Tetracycline antibiotics transfer from contaminated milk to dairy products and the effect of the skimming step and pasteurisation process on residue concentrations

The presence of antibiotics in raw milk and milk derivatives poses a threat to human health and can negatively affect the dairy industry. Therefore, the main object of this study was to investigate the transfer of oxytetracycline (OTC), tetracycline (TC), chlortetracycline (CTC) and doxycycline (DC) from raw, experimental milk contaminated with tetracyclines (TCs) to different dairy products: cream, butter, buttermilk, sour milk, whey, curd and cheese. Additionally the effect of the skimming process on TCs concentrations was tested, as well as the influence of low-temperature long-time pasteurisation. The analyses of TCs in milk and dairy products were performed by an LC-MS/MS method. In order to determine TCs residues in dairy products, an analytical method was developed with the same extraction step for all matrices. TCs molecules were inhomogenously distributed between the milk derivative fractions. The highest concentrations were determined in curd and cheese in the ranges 320–482 µg/kg and 280–561 µg/kg, respectively. Low levels of TCs in butter and whey were observed (11.8–41.2 µg/kg). TCs were found in sour milk (66.0–111 µg/kg), cream (85.0–115 µg/kg) and buttermilk (196–221 µg/kg) at much higher levels than in butter and whey, but lower than in curd and cheese. During the skimming process, the highest yield of cream was obtained after the raw milk was held at 2–8°C for 24 h. The differences in concentrations of TCs between whole milk and skimmed milk, expressed as percentages of recovery, were below 19% (recoveries in excess of 81%). The highest content was observed in milk and cream skimmed at 2–8°C. The degradation percentages for TCs during the pasteurisation process (63°C for 30 min) were below 19%.     

Concentration of furfuryl alcohol in fluid milk,dried dairy ingredients,and cultured dairy products

Maillard reactions occur in dairy products during heat treatment. Furfuryl alcohol (FA) may be found in dairy products as a result of Maillard reactions. The recent posting in California Proposition 65 indicates that FA may be carcinogenic, and for this reason it is crucial to accurately measure FA concentrations in dairy products. The objective of this study was to identify an extraction and quantitation method for FA from dairy products and to determine FA concentrations in milk, dairy powders, and cultured dairy products. Solvent-assisted flavor extraction, solid-phase microextraction, stir bar sorptive extraction with gas chromatography-mass spectrometry and triple quadrupole mass spectrometry were compared for recovery of FA. Internal standards for the quantitation of FA (2-methyl-3-heptanone, furfuryl-d₅ alcohol, 2,5-dimethylphenol, 5-methyl-2-furfuryl alcohol, and 5-methyl furfural) were also compared. Subsequently, fluid milk [high temperature, short time (HTST) and ultrapasteurized], whey protein isolates (3 mo–4 yr), whey protein concentrates (3 mo–4 yr), whole milk powders (1 yr), high and low heat skim milk powders (SMP; 0–8 yr), milk protein isolates (3 mo–3 yr), milk protein concentrates (3 mo–3 yr), Cheddar cheese (mild, medium, sharp, and extra sharp), mozzarella cheese (whole and part skim), cottage cheese (nonfat, low fat, and full fat), sour cream (nonfat, low fat, and full fat), traditional yogurt (nonfat, low fat, and full fat), and Greek-style yogurt (nonfat; n = 139 products total) were evaluated. Furfuryl alcohol was extracted from products by headspace solid-phase microextraction followed by gas chromatography-triple quadrupole mass spectrometry using a ZB-5ms column (30 m × 0.25 mm × 0.25 µm; Phenomenex Inc., Torrance, CA). Furfuryl-d₅ alcohol was used as an internal standard. Each food was extracted in triplicate. Ultrapasteurized milks had higher levels of FA than HTST milks (122.3 vs. 7.350 µg/kg). Furfuryl alcohol concentrations ranged from 0.634 to 26.55 µg/kg in whey protein isolates, 2.251 to 56.19 µg/kg in whey protein concentrates, 11.99 to 121.9 µg/kg in milk protein isolates, and 8.312 to 49.71 µg/kg in milk protein concentrates, and concentrations increased with powder storage. High heat SMP had higher concentrations of FA than low heat SMP (11.8 vs. 1.36 µg/kg) and concentrations increased with storage time. Concentrations of FA in Cheddar and mozzarella cheese ranged from 2.361 to 110.5 µg/kg and were higher than FA concentrations in cottage cheese or sour cream (0.049–1.017 µg/kg). These results suggest that FA is present at higher levels in dairy products that have been subjected to higher temperatures or have been stored longer. Sour cream and cottage cheese had lower levels of FA. Compared with other studies on food products with reported levels of FA, such as coffee (200–400 µg/g), dairy products have very low levels of FA.     

