Paper accepted March 2010 for

publication in Economic Geology

1 Exploration tools for linked porphyry and epithermal deposits: Example from the Mankayan

2 intrusion-centered Cu-Au district, Luzon, Philippines

4 Zhaoshan Chang1*, Jeffrey W. Hedenquist2, Noel C. White3, David R. Cooke1, Michael Roach1,

5 Cari L. Deyell1, Joey Garcia, Jr. 4, J. Bruce Gemmell1, Stafford McKnight5, and Ana Liza Cuison4#

7 1. CODES ARC Centre of Excellence in Ore Deposits, University of Tasmania, Private Bag

8 126, Hobart, Tasmania 7001, Australia

9 2. 99 Fifth Avenue-Suite 260, Ottawa, ON K1S5P5, Canada

10 3. P.O. Box 5181, Kenmore East, Queensland 4069, Australia

11 4. Lepanto Consolidated Mining Company, 21st Fl., BA-Lepanto Bldg., 8747 Paseo de Roxas,

12 1126, Makati City, Philippines

13 5. Geology & Metallurgy, School of Science and Engineering, University of Ballarat, PO Box

14 663, Ballarat VIC 3353, Australia

15

16 *: Corresponding author. Email: Zhaoshan.chang@utas.edu.au

#
17 : Current address: CODES ARC Centre of Excellence in Ore Deposits, University of Tasmania,

18 Private Bag 126, Hobart, Tasmania 7001, Australia

19

20

1
20 Abstract

21

22 The Mankayan mineral district of northern Luzon, Philippines, hosts several significant ore

23 deposits and prospects of various types within an area of ~25 km2, including the Far Southeast

24 porphyry Cu-Au deposit, the Lepanto high-sulfidation epithermal Cu-Au deposit, the Victoria

25 intermediate-sulfidation epithermal Au-Ag vein deposit, the Teresa epithermal Au-Ag vein deposit,

26 the Guinaoang porphyry Cu-Au deposit, and the Buaki and Palidan porphyry Cu-Au prospects, all

27 having formed in a period of about 2 million years, from ~3 Ma. The geologic units include 1) a

28 basement composed of Late Cretaceous to Middle Miocene metavolcanic rocks and volcaniclastic

29 rocks; 2) the Miocene 12-13 Ma tonalitic Bagon intrusive complex; 3) the Pliocene, ~2.2-1.8 Ma,

30 Imbanguila dacite porphyry and pyroclastic rocks; and 4) post-mineralization cover rocks including

31 the ~1.2-1.0 Ma Bato dacite porphyry and pyroclastic rocks and the ~0.02 Ma Lapangan Tuff.

32 Extensive advanced argillic alteration crops out for ~7 km along the unconformity between

33 the basement rocks and the Imbanguila dacite formation, and consists of extensive zones of resistant

34 quartz-alunite pyrophyllite or diaspore, locally with silicic alteration along structures, and a halo

35 of dickite kaolinite. The alteration and its sub-horizontal geometry indicate that it is a lithocap or

36 coalesced lithocaps. The northwest-striking portion is ~4-km long and hosts the Lepanto enargite-

37 Au ore deposit, also controlled by the Lepanto fault. The Lepanto epithermal deposit is related to

38 the underlying Far Southeast porphyry; the quartz-alunite alteration halo of Lepanto is

39 contemporaneous with the ~ 1.4 Ma potassic alteration of the porphyry. There are also silicic-

40 advanced argillic alteration patches ~600 m above the Far Southeast orebody at the present surface;

41 these are interpreted to be perched alteration. There is no systematic mineralogical or textural

42 zoning in the Lepanto lithocap that indicates direction to the intrusive source. Most surface samples

43 of the lithocap contain less than 50 ppb Au, despite many being less than a few hundred meters

44 from underground Cu-Au ore.

2
45 This study found that several characteristics of the Lepanto lithocap change systematically

46 with distance from the causative intrusion: 1) The alunite absorption peak at ~ 1480 nm in the short-

47 wavelength infra-red (SWIR) spectrum shifts to higher wavelengths where the sample is closer to

48 the intrusive center, due to higher Na and lower K content in the alunite; published experimental

49 study indicates that high Na/(Na + K) is related to higher formation temperature. High-Ca alunite,

50 including huangite, also occurs at locations proximal to the intrusive center. 2) Alunite mineral

51 composition analyzed by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-

52 MS) indicates that the Pb content and Ag/Au ratio decrease towards the intrusive center, whereas

53 Sr, La, Sr/Pb and La/Pb increase markedly. 3) Whole-rock compositions, using only non-

54 mineralized (taken as Cu <0.1wt% and Au <0.1ppm) and alunite-bearing samples, show that Pb and

55 Ag/Au, plus Hg and Ag, decrease towards the intrusive center, and Sr/Pb and La/Pb ratios increase.

56 Normalizing whole-rock Pb to the (Na+K) molal content produces a proxy for the alunite mineral

57 composition, and this ratio provides the same indications as the LA-ICP-MS analyses of alunite.

58 The concealed Victoria epithermal veins consist of intermediate-sulfidation mineralization on the

59 southwest flank of the porphyry. The veins are not exposed, but their presence at depth is indicated

60 by subtle alteration (illite or interstratified illite/smectite or smectite + pyrite) and geochemical (As,

61 Se) anomalies at the surface. The anomalies are strongly dependent on erosion level; no anomalies

62 were found where the surface is > ~350 m above the upper extent of the veins. An airborne

63 geophysics survey indicates that the Far Southeast orebody is associated with a wide zone of

64 demagnetization due to extensive magnetite-destructive phyllic alteration. Such low magnetic

65 anomalies beneath or on the margin of a large lithocap elsewhere may deserve attention. The

66 directional indicators and mineralization signatures found in this study have the potential to indicate

67 direction to the intrusive center during exploration of similar porphyry-epithermal districts.

68

3
68 Introduction

69

70 Lithocaps are horizontal to sub-horizontal blankets of residual quartz and advanced argillic

71 alteration of hypogene origin, occurring over intrusions (Sillitoe, 1995a). They can host high-

72 sulfidation epithermal mineralization, particularly within their fracture-controlled roots. Lithocaps

73 are temporally and genetically related to intrusions that may be associated with deeper porphyry-

74 style mineralization (Sillitoe, 1995a, 1999, 2010; Hedenquist et al., 1998). Lithocaps can have large

75 areal extent (>20 km2; Sillitoe, 1995a) and, because they resist erosion, are typically prominent at

76 the surface, which generally makes them easy to find. The presence of a lithocap of large areal

77 extent (A. Arribas, pers. commun., 1999) is encouraging for exploration at an early stage, as it

78 indicates extensive hydrothermal activity and potential for high-sulfidation ore; in addition, there is

79 potential for deeper porphyry and marginal epithermal vein mineralization. Despite the relative ease

80 of finding lithocaps, it may be difficult to further define the location of mineralization within, under,

81 or adjacent to a large lithocap due to the lack of directional indicators. In particular, determining the

82 position of the underlying intrusive center is commonly difficult. In addition, veins on the margin

83 may terminate several hundred meters below the paleosurface, below the level of the lithocap. In a

84 district without outcropping veins, exploration for such characteristic veins is typically difficult.

85 The Mankayan mineral district, northern Luzon, Philippines, was studied in order to develop

86 tools for exploration in such districts, as it is the site of several large intrusion-related ore deposits

87 and prospects. The district lies within a well-defined, 150-km long belt of porphyry Cu deposits in

88 the Central Cordillera of northern Luzon. It is one of the country's richest mining districts, both in

89 terms of proven and potential economic value as well as abundance and diversity of hydrothermal

90 mineralization (Sillitoe and Gappe, 1984). Within an area of ~25 km2 there are several porphyry

91 Cu-Au and epithermal deposits and prospects (Fig. 1). The Lepanto high-sulfidation epithermal

92 deposit and associated lithocap host is located above and adjacent to the Far Southeast porphyry

93 Cu-Au deposit (Fig. 1). In addition to the close spatial relationship (Sillitoe, 1983) and an overlap in

4
 94 alteration and ore mineralogy (Garcia, 1991; Hedenquist et al., 1998), the two ore bodies have been

95 shown to be contemporaneous and genetically linked (Arribas et al., 1995; Hedenquist et al., 1998).

96 The more recently discovered Victoria intermediate-sulfidation vein deposit (Cuison et al., 1998;

97 Claveria, 2001), located within 1 km southwest of the Far Southeast porphyry (Fig. 1), and the

98 adjacent Teresa vein deposit to the south, completes the assemblage of porphyry and related high-

99 and intermediate-sulfidation ore deposits in this intrusion-centered setting.

100 This study examined the surface expressions of the three principle deposits, Lepanto (mined

101 out), Far Southeast (drilled out), and Victoria (now being mined). The ores of these deposits are

102 largely blind, and this study was conducted in order to identify signatures and directional indicators

103 that would have potential application during exploration of similar porphyry-epithermal districts.

104 Such findings should be widely applicable, given the common relationships noted among such

105 deposits (e.g., Sillitoe and Hedenquist, 2003; Sillitoe, 2010), and evidence for transitions between

106 them (e.g., Einaudi et al., 2003).

107

108 Discovery histories of ore deposits in the district

109 The Lepanto enargite-Au orebody was worked for Cu and Au at the start of the Ming

110 dynasty (14th century), and by the local people prior to the 1500s, after which the Spanish became

111 involved. Outcrops consisting of vuggy to massive quartz along the Lepanto fault were first mined

112 near the 1150 m-elevation level, with luzonite-enargite still visible in the old workings in the cliff

113 face (Lepanto is the type locality for luzonite). The Cantabro-Filipino company was the first to

114 conduct large-scale mining in 1865, with at least 1100 t (tonnes) of Cu produced during a 10-year

115 period. The present underground mining activity dates from 1936, when the Lepanto Consolidated

116 Mining Co. commenced mining until the Japanese took over production; Mitsui produced 11,000 t

117 of Cu during the early 1940s. Lepanto Consolidated Mining Co. resumed mining in 1948, and up to

118 1996 a total of 36.3 Mt of ore was produced from the Lepanto mine at an average grade of 2.9

119 percent Cu, 3.4 g/t Au and 14 g/t Ag, with a total of 0.74 Mt Cu, 92 t Au and 393 t Ag recovered.

5
120 The Lepanto mine closed in 1996 with a remaining minable reserve of 4.4 Mt at 1.76 wt percent Cu

121 and 2.4 g/t Au (Claveria et al., 1999a).

