Nutrient Loss in Foods Due to Processing and Storage Susanne Talcott Assoc. Professor Nutrition and Food Science Texas A&M University Luke R. HoLukeward, Ph.D. Overview • Processing Techniques • Examples of Nutrients – Minerals – Vitamins – Botanicals (Polyphenols) Loss of Minerals Due to Processing What impacts minerals in foods – Depleted soils vs. volcanic soils – Organic vs. conventional practices – Selective breeding vs. genetic manipulations – Food composition (fiber, chelators) – Processing? Food Processing – Peeling (physical or chemical) – Dehulling – Trimming/Slicing (sharp or dull knife) – Altering redox states (ie. Added antioxidants) – Concentration/dehydratation/membrane filtration – Soaking, blanching, boiling, frying, brining – Grinding – Roasting and toasting to induce Maillard-complexes – Enzyme treatments (ie. Phytase) – Brewing, steeping, fermenting – Additives: enrichment and fortification Food Composition vs Activity • Minerals that are present may not be bioavailable – “100%” present pre-processing – Assume some physical loss with processing • Processing may increase/decrease bioavailability – Fiber breakdown (physical or enzymatic) – Particle size reduction – Starch hydrolysis – Anti-nutritionals (oxalates, phytates, and other chelators) • Unavailable minerals are still part of its nutritional profile • Released minerals are often detrimental to food quality – AsA + Copper + O2 = superoxide radicals Mineral Analysis Minerals from Ashes • ASH is the residue remaining in a food after complete combustion (oxidation). • What is in foods that won’t burn ??? • How Hot? Total ash determinations may range from 400 to 700°C • There are 2 common methods of ashing: – DRY – WET How Does Ash Relate to Proximate Analysis? • What are the proximates – Moisture, Protein, Fat, Carbohydrate • Sum of other Proximates + Ash = ~100% Ash Content in Common Foods •Most fluid dairy products •Evaporated milk •Nonfat dry milk •Pure fats; oils; and shortenings •Fresh fruits •Dried fruits •Vegetables •Pickles/sauerkraut/ butter •Beans •Fresh meat and poultry 0.5- 1.0% 1.5% 8% 0% 0.2 - 0.8% up to 3.5% 1.0% NaCl added 4% 1% What is Really in the Ashes? • • • • • • • • • Calcium (most all foods except sugar, starch or oil) Phosphorus (dairy, grains, nuts, meats, poultry products) Iron (enriched foods, grains, nuts; meats, eggs, legumes Sodium (primarily from added salt) Potassium (dairy products, F&V, cereals, nuts, meats) Magnesium (nuts, cereals, legumes) Manganese (cereals, F&V, meats) Copper (sea foods, liver, cereals, vegetables) Zinc (sea foods) These can be tested for individually by other methods: Atomic absorption (AA) spectroscopy Inductively coupled plasma (ICP) Ash Determination…. • DRY ASHING – Use of a muffle furnace capable of maintaining 500-600 °C. – Water and volatiles are vaporized and organic compounds are oxidized into H2O, CO2, CO, and oxides – Most minerals are converted to oxide (NO2, CaO, Fe2O3), sulfates, phosphates, chlorides and silicates. – Some minerals are volatile (Fe, Se, Pb, Hg) and dry ashing temperatures should be carefully monitored. • WET ASHING – Use acids alone or in combination with other oxidizing agents. – Nitric, hydrochloric, or perchloric acid are used. Food Processing Examples Cereal Grain Rice Milling • Remove husk, bran, germ by rubbing with abrasive disks or rubber belts • Polish endosperm to glassy finish • Removes bran/germ and nutrients • Brown rice = very little milling Rice Rice Enrichment • Add some vitamins, minerals • Coat rice with nutrients (B-vits, minerals) Parboiling or steeping (converted rice) • “Cook” rice before milling (~10 hrs, 70°C) • Nutrients, vitamins and minerals, will migrate into endosperm (no fortification) Canning in the Literature • Trace minerals were shown to decrease during canning, presumably due to minerals diffusing into the cover solution (Saldamli, 2007). • Most food minerals are water-soluble, so losses are greatest during water-based processes such as boiling (Cermeroglu, 2009) • Cover solution composition, pH, particle size, surface area, and temperature all play a role (Clydesdale, 1991; Saldamly, 2007). Strawberry and Plum Canning (Yagmur and Taskin, 2011) • • • • • • • • • • Raw fruits Slicing, de-seeding, leaf/stem removal 1st wash and sorting (water turns light red) 2nd wash Can washing Filling with fruit Cover solution (ie. sugar-water) Thermal processing Strain fruit from cover solution Analyze for trace minerals by AA Strawberry and Plum Canning (Yagmur and Taskin, 2011) • Results: Trace minerals decreased in the fruit following thermal processing in both fruits…??? Raw Fe 5.84 Cu 0.45 Zn 0.86 Mn 0.53 Plums (ppm) Wash Canned Syrup Entire Can 4.70 2.61 2.17 4.78 0.41 0.31 0.09 0.40 0.81 0.68 0.13 0.81 0.45 0.40 0.09 0.49 Strawberry (ppm) Raw Wash Canned Syrup Entire Can Fe 5.08 4.72 4.60 2.81 7.41 Cu 0.49 0.41 0.36 0.05 0.41 Zn 0.89 0.84 0.72 0.10 0.82 Mn 2.51 2.34 2.11 0.14 2.25 Pectin and Minerals Ca+2 Ca+2 Ca+2 Ca+2 Ca+2 Ca+2 Overall Effect of Processing on Minerals • Minerals are not really sensitive to the heat of food processing – But they can leach out during processing into cooking medium (water/oil). • Some foods are more susceptible to lose than others – 50% decrease for manganese, cobalt, and zinc for canned spinach/beans • Mineral loss can be re-captured into soup, gravy, or sauces • Hard water can increase calcium, magnesium and iron • Soft water can increase sodium. • Processing to decrease phytates, oxylates, and breakdown of insoluble fiber can improve mineral bioavailability Loss of Vitamins Due to Storage and Processing How can Vitamins Be Loss • Removal • Leaching into processing solution • Degradation due to heat or interactions with other food components Do Canned Foods Lose Nutrients? • Fat-soluble vitamins and most minerals are relatively stable – Not affected much by canning • Three vulnerable water-soluble vitamins – Thiamin – Riboflavin – Vitamin C Example 1: Thiamine Thermal Degradation of Vitamin B1 H2N Cl + N - H2C N N HO S Thiazol Pyrimidine Degradation of Thiamine under Basic Condition H2N Cl+ HC N 2 HO S N N - H2N OH- + H2O N HO + N CH3 S N no odor ( Coffee aroma with meaty note ) Degradation of Thiamine under Acidic Condition H2N N H2N N H3C N HO + H+ H2C N + H2O H H2C H3C N C H HO S N + H2O S CHO H2N O HO (CH2)2 CH C CH3 SH Coffee + HCOOH + H2N H+ N N No odor Formation of Thiazole Compounds from Thiamine N HO S -H2O N Reduction S Cocoa Methyl-vinyl-thiazole N S (Cocoa, beef) Methyl, ethyl-thiazole Formation of Furan Compounds from Thiamine O H3C-C-CH-CH2-CH2-OH SH -SH +H + O H3C-C-CH2-CH2-CH2-OH Cyclization From the decomposition of thiamin under acidic condition C O OH CH3 Reduction -H2O O CH3 -H2 CH3 O ( Coffee, tea ) Formation of Furan Compounds from Thiamine O -H2S