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Article

Polyphenols in the Waste Water Produced during the Hydrodistillation of ‘Narcea Roses’ Cultivated in the Cibea River Valley (Northern Spain)

by
Susana Boso
1,
Pilar Gago
1,
José-Luis Santiago
1,
Inmaculada Álvarez-Acero
2,
Miguel-Angel Martinez Bartolomé
2 and
María-Carmen Martínez
1,*
1
Group of Viticulture, Olive and Rose (VIOR), Misión Biológica de Galicia, Consejo Superior de Investigaciones Científicas (CSIC), Carballeira 8, 36143 Salcedo, Spain
2
Service Unit for Analytical, Instrumental and Microbiological Techniques (USTA) of Instituto de Ciencia y Tecnología de Alimentos y Nutrición (ICTAN-CSIC), C/José Antonio Novais, 10, 28040 Madrid, Spain
*
Author to whom correspondence should be addressed.
Horticulturae 2022, 8(5), 376; https://doi.org/10.3390/horticulturae8050376
Submission received: 28 March 2022 / Revised: 20 April 2022 / Accepted: 22 April 2022 / Published: 25 April 2022
(This article belongs to the Section Medicinals, Herbs, and Specialty Crops)
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Versions Notes

Abstract

:
The ‘Narcea rose’ is a recently described yet ancient rose cultivar of interest to the perfume industry. Given its excellent adaptation to the conditions of the place where it was rediscovered, the possibilities of its horticultural/industrial production have been under examination for some time. The hydrodistillation process produces a red-to-brownish mixture of water and rose petals that could contain compounds that could be used in other industrial procedures. Their recovery and further utilization would reduce disposal costs and improve the sustainability of relevant industries. This work reports the quantification, by high-performance liquid chromatography (HPLC–MS) and quadrupole time of flight Q-TOF analyses, of the polyphenol content in the waste water. This waste was found to contain high concentrations of quercetin, gallic acid and ellagic acid, as well as smaller concentrations of kaempferol and its derivatives, all of which can influence plant, human and animal health.

