ARTICLE IN PRESS

Deep-Sea Research II 53 (2006) 1787–1801

www.elsevier.com/locate/dsr2

Alkalinity of the anoxic waters in the Western Black Sea

William T. Hiscock, Frank J. Millero
Department MAC, Rosenstiel School of Marine and Atmospheric Science, University of Miami, 4600 Rickenbacker Cswy,
Miami, FL 33149, USA
Received 1 October 2005; received in revised form 4 February 2006; accepted 9 May 2006
Available online 7 September 2006

Abstract

Measurements of total alkalinity and nutrients were made on samples from discrete depths, aboard the R/V Knorr, May
2001 in the Black Sea. Determination of macronutrient concentrations permits inclusion of these minor bases in alkalinity
calculations and thus improved determination of the carbonate system. The permanent pycnocline maintains vertical
separation of the oxic, suboxic and anoxic waters of the Black Sea. Results show an apparent excess in alkalinity and/or
deficit in hydrogen sulfide from the stoichiometric ratio predicted from the sequential oxidation of Redfield organic matter
by sulfate in the anoxic waters near the center of the western gyre. The lateral ventilation of the main pycnocline by
Bosporus plume waters is responsible for consuming or removing sulfide from the anoxic zone. The removal of sulfide via
intrusion of oxygen-enriched waters and generation of alkalinity and total inorganic carbon dioxide via dissolution of
calcium carbonate results in differing stoichiometry between the upper and lower anoxic zones in the center of the western
gyre. Changes in the distribution of nutrients and hydrogen sulfide are due to the oxidation of particulate organic matter
apparently due to increased productivity in surface waters.
r 2006 Elsevier Ltd. All rights reserved.

Keywords: Black Sea; Anoxic basin; Macronutrients; Biogeochemical cycle; Anoxic/oxic zonation

1. Introduction result of the rise in global sea level. The influx of

The Black Sea is a residual basin of the ancient
Tethys Sea; its present form is hypothesized to have
emerged about 58 million years ago when structural
upheavals in Anatolia split off the Caspian basin
from the Mediterranean (Ryan et al., 1997). During
the last glacial period, the Black Sea was a low
salinity lake. About 7500 years ago (Ryan et al.,
1997) saline water from the Mediterranean entered
the Black Sea through the Bosporus Strait as a
Corresponding author. Tel.: 305 421 4710; fax: 205 421 4144.
E-mail addresses: whiscock@rsmas.miami.edu
(W.T. Hiscock), fmillero@rsmas.miami.edu (F.J. Millero).
saline waters led to a density stratification of the
basin, with depletion of oxygen and development of
sulfide in the deep water. Salinity gradually in-
creased Black Sea until some 3000 years ago when
the existing vertical salinity gradient became estab-
lished (Deuser, 1974; Glenn and Arthur, 1985). At
present, nearly 87% of the Black Sea waters are
anoxic and contain high levels of sulfide.
A permanent halocline at a depth of 100–200 m
separates the brackish, oxygenated surface waters
from the saline, sulfide-rich deep waters (Sorokin,
1983; Kempe et al., 1990; Lyons et al., 1993), acting
as a natural barrier and inhibiting vertical fluxes. A
suboxic zone with undetectable levels of oxygen and

0967-0645/$ - see front matter r 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.dsr2.2006.05.020
 ARTICLE IN PRESS
1788 W.T. Hiscock, F.J. Millero / Deep-Sea Research II 53 (2006) 1787–1801