H3C-C-CH-CH2-CH2-OH H2O SH O OH keto enolization H3C-C-CH-CH2-CH2-OH H3C-C=C-CH2-CH2-OH OH OH OH H3C-CH-C-CH2-CH2-OH O O -H2O Roasted onion, beef, tomato, white bread O CH3 Reducing nutrient loss To reduce the loss of fat-soluble vitamins A and E, cook with very little oil, e.g. grilling or baking. In order to reduce the loss of watersoluble, oxygen-sensitive vitamin C, fruits and vegetables should be cooked using minimal amount of water and cooking time as possible. Most minerals are unaffected by heat. However, potassium can leach (release from cells of food) into cooking liquids. Reducing nutrient loss When vegetables are prepared (e.g. chopping) the cell walls are broken. An enzyme called ascorbic acid oxidase escapes, mixes with and then destroys the vitamin C. The enzyme is destroyed by heat. To reduce loss of vitamin C: • use a sharp knife, keep chopping and shredding to a minimum; • prepare vegetables just before use; • do not store the food in water; • use a small amount of water when cooking; • avoid over cooking as the enzyme is destroyed quickly; • serve immediately after cooking. Loss of Polyphenols from Plantbased Foods Fruits and Vegetables are Living Systems Postharvested Fruits and Vegetables: • Breathe, Eat, Sleep, Tired, Sick, Die • Enzymes still very active • Softening, color change, etc. • Respiration continues long after harvest • Production of water, heat – Glucose + oxygen => CO2 + H2O + Heat • Transpiration continues – Loss of water (wilting) due to evaporation Factors Influencing Phytonutrient Content of Fruits and Vegetables • Genotype • Cultural practices • Environmental growing conditions • Maturation • Postharvest handling and storage conditions • Processing Luke Howard, Food Science Department, University of Arkansas Chemical and Physical Factors Influencing the Stability of Vitamins and Phytonutrients • • • • • • • • Heat Light Oxygen Co-factors Metals Enzymes Chemical structure/solubility Tissue localization: Free vs bound Luke Howard, Food Science Department, University of Arkansas Processing Factors Influencing Phytonutrient Content • Unit operations Washing/cleaning Physical removal of tissues Soaking (beans and peas) Blanching (steam vs water) Particle size reduction Enzyme treatments, pressing, clarification Luke Howard, Food Science Department, University of Arkansas Processing Factors Influencing Phytonutrient Content • • • • Filling and Brining Ratio of product:brine Dissolved oxygen Food additives Luke Howard, Food Science Department, University of Arkansas Processing Factors Influencing Phytonutrient Content Preservation method Thermal process (time and temperature, still vs agitated, aseptic) Freezing process (rate and temperature) Luke Howard, Food Science Department, University of Arkansas Factors Influencing Phytonutrient Content of Fresh-cut Products • • • • • Washing/sanitizing Peel removal Degree of wounding Package atmosphere Storage temperature Luke Howard, Food Science Department, University of Arkansas Processing of Blueberries – Effects on Polyphenolics Luke Howard, Food Science Department, University of Arkansas Fresh Berries (Blueberries, Blackberries, Black raspberries) Analysis of Fresh Berries Frozen Berries Juice Puree Individually Quick Frozen (IQF) Canned (Syrup) Clarified Baking Canning Canned (Water) Non-Clarified Pie-Canned in Water Pie-Frozen Berries Sampling: 1 d, 1 mo, 3 mo, 6 mo Luke