Screening of Wine Extractable Total Phenolic and Ellagitannin Contents in Revalorized Cooperage By-products: Evaluation by Micro-NIRS Technology

Depósito de investigación de la Universidad de Sevilla https://idus.us.es/ “This version of the article has been accepted for publication, after peer review (when applicable) and is subject to Springer Nature’s AM terms of use, but is not the Version of Record and does not reflect post-acceptance improvements, or any corrections. The Version of Record is available online at: http://dx.doi.org/10.1007/s11947-018-2225-z”. Manu sc r ipt Click here to view linked References Click here to download Manuscript B.Baca _ Bocanegra _ Manuscript.docx 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 Scr een ing of wi ne ext rac tab le tot al ph eno lic an d ella git an nin co nte nts in re v al o ri ze d c o o p er a g e b y p r o d u ct s: e valuation by MICRO-NIRS technology Berta Baca-Bocanegra1, J ulio Nogale s -Bueno1, Ignacio García-E s tévez2, M aría Tere s a E s cri b ano-Bailón2, J o s é M iguel Hernández-Hierro1,*and F ranci s co J o s é Heredia1 1Food Colour and Quality Laboratory, Á. Nutrición y Bromatología, F acultad de Farmacia, Univer s idad de S evilla, 41012 S evilla, S pain. 2Grupo de Inve s tigación en P olifenole s (GI P ), Unidad de Nutrición y Bromatología, Facultad de F armacia, Univer s idad de S alamanca, S alamanca, S pain. * Corre sp o nd i n g a u t h or: J o s é M iguel Hernández-Hierro Phone: +34 954556495 E-mail: jmhhierro@u s .e s 1 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 AB S TR A CT The addition of commercial oak wood a s copigment s s ource s ha s been u s ed to get high quality red wine s in the la s t year s . During the contact time, different oak compound s s uch a s p henolic compound s are relea s ed from the wood to the wine, thu s affecting it s organole p tic propertie s s uch a s aroma, color or a s tringency. Wood proce ss ing for the elaboration of barrel s generate s by-product s which al s o s eem to be intere s ting in the oenological field due to it s potential capacity of relea s e high added value compound s for wine. Determi n ing phenolic compound s of wood and it s extractability to the hydroalcoholic medium i s important in the oenological indu s try. The method propo s ed in thi s s tudy cope with thi s i ss ue in an in s itu, non-de s tructive and fa s t way. F or thi s purpo s e, a number of oak by-product s ample s s pectrally repre s entative have been s elected. Selected s pectral data have been correlated with oak wood extractable polyphenol s (extractable total phenolic content and extractable ellagitannin content) by modified partial lea s t s quare s regre ss ion ( M PL S ) u s ing a number of s pectral pre-treatment s . The obtained re s ult s are comparable with tho s e obtained u s ing bench top device s and pre s ent s the advantage of it s eventual friendly u s e out of lab. Development of applicable model s in s itu will allow a greater ver s atility and efficiency for the deci s ion-making in the winemaking proce ss on the adequacy and/or do s age of the s e byproduct s according to the requirement s of the wine. The u s e of cooperage by-product s a s s ource of copigme n t s for wine lead s to a s u s tainable and competitive cooperage indu s try, through wa s te reduction and by-product val o rization. Keywor ds : red wine, oak byproduct, phenolic compound s , ellagitannin, M ICRO-NIR S 2 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 I ntroductio n In grape berrie s , the balance between technological and phenolic parameter s i s a key factor for obtaining quality red wine s , e s pecially in term s of their color. Anthocyanin s are the main re s pon s ible for the colour of red wine s , and their interaction s with other phenolic compound s , called copigment s , allow improving the color s tabilization of aged wine s b y copigmentation or s tabilization reaction s (Boulton 2001; E s cribano-Bailón and Santo s -Buelga 2012). However, grapevine berrie s are commonly harve s ted on the ba s e of tech n ological maturity parameter s often without con s idering properly phenolic maturity. Under warm climatic condition s , it i s a u s ual pattern that grape s have high s ugar co n tent but in s ufficient level s of phenolic compound s (pigment s