Comparison of heat stability of cow's milk subjected to ultra‐high temperature and in‐container sterilisation

Cow's milk of different fat contents with or without stabilising salts was sterilised by in‐container and UHT sterilisation. Heat stability decreased with increasing fat content following both UHT and in‐container sterilisation. Adding small amounts of stabilising salts (6.4 mM) increased heat stability in UHT‐treated milk, while excessive addition (12.8 mM) decreased heat stability. In contrast, increasing stabilising salts from 6.4 to 12.8 mM caused a decrease in heat stability after in‐container sterilisation. Increasing in‐container sterilisation time from 10 to 30 min caused a decrease in heat stability arising from an increase in particle size. This study confirmed discrepancies in heat stability for two sterilisation procedures.     

Milk reversibility following reduction and restoration of pH

The pH of skim milk was adjusted from 6.67 to between 6.00 and 5.45 before being restored with NaOH. Ionic calcium was higher after pH restoration but this did not result in instability during indirect ultra high temperature and in‐container sterilisation. Ionic calcium of pH restored milk increased with increased holding time but the pH restored milk remained stable to in‐container sterilisation. The viscosity of the milk was not affected by pH reversal. However, pH‐restoration reduced rennet coagulation time but milk was still stable when subjected to high temperature treatment. Properties of the soluble phase were measured at high temperature by dialysis.     

Naturally occurring variations in milk pH and ionic calcium and their effects on some properties and processing characteristics of milk

Considerable variations were found for ionic calcium and pH in milk from individual cows. Milk with lower pH tended to have a higher Ca²⁺ concentration, although the relationship was weak. Milk samples with a higher Ca²⁺ concentration and lower pH produced less sediment during in‐container sterilisation, which was contrary to expectations. Rennet coagulation time was lower for milk with a higher Ca²⁺ concentration, but curd firmness was not related to Ca²⁺ concentration. There was a poor correlation between the pH reduction caused by acid addition and that resulting from increasing temperature. Sediment formation was related to pH change at high temperature.     

Comparison of heat stability of goat milk subjected to ultra-high temperature and in-container sterilization

Goat milk with and without stabilizing salt was subjected to in-container and UHT sterilization. Heat stability was assessed by measuring the amount of sediment in the milk. Without stabilizing salts, goat milk usually produced less sediment when subjected to in-container sterilization compared with UHT processing. Addition of stabilizing salts up to 12.8mM resulted in a progressive increase in sediment for in-container sterilization. In contrast, adding stabilizing salts at 6.4mM initially reduced sediment formation in UHT-treated milk but addition of stabilizing salts at 12.8mM increased sediment formation. Adding stabilizing salts to goat milk increased pH, decreased ionic calcium, and increased ethanol stability. Adding up to 2mM calcium chloride increased sediment formation more after UHT treatment than after in-container sterilization. These results suggest that no single mechanism or set of reactions causes milk to produce sediment during heating and that the favored pathway is different for UHT and in-container sterilization processes. Poor heat stability could be induced both by increasing ionic calcium and by decreasing it. Ethanol stability is not a good indicator of heat stability for in-container sterilization, but it may be for UHT sterilization, if milk does not enter the region of poor heat stability found at low concentrations of ionic calcium.     

Effects of stabiliser addition and in-container sterilisation on selected properties of milk related to casein micelle stability

Different stabilising salts and calcium chloride were added to raw milk to evaluate changes in pH, ionic calcium, ethanol stability, casein micelle size and zeta potential. These milk samples were then sterilised at 121 °C for 15 min and stored for 6 months to determine how these properties changed. Addition of tri-sodium citrate (TSC) and di-sodium hydrogen phosphate (DSHP) to milk reduced ionic calcium, increased pH and increased ethanol stability in a concentration-dependent fashion. There was relatively little change in casein micelle size and a slight decrease in zeta potential. Sodium hexametaphosphate (SHMP) also reduced ionic calcium considerably, but its effect on pH was less noticeable. In contrast, sodium dihydrogen phosphate (SDHP) reduced pH but had little effect on ionic calcium. In-container sterilisation of these samples reduced pH, increased ethanol stability and increased casein micelle size, but had variable effects on ionic calcium; for DSHP and SDHP, ionic calcium decreased after sterilisation but, for SHMP, it remained little changed or increased. Milk containing 3.2 mM SHMP and more than 4.5 mM CaCl₂ coagulated upon sterilisation. All other samples were stable but there were differences in browning, which increased in intensity as milk pH increased. Heat-induced sediment was not directly related to ionic calcium concentration, so reducing ionic calcium was not the only consideration in terms of improving heat stability. After 6 months of storage, the most acceptable product, in appearance, was that containing SDHP, as this minimised browning during sterilisation and further development of browning during storage.     

