Continental Shelf Research ()

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Contents lists available at ScienceDirect

Continental Shelf Research

journal homepage: www.elsevier.com/locate/csr

Research papers

Grain-size effect of biogenic silica in the surface sediments

of the East China Sea
Liang Wang, Dejiang Fan, Weiran Li, Yongjie Liao, Xilin Zhang, Ming Liu, Zuosheng Yang
Key Lab of Submarine Geosciences and Technology in the Ministry of Education, Ocean University of China, 238 Songling Road, Qingdao 266100, China

art ic l e i nf o
Article history:
Received 7 April 2013
Received in revised form
4 March 2014
Accepted 6 March 2014
Keywords:
Biogenic silica
Size-fraction
Diatom
Surface sediment
ECS

a b s t r a c t
Q3 Biogenic silica (BSi) is an important parameter for understanding biogeochemical processes and
paleoceanographic records in the ocean, but this proxy still has many challenges when used to
reconstruct changes in the paleoproductivity and evolution of the environment, one of which is the
grain size effect. We analyzed the BSi distribution in different size fractions from 8 surface sediments
collected in the East China Sea (ECS). We observed the particulate characteristics of diatoms in the water
and assessed the grain size effect of BSi. The results suggest the following conclusions: (1) the BSi
content of the surface sediments in the ECS is generally below 1%, and the BSi content of different size
fractions varies signicantly, with largest fraction o16 m, which is approximately 1.11.8 times that in
the bulk sediments. (2) The variation in the BSi content in different size fractions is largely controlled by
the species of diatoms and their cell sizes. In the East China Sea, nano-diatoms are the dominant species,
with dominant cells of 214 m, resulting in a high BSi content in the fraction that is o16 m. (3) The
hydro-dynamic condition affects the diatom cell size distribution and sediment character, and, thus, has
a signicant inuence on the BSi content of different size fractions. Our research suggests that the grain
size distribution of the bulk sediment should be considered when using BSi as a proxy for diatom
primary production.
& 2014 Published by Elsevier Ltd.

1. Introduction
Biogenic silica (BSi) is produced in the euphotic zone by
siliceous plankton, such as diatoms or radiolarians. Radiolarians
are particularly abundant and diverse in the equatorial latitudes,
while diatoms live predominantly in high-latitude areas and along
some continental margins, especially in upwelling areas (De
Wever et al., 2002; Karleskint et al., 2012). Diatoms play an
important role in the global biogeochemical cycle, Nelson et al.
(1995) estimated that more than 40% of all primary production is
attributable to diatoms, suggesting a close coupling of the ocean's
silica and carbon cycles in both the present and the past. They are
also responsible for the majority of silica that is extracted from
ocean waters in the modern ocean.
The role of diatoms in the biological pump, the global signicance of the opal sedimentary record and the reasonably good
overall preservation efciency of biogenic opal all indicate that BSi
is a potentially important paleoproductivity proxy (DeMaster,
1991; Ragueneau et al., 1996, 2000). However, there are still
uncertainties and challenges in using this proxy to interpret the
BSi sedimentary record or to reconstruct changes in paleoproductivity and environmental evolution (Nelson et al., 1995; Anderson
et al., 1998). Deriving accurate information from the sediment
record requires better calibration for this proxy.

As important BSi accumulation regions, the continental marginal seas receive large amounts of terrigenous materials and
strongly inuence the global carbon cycle. However, the measurement and employment of BSi in the marginal seas is signicantly
affected by the sediment grain size, similar to other parameters,
such as element concentration, organic carbon content, and
magnetic susceptibility (Bergamaschi et al., 1997; Lin et al.,
2002; Wang et al., 2009). The grain size distribution of sediment
can affect the opal content because the coarse grain fractions
provide a dilution effect that must be eliminated (Bernrdez et al.,
2005). To limit the inuence of grain size, Bernrdes suggested
using BSi from the muddy fraction as an accurate paleoproductivity proxy (Bernrdez et al., 2005). However, the role that the cell
size of diatoms that have been buried in the seabed sediments
plays in the BSi record needs to be better understood; many
physiological processes that occur in planktonic ecosystems are
size dependent (Huang et al., 1999; Finkel et al., 2008), and the
size distribution of phytoplankton assemblages is a major biological factor that governs the functioning of pelagic food-webs and,
consequently, affects the rate of carbon export from the upper
ocean to deeper layers (Malone, 1980; Huang et al., 1999).
To determine the impact of sediment particle size on the BSi
content of the marginal shelf, we selected 8 surface sediments
with different grain size patterns and 18 pieces of lter

http://dx.doi.org/10.1016/j.csr.2014.03.005
0278-4343/& 2014 Published by Elsevier Ltd.

