Holistic and Sustainable Approach for Recycling and Valorization of

Research Article pubs.acs.org/journal/ascecg

Cite This: ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX

Holistic and Sustainable Approach for Recycling and Valorization of Polyvinylpolypyrrolidone Used in Wine Fining Sandrine S. Ferreira,† Ana J. Alves,† Luís Filipe-Ribeiro,† Fernanda Cosme,‡ and Fernando M. Nunes*,† †

Food and Wine Chemistry Laboratory, Department of Chemistry, and ‡Department of Biology and Environment, Chemistry Research Centre − Vila Real (CQ-VR), University of Trás-os-Montes and Alto Douro, 5001-801 Vila Real, Portugal

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S Supporting Information *

ABSTRACT: Polyvinylpolypyrrolidone (PVPP) is a synthetic water-insoluble polymer widely used as fining agent in the wine industry for removing low-molecular-weight phenolics. Used PVPP, estimated in 2014 of 1037 tons, ends up in the municipal wastewater treatment plants with a detrimental environmental impact. Recycling of PVPP for obtaining fully reusable PVPP and wine phenolic concentrates for the food, cosmetic, and pharmaceutical industries would increase the sustainability of its use. An ammoniacal solution of ethanol allows one to desorb with high recoveries (average 73%) the PVPP adsorbed phenolics with yields ranging from 2.82 to 10.80 g/kg of wet PVPP, depending on the wine. Extracts were nearly pure concerning the phenolics abundance (>89%), without need of further purification. The performance of the recycled PVPP for white wine fining was not significantly different from that of the new PVPP, which can be recycled at least four times without loss of fining performance and allow a good recovery of adsorbed phenolics to be maintained. Results obtained in this work show that by using a simple, cheap, and eco-friendly recycling strategy, it is possible to reuse PVPP for wine fining, providing a cleaner winemaking process and additionally obtain wine phenolic concentrates with high purity, antioxidant, and bioactivity, valuable for other industries. KEYWORDS: polyvinylpolypyrrolidone, recycling, phenolic compounds, fining, wine, sustainability

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INTRODUCTION 1

the global capacity for PVP production was 76 600 ton/year and the PVPP global demand was 5900 ton/year.11 Thirty-two percent of the global wine production in 2014 (270 million of hectoliters)12 corresponds to white wine,13 an estimation of use being 1037 tons of PVPP.14 The use of PVPP creates large amounts of waste to dispose that nowadays ends up in the municipal wastewater treatment plants. There is no literature concerning the fate of PVPP in the environment. Nevertheless, some studies have shown that the structurally similar soluble PVP is recalcitrant, showing no biodegradation and therefore persisting in the environment.15 At current usage values a disposal of 20 000 tons in 20 years are expected. These values can be underestimated16 as there is presently a tendency to increase the PVPP use to replace casein/potassium caseinate14 in white wine fining. Furthermore, after use as PVPP contains significant amounts of adsorbed phenolic compounds, its disposal can have a significant impact on the environment as they are very refractory.17 In the brewing industry two methods have been developed and patented for recycling and reusing PVPP obtained from

2

Using the principles of green chemistry and sustainability, researchers and industries are modifying how products and processes are developed and implemented.3 Waste valorization is becoming an important principle of the sustainability and cleaner production concept,2 where wastes are viewed as a source of raw materials or energy, minimizing their environmental impact.4 Pharmaceutical, cosmetic, food, and nutrition industries obtain their bioactive compounds, namely, phenolic compounds, by extraction from both plants and animals, with an estimated market size of over $250 billion.5 The recovery of valuable compounds from agro-food industries wastes is an emerging field with great potential to drive sustainable production.6,7 Polyvinylpolypyrrolidone (PVPP) is a water-insoluble synthetic polymer produced by cross-linking of polyvinylpyrrolidone (PVP).8 Because of its excellent adsorbent properties, selectivity, stability, inertness, and nonallergenicity,9 it is widely used in food applications such as in the production of wine (up to a maximum dose of 80 g/hL),10 beer, juices, and other beverages to prevent haze formation, removing compounds responsible for bitterness, astringency, browning, and pinking, as well as a clarification and/or stabilization agent.8,9 In 2013 © XXXX American Chemical Society