hydrogen sulfide (H2S) in the center of the Black Sea 47°N

UKRAINE
ROMANIA
(Murray et al., 1989) further inhibits the downward RUSSIA
Sea of
flux of oxygen and all other advective and diffusive 46°N Azov
processes allowing interaction between the oxic/ 45°N
anoxic zones. The onset of hydrogen sulfide, on
average, coincides with the permanent halocline at 44°N
Black Sea
st
16.2. Due to internal waves and long-term 43°N
changes in mean circulation, the actual depth of
42°N
the onset of H2S varies both spatially and tempo-
rally (Shaffer, 1986; Kempe et al., 1990; Lyons 41°N
et al., 1993). However, there has been little change in TURKEY
40°N
the onset of H2S in relation to density (Konovalov
et al., 1999; Konovalov and Murray, 2001), despite 28°E 30°E 32°E 34°E 36°E 38°E 40°E 42°E
the dramatic and well-documented changes observed 43°N
at various levels of the Black Sea ecosystem Black Sea
(Gomoiu, 1992; Mee, 1992; Zaitsev, 1993; Bologa 6
et al., 1995; Cociasu et al., 1996, 1997; Leppakoski
and Mihnea, 1996). The Black Sea has evolved from 5
a highly biodiverse ecosystem, rich in biological 42°N
7-8
resources, to a low biodiversity ecosystem (Zaitsev 2-4
and Mamaev, 1997). The changes have resulted from 9 - 10
the intensive eutrophication of the ecosystem caused
by anthropogenic perturbations in both the Black 41°N
Sea waters and the drainage basins of its major Sea of
Marmara
supplying rivers (Mee, 1992; Mutlu et al., 1994;
Leppakoski and Mihnea, 1996).
TURKEY
The sharp salinity gradient of the main pycno-
40°N
cline is maintained by the freshwater inflow in the 27°E 28°E 29°E 30°E 31°E 32°E
surface layer from rain and rivers and the saline
waters flowing in from the Bosporus Strait. The Fig. 1. Above: The Black Sea. Below: The location of 10 stations
occupied by the R/V Knorr during the 2001 Black Sea Expedition
warm saline waters intruding the Black Sea are
on Leg 1, 21–31 May 2001.
connected to the distant waters of the Atlantic
Ocean by the succession of the narrow and shallow
Bosporus Strait and Sea of Marmara, Dardanelles,
Aegean Sea and the Mediterranean Sea (Fig. 1). All et al., 1991). The lateral ventilation of the main
deep water in the Black Sea forms by mixing pycnocline dramatically effects the redox budget
between the Bosporus outflow and overlying cold and results in the oxidation of H2S (Konovalov
intermediate water (Cold Intermediate Layer (CIL)) et al., 2003).
(Murray et al., 1991). The residence time of the deep The Black Sea environment provides a natural
water with respect to this Bosporus Plume has been laboratory to investigate nutrient regeneration and
estimated from 387 (Murray et al., 1991) to about respiratory processes in an anoxic system (Brewer
2500 years (Ostlund and Dyrssen, 1986; Boudreau and Murray, 1973; Smethie, 1987). In this paper,
and LeBlond, 1989). The Bosporus is a two-layer carbonate and nutrient measurements are reported
system, carrying about 175 km3 yr1 saline water from the 2001 Black Sea Expedition on the R/V
(S
34) from the Mediterranean to the Black Sea Knorr and present new carbonate (pH, total
along the bottom and returning about 350 km3 yr1 alkalinity (TA) and total inorganic carbon dioxide
of low salinity water (S
18) in the upper layer. The (TCO2)) and nutrient ðPO3  þ
4 ; SiðOHÞ4 ; NO3 ; NH4 ;
intrusions of Bosporus plume waters can be traced H2 SÞ measurements made at sea on samples
to a depth of 500–700 m (Murray et al., 1991; Oguz collected near the Bosporus. The most extensive
and Rozman, 1991; Ozsoy et al., 1991) and provide study to date of the carbonate system in the Black
lateral injections of oxygen and other dissolved Sea (Goyet et al., 1991) was based on collected fixed
substances into the main pycnocline (Buesseler with HgCl2 and analyzed in the shore laboratory.
 ARTICLE IN PRESS
W.T. Hiscock, F.J. Millero / Deep-Sea Research II 53 (2006) 1787–1801
The addition of Hg2+ minimizes changes in the
TCO2 in the sample, but also precipitates the H2S
that contributes to the TA of the waters. The
corrections for the loss of H2S are difficult to
calculate and lead to some uncertainties in the
carbonate system. The determination of macronu-
trient concentrations permits inclusion of these
minor bases in alkalinity calculations and thus an
improved determination of the carbonate system. In
addition, measurements near the Bosporus allow us
to examine the effects of lateral intrusions of
oxygen-enriched waters on the stoichiometry of
the chemical reactions in the suboxic and anoxic
waters. The Black Sea shows a dramatic range of
chemical expression, and this investigation details
the carbonate alkalinity (CA), total inorganic
carbon and macronutrient distributions, across the
interface, between (suboxic) and within the anoxic
and oxic layers of the water column.
2. Materials and methods
Measurement of total alkalinity and nutrient
parameters occurred aboard R/V Knorr, 21–31
May 2001. Samples were collected by hydrocasts
throughout the water column using a rosette system
with 10-L Niskin bottles. Repeat casts provided
detailed sampling across the oxic/anoxic interface.
This study, Leg 1 of the 2001 Black Sea Expedition,
focused on the southwestern portion of the Black
Sea, adjacent to the shallow Bosporus Strait. In
total, 44 casts from 10 stations were sampled across
the oxic/anoxic interface and in the deep waters
(Fig. 1). Samples were drawn from the Niskin
bottles into 500-mL borosilicate flasks using silicone
tubing that fit over the petcock. Bottles were rinsed
a minimum of two times and filled from the bottom,
to avoid bubbles. Sample bottles were sealed
with glass stoppers and Apezions grease and stored
at room temperature for a maximum of seven
hours. Periodically duplicate samples were drawn.
Data obtained includes depth profiles of hydro-
graphic properties, potentiometric pHSWS , total
alkalinity, and the nutrient variables: silicic acid,
phosphate, nitrate, ammonia and hydrogen sulfide.
Hydrographic properties for these samples are
tabulated in Appendix A. All cruise tracks, station
locations, participants and data (hydrographic,
oxygen/sulfide, nutrients) are available on the cruise
web site at: www.ocean.washington.edu/cruises/
Knorr2001.
1789
2.1. Macronutrients
Phosphate ðPO3 4 Þ, silicic acid (Si(OH)4), nitrate
NO 3 , nitrite NO  þ
3 , ammonia ðNH4 Þ and hydrogen
sulfide (H2S) were measured utilizing novel liquid
core waveguides (LCW). The colorimetric methods
of Armstrong et al. (1967) and Bernhardt and
Wilhelms (1967) were optimized for continuous flow
analysis, and reaction products were heated to

55 1C to enhance the color development. The
automated colorimetric method for the analysis of
hydrogen sulfide was similar to the method devel-
oped and investigated by Cline (1969). Absorbance
measurements by individual Ocean Optics Spectro-
photometers (S2000) were performed in custom
length Teflon AF-2400 (Dupont) LCW. The range
of linear response desired for the analysis of
inorganic nutrient concentrations was customized
for work in the high concentrations and the oxic/
anoxic environments of the Black Sea.
Although sulfide exists predominately as ionized
HS in seawater ( pHSWS 7–8), it is discussed here as
the total concentration of hydrogen sulfide and
denoted as H2S. The interference of high H2S
concentrations with measurement of phosphate,
silicic acid and nitrate were overcome by sparging
an acidified sample with nitrogen gas from a Balston
N2 generator. The acidified sample remaining after
the alkalinity determination was utilized and a
correction factor (
1%) was made for the dilution
by hydrochloric acid. Secondly, the titrated sample
was pre-equilibrated to a temperature of 25 1C.
Samples suspected of containing H2S were not
analyzed for nitrate because H2S precipitates in the
copperized cadmium reductor. Nitrite concentra-
tions were not analyzed separately due to the
uniformly low concentrations (o1.0 mmol kg1)
found in previous investigations (Friederich et al.,
1990; Codispoti et al., 1991). The sum of nitrite and
nitrate were analyzed simultaneously, discussed here
as the sum of nitrate and nitrite and hereinafter
referred to as NO 3 , unless otherwise specified.
The PO3 4 reagent potassium antimony tartrate
ðKðSbOÞC4 H4 O6 Þ has a known H2S interference.
To minimize the interference of potassium antimony
tartrate and H2S, the concentration of potassium
antimony tartrate was increased. Samples from the
deep anoxic waters with high concentrations of
nutrients were diluted allowing spectrophotometric
measurements to be performed over a smaller linear
dynamic range. The detection limits for the mea-
sured values were: 72.0 mmol kg1 at low levels
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1790 W.T. Hiscock, F.J. Millero / Deep-Sea Research II 53 (2006) 1787–1801