122 The Far Southeast porphyry was discovered in 1980, based in part on the prediction that

123 Lepanto was sitting over a porphyry environment (Sillitoe, 1983). Porphyry fragments at the surface

124 were recognized by Lepanto geologists in outcrops of Imbanguila dacite volcanic products in the

125 1970s. In 1978, the deeper parts of two drill holes, drilled in 1974 about 4 km southeast of Lepanto,

126 were recognized to contain porphyry-type mineralization; subsequent re-assay in mid-1980

127 identified appreciable Cu contents (Sillitoe, 1995b). In 1979, the Cu and Au-mineralized

128 porphyry fragments in outcrop over the eastern end of the Lepanto orebody were recognized as

129 being hosted by a diatreme breccia, i.e., implying derivation from a nearby source at depth (Sillitoe,

130 1995b). An induced polarization (IP) survey in 1979 east of Lepanto identified a 1.5-km long

131 chargeability anomaly, and this was tested by a deep drill hole in April, 1980. The drilling was

132 unsuccessful, intersecting only pyrite thought to be related to Lepanto. A second hole closer to

133 Lepanto was drilled from ~1400-m elevation to 1100 m depth in October, 1980, and low-grade

134 (0.16 wt% Cu, 0.31 g/t Au) mineralization of a leucocratic quartz diorite porphyry stock was

135 intersected in the bottom 200 m of the hole. This successful drill hole confirmed a 1980 model

136 developed from original surface observations that the diatreme-hosted porphyry-altered lithic

137 fragments were transported from the central parts of a porphyry deposit to the surface by eruptive

138 activity (Sillitoe, 1983). Lepanto Consolidated Mining Co. then rehabilitated the 900 m-elevation

139 level 1.5 km from the Lepanto workings into an area that had earlier drill-hole indications of good

140 Cu and Au mineralization. In late 1980, the first drill hole from this underground position, 1000 m

141 in depth, intersected a 475-m interval of 0.46 wt percent Cu and 0.41 g/t Au, with grades increasing

142 downward and continuing to the bottom of the hole; this is considered to be the discovery drill hole.

143 Up to 1986, 75 drill holes totaling 38,000 m were completed from underground on a 100x75 m grid.

144 A further 11,700 m of drilling was conducted in 1992 to 1995 by a partnership, to a depth of 250 m

145 below sea level. The top of the resource is 650 m below the surface, and at a 1.0 wt percent Cu

6
146 equivalent cutoff, the deposit contains 356 Mt at 0.73 wt percent Cu and 1.24 g/t Au, among the

147 highest grades known in porphyry deposits of the Philippines (Concepcin and Cinco, 1989). The

148 core of the porphyry deposit contains 105 Mt at a grade of 0.86 percent Cu and 2.02 g/t Au at 1.8

149 percent Cu equivalent cutoff, considered to be economic for an underground operation in the 1980s

150 (Concepcin and Cinco, 1989).

151 Epithermal veins at Nayak (Fig. 1) and Suyoc (6 km southeast of Nayak) were mined in the

152 past. At Nayak, about 2 km south southwest of the surface projection of the Far Southeast deposit,

153 artisanal miners exploited the outcropping quartz-adularia veins; they have illite halos and contain

154 sphalerite, galena, and Au. These veins were exposed at ~1200-m elevation by river-cut erosion. By

155 contrast, at Suyoc the principal ore was quartz-carbonate-chalcopyrite veins (Gonzalez, 1967). In

156 early 1991, a surface drilling program of 12 shallow holes in the Nayak area defined about 0.3 Mt at

157 an average grade of 3 g/t Au. In 1995, exploration shifted to the Tabbac area, northeast of Nayak

158 and closer to the surface projection of the Far Southeast deposit. In May the sixth surface hole of

159 the year was drilled from 1320-m elevation with a south southeast inclination. At the 1200 m-

160 elevation level, clay alteration with comb-structure milky quartz and sphalerite-galena was

161 intersected with up to 0.7 g/t Au. At the 1000 m-elevation level, strong clay alteration and quartz

162 veins with sphalerite-chalcopyrite were intersected in the same hole, with grades of 1.1 to 25.0 g/t

163 Au over 21.6 m, averaging 3.7 g/t. Subsequently, in September 1995, lateral drilling from the 1000-

164 m level of Lepanto to the west southwest tested an area 100 m east of the surface hole. The drilling

165 intersected eight mineralized zones with grades from 1.3 to 193 g/t Au, with the best interval of 3.8

166 m averaging 112.7 g/t. A crosscut was established from Lepanto at an elevation 50 m below the

167 intersections, and encouraging results led to the development of the Victoria mine, with a 2500 t/d

168 carbon-in-pulp plant becoming operational in March, 1997. The quartz-carbonate epithermal veins

169 had an initial resource estimate of 11 Mt at 7.3 g/t Au; grades of 3-9 g/t are continuous over a 400

170 m-vertical interval, and high-grade ore, >30 g/t Au, is more restricted, with up to 250 m-vertical

171 intervals (Cuison et al., 1998; Disini et al., 1998; Claveria et al., 1999a, b). Subsequent development

7
172 included a twin-ramp decline from near Nayak completed in late 1999. These declines penetrated a

173 fault zone of broken vein material ~ 1 km south of the Victoria veins that assayed up to 3-4 g/t Au.

174 Subsequent underground exploration drilling in a southwest direction from Victoria found the

175 northern extension of this fault zone with better grades, not as high grade as the Victoria veins but

176 with wider brecciated intervals, and this area was denoted Teresa. In October 2004, after seven

177 years of mining, the remaining Victoria resource was 4.6 Mt averaging 5.68 g/t Au at a 2.8 g/t cut-

178 off, and Teresa was 0.8 Mt averaging 5.73 g/t Au.

179 The Guinaoang porphyry Cu-Au deposit occurs 3 km southeast of Far Southeast (Fig. 1).

180 This prospect is largely concealed by post-mineralization rock and shallow-level advanced argillic

181 alteration (quartz-alunite). The advanced argillic alteration was drilled in the 1970s by a Filipino

182 company exploring the area for Lepanto-like mineralization along the southeast extrapolation of the

183 Lepanto fault, principal host to about 70 percent of the Lepanto orebody. Twelve holes, some more

184 than 500 m deep, were drilled without apparent success. However, during subsequent relogging it

185 was recognized that high-sulfidation sulfides overprinted sericitic alteration, and that chalcopyrite is

186 present at greater depths (Sillitoe, 1995b). The area was subsequently mapped by an Australian

187 company in early 1980, who took the initial decision to drill test the area for a porphyry target based

188 on a small outcrop of intermediate argillic alteration beneath hypogene quartz-alunite alteration, as

189 well as the relogging of the earlier drillholes (Sillitoe and Angeles, 1985). Drilling identified

190 porphyry stockwork first present at 200 m depth, and outlined an estimated resource of 500 Mt at a

191 grade of 0.4 percent Cu and 0.4 g/t Au. The mineralization is largely hosted by an altered quartz

192 diorite intrusion 200 to 1000 m below surface.

193

194 Geology of the District

195

196 The geology of the Mankayan district has been summarized by Gonzalez (1956, 1959),

197 Sillitoe and Angeles (1985), Concepcin and Cinco (1989), and Garcia (1991). There are four main

8
198 units in the district: (1) a Late Cretaceous to Middle Miocene basement consisting of Lepanto

199 metavolcanic rocks, Apaoan volcaniclastic rocks, and Balili volcaniclastic rocks; (2) the Miocene

200 tonalitic Bagon intrusive complex; (3) the Pliocene Imbanguila dacitic to andesitic porphyry and

201 pyroclastic rocks, which predates the Far Southeast porphyry Cu-Au mineralization, and hosts much

202 of the Lepanto enargite-Au deposit and the Victoria veins; and (4) post-mineralization cover rocks

203 including the Pleistocene Bato dacitic to andesitic porphyritic lava and pyroclastic flow units, and

204 the Recent Lapangan tuff (Fig. 1).

205 The Lepanto metavolcanic rocks (or green metavolcanic rocks of Ringenbach et al., 1990)

206 are the lowermost stratigraphic unit of the Mankayan district, and crop out in the western part of the

207 district. This unit consists of indurated, tightly packed andesitic to basaltic lavas with minor

208 turbiditic sedimentary rocks. It was cut by mafic dikes, and has subsequently suffered greenschist

209 facies metamorphism. From reconnaissance regional mapping they are inferred to be of Cretaceous-

210 Paleogene age (Fernandez and Pulanco, 1967). This unit has been intruded by the Bagon tonalitic

211 intrusive complex, which has a reported radiogenic age of 12-13 Ma (Sillitoe and Angeles, 1985).

212 The Apaoan volcaniclastic rocks are present in the northeastern part of Mankayan, and consist of

213 green and red thin-bedded siltstone-sandstone. The Balili group overlies the Lepanto metavolcanic

214 and Apaoan volcaniclastic rocks unconformably, and consists of mostly matrix-supported

215 polymictic volcanic conglomerates; fossils indicative of Late Oligocene to Middle Miocene age

216 were found within calcareous horizons (Sillitoe and Angeles, 1985).

217 Both Imbanguila and Bato dacitic units are characterized by complex sequences of volcanic

218 breccias, pyroclastic horizons, and massive porphyritic rocks, as well as dike emplacement during

219 deposit formation (summarized by Hedenquist et al., 1998). These units typically contain easily

220 identified bipyramidal quartz eyes, in addition to feldspar and hornblende phenocrysts. The

221 lithologic and chemical similarities (Hedenquist et al., 1998) make it difficult to determine the exact

222 sequence of activity without conducting further extensive radiometric dating and detailed study of

223 the volcanic facies. The Imbanguila host rock, where dated, was found to be 2.19 0.62 to 1.82

9
224 0.36 Ma (n = 4) (Arribas et al., 1995). The Bato rocks are younger, 1.18 0.08 to 0.96 0.29 Ma (n

225 = 2). Nearby at Guinaoang, igneous biotite from a lapilli tuff associated with a dacite dome has a K-

226 Ar age of 2.90.4 Ma (Sillitoe and Angeles, 1985).

227 The Imbanguila unit lies over the basement rocks and the elevation of the unconformity, i.e.,

228 the base of the Imbanguila unit, is contoured in Figure 2. The contour shows that the Imbanguila

229 unit is associated with two large vents that are close to each other and coalesce at elevations between

230 900 and 1000 m. The unconformity is steep in the lower parts with a ridge between the two

231 depressions, becomes gentler upwards, and flattens to the northwest (Figs. 2 and 3). These two vents

232 are the likely sources of the Imbanguila dacite. The vents are located above the subsequent Far

233 Southeast porphyry alteration and mineralization, which are centered on quartz diorite porphyry

234 dikes that intruded to about 300 to 400 m elevation, below the vents. The distribution of the

235 Imbanguila unit (or units) is spatially related to the Lepanto fault, a splay of the Abra River fault that

236 is part of the Philippine fault system. The Imbanguila unit is also offset by the Lepanto fault,

237 consistent with the multiple-movement history of the fault system.

238 There are also two breccia bodies at the surface. About 1 km northwest of the surface

239 projection of the Far Southeast deposit, a well-defined diatreme breccia crops out above Lepanto at

240 ~1300 m elevation (Fig. 1; near the Upper Tram), cutting Imbanguila dacite. The diatreme breccia

241 contains lithic fragments with biotite and magnetite alteration and bornite-chalcopyrite

242 mineralization (D.G. Malicdem, pers. commun. to Sillitoe, 1983, and observed in this study),

243 indicating derivation from an underlying porphyry deposit. Fresh hornblende from the matrix of this

244 breccia yielded a K-Ar age of 1.43 0.21 Ma (Arribas et al., 1995). This age, coupled with the

245 presence of altered lithic fragments, indicates that there was eruptive activity at the same time as the

246 Far Southeast intrusive magmatism and associated hydrothermal activity (secondary biotite age 1.41

247 0.05 Ma, n = 6; Arribas et al., 1995). The feeder of this unit has not been identified, but it is

248 indistinguishable chemically from Imbanguila and Bato rocks (Hedenquist et al., 1998). A

249 hydrothermal breccia with altered and mineralized porphyry fragments, cemented by sulfide

10
250 minerals, crops out directly above the Far Southeast deposit (Fig. 1).

