Pesticide Residues and Unauthorized Dyes as Adulteration Markers in Chilli Pepper and Tomato

To assess the contamination of processed chilli pepper and tomatoes, a report over the past four decades since the establishment of the Rapid Alert System for Food and Feed (RASFF) was retrieved and analysed. Out of the 887 notification reports assessed for eligibility, 446 were found regarding chilli pepper and tomato contamination. This study identified India as the country of origin with the highest number of reported cases relating to chilli pepper contamination. Italy and Türkiye were the countries with the highest number of reported cases regarding the exportation of adulterated tomatoes to other countries according to the RASFF report. Unauthorized dyes such as Sudan I, III, IV, orange II, rhodamine B, and para red were reported to have been detected in either chilli pepper or tomato in the supply chain. Almost all unauthorized dyes in this study were found to be more than the range (0.5 to 1 mg/kg) of the detection limit of Sudan dye and other related dyes using analytical methods set by the European Union. Unapproved pesticides by the European Union (EU) found in this study were acetamiprid, chlorothalonil, chlorpyrifos, dimethoate, methomyl, monocrotophos, omethoate, oxamyl, and thiophanate methyl. The present study indicates the persistence of chilli pepper and tomato contamination with harmful dyes and pesticide residues despite the ban on the use of certain chemicals in the food chain.


Introduction
Rapid Alert System for Food and Feed (RASFF) has been recognised as a system for reporting food safety issues within the European Union (EU). It was established in 1979 to ensure the flow of information to enable swift reactions when risks to public health are detected in the food chain. Several research articles have been published using the database of RASFF to report on health risk incidents of the global beef supply chain [1], risk analysis of biogenic amines in food [2], meat products, nut products, fish products [3], food products contaminated with Listeria [4], and herbs such as oregano [5]. Condiments used for spices have received relatively little attention and yet play an important role as food ingredients.
Spices, used in whole, broken, or ground forms, are defined as "vegetable products or mixtures thereof, from extraneous matter, used for flavouring, seasoning, and imparting aroma in foods" by the International Standardization Organization [6]. Spices are mostly added in the preparation of food, particularly ready-to-eat food, and are used by consumers as flavouring agents. The safety of food condiments used as spices in the food industry has received little or no attention over the years, although possible contamination of these spices is of key importance to food safety and quality. Most contamination surveys conducted focused on microbes and other secondary metabolites such as mycotoxins. Other contaminants such as chemical contaminants, mainly pesticide residues, are of primary importance in the case of the Capsicum and Solanum families including tomato and chilli pepper [7]. Although spices used in food preparation are in smaller quantities, they add to the contamination levels in the food product when contaminated.
Vegetables such as chilli pepper and tomatoes are highvalue food products and play a significant part as constituents in a host of foods. Most foods cannot reach their final preparation stage without the addition of either chilli pepper or tomato. Tomato is a seasonal crop, mostly traded in its fresh state and widely used in soup preparation in the form of a paste, ketchup, concentrate, or juice. It is rich in nutrients such as lycopene, vitamin C, and beta-carotene, which are essential to human health. The annual production of tomatoes on a global scale is approximately 180 million tonnes [8]. Chilli pepper, on the other hand, is a food recipe used all over the world [9], especially in the form of spices due to its sensory attributes such as pungency and colour [10] and is mainly grown in India, China, Mexico, Spain, and Africa. However, according to the Food and Agricultural Organization (FAO) [11], the leading producer of chilli in the world is China (18.9 million tons), followed by Mexico (3.2 million tons), Türkiye (2.6 million tons), Indonesia (2.5 million tons), and Spain (1.4 million tons).
Due to the seasonal nature of chilli and tomato, they are usually processed into powder and other forms to extend their shelf life. In the processing of these food items, the potential presence of accidental substances or deliberate introduction of foreign materials is added. Other chemicals also form part of the product due to poor cultural practices during production. However, the deliberate addition of other substances is for economic gain to increase the bulkiness of the food items; hence, care must be taken when patronizing them [12].
Dyes such as Sudan dye (I, II, III, and IV), para red dye, yellow dye (metanil yellow), and orange II, among others, have been reported to be present in condiments [13]. The use of these dyes is possibly due to their resemblance to the condiment or spices in question since they may be similar in physical or chemical structure. These dyes that are rampantly used by fraudsters are usually not permitted in food processing. One of the most prominent agents regarding the contamination of spices is pesticide residue of agricultural origin [7].
The widespread use of pesticides, herbicides, and insecticides in agricultural production helps to protect crop plants from insects, pests, and pathogens thereby eliminating yield losses. This also improves the quality and quantity of food crops [14]. Vegetables have seen extensive use of pesticides and herbicides in their production due to their increased demand. The report shows that the use of pesticides has warranted almost a third of global crop production [15]. However, the use of pesticides in crop production without good agricultural practices has resulted in the residue of these chemicals remaining on the crops before harvest. The ingesting of such food crops can be dangerous for the individual. A report in 2018 by the European Food Safety Authority (EFSA) shows the presence of pesticide residue in some 91,015 food samples which exceeded the maximum residue level (MRL) and accounted for 4.5% of the overall food sampled [16]. Pesticide residues such as ethion (0.27 mg/kg), acetamiprid (0.12 mg/kg), methomyl (0.06 mg/kg), methamidophos (0.17 mg/kg), acephate, metalaxyl (0.19 mg/kg), profenofos (0.23, 1.2, 0.24, and 0.21 mg/kg), and formetanate (0.18 mg/kg) were reported to have been detected in paprika [7].
Although efforts are being made to dissipate pesticide residues in some food crops [17], its spillover persists. The current study is aimed at reporting on the contamination of chilli pepper and tomatoes over the last 40 years, from 1980 to 2020, using the RASFF portal database.

