LWT - Food Science and Technology xxx (2015) 1e8
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Antioxidant, antimicrobial, mineral, volatile, physicochemical and microbiological characteristics of traditional home-made Turkish vinegars Ismet Ozturk a, *, Oznur Caliskan a, Fatih Tornuk b, Nihat Ozcan c, Hasan Yalcin a, Mehmet Baslar b, Osman Sagdic b a b c
Erciyes University, Engineering Faculty, Food Engineering Department, 38039, Kayseri, Turkey Yildiz Technical University, Faculty of Chemical and Metallurgical Engineering, Department of Food Engineering, 34210, Istanbul, Turkey TUBITAK Marmara Research Center, Food Institute, 41470, Kocaeli, Turkey
a r t i c l e i n f o
a b s t r a c t
Article history: Received 24 November 2014 Received in revised form 21 February 2015 Accepted 3 March 2015 Available online xxx
In the current study, twenty traditional home-made vinegars collected from different regions of Turkey were characterized in terms of their antioxidant, antimicrobial, mineral and volatile profiles as well as their physicochemical and antimicrobial properties and microbiota. The vinegars were compared to five industrial vinegars according to the characterized properties. Industrial vinegars showed quite high antimicrobial activity while only three traditional vinegars had antimicrobial activity for the all test microorganisms. With respect to these results, traditional vinegars had generally high microbial load; however, they were scarcely detected in industrial vinegars. Physicochemical properties of all vinegars were extremely variable. A total of 61 volatile compounds were determined in the traditional vinegars. The most abundant compounds were a-terpineol and ethyl acetate in some traditional vinegars, while phenethyl alcohol was a common compound detected in the vinegars. Mineral profile of traditional vinegar was determined by using ICP-MS. The most abundant minerals were Na, K and Ca in the vinegars. As a conclusion, traditional Turkish vinegars exhibited very distinct properties independent from raw materials used. © 2015 Elsevier Ltd. All rights reserved.
Keywords: Vinegar Home-made Antioxidant Mineral Volatile
1. Introduction Vinegar is a fermented food that is produced by fermentation of fruits and vegetables containing sugar or starch. Vinegar production is composed of a two-stage fermentation process, namely alcohol fermentation and acetic acid fermentation. First stage is alcohol fermentation during which fermentable sugars are converted to ethanol and CO2 under anaerobic conditions by yeasts which are generally composed of Saccharomyces species. Second stage is acetic acid fermentation where the alcohol formed in the first stage is converted to acetic acid and water under aerobic conditions by acetic acid bacteria including Acetobacter aceti, A. pastorianus ve A. hansenii (Plessi, 2003). Commercial vinegar production is performed with fast or slow fermentation processes. In the fast method, the liquid of damaged fruits is oxygenated and
* Corresponding author. Tel.: þ90 352 207 66 66x32730; fax: þ90 352 437 57 84. E-mail address:
[email protected] (I. Ozturk).
fermentation process is rapidly carried out by submerging the bacterial starter culture. However, slow method is generally used for production of traditional wine vinegars and may take about over the course of weeks or months. In this process, a nontoxic slime that is known as the mother of vinegar comprise yeast and acetic acid bacteria on the surface (Johnston & Gaas, 2006). Vinegar has a diversity of uses such as seasoning, salad dressing and flavoring for foods. On the other hand, it has been also used as a health remedy since ancient times (Tan, 2005). Today, it is well known that vinegar has a number of therapeutic activities including anti-infective properties, antitumor activity and blood glucose control (Johnston & Gaas, 2006). The presence of phenolic compounds in vinegar also provides positive health effects which originate from their antihypertensive effect and strong antioxidant , & Go mez-Cordove s, 2005). In addiactivity (D avalos, Bartolome tion, potential of vinegar as a medicinal remedy has been attributed to the presence of essential amino acids, vitamins, minerals, organic acids and other polyphenols (Adams, 1997).
http://dx.doi.org/10.1016/j.lwt.2015.03.003 0023-6438/© 2015 Elsevier Ltd. All rights reserved.
Please cite this article in press as: Ozturk, I., et al., Antioxidant, antimicrobial, mineral, volatile, physicochemical and microbiological characteristics of traditional home-made Turkish vinegars, LWT - Food Science and Technology (2015), http://dx.doi.org/10.1016/ j.lwt.2015.03.003
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Vinegar has its unique flavor and aroma which are mainly resulted from acetic acid fermentation. Acetic acid which has a pungent flavor is responsible for the basic sensorial characteristic of vinegar. However, other vinegar constituents including organic acids, volatile compounds and other fermentation products also play a role on its organoleptic properties. Diluted acetic acid is not considered as vinegar and when used as an ingredient in food products, it should be declared by its name (FDA, 1989). Vinegars obtained from different sources may have different quality characteristics. Acetification system (fermentation conditions) is also effective on the final quality of vinegar while chemical composition and physicochemical parameters are influenced by these factors (Tesfaye, Morales, Garcıa-Parrilla, & Troncoso, 2002). In spite of the variability in many quality parameters, some general rules about several characteristics such acidity level and presence of heavy metals of vinegars have been established in national and international scale to arrange the commercialization. Therefore, the aim of this study was to characterize the home-made traditional and industrial vinegars manufactured in Turkey with respect to their physicochemical (acidity, turbidity, pH, color and brix), microbiological (lactic acid bacteria, acetic acid bacteria and yeast-mold counts) and bioactive properties, antimicrobial activity, mineral and volatile composition. 2. Materials and methods 2.1. Material Twenty five vinegar samples were collected from various cities in Turkey. Twenty vinegars collected were traditionally homemade and the rest of the samples were industrially produced. 2.2. Physicochemical properties pH values of the vinegars were measured by using a pH meter (InoLab 720, WTW GmbH, Weilheim, Germany) calibrated with buffer solutions (Akbas & Cabaroglu, 2010). A ten mL of vinegar ́was mixed with 20 mL of distilled water and the mixture was titrated up to pH:8.2 by using 0.1 M NaOH. Total acidity was expressed as acetic acid equivalent (Akbas & Cabaroglu, 2010). Brix values of the vinegars were measured using Abbe refractometer (Reichert, Benchtop Refractometers AR 700, New York, USA) calibrated with distilled water. The values were expressed as Brix (Akbas & Cabaroglu, 2010). Turbidity values of the vinegars were determined using a pez turbidimeter (Hach Turbidimeter 2100N, Colorado, USA) (Lo et al., 2005). The values were expressed as NTU (Nepholometric Turbidity Unit). Color values of the vinegars were measured using a chromameter (Lovibond RT Series Reflectance Tintometer, Amesbury, UK) calibrated with standard calibration scale (El Sheikha, Zaki, Bakr, El Habashy, & Montet, 2010). They were expressed as L* (whiteness/ darkness), a* (redness/greenness), and b* (yellowness/blueness). 2.3. Total phenolic content Total phenolic content (TPC) of the vinegars was determined according to Folin-Ciocalteu method described by Singleton and Rossi (1965). Vinegar samples were filtered using a filter of 0.45 mm and appropriately diluted. A four mL of the filtrate was mixed with 2 mL of Folin Ciocelteau's phenol reagent and 1.6 mL of Na2CO3 (7%) and the final mixture was incubated at the room temperature for 90 min. After the incubation, absorbance of the mixture was measured using a spectrophotometer (Shimadzu
UVevisible 1700, Tokyo, Japan) at 760 nm. TPC was expressed as mg gallic acid equivalent (GAE)/L. 2.4. Total flavonoid content Total flavonoid content (TFC) of the vinegars was determined according to the method described by Zhishen, Mengcheng, and Jianming (1999). Vinegar samples were filtered using a filter of 0.45 mm and 1 mL of filtrate was mixed with 4 mL of distilled water. It was mixed with 0.3 mL of NaNO2 (5%), 0.3 mL of AlCl3 (10%) and 2 mL of NaOH (1 M) and the total volume of mixture was finalized to 10 mL by distilled water. The absorbance of mixture was measured at 510 nm using a spectrophotometer (Shimadzu UVevisible 1700, Tokyo, Japan). TFC was expressed as catechin equivalent.
