Bioconcentration of Pesticides in Fish from Rivers and Lakes

Pesticide contamination of river and lake waters from agriculture use is a problem of worldwide importance. Many field data on the pesticide contamination of surface waters and aquatic organisms in rivers and lakes (Amaraneri & Pillala, 2001, Abdel-Halim et al., 2006; Agradi et al., 2000; California Environmental Protection Agency, 2002; California Regional Water Quality Control Board, 2002; California State Water Resources Control Board, 2002; Domagalski, 1996; 1997; Environment Canada, 2002; Ganapathy et al., 1997; Gfrerer et al., 2002a; 2002b; Harman-Fetcho et al., 1999; Hall, 2003; Laabs et al., 2002; Lekkas et al., 2004; Leong et al., 2007; Mansour et al., 2001; Mansour & Sidky, 2003; McConnell et al., 2004; Oros et al., 2003; Rovedatti et al., 2001; Struger et al., 2004; Sudo et al., 2002a; 2002b; 2004; Tanabe et al., 2001; Tsuda et al., 1996a; 1997a; 1998; 1999; Vitanov et al., 2003; Washington State Department of Ecology, 1999; 2000) have been reported in the world. This chapter consisted of (1) Field surveys on pesticide contaminations in rivers and lakes, (2) Bioconcentration of pesticides in the field fish (3) Bioconcentration of pesticides in fish by laboratory experiments (4) Evaluation of the pesticide contamination in the field fish by their laboratory bioconcentration potential data 1. Diazinon, fenitrothion, malathion and fenthion were selected as insecticides and atrazine, simazine, simetryn, molinate and benthiocarb, mefenacet and pretilachlor as herbicides. Surveys on the contamination of the 4 insecticides (Abdel-Halim et al., 2006; Ministry of the Environment, Japan, 2001; Mansour & Sidky, 2003; Ohtsuki, 1994; Tsuda et al., 1992a; 1994; 1998; 2009) and the 7 herbicides (Chiba Prefecture, 2002; 2003; Kanagawa Prefecture, 2000; 2001; Ministry of the Environment, Japan, 1993; 1999; Takino et al., 1998; Tsuda et al., 1996a; 1997a; 2009; Watanugi et al., 1993) in water and fish from rivers and lakes in the world were reviewed from literatures in the past. 2. Bioconcentration factor (BCF) of each 11 pesticide in the field fish was calculated as its bioconcentration potential from the data on the pesticide concentration in the water and fish from the rivers and lakes in the world. 3. Laboratory BCF data of the 11 pesticides in fresh-water fish were reviewed from literatures in the past for the 4 insecticides (Allison & Hermanutz, 1977; De Bruijn & Hermens, 1991; Escartin & Porte, 1996; Fisher, 1985;Goodman et al., 1979; Kanazawa, 1975; 1978; 1981; 1983; 1987; Keizer et al., 1991; 1993; Lockhart et al., 1983; Miyamoto et al., 1979; Nihon Kagaku-busshitsu Anzen-Jyohou Center, 1992; Sancho et al., 1992; 1994; Seguchi & Asaka, 1981; Takimoto et al., 1984; 1987; Tsuda et