Results and Discussion
Very few reported cases of contaminated chilli pepper, and tomatoes were reported in Croatia, Cyprus, Latvia, Luxembourg, Malta, Poland, Romania, Slovakia, Türkiye, Hungary, Ireland, and Lithuania. Nevertheless, Italy (40), the United Kingdom (34), France (33), and Germany (32) recorded the highest notification (in descending order) of contaminated chilli pepper imported into their countries between 2003 and 2020. Germany also recorded 42 cases of contaminated tomatoes, making it the highest notified country, between 1980 and 2020. In this study, Slovakia, Romania, Hungary, Latvia, Malta, and Bulgaria did not record any form of chilli pepper contamination imported into the country. There was equally no recorded case of tomato contamination in Norway, Luxembourg, Türkiye, and Lithuania.
Regarding the number of times notified countries have reported cases of contaminated chilli pepper, Italy recorded 5 times from India, 10 times from Egypt, and 7 times within Italy. The United Kingdom recorded 17 times from India and 6 times from Italy. Germany recorded 5 times from India, Finland recorded 5 times from Thailand, and France recorded 12 times from the Dominican Republic, all within the period between 2003 and 2020, as shown in Table 1. Among the notified countries that reported cases of contaminated chilli pepper, Germany was the country that recorded the highest case of importation of contaminated chilli pepper from 18 countries.
Tomato contamination as reported by the RASFF and notified by Bulgaria was from Türkiye (13 times) and Jordan (8 times) in the period 1980 to 2020. The other notifying countries are as follows: Germany recorded 9 times from Türkiye and 22 times from Italy; Greece recorded 9 times from Türkiye; Denmark recorded 6 times from Italy; the Netherlands recorded 5 times from its own country; Italy recorded 7 times from its own country and 5 times from Türkiye; and Belgium recorded 5 times from Italy. The notifying countries with the highest number of contaminated tomato cases were Italy (9) and Germany (9) from 1980 to 2020. In all, the country of origin with high chilli pepper contamination was India (50 times) followed by Dominican Republic (29 times) and Thailand (27 times). Italy (56 times) and Türkiye (53 times) were the reported countries with high exportation of contaminated tomatoes to other countries according to the RASFF report as shown in Table 1.
Contamination of chilli pepper, as reported by the RASFF portal, started in 2003. In 2004, 40 cases of contaminated chilli pepper ( Figure 2) were recorded from around the world as reported in this study. The high number of recorded cases in 2004 was due to food authorities in other countries embarking on control programmes which resulted in increased RASFF notifications. The actual RASFF notification peaked at 270 cases in 2004 which included chilli pepper, other spices like curry powder, and food items such as sauces, red palm oil, and pasta [19]. In this study, the reported cases dropped to 2 in 2017 and rose to 23 in 2019. Contamination of processed tomatoes was first reported in 1980 by the RASFF portal with cases ranging from one to two between 1980 and 2001 ( Figure 3). A rise in the contamination of tomato cases was reported in 2011, and this dropped to 6 in 2019. The variation in processed chilli pepper and tomato contamination discovered in this study could be attributed to rising food demand caused by a rapidly growing population, as well as the unfavourable spillover effect of food adulteration from other countries [20].

