Ecologicalriskassessmentofheavymetalsinsedimentandhumanhealth
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Environmental Pollution
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Article history: The concentrations of heavy metals (Cr, Cd, Hg, Cu, Zn, Pb and As) in the water, sediment, and fish were
Received 1 August 2010 investigated in the middle and lower reaches of the Yangtze River, China. Potential ecological risk
Received in revised form analysis of sediment heavy metal concentrations indicated that six sites in the middle reach, half of the
18 January 2011
sites in the lower reach, and two sites in lakes, posed moderate or considerable ecological risk. Health
Accepted 6 June 2011
risk analysis of individual heavy metals in fish tissue indicated safe levels for the general population and
for fisherman but, in combination, there was a possible risk in terms of total target hazard quotients.
Keywords:
Correlation analysis and PCA found that heavy metals (Hg, Cd, Pb, Cr, Cu, and Zn) may be mainly derived
Heavy metal
Ecological risk
from metal processing, electroplating industries, industrial wastewater, and domestic sewage. Hg may
Sediment also originate from coal combustion. Significant positive correlations between TN and As were observed.
Health risk Crown Copyright Ó 2011 Published by Elsevier Ltd. All rights reserved.
Fish
Yangtze River
1. Introduction indirectly toxic to the aquatic flora and fauna. The effects of
pollutants may also be detected on land as a result of their bio-
The rapid development of industry and agriculture has resulted accumulation and bio-concentration in the food web (Wu et al.,
in increasing pollution by heavy metals, which are a significant 2005; Zhang and Ke, 2004). Consequently, an analysis of the
environmental hazard for invertebrates, fish, and humans distribution of heavy metals in sediments adjacent to populated
(Uluturhan and Kucuksezgin, 2007). Significant quantities of heavy areas could be used to investigate anthropogenic impacts on
metals are discharged into rivers, which can be strongly accumu- ecosystems and would assist in the assessment of risks posed by
lated and biomagnified along water, sediment, and aquatic food human waste discharges (Hu et al., 2002; de Mora et al., 2004;
chain, resulting in sublethal effects or death in local fish pop- Zheng et al., 2008).
ulations (Megeer et al., 2000; Jones et al., 2001; Almeida et al., Under certain conditions, these metals may accumulate to
2002; Xu et al., 2004). Suspended sediments adsorb pollutants a toxic concentration level which may lead to ecological damage
from the water, thus lowering their concentration in the water (Jefferies and Freestone, 1984). Methods used to evaluate the
column. Heavy metals are inert in the sediment environment and ecological risk posed by heavy metals in sediments include calcu-
are often considered to be conservative pollutants (Wilcock, 1999; lation of the index of geo-accumulation (Porstner, 1989), the
Olivares-Rieumont et al., 2005) although they may be released potential ecological risk index (Håkanson, 1980), and the excess
into the water column in response to certain disturbances (Agarwal after regression analysis (ERA) (Hilton et al., 1985), among which
et al., 2005), causing potential threat to ecosystems (Chow et al., the first two indices are the most popular.
2005; Hope, 2006). Bottom sediments also provide habitats and Several methods have been proposed for estimation of the
a food source for benthic fauna. Thus, pollutants may be directly or potential risks to human health of heavy metals in fishes. The risks
may be divided into carcinogenic and non-carcinogenic effects. For
carcinogenic contaminants, the observed or predicted exposure
* Corresponding author. concentrations are compared with thresholds for adverse effects, as
E-mail address: [email protected] (Z. Yang). determined by dose-effect relationships (Solomon et al., 1996). The
0269-7491/$ e see front matter Crown Copyright Ó 2011 Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.envpol.2011.06.011
Author's personal copy
probability risk assessment technique has been adopted by collected from the main river and lakes in the Yangtze River basin at 17 sites in the
a number of researchers (Solomon et al., 1996; Giesy et al., 1999; middle reach and from 10 sites in the lower reach, in 2007 (Fig. 1).
