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ManitobaIndustry, Tradeand Mines
An Enzyme Leach B-Horizon SoilGeochemical Profile Over the
Pipestone Ti-V Deposit(South, Disseminated and
North Contact Zones),Pipestone Lake, Manitoba
(NTS 63I/5 and 63I/12)
OF99-10
ByM.A.F. Fedikow
Cover:
Georeference:
Keywords:
Soil profile in the vicinity of the Pipestone Lake Ti-V deposit.
NTS area(s) 63I/5 and 63I/12
geochemistry soils
base metals Manitobachlorine Pipestone Lakeenzymes
horizons titaniumleaching vanadium
soil profiles
Suggested reference:Fedikow, M.A.F. 2000: An enzyme leach b-horizon soil geochemical profile over the Pipestone Ti-V
deposit (south, disseminated and north contact zones), Pipestone Lake, Manitoba(NTS 63I/5 and 63I/12); Manitoba Industry, Trade and Mines, Geological Services,Open File Report OF99-10, 34 p.
Open File Report OF99-10
An Enzyme Leach B-Horizon SoilGeochemical Profile Over the Pipestone Ti-VDeposit (South, Disseminated and NorthContact Zones), Pipestone Lake, Manitoba(NTS 63I/5 and 63I/12)by M.A.F. FedikowWinnipeg, 2000
ManitobaIndustry, Tradeand MinesGeological Services
Industry, Trade and Mines
Hon. MaryAnn MihychukMinister
Hugh EliassonDeputy Minister
Geological Services
C.A. KaszyckiDirector
This publication is available in large print, audiotape or braille on request.
TABLE OF CONTENTS
PageSummary .................................................................................................................................................................1Introduction ............................................................................................................................................................1Geological setting of the Pipestone Lake anorthosite complex (PLAC)
and Ti-V-Fe mineralization .....................................................................................................................................1Sample collection and preparation .........................................................................................................................3Sample analysis ......................................................................................................................................................3
Enzyme leach ..............................................................................................................................................3Results ....................................................................................................................................................................5
Field duplicate pairs ......................................................................................................................................5Enzyme leach profiles ..................................................................................................................................5Anomaly:threshold ratios for indicator elements ..........................................................................................10INAA and ICP-AES profiles ........................................................................................................................10
Discussion ..............................................................................................................................................................10Geochemical contribution of parent soil to enzyme leach anomalies .........................................................10Sulphide mineral associations ....................................................................................................................10Niobium, cesium, barium and chlorine anomalies ......................................................................................13
Conclusions ...........................................................................................................................................................13Acknowledgements ................................................................................................................................................13References .............................................................................................................................................................14
FIGURES
Figure 1: Location map for the Pipestone Lake Ti-V deposit enzyme leach survey ...............................................2Figure 2: Local geology of the Pipestone Lake area ...............................................................................................3Figure 3: Detailed geology and the location of the enzyme leach b-horizon sampling transect,
Pipestone Lake Ti-V deposit ..................................................................................................................4Figure 4: Enzyme leach profiles for Cl, Ti, Ni and Cu over the Pipestone Lake Ti-V deposit .................................7Figure 5: Enzyme leach profiles for Zn, Ga, Nb and Cs over the Pipestone Lake Ti-V deposit .............................8Figure 6: Enzyme leach profiles for Ba and Pb over the Pipestone Lake Ti-V deposit ..........................................9Figure 7: Neutron activation profiles for Co, Cr and Ni over the Pipestone Lake Ti-V deposit ..............................11Figure 8: ICP-AES profiles for Cu, Ni and Mg over the Pipestone Lake Ti-V deposit ...........................................12
TABLES
Table 1: Descriptive statistics for elements greater than the lower limit of detection (LLD) ..................................6Table 2: Comparison of parent soil types and levels of concentration of indicator elements
at these sites .........................................................................................................................................9Table 3: Anomaly:threshold ratios for indicator elements over the Pipestone Lake Ti-V deposit ........................10Table 4: Spearman correlation coefficients for enzyme leach indicator elements,
Mn and semi-quantitative Cl (SQCl) ....................................................................................................12
APPENDICES
Appendix I: Enzyme leach field sample descriptions .........................................................................................15Appendix II: Enzyme leach/ICP-MS analytical data for sampling transect L31+50
and field duplicates .......................................................................................................................16Appendix III: Enzyme leach element profiles over the Pipestone Lake Ti-V deposit ...........................................22Appendix IV: Neutron activation and inductively coupled plasma-atomic emission
spectrometry analytical data for sampling transect L31+50 .........................................................32
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SUMMARY
The Pipestone Lake Ti-V-Fe deposit comprises disseminated to near-solid ilmenite and magnetite withina late Archean sill-like layered intrusion known as thePipestone Lake Anorthosite Complex (PLAC). Thedeposit is described as comprising 730 000 000 tons ofwhich 685 000 000 tons averages 70.74 m true width,6325 m length with a grade of 8.37% ilmenite, 17.89% magnetite and 0.2% vanadium pentoxide. Included in thegrade and tonnage is 243 000 000 tons in the MainCentral Zone and the Disseminated Zone that grades 9.28% ilmenite, 23.6% magnetite and 0.28% vanadium pentoxide (Gossan Resources Limited, 1998).A magmatic origin for the Fe-Ti-V mineralization is indicated.
A single transect of 27 b-horizon soil samples wascollected at 25 m sample spacings from hand-dug pits.These were analyzed using the enzyme leach procedureto document single and multisample, low- to moderate-contrast geochemical anomalies over the deposit.Indicator elements comprise the commodity element Ti,late, structurally controlled sulphide-bound metals (Ni,Cu, Pb, Ga, Zn), Nb (Nb-bearing rutile?), Cl, Cs and Baintroduced during late potassium metasomatism.Chlorine forms the widest anomalous response on thetransect and encompasses both the South and Disseminated Zones. The highest contrast anomaly-forming metals include Cu and Cs.
The enzyme leach responses over the DisseminatedZone is a "composite" signature, with the magnitude ofthe anomaly related, in part, to the composition of the parent material. Neutron activation (INAA) and inductively coupled plasma-atomic emission spectrometry (ICP-AES) document high Ni, Co, Cr, Cuand Mg in one of the soil samples marked by an enzymeleach anomaly. The soil at this site is a chrome greenresiduum of the mafic-ultramafic host rocks to the mineralization. This suggests that at least a portion of theenzyme leach anomaly is controlled by metal strippingfrom a detrital component in the soil derived from thePLAC. Enzyme leach responses, however, are markedby multisample, higher contrast anomalies rather than asingle sample spike in INAA and ICP-AES data.
An enzyme leach geochemical survey can assist inthe exploration of repetitions and/or extensions of thisstyle of mineralization particularly since host rocks havebeen overprinted with a late potassium metasomaticprocess and a suite of related sulphide-bound metals.The broad Cl anomaly may be the most useful of the indicator elements for exploration purposes.
INTRODUCTION
Surficial deposits, such as till, lacustrine sand, silt,clay and peat represent serious impediments to mineralexploration. Although the analysis of various size fractions of glacial till, and to some degree boulder tracing, has been successful in delineating gold- andbase metal-enriched heavy metal dispersion fans, the
explorationist is still required to search "up-ice" or withinthe areal influence of these dispersion trains for thesource of the anomalies. In some instances, the till dispersion fans can attain considerable areal dimensions(cf. Kaszycki, 1989). The recent development of geochemical techniques based on sequential, phase-specific and partial digestions coupled with analyticaltechnological advances that permit routine part per billionanalysis has provided an opportunity to "see through"transported and other types of overburden. Anomaliesdefined in this manner generally occur directly over, or inthe immediate vicinity of, the mineralized zone. Theenzyme leach approach to geochemical prospecting represents a commercially available technique that hasapplication to blind and/or buried mineralization. Thisanalytical technique formed the basis for the orientationsurvey conducted over the Pipestone Lake Ti-V deposit.
GEOLOGICAL SETTING OF THE PIPESTONE LAKEANORTHOSITE COMPLEX (PLAC) AND Ti-V-Fe MINERALIZATION
The Pipestone Lake Anorthosite Complex is locatedon the south shore of Pipestone Lake in the Cross Lakeregion of central Manitoba (Fig.1) and is within or proximal to the Cross Lake greenstone belt. The lateArchean PLAC is a sill-like layered intrusion that is 17 kmlong, and averages 800 m in width and contains greenschist to lower amphibolite facies mineral assemblages.
It is flanked to the north by basalt and minor sedimentary rocks of the Pipestone Lake Group and tothe south by tonalite gneiss of the Whiskey Jack GneissComplex (Fig. 2). Numerous east-trending shears areobserved in the area.
The geological setting of the Ti-V-Fe mineralizationwithin the Pipestone Lake Anorthosite Complex has beenthe focus of renewed interest since the publication ofManitoba Energy and Mines Open File Report OF92-1(Cameron, 1992). This report concentrated primarily onthe geological mapping of the PLAC and was subsequently followed up by studies of the characteris-tics of the Ti-V-Fe oxide mineralization in the western partof the PLAC (Peck et al., 1994a, b) and in the central andeastern portions of the PLAC (Jobin-Bevans et al., 1995,1996). Recently, Peck et al. (1998) discuss new insightsinto the PLAC and contained Ti-V-Fe oxide mineraliza-tion.
The disseminated and massive oxide mineralizationin the PLAC form four separate and distinct, laterally continuous layers and layered sequences. The SouthZone is characterized by disseminated, near-solid tosolid oxide ilmenite and magnetite mineralization within interlayered leucogabbro, gabbro, and melagabbro. TheMain Central Zone comprises near-solid to solid oxidelayers that interdigitate with oxide mineralization-bearinggabbro and melagabbro. It varies in thickness from <1 to>20 m. The Main Central Zone is overlain by theDisseminated Zone that comprises a homogeneousmelagabbro layer with a consistent (>10%) content of
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Figure 1: Location map for the Pipestone Lake Ti-V deposit enzyme leach survey.
ilmenite. The lower portion of the Disseminated Zone ismagnetite-enriched. The most northerly of the oxide mineralized zones in the North Contact Zone comprisesoxide-enriched garnetiferous sequences of melagabbro,gabbro, minor leucogabbro and pyroxenite. The NorthCentral Zone is marked by more variable and higherilmenite contents (10-20%) than the underlyingDisseminated Zone. The Disseminated Zone containslate-stage, rare, near-solid to solid ilmenite veins.
Although the current genetic interpretation for the Fe-Ti-V oxide mineralization is magmatic (Peck et al.,1994a), recent field evidence documents solid ilmenite-magnetite stringers that may have been produced as a result of unspecified sedimentary process-es (Jobin-Bevans et al., 1995).
For more detail regarding the geology and nature ofthe oxide mineralized zones in the PLAC, the reader isdirected to the publications cited above. The preceedinggeological description was derived from Jobin-Bevans etal. (1995).