251 Part of the Lepanto ore body (the fault-hosted main ore body; Figs. 3 and 4), a minor portion

252 of the Victoria-Teresa veins, and most of the Far Southeast ore body are hosted by basement

253 metavolcanic or volcaniclastic rocks. Despite these basement host rocks, ore deposits in the

254 Mankayan district are spatially and temporally related to the Late Pliocene to Pleistocene events of

255 intermediate-composition volcanism (Fig. 1).

256 The Lapangan Tuff forms a thin and discontinuous cover of poorly consolidated dacitic air-

257 fall tuff, which is mainly present in the center of the Mankayan district (Sillitoe and Angeles, 1985).

258 Garcia (1991) reported an age of 18,820 679 years from 14C of humic soil in the eastern part of the

259 district.

260 Within the Mankayan district, the prominent fault system is a set of faults trending N50W

261 and N40E (Fig. 1) These faults are considered to be part of the northernmost splay of the

262 Philippine fault, the major tectonic lineament of the Philippine island arc (Sillitoe and Angeles,

263 1985). The northwest-trending part of the system comprises the steep, northeast-dipping Lepanto

264 fault that hosts much of the Lepanto deposit, with open-space growth into fault-related veins

265 (Gonzalez, 1956). A kinematic analysis of the faulting indicates that the N50W-trending faults

266 (e.g., the Lepanto fault) may have formed due to strike-slip movement along the major fault system.

267

268 Mineralization in the District

269

270 The Lepanto high sulfidation deposit

271 The Lepanto high sulfidation ore bodies are hosted in residual quartz and advanced argillic

272 alteration zones, the latter consisting of hypogene alunite, dickite, kaolinite, pyrite and, locally at

273 depth, diaspore and pyrophyllite (Hedenquist et al., 1998). Gonzalez (1956, 1959) provided much of

274 the early framework for understanding the geology, alteration and mineralization. Ores are closely

275 associated with vuggy to massive residual quartz, collectively referred to as silicic alteration.

11
276 Approximately 70 percent of the ore is hosted by the Lepanto fault, with strong brecciation of the

277 silicic ore zone in part possibly resulting from syn-mineral movement that offset alteration zones;

278 the balance of ore is contained in the sub-horizontal blanket of the lithocap (Garcia, 1991). Early

279 paragenetic studies (Gonzalez, 1959) noted that enargite and luzonite was followed by chalcopyrite,

280 tennantite, and gold plus electrum with telluride minerals. Tejada (1989) and Claveria (1997, 1998,

281 2001) further described the paragenesis of Lepanto mineralization, with evidence for early coarse

282 pyrite generated during the largely Cu- and Au-barren leaching event, which formed a core of

283 residual quartz and halo of advanced argillic alteration. This was followed by the high-sulfidation

284 state minerals enargite and luzonite with fine pyrite, largely hosted by the silicic core, and finally by

285 tennantite, chalcopyrite, sphalerite, galena and tellurides plus selenides. The post-enargite stage of

286 sulfides is associated with the introduction of gold, and was accompanied by the deposition of

287 anhydrite plus barite gangue minerals. The tennantite of the gold event at Lepanto may be of

288 intermediate- or high-sulfidation state, depending on its composition (Jannas et al., 1999), although

289 the presence of chalcopyrite indicates the former. Claveria (2000) noted a geochemical zonation in

290 most ore-related elements in Cu-Au zones, without discriminating ores and wall rocks, from the

291 southeast to the northwest along the trend of the Lepanto deposit. For example, Au, Cu, Sb, Se and

292 Te generally decrease towards the northwest and Ca decreases distinctly, whereas Ag and Zn

293 slightly increase.

294

295 The Far Southeast porphyry deposit

296 The Far Southeast porphyry is a concealed deposit. The top of the porphyry-type

297 mineralization is at an elevation of ~900 m, ~550 m below the surface, roughly coincident with the

298 base of the enargite-Au mineralization of the Lepanto orebody. At an elevation of 100 m below sea

299 level, the porphyry orebody is elongate in the direction of the regional northwest-trending structure.

300 The Cu and Au grades are concentric around dikes and irregular intrusive bodies of melanocratic

301 quartz diorite porphyry (Concepcin and Cinco, 1989) emplaced in the basement. Potassic

12
302 alteration consists of a biotite-magnetite K-feldspar assemblage and is associated with veins of

303 vitreous, anhedral quartz. This alteration is partially to pervasively overprinted by alteration

304 assemblages of chlorite plus hematite and/or white mica (SCC, sericite-clay-chlorite; Sillitoe and

305 Gappe, 1984). There is no definitive paragenetic evidence linking Cu sulfide minerals to the early

306 veins of vitreous, anhedral quartz veins (Hedenquist et al., 1998). However, petrographic evidence

307 shows that Cu sulfides are associated mainly with a later event characterized by the formation of

308 euhedral quartz crystals with anhydrite (Hedenquist et al., 1998; Imai, 2000). Cathodoluminescent

309 images show that the early anhedral quartz is overgrown by euhedral quartz (P. Redmond and J.

310 Reynolds, pers. commun., 2000), the latter associated with sulfide deposition and mineral inclusions

311 of illite (Hedenquist et al., 1998). Bleached halos of illite, cm to m wide, accompany these euhedral

312 quartz-anhydrite-white mica-hematite-pyrite-chalcopyrite-bornite veins, both of which cut SCC

313 alteration. Gold in the Far Southeast deposit is present as free grains of electrum associated with

314 chalcopyrite and bornite (Concepcin and Cinco, 1989), and locally is accompanied by Bi-Te-

315 bearing tennantite (Imai, 2000). Upward and outward from the core of economic porphyry

316 mineralization the pervasive SCC assemblage grades from white mica-dominated with minor

317 pyrophyllite locally to an assemblage in which pyrophyllite is abundant, variably accompanied by

318 quartz, anhydrite, and kandite minerals (dickite, nacrite and kaolinite). This pervasively altered rock

319 is overlain and locally cut by a silicic zone with local alunite that hosts the southeast extent of the

320 Lepanto ore deposit; the alunite halo includes a variable assemblage of anhydrite, diaspore, dickite,

321 and/or pyrophyllite (Hedenquist et al., 2001).

322

323 The relationship between Lepanto high-sulfidation deposit and Far Southeast porphyry deposit

324 Early ideas suggested that Lepanto was younger than high-temperature alteration of the

325 underlying porphyry system (Sillitoe, 1983). Dating by Arribas et al. (1995), however, found that

326 the biotite of the porphyry-related potassic alteration and the alunite in the halo to the silicic host of

327 the high-sulfidation orebody were essentially the same age, 1.41 0.05 (n = 6) and 1.42 0.08 Ma

13
328 (n = 5), respectively. This study was the first to demonstrate a coeval age of potassic alteration of a

329 porphyry deposit and its overlying advanced argillic alteration, the latter a lithocap that hosts a

330 high-sulfidation ore deposit. Shinohara and Hedenquist (1997) and Hedenquist et al. (1998) argued

331 that these synchronous alteration events were related to a coupled hypersaline liquid and a low-

332 salinity vapor, formed by separation as the solvus was intersected by critical fluid at depth. The

333 hypersaline liquid remained at depth and caused the potassic alteration, as evidenced by fluid

334 inclusions. The buoyant vapor ascended to shallower depths to form an acidic condensate that

335 leached the rock and created the residual quartz (silicic) and quartz-alunite alteration.

336 A phyllic alteration overprint of the porphyry ore body followed, with illite ages of 1.37 to

337 1.22 0.04 to 0.10 Ma (n = 10; Arribas et al., 1995). Stable isotopic studies of the biotite, alunite

338 and illite indicated that all formed from aqueous fluids with a dominantly magmatic origin,

339 although the alunite-stable fluid was an acidic condensate of magmatic vapor with a variable

340 meteoric water component, the latter progressively and regularly increasing as distance from the

341 porphyry increased, to a distance 4 km to the northwest (Hedenquist et al., 1998). This study was

342 the first to document in detail that the relatively low salinity fluid responsible for the phyllic

343 alteration was also magmatic in origin, rather than meteoric as previously thought. This detail

344 followed the original suggestion of a magmatic origin of phyllic alteration by Kusakabe et al.

345 (1990) based on their study of Chilean porphyry deposits.

346 Mancano and Campbell (1995) conducted the first fluid inclusion study of enargite, and

347 determined that there was a regular decrease within the Lepanto orebody of both homogenization

348 temperature (305 to 195 C) and salinity (~4 to 2 wt% NaCl equivalent) with increasing distance

349 from the porphyry, over a distance of >2 km. This supported the idea that the enargite (and gold)

350 mineralization of Lepanto formed from fluids that originated from the vicinity of the Far Southeast

351 deposit and flowed laterally to the northwest. Further fluid inclusion and stable isotope results

352 indicated that it was the phyllic stage of illite-stable fluid, initially an end-member magmatic fluid

14
353 at ~350 C and 5 wt percent NaCl equivalent, that was likely responsible for the Lepanto

354 mineralization (Hedenquist et al., 1998).

355

356 The Victoria and Teresa veins

357 The Victoria veins are located southwest of the Far Southeast porphyry, and at their closest

358 point are within a few hundred meters of the porphyry (Figs. 1 and 3). Imbanguila dacite porphyry

359 and pyroclastic units host much of the veins, but the veins extend downward into the Balili

360 volcaniclastic and Lepanto metavolcanic units (Fig. 3). The vein distribution has an arcuate shape,

361 from northeast to southeast (Fig. 1), over a horst of the basement rocks. The Victoria veins pinch

362 out upwards at ~1150 m elevation (0 zone) to ~1100 m (4 and 8 zones), and they extend to below

363 the 700 m-elevation level, locally to the 550 m level. Individual veins are mined over a 300 m

364 vertical interval, have widths up to 8 m, and in general strike north northeast with a dip to the

365 southeast, with strike extents of up to 600 m. By contrast, the Teresa veins, subsequently recognized

366 southwest of Victoria in the vicinity of the Nayak decline at an elevation of ~1170 m, tend to occur

367 in wider breccia zones, and strike north-south, parallel to the northerly projection of the surface

368 veins at Nayak. The veins crop out at ~1200 m elevation at Nayak. To the north they are mined at

369 an elevation of ~900-1150 m in the Teresa sector, although narrow veins continue to 850-800 m

370 elevation (Claveria et al., 1999a, b).

371 The alteration halos of the veins have been reported to consist of illite, or locally chlorite,

372 rarely in direct contact with propylitic-altered wall rock (Claveria, 2001; Sajona et al., 2001, 2002).

373 The paragenetic sequence of gangue and ore minerals in the Victoria veins (Claveria, 2001) consists

374 of 1) an early quartz vein stage, associated with an intermediate sulfidation-state assemblage

375 including chalcopyrite, tetrahedrite, and low-Fe sphalerite, as well as pyrite and galena; 2) a

376 carbonate stage of rhodochrosite, with similar sulfides; and 3) a late sulfate stage of anhydrite that is

377 sulfide poor. Bornite and hematite are restricted to the early quartz stage, and gold was introduced

15
378 during the later part of the quartz stage and through the carbonate stage, ending during the sulfate

379 stage.

