da UNIVERSIDADE DA BEIRA INTERIOR
ANALYSIS OF ORGANOPHOSPHOROUS PESTICIDES IN
POSTMORTEM BIOLOGICAL FLUIDS
RAQUEL HELENA CARVALHO SILVA RAPOSO
UNIVERSIDADE DA BEIRA INTERIOR
ANALYSIS OF ORGANOPHOSPHOROUS PESTICIDES IN
POSTMORTEM BIOLOGICAL FLUIDS
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RAQUEL HELENA CARVALHO SILVA RAPOSO
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TABLE OF CONTENTS
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LIST OF FIGURES
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LIST OF TABLES
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ABBREVIATIONS
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ABSTRACT
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JUSTIFICATION AND OBJECTIVES
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I - LITERATURE REVIEW
1. INTRODUCTION
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2. CLASSIFICATION AND CATEGORIZATION
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CHEMICAL ORGANISM OF TOXICITY (WHO) MODE OF ACTION STRUCTURE ACTION a a a a c c a a c a a c c a a a a a a c c a a c c a a ca c a a a a c a c a c c c a a a a a a a ac a c c a a c a a
3. ORGANOPHOSPHOROUS PESTICIDES
3.1. STRUCTURE
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3.2. PHYSICAL -CHEMICAL PROPERTIES
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SOLUBILITY IN VAPOUR ORGANOPHOPHOROUS MOLECULAR MELTING POINT BOILING POINT CHEMICAL STRUCTURE WATER AT 20°C PRESSURE AT PKA PESTICIDE WEIGHT (g/mol) (°C) (°C) (mg/L) 25°C (MPa)
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SOLUBILITY IN VAPOUR ORGANOPHOPHOROUS MOLECULAR MELTING POINT BOILING POINT CHEMICAL STRUCTURE WATER AT 20°C PRESSURE AT PKA PESTICIDE WEIGHT (g/mol) (°C) (°C) (mg/L) 25°C (MPa)
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3.3. MECHANISM OF TOXIC ACTION
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3.4. TOXICOKINETICS
3.4.1. ABSORPTION
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3.8. INTOXICATION CASUISTIC IN THE SOUTH REGION OF PORTUGAL
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4. LEGAL BACKGROUND OF PESTICIDE USAGE AND MANAGEMENT IN PORTUGAL
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4.1. EUROPEAN LEGISLATION
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4.2. PORTUGUESE LEGISLATION
4.2.1. MARKET INTRODUCTION
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4.2.2. MAXIMUM RESIDUE LEVELS
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4.2.3. CLASSIFICATION , LABELING AND PACKAGING
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4.2.4. SEEDS TREATED WITH PLANT PROTECTION PRODUCTS .
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4.2.5. CONDITIONS OF COMMERCIALIZATION AND APPLICATION OF PLANT PROTECTION PRODUCTS .
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5. METHODOLOGY FOR THE DETERMINATION OF PESTICIDES
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CHROMATOGRAPH REFERENC PESTICIDE CATEGORY SPECIES SAMPLE EXTRACTION DETECTION LOD LOQ Y E
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c c ac a ca a a a a a a a a a a a c a a c a a a ac a a a a a a a a a c a a ac a a a a a a a a a a a a a a a a ac a a a a c a a a a a a a a a c ac ca a a a a a a a a ca a a a a c a a a a a a a a a a a a a a a a a a c a a c a a a a c a a a a ac ca a a a c a a a a c a a a a a a c ca a a c aca ac a a ac a a a a a a a a a a ca a a a a a a a a a ac a a
