Journal of Geochemical Exploration 61 Ž1998.

103–112

Enzyme leach anomalies associated with deep Mississippi
Valley-type zinc ore bodies at the Elmwood Mine, Tennessee
a,)
James R. Yeager , J. Robert Clark a , Wallace Mitchell b, Roy Renshaw c

a
ACTLABS, Inc., 11485 W. I-70 SerÕice Road N., Wheat Ridge, CO 80033, USA
b
SaÕage Zinc Inc., P.O. Box 359, GordonsÕille, TN 38563, USA
c
615 Comet DriÕe, NashÕille, TN 37209, USA
Received 5 September 1997; accepted 4 December 1997

Abstract

Deeply buried Mississippi Valley-type deposits that have been or are currently being mined in North America were
initially discovered by drilling. Conventional geochemical methods are ineffective for detecting these ‘blind’ deposits when
they occur deep within sequences of stable-platform carbonates and shales. The ‘enzyme’ leach is a selective analytical
technique for determining trace elements associated with amorphous Mn oxide coatings in soils. In many areas of the world,
the enzyme leach method is useful for detecting low-level geochemical anomalies in soils, which are associated with blind
mineral deposits. Enzyme leach analysis of soils, collected at the Elmwood Mine, Tennessee, revealed high-contrast
anomalies over ore bodies 370 m below the surface. In areas where the soils are in chemical equilibrium, ‘combination’
anomalies occur over Zn ore bodies. These are characterized by asymmetrical halogen halos which occur around a halogen
‘central low’. Commodity metals ŽZn and Pb. and trace elements associated with the ore ŽCd, Ba, and Mn. form apical
anomalies, which occur over the ore bodies and within the halogen halo. Under most circumstances, agricultural practices do
not affect enzyme leach results. However, agricultural activity in central Tennessee appears to have altered the proportion of
amorphous Mn oxides in the soils in some locations. Where the MnO 2-form equilibrium of the soil has been disturbed,
enzyme leach data are erratic. In the one instance where this was encountered, ratioing the data to Mn reveals anomalies
which bracket the blind ore bodies. q 1998 Elsevier Science B.V. All rights reserved.

Keywords: enzyme leach; manganese oxide; Mississippi Valley; Elmwood

1. Introduction ventional geochemical analytical methods are ap-
plied to surficial samples ŽRalph Ericson, John Viets,
One of the acknowledged problems in exploration Elwin Mosier, Ernie Ohle, Paul Gerdemann, pers.
for Mississippi Valley-type ŽMVT. deposits which commun... Numerous mining companies and govern-
occur deep Ži.e. ) 100 m. within the subsurface is ment agencies have conducted pilot studies in the
that they give no geochemical expression when con- Tri-State District, the Viburnum trend, central Ten-
nessee, eastern Tennessee, and southern Illinois, to
determine if conventional geochemical methods could
)
Corresponding author. be used to detect MVT deposits hosted by thick

0375-6742r98r$19.00 q 1998 Elsevier Science B.V. All rights reserved.
PII S 0 3 7 5 - 6 7 4 2 Ž 9 8 . 0 0 0 0 5 - 3

