Ore Geology Reviews 28 (2006) 525 545 www.elsevier.

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Gold and sulphide minerals in Tertiary quartz pebble conglomerate gold placers, Southland, New Zealand
D.M. Falconer a,*, D. Craw a, J.H. Youngson b, K. Faure c
c

Department of Geology, University of Otago, P. O. Box 56, Dunedin, New Zealand b Placer Solutions (2004) Ltd, P. O. Box 5284, Dunedin, New Zealand Institute of Geological and Nuclear Sciences Ltd, P. O. Box 31312, Lower Hutt, New Zealand Received 15 February 2004; received in revised form 2 May 2004; accepted 14 March 2005 Available online 9 January 2006

Abstract Auriferous quartz pebble conglomerates (QPC) formed during Tertiary sedimentary recycling in the Waimumu district, Southland, New Zealand. These sediments contain fine-grained gold of detrital origin with abundant surface textures and goldforms associated with authigenic gold remobilisation. Most authigenic gold contains no detectable silver and occurs as overgrowths on detrital AuAg and AuAgHg alloys that contain up to 13 wt.% Ag, and 9 wt.% Hg. Fine-grained AuAg and AuAgHg alloys are compositionally heterogeneous, exhibiting both well-defined silver-depleted and silver-enriched rims. Rare coarse Au Ag alloy is intergrown with quartz and is homogenous. Discrete grains of authigenic, porous, sheet-like gold occur in carbonaceous mudstone within a QPC sequence. Some QPC contain abundant sulphide minerals. Some of these sulphides (pyrite and arsenopyrite) are of long-distance detrital origin, presumably from the Otago Schist, whereas the bulk of the sulphide suite is marcasite of variably transported diagenetic origin, derived from the erosion of QPC and underlying Tertiary sediments. There has also been authigenic deposition of sulphide minerals in the QPC themselves. These diagenetic sulphides include framboidal and anhedral marcasite, and framboidal and euhedral pyrite. Sulphur isotope data for the sulphide minerals range from 45x to + 18x (relative to VCDT). Sulphur isotope data for euhedral detrital pyrite and arsenopyrite range from 9x to 1x and are most likely derived from the Otago Schist to the north. Both framboidal and anhedral marcasite have lower values (b 20x) reflecting microbial sulphate reduction as a source for the precursor hydrogen sulphide. Anhedral marcasite contains elevated concentrations of Ni, Co, As and Cr, commonly with compositional banding of these metals. Both the gold and diagenetic sulphides from the Belle-Brook QPC are compositionally similar to gold and sulphides from Archaean QPC. Porous, sheet-like authigenic gold is morphologically similar to gold associated with carbonaceous material in the Witwatersrand. In addition, Southland marcasite textures resemble the rounded and banded pyrite in Witwatersrand QPC placers. There is abundant evidence from these Tertiary QPC in southern New Zealand for sedimentary transport of sulphide minerals and post-depositional sulphide mineralisation in the surficial environment despite an oxygen-rich atmosphere. These young deposits thus provide an example of authigenic gold and sulphide textures formed during diagenesis in unmetamorphosed placers. Many of these textures are similar to those commonly ascribed to metamorphic processes in Archaean auriferous QPC. D 2005 Elsevier B.V. All rights reserved.
Keywords: Quartz pebble conglomerate; Authigenic gold; Sulphidation; Marcasite; Framboidal pyrite; Colloform pyrite

* Corresponding author. Fax: +64 3 4821175. E-mail address: falconer.dm@clear.net.nz (D.M. Falconer). 0169-1368/$ - see front matter D 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.oregeorev.2005.03.009

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1. Introduction Gold deposits hosted by quartz pebble conglomerates are a significant source of gold worldwide. The most important are the Archaean QPC gold deposits of the Witwatersrand Basin, South Africa, which have produced about 48,670 t of gold between 1886 and

2000, equating to nearly 40% of all gold produced worldwide (Frimmel and Minter, 2002). The well-documented Witwatersrand orebodies are characterised by gold and sulphide minerals that feature both detrital and authigenic textures (see reviews by Phillips and Law, 2000; Frimmel and Minter, 2002). However, the genesis of QPC-hosted gold and sulphide mineralisation

Fig. 1. (A) Relief map of eastern Otago and Southland showing low relief areas dominated by Tertiary non-marine sequences that contain QPC. Provincial boundary between Otago and Southland indicated. (B) Schematic geological map of Waimumu area showing location of selected sites.

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from the Witwatersrand orebodies are the focus of considerable debate because of the distinction, or lack thereof, between detrital and authigenic textures (MacLean and Fleet, 1989; Phillips and Myers, 1989; Robb and Meyer, 1990; Minter et al., 1993; Myers et al., 1993; Barnicoat et al., 1997, 2001; Phillips and Law, 1997; Fleet, 1998; Minter, 1999; England et al., 2002). Specifically, one of the central issues in these debates is the lack of criteria to distinguish between diagenetic sulphide or gold textures and those resulting from low-grade regional metamorphism or hydrothermal mineralisation. In the absence of well-constrained unmetamorphosed diagenetic assemblages, it is inevitable that a variety of diagenetic textures and geochemical signatures could be erroneously attributed to metamorphic processes. In particular, gold-grain textures in the Witwatersrand deposits are ambiguous because of potential effects of metamorphic recrystallisation (Minter et al., 1993; Barnicoat et al., 1997, 2001). One approach to resolving such controversies is to examine gold and sulphide textures in younger unmetamorphosed QPC that feature gold and sulphide mineralisation, as potential analogues for Witwatersrand-style gold deposits. Such QPC occur in southern New Zealand where both sedimentary and diagenetic processes are able to be better constrained, and therefore more easily understood than those of Archaean QPC (Youngson et al., 2006-this volume). Although some workers claim that the Archaean environment was unique in the Earths history with respect to the occurrence of sulphide minerals in sediments (Phillips and Myers, 1989; Phillips et al., 2001), there is abundant evidence for detrital and diagenetic sulphide mineral occurrences in young non-marine sediments (Clough and Craw, 1989;

Youngson, 1995; Craw and Chappell, 1999; Brown et al., 1999, 2000; Paktunc and Dave, 2002; Falconer, 2003). Despite such occurrences, the search for Witwatersrand analogues remains focussed on similar Archaean terranes (Fox, 2002) rather than expanding this approach to include much younger QPC. This paper documents some aspects of the gold and sulphide mineralogy in QPC gold placers from Southland, New Zealand, especially aspects that might be relevant to interpretation of mineralised Archaean deposits. Thus, despite their economic insignificance, young QPC gold placers such as those in southern New Zealand (Fig. 1A) are a potential analogue for Witwatersrand-style gold mineralisation. 2. Regional geology The QPC described in this study occur in non-marine, fluvial and colluvial sedimentary units of late Oligocene to Pliocene age (Fig. 2). The non-marine strata are commonly underlain by Oligocene marine sedimentary rocks, and the Tertiary sedimentary sequence rests on Permian to Jurassic greywacke basement (Wood, 1956; Isaac and Lindqvist, 1990; Turnbull and Allibone, 2003). The Tertiary non-marine strata are dominated by the Gore Lignite Measures of late OligoceneMiocene age, deposited by a large meandering fluvial system (Isaac and Lindqvist, 1990). Basal deltaic beds are overlain by extensive, generally finegrained lower-delta plain beds and lignites, which are in turn overlain by extensive upper-delta plain conglomerates and mudstones (Isaac and Lindqvist, 1990; Fig. 2). These sediments are at least 500 m thick, although late Tertiary uplift has caused significant erosion of parts of the section (Isaac and Lindqvist, 1990).

