Qualitative and nutritional comparison of goji berry fruits produced in organic and conventional systems

Scientia Horticulturae 257 (2019) 108660

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Qualitative and nutritional comparison of goji berry fruits produced in organic and conventional systems

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Alessandra Cristina Pedroa, , María-Cortes Sánchez-Matab, María Luisa Pérez-Rodríguezb, Montaña Cámarab, José Luis López-Colónc, Fabiane Bacha, Marcelo Bellettinia, Charles Windson Isidoro Haminiukd a Programa de Pós-Graduação em Engenharia de Alimentos, Universidade Federal do Paraná (UFPR), Campus Politécnico, R. Cel. Francisco Heráclito dos Santos 210, Curitiba, PR, Brazil b Departamento de Nutrición y Ciencia de los Alimentos, Facultad de Farmacia, Universidad Complutense de Madrid (UCM), Pza Ramón y Cajal, s/n, E-28040, Madrid, Spain c Instituto de Toxicología de la Defensa, Glorieta del Ejército, 1, 28047, Madrid, Spain d Programa de Pós-Graduação em Ciência e Tecnologia Ambiental, Universidade Tecnológica Federal do Paraná (UTFPR), Curitiba, PR, Brazil

A R T I C LE I N FO

A B S T R A C T

Keywords: Nutrients Food safety Essential minerals Nutritional potential

Goji berries are fruits widely cultivated in Asian countries and have been consumed all over the world due to the high content of nutrients. In this paper, nutrient composition including moisture, ash, minerals (including heavy metals), proteins, lipids (including fatty acids), available carbohydrates (including soluble sugars), organic acids and dietary fiber were determined in organic and conventionally cultivated goji fruits. Physicochemical properties, total titratable acidity, pH, soluble solids, water activity and color were also investigated. Goji berries presented higher contents of available total sugars (67.85 and 75.05%), dietary fiber and essential minerals (Mg, Fe, Zn, Cu and Mn). Fructose was the main soluble sugar identified in organic and conventional fruits (5.45 and 4.92 g/100 g, respectively), followed by glucose and sucrose. Conventional fruits presented Hg and Pb contents above the established limits by the Codex Alimentarius. The linoleic acid was the main fatty acid identified in organic (54.68%) and conventional (37.06%) goji berry. Fructose was the main soluble sugar identified in organic and conventional fruits (5.45 and 4.92 g/100 g, respectively), followed by glucose and sucrose. Citric acid was identified as the main organic acid present in organic and conventional goji berries (0.90 and 1.14 g/100 g, respectively). The parameters, total titratable acidity, pH, soluble solids and water activity were considered as sensorial desirable in both samples. The color parameters indicated the red-orange coloration as predominant in the samples. These results demonstrate that goji fruits present high nutritional and sensory potential as ingredients in the formulation of foods, cosmetics and medicines. However, goji fruits grown in organic systems are better alternatives to ensure the food safety of industrialized products due to its lower content on heavy metals (Cd, Hg and Pb).

1. Introduction

family, being Lycium barbarum L. one of the most cultivated species in China, Tibet and Asia (Potterat, 2010). L. barbarum fruits are considered sources of essential minerals and vitamins, which together with the organoleptic properties make these fruits desirable for consumption (Amagase and Farnsworth, 2011), as the combination of the content of sugars and organic acids is responsible for their appreciable sensory characteristics. These characteristics stimulated the diversified commercialization of goji berry, as raw (in natura), or dried in either the formulation of yogurts, beverages, cereal bars, chocolates, beverages and soups, or even in encapsulated

Berry fruits have been widely consumed all over the world, since they have a high content of nutrients, which besides satisfying the metabolic needs, have a positive impact on human health (Souza et al., 2014). In addition, they attract the consumer by their organoleptic characteristics, such as color, flavor, odor and aroma (MartinezValverde et al., 2000). Among these fruits, the goji berries are gaining importance in different countries of the world. Goji fruits belong to the Solanaceae

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Corresponding author. E-mail address: [email protected] (A.C. Pedro).

https://doi.org/10.1016/j.scienta.2019.108660 Received 6 May 2019; Received in revised form 10 July 2019; Accepted 12 July 2019 0304-4238/ © 2019 Published by Elsevier B.V.

