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1 Keck Geology Consortium 21st Keck Research Symposium in Geology Short Contributions April 28 Dr Andrew P. de Wet, Editor Keck Director Franklin & Marshall College Keck Geology Consortium Franklin & Marshall College PO Box 33, Lancaster Pa, 1763 Dr Amy Rhodes, Symposium Organizer Smith College Keck Geology Consortium Member Institutions: Amherst College Beloit College Carleton College Colgate University The College of Wooster The Colorado College Franklin and Marshall College Macalester College Mt. Holyoke College Oberlin College Pomona College Smith College Trinity University Union College Washington and Lee University Wesleyan University Whitman College Williams College Projects: Tectonic and Climatic Forcing of the Swiss Alps John Garver (Union College), Mark Brandon (Yale University), Alison Anders (University of Illinois), Jeff Rahl (Washington and Lee University), Devin McPhillips (Yale University) Students: William Barnhart, Kat Compton, Rosalba Queirolo, Lindsay Rathnow, Scott Reynhout, Libby Ritz, Jessica Stanley, Michael Werner, Elizabeth Wong Geologic Controls on Viticulture in the Walla Walla Valley, Washington Kevin Pogue (Whitman College) and Chris Oze (Bryn Mawr College) Students: Ruth Indrick, Karl Lang, Season Martin, Anna Mazzariello, John Nowinski, Anna Weber The Árnes central volcano, Northwestern Iceland Brennan Jordan (University of South Dakota), Bob Wiebe (Franklin & Marshall College), Paul Olin (Washington State U.) Students: Michael Bernstein, Elizabeth Drewes, Kamilla Fellah, Daniel Hadley, Caitlyn Perlman, Lynne Stewart Origin of big garnets in amphibolites during high-grade metamorphism, Adirondacks, NY Kurt Hollocher (Union College) Students: Denny Alden, Erica Emerson, Kathryn Stack Carbonate Depositional Systems of St. Croix, US Virgin Islands Dennis Hubbard and Karla Parsons-Hubbard (Oberlin College), Karl Wirth (Macalester College) Students: Monica Arienzo, Ashley Burkett, Alexander Burpee, Sarah Chamlee, Timmons Erickson Andrew Estep, Dana Fisco, Matthew Klinman, Caitlin Tems, Selina Tirtajana Sedimentary Environments and Paleoecology of Proterozoic and Cambrian Avalonian Strata in the United States Mark McMenamin (Mount Holyoke College) and Jack Beuthin (U of Pittsburgh, Johnstown) Students: Evan Anderson, Anna Lavarreda, Ken O Donnell, Walter Persons, Jessica Williams Development and Analysis of Millennial-Scale Tree Ring Records from Glacier Bay National Park and Preserve, Alaska (Glacier Bay) Greg Wiles (The College of Wooster) Students: Erica Erlanger, Alex Trutko, Adam Plourde The Biogeochemistry and Environmental History of Bioluminescent Bays, Vieques, Puerto Rico Tim Ku (Wesleyan University) Suzanne O Connell (Wesleyan University), Anna Martini (Amherst College) Students: Erin Algeo, Jennifer Bourdeau, Justin Clark, Margaret Selzer, Ulyanna Sorokopoud, Sarah Tracy Funding provided by: Keck Geology Consortium Member Institutions and NSF (NSF-REU: )

2 Keck Geology Consortium: Projects Short Contributions Walla Walla GEOLOGIC CONTROLS ON VITICULTURE IN THE WALLA WALLA VALLEY, WASHINGTON: p55-6 Project faculty: CHRISTOPHER OZE: Bryn Mawr College KEVIN R. POGUE: Whitman College THE INFLUENCE OF GEOLOGIC AND ANTHROPOGENIC INTERACTIONS ON GEOCHEMICAL PROCESSES IN THE CRITICAL ZONE OF VINEYARDS NEAR MILTON- FREEWATER, OREGON: p61-66 RUTH INDRICK: Smith College Research Advisor: Robert Newton INFLUENCE OF SOIL COMPOSITION AND SURFACE MATERIALS ON GRAPEVINE TEMPERATURE: p67-71 KARL LANG: College of William and Mary Research Advisor: Greg Hancock TRACING TERROIR: COMPARING ELEMENTAL CONCENTRATIONS IN GRAPEVINES WITH THEIR SOILS: p72-77 SEASON MARTIN, Whitman College Research Advisor: Kirsten Nicolaysen EVALUATION OF SOIL GEOCHEMISTRY IN THE VINEYARDS OF WALLA WALLA, WASHINGTON: p78-83 ANNA ELIZABETH MAZZARIELLO: Bryn Mawr College Research Advisors: Catherine Riihimaki & Christopher Oze VARIATIONS IN TEXTURAL, HYDROLOGIC, AND CHEMICAL PROPERTIES OF SOILS WITHIN THE WALLA WALLA VALLEY AMERICAN VITICULTURAL AREA: p84-89 JOHN NOWINSKI: Carleton College Research Advisor: Mary Savina ELECTRICAL CONDUCTIVITY AS A PREDICTOR OF SOIL CHARACTERISTICS IN THE WALLA WALLA VALLEY, OREGON: p9-95 ANNA WEBER: Williams College Research Advisor: David Dethier Funding provided by: Keck Geology Consortium Member Institutions and NSF (NSF-REU: ) Keck Geology Consortium Franklin & Marshall College PO Box 33, Lancaster Pa, 1763 Keckgeology.org

