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334 CHIMIA 2016, 70, No. 5 Food Authenticity And AdulterAtion

doi:10.2533/chimia.2016.334 Chimia 70 (2016) 334–337 © Swiss Chemical Society Food Adulteration in : From ‘Ravioli’ over ‘’ to ‘Disco Sushi’

Philipp Hubner*

In commemoration of our colleague and friend Rolf Etter (1951–2015), Kantonschemiker Zürich

Abstract: The driving force behind food adulteration is monetary profit and this has remained unchanged for at least the last hundred years. Food adulterations were and still are difficult to uncover because they occur mostly in an unpredictable and unexpected way. Very often food falsifiers take advantage of modern technology in such a way that food adulterations are difficult or sometimes even impossible to detect. Targets for food adulteration were and still are highly priced food items such as spirits, meat, seafood and olive oil. Although difficult to detect, food adulterations were in the past strong driving forces for the development of adequate detection methods in the official food control laboratories and for the enforcement of the food law. A very prominent example in this context is the ‘Ravioli scandal’ in Switzerland in the late 1970s which showed that cheap second-class meat could be processed into products without being discovered for long time. As a consequence the official food control laboratories in Switzerland were reinforced with more laboratory equipment and technical staff. With the introduction of new detection principles such as DNA-based analytical methods new kinds of food adulteration could and can be uncovered. Analytical methods have their limits and in some cases of food fraud there are no analytical means to detect them. In such cases the examination of trade by checking of accounts is the method of choice. Keywords: Checking of accounts · Food adulteration · Meat adulteration · Ravioli scandal · Sushi adulteration

Introduction to uncover subtle falsifications is directly not surprising that the cited booklet con- related to the frequency of occurrence of tains many tables describing various food To give a historical overview of food manipulations which are illegally under- items in great detail. Although the topic of adulteration in Switzerland is a nearly taken with foodstuffs”. impossible task. A small booklet pub- (Original German text: “Jeder lished 1910 with the title ‘Foodstuff and Mensch hat das Anrecht darauf, das, was the Art of Fakery’ (Nahrungsmittel und er verlangt und bezahlt, vom Verkäufer Fälscherkünste,[1] Fig. 1) was an unexpect- zu erhalten, auch wenn dem Käufer, ed aid in indicating that the driving force wie es in den meisten Fällen zutrifft, for food adulteration has remained un- die Möglichkeit fehlt, das Gekaufte zu changed for at least the last hundred years: prüfen. Wie sehr gegen diese allgemeine monetary profit. In the booklet’s preface is Voraussetzung gefehlt wird, zeigen die stated that “every person has the right to in allen Tageszeitungen immer wieder receive from the seller what he asks and auftauchenden Berichte über Bestrafung pays for, even when the buyer usually has von Nahrungsmittelfälschern. Bedenkt no possibility to examine the bought items. man, dass doch nur ein verschwindend However, very often this assumption is kleiner Teil von Nahrungsmittelfälschern wrong, as can be shown by numerous ar- bei den immer noch nicht durchgreifend ticles in the newspapers reporting penali- organisierten Kontrollsystemen ertappt zation of foodstuff falsifiers. Considering wird, so kann man ein kleines Grauen bei that only a vanishingly small proportion der Vorstellung bekommen, wieviel unent- of foodstuff falsifiers is caught due to the deckte Sünden dem gewöhnlich Sterblichen still not rigorously organised control sys- mit dem aufgetischt wird, was er als ir- tems you might be horrified by the notion disches Geschöpf verzehren muss. Die how many undiscovered sins are dished up Schwierigkeit, raffinierte Verfälschungen to ordinary mortals and what you have to zu finden, ist hierbei der direkte Ausdruck consume as a normal person. The difficulty für die Häufigkeit der Manipulationen, die in unberechtigter Weise mit den Nahrungs- und Genussmitteln vorgenom- men werden”.) Fig. 1. The booklet with the title ‘Foodstuff and the Art of Fakery’ (Nahrungsmittel und In order to detect food adulterations it Fälscherkünste) was published in 1910 in *Correspondence: Dr. P. Hubner, Kantonschemiker is important that the corresponding food Stuttgart, . Its content is still valid al- Kantonales Laboratorium Basel Kannenfeldstrasse 2, CH-4012 Basel item is characterised as fully as possible though the analytical techniques have changed E-mail: [email protected] and legally defined. It is in this context a lot in the mean time! Food Authenticity And AdulterAtion CHIMIA 2016, 70, No. 5 335