Received: July 6, 2018 Revised: August 25, 2018 Published: September 11, 2018 A

DOI: 10.1021/acssuschemeng.8b03208 ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX

Research Article

ACS Sustainable Chemistry & Engineering

Figure 1. Schematic representation of the sustainable process proposed for PVPP recycling and recovery of high-purity wine phenolic compounds.

haze removal.18,19 Nevertheless, in both patents the regeneration step uses strong alkali conditions and temperatures: 0.25−0.5 M NaOH, 40−80 °C18 and 0.25−0.5 M NaOH, 60− 80 °C with or without 0.2% sodium hypochlorite.19 Also the direct treatment of PVPP with oxidants has been proposed: hydrogen peroxide (2−3%, 15−60 min, 75−85 °C) and ozone, or combination of both oxidants.18 These hot alkaline conditions render a black colored solution that is treated with an oxidizing agent (0.2% sodium hypochlorite or sodium persulfate) and disposed.19 Although this procedure renders reusable PVPP up to 20 times20 the impact in the environment of phenolic compounds or oxidized products of phenolic compounds is not avoided. This work is aimed at coupling the concepts of waste minimization by recycling, reuse, and waste valorization. Recycling of PVPP and its reuse would decrease its synthesis and disposal that would decrease its environmental impact, and with a suitable recycling strategy for recovering the adsorbed phenolic compounds, it could also constitute a rich and cheap source of valuable wine antioxidant and bioactive phenolic compounds for use in food, cosmetic, and pharmaceutical industries. This would increase the sustainability of the recycling process and of the PVPP use. The main purposes of this work were to develop a simple, cheap, and eco-friendly regeneration strategy for recycling used PVPP in line with the five-stage universal recovery process,6,7to evaluate the effect of the number of recycling cycles on its performance when compared to a new one, and at the same time to obtain valuable phenolic compounds.

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Regeneration of Used PVPPs. The industrially used PVPPs were initially vacuum-filtered to remove the wine still in contact, washed with water (3 × 100 mL), and vacuum-filtered. For PVPP regeneration and recovering the adsorbed phenolic compounds, 100 g of wet PVPPs were mixed with 100 mL of an ethanol solution containing NH3 (0.1 M) and after 15 min at room temperature (a short time was chosen to avoid the possible oxidation of the phenolics at alkaline pH), the suspension was filtered and the filtrate was quickly neutralized to pH ∼ 6.5 with acetic acid. Formic acid was also evaluated. The procedure was repeated three more times. Afterward, the PVPPs were washed with water (3 × 100 mL) and dried in a forced air oven at 50 °C. The volume used in the regeneration step was keep to a minimum volume possible but covering all the PVPP, to decrease the organic solvent usage and the need of acetic acid for neutralization, decreasing the reagent needs, volume to be evaporated, and the cost of the treatment. This option showed good recoveries of the adsorbed phenolic compounds. Filtrates Total Phenolic Content. Total phenolic content of the individual filtrates were determined by the Folin-Ciocalteau method.21 The filtrates were previously diluted (50:1) with 50% (v/v) methanol:water. Results were expressed as gallic acid equivalents. Determination and Quantification of Individual Phenolic Compounds by RP-HPLC. Phenolic compounds in wine and present in the filtrates obtained during each PVPP regeneration step were analyzed by RP-HPLC (Ultimate 3000, Dionex) with a photo diode-array detector (PDA-100, Dionex).22 Detailed methodology is described in the Supporting Information. Determination of Antioxidant Capacity. The scavenging capacity of the ABTS radical ion was measured according to Barros et al.23 The filtrates were previously diluted (50:1) with 50% (v/v) methanol:water. The results were expressed in mmol Trolox equivalents/L. Evaluation of the Fining Performance of the Recycled PVPPs: Fining Experiments. For evaluation of the performance of the recycled industrially used PVPPs (PVPP1, PVPP2, and PVPP3), their fining efficiency was compared to a new PVPP. To each white wine sample (wine 1, 100 mL), 40 g/hL of the different recycled and new PVPPs were added. Wine without addition of PVVP was used as control. Wines were stored at room temperature (3 days) in sealed flasks and afterward centrifuged (537.6g; 15 min) before analysis. Experiments were done in duplicate. Removal efficiency of PVPP was calculated by dividing the final concentration of each phenolic compound in relation to their initial concentration (control wine). Effect of the Recycling Cycles Number in PVPP Performance and Recovery of Adsorbed Phenolic Compounds. To

