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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
0967-0645/$ - see front matter r 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.dsr2.2006.05.020
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1788 W.T. Hiscock, F.J. Millero / Deep-Sea Research II 53 (2006) 1787–1801
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
Anoxic
TCO2 ; pK1 and pHSWS from the potentiometric
titration data (Millero et al., 1993). Samples 17.0
containing high H2S concentrations were examined
first to prevent atmospheric contamination of the 17.5
0 100 200 300 400 500
sample. The accuracy and precision of the titration H2S (µmol kg-1)
system was examined throughout the cruise by
making titrations on Certified Reference Material 0 100 200 300 400
(CRM-Batch 38), and the measured values of TA Oxygen (µmol L-1)
agreed to 72 mmol kg1. The values of TCO2 were Fig. 2. Temperature, salinity, oxygen and hydrogen sulfide versus
calculated from pHSWS and TA using the constants density (st) for selected hydrocasts near the center of the western
of Mehrbach et al. (1973) as reformulated by gyre. The CIL is bounded by 8 1C isotherms, dashed vertical line.
Dickson and Millero (1987). They should be reliable Its core is located at st 14.5-14.6. The main pycnocline is
to 73 mmol kg1. 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
3. Results and discussion 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 thermohaline structure of the Black Sea is a The upper boundary of the anoxic layer is at st 16.2.
defining characteristic and unique in comparison to
its typical oceanic counterparts. The vertical struc- the main pycnocline centered at st 14.5. The
ture is associated to the distribution of properties oxycline below the base of the oxic layer is a region
and processes in the Black Sea. The physical and of decreasing oxygen concentrations occurring
chemical structure of the water column at the center between st 14.4–14.6 and st 15.6–15.9. Below
of the western gyre is best described in terms of the oxic layer and the oxycline is a zone of 40 m,
sigma-t (st) values; typical distributions are depicted which is suboxic and has a lower boundary at st
in Fig. 2. The salinity of the surface waters in the 16.2. Oxygen and hydrogen sulfide are both below
Black Sea is approximately half that of the open- limits of detection in the suboxic zone. The deepest
ocean water and similar in chemical composition parts of the Black Sea are characterized by
(Goyet et al., 1991). A marked increase in salinity, T ¼ 8.5–9.0 1C and S ¼ 22:32, and are in steady-
up to 21, occurs at depths of 50–170 m, below state on a time scale of centuries (Konovalov and
which the salinity increase is much more gradual. Murray, 2001). The onset of H2S and the upper
The increase in salinity is the main control on the boundary of the anoxic layer are generally accepted
pycnocline. There is a prominent temperature to occur at stE16.2 (Konovalov and Murray,
minimum characteristic of the CIL that occurs in 2001). Previous data confirms that the density of
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W.T. Hiscock, F.J. Millero / Deep-Sea Research II 53 (2006) 1787–1801 1791
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;
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
12 12
13 13
14 14
σT
σT
15 15
16 16
17 17
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
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
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)
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
anoxic waters below st 16.9 (400 m) and OArg is The Bosporus plume water introduces a lateral flux
less than 1 in anoxic waters below st 14.8 (60 m). of O2 with the potential to affect the basin-wide
The TA:H2S ratio for this study is higher, distribution of sulfide and consume as much as
TA:H2S ¼ 2.7870.06, in the deep anoxic water 70% of the sulfide sink (Konovalov and Murray,
below st 17.1 (500 m) where calcite is under 2001). Therefore, injection of the Bosporus plume
saturated and there is little influence from lateral could result in consumption of sulfide and thus
influxes evident in the upper portion of the anoxic elevated TA:H2S and TCO2:H2S ratios in the upper
layer and main pycnocline. The TCO2:H2S ratio is anoxic layer. Meanwhile, the classical generator of
also elevated in the deep anoxic water, oceanic alkalinity contributes to the observed
TCO2:H2S ¼ 2.1970.11, and diverges from theory divergence of TA:H2S and TCO2:H2S ratios for
by approximately half of the divergence observed the deep anoxic waters.