food adulteration has remained unchanged Fig. 2. 100-year- for 100 years the analytical methods have old analytical table changed enormously. For instance the cit- with parameters for ed booklet describes differences between analytical differenti- German red wines due to specific weight, ation of German red wine varieties. In the alcohol content, extract, total acidity and meantime Elsass and so on (Fig. 2) whereas modern methods Lothringen belong to use the isotopic distribution for discrimi- , but wine is nation of wines (see e.g. article by Rossier still a target for food in this issue[2]). adulteration! In the following sections some exam- ples of food adulterations in Switzerland from the past four decades are presented.

Ravioli Scandal

In 1978 the well-known Swiss TV consumer program ‘Kassensturz’ reported represented an expert investigation and a Original flasks of Bacardi, Jack Daniels on a ravioli test by the Swiss Foundation tolerable product criticism. Nevertheless, whiskey and tequila were equipped with for Consumer Protection filmed in the the Swiss TV agreed a few months later dispensers and were used for the open bar style of an secret agent thriller.[3] Canned to a settlement. It was noted that the Swiss next to sealed original flasks stored on the ravioli were at that time bestsellers and TV had in no way intended to give the im- racks. In the bar, everything made a correct were especially popular with families. pression that the products manufactured by impression. The competent food inspection However, their composition was mainly the complainant companies were inferior service was asked to take samples from the unknown until that remarkable broadcast or unappetizing. sealed original flasks and from the bottles of ‘Kassensturz’. The test revealed that for A further consequence of the ravioli with the dispenser. In the laboratory both some products the meat percentage was scandal was that the public awareness for Bacardi samples were analysed for higher very low and sometimes the meat was of food adulteration changed dramatically alcohols and flavourings without a signif- dubious quality. ‘Kassensturz’ headlined and the work of the official food control icant difference being observed (Table 1). that the testers even found stomach, heart, bodies in Switzerland was more carefully The only difference was that ethyl acetate kidneys, pancreas, lungs and heads observed than ever. Further, people started was present in 10-fold higher concentra- in some ravioli. Of course, these to read the list of ingredients! tion in the original bottle. However, this ingredients were shown in the broadcast And finally Swiss families stopped eat- difference alone was not sufficient to prove together with a pig’s head. This broadcast ing canned ravioli. a food adulteration. The brilliant idea was was a real eye-opener for viewers. that if spirits are adulterated, this would As a consequence producers of canned be done with water from the local water ravioli recorded losses in sales. They crit- Bacardi Adulteration … or what supply, which has its own ion pattern. The icised that the broadcast gave the impres- you get at the bar is not always measured anion pattern indeed revealed sion ravioli were inferior in general and not what you expect significant differences between the opened just some of the products tested. Two com- and the closed Bacardi bottles.[4] The adul- panies sued the television company. In the Due to a tip from a former employee terator had probably thought of the volatile first instance, the court dismissed the case a big discotheque was suspected of adul- aroma components and the higher alco- in 1982. The court stated that the broadcast terating trademark spirituous beverages. hols, but not of the ion patterns!

Table 1. Analytical differentiation between original Bacardi and Bacardi sampled from the bar. The main difference is the anion pattern due to use of water from the local water supply. n.d.: not detected. yde utanol-2 ate alcohols acetate

Parameter ylb components xanol-1 yl Nitrate Sulf Chloride Methanol Butanol-1 Butanol-2 He yl-1-Propanol-2 Propanol-1 Eth Acetaldeh latile Higher Vo Meth 2-/3-Meth

mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L unit EtOH EtOH EtOH EtOH EtOH EtOH EtOH EtOH EtOH EtOH EtOH mg/L mg/L mg/L original 3n.d. 87 n.d. 220 61 46 67 486 284 14 102 Bacardi bottle

