Chemosphere 41 (2000) 3±6

Copper contamination in paddy soils irrigated with wastewater

Z.H. Cao *, Z.Y. Hu
Institute of Soil Science, Chinese Academy of Sciences, Nanjing, People's Republic of China, 210008

Abstract

Copper (Cu) contamination was investigated in paddy soils where Cu-rich wastewater (12 mg Cu/l) was used for
irrigation. The results showed that Cu contamination increased the soil Cu content from 17.0 mg Cu/kg in the non-
wastewater irrigated soils (NWIS) to 101.2 mg Cu/kg in the wastewater irrigated soils (WIS), and Cu accumulated
mostly in the surface layer (0±10 cm) of the paddy soil. The average Cu contents in brown rice, rice hull and rice straw
from NWIS were 1.4, 7.3 and 14.5 mg Cu/kg, while those from WIS were 15.5, 133.2, and 101.4 mg Cu/kg, respectively.
Correlation analysis revealed that the relationship between the Cu content in the rice straw and the rice hull with the
total Cu content of the soil could be described by an exponential function (R2 ˆ 0.921 and 0.831, respectively; P <0.01).
Rice plants grown in the WIS showed symptoms of black roots, less e€ective tiller, etc. Subsequently, the rice yield
decreased by 18±25% compared with that grown in NWIS. Ó 2000 Elsevier Science Ltd. All rights reserved.

1. Introduction ation measures for polluted soils and reasonable usage

of polluted rice grain and straw.
Fast development of village-owned industries in the
last two decades or so has certainly had positive e€ect on
Chinese economic growth. On the other hand, however,
2. Materials and methods
it not only occupied quality arable land, but also in-
duced severe damage to the agricultural environment.
The studied paddy soil was derived from lake and
Soil pollution with heavy metals due to irrigation with
river deposit located at the Southern part of Yangtze
wastewater is one of the examples. This type of problem
delta. It has been used for rice cultivation for several
is more often reported in coastal areas where are rela-
thousand years. Therefore, a typical paddy soil pro®le
tively highly developed in China (Cao, 1998; Liu, 1991).
was developed with Aa (0±15 cm), Ap (15±25 cm) and
In May 1997, it was observed that on an area of 64 ha
Gw (25±40 cm) layers. Soils are loam clay in texture with
of paddy soil in Yixing County Jiangsu Province, that
pH 6.0±7.7, 16±19 g/kg of organic matter, and 21±
rice seedlings grew very slowly 10 days after transplan-
25 cmol/Kg in CEC.
tation, and seedlings on about 12 ha of paddy ®eld died
According to observation of the degree of abnormal
30 days after transplantation. This observation led us to
rice seedling growth, 3 blocks (about 300 m2 each) of
conduct a ®eld study to understand the causes respon-
®eld were selected: normal rice growth block (NWIS),
sible to the abnormal growth of rice seedlings; to exam
slow growth block (WIS-1) and dead seedling block
the residual concentrations of the toxic substance in the
(WIS-2). In July 1997, a composite soil sample (com-
soils, and the rice plants (brown rice, rice hull and
bined with 10 points of 0±10 cm surface layer soil
straw); to provide a scienti®c basis for devising remedi-
sample) was taken at each block with 3 replicates; a soil
pro®le sample (0±10, 10±20, 20±40 cm layers) was also
taken from each block. At the same time, three samples
*
Corresponding author. Tel.: +86-25-7712-572; fax: +886- of irrigation water from small canals within the area
25-3353-590. were collected. In addition, two samples of e‚uent
E-mail address: zhcao@issas.ac.cn (Z.H. Cao). wastewater discharged from a CuSO4 factory and a

0045-6535/00/$ - see front matter Ó 2000 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 4 5 - 6 5 3 5 ( 9 9 ) 0 0 3 8 3 - 5
4 Z.H. Cao, Z.Y. Hu / Chemosphere 41 (2000) 3±6