Please cite this article as: Wang, L., et al., Grain-size effect of biogenic silica in the surface sediments of the East China Sea. Continental
Shelf Research (2014), http://dx.doi.org/10.1016/j.csr.2014.03.005i

L. Wang et al. / Continental Shelf Research ()

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membranes with diatom cells in the East China Sea. We then

investigated the BSi content of different grain size fractions
together with diatom cell sizes to assess the effect of grain size
on the BSi content and its possible connection with diatom cell
sizes. This research may also help to identify a more sensitive
fraction of BSi in the sediment that may be a preferable proxy in
low BSi content areas.

2. Geographic setting
The East China Sea (ECS) is an important marginal sea for the
research of global change and the carbon cycle, with the largest
terrigenous inputs and high accumulation rates.
The hydrodynamic conditions in the ECS are complex. The main
currents include the Kuroshio Current (KC), the Tsushima Current
(TC), the Yellow Sea Warm Current (YSWC), the Taiwan Warm
Current (TWC), and the Yellow Sea Coastal Current (YSCC) (Liu et
al., 2003, 2007). The warm and salty KC ows northward along the
shelf break of the East China Sea and signicantly inuences the
distribution of water masses and sedimentation (Liu et al., 2007).
The Changjiang River carries approximately 9.2
1011 m3 of freshwater and 4.8
108 t of solid particles to the ECS each year that
ranks 5th and 4th in the world, respectively (Milliman et al., 1985;
Tian et al., 1993). Approximately 40% of the total suspended load
was deposited in the Chanjiang River estuary (Milliman et al.,
1985), and the rest was temporarily deposited offshore or was
later resuspended and transported southward by subsequent
winter storms (Milliman et al., 1985; McKee et al., 1983;
DeMaster et al., 1985).
The surface sediment distribution in the East China Sea has
several apparent patterns. The innermost regions of the shelf are
dominated by silty clay, clayey silt, sandy silt and silt, resulting
from the rapid accumulation of sediments from the Changjiang
River (DeMaster et al., 1985; Qin et al., 1987). The broad middle
shelf is characterized by sand and clayey sand, which are known as
shelf relic sands and were formed during the late Pleistocene and
early Holocene (Niino and Emery, 1961; Milliman et al., 1985).
South of Cheju Island, nearly 400 km away from the coast of China,
the sediment is strikingly more ne-grained than the surrounding
sands (Milliman et al., 1985; Qin et al., 1987). Previous studies have
indicated that the inner shelf mud areas are the modern depocenters of the ECS, with deposition rates of 15 cm yr  1 in the
river mouth and inner shelf and 0.10.5 cm yr  1 in the seaward
distal mud area and middle shelf (DeMaster et al., 1985; Liu et al.,
2006; Xu et al., 2012). The high deposition rates make the ECS,
especially the inner shelf, an important material sink and enables
the establishment of high-resolution or ultra-high-resolution
sedimentary records (Fan et al., 2011).
Together with the huge freshwater input, plentiful nutrients
including dissolved silicate and dissolved inorganic nitrate were
delivered to the ECS, and a unique ecosystem was supported and
maintained in the estuary and its adjacent areas (Li et al., 2007).
Biomarker research has suggested that the sedimentary organic
matter in the distal mud area is mainly from marine lower aquatic
organisms (Guo et al., 2001) and high contents of brassicasterol
and dinosterol in the upwelling areas outside the Changjiang River
mouth and the ZhejiangFujian coastal zone, suggesting a strong
control of marine productivity (Xing et al., 2011).
Diatoms are the dominant phytoplankton and the major contributor to primary production in the ECS, blooming in spring and
summer, especially in August (Luo et al., 2007; Yang et al., 2008).
The diatom cell densities ranged from 0.43
103 to 23.3

103 cells L  1, with an average of 4.61
103 cells L  1 (Gao et al.,
2003). Horizontally, the diatom cell density had a scattered
distribution, while vertically, it was commonly higher in the

surface water layer than in the middle water layer (Gao et al.,
2003). The major diatom species included Skeletonema, Thalassiosira and Chaetoceros, while nano-diatoms and micro-diatoms were
the main constituents in the estuary and its adjacent areas (Li,
2006). In this area, many red blooms were induced by these
diatoms, especially in the upwelling areas outside the Changjiang
River mouth and the ZhejiangFujian coastal zone (Xing et al.,
2011). In recent years, however, the structure of phytoplankton has
changed, along with other algae species that are also increasing
due to the change in the ratio of nutrient inputs (Li et al., 2007; Jin
et al., 2009).