ac c a a c a a a ac a a a c a a c c a a c a a a a a ac a a a a a c a a a a a a ac a a a a a a a a c a a a a c a c c a a c a a ac c a a c a a a ac a a a c a a c c a a c a a a a a ac a
a a ca a a c c a c a a a a c aca a a a a a a a a a ac a a cc ca a c a a a a a a a a a a c a a a a a a a a a a a a c a a a
a a a a c a a a a a a a a c a a a a c a a a c c
a a a ac a a a c a ac a a a a a a a a a a
a a a a a a a a a a c c a a a a ac a a a a a a a a c a a a a a a a c a a a ac a c a a ca a c a a a a a a a a a a a c ac c ac a a a ac ac ac a c a a a ac a a a a a c a a a ac a a a a a a ac a a a
c a c c a a c a a a a a ac a a a c a a a a c a a a a a a ac c a a c c a a a a a a a c c a c a a c a a c a c a
a ac a a ca a ca a a ca a a a ca a ca c a a a a ca a ca a a a a a a a c ca a c a a a c ca a ac a a a a a a
ac ac a a a a a a a a a a ca a a ca ca a a a a c a a a a ca a a ac a a a a a a a c a a ac a a a a a ac a a c a a a a a a a a c ac a a c a a a a ac a c a a a a a ac a a a ac a ac a a c a c c c a ac a a a ca c ac ac a a a a a a c a a a a a a a ca a a a a a a a a ac c a a a a a c a a a c a ca a a a a a a a c ac a c a a ac a c ac a c a a a a c a a a a a ac a c a a a a
II– EXPERIMENTAL
1. INSTRUMENTATION
– a ca
– a
– a c ac a
– a c c
– a ac a c
– a c a c
– a c a a
– c ca
– c a
– c a a
– a a a
1.1. EXTRACTION SYSTEM
ac a a a a c a a
ac a ca cc a a a
1.2. CHROMATOGRAPHIC AND DETECTION SYSTEMS
a a c a a a a a c a a a a c c ac a a a
ca a c c ac
a c c a
2. MATERIAL
2.1. REAGENTS AND SOLVENTS
a a ac a ac c ac a a c ac a a
a c a c c a a
a c a c a a a
2.2. STANDARDS
a a ca a a a a a c a a c a a a a c a
c a a a a a ca a a
a a c a a c a a a a
2.3. BIOLOGICAL SAMPLES a a a c
a a c a a
a a a a
c c a c a a a c
a a a
2.4. WORKING SOLUTIONS
c a a a c a a ca a a a a c c a
a c c a a a
a a a
a c c c a a a
a a a a a a c
a
c a
2.5. BUFFER SOLUTIONS
a a a a c a ca a a ac a a a a c c c
a a a c a c a
a ac c a c ac c
c c c ac a a ac a
a a c
a a ac c ac a a ac a a ac a a c a ac c ac a a a a
3. CHROMATOGRAPHIC AND DETECTION CONDITIONS
a a c c a ca a a a
a c a a a a a a a a a c a
a a a a a a c a ac
a c a c a c
c a a a a ca a a a a c a a
a c a a a a c a a
c c ac
a a c c
4. EXTRACTION PROCEDURE
a a ac c ac a a ac a a a
a a a a c a a a
a a a a a a ac ca a
a c a a a a a c
a a ac a a
a a c a a a a a a
a a c a a a a ac
a c a a a a a a a c
5. RESULTS AND DISCUSSION
5.1. IDENTIFICATION OF COMPOUNDS
c a a c a a c a ac c ca
a ca a a c ac
c a acc a a a c a c a
c c a c a a a
a a a c a c a c
ac c a a c
a a a c c
PESTICIDE RETENTION TIME (MINUTES ) SELECTED IONS
a
a
a
a a
a
a ca a
a a a c a a
a c a ca a c a a a c
c c a c a
5.2. OPTIMIZATION OF THE EXTRACTION PROCEDURE
a ac a a ca a a a a a a c a a c c c a ca a a a a
c a a a a a c a a
a a a a a a a a
a a c c c ac a c
c a a c a a c a a a c a a a a a ac c c a ac c a a c a a
a ac ac ca a a c ac
a a a a a ac ca
ca c ac c c a ac c
a a ca a ca a
a a ac ca a
HLB MAX HLB→MAX
AVERAGE PESTICIDE CONCENTRATION ABSOLUTE DECREASE µg/mL CV AVERAGES CV ABSOLUTE IN AVERAGES ABSOLUTE VALUES a a a a a a
a a a ac
c a
a
BUFFER SOLUTION PH
c
a
a a c c
a ca a c a c c a a a
c a c a a
a c ac a
a ca c a a
a
a a c
VOLUME ELUTION SOLUTION
a a a c ac c a c a c ac a c a
a a
a
a
c a
a a
c a a a a c a a