for the TA:H2S ratio. The divergence in the TA:H2S The earlier results of Goyet et al. (1991) are less
and TCO2:H2S ratios suggests dissolution of CaCO3 reliable due to the addition of mercuric chloride
in the deep anoxic waters. Goyet et al. (1991) relied ðHgCl2 Þ to the TA samples, which resulted in
solely on dissolution of CaCO3 to explain their removal of H2S from the samples. The alkalinity
results. However, the difference between the anoxic of the sample changes due to precipitation of
water above and below st 17.1 (500 m) indicates mercuric sulfide ðHgSÞ by the following reaction:
that lateral injection of oxygen rich Bosporus plume
HgCl2 þ H2 S ! HgS þ 2Hþ þ 2Cl . (9)
waters may produce the observed differences from
the theoretical values. The lateral influx of oxygen The change in alkalinity for the anoxic deep waters
(O2) can directly affect the redox budget within the due to this effect may represent up to 20% of the
main pycnocline and upper portion of the anoxic total alkalinity. In addition, Goyet et al. (1991) did
layer, as shown in Konovalov and Murray (2001) not account for injection of Bosporus plume waters.
(Fig. 4). Dramatic changes in the distribution of the
main reduced redox species, H2S, Mn2þ and NHþ 4, 3.4. Stoichiometry and macronutrients
were observed by Konovalov et al. (2003) to be a
direct result of the lateral influx of O2 associated The stoichiometry of chemical reactions in oxic
with the Bosporus plume. Furthermore, the ratios environments is frequently examined (e.g., Steinberg
of DTA : DH2 S are quite different depending on et al., 1998; Hiscock and Millero, 2005), using the
whether H2S is oxidized by O2 to sulfate ðSO2 4 Þ; Redfield ratio (Redfield et al., 1963). However, the
sulfite ðSO2 3 Þ; thiosulfate ðS 2 O 2
3 Þ or elemental stoichiometry of chemical reactions in the anoxic
sulfur ðS0 or S8 Þ. The change in DTA : DH2 S de- environment of the Black Sea and other anoxic
pends on the form of sulfur formed during sulfide basins utilizes the Richards Eq. (2) (Goyet et al.,
oxidation and the ratios for SO2 2
4 ¼ 2, SO3 ¼ 2, 1991; Zhang and Millero, 1993; Yao and Millero,
2 0
S2 O3 ¼ 1 and S ¼ 0. If sulfide is oxidized to 1995). The stoichiometric ratios for decomposition
SO2 2 2
4 ; SO3 or S2 O3 the total alkalinity would be of organic matter and the associated release of
lowered, whereas if the product is elemental sulfur nutrients during sulfate reduction can be used to
or polysulfides the TA and TCO2 would be examine concentrations of carbon (C), nitrogen (N),
unchanged but H2S would be removed. In addition phosphorous (P), and sulfur (S) in this anoxic
to direct oxidation of H2S, Konovalov et al. (2003) system, Table 1. The theoretical ratios from Eq. (2)
present further details about mechanisms coupling are PO3 þ
4 : H2 S ¼ 0.019 and NH4 : H2 S ¼ 0:30. The
the manganese cycle with the sulfide-elemental ratio of SiðOHÞ4 : H2 S depends on the relative
sulfur–sulfate cycle. The process begins in the oxic abundance of siliceous phytoplankton. The stoi-
layer where dissolved Mn2þ is oxidized to particu- chiometric ratios have been expanded to include
late Mn(III, IV) which then sinks into the anoxic silica (Si) and are typically referred to as the
layer where manganese oxide ðMnO2 Þ acts as an Redfield/Brzezinski proportion; Si:C:N ¼ 0.9:6.6:1
oxidant of H2S (Tebo, 1991; Konovalov et al., (Brzezinski, 1985 ). Using the Richards equation
2003). 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
MnO2 þ HS þ 3Hþ ! Mn2þ þ S 0 ð18S8 Þ þ 2H2 O:
resulting range for the ratio of SiðOHÞ4 : H2 S is
(8) 0.12–1.3.