(o100 mmol kg1) and75.0 mmol kg1 at high levels Salinity

(o350 mmol kg1) for SiðOHÞ4 ; 70.3 mmol kg1 at 18 19 20 21 22
low levels (o25 mmol kg1) and71.3 mmol kg1 at
Temperature (°C)
high levels (o50 mmol kg1) for NHþ 4 ; 71.0 mmol 8 10 12 14 16

Upper σ = ρ ,T,0 - 1000 (kg m-3)

kg1 at low levels (o150 mmol kg1) and 77.5 12.5
mmol kg1 at high levels (o500 mmol kg1) for H2S, Temperature
70.07 mmol kg1 (o10 mmol kg1) for PO3 4 ; and
13.0 Salinity
Oxygen
73.4 mmol kg1 (o20 mmol kg1) for NO 3 . H2S
13.5

Oxic
2.2. pH and total alkalinity 14.0

S
The total alkalinity of seawater (TA) was

t
14.5
evaluated from the proton balance at the alkalinity

Oxycline
Main Pycnocline
equivalence point, pHequiv ¼ 4.5, and zero ionic 15.0
strength in 1 kg of sample, utilizing a multi-point
hydrochloric acid titration with seawater according 15.5

Suboxic
Lower
to the definition of alkalinity of Dickson (1981). A
16.0
program uses a Levenberg-Marquardt nonlinear
least-squares algorithm to calculate the TA, 16.5

TCO2 ; pK1 and pHSWS from the potentiometric
titration data (Millero et al., 1993). Samples
containing high H2S concentrations were examined
first to prevent atmospheric contamination of the
sample. The accuracy and precision of the titration
system was examined throughout the cruise by
making titrations on Certified Reference Material
(CRM-Batch 38), and the measured values of TA
agreed to 72 mmol kg1. The values of TCO2 were
calculated from pHSWS and TA using the constants
of Mehrbach et al. (1973) as reformulated by
Dickson and Millero (1987). They should be reliable
to 73 mmol kg1.
3. Results and discussion
The thermohaline structure of the Black Sea is a
defining characteristic and unique in comparison to
its typical oceanic counterparts. The vertical struc-
ture is associated to the distribution of properties
and processes in the Black Sea. The physical and
chemical structure of the water column at the center
of the western gyre is best described in terms of
sigma-t (st) values; typical distributions are depicted
in Fig. 2. The salinity of the surface waters in the
Black Sea is approximately half that of the open-
ocean water and similar in chemical composition
(Goyet et al., 1991). A marked increase in salinity,
up to 21, occurs at depths of
50–170 m, below
which the salinity increase is much more gradual.
The increase in salinity is the main control on the
pycnocline. There is a prominent temperature
minimum characteristic of the CIL that occurs in
Anoxic
17.0
17.5
0 100 200 300 400 500
H2S (µmol kg-1)
0 100 200 300 400
Oxygen (µmol L-1)
Fig. 2. Temperature, salinity, oxygen and hydrogen sulfide versus
density (st) for selected hydrocasts near the center of the western
gyre. The CIL is bounded by 8 1C isotherms, dashed vertical line.
Its core is located at st
14.5-14.6. The main pycnocline is
located between st
14.5 and 16.5 and separated into upper and
lower parts at st
15.5. The water column is divided vertically
into three layers; oxic, suboxic, and anoxic. Within the oxic layer
is the oxycline, which is located between st
14.4–14.6 and st

15.6–15.9. The suboxic layer extends from about 15.6 to 16.2.
The upper boundary of the anoxic layer is at st
16.2.
the main pycnocline centered at st
14.5. The
oxycline below the base of the oxic layer is a region
of decreasing oxygen concentrations occurring
between st
14.4–14.6 and st
15.6–15.9. Below
the oxic layer and the oxycline is a zone of
40 m,
which is suboxic and has a lower boundary at st

16.2. Oxygen and hydrogen sulfide are both below
limits of detection in the suboxic zone. The deepest
parts of the Black Sea are characterized by
T ¼ 8.5–9.0 1C and S ¼ 22:32, and are in steady-
state on a time scale of centuries (Konovalov and
Murray, 2001). The onset of H2S and the upper
boundary of the anoxic layer are generally accepted
to occur at stE16.2 (Konovalov and Murray,
2001). Previous data confirms that the density of
 ARTICLE IN PRESS
W.T. Hiscock, F.J. Millero / Deep-Sea Research II 53 (2006) 1787–1801 1791

the onset of H2S has varied little over time Salinity

(Vinogradov, 1991; Tugrul et al., 1992). Small 15 20 25 30 35 40
fluctuations in the actual depth of the oxic/anoxic
interface, both spatially and temporally, have been Temperature (°C)
observed on the time scale of a century (Konovalov 8 10 12 14 16 18
0
et al., 1999; Glazer et al., 2006; Yakushev et al.,
2006). The oscillation of the depth, but not density,
of the oxic/anoxic interface results from internal 10
waves, long-term changes in mean circulation and
exchange (Shaffer, 1986; Kempe et al., 1990; Lyons
et al., 1993). 20
Near the Bosporus, warm and saline Mediterra-
nean waters flow from the Sea of Marmara and 30 Temperature
intrude into the western gyre of the Black Sea. The Salinit y

Pressure (db)
salinity and temperature increase in deep water of Oxy gen
the Bosporus to 36.5 and 14.5 1C, in the Bosporus 40
(Fig. 3) The oxygen-enriched water flowing out of
the Bosporus entrains water from the overlying CIL
50
and is laterally injected into the oxic, suboxic and
anoxic zones of the Black Sea (Murray et al., 1991;

