kontrol of pesticides 2007 - dce of pesticides 2007 ... insecticides containing fipronil. 4) plant...

National Environmental Research InstituteUniversity of Aarhus . Denmark

NERI Technical Report No. 691, 2008

Control of Pesticides 2007Chemical Substances and Chemical Preparations

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National Environmental Research InstituteUniversity of Aarhus . Denmark

NERI Technical Report No. 691, 2008

Control of Pesticides 2007Chemical Substances and Chemical Preparations

Teddy KrongaardKitty K. PetersenChristel Christoffersen

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Series title and no.: NERI Technical Report No. 691

Title: Control of Pesticides 2007 Subtitle: Chemical Substances and Chemical Preparations

Authors: Teddy Krongaard, Kitty K. Petersen and Christel Christoffersen Department: Department of Atmospheric Environment Publisher: National Environmental Research Institute

University of Aarhus - Denmark URL: http://www.neri.dk

Year of publication: October 2008 Referee: Rossana Bossi

Financial support: Danish Environmental Protection Agency

Please cite as: Krongaard, T., Petersen, K.K. & Christoffersen, C. 2008: Control of Pesticides 2007. Chemical Substances and Chemical Preparations. National Environmental Research Institute, University of Aarhus, Denmark. 23 pp. - NERI Technical Report No. 691.

http://www.dmu.dk/Pub/FR691.pdf

Reproduction permitted provided the source is explicitly acknowledged

Abstract: Five different groups of products covered by the pesticide regulation were included in the 2007 analytical chemical authority control: 1) Herbicides containing cycloxydim, diflufenican and triflusulfuron-methyl. 2) Fungicides boscalid, dimethomorph, epoxiconazole, fenpropimorph, mancozeb and propamocarb. 3) Insecticides containing fipronil. 4) Plant growth regulators con-taining daminozide. 5) Insect repellents containing icaridin. All samples were examined for the content of active ingredients and for the content of OPEO and NPEO. All samples in this years programme complied with the accepted tolerance limits with respect to the content of the active ingredients as specified in Danish Statutory Order on pesticides. None of the examined samples contained OPEO or NPEO. On the label of seven products, the content of active ingredient was declared only in g/L or g/kg, but not in % (w/w) as required.

Keywords: Control, formulations, pesticides

Layout: Majbritt Pedersen-Ulrich Proof-reader: Christel Ege-Johansen

ISBN: 978-87-7073-068-6 ISSN (electronic): 1600-0048

Number of pages: 23

Internet version: The report is available in electronic format (pdf) at NERI’s website http://www.dmu.dk/Pub/FR691.pdf

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� �� "��&��' 2.1 Herbicides 9

2.1.1 Introduction 9 2.1.2 Samples 10 2.1.3 Results and Discussion 10

2.2 Fungicides 11 2.2.1 Introduction 11 2.2.2 Samples 12 2.2.3 Results and Discussion 13

2.3 Insecticides 15 2.3.1 Introduction 15 2.3.2 Samples 15 2.3.3 Results and Discussion 15

2.4 Plant growth regulators 16 2.4.1 Introduction 16 2.4.2 Samples 16 2.4.3 Results and Discussion 16

2.5 Insect repellents 17 2.5.1 Introduction 17 2.5.2 Samples 17 2.5.3 Results and Discussion 17

2.6 Additives 18 2.6.1 Introduction 18 2.6.2 Samples 18 2.6.3 Results and Discussion 18

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The analytical chemical authority control of pesticide products on the Danish market in 2007 is described in this report. Samples of selected groups of pesticides have been collected from the market and analysed to verify whether the actual contents of the respective active ingredients in the products comply with the labelled content. The tolerance of devia-tion from the labelled content of active ingredient is set by the Danish Statutory Order on pesticides. In addition to the examination of the con-tent of active ingredients, all collected samples are examined for the con-tent of octylphenol ethoxylates (OPEO) and nonylphenol ethoxylates (NPEO). The industry and the Danish authorities have agreed on remov-ing these compounds from all Danish-sold pesticide formulations pro-duced after June 2000.

Five different groups of products covered by the pesticide regulation were included in the 2007 analytical chemical authority control:

1. Herbicides containing cycloxydim, diflufenican and triflusulfuron-methyl.

2. Fungicides containing boscalid, dimethomorph, epoxiconazole, fen-propimorph, mancozeb and propamocarb.

3. Insecticides containing fipronil.

4. Plant growth regulators containing daminozide.

5. Insect repellents containing icaridin.

Satisfactory results were found for all examined pesticide formulations. Thus, the analysed samples of these formulations complied with the ac-cepted tolerance limits with respect to the content of the active ingredi-ents as specified in Danish Statutory Order on pesticides.

None of the examined samples contained OPEO or NPEO.

On the label of seven products, the content of active ingredient was de-clared only in g/L or g/Kg, but not in % (w/w) as required by the Statu-tory Order.

