Environ Monit Assess (2008) 137:329–342
DOI 10.1007/s10661-007-9768-1
Distribution and contamination assessment of heavy metals
in sediment of the Second Songhua River, China
Chunye Lin & Mengchang He & Yuxiang Zhou &
Wei Guo & Zhifeng Yang
Received: 26 September 2006 / Accepted: 6 April 2007 / Published online: 17 May 2007
# Springer Science + Business Media B.V. 2007
Abstract The Second Songhua River was subjected
to a large amount of raw or primary effluent from
chemical industries in Jilin city in 1960s to 1970s,
resulting in serious mercury pollution. However, an
understanding of other trace metal pollution has
remained unclear. The objective of this study was to
investigate trace metal contamination in the sediment
of the river. Bottom sediment samples were taken in
the river between Jilin city and Haerbin city in 2005.
An uncontaminated sediment profile was taken in the
Nen River at the same time. Total concentrations of
Al, Fe, Mg, Ca, K, Na, Ti, Mn, V, Sc, Co, Cu, Cr, Ni,
Pb and Zn in the sediment samples were measured by
ICP-MS or ICP-OES, following digestion with
various acids. Concentrations of Co, Cu, Cr, Ni, Pb
and Zn in the surface sediments were 5.1–14.7, 18.5–
78.9, 2.4–75.4, 7.2–29.0, 13.5–124.4, and 21.8–
403.1 mg/kg, respectively, generally decreasing along
the course of the river from Jilin city to Haerbin city.
Background concentrations of trace metals were
reconstructed by geochemical normalization to a
conservative element scandium. Results showed that
concentrations of Co, Cr, and Ni in the sediment were
Foundation item: The National Basic Research Priorities
Program of China (2004CB418502)
C. Lin (*) : M. He : Y. Zhou : W. Guo : Z. Yang
State Key Laboratory of Water Environment Simulation
School of Environment, Beijing Normal University,
Beijing, 100875, People’s Republic of China
e-mail: c.lin@bnu.edu.cn
generally only slightly higher than or equal to their
background values, while concentrations of Cu, Pb,
and Zn in the some sediment samples were signifi-
cantly higher than their background values. In detail,
the sediment at Jilin city was moderately contaminat-
ed by Cu, and the sediment of the Second Songhua
River was moderately contaminated by Pb and Zn.
The top layer (0–10 cm depth) and bottom layers
(30–46 cm depth) of one sediment profile at Wukeshu
town were generally moderately polluted by Pb and
Zn. Synthetically, the surface sediment in the studied
river section was classified as natural sediment
without ecological risk by the sediment pollution
index (SPI) of Cu, Cr, Ni, Pb and Zn. Only the 30–
45 cm depth of the sediment profile at Wukeshu town
was classified as low polluted sediment by the SPI of
these metals, recording a historical contamination of
the river in the 1960s to 1970s. This buried
contamination of trace metals might pose a potential
risk to water column under disturbance of sediment.
Keywords Trace metal . Sediment . Second Songhua
River . Contamination assessment
Introduction
Following the introduction of trace metal contami-
nants into a river, whether via natural or anthropo-
genic sources, they partition between aqueous (pore
water, overlying water) and solid phases (sediment,
330
suspended particulate matter and biota) (Luoma
1983). Depending on hydrodynamics, biogeochemical
processes and environmental conditions (redox, pH,
salinity and temperature) of rivers, sediments are
recognized as an important sink of heavy metals in
aquatic systems, as well as a potential non-point
source which may directly affect overlying waters
(Thornton et al. 1975; Calmano et al. 1993; Dickinson
et al. 1996). Fine-grained suspended particle can
scavenge contaminants due to their sorptive nature
(Gibbs 1973). Under favorable hydraulic conditions,
suspended particles with contaminants can be depos-
ited on the river bottom, and thus act as an important
reservoir. Changes in sediment chemistry can result in
contaminant remobilisation. Subsequently, exposure
to a different chemical environment could result in
desorption and transformation of contaminants into
more bioavailable or toxic chemical forms (Zoumis
et al. 2001). Therefore, Horowitz (1991) pointed out
that the strong association of numerous trace elements
with sediment (suspended plus bed sediments) indi-
cates that the distribution, transportation and avail-
ability of trace metals in aquatic environment can not
be evaluated intelligently solely through the sampling
and analysis of the dissolved phase. Study of
sediment plays an important role as it has a long
residence time. River sediment, therefore, is an
important source for the assessment of an anthropo-
genic contamination in rivers (Förstner and Wittman
1983; Jain et al. 2005).
The Second Songhua River is one of the most
important rivers in the northeastern China. It has been
well known for a spill of an estimated 100 tons of
toxic substances made up of a mixture of benzene,
aniline and nitrobenzene from Jilin Chemical Co. to
the river in November 2005. The whole length of the
river is about 958 km. The watershed of the Second
Songhua River and its tributaries total 73.4×103 km2,
with an annual mean discharge of 14.8 km3. The
Second Songhua River and Nen River meet near
Songyuan city to form the Songhua River (Fig. 1).
From this confluence, the Songhua River flows
easterly to join the Heilong River on the boundary
between Russia and China. An important petrochem-
ical city of China, Jilin city, is located at the middle
reach of the Second Songhua River. Historically, raw
or primary industrial effluent of Jilin city was usually
discharged to the river, resulting in the serious
mercury pollution of the river during the 1960s to
Environ Monit Assess (2008) 137:329–342
1970s (Jiang et al. 2006; Lin et al. 2007). However,
concentration of other trace metals in the sediments of
the Second Songhua River was not investigated.
Geochmical composition of suspended particulate
and sediment in the major rivers of China including
Yellow River, Changjiang, and Zhujiang were studied
(Qu and Yan 1990; Zhang et al. 1995; Zhang et al.
1998; Wang and Zhang 1999; Chen 2006). Whereas
Chen (2006) reported chemical composition of river-
ine sediment in eastern China, only two samples of
surface sediment were taken in the Songhua River.
The objectives of this study were to determine the
spatial distribution of trace metals in the river bottom
sediments of the Second Songhua River, to clarify the
pollution degree of these metals in the sediment, and
to quantify potentially ecological risk of trace metal
pollution.
Materials and method
Sampling and pretreatment
The methods of sediment sampling and analyzing
were introduced in our previous paper (Lin et al.
2007). Surface sediment samples were taken in
August 2005, using cable operated sediment sam-
plers-Van Veen grabs (Eijkelkamp), and then trans-
ferred to the plastic bags. Sampling sites included
Hadawan at Jilin (JL), Shaokou (SK), Baiqi (BQ),
Wukeshu (WKS), Wujiazhan (WJZ), Songyuan (SY),
Zhaoyuan (ZY), and Haerbin (HB1, HB2) (Fig. 1).
Undisturbed sediment cores of 46 cm depth and
25 cm depth were taken at WKS and Tahucheng
(THC), respectively, using free-fall corer sampler
(made by the Second Institute of Oceangraph, State
Oceanic Administration, China) with plastic tubes
(10 cm internal diameter and 50 cm long). The
sediment cores were sliced into 2 cm layers between
0–10 cm depth and 3 cm layers below 10 cm depth. It
should be noted that THC site is from the Nen River,
which is ca. 30 km west from the confluence of the
Nen River and the SSR. Since there is no industrial
city along the Nen River, sediments from the Nen
River are generally considered to be unpolluted by
trace metals. Hence, samples from the sediment
profile at THC were collected as reference samples
to develop relationships of elemental concentrations.
All sediment samples were freeze-dried in lab,
Environ Monit Assess (2008) 137:329–342 331
Fig. 1 Schematic graph of
sampling sites in the Second
Songhua River (Jilin (JL),
Shaokou (SK), Baiqi (BQ),
Wukeshu (WKS), Wujiazhan