pH-dependent sedimentation and protein interactions in ultra-high-temperature-treated sheep skim milk

Sheep milk is considered unstable to UHT processing, but the instability mechanism has not been investigated. This study assessed the effect of UHT treatment (140°C/5 s) and milk pH values from 6.6 to 7.0 on the physical properties of sheep skim milk (SSM), including heat coagulation time, particle size, sedimentation, ionic calcium level, and changes in protein composition. Significant amounts of sediment were found in UHT-treated SSM at the natural pH (～6.6) and pH 7.0, whereas lower amounts of sediment were observed at pH values of 6.7 to 6.9. The proteins in the sediment were mainly κ-casein (CN)–depleted casein micelles with low levels of whey proteins regardless of the pH. Both the pH and the ionic calcium level of the SSM at all pH values decreased after UHT treatment. The dissociation levels of κ-, β-, and α_S2-CN increased with increasing pH of the SSM before and after heating. The protein content, ionic calcium level, and dissociation level of κ-CN were higher in the SSM than values reported previously in cow skim milk. These differences may contribute to the high amounts of sediment in the UHT-treated SSM at natural pH (～6.6). Significantly higher levels of κ-, β-, and α_S2-CN were detected in the serum phase after heating the SSM at pH 7.0, suggesting that less κ-CN was attached to the casein micelles and that more internal structures of the casein micelles may have been exposed during heating. This could, in turn, have destabilized the casein micelles, resulting in the formation of protein aggregates and high amounts of sediment after UHT treatment of the SSM at pH 7.0.     

Composition and calcium status of acid whey from pasteurized,UHT‐treated and in‐bottle sterilized milks

Whey extracts were obtained from pasteurized, UHT‐treated and in‐bottle sterilized milks. After acidic precipitation of casein the concentration of protein, NPN, lactose, lipid, calcium, magnesium and potassium was determined. Among the parameters examined, protein content was significantly reduced in the whey extracts from UHT‐treated and in‐bottle sterilized milks compared with that from pasteurized milk, while lactose content was increased. Calcium extracted in whey was at least 80% of total calcium of the milk. The total calcium to protein ratio of whey was increased as a function of the thermal treatment of milk, while ionic calcium was about 50% of total calcium in all whey extracts. In vitro protein digestibility was found to be significantly lower in whey from UHT‐treated and in‐bottle sterilized milks than in that from pasteurized milk. Parallel estimation of the percentage of ionic calcium and of the solubility of proteins in the pH range 2–10 indicated that calcium was not involved in the pH‐dependent solubility of proteins extracted in the whey, the extent of solubility being essentially a function of the thermal treatment of milk. The results suggest that calcium was not responsible for the formation of soluble protein macroaggregates with impaired digestibility that are present in whey from milk subjected to heat treatment of increasing intensity.     

Mineral contents and distribution between the soluble and the micellar phases in calcium‐enriched UHT milks

A study concerning the content of mineral elements (calcium, magnesium, sodium, potassium and phosphorus) and the distribution between the soluble and the micellar phases has been carried out on mineral—mainly calcium—enriched UHT milks. Total calcium contents were 1371–1793 mg l^?1 in the 10 brands examined. Percentages of calcium in the soluble phase varied from 23.6 to 37.2%, whereas ionic calcium concentrations found were within a very wide range (44–91 mg l^?1). The different forms of phosphorus were studied by ³¹P‐NMR. Spectra indicated that the majority of the brands employed polyphosphates as stabilizers. Ingredients used to fortify these products consisted of dairy fractions and calcium salts. The modifications in salt balance as consequence of these practices are discussed. Copyright © 2004 Society of Chemical Industry     

无机盐对木瓜蛋白酶凝固大豆分离蛋白凝胶的影响

为研究食品中常见无机盐对木瓜蛋白酶凝固大豆分离蛋白凝胶的影响,以大豆分离蛋白(SPI)为原料,测定添加NaCl、KCl、CaCl2、MgCl2和MgSO4等常见无机盐后木瓜蛋白酶凝固SPI的时间、凝胶质构、凝固过程中pH值及蛋白质降解程度的变化。结果表明：添加一定浓度的无机盐可以缩短凝固时间并提高凝胶强度。相同离子强度下,Ca2+和Mg2+对凝固时间及凝胶强度影响均大于Na+和K+。添加无机盐可使SPI的pH值降低,加酶后pH值再次持续下降,但一定时间后趋于稳定。无机盐的种类和浓度对木瓜蛋白酶凝固SPI过程中蛋白质降解程度影响不明显。SPI中CaCl2的离子强度为15(CaCl2浓度为5mmol/L)时,将酶添加量从0.15%减少到0.1%,可使凝胶强度提高60%。因此,添加适量的一价及二价无机盐可显著缩短酶凝固时间并提高凝胶强度。添加Ca2+和Mg2+等二价阳离子盐类是提高木瓜蛋白酶凝固大豆蛋白凝胶强度的有效途径。     