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Den analytisk kemiske kontrol af pesticidprodukter på det danske mar-ked, der blev udført i 2007 af de danske myndigheder, er beskrevet i denne rapport. Prøver fra udvalgte grupper af bekæmpelsesmidler er blevet samlet fra markedet og analyseret for at verificere om det aktuelle indhold af de respektive aktivstoffer er i overensstemmelse med det de-klarerede indhold. Grænsen for en accepteret afvigelse fra indholdet af aktivstof fra det deklarerede indhold er fastsat i bekendtgørelsen om be-kæmpelsesmidler. Udover kontrol af indholdet af aktivstof er alle ind-samlede prøver kontrolleret for indhold af octylphenolethoxylater (OPEO) og nonylphenolethoxylater (NPEO). Industrien og de danske myndigheder har indgået en frivillig aftale om at udfase disse forbindel-ser fra alle dansk-solgte pesticidprodukter produceret efter juni 2000.

Fem forskellige grupper af produkter er inkluderet i den analytisk-kemiske kontrol, der blev udført af myndighederne i 2007:

1. Herbicider indeholdende cycloxydim, diflufenican and triflusulfuron-methyl.

2. Fungicider indeholdende boscalid, dimethomorph, epoxiconazol, fenpropimorph, mancozeb and propamocarb

3. Insekticider indeholdende fipronil.

4. Vækstregulatorer indeholdende daminozid.

5. Afskrækningsmidler indeholdende icaridin.

Der blev opnået tilfredsstillende resultater for alle undersøgte bekæm-pelsesmidler. Indholdet af aktivstof i alle de analyserede prøver af disse bekæmpelsesmidler var indenfor den accepterede tolerance, der er fast-sat i bekendtgørelsen om bekæmpelsesmidler.

Ingen af de undersøgte produkter indeholdt OPEO eller NPEO

På syv produkter var indholdet af aktivstof kun deklareret i g/l eller g/kg og ikke i % som det ellers er krævet i bekendtgørelsen.

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The Danish Environmental Protection Agency (DEPA) is responsible for the evaluation and the authorisation of all pesticide formulations before the introduction on the Danish market. The requirements of the formula-tions are given in a Statutory Order on pesticides �� , which also states that DEPA is responsible for control of pesticides.

In practice, the authority control activities of pesticides on the market are organised in the following way: the Chemicals Inspection Service at DEPA conducts non-laboratory control and the National Environmental Research Institute conducts the laboratory control of pesticides as assis-tance to DEPA. The present report describes only the part of the author-ity control of pesticides involving laboratory control.

Laboratory control of pesticides covers the analytical chemical examina-tion of technical pesticides or pesticide formulations in order to verify that the products comply with the legal requirements of pesticides as well as with the specification of contents stated in the application for the pesticide product.

Analytical chemical control of pesticides may involve verification of the content of active ingredients as well as the content of auxiliary sub-stances or levels of impurities.

Laboratory control work is carried out as two types of projects: 1) Ordi-nary control by way of planned campaigns, where all products with a common characteristic, e.g. the same active ingredient, are collected from the market and examined, and 2) �� projects, which consist of labora-tory control in connection with administrative work at the regulatory au-thorities, e.g. complaints from users concerning a specific product, the suspicion of a product not complying with regulations or specifications, etc.

Only the first type of laboratory control i.e. campaigns are covered by this report, which describes the laboratory control as performed in 2007.

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Control campaigns conducted in 2007 have covered active ingredients and auxiliary substances belonging to four different groups of pesticides: herbicides, fungicides, insecticides and growth regulators. All analytical chemical control has aimed at examining the content of active ingredient compared with the declared content on the label. Statutory Order in Denmark �� specifies the general tolerance of devia-tion from declared content. These tolerances are given in Table 2.1. In addition to the examination of the content of active ingredients, all sam-ples are examined for the content of octylphenol ethoxylates and nonyl-phenol ethoxylates.

Samples of the various pesticide formulations covered in the 2007 control campaigns have been collected by the Chemical Inspection Service at DEPA during the months March – June 2007 from either whole sale deal-ers/importers or at retailer outlets. One sample of each product has been collected.

Samples were stored at NERI in unopened containers until the time of analysis. The samples were stored at ambient temperature (approx. 20°C) protected from light.

��The tolerance of deviations from declared content of active ingredients (a.i.) in pesticides.

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Conc. ≥ 50

25 < conc. ≤ 50

10 < conc. ≤ 25

2.5 < conc. ≤ 10

Conc. ≤ 2.5

± 2.5% (abs.)

± 5% (rel.)

± 6% (rel.)

± 10% (rel.)

± 15% (rel.)

9

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There are 50 different active ingredients in herbicide formulations avail-able on the Danish market (�� ). Products containing cycloxydim, diflufenican and triflusulfuron-methyl as active ingredients were selected for control in 2007. All products were examined for the content of active ingredient and for the content of octylphenol and non-ylphenol.

Cycloxydim (Figure 1a) is a cyclohexanedione oxime herbicide. It is used only to control weeds in peas, grass seed, rape, potatoes and beets in Denmark. Cycloxydim is a post-emergence, selective systematic herbi-cide, absorbed rapidly by the foliage with translocation. It inhibits the fatty acid synthesis. Herbicide formulations containing cycloxydim were approved for the Danish market in 2005 and have not previously been selected for authority control.