Graphical Abstract

1. Introduction

The ‘Narcea rose’ is an ancient rose cultivar that was recently rediscovered in a private garden in the Cibea River Valley (situated in Cangas del Narcea, among the Cantabrian Mountains of Asturias, northern Spain) [1]. Botanical and genetic studies have shown it to be a natural hybrid of Rosa gallica and Rosa centifolia—and indeed it has characteristics of both. However, it has red-purple petals [1], quite different to the light-pink-coloured petals of the parental species. The Narcea rose is very well adapted to the mountainous area in which it was found, where winters are very cold and solar radiation is variable depending on altitude and orography. It blooms most intensely and with maximum scent production in May. Interestingly, it appears to be little affected by disease and shows good horticultural behaviour.
In recent years, the perfume industry has demonstrated growing interest in the use of natural raw materials from sustainably produced crops. In addition, there is much interest in their environmentally friendly transformation and production with zero waste, or at least waste that can be recycled. In this regard, several papers have been published showing the possible health-related [2,3] and animal feed [4] uses of the wastes produced during the hydrodistillation of R. damascena.
The intensity and persistence of the aroma of rose essential oils is influenced by different factors, including rose variety [5,6], the moment of petal collection, soil type and the cultivation practices to which the plants were subject [7,8,9,10]. Similarly, the polyphenol and antioxidant contents of rose petals are strongly influenced by environmental, geographic and edaphic factors [3,11].
The perfume industry uses two extraction techniques for rose materials: solvent extraction and hydrodistillation. Solvent extraction gives rise to a solid known as ‘rose concrete’ that, after treatment with alcohol to eliminate paraffins and other waxes, generates an intensely scented liquid known as ‘absolute’. The waste generated in this process consists of left-over rose petals impregnated with solvent but which still show their characteristic colour (red, pink or purple, etc.). Solvent extraction is much quicker and more efficient, but it requires more complex installations for the safe storage of the solvents needed. Further, it produces more contaminating wastes that require proper disposal. Fortunately, solvent extraction has been much improved in recent years, and to a large extent the solvents used can be recovered and reused. Hydrodistillation, in contrast, uses no chemical contaminants, although it does require a greater energy input. After 5–7 h of treatment, which provides essential oils and rose water, a red-to-brownish waste (depending on the rose variety used) is generated, composed only of water and petals. During hydrodistillation, volatile aromatic compounds are extracted in the rising vapour of water and lipid droplets. Condensation in the still’s serpentine coil produces two fractions: essential oil and rose water. The polyphenols in the petals, given their water-soluble nature, remain in the waste water left at the end of the process. In fact, some of these give the water its colour.
The leaves, flowers and fruits of certain members of Rosaceae have a long medicinal and culinary history [3,12]. The hips of some species have been used for the treatment of colds and influenza, inflammation and chronic pain [13], and in cosmetic preparations for the skin [14,15]. Many of the medicinal properties of the genus Rosa lie in the high concentrations of polyphenols found in different tissues and organs [16,17]. Studies on the composition of Rosa rose hips [13,14,18,19] have shown that these organs are rich in bioactive compounds, such as ascorbic acid, antioxidants and polyphenols such as anthocyanins and flavonols. Rosa leaves [20,21] and preparations made from the petals [3,17,22,23,24] also contain polyphenols, especially anthocyanins (cyanidins and peonidins) and flavonoids (kaempferol, quercetin, procyanidins and proanthocyanidins). Göktürk-Baydar and Baydar [25], who analysed the extracts of R. damascena green leaves and flowers (fresh and withered), reported catechin and epicatechin to be the most abundant flavonols in the leaves, and gallic acid (phenolic acid) to be the most abundant in the petals. The polyphenol content of R. gallica petals explains the historic medicinal use of this species [20,23,24,26,27].
Polyphenols are secondary plant metabolites with a wide range of structures and functions which possess at least one aromatic ring to which is bound one or more hydroxyl groups. They are classed (and subclassed) depending on the number of phenolic rings they possess and the structural elements these contain. Some are physiologically indispensable [28]; others have roles in the response to light or water stimulus and stress, etc. [29]. Since polyphenols accumulate in certain plant tissues, they may act as micronutrients in the human diet, while their biochemical activities, for example, as antioxidants, anti-inflammatory agents, anticancer compounds and antimutagenic agents [18,24,30], have an influence on human health [31,32,33,34].
Studies have shown the beneficial effects of flavonols in animal and plant health. The procyanidins, in particular, have been ascribed antifungal, antimicrobial and bactericidal properties. It is believed that their bactericidal effect is greater against Gram-positive bacteria, since the external membrane of these organisms lies close to the cytoplasmic membrane [35,36]. Different authors [37,38,39] have indicated that they can be used as feed additives for ruminants; flavonoids improve the production of volatile fatty acids and reduce concentrations of ammonia and methane in the rumen. They also have a positive effect on fermentation (antibiotic effect) and acidosis in the rumen, as well as on bloating.
The aim of the present work was to determine whether certain polyphenols of interest are present in the waste water produced during the hydrodistillation of Narcea roses and thereby provide further evidence of the potential industrial uses of this variety.

2. Materials and Methods

2.1. Plant Material and Cultivation Conditions

The plant material used in this work was obtained from red-purple flowers from different Narcea rose plants (Figure 1), all cultivated in the same plot (altitude 535 m) in the Cibea River Valley (mean annual temperature 12.39 °C, mean absolute maximum temperature 28.21 °C, mean absolute minimum temperature 1.32 °C, annual rainfall 1217.15 mm). The soil in this plot is a highly acidic loam with a moderate organic matter content and with high available phosphate, medium assimilable potassium and mid-range exchangeable magnesium values. Its ion exchange complex ratio is Ca:Mg:K = 70:14:16.