Effects of phosphates and citrates on sediment formation in UHT goats' milk

Sediment formation was investigated during UHT treatment of goats' milk, subjected to indirect treatment at 140 degrees C for 2 s, with upstream homogenisation. Stabilisers evaluated were sodium hexametaphosphate (SHMP), trisodium citrate (TSC), disodium hydrogen orthophosphate (DSHP), and sodium dihydrogen orthophosphate (SDHP). With no added stabiliser, goats' milk produced a heavy sediment on UHT treatment. Addition of SDHP reduced pH, had little effect on ionic calcium and did not substantially reduce sediment. However, addition of SHMP, DSHP and TSC each reduced ionic calcium, increased ethanol stability and reduced sediment. Following stabiliser additions, there was a good correlation between ethanol stability and ionic calcium (R2=0.85) but not between ethanol stability and pH (R2=0.08). Overall, reducing ionic calcium reduced the amount of sediment formed for all these three stabilisers, although there was no single trend line between sediment formation and ionic calcium concentration. Sediment formation was not well correlated with pH for TSC or for SHMP, but it was for DSHP, making it the only stabiliser where sediment formation correlated well both with ionic calcium and pH, which might account for its effectiveness at higher ionic calcium levels. Sediment was much reduced when the temperature was reduced from 140 degrees C to 125 degrees C and 114 degrees C. There were no further changes in sediment on storage for two weeks. Analysis of the sediment showed that it was predominantly fat and protein, with a mass ratio ranging between 1.43:1 and 1.67:1. Its mineral content was usually less than 5% of dry weight. The maximum amounts of P and Ca were found to be 2.32% and 1.63%, respectively.     

Heat stability of milk supplemented with calcium chloride

Calcium chloride (0-25 mM) was added to skim milk powder that was reconstituted to 9% total solids. Heat stability was evaluated between 60 and 120°C for different times by observing whether samples had coagulated, and by measuring the amount of sediment and residual protein in the centrifuged supernatant. Milk samples were also dialyzed during their respective heat treatments to recover the soluble phase at different temperatures to measure pH and ionic calcium. The transition conditions between good and poor heat stability were established for different calcium chloride concentrations and temperatures. As temperature increased, coagulation occurred at lower levels of added calcium chloride. The transition was quite distinct at higher temperatures but less so at lower temperatures; it was initiated by an increase in sediment formation before a firm coagulum was formed. Both pH and ionic calcium decreased in dialysates as temperature increased. No coagulation was observed if Ca(2+) was <0.5 mM and pH was >6.3 in dialysates taken at their respective coagulation temperatures. Being able to measure pH and ionic calcium at high temperatures will allow better understanding of factors affecting heat stability. Electrophoresis of the supernatants permitted identification of the protein fractions participating in the coagulation process. When coagulation was observed below 80°C, substantial amounts of undenatured β-lactoglobulin and α-lactalbumin were found in the supernatant, as well as some soluble casein fractions. All the major whey protein and casein fractions were found in the sediment.     

Effects of different coagulants on coagulation behavior of acid-induced soymilk

Divalent calcium ions can be used into the coagulation procedure of tofu-producing. The different calcium salts also have the difference coagulation process. This paper reports an investigation on the effects of counterions of calcium salts on the coagulation process of soymilk protein by the variation of viscosity. The same amount of Lactobacillus plantarum 70810 was added because of its acid reduction effects, which plays a synergistic effect with calcium salts. Coagulation process of soymilk containing various coagulants was characterized by viscosity under a shear rate of 2 s⁻¹ at 37 °C. The textural properties and pH of tofu prepared from different coagulants were also determined. Results indicated that there are two successive first-order reactions by viscosity analysis, and the coagulation rate constant in the second stage was 4–6 times higher than that the first stage. The coagulation rate among the coagulants followed the anion series: formate > acetate > chloride > lactate. The textural properties also have correlation with the final viscosity of soybean milk mixture after 4.5 h coagulation, whereas the pH has nothing to do with the coagulants behaved. Evidence emerged that counterions of calcium source salts affect the coagulation process of soymilk protein. This fact clearly opens up many possibilities for soymilk coagulation.     