Classification of Hazards for Chilli Pepper and Tomato as
Reported by RASFF. The current study exposed the contaminants of processed tomato and chilli as reported by RASFF from 1980 to 2020. The broad nature of the contaminants or adulterants reported to be present in tomato and chilli pepper was categorized into pesticide residues, composition, mycotoxins, food additives, and so on as shown in Table 2. A total of 104 and 94 pesticide residues were reported to have been found in processed chilli pepper and tomato,    International Journal of Food Science respectively, over the period. Indeed, pesticide residues feature at the top of this study concerning hazard types found in tomato and chilli pepper and are usually among the top issues for products from nonmember countries. Compositions in the form of an unauthorized dye such as Sudan I, III, and IV, rhodamine B, and orange II were reported to have been found in processed chilli pepper and tomato (Table 3). Mycotoxins and microbial contamination were also reported to have been found in chilli pepper and tomatoes. Food spoilage resulting from microbial contamination may be due to the infusion of different microbes through several sources. The contamination reported in this study   [19]. 10 International Journal of Food Science might have come about during the processing of tomato and chilli pepper like harvesting, handling, preparation, distribution, and storage. Although the hazard posed by contamination in spices applies to dynamic contamination capable of multiplication, microbial contamination, or related substances, particularly of pathogenic microorganisms, static contamination by chemical substances such as pesticide residues cannot be ignored [7]. Foreign materials such as glass fragments, metal fragments, and infestation of mould were found only in tomatoes. Metals such as lead, cadmium, chromium, and tin were found in tomatoes together with other migrations of di-(2-ethylhexyl) phthalate (DEHP) ( Table 2). The presence of different types of metals found in tomato and chilli pepper could be classified as an incidental form of adulteration. According to Bansal et al. [21], metals such as mercury, cadmium, and lead are considered very toxic and their intake could be chronic as these metals are associated with organ damage. Packaging defects of processed tomato and chilli pepper such as bulging, absence of labelling, or incorrect labelling were suspected to be a result of contamination. Other forms of hazards identified include environmental pollutants, allergens, organoleptic aspects (deterioration), food additives, and flavourings.
Following the trend of hazard notification as reported in the RASFF annual report, most of the hazards reported in food and its products by notifying countries keep soaring.

Colourants Used to Adulterate Chilli Pepper and Tomato.
Unauthorized colours such as orange II, Sudan dye, rhodamine B, fast garnet, oil orange, and para red were reported to have been found in either processed chilli pepper or tomato. Although these colours were banned to be used in food products, high quantities were reported to be present in either chilli pepper or tomatoes. Orange II in chilli pepper and tomato was in the range of 0.50 to 30.00 mg/kg as shown in Table 3. The amount of rhodamine B reported being present in chilli pepper and tomato ranges from 0.44 to 140.00 mg/kg. Para red was the least colourant reported to have been found in chilli pepper and tomato with an average value of 0.7 and 0.4 mg/kg, respectively. The increased presence of para red in chilli pepper than tomato was also reported by Mustafa et al. [13] in estimating para red dye in chilli powder and tomato sauce. The findings in this study agree with Rao et al. [22] who also reported the presence of soluble dye and rhodamine in chilli powder.
Sudan III, Sudan IV, fast garnet, and oil orange Ss were not found in tomatoes ( Table 3). The reason could be attributed to the fact that the Sudan dye is red in colour and tomato in either processed form does not look reddish; hence, the addition of Sudan dye will make it look suspicious to consumers. However, these dyes belong to the azo family of synthetic dyes widely used as colouring agents in the cloth industry. They have been categorized under class 3 carcinogens by the International Agency for Research on Cancer [23]. According to the European Union and Food Standards Agency, Sudan dye and other related dyes belonging to the azo family are banned to be used as additives to improve colour in foodstuffs for human consumption or commercial benefit [24] because they could pose health issues to the consumer due to their toxic and carcinogenic nature. Sudan I in hot chilli pepper was first reported by the French food control in 2003, and an alert was posted by the EU in the RASFF [25]. This led the EU to ensure that chilli pepper and chilli products imported into member states should be accompanied by an analytical report demonstrating that the consignment does not contain Sudan dye [19]. A detection limit of 0.5 to 1 mg/kg of Sudan dye and other related dyes (see structures in Figure 5) for the analytical method was set by the European Commission [26], but what was observed in this study for chilli pepper and tomato was far more.
Many food manufacturers use these dyes or colourants to cover the ageing effect, mask spoilage, and disguise poor or bad foodstuffs or processed products [13]. The quantity and the type of dye being used are therefore not important to the manufacturer besides achieving their aim.

