Total Cd concentration digested by aqua regia: Cd-CK = 0.43±0.15 mg Cd kg-1; Cd-10 = 9.73±0.05 mg Cd kg-1; Cd-20 = 17.6±0.8 mg Cd kg-1# means ± standard deviation (n = 3); ND: not detectable; The different small letters within same column of same plant tissue stand for statistical significance (
1. Introduction
Heavy metals (HMs) in soils primarily result from the weathering of parent materials and from human activities, which including mining, smelting, application of sludges, and discharge of wastewaters, etc. (Kabata-Pendias & Pendias, 2001). Soil contaminated with HMs has become a worldwide problem and pose a serious threat to the environment (Anwar et al., 2009), leading to losses in agricultural yield and hazardous health effects as they enter the food chain (Salt et al., 1995). Cropping lands contaminated by HMs were mostly resulted from the use of polluted irrigated water in the downstream of discharged water of industrial parks of Taiwan. In 2007, approximate 400 ha of rural soils in Taiwan were contaminated with single or combined HMs and they are fallow according to Soil and Groundwater Pollution Remediation Act (SGWPR Act) announced in 2000 by Taiwan Environmental Protection Administration (Taiwan EPA). There were many techniques been used to treat the HMs-contaminated soils which including isolation, mechanical separation, chemical treatment, electrokinetics, soil washing, and phytoremediation (Mulligan et al., 2001). Various soil amendments were applied to the HMs-contaminated soils to reduce the mobility of HMs in the contaminated soils and thus to decrease their further uptake by crops (Chen & Lee, 1997; Kabata-Pendias and Pendias, 2001; Lee et al., 2004; Mench et al., 1994).
In Taiwan, most of these contaminated sites were restored with turnover/dilution and acid washing methods to reduce the total concentration of HM to conform the regulation announced. Besides the two techniques, phytoremediation was demonstrated to be a feasible method in treating these contaminated lands, which have large areas and low to medium level of HM concentration (Lai et al., 2005). It also accompanies with other environmental agenda, such as biomass energy, biodiversity, carbon sequestration, and soil quality (Dickinson et al., 2009). However, most hyperaccumulators used in removing these HMs have lower biomass and growing rate and thus extending the period needed in decontamination. The application of chemical agents has significant effect on increasing the phytoavailability and accumulation of HMs of plants (Chen & Cutright, 2001; Meers et al., 2004; Meers et al., 2005). However, results of most previous studies showed that chemical agents have negative effect on the growth of Indian mustard, sunflower, or corn and thus decreased the total removal of HMs by plants (Blaylock et al., 2007; Madrid et al., 2003; Turgut et al., 2004). After the application of chemical chelating agents, the risk of groundwater contamination may be increased because the mobility of HMs increased (Jiang et al., 2003; Lai & Chen, 2004; Lai et al., 2005). For those lands with sandy texture or high level of groundwater table, chemical agents should be carefully applied to decrease the health risk of groundwater quality (Lai & Chen, 2006; Wu et al., 2004).
Rice dominates the daily intake of cereals in most Asian countries. In Taiwan, about half of arable land is used as rice-growing field and two rice varieties including Indica and Japonica varieties are cultivated, but the latter is the major one (90%) because of taste preferences. Cadmium (Cd), normally occurs in low concentrations in soils (Wagner, 1993), is a non-essential element for plants and potentially toxic pollutant all over the world. The toxicity of Cd to plant growth, phytosynthesis, carbonhydrate metabolism, and enzyme activities is well documented (Javed & Greger, 2011; Sanita di Toppi & Gabrielli, 1999). Elevated levels of arsenic (As) in soils may potentially enter food chain (Meharg & Hartley-Whitaker, 2002) and increase the risk of cancer development (Anderson et al., 2011). According to the SGWPR Act, the cropping land with total soil Cd concentration (aqua regia soluble) exceeding 5 mg kg-1 will be announced as Soil Pollution Control Site (SPCS) and all farming activities are not allowed. However, many previous field surveys showed Cd-contaminated rice can still be produced from fields with total soil Cd levels lower than 5 mg kg-1. The Standard for the Tolerance of Cd in rice has been reduced from 0.5 mg kg-1 to 0.4 mg kg-1 in 2007. Many studies were also subsidized by governments to assess the food safety of rice cultivated in Cd-contaminated soil. In this paper, we reviewed some previous researches regarding the accumulation of Cd and As of different rice varieties. Its safety after growing in As- or Cd-contaminated soils was also evaluated. For those contaminated lands not suitable for planting crops, the use of phytoremediation and planting non-edible plants may be a candidate for solving this problem. Experimental results of phytoremediation were also illustrated in this paper.
