Geochimica n Cosmochimica Acto Vol. 57, pp.

1419-1432
Copyright 0 1993 Pergamon Press Ltd. Printed in U.S.A.
CUI 16-7037/93/$6.00 + Ml
Trace-metal distributions in seawater and anoxic brines in the eastern Mediterranean Sea
PAUL M. SAAGER, JOHAN SCHIJF,* and HEIN J. W. DE BAAR~
Free University, Dept. of Earth Sciences, De Boelelaan 1085, 1081 HV Amsterdam, The Netherlands
University of Utrecht, Dept. of Earth Sciences, PO Box 80.021, 3508 TA, Utrecht, The Netherlands
Netherlands Institute for Sea Research, PO Box 59, 1790 AB Den Burg, Texel, The Netherlands
(Received September 25, 199 1; accepted in revised form December 15, 1992)
Abstract-The vertical distribution of dissolved and particulate trace metals (Mn, Fe, Ni, Cu, Cd) is
reported for seawater and the anoxic brines of Tyro and Bannock Basins in the eastern Mediterranean.
In normal Mediterranean seawater, the distribution of dissolved trace metals is governed by water mass
circulation, as well as by local input sources. For Cd and possibly Cu, steady-state behaviour is not a
viable assumption, probably as a result of anthropogenic sources. In agreement with previous reports,
no correlation was observed between dissolved Ni, Cu, Cd, and the major nutrients. At the seawater-
brine interface, all trace metals show dramatic changes in concentration. In the brines, the concentrations
of dissolved Fe and Mn are strongly elevated compared to overlying waters, yet probably limited by
formation of solid sulfide and/or carbonate phases. The distributions of dissolved Fe and sulfide show a
remarkable mirror image of those found previously in the Orca brine (Gulf of Mexico), and the ionic
concentration products are approximately the same in all three basins. The difference in absolute Fe and
sulfide concentrations is thought to be caused by a high supply of Fe to Orca Basin. Concentrations of
dissolved Ni, Cu, and Cd in the brines are at least one order of magnitude lower than in overlying waters,
most likely due to formation of solid sulfide phases. We believe these data provide the first indication of
substantial nickel-sulfide (co)precipitation within an anoxic basin. Particulate metal concentrations are
elevated at the seawater-brine interface and are probably associated with the presence of solid sulfide
phases. In addition, the extreme density gradient at the interface will slow the sinking rate of particles
and lead to accumulation of particles at the interface due to accumulation.
INTRODUCTION
PREVIOUS INVESTIGATIONS of dissolved trace metals in the
Mediterranean Sea ( KREMLING and PETERSEN, 198 1; LAU-
MOND et al., 1984; BOYLE et al., 1985; STATHAM et al., 1985;
COPIN-MONTEGUT et al., 1986; SHERRELL and BOYLE, 1988;
MORLEY and BURTON, 199 1) showed that, in contrast with
open ocean waters, there generally exists only a modest cor-
relation ( Alboran Sea) or no correlation at all (western central
Mediterranean) between dissolved trace metals and nutrients.
Concentrations of dissolved trace metals in nutrient-depleted
Mediterranean surface waters are elevated compared to sim-
ilarly nutrient-depleted Atlantic surface waters. Sluggish re-
cycling of nutrients (BOYLE et al., 1985) and non-steady-
state behaviour due to anthropogenic inputs ( BETHOUX et
al., 1990) and other external sources (atmospheric, coastal;
VAN GEEN et al., 1988) have been invoked to explain these
observations. Since the formation areas of important water
masses such as Levantine Intermediate Water reside in the
eastern Mediterranean, this is an interesting area to study
the distribution of trace metals. For the eastern Mediterranean
thus far, only limited information was available about trace-
metal distributions ( KREMLING and PETERSEN, 198 1; SPI-
VACK et al., 1983; COPIN-MONTEGUT et al., 1986).
Recently, two anoxic, brine-filled depressions have been
discovered in the eastern Mediterranean Sea (JONGSMA et
al., 1983; SCIENTIFIC STAFF CRUISE BANNOCK 1984-12,
* Present address: Woods Hole Oceanographic Institution,
Chemistry Department, Woods Hole, MA 02543, USA.
1985). Bannock Basin is located west of Crete and actually
consists of a suite of basins, most of which are interconnected,
Tyro Basin is located south of Crete (Fig. 1) . At both stations,
an extremely sharp interface (Bannock Basin 3323 dbar, Tyro
Basin 3380 dbar) separates oxygenated Mediterranean waters
from anoxic brines with salinities an order of magnitude
higher than normal seawater. Across this interface, many
chemical and physical parameters decrease or increase dra-
matically over less than 1 m (DE LANGE et al., 199Ob). The
sharp density gradient effectively prevents downward mixing
of oxygen, so that the decomposition of organic matter has
led to permanently anoxic conditions in the brine. Sulfide
concentrations in the brine are 2-3 mmol/L (LUTHER et al.,
1990)) second in magnitude only to Framvaren Fjord, Nor-
way ( SK& 1983). In Tyro Basin, the brine has a homogenous
composition, but Bannock Basin is vertically stratified in two
brine layers ( hereafter brine 1 and brine 2 ) that differ slightly
in composition. The brines probably originated from disso-
lution of Messinian evaporites underlying the Mediterranean
seafloor. The brine composition in Tyro Basin reflects dis-
solution of early stage evaporites, mainly consisting of halite;
whereas in Bannock Basin, dissolution of later stage evaporites
is likely to have occurred (DE LANGE et al., 199Oc). The
combination of anoxia and extreme salinity in these brines
may yield interesting distributions of dissolved trace metals.
Thus far, only limited reliable observations exist concerning
the distribution of dissolved trace metals in anoxic brines
(Bannock and Tyro basins, Mn: DE BAAR et al., 1987; DE
LANGE et al., 1990a,b,c. Bannock and Tyro basins, Ba: DE
LANGE et al., 1990~: Al: HYDES et al., 1988. Orca Basin, Fe
and Mn: TREFRY et al., 1984). Additional information about
1419
1420
P. M. Saager, J. Schijf, and H. J. W. De Baat
the origin and chemistry of the brines was publish previ-
ously (VAN HINTE et al., I987; CITA et al., 1989; CITA, 1990;
VAN DER WEIJDEN et al., 1990a).
The vertical distributions of dissolved trace metals have
also been studied in various anoxic basins of approximately
seawater salinity. In anoxic waters, dissolved Cu, Zn, and Cd
reach very low concentrations as a result of sulfide precipi-
tation (JACOBS et al., 1985, 1987; HARALDSSON and WES-
TERLUND, 1988; LANDING and LEWIS, 1991). For Ni, no
evidence of sulfide precipitation exists, and concentrations
are mostly constant throughout the entire water column.
Concen~ations of dissolved Fe and Mn increase dmmati~~ly
at the oxic/anoxic interface, with Fe con~ntmtions decreas-
ing downward below the interface as a result of sulfide pre-
cipitation. Manganese concentrations remain high in anoxic
waters or decrease gradually as a result of sulfide and /or car-
bonate precipitation.
In this paper, the vertical distributions of dissolved and
particulate Fe, Mn, Ni, Cu, and Cd are presented.
SAMPLING AND METHODS
Samples were collected on board RV Tyro at three stations in the
eastern Mediterranean between 21 May and 5 June 1987 (Fig. I ).
We used modified GoFIo-bottles ( BRULAND et al., 1979) mounted
on a new stainless steel frame with Neil-Brown CTD-Rosette. Upon
recovery, the bottles were immediately connect& to Nz-pressure fines
to prevent oxidation of the anoxic samples. Inside the clean air con-
tainer, seawater was filtered through dean 0.4 pm Nuclepore filters
using clean Teflon tubing and filtration units. The samples were acid-
ified to pH 2-3 with quartz-distilled (Q-) HCI and stored in hot-acid
leached polyethylene bottles until analysis in the shore laboratory.