20°0′0″N 30°0′0″N 40°0′0″N

(WJZ), Songyuan (SY)),
Songhua River (Zhaoyuan
(ZY), Haerbin (HB)), and
Nen River (Tahucheng
(THC))

China

90°0′0″E 100°0′0″E 120°0′0″E

110°0′0″E
N
Nen
ri

er
ver

a Riv
hu
ng HB
THC So
ZY
SY WJZ
Se WKS
co
nd BQ
So
ng SK
hu
a JL Effluent discharge site
Ri
ve
r

0 100 200 300

km River Flow direction Sampling site

slightly crushed, passed through 2 mm sieve, and
stored in glass bottles. Total organic carbon (TOC) in
the sediment was measured by TOC instrument
(LiquiTOC, Germany).
Sample digestion and measurement of elemental
contents
0.25 g of sample was weighed and placed into a
50 mL teflon beaker. 5.0 mL HNO3, 10 mL HF, and
2.0 mL HClO4 were added to the beaker which was
heated on an electric heating board for 3 min at 200°C.
The beaker was removed from the heat and allowed to
cool. HNO3 (5.0 mL), 10 mL HF, and 2.0 mL HClO
were added again to the beaker which was heated for
10 min at 200°C on the electric heating board. The
beaker was covered and allowed to stand for 12 h, and
then heated till the fume of HClO4 disappeared.
Immediately 8 mL aqua regia was added to the beaker
which was heated until the residual volume of the
liquid was ca. 2 to 3 mL. The walls of the beaker were
washed with ca. 10 mL deionized water. The solution
was transferred from the beaker to a 25 mL volumetric
polypropylene tube, and diluted to 25 mL with 2%
332
nitric acid. All reagents are analytical grade. The
concentrations of Sc and Pb were measured using
ICP-MS (X Series II, Thermo Electron), while the rest
elements were determined using ICP-OES (IRIS
Instrepid II, Thermo Electron). During the ICP
procedure, after every 10 samples, a set of blank and
standard solutions was measured to monitor the
performance of the instrument. The blank readouts
were used to estimate the detection limit for each
element, which is by definition calculated as three
times the standard deviation of the blank readings. The
detection limits of these elements in the sediment are
given in Table 1.
Together with digestion and measurement of our
sediment samples, four reference sediments, provided
by Institute of Geophysical and Geochemical Explo-
ration, Chinese Academy of Geological Sciences,
were digested and analyzed to check the analytical
quality (Table 2). Relative errors for all elements
except Co, Cr and Sc were generally less than 5%.
Coefficients of variance (CV) were generally less than
5%, while CV of Cr ranged from 0.1 to 12.5%.
Assessment methods of sediment contamination
The Index of Geoaccumulation (Igeo) was first
proposed by Müller (1969) and described by Förstner
et al. (1990) as a quantitative measure of the degree of
metal pollution in aquatic sediments. It uses the
relationship between the measured concentration
(Cn) of the element in the sediment (<2 μm fraction)
and the background concentration (Bn) in the shale
sediment (Eq. 1), and 1.5 is a correction factor due to
lithogenic effluents.


Cn
Igeo ¼ log2 ð1Þ
1:5Bn
Noting that total concentrations of trace metals in
this study were measured in <2 mm fraction of
sediment, we used elemental concentrations in the
continental crust as background concentration (Bn)
(Wedepohl 1995). The following classification is
given for the index of geoaccumulation by Förstner
et al. (1990): <0=practically unpolluted, 0–1=unpol-
luted to moderately polluted, 1–2=moderately pollut-
ed, 2–3 = moderately to strongly polluted, 3–4 =
strongly polluted, 4–5=strongly to very strongly
polluted, and >5=very strongly polluted.
Environ Monit Assess (2008) 137:329–342
Singh et al. (2002) introduced the concept of
sediment pollution index (SPI). SPI is a multi-metal
approach for an assessment of sediment quality with
respect to trace metal concentrations along with metal
toxicity. Developed SPI in this study can be expressed
as:
X .X
SPI ¼ ðEFm  Wm Þ Wm ð2Þ
Cn
EFm ¼
CR
where EFm is ratio between the measured metal
concentration (Cn) and the reconstructed background
metal concentration (CR) instead of the average metal
concentration in shale. Wm is toxicity weight. Toxicity
weight 1 was assigned for Cr and Zn, 2 for Cu and Ni,
and 5 for Pb (Singh et al. 2002). The following
classification is given for the SPI: 0–2 =natural
sediment, 2–5=low polluted sediment, 5–10=moder-
ately polluted sediment, 10–20=highly polluted sed-
iment, and >20=dangerous sediment.
Results and discussion
Geochemical properties of sediments
The geochemical composition of surface sediments is
presented in Table 3. Content of TOC usually was less
than 1%. Contents of major elements of mineral matrix
were 11.7–15.7% for Al2O3, 1.6–4.7% for Fe2O3, 0.3–
1.3% for MgO, 1.1–1.9% for CaO, 2.3–3.3% for
Na2O, and 2.8–3.4 for K2O, respectively. The minor
elemental concentration of Ti and Mn were 1409–
4651 mg/kg and 227–861 mg/kg, respectively. The
trace elemental concentrations of V and Sc were 22.1–
76.1 mg/kg and 2.7–10.8 mg/kg, respectively. Above
mentioned elements generally occur naturally without
authropogenic sources. Compared to Huanghe River
(HH), Changjiang River (CJ), and Zhujiang River (ZJ)
(Table 3) (Zhang et al. 1998; Wang and Zhang 1999),
contents of Al, K and Na in the sediment of the Second
Songhua River are slightly high. Concentration of Fe
in the sediment of the Second Songhua River was
lower than Changjiang River, but generally equal to
Huanghe River and Zhujiang River. On the other hand,
concentration of Ca in the sediment of the Second
Environ Monit Assess (2008) 137:329–342 333

