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En vue de l’obtention du
Délivré par
Institut National Polytechnique de Toulouse (INP Toulouse)
Discipline ou spécialité
Hydrologie, Hydrochimie, Sol, Environnement

Présentée et soutenue par Lobat TAGHAVI
Le 28 septembre 2010

Dynamique de transfert des pesticides en périodes de crue sur les bassins versants
agricoles gascons

Mme Hélène BLANCHOUD, Maître de conférences UPMC, CNRS, EPHE, Paris, examinatrice
Mme Hélène BUDZINSKI, Directrice de Recherche CNRS, ISM, LPTC, Talence, rapporteur
M. Georges MERLINA, IR INP Toulouse, EcoLab, co-directeur de thèse
M. Eric PINELLI, Professeur INP Toulouse, EcoLab, Président
M. Jean-Luc PROBST, Directeur de Recherche CNRS, EcoLab, Toulouse, Directeur de thèse
M. Marc VOLTZ, Directeur de Recherche INRA, LISAH, Montpellier, rapporteur

Ecole doctorale
Sciences de l’Univers, de l’Environnement et de l’Espace (SDU2E)

Unité de recherche
EcoLab, UMR 5245, Laboratoire d’Ecologie Fonctionnelle
Directeur(s) de Thèse
M. Jean-Luc PROBST
M. Georges MERLINA

Mme Hélène BUDZINSKI et M. Marc VOLTZ

To my Divine Protector

To My Dear Parents

To My sisters


I would like first to thank my PhD directors, Professor Jean-luc PROBST and Dr.
Georges MERLINA for their trust and belief in me during my PhD program at INPT (EcoLab).
They, in fact, opened my eyes to a new world with their high level of knowledge of the study
subject. I thank them for their invaluable advice and supervision.

I wish to express my gratitude to the members of the PhD committee for their valuable time to
review my thesis and for their comments.

My very special thanks go to Madame Annick CORREGE, the secretary of EcoLab and my
“French mother”, for her encouragement and support each time I was feeling down. I definitely
owe a debt of gratitude to her.

During the field and laboratory works, I received important technical support from
Mr Gael DURBE, Dr. Vincent ROUSSIEZ and Dr. Frederic BRUNET to whom I would like to
express my gratitude.

I would like to appreciate my friends who gave me tremendous moral support during the week of
exceptional anxiety and excitement, the week before my thesis defense. A very specific thank go
to Floriane BOURDIOL, Desiree EL AZZI, Christine JULIEN, Thierry POLARD,
Roman TEISSERENC, Muhammad SHAHID, Julien ARROYO and all of my friends in
laboratory for their great kindness. They provided me with helpful moments that I cherish for

I would like to express my cordial thanks to my colleague Dr. Christophe LAPLANCHE for the
help and availability he offered me.

I can never forget the sincere friendship and love of my colleagues in EcoLab laboratory. I would
like to express my deepest thanks and profound gratitude to all of them.

I want to express my deepest gratitude towards my colleagues in TANDEM laboratory for their

I would like to give special thanks to my aunt, Madame Brigitte Chevrin for her moral support
and encouragement.

And the most special thanks to my uncle, Dr. Seyf EHDAIE for his help, support and
encouragement. I am indebted to him for everything he taught me.

And last, but not least to those who are the most important people in my life, my parents, and my
sisters, Afsoon, Afshan, Leila and my brother-in-law (Mr Hamid SAKHAIE,
Mr Reza MASHAKZADEH and Mr Maziar SHALAHI). I say thank you and I love you all.

Also I need to mention that the propensity and love go to back to my country to embrace the joys
of my life, my nephew and nieces, Saman, Nazanin and Hania always gave me a sense of courage
and stamina.