Fig. 2. Generalised stratigraphic sequence for the Waimumu area (modified after Isaac and Lindqvist, 1990).

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The upper part of this non-marine sequence is dominated by conglomerates with abundant basement greywacke clasts, and ca. 30 vol.% quartz pebbles derived from the Otago Schist belt to the north (Fig. 1A). This schist belt contains numerous mesothermal vein systems (Craw and Norris, 1991) that have shed gold to form placer accumulations throughout Otago and Southland (Youngson et al., 2006-this volume). Recycling of Tertiary non-marine conglomerates during late Cenozoic uplift resulted in local redeposition of variably quartz-rich QPC (N 80 vol.% quartz pebbles) during the late Miocene and Pliocene (Waimumu and Waikaka Quartz Gravels; MacPherson, 1937; Wood, 1956; Falconer, 2003). Pliocene to Pleistocene immature fluvial conglomerates (Gore Piedmont Gravels; Wood, 1956) were derived from uplifting basement ridges and the pre-existing Tertiary sedimentary sequence, and locally overlie the QPC described above (Fig. 2). Pleistocene fluvio-glacial gravels are restricted to the present major drainage systems. In both Otago and Southland, many of these middlelate Tertiary QPC host economically significant gold placers (Youngson et al., 2006-this volume). 2.1. Mining history In the Waimumu area (Fig. 1B), alluvial gold was historically dredged from several of the principal streams, with 30,000 oz produced before 1904. Hydraulic sluicing was practiced intermittently from the 1930s, with hydraulic excavators and gravity recovery systems utilised until the late 1990s. Numerous small underground workings throughout the district followed relatively rich gold leads in the WaimumuWaikaka Quartz Gravels. The Belle-Brook placer, 5 km south of the historic gold workings, was not discovered until the late 1970s, and has been sporadically mined on a small scale since 1980. The Parker Road QPC have been sporadically mined as a source of road-building aggregate, with gold recovery from this deposit about to commence. The Waimumu area also contains significant economic lignite deposits in the Tertiary non-marine sequence (Isaac and Lindqvist, 1990; Fig. 2). 2.2. Geology of the study area This study focuses on sediments in the Waimumu area (Fig. 1B). Structurally, this area is dominated by the Dunsdale Fault System, a series of north- to northeast-striking reverse faults that dip steeply to the west, and trend for at least 50 km. Some of these faults have uplifts of 400 to 500 m, exposing Murihiku basement

that comprises the nearby Hokonui Hills (Fig. 1B). Belle-Brook, one of the principal localities for this study, is in a structural basin within this fault system, on the downthrown side of the Hedgehope Fault. A second site at Parker Road (Fig. 1B) is similarly located adjacent the Hedgehope Fault. Marcasite for this study was also collected from Hedgehope Stream (Fig. 1B), where the stream is eroding through a section of faulted Gore Lignite Measures (Isaac and Lindqvist, 1990). The upper part of the Tertiary non-marine sequence (Gore Lignite Measures) exposed at Belle-Brook is typically a coarse (up to 15 cm clasts), clast-supported fluvial conglomerate, with poorly defined stratification. Minor stratified sandstone of similar mineralogical composition is interbedded with these conglomerates. Unaltered Gore Lignite Measures conglomerates are bluish in colour and composed of approximately 70 vol.% greywacke cobbles and 30 vol.% quartz clasts. However, most of the Gore Lignite Measures conglomerates at Belle-Brook exhibit moderate to strong kaolinisation of the greywacke component, resulting from the alteration of labile minerals. The heavy-mineral suite is dominated by marcasite, zircon, and garnet, with minor pyrite, arsenopyrite, chromite, rutile, magnetite, and rare gold. Gore Lignite Measures conglomerates at Belle-Brook are unconformably overlain by thin (ca. 1 m) QPC of inferred Pliocene age that have been formed by the erosion and recycling of underlying conglomerates (Clough and Craw, 1989; Falconer, 2003; Youngson et al., 2006-this volume). The quartz component is higher (ca. 95 vol.%) in these recycled sediments, as the altered greywacke clasts disaggregated during erosion and transport. The heavy-mineral suite in these recycled QPC includes zircon, garnet, gold, framboidal and coarse anhedral marcasite, and, less commonly, framboidal pyrite, euhedral pyrite and arsenopyrite. Magnetite is notably rare. Localised deposits of mature Pliocene QPC consisting of 99 vol.% quartz cobbles occur in the non-marine sequence. One such QPC, at Parker Road (Fig. 1B), is at least 5 m thick and overlain by a thin (b 2 m) carbonaceous mudstone. Palynology on the Parker Road carbonaceous mudstone indicates that the environment was an acid swamp, and the climate was temperate to sub-tropical. Pollens and spores from the carbonaceous mudstone indicate an age of 5 to 3.1 Ma which is consistent with deposition following QPC formation. The heavy-mineral suite in the Parker Road QPC is dominated by unaltered chlorite, zircon and garnet, with rare gold and magnetite. However, in rare well-defined channels, comparatively less mature QPC have abundant gold and magnetite. The QPC at

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Parker Road and QPC elsewhere in the Waimumu district do not contain framboidal or anhedral sulphides in the heavy mineral fraction (Craw, 1992; Falconer, 2003). 3. Methods Heavy mineral concentrates from the QPC were collected by panning disaggregated material from outcrops, and from a gold concentration plant at BelleBrook. Mineral concentration did not involve the use of mercury. Sulphide and gold grains for all analytical procedures were handpicked under a stereomicroscope to ensure contamination-free phases were selected. Bulk samples of sulphide material for trace element analyses were selected by hand and analysed by Xray fluorescence in the Geology Department, University of Otago. Analysis followed standard methods and used international rock standards. Follow-up trace element analysis using ICP-MS was carried out by Australian Laboratory Services, Brisbane, Australia. Particular care was taken during bulk sample preparation to avoid cross-contamination between samples. Quartz blanks were routinely prepared in the same way as the sulphide samples, and analysed by the same techniques. Sulphide phases were confirmed optically (using reflected light, oil immersion), and by X-ray diffraction and Gandolfi camera powder patterns. Electron-probe microanalysis (EPMA) of gold and some sulphide minerals were carried out on carbon coated samples with a JEOL JXA 8600 instrument (operated at 25 kV, 20 nA (2 10 8A) beam current, with a 2 Am beam diameter). A procedure documented by Youngson et al. (2002) was used to correct for peak interference between Au and Hg. EPMA detection limits were approximately: As, 0.4%; Cu, 0.1%; Zn, 0.1%; Ni, 0.1%; Co, 0.1%; Fe, 0.1%; S, 0.1%; Au, 0.4%; Ag, 0.2%; Te, 0.5% and Hg, 0.4%. Pure metal standards were used for As, Bi, Sb, Te, Cu, Ni, Co, Fe, Au and Ag, crystalline cinnabar was used for the Hg standard, and sphalerite for Zn and S standards. Core and rim compositions of gold grains were obtained separately. dCoreT analyses refer to the central part of the grain in polished section. Element maps were obtained over a 450 500 Am grid with a semi-quantitative analysis every 1 Am. Scanning electron microscope (SEM) examination of grains was carried out using a Cambridge S-360 instrument, in which operating conditions varied from 15 to 35 kV, and a JEOL 6700F Field Emission SEM operated at 2.5 to 5 kV. Samples were not etched or cleaned in any way prior to mounting on SEM stubs using a fine paintbrush under a