SAMPLE COLLECTION AND PREPARATION
A total of 27 b-horizon soil samples and two duplicatepairs were collected from hand-dug pits on the samplingtransect (Fig. 3). Line 31+50 was selected for sample collection since it crosscuts the South, Disseminated andNorth Contact Zones. Samples were collected from stations 25 m apart and consist of approximately 1 kg of
damp inorganic silty clay, sand and silt b-horizon material that was stored in medium-sized ZIPLOCTM
freezer bags. Parent material collected at site GR-23 is distinctly different from other samples collected along thetransect. The sample comprises chrome green silt interpreted to represent weathered mafic-ultramaficrocks of the PLAC. B-horizon was encountered at anaverage depth of about 30 cm. Care was taken toexclude all organic material from the sample. Samplingwas undertaken in late September and ambient air temperature was constant at approximately 15oC.Sample preparation was undertaken in the laboratories ofthe Geological Services Branch. Samples were air driedon plastic, disposable plates and sieved to obtain the -60mesh size fraction. The -60 mesh size fraction was forwarded to Activation Laboratories Ltd. (Ancaster,Ontario) for multi-element ICP-MS analysis subsequentto enzyme leach extraction. Samples from stations1+50N, 6+25N, 6+50N, 6+75N and 7+00N on the sampling transect were unavailable due to wet swampand disturbed ground.
SAMPLE ANALYSIS
Enzyme leachThe enzyme leach process is a phase-specific leach
that preferentially attacks amorphous manganese oxidecoatings on mineral grains, thereby liberating trace metals that are trapped in this material. Amorphous
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Figure 2: Local geology of the Pipestone Lake area (modified after Cameron, 1992).
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manganese oxide represents an efficient chemical sieveor trap for cations, anions and polar molecules becauseof its large surface area and the random distribution ofsurface charges. The trace elements that are trapped orcomplexed on the amorphous manganese oxides areinterpreted to represent the chemical signatures ofburied, oxidizing mineralization at depth, rather than signatures originating from a transported overburdensource, such as till. It should be noted, however, thatwhere b-horizon development takes place in till the geochemical signature within the b-horizon may bestrongly affected by the weathering of till and the resulting subsequent downward movement of metals.This effect could produce a "transported" till geochemicalsignature in combination with the site specific mineralization-related geochemical signatures and acomposite signature overall. The possible contribution ofparent sediment composition to the overall enzyme leachsignature is not well understood.
Most of the amorphous manganese oxide is developed in the b-horizon, where studies in both aridand humid geological and climatic environments haveestablished that mineral particles within this soil horizonare coated with this authigenic material. The a-soil horizon may not reflect geochemical anomalies identifiedin the b-horizon since the a-horizon may be fairly rapidlyleached of its metallic components. Leached metals arecarried downwards, perhaps as humic- or fulvic-acidcompounds (humates/fulvates?), and trapped or sievedas they encounter the amorphous Mn-oxide coatings on mineral grains in the b-horizon. The chemical composition of the a-horizon can also be significantlyimpacted by the metal content of vegetation contributinglitter to the forest floor. This litter will reflect metalsobtained by vegetation during nutrient acquisition fromsoil horizons tapped by root systems. Accordingly, the a-horizon geochemical signature can reflect the ability ofvarious species to acquire and store metals until suchtime as they are dropped to the forest floor, decomposeand move downward in the soil profile. This source ofmetal may therefore reflect a transported metal signaturerepresenting a clastic component within an exotic till atdepth rather than a buried mineralization signature.
In the vicinity of oxidizing mineralization, the diffusionof relatively volatile metal phases, or metal transport bygases such as Hg-vapour, CO2, Rn, He, N, O2, CO4, Arand S-compounds, undoubtedly occurs as a result of anumber of processes. Metal transport may be effected bydevelopment of an electrochemical or self-potential cell,or possibly as components in soil gases derived frommantle de-gassing (cf. Gold and Soter, 1980; "geogas",Malmquist and Kristiansson, 1984; "earth-gas", Wang etal., 1997). The role of shallow groundwater as the trans-port medium for metals from source to surface is alsobeing investigated (Stewart Hamilton, pers. comm.).Metals carried by one or more of these mechanisms willenrich the amorphous Mn-oxide in the b-horizon in met-als.
The leachate from the b-horizon soil is analyzed byICP-MS for multiple elements at detection limits in the
parts per billion range. Clark (1992, 1993) provides theory and application of the enzyme leach method.
RESULTS
B-horizon soil sample descriptions and the analyticaldata derived from the enzyme leach/ICP-MS procedure,including field duplicate pairs, is presented in AppendicesI and II, respectively. Analyses below the lower limit ofdetection (<LLD) were converted to half the value of theLLD for graphical and statistical procedures. All elements>LLD were plotted against a lithologic section throughthe Pipestone Ti-V deposit, thereby transecting the SouthZone, the Disseminated Zone and the North ContactZone. Enzyme leach response over the North ContactZone could not be properly assessed due to the presence of wet and disturbed swamps that preventedsample collection. Appendix III includes profiles for allelements over the mineralized zones. Neutron activationand inductively coupled plasma-emission spectrometryanalytical data for samples collected from transectL31+50 are presented in Appendix IV. Descriptive statistics for enzyme leach data are given in Table 1.
Field duplicate pairsThe enzyme leach/ICP-MS analytical data from two
b-horizon soil duplicate pairs at stations 31+50, 2+25Nand 31+50, 5+25N on the sampling transect are generally reproducible. The b-horizon at these two sitescomprise light reddish brown clay at 2+25N and a brownsilty clay that is mixed with less oxidized equivalents dueto frost heaving at 5+25N. Duplicates at these two siteswere collected 1 m apart. Manganese contents in theduplicate pairs exhibit the most variability whereas allother elements across the observed measured concen-tration range are reproducible. Manganese varies from130 ppb to 458 ppb in the duplicate pair from 2+25N andfrom 275 ppb to 107 ppb at 5+25N. The elements <LLDin the field duplicate pairs are Be, Sc, Ge, Se, Ru, Pd,Cd, In, Sn, Te, Tm, Lu, Ta, W, Re, Os, Pt, Au, Hg, Tl andBi.
Enzyme leach profilesFigures 4 through 6 illustrate the elevated responses
of elements with proximity to known mineralized zones.These anomalies are plotted for comparative purposesagainst a threshold value derived from a probability plotfor each element.
A broad 6 sample, Cl anomaly encompasses theDisseminated Zone and remains elevated (10,197 to 15,213 ppb) up to the edge of the North Contact Zone(Table 2; Fig. 4). The commodity element Ti forms a sin-gle sample anomaly of 3301 ppb over the DisseminatedZone (Fig. 4) with a lesser response of 1459 ppb over theSouth Zone. If the threshold as determined for Ti usingprobability plots is accurate and represents the upperlimit of background variation then the single sampleresponse over the South Zone is invalid.
Single sample anomalous responses for Ni (128ppb), and Cu (483 ppb) in Figure 4, Nb (16 ppb), Cs (15
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Table 1: Descriptive statistics for elements greater than the lower limit of detection (LLD).
Element Minimum Maximum Median Arith. Mean Standard Deviation
SQLi (10) 5 144 44 43 30SQBe (20) 10 10
SQCl (3000) 1500 15213 3273 5004 4315 SQSc (100) 50 50SQTi (100) 50 3301 383 516 612
V (5) 2.5 428 117 132 99Mn (10) 69 2074 290 577 545Co (1) 3 41 9 13 10Ni (5) 2.5 128 31 36 24
Cu (5) 2.5 483 40 56 85Zn (10) 13 91 23 28 18Ga (1) 0.5 16 4 4 3Ge (1) 0.5 2 0.5 0.6 0.3As (5) 2.5 28 12 12 6Se (30) 15 15Br (30) 15 593 68 110 126Rb (1) 10 149 34 48 34Sr (1) 71 498 216 248 98Y (1) 1 72 32 33 19
Zr (1) 0.5 227 75 83 53Nb (1) 0.5 16 3 3 3Mo (1) 0.5 19 2 3 4Ru (1) 0.5 0.5Pd (1) 0.5 3 0.5 0.9 0.6
Ag (0.2) 0.1 0.8 0.3 0.3 0.2Cd (0.2) 0.1 0.7 0.1 0.2 0.1In (0.2) 0.1 0.1Sn (1) 0.5 3 0.5 0.8 0.8Sb (1) 0.5 6 2 2 1Te (1) 0.5 2 0.5 0.6 0.3I (10) 5 94 48 45 25
Cs (1) 0.5 15 0.5 1.5 3Ba (1) 220 968 421 440 142La (1) 2 129 65 59 33Ce (1) 4 307 82 93 68Pr (1) 0.5 40 21 17 10Nd (1) 2 150 69 66 39Sm (1) 0.5 36 15 16 9Eu (1) 0.5 8 3 3 2Gd (1) 0.5 43 14 16 10Tb (1) 0.5 4 2 2 1Dy (1) 0.5 19 7 8 5Ho (1) 0.5 3 1 1 1Er (1) 0.5 11 5 5 3Tm (1) 0.5 2 0.5 0.7 0.3Yb (1) 0.5 8 3 4 2Lu (1) 0.5 2 0.5 0.6 0.3Hf (1) 0.5 6 2 2 2Ta (1) 0.1 1 0.5 0.5 0.1W (1) 0.5 2 0.5 0.8 0.5
Re (0.1) 0.05 0.05Os (1) 0.5 0.5Pt (1) 0.5 0.5
Au (0.1) 0.05 0.05SQHg (1) 0.5 0.5
Tl (1) 0.5 1 0.5 0.5 0.2Pb (1) 1 28 7 8 5Bi (1) 0.5 0.5Th (1) 0.5 33 13 14 7U (1) 0.5 9 3 4 2
A value of one half the LLD was used for calculations where analyses were less than the LLD. All values in parts per billion. Bracketed figure represents the LLD for that element.
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Figure 4: Enzyme leach profiles for Cl, Ti, Ni and Cu over the Pipestone Lake Ti-V deposit.
Figure 5: Enzyme leach profiles for Zn, Ga, Nb and Cs over the Pipestone Lake Ti-V deposit.
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Figure 6: Enzyme leach profiles for Ba and Pb over the Pipestone Lake Ti-V deposit.
Sample Cl Ti Ba Cu Ni Zn Co Pb Ga Nb Cs
GR-16 (31+50, 4+00N)hematitic grey clay NA 1459 638 80 NA 82 NA 21 NA NA NA
GR-23 (31+50, 5+75N) 15213 3301 NA 483 128 91 41 28 16 16 15hematitic grey clay interlayered
with Cr-green silt-fine sand
GR-24 (31+50, 6+00N) 11836 995 NA 104 NA NA NA 13 10 NA NAlight brown silt with hematitic blotches
Table 2: Comparison of parent soil types and levels of concentration of indicator elements at these sites.
"NA" indicates that element was not anomalous at that site. All concentration levels in parts per billion.
ppb and 5 ppb) in Figure 5, and Ba (968 ppb) (Fig. 6) are documented over the Disseminated Zone. Anomalies forGa (16 ppb and 10 ppb) (Fig. 5) and Pb (28 ppb and 13 ppb) (Fig. 6) are also documented over this Zone.Distinctive anomalous responses are obtained for Zn (82ppb and 50 ppb), Ga (10 ppb) (Fig. 5) and Pb (21 ppb)(Fig. 6) over the South Zone.
Anomaly:threshold ratios for indicator elementsGeochemical contrast for indicator elements is
determined on the basis of anomaly:threshold ratios andsummarized in Table 3. Ratios are rounded to the nearest unit. In general, the geochemical contrast for the indicator elements is in the range of 2-3. This isthe case for the commodity element Ti, the sulphide-related suite as well as Cl, Nb and Ba. Cu and Cs are theexception with threshold ratios of 8 and 5, respectively.
