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Dating paleochannel iron ore by (U-Th)/He analysis of supergene goethite,

Hamersley province, Australia: COMMENT: REPLY

Article in Geology · January 2007

DOI: 10.1130/G23755Y.1

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 Dating paleochannel iron ore by (U-Th)/He analysis of supergene goethite,
Hamersley province, Australia: COMMENT

COMMENT: doi: 10.1130/G22891C.1 results” (p. 174). The authors offered three possible explanations, ignor-
ing the most likely. Despite apparently rigorous inspection of duplicates,
R.C. Morris and without similar data from the analyzed samples, Heim et al. cannot be
Commonwealth Scientific and Industrial Research Organization (CSIRO) sure they avoided look-alike primary matrix or ooid cortex. Both are older
Exploration and Mining, Kensington, Western Australia 6151, Australia than the infill goethite they were trying to date, probably by millions of
M. Kneeshaw years, and could include even older U/Th in former soil components. Note
(formerly) Manager Exploration, BHP Billiton Iron Ore, the wide range in group ages in Heim et al’s Figure 1.
Perth, Western Australia 6057, Australia The validity of the goethite dating is critically dependent upon what
E.R. Ramanaidou was actually sampled. We suggest Heim et al. included unrecognized origi-
CSIRO Exploration and Mining, Kensington, Western Australia 6151, nal matrix and cortex with the infill goethite.
Australia Statistical forcing of data. Heim et al. used progressively larger
age corrections (their Fig. 2), to improve the statistical fit for their con-
Despite their laudable efforts to date the channel iron deposits (CID) clusions. For example, the 20% correction that they used as a He loss
of the Pilbara of Western Australia (WA), Heim et al., (2006) need to “worst-case scenario” (p. 175), increased the calculated ages of the sam-
reassess their sampling and the statistical strategy behind their conclu- ples by 30%–32.8%. These ages were used to argue that “ca. 36 Ma”
sions. Many details they report conflict with data from a major CSIRO- valley fill was ferruginized and cemented from the top down as water
industry research program on CID (Morris et al., 1993; Ramanaidou et al., levels fell, reaching completion in the Pliocene or later (p. 176). Their
2003) and other research (e.g., Stone et al., 2003). extrapolated ~28–36 Ma dates for the start of “ferruginization” assumed
Miocene fluvial goethite/hematite CID of the WA Pilbara range from an “original channel surface” at 505 m (p. 175), but the overlying Iowa
gravelly mudstones and ooid-rich granular rocks with abundant ferru- Eastern Member CID is largely absent from their deposit (their Fig. 1).
ginized wood fragments, to intraformational pebble, cobble, and occasional Thus, the original surface was at least 15 m higher, and likely much
boulder conglomerates. Clays and non-ore polymictic basal and marginal more, assuming continuous erosion since Heim et al.’s “ca. 36 Ma” date.
conglomerates are also present. The largely pedogenically derived iron- Extrapolating to this more likely surface could thus support an unrealis-
rich sediments occupy numerous meandering paleochannels in a mature tic Paleocene or even Cretaceous start for CID sedimentation.
surface on Precambrian granitoids, volcanics, metasediments, banded iron Contemporary deposition of CID matrix. Many features, includ-
formation, and Paleogene valley fill. The porous, consolidated, ooid-rich ing partial alluvial matrix and matrix-supported samples with up to 75%
fine gravels and their intraformational conglomerates from the Yandi and matrix, contradict the top-down infill model. Episodic post-consolidation
Robe deposits are a >7 billion ton resource of export iron ore. partial leaching of matrix with refilling of some voids is demonstrated by
Heim et al. (2006) make a number of erroneous assertions. To begin, various generations of infill goethite, silica, and oxidized siderite. Scours
our CID reports do not describe the goethitized cortex of the ooids and filled by later CID and well-preserved bedding surfaces confirm lithification