2.5. Antiradical activity The antiradical activity of the vinegars was determined as free DPPH radical scavenging capacity (Singh, Chidambara Murthy, & Jayaprakasha, 2002). Vinegar samples were filtered using a filter of 0.45 mm and 0.1 mL of filtrate was mixed with 5 mL of DPPH solutions (0.1 mM) and vigorously mixed with vortex. Following the incubation for 13 min at 27 C in dark conditions, absorbance of the mixture was measured at 517 nm using a spectrophotometer. Antiradical activity (ARA, %) was described as following Eq. (1):
ARAð%Þ ¼
Ac AS 100 Ac
(1)
where Ac and As is absorbance of control (DPPH solution) and the sample, respectively.
2.6. Antimicrobial activity Antimicrobial activity of the vinegars was determined by using agar diffusion method against 10 microorganisms (Escherichia coli ATCC 25922, Listeria monocytogenes ATCC 7644, Salmonella enterica subsp. typhimurium ATCC 14028, Yersinia enterocolitica ATCC 27729, Staphylococcus aureus ATCC 25923, Bacillus cereus ATCC 33019, E. coli O157:H7 ATCC 33150, Klebsiella pneumonia ATCC 13883, Pseudomonas aeruginosa ATCC 17853 and Proteus vulgaris ATCC 13319). Vinegar samples were purified from bacteria by using membrane filter (0.22 mm). Mueller-Hinton Agar was sterilized using autoclave. The agar was cooled to 45e50 C and 1% of fresh bacterial culture was added. The agar containing bacteria was mixed and poured into plates. After the plates hardened, they were holed about 6 mm pore using cork borer. Sterile-filtered vinegar samples were added to the wells. Plates were incubated at 37 C for 24 h and zones around the wells were measured in mm (Sagdic et al., 2013).
Table 1 Microwave oven program. Initial temperature ( C)
Final temperature ( C)
Time (min)
25 90 90 120 120 150 150 175
90 90 120 120 150 150 175 175
5 5 5 5 5 5 5 5
Please cite this article in press as: Ozturk, I., et al., Antioxidant, antimicrobial, mineral, volatile, physicochemical and microbiological characteristics of traditional home-made Turkish vinegars, LWT - Food Science and Technology (2015), http://dx.doi.org/10.1016/ j.lwt.2015.03.003
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Table 2 Physicochemical and microbiological properties of traditional and industrial vinegars. Sample
City
Raw material
pH
TG1 TG2 TG3 TG4 TG5 TG6 TG7 TG8 TG9 TG10 TA1 TA2 TA3 TA4 TA5 TA6 TAR1 TP1 TAL1 TH1 IG1 IA1 IL1 IS1 IP1
Tokat Tokat Nevs¸ehir Kilis Kilis Adıyaman S¸anlıurfa Bursa de Nig Zonguldak Tokat Tokat Kayseri Bursa de Nig Zonguldak de Nig de Nig de Nig de Nig e e e e e
Grape Grape Grape Grape Grape Grape Grape Grape Grape Grape Apple Apple Apple Apple Apple Apple Artichoke Pomegranate Apple-Lemon Hawthorne Grape Apple Lemon Sour cherry Pomegranate
3.90 3.10 3.40 3.72 3.68 3.40 3.64 2.86 3.27 2.70 3.02 3.50 3.44 3.48 3.56 2.71 3.79 3.69 3.64 3.76 2.93 3.10 2.63 3.05 2.88
± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ±
0.02 0.01 0.01 0.01 0.02 0.01 0.01 0.03 0.01 0.01 0.02 0.01 0.01 0.04 0.01 0.02 0.00 0.09 0.01 0.02 0.02 0.02 0.02 0.01 0.01
Total acidity
Brix
± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ±
20.80 9.62 3.91 4.03 1.22 4.21 2.33 6.11 2.37 2.31 12.90 1.83 1.02 2.12 1.44 2.11 1.47 1.32 1.49 1.26 4.12 5.55 2.66 4.85 12.63
1.74 5.72 2.94 1.42 0.32 1.46 0.56 3.00 2.40 4.30 7.20 1.38 1.66 0.66 1.32 4.28 1.22 1.04 1.36 0.82 5.68 4.40 4.34 5.50 3.38
0.06 0.25 0.06 0.07 0.03 0.03 0.03 0.06 0.06 0.03 0.12 0.06 0.09 0.06 0.06 0.09 0.03 0.03 0.03 0.03 0.09 0.07 0.07 0.07 0.03
Turbidity ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ±
0.03 0.09 0.23 0.03 0.19 0.08 0.02 0.02 0.01 0.08 0.05 0.01 0.07 0.04 0.02 0.06 0.01 0.03 0.03 0.02 0.04 0.03 0.01 0.03 0.02
32.5 2738.0 645.3 57.2 2699.3 1186.3 310.0 19.6 53.1 2.3 78.7 193.3 153.7 93.6 70.7 2.1 132.3 523.0 85.5 296.3 5.4 1.2 11.2 16.7 23.8
± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ±
0.5 256.8 53.9 2.9 111.2 43.1 26.8 0.57 1.0 0.1 2.3 4.7 1.1 2.2 1.5 0.1 3.5 3.6 1.2 0.6 0.1 0.3 0.3 0.1 1.2
LAB
AAB
Y-M
<10 <10 5.1 <10 7.4 6.0 <10 <10 2.6 <10 <10 1.5 <10 3.7 7.2 <10 1.4 2.0 5.6 4.6 3.3 <10 <10 <10 <10
<10 <10 5.0 1.3 6.5 <10 6.5 <10 2.5 <10 <10 4.0 1.5 <10 1.1 <10 7.0 8.6 1.6 7.5 <10 <10 <10 <10 <10
2.8 <10 <10 <10 4.7 3.9 2.6 6.8 <10 <10 <10 2.7 3.0 2.9 <10 <10 <10 <10 <10 <10 <10 <10 <10 8.8 <10
103 105 102
103
105 106 106 106 106 106 106 103
104 107 106 107 104
107 105 109 108 108 107 104
103
105 106 106 103
103 102 106
102
T:Traditional home-made vinegar samples, I:Industrial vinegar samples, Total acidity: % (as acetic acid), Turbidity: Nepholometric Turbidity Unit (NTU). LAB: Lactic acid bacteria, AAB: Acetic acid bacteria, Y-M:Yeast-mold.
2.7. Microbiological analysis Vinegars were serially diluted and spread plate technique was used for determination of the microbiological properties of the vinegars. Dichloran Rose Bengal Chloramphenicol (DRBC) Agar was used for detecting the viable cells of molds and yeast. The plates were incubated at 25 C for 3e5 days. De Man, Rogosa and Sharpe (MRS) Agar were used for detecting the viable cells of lactic acid bacteria. The plates were incubated at 30 C for 48 h at anaerobic conditions and cream-white colored colonies were counted. Glucose-yeast extract-calcium carbonate (GYC) Agar wasused for detecting the viable cells of acetic acid bacteria. The plates were incubated at 30 C for 5 days and colonies forming units (cfu) were counted. 2.8. Mineral analysis Mineral analysis was performed according to the method described by Jorhem (1993). One gram of the sample was weighed into teflon microwave digestion vessels. A 5 mL of concentrated nitric acid and 1 mL of hydrogen peroxide were added. Vessels were closed and placed into microwave oven. The oven program given in Table 1 was applied. Initial and final temperatures used in the oven changed between 25-175 C and 90e175 C, for 5 min, respectively. After cooling the vessels, clear digested samples were transferred to 50 mL volumetric flasks and diluted to mark with deionized water. Minerals were inductively determined using a coupled plasma mass spectrometer (ICP-MS) Perkin Elmer Sciex Elan DRC-E (Norwalk CT, USA). The operating conditions of the instrument were: plasma gas flow rate 14.00 L/min, auxiliary gas flow 1.40 L/min, nebulizer gas flow 0.83 L/min and lens voltage 6.25. The argon gas utilized was spectral purity (99.9998%). To quantify minerals Copper (63), Zinc (66), Calcium (44), Chromium (53), Magnesium (26), Manganese (55), Potassium (39), Selenium (78), Sodium (23), cobalt (59), Nickel (60) isotopes were used. Before each experiment, the instrument was tuned for daily performance using Elan 6100 DRC sensitivity detection limit solution. External calibration
technique was followed for the quantitative analysis of the samples. The calibration curves for all the analytes were built on 6 different concentrations. The calibration standards were analyzed at regular intervals to check instrument drift. Also, ultrapure deionized water blanks were analyzed after each standard to check cross contamination. The analytical method followed for determination of analytes was checked by analyzing certified reference material of BCR063 (JRC IRMM) skim milk powder sample. All the results were in accordance with assigned values.
