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International Journal of Food Properties


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Aroma Characterization of Virgin Olive Oil from Two Turkish Olive Varieties by SPME/GC/MS
Arin Kaftan & Y. Elmaci
a a b

Department of Food Engineering, Engineering Faculty , Ondokuz Mayis University , Samsun, Turkey
b

Department of Food Engineering, Engineering Faculty , Ege University , Bornova, zmir, Turkey Published online: 16 Aug 2011.

To cite this article: Arin Kaftan & Y. Elmaci (2011) Aroma Characterization of Virgin Olive Oil from Two Turkish Olive Varieties by SPME/GC/MS, International Journal of Food Properties, 14:5, 1160-1169, DOI: 10.1080/10942910903453371 To link to this article: http://dx.doi.org/10.1080/10942910903453371

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International Journal of Food Properties, 14:11601169, 2011 Copyright Taylor & Francis Group, LLC ISSN: 1094-2912 print / 1532-2386 online DOI: 10.1080/10942910903453371

AROMA CHARACTERIZATION OF VIRGIN OLIVE OIL FROM TWO TURKISH OLIVE VARIETIES BY SPME/GC/MS Arin Kaftan1 and Y. Elmaci2
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Department of Food Engineering, Engineering Faculty, Ondokuz Mayis University, Samsun, Turkey 2 Department of Food Engineering, Engineering Faculty, Ege University, Bornova, Izmir, Turkey
Virgin olive oil samples of Ayvalik and Memecik olive varieties from the Aegean region of Turkey were evaluated for their acidity, peroxide, and color values, and the volatile compounds were investigated by using solid phasemicro extraction/gas chromatography/mass spectroscopy (SPME/GC/MS). The acidity of all the samples were found to be between 0.35 1.0% oleic acid and peroxide values of the oil samples ranged between 1452 meq/O2 kg of oil. The Y, R, and B values of the samples were between 7073.60, 1.304.70, and 03.60, respectively. The SPME/GC/MS results have shown that hexanal (5.6615.48%), 3 hexen 1 ol (3.1212.1%), cis 3 hexenol (6.1513.49%), and 9 octadecenoic acid (5.99-16.01%) were observed as the characteristic volatiles for Ayvalik variety, while trans 2 hexanal (8.65 38.09%) and 3 hexen 1 ol acetate (0.977.43%) were observed as the characteristic volatiles for Memecik variety. Keywords: Virgin olive oil, Virgin olive oil aroma, Virgin olive oil volatiles, Peroxide value, Color, SPME/GC/MS.
1

INTRODUCTION Olive oil obtained from fresh fruit of the olive tree (Olea europeae) is appreciated for its health benecial properties and unique avor. It is a complex food product containing volatile compounds that contribute to its avor distinguishing it from other edible oils. These volatile compounds that are responsible for the avor of olive oil, play a signicant role in consumer choice.[15] The volatile composition of olive oil is effected by the agronomic effects, such as cultivar, ripeness of the fruit, enzymes, soil type, climatic conditions, geographic origin, and technological aspects.[69] When chemical compounds and sensory attributes are analyzed in virgin olive oil, the differences between them are basically due to olive variety[10] or region-specic; Freihat et al.[11] reported that oil produced from the higher altitude had a higher ratio of unsaturated to saturated fatty acid compared to oil produced at the lower altitude. Several studies have been conducted to isolate, identify, and quantify the volatile components of virgin olive oil.[12] The growing interest in virgin olive oil in international
Received 15 July 2009; accepted 30 October 2009. Address correspondence to Arin Kaftan, Technical Programs, Data Kazm Ylmaz Vocational School, Mu gla University, 48900, Data, Mu gla, Turkey. E-mail: akaftan@mu.edu.tr