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was evaporated on a rotary evaporator (Fisatom 802, São Paulo, SP, Brazil) under reduced pressure at 50 ± 2 °C. The residual solvent was evaporated in a forced air oven at 50 ± 2 °C for 2 h. The residue was weighed for yield determination. The oils were transferred to amber flasks, kept under a nitrogen atmosphere, sealed and stored at -20 °C for further analysis. Fatty acids profile was determined by the capillary column gas chromatograph modified method described in AOAC (2006). Approximately 250 mg of lipids was saponified by boiling with 0.5 mol/L NaOH for 10 min. The sample was then boiled for 2 min with 14% (w/v) boron trifluoride-methanol solution following by the addition of n-hexane. After cooling, 30 mL of saturated NaCl solution was added and mixed thoroughly. Finally, 1 μL of the upper phase was injected in a gas chromatograph (Varian, CP3900, USA) with a flame ionization detector (FID); ZB-WAX capillary column (Phenomenex, USA) (60 m x 0,25 I.D., 0,25 μm film thickness). The temperature program as follows: oven: 60 °C (2 min) to 160 °C at 20 °C/min, to 240 °C at 2.5 °C/min, hold 31 min; carrier gas: nitrogen 3 mL/min; detector temperature: 300 °C; injector split mode ratio of 100:1 at 220 °C. The run time for a single sample was 70 min and each sample was analyzed in duplicate. Fatty acid identification was by comparing the retention time of the authentic standard Supelco FAME mix C4-C24 (Bellafonte, PA, USA).

form (Potterat, 2010). Although the dry form of goji berry is the most commonly consumed. However, in the conventional cultivation the application of agrochemicals is high and the drying process can cause accumulation of heavy metals. Considering that the consumption of vegetables with chemical residues can lead to chronic intoxication and the development of diseases, such as cancer (Salgado, 2011), the adoption of organic practices has attracted the attention of the food sector, as it provides environmental balance and preservation of biodiversity, besides producing safer and more nutritious food than its conventional counterparts (Gomiero et al., 2011). Therefore, this study aimed to evaluate the physical characteristics, nutritional composition and the contribution to the recommended dietary allowance (RDA), and heavy metals content of goji fruits grown in the organic and conventional systems, with the purpose of better application of this fruit in different products of the food industry, taking advantage of their unusual colors and flavors. The influence of different farming systems on the nutritional composition of fruits such as blueberry (Wang et al., 2008), strawberry, acerola (Cardoso et al., 2011) and yellow passion fruit (Pertuzatti et al., 2015) has already been studied. 2. Materials and methods

2.6. Available carbohydrates 2.1. Plant material The total sugar was determined by colorimetry using anthrone reagent (Osborne and Voogt, 1986). An amount of 0.5 g of sample was added 52% (v/v) HClO4 and distilled water. The solution was then allowed to stand for 24 h in the dark and filtered. A 1 mL aliquot of this solution was added 0.1% (w/v) anthrone reagent, and heated for 12 min. Then, the absorbance was determined at 630 nm (ThermoFisher-Scientific, Genesys-105, Waltham, Mass., USA) using a glucose standard curve for calibration purpose.

Dehydrated goji berry samples grown in the organic and conventional system were purchased at the Municipal Market of Curitiba/PR, Samples correspond to 2015 season (Organic Certification: IMO Control, Manufactured: Qingdao Ri Tai Food Co., Ltd). Once in the lab, the fruits were lyophilized (L101-Liotop, São Carlos – São Paulo, Brazil) and ground in an analytical mill (MA630/1-Marconi, Piracicaba – São Paulo, Brazil) to 10 mesh and stored in amber glass containers at 4 ± 2 °C until analysis.

2.7. Soluble and insoluble dietary fiber 2.2. Chemicals and standards The determination of the total fiber was performed through enzymatic-gravimetric method (AOAC, 1997). The samples were hydrolyzed with the use of the enzymes alpha-amylase, protease and amyloglucosidase. The samples were vacuum filtered and the soluble and insoluble fibers obtained. The residue was dried at 100 ± 2 °C for 24 h and corrections for ash and protein were made. The total amount of dietary fiber (soluble and insoluble fractions) was calculated from gravimetric data.

Nitric (HNO3), perchloric (HClO4), metaphosphoric (HPO3) and sulfuric (H2SO4) acids were purchased from Vetec® (Rio de Janeiro, RJ, Brazil). Chemical HPLC-grade standards (purity ≥ 95%) were purchased from Sigma-Aldrich (St. Louis, MO, USA). Hexane (C6H14) was purchased from Neon (Suzano, SP, Brazil). Ethanol (C2H6O), acetonitrile (C2H3N) and acetone (C3H6O) were purchased from J.T.Baker (Loughborough, USA). Anthrone reagent was purchased from Merck Millipore (Burlington, Massachusetts, USA). Ultrapure water (Milli-Q) was used in all experiments.