Table 3 Color parameters of the traditional and industrial vinegars. Sample
L*
TG1 TG2 TG3 TG4 TG5 TG6 TG7 TG8 TG9 TG10 TA1 TA2 TA3 TA4 TA5 TA6 TAR1 TP1 TAL1 TH1 IG1 IA1 IL1 IS1 IP1
0.28 5.09 18.67 10.53 14.30 16.55 5.30 8.91 12.87 7.52 4.58 18.59 20.15 16.99 15.60 8.70 12.24 2.74 15.17 18.10 3.11 12.03 15.13 8.25 2.97
a* ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ±
0.04 0.73 0.15 1.39 0.47 0.40 0.12 0.32 0.45 0.04 0.15 0.29 0.19 2.09 0.36 0.68 0.48 0.53 0.39 0.11 0.83 2.43 1.44 1.79 0.68
0.56 4.30 3.68 2.31 6.27 7.05 14.88 4.38 2.42 2.40 6.66 2.64 0.86 0.09 0.60 2.48 0.58 2.37 0.49 1.96 3.75 0.32 0.54 3.19 7.40
b* ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ±
0.02 0.41 0.14 0.28 0.05 0.05 0.20 0.10 0.04 0.02 0.14 0.02 0.02 0.01 0.04 0.05 0.16 0.45 0.03 0.02 0.95 0.01 0.11 0.42 1.87
0.43 5.54 11.08 9.92 5.11 14.11 3.98 11.73 9.93 9.35 7.25 11.98 5.49 3.71 7.02 10.49 5.71 2.43 7.29 10.67 3.35 4.91 2.05 6.39 4.04
± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ±
0.03 0.75 0.62 1.39 0.14 0.16 0.05 0.45 0.21 0.13 0.18 0.16 0.06 0.23 0.06 0.87 0.37 0.52 0.13 0.04 0.94 0.56 0.02 1.02 1.10
T:Traditional home-made vinegar samples, I:Industrial vinegar samples.
Please cite this article in press as: Ozturk, I., et al., Antioxidant, antimicrobial, mineral, volatile, physicochemical and microbiological characteristics of traditional home-made Turkish vinegars, LWT - Food Science and Technology (2015), http://dx.doi.org/10.1016/ j.lwt.2015.03.003
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I. Ozturk et al. / LWT - Food Science and Technology xxx (2015) 1e8
kept in a hotplate (RCT basic, IKA, Germany) at 40 C for 60 min, SPME fiber (75 mm, carboxen/polydimethylsiloxane (CAR/PDMS)) (Supelco, Bellefonte, PA, USA) was exposed to the headspace. The volatile compounds adsorbed to the fiber were desorbed from the injection port at 50 C for 20 min and they were injected to GCeMS in the splitless mode. GCeMS conditions were set as following: The oven temperature was fixed at 40 C for 10 min, heated to 110 C at 3 C/min, from 110 C to 150 C at 4 C/min, and from 150 C to 210 C at 10 C/min, and held at 210 C for 12 min. Helium gas was used as a carrier and it has a flow rate of 1.0 mL/min. The voltage of electron ionization detector was 70 eV (Ozturk et al., 2014). The volatile compounds were identified by using the libraries of Flavor 2, Nist05 and Wiley7n. The peak areas were used directly to give the percentage volatile composition of the vinegars by dividing the area of each peak to the total area under all of the peaks.
Table 4 Bioactivity of the traditional and industrial vinegars. Sample
TPC
TG1 TG2 TG3 TG4 TG5 TG6 TG7 TG8 TG9 TG10 TA1 TA2 TA3 TA4 TA5 TA6 TAR1 TP1 TAL1 TH1 IG1 IA1 IL1 IS1 IP1
1439.52 2228.79 211.59 253.52 240.81 799.34 577.44 389.80 171.77 75.01 353.33 434.88 215.76 40.44 185.33 74.20 236.67 257.53 201.64 306.80 111.57 118.82 42.04 782.53 719.59
TFC ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ±
24.24 83.26 2.35 9.46 34.71 35.10 6.56 46.76 1.74 1.27 95.31 7.55 2.70 2.58 1.69 1.03 12.80 3.65 6.97 5.07 24.69 30.28 0.82 43.17 34.14
DPPH (%)
349.05 180.45 57.23 44.49 207.33 310.40 219.84 29.72 67.63 14.43 59.03 188.43 41.29 10.89 77.16 14.67 149.29 72.44 67.56 136.16 91.17 55.08 13.98 191.28 182.23
± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ±
2.80 5.36 1.40 0.79 3.67 2.69 4.25 0.55 0.92 0.14 1.65 1.83 2.09 0.59 0.72 0.24 2.48 1.67 1.29 0.97 2.70 2.48 1.04 3.33 1.55
75.45 70.75 20.27 25.21 71.37 81.76 89.53 14.39 29.50 4.93 33.47 65.12 24.43 0.53 33.47 6.32 68.89 7.65 32.84 55.59 19.85 26.32 6.50 89.91 90.36
± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ±
0.30 0.80 3.21 0.23 0.82 0.77 0.52 0.88 0.48 0.12 5.53 0.73 3.70 0.10 0.11 2.65 7.25 2.01 0.75 3.86 0.66 2.00 0.21 0.65 0.17
3. Results and discussion 3.1. Physicochemical properties Table 2 shows physicochemical properties of the traditional and industrial vinegar samples. A wide variability was observed in the values, indicating remarkable differences in vinegar qualities. However, it was obvious that this variability was independent from the raw material. pH levels of the vinegars varied from 2.63 to 3.90. In general, traditional vinegars had higher pH values than the industrial ones, and pH values of many samples (85%, n ¼ 17) were above 3.00. pH levels of the samples were in accordance with the previous studies (Akbas & Cabaroglu, 2010; Gerbi, Zeppa, Beltramo, Carnacini, & Antonelli, 1998). Total acidity levels of the vinegar samples were generally correlated with their pH values (Table 2). A big majority (80%) of the traditional vinegar samples was not in conformity with Turkish (Anonymus, 2004) and US regulations (FDA, 1980) that approve minimum acidity value as 40 g/L for vinegars while 80% of the industrial ones had acidity levels correspondent with the legislations. However, according to Codex Alimentarius Commission, total acid content of wine vinegar or other
T: Traditional home-made vinegar samples. I: Industrial vinegar samples, TPC: Total phenolic content (mg gallic acid equivalent (GAE)/L), TFC: Total flavonoid content (mg catechin/L), DPPH: 2.2-diphenyl-1-picrylhydrazyl.
