PHYSICAL AND CHEMICAL CHARACTERISTICS OF SOME NATURAL LICKS USED BY BIG GAME ANIMALS IN NORTHERN ONTARIO L. C. CHAMBERLIN, Ontario Ministry of Natural Resources, District Office, Thunder Bay, Ontario H. R. TIMMERMANN, Ontario Ministry of Natural Resources, Regional Office, Thunder Bay, Ontario B. SNIDER, Ontario Ministry of Natural Resources, District Office, Terrace Bay, Ontario F. DIEKEN, Ontario Ministry of the Environment, Laboratory Services Branch, Rexdale, Ontario B. LOESCHER, Ontario Ministry of the Environment, Laboratory Services Branch, Rexdale, Ontario D. FRASER, Ontario Ministry of Natural Resources, Fish and Wildlife Research Branch, Maple, Ontario Ab~,;t"-a.e.tr Examinations were made of 13 "mineral licks" in northern Ontario known to have been frequented by moose (Odoeoiteu~ vi,,-ginia.nu~), (Atee~ a.tee~) or white-tailed deer and samples of water and soil were collected. All the licks consisted of mud with pools or puddles, and probably all were fed by springs. Many were found at the base of ridges and many contained grey clay. Increased concentration of sodium was the most uniform characteristic of the water, but large amounts of calcium, potassium, and other elements were common. reflected in the soil samples. The high levels were not The influence of sampling methods on studies of mineral licks is discussed. Wild ungulates make extensive use of naturally occurring "mineral licks" in many parts of the world and a variety of hypotheses have been proposed to explain this striking attraction. In many studies it has been assumed or concluded that the use of licks indicates a dietary deficiency of some particular nutrient which is present in unusually high concentrations in the lick material. Single elements which have been mentioned in this respect include sodium (Dalke et al. 1965, Weeks and Kirkpatrick 1976) and sulphur (Hanson and Jones 1976). Chemical analysis commonly shows, however, that many licks contain high levels of a variety of nutrients with no single element common to all licks in an area (eg. Peterson 1953, Wright 200 1956). Faced with such results, Cowan and Brink (1949) suggested that trace elements might be involved. Many studies of ungulate licks have suffered from 2 difficulties. some studies only a small number of elements have been analyzed. In If the results fail to show a single element in all licks tested, the possibility remains that some other essential element accounts for the lick's attractiveness. In other studies lick samples have not been compared to nearby "control" samples to indicate whether the chemical composition of the water or soil in the lick does differ significantly from the surroundings. These problems make it difficult to interpret results. Ungulate licks in Ontario have received only scant attention (Peterson 1955). Accordingly, the present paper documents, as part of a more wide-ranging study, some preliminary observations and results of chemical analysis of water and soil from 13 licks in 3 areas of Ontario. In each case the water analysis included all the cations known to be essential for ruminants, together with the sulfate ion in view of the recent hypothesis of Hanson and Jones (1976). Samples of nonlick material from the same areas were also studied. We are grateful to Messrs. J. McNicol and R. Gollat for valuable assistance in the field, and to J. Scott, T. Pitts, and E. Reardon for useful discussion and analytic services. METHODS Five of the 13 licks were located in the Lake Nipigon area (Fig. 1,2), 7 on the islands of Lake Superior (Fig. 3), and 1 in Thackeray Township in northeastern Ontario between Lake Abitibi and the town of Kirkland Lake. Each lick was visited once during June or July of 1976. Notes were made on the appearance, physical surroundings, and evidence of use by moose or white-tailed deer at the site. Water in the lick was collected in an acid-washed plastic bottle and preserved with 2 ml nitric acid for analyses of trace metallic elements, and in a glass bottle for the remaining analyses. The water was taken from standing pools in the lick or directly 201 Lake Nipigon Licks Fig. 1. Location of the three IImineral lick" areas. Fig. 2. Location of the five lick sites in the Lake