Marine Pollution Bulletin 52 (2006) 1625–1633

www.elsevier.com/locate/marpolbul

Organic carbon and nitrogen stable isotopes in the intertidal

sediments from the Yangtze Estuary, China
a,*
M. Liu , L.J. Hou b, S.Y. Xu a, D.N. Ou a, Y. Yang c, J. Yu a, Q. Wang a

a
Department of Geography, Key Laboratory of Geographical Information Science of the Ministry of Education,
East China Normal University, No. 3663 Zhongshan North Road, Shanghai 200062, PR China
b
State Key Laboratory of Estuarine and Coastal Research, East China Normal University, Shanghai 200062, PR China
c
Institute of Geoscience, Johannes Gutenberg-University Mainz, Becherweg 55099, Germany

Abstract

The natural isotopic compositions and C/N elemental ratios of sedimentary organic matter were determined in the intertidal flat of the
Yangtze Estuary. The results showed that the ratios of carbon and nitrogen stable isotopes were respectively 29.8& to  26.0& and
1.6&–5.5& in the flood season (July), while they were 27.3& to  25.6& and 1.7&–7.8& in the dry season (February), respectively.
The d13C signatures were remarkably higher in July than in February, and gradually increased from the freshwater areas to the brackish
areas. In contrast, there were relatively complex seasonal and spatial changes in stable nitrogen isotopes. It was also reflected that d15N
and C/N compositions had been obviously modified by organic matter diagenesis and biological processing, and could not be used to
trace the sources of organic matter at the study area. In addition, it was considered that the mixing inputs of terrigenous and marine
materials generally dominated sedimentary organic matter in the intertidal flat. The contribution of terrigenous inputs to sedimentary
organic matter was roughly estimated according to the mixing balance model of stable carbon isotopes.
 2006 Elsevier Ltd. All rights reserved.

Keywords: Sedimentary organic matter; Stable carbon and nitrogen isotopes; C/N elemental ratio; Intertidal flat; The Yangtze Estuary; China

1. Introduction organic matter pool in the recent decades (Peterson et al.,

Estuaries and coastal zones are the main channels
between the lands and the oceans, which can trap significant
quantities of natural and anthropogenic organic matter
under the interactions of a series of physical, chemical
and biological processes (Kennedy, 1984; Thornton and
McManus, 1994). Thus estuaries and their adjacent areas
have already become a significant sink of organic matter
within the ecosystems on the earth’s surface. A large magni-
tude of accumulated organic matter has the important eco-
logical significance to sustain higher productivity and
biomass in the estuarine and coastal ecosystems (John
et al., 1988). More and more biogeochemists and ecologists
have already realized the ecological significance of the
*
Corresponding author. Tel.: +86 21 62232117; fax: +86 21 62232416.
E-mail address: mliu@geo.ecnu.edu.cn (M. Liu).
1985; Zhang et al., 1997; Peterson, 1999; Cloern et al.,
2002; Savoye et al., 2003). Although the dynamics of
organic matter in estuaries have been intensively studied,
questions still remain regarding the sources, fate and role
of organic matter in the ecology of estuaries and the coastal
oceans (e.g., Mantoura and Woodward, 1983; Cifuentes
et al., 1988; Peterson et al., 1994; Yunker et al., 1995; Cai
et al., 1998; Cifuentes and Eldridge, 1998; Canuel, 2001;
Harvey and Mannino, 2001 and references therein). The
reasons for these uncertainties include the complex interac-
tions among the various physical, geological and biochem-
ical factors that define each estuarine ecosystem and control
organic matter in these environments (e.g., Howarth et al.,
1991; Fogel et al., 1992; Hobbie, 2000).
Considerable attention in biogeochemical and organic
geochemical studies has been focused on the utilization of
carbon and nitrogen stable isotopes and their elemental