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markets leads the researchers to studies on the qualitative,[13,14] nutritional,[15,16] and organoleptic[10,1719] characteristics of these products. The virgin olive oils produced in different geographical regions of Turkey were compared for some common physicochemical indices and sensory properties to determine the geographic difference among the production regions.[20] Many researches have been conducted to classify virgin olive oils according to origin by utilizing data regarding their volatile composition.[2123] Sensory descriptive analysis studies to cluster virgin olive oils into groups of different geographic origin[10,17,18,21] were also studied. Multivariate statistical methods were used for the classication of the sensory properties of olive oils regarding varieties.[21,24,25] There is little information available in the literature on the volatile composition of olive oils from Turkey. Thus, the aim of the present study was to compare different Turkish virgin olive oil samples by the characterization of their volatile compounds. A total of 30 Turkish virgin olive oil samples from Ayvalik and Memecik varieties grown in the Aegean region of Turkey (Ayvalik and Memecik varieties) were evaluated by SPME/GC/MS for volatile compounds; the other quality parameters determined were acidity, peroxide value, and color. MATERIALS AND METHODS Olive Oil Samples A total of 30, 20052006 year production virgin olive oils from 2 olive varieties (Ayvalik11 samples, Memecik19 samples) grown in Turkey (Ayvalik11 samples, Memecik19 samples) were studied. The origin and variety of the olives used in production of olive oil samples are given in Table 1. The samples were supplied from local producers as virgin olive oil and were kept in dark rooms at room temperature prior to analysis.
Table 1 Origin and the variety of olives used in production of olive oil samples. Sample 1 2 3 4 5 6 7 8 9 10 11 Origin Altinoluk Kkkuyu Edremit Burhaniye Ayvalik Havran Gomec Altinova Zeytindag Ezine Menemen Variety Ayvalik Ayvalik Ayvalik Ayvalik Ayvalik Ayvalik Ayvalik Ayvalik Ayvalik Ayvalik Ayvalik Sample 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 Origin Bayindir Tepekoy Cine Erbeyli I Selcuk Odemis Dalaman Akhisar Bozdogan Kosk Soke Ku sadasi Harsunlu Tire Aydin Kocarli Germencik Ortaklar Erbeyli II Variety Memecik Memecik Memecik Memecik Memecik Memecik Memecik Memecik Memecik Memecik Memecik Memecik Memecik Memecik Memecik Memecik Memecik Memecik Memecik

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Determination of Acidity, Peroxide Value, and Color Indices Acidity analysis[26] and peroxide value (PV) analysis[27] were carried out according to the American Oil Chemists Society (AOCS) method. The results of acidity analysis are given as oleic acid (%) and the results of PV analysis were expressed as milliequivalents of active oxygen per kilogram of oil (meq O2 /kg sample). Color measurement was carried out by using Lovibond PFX 880 Automatic Tintometer (The Tintometer Ltd., Salisbury, UK) and Y (yellowness), R (redness), and B (blueness) values were determined. SPME Extraction

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The volatile compounds were extracted in duplicate by using the SPME technique.[28] Polydimethylsiloxane/divinylbenzene/carboxene (PDMS/DVB/CAR) 50/ 30 m phase thickness ber (Supelco, Bellefonte, PA, USA) was used. A 3 0.01 g of virgin olive oil sample was weighed into a 10-ml vial and sealed. Before sampling, the vials were allowed to equilibrate at 23 C 2 for 2 h. After equilibration, SPME ber was exposed for 30 min to the headspace of the vial and the volatiles were then adsorbed on the ber. Sampling was performed at 40 C. The ber was introduced into the injection port and kept for 3 min for the desorption of volatiles. GC/MS Analysis Separation of the volatiles was performed by using a Hewlett-Packard HP-6890 Gas Chromatograph (Hewlett-Packard, Philadelphia, PA, USA) equipped with a fused silica capillary column HP-5 (Hewlett-Packard) 30 m 0.25 mm ID and 0.25 m coating thickness. The column temperature was programmed as 40 C for 3 min, 8 C/min to 200 C and held for 20 min, then 20 C/min to 280 C[28] with helium as the carrier gas at 0.6 ml/min ow rate. The injector and detector temperatures were set at 270 and 280 C, respectively. Identication of the volatiles was carried out by the same conditions mentioned above by using gas chromatograph coupled to a Hewlett-Packard HP-5973 Mass Selective Detector (Hewlett-Packard) (quadropole). The electron voltage was 70 Ev and mass range was 35350 atomic mass units. Statistical Analysis GC/MS and acidity, peroxide value, and color indices analysis were performed in duplicate for each sample. All data were subjected to analysis of variance (ANOVA) and Duncan test to determine signicant differences (p < 0.05) among samples by using the evaluation version of SPSS 15.0 (Lead Tech. Inc., USA). Cluster Analysis and Principle Component Analysis (PCA) were performed by considering the volatiles of olive oil samples. These processings were performed with the evaluation version of XLSTAT, 2009 software (XLSTAT 11.3, Addinsoft, USA). RESULTS AND DISCUSSION Acidity, Peroxide Value, and Color Indices The acidity, peroxide value, and color indices of the olive oil samples are given in Table 2. The acidity of all the samples were found to be between 0.351.0% oleic acid and