2. Phytoremediation for potted Cd-contaminated soils
The selection of suitable plants is the first and the critical step in conducting a successful phytoremediation. These plants should grow well and accumulate higher concentration of HMs in the harvestable parts when growing in HM-contaminated soils. There were approximately 420 species of plants that can be regarded as hyperaccumulators (Baker et al., 2000). A pot experiment was conducted to test the accumulation capacity of five garden flower species, which was regard as a potential hyperaccumulator previously (Chen & Lee, 1997). Seedlings of them were planted in the artificially Cd-contaminated loamy soils to assess their Cd accumulation when growing in control (Cd-CK) (0.43±0.15 mg kg-l), Cd-10 (9.73±0.05 mg kg-l), and Cd-20 (17.6±0.8 mg kg-l) (Lin et al., 2010). One seedling of Star cluster (
The Cd concentrations in initial seedlings of five plants were not detectable (Cd < 0.38 mg kg-1). After growing in the artificially Cd-contaminated soils for 35 days, five tested plants can significantly accumulate much higher Cd concentrations in their shoots relative to Cd-CK. Among the five plants, Impatiens grown in the Cd-20 treatment had the highest shoot Cd concentration near 100±11 mg kg-1, which was more than the threshold of a Cd hyperaccumulator (100 mg kg-l) reported (Baker et al., 2000). French marigold grown in Cd-10 and Cd-20 treatments accumulated 44.9±0.7 and 66.3±6.5 mg kg-l in their shoots and no toxic symptoms were observed in the appearance during pot experiment. Chen & Lee (1997) reported that Star cluster, Scarlet sage, and Impatiens can accumulate 44, 12, and 42 mg kg-1, respectively, in their leaves when
Besides the accumulated concentration, bioconcentration factor (BCF = shoot HM concentration/soil HM concentration) and translocation factor (TF = shoot HM concentration/root HM concentration) were two indexes most used to evaluate the accumulating capacity of HMs by plants. For a Cd hyperaccumulator (Baker et al., 2000; Mattina et al., 2003), the BCF and TF should more than one besides the high concentration accumulated (100 mg kg-1) (Sun et al., 2009). Experimental result of this study showed that the BCF values of French marigold, Impatiens, Garden verbena, and Scarlet sage were all more than one and ranged from 1.75 to 5.68 (Table 1). However, Impatiens was the only one that its TF was in the levels of 1.01-1.66. According to the standards summarized by Sun et al. (2009) for a Cd hyperaccumulator, Impatiens was a potential Cd hyperaccumulator when growing in the artificially Cd-contaminated soils. The pot experimental result was against with the in-situ selection experiment, possible resulted from the special variation and interaction of HMs in the field.
The total removal of Cd by plants determines the duration needed in decontamination. Although root of plants accumulated higher concentration of Cd in compartment with shoot, the total removal of Cd by shoot was larger because of its larger biomass (Fig. 1). Among the five tested plants, the shoots of French marigold and Impatiens removed 380-510 and 790-820 g Cd plant-1 from Cd-10 and Cd-20. One can calculate the period needed for phytoremediation in an ideal situation, i.e. if the removal of plants of each harvest is a constant and the phytoavailability of Cd will not change with time, etc. It will take approximately 4.6-8.0 years for continuous planting (six times year-1) French marigold and Impatiens to decrease the current Cd concentration (Cd-10 and Cd-20) to below the SPCS for cropping lands (5 mg kg-1). The major drawback of phytoremediation is that it always consumes longer period compared with other techniques. Experimental results show that planting French marigold and Impatiens in Cd-contaminated soils seems to be a feasible method to remove Cd from contaminated soil and the period needed for decontamination is acceptable.
