The present experiment investigated the response of mini plum tomatoes 'Angelle' (red fruit) and 'Dolcenera' (brownish fruit) to foliar applications of Zn-EDTA (1.7 mmol L- 1) and triacontanol (11.4 mu mol L- 1, TRIA), applied either alone or in combination, in terms of carpometric traits, carotenoid and mineral profiles determined on second (CII) and sixth (CVI) clusters. (all-E)-Lycopene was higher and stable across clusters in 'Angelle' (2009 mu g 100 g- 1 FW, on average), whereas 'Dolcenera' showed higher concentrations of (all-E)-(3-carotene and lutein (on average 793 and 92 mu g 100 g- 1 FW, respectively), although both decreased from CII to CVI (-30% and -38%, respectively). Compared to control, both TRIA-based treatments promoted the accumulation of (all-E)lycopene (+20%), (all-E)-(3-carotene (+9%, on average), and total carotenoids (+15%) in fruits, with stronger effects in 'Angelle'. 'Dolcenera' also showed higher concentrations of fruit macrominerals (except Ca), while ZnEDTA application, either alone or combined with TRIA, produced the strongest effects on fruit mineral composition, increasing Zn concentration (+67%, on average) and reducing its variability between clusters. Overall, the results indicate that foliar applications of triacontanol promote carotenoid accumulation in mini plum tomatoes, whereas Zn-EDTA enhances the Zn concentration and stabilizes its levels across clusters. These findings suggest that combining cultivar diversification, including the brownish mini plum typologies, with targeted foliar applications of triacontanol and Zn-EDTA may represent a viable strategy to modulate carotenoid and mineral composition while maintaining a more consistent nutritional profile of greenhouse mini plum tomatoes over the harvest season.

This study examines the fate of inorganic phosphonate residues in grape berries and throughout the winemaking process, focusing on their distribution, transformation, and potential external inputs. Using IC-ICP-MS, phosphonic acid was quantified in berry skins, pulp and seeds as well as in the derived musts and wines. Seeds, representing only ca. 6 % of the total berry mass, showed the highest phosphonate concentrations (436 +/- 117 mg/kg, 30 % of the total average phosphonate per berry), indicating specific but yet unknown accumulation mechanisms. Fermentation of Riesling musts from organically managed, phosphonate-treated vineyards led to slight reductions in residue levels (e.g., from 4.38 to 3.27 mg/L; from 101.47 to 91.17 mg/L in spiked musts). Trials with nine fining agents showed no substantial reduction. For instance, the most effective treatment, gelatin, lowered phosphonate levels in must from 1.53 to 1.42 mg/L, with even smaller effects in wine. Activated carbon had no measurable impact, highlighting the limited efficacy of standard clarification techniques against highly water-soluble anionic residues. Screening of 60 oenological processing aids revealed that 33 % contained quantifiable phosphonate residues, with diammonium phosphate (DAP) showing the highest contamination (up to 166 mg/kg DAP). These findings demonstrate that phosphonate residues persist through vinification and confirm earlier findings that it may be introduced not only in the vineyard, but also during processing, even under alleged organic production standards. Improved monitoring and mitigation strategies are needed to ensure residue compliance and integrity in organic wine production.

This experiment addressed the response of the carrots 'Dordogne' (orange roots), 'Mello Yello' (yellow), and 'Purple Sun' (purple) to different foliar treatments, over two seasons (SI and SII). Plants were treated with either a plant-derived biostimulant (PDB, T1), a biofortifying solution (FeSO4, T2), or their combination (T3) and compared to controls. Root carotenoids peaked in 'Dordogne' (9284 and 8104 μg 100 g-1 FW in SI and SII, respectively) while 'Purple Sun' had the highest minerals and hydroxycinnamic acids levels (64.7 and 80.5 mg 100 g-1 FW). In both seasons, T3 best promoted the root accumulation of iron (+18.2 and + 39.1% in SI and SII), carotenoids (+35.3 and + 35.6%), hydroxycinnamic acids (+73.5 and + 40.9%), and anthocyanins (+30.0 and + 25.6%). Our results highlight the role of different carrot typologies toward the dietary diversification of minerals and phytochemicals, while promoting the use of PDBs and Fe-biofortification to further enhance their nutritional traits.

