Northeastern Naturalist 146 R.B. Owen, Jr., J.R. Longcore, and S.A. Norton 22001144 NORTHEASTERN NATURALIST 2V1(o1l). :2114,6 N–1o5. 31 Characteristics of Two Mineral Springs in Northern Maine Ray B. Owen, Jr.1,*, Jerry R. Longcore2, and Stephen A. Norton3 Abstract - We sampled soil and water at two mineral springs (salt licks) in Baxter State Park, ME, and describe chemical characteristics of each. One site (Wadleigh) is a small spring-fed pond and the other site (Hudson) is a spring with water emerging at the base of a bedrock outcrop; both drain into nearby streams. These sites are frequently visited by Odocoileus virginianus (White-tailed Deer) and by Alces americanus (Moose). Potassium (K) and sodium (Na) concentrations in water were substantially higher at licks than at upstream control sites—Wadleigh Lick: K = 2.33 vs. 0.31 mg/L, Na = 15.7 vs. 1.9 mg/L; Hudson Lick: K = 0.95 vs. 0.19 mg/L, Na = 9.4 vs. 0.9 mg/L. Chloride at the Hudson Lick was 120 vs. 10.7 μeq/L in water upstream. Exchangeable calcium (Ca), K, and magnesium (Mg) in soil at the Wadleigh site were typical of Maine soils but Na was greatly elevated. The elevated concentrations of K and Na in the water are typical of groundwater that has circulated through bedrock, instead of overlying till. Introduction Several authors have detailed chemical aspects of soils and water at cervid concentration areas, often referred to as mineral springs or salt licks, throughout North America (Atwood and Weeks 2002, 2003; Bechtold 1996; Fraser and Hristienko 1981; Fraser and Reardon 1980; Kennedy et al. 1995; Schultz and Johnson 1992; Weeks 1978). Few data are available for Northern New England, although Seton (1927) notes that John Bartman wrote on 14 July 1743 concerning natural licks in northeastern United States, “… the soil, I suppose contains some saline particles agreeable to the deer who come many miles to one of these places.” Some chemical nutrients seem to be limiting for cervids at particular times of the year, especially during gestation, lactation, growth of juveniles, and antler development (Atwood and Weeks 2002, 2003; Kennedy et. al. 1995; Schultz and Johnson 1992). No known natural salt deposits occur in northern Maine or New England. Merriam (1884) reported that he was aware of only one natural lick in the Adirondack Mountains of New York, which was recorded by noted surveyor Verplanck Colvin. He commented: “I observed in a moist place a deposit of marly clay, a rare thing in this region. What was most interesting, however, was the fact that this was a natural deer-lick, many places showing where the deer had licked the clay, possibly obtaining a trifle of potash, alumina, and iron, derived from sulphates from decomposing pyrites.” Use of roadside salt by Alces americanus (Clinton) (Moose) is common in Maine (L. Kantar, ME Department of Inland Fisheries and Wildlife, Bangor, ME, 1Professor Emeritus, Department of Wildlife Ecology, University of Maine, Orono, ME 04469. 2Wildlife Research Biologist, US Fish and Wildlife Service, Retired, Orono, ME 04469. 3Profesor Emeritus, School of Earth and Climate Sciences, University of Maine, Orono, ME 04469. *Corresponding author - buckyandsue@gmail.com. Manuscript Editor: Todd Atwood Northeastern Naturalist Vol. 21, No. 1 R.B. Owen, Jr., J.R. Longcore, and S.A. Norton 2014 147 unpubl. data and pers. com.) and may contribute to collisions with vehicles. In this article, we describe chemical characteristics of two spring-fed sites used by Odocoileus virginianus (Zimmerman) (White-tailed Deer) and Moose in northern Maine. Field-site Description Two salt-lick sites, near Wadleigh Mountain and the outlet stream from Hudson Pond, are 8 km apart and located in Baxter State Park (BSP), Piscataquis County, ME. Both areas are in spruce-fir forest with trees ≈100 years old. Sites reflect heavy use by Moose and White-tailed Deer. Extensive trail systems, some exceeding 1 