Food & Feed safety and quality Gerrit van Duijn gerritvanduijn consultancy MVO course, June 2016 1
Agenda Supply chain control Impurities and contaminants in crude oil The refining process The fate of contaminants Undesirable side reaction products of oil processing Religious food laws Sustainable food supply 2
Traditional supply chain
Exercise List food safety risks of the traditional supply chain.
Traditional Palm oil mill
Seed oil supply chain Oil seed farmers Seed control Oil seed storage Seed control Seed control Meal Oil extraction Crude oil control By-products Oil Processing Consumer goods manufacturers Product control
Seed reception, sampling and storage 7
Palm oil supply chain Plantations Small holders Kernels Oil extraction Fruit bunch grading Crude oil control Previous cargoes Crude oil control By-products Oil Processing Consumer goods manufacturers Product control
Fruit bunch grading
Impurities and contaminants in crude oils 10
Minor component Minor components effect on quality Origin Quality effect Typical level in crude Free Fatty Acids Hydrolysis Off-taste, smoke during frying Seed oils < 2% Palm oil <5 % Max. level in refined 0.1 % Peroxides Oxidation Off-taste 5 15 meq/kg 1 meq/kg Phosphatides Moisture Dirt From cell membranes From oil crop, transport & storage Oil crop and harvest residues Burns at high temperature Components in free water Taste & odour From oil crop Not matching with product taste Metals Soil, milling storage & transport Seed oils: 200 600 ppm P 5 ppm P < 0.2 % 0.05 % Appearance < 0.2 % Not visible Catalyst for oxidation Typical crop taste Bland Fe: 10 ppm Fe: 0.1 0.5 ppm
FOSFA specifications crude and RBD oils FFA M&I P Colour Others max (%) max (%) max (ppm) Lovibond crude degummed Soybean oil 1,25 0,38 250 50Y 5R (1"cell) crude degummed Rapeseed oil 1,75 0,40 300 - C22:1 <2 % crude Sunflower oil 3,00 0,50 - - crude Maize oil 4,00 0,50 500 - crude Palm oil 5,00 pure - - RBD Palm oil 0,10 0,10-3R (5 1/4"cell) MP 33-39 C RBD Palm olein 0,10 0,10-3R (5 1/4"cell) MP < 24 C, IV > 56 RBD Palm stearin 0,20 0,15-3R (5 1/4"cell) MP > 44 C, IV < 48 crude Palm kernel oil 5,00 0,50 - - IV < 19 crude Coconut oil 4,00 1,00 - -
Case: Which contaminants should we analyze crude oils for? Sulphuric acid Poly Aromatic Hydrocarbons Lubricant oil Glass particles Pesticides Iron Dioxin Natural toxins Micro organisms Diesel Hexane Xylene
Contaminants we should analyze crude oils for. YES: Poly Aromatic Hydrocarbons Pesticides Hexane Diesel Lubricant oil Natural toxins NO: Dioxin Sulphuric Acid Micro organisms Glass particles Iron Xylene (except maiden voyages)
Contaminants -effect on health Contaminant Origin Risky oils Limit Heavy metals Soil, milling storage & transport Generally below detection limit Lead: max 0.1 ppm EC regulation 1881/2006 Poly Aromatic Hydrocarbons Drying of oil crop Soft seed oils Coconut oil BaP max 2.0 ppb PAH4 max 10.0 ppb PAH4 max 20.0 ppb EC regulation 835/2011 Pesticides above MRL Crop protection chemicals Seed oils MRL or LOD in oil crop EU directive 91/414/EEC Dioxins and furans Environmental pollution Generally below detection limit Max. 0.75 pg WHO- TEQ/g EC regulation 1239/2011 Dioxins, furans & dioxin like PCB s Environmental pollution Generally below detection limit Max. 1.25 pg WHO- TEQ/g EC regulation 1239/2011 Mycotoxins Mould or fungus Coconut oil, groundnut oil, maize oil Aflatoxins: max 2 ppb B1 and 4 ppb sum B1, B2, G1, G2 EC regulation 1881/2006 Mineral oil hydrocarbons (MOH) Process, storage, transport Palm oil in 1999, Sunflower oil in 2008 Prevent MOH contamination in oils and fats No EU legislation for MOH