INAA and ICP-AES profilesFigures 7 and 8 summarize the anomalous
responses for INAA and ICP-AES data over the mineralized zones. Cr (687 ppm), Ni (362 ppm) and Co(50 ppm) in the INAA data document a single sample"spike" over the Disseminated Zone. This same samplesite is marked by a Cu (89 ppm), Ni (381 ppm) and Mg(4.02%) spike in ICP-AES data. These responses arecontrolled by the mineralogy of the soil sample collectedat this site. The b-horizon is a chrome green, silt to finesand and is derived in part from the weathering and erosion of the host rocks to the mineralized zone. Thehigh Mg, Ni and Cr are reflecting the mafic-ultramafichost rocks whereas the Cu and Co represent a sulphidecomponent in clastic material in the b-horizon.
DISCUSSION
Geochemical contribution of parent soil to enzyme leach anomaliesIndividual b-horizon soil sample descriptions from
sites along transect 31+50 are presented in Appendix Iand document three distinctive types of material that
characterize b-horizon soils over the sampling transect.These are variably oxidized clay, sand and silt. A uniquesoil composition is observed at site GR-23 where ahematitic silt is intermixed with a chrome green silt interpreted to represent a weathered or erosional remnant of the mafic-ultramafic rocks that host oxidemineralization at the PLAC. This chrome green silt wasnot observed in any of the other sample pits on the transect.
Interestingly, the highest contrast signatures, albeitsingle sample responses, for most of the elements interpreted to be indicative of the Disseminated Zonecoincide with the sample of chrome green silt (site GR-23). Anomalous responses associated with thisgreen silt are also observed in samples where a mafic-ultramafic detrital character is not present. Examplesinclude hematitic grey clay at site GR-16 (31+50,4+001N) and light brown silt with hematitic blotches atsite GR-24 (31+50, 6+00N). The indicator elements andtheir concentration levels in each of the three samplesdescribed above are summarized in Table 2.
The geochemical response at site GR-23 suggests a significant contribution of some of the indicator elementsto the overall enzyme leach signature at site GR-23 fromthe parent chrome-green silt. The signature at site GR-23, however, is interpreted to be composite withadditional indicator element concentrations being addedto the sample as they are transported via shallow groundwater or ascending metal-enriched vapours aswell as from parent material. This is substantiated by therecognition of anomalous geochemical responses tozones of oxide mineralization that comprise similar elements (eg. Cl, Ti and Cu) at sites GR-16 and GR-24.The elements Cl-Ti-Cu are moderately correlatedin a Spearman correlation matrix (Table 4).
Sulphide mineral associationsThe observation of anomalous responses for the
metals Ni, Cu, Pb, Ga and Zn over the Disseminated andSouth zones is surprising given the nature of thePipestone Lake Ti-V deposit. The ilmenite-magnetite
Anomaly:threshold Ratio
Cu 483 65 8Cs 15 3 5Pb 28 10.6 3Ga 16 6.2 3Zn 91 35 3Cl 15213 10080 2Ti 3301 2070 2Ni 128 69 2Ba 968 600 2Nb 16 7 2
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Table 3: Anomaly:threshold ratios for indicator elements over the Pipestone Lake Ti-V deposit.
Element Anomaly (ppb) Threshold (ppb)
Elements are ranked from highest to lowest contrast. Ratios are rounded to the nearest unit.
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Figure 7: Neutron activation profiles for Co, Cr and Ni over the Pipestone Lake Ti-V deposit.
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Element Spearman Correlation Coefficients
Mn SQClSQTi 0.355 0.456SQCl -0.02 1
Ni 0.698 0.256Cu 0.392 0.361Zn 0.184 -0.035Ga 0.205 0.296Nb 0.335 0.281Cs 0.089 0.312Ba 0.256 0.019Pb 0.465 0.33
Figure 8: ICP-AES profiles for Cu, Ni and Mg over the Pipestone Lake Ti-V deposit.
Table 4: Spearman correlation coefficients for enzyme leachindicator elements, Mn and semi-quantitative Cl (SQCl).
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oxide mineralogy of these disseminated to near-solidmineralized zones are not associated with sulphide mineralization. Subsequent to the recognition of theenzyme leach patterns for the elements Ni, Cu, Pb, Ga,Zn over this deposit, a re-examination of diamond drilllogs revealed the presence of disseminated pyrite,pyrrhotite and chalcopyrite over core intervals of up to18.5 m (e.g. DDH PL155, 162.5-223.3 ft.) in severallithologies of the PLAC. The sulphide mineralization isdescribed as trace abundance and is associated withshear zones. An east-trending set of shear zones and north-trending brittle faults documented by Cameron (1992) and Jobin-Bevans et al. (1995) may provide pathways for hydrothermal fluid interaction withthe Fe-oxide-rich PLAC and the subsequent formation of disseminated sulphides. These sulphur- and sulphide-bound metals are interpreted to be the cause for enzymeleach Cu, Pb, Ga, Zn (and in part the Ni) anomalies over predominantly oxide mineralization in theDisseminated and South Zones of the Pipestone Lakedeposit.
Niobium, cesium, barium and chlorine anomaliesA single sample Nb response of 16 ppb and the two
sample Cs responses of 15 ppb over the DisseminatedZone as well as a 5 ppb (threshold = 3.5 ppb) responsein the area north of the Disseminated Zone are documented. Although specific examinations for mineralscontaining these elements has not been undertaken it isprobable that the Nb response is attributed to the presence of Nb-bearing rutile (R. Gunter, pers. comm.,1999). The Cs and Ba signature is likely related to the metasomatic effects of the intrusion of a garnet-muscovite-tourmaline granite between 2653-2639 Ma inthe Cross Lake greenstone belt (Mezger et al., 1990).
CONCLUSIONS
This brief orientation survey provides a preliminaryassessment of the usefulness of enzyme leach analyticalmethods in resolving a geochemical signature related tooxide mineralization as occurs within the Pipestone Ti-Vdeposits. Results indicate:1. The South and Disseminated Zones have
distinctive enzyme leach geochemical signa-tures that include Ti (commodity element), Ni,Cu, Pb, Ga and Zn (sulphide-related elements),Nb, Cs, Ba and Cl (alteration and mineralizationelements).
2. The enzyme leach response for Ti, Ni and Cu is interpreted to be a "composite" signature reflecting both primary and secondary geochemical contributions from mafic-ultramafic host rocks of the PLAC andascending metal-enriched vapours from mineralized zones.
3. In this study Cl forms an extensive halo characterized by a high contrast, six sampleresponse that encompasses both the South
and Disseminated Zones. All other indicator elements form one or two sample anomaliesover the mineralized zones.
4. On the basis of anomaly:threshold ratios, indicator elements can be ranked from highest to lowest contrast as follows:Cu>Cs>Pb=Ga=Zn>Cl=Ti=Ni=Ba=Nb.
5. INAA and ICP-AES analyses document the presence of a single sample Mg, Ni, Cr, Coand Cu anomaly over the deposit. This response (site GR-23) is attributed to a mafic-ultramafic component and a sulphidemineral detrital assemblage in the b-horizon.
6. An enzyme leach geochemical survey israpid and cost-effective and, on the basis ofthis orientation survey in the area of the Pipestone Lake Ti-V deposit, has the potentialto reduce large areas of exploration interestto more localized zones suitable for diamonddrill testing.
7. An enzyme leach geochemical survey in thePLAC can be particularly useful where Ti-V mineralization has post-depositional structurally-related sulphide mineralization or secondary(alteration) minerals associated with primaryoxide mineralization. In the absence of post-depositional sulphides, the survey would havebeen less diagnostic.
8. The moderate contrast of enzyme leach indicator elements over this significant zone ofoxide mineralization suggests that the magnitude of the geochemical responsedoes not correlate to the volume and grade of the mineralized target but may be more profoundly affected by the style (oxide/sulphide)of the mineralization.
ACKNOWLEDGEMENTS
Jim Campbell and Richard Gunter of GossanResources Ltd. are thanked for the opportunity to undertake this study. Gossan Resources Ltd. is alsothanked for financial support and access to drill logs andgeological maps. Graham Carlyle is thanked for his enthusiastic assistance with sample collection. ChristineKaszycki and Ric Syme provided constructive criticism.Kelly Proutt typed the manuscript and Bonnie Lenton produced the figures.
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REFERENCES
Cameron, H.D.M. 1992: Pipestone Lake AnorthositeComplex: geology and studies of titanium-vanadiummineralization; Manitoba Energy and Mines,Geological Services, Open File Report OF92-1, 134 p.
Clark, J.R. 1992: Detection of bedrock-related geochem-ical anomalies at the surface of transported over-burden; Explore, v. 76, p. 4-11.
1993: Enzyme-induced leaching of B-horizon soilsfor mineral exploration in areas of glacial overburden;Institution of Mining and Metallurgy, Transactions,Section B: Applied Earth Science, v. 102, p. B19-B29.
Gold, T. and Soter, S. 1980: The deep earth-gas hypoth-esis; Scientific American, v. 242, no. 6, p.154-165.
Gossan Resources Limited. 1998: Annual Report.
Jobin-Bevans, L.S., Peck, D.C., Cameron, H.D.M., andMcDonald, J.P. 1995: Geology and oxide mineraloccurrences of the central and eastern portions ofthe Pipestone Lake Anorthosite Complex; in Reportof Activities, 1995, Manitoba Energy and Mines,Geological Services, p. 74-83.
Jobin-Bevans, L.S., Peck, D.C., and Halden, N.M. 1996:Detailed geological mapping in the central portion ofthe Pipestone Lake Anorthosite Complex; in Reportof Activities, 1996, Manitoba Energy and Mines,Geological Services, p. 75-84.
Kaszycki, C.A. 1989: Surficial geology and till composi-tion, northwestern Manitoba; Geological Survey ofCanada, Open File 2118, 48 p.
Malmqvist, L. and Kristiansson, K. 1984: Experimentalevidence for an ascending microflow of geogas in theground; Earth and Planetary Science Letters, v. 70,no. 2, p. 407-416.
Mezger, K., Bohlen, S.R., and Hanson, G.N. 1990:Metamorphic history of the Archean Pikwitonei gran-ulite domain and the Cross Lake subprovince,Superior Province, Manitoba, Canada; Journal ofPetrology, v. 31, p. 483-517.
Peck, D.C., Cameron, H.D.M., and Corkery, M.T. 1994a:Geological environments and characteristics of Ti-V-Fe oxide mineralization in the western part of thePipestone Lake Anorthosite Complex; in Report ofField Activities, 1994, Manitoba Energy and Mines,Geological Services, p. 113-129.
Peck, D.C., Cameron, H.D.M., and Corkery, M.T. 1994b:Geology and mineral occurrences in the western part of the Pipestone Lake AnorthositeComplex (parts of NTS 63I/4 and 63I/5); ManitobaEnergy and Mines, Geological Services, PreliminaryMap 1994K-1, scale 1:5 000.