pisoids as “vitreous” (as reported by Heim et al. on p. 174). We never occurred soon after sedimentation (Stone et al., 2003). The scours at Yandi
used “botryoidal,” nor did we describe matrix as “late-stage cement,” are 2–10 m deep, to 20 m wide and over 200 m long, with typically steep,
though some post-depositional solution voids in the matrix contain late- sometimes near-vertical margins. In unconsolidated granule material, such
stage infill. Yet Heim et al. attribute these and other incorrect statements to margins would soon slump into the scours to disappear from the CID record.
Ramanaidou et al. (2003). “Botryoidal” is Greek for “bunches of grapes,” Intraformational conglomerate horizons comprising well-rounded pebble-
a texture rare in CID ore. Colloform texture, however, is common in late- and cobble-sized clasts of granular CID confirm a contemporary matrix.
stage goethite which fills or lines some solution voids in the matrix, and at Downward younging of CID “infill” goethite. The altered Lower
times appears vitreous. Goethite infill can appear very similar to original CID basal zone (Heim et al.’s Fig. 1), with its large ochre patches and cavi-
matrix in reflected light—see Heim et al.’s Figure A1 (DR1) in the GSA ties, is evidence of major leaching due to prolonged basal channel water
Data Repository 2006032. They wrongly regard this normally minor com- flow in the past, and the current high water table confirms changing water
ponent as “the ore matrix” (p. 174). levels. The presence of unrecognized contemporary CID matrix, altered
Though shown as “typical Yandi ore,” Figure A1b (DR2006032) variably by later episodic solution and by lesser infill events as flow levels
is from non-ore, polymictic marginal conglomerate, and Figure A1a, fell erratically, as well as by imprecise sampling, is a more valid explana-
although ore, is from intraformational conglomerate. Original channel- tion for the wide-ranging group dates and different younging trends than
fill contains a “large percentage…of Fe-rich clasts” including, the authors the top-down infill model of Heim et al.
claim, “partially weathered, banded iron-formation” (p. 175). This, in fact, REFERENCES CITED
is very rare in CID ore, though common in non-ore marginal conglomerates.
Heim, J.A., Vasconcelos, P.M., Shuster, D.L., Farley, K.A., and Broadbent, G.,
CID are ferruginous sediments, not “ferruginized” or “Fe-metasomatized” 2006, Dating paleochannel iron ore by (U-Th)/He analysis of supergene
as claimed (p. 173); however, it is likely some wood/charcoal was goethite, Hamersley Province, Australia: Geology, v. 34, p. 173–176, doi:
goethitized in the channels. 10.1130/G22003.1.
Sampling CID goethite for dating. The use of “botryoidal” by Heim Morris, R.C., Ramanaidou, E.R., and Horwitz, R.C., 1993, Channel iron deposits
et al. (p. 174) to describe their sampling sources implies masses of pure of the Hamersley Province: Bentley, CSIRO Australia, Exploration and
Mining Report 399R.
secondary goethite, which is misleading. So is the 1.5 mm sample spot in Ramanaidou, E.R., Morris, R.C., and Horwitz, R.C., 2003, Channel iron deposits
Heim et al.’s Figure A1c (DR2006032), since they used “4 mm diameter” of the Hamersley Province, Western Australia: Australian Journal of Earth
drill cores (p. 174), and both are incompatible with the >10 mm fragment Sciences, v. 50, p. 669–690, doi: 10.1111/j.1440-0952.2003.01019.x.
of Figures A1e and A1f. Even 1.5 mm cores could include cortex from Stone, M.S., George, A.D., Kneeshaw, M., and Barley, M.E., 2003, Stratigraphy
and sedimentology features of the Tertiary Yandi Channel Iron Deposits,
adjacent ooids as well as original matrix. From crushed cores, Heim et al. Hamersley Province, Western Australia: Transactions of the Institution of
selected 0.1–3 mm fragments “devoid of detrital phases,” but said, “None Mining and Metallurgy. Section B: Applied Earth Science, v. 112, p. 73–80,
of the samples analyzed in duplicate yields statistically reproducible doi: 10.1179/0371745032501180.