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The stoichiometric values are given in Table 1, oxyhydoxides. The removal of H2S in the upper
and the ratios of macronutrients to hydrogen sulfide portion of the anoxic layer due to injection of O2
versus depth are plotted in Fig. 9. The macronu- results in anomalies that prohibit fitting data
trients; PO3 þ
4 ; NH4 and SiðOHÞ4 , and the carbonate throughout the entire anoxic layer. In addition,
variables; TA and TCO2, are corrected for initial precipitation of hydrogen sulfide in the form of FeS2
values at the onset of the anoxic layer in Fig. 9. The results in the removal of H2S from the upper
vertical distribution of the values of macronutrients portion of the anoxic layer (Muramoto et al., 1991).
to hydrogen sulfide illustrates the variability asso- The removal of H2S in the upper portion of the
ciated with the upper portion of the anoxic layer anoxic layer by oxidation or sulfide formation
(o500 m) as compared to the deeper anoxic layer results in particulate S8 and FeS that can be
(4500 m). In the deep anoxic waters, below st transported to the deep waters. The theoretical
17.1 (500 m), the macronutrient to hydrogen ratio of SiðOHÞ4 : H2 S from remineralization of
sulfide ratios are constant, as compared to the biogenic silica (0.27) is lower than the observed
higher values found in the upper portion of the value of 0.4170.01. The high observed ratios may
anoxic layer. The source of PO3 4 ; NH4
þ
and indicate that silicic acid production is proportional
SiðOHÞ4 in the anoxic layer of the Black Sea is to production of hydrogen sulfide.
respiration of POM. A deficit of sulfide would result The C:N:P ratios for the deep anoxic waters yield
in elevated macronutrient to hydrogen sulfide a stoichiometry of 130:16:1 (Table 1) for organic
ratios, and such a deficit may have resulted from matter and a revised version of the Richards Eq. (2)
removal of sulfide as a result of the lateral injection can be given as
of oxygen-enriched waters of the Bosporus plume.
Macronutrients in the anoxic waters are plotted ðCH2 OÞ130 ðNH3 Þ16 ðH3 PO4 Þ þ 65SO2
4 ! 130HCO3
versus H2S in Fig. 10 . The observed ratios in the þ 65H2 S þ 16NH3 þ H3 PO4 . ð10Þ
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 : The values of Redfield/Brzezinski proportion yields
H2 S ¼ 0:41 0:01 (Table 1). The fit for phosphate Si:C:N ratio ¼ 1.5:7.9:1, and values of the C:N
versus H2S in the anoxic waters did not include data ratio in POM for the Black Sea range from 7.5 to
near the interface where phosphate is affected by the 9.6 (Burlakova et al., 1997; Yilmaz et al., 1998;
adsorption and desorption onto reactive Fe and Mn 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 st17.1.
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W.T. Hiscock, F.J. Millero / Deep-Sea Research II 53 (2006) 1787–1801 1799
250 100
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, Armstrong, F.A.J., Stearns, C.R., Strickland, J.D.H., 1967. The
phosphate, silicate and hydrogen sulfide has im- measurement of upwelling and subsequent biological processes
by means of the Technicon Autoanalyzer and associated
proved determination of the carbonate system in the equipment. Deep-Sea Research Part A 14, 381–389.
oxic/anoxic waters of the Black Sea. The observed Bernhardt, H., Wilhelms, A., 1967. The Continuous Determina-
distribution of macronutrients, hydrogen sulfide tion of Low-Level Iron, Soluble Phosphate and Total
and carbon has changed with respect to earlier Phosphate with the Autoanalyzer, vol. 1. Scova, N.B.
investigations. The increase may be due to eutro- Technicon Symposia. Mediad Inc., New York, NY,
pp. 385–389.
phication and an increase in the primary production
Bologa, A.S., Bodeanu, N., Petran, A., Tiganus, V., Zaitsev,
of the surface waters and increased export of POM Y.P., 1995. Major modifications of the Black Sea benthic and
into the anoxic region (Stelmakh et al., 1998). The planktonic biota in the last three decades. Bulletin de
lateral ventilation of the main pycnocline by l’Institute Oceanographique, Monaco 15, 85–110.
Bosporus plume may be responsible for decreasing Boudreau, B.P., LeBlond, P.H., 1989. A simple evolutionary
model for water and salt in the Black Sea. Paleoceanography
the concentrations of hydrogen sulfide in the anoxic
4, 157–166.
zone. This sulfide removal may result in variation in Brewer, P.G., Murray, J.W., 1973. Carbon, nitrogen and
the stoichiometric ratios between the upper and phosphorus in the Black Sea. Deep-Sea Research Part A 20,
lower anoxic zones. 803–818.