Peck, D.C., Messing, C., Halden, N.M., and Chandler, C.1998: New insights into the petrogenesis of thePipestone Lake Anorthosite Complex and its Ti-V-Feoxide deposits (parts of 63I/5 and 63I/12); in Reportof Activities, 1998, Manitoba Energy and Mines,Geological Services, p.127-134.
Wang, X., Cheng, Z., Lu, Y., Xu, L., and Xie, X. 1997:Nanoscale metals in Earth gas and mobile forms ofmetals in overburden in wide-spaced regional exploration for giant deposits in overburden terrains; Journal of Geochemical Exploration, v. 58, no. 1, p. 63-72.
Appendix 1: Enzyme leach field sample descriptions.
Sample Grid Coordinates Description
GR-1 L31+50, 0+25N grey, visibly unoxidized "pebbly" clay with rootlets
GR-2 L31+50, 0+50N grey, visibly unoxidized "pebbly" clay with rootlets
GR-3 L31+50, 0+75N weakly limonitic grey clay, minor rootlets
GR-4 L31+50, 1+00N "pebbly" weakly hematitic light brown clay
GR-5 L31+50, 1+25N reddish brown "pebbly" clay
GR-6 L31+50, 1+50N no sample possible, wet swamp
GR-7 L31+50, 1+75N "pebbly" reddish brown clay
GR-8 L31+50, 2+00N hematitic and limonitic fine sand
GR-9 L31+50, 2+25N light reddish brown "pebbly" clay (DUPLICATE SITE)
GR-10 L31+50, 2+50N light reddish brown "pebbly" clay, minor rootlets
GR-11 L31+50, 2+75N light reddish brown "pebbly" clay, rootlets
GR-12 L31+50, 3+00N chocolate brown, fine "pebbly" clay
GR-13 L31+50, 3+25N brown "pebbly" clay, minor rootlets
GR-14 L31+50, 3+50N reddish brown clay, minor rootlets
GR-15 L31+50, 3+75N reddish brown "pebbly" clay;sample pit bottoms on outcrop
GR-16 L31+50, 4+00N reddish grey, "pebbly" clay, rootlets
GR-17 L31+50, 4+25N dark reddish brown "pebbly" clay
GR-18 L31+50, 4+50N reddish greyish brown "pebbly" clay
GR-19 L31+50, 4+75N dark reddish brown "pebbly" clay
GR-20 L31+50, 5+00N dark reddish brown "pebbly" clay, minor rootlets
GR-21 L31+50, 5+25N brown silty clay, frost mixing (DUPLICATE SITE)
GR-22 L31+50, 5+50N hematitic-limonitic silt
GR-23 L31+50, 5+75N hematitic silt interlayered with chrome green silt
GR-24 L31+50, 6+00N hematitic blotches in light brown silt
GR-25 L31+50, 6+25N no sample possible, wet swamp
GR-26 L31+50, 6+50N no sample possible, wet swamp
GR-27 L31+50, 6+75N no sample possible, wet swamp
GR-28 L31+50, 7+00N no sample possible, wet swamp
GR-29 L31+50, 7+25N limonitic-hematitic silt
GR-30 L31+50, 7+50N limonitic fine sand, rounded granitoid pebbles
GR-31 L31+50, 7+75N limonitic fine sand, rounded granitoid pebbles
GR-32 L31+50, 8+00N limonitic fine sand, 10 cm leached zone capping sand
15
16
Sam
ple
Dis
tanc
e G
rid R
efer
ence
S.Q
.Li
S.Q
.Be
S.Q
.Cl
S.Q
.Sc
S.Q
.Ti
VM
nC
oN
iC
u
Z
nLL
D10
20
3000
100
100
510
15
510
GR
125
L31+
50, 0
+25N
2910
1054
650
383
9020
7428
4846
23G
R 2
50L3
1+50
, 0+5
0N38
1034
2350
408
65
1
568
3039
3120
GR
375
L31+
50, 0
+75N
2310
5483
5026
215
727
28
3346
21G
R 4
100
L31+
50, 1
+00N
4610
1500
5024
528
277
312
3636
19G
R 5
125
L31+
50, 1
+25N
7410
1500
5055
015
015
3830
4954
34G
R 6
150
L31+
50, 1
+50N
no s
ampl
e-w
et s
wam
pG
R 7
175
L31+
50, 1
+75N
144
1036
0550
497
428
219
725
1835
GR
820
0L3
1+50
, 2+0
0N12
1015
0050
297
2937
412
1731
31G
R 9
225
L31+
50, 2
+25N
3310
1500
5053
777
458
2226
3021
GR
10
250
L31+
50, 2
+50N
2710
1500
5047
510
370
718
3038
26G
R 1
127
5L3
1+50
, 2+7
5N47
1015
0050
23
615
169
79
6860
18G
R 1
230
0L3
1+50
, 3+0
0N87
1030
8550
301
253
205
629
4523
GR
13
325
L31+
50, 3
+25N
4410
1500
5030
518
923
25
2840
26G
R 1
435
0L3
1+50
, 3+5
0N55
1089
3950
617
146
215
631
7250
GR
15
375
L31+
50, 3
+75N
4410
3273
5083
071
290
2038
3827
GR
16
400
L31+
50, 4
+00N
5410
1500
5014
5911
1
108
028
6080
82G
R 1
742
5L3
1+50
, 4+2
5N79
1039
5550
359
244
198
635
5625
GR
18
450
L31+
50, 4
+50N
5610
1500
5043
193
1021
1646
4232
GR
19
475
L31+
50, 4
+75N
5510
1063
050
213
172
393
1063
4221
GR
20
500
L31+
50, 5
+00N
1710
1104
250
297
123
223
733
3418
GR
21
525
L31+
50, 5
+25N
6810
1019
750
408
119
275
825
4717
GR
22
550
L31+
50, 5
+50N
1010
1058
950
293
4714
94
1217
13G
R 2
357
5L3
1+50
, 5+7
5N60
1015
213
5033
0133
3
159
341
128
483
91G
R 2
460
0L3
1+50
, 6+0
0N29
1011
836
5099
511
737
811
4510
434
GR
25
625
L31+
50, 6
+25N
no s
ampl
e-w
et s
wam
pG
R 2
665
0L3
1+50
, 6+5
0Nno
sam
ple-
wet
sw
amp
GR
27
675
L31+
50, 6
+75N
no s
ampl
e-w
et s
wam
pG
R 2
870
0L3
1+50
, 7+0
0Nno
sam
ple-
wet
sw
amp
GR
29
725
L31+
50, 7
+25N
1410
3827
5050
5810
985
3040
14G
R 3
075
0L3
1+50
, 7+5
0N5
1015
0050
502.
569
38
-530
GR
31
775
L31+
50, 7
+75N
510
1500
5050
1327
29
109
18G
R 3
280
0L3
1+50
, 8+0
0N5
1015
0050
506
112
32.
5-5
14Fi
eld
Dup
licat
es
Sam
ple
Dis
tanc
eG
rid R
efer
ence
S.Q
.Li
S.Q
.Be
S.Q
.Cl
S.Q
.Sc
S.Q
.Ti
VM
nC
oN
iC
u
Zn
LLD
1020
3000
100
100
510
15
5
1
0G
R 9
-122
5L3
1+50
, 2+2
5N36
1015
0050
564
7513
016
2530
22
GR
9-2
225
L31+
50, 2
+25N
3310
1500
5053
777
458
2226
30
2
1G
R 2
1-1
525
L31+
50, 5
+25N
6810
1019
750
408
119
275
825
47
1
7G
R 2
1-2
525
L31+
50, 5
+25N
6910
9960
5048
811
710
74
3159
13
App
endi
x II:
Enz
yme
leac
h/IC
P-M
S an
alyt
ical
dat
a fo
r sam
plin
g tr
anse
ct L
31+5
0 an
d fie
ld d
uplic
ates
. All
data
in p
arts
per
bill
ion
(ppb
).
App
endi
x II:
Enz
yme
leac
h/IC
P-M
S an
alyt
ical
dat
a fo
r sam
plin
g tr
anse
ct L
31+5
0 an
d fie
ld d
uplic
ates
. All
data
in p
arts
per
bill
ion
(ppb
). (C
ontin
ued)
17
Fiel
d D
uplic
ates
Sam
ple
D
ista
nce
Grid
Ref
eren
ce
Ga
Ge
As
SeB
rR
bSr
YZr
Nb
Mo
LLD
11
530
301
11
1
11
GR
9-1
225
L31+
50, 2
+25N
50.
56
1549
8433
331
134
30.
5G
R 9
-222
5L3
1+50
, 2+2
5N3
0.5
815
4387
203
27
14
13
0.5
GR
21-
152
5L3
1+50
, 5+2
5N3
0.5
1115
126
2736
620
636
3G
R 2
1-2
525
L31+
50, 5
+25N
30.
514
15
1
2234
408
2657
22
Sam
ple
D
ista
nce
Grid
Ref
eren
ce
Ga
Ge
As
SeB
rR
bSr
YZr
Nb
Mo
LLD
11
530
301
11
11
1G
R 1
25L3
1+50
, 0+2
5N3
118
1526
133
327
4611
43
8G
R 2
50L3
1+50
, 0+5
0N4
0.5
915
4830
189
2010
43
3G
R 3
75L3
1+50
, 0+7
5N4
0.5
1215
104
2729
347
753
3G
R 4
100
L31+
50, 1
+00N
30.
516
1568
2229
647
643
4G
R 5
125
L31+
50, 1
+25N
60.
510
1515
3521
572
227
52
GR
615
0L3
1+50
, 1+5
0Nno
sam
ple-
wet
sw
amp
GR
717
5 L3
1+50
, 1+7
5N5
0.5
1415
1550
378
1453
419
GR
820
0L3
1+50
, 2+0
0N3
0.5
615
5783
200
1523
21
GR
9-2
225
L31+
50, 2
+25N
30.
58
1543
8720
327
141
30.
5G
R 1
025
0L3
1+50
, 2+5
0N4
0.5
1215
312
3419
029
104
32
GR
11
275
L31+
50, 2
+75N
30.
514
1559
318
498
3258
26
GR
12
300
L31+
50, 3
+00N
40.
517
1515
228
308
4155
33
GR
13
325
L31+
50, 3
+25N
51
1415
121
3619
938
633
2G
R 1
435
0L3
1+50
, 3+5
0N4
0.5
1215
192
2620
648
111
30.
5G
R 1
537
5L3
1+50
, 3+7
5N6
0.5
915
3367
220
4213
44
0.5
GR
16
400
L31+
50, 4
+00N
100.
518
1581
107
322
6516
67
7G
R 1
742
5L3
1+50
, 4+2
5N4
0.5
2215
171
2224
850
573
3G
R 1
845
0L3
1+50
, 4+5
0N4
0.5
1415
133
4421
649
148
32
GR
19
475
L31+
50, 4
+75N
40.
517
1511
617
336
5890
22
GR
20
500
L31+
50, 5
+00N
30.
511
1528
110
173
3881
23
GR
21-
152
5L3
1+50
, 5+2
5N3
0.5
1115
126
2736
620
636
3G
R 2
255
0L3
1+50
, 5+5
0N5
0.5
615
1523
124
1345
30.
5G
R 2
357
5L3
1+50
, 5+7
5N16
228
1515
149
261
3614
016
7G
R 2
460
0L3
1+50
, 6+0
0N10
0.5
1815
1561
173
3175
60.