Incorporation of dairy ingredients into wheat bread: effects on dough rheology and bread quality

 Dairy ingredients are used in breadmaking for their nutritional benefits and functional properties. The effects of the traditionally-used whole and skimmed milk powder, sodium caseinate, casein hydrolysate and three whey protein concentrates on dough rheology and bread quality were studied. Whole and skimmed milk powders improved sensory characteristics. Sodium caseinate and hydrolysed casein displayed beneficial functional properties in breadmaking including low proof time, high volume and low firmness. Both ingredients increased dough height measured with the rheofermentometer. Bread with 2% or 4% sodium caseinate added was rated highly in sensory evaluation. Incorporation of whey protein concentrates generally increased proof time, decreased loaf volume and decreased dough height measured with the rheofermentometer. Received: 6 April 1999 / Revised version: 13 July 1999     

Influence of skimmed milk concentrate replacement by dry dairy products in a low fat set‐type yoghurt model system. I: Use of whey protein concentrates,milk protein concentrates and skimmed milk powder

Ten commercial samples of dry dairy products used for protein fortification in a low fat yoghurt model system at industrial scale were studied. The products employed were whey protein concentratres, milk protein concentrates, skimmed milk concentrates and skimmed milk powder which originated from different countries. The gross chemical composition of these dried products were determined, including polyacrylamide gel electrophoresis (SDS‐PAGE) and isoelectric focusing of the proteins, and minerals such as Na, Ca, K and Mg. Yoghurts were formulated using a skim milk concentrated as a milk base enriched with different dry dairy products up to a 43 g kg⁻¹ protein content. Replacement percentage of skim milk concentrated by dry dairy products in the mix was between 1.49 and 3.77%. Yoghurts enriched with milk protein concentrates did not show significantly different viscosity (35.12 Pa s) and syneresis index (591.4 g kg⁻¹) than the two control yoghurts obtained only from skimmed milk concentrates (35.6 Pa s and 565.7 g kg⁻¹) and skimmed milk powder (32.77 Pa s and 551.5 g kg⁻¹), respectively. Yoghurt fortified with the whey protein concentrates, however, was less firm (22.59 Pa s) and had less syneresis index (216 g kg⁻¹) than control yoghurts. Therefore, whey protein concentrates may be useful for drinking yoghurt production. © 1999 Society of Chemical Industry     

Size classification of precipitated calcium phosphate using hydrocyclone technology for the recovery of minerals from deproteinised acid whey

Acid whey is generated during the manufacture of acidified dairy products, such as soft cheeses, acid casein ingredients and strained yoghurts. Examples of these whey‐based by‐products include Cottage cheese acid whey and Greek yoghurt acid whey. Alkalisation of acid whey at elevated temperatures (60 °C) precipitates calcium phosphate, which can be recovered and used as an ingredient. The novel application of a liquid–solid hydrocyclone in the size classification of calcium phosphate from heated and neutralised acid whey was investigated in this study. Factors influencing hydrocyclone performance were tested, and the technology was integrated into a membrane filtration‐based process for the production of milk mineral powders.     