This study investigated the translocation and persistence of inorganic phosphonate in container-grown vines of Vitis vinifera L. cv. Riesling after foliar and soil applications over two consecutive years. Phosphonate concentrations were monitored in leaves, petioles, grape canes, shoot tips, inflorescences, and berries during the season, applying an identical total amount of 3 or 4 sprays of 0.54 or 0.4% (w/v, aq) phosphonate, respectively. The overall uptake of inorganic phosphonate into the leaves was either identical (year 1) or substantially lower (year 2) when spraying 3 times (0.54%) instead of 4 times (0.4%) as expressed by the area under the concentration vs time curve. Residues found in leaves at the end of the vegetation period were also lower when spraying 3 times. Across both years, residues in berries were also significantly lower when applying the 0.54% phosphonate solution (20.2-30.9 mg/kg) 3 times as compared with the 4× application of 0.4% phosphonate (38.5-40.6 mg/kg). Soil applications resulted in a comparably low overall uptake but still yielding measurable residues in berries (6.0 ± 1.2 mg/kg). Further data on grape cane, shoot tips, and inflorescences supported the hypothesis that phosphonate residues in the plant and, ultimately, in the berries and the resulting products might be significantly reduced when spraying 3 times (0.54%) instead of 4 times (0.4%).

The present experiment addressed the effects of a plant-derived biostimulant (PDB, Bioup (R) TF) on fruit quality and composition of two greenhouse cherry tomato cultivars (Caravaggio and Creativo) grown during the autumn-winter. The biostimulant application enhanced the marketable fruit yield up to 1.148 g m(-2) of 'Creativo' (+16 %) and increased the fruit dry matter, firmness, and chroma (C*), particularly of 'Caravaggio' (by 23, 12, and 11 %, respectively). 'Caravaggio' also showed the strongest increase in total polyphenols (+26 %) and carotenoid contents (+50 %) in response to the treatment. This trend paralleled the strongest rise of the in vitro antioxidant activity of its fruit extracts, as revealed by the DPPH and FRAP assays. Moreover, the biostimulant treatment resulted in higher concentrations of 10 among 12 minerals analyzed in fresh fruit. This effect was particularly relevant for calcium, manganese, and copper, whereas 'Caravaggio' proved the strongest rise for potassium, magnesium, sodium, and zinc. Interestingly, the biostimulant application did not promote or even reduced the concentration of nickel in fresh 'Caravaggio' and 'Creativo' (-38 %) fruit, respectively. This suggests that the integration of PDBs in the framework of agronomic strategies could assist in producing Ni-poor tomatoes while increasing, at the same time, their levels in health-promoting minerals.

In the European Union, organic viticulture faces enormous challenges in controlling grapevine downy mildew since the ban on inorganic phosphonates or phosphonic acid in 2013. However, inorganic phosphonate is still detected in organic wines, although the responsible winegrowers often pledge that they had not sprayed phosphonate-containing products in their vineyards. Among several hypotheses on the origin, the emergence of phosphonate from the soil, e.g., due to preceding applications or from contaminated groundwater, is in dis-cussion. This study investigates whether an analytical differentiation of the origin of phosphonate in the plant or the final product might be feasible by examining leaf and petiole tissue. A total of 908 leaf and petiole samples of various grapevine cultivars were collected from a container vine experiment as well as from four experimental vineyard sites in Germany, on which phosphonate was either sprayed onto the plants as part of crop protection (all experiments), applied to the soil (container experiment only) or present as residue from previous applications (vineyard experiments). Phosphonate concentrations in leaves and petioles depended strongly on whether plants had been sprayed or had taken up phosphonate from the soil. Therefore, an index was created and tested using independent datasets from different geographical locations, based on the concentrations found in leaves and petioles. Index accuracy was at 99.1% correct classifications when distinguishing phosphonate origin from the soil versus that from foliar spraying. Furthermore, phosphonate uptake from the soil was shown to allow considerable phosphonate concentrations in the berries and musts, rendering associations of phosphonate resi-dues in wines with accusations of an actual foliar application highly questionable. In brief, our data and index might provide an approach for identifying the source of phosphonate contamination in the grapevine plant and, if suitable sample material is available, also the related products.