Bacardi from n.d. n.d. 57 n.d. 157 44 20 7289 202 12 3214 the Bar 336 CHIMIA 2016, 70, No. 5 Food Authenticity And AdulterAtion

When the manager was confronted with the analytical results, he admitted having bought alcohol for drinking pur- poses together with Bacardi flavour and having mixed the two components with drinking water from the local water sup- ply. The already opened original contain- ers were systematically refilled with adul- terated Bacardi stored behind the bar (Fig. 3). The manager proceeded in a similar fashion with Jack Daniels whiskey and te- quila. Interestingly the operating manager could readily order specific flavours with an Austrian flavour company together with the instructions for reconstitution.

Fig. 3. Left: Bacardi displayed in the bar; right: Bacardi stored behind the bar. Roe or Springbok? Table 2. Identification of venison species by DNA sequencing technology. The best fits from the Venison often is prepared with acidic DNA databank search (Blast search) are given for adulterated venison samples. The homology to wine and herbs, which leads to special aro- the best fit species and to the labelled species is given in %. ma compounds (Wildpfeffer). Although processed venison has a distinct taste the Venison ‘Best fit’ from Homology with Homology to processing per se hampered in the past labelled as Blast search the ‘Best fit’ the labelled the analytical differentiation of the differ- species ent venison species based on isoelectric focusing (IEF). With the introduction of capreolus elaphus 99.5% 89.1% DNA-based detection methods such as Capreolus capreolus Muntiacus muntjak 99.8% 90.4% polymerase chain reaction (PCR) the spe- Cervus elaphus 99.3% 88.9% cies differentiation of processed venison became feasible. The introduction of this rupicapraOvis aries 100% 90.1% detection technology initially led to many Capreolus capreolus 99.3% 88.7% cases of adulterated venison until the falsi- Sus scrofa feraOvis aries 98.2% 86.4% fiers realised that the official food control bodies are able to detect this kind of food Capreolus capreolus Nemorhaedus caudatus 94.9% 87.2% adulteration. At that time often high priced Capreolus capreolus Gazella gazella 91.7% 88.3% (Reh) meat was the target of adul- teration with cheaper types of venison, sometimes even from species from Africa. colour in the course of aging. In order to Airport and at Geneva Airport took sam- DNA sequencing technology helped to stabilise the red colour in some countries ples from suspicious tuna shipments from identify suspicious venison samples with tuna was treated with carbon monoxide the Philippines. Since the samples dis- high accuracy without the need to analyse or with filtered tasteless smoke. Since played a striking unnatural red colour they corresponding reference samples. For in- this colour stabilization is not influenced were forwarded to our laboratory for ex- stance, our laboratory analysed 1999 about by spoilage consumers could be deceived amination of illegal treatment with carbon 30 meat samples.[5] Interestingly, the regarding the freshness of the product. In monoxide. Since we could not detect any processed venison samples were often addition, spoiled tuna is known to contain treatment with CO we assumed a treatment found to be inhomogeneous. Therefore high amounts of histamine which might with red dye. During the subsequent anal- several small pieces from a sample were provoke adverse reactions in consumers. ysis the dyes rhodamine B dye and yellow analysed. Four samples were found to For import into Switzerland each consign- orange S were found in the three suspi- be adulterated. In a roe deer sample we ment of meat and meat products must be cious samples.[6] Rhodamine B is not ap- found pieces of red deer, in another roe accompanied by an official certificate of proved in Switzerland for food or cosmet- deer sample there were pieces of red deer consumption suitability issued by the com- ics. Since rhodamine B is a fluorescent dye and Muntiak, a deer species from Asia. A petent authority of the country of origin. which lights up under UV light the control chamois sample contained pieces of The health certificate for the importation at the border was very easy. Equipped with and red deer. Finally we found a roe deer of fish and fish products was at that time an UV lamp the border veterinarians could sample which contained meat from an an- complemented with a provision explicitly identify the adulterated tuna samples on imal which was at that time not yet in the excluding treatment with carbon monox- the spot. In the lab slang this sample was DNA database. The highest homology was ide or a tasteless smoke. Carbon monox- called ‘disco sushi’ (Fig. 4). found with springbok from Africa. A year ide strongly binds to Fe2+ chelated by the later we found again many foreign animal heme group of myoglobin stabilizing its species in venison samples (Table 2). oxidation status and thus the red colour. (Swiss) German Chicken Furthermore the oxidation by oxygen to Fe3+ is strongly decelerated. In 2005 more Food adulterations cannot always be Disco Sushi than 20% of the controlled tuna samples detected by analytical means. In 2004 the had to be rejected due to illegal treatment official food control body of cantonAargau Fresh tuna is characterised by its red with CO. In January 2006 the border vet- was informed that a well-known chicken meat which becomes an unsightly brown erinarians at the customs offices at Zurich meat producer was suspected of importing Food Authenticity And AdulterAtion CHIMIA 2016, 70, No. 5 337