Pesticides Crop protection during growth Protection of oil seeds during storage and transport Transfer in storage silos
Seed Refined oil Crude oil Pesticide definitions >100 x Health concern ARfD ADI ARfD ADI Intake MRL LOD DL used = Acute Reference Dose = Acceptable Daily = Maximum Residue Limit = Level of Determination = Detection Limit of analytical method GAP = Good Agricultural Practice MRL LOD GAP Food safety DL
Pesticide concentration in oil extraction Concentration factor = 100 / C oil In which: C oil = the fraction of oil in the seed, fruit or kernel (%) 1.0 Endosulfan Level [mg/kg] 0.8 Data from an oil mill, 33 samples over 2 year period 0.6 Seed MRL = 0.5 mg/kg 0.4 0.2 0 Soybeans Average = 0.329 mg/kg Average = 0.068 mg/kg Crude Soybean Oil
Poly Aromatic Hydrocarbons (PAH) Light Benzo(a)pyrene Heavy PAH4 = Chrysene + Benzo(a)pyrene + Benzo(a)anthracene + Benzo(b) fluoranthene
Poly Aromatic Hydrocarbons Sunflower seeds Coconuts PAH contact during drying with exhaust gasses
Benzo(a)pyrene (BaP)in Crude Oils 100 Maximum % samples> 1 ppb 79% BaP (ppb) 10 12% 9% Legal EU limit In refined oil 1 7% 0% Coconut Sunflower Rapeseed Soybean Palm oil
Mineral Oil Hydrocarbons (MOH) MOH = complex mixtures of hydrocarbons derived from crude mineral oil (C10 C50) MOH natural hydrocarbons produced by plants (nearly always odd numbered n-alkanes) Two main types: 1. Mineral Oil Saturated Hydrocarbons or MOSH. Linear and branched alkanes and naphtenes. 65 85 % of crude mineral oil 2. Mineral Oil Aromatic Hydrocarbons or MOAH. Alkyl-substituted poly aromatic hydrocarbons 15 35 % of crude mineral oil. 22
Origin of MOH contamination Seeds/fruits growing Harvesting,storage and handling oil cell oil cell Environmental pollution Solvent of pesticides Diesel or lubricant leakage Post harvest pesticides Anti dusting treatment Contaminated containers Oil milling meal/residue Crude oil Leakage from mineral oil absorber Contaminated hexane Leaking lubricant or hydraulic oil Transport and handling of crude oils Crude oil Leaks from equipment (pumps) Previous cargoes Voluntary adulteration Oil refining/purification Refined oil Use of Thermal Heating Fluids Contamination by lubricant Migration from packaging
Mineral oil hydrocarbons - Example of poor housekeeping
Refining process - introduced in 1900 From decanting to refining due to: Use of coconut oil for margarine Decolouring of cottonseed oil Changing taste Removal of catalyst poisons before hydrogenation. Removal of solvents from extracted oils
lye soap spent earth earth steam exhaust gases CHEMICAL neutralisation bleaching deodorisation CRUDE OIL Cell residues, Water, Hexane Metals, Dirt Free Fatty Acids Colour, Oxides, PAH Flavours, Pesticides, volatiles REFINED OIL PHYSICAL degumming wet dry bleaching deodorisation acid/water acid/water earth spent earth steam acid oil exhaust gases
Oil crop Refining by-products Oil extraction Meal Oil mill Chemical refining Water degumming Lecithin purification Lecithin Acid, alkali Degumming/ neutralization Soap splitting Acid oil BE, AC Steam Bleaching/ filtration Deodorization 170 270 C Refined oil Steam blowing of filters Fatty acid scrubber Acid water to effluent treatment Acid oil or back to crude Condensed steam to effluent treatment Deodorizer distillate Vacuum system bleed to effluent treatment