km, radiate from these sites, indicating historical use over decades The Wadleigh Lick site is a small (0.1 ha; Fig. 1), shallow, spring-fed pond 15 m in diameter, surrounded by large Pinus strobus L. (White Pine), Alnus incana L. (Speckled Alder), grasses and sedges. The area is heavily trampled, with mud banks denuded of vegetation in some places, and the water is opaque with suspended particles. This pond drains 40 m northward into a small, unnamed stream at the south base of Wadleigh Mountain. The Wadleigh Lick site lies on the boundary between the Trout Brook Formation of Middle Devonian age and the slightly older Traveler Rhyolite (Early Devonian) bedrock formation (Rankin and Caldwell 2010). The Trout Brook Formation consists dominantly of inter-layered carbonaceous black terrestrial siltstone and tan arkosic sandstone. Both lithologies contain locally abundant fossil remains of Pertica quadrifaria Kasper and Andrews (a primitive Figure 1. Wadleigh Lick, Baxter State Park, ME. Northeastern Naturalist 148 R.B. Owen, Jr., J.R. Longcore, and S.A. Norton 2014 Vol. 21, No. 1 Fern-like plant) that is one of the oldest and rarest fossil plants, and other species (Kasper and Andrews 1972). The local area is one of the earliest known terrestrial fossil localities in the world (Dorf and Rankin 1962). The Trout Brook Formation is relatively unmetamorphosed, but has been deformed by mild folding and faulting. It lies unconformably on the Katahdin Granite and Traveler Mountain Rhyolite from which it was derived. At the Wadleigh site, the contact is a normal fault. The soil is derived from till deposited during the last glaciation. Ice from the Laurentide Ice Sheet may have persisted in this area as recently as 10,000 years ago. Rooney and Weber (2004) determined that the composition of plant species adjacent to the Wadleigh site was ecologically similar to the surrounding area. The Hudson Lick site is a seepage area with spring water emerging from under a 5-m bedrock outcrop. The local bedrock consists of Seboomook Formation of Lower Devonian age, with cyclically graded-bedded sandstone, siltstones, and slate. The soil, derived from till, has been eroded around the seep, revealing large, flat, flag-like stones with puddles between (Fig. 2). The area drains 35 m into the perennial outlet stream (Hudson Brook) from Hudson Pond. Methods We collected ≈250-g soil samples in August 2002 at four different locations within the Wadleigh Lick and froze them. Samples were analyzed following standard procedures (Northeast Coordinating Committee for Soil Testing 2011) at the University of Maine (Department of Plant, Soil, and Environmental Sciences Laboratory) for exchangeable cations and anions by atomic absorption Figure 2. Hudson Lick, Baxter State Park, ME. Northeastern Naturalist Vol. 21, No. 1 R.B. Owen, Jr., J.R. Longcore, and S.A. Norton 2014 149 spectrophotometry and ion chromatography. In May 2005, we returned to BSP and collected one water sample each from the Wadleigh and Hudson sites, as well as from ≈10 m upstream from where the outflows from the springs enter brooks. We kept water samples cool until filtered and analyzed at the Sawyer Environmental Chemistry Laboratory, University of Maine. US Environmental Protection Agency protocols for water (Martin et al. 1994) were used. Alkalinity (HCO3) discussed herein is based on the calculation of strong base cations (Ca + Mg + Na + K) minus strong acid anions (sulfate, nitrate, chloride; SO4 + NO3 + Cl) and is expressed in equivalents. We did not record pH because of the long delay between sample collection and laboratory analysis. We assumed that stream water and water from salt licks are both ultimately derived from precipitation. We tabulated volumeweighted, average, annual chemistry for precipitation at Greenville, ME (National Atmospheric Deposition Program 2011) for 2005, the year of surface water collection (Table 1). This site is 