5G
R 2
562
5L3
1+50
, 6+2
5Nno
sam
ple-
wet
sw
amp
GR
26
650
L31+
50, 6
+50N
no s
ampl
e-w
et s
wam
pG
R 2
767
5 L3
1+50
, 6+7
5Nno
sam
ple-
wet
sw
amp
GR
28
700
L31+
50, 7
+00N
no s
ampl
e-w
et s
wam
pG
R 2
972
5L3
1+50
, 7+2
5N2
0.5
1115
1519
212
721
10.
5G
R 3
075
0L3
1+50
, 7+5
0N0.
50.
52.
515
1530
711
0.5
0.5
0.5
GR
31
775
L31+
50, 7
+75N
10.
52.
515
1584
155
36
0.5
0.5
GR
32
800
L31+
50, 8
+00N
0.5
0.5
2.5
1515
9985
10.
50.
50.
5
Sam
ple
Dis
tanc
eG
rid R
efer
ence
Ru
PdA
gC
dIn
SnSb
TeI
Cs
Ba
LLD
11
0.2
0.2
0.2
11
110
11
GR
125
L31+
50, 0
+25N
0.5
10.
40.
40.
12
50.
594
0.5
357
GR
250
L31+
50, 0
+50N
0.5
10.
40.
30.
10.
52
0.5
380.
534
8G
R 3
75L3
1+50
, 0+7
5N0.
50.
50.
10.
10.
10.
52
0.5
551
421
GR
410
0L3
1+50
, 1+0
0N0.
50.
50.
10.
10.
10.
54
0.5
611
512
GR
512
5L3
1+50
, 1+2
5N0.
53
0.8
0.3
0.1
0.5
20.
562
156
3G
R 6
150
L31+
50, 1
+50N
no s
ampl
e-w
et s
wam
pG
R 7
175
L31+
50, 1
+75N
0.5
0.5
0.3
0.1
0.1
0.5
30.
549
257
1G
R 8
200
L31+
50, 2
+00N
0.5
0.5
0.1
0.3
0.1
0.5
20.
526
0.5
492
GR
9-2
225
L31+
50, 2
+25N
0.5
10.
50.
10.
10.
52
0.5
320.
544
4G
R 1
025
0L3
1+50
, 2+5
0N0.
51
0.4
0.1
0.1
22
0.5
480.
532
4G
R 1
127
5L3
1+50
, 2+7
5N0.
50.
50.
30.
10.
10.
52
0.5
850.
540
4G
R 1
230
0L3
1+50
, 3+0
0N0.
50.
50.
10.
10.
10.
52
0.5
400.
548
8G
R 1
332
5L3
1+50
, 3+2
5N0.
50.
50.
30.
10.
10.
52
0.5
571
498
GR
14
350
L31+
50, 3
+50N
0.5
10.
40.
20.
10.
52
0.5
610.
541
0G
R 1
537
5L3
1+50
, 3+7
5N0.
52
0.5
0.1
0.1
0.5
10.
536
147
1G
R 1
640
0L3
1+50
, 4+0
0N0.
52
0.6
0.4
0.1
32
0.5
602
638
GR
17
425
L31+
50, 4
+25N
0.5
0.5
0.1
0.1
0.1
0.5
60.
572
0.5
388
GR
18
450
L31+
50, 4
+50N
0.5
20.
60.
70.
10.
51
0.5
480.
533
7G
R 1
947
5L3
1+50
, 4+7
5N0.
51
0.3
0.1
0.1
0.5
20.
558
0.5
402
GR
20
500
L31+
50, 5
+00N
0.5
0.5
0.3
0.2
0.1
0.5
21
540.
533
3G
R 2
1-1
525
L31+
50, 5
+25N
0.5
0.5
0.4
0.1
0.1
12
0.5
863
471
GR
22
550
L31+
50, 5
+50N
0.5
0.5
0.1
0.1
0.1
0.5
12
192
267
GR
23
575
L31+
50, 5
+75N
0.5
0.5
0.5
0.2
0.1
32
0.5
515
968
GR
24
600
L31+
50, 6
+00N
0.5
0.5
0.4
0.1
0.1
22
0.5
445
521
GR
25
625
L31+
50, 6
+25N
no s
ampl
e-w
et s
wam
pG
R 2
665
0L3
1+50
, 6+5
0Nno
sam
ple-
wet
sw
amp
GR
27
675
L31+
50, 6
+75N
no s
ampl
e-w
et s
wam
pG
R 2
870
0L3
1+50
, 7+0
0Nno
sam
ple-
wet
sw
amp
GR
29
725
L31+
50, 7
+25N
0.5
0.5
0.1
0.1
0.1
0.5
0.5
0.5
50.
526
6G
R 3
075
0L3
1+50
, 7+5
0N0.
50.
50.
10.
40.
10.
50.
50.
55
0.5
320
GR
31
775
L31+
50, 7
+75N
0.5
0.5
0.1
0.4
0.1
0.5
0.5
0.5
50.
535
6G
R 3
280
0L3
1+50
, 8+0
0N0.
50.
50.
10.
20.
10.
50.
50.
55
0.5
220
18
Fiel
d D
uplic
ates
Sam
ple
Dis
tanc
eG
rid R
efer
ence
Ru
PdA
gC
dIn
SnSb
TeI
Cs
Ba
LLD
11
0.2
0.2
0.2
11
110
11
GR
9-2
225
L31+
50, 2
+25N
0.5
10.
40.
10.
10.
52
0.5
311
517
GR
9-2
225
L31+
50, 2
+25N
0.5
10.
50.
10.
10.
52
0.5
320.
544
4G
R 2
1-1
525
L31+
50, 5
+25N
0.5
0.5
0.4
0.1
0.1
12
0.5
863
471
GR
21-
252
5L3
1+50
, 5+2
5N0.
50.
50.
20.
10.
10.
50.
50.
565
0.5
451
App
endi
x II:
Enz
yme
leac
h/IC
P-M
S an
alyt
ical
dat
a fo
r sam
plin
g tr
anse
ct L
31+5
0 an
d fie
ld d
uplic
ates
. All
data
in p
arts
per
bill
ion
(ppb
). (C
ontin
ued)
19
App
endi
x II:
Enz
yme
leac
h/IC
P-M
S an
alyt
ical
dat
a fo
r sam
plin
g tr
anse
ct L
31+5
0 an
d fie
ld d
uplic
ates
. All
data
in p
arts
per
bill
ion
(ppb
). (C
ontin
ued)
Sam
ple
Dis
tanc
eG
rid R
efer
ence
LaC
ePr
Nd
SmEu
Gd
TbD
yH
oEr
LLD
11
11
11
11
11
1G
R 1
25L3
1+50
, 0+2
5N66
124
2177
205
243
112
7G
R 2
50L3
1+50
, 0+5
0N34
9710
379
28
15
13
GR
375
L31+
50, 0
+75N
6974
2292
245
222
112
7G
R 4
100
L31+
50, 1
+00N
9610
530
106
255
243
102
7G
R 5
125
L31+
50, 1
+25N
129
307
4015
036
843
419
311
GR
615
0L3
1+50
, 1+5
0Nno
sam
ple-
wet
sw
amp
GR
717
5L3
1+50
, 1+7
5N31
648
317
27
0.5
30.
52
GR
820
0L3
1+50
, 2+0
0N32
667
276
26
0.5
30.
52
GR
9-2
225
L31+
50, 2
+25N
5011
317
6114
314
37
15
GR
10
250
L31+
50, 2
+50N
4482
1453
143
131
61
4G
R 1
127
5L3
1+50
, 2+7
5N62
6415
5813
313
16
14
GR
12
300
L31+
50, 3
+00N
7150
2387
214
202
92
5G
R 1
332
5
L31+
50, 3
+25N
6845
2182
214
182
92
6G
R 1
435
0L3
1+50
, 3+5
0N63
8624
9624
423
211
27
GR
15
375
L31+
50, 3
+75N
6912
122
8921
422
211
27
GR
16
400
L31+
50, 4
+00N
129
269
3613
329
731
417
310
GR
17
425
L31+
50, 4
+25N
8155
2598
244
222
112
6G
R 1
845
0L3
1+50
, 4+5
0N67
140
2178
194
212
102
7G
R 1
947
5L3
1+50
, 4+7
5N10
010
432
128
336
323
153
10G
R 2
050
0L3
1+50
, 5+0
0N66
8721
8118
417
210
26
GR
21-
152
5L3
1+50
, 5+2
5N47
7512
429
210
15
0.5
3G
R 2
255
0L3
1+50
, 5+5
0N29
547
297
27
0.5
40.
52
GR
23
575
L31+
50, 5
+75N
9517
721
6915
314
27
14
GR
24
600
L31+
50, 6
+00N
7895
1864
143
131
71
4G
R 2
562
5L3
1+50
, 6+2
5Nno
sam
ple-
wet
sw
amp
GR
26
650
L31+
50, 6
+50N
no s
ampl
e-w
et s
wam
pG
R 2
767
5L3
1+50
, 6+7
5Nno
sam
ple-
wet
sw
amp
GR
28
700
L31+
50, 7
+00N
no s
ampl
e-w
et s
wam
pG
R 2
972
5L3
1+50
, 7+2
5N15
213
133
0.5
30.
51
0.5
0.5
GR
30
750
L31+
50, 7
+50N
24
0.5
30.
50.
50.
50.
50.
50.
50.
5G
R 3
177
5L3
1+50
, 7+7
5N7
172
61
0.5
20.
51
0.5
0.5
GR
32
800
L31+
50, 8
+00N
24
0.5
20.
50.
50.
50.
50.
50.
50.
5Fi
eld
Dup
licat
es
Sam
ple
Dis
tanc
eG
rid R
efer
ence
LaC
ePr
Nd
SmEu
Gd
TbD
yH
oEr
LLD
11
11
11
11
11
1G
R 9
-122
5L3
1+50
, 2+2
5N65
146
2175
163
173
92
5G
R 9
-222
5L3
1+50
, 2+2
5N50
113
1761
143
143
71
5G
R 2
1-1
525
L31+
50, 5
+25N
4775
1242
92
101
50.
53
GR
21-
252
5L3
1+50
, 5+2
5N52
6212
4810
210
15
13
20
App
endi
x II:
Enz
yme
leac
h/IC
P-M
S an
alyt
ical
dat
a fo
r sam
plin
g tr
anse
ct L
31+5
0 an
d fie
ld d
uplic
ates
. All
data
in p
arts
per
bill
ion
(ppb
). (C
ontin
ued)
Sam
ple
Dis
tanc
eG
rid R
efer
ence
TmYb
LuH
fTa
WR
eO
sPt
Au
S.Q
.Hg
LLD
11
11
11
0.1
11
0.1
1G
R 1
25L3
1+50
, 0+2
5N1
51
30.
51
0.05
0.5
0.5
0.05
0.5
GR
250
L31+
50, 0
+50N
0.5
30.
53
0.5
0.5
0.05
0.5
0.5
0.05
0.5
GR
375
L31+
50, 0
+75N
15
0.5
20.
50.
50.
050.
50.
50.
050.
5G
R 4
100
L31+
50, 1
+00N
0.5
50.
52
0.5
10.
050.
50.
50.
050.
5G
R 5
125
L31+
50, 1
+25N
17
16
0.5
10.