Oil crop Refining by-products Oil extraction Meal Oil mill Physical refining Citric/ Phosphoric acid Acid pretreatment Acid degumming Sludge Sludge BE, AC Bleaching/ filtration Steam blowing of filters Acid oil or back to crude Steam Deodorization 240 270 C Refined oil Fatty acid scrubber Condensed steam to effluent treatment Deodorizer distillate Vacuum system bleed to effluent treatment
The fate of contaminants (1) Contaminant N B D/S Destination Pesticides dissolving in alkaline (e.g. Dichlorvos) X Acid water Pesticides interacting with bleaching earth (e.g. Pirimiphosmethyl) X Spent bleaching earth (SBE) Pesticides removed by stripping (all organophosphorus) X Deodorizer distillate (DD) Heavy PAH X (AC) 50 % of BaP SBE and DD Light PAH X (AC) X SBE and DD 29
The fate of contaminants (2) Contaminant N B D/S Destination Short chain MOSH (< C10) (hexane, gazoline) Medium chain MOSH (< C23) (kerosine, diesel) Long chain MOSH (> C23) (lubricant oil) Dioxins X X X Dryer vacuum outlet X (AC) X X DD Remains in product SBE and DD Mycotoxins (react with water) X X Acid water and SBE 30
Use of by-products in feed Deodorizer distillate from chemical refining is a high risk byproduct preferably not to be used as raw material for animal feed. Deodorizer distillate from physical refining is a medium risk byproduct should only be used in feed after contaminant analyses. Acid oil extracted from spent bleaching earth is a medium risk by-product should only be used in feed after contaminant analyses. Acid oil from soap splitting and filter blowing is a low risk byproduct can be used in feed if crude oil is OK. 31
Undesirable side reaction products of oil processing Trans fatty acids: Side reaction product of: Partial hydrogenation (level > 10 %) High temperature deodorization (level depends on unsaturation, temperature and time) Very stable Negative effect on blood cholesterol and cardio vascular diseases Proposed limit : max. 2 % in oil/fat phase. 32
TFA (%) TFA formation during deodorization 5 4 3 2 Palm oil Sunflower oil Soybean oil 1 0 200 220 240 260 280 Temperature (deg.c)
Undesirable side reaction products of oil processing 3 MCPD esters Precursors: triglycerides, chlorine, acidic conditions Formation at T > 120 C Stable Suspect carcinogenic (Non-genotoxic) Mitigation by improving crude oil supply chain Proposed limit: 0.8 µg/kg body weight/day 34
Undesirable side reaction products of oil processing Glycidyl esters Precursors: diglycerides, heat Formation at T > 220 C Not stable, decomposed by acid activated bleaching earth Suspect carcinogenic and genotoxic Mitigation by reducing deodorization temperature Proposed limit: 1 ppm 35
Religious food laws Examples: Kosher Halal Hindu food rules Origin: 1. Philosophical: Religious food laws cannot be explained since human mind is not capable of understanding divine intentions 2. Health explanations: Some laws correspond to modern ideas of food hygiene, however, many don t. Current application: Besides religious reasons, also linked to purity/food safety by non-believers. 36
Environmental impact Sustainable food supply Sustainable diets: Eating patterns that promote health and well-being and provide food security for the present population while sustaining human and natural resources for future generations *). Food security: All people now, and in the future, have access to sufficient, safe, and nutritious food to maintain a healthy and active life *). Producing more healthy food in a responsible way at reduced environmental impact. Food production *) USA advisory board of dietary guidelines 37
The refiner s challenge Product quality Contaminant removal refining process Conditions Minimize process contaminants And reduced environmental impact!