Introduction
Pesticide contamination of river and lake waters from agriculture use is a problem of worldwide importance. Many field data on the pesticide contamination of surface waters and aquatic organisms in rivers and lakes (Amaraneri & Pillala, 2001, Abdel-Halim et al., 2006Agradi et al., 2000;California Environmental Protection Agency, 2002;California Regional Water Quality Control Board, 2002;California State Water Resources Control Board, 2002;Domagalski, 1996;1997;Environment Canada, 2002;Ganapathy et al., 1997;Gfrerer et al., 2002a;Harman-Fetcho et al., 1999;Hall, 2003;Laabs et al., 2002;Lekkas et al., 2004;Leong et al., 2007;Mansour et al., 2001;Mansour & Sidky, 2003;McConnell et al., 2004;Oros et al., 2003;Rovedatti et al., 2001;Struger et al., 2004;Sudo et al., 2002a;Tanabe et al., 2001;Tsuda et al., 1996a;1997a;Vitanov et al., 2003;Washington State Department of Ecology, 1999; have been reported in the world. This chapter consisted of (1) Field surveys on pesticide contaminations in rivers and lakes, (2) Bioconcentration of pesticides in the field fish (3) Bioconcentration of pesticides in fish by laboratory experiments (4) Evaluation of the pesticide contamination in the field fish by their laboratory bioconcentration potential data 1. Diazinon, fenitrothion, malathion and fenthion were selected as insecticides and atrazine, simazine, simetryn, molinate and benthiocarb, mefenacet and pretilachlor as herbicides. Surveys on the contamination of the 4 insecticides (Abdel-Halim et al., 2006; Ministry of the Environment, Japan, 2001; Mansour & Sidky, 2003;Ohtsuki, 1994;Tsuda et al., 1992a;1994;2009) Ohtsuki, A. (1994) 1 Tama River Basin Common carp < 5～< 5 < 5～< 5 < 5～< 5 Ohtsuki, A. (1994) 1 Tama River Basin Crucian carp < 5 (n=1) < 5 (n=1) < 5 (n=1) Ohtsuki, A. (1994) 2 River in Kanagawa Pref.  In Egypt, malathion were detected in the concentrations of 42.0 μg/l in water and 6 μg/kg wet wt. in tilapia from Lake Qarun in 1998~1999, and diazinon and malathion were detected in the concentrations of 24.6 and 71.9μg/l in water and 21.1 and 19.3 μg/kg wet wt. in tilapia, respectively, from New Damietta Drainage canal in winter of 2001. As shown in Tables 2-1 and 2-2, molinate, simetryn, benthiocarb, mefenacet and simazine were detected in the concentrations of < 0.01~75.5, < 0.01~21.2, < 0.01~0.90, < 0.01~11.2 and < 0.02~2.6 μg/l in water and < 2~1156, < 5~50, < 10~< 10, < 10~324 and < 20~< 20 μg/kg in ayu fish, respectively, from rivers in Shiga Prefecture, Japan from April in 1994 to March in 1996. Benthiocarb and simazine were not detected in the fish in spite of their detections in the river water. Further, molinate, simetryn and benthiocarb were detected in the concentrations of 13.9, 6.6 and 2.2 μg/l in water and 10~170, 30~40 and 250~540 μg/kg in carp, respectively, from Lake Kawakitagata in Ishikawa Prefecture, Japan in 1989.  As shown in Table 3, two insecticides and 10 herbicides in water and 4 herbicides in two species of fish (Hasu and pale chub) were detected from east littoral zone of (C 10 , C 11 and C 13 ) of northern basin of Lake Biwa. As shown in  Table 4. Concentrations of pesticides in fish from littoral zone of Akanoi Bay in southern basin of Lake Biwa in water and 8 herbicides in bluegill were detected from littoral zone of Akanoi Bay (North, Center and South) in southern basin of Lake Biwa. The two insecticides and 12 herbicides were detected in the water from the two littoral areas of Lake Biwa but the two insecticides were not and the only 8 herbicides were detected in the three species of fish from the locations. An example of concentration changes of the 8 herbicides in the water and bluegill from the littoral zone of Akanoi Bay (Center) in southern basin of Lake Biwa is shown in Fig.  1 throughout the survey from May to August in 2007. The concentrations of molinate, bromobutide, simetryne and mefenacet in the water were high in May and June. This result corresponds to the maximum use of the herbicides in paddy fields of Japan. Detections of the 8 herbicides in the fish corresponded well to those in the water, but the order of the herbicide concentrations in the fish was different from that in the water. For example, the concentration of esprocarb was low in the water but high in the fish. This is probably because bioconcentration potential of esprocarb is higher than the other herbicides.

