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Natl. Acad. Sci. Lett.

(JulyAugust 2014) 37(4):375380


DOI 10.1007/s40009-014-0240-9

RESEARCH ARTICLE

Biogenic Silica in the Surface Sediment: A Geochemical Indicator


in Estuarine Environment of Gulf of Kachchh, Gujarat, India
Goutam Kumar A. L. Ramanathan

Received: 17 April 2013 / Revised: 25 August 2013 / Accepted: 5 November 2013 / Published online: 22 July 2014
The National Academy of Sciences, India 2014

Abstract The variation of biogenic silica (BiSi) in the


surface sediments of mangroves of Gulf of Kachchh were
due to the nutrients of overlying surface water, depositional
environment and distance from supplying channels. In the
current study, sediment BiSi is used as geochemical indicators of depositional environments. BiSi in the surface
sediment does follows the trend of organic carbon (OC)
content in the surface sediments, nutrients (NO3-) of
overlaying surface water, sand proportion in the surface
sediment and distance from Arabian sea as reported higher
concentration at Sachana (S3), New Bedi Port (S4), Old
Bedi Port (S5) and Narara (S7). Higher concentration of
NO3- (30.09 4.55 mg/l) and PO43- (1.51 1.18 mg/l)
leads to lower BiSi at Mundra (S1). Strong correlation of
dissolved silica (DSi) (r = 0.91) indicates its significant
influence on BiSi accumulation in the sediments. No significant correlation observed between BiSi in the surface
sediments and SO42-. Lack of significant correlations
among the nutrients indicates the influx of anthropogenic
input and waste discharge containing high nitrogen and
phosphorous compounds into the environment. Principal
component (factor) analysis indicates that accumulation of
BiSi in the sediments was highly enhanced by DSi in the
surface water and anthropogenic phosphate inputs. Nutrient
status of overlying surface water got affected by the
accumulation of the BiSi in the surface sediments and may
alter its productivity. N:P ratio is maintained by NO3oxidation in the ecosystem, which resist the replacement of
diatoms by algal communities.

G. Kumar (&)  A. L. Ramanathan


School of Environmental Sciences, Jawaharlal Nehru University,
New Delhi 110067, India
e-mail: goutamses@gmail.com

Keywords Sediment  Biogenic silica  Organic carbon 


Principal component (factor) analysis

Introduction
Biogenic silica (BiSi) in sediments is known to be an
important parameter to understand the biogeochemical
processes in estuarine and coastal ecosystems. Silicate
represent as one of the major nutrient elements for estuarine and coastal ecosystems, which often dominate phytoplankton communities and have important roles in
planktonic microorganisms (diatoms and radiolarian) [1,
2]. Although Si is a very common element in the biogeosphere, its limited bioavailability is due to the slow
weathering rate of most silicate minerals [3]. BiSi is an
indicator of material input to estuarine sediments. Rivers
are responsible for *80 % of the dissolved silica (DSi)
entering the global ocean and also carry particulate Si, both
lithogenic and biogenic (freshwater diatoms, phytoliths)
that can play a significant role as a source of Si for coastal
diatoms [4]. Anthropogenic activities have resulted in an
increase of nitrogen (N) and phosphorus (P) delivery to the
coastal ocean, which changes the Si:N and Si:P ratios, thus
modifying the silicon biogeochemical cycle, leading to
ecosystem changes [5, 6]. BiSi content in sediments is
found to have a close link with bio-siliceous productivity in
overlying waters [7], and also have a strong potential for
proxy estimation of paleo productivity, as comparatively
stable structure preserved to such an extent in soil and
sediment [810]. Very few reports have been published on
the distributions and variations of nitrogen and phosphorus
in mangroves of Gulf of Kachchh [6, 11]. To the best of our
knowledge, this is the first baseline report dealing with BiSi
content in the intertidal sediments in the mangroves of Gulf

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376

of Kachchh and limited reports in other mangrove ecosystems. The current study is to investigate the productivity
of the ecosystem by understanding the accumulation and
distribution of BiSi in the sediments of mangrove ecosystem, Gulf of Kachchh, Gujarat. The study also aims to
understand the distribution of dissolved nitrate and phosphate in this ecosystem.

