Introduction
In food and beverage manufacturing, it is crucial that products are sold as advertised and produced to a consistently high standard. From changes in ingredient content to variations in taste, texture, appearance or smell, compromising the quality or authenticity of a food product can pose risks to consumer health, while also threatening brand reputation and profitability. Comprehensive testing is necessary not only to protect consumer opinion of a brand, but also to meet food safety and authenticity regulation. While regulation around authenticity is currently less defined than for food safety, this space is evolving fast, with recent years seeing the development of numerous new measures, projects and certification initiatives.
While it forms an essential element of the manufacturing workflow, food authenticity testing remains challenging. Food chains are growing more complex on a global scale, and verifying a substance's origin, composition and quality requires increasing amounts of disparate—and often difficult-to-access—data on potential contaminants, ingredient provenance and more. Smaller producers, in particular, are falling behind in implementing effective solutions to combat food fraud and adulteration, highlighting the importance of implementing innovative workflows that are scalable, adaptable and, therefore, appropriate for manufacturers of all scales and scopes.
Despite these challenges, modern analytical tools enable food manufacturers such as Barilla, a multinational company known for their Italian and pasta products, to accurately and reliably test both the products they receive from their supply chain and those they release to market. This capability is crucial to Barilla’s efforts to maintain brand reputation and profitability and, most importantly, to prioritize the safety of their customers.
Prioritizing Safety—and Protecting Reputation—in the Fight Against Food Fraud
Not all food inauthenticity is created equal. Some adulteration is deliberate—for example, food crime that aims to affect pricing patterns within the food industry, sabotage by employees, or substitutes driven by financial or availability issues.
An interesting example of this is illustrated by research performed by Barilla and Thermo Fisher Scientific [1] on oregano, a herb commonly used for culinary purposes, and found in food and beverage commodities. Oregano is especially vulnerable to fraud driven by price and demand. What’s more, adulteration can escape detection given that oregano leaves cannot be visually distinguished easily from those of some other plants. Using Orbitrap mass spectrometry (MS) technology coupled with headspace solid phase micro-extraction with Arrow technology sampling and Compound Discoverer software, the researchers extracted, concentrated and identified the complex mix of volatiles, responsible for the herb's distinctive aroma, in two samples of ground oregano. They found one sample to contain a substance that was potentially added fraudulently (thymol methyl ether, usually found in coriander seed and thyme oil), demonstrating the value of their technique for compound identification.
Accidental adulteration, meanwhile, arises when compounds are altered or added to food unintentionally; this refers not only to changes or constituents introduced by human hands, but also a variety of natural alterations within a food product. Such changes can slip through due to differences in national and international regulation or can occur within the manufacturing process itself. In a scenario of relevance to Barilla, when pesto genovese (a popular pasta sauce) is produced, some preservation processes can also cause potential effects on composition, taste and aroma. Another Barilla-Thermo Fisher Scientific study, again using Orbitrap MS technology, SPME Arrow sampling and Compound Discoverer software, sought to assess how production processes affect pesto products by determining the volatile profiles of 20 pesto samples manufactured using different technological methods by three different suppliers [2].
The researchers profiled the samples and determined unknown chemical components produced by varying processes and suppliers. For example, the volatile oils linalool and gamma-terpinene were predominant in heat-processed samples, and the provenance of a sample (supplier 1, 2 or 3) [1] could be determined by exploring the pesto’s principal components. In this way, modern analytical methods of food authenticity analysis are increasingly able to explore what is within a given food product and, by characterizing these constituent components, reveal where and how it was created.
Figure 1: Principal Component Analysis (PCA) for n=6 samples suggesting significant differences among the volatile profile of pesto originating from various suppliers.
Although attributes such as taste, aroma and texture are important depending on product type and profiling needs, when testing food for authenticity, safety remains the priority. While required for regulatory compliance, such testing is also essential from a brand perspective to ensure that all products reach the market with the same quality and predictability, to protect reputation and avoid legal issues or economic damage. If the grains or proteins within one of Barilla's pasta products change, for instance, this may affect the texture of the product and threaten its authenticity and reproducibility.
Managing Complex Global Food Chains
The current global landscape emphasizes the need for robust, widespread food safety testing. Ongoing globalization brings ever-longer and more complex food supply chains that may be more vulnerable to stochastic events, such as the COVID-19 outbreak and worsening impacts of climate change. This also increases the risk of adulteration. Each step of the chain may introduce ingredients of unknown provenance or composition. For example, a frozen pizza or a ready meal can comprise ingredients from multiple different producers that have been subjected to numerous production treatments before being combined into a single final product.
