1. Lead Isotope Geochemistry: A Brave New World? Graham R Carr CSIRO Exploration and Mining June 2013

2. Outline Traditional Use of Pb Isotopes in Metallogenic Studies Exploration Geochemistry – General Principles Gossans and Residual Soils Groundwaters Partial Extractions of soils Vegetation U exploration The brave new world - The cost factor – can the commercial labs do better? The confidence factor – will companies use isotopes? SMEDG 26 June 2013

3. Pb Isotopes in Metallogenic Studies (Plumbotectonics) SMEDG 26 June 2013 History of the Earth According to my favorite element – Pb. Really a history of the fractionation of Pb, Th and U in the mantle and crust through geological time. The key information that Pb isotopes provide are: – Relative contributions of mantle-derived and crustal-derived Pb in rocks and ores – Any evidence of U/Th fractionation as a result of high grade metamorphism or the formation U enriched hydrothermal fluids. – Model age

4. Pb Isotopes Thesis: In any geological terrain, mineralisation associated with a major hydrothermal event will have distinctive Pb isotope ratios that can be discriminated from minor mineralisation and from Pb derived from background rocks. The General Exploration problem is – can we measure and interpret these fingerprints in common regolith geochemical samples – rocks, soils, vegetation, groundwater? SMEDG 26 June 2013

5. Pb Isotope Variables Basic Equation: Basic Equation: 206 Pb/ 204 Pb = 206 Pb/ 204 Pb i + 238 U / 204 Pb(e t - 1) 206 Pb/ 204 Pb = 206 Pb/ 204 Pb i + 238 U / 204 Pb(e t - 1) Source Rock Chemistry Time

6. The Growth Curve Concept Simple (unrealistic) Single Stage Model Growth Curve: Co-variation through geological time of a pair of Pb isotope ratios assuming a common, U/Pb (  )Growth Curve: Co-variation through geological time of a pair of Pb isotope ratios assuming a common, U/Pb (  )

7. 34 th International Geological Congress, Brisbane, August 2012 More realistic Two-Stage Model The Growth Curve Concept

8. 34 th International Geological Congress, Brisbane, August 2012 Pb/Pb The Mount Isa Growth Curves

9. Mount Isa Template CODES Masters 2013

10. Relating Ores to Tectonics 1400 1450 1500 1550 1600 1650 1700 Urquhart Shale Lady Loretta Fm.-max Lady Loretta Fm.- min D 1 Lawn Hill Fm. D 2 D 3 Urquhart Shale Syn - sed. Lady Loretta Syn - sed. Lawn Hill Syn - sed. Early Isan LL-Century Isan WFB Cu Late Isan Lawn Hill Vein Age Ma Depositional/Tectonic Age Hydrothermal Age Western Fold Belt CODES Masters 2013

11. “Other” Deposits Different fluids and different source rocks, or…..a small subset of the same source rocks.

12. Large, outcropping gossan in Lower Proterozoic rocks of the Mount Isa Western Fold Belt Geochemically highly anomalous with % Zn and Pb Exploration Prospect – Mount Isa Is it worth drilling?? What is its origin? CODES Masters 2013

13. Pb Isotopes in Regolith Materials Have greatest value in : – discriminating and eliminating the “False Positive” geochemical anomaly – Having greater sensitivity than absolute abundance data in detecting metal derived from a hidden/buried ore source Greatest inhibitors to use: – Cost – Anthropogenic contamination SMEDG 26 June 2013

14. The Two Dimensions of Pb ISOTOPES Conventional use of Pb isotope discrimination High Probability! Probability!FalsePositive LowProbability ConcentrationThreshold BackgroundPopulation AnomalousPopulation CONCENTRATION IsotopeTargetSignature IsotopeBackgroundIsotopeMixing The next GeochemicalFrontier? Very Subtle Anomaly SMEDG 26 June 2013

15. The Problem is Cover SMEDG 26 June 2013

16. Pb Isotopes in Exploration Through Cover Problem – detect and discriminate subtle geochemical signals above buried ore systems Regolith materials that can be used for geochemistry: – Soils – partial extraction geochemistry – Vegetation – Groundwater Pb isotopes can be used to discriminate “anomalous” from “background” in each of these media – also detect anthropogenic contamination. SMEDG 26 June 2013

17. Pb Isotopes in Exploration Through Cover Partial extraction techniques to determine soil metal concentration are commonly used – but the jury is out on their applicability Pb isotopes are potentially a valuable discriminator to assess partial extraction anomalies The technique is based on the ability of isotopes to measure the proportion of end member components with distinctive Pb isotope fingerprints in a mixed system. SMEDG 26 June 2013

18. Pb Mixing Model Target (T) Isotope Ratio 1 Isotope Ratio 2 Background (B) Geochemical Sample (S) Signature 0.75 0.25 0.5 1.0 0 Sig = 0.3 + CBCB RSRS RTRT x RBRB x CTCT CBCB + CTCT CBCB + CTCT = CODES MASTERS 2013 Can be applied to any regolith sample – soil, groundwater, vegetation rock, soil, groundwater, vegetation.