MATERIALS AND METHODS

PVPP Samples. Used PVPP samples were obtained from Portuguese wineries located in three different wine demarcated regions: PVPP1, Alentejo; PVPP2, Vinhos Verdes; and PVPP3, Beira Interior. An unused PVPP was supplied by SAI Enological Company. Detailed characteristics of PVPPs are described in the Supporting Information. Wine Characteristics. Two white wines (Table S1) were used depending on the experiments: wine 1 was used to evaluate the performance of the recycled industrially used PVPPs and wine 2 was used to evaluate the influence of the PVPP recycling cycles number in the adsorption performance of PVPP. B


Research Article

ACS Sustainable Chemistry & Engineering evaluate the influence of the PVPP recycling cycles number in the adsorption performance of PVPP and phenolic compounds recovery, wine 2 was fined with a new PVPP (40 g/hL), and the reduction in the wine phenolic compounds was determined by RP-HPLC. Recycled PVPP was used for fining the same wine and the phenolic compounds adsorption efficiency was measured as described above. PVPP recycling and performance evaluation was repeated four times. The recovery rate was calculated by dividing the amount of phenolic compounds recovered from the PVPP by the amount of phenolic compound adsorbed by PVPP in wine fining. Experiments were performed in duplicate.

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RESULTS AND DISCUSSION For development of an efficient recycling strategy for the PVPP used in the wine industry, three used PVPPs in white wine fining from three different Portuguese wine regions were selected: Alentejo (south), PVPP1; Vinhos Verdes (north), PVPP2; Beira Interior (central), PVPP3. The PVPPs were used for removing browning14 and pinking phenolic compounds.24 Recycling scheme applied is shown in Figure 1. Recovering of Wine Phenolic Compounds from Used PVPP. For desorption of the adsorbed phenolic compounds, an ethanol solution containing NH3 (0.1 M) was used and the PVPPs were washed four times in batch (due to the simplicity of the procedure). Ethanol and ammonia were selected because of their high volatility and allowance to use in foods.25,26 Also, ethanol and ammonia have been assessed as green by solvent and reagents selection guides.27,28 After recovery, acetic acid was used to neutralize the alkaline solution, being selected because of the formation of a volatile buffer,29 suitability for use in foods,30 and additionally being a green solvent.31 Formic acid was also used as in comparison to acetic acid, it has the same advantages and additionally also a lower boiling point. Nevertheless, to avoid the formation of formamide from ammonium formate by unintentionally applying high temperatures, acetic acid was selected. Ethanol was removed by vacuum evaporation and water was added before freeze-drying. Each washing step was analyzed separately for total phenolic compounds (Figure 2a) and their phenolic profile was obtained by RP-HPLC-DAD (Table 1 and Figure S1). The concentration of phenolic compounds in the regeneration solution decreased with increasing number of washing steps (Figure 2a). The amounts of phenolic compounds adsorbed in each PVPP (Table 1) were different and this was certainly dependent on the conditions of the unused PVPP treatment in each winery, dependent on the different wine characteristics associated with the grape varieties used in each region, climate conditions, and winemaking technologies used, as the amount of PVPP used in the three wineries was the same (80 g/hL). The effect of possible different structural characteristics of each PVPP cannot be excluded. For PVPP1, PVPP2 and PVPP3 a total of 21, 20, and 24 phenolic compounds were recovered, respectively, being the most abundant phenolic compounds recovered (+)-catechin (∼42%), chlorogenic acid (∼11%) and (−)-epicatechin (∼11%), for PVPP1, trans-caftaric acid (∼45%), gallic acid (∼23%) and chlorogenic acid (∼16%), for PVPP2 and rutin (∼21%), trans-caftaric acid (∼18%) and chlorogenic acid (∼16%) for PVPP3. The yield of solids recovered ranged from 2.38 g/kg of wet PVPP1 to 10.9 g/kg of wet PVPP2. The percentage of total phenols in the extracts obtained from PVPP after freeze-drying determined by Folin-Ciocalteau method ranged from 54 to