Use of ultrafiltration and supercritical fluid extraction to obtain a whey buttermilk powder enriched in milk fat globule membrane phospholipids

Whey buttermilk, a by-product from whey cream processing to butter, is rich in milk fat globule membrane (MFGM) constituents, which have technological and potential health properties. The objective of this work was to produce a dairy ingredient enriched in MFGM material, especially phospholipids, from whey buttermilk. Whey buttermilk was concentrated by ultrafiltration (10×) and subsequently diafiltered (5×) (10 kDa molecular mass cutoff membrane) at 25 °C and the final retentate was spray-dried. The whey buttermilk powder was submitted to supercritical extraction (350 bar, 50 °C) using carbon dioxide. The membrane filtration removed most of the lactose and ash from the whey buttermilk, and the supercritical extraction extracted exclusively non-polar lipids. The final powder contained 73% protein and 21% lipids, of which 61% were phospholipids. This ingredient, a phospholipids-rich dairy powder, could be used as an emulsifier in different food systems.     

Global Market for Dairy Proteins

This review examines the global market for dairy ingredients by assessing the global demand for dairy products in relation to major dairy ingredient categories. Each broad category of dairy ingredients is reviewed including its definition, production and trade status, key applications, and future trends. Ingredient categories examined include whole and skim milk powders (WMPs, SMPs), whey protein concentrates (WPCs) and whey protein isolates (WPIs), milk protein concentrates (MPCs) and milk protein isolates (MPIs), caseins, and caseinates. Increases in world population and improvements in socioeconomic conditions will continue to drive the demand for dairy products and ingredients in the future. Dairy proteins are increasingly recognized to have nutritional and functional advantages compared to many protein sources, and the variety of ingredients with different protein concentrations, functionality, and flavor can meet the needs of the increasingly global dairy consumption. A thorough understanding of the variety of ingredients, how the ingredients are derived from milk, and how the demand from particular markets affects the supply situation are critical elements in understanding the current ingredient marketplace.     

The Distribution of Fat in Dried Dairy Particles Determines Flavor Release and Flavor Stability

Dried dairy ingredients are utilized in various food and beverage applications for their nutritional, functional, and sensory properties. Dried dairy ingredients include milk powders of varying fat content and heat treatment and buttermilk powder, along with both milk and whey proteins of varying protein contents. The flavor of these ingredients is the most important characteristic that determines consumer acceptance of the ingredient applications. Lipid oxidation is the main mechanism for off‐flavor development in dried dairy ingredients. The effects of various unit operations on the flavor of dried dairy ingredients have been investigated. Recent research documented that increased surface free fat in spray dried WPC80 was associated with increased lipid oxidation and off‐flavors. Surface free fat in spray‐dried products is fat on the surface of the powder that is not emulsified. The most common emulsifiers present in dried dairy ingredients are proteins and phospholipids. Currently, only an association between surface free fat and lipid oxidation has been presented. The link between surface free fat in dried dairy ingredients and flavor and flavor stability has not been investigated. In this review, some hypotheses for the role of surface free fat on the flavor of dried dairy ingredients are presented along with proposed mechanisms.     

Detection of milk powder and caseinates in Halloumi cheese

Halloumi cheese is traditionally manufactured from fresh milk. Nevertheless, dried dairy ingredients are sometimes illegally added to increase cheese yield. Lysinoalanine and furosine are newly formed molecules generated by heating and drying milk protein components. The levels of these molecular markers in the finished Halloumi have been investigated to verify their suitability to reveal the addition of skim milk powder and calcium caseinate to cheese milk. Because of the severe heating conditions applied in curd cooking, genuine Halloumi cheeses (n = 35), representative of the Cyprus production, were characterized by levels of lysinoalanine (mean value = 8.1 mg/100 g of protein) and furosine (mean value = 123 mg/100 g of protein) unusual for natural cheeses. Despite the variability of the values, a good correlation between the 2 parameters (R = 0.975) has been found in all cheeses, considering both the fresh and mature cheeses as well as those obtained from curd submitted to a prolonged cooking following a traditional practice adopted by a very small number of manufacturers. Experimental cheeses made by adding as low as 5% of skim milk powder, or calcium caseinate, or both, to cheese milk fell outside the prediction limits at ±2 standard deviation of the above-reported correlation regardless of curd cooking conditions or ripening length. This correlation may be adopted as a reliable index of Halloumi cheese genuineness.     