380 Sajona et al. (2001) reported homogenization temperatures of ~200 to 260 C and salinities

381 of <1 to about 4 weight percent NaCl equiv. for fluid inclusions in sphalerite, quartz, and

382 rhodochrosite from Victoria. On the 1000 m level in the north, fluid inclusions in rhodochrosite

383 have higher homogenization temperatures than sphalerite. The homogenization temperatures of

384 fluid inclusions in sphalerite, as well as the Fe content in sphalerite, indicates cooling during flow

385 from the south to the north, with oxidation state increasing slightly on cooling, whereas the salinity

386 trend is more complicated.

387 Claveria (2001) reported that the northwestern-most Victoria veins cut advanced argillic

388 alteration and enargite related to the Lepanto deposit. Similar epithermal quartz veins were

389 recognized earlier to cut enargite mineralization in the main Lepanto deposit, near its base (Garcia,

390 1991). Such phenomena were also observed in this study, e.g., anhydrite + quartz + pyrite illite

391 veins cut quartz alunite pyrophyllite diaspore dickite assemblages (Fig. 5). Where enargite

392 and advanced argillic alteration is present in the Victoria area, it is clearly overprinted by quartz

393 veins and related mineralization. Samples of illite from the Victoria veins were dated by the Ar-Ar

394 method at 1.31 0.02 Ma (Sakakibara et al., 2001), and 1.14 0.02 Ma and 1.16 0.02 Ma

395 (Hedenquist et al., 2001). For illite in the wall rock adjacent to veins, Sakakibara et al. (2001)

396 reported illite Ar-Ar ages of 1.55 0.03 Ma and 1.31 0.02 Ma, and a K-Ar age of 1.50 0.07 Ma.

397 The dating results are generally in agreement with the paragenetic observation, with the ~1.5 Ma

398 wall rock alteration ages slightly overlapping with the Far Southeast biotite and alunite ages (1.41

399 0.05, n = 6, and 1.42 0.08 Ma, n = 5, respectively; Arribas et al., 1995). There is a possibility that

400 the wall rocks of the Victoria veins were altered during the nearby Far Southeast Lepanto event

401 (~1.5 Ma), and were further altered during the subsequent Victoria veining event (1.31 to 1.14 Ma).

16
402 The Teresa veins were dated during this study. Although alteration around the Victoria and

403 Teresa veins appears similar, a sample of illite from the 900 m level of the Teresa vein was dated at

404 2.22 0.05 Ma by Ar-Ar analysis (Fig. A1), indicating that this portion of the vein system is older.

405

406 Other deposits and prospects

407 Porphyry alteration assemblages at Guinaoang include sericite-clay-chlorite (SCC) that

408 overprinted an initial potassic assemblage, superseded by sericitic alteration that has a K-Ar age of

409 3.5 0.5 Ma (Sillitoe and Angeles, 1985). A relatively small (1.5 km2) lithocap of advanced argillic

410 alteration overlies the porphyry mineralization. The Guinaoang lithocap locally hosts enargite

411 mineralization similar to Lepanto, albeit much smaller in size (Sillitoe and Angeles, 1985; Trudu,

412 1992). At Buaki, 2 km west of Far Southeast, porphyry-style quartz veins and stockworks crop out

413 at surface. Based on assays of surface samples and underground samples from the 1150 m-level

414 tunnel, a resource of 30 Mt grading 0.4 percent Cu and 0.5 g/t Au was estimated (pers. observation,

415 J. Garcia). The Palidan-Mohong Hill porphyry lithocap prospect 3 km to the south was tested by

416 drilling and tunneling, and the resource is estimated at 100 Mt grading 0.4 percent Cu and 0.4 g/t

417 Au. Alunite in the Mohong Hill lithocap was dated by K-Ar (A. Arribas, pers. commun., 1996) at

418 1.66 0.32 Ma.

419

420 Surface Alteration Patterns

421

422 Lithocap occurrence

423 The most notable surficial alteration feature in the Mankayan district is the extensive advanced

424 argillic alteration. Nearly continuous outcrops of quartz-alunite occur for over ~7 km from the north

425 end of the airstrip south southeast to the Palidan porphyry locality (Figs. 1, 2 and 6a, b). The

426 elevation of the outcrops ranges from ~1050 to 1600 m, mostly at or close to locations where the

427 unconformity between the base of the Imbanguila dacite unit and the basement rocks is intersected

17
428 by the current surface (Fig. 2). Such hypogene advanced argillic alteration with sub-horizontal

429 geometry due to lithologic control constitutes a lithocap (Sillitoe, 1995a).

430 The northern lithocap extends to the southeast below the surface to an area overlying the Far

431 Southeast porphyry, according to underground information. The rocks on the surface above this

432 section of underground lithocap, however, are fresh, except for those directly above the Far

433 Southeast porphyry (Figs. 1, 2 and 4). This ~ 4 km long northwest-trending lithocap hosts the

434 Lepanto ore body and is referred to here as the Lepanto lithocap, for clarity (Fig. 3). The dating of

435 five alunite samples from the Lepanto lithocap, collected over a 4 km distance, from the porphyry to

436 airstrip, indicates that the advanced argillic alteration formed at essentially the same time (1.42

437 0.08 Ma; Arribas et al., 1995). There is a strong structural control on the lithocap, associated with

438 the intersection of the Lepanto fault with the unconformity, a relationship first noted by Gonzalez

439 (1956). The Lepanto fault is the major feeder and many branch faults functioned as subsidiary

440 feeders (Garcia, 1991). Alteration along the faults below the sub-horizontal part constitutes the root

441 zones of the lithocap.

442 There are also patches of advanced argillic alteration located on the surface over the Far

443 Southeast porphyry, 500 to 700 m above the unconformity (Fig. 2) at 1370 to 1450 m elevation.

444 These zones constitute stacked lenses of advanced argillic alteration within the lithocap. Narrow

445 faults containing alunite, including huangite (the Ca-endmember alunite), are present in fresh

446 Imbanguila dacite porphyry in deep gorges below the level of the surficial patches; these faults are

447 believed to be the fluid conduits for the stacked lenses.

448 The Lepanto lithocap, as well as the high-sulfidation mineralization hosted by portions of it,

449 has been shown to be continuous and genetically related to Far Southeast porphyry by dating, fluid

450 inclusion studies and O-H isotope studies, summarized above (Arribas et al., 1995; Mancano and

451 Campbell, 1995; Hedenquist et al., 1998). The Buaki porphyry is present on the western margin of

452 the lithocap, but erosion has exposed the core of this small porphyry system, indicating that it is not

453 related to the Lepanto lithocap; surface samples at Buaki contain porphyry-style quartz stockworks

18
454 overprinted by dickitekaolinite that is interpreted to be part of the Lepanto lithocap. If there were a

455 lithocap generated by the Buaki porphyry, it has been eroded away. Aside from the porphyry

456 fragments in the Upper Tram diatreme ~1 km northwest of Far Southeast (Fig. 1), there is no

457 geological, geochemical or geophysical evidence for any other porphyry systems nearby the

458 Lepanto lithocap.

459 The southern portion of the lithocap that outcrops in the district trends north northwest. It

460 partially covers the Victoria-Teresa veins, extends south to Mohong Hill (Fig. 6b) that overlies the

461 Palidan porphyry, and continues ~0.5 km further south. The potentially older age of Mohong Hill

462 alunite (1.66 0.32 Ma), compared to that of alunite samples in the lithocap northwest of the Far

463 Southeast porphyry (1.42 0.08 Ma), suggests that there may have been more than one intrusive

464 center of volatiles that generated acidic condensates along the same unconformity, with leaching

465 and alteration coalescing to form an apparently single alteration zone along the same permeable

466 horizon. This is consistent with the Palidan porphyry that outcrops below Mohong Hill (Figs. 1 and

467 2). For this reason, this part of the lithocap alteration in the district is excluded from discussion

468 below of zoning in the Lepanto lithocap.

469

470 Lithocap mineralogy and zoning

471 At Lepanto the lithocap is mostly composed of quartz-alunite pyrite, locally with

472 pyrophyllite and/or diaspore. The alunite crystals are typically > 60
m in size with a flaky shape,

473 indicating a hypogene origin, which is consistent with the alunite
34S compositions of +22 to +25

474 per mil (Hedenquist et al., 1998). The principal cliff-forming rocks are composed of quartz-alunite,

475 with the disseminated pyrite commonly oxidized at surface due to weathering. Within the quartz-

476 alunite horizons the silicic centers locally show a vuggy texture, but massive silicic rocks are more

477 common, largely along and proximal to the Lepanto fault. Most of the Lepanto ore is hosted in such

478 massive silicic rocks, although not all the massive silicic rocks are mineralized. On the surface most

479 of these massive silicicalunite rocks are only weakly anomalous in Au (<50 ppb), except at a few

19
480 locations such as the Spanish workings. Cathodoluminescence studies of a few massive silicic

481 samples show that they were originally residual quartz with a vuggy texture and the vugs were

482 subsequently filled by euhedral quartz (Fig. 7). Quartz-alunite horizons are surrounded by dickite

483 kaolinite (Fig. 4). At the end of the airstrip, the dickite kaolinite zone is ~20 m thick both above

484 and below the near-horizontal quartz-alunite zone (Fig. 6a).

485 Zonation in the root zones of the lithocap is similar to the classic pattern noted by Steven

486 and Ratt (1960) at Summitville, USA, with a silicic core that hosts mineralization changing

487 laterally outwards to quartz-alunite then dickite kaolinite (Fig. 4), over a scale of 10s of meters. In

488 contrast, the zonation is vertical in sub-horizontal lithocap horizons, with quartz-alunite in the

489 middle and dickite kaolinite above and below (Figs. 4 and 6a). The silicic core is well developed

490 close to the major fluid conduits, such as the Lepanto fault, but is largely missing elsewhere.

491 Laterally along the lithocap horizon there is no obvious zonation in texture or mineralogy from

492 proximal to distal locations relative to the causative intrusion at Far Southeast, or in any other

493 directions.

494

495 Mineralogy and zoning over intermediate sulfidation veins

496 The surface alteration above the Victoria veins is shown in Figure 8. There is weak white

497 mica pyrite alteration, grading outwards to unaltered rocks that only show evidence of weathering.

498 Except for a few mm-scale carbonate veinlets, no quartz or thick carbonate veins were found on the

499 surface, despite the Victoria veins being up to 8 m wide a few hundred meters below.

500 Illite crystallinity (IC), a term introduced by Kubler (1967), can be used to indicate the

501 formation temperature of white mica. Illite crystallinity was originally measured by X-ray

502 diffraction (XRD) in which the XRD-IC was expressed as the half-height width of the 10- peak.