Table 1 Detection limits (DL) of various elements in the sediment by ICP-OES and ICP-MS

Al2O3 Fe2O3 MgO CaO K2O Na2O Ti Mn V Co Cr Cu Ni Zn Pb Sc

Unit % mg kg−1 mg kg−1

Instrument ICP-OES ICP-MS
DL 0.2 0.05 0.05 0.05 0.05 0.05 10 10 5 1 5 1 1 2 2 1

Songhua River was much lower than Huanghe River
and Changjiang River, but higher than Zhujiang
River. The watersheds of Zhujiang River, Changjiang
River, Huanghe River, and SSR were mainly covered
by Oxisols, Ultisols, Aridisols, and Alfisols, respec-
tively. Hence, concentration of Ca in the sediment of
Huanghe River was higher than that for the rest three
rivers, while Al and Fe concentrations were generally
lower. For SSR, Concentrations of Al, Fe, Mg, Ti, V,
Sc in the surface sediments generally decreased along
river downstream from Jilin to Haerbin, while concen-
tration of K and Na generally increased. Iron generally
occurred as secondary iron oxides and silicate clay
minerals, yet K and Na mainly occurred in the primary
feldspars (Sparks 1995). Thus, the content of second-
ary clay minerals generally decreased with river
downstream, while primary mineral, such as feldspar
and quartz, probably increased. Calcium may occur in
the both primary feldspar and secondary carbonate
minerals, thus spatial change of Ca concentration was
different from either that of Al, Fe and Mg concen-
trations or that of K and Na concentrations. Changes of
compositions of sediment, shown by these naturally
occurring elements, indicated that the background
concentration of trace metals, such as Co, Cr, Cu, Ni,
Pb and Zn, in these sediment samples might be
different. This complicates assessments of potentially
ecological risk of contaminated sediments by these
metals because measured total concentrations do not
automatically infer anthropogenic enrichment. There-
fore, a normalizing technique to account for natural
quantities of element in the sediments was need to

Table 2 Relative errors and coefficients of variance for measured concentrations of elements in reference soil/sediment (n=2)

Ref a Al Fe Mg Ca K Na Ti Mn

RE%b CV%c RE% CV% RE% CV% RE% CV% RE% CV% RE% CV% RE% CV% RE% CV%

GSS1 2.4 2.3 −2.9 1.5 −2.1 1.1 −0.7 2.7 −0.7 1.3 −0.2 0.6 −3.3 3.3 −3.0 1.2
GSS2 5.3 4.0 0.2 1.8 1.8 2.1 2.7 2.5 −1.8 1.9 −0.9 1.5 4.6 2.7 5.5 3.5
GSS3 −4.9 0.9 5.4 0.5 −0.9 2.4 5.3 1.3 −2.5 1.4 −0.1 0.5 1.5 2.4 0.9 2.7
GSS8 3.5 3.9 −1.9 2.5 −0.4 1.0 −0.9 2.3 0.9 0.9 −1.3 0.4 −3.1 0.4 −0.8 0.9
Max. 5.3 4.0 5.4 2.5 1.8 2.4 5.3 2.7 0.9 1.9 −0.1 1.5 4.6 3.3 5.5 3.5
Mini. −4.9 0.9 −2.9 0.5 −2.1 1.0 −0.9 1.3 −2.5 0.9 −1.3 0.4 −3.3 0.4 −3.0 0.9

Ref V Sc Co Cr Cu Ni Pb Zn
RE% CV% RE% CV% RE% CV% RE% CV% RE% CV% RE% CV% RE% CV% RE% CV%
GSS1 −0.6 2.0 2.1 3.0 −3.0 2.8 8.6 4.8 1.6 1.9 −6.2 3.9 −0.4 1.6 −0.2 0.6
GSS2 2.4 3.5 −0.3 4.7 2.5 6.0 13.9 5.8 5.2 2.9 2.1 0.9 1.7 0.1 5.8 6.3
GSS3 −0.8 1.3 −7.0 5.5 10.4 2.9 −4.4 0.1 −3.6 2.7 3.2 5.1 8.0 9.3 2.9 7.1
GSS8 −0.8 3.9 1.5 1.8 −5.0 4.9 −3.3 12.5 −3.7 0.9 −3.0 4.7 −2.7 14.4 −2.9 1.9
Max.d 2.4 3.9 2.1 5.5 10.4 6.0 13.9 12.5 5.2 2.9 3.2 5.1 8.0 14.4 5.8 7.1
Min.e −0.8 1.3 −7.0 1.8 −5.0 2.8 −4.4 0.1 −3.7 0.9 −6.2 0.9 −2.7 0.1 −2.9 0.6
a
Reference materials
b
Percent relative error: ðx  μÞ  100=μ, where x is average of two measurements, μ is true or accepted value
c
Coefficient of variance of two measurements
d
Maximum
e
Minimum
334 Environ Monit Assess (2008) 137:329–342

Table 3 Chemical composition of surface sediments in the Second Songhua River and Songhua River

Sampling site Rivera Distanceb TOC Al2O3 Fe2O3 MgO CaO Na2O K2O Ti Mn V Sc
Name km % % % % % % % mg/kg mg/kg mg/kg mg/kg