92 km southwest from the study area and was the nearest NADP site that monitored amount and quality of precipitation on a weekly basis. Results and Discussion Atmospheric deposition at these sites (Table 1) is typical for all of Maine (National Atmospheric Deposition Program 2005) except that Cl is relatively low because of distance to the ocean and SO4 and NO3 are relatively low because of distance from major pollution sources. Dry atmospheric deposition of soluble material (especially Cl, NO3, and SO4) to foliar surface would likely increase those constituents by as much as 50% (Norton et al. 1988); evapo-transpiration of approximately one third of wet deposition would enhance concentrations an additional 50%. Concentrations of Ca, Mg, NO3, and SO4 were not substantially different among surface water samples (Table 1). Potassium and Na were 5–10 times higher at both lick sites than in the upstream controls. None of the cation concentrations were exceptionally high if, in fact, they reliably represented groundwater that had equilibrated with the underlying bedrock before emergence. Comparison of precipitation Table 1. Water chemistry for salt lick (SL) and upstream control (C) sites in Baxter State Park, Piscataquis County, ME. Cations, mg/L Anions, μeq/L (Al in μg/L) Sample source Ca K Mg Na Al Cl NO3 SO4 PrecipitationA 0.039 0.018 0.011 0.074 n.d.B 4.1 6.7 13.3 Est. dry atmospheric inputC >0.600 >0.027 >0.016 >0.111 n.d. >6.2 >10.0 >20.0 Wadleigh SL 3.900 2.330D 0.640 15.700 94 15.8 2.5 15.9 C 5.140 0.310 0.460 1.900 185 7.4 2.3 41.0 Hudson SL 5.010 0.950 1.620 9.400 255 120.0 15.1 56.8 C 3.010 0.190 0.910 0.900 113 10.7 2.4 54.5 APrecipitation data from National Atmospheric Deposition Program (2005). Bn.d. = not determined. CAn estimate of deposition of dry soluble material to foliar surfaces that enters sites (Norton et al. 1988). DValues in bold are unusual and discussed in the text. Northeastern Naturalist 150 R.B. Owen, Jr., J.R. Longcore, and S.A. Norton 2014 Vol. 21, No. 1 and surface water revealed that most of the four base cations (Ca, K, Mg, and Na) dissolved in the surface-water samples was derived from weathering of bedrock and soil. The dominant minerals contributing to the elevated concentrations are orthoclase (KAlSi3O8) and plagioclase (Cax, Na1-x)Al1+xSi3-xO8). Minor amounts of biotite (K[Fe, Mg]3AlSi3O10[OH]2) and hornblende (another more complex silicate mineral) would contribute Mg and Na as well. Concentrations of cations in groundwater in Maine are typically elevated by as much as a factor of 10 over surface waters in the same terrain (Clausen 1990). Chloride (Cl) was substantially higher in the Hudson Lick than in the Wadleigh Lick or either of the upstream control samples and was unusually high. The Hudson Lick would be classified as a Na (Cl + bicarbonate [HCO3]) water and is the more unusual. The Wadleigh Lick had received, during its underground transit, substantial Na and HCO3 and would be classified as a Na-HCO3 groundwater. The origin of excess Na requires the release of Na+ from the weathering of feldspar (either sodic orthoclase or plagioclase), with the accompanying anion (for electrical neutrality) being derived from the formation of HCO3 - from carbon dioxide (CO2) dissolved in the water. This chemical composition is common in many groundwater samples from Maine. The presence of high Cl at Hudson Lick, however, requires an unusual source. Natural salt (NaCl) deposits are unknown in Maine. The soil parent material, till, likely contains no NaCl and if it did, it would have been depleted by weathering long ago. Additionally, if the elevated Na were derived from NaCl as a source, then the concentration of Cl would need to be close to 300 μeq/L, instead of 120 μeq/L. Further, the control sites have no indication of high Cl. Most surface water in Maine typically does not circulate into the bedrock and then return; most water circulates through