Howard, Food Science Department, University of Arkansas Total Anthocyanin Retention and Polymeric Color in Blueberry Juices 100 25 90 20 70 60 15 50 40 10 30 20 5 % Polymeric color % Retention 80 10 0 0 P 1 (mo) NonClar-ACY 3 (mo) Clar-ACY 6 (mo) NonClar-PC Clar-PC Luke Howard, Food Science Department, University of Arkansas Total Anthocyanin Retention and Polymeric Color in Canned Blueberries 100 40 90 35 80 % Retention 70 25 60 50 20 40 15 30 10 % Polymeric color 30 20 5 10 0 0 P 1 (mo) Water-ACY 3 (mo) Syrup-ACY Water-PC 6 (mo) Syrup-PC Luke Howard, Food Science Department, University of Arkansas % Retention Total Anthocyanin Retention in Blueberries Canned in Syrup 100 90 80 70 60 50 40 30 20 10 0 Syrup Berries P 1 (mo) 3 (mo) 6 (mo) Luke Howard, Food Science Department, University of Arkansas Total Anthocyanin Retention and Polymeric Color in Blueberry Puree 100 45 90 40 80 35 % Retention 30 60 25 50 20 40 15 30 10 20 10 5 0 0 P 1 (mo) 3 (mo) ACY % Polymeric Color 70 6 (mo) PC Luke Howard, Food Science Department, University of Arkansas Total Flavonol Retention in Blueberry Juices 100 90 % Retention 80 70 60 Non-clarified Clarified 50 40 30 20 10 0 P 1 (mo) 3 (mo) 6 (mo) Luke Howard, Food Science Department, University of Arkansas % Retention Total Flavonol Retention in Blueberries Canned in Syrup 100 90 80 70 60 50 40 30 20 10 0 Syrup Berries P 1 (mo) 3 (mo) 6 (mo) Luke Howard, Food Science Department, University of Arkansas Total Flavonol Retention in Blueberry Puree 100 90 % Retention 80 70 60 50 40 30 20 10 0 P 1 (mo) 3 (mo) 6 (mo) Luke Howard, Food Science Department, University of Arkansas % Retention Chlorogenic Acid Retention in Blueberries Canned in Syrup 100 90 80 70 60 50 40 30 20 10 0 Syrup Berries P 1 (mo) 3 (mo) 6 (mo) Chlorogenic Acid Retention in Blueberry Puree 100 90 % Retention 80 70 60 50 40 30 20 10 0 P 1 (mo) 3 (mo) 6 (mo) ORACFL Retention in Blueberry Juices 100 90 % Retention 80 70 60 Non-clarified Clarified 50 40 30 20 10 0 NP P 1 (mo) 3 (mo) 6 (mo) ORACFL Retention in Canned Blueberries 100 90 % Retention 80 70 60 Water Syrup 50 40 30 20 10 0 P 1 (mo) 3 (mo) 6 (mo) ORACFL Retention in Blueberry Puree 100 90 % Retention 80 70 60 50 40 30 20 10 0 P 1 (mo) 3 (mo) 6 (mo) This is all for the exam Phenolic and Antioxidant Changes in Fresh-cut Carrots Processing and Sampling • Carrot coins (with peel removed) packed in ventilated bags • Stored at 4oC • Sampled at 0, 3, 7, 14 and 21 days Chemical Analyses • Phenolics – HPLC HCA quantified as chlorogenic acid equivalents at 320 nm pHBA quantified as hydroxybenzoic acid equivalents at 265 nm • Carotenoids – HPLC C30 column Beta, alpha and carotene isomers quantified as beta carotene equivalents HPLC chromatogram of a canned sample (at 450 nm) with the peak maxima for all-trans(1) lutein, (6) carotene, and (7) -carotene. Other labeled peaks: (2) 13cis , (3) 13’cis , (4) 15cis , (5) 13cis , and (8) 9-cis . PCL Antioxidant Assay • Antioxidant capacity Measured using a Photochem® antioxidant analyzer L + hv + O2 L.+ + O2.- • Detection of excess superoxide radicals left after quenching by antioxidants O2.- + L.