Figure 2. (a) Total phenolic compounds in the washing solutions in the regeneration process for the three used PVPPs from different wine-demarcated regions. (b) Adsorption performance of white wine phenolic compounds of a new PVPP and the same PVPP after one, two, three, and four recycling cycles. (c) Recovery of white wine phenolic compounds adsorbed on a new PVPP and the same PVPP after one, two, three, and four recycling cycles.

68%, this value being approximately 100% (89−134%) when determined by HPLC (Table 1). Folin-Ciocalteau method is known to underestimate the total phenolic concentration in comparison to the HPLC quantification.32,33 These results C


a

D

30.6 32.2

25 26 total mg/L yield g/kg TP g/kg HPLC g/kg TEAC mmol/kg

gallic acid protocatechuic acid (+)-catechin (−)-epicatechin unk. proc.d unk. proc. unk. proc. unk. proc. d.benzoic acid unk.b unk. proc. unk. proc. unk. proc. GRP t-caftaric acid coutaric acid chlorogenic acid caffeic acid p-coumaric acid d.resveratrole ferulic acid resveratrol ethyl caffeic ethyl ferulic ethyl coumaric rutin unk. 0.8 3.2 0.2 7.5 1.2 21.1 0.5 1.0 2.0 0.1 1.3

1.1 3.3 0.2 12.4 1.6 24.6 0.6 1.3 0.2 0.1 0.1

7.5

2.4 1.5 3.2 3.0

2.3 1.5 2.8 3.1

8.3

11.3 1.9 74.0 22.2 1.4

2nd

PVPP1 12.5 2.6 82.9 1.6 1.0

1st

5.1

0.6 2.6 0.1 2.2 0.6 13.0 0.3 0.6 1.6 0.0 1.2

1.8 0.8 4.9

7.7 1.1 59.7 18.8 1.0

3rd

0.7

1.2

0.4 0.0 1.7 0.2 2.0 0.1 0.1 1.1

0.4

0.3

0.6 0.3 5.6 14.4

4th

21.6

2.5 9.5 0.5 23.8 3.6 60.7 1.5 3.0 4.9 0.2 3.8

6.8 3.8 11.4 6.1

32.1 5.9 222.2 57.0 3.4

total

535.8 2.38 1.62 2.13 1562

4.2

0.5 2.0 0.1 2.4 0.1

1.5 6.3 0.5 5.9 0.4 27.6

5.0 223.8 16.3 88.5 6.4

24.0 783.4 72.4 242.3 28.9

3.1 0.9 1.6

0.9 15.1 0.4 3.8

0.9 39.4 2.2 10.5 12.1 1.6 5.1

100.9 7.2

2nd

PVPP2 450.2 28.6 c

1st

1.1

0.3 0.9 0.03 1.4 0.0

2.6 96.3 7.6 54.4 2.4

1.9 0.1 0.7

8.7 0.3 1.0

14.9 4.5

3rd

0.3

0.1

0.03 0.1

0.2 8.6 0.6 6.6 0.2

0.3

1.0 0.1 0.1

3.3 0.5

4th

2448 10.9 5.85 13.4 5842

33.2

2.3 9.3 0.6 9.8 0.5

31.8 1112 96.9 391.8 37.9

17.4 2.6 7.4

1.8 64.2 3.0 15.4

569.3 40.8

total

190.7 15.7

6.5 5.1 2.5 4.3 160.6 15.8 132.6 5.0 11.6 1.5 4.9 0.3 5.9 0.6

14.0 12.0 22.0

94.6 67.7 40.4 24.2 7.6

1st

114.0 5.4

4.4 5.3 6.4 1.7 80.5 7.7 85.2 2.3 7.7 1.6 3.3 1.5 5.9 0.8

11.6 10.0 12.6

35.9 36.5 36.8 22.3 5.6

2nd

PVPP3

32.9 1.4

1.6 2.2 3.7 0.6 23.3 2.3 33.1 0.7 2.9 0.7 1.4 0.8 2.5 0.4

4.3 4.0 3.9

12.1 13.3 20.8 8.8 2.1

3rd

6.6 0.3

0.3 0.5 1.1 0.1 4.4 0.4 8.1 0.1 0.6 0.2 0.2 0.3 0.6 0.0

1.0 1.0 0.8

2.8 3.1 5.7 2.3 0.4

4th

Rt: retention time. bunk: unknown. cn.d.: not detected. dunk. proc.: unidentified procyanidin derivative. ed.resveratrol: glycosylated derivative of resveratrol.