Diflufenican (Figure 1b) belongs to the group of pyridinecarboxamide herbicide. It is used to control weeds in cereals and non-eatable crops. Diflufenican is a selective contact and residual herbicide, absorbed by the shoots, with limited translocation. It inhibits the synthesis of carotenoid. Herbicide formulations containing diflufenican were selected for author-ity control in 1998 but have not previously been selected for authority control.

Triflusulfuron-methyl (Figure 1c) belongs to the big group of sulfony-lurea herbicides. It is used as post-emergence control of a broad range of annual and perennial broad-leaved weeds in beets. Triflusulfuron-methyl is selective due to rapid metabolism in sugar beet. It inhibits the synthesis of the essential amino acids valine and isoleucine, hence stop-ping cell division and plant growth. Herbicide formulations containing triflusulfuron-methyl were selected for authority control in 1997.

SC

OH

O

N

CH2CH2CH3

OCH2CH3

N OHN

CF3

C

F FO �

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SO2NHCONHN

NN

N(CH3)2

OCH2CF3CH3

CO2CH3

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(c)

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The chemical structure of the herbicide active ingredients: cycloxydim (a), diflufenican (b) and triflusulfuron-methyl (c).

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At the time of sampling for the control campaign, one product contain-ing cycloxydim, four products containing diflufenican and two products containing triflusulfuron-methyl were approved for use in Denmark. All products containing cycloxydim and diflufenican were available on the market while one product containing triflusulfuron-methyl was available on the market during the period of the sample collection. One sample of each herbicide product was collected. The samples are listed in Appen-dix I.

The samples containing cycloxydim were analysed in October 2007. The sample containing triflusulfuron-methyl was analysed in January - Feb-ruary 2008 and the samples containing diflufenican were analysed in September - November 2007. One of the diflufenican products was ana-lysed again in July 2008 due to analytical problems, while one result is not reported.

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The contents of cycloxydim were determined using reversed phase high performance liquid chromatography and UV-detector, RP-HPLC-UV�� . The method is developed on the basis of the existing CIPAC method.

The contents of diflufenican were determined using reversed phase high performance liquid chromatography and UV-detector, RP-HPLC-UV (�� ). The method is developed on the basis of the existing CIPAC method and information from the manufacturer.

The contents of triflusulfuron-methyl were determined using reversed phase high performance liquid chromatography and UV-detector, RP-HPLC-UV (�� ). As no CIPAC-method on triflusulfuron-methyl exists, the method is developed on the basis of information from the manufacturer.

Table 2.2 shows agreement between declared and determined content for all six samples containing cycloxydim, diflufenican and triflusulfuron-methyl as active ingredients.

��Content of active ingredient in samples of herbicides.

1) Mean ± 95% confidence limits. 2) Tolerance limits for the content of active ingredients according to the Statutory Order �� .

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Cycloxydim 10.8 % 100 g/L 11.0 ± 0.1 % 10.2 – 12.5 % ATMI 2007-2089

Diflufenican 43.5 % 500 g/L 41.8 ± 0.3 % 41.3 – 45.7 % ATMI 2007-2094

Diflufenican 4 % 40 g/L 4.11 ± 0.03 % 3.6 – 4.4 % ATMI 2007-2096

Diflufenican 4 % 40 g/L 4.04 ± 0.03 % 3.6 – 4.4 % ATMI 2007-2336

Triflusulfuron-methyl 50 % - 48.1 ± 0.6 % 47.5 – 52.5 % ATMI 2007-2098

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41 active ingredients in fungicide formulations are approved in Denmark (�� ). Products containing boscalid, dimethomorph, ep-oxiconazole, fenpropimorph, mancozeb and propamocarb as active in-gredients were selected for control in 2007. All products were examined for the content of active ingredient and for the content of octylphenol and nonylphenol.

Boscalid (Figure 2a) belongs to the group of carboxamide fungicides used in Denmark for the treatment of fungal diseases in a broad range of crops (e.g. cereals, rape, root fruits, onions, cabbages, peas, beans, straw-berry, cherries, plums, salads and leek). Boscalid is a systemic fungicide, which inhibits complex II in the mitochondrial electron transport chain. Fungicide formulations containing boscalid were approved for the Dan-ish market in 2006 and have not previously been selected for authority control.

Dimethomorph (Figure 2b) is a cinnamic acid fungicide. It is used only for the treatment of fungal diseases in potatoes and onions in Denmark. Dimethomorph inhibits the formation of the fungal cell wall. It is a local systemic fungicide with protective and antisporulant. Fungicide formu-lations containing dimethomorph were approved for the Danish market in 2005 and have not previously been selected for authority control.

Epoxiconazole (Figure 2c) is a fungicide, which belongs to the big group of DMI triazoles. It is used in Denmark only for the treatment of fungal diseases in cereals, beets and off label in spinach and seeds. Epoxicona-zole is a broad spectrum systemic fungicide with protective and curative action. It inhibits the C-14-demethylase in sterol biosynthesis. Fungicide formulations containing epoxiconazole were approved for the Danish market in 2003 and have not previously been selected for authority con-trol.