2.2. Collection and Transport of Rose Flowers

Complete rose flowers (on 5 cm stems) were cut on 13 May 2020 from their bushes early in the morning. The stems were stuck in water-soaked phenolic floral foam and the samples were placed in a plastic-lined polystyrene box with a sealable lid. On the evening of the same day, the samples were transported by car to the laboratory, where the next day they were subjected to hydrodistillation.

2.3. Hydrodistillation and the Waste Water Produced

One-hundred-and-fifty grams of rose petals and 450 mL of distilled water were placed in a compact Behr-KOL 2 apparatus with a 1000 mL capacity flask (Figure 2). Two hydrodistillations were performed: one lasting 3 h and the other lasting 4 h. When complete, the remaining contents of the flasks (water and rose petals) were filtered to separate the petals from the now reddish waste water (Figure 3). Waste waters from 3 h and 4 h distillations were then pooled in 500 mL flasks (in a single bottle), allowed to cool to room temperature and then stored in a refrigerator at 4 °C. One week later (21 May) these samples were sent to the Instituto de Ciencia y Tecnología de Alimentos y Nutrición (ICTAN) for analysis.

2.4. Waste Water Analysis

Upon arrival at the ICTAN (22 May), the samples were frozen at −80 °C until analysis. After thawing, the samples were analysed without further dilution or processing to determine the contents of bioactive flavonoids most commonly cited for Rosa leaves and fruits, i.e., cyanidin, kaempferol and quercetin, as well as their derivatives. Flavonols common in plants, including catechin and the Procyanidin B1 (PB1) dimer, were also searched for, as were non-flavonoid polyphenols, such as benzoic acid and its derivatives gallic acid and ellagic acid.
Polyphenols were analysed by high performance liquid chromatography–quadrupole time-of-flight mass spectrometry (HPLC–MS Q-TOF). The HPLC–MS Q-TOF system involved an Agilent 1200 series HPLC equipped with an Agilent ZORBAX Eclipse XDB-C18 column (Santa Clara, CA, USA) (4.6 mm × 150 mm × 5 μm) at 40 °C. The mobile phase consisted of water containing 1% formic acid (A) and acetonitrile with 1% formic acid (B). The elution gradient was 5% B at 0 min, 15% B at 20 min, 30% B at 30 min, 50% B at 35 min, 5% at 37 min and 5% at 40 min. The flow rate was 1 mL/min.
Compound identification/quantification was performed by MS and MS/MS Q-TOF acquisition (2 GHz, low mass range (1700 m/z), negative polarity, drying gas 10 L 350 °C, sheath gas 11 L 350 °C, nebulizer 45 psi, cap voltage 4000 V, fragment or voltage 150 V). A collision energy of 20 V was used for all MS/MS experiments. Data capture and analysis were performed using the Data Analysis B. 05.01 and Qualitative Analysis B. 07.00 routines of the MassHunter Workstation software (Agilent Technologies, Waldbroon, Germany).

Identification and Quantification

The majority of the compounds that appeared in the HPLC chromatogram were identified from their exact mass and fragmentation patterns. They were quantified by making use of the negative polarity signal, extracting the (M-H) (the predomination) for each compound. The quantification patterns used were those of:
  • Cyanidin-glucoside (for the derivatives of cyanidin);
  • Kaempferol-glucoside (for the derivatives of kaempferol); and
  • Quercetin-glucoside (for the derivatives of quercetin and other less abundant compounds).

3. Results

Table 1 shows the majority of compounds identified and quantified, along with their (M-H) values. The quantification pattern for quercetin-glucoside matched one of the compounds identified, confirming its identity.
The most common compounds were quercetin and its derivatives (Figure 4), plus gallic acid and ellagic acid. Among the quercetin derivatives, the most abundant was quercetin-glucoside (quercetin-3-O glucoside), quercetin-rhamnoside and quercetin-galactoside. Kaempferol-rhamnoside and kaempferol-galactoside were also detected.
The quercetin-3-O-glucoside eluted at Rt = 24.3 was confirmed by a pure standard. The presence of a hexose in the molecule was confirmed by the loss of a mass of 162.05 in the first case (Figure 4A), while the presence of a pentose in the molecule (Figure 4B) was confirmed by a loss of 132.04. The fragment obtained with a mass of 301.03 confirmed the presence of quercetin in both cases.