050.
50.
50.
050.
5G
R 6
150
L31+
50, 1
+50N
no s
ampl
e-w
et s
wam
pG
R 7
175
L31+
50, 1
+75N
0.5
10.
51
0.5
10.
050.
50.
50.
050.
5G
R 8
200
L31+
50, 2
+00N
0.5
0.5
0.5
0.5
0.5
0.5
0.05
0.5
0.5
0.05
0.5
GR
9-2
225
L31+
50, 2
+25N
0.5
30.
55
0.5
0.5
0.05
0.5
0.5
0.05
0.5
GR
10
250
L31+
50, 2
+50N
0.5
30.
53
0.5
0.5
0.05
0.5
0.5
0.05
0.5
GR
11
275
L31+
50, 2
+75N
0.5
30.
51
0.5
0.5
0.05
0.5
0.5
0.05
0.5
GR
12
300
L31+
50, 3
+00N
0.5
40.
51
0.5
0.5
0.05
0.5
0.5
0.05
0.5
GR
13
325
L31+
50, 3
+25N
0.5
40.
52
0.5
10.
050.
50.
50.
050.
5G
R 1
435
0L3
1+50
, 3+5
0N1
60.
52
0.5
0.5
0.05
0.5
0.5
0.05
0.5
GR
15
375
L31+
50, 3
+75N
15
0.5
50.
50.
50.
050.
50.
50.
050.
5G
R 1
640
0L3
1+50
, 4+0
0N2
82
50.
51
0.05
0.5
0.5
0.05
0.5
GR
17
425
L31+
50, 4
+25N
0.5
50.
51
0.5
0.5
0.05
0.5
0.5
0.05
0.5
GR
18
450
L31+
50, 4
+50N
16
0.5
40.
50.
50.
050.
50.
50.
050.
5G
R 1
947
5L3
1+50
, 4+7
5N1
60.
52
0.5
10.
050.
50.
50.
050.
5G
R 2
050
0L3
1+50
, 5+0
0N0.
55
0.5
30.
50.
50.
050.
50.
50.
050.
5G
R 2
1-1
525
L31+
50, 5
+25N
0.5
20.
52
0.5
20.
050.
50.
50.
050.
5G
R 2
255
0L3
1+50
, 5+5
0N0.
52
0.5
20.
51
0.05
0.5
0.5
0.05
0.5
GR
23
575
L31+
50, 5
+75N
0.5
30.
54
12
0.05
0.5
0.5
0.05
0.5
GR
24
600
L31+
50, 6
+00N
0.5
30.
52
0.5
20.
050.
50.
50.
050.
5G
R 2
562
5L3
1+50
, 6+2
5Nno
sam
ple-
wet
sw
amp
GR
26
650
L31+
50, 6
+50N
no s
ampl
e-w
et s
wam
pG
R 2
767
5L3
1+50
, 6+7
5Nno
sam
ple-
wet
sw
amp
GR
28
700
L31+
50, 7
+00N
no s
ampl
e-w
et s
wam
pG
R 2
972
5L3
1+50
, 7+2
5N0.
50.
50.
50.
50.
50.
50.
050.
50.
50.
050.
5G
R 3
075
0L3
1+50
, 7+5
0N0.
50.
50.
50.
50.
50.
50.
050.
50.
50.
050.
5G
R 3
177
5L3
1+50
, 7+7
5N0.
50.
50.
50.
50.
50.
50.
050.
50.
50.
050.
5G
R 3
280
0L3
1+50
, 8+0
0N0.
50.
50.
50.
50.
50.
50.
050.
50.
50.
050.
5Fi
eld
Dup
licat
es
Sam
ple
Dis
tanc
eG
rid R
efer
ence
TmYb
LuH
fTa
WR
eO
sPt
Au
S.Q
.Hg
LLD
11
11
11
0.1
11
0.1
1G
R 9
-122
5L3
1+50
, 2+2
5N0.
54
0.5
40.
50.
50.
050.
50.
50.
050.
5G
R 9
-222
5L3
1+50
, 2+2
5N0.
53
0.5
50.
50.
50.
050.
50.
50.
050.
5G
R 2
1-1
525
L31+
50, 5
+25N
0.5
20.
52
0.5
20.
050.
50.
50.
050.
5G
R 2
1-2
525
L31+
50, 5
+25N
0.5
20.
51
0.5
10.
050.
50.
50.
050.
5
21
Appendix II: Enzyme leach/ICP-MS analytical data for sampling transect L31+50 and field duplicates. All data in parts per billion (ppb). (Continued)
Sample Distance Grid Reference Tl Pb Bi Th ULLD 1 1 1 1 1GR 1 25 L31+50, 0+25N 0.5 8 0.5 17 7GR 2 50 L31+50, 0+50N 0.5 8 0.5 11 4GR 3 75 L31+50, 0+75N 0.5 6 0.5 9 3GR 4 100 L31+50, 1+00N 0.5 6 0.5 10 8GR 5 125 L31+50, 1+25N 0.5 8 0.5 33 7GR 6 150 L31+50, 1+50N no sample-wet swampGR 7 175 L31+50, 1+75N 0.5 9 0.5 12 3GR 8 200 L31+50, 2+00N 0.5 4 0.5 8 3GR 9-2 225 L31+50, 2+25N 0.5 8 0.5 19 4GR 10 250 L31+50, 2+50N 0.5 8 0.5 14 3GR 11 275 L31+50, 2+75N 0.5 4 0.5 12 2GR 12 300 L31+50, 3+00N 0.5 6 0.5 10 2GR 13 325 L31+50, 3+25N 0.5 5 0.5 9 2GR 14 350 L31+50, 3+50N 0.5 7 0.5 15 4GR 15 375 L31+50, 3+75N 0.5 9 0.5 25 5GR 16 400 L31+50, 4+00N 0.5 21 0.5 21 9GR 17 425 L31+50, 4+25N 0.5 6 0.5 8 2GR 18 450 L31+50, 4+50N 0.5 8 0.5 19 4GR 19 475 L31+50, 4+75N 0.5 7 0.5 14 2GR 20 500 L31+50, 5+00N 0.5 5 0.5 11 2GR 21-1 525 L31+50, 5+25N 0.5 9 0.5 15 3GR 22 550 L31+50, 5+50N 0.5 6 0.5 19 8GR 23 575 L31+50, 5+75N 0.5 28 0.5 19 6GR 24 600 L31+50, 6+00N 0.5 13 0.5 21 3GR 25 625 L31+50, 6+25N no sample-wet swampGR 26 650 L31+50, 6+50N no sample-wet swampGR 27 675 L31+50, 6+75N no sample-wet swampGR 28 700 L31+50, 7+00N no sample-wet swampGR 29 725 L31+50, 7+25N 0.5 3 0.5 4 0.5GR 30 750 L31+50, 7+50N 0.5 1 0.5 0.5 0.5GR 31 775 L31+50, 7+75N 0.5 4 0.5 5 0.5GR 32 800 L31+50, 8+00N 0.5 1 0.5 0.5 0.5
Field Duplicates
Sample Distance Grid Reference Tl Pb Bi Th ULLD 1 1 1 1 1GR 9-1 225 L31+50, 2+25N 0.5 8 0.5 19 5GR 9-2 225 L31+50, 2+25N 0.5 8 0.5 19 4GR 21-1 525 L31+50, 5+25N 0.5 9 0.5 15 3GR 21-2 525 L31+50, 5+25N 0.5 7 0.5 13 2
Appendix III: Enzyme leach element profiles over the Pipestone Lake Ti-V deposit.
22
23
Appendix III: Enzyme leach element profiles over the Pipestone Lake Ti-V deposit. (continued)
24
Appendix III: Enzyme leach element profiles over the Pipestone Lake Ti-V deposit. (continued)
25
Appendix III: Enzyme leach element profiles over the Pipestone Lake Ti-V deposit. (continued)
26
Appendix III: Enzyme leach element profiles over the Pipestone Lake Ti-V deposit. (continued)
27
Appendix III: Enzyme leach element profiles over the Pipestone Lake Ti-V deposit. (continued)
28
Appendix III: Enzyme leach element profiles over the Pipestone Lake Ti-V deposit. (continued)
29
Appendix III: Enzyme leach element profiles over the Pipestone Lake Ti-V deposit. (continued)
30
Appendix III: Enzyme leach element profiles over the Pipestone Lake Ti-V deposit. (continued)
31
Appendix III: Enzyme leach element profiles over the Pipestone Lake Ti-V deposit. (continued)
32
Elem
ent
Uni
tsG
R-1
GR
-2
G
R-3
GR
-4
G
R-5
GR
-6G
R-7
GR
-8
G
R-9
-1
GR
-9-2
R
E G
R-9
-2
G
R-1
0
GR
-11
G
R-1
2
GR
-13
G
R-1
4
GR
-15
G
R-1
6
GR
-17
G
R-1
8
GR
-19
G
R-2
0
GR
-21-
1
G
R-2
1-2
GR
-22
G
R-2
3
GR
-24
G
R-2
5G
R-2
6G
R-2
7G
R-2
8G
R-2
9
GR
-30
G
R-3
1
GR
-32
GR
-9-1
G
R-9
-2
GR
-21-
1
G
R-2
1-2
GR
-9-2
R
E G
R-9
-2
Met
res
25 50 75 100
125
150
175
200
225
225
225
250
275
300
325
350
375
400
425
450
475
500
525
525
550
575
600
625
650
675
700
725
750
775
800
225
225
525
525
225
225
Grid
Ref
eren
ce
L31+
50, 0
+25N
L31+
50, 0
+50N
L31+
50, 0
+75N
L31+
50, 1
+00N
L31+
50, 1
+25N
L31+
50, 1
+50N
L31+
50, 1
+75N
L31+
50, 2
+00N
L31+
50, 2
+25N
L31+
50, 2
+25N
L31+
50, 2
+25N
L31+
50, 2
+50N
L31+
50, 2
+75N
L31+
50, 3
+00N
L31+
50, 3
+25N
L31+
50, 3
+50N
L31+
50, 3
+75N
L31+
50, 4
+00N
L31+
50, 4
+25N
L31+
50, 4
+50N
L31+
50, 4
+75N
L31+
50, 5
+00N
L31+
50, 5
+25N
L31+
50, 5
+25N
L31+
50, 5
+50N
L31+
50, 5
+75N
L31+
50, 6
+00N
L31+
50, 6
+25N
L31+
50, 6
+50N
L31+
50, 6
+75N
L31+
50, 7
+00N
L31+
50, 7
+25N
L31+
50, 7
+50N
L31+
50, 7
+75N
L31+
50, 8
+00N
L31+
50, 2
+25N
L31+
50, 2
+25N
L31+
50, 5
+25N
L31+
50, 5
+25N
L31+
50, 2
+25N
L31+
50, 2
+25N
Ag
PPM
0.6
0.7
0.7
0.8
0.6
NS
0.7
0.5
0.6
0.6
0.6
0.5
0.5
0.6
0.7
0.6
0.5
0.5
0.6
0.6
0.5
0.6
0.5
0.4
0.6
0.4
0.5
NS
NS
NS
NS
0.4
0.6
0.5
0.4
0.6
0.6
0.5
0.4
0.6
0.6
Hg
PPB
54 40 25 26 23 NS 15 14 17 35 NA 36 45 29 26 26 15 38 38 32 28 31 18 19 5 39 10 NS
NS
NS
NS 15 3 6 3 17 35 18 19 35 NA
Mn
PPM
606
547
555
710
711
NS
384
253
360
412
427
474
538
560
668
508
377
491
482
569
578
516
326
332
196
947
287
NS
NS
NS
NS
220
190
212
154
360
412
326
332
412
427
Sr
PPM
148
163
158
172
149
NS
180
200
153
167
176
154
165
162
161
153
187
160
154
161
159
151
200
200
221
133
228
NS
NS
NS
NS
200
225
204
211
153
167
200
200
167
176
Bi
PPM
-5 -5 -5 -5 -5 NS -5 -5 -5 -5 -5 -5 -5 -5 -5 -5 -5 -5 -5 -5 -5 -5 -5 -5 -5 -5 -5 NS
NS
NS
NS -5 -5 -5 -5 -5 -5 -5 -5 -5 -5
Cd
PPM
-0.5
-0.5
-0.5
-0.5
-0.5
NS
-0.5
-0.5
-0.5
-0.5
-0.5
-0.5
-0.5
-0.5
-0.5
-0.5
-0.5
-0.5
-0.5
-0.5
-0.5
-0.5
-0.5
-0.5
-0.5
-0.5
-0.5
NS
NS
NS
NS
-0.5
-0.5
-0.5
-0.5
-0.5
-0.5
-0.5
-0.5
-0.5
-0.5
V PP
M10
296 12
112
511
7N
S 92 54 104
93 94 102
103
125
118
121
82 103
119
105
120
107
57 58 35 109
50 NS
NS
NS
NS 24 36 43 30 104
93 57 58 93 94
Ca % 1.15
1.06
1.14
1.21
1.12 NS
2.63
1.31
0.78
0.95
0.97
1.16
4.51
1.08
1.25 1
1.08
0.98
1.37
1.13
1.21
1.44
3.46
6.22
1.42
4.63
2.34 NS
NS
NS
NS
8.15
1.31
1.24
1.16
0.78
0.95
3.46
6.22
0.95
0.97
P %0.