Bosporus Plume Waters

Konovalov et al., 2003). This lateral process
effectively controls the residence time of the main
pycnocline and the deepest waters. The depth of
injection of the Bosporus plume into the main
pycnocline and below the colder, less saline CIL is
dependant upon the entrainment ratio (Buesseler
et al., 1991; Murray et al., 1991; Ozsoy et al.,
1995a, b; Samodurov and Ivanov, 1998; Lee et al.,
2002). The core of the CIL is centered at st
14.5
and by definition bounded by 8 1C isotherms
(Konovalov and Murray, 2001). The intrusion of
the Bosporus plume shortens the residence time for
the layer of the main pycnocline to a few years
(Unluata et al., 1990; Buesseler et al., 1991)
compared to several hundred years for the deepest
layer (Murray et al., 1991). A comparison of profiles
of physical and chemical properties from the
southwestern shelf and the center of the western
gyre is shown in Fig. 4, which emphasizes the effect
of lateral injection of the Bosporus plume on the
oxic/anoxic interface. The upper boundary of the
profiles of H2S from the southwestern shelf region
differs significantly from those in the center of the
western gyre. At the center of the western gyre the
onset of H2S is shallow, st E16.2 and depth

110 m, compared to the deeper onset of H2S, st
E16.4 and depth greater than 170 m, near the
southwestern shelf. Temperature and salinity mea-
surements on the southwestern shelf reveal lateral
processes connecting the intrusions of the Bosporus
plume waters, which are identified by their warm
and saline anomalies (Ivanov and Samodurov, 2001;
60
70
80
0 100 200 300
Oxygen (µmol L-1)
Fig. 3. Temperature, salinity, and oxygen versus depth profiles
collected at Station 1 in the Bosporus Straits. The profiles depict
the warm and saline Bosporus waters, which flow from the Sea of
Marmara along the bottom of the Bosporus Straits and are
laterally injected into the western gyre of the Black Sea on the
southwestern shelf.
Konovalov et al., 2003). The lateral intrusions and
ventilation are observed only on the southwestern
shelf and result in small-scale isopycnal and cross-
isopycnal variability compared to the center of the
western gyre of the Black Sea. The influx of
the Bosporus plume waters is evident throughout
the main pycnocline (Konovalov et al., 2003).
3.1. Macronutrients and alkalinity results
A number of hydrocasts were made near the
center of the western gyre, at Station 6 and stations
nearby. The profiles of measured variables are
plotted against density in Fig. 5 and systematically
compared to the decadal time series presented by
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1792 W.T. Hiscock, F.J. Millero / Deep-Sea Research II 53 (2006) 1787–1801

Phosphate is also absorbed onto iron and/or

16.1 manganese oxides in oxic waters and released below
the interface due to the reduction of Fe(III) and
16.2
Mn(IV) by H2S. The maximum phosphate con-
Shelf Stations
16.3 centrations in the deep anoxic water reach approxi-
Sation 6
mately 9.5 mmol kg1. Modest increases of phos-
σT

16.4 phate concentrations may have occurred due to

eutrophication of the Black Sea (Konovalov and
16.5 Murray, 2001); however, this trend is ambiguous
due to the scatter in the temporal data.
16.6
The sum of nitrate and nitrite (NO3 ) increases to
0 10 20 30 40 50 60 70 80 a maximum at st
15.4–15.7 as a result of oxidative
H2S (µmol kg-1) regeneration in a narrow layer located just above
the suboxic zone. There is a nitrite maxima near the
16.1 lower boundary of the NO 3 maximum, correspond-
ing to a zone of denitrification (Murray et al., 2005).
16.2 Samples suspected of containing H2S ðst 416Þ were
not analyzed for nitrate because H2S precipitates in
16.3 the copperized cadmium reductor. Profiles of NO 3
σT

are similar to previous measurements (Codispoti

16.4
16.5
Shelf Stations
Station 6
16.6
8.3 8.4 8.5 8.6 8.7
Temperature (°C)
Fig. 4. Comparison of physical and chemical properties versus st
for the near shore stations of the southwestern shelf and center of
the western gyre. Above: Profiles of H2S. Below: Profiles of
temperature. The dashed horizontal lines represent a st of
16.2.
Konovalov and Murray (2001). As found in the
nearshore stations, the fluctuations in the oxic/
anoxic interface are believed to be at a minimum in
the center of the western gyre (Codispoti et al.,
1991).
The phosphate profile has two maxima. The
shallow maximum is due to the typical regenerative
and respiratory processes in the oxic zone. The
deeper maximum reflects complex scavenging and
desorption of phosphate associated with Mn and Fe
recycling in the suboxic and anoxic zones (Brewer
and Murray, 1973; Shaffer, 1986). Under aerobic
conditions, bacteria accumulate and store phos-
phate when excess dissolved phosphate is available.
Upon depletion of oxygen the stored phosphate is
utilized as an energy source and is eventually
released by bacteria to the surrounding solution
(Carlton and Wetzel, 1988; Gächter et al., 1988;
Toerien et al., 1990; Gächter and Meyer, 1993).
et al., 1991; Tugrul et al., 1992; Konovalov et al.,
1997), although the concentrations of NO 3 at the
maximum are higher,
13.5 mmol kg1. The higher
NO 3 concentrations may result from small changes
in fluxes of particulate nitrogen (Konovalov and
Murray, 2001). The removal of NO 3 occurs by
denitrification in the suboxic layers above st
16.0
and before the onset of H2 S. Denitrification can be
represented by
ðCH2 OÞ106 ðNH3 Þ16 ðH3 PO4 Þ þ 84:8HNO3
! 106CO2 þ 42:2N2 þ 148:4H2 O þ 16NH3 þ H3 PO4 .
ð1Þ
Kuypers et al. (2003) showed that anammox
ðNO þ
2 þ NH4 ¼ N2 þ 2H2 OÞ may also be active in
the Black Sea. NO þ
3 and NH4 concentrations both
go to zero in the suboxic layer at the same density
layer with little overlap. Ammonia concentrations
increase uniformly with depth from the oxic/anoxic
interface and attain maximum values of approxi-
mately 125 mmol kg1. In the suboxic zone nitrate is
used as an oxidant, but there is no concomitant
increase in ammonia.
Silicic acid uptake occurs in the euphotic zone
and dissolution occurs at depth, similar to the open
ocean. Silicic acid concentrations increase more or
less uniformly with depth from below the euphotic
zone and attain a maximum value of approximately
340 mmol kg1. Hydrogen sulfide concentrations
increase below st
16.2 at the center of the western
gyre, with concentrations increasing with depth
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W.T. Hiscock, F.J. Millero / Deep-Sea Research II 53 (2006) 1787–1801 1793