Nipigon area. were taken from only one of the two McIntyre Bay licks. Samples ® Malinski Lick Ignace Island Lick Fig. 3. Location of the seven lick sites on the Lake Superior islands. from the spring source if it could be found. In most cases control samples were collected from a nearby stream or pool which did not appear to be attracting cervids. Water analysis was done using standard laboratory techniques (Ontario Ministry of the Environment 1976). Elements Na, K, Ca, and Mg were analyzed by atomic absorption, sulfate by an automated colorimetric method using methylthymol blue, total Kjeldahl nitrogen and total phosphorus by automated colorimetric techniques using the indophenol blue method, and the molybdenum blue method using stannous chloride. Elements Co, Cu, Mn, Zn, Fe, and Mo were analyzed by atomic absorption after pre-concentration with background correction for Zn and Co. Selenium was analyzed by hydride generation, flameless atomic absorption. For Lake Nipigon and some other sites, samples of soil were collected from well-trampled parts of the lick and from nearby "control" locations which did not appear to attract wildlife. Samples were air dried and analyzed by the Mineral Resources Branch of the Ministry of Natural Resources. Soil analysis for Fe, Mg, Ca, Mn, Cu, Zn, and Co was accomplished by atomic absorption after acid digestion or fusion. The elements Na and K were determined by flame emission, P by a colorimetric method, and Mo by a non flame method; all after acid digestion. RESULTS AND DISCUSSION Description of the Licks 2 The Lake Superior Island licks varied from a few m to several 10's 2 of m in size. or pools. All consisted of mud with standing water in small puddles Slow-seeping springs were believed to be present in all cases but were actually located for only 4 of the 7 sites. Snider's lick was also fed by a small stream running through the lick area. Several of the areas had scattered head-sized boulders partly exposed above the mud, and supported almost no vegetation. The mud was grey clay in some cases and peat or silt in others. 205 Four of the licks were located at the base of ridges. In 3 instances the ridge was a lineament thought to represent a boundary between individual lava flows, and in 1 case was a gabbro dyke (Giguere 1975). The licks were characterized by well-worn game trails leading to them and by many ungulate tracks in the muddy areas. and Snider's) had a definite barnyard odor. All but 2 (Wilson North In addition a very faint sulphide odor could be detected in the water of the Wilson Island South and Molinski licks. Historical observations of ungulate use of Wilson and Copper Island licks have been documented by Snider (1975). At present Wilson, Copper, and Channel Islands are believed inhabited by white-tailed deer, and St. Ignace and Simpson Islands mainly by moose. All but the Channel Island lick are underlain by diabase sills and flows of the Osler Group (intrusive contact) subdivision of Late Precambrian (Keweenawan) bedrock. The Channel Island lick is underlain by sandstone of the Sibley Group (intrusive contact) subdivision of Late Precambrian (Keweenawan) bedrock (Ontario Dept. of Mines 1973). The material overlying the bedrock in the area of the Wilson, Copper, and Channel Island licks is silty to sandy till (ground moraine) and sand (lacustrine deposits), the Simpson Island lick silty to sandy till (ground moraine) and varved or massive clay and silt (lacustrine deposits), and the St. Ignace Island lick bare bedrock eroded by lake action and silty to sandy till (ground moraine) (Ontario Dept. of Lands and Forests 1965). The 5 Lake Nipigon licks had been known sites of ungulate activity in the past, but in 1976 the Shakespeare Island lick no longer appeared to be attracting wildlife. The other licks all had the characteristic "barnyard" appearance with numerous tracks and well-used trails leading to the site. All Lake Nipigon licks were characterized by grey clay in their actively-used muddy areas, and all except the McIntyre Bay lick were surrounded and interspersed by grasses and sedges. Three were associated with slopes or ridges and 2 were in level swamp areas. 