3. Materials and methods

3.1. Sample collection
Eight surface sediments of different types were collected from
the inshore mud area and outer continental shelf in the East China
Sea using a box sampler that was deployed on the R/V Dong Fang
Hong 2 in June 2009. Roughly estimated, the sediments included
muddy sand, sandy silt and clayey silt. Within the sample sites,
C0401, C0403, C0501 and FJA were located in the Changjiang River
mouth or outside of the estuary, C0508 was located in the mud
depocenter southwest of Cheju Island and the other sites, C0701,
C0802 and C1004, were in the mud wedge off the ZhejiangFujian
coast from north to south. All of the samples were subsequently
separated, following the research procedure. First, 5080 g of
sediment were added to a clean beaker, homogenized, and then
dried in an oven at 103 1C. After weighing, a portion was removed
for the bulk sediment, and the remaining portion was separated
into different fractions by wet sieving through a sieve with a
63 mm mesh size. Then, the ne fractions were gradually extracted
on the basis of Stokes' law, following the sequence of o 63 mm,
o32 mm, 3263 mm, o16 mm, 1632 mm. Then the gain size of the
bulk sediment and the BSi content in the different size fractions
were measured.
For the purpose of understanding the relationship between the
distribution of diatoms and their cell size, the character and BSi
distribution of different size fractions from ECS were determined.
Eighteen suspended matter samples from the surface, middle and
bottom layers in the water-column at 6 sites along section DH 3,
collected in 2010, were experimented to observe the characteristics of diatoms with a Scanning Electron Microscope (SEM). The
sampling sites are depicted in Fig. 1. The water samples were
ltered on lters of pore size 0.45 m to get diatoms. At rst, the
water was well-mixed by shaking and turning over softly and
repeatedly; then, about 1050 ml water was ltered based on the
concentration of suspended particulate material (SPM), so as to
obtain enough diatoms and do not interrupt the following observation in SEM. The lters were then dried naturally. Finally, a small
piece of lter was cut for diatom observation by SEM.
3.2. Grain size analysis
Untreated sediments were wet sieved through a set of Standard
Sieves larger than 63 mm. Then, their dry weights were determined
with an analytical balance (resolution of 0.0001g) at 1 intervals,
and the portion o63 mm was measured with a Mastersizer 2000
laser particle size analyzer. Approximately 0.5 g of a pre-homogenized, o 63 mm sediment sample was pretreated using 10 ml of
a 30% H2O2 solution to oxidize the organic matter that was
present. The sample was then dispersed and homogenized using
an ultrasonicator for 30 s to analyze the grain size. The results of
sieving method and Mastersizer method were then integrated to

Please cite this article as: Wang, L., et al., Grain-size effect of biogenic silica in the surface sediments of the East China Sea. Continental
Shelf Research (2014), http://dx.doi.org/10.1016/j.csr.2014.03.005i

L. Wang et al. / Continental Shelf Research ()

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determine the grain size distribution. The measurement error was

within 10%.

suggested that the precision of this extraction procedure was

better than 7 3%.
3.4. SEM observation of the diatom

3.3. Biogenic silica measurements

Numerous techniques have been employed for the measurement of BSi in sediments, of which the wet alkaline methods are
the most popular (DeMaster 1991; Liu et al., 2002). An improved
wet alkaline method was employed in this research. Dried samples
were crushed and homogenized in an agate mortar. Next, 130
140 mg of sediment was put into a 50 ml polypropylene centrifuge
tube. To remove the organics and carbonate, 10% H2O2 and 1 M HCl
were added successively, and then 40.0 ml of 2 M Na2CO3 solution
was added. Then the sample was capped, well mixed and placed in
a water bath that was preheated to 85 1C (Mortlock and Froelich,
1989). After 1, 2, 3, 4, 5 and 6 h of centrifugation, 125 ml of the
supernatant were removed, and the dissolved silica content in the
extractions was measured using the molybdate blue spectrophotometric method (Mortlock and Froelich, 1989; Conley, 1998). The
percent by weight of extracted silica was plotted against time, and
the extrapolated intercept equals the biogenic silica content of the
sample (DeMaster, 1981). Duplicate analysis of the same sample

Fig. 1. The locations of samples and oceanographic setting (the circulation current
system was modied after Liu et al., 2003, 2007), YSWC: Yellow Sea Warm Current;
TC: Tsushima Current; YSCC: Yellow Sea Coastal Current; TWC: Taiwan Warm
Current; CDW: Changjiang Diluted Water; ECSCC: East China Sea Coastal Current;
NJCC: North Jiangsu Coastal Current.

To determine the cell size distribution, the SEM was used to

capture images of the diatoms. Before the observations, a piece of
lter membrane with SPM was cut, posted on a pedestal and then
coated with gold powder within 70 s. The lter membranes were
observed and photographed with a FEI Quanta 200 Environmental
Scanning Electron Microscope in Qingdao Public Security Bureau.
The test voltage was 25 kV, with a maximum resolution of 35 nm.
Finally, the diatom species within the suspended particles were
identied, and statistics describing the diatom size distribution
were determined with the help of AutoCAD.