JL SSH 1.5 0.85 15.75 4.31 0.97 1.60 2.30 2.81 4356 514 67.2 9.6
SK SSH 11.7 0.07 14.50 4.57 1.04 1.84 3.16 2.93 4351 769 67.8 8.8
BQ SSH 67.5 1.41 14.17 4.70 1.29 1.47 2.37 2.75 4651 861 76.1 10.8
WKS SSH 123.4 0.75 14.13 4.20 1.05 1.61 2.66 2.97 4509 807 66.8 9.7
WJZ SSH 189.5 13.49 3.86 0.98 1.74 2.89 2.93 4220 582 63.4 8.1
SY SSH 257.6 0.81 13.46 3.69 0.95 1.90 3.30 3.10 3980 545 56.2 7.7
ZY SH 333.7 0.07 11.74 1.70 0.29 1.15 3.01 3.44 1409 256 22.1 2.7
HB1 SH 486.2 0.09 12.27 1.64 0.32 1.36 3.09 3.45 1954 227 24.0 3.5
HB2 SH 486.3 0.10 12.89 2.66 0.55 1.69 3.31 3.40 4210 408 42.9 5.5
Ave. SHH-SH 13.60 3.48 0.83 1.60 2.90 3.09 3738 552 54.0 7.4
Stdev. SHH-SH 1.21 1.19 0.35 0.24 0.38 0.28 1189 230 19.9 2.9
CV% SHH-SH 8.9 34.1 42.6 15.0 13.0 8.9 31.8 41.7 36.8 38.8
Max. SHH-SH 15.75 4.70 1.29 1.90 3.31 3.45 4651 861 76.1 10.8
Min. SHH-SH 11.74 1.64 0.29 1.15 2.30 2.75 1409 227 22.1 2.7
Ave HH(n=10) 11.14 4.41 5.73 1.67 2.26 3320 512 68.7
Ave CJ(n=11) 13.40 6.02 4.62 0.99 2.51 5827 870 119.3
Ave ZJ(n=8) 12.10 4.86 1.15 0.83 0.41 2.21 4268 658 77.1 9.6
a
SSH: the Second Songhua River; SH: Songhua River; HH: Huanghe River, data are cited from Zhang et al. (1998); CJ: Changjiang
River, data are cited from Zhang et al. (1998); ZJ: Zhujiang River, data are cited from Wang and Zhang (1999).
b
Distance to discharge site of effluent from petrochemical complex of Jilin city.

Table 4 Chemical composition of sediment profile at WKS of the Second Songhua River

Depth Al2O3 Fe2O3 MgO CaO Na2O K2O Ti Mn V Sc

cm % % % % % % mg/kg mg/kg mg/kg mg/kg

0–2 14.30 4.22 1.03 1.53 2.41 2.79 4,520 808 67.8 9.7
2–4 15.04 4.65 1.19 1.48 2.33 2.76 4,727 871 78.3 11.1
4–6 14.19 3.76 0.88 1.59 3.23 3.10 3,891 622 55.6 7.9
6–8 14.61 4.33 1.03 1.65 2.63 2.92 4,433 764 66.0 9.1
8–10 15.04 4.26 0.97 1.73 2.87 3.18 4,084 734 62.1 8.4
10–13 14.51 3.55 0.76 1.81 3.70 3.34 3,365 556 47.4 6.0
13–16 14.74 3.41 0.72 1.88 3.24 3.31 3,365 504 45.9 6.3
16–19 13.95 3.37 0.72 1.86 3.26 3.30 3,346 476 46.2 5.5
19–22 14.24 3.81 0.82 1.76 3.22 3.30 3,670 567 53.0 7.1
22–25 15.57 3.62 0.77 2.01 3.47 3.56 3,612 528 49.0 6.7
25–28 15.08 4.17 0.92 1.98 3.11 3.29 4,447 633 59.3 7.8
28–31 14.50 4.29 1.02 1.76 2.68 3.00 4,399 686 66.1 9.6
31–34 14.62 4.83 1.16 1.65 2.33 2.77 4,747 844 75.3 10.0
34–37 15.18 4.79 1.07 1.84 2.71 2.99 4,543 924 68.8 9.5
37–40 15.21 5.04 1.15 1.80 2.51 2.88 4,839 1112 75.4 10.6
40–43 15.28 5.18 1.17 1.79 2.34 2.79 4,753 1423 77.6 10.7
43–46 15.82 4.80 1.06 1.92 2.87 3.11 4,490 1117 67.9 9.3
Ave. 14.82 4.24 0.97 1.77 2.88 3.08 4,190 775 62.4 8.5
Stdev. 0.52 0.58 0.16 0.15 0.43 0.24 537 257 11.3 1.7
CV% 3.49 13.71 16.78 8.54 15.01 7.87 12.81 33.16 18.03 20.36
Max. 15.82 5.18 1.19 2.01 3.70 3.56 4,839 1423 78.3 11.1
Min. 13.95 3.37 0.72 1.48 2.33 2.76 3,346 476 45.9 5.5
Environ Monit Assess (2008) 137:329–342 335