the glacial overburden, primarily till, in the study area. Groundwater emerging at the lick must have acquired the Cl either from the weathering of unusual mineral assemblages in the bedrock or from deeper groundwater discharging from the Katahdin Granite and related extrusive rocks. Aluminum dissolved in the surface waters is typical for Maine where dissolved organic carbon concentration is in the 5–10 mg/L range. Exchangeable cations in the soil at Wadleigh Lick (Table 2) are normal for Maine forest soils (Rourke 1994) except for substantially elevated exchangeable Na, to be expected from the high Na in the spring. We do not know if, at the two sites, animals ingest Na primarily by intake of water or if they ingest mud Table 2. Soil chemistry data from the Wadleigh Lick, Baxter State Park, Penobscot County, ME. ph given in Mmhos/cm. Exchangeable, mg/kg Samplesite pH EC1 Ca K Mg Na P S Cu Fe Mn Wadleigh1 6.0 0.06 1736 200 158 92 3.1 16 0.5 241 56 Wadleigh2 5.9 0.04 1607 208 202 65 3.2 11 0.6 356 269 Wadleigh3 6.3 0.07 1901 230 198 92 3.3 18 0.3 263 88 Wadleigh4 6.0 0.08 1771 230 172 94 4.4 18 0.3 294 84 Mean 6.03 0.06 1754 217 182 86 3.5 16 0.4 288 124 Stan.Dev. 0.02 121 15 21 14 0.6 3.3 0.15 50 98 Northeastern Naturalist Vol. 21, No. 1 R.B. Owen, Jr., J.R. Longcore, and S.A. Norton 2014 151 containing Na as well. Either method of intake would yield elevated amounts of Na compared with nearby surface water and vegetation sources. It is striking that a preference for these salt licks is manifest with comparatively low concentrations of Na relative to concentrations at licks reported in literature for elsewhere. Of the three elements at high concentrations in the mineral springs, only Na has been linked to the nutritional needs of both White-tailed Deer and Moose. Stockstad et al. (1953) in Montana offered big game animals, including White-tailed Deer, “mineral cafeterias” that consisted of a rack of pots containing mixtures of chemical compounds. Of the 22 mixtures offered, Na-bearing compounds accounted for 95% of consumption. The remaining 5.0% included compounds containing Ca, Co, Cu, Fe, I, K, Mg, P, and S. Phosphorus compounds, except for sodium and ammonium phosphate, received no use. Pletscher (1987) established a nutrient budget for White-tailed Deer at the Hubbard Brook Experimental Forest in north-central New Hampshire. He determined that all nutrients were in balance except Na. Sodium was used 18 times (females) and 9 times (males) more than could be gained through eating terrestrial plants. He estimated that 33% of this deficit was fulfilled by feeding on aquatic plants, and the rest was obtained at roadside sites where NaCl is used for deicing roads. He noted that mineral springs were unknown in his study area. Numerous authors have determined that Na is the important element in mineralspring use (Atwood and Weeks 2003, Chapline and Talbot 1926, Kennedy et al. 1995, Rush 1932, Weeks 1978). In contrast, Dixon (1939) thought that calcium phosphate was the mineral sought at natural licks in Alaska, but noted that Na was the sought element in California. Honess and Frost (1942) analyzed five natural licks in Wyoming and concluded that phosphorus was probably the attracting element, but that NaCl was the desired mineral at one lick. Weeks and Kirkpatrick (1976) stated that spring foliage is succulent and rich in K, leading to a flush of Na from an animal’s body; mineral springs high in Na help balance this loss. Further, these foliage conditions lead to excess stomach acidity (Kreulen 1985) that can be alleviated by consuming HCO3, also abundant at our study sites. We did not do a chemical analysis of the adjacent vegetation, but we found no indication of intensive local feeding. Studies have indicated use at mineral licks is predominately by females during gestation and lactation, by developing fawns, and by yearling males initiating antler growth, all periods of