Dairy Ingredients effects on sausage sensory properties studied by principal component analysis

The effects of dairy ingredients (1, 3, 5%)–ordinary and high-viscosity sodium caseinate, skim-milk powder, whey protein or demineralized whey powder–on sensory properties and instrumental texture and color of sausages, were investigated. Sausages were formulated with 2 or 4% potato starch and cooked to a core temperature of 76 or 82°C. Principal component analysis (PCA) revealed three dominating factors for sensory properties; the first related to dairy ingredients and starch concentrations, the two others to type of dairy ingredients. Results were verified by analysis of variance (ANOVA). Results of sensory analysis were further verified by textural and color analysis using PCA and ANOVA, respectively.     

Effect of Transglutaminase on Physicochemical Properties of Set-style Yogurt

In this study, the effect of some ingredients such as skimmed milk powder, whey, sodium caseinate, calcium caseinate, whey protein concentrate (35, 60 kg/100 kg dry solids), whole milk powder, condensed milk and transglutaminase (TGase) on the properties of set-style yogurt was investigated. These protein and dry matter sources (2%) and TGase (1 U/g milk protein) were added into pasteurized milk and incubated prior to fermentation for 2 h at 40°C. After fermentation, enzyme action was stopped by heating for 1 min at 80°C. The control groups were conducted with addition of these materials into milk without TGase. All of the milk samples were inoculated with yogurt cultures at 45°C, until the pH was dropped to 4.4. Syneresis, gel-strength, acetaldehyde amounts, and the degree of TGase reaction were determined. As a result, yogurt products made from enzyme-treated milk showed increased gel strength and less syneresis. SDS-PAGE results showed that the enzyme TGase produced crosslink formation between different protein fractions of milk. In addition, it was also determined that TGase application caused a decrease in acetaldehyde amounts.     

PEKMEZ-DAIRY DESSERTS FORTIFIED WITH SPRAY-DRIED DAIRY POWDERS: EFFECTS OF THE INTERACTION BETWEEN SKIM MILK POWDER, YOGHURT POWDER AND BUTTERMILK POWDER BY A MIXTURE DESIGN APPROACH

A mixture design approach was used to evaluate the interactions between skim milk powder (SMP), yoghurt powder (YP) and buttermilk powder (BMP) on rheological and sensory properties of dairy dessert mixture samples (DDMS). DDMS was prepared with pekmez powder, which was obtained by spray drying of pekmez, also known as concentrated grape molasses. Among the dairy powders, YP was the component that had the most effect on the viscosity of DDMS. The liking of the panelists was more prominent for the dairy dessert samples including the higher concentrations of YP. Optimum values of SMP, YP and BMP in the mixture were found to be 12–46%, 41–90% and 0–39%, respectively with respect to sensory properties.

PRACTICAL APPLICATIONS

The compositional properties of dairy powders can be changed by their usage at particular combinations, which could give rise to an improvement in their rheological and sensory properties. Such modifications would be of great economical importance to food industry. Dairy powders can be used to improve these properties when optimum combination levels of these dairy powders are taken into consideration. Therefore, information obtained in this study may be useful in practical industrial food product process monitoring and development.     

Determination of lactadherin concentration in dairy by-products by ELISA: Effect of heat treatment and hydrolysis

Lactadherin is a peripheral glycoprotein of the milk fat globule membrane with several attributed biological activities. In this study, we developed an indirect competitive ELISA to determine lactadherin concentration by using a rabbit polyclonal antiserum. The ELISA was applied to quantify lactadherin in several dairy by-products. Of the products tested, raw and commercial buttermilk had the highest concentrations of lactadherin (6.79 and 5.27 mg/g of product, respectively), followed by commercial butter serum (4.86 mg/g), commercial skim milk (4.84 mg/g), and raw whey (1.20 mg/g). The concentration of immunoreactive lactadherin was also determined in dairy by-products after they were subjected to different technological treatments. Thus, raw products were heat treated at combinations of temperature and time typically used in the dairy industry, and commercial products were hydrolyzed using 3 proteolytic enzyme preparations. Heat treatments of whey and buttermilk resulted in a smaller decrease in lactadherin concentration than did hydrolysis as determined by ELISA and electrophoresis. At high temperatures for long durations, the loss of lactadherin was higher in whey than in buttermilk, with the maximal reduction of around 48% found after treating whey at 72°C for 60 min. Hydrolysis of commercial products with proteolytic enzymes resulted in a marked decrease of immunoreactivity within the first 5 min of treatment, which thereafter was constant throughout 4 h of hydrolysis. These results demonstrate that dairy by-products from milk fat processing are good natural sources of lactadherin, although technological processes have to be considered, because they have different effects on lactadherin content.     

