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e1 to e7, 2015
doi:10.2343/geochemj.2.0374
EXPRESS LETTER
Sulfides in oxic seawater over the submarine hydrothermal area of
Kikai Caldera south of Kyushu Island, Japan
N ORIKO NAKAYAMA,* K OTARO SHIRAI , Y UJI SANO, TOSHITAKA GAMO and HAJIME OBATA
Atmosphere and Ocean Research Institute, The University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa, Chiba 277-8564, Japan
(Received December 19, 2014; Accepted May 29, 2015; Online published June 26, 2015)
The concentration of total metal sulfide throughout a water column over a submarine hydrothermal vent in Kikai
Caldera south of Kyushu Island, Japan, at ~350 pmol/kg, was higher than that reported in previous studies, at <50 pmol/
kg below the halocline. Seawater filtered at 0.2 m pore size and unfiltered seawater exhibited almost identical metal
sulfide concentrations throughout the water column, indicating that most metal sulfide existed in dissolved and particulate
forms with diameters <0.2 m. By using a mass balance calculation with the observed sulfide species of free and metal
sulfides and carbonyl sulfide, we showed that ~70% of the metal sulfide supplied from hydrothermal vents were contained
in the water column beyond the halocline without undergoing oxidative loss even after mixing into overlying oxic seawater.
Our findings clearly indicate that sulfide and trace metals emitted from hydrothermal vents form a stable metal-sulfide
complex with diameters <0.2 m. These results also strongly support the recently proposed theory such that metal-sulfide
complexation/nanoparticles play an important role in the long-distance transportation of trace metals in the ocean.
Keywords: dissolved sulfide, long distance transportation of trace metal, hydrothermal source, oxic seawater
INTRODUCTION
Trace metals such as Fe, Cu, and Zn are known as
essential micronutrients for biological production; thus,
their availability impacts the biogeochemical cycles of
oceans (e.g., Bruland et al., 1991). Although oceanic hydrothermal vents are important sources of bioactive trace
metals (Wu et al., 2011; Nishioka et al., 2013; Saito et
al., 2013), the current understanding of the stability and
chemical speciation of oceanic trace metals remains incomplete and inadequate for describing the
biogeochemical cycles and processes of these trace metals (Benner, 2002). A large portion of metal sulfides in
hydrothermal fluid was previously believed to precipitate onto the seafloor in the direct vicinity of the hydrothermal vent or to be rapidly oxidized and removed mostly
within the first few meters above the vent (German et al.,
1990; Feely et al., 1994). Several recent studies have suggested the formation of metal sulfide nanoparticles in
hydrothermal plumes and have pointed out the potential
importance of complex nanoparticle-formation in the
transportation of trace metals over longer distances than
that previously expected (Ycel et al., 2011; Sander and
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Fig. 1. Geographical setting of sampling site and sampling locations (stations 1 and 2) at the Kikai Caldera submarine volcano
(source: Hydrographic and Oceanographic Department, Japan Coast Guard, available at http://www1.kaiho.mlit.go.jp/
GIJUTSUKOKUSAI/kaiikiDB/kaiyo30-2.htm (accessed June 20, 2014)).
ern part of the caldera at a maximum depth of approximately 468 m. Station 2, at 3047.38 N, 13025.00 E, is
in the northeastern part of the caldera near southern
Takeshima Island at a maximum depth of approximately
521 m (Fig. 1).
Seawater samples were collected from appropriate
depths in the water column by using 24
polytetrafluoroethylene (PTFE)-coated Ocean Test Equipment (OTE) bottles, each having a 12 L capacity and an
external stainless steel spring closure. These bottles were
mounted on a Sea-Bird carousel system (Sea-Bird Electronics (SBE), Bellevue, Washington), equipped with an
SBE 9 plus conductivity, temperature, and depth (CTD)
package, an SBE 43 dissolved oxygen sensor, and a
Seapoint fluorometer (Seapoint Sensors, Exeter, New
Hampshire) for chlorophyll-a measurement. Dissolved
oxygen and salinity detected by the sensors were validated by authentic Winkler titration and Autosal salinometer methods, respectively, for discrete seawater samples.
Measurement of pH was conducted by using a PHM93
Reference pH Meter (Radiometer, Copenhagen, Denmark)
within a day after sampling. Two artificial seawater buffer
solutions were used for calibration: Tris (2-Amino-2hydroxymethyl-1,3-propanediol, lot WEK8350; Wako
pure chemical industries, 287-77321) and AMP (2Aminopyridine, lot WEK8351; Wako pure chemical industries, 284-77321).
Seawater samples for the measurements of free sulfide
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N. Nakayama et al.
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Fig. 3. Vertical profiles of observed sulfides species for stations 1 (diamonds) and 2 (circles): (a) free sulfide (H2S + HS +
S 2), (b) metal sulfide complexes (closed: unfiltered, open: after filtering with a 0.2- m pore size filter, (c) carbonyl sulfide
(OCS). Error bars represent the current analytical precision.
higher than those reported for the open ocean with values
of 19 pmol/L in the top 50 m and below 5 pmol/kg at
other depths (Radford-Knoery and Cutter, 1994; Cutter
et al., 1999).