and copigment s ). Wine s made from the s e grape s a r e not able to form much copigmentation and a s a re s ult, t h e color s tabilization does not correctly develop and fall of color normally occurred during winemaking maturation, e s pecially when they are s ubjected to ageing proce ss (Boulton 2001; Ribéreau-Gayon et al. 2006). The addition of commercial oak wood (Del Álamo et al. 2008; Nevare s et al. 2008) or wood compound s (Balík et al. 2017) have been aimed at implementing the production of high quality red wine s in the last year s . During the contact time, different type s of oak com p ound s are relea s ed from the wood to the wine, thu s affecting it s organoleptic propertie s s uch a s aroma, color or a s tringency. Among the s e compound s , ellagitannin s , with s everal hydroxyl group s , can take part in oxidation reaction s (Viva s and Glorie s 1996; Ignacio García-E s tévez et al. 2017) that may favor the polymerization reaction s between flavanol s and between flavanol s and anthocyanin s . F urthermore, they can directly r eact with the s e type s of compound s giving ri s e to flavanol-ellagitannin s or anthocyano-ellagitanin s (Cha ss ain g et al. 2010; Ignacio García-E s tévez et al. 2013; I. García-E s tévez et al. 2013). Thu s , ellagitannin s may be involved in the change s of 3 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 colour during maturation and ageing of wine, helping to improve colour s tability and al s o protecting it again s t oxidation. Wood pr o ce ss ing for the elaboration of barrel s generate s by-product s that s eem to be an intere s ting product in the oenological field due to it s potential capacity of relea s e high added-value compound s for wine. Taking thi s into account, the u s e of barrels hoot wa s te s a s a s ource of copigment s f or wine could become a s u s tainable and profitable alternati v e to get high quality red w ine for the oenological indu s try and to di s po s al of their by p roduct s for the coopera g e indu s try. In thi s s en s e, other product s of the oenological indu s try, a s the grape pomace have been characterized for food wa s te valorization ( P á s coa et al. 2014). Predicti n g phenolic compound s of wood and it s extractability from the matrix to the hydroalcoholic medium could be important in the oenological indu s try. Accordingly, chemical technique s , s uch a s chromatography and ma ss s pectro s copy, have been u s ed in s everal s tudie s focu s ed on evaluate the oak wood phenolic extraction proce ss and how i s the extractability affected by factor s a s oak toa s ted degree or the type of aging performed (Chira and Tei ss edre 2013; I. García-E s tévez et al. 2015; J ourde s et al. 2011). The s e s tudie s achieve very accurate re s ult s but they u s ed de s tructive and time con s uming analy s e s that al s o require the u s e of chemical reagent s . It i s unde s irable when the work flow i s relatively fast. Vibrational s pectro s copy techniques repre s ent emerging analytical procedure, which are enjoying increa s ing popularity in the indu s try a s non-de s tructive, environmental friendly and rapid technique. The different field s of application of the s e technique s highlight it s enormou s ver s atility. I n the oenological s ector, the application of infrared s pectro s copy i s well known and extended. Cla ss ic NIR s pectro s copy ha s been u s ed to determine parameter s in grape s s uch total polyphenol s , extractable anthocyanin s , 4 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 concentration of s ugar s , den s ity ( K emp s et al. 2010), total anthocyanin s (Cozzolino et al. 2006 ) and the main familie s of phenolic compound s ( F errer-Gallego et al. 2011; Ferrer-Gallego et al. 2010). In previou s work s carried out in our laboratory, near infrared h yper s pectral imaging ha s been u s ed to develop s creening method s in order to mea s ure phenol s concentration in grape or grape s eed s (Hernández-Hierro et al. 2013; Nogale s -Bueno et al. 2015; Rodriguez- P ulido et al. 2014). In a further s tep, s pectro s copic method s ba s ed on near-infrared s pectro s copy have al s o s hown great potential for analy s e s of wood for oenological purpo s e s . Giordanengo et al. (2009) u s ed cla ss ic N IR s pectro s copy for the s creening of