Brzezinski, M.A., 1985. The Si:C:N ratio of marine diatoms—
interspecific variability and the effect of some environmental
variables. Journal of Phycology 21, 347–357.
Buesseler, K.O., Livingston, H.D., Casso, S.A., 1991. Mixing
Acknowledgements between oxic and anoxic waters of the Black Sea as traced by
chernobyl cesium isotopes. Deep-Sea Research Part A 38,
The authors thank the crew and captain of the S725–S745.
R/V Knorr and J.W. Murray for his support and the Burlakova, Z.P., Eremeeva, L.V., Konovalov, S.K., 1997.
Particulate organic matter of the Black Sea euphotic zone:
chance to participate on the 2001 Black Sea
seasonal and long term variation of spatial distribution and
Expedition. This research was supported by grants composition. In: Ozsoy, E., Mikaelyan, A. (Eds.), NATO TU-
from the Oceanographic Section of the National Sensitivity to Change: Black Sea, Baltic Sea and North Sea.
Science Foundation (NSF) to F.J. Millero. Kluwer Academic Publishing, Netherlands, pp. 223–238.
ARTICLE IN PRESS
1800 W.T. Hiscock, F.J. Millero / Deep-Sea Research II 53 (2006) 1787–1801
Carlton, R.G., Wetzel, R.G., 1988. Phosphorus flux from lake- (Ed.), Science of the Total Environment. Elsevier Science,
sediments—effect of epipelic algal oxygen production. Lim- Amsterdam, pp. 683–692.
nology and Oceanography 33, 562–570. Goyet, C., Bradshaw, A.L., Brewer, P.G., 1991. The carbonate
Cline, J.D., 1969. Determination of hydrogen sulfide. Limnology system in the black sea. Deep-Sea Research Part A 38,
and Oceanography 14, 454. S1049–S1068.
Coban-Yildiz, Y., Altabet, M.A., Yilmaz, A., Tugrul, S., 2006. Hiscock, W.T., Millero, F.J., 2005. Nutrient and carbon
Carbon and nitrogen isotopic ratios of suspended particulate parameters during the Southern Ocean Iron Experiment
organic matter (SPOM) in the Black Sea water column. Deep- (SOFeX). Deep-Sea Research I 52, 2086–2108.
Sea Research II, this issue [doi:10.1016/j.dsr2.2006.03.021]. Ivanov, L.I., Samodurov, A.S., 2001. The role of lateral fluxes in
Cociasu, A., Dorogan, L., Humborg, C., Popa, L., 1996. Long- ventilation of the Black Sea. Journal of Marine Systems 31,
term ecological changes in Romanian coastal waters of the 159–174.
Black Sea. Marine Pollution Bulletin 32, 32–38. Kempe, S., Liebezett, G., Diercks, A.R., Asper, V., 1990. Water-
Cociasu, A., Diaconu, V., Popa, L., Nac, I., Buga, L., Dorogan, balance in the Black-Sea. Nature 346, 419.
L., Malciu, V., 1997. Nutrient stock of the Romanian Shelf of Konovalov, S.K., Murray, J.W., 2001. Variations in the
the Black Sea in the last three decades. In: Özsoy, E., chemistry of the Black Sea on a time scale of decades
Mikaelyan, A. (Eds.), Sensitivity to Change: Black Sea, Baltic (1960–1995). Journal of Marine Systems 31, 217–243.
Sea and North Sea. Kluwer Academic Publishing, Dordrecht, Konovalov, S.K., Tugrul, S., Basturk, O., Salihoglu, I., 1997.
pp. 49–63. Spatial isopycnal analysis of the main pycnocline chemistry of
Codispoti, L.A., Friederich, G.E., Murray, J.W., Sakamoto, the Black Sea: seasonal and interannual variations. In: Özsoy,
C.M., 1991. Chemical variability in the Black Sea—implica- E., Mikaelyan, A. (Eds.), Sensitivity to Change: Black Sea,
tions of continuous vertical profiles that penetrated the oxic Baltic Sea and North Sea. Kluwer Academic Publishing,
anoxic interface. Deep-Sea Research Part A 38, S691–S710. Dordrecht, pp. 197–210.