0025-326X/$ - see front matter  2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.marpolbul.2006.06.008
1626 M. Liu et al. / Marine Pollution Bulletin 52 (2006) 1625–1633

ratios (C/N) as natural tracers to identify the provenance,

fate and seasonal processes of organic matter in estuarine Jiangsu Province
and coastal marine environments (e.g., Thornton and
McManus, 1994; Zhang et al., 1997; Andrews et al., 1998;
Goñi and Thomas, 2000; Graham et al., 2001; De Braban- XP BM
dere et al., 2002; Goñi et al., 2003; Lepoint et al., 2004). The Cho

r
ve
ngm

Ri
QYK
use of these tracers relies on the existence of gross differ- ing

ao
Isla

im
nd

Ba
ences among natural abundances of stable carbon isotopes,
LHK
stable nitrogen isotopes and C/N elemental ratios in organic
matter from terrigenous and anthropogenic inputs and that SDK
Ya
WSK
from marine and in situ inputs. This approach is often based ng
tze
on the fundamental assumption (a) that sedimentary Es

r
tu

Rive
BLG
organic matter isotopic and C/N ratios are conservative ar
y

ngpu
and (b) that their distributions in natural systems reflect

Hua
only physical admixing of material from compositionally Shanghai CY

distinct end-member sources (Cifuentes et al., 1988; Thorn-

ton and McManus, 1994). Provenance identification can be DH

significantly improved by the simultaneous utilization of

two or more organic tracers, but problems may exist when
tracers are employed in isolation due to poorer resolution of
sources which contribute material with similar or intermedi-
ate ranges of compositions (Thornton and McManus, 1994;
Goñi and Thomas, 2000; Goñi et al., 2003). Sources recog-
nition is also compounded by potential modification of end-
member signatures by biogeochemical processes which are
known to alter the isotopic and elemental composition of
organic matter pools in estuaries.
The Yangtze River is one of the largest rivers in the
world, which ranks the fifth in average water discharge at
its mouth and the fourth in suspended sediment discharge.
A large quantity of organic matter from terrigenous and
marine end-members is deposited in the Estuary and its
adjacent areas (Milliman et al., 1984). Therefore, it has been
already paid more attention to the source, fate and ecolog-
ical significance of organic matter in the Yangtze Estuary.
Previous reports have been published on carbon and nitro-
gen stable isotopes in suspended particulate organic matter
from the Yangtze Estuary in recent years (Tan et al., 1991;
Cauwet and Mackenzie, 1993; Shi, 1993; Wu et al., 2000,
2002, 2003). However, the geochemical characteristics of
carbon and nitrogen stable isotopes in the intertidal sedi-
ment of the Yangtze Estuary have not been presently
reported. Thus, the main objectives of this study are to
explore the spatial and temporal variations of carbon and
nitrogen stable isotopes in sedimentary organic matter in
the intertidal flat, and to further elucidate the sources of
organic matter accumulated in the intertidal sediments at
the study area. The present study also is part of the project
of the biogeochemical cycling of multi-materials in the
Yangtze estuarine and coastal complex ecosystem.
2. Study area
The study area is situated on the Yangtze Estuary and
adjacent coastal tidal flat areas (Fig. 1). The Yangtze Estu-
ary is of particular interest to the biogeochemical and
organic geochemical studies because of its worldwide
Zh LC
eji
an
gP
rov
inc
e Sampling station
Fig. 1. Study area. The figure shows the location of Yangtze Estuary and
the sampling stations during field investigations.
importance. The Yangtze River traverses Central China in
an approximately westerly direction for nearly 6000 km
before discharging through the Yangtze Estuary into the
East China Sea near Shanghai. The Yangtze River is a
primary source of sediments for the widely developed
continental shelf of the East China Sea. The river annu-
ally transports a runoff discharge of 9.0 · 1011 m3 that
carries approximately 5.0 · 108 tons of sediments and
1.2 · 107 tons of particulate organic matter to the Estuary
and its adjacent coastal areas (Milliman et al., 1984; Chen
and Zhong, 1998). More than 80% of the suspended matter
is transported during high runoff periods of the river. About
25% of suspended sediment is deposited in the near shore
area off the river mouth; in addition, 25% is transported
southwards where it settles and remains in the coastal zone.
Very little suspended sediment escapes to the north of the
Estuary, and most of the remaining sediment is transported
and deposited directly offshore (Milliman et al., 1985).
With an area of approximately 904 km2, the tidal flats
developed along the Yangtze estuarine and coastal zone
mainly distribute the South bank of the Yangtze Estuary,
the North bank of the Hangzhou Bay, Chongming Island,
Changxing Island, Hengsha Island and Jiuduansha Island,
which can be divided into high, medium and low tidal flats
from land to sea. However, there are no high tidal flats in
some sections of the South bank of the Yangtze Estuary
and the North bank of the Hangzhou Bay due to human
activities such as the reclamation. The tidal flat areas
between Xupu (XP) to Bailonggang (BLG) are the fresh-