2.8. Ash, mineral composition and heavy metals The incineration method was used for ash determination in goji berry samples (AOAC, 1997). Approximately 0.5 g sample of lyophilized goji berry was incinerated at high pressure in a microwave oven (MLS1200, Muffle Furnace - Milestone, Gelderland, Netherlands) at 550 ± 4 °C for 24 h. The incineration residue was used to determine the heavy metals and mineral composition. The determination of macro and micronutrients of the samples was performed by nitro-perchloric digestion (Nogueira and Souza, 2005). Approximately 0.2 g of sample was digested with concentrated HNO3. After digestion, HClO4 was added and slowly warmed to 200 ± 2 °C until the nitrous oxide vapors were complete. After cooling the samples, purified water was added. The readings for Fe, Cu, Mn, Zn, Na and K were performed directly at the appropriate wavelength for each element, using solutions standard for calibration purposes. The addition of 5% (w/v) C6H8O6 and dilute ammonium molybdate acid solution ((NH4)6M07O24.4H2O) in the samples was performed for P determination, and the addition of 5% (w/v) La2O3 for Ca and Mg determination. All measurements were performed on atomic absorption spectroscopy equipment, and quantification was made through calibration

2.3. Moisture Moisture content of the samples was determined according to AOAC (1997) methodology by dehydration to constant oven weight at 100 ± 2 °C. 2.4. Proteins The protein content was determined according to the Kjeldhal method as described in AOAC (1997). Approximately 0.5 g of sample was digested in concentrated H2SO4, distilled and collected on 0.1 N H2SO4, and titrated with 0.1 N NaOH. Total nitrogen content was calculated and converted to protein content by the conversion factor of 6.25. 2.5. Total lipids and fatty acids composition The extraction of lipids was carried out through a Soxhlet system for 4 h at 60 ± 2 °C according to Horwitz and Latimer (2005). The solvent 2

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Analytical, Madrid, Spain) equipped with a UV–vis detector (Thermo Separation Spectra Series UV100) and Sphereclone ODS(2) Phenomenex column (250 x 4.60 mm, 5 μm) (Torrance, California, USA). The mobile phase consisted of 1.8 mmol/L H2SO4 (pH 2.6) and flow rate of 0.4 mL/min. The peak areas in the chromatograms were quantified through calibration curves of standard solutions of oxalic, tartaric, malic, quinic, citric and fumaric acid at different concentrations.

curves built with standards of each element (AAnalyst 200, PerkinElmer, Waltham, Mass., USA). The residue from the incineration method was weighed and heavy metal analysis (cadmium (Cd), mercury (Hg) and lead (Pb)) were carried out by ICP-MS (Cd and Pb) or cold vapour atomic absorption spectrometry (Hg). 2.9. Contribution to the recommended dietary allowance (RDA)

2.11. Physicochemical properties The results obtained from the nutritional composition of the goji berry samples were compared with the recommended dietary allowance (RDA), according to the Food and Nutrition Board (FNB) of the American Institute of Medicine of the National Academies (Trumbo et al., 2002), which recommends the amount of nutrients needed to meet the requirements of a large part of the healthy population (approximately 98%) (Mahan and Escott-Stump, 2010). The 100 g portion of goji berry was used to evaluate its contribution to human daily nutritional requirements.

The total titratable acidity (TTA) was determined by titration with 0.1 N NaOH to pH 8.1 (AOAC, 1997). The goji berry samples were diluted 1/10 (w/v) in distilled water for determination of pH and total soluble solids (TSS). The pH was measured by potentiometer (MicropH2000, Crison Instrument, Barcelona, Spain) and the TSS by refractometry (PR-1, Atago CO., Tokyo, Japan). The water activity (Aw) of the samples was determined on AQUAlab equipment (BrasEq-Series 3B, São José dos Campos - São Paulo, Brazil). The colors of the samples were determined using a portable colorimeter (MiniScan XE Plus HUNTERLAB, Virginia, USA), brightness D65, with 8 mm aperture.

2.10. Soluble sugars and organic acids

2.12. Scanning electron microscopy (SEM)

The determinations of the contents of soluble sugars and organic acids, as important features for sensorial characteristics of the fruits, were performed by high performance liquid chromatography with refractive index detector (HPLC-IR). The soluble sugars were determined of according Sánchez-Mata et al. (1998). An amount of 0.5 g of sample was mixed with 40 mL of 80% (v/v) ethanol and kept under agitation at 60 ± 2 °C for 45 min. The ethanol was evaporated on a rotary evaporator (Büchi-R-114, MarshalScientific, Cambridge, USA) at 40 ± 2 °C and the volume adjusted to 25 mL with distilled water. The samples were purified on SepPak C18 cartridges (Waters, Milford, Mass., USA), previously washed with 5 mL of methanol followed by 5 mL of water. The sample was filtered, mixed with acetonitrile and filtered again through a 0.45 μm PVDF membrane (Millipore, Bedford, USA) and was injected in HPLC (Micron Analytical, Madrid, Spain) equipped with a differential refractometer detector R401 (Jasco, Madrid, Spain) and Luna column of Phenomenex (250 × 4,60 mm, 5 μm) (Torrance, California, USA). The mobile phase consisted of a mixture of acetonitrile and water (80/20, v/v) at a flow rate of 0.9 mL/min. The peak areas in the chromatograms were quantified by analytical curves of external standardization, made using standard solutions of fructose, glucose and sucrose. The organic acids were determined as described by Sánchez-Mata et al. (2012). Approximately 0.5 g of the sample was weighed and 25 mL of 4.5% (w/v) metaphosphoric acid were added, and kept in the dark under stirring for 15 min and filtered. The extracts were filtered through 0.45 μm PVDF membrane and injected into the HPLC (Micron