The mechanisms of pesticides transport to stream flow were studied in two agricultural nested
catchments of different size in Gascogne region (South West of France): the Save river basin
2 2at Larra (1110 km ) and the Montoussé experimental watershed at Auradé (3.28 km ). The
intensive agricultural practices used in this region lead to an important risk for water
resources by pesticides, especially during storm events. This is why we have paid special
attention on storm events when a large quantity of contaminant was transported during
hydrological periods. Fourteen molecules of pesticides (herbicides and fungicides) were
investigated during the study period. Both of these groups are widely used for agricultural
purposed in these catchments.
The results achieved over the two years monitoring (2007-2009) enable us to emphasize the
principal processes, implied in pesticide transfer on these agricultural catchments. The
majority of compounds are detected during storm runoff events. And, the average
concentrations of some pesticides are exceeded at the authorization limit of the European
-1Union for pesticide concentrations in drinking water (0.1 µg.L for individual pesticides and
-10.5 µg.L for total pesticides).
To better understand the mechanisms of pesticide transport hysteresis, patterns on the
concentration-discharge relationship (result of different concentration of pesticides in rising
and falling limb of storm) were studied. However, clockwise or anticlockwise hysteresis
patterns could be observed for some molecules of pesticide and their controlling factors such
as dissolved organic carbon (DOC), particulate organic carbon (POC) and total suspended
matters (TSM) according to their transfer dynamic in the catchment. We proceeded with
hydrograph separation of the main stormflow components (surface runoff, subsurface flow
and groundwater) so that the main pesticide routing could be traced for its soil-river transfers.
We also came to the conclusion that there is a positive relationship between riverine TSM,
DOC and pesticide, concentrations and the discharges of surface or subsurface runoffs
according to pesticide properties. Pesticide flux calculation shows between 60 to 90% of the
molecule transport takes place during storm periods. Specific flux calculation also
demonstrated the higher flux value in Save catchment than in Aurade with higher pesticide
concentration for a given specific discharge. The latter result may be due to the more
consumption of pesticide in Save catchment. The analyses of pesticides both in filtered and
unfiltered water enabled us to estimate the distribution of pesticides into particulate and
dissolved phases. Moreover, the pesticide flux values allow calculating average partition
coefficients k between dissolved and particulate fractions which present good relationship d
with K values (octanol-water) extracted from literature. The percentage of each pesticide ow
transported as particulate forms is also well correlated to K . ow

Keywords: Pesticides, hysteresis, hydrograph separation, DOC, POC, TSM, flux, K and K d ow

1 2
Table of contents

General Introduction

29 Chapter 1 Pesticide in the environment (Literature review)

29 I: Pesticide history, classification, market and use
29 1 General knowledge
1.1 Pesticides’ definitions 29
1.2 Historical context of pesticide use 30
1.3 Pesticides classification 32
1.3.1 Classification based on chemical structure: inorganic, organic 32
and botanical
1.3.2 Classification and active chemicals 33
33 1.3.3 Classification and pesticide - specifity
1.4 The Market for pesticides (Current Status) 35
1.5 Pesticide usage and consumption 36
36 1.5.1 General context
1.5.2 National context 36
1.5.3 Regional context 36

39 II: Pesticide’s movement
2 Transfer of Pesticide 39
2.1 Pesticide life cycle 39
2.2 Behavior and fate of a pesticide in the environment 40
2.2.1 Transformation processes 40
2.2.2 Transport processes 41
2.2.3 Retention 41
2.3 Most important factors playing a major role in the fate of pesticides in detail 43
2.3.1 Pesticides properties 43
2.3.2 Chemical properties 45
2.3.3 Climatic factors 46
2.3.4 Soil and geologic properties 46
2.4 Pesticide transfer in surface water 48
3 2.4.1 Runoff 49
2.4.2 Stormwater 50
2.5 Principal parameters in pesticide’s transfert 51
2.5.1 Organic matters 51
2.5.2 suspended matters 54
2.6 Interaction between organic and suspended matters with Pesticide 54
2.7 Partitioning between dissolved and particulate phases (K ) 56 d
3 Occurrence of pesticides in water 56
59 Summary

61 Chapter II : Materials and Methods
1 Experimental Study 61
1.1 Study areas (Locations and characteristics) 61
1.2 Climate and Hydrology 63
1.3 Geological substratum and soil characteristic 63
1.4 River water composition 64
1.5 Selection of pesticide 64
1.6 Pesticide families 65
1.7 Sampling 66
2 Technical methods 67
2.1 Extraction of pesticide residues 67
2.1.1 Principle in the liquid liquid extraction 67
2.1.2 Advantage and drawbacks 68
2.2 Methods of analysis 69
2.2.1 Multiresidue analysis 69
2.2.2 GC and MS techniques 70
2.3 Chromatographic conditions and sample preparation 71
2.3.1 Condition of GC/MS 71
2.3.2 Chemical and reagents 72
2.3.3 Calibration standards 73
2.3.4 Detection limit 73
2.4 Analytical methods to measure controlling factors (COD, COP, pH, EC) 73
2.4.1 Dissolved and Particulate organic carbon (DOC-POC) 73