water areas mainly controlled by the Yangtze River runoff,
while the areas from Chaoyang Farm (CY) to Luchao (LC)
 M. Liu et al. / Marine Pollution Bulletin 52 (2006) 1625–1633
are the brackish areas mostly dominated by seawater with
the salinity range of 3&–15& (Hou et al., 2003).
3. Material and methods
According to the geographical and physical background
of the study area, ten sampling stations were selected along
the Yangtze estuarine and coastal tidal flats, involving
Xupu (XP), Baimao (BM), Qiyakou (QYK), Liuhekou
(LHK), Shidongkou (SDK), Wusongkou (WSK), Bailong-
gang (BLG), Chaoyang Farm (CY), Donghai Farm (DH)
and Luchaogang (LC) locations (Fig. 1). Surface sediments
(0–2 cm) at the above stations were collected with a Petite
Ponar grab sampler in July 2002 and February 2003,
respectively. All samples were immediately dried in a
freeze-dryer, and were ground to powder with pestle and
mortar prior to analysis.
Carbon and nitrogen isotopic samples were prepared
using sealed-tube combustion method. About 0.2 g pow-
ered sediments was acid-treated with 1 N HCl for 24 h in
pre-combusted glass test-tubes to remove carbonate (Cai,
1993; Zhang et al., 1997). They were then centrifuged for
removal of solution and the acid-treated sediments were
mixed with 1 g each of CuO, Cu pellets and several inches
of silver wire, and then sealed in evacuated 9-mm quartz
tubes. Quartz tubes were then heated 900 C for 3 h, kept
at 650 C for over 12 h, and cooled to room temperature.
N2 and CO2 gasses were extracted and purified in a vacuum
line and collected in sealed 6-mm glass tubes. The carbon
and nitrogen stable isotopic compositions were determined
in a DELTAplus/XL isotopic ratio mass spectrometer (Finn-
igan MAT Com. USA). Duplicated determinations were
made for each of the samples. The isotopic compositions
of carbon (d13C) and nitrogen (d15N) are expressed by:
d13 C or d15 N ¼ ðRsample  Rstandard Þ=Rstandard  1000 ð1Þ
13 15
where Rsample and Rstandard are the heavy ( C or N) to
light (12C or 14N) isotope ratios of sample and standard,
respectively. The standards for isotopic measure are PDB
for carbon and air for nitrogen. The precision of analysis
is ±0.2& for d13C and ±0.3& for d15N, respectively.
The contents of organic carbon and nitrogen were deter-
mined using a CHN elementary analyzer (VVairo ELIII)
after removing carbonate by leaching with 0.1 N HCl. In
general, the adsorbed inorganic nitrogen was easily elimi-
nated during the pretreatment; yet the fixed inorganic
nitrogen (i.e., NHþ 4 ) in the clay could not be removed
(Kao et al., 2003). Therefore, the measured nitrogen may
have included both organic nitrogen and part of inorganic
nitrogen, and here is defined as total nitrogen (TN).
About 0.5 g of frozen-dried power sediments were
weighted and placed into a 15 ml centrifuge tube. Five ml
of a 45:45:10 solvent mixture (acetone:methanol:water)
was added to each tube, sediments were sonicated, and
pigments were extracted for 24 h at 0 C. Chlorophyll a
concentration was determined using a spectrophotometric
assay and standard equations (Joye et al., 1996).
1627
Sediment grain size analysis was measured using a LS 13
320 Laser grain sizer.
4. Results
4.1. Sediment physiochemical properties
Fig. 2 shows the grain size distribution of sediments
from the intertidal flats along the Yangtze estuarine and
coastal zone. Intertidal sediments from the Yangtze Estu-
ary mainly consisted of fine particles with the grain size less
than 63 lm. One-way ANOVA analysis showed that there
were no pronounced spatial and seasonal changes in the
grain size distribution of sediments at the study area
(p < 0.05). Accordingly, it was hypothesized that the grain
size of sediments had no significant effect on the distribu-
tion differences in stable isotope compositions along the
intertidal flat.
Chlorophyll a concentrations in the intertidal surface
sediments ranged from 0.05 to 8.01 mg g1 dry wt and
0.02 to 6.92 mg g1 dry wt in July 2002 and February
2003, respectively. Fig. 3 shows the spatial and temporal
variations of chlorophyll a in the intertidal sediments from
the Yangtze Estuary. The spatial distributions of chloro-
phyll a indicated that the chlorophyll a contents were rela-
tively greater at XP, WSK and DH stations than at other
locations. However, it was found that there was no pro-
nounced seasonal difference in the chlorophyll a contents
of tidal sediments (ANOVA, p > 0.05).
Concentrations of sedimentary organic carbon in the
intertidal sediments from the Yangtze Estuary were rela-
tively low, being 0.095–1.43%. It is observed in Fig. 4a that
sedimentary organic carbon had the remarkable distribu-
tion differences along the Yangtze estuarine and coastal
zone (ANOVA, p = 0.008). The contents of sedimentary
organic carbon were relatively greater in the freshwater
areas from XP to BLG station, while they were lower
and gradually decreased with the increasing salinity in the
0 100
Jul.
Feb.
80
25
)
4-
60
(%
63
m
50
µm
3µ
(%
>6
40
)
75
20
100
0
0 25 50 75 100
< 4 µm (%)
Fig. 2. The distribution of different particles in the intertidal sediments of
the Yangtze Estuary.
1628 M. Liu et al. / Marine Pollution Bulletin 52 (2006) 1625–1633