The samples were used for the analysis of the electron microscopy of the microstructure in a 260-fold increase using a scanning electron microscope (JSM-6360LV, Akishima, Tokyo, Japan). For each of the samples, they were fixed in copper and metallized supports with a gold layer of 350 Å of thickness, in a vacuum apparatus Polaron E5000. 2.13. Statistical analysis Results were expressed as means ± standard deviation (SD). Statistical analysis of the data was performed by analysis of variance (ANOVA), followed by the Fisher LSD test, at 5% probability (p ≤ 0.05). The t-student test was also used to evaluate the data and p ≤ 0.05 values were considered significant. Statistica 7.0 software (StatSoft Inc. South America, Tulsa, Oklahoma, USA) was used for all statistical analyzes. 3. Results and discussion Table 1 presents the results of the proximal composition, energy value and the contribution to the recommended dietary allowance (RDA) of goji berry samples grown in the organic and conventional systems. All parameters, except for moisture and soluble fibers, were significantly different (p ≤ 0.05) between the organic and conventional samples, using the t-student test.

Table 1 Nutritional composition, energy and contribution to the recommended dietary allowance (RDA) of organic and conventional goji berry. Analysis1 (g/100 g)

Goji berry

RDA (minimum)

%RDA

Organic

Conventional

g/day

Organic

Conventional

Moisture Ash Proteins

15.12 ± 0.10Aa 5.02 ± 0.11Aa 9.57 ± 0.05Bb

15.29 ± 0.18Aa 3.01 ± 0.21Bb 9.72 ± 0.03Aa

Lipids Total sugars Total fibers

4.19 ± 0.55Aa 67.85 ± 0.02Bb 9.88 ± 0.25Bb

2.26 ± 0.41Bb 75.05 ± 1.74Aa 11.27 ± 0.22Aa

Soluble fibers Insoluble fibers Caloric value (kcal/100 g)

2.08 ± 0.13Aa 7.81 ± 0.14Bb 367.06

2.69 ± 0.51Aa 8.58 ± 0.35Aa 381.87

– – ♂ 36 ♀ 46 – ♂♀ 130 ♂ 38 ♀ 25 – – –

– – 26.58% 20.80% – 52.19% 26% 39.52% – – –

– – 27% 21.13% – 57.73% 29.66% 45.08% – – –

1 Values expressed as mean and standard deviation (n = 3). Different uppercase letters in each row indicate significant differences (p ≤ 0.05, t-student). Different lowercase letters in each column indicate significant differences (p ≤ 0.05, ANOVA).

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from 4.19 to 2.26%, respectively. The lipid content of the present study may be considered high when compared to the literature. Data from the USDA. United States Department of Agriculture (2016) and Blasi et al. (2017) show a lipid content of 0.39 and 0.48% for conventional goji, respectively. While the organic cultivation of the fruit showed a content of 3.33% (USDA. United States Department of Agriculture, 2017). The observed differences can be attributed to the cultivation method, harvesting period and region of production (Suárez et al., 2007). In addition, the method and the solvent used in lipid extraction also influence the total lipids content of goji berry samples (Pedro et al., 2019). As showed in Table 1, goji fruits have high carbohydrate content. The content of available carbohydrates (total sugars) of organic (67.85%) and conventional (75.05%) goji was similar to those reported by Endes et al. (2015); USDA. United States Department of Agriculture (2016), 2017 and Yang et al. (2015). Organic and conventional goji berry can be considered a great source of carbohydrates and an important food in the diet, since it provides more than 50% of carbohydrates recommended by the RDA. As shown in Table 1, 100 g of dried fruit (organic and conventional) can provide about 28% dietary fiber recommended by the RDA for women and 42% for men. The total fiber content for organic and conventional fruits (9.88 and 11.27%, respectively) is in agreement with data in the literature (Endes et al., 2015; USDA. United States Department of Agriculture, 2016, 2017). The content of insoluble fibers for the two goji berry samples was approximately 4 times greater than the soluble fibers. Insoluble fibers, such as cellulose, hemicellulose and lignin, are important in the diet to regulate intestinal transit, reducing plasma glucose and cholesterol levels (Trumbo et al., 2002).