Fenpropimorph (Figure 2d) belongs to the group of morpholine fungi-cides used in Denmark only for the treatment of fungal diseases in cere-als and chive. Fenpropimorph affects a range of fungal enzymes by in-hibiting the ergosterol biosynthesis by inhibiting reduction and isomeri-sation. It is a systemic foliar fungicide with protective and curative ac-tion. Fungicide formulations containing fenpropimorph were selected for authority control in 1999.

Mancozeb (Figure 2e) is a alkylenebis(dithiocarbamate) fungicide used in Denmark for the treatment of fungal diseases in potatoes, fruit bushes and trees, peas, onions, cabbages and off label on ornamentals. Man-cozeb affects a broad range of fungal diseases by inactivating sulfhydryl groups in amino acids and enzymes. It is a systemic fungicide with pro-tective action. Fungicide formulations containing mancozeb were se-lected for authority control in 1999.

Propamocarb (Figure 2f) is a fungicide, which belongs to the big group of carbamates. It is used in Denmark for the treatment of phycomycetous diseases in tomatoes, salads, cucumber, potatoes and ornamentals.

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Propamocarb is a systemic protective fungicide absorbed by the roots and leaves. It inhibits the mycelial growth and development of sporangia and spores. Fungicide formulations containing propamocarb were se-lected for authority control in 2001.

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At the time of sampling for the control campaign, six products contain-ing epoxiconazole and mancozeb, four containing propamocarb, two containing fenpropimorph and one containing boscalid and dimetho-morph were approved for use in Denmark. All the products containing fenpropidin, boscalid and dimethomorph were available on the market during the period of the sample collection, while only four out of six products containing epoxiconazole and mancozeb, and three out of four products containing propamocarb were available on the market during the period. One sample of each product was collected. The list of sam-ples is summarised in Appendix I.

The samples containing fenpropimorph were analysed in July 2007. The samples containing epoxiconazole, dimethomorph and mancozeb were analysed in November 2007, samples containing propamocarb were ana-lysed in December 2007 and the sample containing boscalid was ana-lysed in April – May 2008.

C

N

OHNCl

Cl

Cl

C C

O

CH3O OCH3

H

N OC

C

Cl

C

O

CH3O OCH3

H

N OC

(�)-(�)-

(a) (b)

O

CH2

FCl

N

NN

(CH3)3C

CH2

NO

CH3

CH3CH2

CHCH3

(c) (d)

CH2CH2C

HNS

SC

NH

S

SMn++

x

(Zn) y

x:y = 1:0.091

.HClN(CH2)3NHCO2(CH2)2CH3

CH3

CH3

(e) (f) �

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The chemical structure of the fungicide active ingredients: boscalid (a), dimethomorph (b), epoxiconazole (c), fenpropimorph (d), mancozeb (e) and propamocarb (f).

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The content of boscalid was determined using reversed phase high per-formance liquid chromatography and UV-detector, RP-HPLC-UV �� As no CIPAC-method on boscalid exists and no method is received from the manufacturer, the method is developed by NERI.

The content of epoxiconazole was determined using gas chromatogra-phy and flame ionization detector, GC-FID� �� . The method is developed on the basis of the existing CIPAC method.

The content of dimethomorph was determined using reversed phase high performance liquid chromatography and UV-detector, RP-HPLC-UV �� . The method is developed on the basis of the exist-ing CIPAC method.

The content of fenpropimorph was determined using gas chromatogra-phy and flame ionization detector, FC-FID� �� The method is developed on the basis of the existing CIPAC method.

The content of mancozeb was determined as Zn and Mn using atomic absorption spectroscopy (AAS) �!�� and not determined ac-cording to�the CIPAC-method as it is based on titration.

The content of propamocarb was determined using gas chromatography and flame ionization detector, GC-FID�� "�. The method is developed on the basis of the existing CIPAC method and on informa-tion from the manufacturer.

Table 2.3 shows agreement between declared and determined content for all fifteen samples containing boscalid, dimethomorph, epoxiconazole, fenpropimorph, mancozeb and propamocarb as active ingredients. On seven products, the content of active ingredient was declared only in g/L or g/kg, but not in % (w/w) as required according to the Statutory Order �� .

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��% The content of active ingredient in samples of fungicides.

1) Mean ± 95% confidence limits. 2) Tolerated limits for the content of active ingredients according to the Statutory Order �� . 3) Content (expressed as %) not declared. 4) Calculated on the basis of the declared content in g/kg. 5) Calculated on the basis of the declared content in g/L.

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Boscalid 26.7 % - 25.0 ± 0.3% 25.3 – 28.0 % ATMI 2007-2097

