Investigating the impact of regionality on the sensorial and chemical aging characteristics of Pinot noir grown throughout the U.S. West coast.

The sensorial and chemical differences among Pinot noir wines from different vineyard locations were investigated. Grapes of a single Pinot noir clone were grown on twelve different vineyard sites along the U.S. West Coast. Wines from a single vintage (2015) were made using a standardized protocol and equipment. Sensorial (i.e. aroma, taste, and mouthfeel) and chemical (i.e. polyphenolic and volatile) differences were observed among these wines at two aging time points (8- and 20- months). Vineyard location (i.e. latitude and longitude) was one of the main factors describing the major differences between the wines, while other details (i.e. soil type (60 cm), rootstock age, soil pH, rootstock type, and vines/acres) were possibly important for defining unique aging characteristics of certain vineyards. Overall, single clone Pinot noir grapes grown in different regions but made under standardized winemaking produced wines with unique chemical and sensorial profiles, which generally persisted throughout aging.

Vineyard site impact on the elemental composition of Pinot noir wines.

Elemental composition was used to characterize and differentiate 14 wines made from the identical clone of Vitis vinifera cv. Pinot noir (clone 667). The vineyards span distances which range from several hundred meters to 1540 km and their elevations vary from near sea level to nearly 500 m. Twenty-seven elements were observed above the limit of quantitation by using inductively coupled plasma mass spectrometry (ICP-MS) in the wines from at least half of the 14 sites. Concentrations of several elements, including Mo, Er, Na, Li, Cs and Pb, varied by 10-fold across the 14 wines. Multiple factor analysis (MFA) of elemental composition with juice chemistry and site characterization show associations consistent with expectations, such as high Ca with high clay content. These results demonstrate that even when grapevine clone and winemaking protocol are controlled, composition differences in wines produced from sites are mediated by diverse soil and microclimate conditions.

Changes in glycosylation patterns of monoterpenes during grape berry maturation in six cultivars of Vitis vinifera.

Plants conjugate monoterpenoids to sugars, rendering them non-volatile. Hydrolysis of these glycosidic precursors frees the volatile aroma compounds. Here, we profile intact monoterpenyl glycosides in six Vitis vinifera grape berry cultivars. Relative concentrations of twenty-six monoterpenyl glycosides, including nine new putatively identified compounds, were analyzed by UHPLC-QTOF MS/MS at three times during grape maturation (pre-véraison, véraison, and post-véraison). Total glycoside content reached a maximum in Muscat cultivars post-véraison but remained relatively constant in all other cultivars. Three types of monoterpenyl glycosides predominated in all samples: malonylated monoterpenol glucosides, monoterpenol hexose-pentoses, and monoterpendiol hexose-pentoses. The two Muscat cultivars were not differentiated at the earlier developmental stages but could be differentiated post-véraison. In contrast, similarities between Chardonnay and Pinot noir glycoside profiles developed post-véraison. Overall monoterpene glycoconjugation patterns may align with underlying genetic relationships among cultivars. By understanding monoterpene glycoconjugation in wine grapes, scientists and winemakers can better understand grape and wine aromas.

GC-Recomposition-Olfactometry (GC-R) and multivariate study of three terpenoid compounds in the aroma profile of Angostura bitters.

Foods and beverage aroma results from multicomponent mixtures of volatile compounds present in the food that interact with olfactory receptors and produce a perceptual response in the brain. However, the perceptual interactions that occur when complex odor mixtures are combined are not well understood. Here we used Gas chromatography-Recomposition-Olfactometry (GC-R) to better understand the role that individual compounds have on the perceived sensory aroma of bitters. Bitters are the concentrated alcoholic extract of flavorful plant materials with a wide range of complex sensory and chemical aroma profiles that have not been extensively studied. Previously, we demonstrated that Angostura bitters are characterized by complex aroma attributes described as cola, ginger, orange peel, and black pepper and that the volatile composition of Angostura bitters is predominantly composed of terpenoids. Using GC-R to create in-instrument mixtures of the Angostura headspace extracts, the sensory attributes of Angostura extracts with linalool, α-terpinyl-acetate and caryophyllene omitted were evaluated. The omission experiments demonstrated direct and indirect effects of the individual compounds on the aroma attributes of Angostura bitters, through masking, additive, and synergistic interactions. Caryophyllene in particular, which was present in the headspace extracts at concentration only slightly above sensory threshold levels, had a large and unexpected impact on the sensory properties of the mixtures and may be most responsible for the aromas associated with the whole sample. The GC-R and statistical approaches used here provided valuable tools to reveal relationships among individual compounds and aroma attributes of foods that have not been currently theorized using existing analytical approaches.