10 1.6
Y = 11.23*X-0.071
Jul.
R = 0.981
Feb.
P < 0.0001
8
1.2

OC (%)
Chl.a (mg/g)

0.8
4
)
(5.7
ratio
0.4 field
2 Red

0
0.0
0.00 0.04 0.08 0.12 0.16
XP BM QYK LHK SDK WSK BL CY DH LC TN (%)
Fig. 3. Chlorophyll a in the intertidal sediments from the Yangtze Fig. 5. Organic carbon (OC) vs. total nitrogen (TN) in the intertidal
Estuary. sediments from the Yangtze Estuary.

1.6
a Jul.
the intertidal flat were consistent with higher contributions
Feb. of organic matter from terrigenous sources, which usually
1.2
showed higher C/N ratios (C/N elemental ratios >12;
OC (%)

0.8 Kukal, 1971; Aitkenhead and McDowell, 2000).

0.4
4.2. d13C and d15N of sedimentary organic matter
0.0
The d13C values of organic matter in the intertidal sedi-
0.16 ments were in the range of 29.8& to 26.0& and
b 27.3& to 25.6& in July 2002 and February 2003,
0.12
respectively. Fig. 6a presents the spatial distribution and
TN (%)

0.08 the seasonal variations of d13C of sedimentary organic mat-

0.04 ter. The d13C values of sedimentary organic matter were
relatively heavier, and had a narrower range in February
0.00 than in July. Where in July or in February, there was the
XP BM QYK LHK SDK WSK BLG CY DH LC
increasing heavier trend in the d13C values at the gradient
Fig. 4. Organic carbon (OC) and total nitrogen (TN) in the intertidal
sediments from the Yangtze Estuary.

-22 a Jul.
overlying waters in the brackish areas from CY to LC Feb.
-24
station. Fig. 4a also showed that there was no significant
δ C (‰)

seasonal difference in the concentrations of sedimentary -26

organic carbon from most of sampling locations (ANOVA,
-28
13

p > 0.05), with the exception of XP, BM and WSK stations.

