Overview of Chemicals in Food “We the chefs have a responsibility to learn about the chemical makeup of food.”- Joel Robuchon. Today more Americans are focusing on nutritious and safe food. Recommendations from the "Dietary Guidelines for Americans, 2010" emphasize eating fruit, vegetables, whole grains and low-fat or fat-free milk and milk products. We should include lean meats, poultry, fish, beans, eggs and nuts. We are urged to limit consumption of foods that are high in saturated fat, trans fat, cholesterol, sodium and sugar. We are required to consume adequate micronutrients, vitamins, minerals, fibers and foods low in calories, which can be obtained by eating fresh fruits and vegetables. We try to stay away from food that can cause weight gain or health issues. We check nutrition labels to make sure we are consuming the correct amounts of sodium, sugar, fats, vitamins, minerals, and calories. However, American consumers don’t realize there are other things they need to be aware of in their foods: hazardous chemicals or food contamination. Food contamination is the presence in food of harmful chemicals and microorganisms, which can cause consumers to get sick. This book addresses the chemical contamination of foods, and not microbiological contamination. Chemical food safety issues have been the center of media attention over the past decade. Because of advances in analytical detection, chemists can now analyze for and detect more chemicals at much lower concentrations in more foods. They can detect a chemical in nanograms per milliliter (ng/mL or one-billionth of a gram in a milliliter) levels and this raises the question if these levels cause more health problems and concerns about the food supply for consumers than those chemicals detected at the micrograms per milliliter (µg/mL or one-millionth of a gram in a milliliter) level. Although Americans enjoy one of the safest food supplies in the world, the impact of chemical contaminants on consumer health and well-being is often apparent only after many years of prolonged exposure at low levels (e.g. cancer). Chemical contaminants can occur in our food from many sources. They can be introduced at any point in the food chain during production of the raw material, processing, retail distribution, food preparation and consumption. Chemicals that may enter the food supply include the presence of agrochemicals (e.g. pesticides), natural toxins (e.g. mycotoxins), processingproduced toxins (e.g., acrylamide, trans fats, furan), food allergens, heavy metals (e.g. lead, arsenic, mercury, cadmium), industrial chemicals (e.g. benzene, perchlorate), contaminants from packaging materials (e.g. bisphenol A), and deliberate contaminants (e.g. melamine) in our food and animal feed. They typically cause a health concern. The U.S. Food and Drug Administration’s program for chemical contaminants in food (http://www.fda.gov/Food/FoodborneIllnessContaminants/ChemicalContaminants/) provides an overview of the chemicals of concern. Some of these that will be discussed in this book include the following: 1 Pesticides. Pesticides are used to control insects, weeds, and disease throughout the world. People can be exposed to pesticides by different routes including occupation, in the home, at school and in their food. Pesticides are commonly used on fruits and vegetables to control pests that may damage the crops during production, storage or transport. Although their use enhances crop yield and improves the quality of the food produced, pesticide residue levels in food can have a negative effect on the health of humans. Infants, young children, the fetus, and the elderly are more susceptible to pesticide poisoning. Pesticides can affect the nervous, endocrine, immune, and reproductive systems. Eating pesticide-contaminated foods is the most common route of exposure. Chemicals that are no longer used but do not breakdown can remain in the environment for a long period of time. For example, most people in the United States still have detectable levels of DDT in their bodies even though it was banned in the U.S. in 1972. Therefore, it is beneficial to find ways to reduce the levels of pesticide residue in food such as produce to lower the exposure and risk to human health. Acrylamide and furan. Most aisles of our grocery stores contain processed foods: canned, frozen, pasteurized, or microwavable. These have extra sugars, salt and additives to prolong their shelf-life. Many people work and when they get home look for a quick, convenient way to make dinner and they turn to these processed foods. No one has time to prepare meals from scratch as our mothers did. Not only may these processed foods have decreased nutrient levels, but produce chemical and physical changes that can cause a food to be hazardous or contaminated. Heating of foods can generate many different kinds of potentially hazardous chemicals, some of which are carcinogenic and genotoxic. Acrylamide and furan are examples of chemicals that form as a result of heat treatment of food. Cooking or heat processing causes free amino acids and sugars to react via the Maillard reaction, which is a chemical reaction between amino acids and reducing sugars that gives browned foods their desirable flavor. However, some Maillard reactions form toxic products, such as acrylamide. Acrylamide forms in carbohydrate-rich foods that are subject to high temperatures (>120°C) processes such as frying, baking, and extrusion. It is not formed in food that has been boiled or in foods that is not heated. It has been found in potatoes, cereal products, and coffee. Furan is generated in heat-treated commercial foods and it