Dimethomorph -3) 75g/kg 72.1 ± 4 g/kg 67.5 – 825g/kg4) ATMI 2007-2101

Epoxiconazole -3) 50g/L 53.5 ± 0.3g/L 45 – 55g/L5) ATMI 2007-2090

Epoxiconazole -3) 84g/L 85.3 ± 0.4g/L 75.6 – 92.4 g/L5) ATMI 2007-2091

Epoxiconazole -3) 125g/L 130 ± 1g/L 117.5 – 132.5 g/L5) ATMI 2007-2092

Epoxiconazole -3) 125g/L 130 ± 1g/L 117.5 – 132.5 g/L5) ATMI 2007-2525

Fenpropimorph -3) 250g/kg 260.3 ± 0.5g/L 235 – 265 g/L4) ATMI 2007-2091

Fenpropimorph 79.8 % 750g/L 79.5 ± 0.7% 77.3 – 82.3 % ATMI 2007-2102

Mancozeb 24.3 % 301 g/L 28.2 ± 3.1% 22.8 – 25.8 % ATMI 2007-2099

Mancozeb 75 % - 80.9 ± 8.9 % 72.5 – 77.5 % ATMI 2007-2100

Mancozeb -3) 667g/kg 722 ± 79 g/kg 642 – 692 g/kg4) ATMI 2007-2101

Mancozeb 75 % - 78.0 ± 8.6 % 72.5 – 77.5 % ATMI 2007-2122

Propamocarb 20 % 248g/L 20.9 ± 0.2% 18.8 – 21.2 % ATMI 2007-2099

Propamocarb 58.8 % 640g/L 56.1 ± 0.6% 56.3 – 61.3 % ATMI 2007-2198

Propamocarb 66.8 % 722g/L 69.0 ± 0.8% 64.3 – 69.3 % ATMI 2007-2335

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Among the different insecticide formulations available on the Danish market (�� ) the products containing fipronil as active ingredient was selected for control in 2007. All products were examined for the content of active ingredient and for the content of octylphenol and nonylphenol.

Fipronil (Figure 3) belongs to the group of fiproles. It is used in Denmark for the control of specific thrips on ornamentals in green houses. Fipronil is a moderately systemic insecticide toxic by contact and ingestion. It acts as a blocker for the GABA-regulated chloride channel. Insecticide formu-lations containing fipronil were approved for the Danish market in 2002 and have not previously been selected for authority control.

F3C N

Cl

Cl

N CN

SO

CF3NH2

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The chemical structure of the insecticide fipronil.

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At the time of sampling, one product containing fipronil was approved for use in Denmark. The product was available on the market during the period of the sample collection. One sample of the product was collected. The sample list is shown in Appendix I. The sample were analysed in November 2007.

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The content of fipronil was determined using reversed phase high per-formance liquid chromatography and UV-detector, RP-HPLC-UV�� The method is developed on the basis of the existing CI-PAC method.

Table 2.4 shows agreement between declared and determined content for the sample containing fipronil as active ingredient.

��& Content of active ingredient in sample of insecticides

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Fipronil 80% - 79.2 ± 0.6 % 77.5 – 82.5 % ATMI 2007-2337 1) Mean ± 95% confidence limits. 2) Tolerance limits for the content of active ingredients according to the Statutory Order (�� ).

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Among the eleven plant growth regulators available on the Danish mar-ket (�� ) the formulations containing daminozide as ac-tive ingredient was selected for control in 2007, and examined for the content of active ingredients and for the content of octylphenol and non-ylphenol.

Daminozide (Figure 4) is absorbed by the leaves, with translocation throughout the plant to produce more compact plants. It is used in Denmark only for growth regulation of ornamentals in green houses. Daminozide affects the growth by inhibiting internodal elongation. Plant growth regulators containing daminozide were selected for authority control in 1992.

OC

(CH3)2NNH CH2CH2CO2H

��&�The chemical structure of the plant growth regulator daminozide.

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At the time of sampling for the control campaign, one product contain-ing daminozide was approved for use in Denmark. The product was available on the market during the period of the sample collection. One sample of the product was collected. The sample list is shown in Appen-dix I. The sample were analysed in September 2007.

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The content of daminozide was determined using reversed phase high performance liquid chromatography and UV-detector, RP-HPLC-UV�� As no CIPAC-method on daminozide exists, the method is developed on the basis of information from the manufacturer.

Table 2.5 shows agreement between declared and determined content for the sample containing daminozide as active ingredient.

��'�The content of active ingredient in the sample of plant growth regulators

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Daminozide 85 % - 83.9 ± 0.2 % 82.5 - 87.5 % ATMI 2007-2334 1) Mean ± 95% confidence limits. 2) Tolerated limits for the content of active ingredients according to the Statutory Order �� .

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Among the ten insect repellents available on the Danish market (�� ) the formulations containing icaridin as active ingredient was selected for control in 2007, and examined for the content of active ingredients and for the content of octylphenol and nonylphenol.

Icaridin (Figure 5) has the IUPAC name 1-piperidinecarboxylic acid 2-(2-hydroxyethyl)-1-methylpropylester and is also known as picaridine, KBR 3023, and under the INCI name hydroxyethyl isobutyl piperidine carboxylate (INCI; International Nomenclature of Cosmetic Ingredients). It is used against mosquitoes. Insect repellents containing icaridin have not previously been selected for authority control.

��'�The chemical structure of the insect repellent icaridin.

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At the time of sampling for the control campaign, five products contain-ing icaridin were approved for use in Denmark. Four out of the five products were available on the market during the period of the sample collection. One sample of each product was collected. The list of samples is summarised in Appendix I. The sample were analysed in May 2008.

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The content of icaridin was determined using reversed phase high per-formance liquid chromatography and UV-detector, RP-HPLC-UV�� The method is developed on the basis of the existing CI-PAC method and information from the manufacturer.

Table 2.5 shows agreement between declared and determined content for all four samples containing icaridin as active ingredient.

