Volatile Sulphur Compounds in UHT Milk

Al-Attabi, Zahir (2009). Volatile Sulphur Compounds in UHT Milk PhD Thesis, Land, Crop and Food Sciences, The University of Queensland.

       
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Author Al-Attabi, Zahir
Thesis Title Volatile Sulphur Compounds in UHT Milk
School, Centre or Institute Land, Crop and Food Sciences
Institution The University of Queensland
Publication date 2009-08
Thesis type PhD Thesis
Supervisor Bruce D' Arcy
Hilton Deeth
Total pages 172
Total colour pages 27
Total black and white pages 145
Subjects 07 Agricultural and Veterinary Sciences
Abstract/Summary Heating milk to high temperatures such as 140 ºC, as used in ultra high temperature (UHT) processing, causes physical and chemical changes in the milk. The production of a cooked flavour is a major change which reduces consumer acceptance of the UHT milk. It has been correlated with the formation of volatile sulphur compounds (VSCs) that result from milk proteins, principally the whey proteins β-lactoglobulin, containing the the sulphur amino acids cystine, cysteine and methionine. The VSCs in milk, whose concentrations are in the parts per billion to parts per million range, are highly reactive, easily oxidised, and sensitive to heat during thermal processing and analysis; this makes them a challenge to analyse. A sensitive method based on gas chromatography with pulsed flame photometric detection coupled with headspace sampling by solid phase microextraction (SPME/GC/PFPD) was developed to detect these compounds in commercial UHT milk and to investigate their production and disappearance during heating and storage. The SPME/GC/PFPD procedure was optimised using different extraction time (15 min, 30 min, & 60 min) – temperature (30 oC, 45 oC & 60 oC) combinations with CAR/PDMS fibre to obtain maximum sensitivity. A short extraction time (15 min) at low temperature (30 oC) was chosen to provide high sensitivity for detecting all VSCs in UHT milk without introducing artefactual VSCs. The extraction method and GC run time (16 min) make this method simple and fast. Nine VSCs were detected in commercial indirectly processed UHT milk, skim and whole. These are hydrogen sulphide (H2S), carbonyl sulphide (COS), methanethiol (MeSH), dimethyl sulphide (DMS), carbon disulphide (CS2), dimethyl disulphide (DMDS), dimethyl sulphoxide (DMSO), dimethyl sulphone (Me2SO2) and dimethyl trisulphide (DMTS). An additional unknown compound was detected but could not be identified by GC/MS because its concentration was below the detection limit of the MS detector. The concentrations of H2S, DMS and DMTS were higher than their threshold values indicating their importance in milk flavour, especially cooked flavour. Several attempts have been made to reduce the cooked flavour in UHT milk. In the current research, the use of hydrogen peroxide (H2O2) to oxidise the VSCs and thereby reduce cooked flavour was investigated. H2O2 is used as a milk preservative and is generally recognised as safe (GRAS) in USA. Several concentrations of H2O2 (0.001%, 0.005%, 0.01%, 0.02% & 0.03%) were added to milk to assess its effects on VSCs and on whey proteins denaturation in UHT milk. H2O2 effectively reduced the concentration of all VSCs, except DMDS which was increased, presumably by oxidation of MeSH. H2S was completely oxidised or reduced below its threshold value. Low concentrations of H2O2 (0.001% & 0.005%) had no effect on, or decreased, the extent of denaturation of β-lactoglobulin when added after or before processing, respectively. Some UHT plants use severe heating conditions, leading to high levels of denaturation of whey proteins, particularly β-Lg, the main source of the VSCs in milk. Correlations between heat severity, β-Lg denaturation and individual VSC generation were investigated in milk batch-heated at 80 oC and 90 oC, and UHT milk processed at 120-150 oC. In accordance with previous reports, β-Lg was more heat-sensitive than α-La. Only five VSCs were detected. The concentrations of H2S and MeSH correlated well with denaturation of β-Lg and α-La. DMS concentration correlated well with β-Lg in UHT milk but not in the batch-heated milk. CS2 did not show a good correlation with heat intensity and appeared to plateau out after a certain level of heating. Conversely, COS and MeSH seemed to require a certain minimum amount of heat before generation commenced; this corresponded to denaturation of β-Lg above 49% and 89% respectively at 80 oC. The higher concentrations of DMS and H2S in UHT milk compared with batch-heated samples having similar degrees of denaturation suggested other possible sources for their production and the importance of the heat severity in generating them. For example, at high heat intensity, S-methylmethionine and thiamine could be sources of DMS and H2S respectively. Furthermore, in whole milk as used in this work, milk fat globule membrane proteins are another source of VSCs. The outcome of this study will help UHT manufacturers to understand the production and disappearance of the VSCs in commercial UHT milk and how to adjust the processing conditions to avoid generation of cooked flavour. Additionally, the promising results of using low concentrations of H2O2 to oxidise the VSCs will provide the industry with another means of reducing cooked flavour. Before H2O2 use is implemented in UHT processing, future studies are required to evaluate all of its effects, including sporicidal effects. Overall, this study makes a contribution to finding a solution to the cooked flavour problem in UHT milk, thereby increasing market share of this milk in countries such as Australia, the UK and North America where cooked flavour is the main barrier to its consumer acceptance.
Keyword UHT milk, cooked flavour, volatile sulphur compounds, solid phase microextraction, pulsed flame photometric detector, hydrogen peroxide, heat severity, β-lactoglobulin
Additional Notes Colour pages: 67,73-75,77-78,89,92,95,97,99,101,113-114,119-121,132-138,140-142 Landscape pages: 111-112, 116, 119-120 (coloured), 171-172 Require a CD attached with the complementry copy

 
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Created: Wed, 13 Jan 2010, 05:50:25 EST by Al-Attabi, Mr Zahir on behalf of Library - Information Access Service