a a ac a a a a a
c c a a a ca a c a a a a a a
a a c a a
a c a c a a
a a a a a a a a
a a c
6. VALIDATION
a a a a acc a a acc c a
a a c a ca a c c a acc ac c a a a
6.1. SELECTIVITY
c ca c c a a a ca a
ca a a a a c c c a
c a
a a c a a a
a a a ac
ac acc c c a c
a c c a a a a c a
c ac a c a
c a a a ac
a c a a c a a
a a a c
a c c a a a
c a c a c a a a
a c a ca c a a c a a a a c a a a a a
a a a a
a a c a ac a a a a a
TOLERANCE PEAK RELATIVE GC/MS AREA a
a
BLANK SAMPLES FROM POOL 6
c c c c a a a a a a a a a a
c c c c a a a a a c a a c a
c c c c c a c a a a a a a a a a
c c a a a c c a a a a a a a
6.2. LINEARITY
a a a a a a a c a c c a a a a c a a ca a c a a c c a
a a a
a a c a a a a a a a c ac c a
a a ca a
a a ac c a a a a a a a
a a
a a a
Regression Statistics Multiple R 0,990009167 R Square 0,980118151 Adjusted R Square 0,978588778
Standard Error 0,188885931 Observations 15
ANOVA df SS MS F Significance F Regression 1 22,8646331 22,8646331 640,8627302 1,90708E- 12 Residual 13 0,463812633 0,035677895 Total 14 23,32844573
Coefficients Standard Error t Stat P-value Lower 95% Upp er 95% Lower 95.0% Upper 95.0% Intercept 0,1130009 0,07221515 1,564781065 0,141642874 - 0,043010447 0,269012246 -0,043010447 0,269012246 X Variable 1 0,144301944 0,005700194 25,31526674 1,9070 8E-12 0,131987422 0,156616465 0,131987422 0,156616465
a a
a a a SUMMARY OUTPUT
Regression Statistics Multiple R 0,998226389 R Square 0,996455924 Adjusted R Square 0,996183303 Standard Error 0,18435545 Observations 15
ANOVA df SS MS F Significance F Regression 1 124,2253905 124,2253905 3655,0928 2,56485E- 17 Residual 13 0,441830116 0,033986932 Total 14 124,6672206
Coefficients Standard Error t Stat P-value Lower 95% Upp er 95% Lower 95.0% Upper 95.0% Intercept 0,174018253 0,07048305 2,468937611 0,02819100 5 0,021748881 0,326287625 0,021748881 0,326287625 X Variable 1 0,336352955 0,005563474 60,45736349 2,5648 5E-17 0,324333801 0,34837211 0,324333801 0,34837211
a a
a a a
SUMMARY OUTPUT
Regression Statistics Multiple R 0,995942287 R Square 0,991901039 Adjusted R Square 0,991278042 Standard Error 0,325046082
Observations 15
ANOVA df SS MS F Significance F Regression 1 168,2179153 168,2179153 1592,144118 5,5328E -15 Residual 13 1,373514417 0,105654955 Total 14 169,5914298
Coefficients Standard Error t Stat P-value Lower 95% Upp er 95% Lower 95.0% Upper 95.0% Intercept -0,088992362 0,124272102 -0,716108935 0,48658 9422 -0,357465915 0,179481191 -0,357465915 0,179481191 X Variable 1 0,391404835 0,009809232 39,90168064 5,5328 E-15 0,370213278 0,412596392 0,370213278 0,412596392
a
a a
SUMMARY OUTPUT
Regression Statistics Multiple R 0,998185498 R Square 0,996374289 Adjusted R Square 0,996095388 Standard Error 0,168819051
Observations 15
ANOVA df SS MS F Significance F Regression 1 101,8159047 101,8159047 3572,50394 2,97416E -17 Residual 13 0,370498335 0,028499872 Total 14 102,186403
Coefficients Standard Error t Stat P-value Lower 95% Upp er 95% Lower 95.0% Upper 95.0% Intercept 0,043045253 0,064543151 0,666922089 0,5164850 28 -0,096391747 0,182482253 -0,096391747 0,182482253 X Variable 1 0,304507417 0,005094617 59,77042697 2,9741 6E-17 0,293501166 0,315513667 0,293501166 0,315513667
a a a
a a a a
SUMMARY OUTPUT
Regression Statistics Multiple R 0,998641523 R Square 0,997284891 Adjusted R Square 0,997076037 Standard Error 0,128788241
