Adulteration with Sudan Dye Has Triggered Several Spice Recalls

By Thomas Tarantelli
4 Comments
June 30, 2017


• Categories: Food Labs, Food Manufacturing, RC - Food Safety Testing

In the following article, the author reports finding Sudan dye in spices in New York State, making the argument for Class I recalls.

In New York State (NYS), Department of Agriculture and Markets food inspectors routinely sample domestic and imported food from retail markets for food dye determination. For decades, the NYS Food Lab has examined both domestic and imported food for undeclared allowed food dyes and unallowed food dyes utilizing a paper chromatography method. This method works well with water-soluble acid dyes, of which food dyes are a subset.

The NYS Food Lab has participated in four sets of the FAPAS proficiency tests: Artificial Colours in Soft Drinks and Artificial Colours in Sugar Confectionary (Boiled Sweets). The qualitative analysis was by paper, thin layer silica and thin layer cellulose chromatography. Satisfactory results were obtained.

The paper/thin layer chromatography method is a qualitative non-targeted method and has a limit of detection of approximately 1 to 5 ppm (parts per million) depending on the dye. If an unallowed dye is detected, the food product is violated as adulterated and results are forwarded to the FDA.

Some countries have a maximum concentration of allowed food dye in a food product. For example India has a 100 ppm to 200 ppm maximum for their allowed food dyes, in some food, singly or in combination.¹

In early 2011, a food sample of pink colored sugar coated sesame seed from Pakistan was sent to the lab for color determination. The paper chromatography method could not determine any dyes. (As found out later, the unknown pink dye was not an acid dye.) From research it was found that Rhodamine B was a pink water soluble basic dye commonly used as a food adulterant.  A standard was ordered and then a qualitative high performance Liquid chromatography-tandem mass spectrometry (HPLC/MS/MS) method was developed (Waters UPLC Aquity w/Waters Premier XE triple quadrapole) to determine Rhodamine B. After utilizing this new method, Rhodamine B was found in the sugar coated sesame seed.

Rhodamine B is an industrial dye and is not allowed in food anywhere in the world. Industrial dyes are not allowed in food because they are toxic; in fact, some industrial dyes are used for suicide.^2,3,4 In addition, industrial dyes are not made to “food grade” specifications with regard to dye purity, heavy metal (i.e., arsenic and lead) concentrations, subsidiary dye concentrations and concentrations of unreacted precursors. From additional research of news articles and research papers, more industrial dyes were identified as common food adulterants; more dye standards were ordered and incorporated into the HPLC/MS/MS method. The NYS Food Lab’s current HPLC/MS/MS surveillance method includes 36 compounds: Water soluble “acid dyes” and “basic dyes”, organic solvent soluble “solvent dyes”, and several pigments.

The HPLC/MS/MS method has a limit of detection in the ppb (parts per billion) range for some dyes and parts per trillion for other dyes. The FDA has an action level of 1 ppb for certain water-soluble basic dyes (such as Malachite Green) when used as a fish antibiotic. However, due to concern that unallowed dyes might be present due to contamination from packaging, the food lab subsequently set an action level of 1 ppm for unallowed dyes determined by the HPLC/MS/MS method. At levels over 1 ppm, detection of dyes in food would indicate intentional dye usage for coloring food.

The food lab has participated in three rounds of the FAPAS proficiency test, “Illegal Dyes found in Hot Pepper Sauce”. The qualitative analysis was by LC/MS/MS. Satisfactory results were obtained.

Sudan Dyes Considered to be Carcinogenic

“Sudan dyes are not allowed to be added to food. There has been worldwide concern about the contamination of chili powder, other spices, and baked foods with Sudan dyes since they may have genotoxic and carcinogenic effects (according to the International Agency for Research on Cancer)”.⁵

“There have been several documented cases of spices being contaminated with carcinogenic dyes such as Sudan I or lead oxide. We therefore assume that the presence of these chemicals in spice ingredients will be considered a reasonably foreseeable hazard under this rule.”⁶

“Sudan red dyes have been used to color paprika, chili powders, and curries, but are also known carcinogens and are banned for use in foods.” ⁷

Sudan Dyes are a family of more than 10 synthetic industrial “solvent dyes”. Solvent dyes are typically used to color oils and waxes, including shoe polish. Sudan dyes that the food lab has found in spices include Sudan 1 (Sudan I), and Sudan 4 (Sudan IV). Sudan 1, also known as Solvent Yellow 14, is an orange colored dye. Sudan 4, also known as Solvent Red 24, is a blue shade red colored dye.

Positive identification of Sudan 4 is often hindered by the existence of a positional isomer, Sudan Red B (Solvent Red 25). This problem was addressed by using the HPLC/MS/MS method with a transition unique to Sudan 4 (381.2 > 276.0). This information was obtained from one of the two corroborating labs. The food lab has recently identified a transition unique to Sudan Red B (381.2 > 366.1).

Sudan Dyes Found in Spices in Europe

In March 2001, Europe began discovering Sudan dyes in spices. A February 2017 search of Europe’s Rapid Alert System for Food and Feed (RASFF) for “unauthorised colour” and “sudan” in the “herbs and spices” food category resulted in 429 notifications.