12 12

13 13

14 14

σT
σT

15 15

16 16

17 17

0 50 100 150 200 250 300 350 400 450 0 15 30 35 60 75 90 105 120
H2S (µmol kg-1) NH4+ (µmol kg-1)

12 12

13 13

14 14
σT

σT

15 15

16 16

17 17

0 1 2 3 4 5 6 7 8 9 10 0 50 100 150 200 250 300 350

PO43- (µmol kg-1) Si (OH)4 (µmol kg-1)

12 12

13 13

14 14
σT
σT

15 15

16 16

17 17

0 2 4 6 8 10 12 14 3200 3400 3600 3800 4000 4200 4400

NO3- (µmol kg-1) TA (µmol kg-1)

Fig. 5. Distribution of hydrogen sulfide, ammonia, phosphate, silicic acid, nitrate and total alkalinity versus st in the western gyre. The
dashed horizontal lines represent a st of
16.2.

to values as high as 465 mmol kg1 in the bottom While the depth of the onset of H2S has varied
waters. The sulfate ðSO2
4 Þ is reduced to H2S from little, the maximum concentrations of H2S have
the metabolic oxidation of particulate organic increased by
65 mmol kg1 since 1992. The max-
matter (POM) with the stoichiometry represented imum concentration for deep waters increased
by (Richards, 1965 ) from
400 mmol kg1 in 1992 (Konovalov and
Murray, 2001) to our maximum concentration of
465 mmol kg1. The observed increases for macro-
ðCH2 OÞ106 ðNH3 Þ16 ðH3 PO4 Þ þ 53SO2 
4 ! 106HCO3
nutrients, hydrogen sulfide and carbon relative to
þ 53H2 S þ 16NH3 þ H3 PO4 . ð2Þ earlier investigations may be due to increased
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1794 W.T. Hiscock, F.J. Millero / Deep-Sea Research II 53 (2006) 1787–1801

oxidation of POM. There has been increased presented by Yao and Millero (1995) and Millero
nutrient and organic material flux from the major (1995) . The CA is defined by
rivers to the Black Sea. As a result there has been 2
CA ¼ ½HCO
3  þ 2½CO3  (4)
increased nutrient concentrations in the main
pycnocline, increased primary production (Stel- and Fig. 6 shows the calculated CA and TCO2 in
makh et al., 1998), and eutrophication and degrada- relation to the measured total alkalinity and pHSWS .
tion of the marine ecosystem. This has presumably Hydrogen sulfide makes the largest contribution of
resulted in a corresponding increase in the flux of the minor bases to total alkalinity in anoxic waters.
POM reaching the anoxic zone.
Total alkalinity decreases with depth from the 3.3. Production of TA and TCO2
surface to the st
14.0 and then increases to the
sulfide interface at st
16.2. This increase correlates The measured values of TA and pHSWS and
well with the increase in salinity, phosphate and calculated TCO2 and CA versus density are plotted
silicic acid concentrations (Fig. 5). Below the oxic/ in Fig. 6. The values of TA in the oxic surface
anoxic interface, TA increases rapidly due to waters (
3500 mmol kg1) are higher than typical
bacterial anaerobic respiration of organic matter
to bicarbonate and simultaneous reduction of Total Alkalinity (µmol kg-1)
sulfate to hydrogen sulfide. 3200 3400 3600 3800 4000 4200 4400

3.2. Calculations of CA 13

The total alkalinity of seawater was evaluated 14

from the proton balance at the alkalinity equiva-
lence point according to the definition of total
σT

15
alkalinity as defined by Dickson (1981) pHSWS
TA ¼ ½HCO
3 þ 2½CO2
3  þ ½BðOHÞ
4

þ ½OH  16
TA

þ ½HPO2 3 
4  þ 2½PO4  þ ½SiðOHÞ3 O 
þ ½NH3  þ ½HS   ½Hþ F  ½HSO4
17

 ½HF  ½H3 PO4 . ð3Þ 7.3 7.4 7.5 7.6 7.7 7.8 7.9 8.0 8.1 8.2
TA is the concentration of all the bases that pHSWS (@ 25°C)
accept H+ when a titration is conducted to the
Total CO2 (µmol kg-1)
carbonic acid endpoint. For most waters ½HCO 3 , 3000 3200 3400 3600 3800 4000 4200
½CO2 
3  and ½BðOHÞ4  are the most important bases;
however, in the anoxic waters of the Black Sea, 13
½HS  and ½NH3  make significant contributions to
the total alkalinity. Therefore to calculate CA,
14
the contribution of the aforementioned bases as
well as the concentrations of ½HPO2 3
4 , ½PO4 ,
 
σT

½SiðOHÞ3 O , ½HSO4 , ½HF and ½H3 PO4  are 15

TCO2
required. The values of TCO2 were calculated based
CA
on the pHSWS at 25 1C, CA and salinity using the 16
carbonate constants given by Mehrbach et al. (1973)
as reformulated by Dickson and Millero (1987). The 17
visual basic program developed by Pierrot (2002),
which improved the functionality of the original 3000 3200 3400 3600 3800 4000 4200
‘‘CO2 System’’ basic program written by Lewis and Carbonate Alkalinity (µmol kg-1)
Wallace (1998) , was modified to include ½HS  and
Fig. 6. Above: Total alkalinity and potentiometric pHSWS at
[NH3 ] in addition to ½HPO2 3 
4 , ½PO4 , ½SiðOHÞ3 O , 25 1C versus density. Below: Calculated carbonate alkalinity and