The filters were also analysed in the shore laboratory.
This sampling procedure is often used but does not necessarily
collect 100% of the particulate matter. During filtration, large particles
may settle to the bottom of the bottle and thus escape filtration. Since
Iarge settling particles usually make up a very small percentage of
the total particle concentration, the difference is likely to be smah
though. Because of the small samp1e sizes, particle composition could
not be determined and we only determined total particulate tmce-
metal con~ntrations per voiume of water. VAN DER SLXKX et at.
( 1990) also sampled particles at these stations using a shipboard con-
tinuous Bow centrifuge. In the Results Section, the differences between
the two techniques wil1 be discussed. All analytical procedures were
performed inside a class-100 laminar flow hood situated in a clean
air container or laboratory. Nutrient and oxygen data were presented
by HYDES et al. ( 1988) and will not be discussed here. Sulfide data
are from LUTHER et al. ( 1990).
Manganese
Brine samples were diluted with Mini-Q water (Millipore) and
analysed with direct injection graphite-furnace-AAS using standard
addition (Perkin Elmer 5000 atomic absorption spectrophotometer;
HGA 400 heated graphite furnace; AS 40 autosampler). The detection
limit was 100 nmol/kg, and precision of the rn~~rnen~ was about
5% at 5 pmol/kg Mn. Seawater samp1es were pre~oncentra~d with
Cheiex- 100 chromatography f KINGSTON et at., 1978 f and analysed
30
40
30
it-J ?il
FIG. 1. Chart showing locations of the three stations sampled during the ABC cruise: Station 5 (3509N ZO07E).
Bannock Basin (34OI7N 2OOlE), and Tyro Basin f33?4N 2602E).
Trace metals in seawater and anoxic brines
1421
with GFAAS using standard caiibration curves i6 tl, 1 N HNO: since
a comparison with standard addition showed no matrix effects. The
detection limit was 35 pmo!/kg, and precision was about 5% at 2
nmo!/kg. Blanks were below detection limit.
Iron, Nickel, Copper, and Cadmium
For both normal seawater and anoxic brines, samples were pre-
concentrated with APT-DD~/chlorofo~ solvent extraction
( BRULAND et a!., 1979) and analysed with GFAAS (Perkin Elmer
I 100 AAS) using extracted standard calibration curves to correct for
matrix effects. Detection limits were 2 pmo!/kg for Cd, 0.2 nmo!/
kg for Ni, 0.1 nmol/kg for Cu, and 0.2 nmol/kg for Fe. Overal!
procedural blanks were 2 pmo!/kg for Cd, 0.45 nmol/ kg for Ni,
below detection limit for Cu, and 0.5 nmo!/kg for Fe. Samples were
corrected for btanks, as tiey were low and reproducible. Analytica!
precision was about 5% at 100 pmo!/kg Cd and 2 nmol/kg Cu, Ni,
and Fe.
Particles
Filters were leached in hot 7 N Q-HN03 for 2 h. The lea&ate was
evaporated to dryness, and the residue taken up in 0.1 N Q-HN4.
Dissolved residues were then buffered to pH 4.3 with 1 N Q-am-
monium acetate and extracted with APDC-DDDC/ch!oroform sol-
vent extraction ( BRULAND et al., 1979). Extraction efficiency was
zero percent for Mn. The original leachates were analysed directly
for Mn with GFAAS using standard addition to compensate for the
salt matrix. The extracts were analysed for Fe, Ni, Cu, and Cd using
0.1 N Q-HN03 standard vibration curves since no matrix effects
were observed. Con~nt~tions were at least twenty times hi&er than
estimated detection limits except for Cd (0.1 nmolfkg for Fe; Mn 2
pmo!/kg; Cu 3 pmol/kg; Cd 0.1 pmol/kg; Ni 2 pmo!/kg). Overall
procedural blanks were below detection limit. Analytical precision
of the data was about 5%. Accuracy of the particulate trace-metal
concentrations is only about IO-20% due to uncertainties in the
amount of seawater that was filtered.
RESULTS
Hydrography
Hydrographical data are taken from HYDES et al. ( 1988)
and shown summarized in Fig. 2. Quality of the salinity and
tem~rature data did not allow the calculation of potential
density ( cre). This poses restrictions to comparison of the data
between stations.
In reviewing the hydrography ofthe eastern Mediterranean,
MALANOTTE-RIZZOLI and HECHT (1988) showed that few
facts have been reliably assessed as yet. Contradictory obser-
vations exist in the past literature, notably on deep water
masses and deep-water formation areas. Yet some common
trends can be discerned. First, due to the presence of the sills
at the Strait of Sicily (sill depth, 500 m), there is virtually no
exchange of water between the deep western Mediterranean
and the deep eastern Mediterranean. The Strait of Crete (sill
depth, 2000 m) further divides the eastern M~ite~an~n
into the western Ionian basin and the eastern Levantine basin,
but exchange between both basins is believed not to be
impeded to a large extent.
At our stations, three well-defined water masses can be
identified. At the surface, Atlantic Surface Water (ASW)
penetrates as far as the easternmost M~ite~n~n. Due to
extensive heating of surface waters during summer a lid of
warm water is formed, preventing early dissipation of ASW
in the western Mediterranean. In winter, ASW can no longer
be identified east of the Straits of Sicily. At our stations, sa-
linity of these waters varies between 38.4 and 38.9 psu. ASW
Pot. Temperature (C)
-i
13 14 15 16 17 16 19 20
Salinity (p.s.u.)
38.4 38.5 38.6 38.7 38.8 38.9 38.0 39.1
FIG. 2. Vertical profiles of temperature and salinity at Tyro Basin
and Bannock Basin.
extends between 20 and 50 m depth. Imm~iately below,
Levantine Intermediate Water (LIW) is characterized by a
maximum saiinity of 38.9-39.1 psu at 80-200 m depth. LIW
extends between 60 and 400-600 m depth and generally flows
westward. Density surfaces probably shoal eastward, as the
core of LIW at Tyro Basin is located shallower than at Ban-
neck Basin. There is stilt much debate as to the exact for-
mation areas of this water mass, but they all reside in the
easternmost Mediterranean. Below 600 m Mediterranean
deep water is present with a temperature of 13.6C and sa-
linity of 38.66 psu, hereafter called Eastern Mediterranean
Deep Water (EMDW ) . Various contradictory observations
point to different locations as formation areas for this deep
water mass. For both the Ionian and the Levantine basin,
the Adriatic Sea as well as the Aegean Sea have been claimed
as source areas. Neither the general flow direction nor the
renewal time of EMDW has been assessed unequivocally.
Best estimates of deep water residence times are around 100
y ( MALANOTTE-RIZZOLI and HECHT, 1988).
Trace metals
Vertical profiles of dissolved and particulate trace metals
are presented in Figs. 3-7 for Tyro and Bannock basins; data
for all stations are given in Table I.
1422 P. M. Saager, J. Schijf, and H. J. W. De Baar
(a)
Dissolved Mn (nM)
(W Dissolved Mn (MA)
Particulate Mn (PM)
FIG. 3. (a) Vertical profiles of dissolved Mn for Tyro Basin and Bannock Basin: Complete water column. (b)
Dissolved Mn: Expansion of the brine. (c) Particulate Mn concentrations in Tyro Basin and Bannock Basin.
Dissolved Metals
Manganese
In normal Mediterranean seawater, the vertical distribution
of dissolved Mn (Fig. 3a,b) is characteristic of open ocean
waters, indicating particle scavenging as the major removal
process. Concentrations are strongly elevated in surface waters
(2-3.5 nmol/kg), decrease exponentially with depth to very
low values (0.06-0.4 nmol/kg) between 1000 and 2000 m
depth and increase below 2500 m depth towards the seawater-
brine interface. The profiles are in very good agreement with
recent data for the Mediterranean (MORLEY and BURTON,
199 1). Earlier data are higher ( KREMLING and PETERSEN,
198 1 ), presumably as a result of some residual contamination
(BOYLE et al., 1985).