Observations 15
ANOVA df SS MS F Significance F Regression 1 79,20046899 79,20046899 4775,021469 4,53684 E-18 Residual 13 0,215623344 0,016586411 Total 14 79,41609234
Coefficients Standard Error t Stat P-value Lower 95% Upp er 95% Lower 95.0% Upper 95.0% Intercept -0,033017969 0,049238512 -0,670572033 0,51423 0488 -0,139391307 0,073355369 -0,139391307 0,073355369 X Variable 1 0,268567798 0,003886568 69,10153015 4,5368 4E-18 0,260171379 0,276964218 0,260171379 0,276964218
a
a a
SUMMARY OUTPUT
Regression Statistics Multiple R 0,999023994 R Square 0,99804894 Adjusted R Square 0,997898858 Standard Error 0,151653221
Observations 15
ANOVA df SS MS F Significance F Regression 1 152,9423572 152,9423572 6650,043778 5,29361 E-19 Residual 13 0,298983091 0,022998699 Total 14 153,2413403
Coefficients Standard Error t Stat P-value Lower 95% Upp er 95% Lower 95.0% Upper 95.0% Intercept 0,05084546 0,057980285 0,876943947 0,39643373 9 -0,07441333 0,17610425 -0,07441333 0,17610425 X Variable 1 0,373210585 0,004576587 81,54780057 5,2936 1E-19 0,36332347 0,383097699 0,36332347 0,383097699
a a c
a a a
SUMMARY OUTPUT
Regression Statistics Multiple R 0,998137319 R Square 0,996278107 Adjusted R Square 0,995991808 Standard Error 0,208195674
Observations 15
ANOVA df SS MS F Significance F Regression 1 150,8354686 150,8354686 3479,846393 3,52607 E-17 Residual 13 0,563490703 0,043345439 Total 14 151,3989593
Coefficients Standard Error t Stat P-value Lower 95% Upp er 95% Lower 95.0% Upper 95.0% Intercept -0,069281861 0,07959768 -0,870400503 0,399868 902 -0,241242193 0,102678472 -0,241242193 0,102678472 X Variable 1 0,370631051 0,006282923 58,99022286 3,5260 7E-17 0,35705762 0,384204481 0,35705762 0,384204481
AZINPHOS
a
a a
SUMMARY OUTPUT
Regression Statistics Multiple R 0,998285506 R Square 0,996573952 Adjusted R Square 0,99631041 Standard Error 0,234378371
Observations 15
ANOVA df SS MS F Significance F Regression 1 207,7277389 207,7277389 3781,4593 2,05792E- 17 Residual 13 0,714131871 0,054933221 Total 14 208,4418708
Coefficients Standard Error t Stat P-value Lower 95% Upp er 95% Lower 95.0% Upper 95.0% Intercept 0,254411712 0,089607888 2,83916649 0,01394351 4 0,06082564 0,447997784 0,06082564 0,447997784 X Variable 1 0,434947971 0,007073064 61,49357121 2,0579 2E-17 0,419667545 0,450228397 0,419667545 0,450228397
6.3. CALIBRATION CURVES
a a a a c a a a a a ca
c a a a c a a ca a c a c c a ca c c a c a a a a a a
c a c c a c a
a a a a a a
ca ac a a a a c a a c c a a ca a
a c ca
a a a c c a a a
REPEATABILITY CONCENTRATION (µg/mL)
a a a c c c a a a
CALIBRATION DATA
CONCENTRATION (µg/mL)
6.4. LIMITS OF DETECTION AND QUANTIFICATION
a a a a c c c a a c
a a a c c c a a a a acc ac
a c c a c a
c c a a a a a
a a ca a
a c c a c a a
ca a c ac a a a a a a
a a a ca a c c a a ca a a a a a a
acc a a ca
a a a a a
a a a a a
WEIGHING CALIBRATION RANGE PESTICIDE CURVE TYPE SLOPE INTERCEPT R2 LOQ (µg/mL) FACTOR (µg/mL) a
a a
a a
a
a a a
a
a a
a
6.5. INTERMEDIATE PRECISION
c a a a ca c c a a a a a c a a a a
ca a
a c a c c
a a a a a a a a
c a ac c c a c c c
a a c c
c acc a c c a a a a c a
c a a a a
ca a a c c a a a a c a a
acc a c c a a
a a a a c c a a a
a acc acc a c c a a a ca a a
a ca
c a a a a a acc
a c a c a c ca a a ca
a a a c a a a
c a a a a c
a ca
a a c a a a