Table 2 Fatty acid composition of goji berry fruits as % (w/w) of total fatty acid profile1. Fatty acids Lauric acid (C12:0) Myristic acid (C14:0) Palmitic acid (C16:0) Palmitoleic acid (C16:1) Stearic acid (C18:0) Oleic acid (C18:1n9c) Linoleic acid (C18:2n6cc) Linolenic acid n-3 (C18:3n3ccc) Linolenic acid n-6 (C18:3n6ccc) Arachidic acid (C20:0) Arachidonic acid (C20:4n6cccc) Behenic acid (C22:0) Docosadienoic acid cis-13,16 (C22:2) Lignoceric acid (C24:0) SFA2 MUFA3 PUFA4

Organic

Conventional Ak

0.61 ± 0.01 0.12 ± 0.01Am 10.68 ± 0.04Ac 0.38 ± 0.18Al 2.99 ± 0.01Bd 21.01 ± 0.02Ab 54.68 ± 0.16Aa 2.31 ± 0.01Af 2.57 ± 0.01Be 0.68 ± 0.02Bk 1.01 ± 0.04Bh 0.75 ± 0.01Bj 1.25 ± 0.07Bg 0.96 ± 0.07Bi 16.79 ± 0.08Bc 21.39 ± 0.05Ab 61.82 ± 0.10Aa

– – 12.04 ± 2.43Ac – 3.21 ± 0.29Ag 19.58 ± 1.64Ab 37.06 ± 2.09Ba 1.20 ± 0.01Bi 3.48 ± 0.87Af 1.49 ± 0.71Ah 3.70 ± 1.91Af 7.58 ± 2.15Ad 5.61 ± 2.37Ade 5.04 ± 0.63Ae 29.36 ± 0.05Ab 19.58 ± 0.09Bc 51.05 ± 0.06Aa

1 Values expressed as mean and standard deviation (n = 3). Different uppercase letters in each row indicate significant differences (p ≤ 0.05, t-student). Different lowercase letters in each column indicate significant differences (p ≤ 0.05, ANOVA). 2 SFA - satured fatty acids. 3 MUFA – monounsatured fatty acids. 4 PUFA - polyunsatured fatty acids.

The content of proteins, total sugars, total and insoluble fibers of conventional goji were significantly greater (p ≤ 0.05) than that of organic goji. According to Siderer et al. (2005), the higher nutrient content in conventional crops can be explained by the use of chemical fertilizers, which increase the availability and absorption of available nitrogen, essential for the nutritional development of the plant. Organic goji fruits presented higher contents of ash and lipids compared to conventional ones, explained by the plant response to physiological stress situations. Organic plants are more susceptible to attack by pests and pathogens, and fragile to adverse weather conditions. Thus, the plant tends to produce defense compounds, such as fatty acids with antioxidants functions and mineral that act as cofactors, regulating the metabolic pathways of the plant (Peñuelas et al., 2008). The moisture content of both samples is explained by the drying process applied. Drying is widely used in goji fruits in order to improve export logistics, reducing the initial moisture content by approximately five times (Dahech et al., 2013; Nguyên and Savage, 2013). The moisture content determined for organic (15.12%) and conventional (15.29%) goji in dry form was higher than those found in the literature, 7.50% (USDA. United States Department of Agriculture, 2016) and 10.34% (Endes et al., 2015). These differences can be explained by the use of different drying techniques (natural or artificial), which influence the evaporated water content (Donno et al., 2016). The content of ash for organic (5.02%) and conventional (3.01%) dry goji berry samples were higher than in the fresh fruit, 1.06% (Dahech et al., 2013). The reduction of moisture in drying processes causes the concentration of minerals in dried fruit. Mineral nutrients present important functions in plants, acting as cofactors in many enzymatic reactions, such as the biosynthesis of amino acids and organic acids (Watanabe et al., 2015). Protein contents ranged from 9.57 to 9.72% for organic and conventional fruit, respectively. Data from the literature demonstrate a protein content of 8.90 to 14.26% for conventional goji berry (USDA. United States Department of Agriculture, 2016; Endes et al., 2015). Protein content in goji berry corresponds to approximately 26% of RDA for women and 20% for men. Although it contains all the indispensable amino acids, goji fruits have low protein content and are not considered to be optimal sources of amino acids (Donno et al., 2016). The lipid content of goji, organic and conventional fruits ranged

3.1. Fatty acids composition Fatty acids composition (% fatty acids) and their relative contribution to the total lipids of the entire goji fruits in the organic and conventional systems is shown in Table 2. Fourteen fatty acids were identified and quantified in goji berry oils and the most abundant fatty acids in oils of both cultivation systems of goji berry were linoleic (C18:2n6cc) followed by oleic (C18:1n9c), palmitic (C16:0) and stearic (C18:0) acid. This agrees with the results previously obtained by Endes et al. (2015); Blasi et al. (2017) and Rosa et al. (2017). The linoleic acid was the main fatty acid identified in organic and conventional goji berry. This compound is an essential fatty acid derived from the ω-6 family and is not synthesized by animal tissues. Therefore, a diet rich in linoleic acid is extremely important in maintaining the physiological and biological functions (Sánchez-Salcedo et al., 2016). The organic goji berry can be considered a rich source of linoleic acid (54.68%) compared to other berry fruits: açaí berry, 12.59–15.54% (Batista et al., 2016); cranberry, 23.65–29.64% (Chen et al., 2015), maqui berry, 46–46.31% (Brauch et al., 2016) and blueberry, 43.50% (Parry et al., 2005). After grouping of goji berry fatty acids, the abundance order was polyunsaturated (PUFA) > monounsaturated (MUFA) > saturated (SFA) (Table 2). The major fraction of the PUFA represented 61.82% in organic fruit and 51.05% in conventional goji. The MFA also showed considerable percentages in the organic and conventional goji, 21.39 and 19.58%. The SFA fraction was represented for 16.79 and 29.36% in organic and conventional in goji fruits. The high percentage of PFA in oils from goji fruits indicates a profile of important bioactive compounds with great potential for use in the food, cosmetic and pharmaceutical industries (Górnaś and Rudzińska, 2016). The differences in the composition of fatty acids between organic and conventional fruits can be explained by nutritional composition of the soil, influence of genetic factors, fruit ripening and ultraviolet radiation (Connor et al., 2002). In addition, different environmental stresses can cause this variation. Organic vegetables are more intensively attacked by insects and this favor the synthesis of compounds from the primary and secondary metabolism (Macoris et al., 2012). 4