4. Results
4.1. Grain size distribution of the surface sediments
The result of the grain size analysis of the sediment samples is
in agreement with previous analyses of the surface sediments on
the continental shelf in the ECS, indicating that the grain size
properties of the collected sediments were highly variable. In the
mouth of the Changjiang River, sand dominates due to the active
hydrodynamic settings, but the contents of silt and clay increase
signicantly in the mud deposition area.
Sediments at the C0401 and C0403 sites (out of the estuary) are
muddy sand and silty sand, respectively, based on the Folk's
Sediment Classication method; their sand contents are 60% or
slightly greater, and the silt/clay ratios are 2.3 and 1.9, respectively.
Their grain size distribution displayed a bimodal pattern. In the
sediments at C0501 (located in the Changjiang River mouth) and
C0508 (located in the northern ECS and south of Cheju Island), silt
is the dominant fraction, accounting for approximately 61% and
50%, respectively; the sand contents are 16% and 23%, respectively,
with greater clay contents. Thus, these sites are generally composed of sandy silt and displaying approximately normal distributions. The sediments in the FJA (south of the estuary), C0701 and
C0802 (off the ZhejiangFujian coast) are clayey silt, with silt
contents of more than 70% and no sand class fraction; these sites
all display unimodal distributions. The clay content of the sites
slightly decreases from north to south.
The mean size of the sediment at C1004, which is the southernmost site and is located in the middle shelf, with a maximum
water depth of approximately 81 m, becomes coarser compared to
the inner shelf sediments, with the depth and distance to the coast
increasing. This site is comprised of sandy silt, with a sand content
of more than 30% and a silt/clay ratio of approximately 2.2. The
color of the sediments is generally gray at locations deeper than
30 m. The dominant grain size fractions and grain size distribution
patterns are listed in Table 1 and displayed in Fig. 2. These samples

Table 1
Characteristics of the sample sediments.
Site

Longitude

Latitude

Depth (m)

Sand (%)

Silt (%)

Clay (%)

Character

C0401
C0403
C0501
FJA
C0508
C0701
C0802
C1004

122139.4990
123130.7990
122119.6930
122140.6510
125151.3250
122114.7060
121126.5400
121118.2960

31137.9500
31158.2680
31130.0890
30158.2180
30150.7410
29119.8920
27145.2410
26122.6570

34.6
41.0
17.0
22.2
75.0
15.0
29.0
81.0

60
65.1
16.1
0
23
0
0
32.8

27.9
22.9
60.8
74.7
49.0
80.5
89.0
46.2

12.1
12.0
23.1
25.3
28.0
19.5
11.0
21.0

Gray silty sand

Lividity muddy sand with shells
Wheat sandy silt
Yellow clayed silt
Gray sandy silt
Yellow clayed silt
Yellow clayed silt
Caesious sandy silt

Please cite this article as: Wang, L., et al., Grain-size effect of biogenic silica in the surface sediments of the East China Sea. Continental
Shelf Research (2014), http://dx.doi.org/10.1016/j.csr.2014.03.005i

L. Wang et al. / Continental Shelf Research ()

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Fig. 2. Grain size distribution and fraction content of the sediments.

Table 2
BSi content of different fractions of the surface samples (units in 10  2).
Site

Bulk

o 63 mm

o 32 mm

o 16 mm

3263 mm

1632 mm

STD direct

STD normal

C0401
C0403
C051
FJA
C0508
C0701
C0802
C1004
Max
Min
Mean
STD

0.409
0.544
0.322
0.62
0.836
0.618
0.65
0.444
0.836
0.322
0.555
0.162

0.452
0.756
0.444
0.657
0.876
0.592
0.636
0.495
0.876
0.444
0.614
0.152

0.582
0.796
0.433
0.706
0.819
0.714
0.778
0.626
0.819
0.433
0.682
0.13

0.611
0.83
0.601
0.795
0.881
0.869
0.805
0.652
0.881
0.601
0.756
0.115

0.226
0.331
0.485
0.392
0.472
0.527
0.467
0.439
0.527
0.226
0.418
0.098

0.246
0.458
0.226
0.559
0.56
0.557
0.56
0.477
0.56
0.226
0.455
0.141

0.1623
0.2045
0.1304
0.1379
0.1778
0.1266
0.1282
0.0932

0.3967
0.3763
0.4051
0.2219
0.2124
0.2048
0.1972
0.2102

encompassed a large range of grain sizes that were located in

different sedimentary sub-environments and are suitable for
investigating the BSi content from different size fractions.