4. Discussion

Several authors have analysed the polyphenols in the petals of different rose species, with particular interest in anthocyanins, these pigment compounds being responsible for the red-to-purple petal hues of many rose types. In addition, these compounds have also been reported in R. gallica and R. centifolia to show anti-inflammatory [38] and antimutagenic properties [24], respectively.
Cunja et al. [20] studied the anthocyanins and flavonoids in the leaves and petals of different species of Rosa and reported a clear correlation between anthocyanin content and colour. The cyanidins (along with smaller quantities of peonidins and pelargonidins) were reported to be the most abundant anthocyanins in species with pink flowers.
The Narcea rose has red-purple petals, and cyanidins were the most abundant anthocyanins in the waste water produced during the present hydrodistillation experiments—a finding in agreement with that reported by Cunja et al. [20] for R. damascena. It may be this compound that confers the red colour upon this waste water (Figure 3), even though it is not the most abundant polyphenol. Ge and Ma [40], who studied the concentration of anthocyanins in edible roses from Yunnan (China), reported cyaniding-diglucoside to be the most abundant anthocyanin (making up 95% of all such compounds) and proposed these roses as a source of natural pigments for the food industry.
Our data reveal flavonoids in greater quantities than the anthocyanins. These are important bioactive compounds. Several authors report flavonols, especially derivatives of quercetin and kaempferol, to be present in different species of rose [17,20,23]; the bactericidal and antiviral properties of these compounds have been examined in several recent studies [17,41,42]. Other authors have confirmed the importance of these compounds in animal health and concluded that the incorporation of flavonoids into milk and meat products could provide a way of increasing their consumption along with the health benefits they are associated with (especially for people with low levels of flavonoids in their diet).
High concentrations of gallic and ellagic acids have been reported in the hips of other roses [17,43]. Fascella et al. [19], who studied the hips of four rose species, reported the most abundant polyphenols to be derivatives of catechin and galloyls (such as ellagic acid). Other authors indicate that ellagic acid has an important antitumoral effect [44,45,46,47,48].
Like green tea, grapes, red berries, pomegranates, apples and pears, roses (and in particular their leaves) are rich in flavan-3-ols (catechins, epicatechins and proanthocyanidins) [17,30]. However, in the waste water studied here, catechin and Procyanidin B1 (PB1) were detected only in small amounts. It may be that they were degradate in the distillation compared to quercetin, kaempferol and their derivatives. This might be explained by the fact that flavonols, being very polar, are left in the vapour. Moreover, since they are thermosensitive, they become hydrolysed during the hydrodistillation process. Other authors have reported high concentrations of these compounds in the petals of R. damascena and other rose species [20,23,49], while Göktürk-Baydar and Baydar [25] indicated catechin and epicatechin to be the most abundant phenolic compounds in the leaves of this species. In the present work, the low concentration of these compounds in the waste water might reflect a varietal characteristic. Forthcoming analyses of these compounds in fresh petals should throw light on this. It might be that the time that elapsed between the collection of the present flowers and their analysis affected the results obtained [50]. Some authors [9,51,52] indicate that roses need to be collected early in the morning and, if possible, subjected to hydrodistillation immediately, in situ, if their aromatic compounds are to be examined (during transport the flowers deteriorate and lose some of their volatile aromatic compounds). Over longer collection-to-analysis times, it may be that polyphenols are lost, too, explaining the present near-absence of flavanol-3-ols. (Logistically, however, it was impossible to analyse the present samples sooner after their collection.) Finally, the very small amounts of these compounds detected in the present samples might be a reflection of the latter’s treatment in the laboratory. All were stored at 4 °C for some days before being frozen at −80 °C. The effects of handling should be thoroughly studied if the waste water produced in hydrodistillation is to be used to obtain compounds of interest.
Schmitzer et al. [27] report that the concentration of phenolic compounds in petals varies over the development of the flower and that buds contain many more quercetin derivatives, catechins and much more gallic acid than do flowers in later stages of development. Indeed, they indicate that there may be up to six times as much gallic acid in buds then in open flowers. However, the quantity and quality of oils in the petals reaches a maximum when the flowers are completely open [10].
In other crops, such as grapevine [53,54,55], the polyphenol content of the leaves is strongly influenced by climatic and other environmental factors, such as temperature, rainfall, altitude, soil type, crop management, fertilizer availability and collection time [56]. Petkova et al. [3] reported higher phenol and total flavonoid concentrations in water extracts from organically cultivated roses, while Ginova et al. [11] reported total polyphenols and oxidative activity to be higher with altitude. All these factors will need to be studied if oils and rose water of maximum quality are to be extracted from the Narcea rose and the best use is to be made of its hydrodistillation and other wastes.