The middle and lower reaches of the Yangtze River, with many bends, are
Cardwell et al., 1999; Hall et al., 2000; Wang et al., 2002) to fully connected with many lakes. This region, referred to as the “Water Realm” is China’s
utilize available exposure and toxicity data. However, these major agricultural district. Several large and medium-sized cities are distributed
methods have only been used to quantify the health risks of along the river, forming a prosperous industrial belt. In contrast to the wide plains of
carcinogenic pollutants. Current non-cancer risk assessment the middle reach, the downstream plains alongside the river are long and narrow.
Jianghan Plain lies in the north of the middle reach, while Dongting Plain and Poyang
methods do not provide quantitative estimates of the probability of
Plain are situated in the south. Between Hukou and Zhenjiang, a narrow alluvial
experiencing non-cancer effects from contaminant exposure. These plain extends on both sides of the main river. Along the middle and lower reaches of
methods typically are based on the Target Hazard Quotient (THQ). the Yangtze River, the river channel flows slowly and the plain alternates between
Although the THQ-based risk assessment method does not wide and narrow. Below Datong station, tidal influences prevail, the flow becomes
provide a quantitative estimate of the probability of an exposed slower, and sediment deposition is enhanced.
Fig. 1. Map of study area, middle and lower reaches of the Yangtze River. (1) Yichang, (2) Yidu, (3) Jingzhou, (4) Gong’an, (5) Haoxue, (6) Xinchang, (7) Baiji dolphin (Lipotes
vexillifer) protection area, Jianli, (8) Dongting Lake; (9) Chenglingji; (10) Honghu Lake; (11) Yangtze River near Honghu Lake mouth, (12) Jiayu, (13) Paizhou Bay, (14) Wuhan, (15)
Donghu Lake, (16) E’zhou, (17) Liangzi Lake, (18) Jiujiang, (19) Poyang Lake, (20) Anqing, (21) Datong, (22) Wuhu, (23) Jiangning, (24) Nanjing, (25) Zhenjiang, (26) Jiangyin, (27)
Haimen.
3. Results and discussion the lower reach of the main river had the highest mean concen-
trations of Cd, As, TN, and TP. Mean concentrations of metals in the
3.1. Distribution of heavy metals in sediments middle reach were relatively lower. This may be due to the
downstream movement and deposition of suspended sediments
Heavy metal concentrations in sediments in the middle and containing heavy metals, combined with local pollution in the
lower reaches of the Yangtze River basin are summarized in Table 1. lower reaches. The heavy metal concentrations in the sediments
Total nitrogen (TN), total phosphorus (TP), and organic matter (OM) were higher in the lakes than in the river. We suggest that this was
concentrations are also listed for later analysis. The lakes had the due to the higher flow disturbance in the river that led to re-
highest mean concentrations of Hg, Pb, Cr, Cu, Zn, and OM, while suspension and downstream movement of pollutants.
Table 1
Summary statistics of heavy metal concentrations and nutrition elements in sediments in the middle and lower Yangtze River basin (dry weight).
Hg (mg/kg) Cd (mg/kg) Pb (mg/kg) Cr (mg/kg) Cu (mg/kg) Zn (mg/kg) As (mg/kg) TN (%) TP (%) OM (%)
I Minimum 0.011 0.064 20 42 22 48 6 0.015 0.037 2.55
Maximum 0.535 0.77 110 96 67.4 350 63 0.17 0.14 7.38
Average 0.17 0.40 39.32 72.54 44.75 120.42 16.73 0.06 0.07 4.39
S.D. 0.16 0.29 23.94 18.65 15.08 79.18 19.67 0.05 0.03 1.56
CV (%) 95.84 73.07 60.89 25.70 33.70 65.75 117.62 83.97 50.28 35.60
Notes: I Stream in middle reach; II Stream in lower reach; III Lakes in middle and lower reaches; TN is total nitrogen, TP is phosphorus, and OM is organic matter.