Zeiss stereomicroscope. Although the Cambridge SEM did not have an EDS detector, micron-sized dgoldT forms are inferred based on back scatter response, the use of uncoated samples (i.e., less stable minerals readily alter, and/or, vaporise under high kilovolts), along with similarities to macroscopic gold forms or surface textures that are known to be gold. Sulphur isotope analysis of sulphide minerals was analysed by conventional methods at the Institute of Geological and Nuclear Sciences Stable Isotope Laboratory, Lower Hutt, New Zealand. Sulphur for isotope measurement was liberated from the sulphide minerals (single crystals) using the Robinson and Kusakabe (1975) and Kiba et al. (1955) methods, respectively. Results are expressed in the familiar d 34S notation as per mil (x) relative to Canon Diablo troilite (VCDT) standard with a variability of F0.2 per mil (x). 4. Gold 4.1. Morphology Four gold sub-types are identified based on their gross morphology: 1. fine-grained gold; 2. coarse nugget gold with intergrown quartz; 3. jagged-edged gold; and 4. porous, sheet-like gold. At least 95% of the gold occurs as fine-grained gold, with minor coarse gold (ca. 4%) and rare jagged-edged and porous gold (b 1%). Fine-grained gold occurs predominantly as flattened, rounded platy particles that range from 300 to 800 Am in length (Fig. 3A). Most grains are multiply refolded and flattened to a thickness of ca. 15 Am. Grain edges are variably thickened, but not to the extent of the well-developed toroids reported from elsewhere (e.g., Giusti and Smith, 1984; Minter, 1999). Other gold forms that are included in the fine-grained category include variously ball-like, stubby, and elongated cigar-shaped particles. Stubby particles are short (typically 100 Am wide by 300 Am long) and although multiply refolded, they are not flattened (Fig. 3B). Stubby particles are a common component of the fine-grained gold that occurs at Parker Road. These stubby particles typically have deep cavities between refolded and rolled particle limbs, in which a variety of spheroidal, bud-like protrusions and spongy gold forms are well preserved within parts of such cavities (Fig. 3C). Surface textures of rounded plate-like gold particles are characterised by a variety of gold forms that occur either in protected cavities or on open surfaces: spheroidal forms and bud-like protrusions (Fig. 3D), chain and ring structures (Fig. 3E, F); and, rarely, euhedral gold forms (Fig. 3G). All of these inferred

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gold forms are well preserved with no physical deformation. Iron oxide coatings are rare on the fine-grained gold particles. Coarse nugget gold (2 to 6 mm in length), generally with intergrown quartz, is less common than finegrained gold, and occurs only at Belle-Brook (Fig.

3H). This variety is chunky and irregular in shape and has not been flattened. Most particles have complex, and or, branched forms (see Knight et al., 1994) and are variably crystalline in appearance (Clough and Craw, 1989; Falconer, 2003; Falconer and Craw, submitted for publication). Many particles exhibit cavities

Fig. 3. SEM photomicrographs illustrating morphological features of alluvial gold from Parker Road and Belle-Brook. (A) Typical example of finegrained refolded platy gold. (B) Fine-grained gold from Parker Road featuring deep cavities with authigenic gold as shown in C. (C) Authigenic gold forms occurring as chain structures within cavities (scale pertains to left hand image). (D) Spheroidal and bud-like gold forms occurring within shallow cavity on surface of fine-grained gold from Parker Road. (E) Stepped chain structure illustrating polygonal development of individual gold forms (steps) protruding from general gold surface. (F) Variously developed polygonisation of bud-like gold forms and chain structure occurring on general gold surface. (G) Triangular plate gold forms occurring on gold surface. (H) Coarsely crystalline gold from Belle-Brook showing intergrown quartz in bottom right of grain. (I) Jagged-edged gold from Belle-Brook showing thin jagged edges. (J) Close-up of I, showing smooth, clean, striated gold surface that resembles a slickensided surface.

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Fig. 3 (continued).

or large smooth faces reminiscent of sites from which euhedral quartz crystals have been plucked. Irregular grain edges and protrusions are typically rounded and variably infolded. The margins of such infolded rims have not been flattened, except in cases where the infolded protrusion is thin (b100 Am). Euhedral pyrite containing micron-sized gold blebs has been found within some euhedral quartz crystals and occurring within host gold grains (Falconer, 1987). Very small (b 150 Am), thin (1 to 20 Am), jaggededged particles (Fig. 3I) have been observed from one specific sandy-gravel lithofacies within the QPC at Belle-Brook. A notable feature of these particles is the gouged and striated nature of the particularly clean (contamination-free) surface that resembles slickensides (Fig. 3J). Porous, irregular sheet-like particles of gold occur within a carbonaceous horizon at Parker Road (Fig. 4A, B). Such gold particles are extremely thin (b10 Am), up to 4 mm in length, very delicate, and easily damaged even by careful handling. Despite the irregular and pseudocrystalline appearance of these grains, SEM examination shows that well-formed crystals are absent (Fig. 4C). The porous sheet-like gold has a

lacy appearance and abundant delicate protrusions that are generally ca. 5 Am across, many of which are either interconnected or joined to form dchainsT (Fig. 4C, D, E). Most of the delicate features and protrusions that make up the surface of the grains are smooth and lack planar faces. The protrusions show no obvious crystallographic alignment or control, but there is a subtle orthogonal association similar to that exhibited by authigenic gold forms on fine-grained gold (Falconer, 2003). Grain edges are very irregular and thin, with a typical thickness ca. 5 Am. There is no deformation of any of the delicate features on the grain edges, and grain surfaces show no indications of abrasion and little evidence of chemical modification (dissolution along grain boundaries) (Fig. 4E). Crystalline stepped-chain structures are common on the gold surface (Fig. 4F). 4.2. Gold composition Fine-grained gold is predominantly AuAg alloy (72%), with lesser AuAgHg alloy (25%) and minor pure gold (3%) (Table 1). These different gold types are optically indistinguishable and do not appear to be

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Fig. 4. SEM photomicrographs illustrating morphology and surface texture of authigenic porous sheet-like gold from carbonaceous material at Parker Road. (A) Porous, sheet-like gold grain. (B) Portion of grain showing irregular and delicate nature of grain exterior margins. (C and D) Interior of grain illustrating porous nature of interconnected gold forms and bud-like protrusions. (E) Close-up of smooth bud-like gold protrusions that shows no physical deformation. (F) Close-up of crystalline stepped gold forms on porous sheet-like gold surface.