SPIKED CONCENTRATION BIAS * C.V PESTICIDE CONCENTRATION FOUND (%) (%) (µg/mL) (µg/mL) a a a a a a a a a a a c c a
6.6. REPEATABILITY OR INTRADAY PRECISION
c a a a ca c c a a a a a c a a a a
ca a
a a c c a a a a a
c a a c c c a a a
c a a a
c a a a a c a a a a a c a a a a a a a a c c a c a a a a
a a a a a cc c c a a a
a a a a a
SPIKED CONCENTRATION PESTICIDE BIAS C.V CONCENTRATION FOUND
a a a a a a
III – CONCLUSIONS
a c a a a a a a a a
a a a a c a a
ca a c c a a a
a a a a a
a c a c a a a a a a a a a a c a
c a a c
a a c ac a a
c a
a a a a a a
c a ac a a c a a ca c a
a c a a a a
a a a a a a a a c a
c a a a a
a a a c a c a acc ac a a a a a a a a a a a a a a a a a a c a a a c a acc ac a a a
a a
a c c
c a a a ca a a a
c a c a a a ca c ca a a
IV – REFERENCES
• a a cac a acc a a a ac c a a a a a c a ac a c a a a a a a a a a
• a a a c c a a a a a a
• a a aa a a c a c c c c a ca
• a a a a a c a c c a a a
• a c a a a a c a a a a c c a c a a
• a c a c c c a c a a ca a c ca c
• a c ca a a
• a c a a a a a c a c c a a a
• a a a c c a ca c a a a c a ca c a c c ca c a a
• a a a ca a ca a a a a a a c a a c a a a c
• a a a c a a ca a a c a a a a a a a a c a c a a a c
• a a a ca a a c a c c ca a c c c a
• a c c a c a c a c a c c c a
• a a c c a a c c c c a a a
• a a a a a a a a a a c a a a c a a c c a a c a a
• c c c c a c a c a
• a a c c a c a ca c a a a ca a a a ca a
• a a a a a a a a c a a a a c a a a ac ca a ca a
• c a a a a a a a a ca a c a c a a a cc a a c a c a
• a a a a a a a a a c a a a a ac a a a c a a a a c a a a a
• c a a a ca a c c a c a a cc a a a
• a a a a a a a a a a a c a c ac c a c a a a c a a a a
• a a a a c ac a c a a c a a a c ca a a a a a
• a a a a a a a a ca a a a a ca c a a a a c c a a a a a a c c a a
• a c a a c a a a a c a a a a c a a a a
• a a a a a c a a a a c a ca c c a a c c c c a a a ca a
• a c a a a a a a a a a a a a a a ca c a
• a a a a a a a a a a a a a a a a a c a a a c a a a a c a a ca a a a a a
• a a a a a a a a a c a ac a c a a a a a c a a a c a
• a c c a a c a a a a a c c a a c cc a a a a a a
• a a c a a c a a a a c a ca c c a c a a a ca a a a ca a
• a c a a a a c a a c a a ac a a c a a c a a c a ca a a a ca a
• a a a a a c a ca a a c a a a c ca a a c a a a a a a
• a a cc a a c a a a a a a
• a c a a ac a c ac c a a c a a a a a c a a c a a c a a a a a ca c ca a c c a
• a a a a c a a ac a c ac a a c a a a c c c a a a c c c a
• a c c a a a a c a a c a a a c a c ca a c a
• c a ca a a a c c a c a c c a c a a a a a a a
• a a a a a a ca a c a a c a ca a a c c c a a a
• c a c a a a a c a a a c a a a a a ac a a a a
• aca a a a ac a a c a a c a a a c c a a a a
• a a a a c ca a a a a a a a a c cc a a c a a
• a a c a a a a a a c c a a a a a a c a c a c a a a a a a
• a a c c c a a a a a a a a c a
• a a a a a a a c a a a a a a a a a a a c a
• a c a a a a a c c a ca ca a a c a a a a ca a
• a a a a a a c a a a c a a ca c a
• a a a a a a a c c c a a a a ca ca c a
• a c c a c a a a c a a c c c a a c a a a c a ca a c a
• a a a a c c a a a a a a a c c a a
• a c a c a ac a a a a a a a a a c a a a c c a a a a
• aa c a a a c a a a c c a a a a a a
• a a a a c a a ca a a a a c a c a a a a a
• a ac a a a c a c a a a a a a c a
• a a a c a a a a a c a a a c a a a a ca c ca a c c a
• a a a a a a a a a a a a c c ac a a a a ac ac a a
• a a a a a a a a a c a a a a a a c a a a
•
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