TRACING TERROIR: COMPARING ELEMENTAL CONCENTRATIONS IN GRAPEVINES WITH THEIR SOILS SEASON MARTIN, Whitman College Research Advisor: Kirsten Nicolaysen INTRODUCTION The Walla Walla Valley AVA

3 TRACING TERROIR: COMPARING ELEMENTAL CONCENTRATIONS IN GRAPEVINES WITH THEIR SOILS SEASON MARTIN, Whitman College Research Advisor: Kirsten Nicolaysen INTRODUCTION The Walla Walla Valley AVA straddles the border of southeastern Washington and northeastern Oregon (Fig. 1). Carson and Pogue (1996) summarized the geology of the Walla Walla Valley and Meinert and Busacca (2) described the general terroir. The valley contains a wide variety of soils that have been formed on three main types of parent material: 1) wind-deposited silt (loess), 2) lacustrine sand and silt deposited by the Missoula floods, and 3) alluvial fan deposits consisting of basalt gravels derived from the erosion of the Blue Mountains. For this study, soil, root, stem, leaf, and grape juice samples were obtained from 14 vineyards Walla Walla Valley Terroir, the physical environment of a vineyard site, has often been cited as the factor most responsible for the unique flavors of the wines produced from a particular vineyard. This idea implies that the unique soil chemistry of each vineyard directly affects the chemistry of the grapevines and the wines derived from them. Due to its numerous vineyards and wide variety of soil types, the Walla Walla Valley American Viticultural Area (AVA) is an excellent area to test this idea. 72

4 AVA that were chosen to provide a representative distribution of the major soil types and microclimates within the valley. The samples were analyzed and compared to see if soil chemistry is reflected in grapevine chemistry. The three main questions addressed by this research were: How distinct are the soils in the different vineyards with regard to soil chemistry? Do the vines reflect the differences in soil chemistry? Do different areas of the vine root, stem, leaf, and grape have different concentrations of soil-derived elements? SITE SELECTION AND CHARACTERISTICS To address the questions posed above, this paper focuses on three of the 14 sampled vineyards; each was selected to be representative of a distinctive soil terroir (Fig. 1). The vineyards from each terroir are referred to by the name of their soil type - Basalt Cobble,, and. The specific characteristics are discussed below. The vineyards are located on an alluvial fan deposited by the Walla Walla River at the foot of the Blue Mountains. The gravels of the alluvial fan are over 5 m thick in many areas and are composed of basalt cobbles in a matrix of sand, gravel, and loess. The USDA soil survey (Harrison et al., 1964) categorized these soils as a cobbly loam known as the Freewater Series. The vineyards are located in areas where the Columbia River Basalts (CRBs) are covered by at least 15 m of wind-deposited silt. Most of the soils of this type have been categorized as the Walla Walla silt loam, one of the most widespread soils in Walla Walla County (Harrison et al., 1964). The roots of grapevines growing in this thick alkaline soil do not penetrate to deeper layers. The vineyard sampled by this study has a higher elevation, receives more precipitation and is closer to the foot of the Blue Mountains than the vineyards representative of the other soil terroirs. Many vineyards in the Walla Walla Valley AVA are planted in soils developed in areas where less than 1 m of loess overlies the slackwater deposits of the Missoula floods (). Since the uppermost material is loess, in many areas these soils are classified as the Walla Walla silt loam. The Touchet Beds are stratified lacustrine deposits that are less permeable and more strongly alkaline than the overlying loess (Harrison et al., 1964). METHODS Soil, roots, stems and leaves samples were collected in July and grapes were collected in early September. The roots, stems, and leaves were ultrasonically cleaned, dried in an oven, and homogenized using a coffee grinder. Analyses were preformed in triplicate with a Portable X-Ray Fluorescence Spectrometer (PXRF) to determine the elemental chemistry of the vegetation. Grapes were juiced using a metal strainer and acidified with nitric acid. Juice samples were sent to Applied Speciation and Consulting, LLC for Inductively Coupled Plasma Dynamic Reaction Cell Mass Spectrometry (ICP-DRC-MS). Soil samples were sieved and analyzed in triplicate, then calibrated to a known standard using the PXRF. RESULTS AND DISCUSSION Alkali Metals Concentration of potassium in the soil samples is highest in the vineyard, intermediate in the vineyard and lowest in the Basalt Cobble vineyard (Fig. 2A). The soil from the vineyard was taken from a depth of.5 m, and therefore sampled the loess rather than the underlying. The difference in K concentration between the and vineyards is most likely due to a westerly increase in 73