At the seawater-brine interface, the concentration shows
a dramatic gradient of three to four orders of magnitude over
a depth interval of less than 10 m. The first report of this
(DE BAAR et al., 1987) was confirmed by DE LANGE et al.
( 1990b), who by high-resolution sampling at the seawater-
brine interface found this increase to take place over less than
1 m. In Bannock Basin, there is a distinct minimum at the
second interface between brine I and brine 2, with concen-
(a)
Dissolved Fe (nhl)
0
Fe (nM)/salinity ([-34x10)
trations in brine 2 being about 30% lower than in brine 1.
Concentrations are intermediate between the Cariaco Trench
(-600 nmol/kg, JACOBS et al., 1987) and the Black Sea
(-5-8 pmol/kg, LEWIS and LANDING, 199 1) and are two
orders of magnitude lower than at Orca Basin ( x 300 pmol/
kg, TREFRY et al., 1984).
I ron
Dissolved Fe concentrations vary along with the presence
of different water masses (Fig. 4a-c). At Bannock Basin,
concentrations in ASW are high, and Fe minima and maxima
( l-6 nmol/kg) coincide with minima and maxima in salinity.
At Tyro Basin, surface water concentrations are higher than
at Bannock Basin down to 100 m depth. At Bannock Basin,
sampling resolution is sufficient to reveal a gentle maximum
in intermediate waters more or less coinciding with a similar
salinity maximum related to LIW. In both basins, EMDW
has low but variable concentrations with slightly higher levels
at Tyro Basin.
Both in the Tyro and Bannock basins, a very pronounced
dissolved Fe maximum is observed at the seawater-brine in-
terface ( x 100 nmol / kg), more than two orders of magnitude
(W
Dissolved Fe (nM)
FIG. 4. (a) Vertical profiles of dissolved Fe for Tyro Basin and Bannock Basin: Total water column. (b) Dissolved
Fe: Expansion of the brine. (c) Dissolved Fe profile in Bannock Basin with salinity for comparison. Salinity scale has
been modified in order to match trace-metal scale. (d) Particulate Fe concentrations in Tyro Basin and Bannock Basin.
Trace metals in seawater and anoxic brines 1423
(a)
Dirrolvod Ni (nM)
( W
Dissokod MI (nN)
0 2 4 6 B
0.3
Ni (nl)/salinity ((-381x4)
(4
Particulate Ni (PM)
FIG. 5. (a) Vertical profiles of dissolved Ni for Tyro Basin and Bannock Basin: Total water column. (b) Dissolved
Ni: Expansion of the brine. (c) Dissolved Ni profile in Bannock Basin with salinity for comparison. Salinity scale has
been modified in order to match trace-metal scale. (d) Particulate Ni concentrations in Tyro Basin and Bannoek Basin
(see Fig. 4a). Vertical profiles of dissolved Ni for Tyro Basin and Bannock Basin: Total water column.
higher than in the overlying water column. In the brines,
concentrations decrease strongly downward. In Bannock Ba-
sin, a concentration minimum was observed at the interface
between brine 1 and brine 2, in good agreement with similar
minima for Mn, BEE ( SCHIJF, 1992), and concentration steps
for several other parameters (DE LANGE et al., 199Oc; BRE-
GANT et al., 1990; LUTHER et al., 1990). Actual concentra-
tions in the brine are of the same order as for the Black Sea
(LEWIS and LANDING, 199 1) and the Cariaco Trench (JACOBS
et al., 1987) but almost three orders of magnitude lower than
in Orca Basin (TREFRY et al., 1984).
(8
Dlasolved Cu (n&t)
0 2 4 6
(cl
Cu (nM)kallnity ([-38)x4)
Ni ckel
At Tyro Basin and Station 5, the vertical distribution of
Ni is fairly uniform throughout the water column (Fig. Sa-
c ) . Average concentrations are about 0.5 nmol/ kg higher at
former station (5.1 vs. 4.6 nmol/kg). At Bannock Basin,
better sampling resolution showed that concentrations dif-
fered in different water masses (Fig. 5~).
Our data are slightly higher than reported for the deep
Alboran and Ligurian Sea (BOYLE et al., 1985; HUYNH-NGQC
and WHITEHEAD, 1986; MORLEY and BURTON, 1991). These
04
Dissolved Cu (nM)
---I l - I
(4
Paftlculate Cu (PM)
Tml
FIG. 6. (a) Vertical profiles of dissolved Cu for Tyro Basin and Bannock Basin: Total water column. (b) Dissolved
Cu: Expansion of the brine. (c) Dissolved Cu profile in Bannock Basin with salinity for comparison. Salinity scale has
been modified in order to match trace-metal scale. (d) Particulate Cu concentrations in Tyro Basin and Bannock
Basin.
1424
P. M. Saager, J. Schijf, and H. J. W. De Bar
(4
Dissolved Cd (PM)
0
-. -
0.
. 0
0
Cd (pM)lsallnlty ([-3a]xlOO)
03
Dissolved Cd (PM)
(4
Particulate Cd (PM)
FIG. 7. (a) Vertical profiles of dissolved Cd for Tyro Basin and Bannock Basin: Total water column. (b) Dissolved
Cd: Expansion of the brine. (c) Dissolved Cd profile in Bannock Basin with salinity for comparison. Salinity scale has
been modified in order to match trace-metal scale. (d) Particulate Cd concentrations in Tyro Basin and Bannock Basin.
western Mediterranean deep waters contain about 4-4.3
nmol/ kg Ni. Deep water Ni concentrations tend to increase
towards the eastern Mediterranean.
In the brine, concentrations sharply fall to values of 0.4-
2.0 nmol/kg. In Bannock Basin, the concentration in brine
I is about a factor of two higher than in brine 2. In contrast
with Mn and Fe, there is no distinct feature at the interface
between brine I and brine 2. To the best of our knowledge,
the anoxic brine waters of Bannock and Tyro basins constitute
the first observations of Ni concentrations being much lower
than in the overlying oxygenated water column.
centrations in ASW and LIW are elevated (70-100 pmol/
kg) and decrease to uniform deep water values of 40-60
pmol/ kg, with higher values at Tyro Basin, as was also found
for the other metals.
At the seawater-brine interface, a very steep concentration
gradient is observed. In the brine, concentrations are more
than one order of magnitude lower than in the overlying
water column. Similarly low values have previously been re-
ported for other anoxic basins (JACOBS et al., 1985, 1987;
HARALDSSON and WESTERLUND, 1988; LANDING and LEWIS.
1991).
coppet
The vertical distribution of dissolved Cu is also strongly
related to the presence of different water masses (Fig. 6a-c).
At Bannock Basin and Station 5, dissolved Cu concentrations
are elevated in ASW and LIW and decrease below the salinity
maximum at about 200 m depth. At Tyro Basin, concentra-
tions show considerable scatter. Average deep water concen-
trations are about 0.5 nmol/kg higher than at former stations.
Suspended Particles
Munguncrc
In the brines, concentrations are about one order of mag-
nitude lower than in overlying waters. At the interface be-
tween brine 1 and brine 2, scatter in the dataset obscures any
trends. In brine 2, the concentration is almost a factor of two
lower than in brine I.