The contents of total nitrogen in the intertidal surface -30
sediments varied between 0.031% and 0.14 %. The spatial
and temporal variations of total nitrogen presented in 8
Fig. 4b were similar to those of sedimentary organic car- b
bon. There was a good linear relationship of organic car- 6
δ15N ( ‰)

bon with total nitrogen in the intertidal sediment from

4
the Yangtze Estuary as shown in Fig. 5. The regression line
passed very close to the origin, suggesting that the contents 2
of fixed NHþ 4 in the intertidal surface sediments were less
than the expected, and that the measured nitrogen could 0
be used as an estimation of organic nitrogen. Fig. 5 also XP BM QYK LHK SDK WSK BLG CY DH LC

presents that sediments had C/N ratios higher than the Fig. 6. (a) d13C and (b) d15N signatures in the intertidal sediments from
Redfield ratio of 5.7 (wt/wt). The elevated C/N ratios in the Yangtze Estuary.
 M. Liu et al. / Marine Pollution Bulletin 52 (2006) 1625–1633
of increasing salinity in the overlying waters. These values
were largely consistent with those of suspended particulate
organic matter from the Yangtze River reported in the lit-
erature. Tan et al. (1991) have reported that the d13C values
of suspended particulate organic carbon had the range of
26.6& to 23.7& in the Yangtze Estuary. Wu et al.
(2002) found that the annual average d13C values varied
from 27.1& to 23.6& in suspended particulate organic
carbon from the Yangtze Estuary.
The d15N values for sediments varied from 1.6& to 5.5&
and from 1.7& to 7.8& in July 2002 and in February 2003,
respectively. These values in the present study were very
close to those of suspended particulate matter from the
Yangtze Estuary reported by Wu et al. (2002). Fig. 6b pre-
sents that d15N values also had an increasing trend from XP
to LC station. However, the spatial and seasonal distribu-
tions of d15N were relatively more complex, compared with
those of stable carbon isotopes.
5. Discussion
5.1. The distribution features of carbon isotope
The range of stable carbon isotopic ratios of organic
matter is broad in aquatic ecosystems, varying from
30& to  26& in runoff from terrigenous organic carbon
(C3 plants) to 22& to  18& for organic carbon from
marine phytoplankton production (Cifuentes et al., 1996).
Wu et al. (2000) reported that d13C signatures for suspended
matter ranged from 31.2& to 29.8& and 24.3& to 23&
in the upper and lower zone of the Yangtze Estuary, respec-
tively. The estuarine d13C gradient in sedimentary organic
matter at the study area was characterized by a progressive
seaward enrichment (Fig. 6a). The heavy carbon composi-
tions from the lower Estuary could reflect sedimentation
of a large quantity of marine organic matter. The distribu-
tion features of d13C also suggested that sedimentary
organic matter was the mixture of continental derived mate-
rial and marine material. However, the distribution of d13C
also had the apparent fluctuation along the Yangtze estua-
rine and coastal zone, which reflected that some local
additional factors probably exerted an important influence
on d13C signatures of sedimentary organic matter. For
instance, the d13C values in the flood season (July) were rel-
atively more negative at WSK and BM stations, which were
probably attributed to significant riverine inputs of organic
matter from the Huangpu River and Baimao River, respec-
tively (Fig. 1). In addition, it has been reported that benthic
algae, to some extent, might affect carbon isotopic compo-
sitions of sedimentary organic matter. Although no notable
relationship of chlorophyll a with stable carbon isotope was
found at the study area (Fig. 7a), it was considered that the
relatively heavier d13C values shown at part of stations (e.g.,
XP and DH) might be related to the higher contents of chlo-
rophyll a in the intertidal sediments (cf. Figs. 3 and 6a).
Sherr (1982) reported that the benthic algae normally had
the relatively heavy d13C values, and made the greater con-
1629
-24 10
8
-26
δ C (‰)
6
δ N (‰)
-28
13
15
4
-30
2
-32 0
0 2 4 6 8 0 2 4 6 8
Chl.a (mg/g) Chl.a (mg/g)
Fig. 7. Chlorophyll a vs. (a) d13C and (b) d15N signatures in the intertidal