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3.2. Heavy metals concentration in fishes muscles of different fish species from Taihu Lake, and reported
0.228e1.89 Cu, 16e130 Zn, 0.177e0.287 Pb, 0.003-0.021 Cd,
The 469 fish and crayfish samples together comprised 2 classes, NDe0.387 Cr mg/kg dry weight, metals concentration were lower
9 orders, 14 families, 33 genera, and 41 species. Their heavy metals than this study, except Zn. Bustamante et al. (2003) found that
concentration and habitats are listed in Table 2. different fish species Kerguelen Islands contained 0.5e2.5 Cu,
The highest concentrations of Cu, Zn, and Hg were found in 9.2e32.2 Zn, 0.01e0.1 Cd, 0.044e1.19 Hg mg/kg dry weight in the
Eriocheir sinensis. Hemimyzon abbreviata had the highest concen- muscle, results generally were higher than present results, except
trations of Pb and Cd, Leptobotia elongata, and Coreius guichenoti _
Hg. The results reported by Türkmen et al. (2005) from Iskenderun
had the highest concentrations of Cr, and Rhinogobio typus had the Bay were generally lower than present results, except Cr. The
highest concentrations of As. The benthic fauna (e.g. Eriocheir concentrations of Cu, Zn and Pb in fish collected from the Yangtze
sinensis), demersal fish (e.g. Hemimyzon abbreviata, Rhinogobio River were higher than Pearl River on corresponding period,
typus and Leptobotia elongata), and fish that inhabit the lower zone however, Cd, Hg, Cr and As concentrations were lower. Both
of the water column (e.g. Coreius guichenoti), are likely to have Yangtze River and Pear River, heavy metal concentrations in fish
higher heavy metal concentrations than fishes that inhabit the were high in recent years than ten years ago. This demonstrate that
upper water column. We hypothesized that their greater contact heavy metals contaminant in Chinese river are becoming more and
with polluted sediments and their greater uptake of heavy metal more serious.
concentrations from zoobenthic predators would lead to higher
heavy metal concentration in their tissues (Yi et al., 2008). The 3.3. Relationships between heavy metal levels in fish and in the
relationships among heavy metal levels in fish, benthic fauna, environment
water, and sediments are analyzed in Section 3.3.
Heavy metals concentrations in fish of this study and other Heavy metals entering the water body would be absorbed in
literatures are listed in Table 3. Data from the open literatures sediments, and subsequently might migrate as a result of
showed that metal concentrations in muscles of fish varied widely exchanges between water, sediment, and biota, through biological
depending on where and which the animals caught (Table 3). Chi and chemical process. In the 1960s, serious mercury pollution
et al. (2007) measured the concentrations of heavy metals in the occurred in Sweden (Jernelöv et al., 1975), and was later found in
Table 2
Average concentrations of heavy metals and habitat site for fish species (mg/kg, wet weight).
Notes: bold type means the highest concentration of each heavy metals, e means metals concentration below lower detection limit.
Author's personal copy
Table 3
Comparison of heavy metal concentrations in fish with values taken from the open literature.
Canada (Wheatley, 1997). Following these events, researchers assumption that the sensitivity of the aquatic system depends on its
began to pay more attention to pollution by heavy metals. Accu- productivity. The potential ecological risk index (RI) was introduced
mulation of heavy metals in fish results primarily from surface to assess the degree of heavy metal pollution in sediments,
contact with the water, by breathing, and via the food chain. Uptake according to the toxicity of heavy metals and the response of the
by these three routes depends on the environmental levels of heavy environment:
metals in the habitat of the fish. Table 4 lists the heavy metal X
concentrations in these different media. Concentrations of heavy RI ¼ Eri (1)
metals in the sediment were 1000e100,000 times higher than
those in the water. A number of studies have reported a similar
Eri ¼ Tri Cfi (2)
phenomenon (Enk and Mathis, 1977; Anderson et al., 1978;
Burrows and Whitton, 1983; Barak and Mason, 1989). The heavy
metal concentrations were 10e1000 times higher in fish and Cfi ¼ C0i =Cni (3)
benthic invertebrates than those in the water, but lower than
concentrations in the sediments (Table 4). Heavy metals do not where RI is calculated as the sum of all risk factors for heavy metals
degrade in water but are generally not found in high concentra- in sediments, Eri is the monomial potential ecological risk factor, Tri
tions, primarily due to deposition in sediments but also because of is the toxic-response factor for a given substance, which accounts
uptake by plants and animals (Yi et al., 2008). Heavy metals in the for the toxic requirement and the sensitivity requirement, as shown
sediment enter the food chain via the feeding of benthic animals. in Table 5. Cfi is the contamination factor, C0i is the concentration of
The concentrations of heavy metals were highest in the sedi- metals in the sediment, and Cni is a reference value for metals
ments, intermediate in fish and lowest in the water. Demersal fish (Table 5).