206 As in the Lake Superior Island locations, the licks were essentially muddy areas with small pools of standing water, occasionally with exposed boulders. A small stream flowed through the Shakespeare Island lick. All Lake Nipigon lick sites are underlain by Late Precambrian (Keweenawan) bedrock. However, the type associated with the Three Mount Bay lick is a diabase (dikes and sheets) of the Mafic Igneous (contact intermediate) subdivision, that associated with the McIntyre Bay licks is unsubdivided material of the Sibley Group (intrusive contact), and that associated with the island licks is a diabase of the Intrusive Igneous subdivision (Ontario Dept. of Mines 1966, 1973). The material overlying the bedrock at all Lake Nipigon lick sites is silty to sandy till (ground moraine) and varved or massive clay and silt (lacustrine deposits) (Ontario Dept. of Lands and Forests 1965). The Thackeray lick in northeastern Ontario consists of 2 connected ponds with grey clay bottom surrounded by grasses and sedges. Both ponds are fed by a spring-fed stream plus numerous small intermittent springs located throughout the pond areas, and by an occasional massive up-welling of water within the ponds. The surrounding topography is rolling to flat. Extensive use of the lick is made by moose as indicated by numerous heavily-used game trails and the remains of 15 to 20 moose in the immediate area of the ponds. Over the years many moose have been observed in the ponds. The lick area is underlain by dacite, andesite, and basalt of the Intermediate and Mafic Metavolcanics (formerly classified as Keewatin) subdivision of early Precambrian bedrock. A north-south fault is located approximately 400 m to the west. The material overlying the bedrock in the lick area is varved clay of the Barlow-Ojibway deposits laid down during Pleistocene and recent times. Adjacent (within 2 km) are an esker complex and sand and gravel deposits (predominantly glacio-fluvial deposits) 207 (Chamberlin 1975). Chemical Analysis Chemical analysis of the water samples is summarized in Table 1. Table 2 shows the mean concentration of the various substances in the lick and control samples, excluding the Shakespeare Island lick sample because the site no longer appeared to be used by animals, and excluding the Murchison control, Thackeray lick, and Snider's lick samples because of suspected difficulties in sampling as discussed below. Results from the analysis of soil samples from Lake Nipigon sites are summarized in Table 3. DISCUSSION Results of the water analysis must be interpreted with caution. Recent observations (Fraser, Unpublished) indicate that moose and deer detect even tiny springs in a large lick site and actively use the spring water while largely ignoring pools of standing water elsewhere in the lick area. In the present study, water was collected from various points in each lick site not just from the spring source. This may have caused particular problems with the Thackeray, Snider's, and Shakespeare Island samples. Since a stream ran through the lick area in all these cases, it seems likely that the lick sample was greatly diluted with ordinary stream water. In addition the Murchison Island control sample, unlike the other control samples which were collected from moving water, was taken from a pool of standing water near the lick. Its high mineral content suggests that it may have contained some lick water but in insufficient concentration to draw animals away from the main source. These 3 samples were therefore omitted from most of the numerical analysis. Similar difficulties may have affected a Quebec study reported by Bouchard (1970). High levels of Na were found for all 3 licks in which the spring source was conspicuous but in the remaining 16 cases, with no obvious focus for collection of water, the samples had no unusual mineral composition. 