characterised by specific morphological forms or surface textures. Less than 1% of fine-grained gold particles are compositionally homogeneous (Table 1). An element map of one coarse gold grain showed that silver-depleted rims are not developed on either the grain surface or the interior quartzgold grain boundaries. Compositional analysis has not been undertaken

for either jagged-edged or porous sheet-like gold, however, the latter has been examined by EDS to confirm suspected gold forms. The silver content of AuAg alloy ranges from 0.2 (detection limit) to 10.2 wt.% in grain cores, with an average of 3.5 wt.% Ag. However, a single electrum grain contained between 27 and 32 wt.% Ag. AuAg

D.M. Falconer et al. / Ore Geology Reviews 28 (2006) 525545 Table 1 Summary of compositional data for fine-grained gold from BelleBrook and Parker Road, Waimumu AuAg alloy Fine-grained gold (n = 200) Range Ag (wt.%) Av. Ag (wt.%) Rim silver content cf. core Enrichment Depletion Absent (i.e. gold rim) Range Hg (wt.%) Av. Hg (wt.%) Rim mercury content cf. core Enrichment Depletion Absent (i.e. gold rim) Coarse nugget gold with intergrown quartz (n = 1) Av. Ag (wt.%) 72% 0.2410.2 3.48 28% 52% 19% AuAgHg alloy 25% 1.3213.85 6.55 6% 72% 22% 0.439.06 2.17 9% 16% 75%

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2.3

alloy grains were free from quartz and primary sulphide inclusions. The single sample of coarse gold with intergrown quartz that was analysed is an AuAg alloy grain containing 2.3 wt.% Ag. Trace amounts of Cu were detected in only two samples (ca. 0.1 wt.%). No other trace elements were detected (i.e., As, Bi, Zn, Sb, Fe, S, Te; detection limits listed above). Silver content in Au AgHg alloys is typically higher than in AuAg alloys, and ranges between 1.3 and 13.9 wt.% in grain cores, with an average of 6.6 wt.% Ag. Mercury ranges from 0.4 to 9.1 wt.% in grain cores, with an average of 2.2 wt.% Hg. The AuAgHg alloys do not contain inclusions of quartz or primary sulphide. Mineralogically, AuAgHg alloys at Belle-Brook are a-phase alloys of hydrothermal origin, rather than secondary AuAgHg alloys that contain N 17 wt.% Hg (Youngson, submitted for publication). Many AuAg alloys and AuAgHg alloys exhibit well-defined Ag-depleted rims that, in polished sections, are either conformable with the grain margin or irregular in appearance. These two contrasting styles of Ag-depletion are clearly defined by electron microprobe element mapping. Both styles of Ag-depleted rims show a sharply defined and steep gradient separating the bulk of the grain from the depleted rim, and typically contain less than 0.5 wt.% Ag. Element mapping also shows that, in both styles of Ag-depletion, the rim is commonly made up of an extensive inner zone that is Ag-depleted, and a minor outer zone of pure gold on grain margins. Silver enrichment in the rims of gold alloys is less common, with 28% of the AuAg alloys and 6% of the AuAgHg alloys showing Ag-enriched

rims. Gold alloys that were observed to have Agenriched rims were indistinguishable from grains with Ag-depleted rims in terms or morphology. Generally, enrichment of 0.3 to 2 wt.% Ag occurs, although up to 5% Ag-enrichment relative to core composition is exhibited by a single electrum grain. In contrast to the steep compositional gradients typically associated with Ag-depletion, the Ag-enriched rim from this electrum grain shows a more gradual increase in Ag content. With the exception of the electrum grain data were not collected to establish the nature of the core-rim contact for Ag-enriched gold alloys. The distribution of Hg in AuAgHg alloy generally mimics that of Ag, whereby Hg is depleted in rims relative to the core. However, there are subtle differences in the distribution of Ag and Hg within depleted rims, with Hg forming more extensive and wider zones of depletion than Ag. Also, Hg was not detected in 75% of grain rims, whereas Ag is completely absent in only 22% of AuAgHg alloy rims (Table 1). Approximately 20% of all fine-grained gold analysed exhibits a pure gold rim (i.e., N99.9% Au). These pure gold rims occur in conjunction with more extensive Ag-depleted rims (FHg), as well as on grains that do not have Ag-depleted rims (FHg) (Table 1). Unlike Ag-depleted rims, the pure Au rims are commonly discontinuous around a grain margin, and are of varying width. 5. Sulphide minerals The sulphide suite at Belle-Brook is predominantly marcasite (ca. 97 vol.%) that occurs both as finegrained (b 1 mm) framboidal marcasite (Fig. 5A) or anhedral dlumpT marcasite (Fig. 5B) that ranges from 1 mm to 25 cm. Both fine-grained framboidal marcasite and dlumpT marcasite are ubiquitous throughout the matrix of QPC about the Belle-Brook site. Framboidal pyrite (Fig. 5C) is rare in comparison to framboidal marcasite and comprises ca. 1 vol.% of the sulphide suite. In contrast to framboidal marcasite which is widely dispersed throughout the QPC, framboidal pyrite is observed rarely, and generally confined to specific settings within the QPC, such as in narrow (10 cm) horizons above the water table. In outcrop, the occurrence of framboidal marcasite and framboidal pyrite is almost mutually exclusive, with only rare framboidal marcasite found in a framboidal pyrite-bearing locality. Lump marcasite and framboidal pyrite are mutually exclusive. Euhedral pyrite and

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Fig. 5. Morphological features of sulphides from Belle-Brook. (A) Irregular cluster of framboidal marcasite composed of individual framboids made up of microcrystalline marcasite. (B) Variation of anhedral lump marcasite masses (centimeter scale bar). (C) Framboidal pyrite mass, made up of pyrite framboids. (D) Predominantly euhedral sulphide concentrate, illustrating euhedral and rounded pyrite morphologies (py). Dark sooty rounded grains are small anhedral marcasite masses (mc). Well-preserved euhedral arsenopyrite crystals are relatively rare (aspy) (characteristic grains notated for reference). (E) Cubic pyrite in altered marcasite groundmass on anhedral marcasite. (F) Intergrown pyrite cubes illustrating lack of modification to some euhedral pyrite. (G) Abraded and etched pyrite cube with minor patches of Fe-oxide overgrowths. (H) Euhedral arsenopyrite illustrating lack of physical abrasion and well-preserved cleavages. (I) Close-up of microcrystalline marcasite faces (that make up a marcasite framboid) that is undergoing dissolution resulting in a dwool-ballT texture. (J) Close-up of I illustrating aligned octahedral microcrysts. (K) Marcasite cemented QPC (centimeter scale bar). (L) SEM photomicrograph of polished-section surface showing recrystallised marcasite mass with incorporated quartz grains (black) displaying marcasite veining and angular grain boundaries indicating dissolution. Quartz detritus also occurs along former framboidal marcasite grain boundaries.

