Similar results have been reported by
Hartmann and Muller 1982. for Mn, Cu and Ni in
oxic pelagic sediments from the central Pacific.
 et al.r Journal of Marine Systems 25 (2000) 269286
S.P.C. Tankere 283

5.4. Time scales
5.4.1. Turnoer time
By definition Junge, 1974; Hamrud, 1983., the
turnover time is the ratio between the content M . of
a reservoir and the total flux out of it or into it S .:
M
t0s
S
The turnover time may be thought of as the time
it would take to empty the reservoir if the sink S .
remained constant while the sources were zero. A
long turnover time is usually associated with a small
variability in the total inventory Junge, 1974; Ham-
rud, 1983.. If material is removed from the reservoir
by two or more separate processes, each with a flux
Si , where i is a particular process, then the turnover
time with respect to each such process is defined by:
M The residence time of water in compartment 1
t0i s
Si
Table 10 presents turnover times of metals for the
different processes involved in the removal. Turnover
times of metals with respect to sedimentation were
short for compartments 1 and 2 compared with other
processes. In compartment 3, sedimentation was the
main sink for Fe, Mn and Pb, and consequently the
turnover times for these metals with respect to sedi-
mentation were short. For the other metals, the ex-
change with the Ionian Sea had a greater impact on
the content of the reservoir than upwelling or sedi-
mentation and so the corresponding turnover times
were relatively short.
5.4.2. Residence time
The residence time is the average time spent in a
reservoir by an individual molecule. It is therefore
the age of a molecule counted from its introduction
into the reservoir when it leaves the reservoir. When
the reservoir is in steady state d Mrdt s 0., sources
Q . and sinks S . are in balance and the residence
time is equal to the turnover time. Table 11 presents
the residence time of metals in the different compart-
ments of the Adriatic.
Northern Adriatic Sea. was 2 years which is longer
than in compartment 2 less than 5 months. and
compartment 3 less than 1 year.. Compartments 2
and 3 were subject to rapid exchanges and conse-
quently the water was rapidly renewed. In compart-
ment 1, the residence times of metals were signifi-
cantly shorter than that for water, indicating that

Table 10
Turnover times of metals with respect to different processes
Mn Fe Pb Zn Cu Ni
Compartment 1
Contents t. 9695 4549 252 1761 1860 2060
Exchange with compartment 2 year. 2.6 0.1 0.6 1.0 2.3 2.0
Sedimentation year. 0.041 0.001 0.029 0.062 0.290 0.131

Compartment 2
Contents t. 2450 21,514 319 3215 1942 3055
Exchange with compartment 1 year. 4.2 5.8 4.1 4.0 4.0 4.0
Exchange with Ionian Sea year. 0.44 11.3 0.66 0.73 0.43 0.57
Downwelling year. 3.3 44.8 3.6 5.5 3.8 4.9
Particle flux year. 2.6 0.7 13.9 15.0 4.4 18.6
Sedimentation year. 0.02 0.01 0.10 0.27 0.64 0.42

Compartment 3
Contents t. 2149 62,456 721 9837 3592 8000
Exchange with Ionian Sea year. 1.9 75.5 2.3 1.8 1.1 1.4
Upwelling year. 35 976 40 50 35 33
Sedimentation year. 0.05 0.06 0.99 3.7 2.8 2.0
284 et al.r Journal of Marine Systems 25 (2000) 269286
S.P.C. Tankere

Table 11
Residence times R.T.. of water and metals in the Adriatic Sea
Mn Fe Pb Zn Cu Ni Water
Compartment 1
Contents t. 9695 4549 252 1761 1860 2060 3600 = 10 9
Annual inputs tryear. 241,000 8,270,000 9010 30,100 7230 16,800 1776 = 10 9
R.T. year. 0.040 0.001 0.028 0.059 0.257 0.123 2.03

Compartment 2
Contents t. 2450 21,514 319 3215 1942 3055 8800 = 10 9
Annual inputs tryear. 107,000 4,214,000 4020 18,100 8650 14,200 22,769 = 10 9
R.T. year. 0.023 0.005 0.079 0.178 0.225 0.216 0.386

Compartment 3
Contents t. 2149 62,456 721 9837 3592 8000 23,600 = 10 9
Annual inputs tryear. 42,900 980,000 1060 8160 4680 10,000 25,319 = 10 9
R.T. year. 0.050 0.064 0.677 1.20 0.768 0.799 0.932

metals were rapidly removed from the system. In
compartment 2, residence times for Zn, Cu and Ni
were longer than for Mn, Fe and Pb, and approach-
ing that of water. This was to be expected on account
of the lower particle reactivity of Zn, Cu and Ni,
which therefore stay longer in the system. In com-
partment 3, residence times of metals Zn, Cu, Ni
and Pb. were generally longer than in compartment 2
and similar to the residence time of water. Mn and
Fe exhibited short residence times indicating signifi-
cant removal.
5.5. Uncertainties
Uncertainties in the estimates of metal fluxes
were obtained by propagating the errors associated
with water fluxes, suspended particulate fluxes, and
analytical errors, subject to the assumptions made in
interpolation procedures. Analytical errors were gen-
erally small compared to the error associated with
the estimated water fluxes. Evaluation of the errors
on the estimates of metals fluxes was difficult be-
cause there were insufficient observations to test all
the assumptions involved in the interpolation of data.
6. Conclusions
A first order mass balance of 6 different trace
metals Mn, Fe, Pb, Zn, Cu, and Ni. was presented
for a 1-year period for the different compartments of
the Adriatic Sea. In each compartment, the assump-
tion of steady state over a one-year period allowed
quantification of the remobilization fluxes from a
calculation of the input and output fluxes. Although
the uncertainty on the estimates of metal fluxes was
not determined, this mass balance enabled to assess
the dominant geochemical and oceanographic pro-
cesses affecting the metal fluxes in this semi-en-
closed system.
The contribution of the Northern Adriatic to the
rest of the Adriatic Sea was relatively small because
of the restricted water exchange and the losses due to
burial in the sediment. Only 35% Mn., 25% Fe.,
36% Pb., 34% Zn., 37% Cu. and 13% Ni. of
total atmospheric and riverine inputs to compartment
1 was transported to the Central Adriatic Sea.
On an annual scale, the Adriatic Sea appeared to
be a source of dissolved Cu, Mn and Fe for the
Mediterranean Sea through the Strait of Otranto
whereas for dissolved Zn and Pb the Adriatic Sea
appeared to be a net sink. For dissolved Ni, inputs
and outputs through the Strait of Otranto balanced
each other.
The export of dissolved Mn and Fe suggest that
the Adriatic Sea, particularly the Northern part, is an
active basin of mineralization of organic carbon since
remobilization of Mn and Fe from the sediment due
to diagenesis processes appeared to be the main
source of dissolved Mn and Fe. This is in agreement
with the view of the Mediterranean Sea as an active
basin of mineralization Coste et al., 1988..
 et al.r Journal of Marine Systems 25 (2000) 269286
S.P.C. Tankere
Acknowledgements
The authors would like to thank all the col-
leagues, who took part in the EUROMARGE pro-
ject, for sharing their data and ideas. This work was
supported by the European Union in the framework
of the Mediterranean Targeted Project MASTII.,
under the contract CT 93-0052. Dr. F.L.L. Muller
provided helpful comments on the last version of the
manuscript.
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