Plants | Treatments* | Shoot | Root | BCF | TF | |||
------------ mg kg-1 ------------ | ||||||||
Star cluster | Cd-CK | ND b | ND a | ---- | ---- | |||
Cd-10 | 8.20±0.94 a# | 22.7±2.02 a | 0.84 | 0.36 | ||||
Cd-20 | 10.7±2.8 a | 18.9±17.2 a | 0.61 | 0.57 | ||||
French marigold | Cd-CK | ND c | ND c | ---- | ---- | |||
Cd-10 | 44.9±0.7 b | 65.0±17.8 b | 4.61 | 0.69 | ||||
Cd-20 | 66.3±6.5 a | 113±21 a | 3.77 | 0.59 | ||||
Impatiens | Cd-CK | ND c | ND b | ---- | ---- | |||
Cd-10 | 48.9±11.7 b | 29.5±9.6 ab | 5.02 | 1.66 | ||||
Cd-20 | 100±11 a | 99.0±8.4 a | 5.68 | 1.01 | ||||
Garden verbena | Cd-CK | ND b | ND b | ---- | ---- | |||
Cd-10 | 21.5±5.5 a | 39.3±13.5 a | 2.21 | 0.55 | ||||
Cd-20 | 7.63±1.75 b | 49.5±11.2 a | 0.43 | 0.15 | ||||
Scarlet sage | Cd-CK | ND b | ND c | ---- | ---- | |||
Cd-10 | 21.8±7.6 a | 45.9±8.2 b | 2.24 | 0.47 | ||||
Cd-20 | 30.8±5.3 a | 71.0±15.5 a | 1.75 | 0.43 |
3. Phytoremediation for Cr, Cu, Ni, and Zn-contaminated soils
Eight blocks (11 m by 4 m) located in central Taiwan (Fig. 2), which were relatively higher in Cr (chromium), Cu (copper), Ni (nickel), and Zn (zinc) concentrations were used for
After
No. | Plant species | Scientific name | Property |
1 | Bougainvillea |
|
woody |
2 | Rainbow pink |
|
herbaceous |
3 | Serissa |
|
woody |
4 | French marigold |
|
herbaceous |
5 | Rose of Shoron |
|
woody |
6 | Water willow |
|
woody |
7 | Chinese ixora |
|
woody |
8 | Sunflower |
|
herbaceous |
9 | Chinese hibiscus |
|
woody |
10 | Gold dewdrop |
|
woody |
11 | Kalanchoe |
|
herbaceous |
12 | Creeping Trilobata |
|
herbaceous |
13 | Garden Canna |
|
herbaceous |
14 | Garden verbena |
|
herbaceous |
15 | Malabar chestnut |
|
woody |
16 | Purslane |
|
herbaceous |
17 | Common Lantana |
|
woody |
18 | Fancy leaf caladium |
|
herbaceous |
19 | Coleus |
|
herbaceous |
20 | Golden trumpet |
|
woody |
21 | Common melastoma |
|
woody |
22 | Carland flower |
|
herbaceous |
23 | Manaca raintree |
|
woody |
24 | Yellow Cosmos |
|
herbaceous |
25 | Sliver apricot |
|
woody |
26 | Temple tree |
|
herbaceous |
27 | Orchid tree |
|
woody |
28 | Star cluster |
|
herbaceous |
29 | Blue daza |
|
herbaceous |
30 | Cockscomb |
|
herbaceous |
31 | Scandent Schefflera |
|
woody |
32 | Bojers spurge |
|
woody |
33 | Croton |
|
woody |
For Cu, the accumulation capacity of various tested plants was in the order of Cockscomb (117±40 mg kg-1), Garden verbena (84.7±46.6 mg kg-1), and Star cluster (80.4±80.6 mg kg-1). The average Cu concentration of corn and food grains of China was 2.67 and 6.46 mg kg-1 (Chen et al., 1994) and the Cu concentration for foodstuff crops was less than 10 mg kg-1 (Kabata-Pendias & Pendias, 2001). The Cu concentration in the brown rice of Japan and Indonesia was 2.16-4.4, 2.9, and 3.41 mg kg-1, respectively (Iimura, 1981; Masironi, 1977; Suzuki et al., 1980). Although the accumulated Cu concentration of these 33 plants increased after 33 days, the BCF were less than 1.1 because the surface soil has low Cu concentration, ranged from 112 to 122 mg kg-1. Because of the low Ni concentration in the initial plants, the Ni concentration of shoot in the 33 plants increased after
Experimental results also show that the accumulation of HMs of woody and herbaceous plants after growing for 33 days was quite different (Table 2). Similar to the results of Chen & Lee (1997), herbaceous plants have accumulated higher concentration of HMs in comparison to woody plants. Except for the low Ni concentration in initial plants, the increase for HMs concentration in woody plants was about 3.1±2.9 fold for Cu, 2.5±1.5 fold for Cr, and 4.3±3.1 fold for Zn, respectively. Herbaceous plants have higher uptake of HMs in relative to woody plants and their increase on the concentration of HMs are 9.4±6.5 fold for Cu, 5.1±2.7 fold for Cr, and 8.9±6.1 fold for Zn.
