Biodegradation Pathway of the Pyrethroid Pesticide Esfenvalerate by Bacteria from Different

Biodegradation pathway of the pyrethroid pesticide esfenvalerate by bacteria from different biomes

Willian G. Birolli1, Eloá M. Borges1, Marcia Nitschke2 and André L. M. Porto1*

1Laboratório de Química Orgânica e Biocatálise, Instituto de Química de São Carlos, Universidade de São Paulo, Avenida João Dagnone, 1100, Ed. Química Ambiental, Jd. Santa Angelina, 13563-120, São Carlos, SP, Brazil.

2Laboratório de Biotecnologia Microbiana, Instituto de Química de São Carlos, Universidade de São Paulo, Avenida João Dagnone, 1100, Ed. Química Ambiental, Jd. Santa Angelina, 13563-120, São Carlos, SP, Brazil.

Supplementary Material-1. Analytical Curves 2

Supplementary Material-2. Mass spectrum of the esfenvalerate metabolites identified by GC-MS. 4

Supplementary Material-3. Mass spectrum of the esfenvalerate metabolites identified by LC-ToF. 8

Supplementary Material-1. Analytical Curves

The analytical curves are presented in Table 1 and linear estimations in Table 2.

c= (x-B)/A (Equation 1)

Where: c= analyte concentration, mg.L-1

x= analyte area

A= angular coeficient

B= linear coeficient

SM-1.Table 1. Analytical curves for esfenvalerate and its metabolites quantification.

Compound / Curve 1 / Curve 2
Esfenvalerate / -Standard solutions:
50, 300, 550, 800 and 1050.0 mg L-1
-Analytical curve:
c=(Area+41097)/3503 / Only one curve was necessary for this compound
PBAc / -Standard solutions:
25, 80, 135, 190 and 250 mg L-1
-Analytical curve:
c=(Area -3357,9)/4554,7 / -Standard solutions:
5, 12, 19, 26 and 33 mg L-1
-Analytical curve:
c=(Area +1677)/4762
CLAc / -Standard solutions:
25, 80, 135, 190 and 250 mg L-1
-Analytical curve:
c=(Area-576,8)/691,3 / -Standard solutions:
5, 12, 19, 26 and 33 mg L-1
-Analytical curve:
c=(Area +61.8)/683,7
PBAld / -Standard solutions:
25, 80, 135, 190 and 250 mg L-1
-Analytical curve:
C=(Area+2363,9/5015,9 / -Standard solutions:
5, 12, 19, 26 and 33 mg L-1
-Analytical curve:
c=(Area +1253)/4659,2
PBAlc / -Standard solutions:
25, 80, 135, 190 and 250 mg L-1
-Analytical curve:
c=(Area x+8898,2)/6355 / -Standard solutions:
5, 12, 19, 26 and 33 mg L-1
-Analytical curve:
c=(Area +407,9)/6320,2

Linear estimation were also employed (Equation 2, table 2) for concentrations lower than 5 mg.L-1.

c= (x.5)/Y (Equation 2)

Where: c= analyte concentration, mg.L-1

x= analyte area

Y=5 mg.L-1 standard solution area

B= linear coefficient

SM-1.Table 2. Linear estimation equations for esfenvalerate metabolites.

Compound / Linear estimation
PBAc / c=(x.5)/2049
CLAc / c=(x.5)/3598]
PBAld / c=(x.5)/2103
PBAlc / c=(x.5)/29213

Supplementary Material-2. Mass spectrum of the esfenvalerate metabolites identified by GC-MS.

The mass spectra of the identified compounds by GC-MS are presented in SM-2.Fig 1-8.

SM-2.Fig 1. Mass espectrum of 2-(3-hydroxyphenyl)acetic acid (A) in the esfenvalerate biodegradation analysis and (B) NIST 05 mass spectrum library. Elution time was 9.4 min and similarity 97%.

A)

B)

SM-2.Fig 2. Mass espectrum of phenoxybenzoic acid (A) in the esfenvalerate biodegradation analysis and (B) NIST 05 mass spectrum library. Elution time was 15.3 min and similarity 93%.

A)

B)

SM-2.Fig 3. Mass espectrum of 2-(4-chlorophenyl)-3-methylbutanoic acid (A) in the esfenvalerate biodegradation analysis and (B) standard. Elution time was 17.3 min.

A)

B)

SM-2.Fig 4. Mass espectrum of 3-phenoxybenzaldehyde (A) in the esfenvalerate biodegradation analysis and (B) standard. Elution time was 19.1 min.

A)

B)

SM-2.Fig 5. Mass espectrum of 3-phenoxybenzilic alcohol (A) in the esfenvalerate biodegradation analysis and (B) standard. Elution time was 20.7 min.

A)

B)

SM-2.Fig 6. Mass espectrum of methyl 3-phenoxybenzoate (A) in the esfenvalerate biodegradation analysis and (B) standard. Elution time was 21.5 min.

A)

B)

SM-2.Fig 7. Mass espectrum of methyl 3-phenoxybenzoate (A) in the esfenvalerate biodegradation analysis and (B) NIST 05 mass spectrum. Elution time was 22.3 min and similarity 85%.

A)

B)

SM-2.Fig 8. Mass espectrum of methyl 3-phenoxybenzoate (A) in the esfenvalerate biodegradation analysis and (B) standard. Elution time was 22.5 min.

A)

B)

Supplementary Material-3. Mass spectrum of the esfenvalerate metabolites identified by LC-ToF.

The mass sepectra obtained by LC-ToF are presented in SM-3.Fig 1-5.

SM-3.Fig 1. Mass espectrum of (A) PBAc in biodegradation by P5CBNB and (B) standard. Elution time was 22.8 min.

(A)

(B)

SM-3.Fig 2. Mass espectrum of (A) methylPBAc in biodegradation by 135 and (B) standard. Elution time was 29.1 min.

(A)

(B)

SM-3.Fig 3. Mass espectrum of (A) PBAlc in biodegradation by 1E and (B) standard. Elution time was 22.0 min.

(A)

(B)

SM-3.Fig 4. Mass espectrum of (A) CLAc in biodegradation by P5CBNB and (B) standard. Elution time was 24.6 min.

(A)

(B)

SM-3.Fig 5. Mass espectrum of (A) hydroxyPBAc in biodegradation by P5CBNB and (B) isotopic pattern. Elution time was 17.2 min.

(A)

(B)

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