Copper concentrations in oxygenated waters are similar
to those previously reported for the Mediterranean ( LAU-
MOND et al., 1984; BOYLE et al., 1985; MORLEY and BURTON,
199 1). The low concentrations in the anoxic brines are in
good agreement with values reported for Cariaco Trench
(JACOBS et al., 1987), Framvaren Fjord (JACOBSON al., 1985).
and the Black Sea ( HARALDSSON and WESTERLUND, 1988 )
In the oxygenated water column, the concentration ofpar-
ticulate Mn (20- 100 pmol/ kg) is almost one order of mag-
nitude lower than that of dissolved Mn (Fig. 3~). Concen-
trations are of similar magnitude as data for the Sargasso Sea
and northeast Pacific Ocean ( SHERRELL, 1989). In the brine,
an increase of more than one order of magnitude is observed,
two orders of magnitude less than the increase of dissolved
Mn. At Bannock Basin, the particulate Mn concentration at
the seawater-brine interface (20-50 pmol/kg) is much lower
than at Tyro Basin, and in the brine, the concentrations are
about half those in Tyro Basin. For Bannock Basin, sampling
resolution is too poor; but for Tyro Basin, a distinct partic-
ulate Mn maximum is observed at or just above the interface.
Our brine data compare well with levels found in the Black
Sea ( LEWIS and LANDING, I991 ), but the concentration at
the seawater-brine interface is considerably lower. Concen-
trations in overlying waters agree fairly well with pre.vious
data for these basins ( VAN DER SLOOT et al., 1990); however,
in the brine. our values are lower by one order of magnitude.
The vertical distribution of dissolved Cd seems to be related In Tyro Basin, particulate Fe concentrations above the
to the presence of various water masses (Fig. 7a-c). Con- brine are of the same order as dissolved concentrations, then
Trace metals in seawater and anoxic brines 1425
TABLB 1 Dived tmx mtal cmcenmcicm, ** CO-
.a l10t uulyred, bmdcea indicate dm mpected ofcmmhdm
STATION 5 (WWNIzoarB) dismkd cuwmntkms
apul M
Cu cd Ni Fe
(dbar) (m) (m&x) (Pmdnc8) (mlk) (KM@
1 .a 1.89 83 4.75 .*
:: * n:* 2.89 3.12 4.70 4.57 .* l .
.a
:z .L tz :: z: l *
.I
.a
P, .8
2:57
1.59 ;I
s:13 l *
4.18 . .
loo2 .a 1.92 46 5.26 . .
1497 .B 3.12 46 4.61 I.
2ooo .B 2.36 47 4.76 . .
2808 .a 1.98 5.01 l *
2966 n.a 2.32 4.14 .*
TYRO BASIN (3354N/2602E) dissolved cmccnmions
1:: 2.4 .a n.a 1.77 .8 70 4.60 .a la.8 .a
% 0.6 n.a 2.33 2.56
Soo .a 2.63
(1;) 5.09 5.34 2.33 4.61
5.13 2.58
1010 0.4 2.44 56 5.43 5.66
1300 .B 2.57 56 5.04 1.30
1700 0.2 2.95 61 491 2 56
2ooQ
2666
2996
3200
.B
0.25
0:;)
3.41
2.50
0:;;)
.- 4.44
4.84
w;)
2.80
3268 0.4 .a n.a .a .a
3350 1.3 2.67 46 5.33 1.40
3360 0.4 2.20 46 5.78 0.70
3370 .a 2.44 40 5.89 1.31
3390 4320 0.42 :a 1.53 13o
340 4450 .a 1.22 121
3425 4200 .a .a 1.09 19.5
3450 4350 0.27 1.91 59.8
3475 4340 0.48
4
1.33 28.7
BANNOCK BASIN (3418Nn0olE) diSsOlv+d c~rratioS
w hln
C Cd N F
(dbar) (nmolkg) (m&g) @molkg) (motkg) (moeWg)
0 2.86 2.07 .B 457
4176
5 a4
1:07
2.67
:E
1500
1750
z%
2999
3100
3126
3150
3300
3307
3310
3315
3323
3323
3329
3359
3376
3403
3420
3430
3468
3470
3491
3528
3580
3629
3.45
.a
3.50
.a
.a
.B
.a
.a
.a
0.66
.a
.a
.a
.a
0.06
.B
.a
.a
0.09
.a
0.19
.a
.a
n.a
0.54
0.79
0.87
2.17
2.16
46u)
4350
5290
4640
I%
4820
.a
3790
n.a
2870
.a
2570
.a
2910
3780
3750
3480
1.49
2.64
2.36
2.83
2.97
2.40
2.26
3.17
3.04
2.89
2.88
1.71
2.17
1 .a6
1.63
1.79
1.76
1.52
1.80
.a
0.94
3.34
2.49
1.76
.8
I .05
0.86
1.00
0.83
.B
0.60
.B
0.38
.a
0.33
0.46
0.41
0.15
0.14
0.19
0.21
0.35
0.40
0.19
0.58
0.17
0.19
n.a
88
.B
.a
99
.a
92
.a
.a
a3
.a
62
:;
.a
::
45
:
:;
68
:;
68
39
.B
36
.a
3
.a
2
.a
2
2
.a
2
n.a
2
.a
2
.a
:
:
.a
4.97
4.74
5.12
4.98
.a
5.01
5.17
.a
.B
4.85
.a
4.63
4.90
4.50
4.60
.B
.B
.a
4.40
.a
4.56
4.20
.8
4.37
4.26
4.5 1
4.75
.a
4.91
.iI
0.90
.a
0.99
0.94
0.73
0.71
0.46
1.44
0.46
0.66
1.13
0.58
0.35
0.36
0.27
0.39
0.65
6.04
1.35
2.49
0.87
1.24
1.62
1.63
2.26
1.88
.B
0.72
0.40
0.67
.B
0.60
1.53
.a
.B
1.30
2.49
n.a
.B
0.62
0.47
0.70
1.97
0.95
.a
lo6
82.8
23.3
.a
16.2
29.4
27.5
10.8
10.1
12.3
10.4
10.0
10.2
9.59
22.8
20.5
12.9
19.8
16.5
3679 4070 0.22 5
3730 3870 0.27 3784 3620 0.32 ; 0.39 19.5
Table 1, continued. Particulate concentrations. n.a. not
analysed. Brackets indicate data suspected of contamination.
TYRO BASIN (33S4N126W2E) ~utidatc am~cnoationr
ocph M
Cu Cd N
(pnovlrg) (PMw @md/kg) (PGw (
F
e tMWkg)
98 032
3350
7;
134 0:46
39
3:4
3360 0.47 :: 1.8
3370
3375 :3
%!I 0.70 2.0
373 0.20 2 14.6
3380 .P .P .a .B
3400 G 272 0.64 27.3
3425
z
231 0.28 (2)
26.5
3450 262 0.66
3475 217 0.23 z:
17.1
29.4
BANNOCK BASIN (3418N/20WE) particulate cwce!mtios
Deph
C Cd N F
(dbar) (pm%g) (pm&g) (pm&kg) (pm&kg) (nmoeVkg)
3322 18 433 0 29
3322 15 589 0:16
54 13 0
2218
3323
2:;
677 1.38 ; 47.7
:z!
171 1.17 16.6
237 65 0.68 (I$) 7.6
3420 224 0.25 4.6
3470 240 8: 0.30 :: 6.6
increase by a factor of ten in the brine, still of the same order
as dissolved concentrations (Fig. 4d). In Bannock Basin,
concentrations are high and variable at the interface and de-
crease in the brine to values about half those in Tyro Basin.