037
0.02
80.
033
0.03
0.03
1N
S0.
017
0.01
20.
020.
017
0.01
80.
024
0.04
80.
038
0.03
20.
030.
020.
027
0.03
30.
035
0.02
60.
024
0.03
50.
036
0.04
60.
047
0.05
2N
SN
SN
SN
S0.
037
0.03
50.
035
0.04
2
0.02
0.01
70.
035
0.03
6
0.01
70.
018
Al % 8
8.05
9.37
9.91
9.03 NS
7.97
5.48 9
8.35 8.4
8.55
8.01
9.69
9.53
9.65
7.41
8.55
9.82
8.65
9.54
8.81 5.8
5.74
4.97
4.35
5.47 NS
NS
NS
NS
3.75 4.8
4.98
4.72 9
8.35 5.8
5.74
8.35 8.4
Ti % 0.39
0.39
0.41
0.42
0.39 NS
0.34
0.23
0.39
0.38
0.38
0.39
0.35 0.4
0.4
0.41
0.34
0.39 0.4
0.39
0.41
0.37
0.25
0.25
0.19 0.5
0.23 NS
NS
NS
NS
0.13
0.17
0.19
0.15
0.39
0.38
0.25
0.25
0.38
0.38
Mg %
1.36
1.27
1.69
1.85
1.61 NS
1.29
0.63
1.42
1.21
1.25
1.44
1.74
1.86
1.73
1.64
1.02
1.33
1.84
1.44
1.75
1.51
1.48
1.64
0.41
4.02
0.94 NS
NS
NS
NS
2.02
0.31
0.43 0.3
1.42
1.21
1.48
1.64
1.21
1.25
K % 2.7
2.64 2.9
2.99
2.71 NS
2.47
1.47
2.52
2.73
2.68
2.58
2.14
2.96
2.87
2.77
2.42
2.64
2.75
2.81
2.74
2.23
1.59
1.66
1.72
0.98
1.65 NS
NS
NS
NS
1.36 1.4
1.38
1.46
2.52
2.73
1.59
1.66
2.73
2.68
YPP
M22 14 20 24 20 N
S 17 7 14 10 11 19 40 24 22 17 13 22 28 20 25 20 13 13 10 13 12 NS
NS
NS
NS 8 7 7 6 14 10 13 13 10 11
Be
PPM 2 2 2 2 2 NS 2 -2 2 2 2 2 2 2 2 2 -2 2 2 2 2 2 -2 -2 -2 -2 -2 NS
NS
NS
NS -2 -2 -2 -2 2 2 -2 -2 2 2
S % 0.03
0.02
0.02
0.02
0.02 NS
0.03
0.02
0.02
0.02
0.03
0.02
0.05
0.02
0.03
0.02
0.02
0.02
0.02
0.02
0.02
0.03
0.04
0.06
0.02
0.04
0.02 NS
NS
NS
NS
0.07
0.02
0.01
0.02
0.02
0.02
0.04
0.06
0.02
0.03
Mo
PPM
-2 -2 -2 -2 -2 NS -2 -2 -2 -2 -2 -2 -2 -2 -2 -2 -2 -2 -2 -2 -2 -2 -2 -2 -2 -2 -2 NS
NS
NS
NS -2 -2 -2 -2 -2 -2 -2 -2 -2 -2
Cu
PPM
23 20 31 34 32 NS 22 16 29 19 19 27 41 37 33 34 16 27 39 23 31 23 19 22 6 89 20 NS
NS
NS
NS 3 2 7 2 29 19 19 22 19 19
Zn
PPM
80 72 95 103
102
NS 74 46 73 65 68 75 81 98 98 90 57 76 102
83 93 77 38 40 16 56 28 NS
NS
NS
NS 11 12 22 12 73 65 38 40 65 68
Pb
PPM
21 21 24 25 23 NS 20 13 22 21 21 21 18 24 24 20 19 21 22 22 23 21 13 14 13 6 12 NS
NS
NS
NS 8 12 13 13 22 21 13 14 21 21
Ni
PPM
49 46 58 64 58 NS 43 29 51 44 44 50 56 61 59 57 36 52 59 52 61 53 30 32 15 381
27 NS
NS
NS
NS 11 13 26 12 51 44 30 32 44 44
App
endi
x IV
: Neu
tron
act
ivat
ion
and
indu
ctiv
ely
coup
led
plas
ma-
atom
ic e
mis
sion
spe
ctro
met
ry
anal
ytic
al d
ata
for s
ampl
ing
tran
sect
L31
+50.
Hg
data
by
flow
inje
ctio
n (F
IMS)
.
ICP-
AES
Fiel
d D
uplic
ate
Pairs
Ana
lytic
al D
uplic
ates
33
Elem
ent
Uni
ts
GR
-1
G
R-2
GR
-3
G
R-4
GR
-5
G
R-7
GR
-8
G
R-9
-1
GR
-9-2
G
R-1
0
GR
-11
G
R-1
2
GR
-13
G
R-1
4
GR
-15
G
R-1
6
GR
-17
G
R-1
8
GR
-19
G
R-2
0
GR
-21-
1
G
R-2
1-2
GR
-22
G
R-2
3
GR
-24
G
R-2
5G
R-2
6G
R-2
7G
R-2
8G
R-2
9
GR
-30
G
R-3
1
GR
-32
GR
-9-1
G
R-9
-2
GR
-21-
1
G
R-2
1-2
Met
res
25 50 75 100
125
175
200
225
225
250
275
300
325
350
375
400
425
450
475
500
525
525
550
575
600
625
650
675
700
725
750
775
800
225
225
525
525
Grid
Ref
eren
ce
L31+
50, 0
+25N
L31+
50, 0
+50N
L31+
50, 0
+75N
L31+
50, 1
+00N
L31+
50, 1
+25N
L31+
50, 1
+50N
L31+
50, 1
+75N
L31+
50, 2
+25N
L31+
50, 2
+25N
L31+
50, 2
+50N
L31+
50, 2
+75N
L31+
50, 3
+00N
L31+
50, 3
+25N
L31+
50, 3
+50N
L31+
50, 3
+75N
L31+
50, 4
+00N
L31+
50, 4
+25N
L31+
50, 4
+50N
L31+
50, 4
+75N
L31+
50, 5
+00N
L31+
50, 5
+25N
L31+
50, 5
+25N
L31+
50, 5
+50N
L31+
50, 5
+75N
L31+
50, 6
+00N
L31+
50,6
+25N
L31+
50, 6
+50N
L31+
50, 6
+75N
L31+
50, 7
+00N
L31+
50,7
+25N
L31+
50, 7
+50N
L31+
50, 7
+75N
L31+
50, 8
+00N
L31+
50, 2
+00N
L31+
50, 2
+25N
L31+
50, 5
+25N
L31+
50, 5
+25N
Ca %
1 2 -1 -1 -1 -1 3 -1 2 -1 1 4 -1 -1 -1 -1 2 -1 -1 2 2 4 6 -1 4 2 0 0 0 0 8 2 1 -1 2 -1 4 6
Au
PPB
2 4 -2 5 -2 2 -2 -2 -2 -2 4 -2 -2 -2 -2 -2 -2 -2 2 -2 -2 -2 -2 -2 -2 -2 0 0 0 0 -2 -2 -2 -2 -2 -2 -2 -2
Cr
PPM 5 113
103
118
132
123
100
94 113
106
118
95 147
122
132
88 109
128
117
123
110
80 77 48 687
63 0 0 0 0 40 37 65 29 113
106
80 77
Cs
PPM 1 9 7 9 9 9 6 2 8 7 9 7 11 8 9 5 7 10 8 9 8 3 3 1 2 2 0 0 0 0 1 -1 1 -1 8 7 3 3
Hf
PPM
1 5 6 5 5 5 6 8 6 6 6 5 6 6 6 6 5 6 6 5 6 6 6 9 6 7 0 0 0 0 7 6 7 4 6 6 6 6
Fe %
0.01 5.2
4.77
5.82
6.32
6.07
4.53
2.95
5.42
4.51
5.54 5.5
6.89
5.75
6.03
3.65
4.65
6.32 5.4
5.92 5.3
3.09
3.15
1.51
7.76
2.24 0 0 0 0
1.36
1.39
2.27
1.12
5.42
4.51
3.09
3.15
Hg
PPM 1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 0 0 0 0 -1 -1 -1 -1 -1 -1 -1 -1
Ir PPB 5 -5 -5 -5 -5 -5 -5 -5 -5 -5 -5 -5 -5 -5 -5 -5 -5 -5 -5 -5 -5 -5 -5 -5 -5 -5 0 0 0 0 -5 -5 -5 -5 -5 -5 -5 -5
Mo
PPM 1 -1 -1 -1 2 -1 2 -1 -1 -1 1 -1 -1 -1 -1 -1 1 -1 3 -1 -1 2 -1 1 -1 -1 0 0 0 0 -1 -1 -1 -1 -1 -1 2 -1
Rb
PPM
15 182
201
175
196
182
172
52 184
162
180
154
216
179
183
146
194
180
190
182
152
76 91 57 53 71 0 0 0 0 49 43 48 57 184
162
76 91
Ni
PPM
20 -33
-27
-28
-29
-29
-25
-20
-28
-26
-31
100
184
-29
-28
-24
-27
-28
70 -29
67 -20
-20
-20
362
-20 0 0 0 0 -20
-20
-20
-20
-28
-26
-20
-20
Na %
0.01
1.14
1.27
1.06
1.14
1.05
1.31
1.75
1.07
1.27
1.14
1.09
1.15
1.02
1.07
1.41
1.05
0.97
1.21
0.99
0.98
1.49
1.43
1.79
1.11
1.76 0 0 0 0
1.42
1.61
1.65
1.59
1.07
1.27
1.49
1.43
Sb PPM
0.1
0.4
0.5
0.4
0.5
0.4
0.4
0.3
0.5
0.3
0.4
0.6
0.4
0.4
0.4
0.2
-0.1
0.6
0.4
0.4
0.4
0.2
0.2
0.3
-0.1
-0.1 0 0 0 0 0.2
0.1
-0.1
-0.1
0.5
0.3
0.2
0.2
Sc PPM
0.1
16.5
15.1
17 17.6
16.4
13.1 8 15 13.2
17 14.6
18.9
16.4
17.6
11.7
16.5
17.6
16.9
16.8
15.6
9.9
9.7
5.7
17.4
7.3 0 0 0 0 4.1
3.7
5.6
3.3
15 13.2
9.9
9.7
Se PPM 3 -3 -3 -3 -3 3 -3 -3 -3 -3 -3 -3 -3 -3 -3 -3 -3 -3 -3 -3 -3 -3 -3 -3 -3 -3 0 0 0 0 -3 -3 -3 -3 -3 -3 -3 -3
Ag
PPM 5 -5 -5 -5 -5 -5 -5 -5 -5 -5 -5 -5 -5 -5 -5 -5 -5 -5 -5 -5 -5 -5 -5 -5 -5 -5 0 0 0 0 -5 -5 -5 -5 -5 -5 -5 -5
As
PPM
0.5
5.3
5.3
7.1
6.9
9.3
6.9
4.5
7.5
6.5
8.2
9.5
8.7
8.2
8.9
2.5
4.7
8.3
6.2
7.7
8.6
4.9
4.8
2.8
5.4
4.4 0 0 0 0 3.7
2.2
2.9
1.7
7.5
6.5
4.9
4.8
Br
PPM
0.5
8.3
4.2
5.6
4.4
4.8
2.5
3.4
3.9
3.4
6.5
9.7
5.1
5.7
5.4
2.1
2.2
8.3
5.6
7.3
9.5
6.7
6.5
2.4 3 4.3 0 0 0 0 3.4
1.4
-0.5
1.6
3.9
3.4
6.7
6.5
Ba
PPM
50 640
680
670
700
680
650
620
660
730
760
550
860
680
720
770
770
710
750
680
720
610
600
510
300
470 0 0 0 0 400
430
410
400
660
730
610
600
Co
PPM 1 20 18 19 23 24 14 10 18 16 21 18 23 20 19 13 17 20 18 22 18 12 12 5 50 7 0 0 0 0 3 4 8 4 18 16 12 12
App
endi
x IV
: Neu
tron
act
ivat
ion
and
indu
ctiv
ely
coup
led
plas
ma-
atom
ic e
mis
sion
spe
ctro
met
ry
anal
ytic
al d
ata
for s
ampl
ing
tran
sect
L31
+50.