Effects of caseinate, whey and milk powders on the texture and microstructure of emulsified chicken meat batters

The effects of adding dry caseinate, whole milk, skim milk, regular, and modified whey protein powders, at a level of 2 g/100 g, to meat batters were studied. All dairy additives, except for the regular whey, significantly reduced cook loss (30-50% reduction). Caseinate and modified whey formed distinct dairy protein gel regions within the meat batters, as revealed by light microscopy. Both also contributed more to enhancing the textural properties of the meat batters compared to the other dairy proteins; i.e., increasing texture profile analysis fracturability, and hardness, respectively. Overall, the most cost-effective ingredient appeared to be the modified whey, which also provided the best moisture retention.     

Buttermilk as milk powder and whey substitute in compound milk chocolate: Comparative study and optimisation

The aim of this study was to investigate the optimal concentration of milk, whey and buttermilk powder by using mixture design for the formulation of compound milk chocolate. The influence of buttermilk as a milk and whey substitute on the main physicochemical parameters of compound milk chocolate was investigated. The optimisation of the variables indicated that using 35.660% milk powder, 27.957% whey powder and 36.383% buttermilk produced the optimum milk chocolate with the highest desirability without undesirable changes in the quality properties. Chocolates containing equal amounts of buttermilk and milk powder and also equal amounts of whey powder and buttermilk powder demonstrated high consumer acceptability.     

Use of dairy proteins in lean poultry meat batters – a comparative study

The use of dry whole milk, skimmed milk, caseinate, regular and modified whey, at 2% level (w/w) and with 2% additional protein level was studied in a chicken breast meat system with 51% water addition. At the 2% (w/w) level, all dairy proteins significantly reduced cooking loss compared with the control, with caseinate showing the best results. When compared on an equal protein level (2% total protein), the best performing ingredients were the whole milk and modified whey. A similar observation was made in their effect on the products’ hardness and fracturability. A cost analysis revealed that modified whey provided the most economical ingredient even when used in quantities three times greater than that of as caseinate. Microscopy results showed the formation of larger fine‐protein‐matrix regions in the treatments that provided higher fracturability values.     

Feasibility of Discriminating Dried Dairy Ingredients and Preheat Treatments Using Mid-Infrared and Raman Spectroscopy

This study investigated the feasibility of mid-infrared (MIR) and Raman spectroscopy for (i) discrimination of three dried dairy ingredients, namely skim milk powder (SMP), whey protein concentrate (WPC) and demineralised whey protein (DWP) powder, and (ii) discrimination of preheat treatments of dried dairy ingredients using partial least squares discriminant analysis (PLS-DA). PLS1-DA models developed using MIR ranges of 800–1800 and 1200–1800 cm^?1 yielded the best discrimination (correct identification of 97.2% for SMP discrimination and 100% for WPC and DWP discrimination). The best PLS2-DA model using MIR spectroscopy was developed over the spectral range of 800–1800 cm^?1 and produced correct identification of 100% for dairy ingredient discrimination. Models developed using Raman 800–1800 and 1200–1800 cm^?1 spectral ranges correctly discriminated (100% correctly identified) each dairy ingredient. Although all PLS1-DA and PLS2-DA models developed using both spectral technologies for preheat treatment discrimination had good discrimination accuracy (86–100%), they employed a high number of factors (8–9 for the best model). The use of the Martens uncertainty test successfully reduced the number of factors employed (3–4 for the best models) and improved the performance of PLS1-DA models for preheat treatment discrimination (all 100% correctly identified). This feasibility study demonstrates the potential of both MIR and Raman spectroscopy for rapid characterisation of dried dairy ingredients.     