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Table 3 Mineral composition, heavy metals and RDA of goji berry samples. Minerals

RDA (minimum)

Goji berry1

(mg/100 g)

mg/day

Organic

Potassium (K) Sodium (Na) Phosphor (P) Calcium (Ca) Magnesium (Mg)

– – – ♂♀ 1000 ♂ 420 ♀ 310 ♂8 ♀ 18 ♂ 11 ♀8 ♂♀ 0.9 ♂ 2.3 ♀ 1.8

7.42 ± 0.59Af

7.07 ± 0.49Bf

1.96 ± 0.20Ag

1.75 ± 0.30Bg

1.54 ± 0.20Ah 0.98 ± 0.20Bi

0.98 ± 0.01Bh 1.68 ± 0.20Ag

– – –

0.01 ± 0.00Ab 0.07 ± 0.01Ba 0.01 ± 0.00Bb

0.02 ± 0.01Ab 0.16 ± 0.01Aa 0.15 ± 0.01Aa

Iron (Fe) Zinc (Zn) Copper (Cu) Manganese (Mn) Heavy metals (mg/kg) Cadmium (Cd) Mercury (Hg) Lead (Pb)

2200.00 ± 21.02 370.00 ± 5.82Ab 183.75 ± 4.45Bc 149.50 ± 6.36Ad 67.50 ± 3.54Be

%RDA Conventional Aa

2120.00 ± 14.15 178.00 ± 7.02Bc 212.10 ± 7.92Ab 126.00 ± 9.90Bd 73.50 ± 4.95Ae

Ba

Organic

Conventional

– – – 14.95 16.07 21.77 92.75 41.22 17.82 24.50 171.11 44.55 54.44 Maximum level2 (mg/kg) 0.05 0.10 0.10

– – – 12.60 17.50 23.71 88.37 39.28 15.91 21.87 108.89 73.04 93.33

1 Values expressed as mean and standard deviation (n = 3). 2Maximum levels allowed by Codex Alimentarius (2015). Different letters on each line indicate significant differences (p ≤ 0.05, t-student). Different letters in each column indicate significant differences (p ≤ 0.05, ANOVA).

3.2. Mineral composition and heavy metals

3.3. Soluble sugars and organic acids

Mineral composition of organic and conventional goji fruits is showed in Table 3. The organic and conventional goji fruits were characterized by high content of the macroelement K (2200 and 2120 mg/100 g, respectively), followed by Na (370 and 178 mg/100 g), P (183.75 and 212.10 mg/100 g), Ca (149.50 and 126 mg/100 g) and Mg (67.50 and 73.50 mg/100 g). Essential microelements were also determined: Fe (7.42 and 7.07 mg/100 g), Zn (1.96 and 1.75 mg/ 100 g), Cu (1.54 and 0.98 mg/100 g) and Mn (0.98 and 1.68 mg/100 g). The minerals content determined in this study was similar to those reported by Endes et al. (2015) and Llorent-Martínez et al. (2013). The samples this study presented high contents for all macro and microelements studied when compared with other berry fruits: blueberry, bilberry and red berry (Skesters et al., 2014). The recommended dietary allowance (RDA) was also determined in the goji berry samples (Table 3). According to the Food and Nutrition Board (FNB), foods that contain a mineral content above 15% of RDA can be considered as good sources of mineral nutrients. Therefore, considering contents above 15% of the RDA, organic and conventional goji fruits are considered to be excellent sources of the essential nutrients Mg, Fe, Zn, Cu and Mn. As shown in Table 3, organic fruits presented significantly higher levels of K, Na, Ca, Fe, Zn and Cu elements (p ≤ 0.05) than conventional goji. These results can be explained by the application of organic fertilizers, which provide a great amount of nutrients and microorganisms to the soil. Microorganisms accelerate nutrient mineralization and increase the availability of minerals in plants (Zhang et al., 2017). The concentrations of heavy metals in the goji berry samples are shown in the Table 3. Organic goji berry showed concentrations of the toxic elements Cd, Hg and Pb (0.01, 0.07 and 0.01 mg/kg, respectively) within the limits established by the Codex Alimentarius (2015). Conventional fruits presented levels of Hg and Pb (0.16 and 0.15 mg/kg, respectively) above the established maximum levels (Hg and Pb, 0.10 mg/kg for both) and are related to the chemical agents used, which may present high concentrations of these toxic compounds. According to the Codex Alimentarius (2015), the accumulation of these toxic compounds can pose serious risks to human health.