5 K Concentrations A Rb Concentrations B 5 1 Soil Roots Stems Leaves Soil Roots Stems Leaves 35 3 Ca Concentrations C 35 3 Sr Concentrations D Soil Roots Stems Leaves 5 Soil Roots Stems Leaves Fe Concentrations E Zn Concentrations F Soil Roots Stems Leaves Soil Roots Stems Leaves Figure 2. Elemental distribution in soil, root, stem and leaf samples for, and Vineyards A) K concentrations B) Rb concentrations C) Ca concentrations D) Sr concentrations the coarse grain fraction of the surficial loess. The vineyard is located to the east of the Touchet Bed vineyard its loess is therefore more fine-grained (Fig. 1). Coarser-grained loess is likely higher in K due to a greater abundance of K-feldspar and mica. Basalt and its weathering products, which have lower K concentrations than the loess, dominate the soil of the vineyard. The root and stem samples in all three vineyards reflect the K concentrations in the soils, with the highest concentrations in the vineyard and lowest in the vineyard (Fig. 2A). This correlation suggests that K levels in the woody parts of the vine are controlled by the K concentration in the soil, but the deviance from this trend for 74 the stems suggests that plant processes are also playing a role in the K uptake. Potassium concentration in grape juice however, appears unaffected by soil K concentration as shown by the somewhat negative correlation between these values (Fig. 3A). Potassium is concentrated in the stems of the vines (Fig. 2A). It is an extremely mobile element within vines and therefore would be expected to concentrate in the stems rather than the roots and leaves (White, 23). The concentration of elements in general is much less in the grape juice compared to the rest of the plant, possibly because the purpose of fruit in plants is to accumulate sugar to aid reproduction. However, the K concentration in the grapes is at least 1 times higher than the other ele-

6 ments tested (Fig. 3). This supports the thought that K is tied to sucrose accumulation (White, 23). The behavior of Rb should be very similar to K and in the soil samples Rb demonstrates the same trend, with the highest concentration in the vineyard, followed by the vineyard, and the lowest concentrations in the vineyard (Fig. 2B). Unlike K, this trend is not reflected in any of the vegetation samples. Instead, the Basalt Cobble vineyard has the highest concentration of Rb for all the plant samples, and the plant samples for the and vineyards have similar concentrations. In fact, a negative correlation can be drawn between grape juice and soil Rb concentration (Fig. 3B) suggesting that Rb uptake by the plant is not affected by soil concentrations. Alkaline Earth Metals Unlike the alkali metals, the Ca concentrations are highest in the soil samples from the vineyard, followed by the samples from Touchet Beds vineyard, with the lowest concentration in the vineyard samples (Fig. 2C). Similar to K and Rb, the difference between the and vineyard could be explained by distance from the primary source of the loess in the Pasco Basin, which affects grain size. The vineyard also receives less precipitation than the vineyard, causing more calcium carbonate to accumulate at shallow levels in the soil. The high Ca concentration in the vineyard is due to the weathering of the basalt, which contains high calcium mafic minerals such as clinopyroxene and plagioclase. The differences in the soils between the vineyards are not reflected in the plant samples. All the plant samples have relatively similar concentrations, especially the grape juice (Fig. 3C). Soil concentrations of calcium therefore do not appear to be related to the concentrations within the vine. Differences in concentrations between the roots, stems, and leaves do not correspond to the previously documented immobility of Ca within the vine (White, 23). Instead of high concentrations of Ca in the roots, Ca concentrations increase with distance from the root system (Fig. 2C). More research is necessary to explain this behavior. The behavior of Sr should be similar to Ca, but in the soil samples the relative concentration of strontium in the and vineyards is reversed, with concentration greatest in the Basalt Cobble vineyard and lowest in the vineyard (Fig. 2D). As with Ca, this trend is not reflected in the vegetation samples and suggests the plant limits its uptake of Sr and is unaffected by variations in the soil. The negative correlation in Sr concentration between grape juice and soil samples supports this contention (Fig. 3D). In this study, Sr mimicked calcium in its behavior within the plant; it also increases in concentration away from the root system. Transition Metals The Fe concentration in the vineyard soils is similar to the Ca concentrations. The vineyard has the highest Fe concentration, followed by the vineyard, with the lowest concentration of Fe in the vineyard (Fig. 2E). The difference between the and soils may be due to the weathering of iron-bearing minerals that are present in higher concentrations in the coarser grained loess within the vineyard. The high Fe concentration in the Basalt Cobble vineyard results from the weathering of the iron-rich minerals in the basalt. The differences in Fe in the soil samples correlate well with all of the plant samples (Fig. 2E) suggesting that soil Fe concentrations have a direct affect on the accumulation of Fe in the plants (Fig. 3E). Variations in Fe concentration between different parts of the plant demonstrate the limited mobility of iron. Zinc concentrations in the soil samples show the same pattern as iron (Fig. 2F). The Zn concentrations in the plant samples, however, do not correlate with their respective soil samples. Instead, the concentration of Zn in all plant samples in the Basalt 75