4.2. BSi distribution in different size fractions of sediment

The measurement of the BSi content of the samples that were
collected from the ECS ranged from 0.32% to 0.84% in the bulk
samples, with a mean of approximately 0.56%. In the o63 mm
fraction, the samples ranged from 0.44% to 0.88%, with mean of
0.61%. In the o32 mm fraction, the samples ranged from 0.43% to
0.82%, with a mean of 0.68%, and in the o 16 mm classes, the range
was 0.60.89%, with a mean approximately 0.76%. In the 1632 mm
classes, the content was between 0.22% and 0.56%, with an average
of 0.46%, and in the 3263 mm classes, it was between 0.22% and
0.53%, with an average of 0.44%. The standard deviation (STD) of
the BSi content in different size fractions suggests that the highest
value occurred in the bulk samples, and lowest value occurred in
the coarse silt (3263 mm). The BSi content of the samples from
C0401, C0501 and C1004 are generally low, often below 0.6%,
while at the remaining sites, the content was generally above 0.6%,
except in the coarse fraction of sand or coarse silt; at C0508, it was
generally above 0.8%. The data are listed in detail in Table 2.
Generally, the BSi content was between 0.2% and 0.9%, which
is a low value on a global scale. The mean data for BSi in the
8 sample sediments shows indicate that the BSi content decreased
in the following order: o16 mm, o32 mm, o 63 mm, bulk,
1632 mm and 3263 mm (Fig. 3). The values in the o16 mm
fractions are approximately 1.051.86 times the value of the bulk
sediments. The highest value is approximately 1.652.70 times the
lowest value of each sample. The STD data indicate that in the ne

sediments, the variation in the BSi content of different size

fractions is less than that of the coarse sample sediments.
In the coarse samples from sites C0401 and C0403, both of the
STDs for the rare measurement data and the data after normalization (compared to the bulk content) suggest that the BSi
content in different size fractions oscillates dramatically (Table 2).

4.3. The diatom species and their cell sizes in section DH 3

Diatoms are the main constituents of the BSi in the sediments
in coastal areas. The diatom species and their cell size distribution
help to explain the variation in the BSi content from different
portions of sediment. The suspended matter from the 18 water
samples at the 6 sites in section DH 3 that were collected during
the autumn 2010 cruise were observed with the Scanning Electron
Microscope photographed at magnications of 600, 1000, 2000,
5000 or 10,000. Ten species were identied from the images of
suspended particulates, including Thalassiosira, Skeletonema, Chaetoceros, Coscinodiscales, Gyrosigma, Asterionella, etc. Table 3 lists
these results, and their images are provided in Fig. 5.
Diatoms scatter alone or form ocs. Flocs are composed of
mineral debris, organic fragments and other diatoms. Skeletonema
costatum and Thalassiosira spp. are the dominant species, having
nearly the same cell sizes of 214 mm, with peaks of 512 mm
(Fig. 4). The Chaetoceros is a relatively widely distributed species,
with a large cell size of 1060 mm or even greater than 100 mm.
Other diatom species, such as Gyrosigma and Asterionella, were
accidentally observed. The distributions in the water column
reveal that the diatom size in the surface layer is larger than in
the other layers and tended to decrease from the coast to the
outer sea.

Please cite this article as: Wang, L., et al., Grain-size effect of biogenic silica in the surface sediments of the East China Sea. Continental
Shelf Research (2014), http://dx.doi.org/10.1016/j.csr.2014.03.005i

L. Wang et al. / Continental Shelf Research ()

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Fig. 3. The BSi distribution in different size-fraction classes.

Table 3
The abundance and cell sizes of diatom species in section DH 3 in the ECS.
Diatom species

Cell size (mm)

Abundance

Thalassiosira spp.
Skeletonema costatum
Chaetoceros spp.
Coscinodiscales spp.
Gyrosigma spp.
Asterionella spp.

214
314
1060
1460
80120
2545

Major
Major
Middle
Minor
Minor
Minor

5. Discussion
The BSi accumulation in the sediment is related to the processes of uptake of silicic acid by diatoms and the subsequent
silicication, settling of siliceous frustules and burial in the seabed
sediment. However, the inuence of sediment grain size must be
considered when examining the BSi content, except for BSi
accumulation, because of the dilution effect of sediment, especially
in the estuary or coastal areas that have signicant clastic inputs.
The BSi content of different size fractions provides much new
information about diatom production from the variability of the
grain size distribution, and we will discuss the factors inuencing
the BSi distribution in the next section.

5.1. The relationship between the BSi distribution in different size

fractions of the sediment and diatom cell size
The BSi content in different size fractions uctuates based on
the ratio of the difference in diatoms' frustules to other sediment
components. However, the BSi content distribution should follow
the conservation laws of BSi accumulation.
The BSi content in the different size fractions of the samples
have their largest BSi content ratios of approximately 3 at the
same site, and the average BSi content decreases in the following
order: o16 m, 1632 m, 3263 m, and 4 63 m (Fig. 6). The
distributional trend in the BSi concentration is o 16 m 4 o 32 m 4 o 63 m 4bulk in sediment from the same site, with
the BSi concentration of o 16 m being approximately 1.051.86
times the value in the bulk sediments (Fig. 3).