and benthic fauna generally had higher levels of Cu, Cd, Pb, Zn, Hg, The risk factor RI was proposed by Hakanson based on eight
Cr and As compared with those in fish at the upper-middle and parameters (PCB, Hg, Cd, As, Pb, Cu, Cr, and Zn). In this paper, PCBs
middle-lower layers (Table 4 and Fig. 2). Heavy metal concentra- were excluded. Based on the reference values for these elements,
tions were ranked as follows: sediments > demersal fish and the adjusted evaluation criteria for the ecological risk index RI are
benthic fauna > pelagic fish > water. Our results support the listed in Table 6.
hypothesis that the sediment is the major sink for trace metal Using equations (1)e(3) and parameters listed in Table 5, the
pollution and plays an important role in heavy metal uptake by fish potential ecological risk indices Eri and RI for each site were
(Luoma and Bryan, 1978). The heavy metals contained in the sedi- obtained and are listed in Table 7. According to these data, Hg posed
ment are then absorbed and stored in the tissues (Gao, 2001). As a considerable ecological risk at five sites and a moderate risk at
a consequence, controlling the sources of contamination of water two. Additionally, Cd and As also posed relatively high ecological
and sediments in the aquatic system is the key method for risks in these areas. The high ecological risks of these three heavy
protection of the fish resource. metals in freshwater ecosystems are consequences of their high
toxic-response factors. In terms of their spatial distribution, sites
with moderate or considerable potential ecological risk indices for
4. Ecological risk and health risk assessment Hg and Cd were located near to large cities (Wuhan, Nanjing, and
Jiangyin), or ports (Chenglingji), or lakes with high human activity
4.1. Assessment of potential ecological risk (Dongting Lake and Donghu Lake). The highest potential ecological
risk indices for As were found in the lower reach, mainly down-
Håkanson (1980) developed a methodology to assess ecological stream of Poyang Lake. For other metals (Pb, Cu, Cr, and Zn), the
risks for aquatic pollution control. The methodology is based on the potential ecological risk indexes were low. The potential ecological
risk indices for single regulators (Eri) indicated that the severity of
Table 4 pollution of the seven heavy metals decreased in the following
Average heavy metal concentrations in water, sediment and fishes living in different
water depths.
sequence: Hg > Cd > As > Cu > Pb > Cr > Zn.
RI represents the sensitivity of various biological communities to
Heavy metal Cu Zn Pb Cd Hg Cr As toxic substances and illustrates the potential ecological risk caused
Water 0.0028 0.031 0.002 0.0004 0.00004 0.0013 0.00097 by heavy metals. Two sites among twelve in the middle reach of the
Pelagic fish 1.16 6.08 0.48 0.072 0.021 0.123 0.016
main river exhibited moderate or considerable ecological risk. Most
Demersal fish 2.24 8.05 0.57 0.128 0.022 0.365 0.022
and benthic of the lakes and sites in the lower reach of the main river posed
fauna moderate or considerable ecological risk. The RI values were clearly
Sediment 45.7 135.6 37 0.423 0.155 76.4 24.7 related to the degree of anthropogenic disturbance. For example,
Notes: values are mg/kg wet weight for fish tissue and water, and mg/kg dry weight the Tian’ezhou wetland, which is a natural conservation area in
for sediments. China, had the lowest heavy metal concentrations and minimal
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Fig. 2. Distribution of heavy metal in water, sediment, zoobenthos, and pelagic fish. BM: bottom material (sediment), BF: Demersal fish and benthic fauna, PF: pelagic fish, W: water.
potential ecological risk, while sites near to big cities (such as The models for estimating THQ are (Chien et al., 2002):
Wuhan, Nanjing, and Jiangyin) had relatively high ecological risks.
