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Table 1.

Quantification limit using LC-MS/MS for acetamiprid, azoxystrobin, estriol, estrone, progesterone, and testosterone in rat liver.

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Fig 1.

Linearity coefficients of calibration curves for all six compounds (acetamiprid, azoxystrobin, estrone, estriol, progesterone, and testosterone).

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Fig 2.

Experiment design to study the toxicity of acetamiprid and azoxystrobin on rats.

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Fig 3.

A. Column comparison (poroshel, supelco, and synergi) with three compounds (estriol, estrone, and progesterone). HPLC columns comparison (n = 5). Poreshel 120 EC-C18 50X 3 mm, 2.7 μm (Agilent), Titan C18 50 X 2.1 mm, 1.9 μm (Supelco), and Synergi Fusion 50 X 2 mm, 4 μm (Phenomenex). B. Column comparison (poroshel, supelco, and synergi) with three compounds (testosterone, acetamiprid, and azoxystrobin). HPLC columns comparison (n = 5). Poreshel 120 EC-C18 50X 3 mm, 2.7 μm (Agilent), Titan C18 50 X 2.1 mm, 1.9 μm (Supelco), and Synergi Fusion 50 X 2 mm, 4 μm (Phenomenex).

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Fig 4.

Extracted ion chromatogram of azoxystrobin 50 ppb, injection volume of 2, 5, and 25 μL.

a 5 μL injection volume was chosen to achieve maximum detection and quantification limitations.

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Fig 5.

LC-MS/MS chromatograms of a spiked liver sample on LOQ level.

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Table 2.

Mass parameters of parent and daughter ions of pesticides and hormones on LC-MS/MS (n = 5).

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Table 3.

Extraction solvent comparison by using different solvents in the liver tissue (n = 5).

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Table 4.

Effect of acetamiprid and azoxystrobin on the body weight (g) of rats during the two months of exposure.

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Fig 6.

A. Serum testosterone levels and acetamiprid residues levels after a month of different acetamiprid doses treatment of the male rats. Data presented as mean S.E. a Significant difference as compared to 1/40 LD50, and b significant difference as compared to 1/20 of LD50 (n = 4, P≤ 0.05). B. Serum testosterone and progesterone levels as well as acetamiprid residues after 2 months of different acetamiprid doses treatment of male rats. Data presented as mean S.E. a Significant difference as compared to 1/40 LD50, and b significant difference as compared to 1/20 of LD50 (n = 4, P≤ 0.05).

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Fig 7.

A. Serum testosterone levels and azoxystrobin residues after a month of different azoxystrobin doses treatment of male rats. Data presented as mean S.E. a Significant difference as compared to 1/40 LD50, and b significant difference as compared to 1/20 of LD50 (n = 4, P≤ 0.05). B. Serum testosterone and progesterone levels as well as azoxystrobin residues after 2 months of different azoxystrobin doses treatment on male rats. Data presented as mean S.E. a Significant difference as compared to 1/40 LD50, and b significant difference as compared to 1/20 of LD50 (n = 4, P≤ 0.05).

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Fig 8.

A. Testis testosterone and progesterone levels as well as acetamiprid residues after a month of different treatment of acetamiprid doses on male rats. Data presented as mean S.E. a Significant difference as compared to 1/40 LD50, and b significant difference as compared to 1/20 of LD50 (n = 4, P≤ 0.05). B. Testis testosterone and progesterone levels as well as acetamiprid residues after 2 months of different treatment of acetamiprid doses on male rats. Data presented as mean S.E. a Significant difference as compared to 1/40 LD50, and b significant difference as compared to 1/20 of LD50 (n = 4, P≤ 0.05).

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Fig 9.

A. Testis testosterone and progesterone levels as well as azoxystrobin residues after a month treatment of different azoxystrobin doses on male rats. Data presented as mean S.E. a Significant difference as compared to 1/40 LD50, and b significant difference as compared to 1/20 of LD50 (n = 4, P≤ 0.05). B: Testis testosterone and progesterone levels as well as azoxystrobin residues after 2 months treatment of different azoxystrobin doses on male rats. Data presented as mean S.E. a Significant difference as compared to 1/40 LD50, and b significant difference as compared to 1/20 of LD50 (n = 4, P≤ 0.05).

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Fig 9 Expand

Fig 10.

Liver acetamiprid residues after 1 and 2 months treatment of with different doses of acetamiprid on male rats.

Data presented as mean S.E. a Significant difference as compared to 1/40 LD50, and b significant difference as compared to 1/20 of LD50 (n = 4, P≤ 0.05).

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Fig 11.

Liver azoxystrobin residues after 1 and 2 months treatment with different doses of azoxystrobin on male rats.

Data presented as mean S.E. a Significant difference as compared to 1/40 LD50, and b significant (n = 4, P≤ 0.05).

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Table 5.

Mean values of testosterone and progesterone in control samples (n = 4/each month).

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