increased Na need (Atwood and Weeks 2002, 2003; Kennedy et al. 1995; Schultz and Johnson 1992). In southern Indiana, use of licks was skewed to female adults and yearling White-tailed Deer that used licks every 1.2–12.3 days (Wiles and Weeks 1986). Use of licks, particularly by Moose, decreases as aquatic plants become available, but use continues throughout the year (Fraser and Hristienko 1981). As Pletscher (1987) noted, aquatic plants can be a major source of Na. Crossley (1985) studied Moose use of ponds during summer in northern Maine and reported that average Na content of 16 aquatic plant species was 65 times higher than the average of 10 readily consumed terrestrial plant species. One of us (J.R. Longcore) expended >100 hours observing wetlands in Maine and documented extensive use of aquatic plants by White-tailed Deer during late spring and early summer, further substantiating the importance of aquatic plants for large herbivores. Northeastern Naturalist 152 R.B. Owen, Jr., J.R. Longcore, and S.A. Norton 2014 Vol. 21, No. 1 Animals travel considerable distances to frequent mineral springs/licks. Wiles and Weeks (1986) documented White-tailed Deer moving up to 3.2 km to licks, with most movements being <1.5 km. Rice (2010) recorded a single radio-tagged Oreamnos americanus de Blainville (Mountain Goat) traveling 29 km in Washington to reach a lick. At our sites, well-worn paths created by White-tailed Deer and Moose radiated outward >1 km like spokes of a wheel from the springs. Mineral springs have not been documented and seem to be rare in the northeastern US, but where present are heavily used by White-tailed Deer and Moose. Sodium and HCO3 were the main attractants for cervids at our sites as they were for cervids in Montana (Stockstad et al. 1953). Both of our study sites are in the Scientific Forest Management Area, Baxter State Park, ME, and are designated special protection areas within this managed forest. As situated, these sites are surrounded by forestland and isolated, because all roads are closed within >0.7 km from the mineral springs. Because of the unique role of mineral springs in ungulate nutrition and possible benefits to other wildlife species, we recommend similar protection of other known mineral licks in the northeast. Acknowledgments We appreciate the chemical analyses performed by staff of the Sawyer Environmental Chemistry Laboratory (John Cangelosi, Manager) and the Analytical Laboratory in the Department of Plant, Soil, and Environmental Sciences at the University of Maine (Bruce Hoskins, Manager). The staff of Baxter State Park (Jensen Bissel, Director) provided encouragement for this study, access to the sites, and information on local vegetation. This is contribution #3339 of the Maine Agricultural and Forest Experiment Station. Literature Cited Atwood, T.C., and H.P. Weeks, Jr. 2002. Sex- and age-specific patterns of mineral-lick use by White-tailed Deer (Odocoileus virginianus). American Midland Naturalist 148:289–296. Atwood, T.C., and H.P. Weeks, Jr. 2003. Sex-specific patterns of mineral-lick preference in White-tailed Deer. Northeastern Naturalist 10:409–414. Bechtold, J.P. 1996. Chemical characterization of natural mineral springs in northern British Columbia, Canada. Wildlife Society Bulletin 24:649–654. Chapline, W.R., and M.W. Talbot. 1926. The use of salt in range management. US Department of Agriculture, Circular 379. Washington, DC. 32 pp. Clausen, J.L. 1990. The geochemistry of groundwater in Maine. Unpublished M.Sc. Thesis. University of Maine, Orono, ME. 168 pp. Crossley, A. 1985. Summer pond use by Moose in northern Maine. M.Sc. Thesis. University of Maine, Orono, ME. 39 pp. Dixon, J.S. 1939. Some biochemical aspects of deer licks. Journal of Mammalogy 20:109. Dorf, E., and D.W. Rankin. 1962. Early Devonian plants from the Traveler Mountain area, Maine. Journal of Paleontology 36:999–1004 + geologic map. Fraser, D., and H. Hristienko. 