503 The dominant control on IC is argued to be temperature (Frey, 1987), with higher temperature

504 increasing the crystallinity of illite (i.e., larger crystals), resulting in a smaller XRD-IC value

505 (sharper peak shape). Where illite crystallinity studies are determined from Short Wavelength Infra-

20
506 Red (SWIR) spectral features, the SWIR-IC is defined as the AlOH peak depth at ~2200 nm

507 divided by the H2O peak depth at ~1900 nm on a hull quotient SWIR spectrum (Pontual et al.,

508 unpublished manual, 1997). In contrast to XRD-IC, the more crystalline mineral results in higher

509 SWIR-IC values. Measurements of XRD-IC and SWIR-IC on the same samples show that the

510 values have a good negative correlation, meaning that either can be used to determine IC (Chang,

511 unpublished data), and thus indicate relative formation temperature; SWIR data are easy and fast to

512 acquire.

513 Where the tops of the veins are less than ~250 m below the present surface, the outcropping

514 alteration is mostly white mica + pyrite; chlorite is rare and epidote is not observed. The rocks

515 typically also contain halloysite, but this mineral is believed to be caused by weathering. The

516 SWIR-IC of white mica is 0.5-0.7 and the white mica is illite or interstratified illite/smectite

517 according to XRD identification. Where the tops of the veins are deeper, between ~250 to ~350 m,

518 white mica + pyrite alteration is still present at the surface but the SWIR-IC is smaller, 0.3-0.5. This

519 indicates that the white mica is probably smectite, which has been confirmed by XRD analysis. At

520 surface locations where the veins are >350 m below the present surface, only halloysite kaolinite

521 smectite occur; the presence of igneous magnetite and lack of pyrite here suggests that this

522 alteration is due primarily to weathering (Figs. 8a, b).

523

524 Geochemical Patterns: New Insights for Exploration

525

526 SWIR spectral variations of alunite

527 A total of 44 surface samples containing alunite were collected along a 7 km traverse of the

528 quartz-alunite portion of the lithocap (Fig. 9a). Another 25 samples were collected from

529 underground on the 1150, 900, and 700 m levels, between the Lepanto deposit and the northern

530 margin of the Victoria veins, to expand the distribution of alunite samples studied. Most alunite

531 samples are of altered Imbanguila dacitic pyroclastic rocks, as indicated by the residual bipyramidal

21
532 quartz eyes, whereas a few samples may have replaced rocks of the Balili unit. All the alunite

533 samples were measured using the CODES PIMA-II instrument. In addition, the composition of 18

534 alunite samples was determined by laser-ablation Inductively Coupled Plasma-Mass Spectrometry

535 (LA-ICP-MS) for 24 elements (122 analyses), and of these, 12 samples were analyzed by electron

536 microprobe (111 analyses including five analyses of APS - aluminum phosphate sulfate - minerals

537 or APS-alunite mixtures). The microprobe results are shown in Appendix Table A1 and the LA-

538 ICP-MS results in Appendix Table A2.

539 Back-scattered electron images indicate that the alunite is typically zoned, with zones 1-5

540 microns wide, which is mainly due to the variations in Na, K and Ca contents. The major elements

541 of alunite were analyzed using an electron microprobe with 15 micron beam size. In each sample 7-

542 11 analyses were obtained. The composition variation within one sample is typically small

543 compared with the variation between samples. For example, the mole Na/(Na+K) ratio of all the

544 analyses ranges from 0.04-0.96, whereas the variation of this ratio within a sample is typically

545 <0.30, although in low Na samples the range of this ratio is up to 0.51. Figure 9b further illustrates

546 that the intra-sample variation is small relative to the variation of the whole dataset. The Al and S

547 content in all the alunite analyses have little variation, with the average and standard deviation

548 being 20.12 0.35 wt percent and 15.03 0.31 wt percent, respectively; the Ca content is typically

549 low but locally up to 3.89 wt percent. PIMA analyses with a ~ 2 by 10 mm window identified

550 huangite in a few samples (spectrum shown in Appendix Fig. A2). Locally there are small APS

551 minerals included in alunite. A few microprobe analyses of an APS mineral in one sample revealed

552 that it is rich in Sr (10.60-12.61 wt%) with minor Ca (2.53-3.04 wt%), i.e., in the svanbergite-

553 woodhouseite series.

554 In SWIR spectra, K-Na alunites have a strong absorption feature at about 1480 nm

555 wavelength (Fig. A2). The exact position of this feature shifts, related to alunite composition

556 (Thompson et al., 1999). At Mankayan, at least three SWIR spectra were measured on each sample.

557 The variation in the wavelength position of this feature in each sample is typically < 2 nm, with

22
558 only a few exceptions that were up to 4 nm. The average composition of alunite shows a correlation

559 between the alunite Na/(Na+K) ratio and its ~1480 nm feature, with higher wavelength position

560 corresponding to higher Na content in the alunite (Fig. 9b), despite the variations in both the ratio

561 and the wavelength position for each sample. The higher Na content in turn has been demonstrated

562 to correlate positively with formation temperature, supported by alunite experiments (Stoffregen

563 and Cygan, 1990).

564 In the Mankayan district, the alunite feature at ~ 1480 nm in SWIR spectra varies between

565 1479 and 1495 nm. The wavelength peak position of alunite in the Lepanto lithocap generally

566 decreases with increasing distance from the intrusive center (Fig. 9a), particularly to the far

567 northwest extent of the lithocap. Closer to the Far Southeast porphyry deposit, the peak positions

568 generally have higher wavelengths, regardless of the sample elevation, i.e., from the surface (~1350

569 m elevation) or underground (1150, 900, and 700 mL); in particular, the wavelengths of the most

570 distant alunite are all low. The samples from lithocap outcrops in the southern part of the district

571 may be related to the Palidan porphyry, but this remains to be tested with further study and dating.

572 Microprobe results of alunite, hosted by Imbanguila dacite, show that alunite is more Ca-rich closer

573 to the Far Southeast porphyry (Fig. 9c). Huangite, the Ca endmember of alunite, has only been

574 found over the Far Southeast porphyry deposit (Fig. 9c).

575

576 Mineral chemistry of alunite

577 Trace elements in alunite analyzed by LA-ICP-MS included Ca, Sr, La, Ce, Nd, Sm, Eu, Gd,

578 Dy, Er, Yb, Lu, Zr, Ba, Au, Ag, Pb, Sb, Bi, Mn, Fe, Cu, As, and Se. The internal standard used for

579 data reduction was aluminum, which showed little variation in the 111 microprobe analyses. Six to

580 10 LA-ICP-MS analyses were obtained from most of the samples. Similar to the major elements,

581 variation in these trace elements among analyses of the same sample is typically smaller than the

582 variation of the whole dataset. For example, the Pb of the all the analyses ranges from 1 to 7868

583 ppm, whereas Pb variation in analyses of individual samples (maximum minimum) are mostly

23
584 <1200 ppm, particularly in low-Pb samples (Fig. 9d). The intra-sample variation is generally larger

585 in samples containing more Pb, with the largest intra-sample variation being ~3500 ppm in the

586 sample with the highest Pb content (Table A2). Despite the variation in each sample, the samples

587 have significantly different compositions (e.g., Fig. 9d). All the elements plus some element ratios

588 were plotted on base map to examine spatial trends; multiple analyses for each sample were plotted

589 individually, without averaging for each sample, and are represented by the multiple circles at each

590 location (e.g., Fig. 10a, and all other diagrams of this type). These results indicate that the Pb

591 content and the Ag/Au ratio in alunite from the Lepanto lithocap are lower closer to the intrusive

592 center (Fig. 10a and Fig. A3a). In contrast, the Sr content and rare earth elements (REE),

593 represented by La (Figs. A4a, and A4a), and particularly the La/Pb and Sr/Pb ratios (Figs. A5d and

594 A5d), generally increase closer to the intrusive center.

595

596 Lithocap whole-rock geochemical signatures and patterns

597 We determined the geochemical signatures of different types of mineralization and

598 associated alteration by analyzing whole-rock compositions, including major elements and 57 trace

599 elements (ACME Lab, Vancouver, Canada). The elements, sample digestion methods, analytical

600 methods, and detection limits are described in Appendix Table A3. Results below the detection

601 limits were given values of half the detection limit for the purpose of data plotting and

602 interpretation. In total 141 samples were analyzed, with 103 from the surface (Appendix Table A4;

603 Data Repository). In addition, 105 previous analyses of whole-rock samples from Lepanto

604 underground workings, many of them constituting ore, were also available for this study (Claveria,

605 1997).

606 Gold and related elements: The gold anomalies in the lithocap at the surface, associated

607 with quartz-alunite as well as dickite kaolinite zones, are instructive for exploration and

608 assessment of lithocaps elsewhere. A total of 159 analyses of lithocap samples were obtained, of

609 which 60 were from the surface, and these included silicic, quartz-alunite, and dickite kaolinite

24
610 alteration types. Three samples of silicic alteration along structures at the surface contain enargite

611 and >1 g/t Au. They are not considered here for this assessment of gold signature in lithocap

612 alteration, as they represent the later mineralization event, distinct from the early alteration event

613 (Hedenquist et al., 1998).

614 Lithocap samples were collected from above Far Southeast and south of the Buaki 1150 mL

615 portal to ~4 km northwest at the end of the airstrip. Samples close to Buaki are about 100 m west of

616 the surface projection of the Lepanto ore body, whereas samples at the end of the airstrip are nearly

617 2 km northwest from underground Lepanto ore (Fig. 11). This suite of 25 quartz-alunite samples

618 returned gold values of 1 to 46 ppb, averaging only 12 ppb. A silicic sample in this area from the

619 Lepanto fault structure contained 0.7 wt percent Cu as enargite, and 1.1 g/t Au, and is excluded

620 from this average. Other samples of quartz-alunite lithocap at the surface above several Branch

621 veins of enargite, northwest of the surface projection of Victoria and Teresa veins, contain 1 to 70

622 ppb Au, with the 17 samples averaging 27 ppb. Two other samples from the surface projection of a

623 Branch vein of enargite, both associated with silicic alteration along a structure, contain 1.1 and 4.0

624 g/t Au and 0.4 and >2 wt percent Cu, respectively, and are excluded from this consideration.

625 Further south, up to 0.5 km south of Mohong Hill, 13 quartz-alunite lithocap samples, possibly

626 related to the Palidan porphyry, contain 4 to 500 ppb Au, averaging 133 ppb. Two samples in

627 quartz-alunite lithocap close to the Guinaoang porphyry deposit contain 23 and 34 ppb Au.

628 The distribution of Au in quartz-alunite lithocap samples does not show any clear patterns

629 related to the position of the Lepanto orebody, nor does Cu, As, Te, and other ore-related elements,

630 except for higher values in samples of silicic alteration associated with structures. The most notable

631 result is the lack of strong Au enrichment (mostly <50 ppb) in the quartz-alunite lithocap as close as

632 a few hundred meters from the largely blind enargite-Au orebody.

633 Trace-element signatures in alunite-bearing lithocap samples: Although gold and other

634 metals do not define any obvious patterns when data from all of the lithocap samples are plotted

635 together, a selected sample set do have some elements and ratios that show trends relative to the

25
636 causative intrusive center. From the whole sample set, mineralized samples, i.e., defined as

637 containing
0.1 wt percent Cu and/or
100 ppb Au, were first filtered out. In addition, samples not

638 containing alunite were also excluded. The remaining samples from the Lepanto quartz-alunite

639 lithocap show clear spatial trends relative to the Far Southeast porphyry in the following elements

640 and ratios: Hg, Pb, Ag, Sr/Pb, La/Pb, and Ag/Au.