4. Large area phytoremediation experiments of 12 plant species in HMs-contaminated site
Twelve plants species (Table 3) were selected from 33 plant species testing in a site contaminated by combined HMs in central Taiwan (Fig. 2) to study the feasibility of
Results of two times of large area experiments after foregoing 12 plant species were growing for one month and two months showed that they can grow well in this combined HMs-contaminated site. The concentrations of Cr, Cu, Ni, and Zn in the shoots increased after growing for 31 days compared with those of it before planting. The extension of their time of growth, from one month to two months in the contaminated site, has positive effects on increasing their accumulation of HMs. However, the 12 tested plant species could not accumulated higher concentrations of Cr, Cu, Ni, and Zn possibly resulted from the lower concentrations of foregoing HMs. None of the plant species can regard as a hyperaccumulator according to the definition of Baker et al. (2000). After
No. | Plant species | Scientific name | Property |
1 | Chinese ixora |
|
woody |
2 | Garden verbena |
|
herbaceous |
3 | Rainbow pink |
|
herbaceous |
4 | Bojers spurge |
|
woody |
7 | Kalanchoe |
|
herbaceous |
5 | Scandent Scheffera |
|
woody |
6 | Purslane |
|
herbaceous |
7 | Croton |
|
woody |
8 | Serissa |
|
woody |
9 | Garden Canna |
|
herbaceous |
11 | French marigold |
|
herbaceous |
12 | Sunflower |
|
herbaceous |
Plant species | Translocation factor (TF)# | |||
Cr | Cu | Ni | Zn | |
Chinese ixora | 0.41 | 1.28 | 0.22 | 1.40 |
Garden verbena | 0.35 | 0.64 | 0.33 | 2.13 |
Rainbow pink | 0.58 | 0.78 | 0.89 | 1.17 |
Bojers spurge | 0.84 | 1.44 | 0.75 | 1.98 |
Kalanchoe | 0.15 | 1.31 | 0.28 | -- |
Scandent Scheffera | 0.07 | 0.84 | 0.61 | -- |
Purslane | 5.06 | 0.84 | 0.68 | 0.72 |
Croton | 0.05 | 0.38 | 0.25 | -- |
Serissa | 0.40 | 0.90 | 0.57 | -- |
Garden Canna | 0.61 | 0.54 | 0.43 | 1.35 |
French marigold | 0.18 | 0.56 | 0.30 | -- |
Sunflower | 0.21 | 1.39 | 0.41 | 3.15 |
The median and maximum concentrations of Cr, Cu, Ni, and Zn in the topsoil were used in this study to calculate the mean and maximum effect of contaminants. The exposure risk was resulting from the ingestion of contaminated soils (EXPing), inhalation of air containing contaminated soil particles (EXPinh), and absorption by skin (EXPabs). Different equations were used to calculate the carcinogenic and non-carcinogenic risks of contaminants to the health of humans (Lai et al., 2011). Where HQ is the hazard quotient and EXPtotal is the sum of total exposure. There are carcinogenic and non-carcinogenic risks when the values of HQ and TR are less than unitary and 10−6, respectively. The concentrations of Cr, Cu, Ni, and Zn in the topsoil after phytoremediation were estimated by considering the removal of plants. The results showed that although the study site was contaminated with combined HMs, there are no carcinogenic and non-carcinogenic risks (Tables 5 and 6) although some of the total concentrations of Cr, Cu, Ni, and Zn were higher than the SPMSs or SPCSs.