Bioconcentration of pesticides in the field fish
Bioconcentration factor (BCF) of each pesticide in the field fish was calculated as its bioconcentration potential from the field data (Tables 1-1, 1-2, 2-1 and 2-2) on the pesticide concentration in the water and fish from the rivers and lakes in Japan and Egypt.
The BCF values are shown in Table 5 for the 4 insecticides (diazinon, fenitrothion, malathion and fenthion). The BCF values in the two or three species of fish from the rivers in Japan were 20~150 for diazinon, 70~790 for fenitrothion and 20~240 for fenthion. For malathion, its BCF value could not be calculated because of its no detections in the common carp from the two rivers in Japan. This is probably due to its low bioconcentration potential. In Egypt, the BCF values in the tilapia from New Damietta Drainage canal were 0.6 and 0.9 for diazinon and 0.3 for malathion and that in the tilapia from Lake Qarun was 0.1 for malathion. The BCF values of diazinon (0.6 and 0.9) in the tilapia in Egypt were considerably lower than those (20~150) in the two species of fish (pale chub and ayu fish) in Japan.  Table 5. BCF of insecticides in fish from field survey data The BCF values in the rivers and lakes in Japan are shown in Table 6 for the 7 herbicides (molinate, simetryn, benthiocarb, mefenacet, pretilachlor, simazine and atrazine).The BCF values were 15~286 for molinate, 2~163 for simetryn, 56~248 for benthiocarb and 20~36 for mefenacet in the two or the three species of fish (ayu fish, pale chub and dark chub) and 19 for pretilachlor in the pale chub from the rivers. The BCF value of simazine was calculated as 150 (n=1) in the carp from a river but could not calculated in the carp or the pale chub from other rivers. Those of simazine in the carp and the pale chub were estimated to be < 100 and < 33, respectively. For atrazine, its BCF values could not be calculated at all in the three species of fish from the rivers. Those were estimated to be < 50 in Steed barbell, < 50 and < 6.8 in carp and < 22 in crucian carp. This is probably due to its low bioconcentration  Table 6. BCF of herbicides in fish from field survey data

Bioconcentration of pesticides in fish by laboratory experiments
Laboratory BCF data of the 11 pesticides in fresh-water fish were reviewed from literatures in the past and the BCF value of each pesticide in fish was evaluated as its bioconcentration potential.

Evaluation of the pesticide contaminations in the field fish by their laboratory BCF data
The contaminations of the 10 pesticides in the field fish were evaluated by comparing the field BCF data with the laboratory BCF data. The field BCF data of the 4 insecticides in the field fish (Table 5) and the laboratory BCF data  are summarized and compared in Fig. 9. The field BCF data of the 4 insecticides were nearly equal to the laboratory BCF data. Similarly, the field BCF data (Table 6) and the laboratory BCF data (Figs. 6 -7) of the 6 herbicides except atrazine are summarized and compared in Fig. 10. The field BCF data of the 4 insecticides and the 5 herbicides except simazine were nearly equal to the laboratory BCF data. It was revealed that the contamination of 9 pecticides except simazine in fish from the rivers and the lakes was approximately predicted by the laboratory BCF data. Field BCF data of the 5 herbicides (molinate, bromobutide, simetryn, pretilachlor and mefenacet) in the fish from Lake Biwa (Fig. 2) and the laboratory BCF data are shown in Fig.  11. The average field BCF values were nearly equal to the average laboratory BCF values for molinate, bromobutide and pretilachlor but slightly lower for simetryn and slightly higher for mefenacet. The differences in the field and laboratory BCF values of simetryn and mefenacet are not wide, so both of the field and laboratory BCF data are considered to be the same levels for all of the 5 herbicides. From the comparison shown in Fig. 11, it was clarified that the contamination of the 5 herbicides i n t h e f i s h f r o m L a k e B i w a c o u l d b e approximately estimated by the laboratory BCF.

Laboratory BCF
Field BCF Fig. 11. Comparison of laboratory BCF data and field BCF data for 5 herbicides