extractable polyphenol s in s tave s u s ed to manufacture barrel s oak wood. It s u s e wa s then extended for the s election of oak for oenology. S o, M ichel et al. (2013) carried out a validation of the afore s aid method by mean s o f the determination of ella g itannin content and organoleptic propertie s of wine s aging in wood barrel s cla ss ified b y NIR S . F inally NIR hyper s pectral imaging ha s been al s o u s e d for the s creening of the extractable polyphenolic compound s (extractable total phenolic content) in wood coopera g e byproduct by Baca-Bocanegra et al. (2018). Howeve r , de s pite the fa s t and effective proficiency of near-infrared s pectro s copy to predict different parameter s in wine s ector, mo s t of the s e s tudie s carried out at lab imply s ample tran s portation. To s olve thi s problem and fulfill other s ophi s ticated condition s for it s application in the indu s try, new generation of portable/handheld NIR s pectrometer s have been developed within the la s t year s . The s e s y s tem s incorporate the analytical preci s ion for chemical identification and quantitation with a s pectral re s olution equivalent to bench-top in s trument s , allowing for flexibility for in-plant analy s i s s ince the unit can be ea s ily carried and tran s ferred. In the agro-food indu s try the pote n tial of thi s technique ha s been highlighted for a ss e ss ing the quality of fruit s nonde s tructively in the field under different weather condition s (Abu Izneid et al. 2014; 5 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 Antonucci et al. 2011; Camp s et al. 2012). In the viticulture s ector, portable NIR device s have been implemented for a ss e ss ing and monitoring grape ripene ss directly in the field. P henol ripening parameter s s uch a s the concentration of anthocyanin s and polyphe n ol s have been evaluated ( G onzález-Caballero et al. 2012; Guidetti et al. 2010; Larrain et al. 2008). However, refe r ence s for the u s e of thi s technique in the analy s i s of oak wood for oenological purpo s e s have not been found. The development of applicable model s i n s itu will allow a greater ver s atility and efficiency for the real time deci s ionmaking in the vinification proce ss on the adequacy and / or do s age of the s e byproduct s dependi n g on it s s pectral feature s a n d extractability propertie s . The aim of thi s s tudy wa s to devel o p a rapid and reliable method u s ing a portable NIR s pectrometer for the s creening of extractable polyphenol s (extractable total phenolic and ellagitannin content s ) in cooperage byproduct. To our knowledge, thi s i s the fir s t time that portable micro near infrared s pectro s copy technology ha s been applied to face the aforementioned goal s . Material a nd met h o ds Sample s America n non-toa s ted oak (Que r cu s alba L.) s having s , cooperage byproduct, were u s ed for thi s s tudy. S ample s were provided by Tonelería S ala s S .L. (Bollullo s P ar del Condado, Huelva, S pain) and were collected a s previou s ly reported in Baca-Bocanegra et al. (20 1 8). Wood s tave s were s easoned under natural condition s in the open air during 24 month s approximately before being u s ed in the proce ss of making barrel s . In order to achieve r epre s entative s ample s et s, the s ample s were taken at 4 different point s in the proce ss o f making barrel s , s o four s ample s were collected at each date (A, B, C and D). Sample s belonging to A, B and C g roup s are generated by different s awing proce ss e s of the s tave s but alway s in the longit u dinal direction of the fiber s . In detail, an automatic 6 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 or manual proce ss ing of the s tave s i s the only difference between the s ample s A and B re s pectively. With re s pect to the g r oup D, the s ample s are the re s ult of a proce ss ing of the s tave s in the tran s ver s al directi o n of the fiber s . All s ampling point s are pre-molded and pre-toa s ted of the s tave s . S ample s were collected periodically, between J une of 2015 and J anuary of 2016. Two hundred s ample s were collected during the afore s aid period. U pon receipt, the s ample s were s ieved and s ubjected to the s pectral analy s i s . Wood sh aving s ample s were s creened u s ing 2 mm and 10 mm