Nutritional properties of oat‐based beverages as affected by processing and storage

Oat‐based beverages enriched with vitamins and minerals were produced with common hydrothermal treatments and stored at 22 °C for 64 weeks. The effects of decanting on the retention of native vitamins, minerals and fatty acids, and different UHT holding time (5 s or 20 s) at 140 °C on vitamins were investigated. Fatty acid profile, vitamin retention and dissolved oxygen concentration were monitored during storage. The decanting process caused a 47% increase of vitamin B₆ and a 45–74% loss of phosphorus, zinc, calcium and iron. The steam‐injection UHT treatment caused a 60% loss of vitamin D₃ for both holding times and a 30% loss of vitamin B₁₂ for 20 s. During 1 year of storage, oleic and linoleic acids were stable, whereas linolenic acid decreased only slightly, even in the iron‐enriched variety. The dissolved oxygen concentration increased to a low value of 0.71 mg L^?1 and reached a balance after 16 weeks. Most enriched vitamins except vitamins A, D₃ and B₁₂ were stable during ambient storage. Oat‐based beverages with highly retained vitamins can be manufactured by adding vitamins prior to direct UHT treatment with a shorter holding time. Additionally, iron enrichment of such beverages, without affecting the fatty acid profile, can be achieved by filter sterilisation. Copyright © 2007 Society of Chemical Industry     

Measurement of ionic calcium, pH, and soluble divalent cations in milk at high temperature

Dialysis and ultrafiltration were investigated as methods for measuring pH and ionic calcium and partitioning of divalent cations of milk at high temperatures. It was found that ionic calcium, pH, and total soluble divalent cations decreased as temperature increased between 20 and 80°C in both dialysates and ultrafiltration permeates. Between 90 and 110°C, ionic calcium and pH in dialysates continued to decrease as temperature increased, and the relationship between ionic calcium and temperature was linear. The permeabilities of hydrogen and calcium ions through the dialysis tubing were not changed after the tubing was sterilized for 1 h at 120°C. There were no significant differences in pH and ionic calcium between dialysates from raw milk and those from a range of heat-treated milks. The effects of calcium chloride addition on pH and ionic calcium were measured in milk at 20°C and in dialysates collected at 110°C. Heat coagulation at 110°C occurred with addition of calcium chloride at 5.4 mM, where pH and ionic calcium of the dialysate were 6.00 and 0.43 mM, respectively. Corresponding values at 20°C were pH 6.66 and 2.10 mM.     

The measurement and significance of ionic calcium in milk – A review

The measurement of ionic calcium in milk and milk products is of vital importance in understanding the role of calcium in milk. This review compares the methods of measurement including ion equilibration, murexide and ion selective electrodes. Secondly the variations in milk from individual cows and goats, and in bulk milk samples are reviewed. The third section examines the differences in ionic calcium in relation to processing: addition and removal of calcium and other salts, rennet coagulation, miscellaneous influences, filtration and evaporation and drying are all reviewed. Finally the review considers why ionic calcium measurement is not more widely measured within the diary industry and argues that it could be beneficial to do so.     

Effects of chloride,thiocyanate and sulphate salts on β‐lactoglobulin–pectin associative complexes

Protein–polysaccharide complexes are used to improve protein stability and encapsulate high‐value ingredients, yet the influence of different salts on their formation has not been investigated. Using light scattering and turbidimetry, effects of chloride, sulphate and thiocyanate salts on β‐lactoglobulin and pectin complexes (protein/pectin ratio = 2:1 and 4:1) were determined in relation to effects of pH and ionic strength. Effects of anions on complex formation were significant at 25 mmol kg^?1 added ionic strength. Cation effects were not significant. At 100 mmol kg^?1 ionic strength, pH of complex formation increased with sulphate salts (pH 5.1) relative to chloride and thiocyanate salts (pH 4.9), while pH of coacervation increased with sulphate salts (pH 4.7) and decreased with thiocyanate salts (pH 4.4) relative to chloride salts (pH 4.6). Pure β‐lactoglobulin stability was otherwise reduced with thiocyanate salts below pH 5, implying a significant effect of pectin interactions.     