VIRGIN OLIVE OIL FROM TURKISH OLIVE VARIETIES Table 2 Acidity, peroxide value, and color indices of virgin olive oil samples. Ayvalik PV (meq O2 kg1 ) 20 20 15 20 14 18 18 23 49 49 34 Acidity (oleic acid %) 0.90 0.90 0.60 0.60 1.00 0.80 0.80 0.65 0.63 0.72 0.86 Color indices Y 73.04 70.00 70.00 70.00 71.90 71.30 70.30 70.90 70.00 70.00 70.00 R 2.40 2.30 3.10 2.80 4.30 3.60 2.30 2.40 3.00 2.20 3.10 B 3.40 0 0 0 1.90 1.30 0.30 0.90 0 0 0 PV (meq Sample O2 kg1 ) 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 20 20 14 20 20 18 20 28 24 18 26 20 17 14 17 18 17 52 52 Memecik Acidity (oleic acid %) 0.60 0.60 1.00 0.90 1.00 1.00 0.80 0.80 0.90 0.60 0.80 0.80 0.70 0.90 0.80 0.90 0.90 0.68 0.35

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Color indices Y 70.00 73.60 72.90 70.70 72.90 70.40 71.70 73.30 71.30 70.00 72.90 70.00 71.50 72.90 70.00 70.50 70.80 72.30 70.00 R 1.30 3.70 4.70 2.40 3.40 3.70 2.90 3.60 3.40 2.80 3.30 3.50 3.80 4.20 2.20 2.50 2.50 3.10 3.10 B 0 3.60 2.90 0.70 2.90 0.40 1.70 3.30 1.30 0 2.90 0 1.50 2.90 0 0.50 0.80 2.30 0

Sample 1 2 3 4 5 6 7 8 9 10 11

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PV: Peroxide value; Y: yellowness; R: redness; B: blueness.

fell within the accepted value (2.0%) for virgin olive oils.[29] The origin and variety of the olive oils had no signicant inuence on acidity; this was also mentioned in a study conducted on Tunusian virgin olive oils.[30] Peroxide values of the oil samples ranged from 14 to 52 meq/O2 kg of oil. The upper limit of 20 meq/O2 kg of oil for peroxide value was established for virgin olive oils.[29] The oils studied in this research were supplied as virgin olive oils; however, four samples (8, 9, 10, 11) from Ayvalik and ve samples (19, 20, 22, 29, 30) from Memecik variety were found to have signicantly high peroxide values. In a study conducted on olive oils of Turkey, 5 out of 15 virgin olive oils from different regions of Turkey were found to be above the dened limit for the PV.[20] The Y, R, and B values of the samples were in the range of 70 to 73.60, 1.30 to 4.70, and 0 to 3.60, respectively. Measurement of color is typically used to provide information on carotene and chlorophyll content of olive oil. R value is associated with -carotene level, whereas Y and B values are associated with chlorophyll level.[31] The ANOVA has shown that olive variety had no signicant (p < 0.05) effect on parameters, such as acidity, peroxide value, and color indices. As stated by Ranalli and Angerosa[32] and Kiritsakis et al.,[33] these parameters are basically affected by factors, such as improper handling and storage of olives. SPME/GC/MS Analysis SPME analysis revealed a total of 21 volatiles in Ayvalik and 22 volatiles in Memecik variety (Tables 3 and 4). A number of seven substances (trans-2-hexanal, 3 hexene 1 ol acetate, 3 ethyl 1,5 octadiene, nonanal, 9 octadecenoic acid, -copaene, -farnesene) were