ŽFig.. Koch and Schuenemeyer. Also. In the 2. Above this uncon- effort in the Knox Group in central Tennessee. The mine began production in 1975 and is currently one of the leading Zn producers in the United States.R. and in 1967 New Jersey Zinc finally intersected ore grade and thickness in hole number 79.. decided to undertake a major exploration major erosional unconformity. the area. Tennessee. Site description 1960s and 1970s. the two uppermost formations of the Knox Group. in the early 1960s the New Jersey Ž46–107 m thick. of unmineralized continental shelf carbonates and shales. All of these The area lies along the crest of the Nashville dome methods failed. 1977. and the underlying Kingsport formation the Knox Group. The top of the Mascot is a Zinc Co. 1. and Gaylord stones. p.104 J. Location of Elmwood Mine relative to the axis of the regimes.. The ore deposits occur in breccia bodies in lahan. Nashville dome ŽGaylord. Yeager et al. In the exploration program which led ŽFig. typically 8 to 10 km apart. . The rocks dip 4–9 m per km away from the central Tennessee. The unconformity between the Knox and the overlying middle Ordovician lime- stones is at least 90 m.r Journal of Geochemical Exploration 61 (1998) 103–112 sequences of continental platform sediments. The program was begun in 1964. aqua regiarAAS and selective extractionrAAS methods were employed. recently aqua regiarICP–OES was used. and are associated with a major unconform- Ž1995. Al- though the Knox Group does not outcrop in central Tennessee. There is no significant faulting in geochemistry provided no useful information ŽCal. It was also hoped that evidence could be found of dispersive processes which might help in the interpretation of selective leach data. Widely spaced holes. As most of the large deposits in the east ity. geophysics. records from oil and gas test wells re- ported the occasional occurrence of Zn mineraliza- tion in its upper portion. were drilled using a random statistical procedure for selecting drill sites ŽCallahan. Knowing that geochemistry and geophysics would not work on such deeply buried targets.. it was necessary to deter- mine if similar enzyme leach anomaly patterns would be associated with buried mineral deposits in this climate. as had been observed in other climatic Fig. and as much as 460 m beneath the surface in the area explored. 1995. the now famous ‘Random Walk’ with a drill rig was employed as the explo- ration method. and more The geology of the region is relatively simple.. 1388.. a Discovery of the central Tennessee zinc district series of Cambro–Ordovician dolomites and lime- has been described by Callahan Ž1977. 2. surface geology. which is the southern end of the Cincinnati to the discovery of the Elmwood zinc deposit in Arch. A pilot study was initiated in 1996 to determine if the highly selective enzyme leach could be used to detect these totally blind MVT ore bodies beneath approximately 370 m Ž1200 ft. They are hosted by the Mascot formation Ž76–200 Tennessee district are in the Kingsport formation of m thick. This discovery would eventually become the Elmwood Mine near Gordonsville. 1977. and axis of the arch. 1. 1982.

r Journal of Geochemical Exploration 61 (1998) 103–112 105 Fig. but their random distribution . and they were considered ‘over. and Gay. since they contain no result of dissolution of the Mascot and Kingsport recognizable evidence as to whether or not the un. formations. galena. Yeager et al. formity lie several middle Ordovician limestone for. ized in some places. These formations range in thickness from terbedded limestones and dolomites.. fluorite and barite. during karstification were invaded by mineralizing eralized. The Mascot and Kingsport formations are in- mations. More complete descriptions of the geology brines. Later.R. Part B is an expanded-scale section of only the host units in the Gordonsville area Žmodified from Gaylord. sphalerite. These collapsed cave systems are intensely mineral- lord Ž1995. Group. the collapse breccias which formed derlying Mascot and Kingsport formations are min. an extensive karst topography developed as a burden’ during the drilling. 2.. During the for- 90 m to more than 300 m in the area explored by mation of the unconformity at the top of the Knox New Jersey Zinc. in Tennessee Division of Geology Ž1969. and the open spaces were partially filled with of the area and of the Elmwood Mine are published calcite. Part A is a generalized stratigraphic section for central Tennessee. J. pyrite. 1995.

and ground for that element. Trace ele- gardening implement Žflat-bladed pick ax.r Journal of Geochemical Exploration 61 (1998) 103–112 and unpredictable size and shape make them difficult to find and evaluate. whereas one traverse was Consistently low values for an element over barren located mostly in pasture. since the anoma- Savage Zinc Inc. Approximately 200 g of B-horizon to forest. and sieved using a stainless 3. intervals along the traverses. The uncultivated areas are covered by material from each site was placed in a 13 = 18 cm hardwood deciduous forests mixed with pine and Ziplock ŽTM. analysis. and the resulting values total of 185 sites were sampled.5 m Ž100 ft. Sample collection. 1977. and data plotting steel screen for the minus-60-mesh fraction of the Sampling was undertaken in early March. and elevations range be- tween 140 and 250 m above sea level. Most of the along river floodplains and along streams.3 m Ž8–12 inches. below a thin A horizon. Rolling hills and bottomland with mixed fields and forests characterize the landscape. there is an orange-brown to brown B horizon which fre- quently contains cherty residuum produced by weathering of the Paleozoic carbonate rocks.. just as the vegetation was beginning to bud in the Each sample was leached using the enzyme leach early spring. 1389.2–0. At the Elmwood Mine. the follow-up drill hole to the discovery hole was sited 30 m to the north. and Clark which crossed ore bodies located roughly 370 m Ž1993. most of the land had been cleared for agricul- ture. Anomalous trace elements at 30. the B horizon is characteristically a dark brownish-gray material that also contains abundant cherty residuum.106 J. 1996. The climate of central Tennessee is temperate and humid. 1995. Yeager et al. again below a thin A horizon. Cane breaks are found in scattered areas marked with a site identification number. Ž1990.. disaggregated. and 56 analyses were determined by Ž1200 ft. In rela- tively treeless areas. soil. the samples were air-dried. A were also ratioed to Mn. A ‘grubbing hoe’ were plotted as another set of variables. of the ore bodies were not revealed until after the Detailed statistical evaluation and multivariate analy- analytical data had been generated and submitted to sis of the data were not necessary. After being shipped to the laboratory. p. For example. Map showing location of zinc ore bodies relative to the two pilot sampling traverses presented in this paper. charac- terized by high humidity and moderate to hot tem- peratures. 1900s. The locations ICP–MS using a Perkin Elmer Elan Model 6000. Weathering is best described as subtropical. deep drilling from the surface has been the primary tool for finding new ore bodies. but early in this century many of the fields on the hillsides were abandoned and allowed to return to dig the holes. and it missed the ore body ŽCallahan.R. Three traverses had been surveyed procedure described in Clark et al. soils were damp when they were collected. Samples were collected bedrock were used to establish the typical back- typically at a depth of 0. In the 1800s and early Fig. was used ments and ratios which showed contrast above the . beneath the surface ŽFig. Most of the cultivated land is in pasture. in largely forested upland. with hot summers and moderate winters.. Two of the traverses were located lies were obvious when the raw data were inspected. plastic freezer bag which had been cedar trees. In dense forests. 3. 3. Soils are typical of those produced by subtropical weathering of carbonate rocks.