+ L (luminescence) HCA and pHBA Contents of Fresh-cut Carrots During Storage 25 HCA pHBA 20 20 15 15 10 10 5 5 0 0 0 5 10 15 Storage Time (days) 20 25 pHBA (mg pHBAE/100 g FW) HCA (mg CAE/100 g FW) 25 AOX Capacity (umol TE/100 g FW) Antioxidant Capacity of Fresh-cut Carrots as Affected by Storage 350 300 250 200 150 100 50 0 0 5 10 15 Storage Time (days) 20 25 Relationship Between HCA Content and Antioxidant Capacity AOX Capacity (umol TE/g FW) 300 250 R2=0.988 200 150 100 50 0 0 2 4 6 8 10 12 HCA (mg CAE/100 g FW) 14 16 18 Alpha, Beta and Total Carotene Contents of Fresh-cut Carrots as Affected by Storage Total Carotene (mg/100g FW) 12 10 Alpha Beta Total 8 6 4 2 0 5 10 15 Storage Time (days) 20 25 Other Studies Effect of Cooking on Total Flavonoid Content of Spinach Concentration (mg/kg FW) 1200 1000 800 600 400 200 0 Fresh Cooking Water Cooked Tissue Sum Gil et al. (1999) J. Agric. Food Chem., 47, 2213-2217. Effects of Thermal Processing and Canned Storage on Total Phenolic Content in Peaches Total phenolics (mg/kg FW) 400 350 300 250 213F (40 min) 220F (10 min) 230F (2.4 min) 200 150 100 50 0 0 3 6 Storage Time (months) Asami et al. (2003), J. Sci. Food Agric., 83, 56-63 Comparison of Individual Procyanidin Oligomers in Frozen and Canned Clingstone Peaches Normalized Peak Area 0.6 0.5 0.4 0.3 Frozen Canned 0.2 0.1 0 M o on m er m Di er im Tr er T m ra t e er Pe am t n er er am am t x p He He er Asami et al. (2003), J. Sci. Food Agric., 83, 56-63 Total Flavonoid Content of Frozen Vegetables During Storage Total flavonoids (mg/kg DW) 800 700 600 500 Fresh Blanched 6 mo 12 mo 400 300 200 100 0 Cauliflower Broccoli Cabbage Puupponen-Pimia et al. (2003), J. Sci. Food Agric., 83, 1839-1402 Total Carotenoid Content of Frozen Vegetables During Storage Total Carotenoids (mg/100g DW) 4.5 4 3.5 3 Fresh Blanched 6 mo 12 mo 2.5 2 1.5 1 0.5 0 Pea 1 Pea 2 Carrot 1 Carrot 2 Spinach Puupponen-Pimia et al. (2003), J. Sci. Food Agric., 83, 1839-1402 % Retention Retention of Flavonoids in Canned Green Beans Price et al. (1998) J. Agric. Food Chem., 46, 4898-4903. Retention of Polyphenolics in Pasteurized Blueberry Juice 60 40 30 20 10 ac id hl or og en ic C Pr oc ya ni di ns no ls Fl av o nt ho c ya ni ns 0 A % Retention 50 Skrede et al. (2000), J. Food Sci., 65, 357-364 Concentration (mg/100g FW) Effect of Cooking on Procyanidin Content of Pinto Beans 800 700 Monomers Dimers Trimers 4-6 mers 7-10 mers > 10 mers Total PCs 600 500 400 300 200 100 0 Raw Simmered Gu et al. (2004) J. Nutr. 134: 613-617 Changes in Antioxidant Activity as Affected by Heating Nicoli et al. (1999) Trends Food Sci. Tech. 10:94-100 Changes in the Overall Antioxidant Properties of Foods as Affected by Heating No changes • No changes in naturally occurring AOX • Loss of native AOX = formation of compounds with novel or improved AOX • Improvement of AOX properties of native compounds • Formation of novel compounds having AOX properties (MRPs) Nicoli et al. (1999) Trends Food Sci. Tech. 10:94-100 Conclusions • Different unit operations and preservation methods markedly affect the retention of fruit and vegetable phytonutrients and antioxidant capacity • Increased number of processing steps exacerbates phytonutrient losses • Processing by-products are a potentially rich source of phytonutrients • Water-soluble phytonutrients readily leach into liquid canning media Conclusions • Fresh-cut produce may exhibit high antioxidant capacity due to the synthesis and accumulation of wound-induced phenolic compounds • Mitigation strategies are needed to prevent losses of phytonutrients during processing • More research is needed on the bioavailability of phytonutrients in processed foods