me s h s ieve s placed in tandem. Only s have s of each s ample which were retained between them were taken into account in the a ss ay. After that, wood s having s were placed in s toppered pla s tic s bag s and s tored in a dry chamber until use. Spect r al data acqui s ition. The s pectral reflectance data were collected u s ing M icroNIR P ro Lite 1700 device (VIAVI, S anta Ro s a, California, U S A), an in s trument de s igned to mea s ure diffu s e reflectance in the NIR region of the electromagnetic s pectrum. The M icroNIR owe s it s s mall s ize to the novel thin-film linearly variable filter (LV F ) u s ed a s the di s per s ive element. The LV F i s directly cou p led to a linear detector array (128-pixel uncooled InGaA s photodiode array), covering the s pectral range between 908 and 1676 nm ( s pectral re s olution of 6.2 nm). The filter coating in the LV F i s wedged in one direction and a s a re s ult of the varying film thickne ss ; the wavelength tran s mitted through the filter varie s linearly in the directi o n of the wedge. The LV F make s each pixel of the detector re s pond to a different wa v elength. Thi s ultra-compact s pectro s copic engine i s coupled w ith a tung s ten lamp s diffu s e illumination s y s tem. An image of the M icroNIR s pectrometer and M icroNIR´ s optical de s igned, adapted from VIAVI u s er manual, i s provided in Online Re s ource 1. 7 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 U s e of developed method fo r the s c r eening of ext r actable polyphenol s The method s developed in the preceding s ection were u s ed to predict the extractable content of total phenol s and total ellagitannin s in the whole of wood s et. The re s ult s s how a s ub s tantial variability in the reference parameter s within each group of s ample s (Fig.3). The variability of oak w o od extractive s ha s been demon s trated by different author s (Dou ss ot et al. 2002; S nak k er s et al. 2000). P henol s content ha s been found to vary even from the s ame provenance, the s ame tree and the s ame piece of timber ( M a ss on et al. 1995). Zahri et al. (2008) reported that total phenol s content in wood varied according to the di s tance f r om the oak tree pith. Thi s ob s ervation confirmed previou s s tudie s which determined that the concentration of s oluble tannin s in oak tree decrea s e with age tree. A large amount of tannin s and phenolic monomer s in wood can form polymer s and copolymer s with cell-wall component s with time and then their s olubility would be reduced ( P eng et al. 1991; Viriot et al. 1994). In addition, an inter group variability of oak wood extractive s ha s been found. S ample s generate d by a proce ss ed of the s tave s in the longitudinal direction of the fiber s hold higher extractable polyphenol s content than tho s e obtained after proce ss ing s tave s in the tran s ver s al direction. On the ba s i s of the s e re s ult s , it can be a ss umed that the s tructure of the s ample s could be involved in the s e extractable content difference s . Concl us io n The M PL S model performed confirmed that s pectral analy s i s developed from M icroNIR i s a promi s ing techniq u e for in s itu routine a ss e ss ment of the extractable polyphe n olic compound s in wood cooperage byproduct. Thi s methodology wa s able to predict, in s itu, the extractable polyphenolic content of a s ample ba s ed on s pectral feature s a s the predictor variables. The obtained re s ult s are comparable with tho s e obtained u s ing other bench-top device s and pre s ent s the advantage of it s eventual 14 friendly u s e out of lab. The u s e of a portable micro s pectrometer implie s very 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 intere s ting feature s , s ince at a lower co s t objective and in s tantaneou s s pectro s copic mea s urement s can be carried out i n s itu with the advantage of it s portability, due to it s s mall s ize. Development of applica b le model s in s itu will al s o allow a greater ver s atility and efficiency for the deci s ion-making in the winemaking proce ss on the adequacy and / or do s age of the s e byproduct s according to the requirement s of the wine. The u s e of cooperage by-product as s ource of copigment s for wine i s a s u s tainable and profitable alternative to get high