Zn | Cr | Cu | Ni | |||||||||
Med. | Max. | Med. | Max. | Med. | Max. | Med. | Max. | |||||
Before phytoremediation | ||||||||||||
EXPinh | 5.9×10−6 | 1.1×10−5 | 1.4×10−6 | 3.5×10−6 | 1.5×10−6 | 2.1×10−6 | 3.7×10−6 | 7.0×10−6 | ||||
EXPing | 2.7×10−4 | 5.2×10−4 | 6.5×10−5 | 1.6×10−4 | 7.1×10−5 | 9.6×10−5 | 1.7×10−4 | 3.2×10−4 | ||||
EXPabs | 4.7×10−5 | 8.9×10−5 | 1.1×10−5 | 2.8×10−5 | 1.2×10−5 | 1.6×10−5 | 3.0×10−5 | 5.6×10−5 | ||||
HQ | 1.0×10−3 | 2.0×10−3 | 2.5×10−2 | 6.2×10−2 | 3.0×10−3 | 4.1×10−3 | 9.8×10−3 | 1.9×10−2 | ||||
After phytoremediation | ||||||||||||
EXPinh | 5.8×10-6 | 1.1×10-6 | 1.4×10-6 | 3.5×10-6 | 1.5×10-6 | 2.0×10-6 | 3.7×10-6 | 7.0×10-6 | ||||
EXPing | 2.6×10-4 | 5.1×10-4 | 6.4×10-5 | 1.6×10-4 | 7.0×10-5 | 9.5×10-5 | 1.7×10-4 | 3.2×10-4 | ||||
EXPabs | 4.5×10-5 | 8.8×10-5 | 1.1×10-5 | 2.8×10-5 | 1.2×10-5 | 1.6×10-5 | 2.9×10-5 | 5.5×10-5 | ||||
HQ | 1.0×10-3 | 1.9×10-3 | 2.4×10-2 | 6.1×10-2 | 2.9×10-3 | 4.0×10-3 | 9.7×10-3 | 1.8×10-2 |
Cr | Ni | |||
Med. | Max. | Med. | Max. | |
Before phytoremediation | ||||
EXPinh
|
2.1×10−8 | 5.1×10−8 | 5.3×10−8 | 1.0×10−7 |
TR | 7.0×10−7 | 1.8×10−6 | 3.7×10−8 | 7.0×10−8 |
After phytoremediation | ||||
EXPinh
|
2.0×10-8 | 5.0×10-8 | 5.3×10-8 | 1.0×10-7 |
TR | 6.9×10-7 | 1.7×10-6 | 3.7×10-8 | 7.0×10-8 |
5. Uptake characteristics of different rice varieties growing in Cd-contaminated soils
In 2005 and 2006, field studies were conducted in Taiwan to investigate the uptake characteristics of rice varieties growing in 19 different paddy fields in three counties across the western plains in Taiwan (Römkens et al., 2009). The studied fields were located at the towns of Chang-hua (three fields), Ho-Mei (three fields), Lu-Kang (two fields), Hsin-Chu (three fields), and Pa-Deh (eight fields) (Fig. 3). Twelve rice cultivars of Indica or Japonica varieties were planted in each field with 5-9 replicates for each cultivar depends on the field size. Samples of topsoil (0-25 cm) and rice plants at full maturity were collected together at the same location in studied fields in May (harvest 1) and November (harvest 2) of the two years. Total numbers of soil and rice plant samples in this study were both 3,198. The total soil Cd concentration in studied fields ranged from 0.06 mg kg-1 to as high as 27.8 mg kg-1, the maximum level is about 6-fold higher than the SPCS (5 mg kg-1) enacted in Taiwan. Around 27% of the studied field area was defined as Cd-contaminated soil according to the SGWPR Act.