The BSi content was dependent on the supply of diatom

skeleton or frustules, and the diatom cell size should play an
important role in the BSi content in the different size fractions.
Therefore, the cell size structure and the dominant diatom species
must be investigated. It is well-known that the size structure of
primary producers, or photo-plankton, is a basic index in the
marine environment. Many studies have described the phytoplankton community in the coastal area, which is signicantly
inuenced by upwelling, freshwater mixing or both, and is
dominated by the size classes 420 mm and 320 mm. In contrast,
the nutrient-depleted offshore shelf water is dominated by
o3 mm phytoplankton (Chen, 2000). Diatoms are considered to Q4
be the most important phytoplankton component in the marginal
seas, and their cell sizes depend on the physiological character and
the living environment. Another factor affecting cell size is the
inuence of sinking. Excessive sinking is fatal for diatoms because
they require sunlight to obtain energy. Diatoms have a size limit
within the same species and even among different species. The
minimum diatom cell sizes are 24 m in equivalent spherical
diameter, with the largest species being about 2 mm or more.
Variation in physiological activity selects for a greater range in
diatom size (Finkel et al., 2005). Under different nutrient conditions, diatoms with small cell sizes generally acquire limiting
nutrients more efciently because of its high surface area to
volume ratio and, therefore, are competitively advantageous under
nutrient limitation (Smith and Kalff, 1982). Similar to many Q5
estuarine and coastal areas in the world (Claereboudt et al.,
1995; Pinckey et al., 1998), in the ECS, nano-diatoms (320 m)
and micro-diatoms (4 20 m) dominated the diatom size structure (Li, 2006).
Diatoms are the only contributor of BSi in the marginal seas,
especially in the ECS. According to historical materials, the major
species and genera of diatoms in the water column are Skeletonema spp., Thalassiosira spp., Chaetoceros spp., Pseudonitaschia
pungus, and Rhizosolenia spp. (Li, 2006; Xie, 2006; Gao et al.,
2003). The dominant diatoms and their proportion changes
seasonally and annually (Li, 2006). Consider, for example, Skeletonema, which is a common planktonic species that is present in the
East China Sea during all seasons. It blooms in the late spring and
early summer (Wu et al., 2004). From 1986 to 1993, Skeletonema
blooms accounted for 27% of the total algal abundance in the East

Please cite this article as: Wang, L., et al., Grain-size effect of biogenic silica in the surface sediments of the East China Sea. Continental
Shelf Research (2014), http://dx.doi.org/10.1016/j.csr.2014.03.005i

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L. Wang et al. / Continental Shelf Research ()

Fig. 4. Cell size distribution of Thalassiosira spp. and Skeletonema costatum.

Fig. 5. The diatom species in the suspended particles in section DH 3.

China Sea (Hong, 2003). Zhang et al. (2010) reported on the close
correlation between Skeletonema resting stages, germination and
bloom initiation. Skeletonema can tolerate long periods of adverse
environmental conditions by forming physiologically dormant
cells.
In this research, the dominant species in the water-column are
Skeletonema spp. and Thalassiosira spp., based on the images of all
of the diatom species that were collected from the suspended
particles. Their cell size generally ranged from 2 m to 14 m (i.e.,
nano-diatoms), and the diatom size structure suggested the
absolute advantages of diatoms smaller than 20 m (Fig. 6). Except
for the plankton cells, the benthic species constitute a large

portion of the BSi, especially along the shallow coast, and their
cell sizes are larger than the plankton cells, to some extent.
In general, the diatoms' size structure concentrated the BSi in
the ne fraction of o 16 m or o 32 m and, thus, controlled the
distributional pattern of BSi in different size fractions in the
sample sediments.

5.2. The settling processes of diatoms and preservation efciency

It is apparent that the partitioning between recycling and burial
is controlled by competition during the dissolution process (Khalil

Please cite this article as: Wang, L., et al., Grain-size effect of biogenic silica in the surface sediments of the East China Sea. Continental
Shelf Research (2014), http://dx.doi.org/10.1016/j.csr.2014.03.005i

L. Wang et al. / Continental Shelf Research ()

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Fig. 6. The average BSi content in the collected samples and diatom cell size distribution of all of the diatoms in the suspended particles (the dash line represents the average
BSi content in the o 16 m, o 32 m, and o 63 m fractions and in the bulk sediments).