The 429 RASFF notifications arranged by year and by maximum concentration reported of Sudan 1 and Sudan 4 during that year are listed in Table I.

In a search of the FDA’s Import Alert 45-02 (Detention Without Physical Examination and Guidance of Foods Containing Illegal and/or Undeclared Colors) the author could find no record of spices violated for Sudan dye adulteration.

In a search of the FDA’s Enforcement Reports the author could find no record of spices violated for Sudan dye adulteration.

Industrial Dyes in Food: Class II or Class I Recall?

The NYS Food Lab and the FDA routinely find imported food containing unallowed food dyes such as Ponceau 4R, Amaranth and Carmoisine. These unallowed food dyes are allowed for use in food in other parts of the world, while not allowed in the USA. Foods containing unallowed food dyes are violated as adulterated and a Class II recall will occur. Sudan dyes are not allowed as food dyes anywhere in the world. They are industrial dyes, used in coloring oils and waxes, such as shoe polish.

“Class I recall: A situation in which there is a reasonable probability that the use of or exposure to a violative product will cause serious adverse health consequences or death.

Class II recall: A situation in which use of or exposure to a violative product may cause temporary or medically reversible adverse health consequences or where the probability of serious adverse health consequences is remote.”⁸

With a Class II recall, there is no consumer notification. In contrast, as part of a Class I recall, a press release is issued. Consumers who have purchased the product might be informed and may discard the product or return it for a refund.

Continue to page 2 below.

Spice Usage: ½ gram per serving or 600 grams per month?

In the Code of Federal Regulations (CFR) Title 21, the serving size per meal for spice is referenced as ½ gram.⁹ However, certain ethnic groups may consume a daily amount of 20 grams of spice per person.¹⁰ Twenty grams of spice per day would yield a monthly usage of approximately 600 grams of spice per person.

Sampling and Results

In May 2013 a 25-gram canister of turmeric powder was sent to the lab for color and heavy metal analysis, sampled from a retail market in Brooklyn. Sudan 1 was determined in the sample. At this time, the LC/MS/MS determination was qualitative. The sample was violated for containing unallowed dye, resulting in a Class II recall (This sample was found to contain approximately 700 ppb Sudan 1 in a January 2017 re-analysis).

In December 2013, a 250-g. canister of ground red pepper, labeled as “Red Chili Ground (Special)” was sent to the lab for color analysis from a retail market in Brooklyn, New York. It was apparent from the LC/MS/MS data that this sample had high amounts of unallowed dyes Sudan 1 and Sudan 4. At that time, the NYS Food Lab had only a qualitative method, so subsamples were sent to two labs, both of which could perform a quantitative analysis of the spice. One lab reported greater than 300 ppm Sudan 1 and  greater than 300 ppm Sudan 4. The second lab results were similar. The violation of this “Red Chili Ground (Special)” resulted in a Class II recall.

In March 2014, a “sampling blitz for color” was conducted in the Albany, New York area. Twenty-three samples were taken at 12 markets. One sample of paprika was selected because the clear plastic bag package was stained red. LC/MS/MS data on this sample of paprika indicated high amounts of unallowed dyes Sudan 1 and Sudan 4, as well as unallowed acid dyes Orange II and Acid Black 1. Again, a subsample of the paprika was sent to two labs for confirmation. Again, results from both labs were similar, 720 ppm Sudan 1 and 910 ppm Sudan 4. The violation of this paprika resulted in a Class II recall. Also taken as a sample on this “sampling blitz” was a turmeric powder. Sudan 1 was found in this turmeric powder, and it also was violated for containing unallowed dye (This sample was found to contain approximately 200 ppb Sudan 1 in a January 2017 re-analysis).

In November 2014, a turmeric sample from a Brooklyn retail market was sent to the NYS Food Lab for analysis. By this time, the lab had completed a validated method for quantitative determination of Sudan 1 in spices. The turmeric was found to contain unallowed dye Sudan 1 at 1015 ppm and also unallowed acid dyes Metanil Yellow and Orange II. The violation of this turmeric resulted in a Class II Recall. Additional sampling of this brand turmeric resulted in two additional violations. Sampled in December 2014, the first was found to contain 641 ppm Sudan 1, Orange II, and Metanil Yellow. Obtained in February 2015, the second sample was found to contain 144 ppm Sudan 1. Both were Class II recalls.

Repeated and routine sampling of spices for color analyses indicated a trend: Spice samples from ethnic markets that lacked a container code were more likely to be violative.

In February 2016, a 7-oz. bag of red pepper powder (without a container code) was sent to the lab from a Brooklyn retail market. This sample of “Red Chili Powder” was found to contain unallowed dyes Sudan 1 at 599 ppm and Sudan 4 at 96 ppm. Additional sampling of Chili powder was done at the market of the same brand but different size containers. This resulted in a 14 oz. container of “Red Chili Powder” found to contain 329 ppm Sudan 1, 55 ppm Sudan 4 and unallowed acid dye Metanil Yellow. The violation of these products resulted in Class II recalls.