2.9. Volatile compounds Volatile profile of the vinegar samples was determined using a Gas Chromatography-Mass Spectrometry GCeMS (Agilent 7890A GC system, Avondale, USA) equipped with a mass selective detector (Agilent Technologies, Avondale, USA) and HP-5MS capillary column (30 m 0.250 mm i.d.; film thickness 0.25 mm). A five mL of the vinegar was placed into GCeMS vial and sealed with PTFE-faced silicone septum (Supelco, Bellefonte, PA, USA). While the vials were
Table 5 Antimicrobial activity of the traditional and industrial vinegars against some pathogens (inhibition zone. mm). Sample E. coli TG1 TG2 TG3 TG4 TG5 TG6 TG7 TG8 TG9 TG10 TA1 TA2 TA3 TA4 TA5 TA6 TAR1 TP1 TAL1 TH1 IG1 IA1 IL1 IS1 IP1
e 11.24 e e e e e 8.98 e 8.61 10.75 e e e e 8.54 e e e e 8.20 9.14 8.31 7.78 7.85
± 1.25
± 0.73 ± 0.28 ± 1.36
± 0.42
± ± ± ± ±
0.36 2.23 0.50 1.18 0.37
L. monocytogenes S. typhimurium Y. enterocolitica S. aureus
B. cereus
e 30.71 14.59 e e e e 10.18 e 17.67 25.84 e e e e 17.68 e e e e 17.73 17.51 16.74 18.05 15.62
10.66 16.52 13.01 12.40 e 11.63 7.37 13.25 13.68 18.18 23.56 11.25 7.74 10.96 10.19 14.46 e 10.45 11.30 9.06 14.50 15.27 16.80 14.78 17.37
± 5.66 ± 0.21
± 1.98 ± 3.81 ± 1.66
± 0.22
± ± ± ± ±
1.94 2.11 2.99 1.48 1.32
e 11.96 10.28 8.21 e e e 7.21 e 10.31 11.41 e e e e 9.54 e e e e 7.86 8.88 8.12 10.13 9.08
± 1.18 ± 1.62 ± 0.33
± 0.74 ± 1.75 ± 0.98
± 0.95
± ± ± ± ±
0.64 0.37 0.30 1.14 0.64
8.11 ± 0.36 17.94 ± 4.13 12.41 ± 1.15 e e 8.03 9.08 9.91 10.42 18.08 e 9.14 e 6.83 10.70 e e e e 14.66 12.94 13.60 9.02 11.38
± ± ± ± ±
0.11 1.50 0.19 0.62 1.45
± 0.51 ± 0.47 ± 0.54
± ± ± ± ±
1.05 1.28 1.27 0.87 1.17
e 10.85 e e e e e 9.01 e e 20.12 e e e e 7.64 e e e e 8.41 9.34 11.31 13.82 10.36
± 1.75
± 1.18
± 0.28
± 0.40
± ± ± ± ±
1.38 0.84 0.65 1.03 1.73
± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ±
E. coli O157:H7 K. pneumoniae P. aeruginosa P. vulgaris
1.15 e 0.82 11.69 0.13 7.56 0.23 e e 1.69 e 0.79 e 1.97 e 0.93 8.51 2.59 7.99 0.82 15.16 0.26 e 0.21 e 1.06 e 0.39 e 0.09 10.40 e 1.24 e 0.47 e 1.48 e 0.55 7.83 0.85 8.42 1.92 10.26 2.64 7.81 2.23 8.88
± 1.51 ± 0.52
± 1.74 ± 0.74 ± 4.71
± 0.64
± ± ± ± ±
0.52 1.26 1.39 0.89 1.39
8.96 15.91 15.55 e e e e 12.50 7.46 11.24 20.80 e e e e 11.72 e e e e 11.22 10.21 7.81 7.97 6.90
± 1.07 ± 1.53 ± 1.89
± ± ± ±
2.16 0.52 1.92 0.98
± 0.43
± ± ± ± ±
1.66 0.90 0.91 0.66 0.17
e 13.86 14.71 8.27 e e e 8.03 8.76 9.99 13.73 7.28 10.43 e 6.88 10.43 e e 6.18 e 11.15 10.31 9.89 12.62 10.06
± 0.49 ± 0.70 ± 0.20
± ± ± ± ± ±
0.74 0.96 0.44 2.16 0.32 1.76
± 0.94 ± 0.09
± 0.18 ± ± ± ± ±
1.52 0.72 0.99 2.05 1.54
e 14.52 7.25 e e e e 9.14 e 8.32 10.29 e e e e 7.12 e e e e 9.05 8.46 8.66 8.56 9.03
± 0.42 ± 0.23
± 0.51 ± 0.18 ± 1.92
± 0.32
± ± ± ± ±
0.39 0.99 0.61 0.68 0.96
e: not determined. T: Traditional home-made vinegar samples. I: Industrial vinegar samples.
Please cite this article in press as: Ozturk, I., et al., Antioxidant, antimicrobial, mineral, volatile, physicochemical and microbiological characteristics of traditional home-made Turkish vinegars, LWT - Food Science and Technology (2015), http://dx.doi.org/10.1016/ j.lwt.2015.03.003
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Table 6 Mineral content of the traditional and industrial vinegars. Sample Se
Cr
Cu
Mg
Co
Na
K
Ca
Ni
Mn
TG1 TG2 TG3 TG4 TG5 TG6 TG7 TG8 TG9 TG10 TA1 TA2 TA3 TA4 TA5 TA6 TAR1 TP1 TAL1 TH1
0.12 0.04 0.11 0.16 0.14 0.11 0.11 0.10 0.06 0.03 0.09 0.12 0.11 0.06 0.05 0.07 0.09 0.05 0.07 0.09
± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ±
0.01 0.00 0.02 0.02 0.01 0.01 0.01 0.01 0.00 0.00 0.01 0.01 0.02 0.01 0.01 0.01 0.01 0.00 0.01 0.01
0.60 0.17 0.14 0.19 0.12 0.18 0.08 0.14 0.04 0.05 0.12 0.07 0.05 0.19 0.05 0.04 0.05 0.03 0.04 0.04
± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ±
0.09 0.04 0.00 0.02 0.01 0.01 0.01 0.01 0.00 0.01 0.01 0.01 0.00 0.02 0.00 0.00 0.01 0.00 0.00 0.00
0.34 0.15 0.02 0.04 0.32 0.16 0.28 0.06 0.50 0.04 0.31 0.05 0.14 0.07 0.34 0.04 0.15 0.07 0.06 0.03
± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ±
0.01 0.01 0.00 0.01 0.01 0.01 0.01 0.00 0.01 0.01 0.00 0.01 0.00 0.01 0.02 0.01 0.01 0.02 0.00 0.00
11.50 5.00 3.60 3.30 8.70 4.80 2.70 7.20 2.50 0.60 1.40 2.00 1.50 4.90 3.20 0.60 1.00 1.20 1.60 3.80
0.13 0.01 0.02 0.00 0.00 0.01 0.00 0.01 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.00
± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ±
0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
0.52 0.78 0.36 0.67 2.42 0.61 0.35 1.46 2.56 1.70 0.89 2.18 1.99 0.56 8.81 3.50 2.19 2.15 2.31 1.50
± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ±
0.03 0.05 0.01 0.06 0.13 0.06 0.03 0.21 0.69 0.19 0.10 0.26 0.25 0.03 0.78 0.16 0.28 0.45 0.48 0.36
6357.00 30.20 86.70 45.10 15.90 1371.40 21.60 1181.20 34.00 21.80 29.00 319.10 27.50 4070.20 32.20 25.70 58.10 27.10 28.20 73.90
± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ±
265.50 1.50 2.30 1.30 1.10 37.70 1.20 109.50 3.10 1.10 0.80 8.60 1.70 251.80 1.90 3.90 1.80 1.70 2.10 4.30
4079.20 3639.10 1434.80 2070.20 1290.00 1994.70 1573.80 708.00 736.10 5.60 1599.70 1224.40 814.60 627.10 770.50 7.40 1115.10 886.30 874.30 864.90
± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ±
151.20 92.60 58.30 41.40 78.50 44.00 57.60 66.00 27.40 1.00 41.60 34.40 26.90 32.80 37.40 1.90 11.90 16.10 9.70 42.60
931.90 351.00 175.30 138.30 149.50 273.40 108.90 342.90 161.30 88.6 226.00 94.10 82.10 122.70 164.10 104.2 224.40 150.70 175.40 156.30
± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ±
37.10 10.30 7.70 2.60 3.40 5.70 2.30 37.30 14.80 11.6 7.30 6.90 6.90 9.20 14.20 16.9 3.40 7.80 15.40 15.20
0.22 0.06 0.07 0.04 0.07 0.10 0.03 0.07 0.08 0.04 0.12 0.03 0.28 0.05 0.15 0.11 0.09 0.06 0.13 0.07
± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ±
0.01 0.00 0.01 0.00 0.01 0.00 0.01 0.00 0.01 0.01 0.02 0.01 0.01 0.01 0.03 0.01 0.00 0.01 0.03 0.01
2.18 2.23 1.11 0.67 0.10 0.56 0.21 0.70 0.42 0.09 0.57 0.35 0.14 0.09 0.34 0.08 0.33 0.31 0.20 0.38
± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ±
0.19 0.06 0.05 0.01 0.05 0.01 0.01 0.08 0.01 0.01 0.01 0.04 0.02 0.00 0.05 0.01 0.03 0.05 0.01 0.03
IG1 IA1 IL1 IS1 IP1
0.06 0.07 0.04 0.04 0.04
± ± ± ± ±
0.01 0.01 0.01 0.01 0.00
0.07 0.06 0.05 0.07 0.07
± ± ± ± ±
0.00 0.01 0.00 0.00 0.00
0.04 0.07 0.05 0.09 0.13
± ± ± ± ±
0.01 134.70 ± 4.10 0.01 60.30 ± 7.30 0.01 51.00 ± 1.20 0.01 136.60 ± 13.50 0.02 76.70 ± 3.40
0.02 0.01 0.01 0.01 0.01
± ± ± ± ±
0.00 0.00 0.00 0.00 0.00
1.53 1.62 1.33 1.64 0.59
± ± ± ± ±
0.14 0.22 0.11 0.16 0.04
259.50 150.60 104.90 158.40 123.30
± ± ± ± ±
6.80 19.00 1.40 13.30 6.10
888.70 1254.20 113.80 1100.50 1348.30
± ± ± ± ±
22.00 114.30 1.20 77.30 53.30
125.10 201.70 134.70 89.20 156.20
± ± ± ± ±
7.30 29.70 2.80 8.10 3.02
0.13 0.08 0.07 0.09 0.05
± ± ± ± ±
0.01 0.01 0.01 0.01 0.00
0.55 0.67 0.16 0.68 0.59
± ± ± ± ±
0.02 0.10 0.01 0.06 0.02
243.70 188.90 89.30 135.50 112.90 134.10 47.20 77.50 48.70 6.70 86.90 73.20 36.50 62.00 51.80 7.10 74.80 49.40 52.20 61.40
± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ±
Zn
T:Traditional home-made vinegar samples. I: Industrial vinegar samples, Se: Selenium, Cr: Chromium, Cu: Copper, Mg: Magnesium, Co: Cobalt, Zn: Zinc, Na: Sodium, K:Potassium, Ca: Calcium, Ni: Nickel, Mn: Manganese.
type of vinegars should not be less than 60 g/L and 50 g/L, rez-Olmos, & Ruiz, 1995) respectively (CAC, 2000). (Lapa, Lima, Pe found total acidity levels of 9 commercial vinegar samples to be higher than 4% using conventional and automatic test methods. Brix (%) parameter indicates the percentage of soluble solids including sugar, salts and proteins in an aqueous sample. However, Brix generally represents the sugar equivalents in the samples such lesas vinegar, omitting other soluble materials (S aiz-Abajo, Gonza iz, & Pizarro, 2004). In this study, brix values of the vinegars Sa varied in a wide range (from 1.02 to 20.80), representing a high variability. Brix value is closely related with the fermentation as level of sugars decreases with the activity of fermentation microorganisms (Masino, Chinnici, Bendini, Montevecchi, & Antonelli, 2008). Type of starter cultures and raw material are other responsible factors for variability in brix values of different vinegars. iz-Abajo et al. (2004) found Literature also supports our findings. Sa brix values of wine and alcohol vinegars at concentrations varying from 3.80 to 5.00 and from 3.30 to 3.40, respectively. In another study, brix values of traditional balsamic vinegars were all above 55.00 (Masino et al., 2008). Turbidity is an important quality attribute of liquid foods since consumers generally demand less turbid products for their preferences. Turbidity of juices is a result of presence of suspended solids in the liquid medium. As is seen in Table 2, turbidity levels of the industrial and traditional vinegars were variable between 1.2 ± 0.3 and 2738 ± 256.8 NTU. The traditional grape vinegars had highest turbidities, while those of the industrial samples showed relatively lower values, indicating that a turbidity reduction procedure was likely applied to the industrial vinegar samples since it is a common application in vinegar industry to make vinegar clarification by different methods such as microfiltration and ion pez, 2002; Lo pez et al., 2005). exchange (Achaerandio, Güell, & Lo Microbiological properties of the vinegars are seen in Table 2. The counts of lactic acid bacteria (LAB), acetic acid bacteria (AAB), and total yeast and molds were under the detection limits in 13 (% 52), 13 (%52) and 16 (%64) vinegar samples, respectively. In the rest of the samples, AAB levels were relatively higher than those of LAB,
and total yeast and molds. Both LAB and AAB were found in 9 of the vinegar samples (36%), while 7 samples (28%) were free for all microorganisms tested. All the results were generally in accordance with the results obtained by (Sengun, 2013), who reported that the counts of total mesophilic aerobic bacteria (TMAB), yeast, LAB and AAB of 8 commercial fig vinegars ranged from 2.26 to 7.29 log cfu/ mL, <1.00 to 6.49 log cfu/mL, 0.81 to 8.20 log cfu/mL and 2.68 to 8.23 log cfu/mL, respectively, while the samples were negative for mold, S. aureus, L. monocytogenes, Salmonella spp., E. coli and B. cereus. AAB, belonging to the genus of Acetobacter are the basic microorganisms responsible for the production of vinegar throughout oxidation of ethanol to acetic acid (Ilabaca, Navarrete, Mardones, Romero, & Mas, 2008). Therefore, many of the studies have been conducted to determine the diversity of AAB in vinegar processing (Gullo, Caggia, De Vero, & Giudici, 2006; Ilabaca et al., 2008; Nanda et al., 2001). Color properties of the industrial and traditional vinegar samples are shown in Table 3. L* values, indicating the brightness, ranged from 0.28 to 20.15. Traditional apple vinegars had remarkably higher L* values except for one sample. Both a* and b* values of the samples were almost variable among the samples, indicating that color properties of the vinegars were very different from each other. Color is an important factor affecting consumer perception pez et al., 2005). In general, color propwhen buying vinegar (Lo erties of vinegars are evaluated by sensorial analyses and spectrorcel, Caro, & Pe rez, 2002; photometric methods (Palacios, Valca Tesfaye et al., 2002). In the unique study in which color was determined with chromameter, Li, Lo, and Moon (2014) found that L* value of Hericium erinaceus vinegars ranged from 87.86 to 88.23 during fermentation, representing a very distinct color property from those of the samples in the present study. 3.2. Bioactive properties Bioactive properties, namely total phenolic and flavonoid contents (TPCs and TFCs) and DPPH radical scavenging activities of the traditional and industrial vinegar samples are tabulated in Table 4.
