3-MCPD & 3-MCPD ester Food processed contaminants

Transcription

1 -MCPD esters: Current Knowledge and Status Nuzul Amri Ibrahim Muhamad oddy amli aznim Arni Abdul azak Ainie Kuntom Malaysian Palm il Board Introduction utline -MCPD and -MCPD ester esearch by others Mechanism hypothesis A quick look at refining Studies in MPB Adoption of Bf 8 and ACS cd 9a- Mitigation studies Conclusions/ ecommendations -MCPD & -MCPD ester Food processed contaminants EFSA eport 6 Compound -monochloropropanediol (-MCPD) -monochloropropanediol ester (-MCPDE) Effect to health Possibly carcinogenic to humans Nephrotoxic (EFSA eport 6) Nephrotoxic (EFSA eport 6) q - and -MCPD esters and glycidyl esters were detected in vegetable oils q -MCPD ester and free forms are nephrotoxic (damage to kidney) v Esterified and free forms were assumed to contribute equally to internal exposures. v TDI:.8 µg/kg bw/day Classification by International Agency for esearch on Cancer

2 Chemical structure Studies on -MCPD & -MCPDE Cl -MCPD ester H H Cl -MCPD Year Presence of free -MCPD/ -MCPD ester in food Hydrolysed vegetable protein, e.g soy sauce (free) 98 Spanish rapeseed oil (ester) 4 Processed food: toasted bread, cheese, cooked meat, salami, infant formula, coffee and creamer (ester) 6 Vegetable oils (ester) 9 Infant and baby food (ester) -MCPD esters Formation Mechanism Hypothesis Family of chloropropanols Categorized as food-processed contaminant Mainly in refined oils Due to heat and presence of chloride H Acylglycerol = alkyl = H or C H + -H + Cyclic acyl oxonium ion Cl - Cl + Cl - & - MCPD ester -MCPD -MCPD ILSI eport 9, Brussels

3 Physical refining process Crude palm oil Phosphoric acid is added A quick look at physical refining process Bleaching clay is added Degumming Bleaching Phosphoric acid and gums Filter Press Deodorisation Gums/Clays and phosphoric acid are removed efined palm oil Source of H + and Cl - Studies in MPB From acid and acid activated clays H Acylglycerol H + -H From oil, water and clays + Cyclic acyl oxonium ion Cl Cl & - MCPD esters Cl. Adoption of method of analyses Bf 8 to 4 ACS cd 9a- Since 5. Mitigation measures = alkyl = H or C -MCPD -MCPD

4 Area ratio of -MCPD and deuterated -MCPD Bf Method 8 epeatability of results mg of oil/fat sample Concentration (mg/kg), n = 6 % ecovery (± SD) SD (%) Internal standard (d 5 --MCPD) (±.)...8 (±.). Acidic transesterification with H S 4 (hydrolysis for 8h at 4 C) (±.8) (±.5). Neutralization with NaHC Derivatization with PBA GC-MS Analysis Calibration curve GC chromatogram y =.6x +. ² = Spiking level of -MCPD (mg/kg)

5 Participation in Bf ring test Cross check with other laboratories Values -MCPD ester results (mg/kg) Bf actual values (range).6.9 Samples -MCPD ester levels (mg/kg) MPB Unilever Eurofins eported values (mean.6.5 range from six laboratories) MPB values (range) <.5.5 Bleached palm oil BD palm oil A BD palm oil B ACS Method Cd 9a- mg oil/fat sample Add internal standards + THF Conversion of GE to -MBPD monoesters in bromide salt Conversion of - and -MCPD esters and -MBPD esters into free form in acid methanolic solution Extraction of fatty acid methyl esters Derivatization of - and -MCPD and - MBPD with Phenylboronic acid (PBA) GC-MS Analysis Conc. Level epeatability of results Day Day Day Mean Std Dev SD *Percentage recovery for -MCPDE & -MCPDE (LD =.) Conc. Level Day Day Day Mean Std Dev SD *Percentage recovery for GE (LD =.5)