19. Pb In Soils – The Pb Soil Model - 1 The possible sources of Pb in a regolith sample are: – Crystallization Pb – that is, Pb incorporated in the primary mineral lattice at the time of formation – Radiogenic Pb – Pb that have derived from the decay of U and Th in the period since crystallisation – Regolith Pb – labile Pb that has been transported to the sample through regolith processes. SMEDG 26 June 2013

20. Sources of Pb in a Regolith Sample U U U U Pb U U U U A B U U U U Pb Pb C SMEDG 26 June 2013

21. Pb In Soils – The Pb Soil Model - 1 Fixed Mobile Total (Strong Acid) Partial (AmAc) Background Ratio Target Ratio Pb BF Pb BM Pb TM R Par R Tot R Par is the measured isotope ratio of the partial extraction R Tot is the measured isotope ratio of the total extraction SMEDG 26 June 2013

22. The use of Pb isotopes in soil geochemistry requires a knowledge of the target and background isotope populations In an initial orientation survey both total and partial extractions are required. Follow up surveys can be based just on partial extractions Pb In Soils – The Pb Soil Model - 2 SMEDG 26 June 2013

23. Soil contains “Fixed” and “Mobile” components. The boundary between these will vary for different soils and depends on the strengths of the acid leaches used to liberate the metal. In any one sampling exercise where the media are similar across the terrain and the analytical procedures standardised, the “Background” population will incorporate a proportion of Pb fixed in the sample (Pb BF ) and Pb that has been mobilised by weathering from within the sample or from the surrounding background rocks (Pb BM ). It may also contain a component of mobile Pb that has been derived from a Target source buried beneath the cover rocks - or through anthropogenic contamination (Pb TM )! Pb In Soils – The Pb Soil Model - 3 SMEDG 26 June 2013

24. Pb In Soils – The Pb Soil Model - 4 From the generalized mixing model we can derive equations to calculate the concentration of each Pb component of the soil sample: Where Pb Tot and Pb Par are the measured total and partial Pb concentrations, Sig Tot is the Pb isotope signature of the “total” solution Pb TM = Sig Tot x Pb Tot Pb BM = Pb Par _ Pb TM Pb BF = Pb Tot _ Pb Par Fixed Mobile Total (Strong Acid) Partial (AmAc) Background Ratio Target Ratio Pb BF Pb BM Pb TM R Par R Tot SMEDG 26 June 2013

25. Partial Extraction Geochemistry Anomalies appear to form in soils over covered mineralisation via processes that transport target and indicator elements through the covered sequence to the near surface. Possible mechanisms for this transport include: – Geogas carrier – Electro-chemical potential – Interaction of geogas and soil – Interaction of soil and groundwater – Residual effects – Bioturbation – Biological migration SMEDG 26 June 2013

26. Research Procedure Thesis: – Pb isotopes in soils potentially retain “a memory” of their source – thus we can determine whether the Pb has derived from hidden mineralisation or from a non-mineralisation source. – We can extract the most mobile Pb from most samples at very low concentrations and differentiate this potentially transported Pb from Pb that is residual in the soil minerals. Procedure: – Undertake case histories at sites where there is known covered mineralisation and where there is no anthropogenic contamination – Study a range of deposits from shallow to deep burial. SMEDG 26 June 2013

27. Conclusions of Study 1.We have not seen isotopic or trace element anomalies through thick (> 50m) cover. 2.We have seen clear, very sensitive isotopic anomalies through shallow cover over mineralisation with very subtle or no trace element anomalies. 3.We have seen anthropogenic contamination in a variety of situations where it was not expected and which place in doubt the conclusions of many previous studies. 4.We can recognise anomalies associated with anthropogenic contamination. 5.We have not seen anomalies that can be ascribed to vapour transport SMEDG 26 June 2013

28. The Pb Soil Model – CASE HISTORY HYC HYC is a sediment –hosted massive sulfide deposit of approximately 400 Mt in the Proterozoic of the Northern Territory. The host unit sub-crops beneath alluvial sediments but the ore is deep within the stratigraphy. Numerous attempts have been made to detect the mineralization in the overlying regolith. SMEDG 26 June 2013

29. HYC Deposit SMEDG 26 June 2013

30. HYC Deposit SMEDG 26 June 2013

31. 206204 Pb/Pb 207 204 Pb/ Pb 16.017.218.419.6 15.4 15.6 15.8 16.0 Analytical Precision HYC Target Signature 1 0.5 0 Background Population HYC Base Metal Deposit Northern Territory All soils Threshold HYC – Pb Isotope Data SMEDG 26 June 2013

32. HYC – Test line downslope from a 60 year old drill hole SMEDG 26 June 2013

33. 34 th International Geological Congress, Brisbane, August 2012 HYC – Test line downslope from a 60 year old drill hole

34. 34 th International Geological Congress, Brisbane, August 2012 HYC – Test line downslope from a 60 year old drill hole Pb TM Pb BM Pb BF