5. Conclusions

In conclusion, the present work shows that waste water produced during the hydrodistillation of Narcea rose petals is rich in quercetin and its derivatives, gallic and ellagic acids. Among the quercetin derivatives, the most abundant was quercetin-glucoside, quercetin-rhamnoside and quercetin-galactoside. Kaempferol-rhamnoside and kaempferol-galactoside were also detected. According to reports in the literature, many of these compounds have antioxidant and other properties beneficial to health. The high concentration of these compounds in this waste water render it suitable as a raw material for developing nutraceutical, pharmacological, animal feed and even human and plant health products. However, one of the best applications could be dermocosmetic production, which could benefit from the water and the compounds inside. Protocols need to be developed to take advantage of this polyphenol-rich water.

Author Contributions

S.B. and M.-C.M. proposed the study, planned and directed it, set goals, undertook experimental work, analysed and interpreted the results, and wrote the draft of the article. J.-L.S., I.Á.-A. and M.-A.M.B. undertook experimental work and helped write the draft of the article. P.G. helped write the draft of the article. All authors have read and agreed to the published version of the manuscript.

Funding

This research received no external funding.

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

Not applicable.

Acknowledgments

The authors thank E. Zubiaurre, I. González and A. Costas for technical assistance. The English manuscript was prepared by Adrian Burton (www.physicalevidence.es accessed on 27 March 2022).

Conflicts of Interest

The authors declare no conflict of interest.