4.7 7.9 11.9 18.9 21.2 22.8 23.8 24.5 29.9 30.2 35.2 36.3 41.0 9.4 10.1 14.1 16.3 17.5 22.9 25.6 26.9 27.3 33.7 43.4

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24

Rta

344.2 22.8 1613 4.78 2.74 6.45 2738

12.8 13.1 13.7 6.7 268.8 26.2 259.0 8.2 22.8 4.0 9.8 2.9 14.9 1.8

30.9 27.0 39.3

145.4 120.6 103.7 57.6 15.7

total

11.2 ± 0.8 3.7 ± 0.3 2.6 ± 0.2 1.7 ± 0.1 0.6 ± 0.1 0.4 ± 0.1 0.4 ± 0.1 0.2 ± 0.1 0.6 ± 0.1 0.2 ± 0.1 3.1 ± 0.2 28.3 ± 2.2

0.17 ± 0.01 27.5 ± 1.7

1.1 ± 0.1 2.5 ± 0.2

mg/L

wine 2

8.2 ± 0.1 1.7 ± 0.0 2.9 ± 1.7 0.86 ± 0.01 0.37 ± 0.02 0.084 ± 0.020 0.18 ± 0.08 0.05 ± 0.01 0.02 ± 0.00

0.02 ± 0.01

9.2 ± 0.7 3.5 ± 0.0

0.21 ± 0.30

mg/L

wine 1

Table 1. Concentration of Individual Phenolic Compounds Determined by HPLC (mg/L) in Each Washing Step in the Regeneration of PVPP, Yield of Solids (g/kg of PVPP), Total Phenolic Compounds Content (g/kg of PVPP), Antioxidant Activity (mmol of Trolox/kg of PVPP), and Concentration of Phenolics Present in the Control White Wines Used (mg/L)

ACS Sustainable Chemistry & Engineering Research Article


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Figure 3. Removal capacity (%) of phenolic compounds for the new unused PVPP (white column) and regenerated industrially used PVPPs with the developed procedure (PVPP1, light gray column; PVPP2, medium gray column; PVPP3, dark gray column). A, gallic acid; B, (+)-catechin; C, (−)-epicatechin; D, unidentified derivative of procyanidins; E, chlorogenic acid; F, caffeic acid; G, p-coumaric acid; H, ferulic acid; I, resveratrol; J, ferulic acid ethyl ester; K, rutin; and L, total phenolics compounds removal (mg/L). Data are expressed as percentage of control wine without treatment, as mean ± SD (n = 2). For each polyphenol, bars with the same letter are not significantly different (ANOVA, p < 0.05).

chlorogenic acid, p-coumaric acid, and (−)-epicatechin, PVPP2 and PVPP3 presented the same efficiency as the new PVPP, and for rutin, PVPP2 presented the same efficiency as the new PVPP while PVPP3 was unable to reduce the rutin concentration and PVPP1 was slightly less efficient than the new PVPP. Phenolic compounds removal efficiency of PVPPs were in accordance with the known adsorption capacity of PVPP for phenolic compounds shown to increase with the number of hydroxyl groups and decrease with the introduction of methoxyl groups: resveratrol > (+)-catechin > gallic acid > caffeic acid > ferulic acid > p-coumaric acid.9,51−54 The glycosylation of phenolic compounds decreases their affinity for PVPP, as observed for rutin.52 The total amount of phenolic compounds removed from the wine were not significantly different for the three recycled PVPPs in comparison to the new PVPP (Figure 3L). The small differences observed can be due to the specific structural features of each PVPP. Effect of the PVPP Recycling Cycles Number in the PVPP Fining Efficiency and Recovery of Adsorbed Phenolic Compounds. To evaluate the effect of increasing number of recycling steps of PVPP on its adsorption performance, the fining efficiency of a new PVPP was compared to the fining efficiency of the same PVPP recycled four times (Figure 2b) in the same wine (wine 2, Table 1). The fining efficiency of the new PVPP was 5.03 g of total phenolic compounds by kg of PVPP. (+)-Catechin, and resveratrol were removed to undetectable levels followed by rutin (74% removal), protocatechuic acid (22% removal), chlorogenic acid and caffeic acid ethyl ester (17% removal), pcoumaric and ferulic acids (6% removal), and trans-caftaric acid (5% removal). Fining efficiency of the recycled PVPP until