��'�The content of active ingredient in the samples of insect repellents.

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Icaridin 20 % 191 mg/ml 20.0 ± 0.1 % 18.8 - 21.2 % ATMI 2007-2371



Icaridin 10 % 100 mg/ml 9.6 ± 0.1 % 9 - 11 % ATMI 2007-2374 1) Mean ± 95% confidence limits. 2) Tolerated limits for the content of active ingredients according to the Statutory Order �� .

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Among the many additives used in pesticide formulations, nonylphenol ethoxylates (NPEO) and octylphenol ethoxylates (OPEO) were selected for control in 2006. All the formulations examined for the content of ac-tive ingredient as described in the previous parts of this report have also been examined for the content of NPEO and OPEO.

NPEO and OPEO belong to the group of alkylphenol ethoxylates (APEO), a group of surface-active compounds which is widely used in the formulation of plant protection products. They are added to the for-mulation to change the physical properties e.g. to facilitate the transport of the active ingredient into the plants or into the insects. In the 1990’s APEO was recognised to have estrogenic effects. This kind of substances is suspected to be the contributory reason for the decrease in the male reproduction ability, and to the increase in the cases of abnormality in the male sexual organs and the cases of testicle cancer. The same effects are also seen in wild living male animals. OPEO is not used as widely as NPEO in pesticide formulations, but the estrogenic effect is several times higher. The industry and the Danish authorities have agreed on remov-ing these compounds from all Danish-sold pesticide formulations pro-duced after June 2000 except for few exceptions given by the Danish au-thorities. Dealers are allowed to sell stocks after this date.

��(�The chemical structure of the additive nonylphenol ethoxylate. The structure of octylphenol ethoxylate is similar, C9H19 is replaced with C8H17.

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Beside the examination of the content of active ingredient all pesticide formulations sampled in 2007 are examined for content of NPEO and OPEO. The sample list is shown in Appendix I

The samples were analysed in February 2008.

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The content of NPEO and OPEO was determined by using reversed phase high performance liquid chromatography and MS-detector, RP-HPLC-MS �� As no CIPAC-method on NPEO and OPEO exists, the method was developed in the laboratory. The analytical method is capable of analysing NPEO and OPEO simultaneously.

19

��)�The content of NPEO and OPEO in samples of pesticide formulations.

�� $�� $��

��*� +!,�,+!,�

�� $��* ��

+!,� ��,+!,�

23 0/0 23

Table 2.7 shows that none of the 23 examined samples contain OPEO or NPEO.

20

�� !��

Five different groups of products covered by the pesticide regulation were included in the 2007 analytical chemical authority control:

1. Herbicides containing cycloxydim, diflufenican and triflusulfuron-methyl.

2. Fungicides containing boscalid, dimethomorph, epoxiconazole, fen-propimorph, mancozeb and propamocarb.

3. Insecticides containing fipronil.

4. Plant growth regulators containing daminozide.

5. Insect repellents containing icaridin.

All products were examined for the content of the active ingredients. In addition to the examination of the content of active ingredients, all col-lected samples were examined for content of octylphenol ethoxylates and nonylphenol ethoxylates.

Satisfactory results were found for all examined pesticide formulations. Thus, the analysed samples of these formulations complied with the ac-cepted tolerance limits with respect to the content of the active ingredi-ents as specified in Danish Statutory Order on pesticides.

None of the examined samples contained OPEO or NPEO.

On the label of seven products, the content of active ingredient was de-clared only in g/L or g/kg, but not in % (w/w) as required by the Statu-tory Order.

21

��

�� # � ��: Analysemetode. Bestemmelse af cycloxydim som aktivstof i bekæmpelsesmidler. (Method of Analysis. Determination of cycloxydim as active ingredient in pesticides. National Environmental Research Institute). 5 pp. (In Danish).�

�� # � ��: Analysemetode. Bestemmelse af diflufenican som aktivstof i bekæmpelsesmidler. (Method of Analysis. Determination of diflufenican as active ingredient in pesticides. National Environmental Research Institute). 6 pp. (In Danish).�

�� # � ��: Analysemetode. Bestemmelse af triflusulfuron-methyl som aktivstof i bekæmpelsesmidler. (Method of Analysis. Deter-mination of triflusulfuron-methyl as active ingredient in pesticides. Na-tional Environmental Research Institute). 4 pp. (In Danish).

�� # � ��: Analysemetode. Bestemmelse af boscalid som ak-tivstof i bekæmpelsesmidler. (Method of Analysis. Determination of boscalid as active ingredient in pesticides. National Environmental Re-search Institute). 6 pp. (In Danish).

�� # ��: Analysemetode. Bestemmelse af epoxiconazol som aktivstof i bekæmpelsesmidler. (Method of Analysis. Determination of epoxiconazole as active ingredient in pesticides. National Environmental Research Institute). 5 pp. (In Danish).

�� # ��: Analysemetode. Bestemmelse af dimetomorph som aktivstof i bekæmpelsesmidler. (Method of Analysis. Determination of dimetomorph and cyprodinil as active ingredient in pesticides. National Environmental Research Institute). 6 pp. (In Danish).

