www.eurofins.de

Technical developments

of residue analysis

Technical developments of residue analysis

Johannes Jaschik

14/02/2020

Residue analysis

2Technical developments of residue analysis

REGULATION (EC) No 1107/2009

Non visible !

We looking for residues (mainlyactive substances or metabolites) ofpesticides in products for which weexpect no use of these pesticides.

That means although we doing residue analysis - in mostcases we analysing contaminants in the given product.

Residue analysis

There is no analytical possibility to distinguish whether the

substance detected was used on the product or originates

from a contamination.

3Technical developments of residue analysis

For residue analyis often either GC- and/or LC-MS/MS detection is used

Approach of Residue analysis

4Technical developments of residue analysis

Evaluation based on a residue analysis for a productdepends on the scope and the sensitivity of theanalytical method(s).

Is it possible to check for all residues in foodstuff?

Free of pesticide residues?

Although this may be correct it can not be provencompletely.

Analytical strategy for pesticides

How can pesticides be detected?

Multi method II(a few years ago)

Pesticides sold/used todayPesticides sold/used in the past

G

G

G

Technical developments of residue analysis 5

G

SingleMethods(e.g. Bromid)

Group methods

Multi method I(a few years ago)

Analytical strategy for pesticides

How can pesticides be detected?

Multi method I(today)

Pesticides sold/used todayPesticides sold/used in the past

G

G

G

Technical developments of residue analysis 6

G

So even using always a multi method for analysis

limits findings to the scope of the multi method.

Multi method II(today)

Group methods

SingleMethods(e.g. Bromid)

Scope of analysis (lab)

7Technical developments of residue analysis

How is this list created?

• Historical development

• Data from customers

• Information on legal developments

• Admission in countries of origin

• Specific for certain products

(experience)

• Practically/technically feasible

Development multi method: possibilities

Scope changed over the time. In general getting broader, covering

more substances and furthermore getting more sensitive.

8Technical developments of residue analysis

• New analytical measurementssystems (LC-MS/MS)

• Better, more senstivemeasurement options

• New sample extractionmethods (e.g. Quechers)

• Better software solutions• Information about new

substances• Availability of reference

materiale.g. Fipronil RL

dropped to a few ppb

within the multi method

Reasons: e.g. MRL lowered for Fipronil

Scope

Single methods (Glyphosate)

For single methods development is similar

9Technical developments of residue analysis

Glyphosate(RL: 0.1 mg/kg)

Glyphosate, AMPA,

Glufosinate(RL: 0.001

- 0.01 mg/kg)

Reason: pressure form organic products !

New method -new validation

New analytical measurements systems (LC-MS/MS)

Better, more senstive measurement options

New sample preparation methods (e.g. derivatisation)

Single Methods (Phosphonic acid)

Because of the requirement to achieve an RL for

phosphonic acid 0.01 mg/kg a separate method was

developed.

10Technical developments of residue analysis

Fosetyl(RL: 0.01 mg/kg)Phosphonic acid(RL: 0.1 mg/kg)

Phosphonic acid,(RL: 0.01 –0.05 mg/kg)

New method

Driver for development

As many pesticides as possible, at

the level of limit values.

11Technical developments of residue analysis

Pesticides not mentioned regulated with MRL 0.01 mg/kg

EU Regulation 396/2005 for pesticide residues in food

International Federation of

Organic Agriculture Movements

Action level / Orientation value

for pesticides:0.01 mg/kg

Why analysis?

Food safety / Knowledge (Fraud)!

In a few cases MRL evenlower than 0.01 mg/kg.

Multi method

Reporting levels, always more sensitive, always better, all at the

same level?

What is a multi method?

Always a compromise:

12Technical developments of residue analysis

Due to the different

chemical properties,

these substances can be

determined individually,

but not all equally good.

• Broad scope• Maximum number of substances in

one analytical run• Robust• Reliable• Fast• … and of course cost-effective

5 10 15Time, min

0.0

2.0e5

4.0e5

6.0e5

8.0e5

Chromatogram with 52 pesticides at the same level (1 mg/kg)

Multi method (LC-MS/MS)

Desmediphamhas the lowest

sensitivity

5 10Time, min

0

500

1000

1500

2000

2500

3000

Pirimicarbhas the highest

sensitivity

Exp. Val. Ratio: 3.00 RT Window: 30.0 sec

10Time, min

0.0

1.0e5

2.0e5

3.0e5

4.0e5

5.0e5

6.0e5

7.0e5

8.0e5

Intensity, cps

Technical developments of residue analysis 13

Why not low RLs at ppb for all?

14Technical developments of residue analysis

Multi

method

costs, time, efficiency

Analysis of organic products: Besides food safety -

Identify food fraud or avoidable contamination

Technical limits toenlarge the scopeor improvesensitivity

Is contamination at very lowlevel avoidable?

Is an analytical result at a verylow level helpful for indication?

special singlemethod

new multi method

new equipment

Solutions?

15Technical developments of residue analysis

Although residue analysis give an (important) indication

of the current residue situation in a given product –

for an evaluation of an organic product it is

neccessary to get an overview about the

whole picture of your product to draw

the right conclusions

(and take approbiate actions).

Final note

16

Thank you very much!

Johannes Jaschik

Analytical Service Manager

Fon: +49-(0)40-881 448-452

info@eurofins.de

www.eurofins.de

Johannes Jaschik

Analytical Service Manager

Fon: +49-(0)40-881 448-452

info@eurofins.de

www.eurofins.de

?

Technical developments of residue analysis