et al., 2007), in which the sinking speed of diatom cells will affect
the BSi dissolution and preservation efciency signicantly.
Diatoms live in the water alone or as diatom chains, and after
their death, the cell sinks solely or in a chain, even occasionally
forming ocs with other materials. Generally, the sinking speed of
a diatom ranges from several centimeters to about hundred
meters per day (Smayda, 1970; Logan and Alldredge, 1989).
According to the model of Miklasz and Denny (2010), the sinking
speeds of single diatoms with cell sizes between 4 m and 20 m
range from 0.5 m d  1 to 8 m d  1, and the relationship between
the maximum sinking speed and size depends on size, density, and
the thickness of the frustule of the species. Meanwhile, many
nano-diatoms, like the Thalassiosira, tend to form chains with tens
of cells, and the settling speed of the majority of chain-forming
diatom species is equivalent to, or slightly faster than, a single
large cell (Miklasz and Denny, 2010). With a large volume
of terrigenous clastics and organismal secretion input, diatoms
are prone to forming aggregates or ocs with other particles.
The mean in situ settling speed of newly formed ocs was
1177 56 m d  1, which is two orders of magnitude faster than
non-aggregated diatoms (Alldredge and Gotschalk, 1989). At the
same time, a rapid, episodic export of surface-derived primary
production to the ocean bottom via mass occulation and settling
of diatom blooms can occur prior to consumption by pelagic
grazers and signicantly affects the BSi preservation efciency.
The East China Sea has a very broad continental shelf, and in most
areas, the water depth is less than 100 m, allowing diatoms to
settle to the seabed over several days or weeks.
In the East China Sea, the silica concentration is approximately
221 mol L  1 (L and Song, 2007), while the maximum silica
concentration is approximately 200300 mol L  1 at ocean temperatures (Zhang, 2004; Lu, 2006). Therefore, diatoms will dissolve
even when they live in the water. The specic dissolution rate of
BSi in seawater, Vdis, has been shown to conform to the following
rate equation (Hurd and Birdwhistell, 1983):



V dis k SiOH4 sat  SiOH4 Asp
1
where k is the rst-order rate constant (cm h  1), [Si(OH)4]sat
represents the solubility of BSi (mol cm  3), [Si(OH)4] is the
ambient silicic concentration (mol cm  3) and A represents the
specic surface area of the BSi present (cm2 mol  1). Unfortunately,
there is no reference for the dissolution rate in the ECS. However,
according to research in Jiaozhou Bay in east China, the specic
dissolution rate is approximately o0.023 d  1, and the dissolution
rate is o0.009 mol L  1 d  1 (Liu et al., 2008). These results
indicate that the diatom frustule may dissolve to some extent,
but the dissolution rate will not be very fast and along the sinking
pathway from the euphotic layer to the seabed sediment there will

still be a high proportion of the diatom frustule left to be buried in

the surface sediment. The images of the diatoms in particulate
matters from the bottom layers help to support this idea. In fact,
the study by Fan et al. (2011) also revealed that the diatom record
can be well preserved. Liu et al. (2005) reported that the BSi
accumulation rates were 0.1811.6 mol m  2 yr  1 in the study
region of the East China and Yellow Seas, and the output ux of
BSi from the euphotic layer was still huge.
Except for the inuence of diatoms' own factors, the sinking of
their frustules and their subsequent preservation in the sediment
are also related to the sediment accumulation rate in situ. Previous
studies in the ECS have revealed that the sedimentation rate is
about 13 cm yr  1 in the inner shelf, with the highest rate of
approximately 5 cm yr  1 in the mouth of the Changjiang River.
Offshore, in the mud zone south of Cheju Island, it is approximately 0.3 cm yr  1 (Liu et al., 2006). According to the research by
Ragueneau et al. (2000) concerning the sediment accumulation
rates and preservation efciency of silica deposited at the seaoor,
diatom frustules should be almost completely preserved at the
research sites after buried in the sediments. Fan et al. (2011) also
reported that the diatom fracture settled down to the seabed
rapidly, and Yang et al. (2008) suggested that the BSi was a stable Q7
reserve. Liu et al. (2005) estimated the BSi burial efciency in the
ECS to be between 36% and 97%, which is higher than the
Equatorial Pacic Ocean (6.4%) (Ragueneau et al., 2001), the global
ocean average ( 20%) (Trguer et al., 1995) and most coastal Q2
environments (1.917.1%) (DeMaster et al., 1996). In summary,
diatoms in the East China Sea could sink to the seabed quickly and
be buried with a very high efciency.
5.3. The inuence of the hydrodynamic condition on the BSi content
The hydrodynamic condition affects the surface sediment
characteristics, diatom distribution and subsequent settling and
transport; therefore, its inuence must be considered when
discussing the distribution of BSi content in the research area.
First, the sediment particle size distribution, which is a critical
factor controlling the BSi content variation and may complicate
the indications of BSi under some conditions, is controlled by the
hydrodynamic characteristics and source. In the estuary, where
runoff and waves are powerful, the sediment size tends to be
coarse, consisting of sand or mud and sand. At sites C0401 and
C0403, the sand fraction accounts for more than 60% by weight,
and the BSi contents in the 1632 m and 3263 m size fractions
were the lowest among the 8 samples. In the inner shelf mud belt
off the coast of ZhejiangFujian (e.g., site FJA, C0701 and C0802)
where the coastal current dominates the particle transport, the
sediments are ne, consisting of silt or silty clay, and the BSi