Material and Methods


Collection and Preservation of Samples
Representative surface sediment samples (n = 21) from
various sites of inter-tidal regions of mangroves ecosystem
viz. Mundra (S1), Jodiya (S2), Sachana(S3), New Bedi Port
(S4), Old Bedi Port (S5), Sikka (S6), and Narara (S7), were
collected during November 2008, taking consideration of
anthropogenic input, mixing zones, natural weathering
input zones, etc. (Fig. 1). The samples were thoroughly
homogenized at the sealed polyethylene plastic bags and
kept in ice chest. Water samples (n = 22) from these
locations were collected in pre-washed polythene bottles
for nutrient analysis. The samples were kept frozen in ice
chest till the transfer in the laboratory, where analysis was
done.
Physico-chemical Analysis of the Surface Sediment
and Water
The pH, temperature and total dissolved solids (TDS) in
water were measured onsite using the Thermo-Orion Water
Analysis Kit (Model Beverly, MA, 01915, USA). Salinity
of the water samples were measured using refractometer.

Fig. 1 Showing study area in Gulf of Kachchh, Gujarat, India

123

G. Kumar, A. L. Ramanathan

Nitrate (NO3-), sulphate (SO42-), bicarbonate (HCO3-),


phosphate (PO43-) and inorganic silica (HSiO3-) were
analyzed by using standard methods [12].The dry sieving
was carried out by electromagnetic sieve shaker (Fritsch
Analysette-3) into 250 lm (medium sands), 125 lm (fine
sands), 63 lm (very fine sands), 37 lm (very coarse silt)
and \37 lm (clay). The further separation of 63 lm was
done by wet sieving adopting Attenburg sedimentation
cylinders methods based on Stokes law. The textural
parameters were computed using the formulae of Folk and
Ward [13]. Organic carbon (OC) of the sediment samples
were estimated by using WalkleyBlack method [14]. The
determination of BiSi in well powdered sediment using a
modification of the procedure by [15]. Well powdered
dried sediment (25 g) in duplicate were weighed in polythene bottles (100 ml size) and extracted with 1 % sodium
carbonate (Na2CO3) in a *85 C water bath for 5 h (pH
10.6). At 3, 4 and 5 h, 1 ml samples for Si analysis were
taken from each bottles and diluted with 9 ml of 0.021 N
HCl solution. The Si concentrations of the samples were
analyzed spectrophotometrically [16]. BiSi concentration
in the sediments was then calculated by using a linear
regression for the 3, 4 and 5 h time points.
Statistical Analysis
Correlation analysis is a bivariate method commonly used
to measure and establish the relationship between two
variables and generally used to measure the degree of
dependency of one variable to other. Factor Analysis was
done by using SPSS software (Version 10.0). The factors
were extracted by using Varimax rotation with Kaiser
Normalization scheme to explain observed relationship
among the variables. The mode of factor analysis is

377
Temp. (C)

25
20

10

pH

30

0
S1 S2 S3 S4 S5 S6 S7

S1 S2 S3 S4 S5 S6 S7

Location

DO

PO43- (mg/l)

10
5
0

S1 S2 S3 S4 S5 S6 S7

Results and Discussion

3.50

1600

3.00

1400

2.50

1200
1000

2.00

800

1.50

600

1.00

400

0.50

200

BiSi (mg/Kg)

Org. C (mg/Kg)

0.00
S2

S3

S4

S5

S6

S7

Location
Org.

Biogenic Silica

Fig. 2 Relation between organic carbon and biogenic silica in the


surface sediment

15

2
0

Location

DSi

10
5
0
S1 S2 S3 S4 S5 S6 S7

Location

PO43-

S1 S2 S3 S4 S5 S6 S7

NO3- (mg/l)

H3SiO3 (mg/l)