4..5 Pb 7 41 6 . 1993. and I produced the elements.000 20 Br 300 189. and Cd and could be evaluated on the same figure. verse 3 in the Elmwood pilot study is in a mostly lous values at some of the sample sites. Ba and Mn are represen- tative of a ‘gangue suite’ of trace elements. display highly anoma. Zinc and Cd form an highest anomaly contrast in the test set of samples. anomalous value Žppb. subtle anomalous values for that particular variable whatever process is mobilizing Zn.R. The anomalies that were revealed diagnostic as the halogens in identifying the location were then compared to the locations of MVT ore of reduced bodies in the subsurface. with a peak contrast of more than 600-times back. and the Elmwood profile. 4. Max. and anoma- followed by ICP–OES determination of 30 elements lies for these elements are apparent in the Elmwood as is typically performed on most geochemical soil enzyme leach data. Pb. samples. 4. causing them to migrate to the surface is not effec- For comparative purposes.6 38 60 Zn 50 278 5. ground ŽTable 1.. This. Bromine had the anomaly over their source. Miner- Table 1 Maximum enzyme leach anomaly contrast ratios Žanomalyrbackground. Tra- ments ŽCl. Results and discussion The key to interpreting the anomalies occurring Several members of the oxidation suite of ele. indicates a strong likelihood that there are around the reduced body at depth ŽFig.. radical anomaly contrast at one sample subsurface. J. and I. anomaly and the apical anomaly over the ore. for key elements in the Elmood Mine soil survey Element Typical background value Žppb.r Journal of Geochemical Exploration 61 (1998) 103–112 107 apparent local background were plotted as profiles but the patterns for these two elements were not as for each traverse... Cl. Of the Within this halo. Mo. show anomalies with emphasize the spatial relationship between the halo strong contrast above background values ŽTable 1. this element was not found to be anomalous at cally anomalous values were truncated so that more the surface in any of the areas tested. commodity metals. 4.. anomaly contrast ratio Cl 10. Br. Data from two other members of Bromine is included in profiles B and C of Fig. In a silicate host-rock setting. reduced bodies beneath the areas sampled. and gangue-suite elements form an apical most consistent anomaly patterns..000 603 I 200 1170 5.8 As 10 39 4 Mo 10 495 50 Cd 0. and it produced a ‘combination cates that oxidation reactions are probably occurring anomaly’ pattern ŽClark. Cl. ingly. Br. This indi. and As. forested area. 4 to the oxidation suite. visually suppressing the pattern for that vari. as do Ba and Mn ŽFig. proved to be useful in detecting ore bodies in the Sometimes. profile A. associated trace oxidation suite elements. profile B. Apparently. and those variables to be plotted on the same figure. they would be considered to be part of an alteration suite. and bodies in the subsurface. Yeager et al. In such cases drasti. Mine is the leading world resource for Ge. in the subsurface in the area that was sampled. In central Tennessee.000 200. Mo and As. Data from geochemically Cd. The halogens. were related trace elements were scaled in order to allow anomalous in the enzyme leach data ŽTable 1. Zinc. Pb. Br. Surpris- able in the rest of the profile. profile C. I. over the Elmwood Mine is pattern recognition. Max. form an asymmetrical halo at the surface in turn. which are strongly enriched in the ore. apical anomaly over the ore body 370 m below ŽFig. Barium and Mn are enriched in the also subjected to the standard aqua regia digestion gangue minerals associated with the ore. the soil samples were tive for Ge. Sphalerite in central Tennessee zinc de- site would control the scaling of a geochemical posits is highly enriched in Ge.