Deuser, W.G., 1974. Evolution of anoxic conditions in the Black Konovalov, S.K., Eremeev, V.N., Suvorov, A.M., Khaliulin,
Sea during the Holocence. In: Degens, E.T., Ross, D.A. A.K., Godin, E.A., 1999. Climatic and anthropogenic
(Eds.), The Black Sea—Geology, Chemistry and Biology. The variations in the sulfide distribution in the Black Sea. Aquatic
American Association of Petroleum Geologists, Tusla,
Geochemistry 5, 13–27.
Oklahoma, pp. 133–136.
Konovalov, S.K., Luther III, G.W., Friederich, G.E., Nuzzio,
Dickson, A.G., 1981. An exact definition of total alkalinity and a
D.B., Tebo, B.M., Murray, J.W., Oguz, T., Glazer, B.,
procedure for the estimation of alkalinity and total CO2 from
Trouwborst, R.E., Clement, B., Murray, K.J., Romanov,
titration data. Deep-Sea Research Part A 28, 609–623.
A.S., 2003. Lateral injection of oxygen with the Bosporus
Dickson, A.G., Millero, F.J., 1987. A comparison of the
plume—fingers of oxidizing potential in the Black Sea.
equilibrium constants for the dissociation of carbonic-acid
Limnology and Oceanography 48, 2369–2376.
in Seawater Media. Deep-Sea Research Part A 34, 1733–1743.
Kuypers, M.M.M., Sliekers, A.O., Lavik, G., Schmid, M.,
Dunne, J.P., Murray, J.W., Aufdenkampe, A.K., Blain, S.,
Jørgensen, B.B., Kuenen, J.G., Sinninghe Damsté, J.S.,
Rodier, M., 1999. Silicon-nitrogen coupling in the equatorial
Strous, M., M., J.M.S., 2003. Anaerobic Ammonium oxida-
Pacific upwelling zone. Global Biogeochemical Cycles 13,
tion by anammox bacteria in the Black Sea. Nature 422,
715–726.
608–611.
Dyrssen, D., 1985. Some calculations on Black Sea Chemical
data. Chemica Scripta 25, 199–205. Lee, B.S., Bullister, J.L., Murray, J.W., Sonnerup, R.E., 2002.
Dyrssen, D., 1986. Stagnant sulfidic basin waters. Science of the Anthropogenic chlorofluorocarbons in the Black Sea and the
Total Environment 58, 161–173. Sea of Marmara. Deep-Sea Research I 49, 895–913.
Friederich, G.E., Codispoti, L.A., Sakamoto, C.M., 1990. Bottle Leppakoski, E., Mihnea, P.E., 1996. Enclosed seas under man-
and pumpcast data from the 1988 Black Sea expedition. induced change: a comparison between the Baltic and Black
Monterey Bay Aquarium Research Institute Technical Report Seas. Ambio 25, 380–389.
90-3. Monterey Bay Aquarium Research Institute, Monterey Lewis, E., Wallace, D.W.R., 1998. Basic Program for CO2
Bay, 224pp. System in Seawater. ORNL/CDIAC-105. Oak Ridge Na-
Gächter, R., Meyer, J.S., 1993. The role of microorganisms in tional Laboratory.
mobilization and fixation of phosphorus in sediments. Lyons, T.W., Berner, R.A., Anderson, R.F., 1993. Evidence for
Hydrobiologia 253, 103–121. large preindustrial perturbations of the Black-Sea Chemo-
Gächter, R., Meyer, J.S., Mares, A., 1988. Contribution of cline. Nature 365, 538–540.
bacteria to release and fixation of phosphorus in lake- Mee, L.D., 1992. The Black Sea in crisis—a need for concerted
sediments. Limnology and Oceanography 33, 1542–1558. international action. Ambio 21, 278–286.
Glazer, B.T., Luther III, G.W., Konovalov, S.K., Friederich, Mehrbach, C., Culberson, C.H., Hawley, J.E., Pytkowicz, R.M.,
G.E., Trouwborst, R.E., Romanov, A.S., 2006. Spatial and 1973. Measurement of the apparent dissociation constants of
temporal variability of the Black Sea suboxic zone. Deep-Sea carbonic acid in seawater at atmospheric pressure. Limnology
Research II, this issue [doi:10.1016/j.dsr2.2006.03.022]. and Oceanography 18, 897–907.