7 16 K grape juice v. soil A 8 Rb grape juice v. soil B Ca grape juice v. soil Fe grape juice v. soil C E Sr grape juice v. soil Zn grape juice v. soil D F Cobble and vineyards is similar, while the concentrations in all of the Touchet Bed vineyard plant samples is significantly higher (Fig. 2F). There is a slight negative correlation between grape juice and soil concentrations (Fig. 3F). These observations suggest that soil concentrations are not the primary influence on uptake and accumulation of Zn within the vine. Zinc concentrations are highest in the root samples, intermediate in the stems, and lowest in the leaves (Fig. 2F). The greater concentration of Zn in the Figure 3. Correlation between grape juice concentration and soil concentration for all elements. Negatively correlated elements suggest plant processes are the major factor in bioaccumlation of elements, while positive correlations infer that soil elemental concentrations directly effect bioaccumulation. A) K concentrations are negatively correlated B) Rb concentrations are negatively correlated C) Ca concentrations are negatively correlated D) Sr concentrations are negatively correlated E) Fe concentrations are positively correlated F) Zn concentrations are negatively correlated roots implies that Zn is relatively immobile within the vines, or is involved in chemical reactions between the soil and the roots. CONCLUSIONS Chemical differences in soils can be explained by variability in the mineralogy of soil parent materials within the Walla Walla Valley AVA. The absorption, transportation, and accumulation of mineral nutrients by grapevines are complex processes controlled by many variables. Plant-controlled chemical reac-

8 tions at the interface between the soil and root are at least as important as the mineralogy, texture, and hydrology of the soils themselves. The results of this study are in line with previous research on elemental behavior in grapevines, regarding the bioaccumulation of elements such as K, Fe and Zn. However, the distribution of Rb, Ca and Sr within the vines did not show the patterns expected based on previous research. Of all the elements tested, only Fe showed a direct correlation between soil and plant concentrations. Iron is therefore the only element that could be used to fingerprint the grape juice to a particular soil terroir of the Walla Walla Valley AVA. Further research is needed to determine the role of Fe in the synthesis of the flavor and aroma compounds responsible for the sensual expression of terroir in wine. BIBILOGRAPHY Carson, R.J., and Pogue, K.R., 1996, Flood Basalts and Glacier Floods: Roadside Geology of parts of Walla Walla, Franklin, and Columbia Counties, Washington: Washington Division of Geology and earth Resources, Information Circular 9, 47 p. Harrison, E.T., Donaldson, N.R., McCreary, F.R., Ness, A.O., and Krashevski, S., 1964, Soil Survey of Walla Walla County Washington, United States Department of Agriculture, Soil Survey Report, Series 1957, n. 16, 138 p. Meinert, L.D. and Busacca, A.J., 2, Geology and Wine 3: Terroirs of the Walla Walla Valley Appellation, southeastern Washington State, USA: Geoscience Canada, v. 27, n. 4, p White, R.E., 23, Soils for Fine Wines, Oxford University Press, Oxford, 279 p. 77

GEOLOGIC CONTROLS ON VITICULTURE IN THE WALLA WALLA VALLEY, WASHINGTON

21st Annual Keck Symposium: 2008 GEOLOGIC CONTROLS ON VITICULTURE IN THE WALLA WALLA VALLEY, WASHINGTON CHRISTOPHER OZE: Bryn Mawr College KEVIN R. POGUE: Whitman College INTRODUCTION TERROIR The critical