Bovine milk composition parameters affecting the ethanol stability

The objective of the present work was to identify the compositional parameters of raw milk that affected ethanol stability at natural pH when natural milk conditions were not modified. Heat stability, measured as coagulation time (CT), was included in the analysis to verify relation to alcohol test. Statistical models were proposed for alcohol and heat (CT) stabilities. Milk samples of good hygienic quality from dairy farms were classified in two groups according to their alcohol stability. Unstable samples to ethanol (72%, v/v) presented lower values of pH, somatic cells count, casein and non-fat-solids relative to ethanol stable samples (ethanol at 78%, v/v or more); whereas freezing point, chloride, sodium and potassium concentrations were higher in the unstable group. Logistic regression and multiple regression were applied to modelling alcohol and heat stability behaviour respectively. Chloride, potassium, ionic calcium and somatic cell count were included in the alcohol regression model, whereas calcium, phosphorous, urea, pH and ionic calcium were part of CT model. Ionic calcium was the only measured variable that contributed to both models; however coagulation time was noted to be more sensitive to ionic calcium than alcohol. The relation between ionic strength and casein was found to contribute to the alcohol model but not to the CT model. However, the interaction calcium plus magnesium plus phosphorous and casein contributed only to CT model.     

羊奶酪蛋白热稳定性的研究

以莎能和关中羊奶为原料,通过从羊奶中提取酪蛋白,分别在不同的pH、温度以及添加不同浓度的Ca^2＋、柠檬酸钠、三聚磷酸钠、干酪素的条件下测定酪蛋白的热凝固时间（HCT）,研究其对羊奶酪蛋白热稳定性的影响。结果表明,pH在6．8时酪蛋白的热稳定性最好,高温会降低酪蛋白的热稳定性,钙离子可以降低羊奶酪蛋白的热稳定性,适量的柠檬酸钠或三聚磷酸钠可以有效提高羊奶酪蛋白的热稳定性,干酪素对酪蛋白稳定性影响不明显。     

Seasonal variations in composition,properties, and heat-induced changes in bovine milk in a seasonal calving system

We determined seasonal variations in the composition and characteristics of bovine milk, as well as heat-induced changes in the physicochemical properties of the milk, in a typical seasonal-calving New Zealand herd over 2 full milking seasons. Fat, protein, and lactose contents varied consistently during the year in patterns similar to those of the lactation cycle. Seasonality also had significant effects on milk calcium, ionic calcium, fat globule size, buffering capacity, and ethanol stability, but not on casein micelle size. The ratio of casein to total protein did not vary significantly over the season, but late-season milk had the highest content of glycosylated κ-casein (G-κ-CN) and the lowest content of α-lactalbumin in both years. We observed significant between-year effects on protein, total calcium, ionic calcium, pH, and casein:total protein ratio, which might have resulted from different somatic cell counts in the 2 years. Compared with heating at 90°C for 6 min, UHT treatment (140°C for 5 s) induced greater dissociation of κ-casein, a similar extent of whey protein denaturation, a lower extent of whey protein–casein micelle association, and a larger increase in casein micelle size. Indeed, UHT treatment might have triggered significant dissociation of G-κ-CN, resulting in aggregation among the casein micelles and increased apparent mean casein micelle diameter. Seasonality had significant effects on the partitioning of G-κ-CN between the micelle and the serum phase, the extent of whey protein–casein micelle association under both heating conditions, and the casein micelle size of the UHT milk.     

Natural variations of citrate and calcium in milk and their effects on milk processing properties

Natural variations among milk constituents, and their relations to each other as well as to processing parameters, represent possibilities for differentiation of milk to produce high-quality natural products. In this study, we focused on natural variations in milk citrate and its interplay with calcium distribution in milk, in relation to processing properties. Milk samples from individual cows from farms varying in feeding and management practices were collected from April to June 2017 to maximize natural variations in citrate and calcium. Chemical composition, rennet coagulation properties, and ethanol stability were analyzed for all milk samples. We focused particularly on calcium distribution and citrate content and the correlation of these to other milk parameters. No significant change in citrate content was observed during the sampling period, which suggests that mechanisms other than feeding affect citrate levels in milk. Several significant correlations were found, including a positive correlation between complexed serum calcium and citrate, and a negative correlation between urea and ionic calcium. These are both of interest in relation to further processing, as with regard to the stability of UHT milk and in cheese making. Although the correlation between complexed serum calcium and citrate may be explained by their affinity, the underlying driver for the negative relationship between natural milk urea and ionic calcium needs to be clarified by further studies. Furthermore, milk from the different farms varied not only with regard to organic versus conventional farming systems; feeding practices between farms also play an important role in milk composition and functionality. However, none of the differences in milk composition between farms were found to decrease milk functionality and thus would probably not cause any processing problems.