Methanol, a hepato- and neurotoxic compound, is present in apple-based beverages as a by-product of the enzymatic degradation of pectin. Stable isotope dilution assay (SIDA) employing gas chromatography-mass spectrometry (GC-MS) is the state-of-the-art method for methanol determination in beverages. Despite higher initial investment costs, quantitative 1H NMR spectroscopy (qNMR) is a simpler and faster analytical technique to quantify numerous analytes in liquid foods. Beyond targeted analyses, qNMR spectral fingerprints in the product might be used for non-targeted analytical goals, such as adulteration and contamination detections. Here, an existing 1H-qNMR method used for wine profiling was optimised for methanol quantification in apple-based products, including cross-validation against a SIDA-HS-GC-MS method and reference values from interlaboratory trials. The optimisation involved a pivotally important estimation of a correction factor by an external calibration approach, making qNMR results comparable to SIDA-HS-GC-MS. The optimised qNMR method is suggested to be an alternative for methanol quantification in beverages.

Potassium dihydrogen phosphonate had been allowed as a plant strengthener in organic viticulture in the European Union only until 2013, supporting the control of grapevine downy mildew. Therefore, low or nondetectable levels are a prerequisite for marketing of organic wines and, consequently, validated analytical methods are of major interest. Herein, two methods based on ion chromatography conductivity detection (IC-CD) or ion chromatography inductively coupled plasma mass spectrometry (IC-ICP-MS) for the determination of phosphonic acid (H3PO3) from 14 different plant matrices of Vitis vinifera L., wine, and soil were developed, validated, and compared. Extraction recoveries ranged from 95.1 to 99.3%. Limits of quantification (LOQ) ranged in liquid and solid samples from 3.8 to 16.8 μg/kg and 0.08 to 2.41 mg/kg for ICP-MS detection and from 39.9 to 593.7 μg/kg and 3.51 to 58.7 mg/kg for CD, respectively. Data on a current anonymized selection of 100 conventionally and 30 organically produced wines are briefly presented to demonstrate the suitability of the method.

Mycotoxins are frequently found in fruits and fruit juices. However, data about occurrence and fate of mycotoxins along the fruit juice processing chain are currently insufficient. Herein, a liquid chromatographic/tandem mass spectrometric (LC–MS/MS) multi-mycotoxin method was developed and applied to investigate the effect of technological unit operations on the fate of three of the most relevant mycotoxins along the processing chain for cloudy and clear apple juice, namely patulin (PAT), ochratoxin A (OTA), and alternariol (AOH). Raw juice obtained directly after dejuicing was spiked with the aforementioned mycotoxins at pilot-plant scale prior to subjecting it to different technological unit operations. Regarding clear apple juice production treatment with a pectinolytic enzyme preparation, and pasteurization were insignificant for mycotoxin reduction, but fining with subsequent filtration was effective, although the mycotoxins showed different affinity towards the tested agents. The most effective fining agent was activated charcoal/bentonite in combination with ultrafiltration, which removed OTA (54 µg/L) and AOH (79 µg/L) to not quantifiable amounts (limit of quantification (LOQ) 1.4 and 4.6 µg/L, respectively), while PAT was reduced only by 20% (from 396 to 318 µg/L). Regarding cloudy apple juice production, all studied processing steps such as centrifugation and pasteurization were ineffective in reducing mycotoxin levels. In brief, none of the common steps of clear and cloudy apple juice production represented a fully effective safety step for minimizing or even eliminating common mycotoxins. Thus, ensuring the sole use of sound apples should be of utmost importance for processors, particularly for those manufacturing cloudy juices.