In March 2016, a 6-oz. canister of paprika (without a container code) was taken at a retail market in Schenectady, New York. The inspector thought the sample looked “too red”. This sample of paprika was found to contain unallowed dyes Sudan 1 at 850 ppm and Sudan 4 at 2400 ppm. Sampling and analyses of the same brand paprika but different size containers, and same brand spices from the same market resulted in no additional violations for unallowed dye. This sample of paprika contains a concentration of unallowed dye Sudan 4 as high as Europe’s worst sample as reported in the RASFF. The violation of this paprika sample resulted in a Class II recall.

In April 2016, a red pepper powder “Red Chili Supreme” (without a container code) was sampled from a retail market in the Bronx, New York. This sample of “Red Chili Supreme” was found to contain unallowed dyes Sudan 1 at 687 ppm, Sudan 4 at 43 ppm, Sudan 3 at 1.2 ppm and Oil Orange SS (solvent soluble) at 1.7 ppm. No additional same product, same brand, different container size were found to sample. The violation of this “Red Chili Supreme” resulted in a Class II recall.

In July 2016, an 80-g. bag of “Red Chili” powder was sampled at from a retail market in Ridgewood, New York. This product was found to contain 1.73 ppm Sudan 1. It was violated as adulterated, a Class II recall for unallowed dye.

In December 2016, a ground red pepper, labeled as “Red Chili Ground (Special)” was sampled from a retail market in Brooklyn, New York. This product was the same exact product found to contain Sudan 1 and Sudan 4 in December 2013. The current product declared “FD&C 40”, and was found to contain Allura Red. Unfortunately, the product was also found to contain 51.5 ppm Sudan 1 and 9.47 ppm Sudan 4. It was violated as adulterated, resulting in a Class II recall.

In January 2017, a 7-oz. bag of “Red Chili Powder” was sampled at a retail market in Selden, New York. This was the same product and brand found to contain Sudan 1 and Sudan 4 in February 2016. The current “Red Chili Powder” was found to contain 213.1 ppm Sudan 1 and no Sudan 4. Sample was violated for containing unallowed dye and a Class II recall resulted.

Summary

Sixteen spice samples, five turmeric, two paprika and seven red pepper (chili), one Malathy and a Madras Curry Masala (spice mix), have been found adulterated with Sudan dye over a period of 45 months (see Table II).

Sampling and analysis continue to present.

Foods and spices found to contain Sudan dyes are currently violated as a Class 2 recall. However, Sudan dyes are considered carcinogenic and spices have been found with high concentrations of Sudan dyes which certain ethnic groups consume a considerable amount. Therefore, a Class 1 recall is recommended for foods and spices found to contain Sudan dyes and other industrial dyes.

A roadmap to dealing with this problem is already in place; all that is required is the resources to do the work. New York is trying to do its part. Maybe it is time for others to follow suit.

References

1. Food Safety and Standards Authority of India. Appendix  A: List of Food Additives. Retrieved from http://old.fssai.gov.in/Portals/0/Pdf/appendix_a_and_b_revised(30-12-2011).pdf.
2. Subburajl, A. (2012). “A chemical dye emerges the city’s favourite poison”. The Times of India. Retrieved fromhttp://timesofindia.indiatimes.com/city/coimbatore/A-chemical-dye-emerges-the-citys-favourite-poison/articleshow/12565043.cms.
3. Hisham, Md., et al. (2013). Auramine-o and Malachite Green Poisoning: Rare and Fatal. Indian Journal of Pharmacy Practice. Retrieved from http://www.ijopp.org/sites/default/files/IJOPP_6_4_2013_16.pdf.
4. Sherfudeen, K.M., et al. (2015). Cow dung powder poisoning. Indian Journal of Critical Care Medicine. (19)11: 684-686.  Retrieved from http://www.ijccm.org/article.asp?issn=0972-5229;year=2015;volume=19;issue=11;spage=684;epage=686;aulast=Sherfudeen.
5. Chen, H. and Cerniglia, C. (2008). Food Safety Research – Azo/Sudan Dyes . Microbiology, 154:2659-2667.
6. Part 117, FSMA Supplemental Notice of Proposed Rulemaking for Current Good Manufacturing Practice and Hazard Analysis and Risk-Based Preventive Controls for Human Food, Docket No. FDA-2011-N-0920
7. Johnson, R. (2014). Food Fraud and “Economically Motivated Adulteration” of Food and Food Ingredients, January 10, 2014, Congressional Research Service, page 4.Retrieved from https://www.fas.org/sgp/crs/misc/R43358.pdf.
8. FDA. Safety. Recalls, Market Withdrawals, & Safety Alerts. Retrieved from http://www.fda.gov/Safety/Recalls/ucm165546.htm.
9. FDA. CFR – Code of Federal Regulations Title 21. Retrieved from http://www.accessdata.fda.gov/scripts/cdrh/cfdocs/cfcfr/cfrsearch.cfm?fr=101.12
10. Mubeen, H., et al. (2009). Investigations of Heavy Metals in Commercial Spices Brands. New York Science Journal.  2(5), ISSN 1554-0200.