Concentrations are of the same magnitude as dissolved con-
centrations. Particulate Fe concentrations in the brines are
in good agreement with those reported for anoxic waters of
the Black Sea (LEWIS and LANDING, 199 1). For overlying
waters and the interface, our data further agree fairly well
with previous reports for these basins by VAN DER SLOOT et
al. ( 1990), but brine values are lower by one order of mag-
nitude, the same difference as observed for Mn. Their data
represent total particulate concentrations measured by neu-
tron activation, whereas our data represent a leached fraction
with 7N HN03. This might explain part of the discrepancy,
but not all since it is unlikely that more than about 70% of
particulate Fe will be refractory (LEWIS and LANDING, 199 1 ),
resisting the acid-leach with 7N HN03. The difference may
further be attributed to oxidation of their anoxic brine samples
during ondeck centrifugation, leading to precipitation of Fe
and Mn oxyhydroxides ( TROUP et al., 1974), since apparently
no precautions had been taken to avoid oxidation both during
sampling and centrifuging (VAN DER SLOOT et al., 1990).
Nickel
At Tyro Basin, particulate Ni concentrations in oxygenated
water are about two orders of magnitude lower than dissolved
concentrations (Fig. 5d) and are similar to those measured
for the Sargasso Sea and the Pacific Ocean ( SHERRELL, 1989).
Concentrations increase by about a factor of 2-4 across the
seawater-brine interface and are only one order of magnitude
lower than dissolved concentrations. In Bannock Basin, a
sharp maximum at the seawater-brine interface is observed.
Concentrations decrease sharply into the brine much like
particulate Fe, Cu, and Cd and are about twice as low as in
Tyro Basin.
Copper
In the oxygenated waters at Tyro Basin, particulate Cu
concentrations are an order of magnitude below dissolved
1426 P. M. Saager, J. Schijf, and H. J. W. De Baar
levels (Fig. 6d). Both in Tyro and Bannock Basin, particulate
Cu concentrations show a pronounced maximum at or above
the seawater-brine interface, decreasing in the brines to values
of the same order as dissolved Cu. Concentrations at Tyro
Basin are twice those at Bannock Basin. They are slightly
higher than reported for the Sargasso Sea and the northeast
Pacific Ocean (SHERRELL, 1989).
For oxygenated waters, our data are more than one order
of magnitude lower than data by VAN DER SLOOT et al.
( 1990), and in the brine, almost two orders of magnitude.
Their particulate Cu and Zn data are very high in comparison
with open ocean inanitions ( SHERRELL, 1989) or aeolian
dust from the central M~te~n~n ( TO~WADIN et al., 1984 ) .
Such a large difference is unlikely and hints at contamination,
where the rubber strings of the Niskin bottles used for ob-
taining deep water samples are well-known sources of Cu
and Zn (SPENCER and BREWER, 197 1). Latter explanation
is supported by the fact that the difference was much less for
other elements (Al, Mn, Fe, Co). This is consistent with the
much lower concentrations of particulate Cu and Zn for sur-
face waters that had been sampled (VAN DER SLOOT et al.,
1990) with a membrane pump from the bow of the ship. For
brine samples, the centrifuging method may have led further
to oxidation of dissolved Mn and Fe and resulted in precip
nation of FeMn~xyhydroxides. These, in turn, could have
scavenged considerable amounts of trace metals, thus ex-
plaining the discrepancy between their data on the one hand
vs. our data and results from the Black Sea and Framvaren
Fjord on the other hand ( HARALDSSON and WESTERLUND,
1988; LANIXNC and LEWIS, 199 1).
Cadmium
In oxygenated waters, particulate Cd concentrations are
two orders of magnitude lower than dissolved concentrations
(Fig. 7d) and near the detection limit. Therefore, the data
show considerable scatter and must be considered as maxi-
mum values. Otherwise, ~n~entmtions are in fair agreement
with results for the Sargasso Sea and Pacific Ocean (SHER-
RELL, 1989). In Bannock Basin, concentrations decrease in
the brine below a maximum at the seawater-brine interface.
In Tyro Basin, particulate Cd concentrations scatter much
and show no trend in the brine. Actual concentrations are
similar to those reported for anoxic waters of Framvaren
Fjord and the Black Sea ( HARALDSSON and WESTERLUND,
1988).
DISCUSSION
Oxygenated Waters
As in the western basin, the vertical distributions of Ni,
Cu, and Cd in the eastern Mediterranean are not correlated
with those of the nutrients. Ineffective recycling of nutrients,
as well as non-steady-state behaviour, seem likely explana-
tions (BOYLE et al., 1985; SHERRELL and BOYLE, 1988;
BETHOUX et al., 1990). This being said, we will focus here
on the distinctly different metal concentrations in various
water masses.
Surface water concentrations are higher than reported for
the western and central Mediterranean, consistent with pre-
vious observations ( SP~VACK et al., 1983; HYDES et al., 1988).
Continuous atmospheric input is at present the most plausible
explanation. Atmospheric Cu and Cd fluxes exceed river input
by at least one order of magnitude (MARTIN et al., 1989).
For Cd, most of this flux is attributed to anthropogenic sources
( DULAC et al., 1987). Sediment-derived metal fluxes as sug-
gested by KREMLINC~ and PETERSEN ( 198 1) cannot be ruled
out but are probably of minor importance. Concentrations
of Al increase considerably from west to east ( HYDES et al.,
1988), emphasizing the importance of atmospheric input
( GANOR and MAMANE, 1982; BUAT-MFNARD et al., 1989).
However, Mn concen~ations in ASW do not increase east-
ward. Apparently, Mn is subject to more intensive particle
scavenging than Al, leading to fast removal of dissolved Mn
from surface waters, as is also inferred from the vertical pro-
files. The less reactive nature of dissolved Al in the Mediter-
ranean Sea has previously been inferred from its strong cou-
pling with dissolved silica (MACKENZIE et al., 1978; HYDES
et al., 1988 1. The differences in surface water Mn, Fe, and
Al concentrations between Bannock and Tyro stations are
probably a local and temporal phenomenon. KREMLING and
PETERSEN ( 198 I ) reported high surface water Mn concen-
trations for a station close to the coast of Libya, but they
found no significant maxima at a station close to Tyro Basin,
just south of Crete. Their samples were taken near the end
of the year. These observations are in good agreement with
meteorological data ( MAY, 1982 ) , indicating that prevailing
wind directions change from predominantly northern winds
during summer to mainly west and southwestern winds in
winter. Apparently, the elevated dissolved surface water con-
centrations are quickly removed by intensive particle scav-
enging. As all surface water enrichments are consistent with
atmospheric input sources, there is no need to invoke sedi-
mentary fluxes.
Higher metal concentrations are observed in LIW relative
to ASW. Concentration maxima in intermediate waters in
the western M~ite~nean (BOYLE et al., 1985; COPIN-
MONTEGUT et al., 1986; HUYNH-NGOC and WHITEHEAD,
1986; SHERRELL and BOYLE, 1988 ) are probably also related
to the presence of LIW. The formation areas of LIW are not
well established but are believed to be located in the eastern-
most Mediterranean ( MALANOTTE-RIZZOLI and HECHT,
1988 ). No trace-metal data are available for this part of the
Mediterranean, but high concentrations due to the general
concentration increase in eastward direction would be ex-
pected ( SPIVACK et al., 1983). For Cd and Ni, LIW largely
retains its preformed signal on its way to the western Medi-
terranean, and trace-metal concentrations remain more or
less constant. For Cu, levels decrease somewhat, indicative
of continued particle scavenging. In contrast, deep water
concentrations between both basins differ considerably. Due
to the presence of the sill at the Strait of Sicily, deep water
exchange is largely impeded, as demonstrated by the different
hydrographical conditions in both basins ( PLAKHIN, 197 1,
1972).