is produced through heating of natural food constituents and reactions of carbohydrates, ascorbic acid, and polyunsaturated fatty acids in food. It can be found in roasted coffee, instant coffee, and processed baby foods. Acrylamide and furan are both potential human carcinogens that occur in food as a result of cooking or heat processing. Both compounds became internationally important food contaminants within the last several years. Trans fatty acids and benzene. Several chemicals are formed through nonthermal processes or during storage. Two of these chemical hazards that have been in the public and scientific media include trans fatty acids in hydrogenated fats and oils and benzene in soft drinks. Recently, health implications have been associated with trans fatty acids in foods. Trans fatty acids are commercially produced by partial hydrogenation of edible oils. Partially hydrogenated 2 oils have been used in food for many reasons. Hydrogenation increases product shelf life and decreases refrigeration requirements. Hydrogenation is a chemical reaction between molecular hydrogen (H2) and another compound or element, usually in the presence of a catalyst such as nickel, palladium or platinum. Trans fatty acids are found in foods such as margarines, spreads, shortenings, frying fats, and specialty fats and occur naturally in foods such as milk, butter, and tallow. Trans fat has been shown to consistently be associated with risk of coronary heart disease in part by raising levels of the low-density lipoprotein LDL (so-called "bad cholesterol"), lowering levels of the high-density lipoprotein HDL ("good cholesterol"), and increasing triglycerides in the bloodstream. Health professionals recommend reducing consumption of foods containing trans fatty acids. On 16 June 2015, the FDA finalized its determination that trans fats are not generally recognized as safe, and set a three year time limit for their removal from all processed foods. Benzene, a carcinogenic chemical, has been found in soft drinks and is a public health concern. This contamination has caused an uproar among environmentalists and health officials. The benzene forms from decarboxylation, a chemical reaction that removes a carboxyl group and releases carbon dioxide (CO2), of the preservative benzoic acid in the presence of ascorbic acid (vitamin C) and metal ions (iron and copper) that act as catalysts, especially under heat and light. Benzoic acid is often added to drinks as a preservative in the form of its salts sodium benzoate (E211), potassium benzoate (E 212), or calcium benzoate (E 213). Citric acid may accelerate production of benzene when combined with these acids. Other factors that affect the formation of benzene are heat and light. Storing soft drinks in warm conditions speeds up the formation of benzene. The regulatory limit for benzene in drinking water and bottled water is 5 nanograms per milliliter, but there is no limit on soft drinks. Benzene levels detected in some soft drink products were higher than the regulatory limit of bottled water. Soft drink manufacturers have reformulated their beverages to reduce or eliminate benzene formation. Benzene levels in some soft drink products and especially in new beverage formulations need to be monitored to ensure that benzene levels are minimized. Bisphenol A. Food packaging is essential to the food manufacturing process. It is important that there is no migration of the chemicals from the packaging into the food. Care must be taken when manufacturing proper packaging. Bisphenol A (BPA) has attracted much public attention. This compound is used to make certain plastics and epoxy resins. In the food industry, it is used to make polycarbonate bottles and epoxy resins. Polycarbonate is used in water and baby bottles, and epoxy resins are used as coatings on the inside of many food and beverage cans. Studies have shown that BPA can migrate from packaging material into a variety of canned vegetables and fruits, meats, beverages, and liquid infant formulas. Because of its estrogenic effects, there is concern about BPA’s suitability in food containers. In July 2012, the FDA announced that it would no longer allow BPA in baby bottles and children’s drinking cups. However, there are no restrictions for its use in other consumer products. 3 Food allergens. Food allergies can range from mildly irritating to life-threatening. An estimated 30,000 Americans go to the emergency room each year to get treated for severe food allergies, according to the Food Allergy and Anaphylaxis Network (FAAN). It is estimated that 150 to 200 Americans die each year because of allergic reactions to food. According to the Centers for Disease Control and Prevention, food allergies are a growing food safety and public health concern that affect an estimated 4%–6% of children in the United States. Researchers estimate that up to 15 million Americans have food allergies. Eight foods account for 90 percent of all reactions: milk, eggs, peanuts, tree nuts, soy, wheat, fish and shellfish. Even trace amounts of a food allergen can cause a reaction. As of today, there has been no known treatment for life-threatening food allergens, only prevention of the allergic reaction by avoidance of exposure to the allergen. The Food Allergen Labeling and Consumer Protection Act (FALCPA) was introduced in 2004 by the FDA to improve food labeling information for the millions of consumers who suffer from food allergies. Food labeling of the presence of major food allergens provides awareness to sensitive consumers regarding products they should avoid consuming. However, allergens can still inadvertently appear in a product