Hg
data
by
flow
inje
ctio
n (F
IMS)
. (C
ontin
ued)
INA
A
Det
ectio
n Li
mit
Fiel
d D
uplic
ate
Pairs
34
Elem
ent
Uni
ts
GR
-1
G
R-2
GR
-3
G
R-4
GR
-5
G
R-7
GR
-8
G
R-9
-1
GR
-9-2
G
R-1
0
GR
-11
G
R-1
2
GR
-13
G
R-1
4
GR
-15
G
R-1
6
GR
-17
G
R-1
8
GR
-19
G
R-2
0
GR
-21-
1
G
R-2
1-2
GR
-22
G
R-2
3
GR
-24
G
R-2
5G
R-2
6G
R-2
7G
R-2
8G
R-2
9
GR
-30
G
R-3
1
GR
-32
GR
-9-1
G
R-9
-2
GR
-21-
1
G
R-2
1-2
Met
res
25 50 75 100
125
175
200
225
225
250
275
300
325
350
375
400
425
450
475
500
525
525
550
575
600
625
650
675
700
725
750
775
800
225
225
525
525
Grid
Ref
eren
ce
L31+
50, 0
+25N
L31+
50, 0
+50N
L31+
50, 0
+75N
L31+
50, 1
+00N
L31+
50, 1
+25N
L31+
50, 1
+50N
L31+
50, 1
+75N
L31+
50, 2
+25N
L31+
50, 2
+25N
L31+
50, 2
+50N
L31+
50, 2
+75N
L31+
50, 3
+00N
L31+
50, 3
+25N
L31+
50, 3
+50N
L31+
50, 3
+75N
L31+
50, 4
+00N
L31+
50, 4
+25N
L31+
50, 4
+50N
L31+
50, 4
+75N
L31+
50, 5
+00N
L31+
50, 5
+25N
L31+
50, 5
+25N
L31+
50, 5
+50N
L31+
50, 5
+75N
L31+
50, 6
+00N
L31+
50,6
+25N
L31+
50, 6
+50N
L31+
50, 6
+75N
L31+
50, 7
+00N
L31+
50,7
+25N
L31+
50, 7
+50N
L31+
50, 7
+75N
L31+
50, 8
+00N
L31+
50, 2
+00N
L31+
50, 2
+25N
L31+
50, 5
+25N
L31+
50, 5
+25N
W
PPM 1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 2 -1 -1 -1 -1 3 -1 -1 -1 -1 -1 0 0 0 0 -1 -1 -1 -1 -1 -1 -1 -1
Sn %
0.01
-0.0
1-0
.01
-0.0
1-0
.01
-0.0
1-0
.01
-0.0
1-0
.01
-0.0
1-0
.01
-0.0
1-0
.01
-0.0
1-0
.01
-0.0
1-0
.01
-0.0
1-0
.01
-0.0
1-0
.01
-0.0
1-0
.01
-0.0
1-0
.01
-0.0
10 0 0 0
-0.0
1-0
.01
-0.0
1-0
.01
-0.0
1-0
.01
-0.0
1-0
.01
La PPM
0.5
72.2
48.3
59.7
71 61.7
51.3
24 59.9
47.6
70.1
113
75.7
63.2
57.7
43.9
66.9
83.9
63.4
72 55.4
32.8
35.2
18.8
21.8
24.5 0 0 0 0
15.5
11.7
15.3
9.6
59.9
47.6
32.8
35.2
Ce
PPM 3 172
145
122
149
142
98 37 138
115
174
138
151
117
137
101
189
107
184
137
127
57 63 42 50 46 0 0 0 0 35 24 35 20 138
115
57 63
Sm PPM
0.1
8.6
5.6
7.1
8.7
7.2
6.2
2.9
5.6
4.3
8.8
12.5
9.6
7.4
6.9
5.3
8.1
9.9
8.2
8.9
7.7
4.2
4.3 3 4.2
3.6 0 0 0 0 2.4
1.7
2.1
1.5
5.6
4.3
4.2
4.3
Nd
PPM
5 60 36 45 52 46 41 14 44 32 56 85 60 46 44 33 54 68 54 59 49 28 28 18 21 22 0 0 0 0 15 7 10 7 44 32 28 28
Eu PPM
0.2 2 1.3
1.9 2 1.8
1.4
0.7
1.4
1.2
2.1
2.9
2.1
1.8
1.5
1.3 2 2.3
1.7 2 1.8 1 1 0.9
1.2
1.1 0 0 0 0 0.7
0.6
0.6
0.5
1.4
1.2 1 1
Tb PPM
0.5
1.1
-0.5
-0.5
-0.5
0.6
-0.5
-0.5
-0.5
-0.5 1 1 -0.5
-0.5
-0.5
-0.5 1 -0.5
-0.5
-0.5
-0.5
0.6
0.6
-0.5
-0.5
-0.5 0 0 0 0 -0.5
-0.5
-0.5
-0.5
-0.5
-0.5
0.6
0.6
Yb PPM
0.2 3 2.4
2.5 3 2.3
2.2
1.3
1.8
1.8
3.1
3.6 3 2.5
2.3 2 2.7
3.1
2.7
2.8
2.7
1.6
1.5
1.6
1.7
1.5 0 0 0 0 1.2
0.8
1.1
0.7
1.8
1.8
1.6
1.5
Lu PPM
0.05 0.5
0.38
0.48 0.5
0.48
0.41
0.22
0.33
0.31
0.52
0.65 0.6
0.44
0.47
0.37 0.5
0.56 0.5
0.54
0.44
0.27
0.26
0.27
0.27
0.29 0 0 0 0
0.21
0.15
0.21
0.13
0.33
0.31
0.27
0.26
Sr %
0.05
-0.0
5-0
.05
-0.0
5-0
.05
-0.0
5-0
.05
-0.0
5-0
.05
-0.0
5-0
.05
-0.0
5-0
.05
-0.0
5-0
.05
-0.0
5-0
.05
-0.0
5-0
.05
-0.0
5-0
.05
-0.0
5-0
.05
-0.0
5-0
.05
-0.0
50 0 0 0
-0.0
5-0
.05
-0.0
5-0
.05
-0.0
5-0
.05
-0.0
5-0
.05
Ta PPM
0.5
-0.5
1.3
1.4
-0.5 1 -0.5
-0.5
1.2
1.4
1.1
0.8 2 1.8
-0.5
1.3
1.4
-0.5
-0.5
1.6
0.6
-0.5
-0.5
-0.5
1.1
1.4 0 0 0 0 -0.5
-0.5
-0.5
-0.5
1.2
1.4
-0.5
-0.5
U
PPM
0.5
3.2
2.1
3.1
4.7
2.5
1.9
0.7
2.9
2.6
2.2
2.7
3.3
-0.5
3.3
2.1
2.5
3.2
2.7
3.1
3.4
0.8
0.8
1.2
-0.5
-0.5 0 0 0 0 -0.5
0.9
1.1
-0.5
2.9
2.6
0.8
0.8
Th PPM
0.2
21.2
18 23.4
25 23.6
17.7
7.6
21.2
20.4
23.5
21.3
27.5
22.8
25.5
16 22.7
25.4
25.5
24.6
24.6
10.2
11.8
5.6 6 7.3 0 0 0 0 4.2
4.5
6.5
3.2
21.2
20.4
10.2
11.8
Zn PPM
50 147
146
132
129
156
118
67 107
105
144
121
109
92 153
75 115
145
107
123
121
-50
-50
-50
82 -50 0 0 0 0 -50
-50
-50
-50
107
105
-50
-50
App
endi
x IV
: Neu
tron
act
ivat
ion
and
indu
ctiv
ely
coup
led
plas
ma-
atom
ic e
mis
sion
spe
ctro
met
ry
anal
ytic
al d
ata
for s
ampl
ing
tran
sect
L31
+50.
Hg
data
by
flow
inje
ctio
n (F
IMS)
. (C
ontin
ued)
INA
A
Det
ectio
n Li
mit
Fiel
d D
uplic
ate
Pairs