½HSO4 , ½HF and ½H3 PO4 . The dissociation con- total inorganic carbon dioxide at in situ temperature and pressure
stants needed to make these calculations were versus density for Station 6 at the center of the western gyre.
 ARTICLE IN PRESS
W.T. Hiscock, F.J. Millero / Deep-Sea Research II 53 (2006) 1787–1801 1795

oceanic values as a result of the low salinity and high The relationship between TA and TCO2 should give
total alkalinity of river waters entering the Black Sea a slope of
(Dyrssen, 1985, 1986). The variations in TA are small  
DTA 106 þ 16  2
in comparison to the change in calculated TCO2  ¼ 1:13. (7)
DTCO2 106
concentrations above the oxic/anoxic interface. The
increase of TCO2 below the surface water is The linear correlation between these properties
indicative of oxidation of organic material by oxygen corroborates that TA and TCO2 increase propor-
below the photic zone. The increase in TCO2 tional to hydrogen sulfide release (Fig. 7). The
coincides with a decrease in pHSWS . The oxidation observed TA:H2S slope is 2.6570.01, which is
of a carbohydrate by oxygen in the oxic layer greater than the theoretical value of 2.3. The
consumes O2 and produces an equivalent amount difference between these values indicates there is
of CO2 while not effecting total alkalinity. The either a deficit of sulfide and/or an excess of TA.
decomposition of organic matter and associated Dyrssen (1985) suggested a small fraction of
release of nutrients proceed through the action of hydrogen sulfide is removed by iron sulfide without
heterotrophic bacteria in the water column. The altering TA and TCO2. In addition to sulfate
oxidative degradation or aerobic respiration of reduction, bacterial formation of ammonia affects
bacteria is restricted to the oxic layer, but miner- the proton balance and contributes to the increase
alization of organic mater is not restricted solely to of TA and TCO2 in the anoxic, sulfide containing
the oxic layer. After oxygen is depleted, bacteria use
other oxidants in a stepwise progression based on the
decreased energy yield from the reactions. The σt = 17.1
sequence of oxidants is nitrate ðNO ~500 m
3 Þ; manganese 4600
dioxide (MnO2), iron oxides ðe:g:; FeOOHÞ and TA
sulfate ðSO2 4 Þ; which are reduced to ammonia
4400 TCO2
TA and TCO2 (µmol kg-1)

ðNHþ 4 Þ; nitrogen (N2), nitrous oxide (N2O), dissolved 4200

manganese (Mn2+), iron (Fe2+) and hydrogen
sulfide ðHS Þ, respectively. 4000
The increasing concentrations in both TA and 3800
TCO2 in anoxic waters reflect the net effect of all
3600
oxidation-reduction reactions on the carbon and
proton balances. The increase of CA indicates that 3400
natural oxidants are progressively used for the
3200
oxidation of organic material and production of 0 50 100 150 200 250 300 350 400 450
CA. The normalized TA ðNTA ¼ TA  35=SÞ and HS- (µmol kg-1)
normalized TCO2 ðNTCO2 ¼ TCO2  35=SÞ in the
4600
bottom waters of the Black Sea are

6950 mmol kg1 for NTA and
7100 mmol kg1 4400
for NTCO2, about 3 times greater than the open- 4200
TA (µmol kg-1)

ocean values 2350 and 2050 mmol kg1. The in-

creases of TA and TCO2 in the anoxic layer are due 4000
to oxidation of organic material by sulfate reduc- 3800
tion. Assuming the stoichiometry of Eq. (2), the
3600
relationships between TA and TCO2 to H2 S
concentrations give slopes of 3400
  3200
DTA 106 þ 16  2 3200 3400 3600 3800 4000 4200
 ¼ 2:3, (5)
DH2 S 53 TCO2 (µmol kg-1)

Fig. 7. Above: TCO2 and TA versus hydrogen sulfide in the

anoxic water. Below: TCO2 versus TA in the anoxic waters. The
  linear fits are corrected for biases in the slope by calculating the
DTCO2 106
 ¼ 2:0. (6) geometric mean of Model I regressions of the variables with axes
DH2 S 53 reversed. Results are given in Table 1.
 ARTICLE IN PRESS
1796 W.T. Hiscock, F.J. Millero / Deep-Sea Research II 53 (2006) 1787–1801

waters. Furthermore, Eq. (3) for total alkalinity

does not take into account organic bases that may 13
contribute to the alkalinity and thus the difference
between the observed and theoretical ratios of 14
TA:TCO2. The nature of this organic fraction is
still uncertain, but it has been suggested that the

σT
15
organic fraction consists of amino acids or humic
substances. Since the true nature of the organic
16
fraction has not been determined, there are still
doubts about how it fits into the definition of
alkalinity and how the data should be treated and 17
normalized. The observed TCO2:H2S slope is
0 1 2 3 4 5 6 7 8
2.0270.02, in agreement with the theoretical Saturation State of Calcite
value of 2.0, indicating that the observed difference
in the TA:H2S represents a source in TA. The
13
linear correlation between TA and TCO2 in the
anoxic waters shows a slope of TA:TCO2 of
1.3270.01, which is higher than the theoretical 14
value of 1.13 and also suggests another contribution
to the TA.
σT
15
Values determined by Goyet et al. (1991) yielded
an ratio of 3.05 for TA:H2S (Table 1), which was 16
higher than that found in this study. Elevated TA
values could be due to the alkalinity generated by
17
dissolution of CaCO3 in the acidic CO2-rich deep
waters. The saturation coefficients of both calcite 0 1 2 3 4 5
and aragonite OCal and OArg show under saturation Saturation State Aragonite
at depth and support the hypothesis of dissolution Fig. 8. Calculated saturation states (O) of calcite and aragonite
of CaCO3 (Fig. 8). The value of OCal is less than 1 in for Station 6 at the center of the western gyre.