Glenn, C.R., Arthur, M.A., 1985. Sedimentary and geochemical Millero, F.J., 1995. Thermodynamics of the carbon-dioxide
indicators of productivity and oxygen contents in modern and system in the oceans. Geochimica Et Cosmochimica Acta
ancient basins—the Holocene Black-Sea as the Type Anoxic 59, 661–677.
Basin. Chemical Geology 48, 325–354. Millero, F.J., Zhang, J.Z., Lee, K., Campbell, D.M., 1993.
Gomoiu, M.T., 1992. Marine eutrophication syndrome in the Titration alkalinity of seawater. Marine Chemistry 44,
north-western part of the Black Sea. In: Vollenweider, R.A. 153–165.
ARTICLE IN PRESS
W.T. Hiscock, F.J. Millero / Deep-Sea Research II 53 (2006) 1787–1801 1801
Muramoto, J.A., Honjo, S., Fry, B., Hay, B.J., Howarth, R.W., Tool for the Black Sea, Symposium on Scientific Results.
Cisne, J.L., 1991. Sulfur, iron and organic carbon fluxes in the Kluwer Academic Publishing, Netherlands, pp. 221–235.
black sea—sulfur isotopic evidence for origin of sulfur fluxes. Shaffer, G., 1986. Phosphate pumps and shuttles in the Black-
Deep-Sea Research Part A 38, S1151–S1187. Sea. Nature 321, 515–517.
Murray, J.W., Jannasch, H.W., Honjo, S., Anderson, R.F., Smethie Jr., W.M., 1987. Nutrient regeneration and denitrifica-
Reeburgh, W.S., Top, Z., Friederich, G.E., Codispoti, L.A., tion in low oxygen fjords. Deep-Sea Research Part A 34,
Izdar, E., 1989. Unexpected changes in the oxic anoxic 983–1006.
interface in the Black-Sea. Nature 338, 411–413. Sorokin, Y.I., 1983. The Black Sea. In: Ketchum, B.H.
Murray, J.W., Top, Z., Ozsoy, E., 1991. Hydrographic properties (Ed.), Estuaries and Enclosed Seas. Elsevier, New York,
and ventilation of the Black-Sea. Deep-Sea Research Part A pp. 253–292.
38, S663–S689. Steinberg, P.A., Millero, F.J., Zhu, X.R., 1998. Carbonate system
Murray, J.W., Fuchsman, C., Kirkpatrick, J., Paul, B., Kono- response to iron enrichment. Marine Chemistry 62, 31–43.
valov, S.K., 2005. Species and d15N signatures of nitrogen Stelmakh, L.V., Yunev, O.A., Finenko, Z.Z., Vedernikov, V.I.,
transformations in the suboxic zone of the Black Sea. Bologa, A.S., Churilova, T.Y., 1998. Peculiarities of seasonal
Oceanography 18, 36–47. variability of primary production in the Black Sea. In: Ivanov,
Mutlu, E., Bingel, F., Gucu, A.C., Melnikov, V.V., Niermann, L.M., Oguz, T. (Eds.), NATO TU-Black Sea Project
U., Ostr, N.A., Zaika, V.E., 1994. Distribution of the new Ecosystem Modeling as a Management Tool for the Black
invader mnemiopsis Sp and the resident Aurelia-Aurita and Sea, Symposium on Scientific Results. Kluwer Academic
Pleurobrachia-Pileus populations in the Black-Sea in the years Publishing, Netherlands, pp. 93–104.
1991–1993. ICES Journal of Marine Science 51, 407–421. Tebo, B.M., 1991. Manganese (II) Oxidation in the Suboxic Zone
Oguz, T., Rozman, L., 1991. Characteristics of the Mediterra- of the Black Sea. Deep-Sea Research Part A 38, S883–S905.
nean underflow in the Southwestern Black-Sea Continental- Toerien, D.F., Gerber, A., Lotter, L.H., Cloete, T.E., 1990.