In the present study, nutritionally relevant constituents of wild-growing B. guineensis palm fruit from Costa Rica were assessed. In the edible exo- and mesocarp, 24 soluble free and six insoluble bound phenolic compounds were found. Anthocyanins, catechin mono- and oligomers, quercetin O-glycosides, in addition to apigenin- and luteolin C-glycosides were identified in the soluble free fraction, totalling to 17 and 398 mg/100 g of fresh weight (FW) in the meso- and exocarp, respectively. The insoluble-bound phenolic compounds exclusively comprised phenolics acids (9.4 and 39 mg/100 g of FW, respectively). Among 15 different carotenoids, (all-E)-beta-carotene and (all-E)-lutein prevailed. Total carotenoid levels in meso- and exocarp amounted to 363 and 1728 mu g/100 g of FW, respectively. Among tocochromanols, merely alpha-tocopherol was found in quantifiable concentrations (230 and 2401 mu g/100 g of FW, respectively). In the kernel, total lipids represented 34.1% of the dry matter, mainly consisting of saturated fatty acids (90.0%). Hereby, lauric (56.3%) and myristic acid (23.0%) were the most abundant ones. Nutritionally relevant elements of the exocarp, mesocarp, and kernel were assessed by ICP-MS. In particular, the kernel was rich in magnesium and iron (68 and 2.65 mg/100 g of FW, respectively) and hence, a good nutritional source for these elements. Concluding, the present study is the first detailed report on the composition of the edible fractions of B. guineensis fruit, highlighting the nutritional, but also the hitherto unexploited industrial potential of this underutilised crop.

This study reports a clear-cut relationship of the technological use of specific filter aids with highly variable vanadium levels in beer, wine, and fruit juices. First, the previously reported broad range of vanadium levels was confirmed in 68 commercial beverages by ICP-MS. Since cloudy apple juices exhibited significantly lower vanadium amounts than clear apple juices, filter aids used for clarification were analyzed and found to contain substantial and highly variable amounts of vanadium, particularly in all analyzed diatomite (38-368 mg vanadium per kg filter aid), but not in perlite products ( < 4 mg/kg). Subsequent pilot-scale precoat filtration experiments (170 L/batch) proved vanadium to be released from diatomite (Kieselguhr), increasing its levels from ca. 2.1-2.6 mu g/kg unfiltered to 27-201 mu g/kg filtered juice, depending on the use of diatomites high or low in vanadium. Thus, filter aid selection was shown to modulate the vanadium concentrations in clarified beverages.

Methyl jasmonate (MeJ) induced biosynthesis of volatile organic compounds (VOCs) was observed in a time-course experiment with grape berries of Vitis vinifera cv. Lemberger. A rapid emission of linalool within 2-6 hours after application of the elicitor was observed, followed by the emission of additional monoterpenes, indole and homo-as well as sesquiterpenes within 36 hours. The parallel application of [5,5-H-2(2)]-1-deoxy-D-xylulose (d(2)-DOX) confirmed the rapid de novo synthesis of the induced terpenes, especially linalool. Indole and the dehydroterpene cosmene were detected for the first time as defense related volatiles in grape berries.