copper ingot factory nearby, and one water sample from 3.2. Copper distribution in the soil-rice system
the big irrigation ditch where receiving the wastewater
were also taken. There were three replicates for each. As
3.2.1. Soil Cu concentration
for rice plant samples, ten bunches of rice plants from
The concentrations of soil Cu in WIS-1 and WIS-2
each block were sampled to exam tillers, shoot height,
blocks were 1.6 and 5.1 folds higher than in soil of
root number and root length at the tiller stage (in July
NWIS block, and were 1.3 and 4.1 times higher than
1997). Finally, two square meters of rice plants with 3
that of Cu background value in Jiangsu soils (Table 2).
replication were harvested from each block to determine
The concentration of Cu in soils decreased gradually
grain yield.
with soil depth; especially in WIS. Copper concentration
Copper concentrations in the water samples were
ratio of layers 0±10 cm, 10±20 cm and 20±40 cm in the
directly determined by atomic absorption spectroscopy
WIS-2, WIS-1 and NWIS were 7.4:1.5:1; 2.2:1.3:1 and
(AAS), while the soil and plant samples were acid di-
1.3:1.2:1, respectively (Fig. 1). This indicated that the
gested with HNO3 ±HClO4 , and then analysed by AAS
majority of Cu accumulated in the surface layer (0±
according to the method described by Liu (1996). The
10 cm) of WIS. The results are in agreement with other
soil pH, CEC, texture and organic matter were deter-
surveys involving soil Cu pollution (Deluisa et al., 1996;
mined by the methods described by Black et al. (1965).
Lepp et al., 1997).

3. Results 3.2.2. Rice plant copper concentration

The Cu contents of the rice plants from each block at
the tiller stage are presented in Table 3. The mean Cu
3.1. E€ects of wastewater irrigation on rice plant growth
contents of the rice plants from WIS-1 and WIS-2 were
3.5 and 12.5 times higher than those from NWIS
There was no adverse e€ect 50 days after rice seed-
lings had been transplanted in NWIS, while those grown
in WIS had no e€ective tiller at all. The total number of
roots, the longest root per hill of rice plant in WIS-1 and
WIS-2 were 79% and 32%, and 67% and 33% of those in
NWIS, respectively. The percentage of white roots in
total number of rice roots grown in WIS were 30% less
than grown in NWIS. The heights of rice shoots in WIS-
1 and WIS-2 were 82% and 54% of those in NWIS
(Table 1). Clearly, the rice grown in WIS-1 and WIS-2
showed abnormal growth. Fig. 1. Copper distribution at soil pro®les of various blocks.

Table 1
Morphological properties of rice plant growth at tiller stagea
Block No. of Height of rice plant No. of roots per hill Longest root per hill Percent of white
tiller per cm % No. % cm % roots in total
hill number of roots
NWIS 39 ‹ 2.6 100 95 ‹ 7 100 15 ‹ 1.2 100 32
NWIS-1 0 32 ‹ 2.1 82 75 ‹ 5 79 10 ‹ 1.4 67 21
NWIS-2 0 21 ‹ 1.7 54 30 ‹ 6 32 5 ‹ 0.5 33 20
a
Data are means of 10 hills of rice plants from each block.

Table 2
Concentrations of copper in the soils of various blocks
Concentration NWIS WIS-1 WIS-2
Range Mean Range Mean Range Mean
C (mg Cu/kg) 17.0±18.8 17.6 ‹ 1.0 19.6±31.5 28.2 ‹ 6.7 66.8±101.2 90.6 ‹ 12.9
CWIS /CNWIS 1.6 5.1
C/BGa 0.8 1.3 4.1
a
Copper background value in Jiangsu soil was 22.3 mg Cu/kg (NEPA, 1990).
 Z.H. Cao, Z.Y. Hu / Chemosphere 41 (2000) 3±6 5

Table 3
Concentrations of copper in rice plants at the tiller stagea
Blocks NWIS WIS-1 WIS-2
Range Mean Range Mean Range Mean
C (mg Cu/kg) 11.8±13.6 12.7 ‹ 2.8 34.2±64.3 44.9 ‹ 17.3 101.4±226.5 159.0 ‹ 60.7
CWIS /CNWIS 3.5 12.5
a
Data are means of ten hills of rice plants from each block.

Table 4
Concentrations of copper in rice plants at the harvest stagea
Rice plant NWIS WIS-1 WIS-2
b
Brown rice C (mg Cu/kg) 1.4 ‹ 0.2 (1.1±1.6) 6.4 ‹ 2.7 (4.4±11.2) 15.5 ‹ 3.7(12.9±18.2)
CWIS /CNWIS / 4.6 11.1
C/BGc 0.4 1.8 4.4
Rice hull C (mg Cu/kg) 73 ‹ 1.7 (5.9±9.1) 26.8 ‹ 10.1 (9.0±32.2) 133.2 ‹ 26.4 (114.5±151.9)
CWIS /CNWIS / 3.7 18.3
Rice straw C (mg Cu/kg) 14.5 ‹ 2.5 (11.8±14.5) 33.9 ‹ 6.9 (27.8±40.0) 101.4 ‹ 46.7 (68.3±134.4)
CWIS /CNWIS / 2.3 9.3
a
Data are means of ten hills of rice plants from each block.
b
Data in parentheses were the range of Cu content.
c
BG: Background concentration of Cu in brown rice at the study area (NEPA, 1990; Chen, 1996).