arsenopyrite are common in heavy mineral concentrates (Fig. 5D) from the mining operation at BelleBrook. Rare euhedral pyrite is found intergrown with anhedral lump marcasite (Fig. 5E). Variably modified euhedral pyrite (Fig. 5F, G) comprises ca. 1 vol.%, of the total sulphide fraction, whilst arsenopyrite (Fig. 5H) makes up less than 1 vol.% of the sulphide fraction. There is no evidence for Fe-oxide replacement of sulphides, although minor Fe-oxide overgrowths do occur on some pyrite grains (Fig. 5G). Lump marcasite (2 to 25 cm) was also collected from a raised gravel bar at a second site at Hedgehope Stream. At this locality, goethite pseudomorphing marcasite is a notable feature. Marcasite has not been observed from other QPC in the Waimumu district, despite other large

QPC exposures (commercial aggregate quarries) existing within 3 km of Belle-Brook at Parker Road. 5.1. Framboidal and anhedral iron sulphides: morphology and textures Framboidal marcasite is composed of aggregates of framboids that commonly have irregular (Fig. 5A) and more rarely branched forms. The mineralogy of the framboidal masses was confirmed optically, and that of individual framboids by XRD analyses (Gandolfi camera). Individual spheroidal framboids range from 50 to 150 Am in diameter and are composed of interpenetrating marcasite crystals ranging in size from 10 to 40 Am. Crystal faces are generally well

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developed and well preserved, and are usually free of alteration products such as gypsum. Although marcasite microcrysts are generally well preserved, they commonly show various degrees of surface dissolution that affects crystal edges and corners. This dissolution of marcasite microcryst faces has the appearance of a wool-ball texture (Fig. 5I) that reveals individual marcasite microcrysts are composed of yet smaller octahedral microcrysts 0.3 to 1 Am across (Fig. 5J). In polished section, individual marcasite framboids consist of finely divided fibrous to

radial marcasite crystals. Marcasite framboids rarely have a discrete core, although pyrite microcrysts making up a single pyrite framboid are found as a core in rare cases. Aggregates of framboidal marcasite form anhedral masses, ranging from 0.5 mm up to 20 cm in length, in samples from Belle-Brook (Fig. 5B), and up to 25 cm in length from Hedgehope Stream. Regardless of size, anhedral masses are generally sub-rounded to rounded in appearance. In hand specimen, anhedral dlumpT marcasite has a variety of surface textures

Fig. 6. Anhedral dlumpT marcasite textures as viewed under reflected light (oil immersion). (A) Coarsely bladed marcasite, outer zoning reflects elevated Ni and As. (B) Radiating finely divided marcasite showing fan-shaped plumose texture. (C) Finely divided radial marcasite with multiple concentric bands truncated by adjacent quartz grain(s). Note development of polygonisation of banding. (D) Cluster of recrystallising radial marcasite spheroids that are colloform banded. Note framboidal pyrite core in more coarsely bladed marcasite spheroid. (E) Concentric, crystallographically zoned marcasite with swallow-tail marcasite twins. (F) General texture of lump marcasite undergoing recrystallisation showing variably deformed individual marcasite framboids. Replacement of cellular structures occurs in the centre of field of view.

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ranging from smooth to finely or coarsely crystalline, to knobbly. Variably recrystallised marcasite overgrowths are common on quartz clasts. These marcasite overgrowths reach 2 to 3 cm in length, and 1 to 2 mm in thickness. Rarely, some horizons in QPC outcrops are cemented with marcasite on the cm scale (Fig. 5K). Quartz grains (up to 1 mm across) consistent with those from the QPC matrix are commonly observed occurring on anhedral lump marcasite surfaces. Although quartz grains on the surface are rounded, in section quartz grains incorporated are typically angular (Fig. 5L). Veinlets of recrystallised framboidal marcasite (micron-to-millimeter scale) extend through adjacent quartz grains along fractures, and some such quartz grains have become disaggregated and brecciated by veinlet emplacement. These quartz grains are commonly characterised by angular or irregular grain boundaries that feature concave embayments (Fig. 5L). In polished section, lump marcasite typically consists of a wide range of variably recrystallised textures as the sulphide develops a foam texture and becomes increasingly massive during recrystallisation. Variably recrystallised lump marcasite include the following textures: finely divided (2 to 20 Am) acicular needles; medium-grained lath-like marcasite; coarse-grained bladed marcasite (Fig. 6A); coarsegrained prismatic marcasite; plumose fans of finegrained acicular marcasite (Fig. 6B); coarse-grained polygranular marcasite; marcasite that has replaced cellular structures in plant material; as well as foam textured and massive marcasite. Concentric banding defined by differences in reflectance and incorporation of impurities also occurs (Fig. 6C, D). Concentric banding may consist of either widely spaced single bands, or, closely spaced multiple bands. Well-defined crystallographically zoned marcasite features prominent swallow-tail contact twins, common on {101} faces (Fig. 6E). More rarely, clusters of framboids that are variably modified by polygonisation are preserved (Fig. 6F). Framboidal pyrite (Fig. 5C) is composed of subspherical to irregular aggregates of framboids typically 200 to 600 Am in length. Individual framboids are compact and form well-constrained spherical to subspherical masses, ranging from 10 to 40 Am in diameter. Framboids are characteristically composed of unordered uniformly sized octahedral pyrite microcrysts up to 1 Am across. Microcrysts, framboids and framboidal masses are well preserved, with little development of alteration products, evidence of dissolution, or overall physical degradation.

5.2. Euhedral sulphides: morphology Euhedral pyrite cubes range in size from 0.5 to 4 mm, with an average size of ca. 2 mm (Fig. 5F, G). Pyrite occurs predominantly as single cubes, less commonly as intergrown cubes, and rarely, as pyritohedra or pyritohedral clusters. Octahedral forms were not observed. Crystal faces and edges generally show very little, if any, physical degradation such as abraded edges or corners, and striations are well preserved. Pyrite faces are untarnished and typically free of visible alteration products such as sulphates or Feoxides, although rare marcasite overgrowths do occur on the faces of some crystals. Despite a lack of significant physical modification and abrasion of crystals, heavily etched and pitted crystals are common (Fig. 5G). Euhedral pyrite associated with anhedral marcasite is observed with relatively significant etching along corners and edges despite a physically protected setting (Fig. 5E). Arsenopyrite is rare in the sediments studied and occurs as well-preserved prismatic crystals up to 4 mm in length with minor abrasion (Fig. 5H). Striations and cleavage surfaces are well preserved. Crystals are typically untarnished and free from visible alteration products. Some euhedral arsenopyrite has overgrowths of anhedral pyrite. 5.3. Sulphide composition All of the recrystallised anhedral lump marcasite analysed during this study contained elevated Ni, Co, As, Cr and, to a lesser extent, Cu, Zn, Pb and W (Table 2). Element mapping shows that Ni F Co occur in concentric bands (Fig. 7) that correspond with relatively

Table 2 Summary of selected trace element concentrations (ppm) for anhedral lump marcasite from Belle-Brook and Hedgehope Stream Sample Belle-Brook marcasite Minimum Maximum Average Number Hedgehope marcasite Minimum Maximum Average Number Cr Ni Cu Zn As 12 129 70 29 15 108 26 11 Pb Coa Wa

34 180 1449 20 157 412 5753 29 29 49 402 185 11 449 5195 2291 11

17 219 6 195 16.4 260 6861 27 7010 139 78 1624 15 3527 60.6 29 29 29 9 9 16 1494 6 295 214 40 2666 12 3360 442 30 1844 8 1628 312 11 11 11 3 3

Samples analysed by XRF, with the exception of ICP-MS for W and Cr. a ICP-MS.