The biosynthesis of the diterpenoid steviol glycosides rebaudioside A and stevioside in nonrooted cuttings of Stevia rebaudiana was investigated by feeding experiments using the labeled key precursors [5,5-(2)H2]-mevalonic acid lactone (d2-MVL) and [5,5-(2)H2]-1-deoxy-d-xylulose (d2-DOX). Labeled glycosides were extracted from the leaves and stems and were directly analyzed by LC-(-ESI)-MS/MS and by GC-MS after hydrolysis and derivatization of the resulting isosteviol to the corresponding TMS-ester. Additionally, the incorporation of the proffered d2-MVL and d2-DOX into volatile monoterpenes, sesquiterpenes, and diterpenes in glandular trichomes on leaves and stems was investigated by headspace-solid phase microextraction-GC-MS (HS-SPME-GC-MS). Incorporation of the labeled precursors indicated that diterpenes in leaves and monoterpenes and diterpenes in glandular trichomes are predominately biosynthesized via the methylerythritol phosphate (MEP) pathway, whereas both the MEP and mevalonate (MVA) pathways contribute to the biosynthesis of sesquiterpenes at equal rates in glandular trichomes. These findings give evidence for a transport of MEP pathway derived farnesyl diphosphate precursors from plastids to the cytosol. Contrarily, the transport of MVA pathway derived geranyl diphosphate and geranylgeranyl diphosphate precursors from the cytosol to the plastid is limited.

The sesquiterpene biosynthesis in the exo- and mesocarp of grape berries (Vitis vinifera cultivar Lemberger) was investigated using in vivo feeding experiments with the key precursors [5,5-²H2]-mevalonic acid lactone (d2-MVL) and [5,5-²H2]-1-deoxy-D-xylulose (d2-DOX). The experiments demonstrate a de novo sesquiterpene biosynthesis in the exocarp, whereas no incorporation of the precursors was detectable in the mesocarp. Furthermore, sesquiterpenes were generated with a high incorporation rate via both pathways; the classical cytosolic mevalonic acid pathway as well as the plastidial DOXP/MEP route, demonstrating a substrate transport from plastid to cytoplasm.

The participation of the mevalonic acid (MVA) and 1-deoxy-d-xylulose 5-phosphate/2-C-methyl-d-erythritol-4-phosphate (DOXP/MEP) pathways in sesquiterpene biosynthesis of grape berries was investigated. There is an increasing interest in this class of terpenoids, since the oxygenated sesquiterpene rotundone was identified as the peppery aroma impact compound in Australian Shiraz wines. To investigate precursor supply pathway utilization, in vivo feeding experiments were performed with the deuterium labeled, pathway specific, precursors [5,5-2H2]-1-deoxy-d-xylulose and [5,5-2H2]-mevalonic acid lactone. Head Space-Solid Phase Micro Extraction-Gas Chromatography-Mass Spectrometry (HS-SPME-GC–MS) analysis of the generated volatile metabolites demonstrated that de novo sesquiterpene biosynthesis is mainly located in the grape berry exocarp (skin), with no detectable activity in the mesocarp (flesh) of the Lemberger variety. Interestingly, precursors from both the (primarily) cytosolic MVA and plastidial DOXP/MEP pathways were incorporated into grape sesquiterpenes in the varieties Lemberger, Gewürztraminer and Syrah. Our labeling data provide evidence for a homogenous, cytosolic pool of precursors for sesquiterpene biosynthesis, indicating that a transport of precursors occurs mostly from plastids to the cytosol. The labeling patterns of the sesquiterpene germacrene D were in agreement with a cyclization mechanism analogous to that of a previously cloned enantioselective (R)-germacrene D synthase from Solidago canadensis. This observation was subsequently confirmed by enantioselective GC–MS analysis demonstrating the exclusive presence of (R)-germacrene D, and not the (S)-enantiomer, in grape berries.