sediment from the Yangtze Estuary.
tribution to carbon isotopic compositions of organic matter
in the intertidal sediments.
There was an apparent seasonal variability in the d13C
values that were more negative in July (Fig. 6). This phe-
nomenon was largely consistent with the seasonal partitions
of water discharge and suspended sediment discharge of the
Yangtze Estuary. The water discharge in the flood seasons
accounted for approximately 71.1% of the annual water dis-
charge, while the suspended sediment discharge in the flood
seasons occupied more than 87.4% of the annual total of
suspended sediment discharge (Shen et al., 2000). It led to
the sedimentation of large amounts of terrigenous organic
matter with lower d13C signatures along the Yangtze estua-
rine and adjacent areas in the flood seasons (Wu et al.,
2000). Therefore, we considered that water discharge of
the Yangtze River dominated the seasonal fluctuation of
d13C.
Theoretical considerations (Hayes, 1983) predict and
laboratory studies (Macko and Estep, 1984) have confirmed
that kinetic isotope effects associated with assimilation and
microbial respiration of organic matter result in the 13C
enrichment of residual material. However, the seaward
13
C enrichment of sedimentary organic matter observed
here appeared unlikely to reflect selective bacterially-medi-
ated removal of 12C from influxed terrigenous organic
matter (Thornton and McManus, 1994). This is also sup-
ported by the results of several studies indicating minimal
change in the d13C composition of organic detritus follow-
ing extensive and prolonged microbial decomposition
(Gearing et al., 1984; Fenton and Ritz, 1988).
5.2. The distribution features of nitrogen isotope
It has been reported that the terrigenous detrital organic
matter is generally characterized by a low d15N signature
while the marine component has a relatively higher d15N
value (Mariotti et al., 1984; Peterson et al., 1985; Thornton
and McManus, 1994). Wu et al. (2002) also drew a similar
conclusion when they studied the seasonal variability of
1630 M. Liu et al. / Marine Pollution Bulletin 52 (2006) 1625–1633
nitrogen isotope of suspended particulate matter in the
Yangtze Estuary. Accordingly, it explains the progressive
seaward enrichment of d15N from XP to LC station. Nev-
ertheless, in comparison of stable carbon isotopes, nitrogen
isotopic compositions had more complex seasonal and
spatial fluctuations (Fig. 6). This indicates that additional
factors had the significant influences on the distributions
of d15N in sedimentary organic matter. Nitrogen isotopic
compositions could be easily modified by a series of com-
plex biogeochemical processes on some time scales.
Dynamic cycling of nitrogen is subject to kinetic isotope
fraction effects especially during the biogenic transforma-
tion and recycling of dissolved and particulate nitrogen
compounds (Owens, 1987; Cifuentes et al., 1988; Wu
et al., 2003). It was expected that nitrogen cycling in the
Yangtze estuarine and tidal flat would create isotopically
enriched in sedimentary organic matter through decompo-
sition. Heavier d15N values corresponded with high C/N
ratios, which suggested the latter are produced principally
as a result of organic matter diagenesis (Fig. 8; r = 0.7,
p = 0.005) (Thornton and McManus, 1994; Cifuentes
et al., 1996). As microbial mineralization proceeds and
the total amount of nitrogen presented is reduced. 14N is
preferentially lost from the organic substrate, which
become progressively enriched in 15N. Consequently,
higher decomposed organic matter will contain little nitro-
gen but with enriched in 15N. However, it has also been
reported that nitrogen isotopic enrichment during organic
decomposition was relative to heterotrophic microorgan-
isms (Macko and Estep, 1984). Heterotrophic microorgan-
isms active in deamination also affected nitrogen isotopic
composition of organic matter by their own biomass, mak-
ing it quite different from the original provenance of
organic matter. The effects of heterotrophs were docu-
mented by Caraco et al. (1998) who found that the d15N
of microbially reworked terrestrial particulates increased