Soil pH, CEC (Cation Exchange Capacity), and soil organic matter (SOM) varied widely in the 19 paddy fields (Table 7). Cadmium concentrations in rice grains were quite different among cultivars even though they were planted in soils with comparable soil properties and total soil Cd levels. Overall, median Cd concentrations in rice grains of Indica variety were 2-3 times higher than that of Japonica variety no matter the rice is planted in low or high Cd-contaminated fields or in different climates (Fig. 4). Higher variation was found in the concentration of Cd in Indica brown rice compared with that in Japonica brown rice. Some studies also found that Cd accumulation in brown rice of Indica was 1.54 times higher than that of Japonica. This uptake characteristic of rice varieties is important for selecting rice cultivars with low Cd accumulating ability in rice grain planted in slightly Cd-contaminated soil.
pH | CEC (cmol+ kg-1) | SOM (%) | Total Cd (mg kg-1) | |
Japonica | 3.8-7.2 | 2.6-24.2 | 1.4-9.5 | 0.06-27.8 |
Indica | 4.1-7.0 | 2.6-25.1 | 1.3-10.2 | 0.08-25.9 |
Liu et al. (2007) reported that Cd was not evenly distributed in different parts of rice grain. The results of their pot experiments planting six rice cultivars (include Indica, Japonica, hybrid Indica, and New Plant type) in artificially Cd-contaminated soil showed that the average percentage of Cd quantity accumulated in chaff, cortex (embryo), and polished rice were about 15%, 40%, and 45%, respectively. The cortex occupied only 9% of the grain dry weight in average but the polished rice occupied 71%, so Cd concentration in cortex is significantly higher than that in polished rice. They suggested that polished rice produced from Cd-contaminated fields may be safer for consumers than brown rice. However, Moriyama et al. (2003) reported that Cd concentration in six Japonica rice cultivars reduced only 3% in average after milling process. A study using
6. Various Cd uptake models were used to efficiently predict their accumulation
Total Cd concentration in soil is not a reliable index to determine whether rice grain is safe for consumers. Rice varieties and soil characteristics such as soil pH, Eh (redox potential), CEC, texture, and SOM are important factors affecting Cd concentration in rice grain. To determine whether a rice-growing field can produce safe rice grains with Cd levels lower than FQS (food quality standard), it is necessary to develop a simple and reliable soil tests to predict available Cd concentration in rice grains.
Previous studies indicated that 0.01M CaCl2, 0.1M HCl, 0.43M HNO3, and 0.05M EDTA (Na2-EDTA 2H2O) are ideal extractants to estimate soil available Cd concentration (Houba et al., 1997; Nelson et al., 1959; Tiwari & Kumar, 1982). This study compared these methods to assess which method is better for predicting Cd levels in rice grains. The best well-performed regression equation to predict Cd levels in rice grain was presented here using soil available Cd and Zn concentrations determined by 0.01M CaCl2:
The CaCl2 extractable Zn is also included in the equation because it is able to compete with Cd for plant uptake and reduce toxic effects of Cd. The critical concentrations of CaCl2-extractable Cd in soil under different levels of soil CaCl2-extractable Zn are constructed for farmers and authorities in Taiwan to prevent the production of Cd-contaminated rice by using above equations.
The concentration of CaCl2-extractable Zn in soil ranged usually from 0.1 to 50 mg kg-1 when the total soil Zn concentration is less than 600 mg kg-1, the SPCS for cropping lands enacted in Taiwan. According to the equations, less Cd will be accumulated in rice grain if the soil CaCl2-extractable Zn is getting higher, therefore, only the critical concentrations of CaCl2-extractable Cd in soil under the soil CaCl2-extractable Zn lower than 50 mg kg-1 are presented. If the measured soil CaCl2-extractable Cd is higher than the critical value, it is possible to produce rice grain with Cd concentration exceeding the Standard for the Tolerance of Cd in rice (0.4 mg kg-1) (Table 8). Further studies are required to validate the practicability of regression equations.
Rice variety | CaCl2-extractable Zn in soil (mg kg-1) | |||||||
Indica | 0.007 | 0.019 | 0.035 | 0.046 | 0.060 | 0.071 | 0.079 | 0.086 |
Japonica | 0.027 | 0.060 | 0.105 | 0.133 | 0.168 | 0.193 | 0.213 | 0.230 |
To predict Cd concentration in rice grain, Simmons et al. (2008) also developed a regression equation using soil pH (1:5) and CaCl2 extractable Cd determined on field-moist samples collected during the grain-filling period. The equation can predict Cd concentrations in unpolished rice grain with an r2 value of 0.638. If air-dried soil samples were used for Cd–CaCl2 and pH determination, the regression equation cannot explain the variability of Cd levels in rice grain. Air-drying may affect soil sample conditions to an extent that CaCl2 extractable Cd cannot represent Cd availability in soil compared to extracts collected from field-moist soil. However, the soil samples used for developing regression equations in the study of Taiwan as mentioned above were air-dried and collected during rice harvest period, an easier pretreatment for soil samples and more suitable for routine monitoring.