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Table 3 Volatiles identied in virgin olive oils of the Ayvalik variety by SPME/GC/MS. Volatiles (% area) Pentanal Hexanal 3 Hexen-1 ol 2 Hexenal Trans 2 hexanal 2,4 Hexadienal Benzaldehyde 3 Hexen-1 ol acetate 3 Ethyl 1,5 octadiene Trans -ocimene Limonene Nonanal 9 Octadecenoic acid -Zingiberene -Copaene 2 Heptanal -Bergamote -Farnesene Cis 3 hexenol -Sesquifellandrene Heptadecene RT A1 A2 A3 A4 A5 A6 A7 A8 A9 A10 A11

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3.79 0.12 0.09 0.13 0.17 0.09 2.66 0.11 0.17 0.06 0.05 1.45 6.20 10.02 13.25 8.43 7.35 10.15 5.66 9.32 5.67 10.93 15.48 8.05 7.30 9.45 12.1 8.30 8.78 9.18 3.12 10.52 4.18 8.89 7.71 7.69 7.55 1.34 0.62 1.32 1.78 1.66 1.96 1.60 1.19 11.58 7.34 4.27 7.74 11.24 7.84 4.80 4.02 2.93 3.74 0.18 0.46 0.15 0.38 0.41 9.32 0.94 0.13 9.72 0.83 1.94 10.55 1.93 0.97 1.99 1.34 0.62 1.32 1.78 0.38 0.41 0.46 0.15 10.87 4.88 4.14 3.97 3.53 3.81 7.94 5.81 0.30 2.34 3.45 0.65 11.43 0.88 0.67 1.44 1.20 0.67 1.27 0.87 11.76 0.14 13.32 1.22 1.51 0.57 0.55 0.98 0.96 1.07 0.93 0.67 0.78 0.87 14.60 10.56 7.96 16.01 12.20 14.43 7.05 14.53 5.99 6.77 7.50 6.67 17.79 0.25 0.42 0.47 18.49 0.06 0.30 0.38 0.42 0.36 0.08 0.56 0.10 0.34 0.21 0.77 19.25 0.50 19.75 0.16 0.37 20.52 1.64 2.01 2.68 2.67 1.77 0.10 1.62 0.09 1.59 2.12 0.98 20.53 9.46 11.64 13.49 9.79 12.61 12.42 8.72 10.11 9.27 6.15 7.48 20.94 0.60 0.76 0.80 0.66 1.02 25.11 0.05 1.13 0.51 1.37

RT: retention time; A1A11: Ayvalik variety.