The concentrations of total and dissolved metal-S remained constant within the analytical error throughout
the water column at 332354 pmol/kg. The observed uniform vertical profiles clearly indicate that most of the
metal sulfide existed in a dissolved form throughout the
water column, whether completely dissolved or in
particulate form with diameters <0.2 m, with high stability even in the oxic conditions of the study area.
The average concentration of OCS was ~40 pmol/kg
in the upper 40 m, which is slightly higher than that below the 40 m at ~30 pmol/kg. OCS in seawater has two
production processes: that through the photolysis of dissolved organic sulfur compounds in surface waters
(Andreae and Ferek, 1992) and that through bacterial respiration/regeneration of organic matter in deeper waters
in a process known as dark production (Radford-Knoery
and Cutter, 1994; Ulshfer et al., 1996; Flck and
Andreae, 1996). Hydrothermal fluids contain little OCS
and are thus not the source of OCS (Chin and Davis,
1993).
In order to assess the contribution of hydrolysis of
OCS and other potential sources for the H2S, we first examined the ratio between the free-S and OCS concentrations, since OCS has been considered as the primary
source of H2S in oceans. Table 1 shows the depth variation of the ratios at both stations. The ratios were lowest
at the surface, at 0.70.9, and increased with depth to
reach the maximum at 1.62.0 below 330 m. In previous
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N. Nakayama et al.
Table 1. Concentrations of free sulfide and carbonyl sulfide (OCS) and their ratios at different depths at
stations 1 and 2
Depth (m)
COS (pmol/kg)
Ratio (Free-S/OCS)
20
40
60
100
200
250
300
350
410
458
31
28
29
37
36
40
49
49
59
60
40
39
35
31
29
30
29
28
30
35
0.8
0.7
0.8
1.2
1.2
1.3
1.7
1.8
2.0
1.7
20
40
60
100
200
300
320
370
470
510
29
31
30
33
38
43
47
47
54
55
34
40
36
31
31
31
31
29
34
34
0.9
0.8
0.8
1.0
1.2
1.4
1.5
1.6
1.6
1.6
[Total sulfidess ] =
khyd [OCS]
[ ]
koxid [O 2 ] + kIO F IO 3
3
0.5
(1)
where k hyd is the rate constant of OCS hydrolysis calculated on the basis of the result reported by Radford-Knoery
and Cutter (1994) in addition to the observed salinity, pH,
and temperature. koxid is the oxidation rate constant calculated by using the equation proposed by Millero et al.
(1987); kIO3 is the rate constant for the oxidation of iodate-sulfide; and F is the fraction of free-S to the total-S
(Cutter et al., 1999). We adopted 630 mol0.5/h for kIO3
as reported by Zhang and Whitfield (1986). Because iodate was not determined in the present study, we estimated its content by applying the salinity-iodate relationship observed in the East China Sea (Wong and Zhang,
2003; Wong et al., 2004). The fraction of free-S to the
total-S (F), 0.08 to 0.09, was obtained from the current
field observations.
The model calculation showed that the observed total-S values were 3 times higher than those predicted by
the model (total sulfidess) in the upper 100 m and were
1014 times higher below the depth of 330 m, which is
inside the caldera rim (Fig. 4). It should be also noted
that the observed total-S was still two to three times higher
than that predicted by the model even if we exclude the
effect of the oxidation loss by IO3. In the open oceanic
region, the exclusion of the IO 3 oxidation process is
known to lead to overestimations of the total-S concentration (Cutter et al., 1999).
The difference between our observation and the model
prediction, even without considering the IO3 oxidation
process, clearly indicates the existence of an additional
source of total-S in the present study area. The most plausible explanation is the direct emission of free-S and
sulfide-forming metals such as copper, iron, and zinc from
hydrothermal vents to the ocean in Kikai Caldera. Metal
sulfide can also be formed through bacterial H2S production within macroscopic particles in an oxic water environment and in anoxic ocean sediment (Cutter and
Krahforst, 1988; Radford-Knoery and Cutter, 1994). In
this studied area, however, low primary production was
estimated on the basis of previous studies using in situ
chlorophyll-a sensor data (Yamaguchi et al., 2012, 2013).
In the East China Sea, low organic sedimentation was
reported below the continental shelf slope (Oguri et al.,
Metal sulfides in oxic seawater
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N. Nakayama et al.
AcknowledgmentsWe thank Dr. Nobuo Tsurushima for lending us the FPD equipment and the scientists who participated
in the KS-14-10 (leg 1) research cruise for their kind assistance with the sample collection. We also thank the captain and
crew of R/V Shinsei Maru for their support. NN also thanks
Dr. Hiroshi Furutani for valuable discussion at various stages
of this study. We also thank two anonymous reviewers for their
valuable comments which improved the manuscript. This study
was partly supported by a Grant-in-Aid for Scientific Research
(A) (No. 2353001) from MEXT and a Grant-in-aid for Young
Scientists (B) (No. 24710002) from the Japan Society for the
Promotion of Science.
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