6 MPB Eurofins SGS MPB Eurofins SGS MPB Eurofins SGS mg/kg Cross check with European labs. (ACS -in- method) Mitigation measures Crude palm oil BD palm oil BD palm olein BD palm stearin bjectives To evaluate the possible factors responsible for formation of -MCPD esters during refining of CP. To suggest possible solutions/alternatives to minimise the formation. -MCPD ester levels Glycidol ester levels -MCPD ester levels *MPB (ACS Cd 9a); SGS (ACS Cd 9b); Eurofins (ACS Cd 9c) kg/batch refining pilot plant Pilot-plant scale refining: Condition Parameter Standard H P 4 (%). Acid activated b/clay(%) Deod n temp( C) 6 Duration(h).5 Modified

7 -MCPDE content, mg/kg Colour, ed Experiments Effect of temperature Ö Compare Standard refining process with modified conditions Effect of degumming, acid activated clays, natural clays and deodorization temperature. Ö Checked acidity of clays and chloride contents. Ö Monitor the formation of -MCPD ester esults Deodorization temperature, o C MCPDE Colour Effect of deodorization temperature at C Variables: Phos acid and b/clay -MCPDE, mg/kg Deod n temp: C*./././././ Phos. acid/b. clay, % 6 C *esidence time: hours Acidity of clays (ph) Acid activated clays A A A Natural clays N N N ph

8 Correlation between ph of clays and formation of -MCPD esters Total chloride contents. Acid degumming experiments Clays (n=6) 6-5 ppm. Water(n=7) 7-8 ppm -MCPD esters content (ppm) =.9759 Phosphoric(n=8) - ppm Citric acid(n=) ppm CP(n=) 8-9 ppm Analysed by a commercial laboratory (March-April ) ph Effect of Cl in bleaching clay Effect of rinsing Deodorization temp: 6 C 6 -MCPDE content, mg/kg = MCPDE content, mg/kg 5 4 Not rinsed insed X insed X Level of Cl in bleaching clay, mg/kg The level of Cl in b/clay shows positive correlation with the formation of the esters CP samples esults

9 Deodorisation-time effect (K. Hrncirik, Berlin, ) eport by other researchers Formation of MCPD esters occurs within first mins Effect of Diacylglycerols Bertrand Matthaus (, ACS Mtg) Effect of DAG Sample Feed oil TL IM h TL IM 9h TL IM h TL IM 4 h DAG,% MCPDE, mg/kg MCPDE DAG

10 Effect of FFA and DAG Fresh Day Day Hydrolysed FFA, % DAG, % MCPDE, mg/kg <LD <LD Levels of FFA and DAG are not directly correlated to the formation of the esters bservations Acid degumming followed by bleaching causes formation of -MCPD esters in bleached oils. insing of CP prior to refining could reduce the formation of the esters FFA and DAG are not directly correlated to the formation of -MCPD esters High deodorization temperature led to high formation of the esters Factors for consideration. Bleaching Levels of chloride in clays Acidity of clays HCl or sulphuric acid activation of clays Time and temperature. Deodorization Temperature Time Chloride content in oil Acidity of oil Conclusion Factors that cause the formation of -MCPD ester Acid degumming Total chloride content in bleaching clay ph of bleaching clay High deodorization temperature Presence of Cl in CP

11 ecommendations Combine acid degumming with water degumming Use bleaching clay with the lowest total chloride content, while the ph should be almost neutral to alkaline. educe deodorization temperature From 6 C to C inse CP prior to refining Current study Mitigation measures for -MCPD esters: Identification of source of chloride at plantations and palm oil mills To find mitigation measures for eliminating chloride in CP Midstream: mills operation Upstream: plantation activities H Acylglycerol = alkyl = H or C H + -H + Cyclic acyl oxonium ion Cl Cl & - MCPD ester -MCPD Cl -MCPD Current situation Maximum level has not been regulated JECFA will meet in ome, November 6 Nonetheless, Malaysian refineries should be proactive