2. Pollution Sources and Survey History of HMs Contaminated Sites in Taiwan
Over 100,000 industrial plants are currently registered in Taiwan, and approximately more than 20% of them undoubtedly produce hazardous wastewater. Taiwan’s government has obtained detailed information regarding solid waste disposal from 18,000 of these plants. Most plants generating wastewater and solid waste are located in more than 90 industrial parks administered by the government. However, about 50% of industrial parks offer a centralized system for wastewater collection and treatment. Approximately 30 wastewater treatment plants operate in the industrial parks, and the treatment capacity of the wastewater from 2,103 factories is 110,000 m
3/day. However, 2,037 factories are responsible for treating their own wastewater (158,000 m
3/day). Nevertheless, factories without registration outside the industrial parks were excluded in the above estimation of wastewater generation. Illegal discharge of swine wastewater caused the accumulation of nutrients (N, P, and soluble salts) and HMs (Cu and Zn) in nearby bodies of water. Paddy fields were consequently contaminated by this wastewater, which ran through the irrigation canal systems. Additionally, about 40% of the rivers in Taiwan have been contaminated by solid wastes and wastewater [
12]. It is estimated that 30 million tons of industrial solid wastes are generated in Taiwan each year. These hazardous wastes comprise 10% of the total.
Rice (
Oryza sativa L.), one of the most important cereal crops in the world, is the staple food in Taiwan. The total paddy field area is approximate 0.4 million ha, which is one-half of agricultural land in Taiwan. However, the paddy fields of Taiwan are threatened by a high potential for contamination. On the other hand, water resources for rice production in Taiwan have been contaminated by the illegal discharge of industrial and livestock wastewater, so that the paddy soil quality and rice safety have been adversely affected by HMs-contaminations [
13,
14]. Paddy fields are characterized by their submergence in water. The irrigation water may be contaminated by the above mentioned source of contamination [
15]. As a result, the paddy soils have been contaminated not only by the HMs, but also by the residual HMs from the wastewater both of which are retained by sediments in the irrigation canal system. Over a long period, the increase of HM levels in the sediments also played a role as a contamination source of paddy soils in addition to the HMs directly transported into the rural soils from wastewater.
3. Exposure Assessment of the Contaminated Sites
Three transmission media that must be considered for calculating the risk of HMs, namely soil, groundwater, and air. The HMs may be ingested by humans from these pathways, which are listed as follows:
3.1. Exposure PATHWAys of Soil Medium
3.1.1. Oral intake [16]
Oral intake of HMs from soil medium can be calculated by the following equation:
Intakeoral-soil: exposure dose of oral intake (mg/kg/day)
Csoil: concentration of concerned pollutant (mg/kg)
IRoral-soil: ingestion rate (mg/day)
EF: exposure frequency (day/year)
ED: exposure period (year)
BW: body weight (kg)
AT: average time (day)
CF: conversion factor (kg/mg)
3.1.2. Dermal intake [17]
Dermal intake of HMs from soil medium can be calculated by the following equation:
Intakedermal-soil: exposure dose of dermal intake (mg/kg/day)
DAevent: exposure dose of each event (mg/cm2)
EV: event frequency (1/day)
SA: skin surface area (cm2)
fsa: ratio of surface of upper arm to body
3.2. Exposure Pathways of Groundwater Medium
3.2.1. Infiltration from soil to groundwater [18]
If the HMs downward moves and enters the groundwater, the consequent risk in groundwater depends on the concentration of HM presented in groundwater. If the concentration of a HM resulted from the downward movement (C
water) is greater than the initial concentration in groundwater (C
i), C
water is used to calculate the risk. The C
i is used on the contrary. For HMs, the C
water can be calculated using the following equation:
Cwater: concentration of concerned pollutant in groundwater (mg/L)
Csoil: concentration of concerned pollutant in soil (mg/kg)
I: infiltration rate (cm/year)
Kd: partition coefficient (cm3-water/g-soil)
W: maximum width between pollution source and groundwater (cm)
Ugw: flow rate of groundwater (cm/year)
ägw: height of mixing layer of groundwater (cm)
3.2.2. Oral intake [16]
Oral intake of HMs from groundwater medium can be calculated by the following equation:
Intakeoral-water: exposure dose of oral intake (mg/kg/day)
Cwater: concentration of concerned pollutant in groundwater (mg/L)
IRoral-water: amount of drinking (L/day)
3.2.3. Dermal intake [17]
Intake resulted from using contaminated groundwater during taking a bath or in regular washing and thus the contact with skin: the intake can be calculated by the following equation for HMs.