Brus et al. (2009) recently developed a multiple regression model using 0.43M HNO3 extractable Cd, pH, clay, and SOM as predictors to predict Cd levels in rice grain harvested form the paddy fields in Fuyang, Zhejiang province, China. The model performed much better (r2 adj = 0.661) than the linear model using only 0.01M CaCl2 extractable Cd as a predictor (r2 adj = 0.281). The field study in Taiwan as mentioned above also developed a multiple regression model using 0.43M HNO3 extractable Cd, pH, and CEC to predict Cd levels in rice grain. Although the model using more predictors to reflect the effects of pH and CEC on the availability of Cd, it did not perform much better (r2 = 0.81 and 0.74 for Japonica and Indica, respectively) than the model using 0.01M CaCl2 extractable Cd and Zn as predictors (r2 = 0.86 and 0.73 for Japonica and Indica, respectively). Therefore, the latter simpler model is preferred to be validated and used in Taiwan. Since different environmental and soil factors affect the accumulation of Cd in rice grain in different ways and extents, the predicting models developed by using local data will be more reliable to be used for the specific area.
7. As-contaminated soils in Guandu plain
Arsenic is a contaminant of public concern since it is highly toxic and carcinogenic. It may be accumulated in plants and eventually be transferred to humans through the food chain. A regular monitoring for HM concentrations in soil conducted by Taipei government found that some soil samples in Guandu Plain were contaminated by As. Further comprehensive survey conducted in 2006 showed that more than 60 ha of rice-growing soils located in that area were contaminated by As. The maximum As concentration in topsoil (0-15 cm) reached 535 mg kg-1 in this area, which was almost 9 times of the SPCS (60 mg kg-1) enacted in Taiwan. The contamination source of As in this area may come from the hot spring water of Thermal Valley. The hot spring water flowed out and mixed with the stream water which was used as irrigation water for the As-contaminated area of the Guandu Plain (Chang et al., 2007). Some studies indicated that the soil parent materials may also contribute to the high levels of As in soils of Guandu Plain (Su & Chen, 2008; Wu, 2007).
Arsenic in soils occurs mainly as inorganic species (Huang, 1994). In well-aerated soils, arsenate (As(V)) is the predominate form, whereas in reduced environment such as paddy soils, arsenite (As(III)) species prevails. Previous studies showed that As(V) in aerated soils will be reduced to more mobile and toxic As(III) in paddy soils and transferred to rice (Huang, 1994; Masscheleyn et al., 1991). Since As(III) is much more toxic, more soluble, and more mobile than As(V), it is a big chance that arsenic in rice-growing soils in Guandu Plain may transfer to rice and reduce rice yield or even impairs food safety. Meharg & Rahman (2003) indicated that As levels of paddy soils in Bangladesh irrigated with As-contaminated groundwater reached only 46 mg kg-1 but the As concentration in rice grains were as high as 1.7 mg kg-1 DW. Liao et al. (2005) also reported high levels of As in rice (0.5-7.5 mg kg-1 DW) grown on As-contaminated soils in China. Whether the rice produced in highly As-contaminated soil in Guandu Plain is safe for human consumption or not is an emergent and important issue of local residents and government agency.
8. Uptake characteristics of two rice varieties growing in highly As-contaminated soils
In 2007, thirteen topsoil (0-15 cm) and rice (
Although total soil As concentrations varied widely from 12.4 to 535 mg kg-1, As concentrations in brown rice were all below 0.35 mg kg-1 DW and no adverse effects were shown on rice growth (Fig. 6). The Standards for the Tolerance of HMs in rice enacted in Taiwan does not include As. According to the statutory limits of As concentration in cereals or food crops constructed in different countries, the rice harvested from the As-contaminated soils in Guandu Plain was still safe for consumers.