detected as common volatiles in both varieties. Considering the volatiles of each variety separately, hexanal, 3 hexen 1 ol, cis 3 hexenol, and 9 octadecenoic acid were relevant for Ayvalik variety, whereas, trans 2 hexanal and 3 hexen 1 ol acetate were determined relevant for Memecik variety. Pentanal, hexanal, 3 hexen 1 ol, 2 hexenal, and cis 3 hexenol were determined only in Ayvalik oils, whereas 2, 4 hexadienal, trans -ocimene, limonene, 4, 8 dimethyl 1, 3, 7 nonatriene, 2 decenal, 2 heptanal, and -muralene were determined in Memecik oils. A comparison of the acidity, peroxide value, and color indices of the olive oil samples with the SPME/GC/MS results is difcult. Since no signicant (p < 0.05) effect of olive variety was detected on parameters, such as acidity, peroxide value, and color indices, these parameters cannot be the determinants of the volatile compounds. Haddada et al.[30] and Baccouri et al.[34] stated that chemical composition of olive oils had no sgnicant inuence on volatile composition of olive oils. The cluster diagram obtained with volatiles of olive oil samples is shown on Fig. 1. Three main clusters were formed: cluster 1 was represented by Ayvalik variety (A1A11), cluster 2 was represented by Memecik variety olive oil samples from M12 to M28, while Memecik variety olive oil samples M29 and M30 formed cluster 3. According to PCA results, two principle components were found to explain 41.18% and 12.29% of total variation and by using the two components, a bi-plot diagram was generated (Fig. 2). Both cluster analysis and PCA results indicated a similar grouping and showed the difference between the samples. The rst group is composed of Ayvalik variety (A1A11) and the second group is characterized by Memecik variety (M12M28). Moreover, the third group is composed of only two samples from Memecik variety (M29 and M30). It can be seen from the gure that there is a great difference in terms of volatile

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Table 4 Volatiles identied in virgin olive oils of the Memecik variety by SPME/GC/MS. M14 22.56 1.17 6.09 2.07 4.06 7.53 3.92 0.51 1.23 1.62 5.32 0.33 2.14 0.59 0.47 1.77 0.30 0.27 0.62 2.89 5.14 0.90 2.18 1.25 0.15 0.99 1.17 1.35 1.36 0.42 2.23 0.77 0.42 1.09 0.96 3.45 0.40 2.24 0.60 0.40 0.94 1.44 7.34 0.26 2.21 0.75 0.26 0.78 3.29 0.20 0.96 3.93 0.63 1.00 2.44 0.26 0.74 3.81 0.36 0.46 3.36 0.34 0.97 0.30 1.62 4.86 0.57 1.93 0.57 0.72 0.78 1.51 0.43 0.63 1.03 9.27 0.56 1.95 0.34 0.13 0.13 0.86 5.92 0.41 0.27 1.37 3.98 0.41 2.07 0.38 0.45 1.26 0.49 1.25 6.64 0.54 2.48 0.18 0.38 1.17 0.16 1.52 9.98 0.66 2.62 0.35 0.19 0.19 1.03 0.79 2.39 8.52 0.76 17.64 0.58 0.19 0.19 1.86 0.35 1.24 1.69 0.20 2.15 0.42 1.01 1.22 4.27 0.54 0.98 3.00 0.67 0.97 6.13 0.25 1.64 3.52 0.21 0.91 5.64 1.22 1.24 1.31 6.15 0.63 2.16 0.63 0.46 1.43 18.55 0.51 3.08 2.48 28.24 1.05 0.72 1.02 3.30 1.40 2.03 31.07 1.64 3.67 1.44 2.08 29.28 1.47 0.31 2.84 2.18 17.56 0.99 27.81 1.29 1.62 1.72 3.21 2.04 35.07 0.55 1.07 1.04 37.36 1.37 3.62 1.55 2.59 35.16 1.66 4.15 5.76 37.64 1.99 1.00 1.43 3.40 2.20 26.84 1.23 2.57 1.65 1.53 25.56 1.83 0.63 3.58 1.71 35.07 0.55 1.36 1.04 3.93 0.63 1.00 1.35 7.48 0.57 2.23 0.83 0.15 1.09 M15 M16 M17 M18 M19 M20 M21 M22 M23 M24 M25 M26 M27 M28 32.39 1.79 3.30 4.79 0.97 0.29 0.83 1.16 2.15 0.34 2.87 0.72 0.38 1.00 M29 9.71 28.09 1.11 3.07 2.28 1.15 1.05 2.69 2.18 0.48 3.73 2.44 0.54 1.24 M30 8.65 3.08 10.27 0.97 2.75 0.95 17.98 1.64 1.47 2.23 0.39 7.82 0.93 0.67 2.60

Volatiles (% area)