Please cite this article in press as: Ozturk, I., et al., Antioxidant, antimicrobial, mineral, volatile, physicochemical and microbiological characteristics of traditional home-made Turkish vinegars, LWT - Food Science and Technology (2015), http://dx.doi.org/10.1016/ j.lwt.2015.03.003
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I. Ozturk et al. / LWT - Food Science and Technology xxx (2015) 1e8
Table 7 Major volatile compounds of the traditional vinegars. Volatile compounds Acids Hexanoic acid Octanoic acid Propionic acid 3-Hexenoic acid Propanoic acid Decanoic acid Acetic acid Sorbic Acid Isovaleric acid Alcohols Phenethyl alcohol 1-Pentanol Amyl alcohol Nonanol Iso amyl alcohol 1-Hexanol 2-Ethyl-1-hexanol 1-pentyne-4-en-3-ol Fenchyl alcohol a-methylbenzyl alcohol cis-geraniol Alkanes n-hexadecane 2-nonanone n-octadecane n-tetradecane Vitispirane Aldehydes trans-2-heptenal Benzaldehyde trans-2-octenal n-decanal 2-Furancarboxaldehyde Esters Ethyl acetate Isoamyl acetate Ethyl heptanoate Phenethyl acetate Ethyl octanoate Ethylphenyl acetate Diethyl succinate Ethyl laurate Ethyl palmitate Ethyl benzoate Ethyl nonanoate Ethyl-3-hexenoate Ethyl trans-4-hexenoate Ketones 2-Furyl-methylketone g -nonalactone Phenol 2-methoxy-4-methyl-phenol Phenol. 2-ethyl4-ethyl-phenol Nonylphenol isomer Terpenes g-terpinene p-cymene Myrcene Limonene Linalol Eugenol 1,2,4-trimethyl-benzene Styrene a-Terpineol Terpinene-4-ol 4-ethyl-1, 2-dimethoxy-benzene Other Urea
TG1
TG2
TG3
TG4
TG5
TG6
TG7
TG8
TG9
TG10
TA1
TA2
TA3
TA4
TA5
TA6
TAR1
TP1
TAL1
TH1
e e e e e e 3.7 e e
1.6 1.1 e e e e e e e
e e e e e e e e e
e e e e e e e e e
e 2.9 e e e 1.6 e e e
e 1.8 e e e 1.2 e e e
e 3.5 e e e 2.2 e e e
3.9 3.2 e e e e 56.7 e 13.8
1.3 2.3
e e e e e e 12.5 e e
4.2 6.4 e e e 1.5 e e 10.3
6.4 17.8 e e e 10.4 29.8 e 8.4
2.5 9.2 e e e 2.5 5.3 e 1.0
2.3 4.0 5.9 4.4 e 1.2 e 2.3 e
e e e 5.5 e e e e e
e 1.5 e 26.3 7.0 e 4.9 e e
1.2 2.3 3.5 13.0 e 1.0 e
1.1
20.5 e e e 3.8 e
e e e e e e 63.1 e e
2.7 8.4 e e e 1.6 e
e 1.4 2.7 10.6 e e e e e
10.7 2.3 e e e e e e e e e
6.0 e e e e e e e e e e
e e e e e e e e e e e
4.8 e 1.6 e e e e e e e e
10.8 e 3.3 1.5 e e e e e e e
7.8 e e e 1.1 e e e e e e
11.5 e 2.1 e e e e e e e e
1.9 e e e e e 1.0 e e e e
9.9 e e e 1.3 e e e e e e
e e e e e e e e e e 1.4
1.7 e e e e e e e e e e
9.0 e e e 2.3 e e e e e e
11.3 e e e e e e e e e e
19.7 e 3.2 2.5 e 1.5 e e e e e
3.4 e e e e e e e e 2.5 e
e e e e e e e e e e 9.1
1.7 e e e e e e 1.1 e e e
2.5 e e e e e e e e e
1.1 e e e e e e e 1.2 e e
1.5 e e e e e e e e 1.1 e
e e e e e
e e e e e
e e e e e
1.2 e e e e
e e e e e
e e e e e
e e e e e
e e e e e
e e e e 2.3
2.7 e e e
e e e e e
e 1.4 e 2.3 1.4
e e e e e
1.3 e e e e
e e e e e
e e 5.0 e e
e e e e e
e e e e e
e e e e e
e e e e e
e e e e 2.1
1.0 9.4 2.2 e 6.4
e e e e e
e e e e e
e e e e e
e e e e e
e e e e e
e 2.3
e e e e e
e e e 1.2 e
e e e e 1.1
e e e e e
e e e e e
e e e e e
e e e e e
e e e 6.5 e
e e e e e
e e e e e
e e e e e
e e e e e
26.7 1.4 1.1 4.2 2.5 2.0 3.5 1.3 1.7 e e e e
11.3 3.3 e 6.3
28.2 1.1 1.1 1.8
1.6 e e 1.4 1.1 e e e
10.0 1.3 1.0 e 3.5 e e e e 43.2 e e e
29.3 2.0 3.7 2.1 5.6 e e 2.6 e e e e e
21.3 2.6 e 2.0 21.7 e e 15.6 e e e e e
2.1 e e e
2.1 4.2 e 7.3 e e 1.5
e e e 4.9 e e e e e e e e e
e e e 3.4
1.3 e 5.4 e e e e e
e e e e e e e e
e 3.6 e 2.3 4.6 e e 1.9
1.4 e e 16.4
e e e e e e e e e e e e e
e 6.1 e 3.1
e e 12.9 e e 1.1 e e
10.5 1.5 4.6 e 19.5 e e 2.9 1.3 e e e e
2.8 1.7 e e
e e e 1.3 e e e e e e e e 1.2
e e e e e e e e e e e e e
e e e e e e e e e e e 3.7 e
e e e e e e e e e e e 3.2 e
e e e e e e e e e e e 2.5 e
e e e e e e e e e e e 3.3 e
e e
e e
e e
e e
e e
e e
e e
e e
e e
e e
e e
e e
e e
e e
e e
e e
e e
e e
e e
e e e e
e e e e
e e e e
e e e e
e e e e
e e e e
e e 3.6 e
e e e e
e e e e
e e e
e e e e
e 1.1 e e
e e e e
e e e e
e e e e
e e e 20.8
e e e e
e e e e
e 1.3 e e
5.6 e e e
e e e 16.3 e e e e e e e
e e e e e e e e e e e
e e e 26.0 e e e e e e e
1.9 2.3 e 26.2 e e e e e e e
e e e 7.6 e e e e e e e
1.3 4.8 e 15.0 e e e e e e e
e e e e e e e e e e e
e e e e e e e 3.1 e e e
e e e e e e e e e e e
e 1.9 e 2.3 e e 1.7 e e e e
e e 1.4 65.2 e e e e 1.9 e e
e e e e e e e e e e 1.6
e e e e e 7.1 e e e e e
e e e e e e e e e e e
e e e e 1.1 e e e 39.8 5.1 e
e 14.2 e 16.3 e e 9.3 e e e e
e e e e e 1.7 e e 32.1 3.5 e
e e e 1.3
e e e e 1.4 e e e 53.7 5.3 e
e e e 1.2 e e e e 52.9 2.6 e
22.5
e 2.1
e e e e e e e e 1.0 1.2
e
e e e 54.1 3.3 e
e
T:Traditional home-made vinegar samples.
Please cite this article in press as: Ozturk, I., et al., Antioxidant, antimicrobial, mineral, volatile, physicochemical and microbiological characteristics of traditional home-made Turkish vinegars, LWT - Food Science and Technology (2015), http://dx.doi.org/10.1016/ j.lwt.2015.03.003
I. Ozturk et al. / LWT - Food Science and Technology xxx (2015) 1e8 Table 8 Major volatile compounds of industrial vinegars. Volatile compounds Acids Hexanoic acid Octanoic acid Decanoic acid Propanoic acid 3-hexenoic acid Alkanes Vitispirane Aldehydes 2-furancarboxaldehyde n-decanal Benzaldehyde 5-methyl-2-furancarboxaldehyde Alcohols Amyl alcohol 1-hexanol Fenchyl alcohol Isoamylalcohol Phenethyl alcohol Isoamyl alcohol Amines Oxime-, methoxyphenyl Esters Ethyl acetate Isoamyl acetate Ethyl laurate Diethyl succinate Ethyl-2methyl butyrate Hexyl acetate Ethyl-3-hexenoate Benzyl acetate Ethylphenyl acetate Phenethyl acetate Fenchyl acetate Furans Furfural Phenols 2,4-di-tert-butyl- phenol Terpenes Limonene p-cymene 1,4-cineole 1,2-dihydro-1,1, 6-trimethyl-Naphthalene Terpinene 1-ol a-terpineol Isoborneol Eucalyptol
IG1
IA1
IL1
IS1
IP1
1.5 15.6 14.4 e e
e e e e e
e e e e e
1.5 2.1 e 3.5 1.5
1.1 3.5 e e e
e
e
3.5 e e e
e 1.8 1.7 e
e e e e
4.4 e 14.0 1.9
1.7 e 12.8 e
1.9 e e e 3.5 e
e e 5.1 e e e
e 1.0 e e e e
e e e e 5.7 1.0
e e e 2.1 7.6 e
e
e
10.21
e
9.2 10.6 1.3 2.5 e e e e e 4.1 e
31.1 3.4 e e e e e e e e 1.4
30.4 e e e 5.8 1.1 e e e e e
7.5 5.9 e e e e 1.1 1.4 1.9 7.2 e
14.5 18.6 e e e e e 1.6 e 11.7 e
e
e
12.9
e
e
e
e
e
e
4.0
2.0
7.75
e
1.6
1.1 e e 1.9
2.2 4.3 5.7 e
7.3 e e 1.2
e e e e
e e e 2.0
e 1.5 e e
1.3 e 1.8 4.9
e 4.1 e e
e e e e
e 1.2 e e
I: Industrial vinegar samples.