show that the extracts had a high purity in terms of phenolic compounds and, depending on the intended application, do not need further purification, therefore decreasing the cost and increasing the simplicity of the procedure. If even single phenolic compounds were needed, the high abundance of the extracts will facilitate their purification. Phenolic compounds recovered from industrially used PVPP (3−11 g/kg) were similar or even higher than those obtained from winery industry byproducts (9−13 g/kg),34−37 citrus peels (0.53 g/ kg),38 and elderberry branches (6.3 g/kg)21 to name only a few agricultural wastes considered rich sources of phenolic antioxidants. As expected from the phenolic abundance of the extracts, they presented high antioxidant activity39 (Table 1). A significant correlation between the amount of total phenolic compounds and antioxidant activity of the extracts obtained in each washing step for the three PVPPs (y = 0.0082x − 1.2864; r = 0.981, p < 0.05) was observed. In addition to its antioxidant capacity,40 studies have shown that phenolic compounds can present anti-inflammatory,41 antibacterial,42 anticarcinogenic,43 antithrombotic,44 neuroprotective,45,46 and cardioprotective activities.47 Efficiency of Recycled PVPP in the White Wine Fining Performance. To evaluate the efficiency of the recycled PVPPs fining performance, their efficiency was compared to a new PVPP. The wine used presented a concentration in the range of that reported in the literature,48−50 being a typical white wine from the Douro region (Table 1). All PVPPs were able to be removed to undetectable levels: gallic acid, (+)-catechin, resveratrol, and an unidentified procyanidin present in the wine. The efficiency of the recycled PVPPs were similar to the new one on the reduction of caffeic acid, ferulic acid, and ferulic acid ethyl ester (Figure 3). For E


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Figure 4. Projection of PCA data obtained for the new and the same recycled PVPPs after one, two, three, and four recycling cycles for (a) phenolic compounds removal in white wines; *, trans-caftaric acid, coutaric acid, caffeic acid, chlorogenic acid, caffeic acid ethyl ester, p-coumaric acid, and p-coumaric acid ethyl ester; (b) weight percentage of phenolic compounds obtained after elution of adsorbed phenolic compounds using the procedure developed; **, caffeic acid, caffeic acid ethyl ester, p-coumaric acid, p-coumaric acid ethyl ester, chlorogenic acid, resveratrol, and d.resveratrol.

including grape stalks, pomace, skins, seeds, wine lees, and spent filter cakes.30 Currently, the delivery of part or all byproducts to distillation can be made compulsory or voluntary in Europe,55 depending on the Member State. Grape pomace (skins, seeds, and pulp) and wine lees are currently used for distillation, for ethanol production, for recovering coloring agents, and in the case of wine lees and filter cake to produce tartaric acid.34 The recycling of PVPP could follow the already established routes for these winery byproducts, as often distilleries or tartrate/coloring extracts production industries have already implemented residues collection networks and equipment that can be partly adapted to this new process, as for example distillation units for recovering the ethanol used in the recycling process. Industrially, several options are available for processing the used PVPP. One of the simplest solutions being the regeneration of PVPP in batch reactors, preferably with upflow but also downflow of the regeneration solution can be used. This process needs only a neutralization vessel for the pH adjustment of the resultant regeneration solution, dosing valves, dosing pumps, and a control system (Figure 5). In conclusion, used PVPP obtained from white wine fining is a cheap and abundant source of wine phenolic compounds. Recycled PVPP presented an identical fining efficiency