Trace-metal concentrations are lower in EMDW than ASW
and LIW for Mn, Fe, and Cd at both stations and for Cu
only at Bannock Basin. Nickel concentrations are fairly uni-
form throughout the water column. The strong concentration
decrease of dissoIved Mn, Cu, and Fe could be explained by
Trace metals in seawater and anoxic brines
1427
continuous particle scavenging. It is difficult to explain the
concentration decrease of Cd by scavenging processes, since
open ocean profiles of Cd show no indication of strong scav-
enging behaviour. Nickel does not show any evidence of
scavenging, and there is no reason to believe that Cd would
be significantly more particle reactive than Ni. Control of
the dissolved Cd distribution by scavenging is not supported
by the very low particulate Cd concentrations either (see be-
low ) . Also, particulate-dissolved ratios are equal for Cd and
Ni and an order of magnitude lower than for Cu, Mn, and
Fe. If deep water Cd covcentrations reflect a preformed signal,
surface water concentrations at the deep water formation
areas must be well below average surface water levels at our
stations. Both the southern Adriatic Sea and the Aegean Sea,
believed to be deep water formation areas for the Ionian and
the Levantine basins, are close to populated areas. Although
no data have been published for these areas, it is highly un-
likely that surface water concentrations will be as low as our
deep water values. Preliminary data seem to confirm this
notion ( BOYLE and LEA, 1992). It therefore seems most likely
that at present the eastern Mediterranean is not at steady
state and that the high surface water concentrations, at least
of Cd and possibly Cu, are a recent feature, caused by an-
thropogenic inputs (MARTIN et al., 1989; DULAC et al., 1987).
Apparently, anthropogenic sources are less significant for Mn,
Fe, and Ni.
Lastly, deep water Fe, Ni, and Cd concentrations in
EMDW are higher at Tyro Basin than at Bannock Basin and
Station 5. This is in support of theories suggesting different
deep water formation areas for the Levantine and Ionian
basins and further suggests that exchange of deep water be-
tween both basins is impeded by the presence of the sill at
the Strait of Crete, in contrast with the literature report (cf.
MALANOTTE-RIZZOLI and HECHT, 1988).
The Brines
General trends are very similar to previous observations
in Framvaren Fjord (JACOBS et al., 1985; HARALDSSON and
WESTERLUND, 1988), the Cariaco Trench (JACOBS et al.,
1987 ) , and the Black Sea ( HARALDSSON and WESTERLUND,
1988; LANDING and LEWIS, 1991; LEWIS and LANDING,
1991). Dissolved Fe and Mn are extremely elevated at the
seawater-brine interface as a result of reductive dissolution
of Fe- and Mn-oxyhydroxides adsorbed on settling particles
and then decrease downward in the brines due to sulfide pre-
cipitation. Dissolved Cu and Cd decrease sharply due to sul-
fide precipitation, probably by incorporation into Fe-sulfides
(LUTHER et al., 1980, 1986). In reducing environments, Mn-
precipitation with carbonates has often been proposed as
limiting dissolved Mn concentrations (cf. MIDDELBURG et
al., 1987 ). This process could be important for Bannock and
Tyro basins; yet preliminary modelling (unpublished results)
indicates that carbonate anions are complexed extensively
by Mg and Ca, rendering the free carbonate concentration
low. It is possible that dissolved Mn concentrations are kept
low (cf. Orca Basin, TREFRY et al., 1984; Black Sea, LEWIS
and LANDING, 199 1) by precipitation as Mn-sulfides or co-
precipitation with pyrite. However, there are some contra-
dictory observations arguing against this option, which shall
be discussed in a following section.
The depletion of Ni in the brines is most intriguing and
to the best of our knowledge has not been witnessed before.
Nickel concentrations in anoxic waters of Cariaco Trench
(JACOBS et al., 1987) and Framvaren Fjord (JACOBS et al.,
1985; HARALDSSON and WESTERLUND, 1988) are much the
same as in the overlying oxygenated waters. In anoxic waters
of the Black Sea, LANDING and LEWIS ( 199 1) measured Ni
concentrations which were at most 40% lower than overlying
waters. Yet such a decrease was not found by HARALDSSON
and WESTERLUND ( 1988), who studied virtually the same
Black Sea location about four years earlier. On the other
hand, these anoxic seawaters presumably are all supersatu-
rated with respect to a solid Ni-sulfide phase (JACOBS et al.,
1985 ) . Also, Ni concentrations in Fe-sulfide minerals in salt
marsh sediments can be as high as a few percent (LUTHER
et al., 1980). One should also keep open the possibility that
Ni concentrations are regulated by coprecipitation with cal-
cium-carbonate. Total alkalinity at Bannock Basin and Tyro
Basin is much higher than at the anoxic basins of normal
salinity. No Ni analyses of local carbonate phases are avail-
able, however, to support this theory.
Just like Ni, dissolved U also showed strong depletion in
the brines (VAN DER WEIJDEN et al., 199Ob) but not in anoxic
basins of seawater salinity. This was attributed to the very
long residence times of the brine water, in combination with
the extremely high sulfide levels of the brine waters. The pre-
cipitation of a solid Ni- (or U-) phase would in general be
kinetically hindered and only be possible if the residence time
of the water is long enough to enable precipitation of a solid
phase. It must be noted that, in that case, reaction rates would
be extremely slow. There are some hydrographic consider-
ations to this theory in the case of Ni. In Framvaren Fjord,
the residence time of the water is on the order of 1000 yr,
and sulfide levels of deep waters are even higher than at Ban-
neck and Tyro basins ( SKEI, 1983), yet no Ni depletion was
observed at this site. If kinetic considerations are indeed a
key factor in determining the Ni- and U-depletions, this would
imply very high residence times for Bannock and Tyro Basins
and be in support of age estimates, based on oxygen isotope
measurements, of several thousands of years for these waters
( STENNI and LONGINELLI, 1990).
Alternatively, due to the high ionic strength and the ionic
composition, solubility products of metal-sulfides may be
entirely different from those in anoxic seawater of normal
ionic strength. Probably also, stability constants for most
metal-anion complexes change by several orders of magnitude
at these high ionic strengths (F. Millero, pers. commun.).
Unfortunately, the exact thermodynamic calculation of ionic
activity products and state of saturation with respect to the
least soluble solid phase is not trivial. First, the assessment
of activity coefficients in such a hypersaline medium is dif-
ficult. Secondly, thermodynamic formation constants of the
dissolved metal complexes in the brine are only partly known,
and thus calculation of the speciation of the metals in the
brine is highly speculative. Also, pH is an $-defined concept
in a solution with such a high ionic strength, making spccia-
tion calculations of sulfide quite challenging (S*-, HS-, H$,
various polysulfides) . Lastly, the selection of proper pure solid
phases or solid solutions from the literature data is not an
unequivocal issue. With the present dataset, it is not possible
1428 P. M. Saager, J. Schijf, and H. J. W. De Baar
to distinguish between kinetic hindrance, sulfide precipitation,
or carbonate precipitation as the mechanism responsible for
the observed N&depletion in the brines.
Comparison of our Fe data and sulfide data of LUTHER et
al. ( 1990) with those reported for Orca Basin ( WIESENBURC
et al., 1985) yields some remarkable features. Apart from
exact concentrations, the profiles of dissolved Fe and sulfide
in Bannock and Tyro basins are the mirror image of those
in Orca Basin (Fig. 8). Given these opposite trends, the ionic
concentration products are actually very similar in all three
basins (Table 2 ). At comparable total dissolved salts content
(Table 2), the ionic activity products may also be similar;
hence, it is conceivable to postulate solubility control by one
and the same solid iron-sulfide phase, most likely FeS, as
proposed by LUTHER ( 199 1). As with Ni, it is difficult to
provide a solid theoretical framework to determine the ther-
modynamic state of the dissolved species with respect to solid
Bannock Basin
1 2 3
sulfide (mmol/l) or Fe x 0.02 (nmol/kg)
Orca Basin
-2500 -II
0.0 10 20 3.0
sulfide (Fmol/l) or Fe x 0.08 (pmol/kg)
FIG. 8. Vertical distributions of dissoved Fe and H2S in Bannock
Basin and Orca Basin (data from WIESENBLJRG et al., 1985).