Cd.108 J. Zn. I. 4.R.r Journal of Geochemical Exploration 61 (1998) 103–112 Fig. Br. Yeager et al. Geochemical profiles from traverse 3 for Cl. and Mn over an MVT zinc ore body approximately 370 m below the surface. Ba. .

lies over a 15-m thick ore body that grades 5% Zn. and I. 6. profile B.. 5. Br. un. J. One such occurrence terns for a number of trace elements along traverse 1. Mn and Zn data from traverse 1. The central low of one halo also has a Mn and Ba anomaly ŽFig. kind of anomaly between sites 1010 and 1030. . confused pattern that is difficult to interpret. Geochemi. If that is the situa. and that part depth of roughly 370 m below surface.. and the other central low is over an 8-m thick ore tion. and PbrMn ratios also define the same Traverse 1 presents a different picture. The ZnrMn.r Journal of Geochemical Exploration 61 (1998) 103–112 109 alization was not confined to the ore bodies.. ratioing to Mn would tend to eliminate the 3.R. 5. Consequently. CdrMn. Yeager et al. and Zn ŽFig. but so open spaces in the host formations were mineralized much noise is present in the background data that the wherever they were penetrated by mineralizing patterns are ambiguous ŽFig.. Manipulation of the brines. profile C. which supports this interpretation. previous paragraph. It appears that there is some apical part of a combination anomaly. data by ratioing the erratic trace elements to Mn economic mineral occurrences in the upper Knox eliminated the noise and produced interpretable pat- Group over much of the area. Both ore bodies lie at a small to produce an oxidation anomaly. 6.. the Fig. Therefore. unlike possibly representing an apical high over ore. may be present beneath the small Zn anomaly at site Chlorine. Br. Br. of the profile would lack a halogen halo. the mineral occurrence responsible may be too body that grades 7% Zn. The same part of traverse 3 adjacent halos ŽFig. A weak high for the ZnrMn ratio cal profiles for Cl. reveal two 3002 ŽFig. show a occurs in the center of one of these anomalies. 5. halos ŽFig. when ratioed to Mn. 4.. Geochemical profiles for Cl. 4. I. I. scattered. How- the typical pattern for a mid-continent MVT Žtraverse ever. there are small. Rather.

r Journal of Geochemical Exploration 61 (1998) 103–112 Fig.R. Br. I. Zn. and Pb to Mn. Yeager et al. 6. Traverse 1 enzyme leach anomalies over deep ore bodies revealed by ratioing Cl. .110 J. Cd.

and cultivated areas. However. relatively warm ing trace elements. this cannot be taken as a rule. In order to projects. form of MnO 2 is a small component of the total Mn tween regions. the agricul- tween this area and the area underlying the other two tural limestone undergoes rapid chemical weathering. the amorphous since agricultural practices differ considerably be. In all previous projects in leased becomes amorphous manganese dioxide. 7. traverses. climate results in the rapid depletion of fertility of Out of hundreds of pilot studies and exploration limestone soils when they are cultivated. Land use is the most obvious difference be. much of the Mn which is re- that is mainly in pasture. . available trace elements. Traverse 1 crosses an area limestone weathers. Normally. Waste rock from the Elmwood about the chemistry of the soils along this traverse Mine is sold for this purpose to the local farms. Traverses 2 and 3 are located in areas There is the distinct possibility that. ‘sweeten’ the soil and retain its fertility. it is not necessary with the rest of the pilot study since Mn was introduced into the host formations by data. there are few situations where ratioing en. In this climate. when Much of the waste from the mine is enriched in Mn. agricultural activity proved to have acts like a sponge soaking up large amounts of any virtually no effect on enzyme leach data.R. In the oxides in the soil. the disproportionate Fig. Over time. the mineralizing brines. as the crushed which are mostly forested. J. it is com- zyme leach data to leachable Mn was useful. Aqua regiarICP–OES Zn profiles on traverses 1 and 3. that makes it necessary to ratio the data to Mn.r Journal of Geochemical Exploration 61 (1998) 103–112 111 true anomaly pattern is likely to be altered by ratio. southeastern United States the humid. Yeager et al. A mon practice to spread crushed agricultural lime- hypothesis is needed to explain what is different stone on the fields.