Pesticide Residues Present in Chilli Pepper and Tomato.
This study shows evidence of the use of unapproved

12
International Journal of Food Science pesticides. The substances marked with • are not authorized in the EU at the time of this study as shown in Figures 6 and 7. This includes acetamiprid, chlorothalonil, chlorpyrifos, dimethoate, methomyl, monocrotophos, omethoate, oxamyl, and thiophanate methyl which were found in both chilli pepper and tomato. Carbendazim, formetanate, and triazophos (5.69, 4.05, and 4.11 mg/kg, respectively) were some of the chemical compounds with high residual levels reported to have been found in chilli pepper ( Figure 6). The highest pesticide residues reported to be present in processed tomatoes were thiophanate methyl (20.26 mg/kg), fludioxonil (27.36 mg/kg), Di-isononyl phthalate (20.70%), and bromide (84.9 mg/kg) as shown in Figure 7.
On tomato surface, other substances like thiabendazole, carbendazim, and chlorpyrifos have been found [27]. The most frequently reported pesticide residues in chilli pepper and tomato and the number of notifications can vary from year to year [28]. Besides pepper and tomatoes which are used as spices, other types of products that have been found to contain pesticide residues as reported by the RASFF annual report [28] include cereals and bakery products, cocoa and cocoa preparations, coffee and tea, fruits, and vegetables. Recent studies show that some of the pesticides reported in this study are highly dangerous to human health and the environment especially pesticides in the chemical groups of organophosphates (malathion, chlorpyrifos, dimethoate, dichlorvos, cypermethrin, and ethion, see Figure 8) and organochlorine (dicofol) [29,30]. The number of pesticide residues reported in this study is due to misuse, overuse, improper application of pesticides to the crops, illegal use of pesticides not registered and authorized for crops, and inadequate harvest or storage conditions (waiting period of the last pesticide application) [29]. Again, most countries do not have guidelines for highly dangerous pesticide use [31]. Therefore, the use of such crop commodities as raw materials for food production becomes a reasonable source for the occurrence of pesticide residues in processed foods as reported in this study.
The official limits for pesticide residues including condiments used for spices can be found in the Codex Alimentarius [32]. Table 4 provides information on some tolerable levels of pesticides that are currently used in the food production chain, and some of these compounds were reported in this study as shown in Figures 6 and 7. However, the established maximum residue limits (MRLs) are based on national conditions and practices and are possible for different countries to set different MRLs for the same pesticide or food commodity. Hence, it is likely that a pesticide legal in one country is not authorized for use in another country where it is not considered necessary for pest control. This, therefore, results in unfair barriers to trade.
According to Röösli et al. [29], the use of unauthorized pesticides not only disturbs the soil conditions but also destroys the biocontrol agents in the soil which need to be cared for and developed through the reduction of chemical usage in agriculture. Humans get exposed to pesticides found in food through ingestion and dermal contact [29]. Exposure to pesticides has been linked to many health problems such as diminished intelligence, immune suppression, reproductive abnormalities, hormone disruption, cancer, and neurological and behavioural disorders, especially among children [29,33,34]. The Food and Agricultural Organization (FAO) [35] reported that billions of people in the world depend on agriculture for their livelihoods, hence the increase in exposure to pesticide usage. The presence of pesticide residues in crops has affected the importation and exportation of crops from one country to another country [29].
As revealed in this current study, the unauthorized pesticides and colours are mostly cheap; hence, farmers indulge in the act to get them and indiscriminately apply them to their crops. Again, due to the high demand for tomatoes, most producers do not wait for the recommended safe period of the pesticides they use before the crops are harvested for market and export. Some eco-friendly measures that can be adopted to reduce pesticide residue on crops include spraying the crops with a mixture of water extract from the bark of Tamarindus indica fruit and leaves of the neem tree [29,36,37]. This helps to control fungal infections without any adverse effects on the crops.
To minimize these forms of contamination, there is a need to adopt good agricultural practices (GAP) before and after harvesting agricultural produce. The presence of pesticide residues found in these vegetables is mostly due to over and indiscriminate doses of synthetic fertilizers and pesticide application. Although some foods may contain natural toxins, the presence of unauthorized pesticide residue can pose more danger to the consumers' health. This needs to be replaced by the need-based application of safe and recommended pesticides as this will help reduce chemical use in general. Before exporting food items to other nations, food safety authorities in the country of origin should conduct routine surveillance, monitoring, inspection, and random sampling of food products, including processed tomatoes and chilli pepper. Food Safety Officers of the State can create quick tests for the identification of adulterants, particularly banned colours, so that citizens can identify adulteration in their own homes and raise consumer awareness of food safety.

Conclusion
The findings of this study indicate that the exportation of contaminated processed chilli pepper and tomato is common. Unauthorized dyes such as orange II, Sudan dye, rhodamine B, fast garnet, oil orange, and para red were reported to have been found in either processed chilli pepper or tomato. Carbendazim (5.69 mg/kg) and bromide (84.9 mg/ kg) were some of the chemical compounds with high residual levels reported to have been found in processed chilli pepper and tomato, respectively. The levels of contaminants reported in this study are alarming despite the ban on certain dyes and pesticides used in the food chain. There should be more rigorous and routine testing of products originating from countries to help curb the menace by providing risk managers with a sound evidence base for designing future monitoring programmes.

Conflicts of Interest
The authors declare that there is no conflict of interest regarding the publication of this paper. 14 International Journal of Food Science