641 Mercury is low (less than ~ 130 ppb) above or close to the Far Southeast porphyry, and is

642 higher to the northwest, along the inferred major fluid-flow direction of the Lepanto lithocap (Fig.

643 12a). About 4 km to the northwest, at the end of the airstrip, Hg concentrations are the highest,

644 about 4000 ppb. When all non-mineralized samples (Cu < 0.1 wt percent and Au <100 ppb) of all

645 advanced alteration types are plotted together, including those without alunite, this trend is not clear

646 (Fig. 12b). Ore samples, which are much higher in Hg (up to 38,000 ppb), further obscure this

647 trend.

648 Lead also shows a trend of higher values with increasing distance from the Far Southeast

649 intrusive center and the enargite ore bodies (Fig. 10b). At proximal locations, the Pb content in the

650 alunite-bearing samples is <40 ppm, whereas about 1-2 km northwest of the surface projection of

651 the enargite ore bodies, Pb increases to about 90-150 ppm. In contrast with Hg, Pb does not increase

652 significantly until far from the intrusive center. When all non-mineralized samples are plotted,

653 including those without alunite, the trend in Pb is obscure (Fig. 10c). Mineralized samples contain

654 much higher Pb (up to 1790 ppm); adding them further obscures the trend. Other elements or ratios

655 that show trends in non-mineralized, alunite-bearing rocks include Ag, Ag/Au (both decrease

656 towards the porphyry center; Figs. A3c and A3d), and La/Pb and Sr/Pb ratios (both increase

657 towards the porphyry center; Figs. A4d and A5d).

658 The fact that clear geochemical trends are detected only in alunite-bearing samples suggests

659 that the anomalies are related to alunite. Normalizing the whole-rock Pb to moles of (Na+K),

660 assuming the Na and K in the whole rock mostly resides in alunite of the quartz-alunite lithocap,

661 improves the trend (Fig. 10d), supporting the contention that Pb in non-mineralized samples is

26
662 largely hosted by alunite. This assertion is confirmed by LA-ICP-MS analyses of alunite (Fig. 10-

663 a), which show that alunite contains up to ~8000 ppm Pb in the lattice; the alunite mineral

664 chemistry has the same trend as the whole rock compositions.

665

666 Halos above intermediate sulfidation veins

667 At the present surface 150 to 450 m above the Victoria and Teresa veins, there are weak but

668 detectable As (Fig. 13a) and Se (Fig. 13b) anomalies. Above the surface projections of the veins, As

669 is typically > 8 pm whereas the rocks a few 100 m from these positions contain less than this

670 amount. For Se the anomalous level above veins is > 0.5 ppm; there is a poor correlation between

671 Se and S (a proxy for pyrite content). For reference, the least-altered rock contains 0.2 ppm As and

672 0.1 ppm Se. Other elements of the 57 analyzed do not show any consistent difference in rocks at the

673 surface projects of the veins and some distance away. For example, the Au values range from below

674 the detection limit (0.2 ppb) to 46 ppb above the veins, compared to <0.2 ppb to 23 ppb away from

675 the veins laterally. Silver content at the surface above the veins ranges from 8 to 214 ppm,

676 compared to 10 to 240 ppm a few 100 m away from the surface projection of the veins. Thus,

677 geochemical anomalies above the upper limit of the veins are subtle but real for a limited group of

678 elements.

679

680 Geophysics

681

682 In August, 1997, following recognition of the economic significance of the Victoria veins to

683 the south of the then-depleted Lepanto orebody, Lepanto Consolidated Mining Co. decided to fly an

684 airborne geophysical survey over the prospective area. The survey was contracted to World

685 Geoscience (WGC) and was flown in a helicopter with lines 100 and 200 m apart oriented north-

686 south, with nominal sensor terrain clearance of 40 m. Magnetic data were collected using Scintrex

687 equipment with intrinsic resolution of 0.0001nT, a cycle rate of 0.1 sec and sample interval of 4 m.

27
688 Radiometric data were collected using a Picodas 256 channel spectrometer with a cycle rate of 1 sec

689 and sampling interval of 40 m, connected to a 16.75 l NaI crystal. Total magnetic intensity, digital

690 terrain model and standard 4 channel radiometrics (K, U, Th) were provided as located and gridded

691 data. The discussion presented here relates to a 7 km2 area centered on the Victoria veins, flown at

692 100-m line spacing; this area covers all the known significant deposits in the Mankayan district.

693 The Mankayan district is particularly challenging for interpretation of aeromagnetic data, as

694 it contains multiple shallow-dipping volcanic units of different ages and compositions with multiple

695 intrusions and extensive hydrothermal alteration. As a result, the magnetic susceptibility can be

696 expected to vary widely over short distances, and remanence effects must also be anticipated. In

697 addition, the area lies close to the magnetic equator, so magnetic features are displaced as a result of

698 the shallow (20N) magnetic inclination. In processing of magnetic data acquired at low latitudes,

699 spatial frequency domain reduction-to-the-pole (RTP) transformations of total magnetic intensity

700 data are used to shift anomalous features to overlie their source. The magnetic data acquired by

701 WGC were presented as images in which RTP transformations had been done (Fig. 14).

702 The magnetic character of stratigraphic units was assessed from the magnetic response

703 correlated with mapped geology. Both the Lepanto metavolcanic rocks and the Balili volcaniclastic

704 rocks in the basement are variably magnetic, with many high frequency (i.e., small) anomalies. The

705 Imbanguila dacite porphyry is effectively non-magnetic close to the porphyry ore deposit but

706 moderately magnetic elsewhere. The Imbanguila pyroclastic rocks are variably magnetic. The post-

707 mineralization Bato pyroclastic deposits are likely thin (100-200 m) and the magnetic character of

708 these units may be due to underlying Bato dacite intrusions or older units.

709 The magnetic expression of mineralization was examined by overlying known ore bodies on

710 the magnetic image. It is apparent that the Far Southeast orebody lies in a zone of lower RTP total

711 magnetic intensity, corresponding to the extensive zone of magnetite destructive alteration; this was

712 due to the phyllic overprint of potassic alteration at depth, as well as more shallow advanced argillic

713 alteration of fresh rock. There is no apparent indication of the deep magnetite-rich potassic alteration

28
714 that occurs below ~300 to 400 m elevation, i.e., ~1 km below the surface (average susceptibility for

715 core from the Far Southeast potassic zone is 0.05 SI). Forward modelling of a 400-m diameter

716 cylinder with a depth extent of 1000 m and a top 900 m below the surface indicates that the expected

717 magnetic response of the deep potassic zone is broad and low amplitude, and thus would not be

718 detectable in the presence of other anomalies. The Guinaoang porphyry deposit to the southeast

719 occurs in an area of subdued response and also has no apparent magnetic expression. The Lepanto

720 high-sulfidation orebody, and its host lithocap, which has a shallow southeast plunge towards the

721 Far Southeast porphyry, has no apparent magnetic expression. There is a general, although not exact,

722 association between the Victoria and Teresa vein systems and zones of demagnetization or reverse

723 magnetization.

724 Comparison of topographic lineaments interpreted from the digital elevation model (DEM)

725 derived from the airborne geophysical data, magnetic lineaments interpreted from the RTP total

726 magnetic intensity, and the geological map (Fig. 1) shows that many northwest-trending topographic

727 lineaments correspond to mapped faults. Some of the northeast-trending lineaments, as defined by

728 topography and magnetic data, correspond to mapped faults, but there are many additional

729 lineaments that may represent other structures.

730 The radiometric image clearly maps out the basement units (Lepanto metavolcanic rocks and

731 Bagon intrusion). The Imbanguila and Bato units have a variable response, between and within

732 units. However, there is no obvious radiometric expression of any of the mineralized systems.

733

734 Summary and Discussion

735

736 Genetic link between porphyry and lithocap: the basic processes

737 The genetic link between porphyry-style alteration-mineralization and lithocap was implied

738 in Sillitoes (1995a) definition of lithocap. This genetic link was demonstrated in the Mankayan

739 district through field observation, radiometric dating, fluid inclusion studies, and stable isotope

29
740 studies (Arribas et al., 1995; Mancano and Campbell, 1995; Hedenquist et al., 1998). Typically the

741 formation of porphyry-related alteration involves the early-stage separation of hypersaline liquid

742 and vapor as a magmatic critical fluid intersects its solvus (Henley and McNabb, 1978). The

743 hypersaline liquid causes the deep potassic alteration, whereas the vapor, being buoyant, ascends

744 toward the surface along structures. Magmatic gases such as HCl and SO2 fractionate to the vapor

745 and, after condensing into groundwater, form an acidic liquid. The condensate becomes more

746 reactive as it cools and the acids increasingly dissociate, and this causes leaching, forming residual

747 quartz cores with halos of advanced argillic alteration (quartz-alunite dickite-kaolinite) (Ransome,

748 1907; Steven and Ratt, 1960; White, 1991; Rye, 1993; Hedenquist et al., 1998). If the ascending,

749 structurally controlled acidic fluid encounters a permeable horizon, either an unconformity or one or

750 more rock units, the reactive fluid will flow along and cause intense leaching and alteration in that

751 layer, creating a lithocap above and lateral from the causative intrusion (Sillitoe, 1995a; Hedenquist

752 and Taran, 2010).

753 At Mankayan, the intrusions related to the Far Southeast porphyry deposit exsolved the fluid

754 which subsequently separated to hypersaline liquid and vapor (Shinohara and Hedenquist, 1997),

755 the latter subsequently forming an acidic condensate. The unconformity between the basement and

756 Imbanguila units channeled the flow of this condensate, facilitated by the Lepanto fault, and the

757 leaching and alteration along the path produced the Lepanto lithocap (Hedenquist et al., 1998). The

758 lithocap extends prominently to the northwest from the Far Southeast porphyry, rather than in all

759 the directions, due in part to the nature of the unconformity and the local geology. The

760 unconformity has a cone shape with two vent-related depressions (Fig. 2). It is speculated that the

761 vapors and subsequent acid condensates ascended from the northwestern depression, the

762 northwestern side of which is less steep, and therefore the condensates could flow unobstructed to

763 the northwest. In contrast, the southeastern side of the cone has a steeper slope, and turns downward

764 towards the southeastern depression at 900-1000 m elevation (Fig. 2). Any condensate ascending

765 along the unconformity to the southeast would lose its permeable channel at this elevation, as hot

30
766 fluids tend not to move downwards. The rock above this section of the unconformity is mostly

767 dacite porphyry and it has low permeability (Fig. 1), which would hinder further fluid ascent and

768 flow to the southeast. In summary, the geometry of the unconformity and the spatial distribution of

769 the rock units may have caused the asymmetry of the lithocap.