35. Pb (ppm) HYC Contamination Line Surface Samples HYC Soil Pb Model Components Surface Samples SMEDG 26 June 2013

36. 34 th International Geological Congress, Brisbane, August 2012 Pb (ppm) HYC Contamination Line 30 cm Samples HYC Soil Pb Model Components 30 cm Samples

37. HYC – The Lesson Learnt Pb isotopes are very sensitive to labile, “target” Pb that cannot be discriminated by normal geochemistry This will apply also where the source is geological – not anthropogenic Case history studies to determine the effectiveness on novel geochemical techniques anywhere near historic mining or exploration is very very problematic! SMEDG 26 June 2013

38. Pb ISOTOPES – A VEGETATION EXAMPLE SMEDG 26 June 2013

39. Vegetation 6km from an Archaean VMS Mine SMEDG 26 June 2013

40. Surface Soil (S) Sub-surface Soil (SS) SA AmAc Strong Acid Ammonium Acetate Phyllode Twig 206204 Pb/Pb 2 0 7 2 0 4 P b / P b 13.015.518.020.5 14.4 14.8 15.2 15.6 16.0 Analytical Precision Out of District Trucked Ore 14 SAmAc 13 SAmAc 13Phyllode 14Phyllode 14 Twig 13 Twig 14 S SA 13 S SA 13 SS SA 14 SS SA 13 SSAmAc 14 SSAmAc (940ppb) (920ppb) (150ppb) (86ppb) (180ppb) (390ppb) (175ppb) (72ppb) Surface Soil (S) Sub-surface Soil (SS) SA AmAc Strong Acid Ammonium Acetate Phyllode Twig 206204 Pb/Pb 2 0 7 2 0 4 P b / P b 13.015.518.020.5 14.4 14.8 15.2 15.6 16.0 Analytical Precision 14 SAmAc 13 SAmAc 13Phyllode 14Phyllode 14 Twig 13 Twig 14 S SA 13 S SA 13 SS SA 14 SS SA 13 SSAmAc 14 SSAmAc (940ppb) (920ppb) (150ppb) (86ppb) (180ppb) (390ppb) (175ppb) (72ppb) Partial Extraction and Vegetation

41. Groundwater in vicinity of Archaean VMS deposit CODES MASTERS 2013

42. MIXING MODEL SENSITIVITY SMEDG 26 June 2013

43. 34 th International Geological Congress, Brisbane, August 2012 Theoretical Anomaly Distance P b ( p p m ) Background (Pb /Pb ) BM BF = K Anomaly Pb TM Anomaly caused by addition of Pb to soil from target orebody

44. 3.02.52.01.51.0 0.8 0.6 0.4 0.2 0.0 Signature Model Sensitivity Anomaly/Background S i g n a t u r e Partial 1.3 1.02 SMEDG 26 June 2013

45. Cover = Homogeneous, background Pb SMEDG 26 June 2013

46. 34 th International Geological Congress, Brisbane, August 2012 Weld Range – Western Australia 206204 Pb/Pb 207 204 Pb/ Pb 13.014.415.817.218.620.0 14.4 14.8 15.2 15.6 16.0 Analytical Precision Achaean Target Background Soils Anomalous Soils Background Populations Archaean 500 times MC-ICPMS Precision

47. Bluebush – NW Qweensland 206204 Pb/Pb 207 204 Pb/ Pb 1617181920 15.40 15.55 15.70 15.85 Analytical Precision All soil analyses Proterozoic Target Background Populations Proterozoic SMEDG 26 June 2013 250 times MC-ICPMS Precision

48. This study HNO3/HCl 50850N This study NaAc 50850N Gulson HNO3/HCl 50850N Gulson HNO3/HCl 50740N This study HNO3/HCl 50740N Background Populations Palaeozoic 75 times MC-ICPMS Precision

49. Analytical Precision MC-ICPMS 16.935+/-0.006 (+/- 0.035%) Conv. TIMS 16.929+/-0.023 (+/- 0.14%) HR-ICPMS 16.806+/-0.044 (+/- 0.26%) Quad-ICPMS ?????? (but probably ~ 0.5%) SMEDG 26 June 2013

50. 207206 Pb / Pb 208 206 Pb/ Pb 0.800.860.920.98 2.02 2.13 2.24 Background Population Soils Showing Mixing Target (HYC) Analytical Precision MC- ICPMS TIMS What is needed? 100% 50% 0% Percent Target Population How Much precision do we need? SMEDG 26 June 2013 Precision of 1% would represent: 2.5% of the total expected range of data for Archaean soils, 5% of the total expected range for Proterozoic soils, 17% of the total expected range for Palaeozoic soils.

51. Pb Isotopes – What we need to do To develop a robust exploration technology we need to: – Reduce cost of analyses – very large datasets with lower precision rather than small datasets with high precision, <$50 per sample – Undertake case histories to validate the technique in greenfields terrains – minimal to no drilling – no mining. SMEDG 26 June 2013