Most of the bioactive properties of the samples varied in a wide range and were not correlated with each other. Among the traditional vinegar samples, the highest TPC, TFC and antiradical activity levels were obtained in the grape vinegars while the sour cherry (IS1) and pomegranate vinegars exhibited the highest levels among the industrial ones. TA4 sample had the lowest levels in terms of all the parameters measured. TPCs of the vinegars ranged from 42.04 mg gallic acid equivalent (GAE)/L to 2228.79 mg GAE/L while DPPH scavenging activities varied in the ranging levels from 0.53% to 90.36%. Bioactive properties of vinegars can vary in a wide range depending on the type of raw material. The differences in the antioxidant activities among grape juice, wine, and wine vinegars were attributed to their different phenolic contents and compositions and to other non-phenolic antioxidants present in the samvalos et al., 2005). Ubeda et al. (2011) reported that total ples (Da phenols index (TPI) and antioxidant activity of persimmon vinegars were always higher than those obtained from white and red-wine vinegars. Sakanaka and Ishihara (2008) found that phenolic contents and radical-scavenging activities of vinegar made from
7
persimmon Saijyo varieties, and unpolished rice vinegar were higher than those of unpolished rice vinegar and apple vinegar. In the present study, bioactive properties of the apple vinegars were low according to bioactivity results of grape vinegars. 3.3. Antibacterial activity Table 5 shows antibacterial activity of the vinegar samples against selected bacteria. Sensitivity of the bacteria to the vinegars was highly variable. Two traditional vinegar samples (TG5 and TAR1) did not show any inhibitory effect on the bacterial strains while industrial vinegar samples exhibited antibacterial activity against all the test bacteria. TG2 and/or TA1 were the samples showing the highest antibacterial activity. B. cereus was observed as the most sensitive strain, which 90% and 100% of the traditional and industrial vinegar samples showed antibacterial activity at varying levels. Considering the industrial vinegar samples overall, all test bacteria had sensitivity to all vinegars at different levels. Liquids with high acidity such as diluted organic acids and vinegars are capable of inhibiting microbial growth or survival depending on their acidity level. Weak acids including acetic acid show their antimicrobial activity by traversing the microbial membrane to undissociated form and dissociating in accordance with the intracellular pH and liberating a proton in the cytoplasm (Salmond, Kroll, & Booth, 1984). Vinegars, containing considerable amounts of acetic acid, have been known to have strong antimi€ nül, 1992; Medina, crobial activity against bacteria (Karapinar & Go ~o, & Romero, Brenes, & de Castro, 2007) and fungi (Pinto, Neves, Lea Jorge, 2008; Wen-Qiao et al., 2005). 3.4. Mineral contents Table 6 shows mineral contents of the vinegar samples. In general, Na, K and Ca were the most abundant minerals present in the vinegars. It was attention grabbing that the sample coded as TG1 was the richest one in terms of the amounts of a group of minerals, namely Cr, Mg, Na, K and Ca. Quantities of Cu þ Mg of the traditional and industrial vinegars ranged from 0.629 mg/L to 9.147 mg/L and from 0.724 mg/L to 1.730 mg/L, respectively. These results were in conformity with the maximum limit, which was 10 mg/L, approved by Turkish Food Codex (Anonymus, 2002). Ni and Se, of which quantities were always lower than 0.300 mg/L, were the minerals with the lowest amounts among the other minerals tested. 3.5. Volatile compounds In the present study, volatile compounds found in the traditional and industrial vinegar samples were listed in Tables 7 and 8, respectively. A total of 61 and 38 volatile compounds were determined in the traditional and industrial vinegar samples, respectively. a-terpineol and ethyl acetate were the most abundant volatile compounds, being major constituents of 25% (n ¼ 5) and 15% (n ¼ 3) of the traditional vinegars, respectively. Ethyl acetate was mainly found in the vinegars produced from grape while aterpineol was not observed in any of the grape vinegar samples. Ethyl acetate is the most prevalent ester in grape wines and proreau-Gayon, Glories, duced with bacterial fermentation (Ribe Maujean, & Dubourdieu, 2006). Acetic acid constituted 56.7% and 63.1% of two grape vinegars, TG8 and TG10, respectively. Urea was a constituent of only one sample (TG2) as the major component. This compound has particular importance since together with the ethanol, this substance is a precursor of ethyl carbamate, which is a carcinogenic compound present in fermented beverages (Maestre et al., 2008). Similarly, for the traditional samples, ethyl acetate
Please cite this article in press as: Ozturk, I., et al., Antioxidant, antimicrobial, mineral, volatile, physicochemical and microbiological characteristics of traditional home-made Turkish vinegars, LWT - Food Science and Technology (2015), http://dx.doi.org/10.1016/ j.lwt.2015.03.003
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was detected in all samples with considerable amounts, being the major compound of IA1 and IL1. Octanoic acid and isoamyl acetate were the major volatile constituents of IG1 and IP1, respectively. Isoamyl acetate is formed by reaction of acids with alcohol during vinegar fermentation and characterized by a banana odor reau-Gayon et al., 2006). (Ribe 4. Conclusions This study showed that Turkish traditional vinegars have lower antimicrobial activity according to the industrial vinegars. Also, traditional vinegars had higher lactic acid bacteria, acetic acid bacteria, and yeast and mold loads as compared to the industrial samples. Most abundant compounds in some traditional vinegar were determined as a-terpineol and ethyl acetate. Besides, the results determined by using ICP-MS of the study indicated that traditional vinegar is generally richer in Na, K and Ca than other minerals. In conclusion, this study demonstrated that characteristics of the Turkish traditional vinegars were very diverse and different from those of the industrial vinegars. References pez, F. (2002). Continuous vinegar decolorization with Achaerandio, I., Güell, C., & Lo exchange resins. Journal of Food Engineering, 51(4), 311e317. Adams, M. R. (1997). Vinegar. In B. B. Wood (Ed.), Microbiology of fermented foods (pp. 1e44). US: Springer. Akbas, M., & Cabaroglu, T. (2010). A research on the determination of compositions of grape vinegars produced in Turkey and their conformity to food legislation. The Journal of Food-The Turkish Association of Food Technology, 35(3), 183e188. Anonymus. (2002). Gıda Maddelerinde Belirli Bulas¸anların Maksimum Seviyelerinin , 2002/63 C.F.R. x 24885. Belirlenmesi Hakkında Teblig Anonymus. (2004). Vinegar - product made from liquids of agricultural origin - definitions, requirements, marking (Vol. TS 1880 EN 13188:2003). Ankara. CAC. (2000). Codex alimentarius commission. Proposed draft revised regional standard for vinegar Retrieved August 2014, from ftp://193.43.36.92/codex/ Meetings/CCEURO/cceuro22/CL00_18e.pdf. , B., & Go mez-Cordove s, C. (2005). Antioxidant properties of D avalos, A., Bartolome commercial grape juices and vinegars. Food Chemistry, 93(2), 325e330. El Sheikha, A. F., Zaki, M. S., Bakr, A. A., El Habashy, M. M., & Montet, D. (2010). Biochemical and sensory quality of physalis (Physalis pubescens L.) juice. Journal of Food Processing and Preservation, 34(3), 541e555. FDA. (1980, 27/07/2009). Vinegar, definitions e adulteration with vinegar eels. Retrieved August 2014, from http://www.fda.gov/iceci/compliancemanuals/ compliancepolicyguidancemanual/ucm074471.htm. 09/12/2009 FDA. (1989). Acetic acid - use in foods - labeling of foods in which used. Retrieved August 2014, from http://www.fda.gov/ICECI/ComplianceManuals/ CompliancePolicyGuidanceManual/ucm074577.htm. Gerbi, V., Zeppa, G., Beltramo, R., Carnacini, A., & Antonelli, A. (1998). Characterisation of white vinegars of different sources with artificial neural networks. Journal of the Science of Food and Agriculture, 78(3), 417e422. Gullo, M., Caggia, C., De Vero, L., & Giudici, P. (2006). Characterization of acetic acid bacteria in “traditional balsamic vinegar”. International Journal of Food Microbiology, 106(2), 209e212. Ilabaca, C., Navarrete, P., Mardones, P., Romero, J., & Mas, A. (2008). Application of culture culture-independent molecular biology based methods to evaluate acetic acid bacteria diversity during vinegar processing. International Journal of Food Microbiology, 126(1e2), 245e249. Johnston, C. S., & Gaas, C. A. (2006). Vinegar: medicinal uses and antiglycemic effect. Medscape General Medicine, 8(2), 61e67. Jorhem, L. (1993). Determination of metals in foodstuffs by atomic absorption spectrophotometry after dry ashing: NMKL interlaboratory study of lead, cadmium, zinc, copper, iron, chromium, and nickel. Journal of AOAC International, 76(4), 798e813. € nül, S¸. A. (1992). Effects of sodium bicarbonate, vinegar, acetic Karapinar, M., & Go and citric acids on growth and survival of Yersinia enterocolitica. International Journal of Food Microbiology, 16(4), 343e347. rez-Olmos, R., & Ruiz, M. P. (1995). Simultaneous Lapa, R. A. S., Lima, J. F. C., Pe automatic potentiometric determination of acidity, chloride and fluoride in vinegar. Food Control, 6(3), 155e159.