the fourth recycling cycle was not significantly different (ANOVA, p < 0.141) from that of the new PVPP. Adsorption capacity of the regenerated PVPP obtained using the method developed in this work when compared to that of the new PVPP was identical to that observed for the developed recycling strategies used in the brewing industry.18,19 Phenolic compounds adsorption pattern of the new PVPP and recycled PVPPs after recycling four times did not present noticeable differences, as PC1 obtained by PCA using PVPPs as variables and the removal percentage of phenolic compounds as objects account for 98% of the original variance. All PVPPs either new or recycled showed a high correlation with PC1 (Figure 4a). To evaluate the recovery of the adsorbed phenolic compounds in each application of the PVPP to the white wine, the phenolic compounds adsorbed were removed from the PVPP using the recycling protocol developed. The recovery of phenolic compounds for the new PVPP was on average 83.6 ± 10.3% of the adsorbed phenolic compounds (Figure 2c), not being significantly different from 100% (p < 0.266). Recovery of the phenolic compounds adsorbed on the recycled PVPPs were not significantly different than those on the new PVPP (ANOVA, p < 0.139). Phenolic compounds recovered (weight percent) from the new PVPP and recycled PVPPs did not show noticeable differences, as again, PC1 using PVPPs as variables and the weight percentage of phenolic compounds as objects accounts for 99.6% of the original variance. All PVPPs either new or recycled showed a high correlation with PC1 (Figure 4b). The phenolic compounds recovered were distributed according to PC1 in order of their abundance (Figure 4b). Rutin was the main recovered phenolic (35% w/w), followed by trans-caftaric acid (26% w/w), chlorogenic acid (16% w/w), and coutaric acid (6% w/w), with the remaining phenolic compounds being present with an abundance less than 2% (w/w). PVPP is also allowed and used in red wine fining,10 although with lower expression, and therefore the recycling of industrially used PVPP in red wine fining could also be done by the same method with no anticipated problems. Besides the PVPP waste, mainly produced in the final steps of the winemaking process, wine production from grapes to the final wine generates huge amounts of other byproducts

Figure 5. Conceptual scheme of the PVPP recycling process and recovery of wine phenolic compounds. F


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compared to new PVPP. Repeated recycling of PVPP until four cycles did not chang significantly its adsorption capacity and recovery of the adsorbed phenolic compounds. PVPP recycling by applying a low cost and eco-friendly procedure, that is, mild conditions (room temperature) and green and food-grade reagents and solvents (that can also be recycled) and PVPP reuse could decrease its synthesis and disposal in wastewater treatment plants, decreasing at the same time the phenolic load of the effluents generated by the wine industry. The phenolic compounds recovered, depending on the intended use, does not need additional purification procedures because of its high abundance in phenolic compounds. These phenolic compounds have interesting biological activities that can be used by other industries such as food, cosmetic, and pharmaceutical. By implementation of this new process, using the already available winery byproducts routes and installed capacity in the winery byproducts processing industries, the sustainability of winemaking could be improved.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acssuschemeng.8b03208.

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Details of the experimental procedures, statistical analysis, and HPLC-DAD chromatograms (PDF)

AUTHOR INFORMATION

Corresponding Author

*CQ-VR, Chemistry Research Centre, Food and Wine Chemistry Lab., Chemistry Department, University of Trásos-Montes and Alto Douro, Quinta de Prados, 5000-801, Vila Real, Portugal. E-mail: [email protected]. Phone: +351 259 350 242; Fax: +351 259 350 480. ORCID

Fernando M. Nunes: 0000-0001-5540-318X Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This research was supported by European Investment Funds by FEDER/COMPETE/POCI under POCI-01-0145-FEDER007728 and funds from the Portuguese Foundation for Science and Technology (FCT) to CQ-VR (PEst-OE/QUI/UI0616/ 2014). This study has received funding from FEDER, Interreg España-Portugal Programme, under the framework of the Project ref 0377_IBERPHENOL_6_E. S.S.F. acknowledges the financial support provided by the European Social Funds and the Regional Operational Programme Norte 2020 (operation NORTE-08-5369-FSE-000054)

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