TABLE 2. Upper panel: Ionic compositions of Bannock and Tyro
Basin (suIti& dataof m et al.. 1990) compared with data from
Chca Basin (data of WIESENBIJRG et al.. 1985 ).
Lower panel: Major ionic composition (mostly Na and Cl) of Orca
(SHOKES et al.. 1977). Bannock and Tvro basins (DE LANGE et al..
r
199Oc).
species
(mmw
Bannock Tym Orca Basin
Basin Basin
I
Na+ 4200 5300 4720
K+ 125 19 19
cat
16.22 35 32
MC
613.644 71 51
Cl- 5400 5350 5000
SO42-
104.135 53 47
CC+- 4.1-4.2 4 45 5
salinity 322-326 ? 320
cond. @S/cm) 177 191 ?
phases. Nevertheless, the initial formation of (amorphous)
FeS as a direct control on dissolved concentrations may be
postulated (LUTHER, 1991 ), likely followed by transforma-
tion to pyrite framboids (JACOBS et al., 1985).
The low sulfide concentrations in Orca Basin have been
interpreted as the result ofgreatly decreased bacterial activity
in the brine due to the high salt content ( WIESENBURG et al.,
1985). In light of the high sulfide levels found in Bannock
and Tyro basins (with similarly high salt contents as Orca
Basin), this explanation now has to be abandoned. The dif-
ference must probably be sought in differences in Fe input
into the brine basins. In that case, sulfide concentrations in
Orca Basin are not limiting the Fe concentration, but rather
are limited by the high Fe concentration. Figure 8 suggests
that the input of Fe into Orca Basin is much larger than into
Bannock and Tyro basins. Possible sources of Fe are disso-
lution of Fe-oxides on settling particles and influx of sedi-
mentary Fe by slumping and turbidites. However, such a
large difference will not be the result of a great difference in
atmospheric Fe-input, in view of the enormous dust input
into the Mediterranean, which would create an opposite effect
( GANOR and MAMANE, 1982). In the Orca Basin, turbidites
are a common phenomenon ( ADDY and BEHRENS, 1980),
as well as in Bannock and Tyro basins (CAMERLENGHI,
1990). The difference would then have to be ascribed to dif-
ferences in the frequency of turbidite deposition and the
leachable Fe content of the turbidites. Recently, intense mud
flows were observed for Orca Basin (BROOKS et al., 1990).
The Orca Basin brine probably originates outside of the basin,
flowing over the sea floor into the basin (BROOKS et al., 1990).
It is possible that this brine has become enriched in Fe before
entering the basin. In contrast, Bannock and Tyro brines are
formed by dissolution of evaporites outcropping on the walls
of the basins themselves ( CAMERLEINGHI, 1990).
Interestingly, concentrations of Fe and Mn and, to a lesser
extent Ni and Cu, in the two brines of Bannock Basin differ
significantly, along with many other chemical parameters (cf.
DE LANGE et al.. 1990~). The differences in Mn concentra-
Trace metals in seawater and anoxic brines 1429
tions cannot be explained by alteration of the brines prior to
outflow into the basin as in Eqn. 1:
Mg2+ + ( 1 + x)SO:- + (2 + x)CaCOs
+ (2 + 2x)HzO + CaMg(CO&
+ (1 + x)CaS04~2H20/ + xCO:-, (1)
where dolomite incorporates large quantities of Mn. DE
LANGE et al. ( 199Oa) showed that the upper brine has un-
dergone more extensive dolomitization than the lower brine.
As dolomite was found to incorporate large amounts of other
ions such as Mn (DE LANGE et al., 199Oa; ZENGER et al.,
19801, this would tend to decrease the Mn concentrations
in brine 1 relative to brine 2. In fact, the opposite was found
(Fig. 3b). Coprecipitation of Mn with calcium-carbonate may
account for the difference. Alkalinity increases from 2.7 peq/
kg in seawater to 4 peq / kg in brine 1 to 4.2 peq / kg in brine
2 (from DE LANGE et al., 199Ob). Latter increase normalized
to Mediterranean seawater is of approximately similar mag-
nitude as the decrease of Mn. Although carbonate data were
not published, CO:- concentrations seem very similar in both
brines (De Lange, pers. commun.; unpubl. i-es.), thus arguing
against carbonate precipitation as the mechanism responsible
for the difference in Mn concentrations between the two
brines.
As mentioned earlier, it would be possible that Mn con-
centrations in the brine are limited by precipitation of sulfides.
This is supported by the fact that the apparent ion concen-
tration products of Mn and sulfide are similar in brine 1 and
brine 2 (10.1 * IO-, 11.4. 10-2, respectively). Also, the
dissolved profiles of Mn and sulfide show an opposite trend
in the two brine layers. Actual activity products may be either
more different or more similar in view of small differences
in ionic strength and composition between the two brine lay-
ers ( DE LANGE et al., 199Oc). Particulate Mn concentrations
in the brine are one order of magnitude higher than in ox-
ygenated overlying waters but are still very low, and Fe-sul-
fides in the water column do not seem to contain high con-
centrations of Mn. Higher particulate Mn concentrations may
be caused by incorporation into sulfides but may also partly
be caused by much lower sinking rates in brine water due to
the high density ( = 1.2 kg/L). Unfortunately, we have no
info~ation about particle com~sition. Other anoxic basins
of normal salinity often appear to be just saturated with re-
spect to MnS-phases (JACOBS et al., 1987). Thus, water col-
umn data do not seem to support in situ precipitation of Mn-
sulfide phases as the major process determining the Mn con-
centrations in the brines. On the other hand, the sink for Mn
may well be located in the sediment. Due to their restricted
size, horizontal mixing along isopycnals may be of consid-
erable importance in the basins, and the seawater composition
could well be in steady state with respect to porewaters at the
sediment-water interface. Dissolved Mn and sulfide would
then be transported along isopycnals to the sediment-water
interface and there be removed in the sediment. This need
not be a pure Mn-S phase but could well be FeS which con-
tains Mn (LUTHER et al., 1986).
The distribution of dissolved Fe is probably determined
by FeS and subsequent formation of pyrite (LUTHER, 199 1).
Apparent concentration products of [Fe] [ HS-j in the two
brines are very similar (Table 2) + This process may also ac-
count for the difference in Ni and Cu. Pyrite framboids have
been observed in the water column (VAN DER SLOOT et al.,
1990). The dramatic concentration decrease below the sea-
water-brine interface argues for in situ removal of Fe.
Also, Mn and Fe exhibit a minimum at the interface be-
tween brine 1 and brine 2. The mi~mum of Mn and maxima
of phosphate and aikalinity at the interface of brine 1 and
brine 2 have been explained as resulting from recent dolomite
precipitation and carbonate recrystallization at the interface,
according to Reaction 1 (DE LANGE et al., 1990a). The min-
ima for Fe and REE (SCHIJF, 1992) may be related to the
same process.
The temperature profile in the upper brine of Bannock
Basin is characterized by a multilayered structure ( BOLDRIN
and RABITTI, 1990)) indicating it is less well mixed than the
lower brine and the brine in Tyro Basin. This small-scale
structure is also revealed by F- and HzS and to a lesser extent
is still shown by the ~st~butions of dissolved Fe, Mn, and
REE ( SCHIJF, 1992). From the interface to about 3335 dbar
depth, the temperature is constant and this layer is charac-
terized by the very distinct maxima for Mn (DE LANGE et
al., 1990b), Fe, and REE at the seawater-brine interface with
concentrations dropping dramatically to the base of this layer.