from 4& to +9&.
8
6
δ N (‰)
4
15
2 6
0
6 8 10 12 14
C/N
Fig. 8. d15N signatures vs. C/N elemental ratios in the intertidal sediments
from the Yangtze Estuary.
5.3. The variation of C/N elemental ratios
The C/N elemental ratio often acts as an indicator of the
predominant sources of organic matter in the aquatic eco-
systems (e.g., Matson and Brinson, 1990; Thornton and
McManus, 1994; Andrews et al., 1998; Graham et al.,
2001). Phytoplankton C/N ratio varies from 6 to 9 in the
natural system (Hollugan et al., 1984). Bacterioplankton
are nitrogen-rich and have C/N ratio of 2.6–4.3 (Lee and
Fuhrman, 1987). The C/N ratio of the terrigenous organic
matter is significantly higher and more than 12 (Hedges
and Man, 1979). The C/N ratios of sedimentary organic
matter in the intertidal flats have the range of 8.01–12.30
(Fig. 9), which were similar to the previous in the Yangtze
Estuary (Tan et al., 1991). Given that the C/N ratio strongly
reflects the sources of organic matter, it is expected that
there exists a significant negative correlation between d13C
and C/N ratios (i.e., organic matter with high C/N ratio
has much light d13C value) (Wu et al., 2002). However, it
was shown that C/N ratios against d13C had no pronounced
relationship at the study areas (Fig. 10; r = 0.29, p =
0.20). This should be attributed to the decomposition pro-
cesses (e.g., autolysis, leaching and microbial mineraliza-
tion) of organic matter (Thornton and McManus, 1994;
Wu et al., 2003). In general, the C/N ratio of sedimentary
organic matter might be expected to decrease or increase
during decomposition with various sources. Such variation
could make the C/N ratio superimposed on the estimation
of different sources of organic matter (Thornton and Mc-
Manus, 1994).
5.4. Provenance of sedimentary organic matter
The potential sources of organic matter in intertidal eco-
systems are generally expected to include terrestrial detri-
tus, marine material, in situ primary producer (e.g.,
benthic algae) and sewage. It was reported by Riera et al.
14
Jul.
Feb.
12
10
8
C/N
2
XP BM QYK LHK SDK WSK BLG CY DH LC
Fig. 9. C/N elemental ratios in the intertidal sediments from the Yangtze
Estuary.
 M. Liu et al. / Marine Pollution Bulletin 52 (2006) 1625–1633
-30
-29
-28
δ13C (‰)
-27
-26
-25
6 8 10 12
C/N
Fig. 10. d13C signatures vs. C/N elemental ratios in the intertidal sedi-
ments from the Yangtze Estuary.
(2000) that the higher enrichment of stable isotopes in sed-
imentary organic matter was mainly attributed to benthic
primary producers. However, it was found in this study that
chlorophyll a had the insignificant correlation with d13C
and d15N (Fig. 7; r = 0.063 and 0.019, respectively), show-
ing that benthic primary producers made little contribution
to sedimentary organic matter in the entire intertidal flat. In
addition, it has been reported in the literature that industrial
and domestic sewage discharge had the significant influence
on carbon isotopic compositions of organic matter in
poorly flushed estuaries (Andrews et al., 1998). Neverthe-
less, the effects of sewage on isotopic compositions can be
neglected in macrotidal estuaries (Salomons and Mook,
1981; Fontugne and Jouanneau, 1987; Cai et al., 1988).
Likewise, Wu et al. (2002) also found that sewage had an
insignificant impact on carbon and nitrogen stable isotopic
compositions of suspended particulate matter in the Yan-
gtze Estuary. Hence, it was hypothesized that sewage could
not affect the isotopic compositions of organic matter for
consideration of strong self-purification of the Yangtze
Estuary and deep-water discharge of sewage through the
outfalls away 10 km away from the coastal line (Hou
et al., 2002). Therefore, we considered sedimentary organic
matter derived mainly from the terrigenous and marine
inputs in the intertidal flat of the Yangtze Estuary.
The fractional contributions of terrigenous inputs to the
intertidal sedimentary organic matter could be quantita-
tively estimated using the following mixing equation of
carbon isotope (Schultze and Calder, 1976):
X ¼ F tX t þ F mX m
Thus
F t ¼ ðX  X m Þ=ðX t  X m Þ
13
where X(&), Xt(&) and Xm(&) are the d C ratios of,