The sources of heavy metal pollution in the main river and the lakes EFr EDtot FIR C
THQ ¼ 103 (4)
of this area are influenced by many factors, both natural and man- RfDo BWa ATn
made. Many tributaries discharge into the main river and the lakes where THQ is the target hazard quotient; EFr is exposure frequency
while, at the same time, the gradient of the river gradually becomes (365 days/year); EDtot is the exposure duration (70 years, average
reduced, leading to decreasing flow velocity and increasing depo- lifetime); FIR is the food ingestion rate (g/day); C is the heavy metal
sition of chemical elements. concentration in fish (mg/g); RfDo is the oral reference dose (mg/kg/
day, Table 9); Bwa is the average adult body weight (55.9 kg); and
4.2. Health risk from consuming fish ATn is the averaging exposure time for non-carcinogens (365 days/
year number of exposure years, assuming 70 years).
4.2.1. Determination of target hazard quotients (THQ) It has been reported that exposure to two or more pollutants may
The THQ, which is the ratio between the exposure and the result in additive and/or interactive effects (Hallenbeck, 1993). In this
reference doses (a Reference Dose or RfD), is used to express the study, the total THQ is treated as the arithmetic sum of the individual
risk of non-carcinogenic effects. If the ratio is less than 1, there will metal THQ values, derived by the method of Chien et al. (2002):
not be any obvious risk. Conversely, an exposed population of
concern will experience health risks if the dose is equal to or greater Total THQ ðTTHQ Þ ¼ THQ ðtoxicant 1Þ þ THQ ðtoxicant 2Þ
than the RfD. The method for the determination of THQ was þ / / þ THQ ðtoxicant nÞ ð5Þ
provided in the United States EPA Region III risk-based concentra-
tion table (USEPA, 2000). The dose calculations were carried out 4.2.2. Health threat from consuming fish
using standard assumptions from an integrated United States EPA Estimates of fish consumption in coastal cities of China (Jiang
risk analysis. Assumptions for the health risk calculation in this et al., 2005; Zhang et al., 2001), indicate that the general pop-
paper are list in Table 8: ulation eats 105 g/day of fish and crayfish and fishermen consume
A THQ value below 1 means that the level of exposure is smaller
than the reference dose; a daily exposure at this level is believed to Table 6
be unlikely to cause any adverse effects during a person’s lifetime. Terminology used to describe the risk factor Eri and RI as suggested by Håkanson
(1980).
Table 7 Table 8
Heavy metal potential ecological risk indexes of the Yangtze River system. Assumptions for THQ calculation.
Table 11
Correlation coefficients between different heavy metal elements in sediment (n ¼ 27).
Hg Cd Pb Cr Cu Zn As TN TP OM
Hg 1
Cd 0.650** 1
Pb 0.581** 0.584** 1
Cr 0.549** 0.746** 0.762** 1
Cu 0.705** 0.755** 0.729** 0.891** 1
Zn 0.36 0.432* 0.796** 0.715** 0.610** 1
As 0.168 0.196 0.073 0.075 0.143 0.068 1
TN 0.296 0.122 0.043 0.018 0.157 0.013 0.727** 1
TP 0.013 0.078 0.223 0.121 0.051 0.02 0.521* 0.613** 1
OM 0.087 0.012 0.305 0.504* 0.372 0.238 0.016 0.176 0.239 1
Table 12
Total variance explained and component matrices for the heavy metals in surface sediments from the Yangtze River basin.
Component Initial eigenvalues Extraction sums of squared loadings Rotation sums of squared loadings
F1 F2 F1 F2
Cu 0.93 0.09 0.92 0.19
Cr 0.93 0.06 0.93 0.04
Pb 0.87 0.28 0.9 0.19
Cd 0.83 0.25 0.79 0.34
Zn 0.77 0.39 0.8 0.3
Hg 0.75 0.27 0.72 0.34
As 0.11 0.89 0.02 0.9
Table 13
Total variance explained and component matrices for the sediment heavy metals concentration across the river.