Table 1
Stoichiometric ratios in the anoxic and deep anoxic waters for the 2001 Black Sea expedition compared to theory and 1988 Black Sea
Expedition

Model Black Sea 2001 Black Sea 1988

Anoxica Deep Anoxica

TCO2:H2S 2.00 2.0270.02 2.1970.11 2.30c

TA:H2S 2.30 2.6570.01 2.7870.06 3.05c
TA:TCO2 1.13 1.3270.01 1.2770.01 1.32c
PO3
4 :H2S 0.019 0.01170.001 0.01770.001 0.009d
NH+ 4 :H2S 0.30 0.2670.01 0.2870.01 0.23d
Si(OH)4:H2S 0.27b 0.5370.01 0.4170.01 0.61d
C:N:P 106:16:1 190:25:1 130:16:1 255:25:1e
Si:C:N 0.9:6.6:1b 2.0:7.7:1 1.5:7.9:1 2.7:10:1
a
The stoichiometric ratios observed during the 2001 Black Sea Expedition are corrected for biases in the slope by calculating the
geometric mean of Model I regressions of the variables with the axes reversed. Error values represent the standard error of the calculated
slopes.
b
Si:N for diatoms averages 0.90 in the open ocean Brzezinski (1985).
c
Ratios for TCO2 and TA to H2S are from Goyet et al. (1991).
d
Calculations based on data report for 1988 Black Sea Expedition by Friederich et al. (1990).
e
Ratio for C:N:P from Yao and Millero (1995).
 ARTICLE IN PRESS
W.T. Hiscock, F.J. Millero / Deep-Sea Research II 53 (2006) 1787–1801
anoxic waters below st
16.9 (
400 m) and OArg is
less than 1 in anoxic waters below st
14.8 (
60 m).
The TA:H2S ratio for this study is higher,
TA:H2S ¼ 2.7870.06, in the deep anoxic water
below st
17.1 (
500 m) where calcite is under
saturated and there is little influence from lateral
influxes evident in the upper portion of the anoxic
layer and main pycnocline. The TCO2:H2S ratio is
also elevated in the deep anoxic water,
TCO2:H2S ¼ 2.1970.11, and diverges from theory
by approximately half of the divergence observed
for the TA:H2S ratio. The divergence in the TA:H2S
and TCO2:H2S ratios suggests dissolution of CaCO3
in the deep anoxic waters. Goyet et al. (1991) relied
solely on dissolution of CaCO3 to explain their
results. However, the difference between the anoxic
water above and below st
17.1 (
500 m) indicates
that lateral injection of oxygen rich Bosporus plume
waters may produce the observed differences from
the theoretical values. The lateral influx of oxygen
(O2) can directly affect the redox budget within the
main pycnocline and upper portion of the anoxic
layer, as shown in Konovalov and Murray (2001)
(Fig. 4). Dramatic changes in the distribution of the
main reduced redox species, H2S, Mn2þ and NHþ 4,
were observed by Konovalov et al. (2003) to be a
direct result of the lateral influx of O2 associated
with the Bosporus plume. Furthermore, the ratios
of DTA : DH2 S are quite different depending on
whether H2S is oxidized by O2 to sulfate ðSO2 4 Þ;
sulfite ðSO2 3 Þ; thiosulfate ðS 2 O 2
3 Þ or elemental
sulfur ðS0 or S8 Þ. The change in DTA : DH2 S de-
pends on the form of sulfur formed during sulfide
oxidation and the ratios for SO2 2
4 ¼ 2, SO3 ¼ 2,
2 0
S2 O3 ¼ 1 and S ¼ 0. If sulfide is oxidized to
SO2 2 2
4 ; SO3 or S2 O3 the total alkalinity would be
lowered, whereas if the product is elemental sulfur
or polysulfides the TA and TCO2 would be
unchanged but H2S would be removed. In addition
to direct oxidation of H2S, Konovalov et al. (2003)
present further details about mechanisms coupling
the manganese cycle with the sulfide-elemental
sulfur–sulfate cycle. The process begins in the oxic
layer where dissolved Mn2þ is oxidized to particu-
late Mn(III, IV) which then sinks into the anoxic
layer where manganese oxide ðMnO2 Þ acts as an
oxidant of H2S (Tebo, 1991; Konovalov et al.,
2003).
MnO2 þ HS þ 3Hþ ! Mn2þ þ S 0 ð18S8 Þ þ 2H2 O:
(8)
1797
The Bosporus plume water introduces a lateral flux
of O2 with the potential to affect the basin-wide
distribution of sulfide and consume as much as

70% of the sulfide sink (Konovalov and Murray,
2001). Therefore, injection of the Bosporus plume
could result in consumption of sulfide and thus
elevated TA:H2S and TCO2:H2S ratios in the upper
anoxic layer. Meanwhile, the classical generator of
oceanic alkalinity contributes to the observed
divergence of TA:H2S and TCO2:H2S ratios for
the deep anoxic waters.
The earlier results of Goyet et al. (1991) are less
reliable due to the addition of mercuric chloride
ðHgCl2 Þ to the TA samples, which resulted in
removal of H2S from the samples. The alkalinity
of the sample changes due to precipitation of
mercuric sulfide ðHgSÞ by the following reaction:
HgCl2 þ H2 S ! HgS þ 2Hþ þ 2Cl . (9)
The change in alkalinity for the anoxic deep waters
due to this effect may represent up to 20% of the
total alkalinity. In addition, Goyet et al. (1991) did
not account for injection of Bosporus plume waters.
3.4. Stoichiometry and macronutrients
The stoichiometry of chemical reactions in oxic
environments is frequently examined (e.g., Steinberg
et al., 1998; Hiscock and Millero, 2005), using the
Redfield ratio (Redfield et al., 1963). However, the
stoichiometry of chemical reactions in the anoxic
environment of the Black Sea and other anoxic
basins utilizes the Richards Eq. (2) (Goyet et al.,
1991; Zhang and Millero, 1993; Yao and Millero,
1995). The stoichiometric ratios for decomposition
of organic matter and the associated release of
nutrients during sulfate reduction can be used to
examine concentrations of carbon (C), nitrogen (N),
phosphorous (P), and sulfur (S) in this anoxic
system, Table 1. The theoretical ratios from Eq. (2)
are PO3 þ
4 : H2 S ¼ 0.019 and NH4 : H2 S ¼ 0:30. The
ratio of SiðOHÞ4 : H2 S depends on the relative
abundance of siliceous phytoplankton. The stoi-
chiometric ratios have been expanded to include
silica (Si) and are typically referred to as the
Redfield/Brzezinski proportion; Si:C:N ¼ 0.9:6.6:1
(Brzezinski, 1985 ). Using the Richards equation
yields a SiðOHÞ4 : H2 S ratio of 0.27. The Si:N ratio
in the open ocean ranges from 0.41 to 4.38
(Brzezinski, 1985; Dunne et al., 1999 ), and the
resulting range for the ratio of SiðOHÞ4 : H2 S is
0.12–1.3.
 ARTICLE IN PRESS
1798 W.T. Hiscock, F.J. Millero / Deep-Sea Research II 53 (2006) 1787–1801