Some contaminants or adulterants may be present in relatively tiny amounts within highly complex samples, requiring sensitive tools and robust workflows to detect (especially for mixed or homogenous liquid ingredients, which can be particularly difficult to characterize). Additionally, different samples and stages of production require different approaches. Barilla emphasizes the importance of balancing targeted and non-targeted analyses via a two-step workflow: an initial, rapid, ‘first pass’ screening approach to identify potential contamination, followed by a deeper, more accurate confirmatory approach to characterize it. Smaller enterprises often lack the capacity to handle food inauthenticity risks internally; to establish such a two-step way of working, they can benefit from working with external collaborators to verify the safety of their supply chain.
Methods of Rapid and Confirmatory Food Testing
Advanced analytical instruments based on gas chromatography– and liquid chromatography–mass spectrometry (GC-MS and LC-MS, respectively) offer a way to overcome the challenges of food authenticity testing and can be applied to both rapid and confirmatory analysis.
For rapid 'first pass' screening, spectroscopic methods, such as the ones based on infrared instruments and ion mobility spectrometers, are able to create compound fingerprints, and instruments can be trained to check for specific parameters (such as the stability or quality of a raw material). The most effective confirmatory methods, on the other hand, are based on techniques such as MS, isotopic methodologies and nuclear magnetic resonance (NMR) spectroscopy. In their testing workflows, Barilla uses Thermo Fisher Scientific instruments for low- and high-resolution LC-MS (ion trap and Orbitrap), Fourier-transform infrared (FTIR) spectroscopy, and low-resolution GC-MS. In the future, they hope to introduce high-resolution GC-MS, FTIR microscopy and Raman spectroscopy to expand their capabilities.
Barilla’s array of sensitive, flexible instruments has proven effective when applied to complex product integrity issues, such as the freshness of egg products [3]. The use of fresh eggs in commercialized commodities is difficult to include in legal frameworks. While legislation sets thresholds for some parameters as indicators of freshness (organic acid content and metabolism, for example), these could be inadequate at reflecting real egg freshness. To advance this analysis, Barilla created a fingerprint of egg freshness over shelf lifetime with minimal sample preparation using ultrahigh‐pressure LC–high‐resolution MS (UHPLC‐HRMS). Their metabolomic approach and experimental design enabled them to select and identify over 30 freshness-related compounds, and train their instruments to screen for fresh and non-fresh egg products using these compounds as chemical markers for freshness.
Another Barilla study in this area demonstrated the power of parallel chemometric analysis using both GC-ion mobility spectrometry (GC-IMS) and solid-phase micro extraction-GC-MS (SPME-GC-MS) [4]. This approach sensitively performed volatile fingerprinting with GC-IMS to predict and assess the freshness of egg samples, while a selection of chemical marker compounds, those related to egg thermal degradation, were identified and analyzed by parallel SPME-GC-MS.
Across their food testing analysis, Barilla begins with high-resolution MS to identify molecular markers (for freshness, for example) and then moves to low-resolution MS to perform follow-up analyses for these markers. Their suite of advanced instruments enables the company to use a mix of high-and low-resolution analyses in their testing, creating an integrated two-step testing workflow that moves effectively from non-targeted (rapid screening) to targeted (confirmatory).
Conclusion
Despite the many challenges inherent in food authenticity testing, innovative tools and multi-step workflows based on LC-MS and GC-MS—both rapid and confirmatory, of high and low resolution—can now equip food manufacturers with advanced methodologies by which to verify food safety and integrity. Systems such as Thermo Fisher Scientific’s Orbitrap mass spectrometers can differentiate between the technological processes that went into manufacturing a product, identify and characterize unknown compounds, and establish new techniques for validating raw material parameters, such as freshness and stability. Ensuring food products remain authentic, safe and of high-quality from production to consumption is key to safeguarding customer health and satisfaction—and essential to protect brand reputation and financial performance.
References
[1] Riccardino, G., Cojocariu, C. I., Roberts, D., and Suman, M. (2019) A comprehensive strategy for confident detection of oregano adulteration by GC-Orbitrap mass spectrometry.
[2] Riccardino, G., Cojocariu, C. I., Roberts, D., and Suman, M. (2019) Chemometric Assessment of Volatile Fraction of Pesto by SPME Arrow GC Orbitrap Mass Spectrometry.
[3] Cavanna, D., Catellani, D., Dall’Asta, C., Suman, M. (2018) Egg product freshness evaluation: A metabolomic approach. Journal of Mass Spectrometry 53(9).
[4] Cavanna, D., Zanardi, S., Dall’Asta, C. and Suman, M. (2019) Ion mobility spectrometry coupled to gas chromatography: A rapid tool to assess eggs freshness. Food Chemistry 271, pp. 691–696.