distinguish anthropogenic trace metals from pristine
trace metals.
Sedimentary profile can reflect the history of river
pollution, thus a sediment profile at WKS was
sampled and characterized (Table 4). Depending on
historically hydraulic condition, chemical composi-
tion of sediment changed along the profile, indicated
by relatively high coefficients of variance. Generally,
concentrations of K and Na mainly in the primary
feldspars showed a contrary change to Al, Fe, Mg, V
and Sc mainly in the secondary clay minerals.
Reconstruction of pristine concentration of trace
metals in the sediments
In order to estimate quantitatively the anthropogenic
trace metals in the sediment, their background
concentration must be known. Previous researches
often used an average lithogenic background value
(Müller 1969), an average concentration in shale
(Förstner et al. 1990; Singh et al. 2002), or an
average value of measured concentration before
industrialization (Hakanson 1980) to assess trace
metal pollution in sediments. Loring (1990) indicated
that provenance and grain size are two of the most
important parameters controlling the sedimentary
variability of trace metals which has to be compen-
sated for by a normalization procedure. Therefore,
geochemical normalization of trace metal data to a
variety of conservative elements is often used to
16
y = 0.8545x + 2.5117
R2 = 0.8765
12
Co (mg/kg)
evaluate sediment quality. The requirement for a
proper conservative tracer reference element includes:
(1) the reference element covaries in proportion to the
naturally occurring concentrations of the metal of
interest; (2) the reference element is not added or only
added in the marginal quantity by anthropogenic
sources; (3) the reference element is stable and is
not subject to environmental influences such as
reduction/oxidation, adsorption/desorption, and other
diagenic processes; (4) the concentration of reference
element can be quantitatively determined accurately
(Luoma 1990; Banin et al. 1998). Some researches
used Al (Trefry et al. 1985; Schropp et al. 1990;
Sutherland 2000), Cr (McMurtry et al. 1995), Fe
(White and Tittlebaum 1985; Schiff and Weisberg
1999; Jain 2004; Singh et al. 2005), Li (Loring 1990),
Mn (Loska et al. 1997; Liu et al. 2005), and Ti
(Horowitz et al. 1988) as reference elements.
In order to decide a conservative reference element
in the studied watershed, one sediment profile was
taken at THC site of the Nen River, generally
considered to be uncontaminated by trace metals.
Relationship among elemental concentrations in the
sediment profile was quantified. It was found that Sc
content in the sediment profile is significantly linearly
correlated with most elements including trace metals
(Fig. 2). Anthropogenic source of Sc is seldom and Sc
is stable in environment and can be accurately
measured in the lab. Hence, Sc was previously used
as a conservative element by some researchers (Lee
100 40
y = 5.0578x + 5.009 y = 2.575x - 5.2808
80 2
R = 0.9341 30 R2 = 0.9857
Cu (mg/kg)

Cr (mg/kg)

60
8 20
40
4 10
20

0 0 0
0 5 10 15 0 5 10 15 0 5 10 15
Sc (mg/kg) Sc (mg/kg) Sc (mg/kg)

40 40 100
y = 2.7522x - 2.6089 y = 1.9358x + 4.6205 y = 5.442x + 3.728
2
R = 0.9546 30 R2 = 0.9286 80 R2 = 0.9924
30
Pb (mg/kg)

Zn (mg/kg)
Ni (mg/kg)

60
20 20
40
10 10
20

0 0 0
0 5 10 15 0 5 10 15 0 5 10 15
Sc (mg/kg) Sc (mg/kg) Sc (mg/kg)
Fig. 2 Relationships between trace metals and Sc in the reconstruct background concentrations of these trace metals in
uncontaminated sediment profile at Tahucheng (THC) site of sediment of the Second Songhua River and Songhua River
the Nen River. Equations in each sub-figures were used to
336 Environ Monit Assess (2008) 137:329–342

et al. 1994; Steinmann and Shotyk 1997; Banin et al. as those of Gomit and Yamuna rivers in India,
1998; Shotyk et al. 2001). We use equations in Fig. 2 Toyohira river in Japan, and Illinois rivers in USA
to reconstruct the background concentrations of trace (Table 5). However, they are much lower than those
metals in the sediments of the Second Songhua River. in the fresh sediment of the Ganga Plain in India.
Measured and reconstructed metal concentrations
Spatial change of trace metals (Co, Cr, Cu, Ni, Pb in the sediment samples are shown in Fig. 3. The
and Zn) in the sediment measured concentrations of trace metals in the
sediment were characterized by highly spatial change.
Average concentrations of trace metals in surface Total measured concentrations of Co, Cr, Cu, Ni, Pb,
sediment of SSR are generally in the same magnitude and Zn in the sediment were 5.1–13.5, 18.5–69.6,

16 Reconstructed backgournd concentration 80 Measured concentration

Co concentration (mg/kg)

Cr concentration (mg/kg)
70
12 60
50
8 40
30
4 20
10
0 0
JL SK BQ WKS WJZ SY ZY HB1 HB2 JL SK BQ WKS WJZ SY ZY HB1 HB2
Sampling sites Sampling sites

80 30
Cu concentration (mg/kg)

Ni concentration (mg/kg)

70
25
60
20
50
40 15
30
10
20
5
10
0 0
JL SK BQ WKS WJZ SY ZY HB1 HB2 JL SK BQ WKS WJZ SY ZY HB1 HB2
Sampling sites Sampling sites

40 160
Pb concentration (mg/kg)

Zn concentration (mg/kg)

35 140
30 120
25 100
20 80
15 60
10 40
5 20
0 0
JL SK BQ WKS WJZ SY ZY HB1 HB2 JL SK BQ WKS WJZ SY ZY HB1 HB2
Sampling sites Sampling sites
Fig. 3 Variation in the reconstructed background concentrations and measured concentrations of Co, Cr, Cu, Ni, Pb, and Zn along the
course of river from Jilin (JL) city to Haerbin (HB) city
Environ Monit Assess (2008) 137:329–342 337

Table 5 Concentrations of trace metals in the SSR as well as several rivers on the world

SSR Gomtia Gangab Yamunac Illinoisd Toyohirae

Present study India India India USA Japan

Ave Std Ave Std Ave Std Ave Ave Ave

Co mg/kg 9.97 3.10 19.89 3.54

Cr mg/kg 49.42 18.63 20.89 11.75 240.57 138.09
Cu mg/kg 23.58 23.36 43.48 36.58 156.84 235.64 22.2 19 22
Ni mg/kg 18.75 6.77 23.46 11.94 84.79 75.09
Pb mg/kg 23.76 8.88 32.88 21.93 73.75 129.45 60.3 28 24
Zn mg/kg 90.29 52.12 63.65 51.36 308.10 391.36 59.2 81 152
a
Singh et al. 2005. b Singh et al. 2002. c Jain 2004. d Mathis and Cummings 1973. e Sakai et al. 1986.