Acid-induced gelation of whey protein polymers: effects of pH and calcium concentration during polymerization

Heating whey protein dispersions (90°C for 15 min) at low ionic strength and pH values far from isoelectric point (pH>6.5) induced the formation of soluble polymers. The effect of mineral environment during heating on the hydrodynamic characteristics and acid-induced gelation properties of polymers was studied. Whey protein dispersions (80 g/l) were denatured at different pH (6.5–8.5) and calcium concentrations (0–4 mm) according to a factorial design. At pH 6.5, the hydrodynamic radius of protein polymers increased with increasing calcium concentration, while the opposite trend was observed at pH 8.5. Intrinsic viscosity results suggested that heating conditions altered the shape of protein polymers. Whey protein polymers were acidified to pH 4.6 with glucono-δ-lactone and formed opaque particulate gels. The storage modulus and firmness of gels were both affected by conditions used to prepare protein polymers. As a general trend, polymers with high intrinsic viscosity produced stronger gels, suggesting a relationship between polymer shape and gel strength.Acid gelation properties of whey protein polymers makes them suitable ingredients for yoghurt applications. Using whey protein polymers to standardize protein content increased yoghurt viscosity to 813 Pa.s while using skim milk powder at same protein concentration increased yoghurt viscosity to 393 Pa.s. Water holding capacity of protein polymers in yoghurt was 19.8 ml/g compared to 7.2 ml/g for skim milk powder protein. Acid gelation properties of whey protein polymers are modulated by calcium concentration and heating pH and offers new alternatives to control the texture of fermented dairy products.     

Fate of pyrrolizidine alkaloids during processing of milk of cows treated with ragwort

ABSTRACT

To investigate the fate of pyrrolizidine alkaloids (PAs) during milk processing, milk of cows treated via rumen fistula with a mixture of 84% (w/w) ragwort (Jacobaea vulgaris, syn. Senecio jacobaea) and 16% narrow-leaved ragwort (Senecio inaequidens) was processed using laboratory scale heating systems with industrial settings. Pasteurised and sterilised (UHT) milk were produced, as well as set-type yoghurt and cheese. Samples were analysed for 29 PAs using LC-MS/MS, of which 11 PAs were detected above LOQ in the samples (0.1 µg l^?1). Alterations in the PA concentration and composition between the standardised milk and the corresponding end-product(s) were evaluated. The heat treatments applied for pasteurisation and UHT sterilisation to prepare semi-skimmed consumption milk did not affect the PA levels in the end-products. In yoghurt, after fermentation of standardised milk (6 h, pH 4.4), 73% of total PAs were recovered. The PA concentration, specifically dehydrojacoline, was decreased, although not quantifiable, during cheese production. A further decrease of 38% during 6 weeks of ripening was observed. The results show that the PA concentration of natural contaminated cow’s milk is not affected by heat treatment applied for pasteurised and sterilised milk, but that microbial fermentation of the milk leads to a lowered PA concentration in yoghurt and cheese. This is probably due to microbiological degradation, since PAs are fairly stable under acidic conditions.     

Invited review: The effect of native and nonnative enzymes on the flavor of dried dairy ingredients

Dried dairy ingredients are used in a wide array of foods from soups to bars to beverages. The popularity of dried dairy ingredients, including but not limited to sweet whey powder, whey proteins and milk powders, is increasing. Dried dairy ingredient flavor can carry through into the finished product and influence consumer liking; thus, it is imperative to produce a consistent product with bland flavor. Many different chemical compounds, both desirable and undesirable, contribute to the overall flavor of dried dairy ingredients, making the flavor very complex. Enzymatic reactions play a major role in flavor. Milk contains several native (indigenous) enzymes, such as lactoperoxidase, catalase, xanthine oxidase, proteinases, and lipases, which may affect flavor. In addition, other enzymes are often added to milk or milk products for various functions such as milk clotting (chymosin), bleaching of whey products (fungal peroxidases, catalase to deactivate hydrogen peroxide), flavor (lipases in certain cheeses), or produced during the cheesemaking process from starter culture or nonstarter bacteria. These enzymes and their possible contributions will be discussed in this review. Understanding the sources of flavor is crucial to produce bland, flavorless ingredients.