Component Initial eigenvalues Extraction sums of squared loadings Rotation sums of squared loadings
F1 F2 F1 F2
Haoxue 0.997 0.073 0.991 0.132
Yichang 0.997 0.079 0.992 0.126
Paizhouwan 0.995 0.086 0.992 0.119
Jiujiang 0.995 0.044 0.983 0.159
Jiangning 0.991 0.093 0.952 0.293
Zhenjiang 0.99 0.067 0.982 0.136
E’zhou 0.986 0.13 0.992 0.073
Wuhan 0.985 0.141 0.993 0.062
Jingzhou 0.984 0.136 0.991 0.068
Yidu 0.984 0.077 0.979 0.125
Nanjing 0.981 0.134 0.988 0.069
Haimen 0.972 0.084 0.935 0.28
Dongting Lake 0.968 0.181 0.985 0.021
Jiangyin 0.965 0.021 0.94 0.217
Donghu Lake 0.957 0.03 0.943 0.166
Gong’an 0.952 0.097 0.952 0.1
Honghukou 0.944 0.172 0.959 0.024
Jiayu 0.929 0.165 0.943 0.027
Tian’ezhou 0.925 0.068 0.919 0.122
Honghu Lake 0.891 0.208 0.914 0.022
Liangzi Lake 0.865 0.125 0.821 0.298
Xinchang 0.854 0.465 0.742 0.629
Chenglingji 0.838 0.094 0.801 0.263
Datong 0.138 0.985 0.066 0.992
Wuhu 0.072 0.965 0.127 0.96
Poyang Lake 0.398 0.897 0.207 0.96
Anqing 0.601 0.794 0.427 0.9
(Yang et al., 2009), the source of heavy metals in this area comes the Yangtze River. On the basis of investigations at 27 stations
mainly from metal processing, electroplating industries, industrial within the watershed, heavy metal concentrations in the water,
wastewater, and domestic sewage. Mercury (Hg) was poorly surface sediments, fishes and benthic fauna were measured,
correlated with the other five heavy metals, perhaps because the potential ecological risk indices were calculated, the health risk was
main source of this pollutant is coal combustion. evaluated, and the possible sources of pollution were analyzed.
In the second component (F2, a contribution rate of 17.17%), As In general, the sediment heavy metal concentrations in the
showed much higher values than other heavy metals. The correlation lower reach of the Yangtze were higher than in the middle reach.
analysis also indicated that As had no significant correlation with the Furthermore, sediment heavy metal accumulation was much
other six heavy metals, and was significantly correlated with TN. higher in the lakes compared to the main river, perhaps due to the
PCA for heavy metals in sediment across the river was con- lower turbulence and mixing in the lacustrine environment. The
ducted to find the heavy metals distribution in 27 samples sites heavy metal concentrations in the sediment were 1000e100,000
(Table 13). According to the results, heavy metals concentrations in times higher than those in the water. The metals in fish and
sediment of 27 sample sites could be grouped into a two- invertebrate tissues were intermediate between the sediment and
component model, which accounted for 94% of all the data varia- the water. Fish living near the river or lake bed and feeding on
tion. The initial component matrix that Poyang Lake, Anqing, benthic invertebrates thus had higher concentrations of heavy
Datong and Wuhu were associated, displaying high values in the metals when compared with fish living in the upper or middle
second component (F2, a contribution rate of 14.25%), other 23 zones of the water column. Most heavy metals are transferred
sample sites showed a strong association with the first factor (F1, through the food chain via the following route: sediment e zoo-
a contribution rate of 79.75%). The rotation of the matrix show benthos e benthonic carnivores e human.
similar grouping with initial component matrix. The results imply Analysis of the potential ecological risk of sediment heavy metal
that some different anthropogenic activities occurred in the reach concentrations showed that some sample sites in the middle and
from Poyang Lake to Wuhu. lower reaches of the Yangtze River presented a relatively high
ecological risk. According to the potential ecological risk index for
6. Conclusions a single regulator (Eri), Hg represented a moderate risk at 7.4% of
sites, and a considerable risk at 18.5% of sites; Cd posed a moderate
Heavy metal pollution is an important problem for the Yangtze risk in 37% and As in 22% of the regions. The ecological risk for all
River basin. The aim of this paper was to study the regional impacts factors (RI) showed that 7.4% of sample sites belonged in the cate-
of heavy metals (Hg, Cu, Cr, Zn, Cd, Pb, and As) on the watershed of gory of considerable risk, and 33% were of moderate risk. Analysis
Author's personal copy
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