RT

M12

M13

7.74 9.32 9.72 10.50 10.55 10.68 10.87

37.97 1.66 3.92 0.88

38.09 1.96 0.80 0.80 7.43 2.86

Trans 2 hexanal 2,4 Hexadienal Benzaldehyde Octanal 3 Hexen 1 ol acetate Hexyl acetate 3 Ethyl 1,5 octadiene Trans -ocimene Limonene 4,8 Dimethyl 1,3,7 nonatriene Allo ocimene Nonanal 9 Octadecenoic acid 2 Decenal -Copaene 2 Heptanal Eromophylene -Muralene -Farnesene -Sesquifellandrene Aromadendren

11.43 11.76 12.81

1.87 0.46 0.97

1.26 0.15 0.33

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13.09 13.32 14.60 15.62 18.49 19.25 19.48 19.64 20.52 20.94 20.94

0.72 0.51 0.33 1.99 0.38 0.74 1.15

0.44 7.46 0.39 2.39 0.25 0.59 0.97

RT: retention time; M12M30: Memecik variety.

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Dendrogram 8057 7057 6057 Dissimilarity 5057 4057 3057

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2057 1057 C2 M12M28 C1 A1A11 C3 M29M30

Figure 1 Dendogram obtained from the cluster analysis of Ayvalik and Memecik variety olive oils.
Biplot (axes F1 and F2: 53,47 %)

15 M30 M29 10 limonene octanal


F2 (12,29 %)

alpha farnesene 5 2-heptanal alpha copaene 2,4 hexadienal nonanal 4,8 dimethyl 1,3,7 nonatriene M20 alpha muralene M19 M17 M18 M16 2 decenal M26 M21M27M28 M24 M25 M12 M14 trans-beta ocimen M22 M23 hexyl acetate M15 M13 3 hexen 1 ol asetate trans-2 hexanal 10 5 0
F1 (41,18 %)

A2 A9 3 hexen 1ol alpha zingiberene hexanal A4 2 hexenal cis 3 hexenol A10 A5 3 ethyl 1,5 octadiene A3 A7 9 octadecenoic acid A1 A11 A8 pentanal A6

5 15

10

15

Figure 2 PCA scatterplot of Ayvalik and Memecik variety olive oils (color gure available online).

compounds characterizing the composition of these three groups. Hexanal, 3 hexen 1 ol, cis 3 hexenol, and 9 octadecenoic acid were observed as the corresponding volatiles for Ayvalik variety, while trans 2 hexanal and 3 hexen 1 ol acetate were determined as the corresponding volatiles for Memecik variety. M29 and M30 samples, which formed cluster 3, were characterized by a high amount of limonene and octanal. In a study conducted by Cavalli et al.,[5] trans 2 hexanal and hexanal were detected as the major volatiles in French Cailletier olive oil samples. In another study on Tunusian virgin olive oils,[30] trans 2 hexanal was found to be the major volatile followed by hexanal. Angerosa et al.[6] stated that

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cultivar inuence can be evidenced by the different amounts of C6 compounds, namely: hexanal, hexan 1 ol, hexyl acetate, trans 2 hexanal, cis 3 hexen 1 ol, 3 hexen 1 ol acetate. In a study conducted by Baccouri et al.,[34] hexanol, 3 hexen 1 ol, 2 hexenal, and 2 hexen 1 ol have been reported as strongly dependent on cultivar effect. CONCLUSION Our results demonstrated that for acidity, peroxide value, and color indices, it is observed that variety does not have any effect on these chemical parameters. However, determination of volatiles of olive oils allowed the detection of signicant differences in terms of volatile compounds characterizing Ayvalik and Memecik varieties. The results indicate that hexanal, 3 hexen 1 ol, cis 3 hexenol, and 9 octadecenoic acid were characteristic for Ayvalik variety, whereas trans 2 hexanal and 3 hexen 1 ol acetate were characteristic for Memecik variety. However, considering the inuence of seasonal changes these results must be conrmed by the study of a larger number of olive oil samples from various years of production to support the results obtained by this rst screening. ACKNOWLEDGMENTS
The authors wish to acknowledge the support of E.U. Research Fund for completion of this research.

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