respectively, the sample, terrigenous end-member and mar-
ine end-member, and Ft(%) and Fm(%) (given by 1  Ft) are
1631
100
Jul.
Feb.
75
Rt (%)
50
25
0
14 XP BM QYK LHK SDK WSK BL CY DH LC
Fig. 11. The contribution of terrigenous input to the sedimentary organic
matter in the intertidal sediments from the Yangtze Estuary.
the respective terrigenous and marine organic matter frac-
tions in the sample. For the purpose of this exercise, Xt and
Xm were respectively assigned to averages of 30 and
23.5 calculated from the present study and the previous
literature (Tan et al., 1991; Cauwet and Mackenzie, 1993;
Shi, 1993; Wu et al., 2000, 2002). The values of Ft ranged
from 50.3% to 97.1% and from 45.7% to 61.4% in July
and February, respectively. Fig. 11 shows that the values
of Ft were obviously greater in July than in February, con-
sistent with the seasonal distributions of water discharge
and suspended sediment discharge near the Yangtze Estu-
ary (Shen et al., 2000). The higher values of Ft in July re-
flected that the terrigenous inputs dominated the sources
of organic matter in the intertidal system in the flood sea-
son. The spatial distributions of Ft were characterized by
gradually declining trends from XP to LC station, reflect-
ing that the terrigenous contributions to sedimentary
organic matter pool decreased bit by bit from the fresh-
water areas to the brackish areas. In addition, peak values
of Ft at BM and WSK in July were remarkably attributed
to the coastal riverine inputs of organic matter from
Baimao River and Huangpu River.
6. Summary and conclusions
The values of d13C of sedimentary organic matter from
the intertidal flat of the Yangtze Estuary had the remark-
able seasonal variations, and ranged from 29.8& to
26.0& and 27.3& to 25.6& in the flood season (July)
and in the dry season (February), respectively. It was con-
sidered that the seasonal distributions of water discharge
ð2Þ and suspended sediment discharge dominated the temporal
variations of d13C for sedimentary organic matter. In
general, the spatial distributions of d13C were mainly
ð3Þ
controlled by the mixing inputs of terrigenous and marine
components.
The d15N ratios varied from 1.6& to 5.5& and from
1.7& to 7.8& in July and February, respectively. It was
1632 M. Liu et al. / Marine Pollution Bulletin 52 (2006) 1625–1633
found that the distributions of d15N signal had been mod-
ified by dynamic cycling of nitrogen (e.g., organic matter
diagenesis). Thus, it was expected that the nitrogen isotopic
compositions were co-regulated by the provenance of
organic matter and the biogeochemical processes.
It was found sedimentary organic matter mainly derived
from the terrigenous and marine inputs in the intertidal flat
of the Yangtze Estuary. Compared with d15N and C/N ele-
mental ratios, d13C was considered as a reliable indicator of
the sources of organic matter in the intertidal sediments.
Thus d13C as a tracer was used to estimate the contribution
of terrigenous inputs to sedimentary organic matter accord-
ing to a simple mixing balance model. The calculated results
showed that terrigenous materials were the dominant
sources of sedimentary organic matter in the intertidal flat,
and that the terrigenous inputs were markedly greater in
July than in February, probably related to the seasonal dis-
tributions of water discharge and suspended sediment dis-
charge at the mouth of the Yangtze Estuary.
Acknowledgements
This research is part of the project of the biogeochemical
cycling of multi-materials in the Yangtze estuarine and
coastal complex ecosystem supported by the National
Natural Science Key Foundation of China (Grant Nos.
40131020 and 49801018), Foundation for University Key
Teacher by the Ministry of Education, Shanghai Priority
Academic Discipline Project, China Postdoctoral Founda-
tion (No. 2005037135) and Shanghai Postdoctoral Foun-
dation (No. 04R214122). The authors thank Prof. Q.Z.
Xu and Prof. Y.L. Ba for their analytic assistance in the
laboratory work. The anonymous reviewers are thanked
for their constructive comments on a preliminary draft of
the manuscript.
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