Soluble sugars and organic acids play important roles in the nutritional quality and organoleptic characteristics of fruits, such as taste, flavor and texture (Mikulic-Petkovsek et al., 2007). Soluble sugars and organic acids from the organic and conventional goji berry samples were identified and quantified by HPLC-IR (supplementary material, Fig. S1 and S2). The results of the sugars and organic acids analysis are presented in Table 4. The main sugar identified in the analyzed organic and conventional samples was fructose (5.45 and 4.92 g/100 g), followed by glucose (4.15 and 4.46 g/100 g) and sucrose (0.33 and 0.37 g/100 g), previously reported by Mikulic-Petkovsek et al. (2012). The fructose and glucose contents showed a significant difference (p ≤ 0.05) between organic and conventional samples. The low sucrose content determined in the goji berry samples may be strongly related to enzymatic hydrolysis during the maturation process and after the translocation of the leaves (Ruiz-Rodríguez et al., 2011; Mikulic-Petkovsek et al., 2012). The high content of fructose is organoleptically desirable as this sugar is sweeter than glucose and sucrose, a key feature for consumer acceptability (Wang et al., 2009). Citric acid was the main organic acid present in organic and conventional goji berry samples (0.90 and 1.14 g/100 g, respectively), Table 4 Sugars and organic acids of goji berry samples1. Compounds (g/100 g)

Samples Organic

Fructose Glucose Sucrose Oxalic acid Tartaric acid Quinic acid Malic acid Citric acid Fumaric acid

5.45 4.15 0.33 0.66 0.21 0.04 0.07 0.90 0.18

± ± ± ± ± ± ± ± ±

Conventional Aa

0.13 0.25Bb 0.06Ac 0.01Bb 0.01Ac 0.01Af 0.00Be 0.02Ba 0.01Ad

4.92 4.46 0.37 0.72 0.11 0.05 0.11 1.14 0.18

± ± ± ± ± ± ± ± ±

0.31Bª 0.26Ab 0.15Ac 0.01Ab 0.01Bc 0.00Af 0.01Ae 0.01Aa 0.00Ad

1 Values expressed as mean and standard deviation (n = 3). Different uppercase letters in each row indicate significant differences (p ≤ 0.05, t-student). Different lowercase letters in each column indicate significant differences (p ≤ 0.05, ANOVA).

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blue) (Voss, 1992). As shown in Table 5, it can be said that the organic and conventional fruits presented opaque or "black" luminosity, with the L* ranging from 38.79 and 34.83, respectively. Regarding the shades, goji fruits showed orange-reddish color. The coloring of goji fruit is attributed to large amount of carotenoids, important pigments responsible for the yellow, orange and red color of many fruits and vegetables (Amagase and Farnsworth, 2011). Organic and conventional fruits showed significant differences (p ≤ 0.05) for all analyzed parameters (Table 5). Conventional fruits presented higher TTA (4.60 meq NaOH/100 g) compared to organic fruits (3.84 meq NaOH/100 g), related to the higher content of organic acids identified in conventional fruits (Table 4), according to data presented above. These results demonstrate that conventional goji berry have higher astringency compared to fruits grown in the organic system. Organic fruit showed higher values of pH (5.50) when compared to conventional ones (5.31). These results demonstrate a lower acidity in organic fruits, an important characteristic for the consumer acceptance of the product (Borguini et al., 2003). The TSS content was higher for conventional fruits (15°Brix) compared to organic fruits (14.50°Brix), related to the degree of maturation and total and reducing sugar content. These characteristics affect attributes such as taste, sweetness, acidity and flavor (Miguel, 2007). Conventional goji berry showed higher Aw value (0.37) compared to organic goji berry (0.34) and these differences may be related to the applied drying method, which will influence the final water content in the food. In addition, the drying process can modify the chemical constitution of the fruit, changing the content of TSS, organic acids and phytochemical compounds (Nunes et al., 2016). The color parameter showed that organic fruits presented higher values of L * (38.79) than the conventional fruits (34.83), indicating a more intense coloration. These results may be related to the content of carotenoids, which influence the incidence of light and ripening (Pertuzatti et al., 2015).