The mangroves of Gulf of Kachchh, Gujarat is of particular


interest to nutrient cycling because of its importance for
transportations of terrigenous nutrients to coastal seas.
Water temperature (25.6729.33 C), pH (7.539.15), DO
(5.597.96 mg/l), PO43- (0.332.54 mg/l) and H4SiO4
(1.269.89 mg/l) were reported. Nutrient status of overlying
surface water also affected the accumulation of the BiSi in
the surface sediments. N:P ratio can be maintained by NO3oxidation in the ecosystem, which resist the replacement of
diatoms by algal communities. But high anthropogenic
inputs of N and P can leads to succession of non-diatom
phytoplankton community by inducing DSi limitation of
diatom communities [17, 18]. Higher concentration of NO3(30.09 4.55 mg/l) and PO43- (1.18 1.51 mg/l) at
Mundra (S1) may leads to succession of non-diatom phytoplankton community. Hence, lower concentration of BiSi
in the surface sediments was reported. The concentrations of
PO43- in the surface water was reported as 0.33 0.11 mg/l
and 0.34 0.05 mg/l at Jodiya (S2) and Sikka (S6),
respectively, which is lower than other locations but also
having low OC content in the sediment may be the cause of
lower concentration of BiSi in the surface sediments
(Fig. 2). In the study Avecinia marina is the dominated
mangrove species and also major source of OC input. Silt
content in the surface sediment ranges from 0.60 to 22.80 %.
Negligible proportion of clay was reported in the study area

S1

Location

Hydro-geochemistry of Surface Water

pH

Location

DO(mg/l)

R-mode or Q-mode. Factor analysis is termed R-mode


when the concern is interrelationships among the variables
and when concern is the interrelationships between samples Q-mode is applicable [6]. R-mode factor analysis was
used to identify major factors controlling the hydro-geochemistry of surface water and surface sediments of Gulf
of Kachchh. Eigen value is \1 reflects significant contribution of corresponding factor.

Temp. (oC)

Biogenic Silica in the Surface Sediment

100

NO3-

50
0
S1 S2 S3 S4 S5 S6 S7

Location

Fig. 3 Surface water qualities of mangroves of Gulf of Kachchh,


Gujarat

[19]. In the current study, the concentration of BiSi in the


surface sediment does not strictly follows the trend of grain
size of the sediment. A close relationship of BiSi with OC
was reported by Lijun et al. [20]. BiSi content in the surface
sediment follows the trend of OC content in the surface
sediments except Mundra (S1). Lower concentration of BiSi
in surface sediment at Mundra (S1) may be due to higher
concentration of NO3- (30.09 4.55 mg/l) and PO43(1.51 1.18 mg/l) in the overlaying surface water. Sedimentary diatom can be used as a proxy for surface water
silicic acid utilization [21]. Lower BiSi content in the surface
sediment at Mundra (S1) and Sikka (S6) can be explained by
lower utilization of overlaying surface water silicic acid
(Fig. 3; Table 1). Depositional environment at the time of
accumulation as well as distance from supplying channels
affects the diatom input to the surface sediments. The supply
of diatoms and suspended sediment in the estuarine water
column, controlled by tidal in-undation and geomorphological set-up [9, 22, 23]. In the study area, Arabian Sea is the
source of diatom and sediment input. The concentration of
BiSi in the surface sediment almost follows this trend except
at Sikka (S6) and Mundra (S1). At Sikka (S6), low OC and
high sand proportion in the surface sediment leads to low
BiSi concentration in the surface sediment whereas succession of non-diatom phytoplankton community causes lower
BiSi at Mundra (S1). Dissolved oxygen (DO) content in the
surface water reflects mixing of surface water shows that low
DO is due to consumption of DO. Geomorphological set-up,
distance from Arabian Sea and lack of major river flow leads
to low mixing at Sachana (S3), which may results lower
concentration of DO at Sachana (S3). However, higher
concentration of BSi (907.16 6.99 mg/kg) at Sachana
(S3) can be explained by the relatively higher OC (%) in the

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378

G. Kumar, A. L. Ramanathan

Table 1 Sediment characteristics (in average) of various sampling stations


S1

S2

S3

S4

S5

S6

S7

Sand (%)

77.20

78.50

94.80

95.50

96.40

96.30

Silt (%)

22.80

21.50

5.20

4.50

3.60

3.60

0.60

3.25

1.78

2.80

2.09

2.18

1.47

2.54

68.13

132.00

907.16

1,367.67

1,213.00

428.30

1,200.67

Org. C (%)
BiSi (mg/kg)

surface sediment (Table 1). SO-2


4 concentration in the surface water ranged between 4,422.53 and 8,442.03 mg/l,
which may be the controlling factor for pH of the surface
water. BiSi dissolution is controlled by pH and temperature
[24]. In the current study, little spatial variations of pH and
temperature reported, which may not be the controlling
factor for BiSi deposition in the surface sediments.
Statistical Analysis
Correlation Analysis
Various parameters considered for correlation analysis. A
strong correlation was observed between BiSi with DSi
(r = 0.91) and PO43- (r = 0.96) indicates these factors
significantly influence the BiSi in the sediments (Table 2).
Lack of significant correlations among NO3- and SO42indicate the influx of anthropogenic input and waste discharge containing these compounds from surface runoff
into these environments.