1981. Activity of Moose and White-tailed Deer at mineral springs. Canadian Journal of Zoology 59:1991–2000. Fraser, D., and E. Reardon. 1980. Attraction of wild ungulates to mineral-rich springs in central Canada. Holarctic Ecology 3:36–40. Northeastern Naturalist Vol. 21, No. 1 R.B. Owen, Jr., J.R. Longcore, and S.A. Norton 2014 153 Honess, R.F., and N.M. Frost. 1942. A Wyoming Bighorn Sheep study. Wyoming Game and Fish Department Bulletin No.1:86–92. Kasper, A.E., Jr., and H.M. Andrews, Jr. 1972. Pertica, a new genus of Devonian plants from Northern Maine. American Journal of Botany 59:897–911. Kennedy, J.F., J.A. Jenks, RL., Jones, and K.J. Jenkins. 1995. Characteristics of mineral licks used by White-tailed Deer (Odocoileus virginianus). American Midland Naturalist 134:324–331. Kreulen, D.A. 1985. Lick use by large herbivores: A review of benefits and banes of soil consumption. Mammal Review 15:107–123. Martin, T.D., C.A . Brockhoff , and J.T. Creed . 1994. Method 200.15. Determination of metals and trace elements in water by ultrasonic nebulization inductively coupled plasma atomic spectrometry. US Environmental Protection Agency, Cincinnati, OH. 49 pp. Merriam, C.H. 1884. The Mammals of the Adirondack Region, Northeastern New York. Published by the Author. Reprinted from Vols. I & II, Transactions of the Linnaean Society. Press of L.S. Foster, New York, NY. 316 pp. National Atmospheric Deposition Program. 2005. Available online at http://nadp.sws.uiuc. edu/data/ntndata.aspx. Accessed October 2012. Northeast Coordinating Committee for Soil Testing. 2011. Recommended soil testing procedures for the northeastern United States. Northeastern Regional Publication No. 493, 3rd Edition, (NEC-1012) Agricultural Experiment Stations of CO, DE, ME, MD, MA, NH, NJ, NY, PA, RI, VT, WV. 121 pp. Norton, S.A., J.S. Kahl, D.F. Brakke, G.F. Brewer, T.A. Haines, and S.C. Nodvin. 1988. Regional patterns and local variability of dry and occult deposition strongly influence SO4 concentrations in Maine lakes. Science of the Total Environment 72:183-196. Pletscher, D.H. 1987. Nutrient budgets for White-tailed Deer in New England, with special reference to sodium. Journal of Mammalogy 68:330–336. Rankin, D.W., and D.W. Caldwell. 2010. A Guide to the geology of Baxter State Park and Katahdin. Maine Geological Survey, Augusta, ME. 80 pp.+ two maps. Rice, C.G. 2010. Mineral lick visitation by Mountain Goats, Oreamnos americanus. Canadian Field Naturalist 124:225–237. Rooney, S.C., and J.E. Weber. 2004. Vegetation study in a high deer use area near the Wadleigh Mt. Road. Report to Baxter State Park, Millinocket, ME. 15 pp. Rourke, R.V. 1994. Chemical and physical properties of the Chesuncook, Colonel, Dixfield, and Telos Soil Map Units. Maine Agricultural and Forest Experiment Station, Technical Bulletin 155. Orono, ME. 61 pp. Rush, W.M. 1932. Northern Yellowstone Elk study. Montana Fish and Game Commission, Helena, MT. 131 pp. Seton, E.T. 1927. Lives of the game animals. Volume 8, Number 3, Second Edition. Doubleday and Doran and Co., Inc., Garden City, New York, NY. 760 pp. Schultz, S.R., and M.K. Johnson. 1992. Effects of supplemental mineral licks on Whitetailed Deer. Wildlife Society Bulletin 20:303–308. Stockstad, D.S., M.S. Morris, and E.C. Lory. 1953. Chemical characteristics of natural licks used by big game animals in western Montana. Transactions of the North American Wildlife Conference 18:247–258. Weeks, H.P., Jr. 1978. Characteristics of mineral licks and behavior of visiting White-tailed Deer in southern Indiana. American Midland Naturalist 100:384–395. Weeks, H.P., Jr., and C.M. Kirkpatrick. 1976. Adaptations of White-tailed Deer to naturally occurring sodium deficiencies. Journal of Wildlife Management 40:610–625. Wiles, G.J., and H.P. Weeks, Jr. 1986. Movements and use patterns of White-tailed Deer visiting natural licks. Journal of Wildlife Management 50:487–496.