2.4–75.4, 7.2–27.6, 13.5–37.0, and 21.8–150.5 mg/
kg, respectively. In general, both measured and
reconstructed metal concentrations showed a decreas-
ing trend along the course of the river from Jilin to
Harbin, which is in accordance with the variation of
Al and Fe contents. The measured concentrations of
Co and Cr in the sediment the Second Songhua River
were only slightly higher than the reconstructed
background concentration of them, while the mea-
sured concentrations of Cu, Zn, and Pb in the
sediment of the Second Songhua River, especially
near to Jilin city, were generally significantly higher
than the reconstructed background concentration of
them. The measured concentration of Ni in the
sediment was generally equal to the reconstructed
background concentration of it. For Songhua River,
the measured concentrations of all six trace metals
were generally equal to the reconstructed background
concentrations of them. Therefore, the sediment in the
Second Songhua River, especially near to Jilin city, is
significantly contaminated by Zn, Cu, and Pb,
indicating that anthropogenic source was from chem-
ical industrial complex in Jilin city.
Concentration profiles of Co, Cr, Cu, Ni, Pb and
Zn in the sediment at WKS site of the Second
Songhua River were shown in Fig. 4. The measured
concentrations of Co, Cr, Cu, Ni, Pb and Zn in the
sediment profile were 9.8–14.7, 45.4–78.9, 11.5–45.0,
17.0–29.0, 16.1–124.4, and 98.3–403.1 mg/kg, re-
spectively, while the reconstructed background con-
centrations of them were 7.2–11.9, 32.9–61.0, 8.9–23.2,
12.6–27.8, 15.3–26.0, and 33.8–63.9 mg/kg, respec-
tively. For Co, Cr and Ni, the measured concentration
showed a consistent change along the sediment profile
with the reconstructed background concentration. In
addition, the measured concentrations of Co, Cr, and Ni
in the sediment profile were generally equal to or
slightly higher than the reconstructed background
concentration. However, the measured concentrations
of Cu, Pb and Zn in the sediment under the 30 cm depth
of the profile were significantly much higher than the
reconstructed background concentrations of them, indi-
cating historically anthropogenic sources of them.
Measured mercury concentration in this sediment
profile changed in the same way as Cu, Pb and Zn
(Lin et al. 2007). This showed that very high concen-
trations of Cu, Pb and Zn in the sediment under the
30 cm depth of the profile were due to effluent
discharge to the river from chemical industrial complex
in Jillin city during the period of 1960s to 1970s (Lin
et al. submitted). The measured concentration of Zn in
the sediment above the 30 cm depth of the profile was
also much higher than its reconstructed background
concentration. Variation in concentration of Zn along
both the course of the river and the sediment profile at
WKS showed anthropogenic source of Zn has existed
since 1960s. These buried contaminants may remobi-
lize and release to water column and thus became
secondary pollution source under disturbance of
sediment (Zoumis et al. 2001; Eggleton and Thomas
2004).
Assessment of sediment quality of the Second
Songhua River
Variations of Igeo, EF, and SPI along the course of the
river are shown in Fig. 5. The values of Igeo for Co,
Cr and Ni were less than 0 over the whole course of
the river, indicating the sediment was not practically
contaminated by Co, Cr, and Ni. Whereas riverine
338 Environ Monit Assess (2008) 137:329–342

Fig. 4 Variation in the Co (mg/kg) Cr (mg/kg)

reconstructed background 0 10 20 0 50 100
concentrations and mea-
sured concentrations of Co, 0 0
Cr, Cu, Ni, Pb, and Zn
along the sediment profile at
10 10
Wukeshu (WSK) site of the
Second Songhua River

Depth (cm)

Depth (cm)
20 20

30 30

40 40

50 50

Cu (mg/kg) Ni (mg/kg)
0 20 40 60 0 10 20 30 40
0 0

10 10
Depth (cm)

Depth (cm)
20 20

30 30

40 40

50 50

Pb (mg/kg) Zn (mg/kg)
0 50 100 150 0 200 400 600
0 0

10 10
Depth (cm)

Depth (cm)

20 20

30 30

40 40

50 50

Reconstructed background concentration

Measured concentration
Environ Monit Assess (2008) 137:329–342 339

2.0
Co Cr Cu Zn slowly decreased from 2.5 at JL site to 1.0 at HB
1.0 Ni Pb Zn site. However, SPI, including Cr, Cu, Ni, Pb, and Zn
0.0 variables, generally was about 1–1.7, with gradually a
decreasing trend along river course downstream,
Igeo

-1.0
because the toxicity weights of both Zn and Cu are
-2.0 small. Therefore, on the whole, the stream sediment in
-3.0 the Second Songhua River was classified by the SPI
of these metals as natural sediment, without ecolog-
-4.0
JL SK BQ WKS WJZ SY ZY HB1 HB2
ical risk.
Sampling sites Variations of Igeo, EF, and SPI along the sediment
profile at WKS site of the Second Songhua River are
4.0 shown in Fig. 6. The values of Igeo for Co, Cr, Cu,
and Ni were less than 0 over the whole profile,
Enrichment factor

3.0 classifying the sediment profile as practical uncon-

tamination by these metals. The top layers (0–10 cm
2.0 depth) and bottom layers (>30 cm depth) of this
sediment profile were moderately polluted by Pb and
1.0 Zn, while middle layers might not be contaminated by
them. The enrichment factors of Co, Cu, Cr, and Ni in
0.0 the sediment profile were in the range of 0–2, while
JL SK BQ WKS WJZ SY ZY HB1 HB2
Sampling sites enrichment factor of Zn was about 2–4. Lead was
mainly enriched under 30 cm depth of the profile.
2.0 SPI, including Cr, Cu, Ni, Pb, and Zn variables,
generally was about 0 to 2 in the 0–30 cm depth and
1.5 2–4 under 30 cm depth of the profile. Therefore, on
the whole, the 0–30 cm depth of the sediment profile
SPI