770 All lithocaps have structural roots, or feeders, along which the acidic condensate ascends.

771 But not all structurally controlled zones of hypogene advanced argillic alteration have associated

772 lithocaps (Sillitoe, 1999), either because they did not intersect permeable horizons, or such horizons

773 have subsequently been eroded. If there are multiple permeable layers or perched water tables, it is

774 possible that multiple, stacked horizons of lithocap will form. In the Mankayan district, the patches

775 of advanced argillic alteration above the Far Southeast porphyry lie far above the basement-

776 Imbanguila unconformity (Fig. 2) along which the majority of the advanced argillic alteration

777 occurs. These patches are probably connected by fractures with the main lithocap below, and thus

778 constitute perched horizons. Erosion in the Mankayan district has been minimal since the formation

779 of Far Southeast-Lepanto system, <500 m based on pressure estimates from fluid inclusion studies

780 at Far Southeast (Hedenquist et al., 1998), in part due to its youth, meaning that only a portion of

781 the quartz-alunite lithocap is presently exposed (Fig. 2; compare the elevation of the unconformity

782 with that of outcropping quartz-alunite, formed at and above the unconformity).

783

784 Formation of high-sulfidation epithermal deposits: a two-stage process

785 Hypogene advanced argillic alteration forms during the initial stage of porphyry

786 development, during vapor discharge. Mineralization, if present, forms in a subsequent stage

787 (White, 1991), as seen at Lepanto (Hedenquist et al., 1998) and other high-sulfidation deposits

788 (Sillitoe and Hedenquist, 2003). Hedenquist et al. (1998) demonstrated that the Lepanto high-

789 sulfidation mineralization is caused by the phyllic-stage lower salinity fluid, following early

790 alteration that produced potassic alteration at depth and the lithocap alteration closer to the surface.

31
791 In the Mankayan district, only part of the lithocap is mineralized. The ore bodies are located

792 at deeper positions and relatively close to the intrusive source (Figs. 1 and 3). The majority of ore

793 (~70%) lies in structural roots, principally the Lepanto fault (Fig. 4). Within the lithocap that

794 extends ~4 km northwest from the intrusion, mineralized roots occur up to ~ 2.5 km from the

795 intrusive source, whereas most of the mineralized horizons are within ~1.5 km of the intrusion (Fig.

796 1). Lithocaps elsewhere show many similar characteristics that in general indicate the potential for

797 high-sulfidation mineralization, but most are not strongly mineralized. One reason for this may be

798 due primarily to hydrological reasons, i.e., the subsequent mineralizing fluid that comes after the

799 early acidic condensate of vapor may not be able to ascend to the elevation of the lithocap,

800 especially to the upper horizons of a perched lithocap. For example, the patches of advanced argillic

801 alteration at the surface directly above Far Southeast are barren; likewise, the upper lithocap

802 horizon over the Quimsacocha deposit, Ecuador, is also largely barren (IAMGold staff, pers.

803 commun., 2007). Alternatively, the later mineralizing fluid may have been minor or non-existent

804 (Einaudi et al., 2003). Where the deeper porphyry environment is exposed, the mineralized portion

805 of the lithocap may have been eroded (R.H. Sillitoe, pers. commun., 2007).

806

807 Zonation in mineralogy and texture

808 At Mankayan, the alteration halo to structural feeders of the Lepanto lithocap and ore

809 deposit are zoned (Fig. 4), similar to the classic zonation pattern at the structurally controlled

810 Summitville high sulfidation epithermal deposit (Steven and Ratte, 1960); the alteration zonation,

811 from structure to margin, commonly has a scale of 10s of meters. The horizontal part of the lithocap

812 shows a vertical zonation, with quartz-alunite in the middle and dickite kaolinite above and

813 below, also at a scale of 10s of meters. Silicic zones at Lepanto, vuggy or massive in texture, largely

814 occur in proximal locations close to the feeder structure(s) and tend to be absent in distal locations,

815 similar to other lithocap horizons (Sillitoe, 1995a). For exploration of lithocaps up to tens of square

32
816 kilometers in size, such local alteration zonation is of limited use. At the kilometer scale, there is no

817 systematic mineralogical or textural zonation relative to the intrusive source in the Lepanto lithocap.

818

819 Signatures in alunite

820 Alunite is commonly one of the most abundant minerals in lithocaps, as at Mankayan. SWIR

821 spectral features of alunite and some trace elements in alunite show indications of systematic

822 variations relative to the Far Southeast porphyry source. The alunite absorption peak at ~ 1480 nm

823 of the SWIR spectrum shifts to higher wavelength positions closer to the Far Southeast porphyry

824 (Fig. 9a). The Pb content in alunite and the Ag/Au ratio are lower closer to the intrusive center (Fig.

825 10a and Fig. A3a), whereas Sr, Sr/Pb, La, and La/Pb increase (Figs. A4a, A4b, A5a, and A5b).

826 The variation in the ~1480 nm feature of alunite is related to its Na/(Na+K) composition

827 (Fig. 9b), which is directly correlated to the temperature of formation (Stoffregen and Cygan, 1990).

828 This is consistent with the spatial distribution of the samples relative to the intrusive heat source,

829 with Na-rich samples closest to the Far Southeast porphyry.

830 Lead in alunite is higher in distal positions (Fig. 10a), probably because Pb substitutes for K,

831 as the ionic radius of Pb2+ (1.32) is closer in size to K+ (1.33) than to Na+ (0.98). Since alunite with

832 higher K forms in distal positions at lower temperature compared to alunite with higher Na, Pb also

833 has a higher concentration in distal alunite. The ionic radius of Ag+ (1.13) is not particular close to

834 K+ (1.33) or Na+ (0.98), which may explains why the Ag content of alunite does not have a good

835 trend (Fig. A3b). The alunite Ag/Au ratio, however, has a good trend, decreasing towards the

836 intrusive center (Fig. A3a), probably because Au+ (ionic radius 1.37) tends to substitute for K+

837 (1.33), and the Ag/Au ratio magnifies this signal. The elements Sr2+ (1.27) and La3+ (1.04) are

838 probably more related to Ca2+ (1.06) than to Na+ or K+, due to both ionic radii and charge

839 considerations. Their contents in alunite have a trend that increases near the intrusive center (Figs.

840 A4a and A5a), consistent with the distribution of high-Ca alunite (up to 3.9 wt%) and huangite (Ca

841 alunite) closer to Far Southeast (Fig. 9c). The La/Pb and Sr/Pb ratios magnify these signals. In

33
842 addition to crystal lattice effects, the solubility of these trace elements at different temperatures may

843 also have played a role. For example, Pb may have a higher solubility at higher temperature in

844 proximal locations, resulting in its transport to cooler, distal location, where it is then incorporated

845 into alunite.

846

847 Signatures in whole-rock composition of lithocap samples

848 The Lepanto lithocap does not have significant anomalies of Au. Lithocap samples of

849 quartz-alunite, even only a few hundreds of meters away from the Lepanto ore bodies, contain < 50

850 ppb Au. Gold is not appreciably introduced during the early vapor condensate-related leaching and

851 lithocap development, consistent with the extremely low Au content of near-surface, low-pressure

852 magmatic vapors (Hedenquist et al., 1994; Hedenquist, 1995), in contrast to the higher metal

853 contents in high-pressure volcanic vapor (Hedenquist, 1995), and in vapor-rich inclusions from

854 high-pressure porphyry depths (Heinrich, 2005). This lack of Au in the early, near-surface (i.e.,

855 low-pressure) vapors explains the <50 ppb Au anomaly in whole rock within the Lepanto lithocap.

856 Gold content is also low in alunite, averaging 97 ppb, with the highest value 840 ppb. As the ionic

857 radius of Au+ (1.37) is similar to K+ (1.33), it is argued that Au would have substituted in alunite if

858 Au had been present at the time of alunite formation. When all whole-rock samples were plotted

859 without discrimination, patterns were not found for any other elements of the 57 elements

860 (Appendix Tables A3 and A4) analyzed, as well as many element ratios.

861 However, this study did find geochemical patterns zoned in the Lepanto lithocap relative to

862 the Far Southeast porphyry, the intrusive source, in selected suites of samples from the Lepanto

863 lithocap, namely non-mineralized (Cu < 0.1 wt % and Au < 100 ppb), alunite-bearing samples. As

864 noted for this lithocap, Hg, Pb, Ag, and Ag/Au decrease and La/Pb and Sr/Pb increase towards the

865 intrusive center. Selecting non-mineralized samples restricts the samples to all having formed in the

866 early leaching and alteration stage, relatively free of overprinting by later mineralizing fluids which

867 may complicate trends. Consequently, these patterns indicate the direction to the intrusive source of

34
868 volatiles. Filtering out samples without alunite constrains the samples to be formed under similarly

869 acidic conditions, and to have the same mineralogic nature. The sample filtering practice is essential

870 for selecting rocks formed at approximately the same time and under similar conditions, and by

871 fluids dominated by magmatic characteristics. The selected samples can then be more reliably

872 compared to one another, even though variations in geology may also have an effect.

873 Mercury is volatile and is therefore expected to deposit at relatively lower temperatures and

874 at distal locations. The whole-rock Pb content has the same trend as alunite Pb content, increasing

875 away from the intrusive center (Fig. 10b), indicating that the Pb content in the quartz-alunite

876 alteration is dominantly controlled by Pb in alunite. Normalizing whole-rock Pb content with the

877 K+Na content (molar Pb/[K+Na]) provides a proxy for alunite Pb content, as K and Na in alunite-

878 bearing, advanced argillic altered rocks mostly reside in alunite. In whole-rock data, Au itself does

879 not define a good trend, whereas whole-rock Ag content does change systematically, increasing

880 away from the intrusive center (Fig. A3d). In whole-rock data, the La/Pb and Sr/Pb ratios retain the

881 trend noted from alunite composition, increasing towards the intrusive center, but the La and Sr

882 trends are less clear, indicating these elements probably do not occur only in alunite.

883 The trends shown in alunite compositions and the composition of non-mineralized, alunite-

884 bearing whole-rock samples from the lithocap indicate the direction to the paleo-thermal source for

885 the initial-stage leaching and alteration event. Such trends do not point to ore but they help to

886 indicate areas with a higher potential for mineralization, because porphyry-style mineralization

887 occurs in and adjacent to the intrusive source, and high-sulfidation mineralization also tends to

888 occur proximal to intrusive source(s) and related structures. To use the vectors, the outcrops of

889 lithocap alteration are assumed to be genetically linked. Any evidence of such a relationship,

890 primarily geological relationships but also dating, increases the confidence in the results.

891

892 Surface signatures of concealed intermediate-sulfidation epithermal veins

35
893 At the present erosional surface above the Victoria intermediate-sulfidation veins, there are

894 subtle alteration (illite to interstratified illite/smectite to smectite + pyrite) and geochemical (As, Se)

895 expressions. Combining the results of alteration mineralogy, illite crystallinity, and geochemical

896 anomalies may improve the targeting of such a vein prospect, despite the anomalies being weak. In

897 a district such as at Mankayan with known porphyry and/or high-sulfidation deposits, or even a

898 district containing a barren lithocap, alteration and geochemical anomalies can nevertheless provide

899 indications of the location of vein targets worthwhile to drill test. The subtlety of signatures is

900 strongly dependent on the erosion level; therefore, even if such indications are not present at some

901 erosional surfaces, e.g., >350 m above the upper extent of veins similar to those in the Mankayan

902 district the potential of the district should not be ignored if there are other indications of

903 mineralization potential, e.g., mineralized fragments in an exposed diatreme, or within 2-3 km of a

904 porphyry deposit or lithocap.