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Horticulturae 08 00376 g001 550
Figure 1. A Narcea rose in flower.
Figure 1. A Narcea rose in flower.
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Figure 2. Hydrodistillation apparatus with flask charged with petals.
Figure 2. Hydrodistillation apparatus with flask charged with petals.
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Figure 3. (a) Flask containing petals and water-view during hydrodistillation. (b) Flask containing waste water from the hydrodistillation process.
Figure 3. (a) Flask containing petals and water-view during hydrodistillation. (b) Flask containing waste water from the hydrodistillation process.
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Figure 4. MS/MS spectra typical fragments for Quercetin-hexoside (Quercetin-3-O-Glucoside) (A) and Quercetin-pentoside (B).
Figure 4. MS/MS spectra typical fragments for Quercetin-hexoside (Quercetin-3-O-Glucoside) (A) and Quercetin-pentoside (B).
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Table
Table 1. Phenolic compounds identified in the waste water of Narcea rose hydrodistillations.
Table 1. Phenolic compounds identified in the waste water of Narcea rose hydrodistillations.
ANTHOCYANINSM-HFormulaScore%MS/MSFragment IdentityTR minMeans (µg/g)S.D
CYANIDIN-DIGLUCOSIDE609.1461C27H31O1697.9285Cyanidin6.913.453.01
FLAVONOLS 1M-HFormulaScore%MS/MSFragment identityTR minMeans (µg/g)S.D
KAEMPFEROL285.0405C15H10O697.6 34.213.762.53
KAEMPFEROL-PENTOSIDE417.0827C20H18O1097.9285Kaempferol27.613.760.70
KAEMPFEROL-PENTOSIDE417.0827C20H18O1096.9285Kaempferol28.237.991.88
KAEMPFEROL-RHAMNOSIDE431.0984C21H20O1096.4285Kaempferol28.852.045,90
KAEMPFEROL-HEXOSIDE (GALACTOSIDE)447.0933C21H20O1198.9285Kaempferol25.721.811.24
KAEMPFEROL-RUTINOSIDE593.1301C30H26O1399.2285Kaempferol31.915.342.46
TOTAL KAEMPFEROL DERIVATIVES 154.7014.71
QUERCETIN301.0354C15H10O796.6 31.373,8412.28
QUERCETIN-PENTOSIDE433.0776C20H18O1194.8301Quercetin25.150.734.40
QUERCETIN-PENTOSIDE433.0776C20H18O1199.2301Quercetin25.512.141.18
QUERCETIN-PENTOSIDE433.0776C20H18O1196.2301Quercetin26.1155.965.25
QUERCETIN-RHAMNOSIDE447.0933C21H20O1199.7301Quercetin26.6216.5311.60
QUERCETIN-HEXOSIDE (GALACTOSIDE)463.0882C21H20O1299.6301Quercetin23.7239.847.24
QUERCETIN-3-O-GLUCOSIDE463.0882C21H20O1299.1301Quercetin24.3260.119.73
QUERCETIN-HEXOSIDE-RHAMNOSIDE609.1250C30H26O1497.9301Quercetin30.240.915.14
QUERCETIN-RUTINOSIDE609.1461C27H30O1697.7301Quercetin23.7126.840.98
TOTAL QUERCETIN DERIVATIVES 1176.9045.52
FLAVANOLS AND PHENOLICS ACIDM-HFormulaScore%MS/MSFragment identityTR minMeans (µg/g)S.D
CATEQUIN289.0718C15H14O697.8 9.739.821.35
PROCYANIDIN B1577.1351C30H26O1294.9 8.112.540.62
ELLAGIC ACID300.9990C14H6O898.6 22.9406.2923.74
DERIVATIVE ELLAGIC ACID425.0150C20H10O1197.4300Ellagic acid27.7250.2132.95
GALIC ACID169.0142C7H6O581.1 2.9726.9623.47
TOTAL FLAVANOLS AND PHENOLICS ACID 1435.8282.13
TOTAL µg/g sample 2780.87145.37
[M-H]: Exact mass of the isotopes of an element; Formula: refers to neutral molecule; Score: Percentage of reliability of proposed formula according to exact mass and isotopic distribution; MS/MS: Majority fragment in MS/MS fragmentation confirmed to be derived from one of the compounds; TR: Retention time; S.D.: Standard deviation. 1 Quercetin derivatives eluted over three retention times and thus considered different isomers.
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Boso, S.; Gago, P.; Santiago, J.-L.; Álvarez-Acero, I.; Martinez Bartolomé, M.-A.; Martínez, M.-C. Polyphenols in the Waste Water Produced during the Hydrodistillation of ‘Narcea Roses’ Cultivated in the Cibea River Valley (Northern Spain). Horticulturae 2022, 8, 376. https://doi.org/10.3390/horticulturae8050376

AMA Style

Boso S, Gago P, Santiago J-L, Álvarez-Acero I, Martinez Bartolomé M-A, Martínez M-C. Polyphenols in the Waste Water Produced during the Hydrodistillation of ‘Narcea Roses’ Cultivated in the Cibea River Valley (Northern Spain). Horticulturae. 2022; 8(5):376. https://doi.org/10.3390/horticulturae8050376

Chicago/Turabian Style

Boso, Susana, Pilar Gago, José-Luis Santiago, Inmaculada Álvarez-Acero, Miguel-Angel Martinez Bartolomé, and María-Carmen Martínez. 2022. "Polyphenols in the Waste Water Produced during the Hydrodistillation of ‘Narcea Roses’ Cultivated in the Cibea River Valley (Northern Spain)" Horticulturae 8, no. 5: 376. https://doi.org/10.3390/horticulturae8050376

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