Apparently, removal processe s, such as pr~pi~tion of sul-
fides (DE LANGE et al., 199Oc), occur much faster than mix-
ing. At the interface between brine 1 and brine 2, concen-
trations of dissolved Mn, Fe, and REE show a distinct min-
imum, where the strong temperature gradient also argues
against any vertical mixing across this interface. Also, the
con~ntmtion differences between the various layers are not
eroded by mixing, indicating that mixing between the iayers
is limited. These results imply that vertical advection diffusion
models to model trace-metal profiles in the brines, such as
used for the Black Sea (SPENCER and BREWER, 197 1) , would
be invalid in the brines or at the seawater-brine interface.
This type of model only applies when potential tem~mture
and salinity are linearly related and horizontal advection is
negligible. The former condition is not valid, and the latter
may not be valid either. Due to the restricted size of the
brines, lateral transport along isopycnals into and from the
sediment may in fact dominate transport.
Particulate Metals
Particulate metal concentrations in the overlying oxygen-
ated waters were all lower than dissolved concentrations. The
particulate-dissolved ratio varies from element to element.
Taking the particulate con~ntration at Tyro Basin at 3300
m depth as best representing the overlying oxygenated water
column, the ratio decreases in the order Fe > Mn F+: Cu >
Cd(?) = Ni, the uncertainty of Cd reflecting the limited
quality of particulate concentrations near the detection limit.
This order reflects both the relative particle affinity of each
metal and partly the amount present in the refractory fraction.
Only for Fe, this fraction is thought to be large ( SHERRELL,
1989). Pyrite dissolves in hot nitric acid. The ratio for Fe
and Mn is about one and reflects the well-known particle
reactivity of both elements (cf. LANDING and BRULAND,
1987). The ratio for Cu is also significantly higher than for
i430
P. M. Saager, J. Schijf, and H. J. W. De Baar
Cd and Ni and is in accordance with the scavenging behaviour
of this element as reflected in the dissolved vertical profiles
in the open ocean (BOYLE et al., 1977). Cadmium and Ni
are least particle-reactive. This further supports our previous
remark that scavenging does not account for the strong con-
centration difference of Cd between ASW and LIW relative
to EMDW.
In the brine, this order changes to Fe > Cu( XCd?) > Ni
B Mn. The major difference with the oxygenated waters is
the position of Mn. Manganese is much more soluble in a
reducing environment, as clearly shown by the very low par-
ticulate-dissolved ratio of about 10m4. This would not support
an in-situ sink for Mn, also because the turn-over time of
particles would have to be very rapid in order to quantitatively
remove dissolved Mn from the water column. In view of the
high density of water in the brines, this is not very likely.
Particulate Mn concentrations just above the seawater-brine
interface do not show a pronounced maximum and are lower
than reported for the Black Sea (LEWIS and LANDING, 199 1).
Besides the possibility that this is just an artefact due to the
poor sampling resolution in relation to the sharp and small
interface (DE LANGE et al., 1990b), it may be the result of
the strong density gradient. This prevents turbulent exchange
of dissolved Mn across the interface, which upon oxidation
would have precipitated as Mn oxides. At Orca Basin, par-
ticulate Mn concentrations above the seawater-brine interface
are much higher, in keeping with the orders of magnitude
higher (eddy) diffusion coefficients calculated for Orca Basin
( WIESENBURG et al., 1985).
In the brines, the particulate-dissolved Fe ratio still is about
one. The higher particulate concentrations are probably
brought about by precipitation as Fe-sulfides, which, however,
have a higher solubility than Fe-oxyhydroxides, thus allowing
higher dissolved Fe concentrations in the brine than in ox-
ygenated water. The presence of Fe-sulfide phases and pyrite
framboids was demonstrated by SEM (VAN DER SLOOT et
al., 1990). Only a very small part of the Fe will be related to
the alumino-silicate (detrital) fraction, namely approximately
the particulate Fe concentration of the overlying waters, thus
less than lO% ofthe total partjcufate fraction. Fe-monosulfid~
incorporate significant quantities of Mn (LUTHER et al.,
1980), possibly as a solid solution with MnS, but lose most
of it during conversion to pyrite.
Particulate-dissolved ratios of Cu and Cd are higher than
that of Ni, in accordance with the observation that Ni-de-
pletion is seldom observed in anoxic basins. Nickel appears
to be less particle-reactive than Cu and Cd in anoxic waters
of Bannock and Tyro brines. Pure sulfides of Ni, Cu, and Cd
are hardly ever present in anoxic marine environments, and
it is thought that pyrite may account for the removal of these
elements from the water column (LUTHER et al., 1980, 1986).
This still does not explain the dist~bution of Ni, since pyrite
has been demonstrated in other anoxic basins as well ( SKEI,
1983), although Ni depletion was not observed. Lastly, it is
possible that Ni, Cu, and Cd are associated with particulate
organic matter found near the interface ( WENNEKE and DE
LANGE, 1990). VAN DER SLOOT et al. ( 1990) found Fe and
Zn to be associated with particles of biological origin, also
containing P, S, and Ca. Cu, however, appeared to be asso-
ciated exclusively with Fe-phases, most likely pyrite. Nickel
and Cd were not measured by them.
There is a striking difference in particulate trace-metal dis-
tribution between the Tyro and Bannock basins, both qual-
itatively and quantitatively. ERBA (1989) showed that pel-
liculate particles at the seawater-brine interface of both basins
differ in colour, in aspect, and in concentration density, being
most abundant in Bannock Basin. She attributed this to fre-
quent disturbance of the interface at Tyro Basin by turbidites.
In Bannock Basin, particulate Fe, Ni, Cu, and Cd concen-
trations in the brine are in fact not significantly higher than
in normal Mediterranean seawater. Only at the interface are
levels very high, but in the brine they again decrease sharply
with depth. In situ formation of solid phases such as pyrite
at the interface and stagnation of sinking particles due to the
strong density gradient may account for such a particle max-
imum (e.g., ERBA, 1989; DE LANGE et al., 1990a; VAN DER
SLoor et al., 1990).
Finally, the concentration of particles in the brine will be
greatly influenced by their sinking rate in the brine. The ratio
of sinking particles to suspended particles in the brines may
be completely different from the overlying seawater and may
also be different between the Tyro and Bannock basins. Fu-
ture studies should pay careful attention to the particle cycle
in the brines, preferably by combination of in situ filtration
techniques ( SHERRELL, 1989) and sediment traps.
1)
2)
3)
4)
CONCLUSIONS
The distributions of dissolved Ni, Cu, and Cd in the east-
ern Mediterranean are governed by the general water cir-
culation and local input. There is no correlation with the
nutrients. This is in agreement with previous reports for
the western Mediterranean.
The vertical dist~bution of Cd indicates that the eastern
Mediterranean is probably not in a steady-state situation,
likely as a result of anthropogenic input.
At the seawater-brine interface, reductive dissolution of
Fe and Mn occurs. In the brines, the concentrations of
al1 trace metais appear to be limited by formation of i n-
soluble sulfide phases. Precipitation with carbonates may
be of importance for Mn and possibly Ni. For Ni, this is
the first report of such dramatic depletion in an anoxic
basin. Possible mechanisms include kinetic hindrance of
sulfide precipitation, different thermodynamic conditions
with respect to solid phases as a result of the high ionic
strength, and ionic com~sition of the brines compared
to normal salinity anoxic basins and precipitation by car-
bonate phases.
The profiles of dissolved Fe and sulfide are the mirror
image of those found previously in the Orca brine (Gulf
of Mexico), yet the ionic concentration products are
strikingly similar in all three basins.
Acknowledgments-We thank officers and crew of the RV Tyro for
their assistance during sampling. Jeroen de Jong is thanked for the
dissolved Mn analyses of the brine samples. Comments by G. Luther
and an anonymous reviewer considerably improved the manuscript.
This research project was supported by the Netherlands Council of
Oceanic Research (NRZ ) .
Ediforinl bundling: F. J. Miller0
Trace metals in seawater and anoxic brines
1431
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