respectively. The Cu contents of the rice plants from

each block at harvest stage are shown in Table 4. The
mean contents of Cu in brown rice from WIS-1 and
WIS-2 were 4.6 and 11.1 times higher than those from
NWIS, respectively; and were 1.8 and 4.4 folds higher
than the Cu background value of rice grown in study
area. The mean concentrations of Cu in rice hull from
WIS-1 and WIS-2 were 3.7 and 18.3 times higher than
those from NWIS, respectively; and the mean contents
of Cu in rice straw from WIS-1 and WIS-2 were 2.3 and Fig. 2. Correlationship between soil and rice plant Cu
9.3 folds higher than those from NWIS, respectively. concentration at the tiller stage.
Since the brown rice, rice hull and rice straw from WIS-2
were severely contamination by Cu, they should not be
used as food and feed.
According to Table 4, Cu in the rice plants grown in
NWIS was mainly accumulated in the rice straw, and
then in the rice hull; when compared with the rice grown
in WIS, where Cu was mainly accumulated in the rice
hull, rather than in rice straw. These results are partly
agree with the results reported by Lidon and Henriques,
(1993), and Abuzid and Obukhov, (1992), their experi-
ments indicated the Cu was accumulated in roots and
shoots of plants.
Fig. 3. Relationship between Cu concentrations of soils and
3.3. Correlation between copper concentration of rice rice plants at the harvest stage.
plants and soils

Correlation analysis indicated that the Cu concen- and Cu concentration in the rice straw and hull at the
tration of rice plants at tiller stage showed a statistically harvest stage also showed a exponential relationship
signi®cant exponential relationship with the total Cu with the total Cu concentration in the soils (R2 ˆ 0.921
concentration in the soils (R2 ˆ 0.9574, P<0.01) (Fig. 2), and 0.831 respectively, P<0.01) (Fig. 3). However, Cu
6 Z.H. Cao, Z.Y. Hu / Chemosphere 41 (2000) 3±6
Table 5
Rice grain yielda
Block Yield (t/ha) % 1. The Cu concentration in the soils increased from
NWIS 8.61 ‹ 0.5 100
WIS-1 7.09 ‹ 0.4 82
WIS-2 6.44 ‹ 0.2 75
a
Data are means of 2M2 samples of 3 replicates from each
block.
concentration of brown rice at the harvest stage showed
a linear relationship with the total Cu concentration in
the soils (R2 ˆ 0.8384, P<0.01) (Fig. 3).
3.4. Rice grain yield
According to the measurement of rice plants from
2M2 samples, the e€ective ears of rice grown in WIS-2
and WIS-1 were only 68% and 81% of those grown in
NWIS, respectively; while the heights of rice plants
grown in WIS-2 and WIS-1 were 70% and 84% of those
grown in NWIS, respectively. Therefore, the rice grain
yields grown in WIS decreased by 18±25% compared
with those in NWIS (Table 5).
4. Discussion
Two factories (CuSO4 factory and cooper ingot fac-
tory) were responsible for Cu-rich wastewater in the
study area, although only the wastewater discharged
from the CuSO4 factory was much higher than the
permitted standard for wastewater irrigation. Over the
past ten years, wastewater from the CuSO4 factory was
directly drained into canals and then into the lower
reaches of the study site. Due to dilution, the Cu con-
centration decreased signi®cantly to only 0.1 mg Cu/l
and Cu polluted soils did not show any problems under
normal weather condition (1200 mm annual precipita-
tion). However, during March±May 1997, the extremely
dry weather caused the canal water ¯owed backward
due to continuous water pumping form the upper
reaches for irrigation. The wastewater discharged from
the CuSO4 factory was not well diluted before irrigation,
and was even pumped directly into the paddy ®eld.
Therefore, the copper pollution resulted from the acci-
dental use of Cu-rich water for irrigation.
The critical Cu concentration in plants showing Cu
toxicity is 20 mg Cu/kg (Liu, 1996). The concentrations
of Cu in the rice plants grown in WIS-1 and WIS-2 were
well above the critical value (Table 4). This suggested
that the abnormal rice growth was due to direct acute
Cu toxicity.
5. Conclusion
17.0 mg Cu/kg in non-wastewater irrigated ®eld to
101.2 mg Cu/kg in the wastewater (12 mg Cu/l) irri-
gated ®elds.
2. Copper accumulated mainly in the surface soil layer
(0±10 cm) due to Cu-rich wastewater irrigation.
3. The Cu contents of rice straw and rice hull exponen-
tially related to the total Cu contents in soils
(R2 ˆ 0.921 and 0.831 respectively, P<0.01).
4. About 18±25% of rice yield decrement were caused by
Cu pollution derived from wastewater irrigation.
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