�� # � ��: Analysemetode. Bestemmelse af fenpropimorph som aktivstof i bekæmpelsesmidler. (Method of Analysis. Determination of fenpropimorph as active ingredient in pesticides. National Environ-mental Research Institute). 5 pp. (In Danish).�

�� # ��"�: Analysemetode. Bestemmelse af propamocarb som aktivstof i bekæmpelsesmidler. (Method of Analysis. Determination of propamocarb as active ingredient in pesticides. National Environmental Research Institute). 5 pp. (In Danish).

�� # � ��: Analysemetode. Bestemmelse af fipronil som ak-tivstof i bekæmpelsesmidler. (Method of Analysis. Determination of fipronil as active ingredient in pesticides. National Environmental Re-search Institute). 6 pp. (In Danish).

�� # � ��: Analysemetode. Bestemmelse af daminozid som aktivstof i bekæmpelsesmidler. (Method of Analysis. Determination of daminozide as active ingredient in pesticides. National Environmental Research Institute). 6 pp. (In Danish).

22

�� # � ��: Analysemetode. Bestemmelse af icaridin som ak-tivstof i bekæmpelsesmidler. (Method of Analysis. Determination of icaridin as active ingredient in pesticides. National Environmental Re-search Institute). 8 pp. (In Danish).

�� # ��: Analysemetode. Bestemmelse af NPEO og OPEO i bekæmpelsesmidler. (Method of Analysis. Determination of NPEO and OPEO in pesticides. National Environmental Research Institute). 11 pp. (In Danish).

��: Bekendtgørelse om bekæmpelsesmidler. Miljømi-nisteriets bekendtgørelse nr. 533 af 18. juni 2003. (Statutory Order on Pes-ticides. Statutory Order from the Ministry of the Environmen, No. 533 of June 18, 2003).�

��: Oversigt over godkendte bekæmpelsesmidler 2006. http://www2.mst.dk/databaser/Bekaemp/2007%20Oversigt.rtf (Da-nish EPA, 2006: List of Approved Pesticides 2006, Danish Environmental Protection Agency). (In Danish).

!�� : Analysemetode. Bestemmelse af mancozeb som ak-tivstof i bekæmpelsesmidler. (Method of Analysis. Determination of mancozeb as active ingredient in pesticides. National Environmental Re-search Institute). 5 pp. (In Danish).�

#�� $ % &��' The Pesticide Manual. 13th Ed. British Crop Protec-tion Council, Hampshire. United Kingdom.

23

(��)��

�� "� �� "� �� "��0�� !��#��

��Herbicides

�� +� �� $�� $�� !"#��$��

Cycloxydim Focus Ultra Liquid BASF 2007-2089

Diflufenican DFF Liquid Bayer 2007-2094

Diflufenican Zeppelin Granulate Bayer 2007-2096

Diflufenican Zeppelin – Garden langtidsvirkende Granulate Bayer 2007-2336

Triflusulfuronmethyl Safari Granulate DuPont 2007-2098

��Fungicides

�� +� �� $�� $�� !"#��$��

Boscalid Signum Granulate BASF 2007-2097

Dimethomorph Acrobat Granulate Cyanamid 2007-2101

Epoxiconazole Opera Liquid BASF 2007-2090

Epoxiconazole Opus Team Liquid BASF 2007-2091

Epoxiconazole Opus Liquid BASF 2007-2092

Epoxiconazole Opus Liquid 3A Kemi 2007-2525

Fenpropimorph Opus Team Liquid BASF 2007-2091

Fenpropimorph BASF Corbel Liquid BASF 2007-2102

Mancozeb Tattoo Liquid Bayer 2007-2099

Mancozeb Dithane NT Powder Dow AgroSciences 2007-2100

Mancozeb Acrobat Granulate Cyanamid 2007-2101

Mancozeb Tridex DG Granutale BASF 2007-2122

Propamocarb Tattoo Liquid Bayer 2007-2099

Propamocarb Previcur Liquid AgrEvo 2007-2198

Propamocarb Proplant Liquid Agriphar 2007-2335

��%�Insecticides

�� +� �� $�� $�� !"#��$��

Fipronil Regent WG Granulate BASF 2007-2337

��&�Plant Growth Regulators

�� +� �� $�� $�� !"#��$��

Daminozide Alar SP Powder AgrEvo 2007-2334

��'�Insect repellents

�� +� �� $�� $�� !"#��$��

Icaridin Autan Aktive Lotion Lotion SC Johnson scandinavia 2007-2371

Icaridin Autan Aktive Pumpespray Lotion SC Johnson scandinavia 2007-2372

Icaridin Autan Aktive Stift Stick SC Johnson scandinavia 2007-2373

Icaridin Autan Family Milk Creme SC Johnson scandinavia 2007-2374

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At NERI’s website www.neri.dk you’ll fi nd information regarding ongoing research and development projects.

Furthermore the website contains a database of publications including scientifi c articles, reports, conference contributions etc. produced by NERI staff members.

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NERI’s website www.neri.dk contains a list of all published technical reports along with other NERI publications. All recent reports can be downloaded in electronic format (pdf) without charge. Some of the Danish reports include an English summary.