Zavala & Duxbury (2007) suggested a global “normal” range of As concentration in rice as 0.08-0.20 mg kg-1, according to the combination of data set (n = 411) from their study and literatures. They also found that As levels in rice produced from Asia were significantly lower than that from U.S. or EU (Table 9). The As concentration in the majority of rice samples from Asia were lower than 0.098 mg kg-1. Compared with their findings, the As levels in rice grain produced in Guandu Plain were higher than the suggested global normal range even though they did not exceed the statutory limits. However, a pot experiment conducted in Taiwan also showed that As concentrations in brown rice ranged from 0.1 mg kg-1 to as high as 0.4 mg kg-1, even the rice was cultivated in soils not seriously contaminated by As (total As < 25 mg kg-1) (Simmons et al., 2008). In the study of Zavala & Duxbury (2007), the rice samples collected from many countries may not be representative of major rice consumption in those countries, it is necessary to conduct a comprehensive survey for As concentrations in different rice cultivars produced in Taiwan to estimate the normal levels of As in rice and compared with the data from Guandu Plain.
Country/Institute | Regulation item | Statutory limit | Reference |
Australia | cereals | 1 mg kg-1 FW | Brus et al., 2009 |
Canada | food crops | 1 mg kg-1 FW | Zandstra & Kryger, 2007 |
China | rice | 0.15 mg kg-1 DW* | URL, 2005 |
New Zealand | cereals | 1 mg kg-1 FW | Brus et al., 2009 |
Switzerland | food crops | 4 mg kg-1 DW | Gulz et al., 2005 |
United Kingdom | food in sale | 1 mg kg-1 FW | Warren et al., 2003 |
Many studies found that the arsenic concentration in rice grain harvested from As-contaminated soil could reach above 0.7 mg kg-1. However, rice produced in Guandu Plain is not apparently affected by As-contaminated soil. The availability of As in soil may be very low. To investigate the distribution of As forms associated with soil solid phases, an As-specific sequential extraction procedure proposed by Wenzel et al. (2001) was conducted for the collected 13 soil samples.
The results showed that relative portions of all As fractions were similar in 13 collected soil samples even the total soil As levels varied widely. The level of non-specifically-bound As in soil samples were all below 0.7% of total arsenic concentration in soils. Since the non-specifically-bound As represented the bioavailable As in soils and correlated well with As concentrations in soil solution collected in fields, the extremely low concentration of this As fraction may explain the facts that arsenic concentration in brown rice cultivated in highly As-contaminated soils of Guandu Plain were all below 0.35 mg kg-1 (Fig. 6) and no adverse effects on rice growth.
Abedin et al. (2002) conducted a pot experiment using As-contaminated irrigation water to grow rice and suggested that As can be readily transferred from root to shoot if As levels in root exceeded the As storage capacity. However, a possible protection mechanism may exist in rice straw and husk to inhibit As accumulation in rice grain because the ratio of As concentration in grain/husk/straw is around 1/10/100 at the highest arsenate treatment (As levels in irrigation water = 8 mg L-1). This suggested that the suppression of As transfer from rice husk to grain may play a key role in reducing As concentration in rice grain. Since the primary As forms in soil environments are As(III) and As(V), As uptake by rice in paddy fields may mostly accumulate in rice roots. These transferring characteristics of As in rice may also contribute to the fact that low As levels in rice grain was found in Guandu Plain.
The amorphous hydrous Fe and Al oxide-bound As was the major fraction in soils (>50% of total As). This suggested that the amorphous materials in soils may play a central role in limiting the availability of arsenic in soils. However, the levels of specifically-bound As were around 10% of total arsenic in soils. Since the total arsenic concentration in some soils were very high and the application of lime materials or phosphorus fertilizer may potentially mobilize the specifically-bound As, further studies on these potential risks to agroecosystems were absolutely required.
Each fraction of arsenic in soil had significant linear relationship with total arsenic concentration in soil. This suggested that a single source of As contamination in Guandu Plain and the soil properties affected As adsorption in this area were similar. A significant linear relationship was found between Alo + 1/2Feo (%) in soil and total soil As concentration (mg kg-1) (r2= 0.89,
9. Conclusion
According to pot experiments and
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