Table 5 Total titratable acidity, pH, total soluble solids, water activity and color of organic and conventional goji berry. Analysis1

TTA2 (meqNaOH 0,1 N/100 g) pH TSS3 (°Brix) Water activity (Aw) Color4 (L*) (a*) (b*)

Goji berry Organic

Conventional

3.84 ± 0.22b 5.50 ± 0.01a 14.50 ± 0.04b 0.34 ± 0.01b 38.79 ± 0.33a 32.42 ± 0.61a 39.79 ± 0.79a

4.60 ± 0.20a 5.31 ± 0.04b 15.00 ± 0.12a 0.37 ± 0.01a 34.83 ± 0.84b 31.82 ± 0.40a 34.99 ± 0.65b

1

Values expressed as mean and standard deviation (n = 3). Total titratable acidity. 3 Total soluble solids. 4 L* variation between white and black, a* variation between red (+) and green (-) and b* variation between yellow (+) and blue (-). In each row, different letters indicate significant differences (p ≤ 0.05, t-student). 2

followed by oxalic, tartaric, fumaric and lower concentrations, malic and quinic acids (Table 4). Studies show that citric acid, due to their antioxidant activity, may have a protective role against various diseases through the chelation of metals and stabilization of reactive species (free radicals) (López-Bucio et al., 2000; Seabra et al., 2006). The content of all organic acids identified, except for quinic and fumaric, showed a significant difference (p ≤ 0.05) between organic and conventional fruits. Different organic acid contents in goji bery samples were determined in the literature. Citric and malic acids were the main organic acids present in goji berry, identified by Mikulic-Petkovsek et al. (2012), while for Donno et al. (2016) the main organic acid was the quinic. These variations can be explained by the influence of factors such as cultivar, stage of maturation, fertilization, irrigation and soil composition (Feltrin, 2002).

4. Conclusions 3.4. Physicochemical properties

Variability in nutrient composition was observed between goji fruits grown in the organic and conventional systems. However, the two forms of cultivation can be considered sources of nutrients. Goji fruits grown in the conventional system showed a higher content of proteins, total sugars and total fibers, while organic fruits had higher levels of ash and lipids. According to the recommended dietary allowance (RDA), goji berry is a source of the essential nutrients Mg, Fe, Cu and Mn, contributing positively to the diet. The concentration of the toxic elements Cd, Hg and Pb of organic fruit is within the limits established by the Codex Alimentarius, while conventional fruits presented Hg and Pb levels above the established maximum levels. The linoleic acid was the main fatty acid identified in organic and conventional goji berry. Three main sugars (fructose, glucose and sucrose) were identified and quantified in the goji berry samples, with fructose being the predominant sugar. Among the identified organic acids, citric acid was found in higher content, followed by oxalic, tartaric, fumaric, malic and quinic acids. The parameters, ATT, pH, SST, Aw and color were sensorially desirable for organic and conventional fruits. Therefore, goji berries can be a good ingredient for the food industry and goji fruits grown in organic systems are better alternatives to ensure the food safety of industrialized products due to its lower content on heavy metals (Cd, Hg and Pb).

Table 5 shows the analytical parameters of total titratable acidity (TTA), pH, total soluble solids (TSS), water activity (Aw) and color of the organic and conventional goji berry samples. Organic and conventional goji samples presented TTA results (3.84 and 4.60 meq NaOH/ 100 g), pH (5.50 and 5.31) and TSS (14.50 and 15°Brix) close to those reported by Donno et al. (2016) and Zhang et al. (2017). The TTA in fruits relates the content of organic acids with sensory characteristics, such as astringency. In addition, organic acids play an important role in the nutritional maintenance of fruits (Ferreira et al., 2010). Drying process of the organic and conventional goji berry samples allowed a low Aw (0.34 and 0.37, respectively) (Table 5). Fig. 1A and B show that dried commercial goji fruits have roughened structures with small depressions, characteristic of products with low Aw. In addition, after the drying process, sugar-rich fruits tend to be hygroscopic due to structural changes of these molecules, such as the high degree of amorphism. These changes are undesirable, especially in products marketed in powder, due to the high agglomeration of the sugar molecules. In addition, they make the product sensitive to physical, chemical and microbiological changes, which detract from shelf life and product stability (Alves et al., 2008). Micrographs of crushed samples of organic and conventional goji berry (Fig. 1C and D) show such agglomeration phenomenon, related to the high sugar content and the hygroscopic potential of goji berry fruits. Color is an important attribute in the food industry, as it is a parameter of quality that influences consumer acceptance of the product. The determination of color in foods is performed through the L*, a* and b* system. The L* indicates brightness, ranging from 0 (opaque or "black") to 100 (transparent or "white"), a* positive values indicate red tint (-a*, green), and positive b* values indicate hue yellow (-b*,

Acknowledgements The authors would like to thank the following fomenting agents for financial support: CAPES/PROAP, Universidade Federal do Paraná (UFPR), ALIMNOVA-UCM research group and Art.83 project ref: UCM 252/2017, and Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq). 6

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Fig. 1. Micrographs of whole goji berries: organic (A) and conventional (B), and crushed goji berries: organic (C) and conventional (D).

Appendix A. Supplementary data

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