208 Table 1. Chemical composition (ppm) of water from the lick and control sites. N P Lick samples S04 Na K Ca Mg Co Cu Mn Zn Fe Mo Se Kelvin Island 3.6 0.44 14.0 62.0 5.1 45.0 9.0 <0.04 0.05 0.55 0.14 74.0 <0.01 0.002 Murchison Is. 9.2 2.2 40.0 110.0 13.0 340.0 30.0 <0.04 0.06 2.2 0.11 65.0 0.02 <0.001 <0.001 7.0 1.1 23.0 170.0 10.0 27.0 2.5 <0.02 0.06 0.55 0.08 39.0 0.02 McIntyre Bay 15.0 6.1 15.0 540.0 7.5 2740.0 50.0 <0.04 0.14 3.4 0.08 74.0 0.01 0.01 Shakespeare Is. 18.0 1.8 42.0 3.0 7.1 34.0 11.0 0.05 1.4 1.8 0.35 58.0 0.02 <0.001 Three Mt. Bay Wilson Is. South 2.6 0.6 11.0 44.0 1.5 12.0 2.0 0.02 0.02 0.16 0.03 16.0 0.01 0.004 Wilson Is. North 7.2 1.1 11.0 23.0 3.3 12.0 3.0 <0.02 0.02 0.42 0.02 35.0 0.01 <0.001 <0.01 5.2 0.02 <0.001 Copper Island Channel Is. st. Ignace Is. 6.2 0.20 10.0 12.0 8.1 6.0 1.5 <0.02 0.02 0.05 45.0 0.04 11.0 54.0 11.0 24.0 4.5 <0.02 0.03 0.4 0.8 0.04 10.0 120.0 2.8 104.0 7.5 <0.01 0.02 0.03 17.0 0.01 0.005 0.07 <0.01 2.7 <0.01 <0.001 <0.001 IV Molinski 15.0 8.0 46.0 11.0 10.0 2.5 0.01 0.03 0.21 0.02 12.0 0.01 ~ Snider's 7.2 1.1 10.0 4.0 0.7 7.0 2.5 <0.02 0.03 0.45 0.02 17.0 <0.01 <0.1 0.02 10.0 2.0 1.4 27.0 7.6 <0.002 0.007 0.028 0.006 1.7 <0.002 <0.001 Kelvin Island 0.8 0.04 8.0 3.0 0.4 16.0 1.0 <0.01 <0.01 0.04 0.03 1.2 0.0 <0.001 Murchinson Is. 7.2 0.08 18.0 27.0 3.3 308.0 Three Mt. Bay 0.2 0.04 8.0 4.0 0.7 17.0 13.0 2.0 0.04 a 0.12 a 2.4 a McIntyre Bay 0.4 0.08 4.0 2.0 0.3 25.0 5.0 a a a 0.25 a a 76.0 a a 0.02 a a <0.001 <0.001 a Shakespeare Is. 1.4 0.2 17.0 2.0 2.2 17.0 1.0 0.01 0.03 0.29 <0.01 9.0 <0.01 Wilson Is. South 0.2 0.08 10.0 1.0 <0.1 8.0 3.0 <0.01 <0.01 <0.01 <0.01 0.28 Wilson Is. North 0.2 0.08 10.0 3.0 0.2 10.0 1.5 <0.01 <0.01 0.01 <0.01 Malinski Creek 0.6 <0.02 8.0 3.0 0.5 13.0 0.5 <0.01 <0.01 <0.01 <0.02 Thackeray streamb 0.2 <0.02 9.0 2.0 0.7 26.0 5.2 <0.002 Thackerayb 0.56 0.004 Control samples a Sample contaminated before analysis. b Median of 3 samples. 0.006 0.022 0.012 0.01 0.01 0.002 1.4 <0.01 <0.001 0.22 <0.01 <0.001 0.058 <0.002 <0.001 Table 2. Mean values (ppm) for the chemical composition of lick and control water samples, with the ratio of lick mean to control mean for each element or ion. N a Mean lick sarnple b Mean control sample Ratio P S04 Na 11.52 1.24 15.30 118.10 8.68 0.50 0.06 9.25 2.50 0.63 23.0 20.7 1.7 N 6a b Omitting Shakespeare, Thackeray, Snider. Omitting Murchison. K 47.2 13.8 Ca 332.0 Mg 11.25 Co Cu Mn Zn Fe 0.01 0.04 0.80 0.05 33.99 16.50 2.40 0.005 0.01 0.06 0.01 2.03 20.1 4.7 2.0 4.0 3.3 5.0 16.7 Mo 0.01 Se 0.002 0.005 0.005 2.0 0.4 Table 3. Analysis of soil samples from the 5 Lah:e Nipigon area sites. As Epm As percent NaO K2 0 CaD MgO Murchison Is. lick 1.83 1.86 12.3 Murchison Is. control 1.78 1. 95 12.5 Kelvin Is. lick 1.54 2.12 Kelvin Is. control 1. 97 1. 93 Shakespeare Is. lick 1.86 Shakespeare Is. control 2.08 McIntyre Bay lick 2.13 1.33 13.5 McIntyre Bay control 2.24 1.06 7.5 Three Mt. Bay li~k Fe203 P2 0 5 Mn CU Zn Co 4.00 3.60 0.10 4.10 4.00 0.10 530 22 52 10 530 26 61 13 3.60 2.30 4.80 0.05 540 3.50 2.30 5.80 0.11 1070 31 75 16 34 108 24 2.22 3.20 2.90 6.70 0.10 860 1. 62 5.40 4.20 8.70 0.10 1070 146 146 26 260 120 28 7.40 5.00 0.11 590 45 42 16 6.10 6.20 0.12 750 39 69 21 2.54 1. 52 7.40 3.80 4.20 0.10 520 22 40 14 Three Mt. Bay control 2.40 1. 52 5.30 3.30 5.30 0.08 830 28 59 17 Mean lick 1.98 1.81 8.00 4.08 4.86 0.09 608 53 71 16 Mean control 2.09 1.61 6.84 4.00 6.00 0.10 854 77 83 20 211 Mo <1 <1 <1 The remaining lick samples show striking differences from control samples for many of the ions. However, subsequent study (Fraser, Unpublished) has shown that in muddy samples of water, much of the N, P, Fe, and trace metals can be held on the suspended solid matter. Therefore, the quantity of these substances present probably depended in part on the muddiness of the water. A study using filtered samples will be required to investigate genuine differences between lick and control samples for these elements. Among the remaining ions, major differences between lick and control samples were seen for Na, Ca, and K. Concentration of Na in lick samples ranged from 4.8 to 216.0 times greater than the average of the control samples. For Ca and K the ranges were 0.6 to 166.1 and 2.4 to 20.6 respectively. In general the differences between lick and control samples were greatest in the case of Na. Differences in sulfate concentration were generally small. In view of the large number of differences between lick and control samples, preference trials will presumably be needed to determine whether any single element is the basis of the lick's attraction. Stockstad et al. In such a