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Pesticides and contaminants in organic products: Herbicides Dr. Günter Lach, February 2019

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Page 1: Herbicides Febr 2019 · February 2019 How is the MRL definition of the pesticide? Does it cover only one analyte or also metabolites / degradation products / conjugates? 4 Example:

Pesticides and contaminants in organic products:

Herbicides

Dr. Günter Lach, February 2019

Page 2: Herbicides Febr 2019 · February 2019 How is the MRL definition of the pesticide? Does it cover only one analyte or also metabolites / degradation products / conjugates? 4 Example:

February 2019

Paraquat

2

2,4-D

Haloxyfop

MCPA

Page 3: Herbicides Febr 2019 · February 2019 How is the MRL definition of the pesticide? Does it cover only one analyte or also metabolites / degradation products / conjugates? 4 Example:

February 2019

Paraquat

3

2,4-D

Pendimethalin

Glyphosate

Prosulfocarb

Haloxyfop

MCPA

ImazamoxPropyzamid

Dichlorprop

……

Page 4: Herbicides Febr 2019 · February 2019 How is the MRL definition of the pesticide? Does it cover only one analyte or also metabolites / degradation products / conjugates? 4 Example:

February 2019

How is the MRL definition of the pesticide?Does it cover only one analyte or also metabolites / degradation products / conjugates?

4

Example: Phenoxycarboxylic acids like f. ex. Haloxyfop or 2,4-D

The MRL definitions are complex:

Haloxyfop = sum of Haloxyfop, its’ esters, its’ salts and its’ conjugates

2,4-D = sum of 2,4-D, its’ salts, its esters and its’ conjugates

RESIDUE DEFINITON

Page 5: Herbicides Febr 2019 · February 2019 How is the MRL definition of the pesticide? Does it cover only one analyte or also metabolites / degradation products / conjugates? 4 Example:

February 2019

ANALYTICAL APPROACH

Questioning the analytical resultsCan the “entire” pesticide be analysed by a multi-method? Or is a single residue method or an additional analytical step necessary?

5

Example Haloxyfop: This pesticide requires an extra step (“Hydrolysis”) to cover all components which are relevant like free acid, esters, and conjugates.

What influence does this aspect have on the reported laboratory result?

And: what are “conjugates”?

Page 6: Herbicides Febr 2019 · February 2019 How is the MRL definition of the pesticide? Does it cover only one analyte or also metabolites / degradation products / conjugates? 4 Example:

February 2019 6

Levels of 2,4-D in lemons without and with hydrolysis (Data: Acidic pesticides using QuEChERS method, CVUA Stuttgart)

Analysis of Acidic Herbicidesincluding a “hydrolysis step”

Page 7: Herbicides Febr 2019 · February 2019 How is the MRL definition of the pesticide? Does it cover only one analyte or also metabolites / degradation products / conjugates? 4 Example:

February 2019

and … particular esters(f.ex. Haloxyfop-methyl)

Haloxyfop-moiety

7

Residues of Haloxyfop in food products

Laboratories are usually able to detect only Haloxyfop (acid)

Page 8: Herbicides Febr 2019 · February 2019 How is the MRL definition of the pesticide? Does it cover only one analyte or also metabolites / degradation products / conjugates? 4 Example:

February 2019

Haloxyfop-glucoside:Substitute “-Me” by “Glucoside”

Haloxyfop-moiety

8

Conjugates of Haloxyfop

Haloxyfop-glutamate:Substitute “-Me” by “Glutamate”

Haloxyfop-aspartate:Substitute “-Me” by “Aspartate”

Haloxyfop-???:Substitute “-Me” by “???”

There might be much more “conjugates”, which we don’t know ➔ nature is very creative!

Page 9: Herbicides Febr 2019 · February 2019 How is the MRL definition of the pesticide? Does it cover only one analyte or also metabolites / degradation products / conjugates? 4 Example:

February 2019

ANALYTICAL APPROACH

9

The laboratories are required to analyse the samples in a different way ➔ alkaline hydrolysis (H2O, NaOH, time, high temperatures)

Page 10: Herbicides Febr 2019 · February 2019 How is the MRL definition of the pesticide? Does it cover only one analyte or also metabolites / degradation products / conjugates? 4 Example:

February 2019

Haloxyfop-estersHaloxyfop-glucoside / -glutamate /

-aspartate / -…Haloxyfop-moiety

10

Residues of Haloxyfop in food products

Laboratories are usually able to detect only Haloxyfop (acid)

H2O, NaOH, time, high temperatures = “Hydrolysis”

Page 11: Herbicides Febr 2019 · February 2019 How is the MRL definition of the pesticide? Does it cover only one analyte or also metabolites / degradation products / conjugates? 4 Example:

February 2019

ANALYTICAL APPROACH

11

1. relana® Method Ring Test June 2018

Acidic Herbicidesin Clementine and Flaxseed

2. relana® Method Ring Test December 2018

Acidic Herbicides (Conjugates)in Clementine

Page 12: Herbicides Febr 2019 · February 2019 How is the MRL definition of the pesticide? Does it cover only one analyte or also metabolites / degradation products / conjugates? 4 Example:

February 2019

ANALYTICAL APPROACH

12

• Haloxyfop (acid)• Haloxyfop-methyl (ester)• MCPA (acid)• MCPA-2-ethylhexyl (ester)• 2,4-D (acid)• 2,4-D-2-ethylhexyl (ester)• Dichlorprop (acid)• Dichlorprop-butotyl (ester)

relana® Method Ring Test June 2018

Acidic Herbicidesin Clementine and Flaxseed

• Haloxyfop-glutamate (conjugate)

• MCPA-glucoside (conjugate)

• no conjugate

• Dichlorprop-aspartate (conjugate)

Page 13: Herbicides Febr 2019 · February 2019 How is the MRL definition of the pesticide? Does it cover only one analyte or also metabolites / degradation products / conjugates? 4 Example:

February 2019

Haloxyfop-glutamate:Conditions of the alkaline hydrolysis are not appropriate to cover glutamate-conjugates! ➔ results are (much) too low!

13

Haloxyfop-glutamate

statistical mean: 39% of spike

70% spiked level

spiked level

120% spiked level

0,0000,0100,0200,0300,0400,0500,0600,0700,0800,0900,1000,1100,1200,1300,1400,1500,160

3 7 2 4 11 9 5 10 6 1 8

Halo

xyfo

p su

m (h

ydro

lysi

s) [m

g/kg

]

laboratory code

Haloxyfop sum (hydrolysis)

Page 14: Herbicides Febr 2019 · February 2019 How is the MRL definition of the pesticide? Does it cover only one analyte or also metabolites / degradation products / conjugates? 4 Example:

February 2019

Dichlorprop-aspartate:Conditions of the alkaline hydrolysis are not appropriate to cover aspartate-conjugates! ➔ results are (much) too low!

14

Dichlorprop-aspartate

statistical mean: 36% of spike

70% spiked level

spiked level

120% spiked level

0,0000,0100,0200,0300,0400,0500,0600,0700,0800,0900,1000,1100,1200,1300,1400,1500,1600,1700,1800,190

7 4 5 3 1 2 9 11 10 6 8

Dich

lorp

rop

sum

(hyd

roly

sis)

[mg/

kg]

laboratory code

Dichlorprop sum (hydrolysis)

Page 15: Herbicides Febr 2019 · February 2019 How is the MRL definition of the pesticide? Does it cover only one analyte or also metabolites / degradation products / conjugates? 4 Example:

February 2019

MCPA-glucoside:Conditions of the alkaline hydrolysis are appropriate to cover glucoside-conjugates! ➔ results are OK!

15

MCPA-glucoside

statistical mean: 76% of spike

70% spiked level

spiked level

120% spiked level

0,000

0,050

0,100

0,150

0,200

5 11 1 4 7 9 2 6 3 10 8

MCP

A su

m (h

ydro

lysi

s) [m

g/kg

]

laboratory code

MCPA sum (hydrolysis)

Page 16: Herbicides Febr 2019 · February 2019 How is the MRL definition of the pesticide? Does it cover only one analyte or also metabolites / degradation products / conjugates? 4 Example:

February 2019

ANALYTICAL APPROACH

16

relana® Method Ring Test December 2018

Acidic Herbicides (conjugates) part 2in Clementine

Part 1• Haloxyfop-glutamate• MCPA-glucoside• 2,4-D no conjugate• Dichlorprop-aspartate

Part 2• Haloxyfop-glucoside• MCPA-glucoside• 2,4-D-glucoside• Dichlorprop-glucoside

Page 17: Herbicides Febr 2019 · February 2019 How is the MRL definition of the pesticide? Does it cover only one analyte or also metabolites / degradation products / conjugates? 4 Example:

February 2019

2,4-D-glucoside:statistical mean =72% of spiked level

17

Glucoside-conjugates

120 % spiked level

statistical mean

70 % spiked level

0,000

0,100

0,200

0,300

5 2 7 4 3 8 6 10 9 1laboratory code

statistical mean

70% spiked level

spiked level

120% spiked level

0,000

0,010

0,020

0,030

0,040

0,050

0,060

0,070

5 3 6 1 2 7 8 4 9 10laboratory code

Dichlorprop-glucoside:statistical mean =81% of spiked level

y-axis: concentrations in mg/kg y-axis: concentrations in mg/kg

Page 18: Herbicides Febr 2019 · February 2019 How is the MRL definition of the pesticide? Does it cover only one analyte or also metabolites / degradation products / conjugates? 4 Example:

February 2019

Haloxyfop-glucoside:statistical mean =74% of spiked level

18

Glucoside-conjugates

MCPA-glucoside:statistical mean =80% of spiked level

statistical mean

70% spiked level

spiked level

120% spiked level

0,000

0,020

0,040

0,060

0,080

0,100

0,120

0,140

0,160

0,180

4 6 2 7 3 8 9 1 10 5laboratory code

statistical mean

70% spiked level

spiked level

120% spiked level

0,000

0,010

0,020

0,030

2 4 7 3 6 8 1 5 9 10laboratory code

y-axis: concentrations in mg/kg y-axis: concentrations in mg/kg

Page 19: Herbicides Febr 2019 · February 2019 How is the MRL definition of the pesticide? Does it cover only one analyte or also metabolites / degradation products / conjugates? 4 Example:

February 2019

Overall result of the method ring tests:

Glucosides:Conditions of the alkaline hydrolysis are appropriate to cover glucoside-conjugates! ➔ results are OK!

Other conjugates like aspartates, glutamates and perhaps others are not covered by the alkaline hydrolysis approach!

➤ more research necessary!

19

Acidic Herbicides

➤ in the meantime: Results of acidic herbicides measured by applying the alkaline hydrolysis approach are often closer to the true value than the results of the sum of free acids + esters only.

But bear in mind, that the entire levels might be even higher, considering the fact, that not all conjugates might be covered!

Page 20: Herbicides Febr 2019 · February 2019 How is the MRL definition of the pesticide? Does it cover only one analyte or also metabolites / degradation products / conjugates? 4 Example:

February 2019 20

Imazamox – an “alternative” herbicide

Ø Commercial introduction: 2001 (BASF: “Beyond®”, “Raptor®”)

Ø Contact and residual activity, inhibits plant amino acid synthesis

Ø Targeted weeds: Grass and broadleaf weeds, Common reed (Phragmites australis), Flowering rush (Butomus umbellatus), Curly-leaf pond weed (Potamogeton crispus)

Ø Uses: Pre- or post-emergence control of weeds in maize, rape, alfalfa, peas and beans (edible legumes), at 36–56 g/ha; pre-emergence control of weeds in ‘Clearfield’ imidazolinone-resistant wheat, rape and sunflowers.

Sources: PPDB of the Universtity of Herfordshire (UK); The Pesticide Manual, BCPC (UK)

Page 21: Herbicides Febr 2019 · February 2019 How is the MRL definition of the pesticide? Does it cover only one analyte or also metabolites / degradation products / conjugates? 4 Example:

February 2019 21

Imazamox – an “alternative” herbicide

Page 22: Herbicides Febr 2019 · February 2019 How is the MRL definition of the pesticide? Does it cover only one analyte or also metabolites / degradation products / conjugates? 4 Example:

February 2019 22

Product Imazamox concentration in mg/kg

Sunflower seeds (bio) 0,003 up to 0,021 (0,042*)

Lentils (bio) 0,026 up to 0,035

Lentils (conv.) 0,010 up to 0,032

Rice (bio) 0,012

Rice (conv.) 0,003 up to 0,007

Imazamox – an “alternative” herbicide

*source: SKAL (NL)

Analytical data provided by

Page 23: Herbicides Febr 2019 · February 2019 How is the MRL definition of the pesticide? Does it cover only one analyte or also metabolites / degradation products / conjugates? 4 Example:

February 2019 23

Propyzamide – an “alternative” herbicide

Ø Commercial introduction: 1969 (Dow AgroScience: “Kerb®”)

Ø Selective systemic herbicide, absorbed by the roots

Ø Targeted weeds: Certain grasses; broad-leaved weeds includingchickweed, mayweed, poppy, black bindweed, fat hen, speedwells

Ø Uses: Pre- and early post-emergence control of annual andperennial grass and some broad-leaved weeds, in fruit, vines, lettuce, endive, chicory, brassicas, oilseed rape, legumes, alfalfa, clover, ..., artichokes, sugar beets, ..., fallow land and forestry

Sources: PPDB of the Universtity of Herfordshire (UK); The Pesticide Manual, BCPC (UK)

Page 24: Herbicides Febr 2019 · February 2019 How is the MRL definition of the pesticide? Does it cover only one analyte or also metabolites / degradation products / conjugates? 4 Example:

February 2019 24

Propyzamide – an “alternative” herbicide

Ø Actual results: f. ex. 0,02 mg/kg in kohlrabi (stem turnip)

Page 25: Herbicides Febr 2019 · February 2019 How is the MRL definition of the pesticide? Does it cover only one analyte or also metabolites / degradation products / conjugates? 4 Example:

… keep an eye on …

… Herbicides …