ABSTRACTTo investigate the profiles of sesquiterpene hydrocarbons in grape berries at different developmental stages several cultivars of Vitis vinifera (Gewürztraminer, Riesling, Yellow Muscat, Shiraz, Lemberger, Cabernet Sauvignon) were analysed during ripening. Therefore, HS‐SPME‐GC‐MS measurements were performed with intact grape berries. The measurements demonstrated that grapes emit numerous sesquiterpene hydrocarbons and that the sesquiterpene profile exhibits a characteristic profile, depending on the variety and the developmental stage. In particular, bicylic sesquiterpenes with a cadinane backbone increased during ripening, while acyclic sesquiterpenes such as (E,E)‐α‐farnesene decreased, except for Gewürztraminer which shows increasing amounts of acyclic sesquiterpenes towards harvest. Furthermore, the profiles of the emitted sesquiterpenes differed significantly. In particular, Gewürztraminer possessed remarkably high amounts of (E,E)‐α‐farnesene, (3E,6Z)‐α‐farnesene and (E,E)‐methylfarnesoate, while the sesquiterpene profiles of Riesling, Lemberger, Shiraz and Yellow Muscat were dominated by bi‐ and polycyclic sesquiterpenes. Cabernet Sauvignon showed only minor profile changes during ripening and its comparatively low sesquiterpene hydrocarbon amounts were dominated by (E)‐β‐caryophyllene, α‐humulene and an unidentified sesquiterpene. Copyright © 2012 John Wiley & Sons, Ltd.

The temperature-dependent transformation of π–π-stabilized stacked malvidin–catechin structures towards polymeric-type structures was studied by photoluminescence (PL) and anisotropy decay studies. The results show an immediate decrease of the anisotropy decay after elevating the temperature from 293K to 303K or 313K, while only a very slow increase in the anisotropy decay could be observed when the samples were kept at these elevated temperatures for a longer time such as a few days. The slow polymerization of the malvidin–polyphenol system could be identified as the main process responsible for the change in optical properties by the comparison of the time-dependence of the anisotropy decay with the change observed in the PL intensity. Measurements were also conducted in red wines, where we observed similar results. This suggests a possibly broader relevance of our results for all systems, where anthocyanins and polyphenols are present in considerable concentrations.

The 4-ethylphenol (4-EP), 4-ethylguaiacol (4-EG), and 4-ethylcatechol (4-EC) concentrations were determined in 1.312 bottled wine samples from the German ‘Württemberg’ region by means of HPLC coupled with fluorescence detection. 4-EC was not detected in quantifiable concentrations in any of the samples analysed. 6.4% of the wines showed 4-EP and 4-EG concentrations over the detection limit of 16 μg/L for 4-EP and 7 μg/L for 4-EG. 1.8% of all wines were over the odour threshold. For white wines it was shown that 4-EG is the only tainting compound and that 0.3% of the wines contain 4-EG above the sensory threshold. The 4-EP and 4-EG contents averaged 17.7 and 4.7 μg/L in red wine and 2.2 and 1.0 μg/L in white wine, respectively. Based on the analytical results a statistical evaluation was performed to assess the impact of various parameters, such as wine type, storage, residual sugar content, etc., which are known to influence ethylphenol concentration. A significant difference between white wine and wine made from red grape varieties was observed. Wine stored for a long time period in wooden casks showed especially high ethylphenol content. Only a slight tendency was observed regarding the residual sugar, alcohol, total acidity and SO2 content. Based on our data, we cannot confirm the results published by some authors that varieties show significant differences with regard to their ethylphenol ratios.

1,312 wines from the Wurttemberg region (Germany) were analyzed by means of HPLC-UV/VZs-FLD for their content of 4-vinylphenol and 4-vinylguanacol. Vinylphenols were mainly detected in white wines 177 concentrations between non-detectable and 1,207 mu g/l. Only T 2.13 % of all wines show vinylphenol contents above the sensory threshold. Statistical analysis revealed that there is no correlation between the content of vinylphenols and the results of the sensory evaluation of 'Qualitatswein'. Thus, we suppose that vinylphenols do not have a significant impact on the aroma profile of German wines from the Wurttemberg region.