because of incorrect labelling or cross-contamination during manufacturing. Mycotoxins. Mycotoxins are toxic secondary metabolites, chemicals that are not directly involved in the normal growth, development, or reproduction of an organism, produced by certain fungi that occur naturally and can contaminate food during growth in the field, processing, transportation or storage. These toxic metabolites can cause important economic loss. Mycotoxins are considered both poisonous and chronic hazards and are best avoided by implementing good agricultural and manufacturing practices. Many mycotoxins are stable to heat and food processing procedures and are found in many agricultural products including grains, fruits, and vegetables. The most toxin-producing fungi found in food, the Penicillium, Fusarium, and Aspergillus genera, are the greatest significance in food safety. From the more than 1000 mycotoxins that are known to form, those having the most public health and economic relevance include the aflatoxins, ochratoxins, trichothecenes, zearalenone, and fumonisins. Consumers may exhibit various toxicological outcomes from ingestion. Some mycotoxins of greatest concern are aflatoxins in corn, peanuts, tree nuts, rice and cottonseed; fumonisins in corn, wheat, barley, and rice; and ochratoxin in wheat, barley, oats, rye, sorghum peanuts, wine, beer and raisins. Government agencies have tried to control mycotoxins in the food supply by establishing guidelines and action levels and monitoring the food supply. Many international agencies are attempting to universally standardize regulatory limits for mycotoxins. The U.S. Food and Drug Administration has regulated and enforced limits on concentrations of mycotoxins in foods and feed industries since 1985. However, there is still not enough data on some mycotoxins in the U.S. due to the lack of reliable testing methods. As the U.S. population has grown in both size and ethnic diversity, the quantity and variety of food consumed and imported in the United States has increased correspondingly. According to the U.S. Department of Agriculture Economic Research Service, in 2009, U.S. food consumption 4 totaled 654 billion pounds, or more than 2,100 pounds per capita. Of this amount, imports accounted for 17 percent (110 billion pounds), or 358 pounds per capita. Imports have increased in the United States because much of the fresh food cannot be produced domestically due to climate conditions or can grow only in certain seasons. Also, some imported foods cost less to produce than the domestically grown ones. Consumers prefer an increasingly wider selection of food products, such as tropical fruit, vegetables, nuts, premium coffee, wines and beers, cheeses, confections, grain products, and processed meats that they cannot obtain domestically. FDA has more than 1,300 inspectors conducting field activities, primarily food and feed inspections and investigational activities. The FDA inspectors sample just 1.3 percent of all imported food shipments entering the country and perform few on-site inspections of foreign farms and food processing plants. According to the FDA, about $2 trillion worth of products enter the U.S. each year from more than 230 countries, which makes it impossible to physically examine every product entering the country. Since there are not enough inspectors at the borders, there have been incidents of illegal food imports entering the U.S. The FDA is responsible for inspecting all imported foods except for meat and egg products, which are regulated by the Food Safety and Inspection Service, part of the U.S. Department of Agriculture. Importers of food products into the U.S. are responsible for ensuring that the products are safe, clean, nutritious, and labeled according to U.S. requirements. Foreign inspectors are required to identify potential food safety problems before products arrive in the United States, to determine whether a firm is in compliance with FDA’s requirements and food safety standards, to assist FDA in determining admission status for food products imported into the United States, and to help ensure that food products that FDA is in charge of meet U.S. requirements under the Federal Food, Drug and Cosmetic (FD&C) Act. Different countries have different regulations than the U.S. Both imported and domestically-produced foods must meet the same food safety requirements to prevent intentional and inadvertent contamination of food. Melamine. There were several food recalls of melamine after pets were poisoned and children had severe kidney damage due to melamine-contaminated food. In 2007, pet food manufacturers issued recalls after they found their products had been contaminated with melamine. This caused serious illnesses or deaths in some of the animals that had eaten them. The U.S. FDA first detected and identified the melamine adulterant in pet food. The pet foods contained wheat gluten and rice protein as sources of protein for the animals’ diets. The wheat gluten and rice protein contained melamine, amelide, amiline, and/or cyanuric acid and were imported from a manufacturer in China. Cats and dogs consuming the food developed symptoms of kidney failure, including loss of appetite, vomiting, lethargy, frequent urination, increased thirst and in some cases, ultimately death. Melamine, in combination with amelide, aniline, and/or cyanuric acid appears to form highly insoluble crystals in the animal’s kidney, resulting in kidney damage. The Chinese suppliers had added these compounds to the pet food to increase the measured level of protein. These adulterants are high in nitrogen and artificially provided high protein levels when the wheat gluten/rice protein samples were tested. FDA issued import alerts after it detected melamine in wheat gluten and rice protein products. 