Shelf Slope Region. Oceanologica Acta 14, 433–444. Enhanced biological phosphorus removal in activated-sludge
Ostlund, H.G., Dyrssen, D., 1986. Renewal rates of the Black Sea systems. Advances in Microbial Ecology 11, 173–230.
deep water. The chemical and physical oceanography of the Tugrul, S., Basturk, O., Saydam, C., Yilmaz, A., 1992. Changes
Black Sea. Reports of the chemistry of the sea XXXIII. in the hydrochemistry of the Black-Sea inferred from water
University of Göteborg, Göteborg, Sweden. density profiles. Nature 359, 137–139.
Ozsoy, E., Top, Z., White, G., Murray, J.W., 1991. Double Unluata, U., Oguz, T., Latif, M.A., Ozsoy, E., 1990. On the
diffusive intrusion, mixing and deep convection processes in physical oceanography of the Turkish Straits. In: Pratt, L.J.
the Black Sea. In: Izdar, E., Murray, J.W. (Eds.), Black Sea (Ed.), The Physical Oceanography of Sea Straits. Kluwer
Oceanography. Kluwer Academic publishing, Netherlands, Academic Publishing, Netherlands, pp. 25–60.
pp. 17–42. Vinogradov, M.E., 1991. The sulfide onset and variations in
Ozsoy, E., Latif, M.A., Besiktepe, S.T., Gaines, A., 1995a. depth of it in the Black Sea. Okeanologiya (Oceanology) 31,
Fluorescent dye measurements of the mixing and transport of 414–420 (in Russian).
waste-water discharge in the Bosporus. Water Science and Yakushev, E.V., Chasovinkov, V.K., Debolskaya, E.I., Egorov,
Technology 32, 61–68. A.V., Makkaveev, P.N., Pakhomova, S.V., Podymov, O.I.,
Ozsoy, E., Latif, M.A., Tugrul, S., Unluata, U., 1995b. Yakubenko, V.G., 2006. The northeastern Black Sea redox
Exchanges with the Mediterranean, fluxes, and boundary zone: Hydrophysical and hydrochemical structure and varia-
mixing processes in the Black Sea. Bulletin de l’Institute bility. Deep-Sea Research II, this issue [doi:10.1016/
Oceanographique, Monaco 15, 1–25. j.dsr2.2006.05.019].
Pierrot, D., 2002. Basic program for CO2 system in seawater. Yao, W., Millero, F.J., 1995. The chemistry of the anoxic waters
Microsoft Excel Visual Basic, RSMAS, University of Miami. in the Framvaren Fjord, Norway. Aquatic Geochemistry 1,
Redfield, A.C., Ketchum, B.H., Richards, F.A., 1963. The 53–88.
influence of organisms on the composition of sea-water. In: Yilmaz, A., Tugrul, S., Polat, C., Ediger, D., Coban, Y., Morkoc,
Hill, M.N. (Ed.), The Sea. Interscience, New York, pp. 26–77. E., 1998. On the production, elemental composition (C, N, P)
Richards, F.A., 1965. Anoxic basins and fjords. In: Riley, J.P., and distribution of photosynthetic organic matter in the
Skirrow, G. (Eds.), Chemical Oceanography. Academic Press, Southern Black Sea. Hydrobiologia 363, 141–156.
New York, pp. 611–646. Zaitsev, Y.P., 1993. Impacts of Eutrophication on the Black Sea
Ryan, W.B.F., Pitman, W.C., Major, C.O., Shimkus, K., fauna. Fisheries Council for the Mediterranean Studies and
Moskalenko, V., Jones, G.A., Dimitrov, P., Gorur, N., Reviews. FAO, Rome, pp. 63–86.
Sakinc, M., Yuce, H., 1997. An abrupt drowning of the Zaitsev, Y.P., Mamaev, V., 1997. Biological Diversity in the
Black Sea shelf. Marine Geology 138, 119–126. Black Sea: A Study of Change and Decline. United Nations
Samodurov, A.S., Ivanov, L.I., 1998. Processes of ventilation of Publishing, New York, 208pp.
the Black Sea related to water exchange through the Zhang, J.Z., Millero, F.J., 1993. The chemistry of the anoxic
Bosporus. In: Ivanov, L.M., Oguz, T. (Eds.), NATO TU- waters in the Cariaco Trench. Deep-Sea Research I 40,
Black Sea Project Ecosystem Modeling as a Management 1023–1041.