Please cite this article as: Wang, L., et al., Grain-size effect of biogenic silica in the surface sediments of the East China Sea. Continental
Shelf Research (2014), http://dx.doi.org/10.1016/j.csr.2014.03.005i

L. Wang et al. / Continental Shelf Research ()

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contents in the o16 m, o32 m and o63 m fractions were

relatively higher than in the samples from C0401 and C0403. Due
to high proportion of ne particles, the BSi contents within the
size fractions of each sample are similar to those in their bulk
sediments. The sediment in the northern ECS and south of Cheju
Island (e.g., site C0508) corresponded to areas with mixing
hydrodynamics. This area is in the transition zone between the
littoral water and the open sea. It is controlled by the Yellow Sea's
Warm Current for most of the year, which is another branch of the
Kuroshio Current (Su et al., 1989). Formal research in this area has
indicated that the o16 m fraction accounts for 8090% of the
surface sediments (Guo et al., 2002). The BSi content in this area,
as for Site C0508, is relatively high due to the larger proportion of
ne fraction sediment than at the river's mouth.
Second, the diatom cell size distribution also corresponds to
the hydrodynamic conditions. Large diatoms can only live in the
turbulent waters, where their large size helps to prevent settling.
In an enclosed environment where the water exchange is slow and
the nutrient supply is limited, small diatoms survive and constitute the majority of the phytoplankton. Thus, the transport and
accumulation of diatoms is closely related to the hydrodynamic
environment. As a suspended load, diatom frustules tend to
accumulate in environments with low hydrodynamic conditions.
Otherwise, diatom skeletons would remain in the water column
and be transported continuously in an active hydrodynamic
condition. In the ECS, the ne sediments usually exist in the weak
hydrodynamic environment; therefore, their BSi contents are
generally higher than those in other locations.
However, at some sites, such as C0508, where the sediment is
relatively coarse (i.e., sand content approximately 23%), the BSi
content is also high. It may be induced by the high primary
production and low sedimentation rate in the cyclonic eddy
environment. In this area, the supply of terrigenous materials is
limited compared to that in the estuary and inner shelf. The
vigorous production of diatoms reduces the dilution effect of
terrigenous fragments.
In a complex hydrodynamic environment, due to the grain size
inuence, the BSi in the muddy fraction was formerly used as a
paleoproductivity proxy for some continental shelf regions
(Gonzlez-lvarez et al., 2005; Bernrdez et al., 2005). The
research of Bernrdez et al. (2005) in the Ra de Vigo and Galician
continental shelf suggests that, for the core samples, there was no
correlation between the BSi content in the ne and bulk fractions,
while for the surface sediments there was a good correlation
between the BSi content in both fractions, making it difcult to
assess the actual effect of grain size. However, if the sediment
grain size distribution changes synchronously with the diatom cell
size, the selection of ne fractions may be unnecessary. We found
that determining the BSi content of the ne fractions is unnecessary when the proportion of coarse grains is small and the
hydrodynamic setting is relatively weak. However, in intensive
hydrodynamic environments, the selection of sediments over a
limited size scale may produce different results for BSi accumulation and distribution compared to the bulk sediment. This technique will help to illustrate the evolution of diatom production.

6. Conclusion
Based on the results and discussion, we suggest the following
conclusions:
(1) The BSi content in the surface sediments in the East China Sea
are generally below 1% by weight. The BSi contents in different
size fractions vary signicantly, with the highest content in the

o16 m, approximately 1.11.8 times that in the bulk

sediments.
(2) The variation in the BSi content in different size fractions is
mainly controlled by the diatom species and their cell sizes. In
the ECS, nano-diatoms are the dominant species, with main
cells of 214 m. These cells would sink to the seabed quickly
and be preserved efciently, resulting in a high BSi content in
the fraction o16 m.
(3) The hydrodynamic condition affects diatoms' cell size distribution and sediment character and, thus, has a signicant
inuence on the BSi content of different size fractions.
(4) The grain size distribution of the bulk sediment should be
considered when BSi is used as the proxy for diatom primary
production.

Acknowledgments
The authors thank the crew of the R/V Dong Fang Hong 2 for
kindly assisting with the sediment collection on the cruises in June Q8
2009. This study was supported by the National Natural Science Q9
Foundation of China (41376055, 41030856) and the Ministry
of Science and Technology of People's Republic of China
(2010CB951202).
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Please cite this article as: Wang, L., et al., Grain-size effect of biogenic silica in the surface sediments of the East China Sea. Continental
Shelf Research (2014), http://dx.doi.org/10.1016/j.csr.2014.03.005i