study, (1953) found that only Na compounds were consistently attractive to the animals in their study area although local natural licks had high levels of a number of elements. Possible contamination of the samples by urine from the animals was considered, but the N content of the lick water and its probable relation to the muddiness of the sample does not suggest that this occurred. Despite large differences between lick and control samples of water, the soil samples showed little effect. results. Previous stUdies have had similar Knight and Mudge (1967:295) reported "erratic differences" between rock samples taken in lick and nonlick sites, but found high levels of Na in all 3 of their lick water samples. In a New Brunswick study, qualitative analysis showed no substantial differences between lick and control samples of soil, but there was large variation in the mineral 212 composition of lick water, including high levels of Na in most of the samples (Wright 1956). Although serving to describe some features of the 13 licks, this study does not give conclusive evidence of a single factor which attracts moose and deer. The water was rich in Na in all 10 of the actively-used licks for which substantial dilution of the sample was not suspected. However, there were many other differences between lick and control samples. Many licks were rich in Ca and K, and high levels of dissolved N, P, Fe, and trace metals cannot be ruled out. Even the clay soil, which was found in a number of lick sites, might act as an attraction: in some European licks, ingestion of clay is thought to aid digestion (Bubenik, personal communication). Furthermore, although Na may be the attracting element, high levels of other elements may also be of benefit to the animals. In future studies of spring-based licks, samples should be collected directly from the spring source or in some other way which parallels ingestion by the animals as determined by behavioral observation, and comparisons should include filtered and unfiltered water. LITERATURE CITED Bouchard, R. 1970. Matane 1965. Etude chimique preliminaire des vasieres de la reserve Service de la Faune du Quebec. Chamberlin, L.C. 1975. The fabled moose graveyard? Rapport 5:343-352. Trans. 11th N. Am. Moose Conf. and Workshop (in press). Cowan, I. McT. and V.C. Brink. 1949. Natural game licks in the Rocky Mountain national parks of Canada. J. Mammal. 30:379-387. Dalke, P.O., R.D. Beeman, F.J. Kindel, R.J. Robel, and T.R. Williams. 1965. Use of salt by elk in Idaho. Giguere, J.E.' 1975. J. Wildl. Manage. 29:319-332. Geology of St. Ignace Island and adjacent islands, district of Thunder Bay. Ontario Min. Nat. Res. Geolog. Rep. 118: 1-35. Hanson, H.C. and R.L. Jones 1976. Ross' geese. The biogeochemistry of blue, snow, and Spec. publ. No.1, Illinois Nat. Hist. Surv. Knight, R.R. and M.R. Mudge. 1967. Characteristics of some natural licks in the Sun River area, Montana. J. Wildl. Manage. 31:293-299. Ontario Dept. of Lands and Forests. 1965. Map S265. 213 Thunder Bay. Surficial geology. Ontario Dept. of Mines. 1966. Tashota-Geraldton sheet. Geological compilation series. Thunder Bay and Cochrane districts. Map 2102. _________________________ . 1973. Nipigon-Schreiber sheet. Geological compilation series. Thunder Bay district. Ontario Ministry of the Environment. 1976. for environmental samples. Peterson, R.L. 1953. in Ontario. Laboratory Br. Studies of the food habits and the habitat of moose Contributions of the Royal Ontario Mus. Zool. Palaeont. No. 36. ______________ • 1955. North American moose. Snider, B. 1975. Island. Map 2232. Handbook of analytical methods Univ. Toronto Press. 280pp. Preliminary faunal report on Wilson Island and Copper June 1975. Unpubl. Rep. Ontario Min. Nat. Res., Terrace Bay, Ontario. Stockstad, D.S., M.S. Morris, and E.C. Lory. 1953. Chemical characteristics of natural licks used by big game animals in western Montana. Trans. N. Am. Wildl. Conf. 18:247-258. Weeks, H.P. and C.M. Kirkpatrick. 1976. Adaptations of white-tailed deer to naturally occurring sodium deficiencies. J. Wildl. Manage. 40: 610-625. Wright, B.S. 1956. The moose of New Brunswick. 214 Rep. Univ. New Brunswick.
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