© 2007 Geological Society of America. For permission to copy, contact Copyright Permissions, GSA, or editing@geosociety.org.

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 REPLY: doi: 10.1130/G23755Y.1 petrographically, and investigated under a SEM and an EM. Bench-top
and synchrotron-based XRD of goethite cement extracted by this proce-
P. M. Vasconcelos dure confirms pure goethite concentrates.
J. A. Heim We cannot completely reject the suggestion made by Morris et al.
Earth Sciences, University of Queensland, Brisbane, that some of goethite grains could be partially mixed with goethite from
Queensland 4072, Australia the cortices of pisoliths. However, even if small amounts of cortices were
K. A. Farley included, none of the samples that we have analyzed so far contain signifi-
D. L. Shuster cant amounts of this detrital goethite. We stringently excluded texturally
Geological and Planetary Sciences, California Institute of Technology, distinctive cortex phases from the picked sample aliquots, so any conceiv-
Pasadena, California 91125, USA able contamination must be very small. The poorest (U-Th)/He age repro-
G. Broadbent ducibility is observed for a sample with a 1-cm-thick late-stage goethite
Rio Tinto Exploration—Australasia Region, 37 Belmont Avenue, vein, which is petrographically devoid of any detrital phase. Therefore, the
Belmont, Western Australia 6104, Australia small but statistically significant age irreproducibility cannot be explained
by admixture of pisolith cortices and warrants further investigation.
Morris et al. correctly point out that we misquoted their work and at- Morris et al. also accuse us of statistically forcing our data. There
tributed to them observations that they did not report in Ramanaidou et al. is very little statistical treatment of the data. We used linear regressions
(2003). Eager to acknowledge nearly two decades of descriptive work on simply to illustrate how the (U-Th)/He age reproducibility for duplicate
Yandi-type orebodies by the Commonwealth Scientific and Industrial Re- samples affects an extrapolation of the (U-Th)/He dates to the projected
search Organization, we inadvertently attributed both their and our textural original surface of the channel. As stated in Heim et al. (2006), duplicate
observations to them. We apologize for that mistake. As for the petrographic aliquots yield a narrow range of ages, but the uncorrected 4He ages are
descriptions, minerals and textures identified, and implications for the evo- not within analytical uncertainty. This irreproducibility could have vari-
lution of the Yandi deposit, we stand by our data and interpretations. ous possible sources: (1) we underestimated errors in 4He extraction and
Morris et al. state that the terms “vitreous,” “botryoidal,” and “late- measurement, (2) we underestimated errors in U and Th analysis, (3) the
stage” cement do not accurately describe typical ore textures at Yandi or samples lost various amounts of U and/or Th, (4) the samples lost different
other channel iron deposits (CIDs). They also suggest that the material amounts of 4He during their geologic history or during sample prepara-
that we describe does not constitute typical Yandi ore. tion, and (5) the finely laminated vitreous goethite samples contain various
The samples used for geochronology were collected from active generations of supergene goethite, spanning a range in ages. Procedures
mine faces at the Yandi deposit. Most samples were collected at the and the statistics for the treatment of analytical error in U and Th analysis
middle of the Yandi paleochannel, with some samples collected from the by ICP-MS, and 4He analysis by mass spectrometry, are well-established
channel margins, as shown in Heim et al. (2006), Figure 1. Because it is a and treated in Farley (2002). As stated in our paper, we cannot and do not
polymictic marginal conglomerate, the sample shown in Data Repository address possible U and Th gains or losses. Some grains may indeed con-
Figure A1b (Heim et al., 2006) is not typical Yandi ore. However, it is a tain various proportions of supergene goethite from different generations;
CID-facies and thus genetically linked to CID formation. we can only address this issue by increasing spatial resolution. On the
The Yandi CID samples contain fragments of detrital hematite, other hand, we can quantify 4He loss through 4He/3He geochronometry.
4
goethite, and ferruginized wood; some samples also contain ferruginized He/3He experiments routinely show that natural goethites have diffu-
clay pods. All detrital grains are cemented together by late-stage goethite. sively lost 0% to a maximum of 20% of radiogenic 4He since precipitation.
Goethite cement varies from microns to centimeters in thickness, invari- We applied the worst-case scenario to all samples. Extrapolating the geo-
ably shows a finely laminated texture, is highly crystalline and indurated, chronological data to the original channel surface illustrates an approach
varies from dark brown to black on freshly broken surfaces, and has a to estimate the end of aggradation and the onset of post-depositional
vitreous lustre (DR Appendix 1, Heim et al., 2006). Concentric goethite goethite cementation of the channel sediments; we can only estimate this
cement surrounding clasts could be described as having a “colloform” tex- age within ± 20% margin of error.
ture. Clasts surrounded by colloform goethite and cemented by colloform Since the goethite cements that we investigated are demonstrably
late-stage goethite form a mass that resembles a “bunch of grapes;” there- late-stage phases, they also provide clear minimum ages for the host sedi-
fore, “botryoidal texture” accurately describes this material. We interpret ments. The downward decrease in goethite cement ages evident in our data
the goethite cement to be “late-stage” based on paragenetic relationships. is not explained by any conceivable sediment depositional mechanism, as
Vitreous goethite binds together clastic grains and partially or completely proposed by Morris et al. The geochronological results strongly suggest
fills pores (DR Appendix 1, Heim et al., 2006). When more than one gen- a pre-Miocene age for the channel sediments, which were subsequently
eration of vitreous goethite exists, cross-cutting relationships are clear. altered by post-deposition weathering and goethite cementation to form
Therefore, we maintain that (1) Yandi-type ore contains vitreous CID ore at Yandi.
goethite, (2) vitreous goethite is a late-stage cement, and (3) samples
composed of detrital grains surrounded by vitreous goethite display a REFERENCES CITED
botryoidal texture.
Morris et al. suggest that we mixed original matrix and cortex with Farley, K.A., 2002, (U-Th)/He dating: Techniques, calibrations, and applications,
our late-stage goethite and doubt our ability to recover pure goethite from in Porcelli, D., Ballentine, C.J., and Wieler, R., eds., Reviews in Mineralogy
and Geochemistry: Noble Gases in Geochemistry and Cosmochemistry:
1.5-mm growth zones with a 4-mm-diameter drill core. As described by Washington, D.C., Mineralogical Society of America, p. 819–844.
Heim et al. (2006), the 4-mm drill core is the first stage of a systematic Heim, J.A., Vasconcelos, P.M., Shuster, D.L., Farley, K.A., and Broadbent, G.C.,
sample recovery and characterization process. After drilling, the 4-mm 2006, Dating palaeochannel iron ore by (U-Th)/He analysis of supergene
core is crushed to 0.1–3 mm grain size and sieved, washed in ethanol, and goethite, Hamersley Province, Australia: Geology, v. 34, no. 3, p. 173–176,
doi: 10.1130/G22003.1.
only pure goethite grains (easily recognized with the aid of a binocular Ramanaidou, E.R., Morris, R.C., and Horwitz, R.C., 2003, Channel iron deposits
microscope) are picked. We select 5–10 grains for geochronology, while of the Hamersley Province, Western Australia: Australian Journal of Earth
an aliquot of visually pure grains are mounted in epoxy disks, described Sciences, v. 50, p. 669–690, doi: 10.1111/j.1440-0952.2003.01019.x.

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