Intakedermal-water: exposure dose of dermal intake (mg/kg/day)
DAevent: exposure dose of each event (mg/cm2)
EVshower: frequency of each event (1/day)
3.3. Exposure Pathways of Air Medium [16,19]
Inhalant intake of HMs from air medium can be calculated by the following equation:
Intakeinh-soil: exposure dose of inhalant intake (mg/kg/day)
Cair: concentration of HM in air (mg/m3)
Csoil: concentration of HM in soil (mg/kg)
Pe: particulate emission rate (g/cm2/sec)
W: maximum width of HM-contaminated site parallel with the wind (cm)
Uair: wind speed above the HM-contaminated site (cm/sec)
3.4. Exposure of HM via Rice
Because HMs are absorbed by humans through the food chain from edible crops grown in contaminated soils, the concentrations of HMs in brown rice may be a critical problem for food safety herein. Rice is the staple food for daily consumption in Taiwan. Exposure via rice is therefore an important concern in the health of the population. The estimated daily intake (mg/kg/day BW) of HMs via rice consumption can be calculated as:
where C
on (g/person/day) is the daily average consumption of brown rice in Taiwan, C (mg/kg) is the concentration of HMs in the contaminated rice, ED is exposure duration (70 years, equivalent to the average life), EF is exposure frequency (365 days/year), BW (kg/person) represents body weight, and AT is average time (365 days year/number of exposure years, assuming 70 years in this study). The average daily brown rice intake of adults and children was considered to be 100 and 50 g/person/day, respectively, and average adult and child body weights were considered to be 65 and 30 kg, respectively.
The regulation for Cd in brown rice in Taiwan is 0.4 mg/kg, while the upper limit of background Cd contents of representative rural soil is 3 mg/kg. If the total soil Cd content is higher than 5 mg/kg, most of the corresponding brown and polished rice is considered as Cd-contaminated rice [
2].
Various rice cultivars have been cultivated in 19 Cd-contaminated paddy fields in Taiwan to evaluate the uptake of Cd [
14]. The total soil Cd concentrations ranged from <0.1 mg/kg to almost 30 mg/kg, that is, background levels to heavily Cd-contaminated soils, respectively. In each field, 12 rice cultivars of Indica and Japonica varieties were planted on plots for each cultivar. The Cd concentrations in rice grains were quite different among rice varieties. The Indica species accumulated high concentrations of Cd in their rice grains [
14]. For all Indica species, median levels of Cd in the rice grains exceeded the food quality standard (FQS) in the EU (0.2 mg/kg) as well as the FQS used in the WHO, Japan, and Taiwan (0.4 mg/kg). However, the Indica species was not suitable for cropping on paddy soils contaminated with Cd [
20]. Cadmium contents in the rice grains of the Japonica species are lower than those of Indica species, although median Cd grain levels are close to or in excess of FQS in the EU. Even the total soil Cd levels below 0.3 mg/kg, a large number of rice grain samples of Indica and Japonica varieties did not meet the FQS. For Indica varieties, the percentage of samples in which Cd levels exceeded the FQS of 0.2 or 0.4 mg/kg was 51.1% and 11.3%, respectively. Hence, Indica varieties cannot be grown safely in Cd enriched soils without a considerable risk of exceeding the FQS in the EU. Moreover, the WHO set the provisional tolerable weekly intake of Cd for adult persons at 7 ìg/kg body weight/week [
21], which means that the daily exposure via the abovementioned contaminated rice, will pose a serious risk for human health based on the calculation of
Equation 9 in this paper.
The SCS of Cd (5 mg/kg) with
aqua regia measurement for total analysis in the SGWPR Act in Taiwan was found unsuitable to assess the suitability or food safety for rice production. When the total soil Cd concentrations were below 5 mg/kg, 30% and 17 % of the grain samples of Japonica varieties did not meet the FQS of 0.2 and 0.4 mg/kg, respectively. For Indica varieties, these percentages increased to 41% for 0.4 mg/kg FQS to 73% for 0.2 mg/kg FQS [
14]. These results clearly stressed the need to develop alternative soil testing methods or soil–plant uptake models to predict Cd uptake by rice grains in order to identify soils where rice can be grown safely [
22].
3.5. Case Study of Exposure Assessment on HMs in Brown Rice of Different Varieties
The above case showed that the quality of rice did not meet the FQSs, which has affected consumer faith regarding the quality of rice. Many examples stress the need to predict the availability of HMs in soils in order to estimate the risk related to its uptake by crops. Due to differences in soil characteristics and pollutants in soil, the degree of availability is different, which has resulted in a wide range of soil quality standards.
Soil pH has a major influence on the availability of HMs that present predominantly as cations (Cu
2+, Co
2+, and Pb
2+). Under acid conditions, sorption of HM cations by soil colloids is at a minimum, and the solution concentrations are relatively high. There is a relationship between the concentrations of HMs in the soil solution (HM
solution) and those in the rice (HM
rice). This relationship can be described in
Equation 10.
The values of á
1 and â
2 can be derived from experimental data by linear regression after log transformation of the data. However, the concentration in soil solution is difficult to determine, so usually the total HM content was determined. There is a good relationship between soil properties and the HM content in the soil (HM
soil) and the concentration in the soil solution (HM
solution) [
13]. If soil data of organic matter (OM), clay (the percentage <2 μm), and pH are available, these data can also be used to predict the uptake of HMs by rice.
The values of á
2, â
2, ã
1, ä
1, and å
1 can be derived from experimental data by linear regression after log transformation of the data. The addition “2” indicates that á and â in
Equation (11) differ from those in
Equation (10). The last two
Equations, 10 and
11, can be combined in
Equation (12) to predict the uptake by rice directly from soil properties without measuring the soil solution [
14].
The values of á
3, â
3, ã
2, ä
2, and å
2 in
Equation (12) can be derived from the combination of
Equations (10) and
(11) and they will be different from those in
Equations (10) and
(11). Although some models clearly need to be improved, experimentally derived models were used to calculate the risk for rice cropping. This calculation was done by calculating the critical levels of Cd in the soil above which the Cd content of brown rice exceeds the FQS.