A comparison of sorptive extraction techniques coupled to a new quantitative, sensitive, high throughput GC-MS/MS method for methoxypyrazine analysis in wine.

Methoxypyrazines are volatile compounds found in plants, microbes, and insects that have potent vegetal and earthy aromas. With sensory detection thresholds in the low ng L(-1) range, modest concentrations of these compounds can profoundly impact the aroma quality of foods and beverages, and high levels can lead to consumer rejection. The wine industry routinely analyzes the most prevalent methoxypyrazine, 2-isobutyl-3-methoxypyrazine (IBMP), to aid in harvest decisions, since concentrations decrease during berry ripening. In addition to IBMP, three other methoxypyrazines IPMP (2-isopropyl-3-methoxypyrazine), SBMP (2-sec-butyl-3-methoxypyrazine), and EMP (2-ethyl-3-methoxypyrazine) have been identified in grapes and/or wine and can impact aroma quality. Despite their routine analysis in the wine industry (mostly IBMP), accurate methoxypyrazine quantitation is hindered by two major challenges: sensitivity and resolution. With extremely low sensory detection thresholds (~8-15 ng L(-1) in wine for IBMP), highly sensitive analytical methods to quantify methoxypyrazines at trace levels are necessary. Here we were able to achieve resolution of IBMP as well as IPMP, EMP, and SBMP from co-eluting compounds using one-dimensional chromatography coupled to positive chemical ionization tandem mass spectrometry. Three extraction techniques HS-SPME (headspace-solid phase microextraction), SBSE (stirbar sorptive extraction), and HSSE (headspace sorptive extraction) were validated and compared. A 30 min extraction time was used for HS-SPME and SBSE extraction techniques, while 120 min was necessary to achieve sufficient sensitivity for HSSE extractions. All extraction methods have limits of quantitation (LOQ) at or below 1 ng L(-1) for all four methoxypyrazines analyzed, i.e., LOQ's at or below reported sensory detection limits in wine. The method is high throughput, with resolution of all compounds possible with a relatively rapid 27 min GC oven program.

Profiling monoterpenol glycoconjugation in Vitis vinifera L. cv. Muscat of Alexandria using a novel putative compound database approach, high resolution mass spectrometry and collision induced dissociation fragmentation analysis.

In this work we present a novel approach for the identification of plant metabolites using ultrahigh performance liquid chromatography coupled to accurate mass time-of-flight mass spectrometry. The workflow involves developing an in-house compound database consisting of exact masses of previously identified as well as putative compounds. The database is used to screen accurate mass spectrometry (MS) data to identify possible compound matches. Subsequent tandem MS data is acquired for possible matches and used for structural elucidation. The methodology is applied to profile monoterpene glycosides in Vitis vinifera cv. Muscat of Alexandria grape berries over three developmental stages. Monoterpenes are a subclass of terpenes, the largest class of plant secondary metabolites, and are found in two major forms in the plant, "bound" to one or more sugar moieties or "free" of said sugar moieties. In the free form, monoterpenes are noted for their fragrance and play important roles in plant defense and as attractants for pollinators. However, glycoconjugation renders these compounds odorless, and it is this form that the plant uses for monoterpene storage. In order to gain insight into monoterpene biochemistry and their fate in the plant an analysis of intact glycosides is essential. Eighteen monoterpene glycosides were identified including a monoterpene trisaccharide glycoside, which is tentatively identified here for this first time in any plant. Additionally, while previous studies have identified monoterpene malonylated glucosides in other grapevine tissue, we tentatively identify them for the first time in grape berries. This analytical approach can be readily applied to other plants and the workflow approach can also be used for other classes of compounds. This approach, in general, provides researchers with data to support the identification of putative compounds, which is especially useful when no standard is available.

Regional sensory and chemical characteristics of Malbec wines from Mendoza and California.

Malbec grapes are widely grown and studied in Argentina, whereas the smaller production in California is less well known. This study sought to define and compare Malbec wine compositions from various regions in Mendoza, Argentina and California, USA. The Malbec wines were clearly separated, based on their chemical and sensory profiles, by wine region and country. Descriptors of Malbec wines were aromas of cooked vegetal, earthy, soy and volatile acidity, as well as acidic taste and astringent mouthfeel, regardless of the region of origin. Malbec wines from Mendoza generally had more ripe fruit, sweetness, and higher alcohol levels, while the Californian Malbec wines had more artificial fruit and citrus aromas, and bitter taste. Compositional differences between the two countries were related more to altitude than precipitation and growing degree days. To our knowledge, this is the first time that an extensive regionality study has been attempted for Malbec wines.