quality red wine for the oenological indu s try and to di s po s al of their byproduct s for the cooperage indu s try. The variability in oak wood extractive s within the s ame provenance ha s been ob s erved. M oreover, extractable polyphenol s content difference s between wood s ample s generate d by longitudinal and tran s ver s al cutting of the fiber s have been al s o found. Nonethele ss , a comprehen s ive s tudy s hould be made in order to obtain more information about how wood s tructure and / or morphology change s within different level s of phenolic compound s extractability. Ac k nowle d gme n t s The S pani s h M ini s terio de Economía y Competitividad i s thanked for project AGL201 7 -84793-C2. Univer s idad de S evilla i s thanked for B. Baca-Bocanegra predoctoral grant (V PP I-II.2) and J . Nogale s -Bueno po s tdoctoral grant (V PP I-II.4). I. García-E s tévez thank s F EDER-Interreg E s pana- P ortugal P rogramme ( P roject ref. 0377_IBER P HENOL_6_E) for hi s po s tdoctoral grant. The author s thank the technical s taff of Biology S ervice [ S ervicios Generale s de Inve s tigación ( S GI), Univer s idad de Sevilla]. They al s o thank Tonele r ía S ala s S .L. (Bollulo s P ar del Condado, Huelva, Spain) f o r s upplying the cooperage byproduct s ample s . 15 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 Conflict of In tere s t The author s declare that they have no conflict of intere s t. 16 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 Refere n ce s Abu Izneid, B., F adhel, M . I., Al- K harazi, T., Ali, M ., & M iloud, S . (2014). De s ign and develop a nonde s tructive infrared s pectro s copy in s trument for a ss e ss ment of mango ( M angifera indica) quality. 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Ame r ican Jou r nal of Enology and Viticultu r e, 47(1), 103-107 Zahri, S . , M oubarik, A., Charrier, F., Chaix, G., Baillere s , H., Nepveu, G., et al. (2008). Q uantitative a ss e ss ment of total phenol content s of European oak (Quercu s 22 petraea and Quercu s robur ) by diffu s e reflectance NIR s pectro s copy on s olid 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 w ood s urface s . Hol z fo rs chu n g, 62(6), 679-687 23 T able 2 Click here to download Table Table 2.doc Ta b le 2. Calibration s tati s tical de s criptor s for the model s developed in the NIR zone clo s e to 908 - 1676 nm. Reference P arameter S pectral pretreatment T outlier s P L S factor s Na E s t. M in S Db Est. Max S ECc ( mg g-1 wood ) R S Qd S ECVe S E P f ( mg g-1 wood ) EPCg EECh Ca s talagin Ve s calagin Gradinin Roburin E S NV 2,5,5,1 0 S tandard MS C 1,5,5,1 0 S tandard MS C 1,5,5,1 0 None 1,5,5,1 1 Detrend 2,5,5,1 2 S tandard MS C 1,5,5,1 0 4 18 0 14.92 68.23 2 18 0 4.66 19.04 2 18 0 1.99 8.00 2 17 0 1.44 6.04 3 16 0 0.55 2.34 2 18 0 0.30 1.16 2.07 0.98 1.30 0.92 0.66 0.90 0.36 0.94 0.09 0.98 0.08 0.91 3.83 5.86 1.76 2.07 0.85 0.90 0.53 0.71 0.13 0.16 0.11 0.13 a N: number of samples (calibration set); b SD: standard deviation; c SEC: standard error of calibration; d RSQ: coef fi cient of determination (calibration set); e SECV: standard error of cross-validation (7 cross-validation groups); f SEP: standard error of prediction (external validation); g EPC: extractable total phenolic content (mg g -1 of wood, expressed as gallic acid equivalents); h EEC: extractable total ellagitannin content (mg g -1 of wood, expressed as sum of individual ellagitannins) T able 3 Click here to download Table Table 3.doc Table 3. M ain s tati s tical de s criptors for reference parameter s in validation s et. Set Validatione Reference P arameter s E P C c EECd Ca s talagin Ve s calagin Gradinin Roburin E Na M aximum M ean 15 56.54 32.03 14 14.44 7.50 13 5.50 2.91 13 4.85 2.82 10 1.57 0.83 12 0.78 0.43 M inimum S D b 11.26 17.7 3 1.40 4.49 0.51 1.73 0.67 1.53 0.25 0.48 0.09 0.26 a N: number of samples; b SD: Standard deviation; c EPC: extractable total phenolic content (mg g -1 of wood, expressed as gallic acid equivalents); d EEC: extractable total ellagitannin content (mg g -1 of wood, expressed as sum of individual ellagitannins); e Validation: statistical descriptors for the reference parameters of the samples allocated in the validation set after remove the samples that presented reference values outside the applicability of the calibration models.