.B. center of the halo. Misra. another likely location for contamination. J. tural practices. Tennessee. which were added to the host rocks ŽLower Ordovician. the subsurface. Combina. Method of Geochemical Prospecting. Mississippi Valley-type deposits located deep within the carbonate sedimentary section in central References Tennessee are undergoing an unknown subtle chemi- cal process which is dispersing trace elements to the Callahan. I. Halogens seem to form an asymmet. Guideb. Enzyme leaching of surficial geochemical samples for detecting hydromorphic enzyme leach technique of soil analysis. Econ. Zn plots are included ble for these noisy data. If liming are difficult to interpret. W. Cd. These anomalies can be detected with the Clark. Geol.112 J. Acknowledgements The authors are grateful to the Savage Zinc Co. De. Rep. ate rocks. pp. Geology of the Elmwood and Gordonsville Mines. 1990. which bracket the ore bodies that lie 370 m below Zinc sulfate is a popular additive in salt blocks the surface. placed in livestock feeding areas.L.. ŽSect.R.R. In the Elmwood pilot study. Gaylord.. 22. G. The soil anomalies which Inst. G. The highest Zn ratioing data from actively cultivated fields to Mn values on both traverses appear to be related to eliminated the erratic signals. 1977. Zn.H. The history of the discovery of the zinc surface.. In: Gold ’90.. 1995. ŽEd. 77. Possibly. phous manganese oxides in the soil.385. concept and consequence.S. Meier. B: Appl. anomalies over their source. Trans. 1382–1392. On traverse 1. just downslope from a fence. 653–663.. such Barite Deposits of North America. United migrated through substantial thicknesses of carbon. also appear to form apical liming would decrease.. Central Tennessee zinc district — an update. tion of these anomalies. they may also be anomalous in the Tennessee Division of Geology. Society of Mining Engineers. J. from traverses 1 and 3 ŽFig. Min.H. Enzyme-induced leaching of B-horizon soils for gradual oxidation process is involved in the forma. of East Tennessee. J. 7. J. 5. and Pb. and the effect should eventu. K.r Journal of Geochemical Exploration 61 (1998) 103–112 level of amorphous MnO 2 introduced by artificial during mineralization. form at the surface from this dispersion process have Clark. 1993.. This produced high- cultural activities.. Areas which are under active cultivation in central high values for a number of elements in the raw Tennessee may yield noisy enzyme leach data that enzyme leach data for traverse 1 ŽFig. For example. then ratioing the data to Mn would agricultural limestone to the fields has resulted in a tend to reduce the influence of this agricultural factor rapid precipitation of abnormal amounts of amor- on the data. In: rical halo which brackets the ore body at depth. 189–207. for allowing access to the property and for giving permission to publish this paper. Metall. Koch. 19. States Patent 5. ally disappear. B19–B29. Clark. Yeager et al. 1995. The presence of halogen halos flanking the deposit at Elmwood. Non-ore elements. Carbonate-Hosted Lead–Zinc–Fluorite– Commodity metals and related trace elements. the highest value is in a pasture. 1982. directly over the ore body. On traverse 3. Econ.. this freshly precipitated material could be responsi- ing ore bodies. Br. can form an apical anomaly in the Ser. mineral exploration in areas of glacial overburden . 20 pp.. trace elements trapped by element patterns that could be related to the underly. Papers on the stratigraphy halo around the deposit. This could account for the erratic. Conclusions Inc. and Pb. Earth Sci.C. Exploration for zinc in pending on the strength of the oxidation process in Middle Tennessee by drilling: a statistical analysis...827. Geol. . Soc. 102. 1969. Cd. W. areas directly above the ore bodies suggests that a Econ. Because the Aqua regiarICP–OES analyses of the same soil enzyme leach is designed to be selective for amor- samples did not yield any distinct anomalies or trace phous manganese oxides.. of the soil has not been altered by current agricul. 173–204. Schuenemeyer. 5. as Zn. the addition of introduces Mn. 72. Geol.R. Riddle. anomalies are in an area of active cattle feeding. trace-element anomalies associated with precious-metal miner- tion anomalies seem to be frequently associated with alized bedrock buried beneath glacial overburden in northern the deeper deposits in areas where the Mn chemistry Minnesota. Invest. the highest Zn contrast halo anomalies for Cl.R. Ch. 23. such as and mine geology of the Kingsport and Mascot Formations Mn and Ba. A.