The stoichiometric values are given in Table 1,
and the ratios of macronutrients to hydrogen sulfide
versus depth are plotted in Fig. 9. The macronu-
trients; PO3 þ
4 ; NH4 and SiðOHÞ4 , and the carbonate
variables; TA and TCO2, are corrected for initial
values at the onset of the anoxic layer in Fig. 9. The
vertical distribution of the values of macronutrients
to hydrogen sulfide illustrates the variability asso-
ciated with the upper portion of the anoxic layer
(o500 m) as compared to the deeper anoxic layer
(4500 m). In the deep anoxic waters, below st

17.1 (
500 m), the macronutrient to hydrogen
sulfide ratios are constant, as compared to the
higher values found in the upper portion of the
anoxic layer. The source of PO3 4 ; NH4
þ
and
SiðOHÞ4 in the anoxic layer of the Black Sea is
respiration of POM. A deficit of sulfide would result
in elevated macronutrient to hydrogen sulfide
ratios, and such a deficit may have resulted from
removal of sulfide as a result of the lateral injection
of oxygen-enriched waters of the Bosporus plume.
Macronutrients in the anoxic waters are plotted
oxyhydoxides. The removal of H2S in the upper
portion of the anoxic layer due to injection of O2
results in anomalies that prohibit fitting data
throughout the entire anoxic layer. In addition,
precipitation of hydrogen sulfide in the form of FeS2
results in the removal of H2S from the upper
portion of the anoxic layer (Muramoto et al., 1991).
The removal of H2S in the upper portion of the
anoxic layer by oxidation or sulfide formation
results in particulate S8 and FeS that can be
transported to the deep waters. The theoretical
ratio of SiðOHÞ4 : H2 S from remineralization of
biogenic silica (0.27) is lower than the observed
value of 0.4170.01. The high observed ratios may
indicate that silicic acid production is proportional
to production of hydrogen sulfide.
The C:N:P ratios for the deep anoxic waters yield
a stoichiometry of 130:16:1 (Table 1) for organic
matter and a revised version of the Richards Eq. (2)
can be given as
ðCH2 OÞ130 ðNH3 Þ16 ðH3 PO4 Þ þ 65SO2
4 ! 130HCO3


versus H2S in Fig. 10 . The observed ratios in the
deep anoxic waters were PO3 4 : H2 S ¼ 0:017
0:001, NHþ 4 : H 2 S ¼ 0:28  0:01 and SiðOHÞ4 :
H2 S ¼ 0:41  0:01 (Table 1). The fit for phosphate
versus H2S in the anoxic waters did not include data
near the interface where phosphate is affected by the
adsorption and desorption onto reactive Fe and Mn
þ 65H2 S þ 16NH3 þ H3 PO4 . ð10Þ
The values of Redfield/Brzezinski proportion yields
Si:C:N ratio ¼ 1.5:7.9:1, and values of the C:N
ratio in POM for the Black Sea range from 7.5 to
9.6 (Burlakova et al., 1997; Yilmaz et al., 1998;
Coban-Yildiz et al., 2006).

0 0

-500 -500
Pressure (db)

σt ~17.1

-1000 -1000

-1500 -1500

-2000 -2000

0.00 0.01 0.02 0.03 0.04 0.05 0.22 0.26 0.30 0.34 0.38 0.1 0.2 0.3 0.4 0.5
∆PO43- : H2S ∆NH4+ : H2S ∆Si (OH)4 : H2S

Fig. 9. Ratio of phosphate, ammonia and silicic acid concentrations to hydrogen sulfide concentrations versus depth for the anoxic waters
of the Black Sea. The dashed vertical lines represent the theoretical ratios for PO3 þ
4 : H2 S, NH4 : H2 S, and SiðOHÞ4 : H2 S. The solid
horizontal line represents a depth of 500 m and st
17.1.
 ARTICLE IN PRESS
W.T. Hiscock, F.J. Millero / Deep-Sea Research II 53 (2006) 1787–1801 1799

σt = 16.2 σt = 16.7 σt = 17.1

~125 m ~250 m ~500 m
12
350 140
11
300 120
10
Si (OH)4 (µmol kg-1)

250 100

NH4+ (µmol kg-1)

PO43- (µmol kg-1)

9
200 80
8
150 60
7

100 40 6
Si(OH)4
NH4 +
50 20 5
PO43-
0 0 4
0 50 100 150 200 250 300 350 400 450
H2S (µmol kg-1)

Fig. 10. Silicic acid, ammonia and phosphate versus hydrogen sulfide in the anoxic waters. The dashed vertical lines represent isopycnal
surfaces. The linear fits are corrected for biases in the slope by calculating the geometric mean of Model I regressions of the variables with
axes reversed, results are in Table 1.

4. Conclusions References

The inclusion of minor bases: borate, ammonia,
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the concentrations of hydrogen sulfide in the anoxic
zone. This sulfide removal may result in variation in
the stoichiometric ratios between the upper and
lower anoxic zones.
Acknowledgements
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