Pesticide residue analysis: New TrendsMichal Godula, Ph.D.EU Marketing ManagerFood Safety & EnvironmentalThermo Fisher Scientific

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Why pesticide analysis?

• Extensively used in agriculture to control pests & improve yields• More than 1000 different active substances used• Thoroughly tested and evaluated before approval

BUT

• Sometimes not applied in accordance with intended purpose • GAP sometimes not respected• Signicant public concerns about pesticide use• Regulatory requirements

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Pesticide facts

2001 WW Pesticide usage

2006, UKhttp://pusstats.csl.gov.uk/mygraphresults.cfm

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EU Pesticide residue regulations

Until 1 September 2008 legislation only partially harmonized

EU- MRLs ± 250 pesticides National MRLs ± 850 pesticides

76/895/EEC (fruits and vegetables) No harmonized risk assessment for EU 86/362/EEC (cereals) consumers, Trade problems86/363/EEC (animal products)90/642/EEC (fruits and vegetables)

Regulation 396/2005• > 490 pesticides• > 145.000 MRLs• General MRL 0.01 mg/kg

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EU pesticide monitoring programs

2008 Annual Report on Pesticide ResiduesEFSA Journal 2010; 8(6):1646

•Number of pesticides analyzed: up to 700

•Baby food samples > MRL: 0.2%

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Workflow for analysis of pesticide residues

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Challenges of pesticide residue analysis

• Sample variability (matrix)• Different compound characteristics• Number of samples• Number of analytes monitored• Low levels controlled ( <10 ng/g )• Fast response required

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Sample preparation: Key step to success

Fussell, et al. (2007) Food Additives & Contam. , 24:1247-1256

Cryogenic milling

effect on pesticide

levels

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Analytical method parameters to optimize:

Performance

SpeedCosts

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Sample preparation by QuEChERS

SampleSample

ExtractionExtraction

Dispersive SPEDispersive SPE

CentrifugationCentrifugation

For: moisture > 75%, low fat fruits and vegetables

LOQ: < 10 ng/g

229 pesticides

AOAC 2007.01 Method

CentrifugationCentrifugation

DeterminationDetermination

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Simplified sample preparation challenges

Clean-up efficiency

Detection selectivity

MS/MS

Orbitrap MS

HPLC-UV

GC-ECD, NPD

HPLC-FLD

Simple extraction

SPE

IAC

QuEChERS

LC-MS

GC-MSGPC

LLE

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Routine lab requirements

• Simplified sample preparation• Fast analysis (screening and

confirmation in one run)• Rapid data evaluation

While• LOQs/RSDs achieved• Confidence in results• Easy to use• Low maintenance and running costs

LOW COSTS!

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Mass spectrometry in pesticide analysis

• Simple sample preparation: QuEChERS, extract-n-shoot• Targeted analysis and quantitation using• Single and Triple Quadrupoles (SIM, SRM) coupled to LC (UHPLC) and GC

Sample QuEChERSGC/MS/MS

LC/MS/MS

• Limited screening capability of MS/MS (~ 250-300 compounds)• Data evaluation is time consuming• Multiple instruments to cover whole scope of method• Limited information contained

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Alternative approach: Non targeted data acquisition

• Non-targeted analysis using Full Scan MS instruments• Time-of-Flight or• Orbitrap instruments: excellent mass accuracy and resolution

Sample All data acquisition

Data evaluation

Accurate mass search

Spectral library search

Quantitation/Confirmation

Reporting

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Benefits of High Resolution approach

• Non targeted acquisition (all info gathered)• No analyte specific setup: 1 set of conditions• Theoretically unlimited number of analytes• Meeting analytical criteria (LODs, RSDs)• Multi-methods possible (pesticides+mycotoxins)• Retrospective data analysis (unknowns)

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• Data extraction from raw files• Simplification of data• Screening against libraries• Confirmation/Quantification• Reporting (instrument reports)

• Laboratory Information management System (LIMS)

Customer Report

But: data acquired is enormous

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Pesticide residues - outlook

• Multi-residue methods are a “must” - save time and costs

• In routine pesticide analysis costs/throughput and performance will be the requirements

• New technology (High Resolution MS) provides tools to extend scope of methods

• Data managements streamlining will help to reduce costs

• Direct sample analysis is to be explored (DART-MS)

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Food Safety is a Global Issue