Food Safety Alert! Shimadzu's Solutions to Ethylene Oxide Analysis

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Even though Ethylene oxide (EtO/EO) is well-known to be a toxic compound with carcinogenic and mutagenic concerns, it has been widely used for fumigation in the Food industry for effectively reducing or eliminating microbiological contamination with bacteria/fungi. Once in contact with food, EtO undergoes various reactions within the matrix, further producing reaction products such as ethylene glycol, 2-chloroethanol (2-CE) and 2-bromoethanol, which are also toxic in nature. Hence, the use of EtO for food fumigation has been phased out in many countries worldwide, due to toxicological concerns. In the EU, the use of EtO for the disinfection of foodstuffs, e.g. in storage areas, is not permitted (ECHA, 2020). EU has proposed separate maximum residual limits (MRLs) for EtO and its primary metabolite 2-CE in different food and agriculture commodities ranging from 0.02 to 0.1 mg/kg (Commission Regulation (EU) 2015/868).

The recent recall of food products exported to the EU due to non-compliance with EU regulations, has highlighted the importance of quantitation of EtO & 2-CE residues in food.

To ensure the quality and safety of food products, the European Rapid Alert System for Food and Feed (RASFF) prohibits the sales of goods exceeding the MRL values of 0.05 mg/kg (or 50 ppb) for the sum of EtO and 2-CE.

An Emerging Food Safety Concern

Commodities such as spices, oilseeds and nuts are especially susceptible to EtO/2-CE post-fumigation and combine high lipid content with low water content. One example is sesame seeds, where EtO fumigation is used (particularly in many developing countries as a countermeasure) to reduce contamination with salmonella and other fecal bacteria.

After fumigation with EtO, evaporation and reactions with matrix constituents are the main dissipation pathways of EtO in food. EtO undergoes various reactions within the matrix and generates a number of reaction products, including ethylene glycol, diethylene glycol, 1,4-dioxane, 2-bromoethanol and ethylene chlorohydrin (2-CE). EtO also reacts directly with matrix components such as amino acids, purines and fatty acids to form hydroxyethyl adducts. 2-CE is the most prominent reaction product of EtO and is itself an extremely hazardous substance. In the matrix, 2-CE undergoes reactions with fatty acids to form 2-CE esters. EtO, 2-CE and their various reaction products are only removed to a limited extent during aeration and many of them can serve as markers for EtO fumigations.

Naturally, EtO fumigation requires strict quality control. Neglect can result in cases such as the 2020 discovery in India where EtO was still above the regulated limits in treated sesame seeds.

To grasp the key insights and understand how EtO presents a food safety concern in just 2 mins, download our infographic below.

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Analytical Methods For Fast and Robust Testing 

With EtO so useful yet so toxic to people, it becomes imperative to ensure the trace amounts left in foods are well within safe guidelines for human consumption. To ensure food quality and protect food safety, Shimadzu offers comprehensive solutions to analyze EtO and 2-CE in various food matrices, whether it is agricultural (oil seeds), spices, processed foods, ayurveda and herbal or more.

The solutions offered by Shimadzu can be summarized here:

Matrix Covered Technique
Instrument
Sesame Seeds Liquid Injection (EtO & 2-CE) GCMS-TQ8050 NX with AOC-20i/s
Dynamic Headspace (EtO & 2-CE) - Solvent extraction GCMS-TQ8050 NX with HS-20 NX
Dynamic Headspace (EtO & 2-CE) - Direct sample in HS vial GCMS-TQ8040 NX with HS-20 NX
Liquid Injection (2-CE) -Conversion Method GCMS-TQ8040 NX with AOC-20i/s
Dynamic Headspace Injection (2-CE) – Conversion Method GCMS-TQ8040 NX with HS-20 NX
Chilli Powder Chicken Masala Dynamic Headspace (EtO & 2-CE) - Solvent extraction GCMS-TQ8040 NX with AOC-30i
Dynamic Headspace (EtO & 2-CE) - Solvent extraction GCMS-TQ8050 NX with AOC-20i/s
Dynamic Headspace (EtO & 2-CE) - Direct sample in HS vial GCMS-TQ8050 NX with HS-20 NX
Dynamic Headspace (EtO & 2-CE) - Solvent extraction GCMS-TQ8050 NX with HS-20 NX
Kitchen Masala Dynamic Headspace (EtO & 2-CE) - Solvent extraction GCMS-TQ8050 NX with HS-20 NX
Amala Powder Dynamic Headspace (EtO & 2-CE) - Solvent extraction GCMS-TQ8050 NX with HS-20 NX
Ashwagandha Powder Dynamic Headspace (EtO & 2-CE) - Solvent extraction GCMS-TQ8050 NX with HS-20 NX
Boswellia Serrata Powder Liquid Injection (EtO & 2-CE) GCMS-TQ8050 NX with AOC-20i/s
Dynamic Headspace (EtO & 2-CE) - Solvent extraction GCMS-TQ8050 NX with HS-20 NX
Noodles Liquid Injection (EtO & 2-CE) GCMS-TQ8050 NX with AOC-20i/s

Download the eBook below for full access to the end-to-end workflow solutions.

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Application Spotlight: Analysis of Ethylene Oxide in Ramen (Instant Noodle) by GC-MS/MS

In light of the food safety concern brought by the EtO, the EU Reference Laboratories for Residual of Pesticides-Single Residue Method (EURL-SRM) has provided a method to effectively analyze EtO and 2-CE in sesame seeds.

In this test method, common samples are extracted by the QuEChERS method and dry samples with high oil content are extracted by the QuOil method. Both EtO and 2-CE are analyzed simultaneously without separate hydrolysis.

Furthermore, to solve the problem whereby the extraction solvents - acetonitrile and residual water - may negatively affect the GC column and the MS filament, the method proposed the use of programmable temperature vaporization (PTV) injector, which is an inlet capable of temperature programming.

Herein, Shimadzu presents a workflow solution that can be applied to the analysis of residual EtO and 2-CE in ramen instant noodle using GC-MS/MS equipped with PTV based on EURL-SRM (Analysis Method for EtO and 2-CE in Sesame).

Using Shimadzu’s GCMS-TQ8050 NX, the analysis method was successfully evaluated with the coefficient of determination (R2) of the calibration curves for both EtO and 2-CE to be >0.999. In the recovery test, the average recovery rates were confirmed at 98.9% and 106.3%, respectively for EO and 2-CE, while the %RSD were 4.7% and 3.4%, correspondingly.

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Shimadzu's Advanced Solutions for EtO Analysis

The Shimadzu triple-quad GCMS-TQ8050 NX, equipped with a highly efficient detector and three forms of noise-reduction technology, is capable of performing unprecedented quantitative GC-MS/MS analyses of ultra-trace amounts down to the femtogram level. With its ultra-high sensitivity and high mass resolution, a whole new realm of quantitative analysis can be offered, with reduced maintenance frequency, lower long-term operational costs, and less downtime.​

Its key features include:
- Enhanced sensitivity enables ultra-trace level analysis
- Simplified user maintenance allows operators to change parts quickly
- Reduces maintenance frequency and long-term operational costs

For More Resources: Watch On-Demand Session on Our Digital Classrooms

In this session on Digital Classrooms, learn about Shimadzu’s GCMS solutions in analyzing ethylene oxide in different food matrices, such as sesame seeds and instant noodles. Our expert, Dr. Jackie will help you gain deeper insights into EtO analysis and its regulatory perspectives.

Learning Objectives:

  • Significance and regulatory implications of analyzing EtO and 2-CE in various food matrices
  • Importance of quantitation of EtO and 2-CE at trace level
  • Recognize the applicable EU-MRLS (Maximum Residue Limits as per European Commission)
  • Find out more about industry challenges and the solutions that are being offered by our application specialists
  • Understand the options available for analysis techniques with their own merits and demerits
  • Discover the most reliable and sensitive methods developed using GCMS-HS for analysis of EtO and 2-CE in challenging matrices

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