99.40

(anthropogenic) inputs. Sedimentary diatom can be used as


a proxy for surface water silicic acid utilization [21]. A
higher concentration of BiSi in the surface sediment was
reported at Sachna (S3), New Bedi Port (S4), Old Bedi Port
(S5) and Narara (S7) can be explained by high utilization
of dissolves silica of overlying water (Fig. 3; Table 1).
Factor 2 accounts for 29.58 % variance in the dataset and
shows strong loading of Cl-, EC and DO, which describes
contribution from saline environment with good mixing
condition. A negative loading of NO3- indicates nitrate
oxidation in the ecosystem, which leads to resist the
increase in N: P ratio. Hence, the diatoms did not replaced
by algal communities. Factor 3 accounts for 23.44 % variance in dataset and shows high loading of pH and SO42-,
represents contribution from sulphate mineral dissolution,
sulphide oxidation or anthropogenic inputs in the environment (Table 3). But lack of significant correlations
among the nutrients indicates the anthropogenic inputs of
SO42- compounds in the ecosystem.

Factor Analysis

Conclusion

Three factors with an Eigen value [1 were identified,


which explain about 83.86 % of the total variance. Factor 1
account 30.84 % variance in the dataset and shows high
loading of PO43-, DSi (H4SiO4) and BiSi. This factor
explains contribution of silica (riverine) and phosphate

The depositional environment and nutrient status of overlying surface water, affected the accumulation of the BiSi
in the surface sediments. Higher concentration of NO3and PO43- in the surface water at Mundra (S1) may result
succession of non-diatom phytoplankton community and

Table 2 Pearsons correlation matrix of various parameters of surface water and BiSi
Temp.

pH

EC

DO

Cl-

Temp.

pH

0.71

EC

0.21

0.37

1.00

DO

0.23

0.59

0.32

1.00

Cl-

0.22

0.44

0.95

0.31

1.00

NO3

NO3-

PO43-

SO-2
4

DSi

1.00

-0.04

-0.18

-0.65

-0.75

-0.56

1.00

PO43-

0.10

0.07

0.65

0.19

0.59

-0.38

1.00

SO42-

0.53

0.56

-0.05

0.30

-0.21

0.08

0.02

DSi

-0.24

-0.24

0.40

-0.16

0.23

-0.07

0.78

0.18

1.00

BiSi

-0.07

0.01

0.60

0.10

0.50

-0.26

0.96

0.10

0.91

123

BSi

1.00
1.00

Biogenic Silica in the Surface Sediment

379

Table 3 Principal and varimax rotated R-mode factor loading matrix


Variables

Factor 1

Factor 2

Factor 3

Communities

Temp. (C)

0.147

0.828

0.713

pH

-0.108

0.404

0.841

0.883

EC

0.494

0.784

DO

-0.137

0.680

Cl-

0.361

0.826
-0.874

0.769

PO43-

0.880

-0.242

0.912

SO42-

0.164

DSi

0.971

BiSi

0.961

NO3-

0.414

0.872
0.222

0.973

2.958
29.583

2.344
23.440

% Of cumulative variance

30.840

60.423

83.863

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Acknowledgments This research was supported by the University


Grant Commission (UGC), India by awarding Junior Research Fellowship (JRF) under CSIR-UGC Fellowship Programme. The authors
also thanks to the Forest Department of Gujarat for granting permission to carry out the current research work.

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hence low accumulation of BiSi in the surface sediments.


BiSi accumulation in the surface sediments follows trends
of OC in the sediments and distance from supplying
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BiSi. Lack of significant correlations among the nutrients
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Factor analysis shows accumulation of BiSi in the sediments was highly enhanced by DSi in the surface water and
anthropogenic phosphate inputs as high loading of PO43-,
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