Li, T., Lo, Y. M., & Moon, B. (2014). Feasibility of using Hericium erinaceus as the substrate for vinegar fermentation. LWT e Food Science and Technology, 55(1), 323e328. pez, F., Pescador, P., Güell, C., Morales, M. L., García-Parrilla, M. C., & Lo Troncoso, A. M. (2005). Industrial vinegar clarification by cross-flow microfiltration: effect on colour and polyphenol content. Journal of Food Engineering, 68(1), 133e136. ~ as, I. M., Peinado, R., Jime nez-Ot, C., García-García, I., & Maestre, O., Santos-Duen Mauricio, J. C. (2008). Changes in amino acid composition during wine vinegar production in a fully automatic pilot acetator. Process Biochemistry, 43(8), 803e807. Masino, F., Chinnici, F., Bendini, A., Montevecchi, G., & Antonelli, A. (2008). A study on relationships among chemical, physical, and qualitative assessment in traditional balsamic vinegar. Food Chemistry, 106(1), 90e95. Medina, E., Romero, C., Brenes, M., & de Castro, A. (2007). Antimicrobial activity of olive oil, vinegar, and various beverages against foodborne pathogens. Journal of Food Protection, 70(5), 1194e1199. Nanda, K., Taniguchi, M., Ujike, S., Ishihara, N., Mori, H., Ono, H., et al. (2001). Characterization of acetic acid bacteria in traditional acetic acid fermentation of rice vinegar (komesu) and unpolished rice vinegar (kurosu) produced in Japan. Applied and Environmental Microbiology, 67(2), 986e990. Ozturk, I., Karaman, S., Baslar, M., Cam, M., Caliskan, O., Sagdic, O., et al. (2014). Aroma, sugar and anthocyanin profile of fruit and seed of mahlab (Prunus mahaleb L.): optimization of bioactive compounds extraction by simplex lattice mixture design. Food Analytical Methods, 7(4), 761e773. rcel, M., Caro, I., & Pe rez, L. (2002). Chemical and biochemical Palacios, V., Valca transformations during the industrial process of sherry vinegar aging. Journal of Agricultural and Food Chemistry, 50(15), 4221e4225. Pinto, T. M. S., Neves, A. C. C., Le~ ao, M. V. P., & Jorge, A. O. C. (2008). Vinegar as an antimicrobial agent for control of Candida spp. in complete denture wearers. Journal of Applied Oral Science, 16, 385e390. Plessi, M. (2003). Vinegar. In B. Caballero (Ed.), Encyclopedia of food sciences and nutrition (2nd ed.). (pp. 5996e6004). Oxford: Academic Press. reau-Gayon, P., Glories, Y., Maujean, A., & Dubourdieu, D. (2006). Alcohols and Ribe other volatile compounds. Handbook of Enology, 51e64. John Wiley & Sons, Ltd. Sagdic, O., Ekici, L., Ozturk, I., Tekinay, T., Polat, B., Tastemur, B., et al. (2013). Cytotoxic and bioactive properties of different color tulip flowers and degradation kinetic of tulip flower anthocyanins. Food and Chemical Toxicology, 58, 432e439. iz-Abajo, M.-J., Gonza les-Sa iz, J.-M., & Pizarro, C. (2004). Classification of wine Sa and alcohol vinegar samples based on near-infrared spectroscopy. Feasibility study on the detection of adulterated vinegar samples. Journal of Agricultural and Food Chemistry, 52(25), 7711e7719. Sakanaka, S., & Ishihara, Y. (2008). Comparison of antioxidant properties of persimmon vinegar and some other commercial vinegars in radical-scavenging assays and on lipid oxidation in tuna homogenates. Food Chemistry, 107(2), 739e744. http://dx.doi.org/10.1016/j.foodchem.2007.08.080. Salmond, C. V., Kroll, R. G., & Booth, I. R. (1984). The effect of food preservatives on pH homeostasis in Escherichia coli. Journal of General Microbiology, 130, 2845e2850. Sengun, I. Y. (2013). Microbiological and chemical properties of fig vinegar produced in Turkey. African Journal of Microbiology Research, 7(20), 2332e2338. Singh, R. P., Chidambara Murthy, K. N., & Jayaprakasha, G. K. (2002). Studies on antioxidant activity of pomegranate (Punica granatum) peel extract using in vivo models. Journal of Agricultural and Food Chemistry, 50(17), 4791e4795. Singleton, V. L., & Rossi, J. A. (1965). Colorimetry of total phenolics with phosphomolybdic-phosphotungstic acid reagents. American Journal of Enology and Viticulture, 16, 144e158. Tan, S. C. (2005). Vinegar fermentation. Lafayette, US: Master of Science, Louisiana State University. Retrieved from http://ucfoodsafety.ucdavis.edu/files/192137. pdf. Tesfaye, W., Morales, M. L., Garcıa-Parrilla, M. C., & Troncoso, A. M. (2002). Wine vinegar: technology, authenticity and quality evaluation. Trends in Food Science & Technology, 13(1), 12e21. Ubeda, C., Hidalgo, C., Torija, M. J., Mas, A., Troncoso, A. M., & Morales, M. L. (2011). Evaluation of antioxidant activity and total phenols index in persimmon vinegars produced by different processes. LWT e Food Science and Technology, 44(7), 1591e1596. Wen-Qiao, W., Xiao-Mei, X., Jin-Duo, L., Zhi-Qiang, M., Xiu-Ying, H., Xiao-Feng, Z., et al. (2005). Fungicidal activity of bamboo vinegar against several phytopathogenic fungi. Acta Phytopathologica Sinica, 35(6), 99e104. Zhishen, J., Mengcheng, T., & Jianming, W. (1999). The determination of flavonoid contents in mulberry and their scavenging effects on superoxide radicals. Food Chemistry, 64(4), 555e559.
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Please cite this article in press as: Ozturk, I., et al., Antioxidant, antimicrobial, mineral, volatile, physicochemical and microbiological characteristics of traditional home-made Turkish vinegars, LWT - Food Science and Technology (2015), http://dx.doi.org/10.1016/ j.lwt.2015.03.003