5 In September 2008, several companies in China were connected to a scandal involving milk and infant formula which had been adulterated with melamine, leading to kidney stones and other renal failure, especially among young children. By December 2008, nearly 300,000 people had become ill, with more than 50,000 infant hospitalizations and six infant deaths. Melamine was added to increase the protein content after water was added to fraudulently dilute the milk. Melamine can cause the protein content of food to appear higher than the true value. Because of the highly publicized incidents of food contamination and adulteration in the Chinese food supply and in U.S. food imports, a U.S. Government Interagency Working Group on Import Safety issued an Action Plan for Import Safety and the U.S. FDA issued a Food Protection Plan in 2007. FDA opened its first overseas office in China in 2008. Toxic Metals: Lead-based and other heavy-metal based inks used for labeling candy wrappers have been a regulatory issue in the past. Although the U.S. and European Union have banned the use of heavy metal-based inks in food wrappers, lead has been found in the wrappers of candy imported from Mexico. Lead-based inks have been found on both the exterior and interior surfaces. It becomes a problem when lead from a lead-based printing ink is found on the portion of the package that directly contacts the food or, if the lead migrates into the packaged food. The product would be in violation of the Federal Food, Drug, and Cosmetic Act. Certain ingredients such as chili powder and certain types of salt used in Mexican candy products also may contain lead. In 2006, FDA issued guidance regarding lead to lower children’s exposure to small traces of lead present in certain candies and set a limit of 0.1 mg/kg. Ceramic pottery made by several manufacturers in Mexico that can be used as serving bowls also contain lead that may leach into food. In 2010, FDA published guidance for industry to address safety and labeling concerns for traditional pottery that may contain lead. Lead exposure in small amounts does not cause a significant health risk. However, exposure to larger amounts can cause lead poisoning, which can affect almost every part of our body. Arsenic is present in the environment as a naturally occurring substance or as a result of contamination from human activity. It exists in at least two forms, inorganic and organic. It is more toxic in its inorganic form, which is carcinogenic. Arsenic in the food supply has created much discussion in recent years among the public, scientific and regulatory fields. The U.S. Environmental Protection Agency (U.S. EPA) established exposure limits of arsenic and lead in drinking water of 10 ng/mL and 15 ng/mL, respectively. Apple juice was also found to contain arsenic because lead arsenate pesticides were a popular pesticide for apple and other fruit orchards used in Canada, the U.S., New Zealand, and Australia. These trees absorb arsenic from the soil and water. In 2013, the FDA proposed an action level of 10 ng/mL, for apple juice, similar to that for water. Arsenic may be present in many foods including grains, fruits, and vegetables due to absorption through the soil and water. While most crops don’t readily take up much arsenic from the ground, rice is different because it takes up arsenic from soil and water more readily than other grains. In addition, some seafood has high levels of less toxic organic arsenic. There are no standards for arsenic in food products although food sources are the main source of exposure. Long-term exposure to high levels of arsenic is associated with higher rates of skin, bladder, and lung cancers, as well as heart disease. 6 To increase consumers’ safety with regard to contaminants, FDA developed the FDA Food Protection Plan in 2007, which focuses on both domestic and imported food and attempts to address both unintentional and deliberate contamination of the nation’s food supply. This plan relies on an approach of prevention, intervention and response to build safety into every step of the food supply chain. It complements the Presidential Initiative: Import Safety Action Plan that recommends how the U.S. can improve the safety of all imported products. The Import Safety Action Plan lays out short-term and long-term recommendations to increase product safety at every step of the import life cycle. Together, these efforts will provide a food protection structure that ensures that the U.S. food supply remains safe. Although safe levels of human exposure have been set for many chemicals, there is concern that many more new chemicals may be on the rise and which may cause detrimental effects as some of the aforementioned chemicals. However, the effects of low level exposures to chemicals are uncertain. Consumers are encouraged to avoid imported foods as well as specific fruits and vegetables. They are advised to purchase organic products instead of conventional ones and to avoid those fruits and vegetables that contain the highest levels of pesticide contamination. Organic products are produced without the use of toxic and persistent pesticides and synthetic nitrogen fertilizers, antibiotics, synthetic hormones, genetic engineering or irradiation. According to the Centers for Disease Control and Prevention (CDC), those who consume large amounts of fruits and vegetables on a daily basis are less likely to suffer from health problems such as high blood pressure, type 2 diabetes and stroke. 7