1.0 was classified by the SPI of these metals as natural

0.5
0.0
JL SK BQ WKS WJZ SY ZY
Sampling sites
Fig. 5 Variations of geoaccumulation index (Igeo), enrichment
fact (EF) and sediment pollution index (SPI) along the course
of the river from Jilin (JL) city to Haerbin (HB) city
sediment at Jilin site was moderately polluted by Cu
with about 1 of Igeo value, it was not polluted by Cu
after Jilin city. For Pb and Zn, however, Igeo ranged
from about 0.3 to 0.7 in the sediment of the Second
Songhua River and generally was less than 0 for
Songhua River, suggesting moderate pollution and
unpollution, respectively. Enrichment factors of Co,
Cr, and Ni were around 1 over the whole course of the
river, showing no enrichment of these metals. Lead
was slightly enriched in most sampling sites, with ca.
1.2 to 1.5 of EF value. EF of Cu quickly decreased
from ca. 4 at JL site to 1.2 at WKS site, while EF of
sediment without ecological risk, but the 30–46 cm
depth of the sediment profile was classified as low
polluted sediment.
Whereas concentration of trace metals in the
HB1 HB2 sediments of Zhujiang River, Changjiang River, and
Huanghe River were measured (Zhang et al. 1995;
Zhang et al. 1998; Wang and Zhang 1999), potential
ecological risk assessment caused by these trace
metals was not carried out. Sporadic researches
reported potential ecological risk of trace metals in
other rivers in China. Sediment in Huaihe River
(Jiangsu section) was classified as low potential
ecological risk by Cd, As, Hg, Pb, Cu, and Zn
(Huang et al. 2004). Sediment in Haihe River was
characterized by low to moderate potential ecological
risk by Cu, Cd, Pb, Zn, and Cr (Wang and Sun 2005).
The distribution of pollutants (Cu, Pb, Zn, Cd, As, Cr)
in the sediment of Leanjiang River was divided into
four sections with low to very high potential
ecological risk. Whereas potential ecological risk
caused by Co, Cr, Cu, Ni, Pb, and Zn in the surface
sediment of the Second Songhua River was very low,
340
Igeo
-3 -2 -1 0 1 2 3
0 0
Co
10 Cr 10
Cu
Depth (cm)
Depth (cm)
20 20
Ni
Pb
30 30
Zn
40 40
50 50
Fig. 6 Variations of geoaccumulation index (Igeo), enrichment fact (EF) and sediment pollution index (SPI) along the sediment
profile at Wukeshu (WKS) site of the Second Songhua River
the sediment was contaminated strongly to extremely
by Hg (Lin et al. submitted).
Conclusions
Based on spatial variation of their concentration in
sediment, elements were divided into two groups.
Group one includes Al, Fe, Mg, Mn, Ti, V, and Sc
etc., generally occurring in the clay minerals. Group
two includes Na and K, mainly occurring in the
primary feldspars. Elemental concentration in the
grope one generally decreased along the course of
the river from Jilin to Haerbin, while elemental
concentration in group two generally increased.
Changes in the contents of matrix elements in the
sediment showed the primitive concentration of trace
metals in each sediment sample might be different.
Scandium content in the uncontaminated sediment
samples is significantly linearly correlated to contents
of most elements, including Co, Cu, Cr, Ni, Pb and
Zn. These linear relationships were used to recon-
structed the primitive or background concentrations of
trace metals in the sediment. Results indicated that
concentrations of Co, Cr, and Ni in the surface
sediment and sediment profile were generally only
slightly higher than or equal to their background
value, while concentrations of Cu, Pb, and Zn in some
sediment samples were significantly higher than their
background values.
Igeo value indicated that the sediment at Jilin city
was moderately contaminated by Cu, and the sedi-
ment of the Second Songhua River was moderately
Environ Monit Assess (2008) 137:329–342
Enrichment factor SPI
0 2 4 6 8 0 1 2 3 4
0
Co
10
Cr
Cu
Depth (cm)
20
Ni
Pb 30
Zn
40
50
contaminated by Pb and Zn. However, the sediment in
the whole studied river section was classified as
natural sediment without ecological risk by the SPI of
the trace metals.
The top layer (0–10 cm depth) and bottom layers
(30–46 cm depth) were generally moderately polluted
by Pb and Zn, indicated by Igeo. Nevertheless, only
the 30–45 cm depth of the sediment profile was
classified as low polluted sediment by the SPI of the
trace metals. This buried contamination of trace
metals might pose a potential risk to water column
under disturbance of sediment.
References
Banin, A., Eshel, G., & Roehl, K. E. (1998). Heavy metal
and trace element adsorption to recharge basin soils of
Shafdan reclamation project, 1997–1998 (215 p).
Rehovot, Israel: Research report submitted to Mekorot
Water Co.
Calmano, W., Hong, J., & Forstner, U. (1993). Binding and
mobilization of heavy metals in contaminated sediments
affected by pH and redox potential. Water Science and
Technology, 28, 223–235.
Chen, J. (2006). Principle of river water quality and Chinese
river quality. Beijing, China: Publishing House of Science,
(In Chinese).
Dickinson, W. W., Dunbar, G. B., & McLeod, H. (1996).
Heavy metal history from cores in Wellington Harbour,
New Zealand. Environmental Geology, 27, 59–69.
Eggleton, J., & Thomas, K. (2004). A review of factors
affecting the release and bioavailability of contaminants
during sediment disturbance events. Environment Interna-
tional, 30, 973–980.
Förstner, U., Ahlf, W., Calmano, W., & Kersten, M. (1990).
Sediment criteria development – Contributions from
Environ Monit Assess (2008) 137:329–342
environmental geochemistry to water quality management.
In D. Heling, P. Rothe, U. Förstner, & P. Stoffers (Eds.),
Sediments and environmental geochemistry: Selected
aspects and case studies (pp. 311–338). Berlin Heidelberg:
Springer.
Förstner, U., & Wittman, G. T. W. (1983). Metal pollution in
aquatic environment (484 pp). Berlin, Heidelberg New
York: Springer.
Gibbs, R. L. (1973). Mechanisms of trace metal transport in
rivers. Science, 214, 441–443.
Hakanson, L. (1980). An ecological risk index for aquatic
pollution control: A sedimentological approach. Water
Research, 14, 975–1001.
Horowitz, A. J. (1991). A primer in sediment-trace element