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Fig. 7. Electron microprobe element maps of marcasite from Belle-Brook. (A) Nickel map illustrating elevated Ni in marcasite framboids. (B) Lump marcasite that is variably recrystallised showing elevated Ni bands that correspond with concentric bands observed under reflected light. (C) Lump marcasite showing large-scale depletion and enrichment of elevated nickel-rich bands. (D) Massive marcasite featuring colloform style banding of elevated Ni-rich marcasite. All element maps are 500 Am across, darker colours indicate more elevated Ni concentration.

rare, but well defined, concentric bands observed under reflected light. Simple concentric compositional bands occur in individual framboidal marcasite grains (Fig. 7A), whereas complex truncated bands are characteristic of the variably recrystallised lump marcasite (Fig. 7BD). Nickel-rich bands are 1 to 3 Am wide and contain up to 12 wt.% Ni (EPMA) as Ni-bearing marcasite, with subordinate Co enrichment. Bands containing both Ni and Co have an average Co : Ni ratio of 0.6 (EPMA analysis, n = 80). Elevated Ni occurs rarely as a compositionally zoned, crystallographically controlled overgrowth within some anhedral lump marcasite. Arsenic distribution in both fine-grained and anhedral lump marcasite is less clearly defined, as As is generally present at, or below, the detection limit of the microprobe. However, compositionally zoned As-rich marcasite is observed in rare samples.

Microprobe analysis of euhedral pyrite indicates the occurrence of rare arsenian pyrite containing up to 1.3 wt.% As. Compositionally distinct overgrowths were not apparent in the arsenian pyrite, but a Nibearing (6 wt.% Ni) alteration rim was observed for one euhedral detrital pyrite crystal. 5.4. Sulphur isotope data Sulphur isotope analysis was carried out on framboidal marcasite (b400 Am in diameter), rounded framboidal masses (2 to 3 mm in diameter), anhedral lump marcasite, euhedral pyrite, and euhedral arsenopyrite from Belle-Brook. One sample of anhedral lump marcasite from Hedgehope Stream was also analysed. Analyses of sulphide minerals show a wide range in d 34S values, between 45x and

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Fig. 8. Distribution of sulphur isotope values for marcasite, pyrite and arsenopyrite from Belle-Brook.

+ 18x (Fig. 8, Table 3). Marcasite samples generally have the lowest values (typically less than about 20x), pyrite samples the heaviest (N 0%) and arsenopyrite has values in-between. 6. Discussion 6.1. Gold morphology and composition The morphology of the fine-grained gold at BelleBrook and Parker Road clearly shows that it is detrital (Fig. 3A, B). The gold composition is consistent with derivation from the Otago Schist, where low-silver Au Ag and AuAgHg alloys occur in primary and placer
Table 3 Sulphur isotope compositions (x) for detrital and diagenetic sulphides from Belle-Brook and Hedgehope Stream Sample number Belle-Brook BS-1 B4-17 B4-1 B4-4 B4-8 BFG-1 B4-20 BP-1 BP-2 BP-3 BP-4 BA-1 BA-2 Hedgehope H2-1 Sulphide description Framboidal marcasite Anhedral lump marcasite Anhedral lump marcasite Anhedral lump marcasite Anhedral lump marcasite Fine-grained (b3 mm) lump marcasite Recrystallised diagenetic pyrite Pyrite (detrital) Pyrite (detrital) Pyrite (detrital) Pyrite (detrital) Arsenopyrite (detrital) Arsenopyrite (detrital) Lump marcasite d 34S 28.6 28.6 21.5 12.1 27.4 45.4 2.0 +13.3 0.9 +16 8.8 9.9 1.3 18.2

deposits (Youngson and Craw, 1993; Youngson et al., 2002; MacKenzie and Craw, 2005). Relatively highsilver (N 10 wt.% Ag) AuAgHg alloy occurs sporadically in many placers throughout the region, but the electrum observed from Parker Road contains the most Ag-rich electrum yet documented in the South Island. The textures of the coarse nuggetty gold from BelleBrook are ambiguous. Many grains show little or no transport-induced modification. However, there are no known auriferous primary sources proximal to BelleBrook. Authigenic gold mobilisation and deposition has been inferred for gold particles from many Southland and Otago QPC placers (Falconer, 1987; Clough and Craw, 1989; Craw, 1992; Craw and Youngson, 1993; Youngson and Craw, 1993; Falconer, 2003; Falconer and Craw, submitted for publication). Authigenic gold in these deposits typically has a low Ag content, and is commonly confined to irregular overgrowths on detrital grains. In this study the authigenic addition of gold is inferred for silver-free gold rims on the exterior of approximately 20% of both gold alloy types (Table 1). The porous, sheet-like gold grains from Parker Road (Fig. 4) are inferred to be entirely authigenic based on their extremely delicate textures which could not survive sedimentary transport. Such discrete grains of authigenic gold have not previously been documented from Southland, although they have been reported from Quaternary eluvial sediments in Central Otago (Craw and Youngson, 1993; their Fig. 4). As with the porous, sheet-like authigenic gold, many of the smaller inferred authigenic gold forms of this study are of a more spheroidal rather than crystalline nature.

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However, they commonly have a poorly developed polygonal appearance and subtle crystallographic control (Fig. 3E, F). Jagged-edged particles (Fig. 3I) have been found at only one locality. Despite their small size, they are conspicuous in samples because of their particularly bright and shiny appearance. Rare coarse gold with intergrown quartz and abundant framboidal pyrite (no marcasite) are also features of this specific locality. Although there is no surface expression, faulting is suspected at this locality based on ground conditions and groundwater activity (spring) in the sandygravely sediments. 6.2. Origin of sulphide minerals Approximately 97% of the sulphide minerals examined in this study are marcasite. This marcasite occurs in a variety of forms that are considered to be diagenetic in origin, and formed as an authigenic phase in pore spaces in the Tertiary non-marine sediments and their recycled derivatives (QPC). This diagenetic interpretation is based on morphology (framboidal), together with the lack of primary or basement source, and is supported by sulphur isotope data. Both lump and finegrained marcasite from Belle-Brook and Hedgehope that contain Ni and Co enriched bands, had an average Co : Ni ratio of 0.6, which is consistent with the assumption that Co : Ni values less than one are often associated with a sedimentary (diagenetic) origin (Loftus-Hills and Solomon, 1967). Use of Co : Ni ratios to discriminate between different formation environments is questioned by some workers (Utter, 1978; Raiswell and Plant, 1980; Meyer et al., 1990). The broad spread of Co : Ni ratios between 0.1 and 2.9 in this study shows that the assertions of Loftus-Hills and Solomon (1967) may be an oversimplification. There are three main probable inputs of sulphur into the sediments: (1) atmospheric deposition, (2) weathering of parent material and; (3) plant residue. Atmospheric sulphur reaches soil via sulphate aerosols from volcanoes and sea spray. Volcanoes are not considered to be a likely source of sulphur in Southland. High d 34S values (+ 15x to + 21x) of soluble, adsorbed sulphate in New Zealand soils (including those in Southland) are attributed to addition of modern sea spray or precipitation high in marine sulphate (Kusakabe et al., 1976). This appears to be the case even for sites distant from the sea with low rainfall. Plant residues have similar values (about 1x to 3x less) as the soils. The most significant source of sulphur in most soils is from minerals, usually locally derived (Krouse et al.,

