Rancidity Development in Macadamia Kernels As Determined by Head-space Hexanal Concentration Aijun Yang and Cameron McConchie September 2009
Lipids in Macadamia Oil Macadamia nut high in oil (>72%) Macadamia oil is High in mono-unsaturated fatty Palmitic acids (>80%) (c16:0) Macadamia oil 7 9 Low in poly-unsaturated fatty acids Stearic (PUFA) 2-4 3.6 (C18:0) similar to olive oil in FA profile Palmitoleic Hydroperoxides (ROOH) from the 15.5 2.4 (C16:1) oxidation of PUFA further decomposed to a complex variety of Oleic 65 80 secondary oxidation products. (C18:1) Volatiles at very low concentrations Linoleic cause rancidity and decrease the (C18:2) 1.5 5 quality of oils and lipid-containing foods. Linolenic 0.1-0.2 0.5 (C18:3) Olive oil
Methods monitoring rancidity development For initial (primary) oxidation products hydroperoxides Conjugated dienes (CDHP) Peroxide Value (PV) Chromatography For secondary oxidation products carbonyl compounds p-anisidine Value (pav) Conjugated trienes TBA or TBARS (Thiobarbituric acid reactive substances) Free fatty acids (FFA) For volatiles attributing to the off-flavour GC, GC-MS: specific and total volatiles HPLC, HPLC/MS Sensory
Volatiles Cause rancid flavour at ppm levels Closely correlated with sensory and consumer acceptability Major volatiles contributing to rancid flavour Hexanal: from C18:2 (1.5%) Octanal: from C18:1 (65%) Measured on GC or GC/MS Solid-phase microextraction (SPME)-GC: simple, sensitive, quantitative Linear response for major volatiles contributing to rancidity Peak area 40000 30000 20000 10000 0 SPME-GC of headspace volatile standards Pentanal R 2 = 0.996 Hexanal R 2 = 0.994 Octanal R 2 = 0.991 Heptanal R 2 = 0.989 1-Octanol R 2 = 0.993 0.0 0.5 1.0 1.5 2.0 2.5 Standards (ug/g)
Effects of storage temperature and duration on hexanal production (Salter et al 2005) -2.5 Hexanal ln(ug/g kernel) -3.0-3.5-4.0-4.5-5.0-5.5-6.0 Day 28 Day 56 Day 91 Day 140-6.5 20 25 30 35 40 45 50 55 60 Storage Temperature( o C)
Accelerated Aging Trial Determine rancidity development in raw and roasted kernels stored at 40 or 22 o C 3 roasting regimes (temperature/duration) 2 moisture content (1.5 and 2.5%) 2 cultivars (A16 and OV) Rancidity determined during storage using SPME headspace volatiles from whole kernels Septum jars with kernels warmed in 30 o C water bath for 5 min SPME fibre (PDMS/DVB, 65 µm) exposed to sample for 20 min Fibre then desorbed at 220 o C in injector port for 3 min (splitless) Column: SGE BP20 (30 m x 0.25 mmm ID x 0.25 µm film) Oven program: 40 o C 5 min 12C/min to 240 o C 240 o C 5 min Detector: flame ionisation detector (FID), 280 o C
Headspace volatiles SPME for GC
Headspace volatile profile in raw kernels stored at 40 o C A16 2.5% - 0 Wk 12 10 8 6 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 20 15 10 Hexanal Heptanal Octanal Nonanal 1-Octanol OV 2.5% - 8 wk Carboxylic acids 5 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26
Hexanal in raw and roasted kernels stored for 24 weeks Hexan a l (p p m ) 5 4 3 2 1 A16-1.5 A16-2.5 OV-1.5 OV-2.5 22 o C Raw Hexanal (ppm) 5 4 3 2 1 22 o C Roast Hexan al (p p m) 0 0 12 24 5 40 o C Raw 4 3 2 1 Hexanal (ppm) 0 0 12 24 5 40 o C Roast - Pooled 4 3 2 1 0 0 4 8 12 16 20 24 0 0 4 8 12 16 20 24 Weeks of storage Weeks of storage
Results Higher hexanal levels in OV than A16 at the beginning. At 22 o C negligible change in hexanal levels in A16 progressively higher level of hexanal detected in OV. At 40 o C, hexanal levels increased rapidly in OV within 4-8 weeks and continue to increase until 24 weeks stable in A16 until after 8 weeks when started to increase. Similar differences and trends between cultivars and moisture contents for roasted kernels, with slower increase in hexanal production in OV.
Summary Kernels with poor initial storage properties deteriorates more rapidly. Roasting has minimal effects on the rate of deterioration. Similar ranking of deterioration for kernel source and treatments at ambient and accelerated storage conditions. Head-space hexanal levels determined using SPME-GC responsive to the aging treatments sensitive method for monitoring rancidity development application as sensitive indicators of kernel stability under accelerated aging treatments Further research proposed to relate head-space hexanal levels to consumer perceptions of kernel quality.