Fig. 4. ‘Disco Sushi’. Conclusion Tuna samplesunder daylight Top: CO treated, untreated and colour- Since the driving force for food adul- ed tuna samples teration is mainly monetary profit, often in standard light. high-value food items such as wine, spir- Bottom: the same three samples under its, meat, seafood and olive oil are target- UV 366 nm light. The ed. Mostly food adulterations were and Disco Sushi sample still are difficult to detect because they lights up! are often unpredictable and unexpected. Thus, for the unpredictable and unexpected often is the key factor for suc- cessful discovery of food adulteration by official food control authorities. The good message is that there is more than enough Tuna samplesunderUV366nm light work for all of us; the bad message is that we will often be one step behind the food falsifier if we do not start to think as they do! And keep in mind that analytical meth- ods have their limits and in some cases of food fraud there are no analytical means to detect them. In such cases the exami- nation of trade by checking of accounts is the method of choice. Good and close col- laboration between food analysts and food inspectors is the most powerful tool in the fight against food adulteration.

CO treateduntreated coloured tuna Received: December 30, 2015

[1] A. Reitz, ‘Nahrungsmittel und Fälscherkünste’, chicken meat from Germany and selling it Since there was the suspicion that this Kosmos, Gesellschaft der Naturfreunde, Stuttgart, 1910. as Swiss chicken meat. There is probably food adulteration had taken place over [2] J. S. Rossier, V. Maury, L. Gaillard, E. no analytical technique available to distin- many years the food control authority of Pfammater, Chimia 2016, 70, 338. guish between German and Swiss chicken Aargau re-examined the company’s re- [3] http://www.srf.ch/konsum/themen/serien/40- meat! Thus, the food inspection service cords for the years 2001 to 2004. A total of jahre-kassensturz/die-lebensmittel-skandale# 300 tons of chicken and meat were [4] Jahresbericht Kantonales Amt für controlled the books of the incriminated Lebensmittelkontrolle St. Gallen, 2003. company and found that in November and imported from Germany. After processing [5] Jahresbericht Kantonales Laboratorium Basel- December 2004 a total of 1’100 kg high (removal of skin and bones, filleting, re- Stadt, 1999. quality chicken breast fillet were import- packing) 230 tons remained, which were [6] Jahresbericht Kantonales Laboratorium Basel- ed from Germany. 240 kg of this meat sold as Swiss meat.[7] The price difference Stadt, 2006. [7] Jahresbericht Kantonales Labor Aargau, 2005. were correctly sold as German chicken between German and Swiss chicken meat breast fillet. 720 kg of this chicken meat at that time was 3 CHF/kg. Altogether the were stored frozen in portions of 500g la- unjustified profit amounted to 700’000 belled as cut chicken breast Switzerland. CHF! From a total volume of sales of However, this batch was blocked since a 13’400 tons, 1.7% was not correctly la- labelling mistake seems to have happened. belled and the case went to the court. The The official food control body confiscated responsible person was sentenced to 6 this meat. For the missing 140 kg chick- months prison and a fine of 10’000 CHF. In en meat there were no available papers to addition 200’000 CHF of the illegal profit trace its fate. had to be reimbursed to the state.