1996). Some of these minerals will be detrital sulphides from local formations or they may be authigenic sulphides precipitated from dissolved sulphate. Euhedral pyrite that occurs at Belle-Brook may be from the Otago Schist, however, Tertiary marine sediments of Otago and Southland commonly contain pyrite as cubes and granular masses, and these may also constitute a source of detrital sulphide in the Southland QPC. In the Waimumu district, Chatton Marine Formation sediments are exposed along the northern extension of the Hedgehope Fault, thus providing a local source of euhedral diagenetic pyrite. It is also possible that diagenetic euhedral sulphides were derived from deltaic and lower delta plain sediment of the Gore Lignite Measures overlying the marine strata. Euhedral pyrite grains from these different sources (Otago Schist, Gore Lignite Measures and Chatton Marine Formation) are apparently indistinguishable in terms of morphology. The wide range of d 34S values ( 45x to +18x) for sulphides in the Southland QPC suggests varied sources for sulphur and fractionation effects during sulphide mineral formation. Possible sources of detrital sulphides (euhedral pyrite and euhedral arsenopyrite) or sulphur from weathering of these minerals are: (1) the Otago Schists (d 34S values 5x to + 1x; Ashley and Craw, 1995; Craw et al., 1995); (2) pyrite in the Gore Lignite Measures (d 34S values about 6x; Table 3) and; (3) the Chatton Marine Formation which is a potential source of sulphur with values similar to those in the adsorbed soil sulphate (+ 15x to +21x; Kusakabe et al., 1976). Inorganic and microbial sulphate reduction (MSR) are two important controls on isotope fractionation of sulphur during diagenesis. Both these processes yield 34 S-depleted sulphide. The sulphur isotope fractionation between sulphate and sulphide is approximately +22x during inorganic sulphate reduction (Harrison and Thode, 1958), but laboratory studies have shown that fractionations are variable and larger during MSR (up to ca. 45x; Kaplan and Rittenberg, 1964). Still, larger fractionations (N+ 70x; Canfield and Teske, 1996) have been documented in nature. An enrichment of the lighter 32S in the hydrogen sulphide as a consequence of MSR during diagenesis results in a corresponding accumulation of the heavy isotope (34S) in the residual water. MSR can take place as long as; organic matter is present to be metabolised by bacteria; reactive iron is present to neutralise H2S and; sulphate is available as a reactant. The low d 34S values of the marcasite in this study are consistent with a diagenetic or authigenic origin. The d 34S value of dissolved sulphate from which the

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marcasite would have formed is not known, but the presence of marine formations (Chatton Marine Formation) and the likelihood that sea spray may have been a source for sulphur, suggest that values would have been relatively elevated (between +10x and + 20x). This indicates sulphatesulphide fractionations between + 20x and +60x and that microbial sulphate reduction was probably the dominant control. Euhedral pyrite and arsenopyrite, which occur only in minor quantities (ca. 2 vol.%) in the QPC, have relatively elevated values ( 10x to + 13x) that may reflect a detrital or possibly diagenetic/authigenic from either microbial or inorganic sulphate reduction of 34S-enriched residual sulphate. In Otago and Southland, sulphide deposition is part of the widespread diagenetic processes that occur in non-marine sediments (Craw, 1994; Youngson, 1995; Youngson et al., 2006-this volume). These processes are also responsible for kaolinisation of greywacke clasts and mobilisation of gold (Clough and Craw, 1989; Craw, 1994). It is likely that the most spectacular marcasite from Belle-Brook formed by post-Pliocene authigenic deposition from groundwater in the Pliocene QPC (Clough and Craw, 1989; Falconer, 2003). A similar occurrence of authigenic pyrite and marcasite formation during shallow diagenesis is documented from Pleistocene sediments within localised sulphate reducing zones associated with lignite in the Mogothy aquifer, Long Island, New York (Brown et al., 1999, 2000). Similarly, authigenic framboidal pyrite occurs at Elliot Lake, Canada, in 30-year old partially saturated tailings dumps that previously did not contain framboidal pyrite (Paktunc and Dave, 2002). 6.3. Gold textures resembling Witwatersrand gold textures Fibrous gold (Utter, 1979) and filamentous gold (Hallbauer and van Warmelo, 1974; Hallbauer, 1975, 1981; Hallbauer and Barton, 1987) extracted from carbonaceous matter (kerogen) is similar to the porous, sheet-like gold from carbonaceous mudstone at Parker Road (Fig. 4). The Witwatersrand samples were derived from ashing carbonaceous material at 500 8C. In contrast, the Parker Road gold was hand-panned from moderately lithified near-surface carbonaceous mudstone. However, the gold forms themselves are strikingly similar. A biomineralisation origin involving prokaryotic communities (i.e., algal and fungal mats) has been suggested for the Witwatersrand (Grosovsky, 1983; Mossman and Dexter-Dyer, 1985; Mossman et al., 1999). Li and Sieradzki (1992) document similar,

but not sheet-like, porous gold derived as a result of silver dissolution from AuAg alloy. Some authigenic gold textures described from BelleBrook resemble Witwatersrand secondary gold textures ascribed to metamorphic processes. Linked crystalline and stepped structures from the Witwatersrand (Minter et al., 1993) are similar to chain structures and crystalline gold forms from this study (Fig. 3E, F and 4F). Irregular grains with jagged edges are commonly reported from the Witwatersrand (Hallbauer and Utter, 1977; Utter, 1979; Minter et al., 1993). Although similar grains are generally absent from the QPC in this study, rare very small jagged-edged grains do occur at Belle-Brook (Fig. 3I). Compositionally, the gold of this study is similar to that from the Witwatersrand (Feather and Koen, 1975; Hallbauer and Utter, 1977; Utter, 1979; Von Gehlen, 1983; Oberthur and Saager, 1986; Reid et al., 1988; Frimmel et al., 1993; Frimmel and Gartz, 1997). Finegrained gold from this study is heterogeneous, in contrast to the generally homogeneous Witwatersrand gold. Limited data from the Belle-Brook coarse-grained gold indicate that it may be homogeneous. 6.4. Marcasite textures resembling Witwatersrand pyrite textures The resemblance of concretionary Witwatersrand pyrite textures to those commonly exhibited by marcasite has been noted by a number of workers (Dimroth, 1979; Hallbauer and von Gehlen, 1983; Barton and Hallbauer, 1996; England et al., 2002). Marcasite textures resembling oolitic-colloform pyrite documented by England et al. (2002) are ubiquitous at BelleBrook (Fig. 6CF). England et al. (2002) inferred that such grains may result from the pyritization of carbonate or evaporite ooids. Similarly, England et al. (2002) inferred chevron and swallow-tail pyrites to be pseudomorphs after gypsum. The occurrence of these styles of replacement in some places is not disputed. However, at Belle-Brook, there is no evidence for pseudomorphic replacement of carbonate, evaporite, or Fe-oxides for these natural marcasite textures. Many of these bpseudomorphic replacementQ forms are similar to a variety of bladed marcasite textures that occur at a range of scales in recrystallised lump marcasite from Belle-Brook (Fig. 6A, E). Porous pyrite surrounded by a pyritic cement, and concretionary pyrite with euhedral-to-subhedral microcryst cores documented by England et al. (2002) are similar to the common pyrite marcasite association in which pyrite framboids are surrounded by variously massive to radial marcasite.