chemistry. Chelsea, MI, USA: Lewis.
Horowitz, A. J., Elrick, K., & Callender, E. (1988). The effect
of mining on the sediment-trace element geochemistry of
cores from the Cheyenne River arm of Lake Oahe, South
Dakota, USA. Chemical Geology, 67, 17–33.
Huang, H., Yu, Y., Wang, X., & Wang, L. (2004). Heavy metal
contamination and ecological risk assessment in sediment
of Huai River. Environmental Pollution and Control, 26
(3), 207–208, 231 (In Chinese).
Jain, C. K. (2004). Metal fraction study on bed sediments of
River Yamuna, India. Water Research, 38, 569–578.
Jain, C. K., Singhal, D. C., & Sharma, M. K. (2005). Metal
pollution assessment of sediment and water in the river
Hindo, India. Environmental Monitoring and Assessment,
105, 193–207.
Jiang, G., Shi, J., & Feng, X. (2006). Mercury pollution in China.
Environmental Science & Technology, 40, 3672–3678.
Lee, D. S., Garland, J. A., & Fox, A. A. (1994). Atmospheric
concentrations of trace elements in urban areas of the United
Kingdom. Atmospheric Environment, 28, 2691–2713
Lin, C., He, M., Zhou, Y., Guo, W., Quan, X., & Yang, Z.
(2007). Mercury contamination and dynamics in the
sediment of the Second Songhua River. Soil and Sediment
Contamination (in press).
Liu, W., Zhao, J., Ouyang, Z., Söderlund, L., & Liu, G. (2005).
Impacts of sewage irrigation on heavy metal distribution
and contamination in Beijing, China. Environment Inter-
national, 31, 805–812.
Loring, D. H. (1990). Lithium – A new approach for the
granulometric normalization of trace metal data. Marine
Chemistry, 29, 155–168.
Loska, K., Cebula, J., Pelczar, J., Wiechula, D., & Kwapulinski,
J. (1997). Use of enrichment, and contamination factors
together with geoaccumulation indexes to evaluate the
content of Cd, Cu, and Ni in the Rybnik water reservoir in
Poland. Water, Air and Soil Pollution, 93, 347–365.
Luoma, S. N. (1983). Bioavailability of trace metals to aquatic
organisms – A review. Science of the Total Environment,
28, 1–22.
Luoma, S. (1990). Processes affecting metal concentrations in
estuarine and coastal marine sediments. In R. Furness & P.
Rainbow (Eds.), Heavy metals in the marine environment
(pp. 51–66). Boca Raton, FL, USA: CRC.
Mathis, B. J., & Cummings, T. F. (1973). Selected metals in
sediments and biota in Illinois river. Journal of the Water
Pollution Control Federation, 45, 573–583.
341
McMurtry, G. M., Wiltshire, J. C., & Kauahikaua, J. P. (1995).
Heavy metal anomalies in coastal sediments of Oahu,
Hawaii. Pacific Science, 49, 452–470.
Müller, G. (1969). Index of geoaccumulation in sediments of
the Rhine river. GeoJournal, 2, 108–118.
Qu, C., & Yan, R. (1990). Chemical composition and factors
controlling suspended matter in three major Chinese
Rivers. Science of the Total Environment, 97/98, 335–346.
Sakai, H., Kojima, Y., & Saito, K. (1986). Distribution of
metals in water and sieved sediments of Toyohira River.
Water Research, 20, 559–567.
Schiff, K. C., & Weisberg, S. B. (1999). Iron as a reference
element for determining trace metal enrichment in South-
ern California coastal shelf sediments. Marine Environ-
mental Research, 48, 161–176.
Schropp, S. J., Lewis, F. G., Windom, H. L., Ryan, J. D., Calder,
F. D., & Burney, L. C. (1990). Interpretation of metal
concentrations is estuarine sediments of Florida using
aluminum as a reference element. Estuaries, 13, 227–235.
Shotyk, W., Weiss, D., Kramers, J. D., Frei, R., Cheburkin, A. K.,
Gloor, M., et al. (2001). Geochemistry of the peat bog at
Etang de la Gruere, Jura Mountains, Switzerland, and its
record of atmospheric Pb and lighogenic trace metals (Sc, Ti,
Y, Zr, and REE) since 12,370 14C yr BP. Geochimica et
Cosmochimica Acta, 65(14), 2337–2360.
Singh, K. P., Malik, A., Singh, S., Singh, V. K., & Murthy, R. C.
(2005). Estimation of source of heavy metal contamination
in sediments of Gomti River (India) using principal
component analysis. Water, Air, and Soil Pollution, 166,
321–341.
Singh, M., Müller, G., & Singh, I. B. (2002). Heavy metals in
freshly deposited stream sediments of rivers associated
with urbanization of the Ganga Plain, India. Water, Air,
and Soil Pollution, 141, 35–54.
Sparks, D. L. (1995). Environmental soil chemistry. San Diego:
Academic.
Steinmann, P., & Shotyk, W. (1997). Geochemistry, mineralo-
gy, and geochemical mass balance on major elements in
two peat bog profiles (Jura Mountains, Switzerland).
Chemical Geology, 138, 25–53.
Sutherland, R. A. (2000). Bed sediment-associated trace metals
in an urban stream, Oahu, Hawaii. Environmental Geolo-
gy, 39(6), 611–627.
Thornton, J. A., McComb, A. J., & Ryding, S. O. (1975). The role of
sediments. In A. J. Mccomb (Ed.), Eutrophic shallow estuaries
and lagoons (pp. 205–223). Boca Raton, FL, USA: CRC.
Trefry, J. H., Metz, S., & Trocine, R. P. (1985). A decline in lead
transport by the Mississippi River. Science, 230, 439–441.
Wang, S., & Sun, J. (2005). Evaluation on potential ecological
risk of heavy metal pollution of sediments in Hiahe River.
Environmental Engineering, 23(2), 62–64, (In Chinese).
Wang, L., & Zhang, C. (1999). Concentration and speciation of
27 elements in sediments and suspended matter from
Guangzhou section of the Pearl River. Journal of Basic
Science and Engineering, 7, 12–20, (In Chinese).
Wedepohl, K. H. (1995). The composition of the continental
crust. Geochimica et Cosmochimica Acta, 59, 1217–1239.
White, K. D., & Tittlebaum, M. E. (1985). Metal distribution
and contamination in sediments. Journal of Environmental
Engineering, 111, 161–175.
342
Zhang, C., Wang, L., & Zhang, S. (1995). Metals speciation in
sediments and suspended matter in the middle-lower
reaches of the Changjiang River. China Environmental
Science, 15, 342–347 (In Chinese).
Zhang, C., Zhang, S., Wang, L., & Wang, L. (1998).
Comparison of geochemistry of metals in sediments from
Environ Monit Assess (2008) 137:329–342
some typical rock areas. Acta Goegraphica Sinica, 53,
314–322, (In Chinese).
Zoumis, T., Schmidt, A., Grigorova, L., & Calmano, W.
(2001). Contaminants in sediments: Remobilisation and
demobilisation. Science of the Total Environment, 266,
195–202.