Nr./No. 2008

Nr. 676 Fodring af kortnæbbede gæs om foråret i Vestjylland. Biologiske fakta til understøttelse af fremtidig forvaltningsstrategi. Af Madsen, J. 20 s. (elektronisk)

675 Annual Danish Emission Inventory Report to UNECE. Inventories from the base year of the protocols to year 2006. By Nielsen, O.-K. et al. 504 pp. (electronic)

674 Environmental monitoring at the cryolite mine in Ivittuut, Spouth Greenland, in 2007. Johansen, P. et al. 31 pp. (electronic)

672 Revised emission factors for gas engines including start/stop emissions. Sub-report 3 (NERI). By Nielsen, M., Illerup, J.B. & Birr-Petersen, K. 67 pp. (electronic)

671 DEVANO. Decentral Vand- og Naturovervågning. Programbeskrivelse 2008. Af Boutrup, S. & Jensen, P.N. (red.). 33 s. (elektronisk)

670 Prioriteringsmetoder i forvaltningen af Habitatdirektivets naturtyper og arter i Natura 2000-områder. Af Skov, F. et al. 36 s. (elektronisk)

669 Identifi kation af referencevandløb til implementering af vandrammedirektivet i Danmark. Kristensen, E.A. et al. 55 s. elektronisk)

668 Brændefyring i hjemmet – praksis, holdninger og regulering. Af Petersen, L.K. & Martinsen, L. 48 s. (elektronisk)

667 Denmark’s National Inventory Report 2008. Emission Inventories 1990-2006 – Submitted under the United Nations Framework Convention on Climate Change. By Nielsen, O.-K. et al. 701 pp. (electronic)

666 Agerhønens biologi og bestandsregulering. En gennemgang af den nuværende viden. Af Kahlert, T., Asferg, T. & Odderskær, P. 61 s.

665 Individual traffi c-related air pollution and new onset adult asthma. A GIS-based pilot study. By Hansen, C.L. et al. 23 pp.

664 Aluminiumsmelter og vandkraft i det centrale Grønland. Datagrundlag for natur og ressourceudnyttelse i forbindelse med udarbejdelse af en Strategisk Miljøvurdering (SMV). Af Johansen, P. et al. 110 s.

663 Tools to assess conservation status on open water reefs in Nature-2000 areas. By Dahl, K. & Carstensen, J. 25 pp.

662 Environmental monitoring at the Nalunaq Gold Mine, South Greenland, 2007. By Glahder, C.M., Asmund, G. & Riget, F. 31 pp.

661 Tilstandsvurdering af levesteder for arter. Af Søgaard, B. et al. 72 s.

660 Opdatering af vurdering af anvendelse af SCR-katalysatorer på tunge køretøjer som virkemiddel til nedbringelse af NO2 forureningen i de største danske byer. Af Ketzel, M. & Palmgren, F. 37 s.

659 Optimering af behandlingseffekten i akvakultur. Minimering af forbrug og udlednbing af hjælpestoffer. Af Sortkjær, O. et al. 124 s. (also available in print edtion).

658 Danske kystklitter – vegetation og jordbundskemi. Analyse af NOVANA-data 2004-2006. Af Damgaard, C., Nygaard, B. & Nielsen, K.E. 66 s.

657 High density areas for harbour porpoises in Danish waters. By Teilmann, J. et al. 40 pp.

656 Manglende indberetninger til vildtudbyttestatistikken i jagtsæsonen 2006/07. Af Asferg, T. 21 s.

654 Rapportering af Luftemissioner på Grid. Metoder og principper. Af Jensen, M.T. et al. 56 s.

653 Control of Pesticides 2006. Chemical Substances and Chemical Preparations. By Krongaard, T., Petersen, K.K. & Christoffersen, C. 25 pp.

652 A preliminary strategic environmental impact assessment of mineral and hydrocarbon activities on the Nuussuaq peninsula, West Greenland. By Boertmann, D. et al. 66 pp.

651 Undersøgelser af jordhandler i forbindelse med naturgenopretning. Af Jensen, P.L., Schou, J.S. & Ørby, P.V. 44 s.

650 Fuel consumption and emissions from navigation in Denmark from 1990-2005 – and projections from 2006-2030. By Winther, M. 108 pp.

[Blank page]

National Environmental Research Institute 978-87-7073-068-6University of Aarhus . Denmark ISSN 1600-0048

Five different groups of products covered by the pesticide regulation were included in the 2007 analytical chemical authority control: 1) Herbicides containing cycloxydim, diflufenican and triflusulfuron-methyl. 2) Fungici-des boscalid, dimethomorph, epoxiconazole, fenpropimorph, mancozeb and propamocarb. 3) Insecticides containing fipronil. 4) Plant growth re-gulators containing daminozide. 5) Insect repellents containing icaridin. All samples were examined for the content of active ingredients and for the content of OPEO and NPEO. All samples in this years programme complied with the accepted tolerance limits with respect to the content of the active ingredients as specified in Danish Statutory Order on pesticides. None of the examined samples contained OPEO or NPEO. On the label of seven products, the content of active ingredient was declared only in g/L or g/kg, but not in % (w/w) as required.

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kontrol of pesticides 2007 - dce of pesticides 2007 ... insecticides containing fipronil. 4) plant...

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