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Witwatersrand pyrite with concentric banding is commonly ordered into hexagonal arrays similar to those observed in Belle-Brook framboidal and anhedral marcasite (Figs. 6C, D and 7A). Hence, it is suggested that at least some of the sulphide textures seen in Witwatersrand sulphides were initially the result of diagenetic marcasite formation. Although sulphur isotope signatures are probably preserved, it is not known whether marcasite textures as observed at Belle-Brook could survive solid state transformation to pyrite at temperatures N160 8C during metamorphism. However, diagenetic pyrite textures that have survived greenschist facies metamorphism are commonly reported, and colloform banding in diagenetic pyrite has reputedly even survived granulite facies metamorphism (Park, 1994). Belle-Brook marcasite is compositionally similar to porous round pyrite grains from the Witwatersrand in terms of its elevated Ni and Co levels and Co : Ni ratios (Meyer et al., 1990). Oscillatory-zoned pyrite from Witwatersrand orebodies (MacLean and Fleet, 1989) is similar to the less-common compositional style of As zoning at Belle-Brook. 6.5. Sulphide stability in a fluvial environment The detrital nature of rounded Witwatersrand sulphides has received much attention, particularly regarding their stability during transportation in an oxygen-poor atmosphere (Krupp et al., 1994; Fleet, 1998; Phillips et al., 2001; England et al., 2002). The Southland placer environment shows that both marcasite and pyrite can form by diagenetic processes within millimeter to meter of the surface under an oxygenated atmosphere (Youngson, 1995; Craw and Chappell, 1999; Falconer, 2003). Furthermore, these sulphides can survive erosion and transport in surface streams, to be reburied in younger sediments. Marcasite can be transported for at least short distances under oxic, but acid, conditions and remain stable without alteration to Fe-oxide. Pyrite and arsenopyrite can be transported for tens of kilometers in fluvial systems (Craw et al., 2003). 6.6. Sulphidation textures The role of sulphidation remains a central issue in the Witwatersrand debate (Phillips and Myers, 1989; Reimer and Mossman, 1990; Myers et al., 1993; Phillips and Law, 2000; Phillips et al., 2001). Magnetite, ilmenite and hematite are generally absent from the Witwatersrand orebodies (Feather and Koen, 1975). These Fe and Ti oxides are also rare at Belle-Brook,

but are present elsewhere in Otago and Southland QPC. Notably, Fe and Ti oxides are abundant in some QPC material recycled from Gore Lignite Measures at Parker Road, some 3 km north of Belle-Brook. There is no textural evidence to support replacement of these missing Fe and Ti oxides by sulphides at Belle-Brook, or elsewhere in Otago and Southland placers where they are scarce (Falconer, 2003; Youngson et al., 2006-this volume). Consequently, it is considered unnecessary to invoke a sulphidation process to account for their scarcity or absence. Although the replacement of Fe and Ti oxides by leucoxene is suggested by some in the Witwatersrand (Feather and Koen, 1975; Reimer and Mossman, 1990), the lack of leucoxene precludes this interpretation at Belle-Brook. The resemblance of bmud-ballQ pyrite to pisolites both in terms of morphology and trace element composition has been noted (Phillips and Myers, 1989; Phillips et al., 2001) but as suggested in this study, such textures and compositions are common in diagenetic marcasite. Belle-Brook anhedral marcasite with truncated concentric bands occurs as authigenic grains adjacent to detrital quartz grains (Fig. 6C). Thus, truncated bands in diagenetic sulphides are not necessarily associated with transportation, but rather, may be the result of dissolution processes occurring amongst the precipitating sulphides, detrital quartz and the pore fluid. However, minor transportation and abrasion of concentrically banded sulphides at Belle-Brook would also result in truncated banding similar to that documented from the Witwatersrand (MacLean and Fleet, 1989; Fleet, 1998; Phillips et al., 2001; England et al., 2002). 7. Conclusions The Belle-Brook and Parker Road gold placers are characterised by detrital gold and diagenetic sulphides exposed by small-scale alluvial gold mining in Tertiary to recent non-marine QPC. At Waimumu the QPC are unmetamorphosed, poorly lithified, relatively undeformed, and are unlikely to have been buried more than 100 m since deposition. Well-preserved, porous, sheet-like gold and microscopic gold overgrowths at Belle-Brook and Parker Road localities suggest authigenic gold mobility at the micron and individual-grain scales. Sulphur isotope data support an authigenic or early diagenetic origin for marcasite ( 45x to 20x), as it most likely formed from hydrogen sulphide produced by microbial sulphate reduction. Pyrite and arsenopyrite d 34S values ( 1x to + 16x) are consistent with a detrital origin from the Otago Schist,

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the Gore Lignite Measures, or formation by inorganic sulphate reduction from waters with elevated d 34S values. The sulphide suite at Belle-Brook is dominated by variably rounded and transported diagenetic marcasite that features a range of concentric banded textures locally enriched in Ni F Co. This diagenetic marcasite is compositionally and texturally similar to the rounded, concentrically banded pyrite commonly reported from Witwatersrand QPC. Therefore, the QPC placer environment at Belle-Brook, in particular, can be used to constrain the continuum of sulphide mineral deposition and transformations that probably also occurred during diagenesis in ancient fluvial environments. Acknowledgements The findings documented are from the first authors MSc thesis. Financial support was provided by University of Otago Geology Department research funds. Expert assistance with SEM analysis was provided by the South Campus Electron Microscopy Unit, in particular, M. Gould, S. Johnstone and L. Girvan. Acquisition of microprobe data was facilitated by D. Chappell and L. Patterson. D. Walls expertly assisted with XRF, XRD and Gandolfi camera work. B. Pooley, M. Trinder and S. Read provided technical assistance. We appreciate the assistance of P. Warnes (GNS, Lower Hutt) who provided analyses of sulphur isotopes. J. Smith is thanked for access to mine sites and general assistance in the field. Useful discussions with J. Knight are gratefully acknowledged. Prompt and constructive reviews by J. Mauk and G. Els significantly clarified the manuscript. References
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