905

906 Geophysical signatures

907 In the Mankayan district airborne magnetic imagery is complex and difficult to interpret,

908 reflecting the combined effects of low magnetic inclination, magnetic topography and remnant

909 magnetization in an area with complex and variable volcanic stratigraphy and many intrusions. The

910 airborne geophysical data have not provided any signatures that can be confidently related directly

911 to ore bodies. There is no direct surface expression of the magnetic alteration in the ~1000-m deep

912 core of the Far Southeast porphyry deposit, but the ore body occurs in a large zone with obvious

913 demagnetization, providing an indirect guide. Importantly, this survey indicates that not all

914 porphyry deposits are associated with a positive magnetic anomaly, if magnetite-bearing potassic

915 alteration is overprinted by other alteration types. The are several magnetic anomalies of relative

916 lows present in the Mankayan district (Fig. 14), but the one above Far Southeast is special in that it

917 is at the end of a ~4 km elongated lithocap. This indicates that integrating geophysical findings with

918 geological knowledge may help increase confidence in targeting. In a district that contains many

36
919 low magnetic anomalies, those closest to the margin of (or beneath) a large lithocap may deserve

920 priority in follow-up investigation.

921 The Guinaoang porphyry deposit and the Lepanto high-sulfidation deposit have no apparent

922 expression. The Victoria and Theresa vein systems can be tentatively related to a zone of probable

923 demagnetization, consistent with the white mica pyrite alteration. Radiometric data reflect

924 bedrock units, but show no effects of mineralization. Numerous linear features are apparent

925 according to digital elevation model (DEM) and RTP total magnetic intensity images. Most have

926 been confirmed to be faults by mapping, whereas some northeast-trending lineaments have not been

927 recognized in mapping and deserve exploration as possible sites for mineralized veins. Thus, the

928 geophysical survey, while not pointing directly to ore, has provided potential targets for

929 investigation in the Mankayan district.

930

931 General Implications for Exploration

932

933 The presence of a lithocap indicates an epithermal level of erosion, and the potential for epithermal

934 and/or porphyry mineralization nearby. This is clearly demonstrated in the Mankayan district and at

935 many other locations worldwide. New exploration tools and lessons that can be learnt from this

936 study in the Mankayan district include the following points.

937 Alteration mapping, aided by SWIR equipment, is essential to assess the advanced argillic

938 lithocap environment, as is mapping of lithology and structures. However, alteration by itself may

939 be insufficient to point to the causative intrusive source. Vectors found in this study include: 1) the

940 alunite peak position at ~1480 nm on SWIR spectrum shifts towards higher wavelength in samples

941 that are closer to the intrusive source of acidic condensates. 2) In alunite the Pb content and Ag/Au

942 ratio decrease closer to the intrusive center, whereas Sr, La, La/Pb, and Sr/Pb increase. 3) The

943 whole-rock composition of alunite-containing, non-mineralized (< 0.1 % Cu and < 100 ppb Au)

944 lithocap samples can also point to the intrusive source: Hg, Pb, Ag, and Ag/Au decrease and La/Pb

37
945 and Sr/Pb increase towards the intrusive center. Normalizing whole-rock Pb to the (Na+K) moles is

946 a proxy for the alunite mineral composition, and as demonstrated in the Mankayan district, the ratio

947 provides the same indication as alunite compositions. This is useful, as whole-rock analyses are

948 much less expensive, with a faster turn-around time, than LA-ICP-MS analyses. These vectors point

949 to the causative intrusive source that is the potential center to mineralization, including porphyry

950 and high-sulfidation deposits.

951 The gold anomaly in the quartz-alunite alteration of a lithocap can be quite low (<50 ppb),

952 even within a few hundred meters of the surface projection of underground ores. A prospect should

953 not be discarded only based on a low level of gold anomaly in quartz-alunite alteration, particularly

954 if the lithocap is large. It is critical to locate the structural feeders of lithocaps, as high-sulfidation

955 mineralization if present is most likely to be concentrated there. In addition, the presence of

956 silicic alteration is much more indicative of prospect potential than pervasive quartz-alunite or clay

957 alteration, particularly that associated with structures. Stacked lithocap horizons may occur, and in

958 such cases the lower layers have a better chance of being mineralized (e.g., Quimsacocha).

959 Low magnetic anomalies on the margin of a large lithocap, particularly at the end of an

960 elongate, structurally controlled lithocap, deserve special attention, as the anomaly may be caused

961 by demagnetization due to porphyry-style alteration, e.g., either phyllic or advanced argillic

962 overprint of potassic alteration.

963 White mica pyrite alteration, coupled with various elements of the epithermal suite both

964 As and Se at Mankayan may indicate the presence of concealed intermediate-sulfidation

965 epithermal veins, especially in a district with known porphyry or high-sufidation mineralization or

966 large lithocaps. The signatures are strongly dependent on the erosion level, and are typically quite

967 subtle in positions several hundred meters over veins, and hence an assessment of the degree of

968 erosion is essential.

969

970 Acknowledgements

38
971

972 We are grateful to Mr. Bryan Yap, President of Lepanto Consolidated Mining Company, for

973 permission to conduct this study in the Mankayan district, for providing access to the air magnetic

974 and radiometric survey results, and for permission to publish the outcome of this study. This work is

975 part of AMIRA Project P765, completed in December, 2006, at CODES, University of Tasmania.

976 The project was sponsored by Anglo American, Anglo Gold Ashanti, Gold Fields, Newcrest,

977 Newmont, Placer Dome, and Teck Cominco, as well as Barrick in the final year, with additional

978 funding provided by the Australian Research Council. We acknowledge the discussion and ideas

979 provided by representatives of the sponsoring companies, and assistance by the AMIRA research

980 coordinator Alan Goode. We thank Lyndon Bradish and Froilan Conde, plus many other Lepanto

981 staff, including Bene, Danny, Ed, Louie, Perfecto, Perry, Ric, and Willy, for their assistance, and

982 Dave Braxton for help in the field. Paddy Waters of Anglo American Philippines generously

983 provided logistic support and funding for some of the whole-rock geochemical analyses. We

984 appreciate the help from CODES staff, including Simon Stephens for sample preparation, Sarah

985 Gilbert and Leonid Danyushevsky for LA-ICP-MS analyses, and June Pongratz for report

986 preparation. We thank Roger Stoffregen for comments on an early version of the manuscript, and

987 John Thompson and Raymond Jannas for useful reviews.

988

39
 988 References

989

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1019 Foundation.

1020 Einaudi, M.T., Hedenquist, J.W., and Inan, E., 2003, Sulfidation state of hydrothermal fluids: The

1021 porphyry-epithermal transition and beyond: in Simmons, S.F., and Graham, I.J., (eds.),

1022 Volcanic, geothermal and ore-forming fluids: Rulers and witnesses of processes within the

1023 Earth: Society of Economic Geologists and Geochemical Society, Special Publication 10,

1024 Chapter 15, p. 285-313.

1025 Fernandez, J.C., and Pulanco, D.M., 1967, Reconnaissance geology of northwestern Luzon,

1026 Philippines: in Proceedings, 2nd Geological Convention and 1st Symposium on the Geology

1027 of the Mineral Resources of the Philippines and Neighboring Countries, Manila, Geological

1028 Society of Philippines, v. 1, p. 35.

1029 Frey, M., 1987, Very low-grade metamorphism of clastic sedimentary rocks: in: Frey, M., ed., Low

1030 Temperature Metamorphism, Blackie & Son Ltd, Glasgow, p. 9-58

1031 Garcia, J.S., Jr., 1991, Geology and mineralization characteristics of the Mankayan mineral district,

1032 Benguet, Philippines: Geological Survey of Japan, Report 277, p. 21-30.

1033 Gonzalez, A.G., 1956, Geology of the Lepanto copper mine, Mankayan, Mountain province:

1034 Philippines Bureau of Mines Special Projects Series 16, p. 17-50.

1035 Gonzalez, A.G., 1959, Geology and genesis of the Lepanto copper deposit, Mankayan, Mountain

1036 Province, Philippines: Unpublished Ph.D. dissertation, Stanford University, 102 p.

41
1037 Gonzalez, A.G., 1967, Copper-gold mineralization in the Mankayan-Suyoc district, Mountain

1038 Province: Geological Society of the Philippines Geological Convention, 2nd, Manila,

1039 Proceedings, v. 2, p. 260.

1040 Hedenquist, J.W., 1995, The ascent of magmatic fluids: Eruption versus mineralization: in

1041 Thompson, J.F.H., editor, Magmas, Fluids and Ore Deposits, Mineralogical Association of

1042 Canada, Shortcourse, v. 23, p. 263-289.

1043 Hedenquist, J.W., Aoki, M., and Shinohara H., 1994, Flux of volatiles and ore-forming metals from

1044 the magmatic-hydrothermal system of Satsuma Iwojima volcano: Geology, v. 22, p. 585-588.

1045 Hedenquist, J.W., Arribas, A., Jr., and Reynolds, T.J., 1998, Evolution of an intrusion-centered

1046 hydrothermal system; Far Southeast-Lepanto porphyry and epithermal Cu-Au deposits,

1047 Philippines: Economic Geology, v. 93, p. 373-404.

1048 Hedenquist, J.W., Claveria, R.J.R., and Villafuerte, G.P., 2001, Types of sulfide-rich epithermal

1049 deposits, and their affiliation to porphyry systems: LepantoVictoriaFar Southeast deposits,

1050 Philippines, as examples: ProExplo Congreso, Lima, Per, 24-28 April, 2001, CD release.

1051 Hedenquist, J.W., and Taran, Y.A., 2010, Formation of advanced argillic lithocaps and relationship
1052 to their intrusive sources: Implications for exploration of associated epithermal and porphyry
1053 deposits: Economic Geology (submitted).
1054 Heinrich, C.A., 2005, The physical and chemical evolution of low-salinity magmatic fluids at the

1055 porphyry to epithermal transition: a thermodynamic study: Mineralium Deposita, v. 39, p.

1056 864-889.

1057 Heinrich, C.A., Gnther, D., Audtat, A., Ulrich, T., and Frischknecht, R., 1999, Metal fractionation

1058 between magmatic brine and vapor, determined by microanalysis of fluid inclusions:

1059 Geology, v. 27, p. 755758.

1060 Henley, R.W., and McNabb, A., 1978, Magmatic vapor plumes and ground-water interaction in

1061 porphyry copper emplacement: Economic Geology, v.73, p. 1-20.

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1062 Imai, A., 2000, Mineral paragenesis, fluid inclusions and sulfur isotope systematics of the Lepanto
1063 Far Southeast porphyry Cu-Au deposit, Mankayan, Philippines: Resource Geology, v. 50, p.
1064 151-168.
1065 Jannas, R.R., Bowers, T.S., Petersen, U., and Beane, R. E., 1999, High-sulfidation deposit types in
1066 the El Indio district, Chile: Society of Economic Geologists Special Publication No. 7, p.
1067 219-266.
1068 Kubler, B., 1967, La cristallinite de Iillite et les zones tout a fait superieures du metamorphisme: in
1069 Etages tectoniques, Colloque de Neuchatel 1966, pp. 105-121, A la Baconniere, Neuchatel,
1070 Suisse.
1071 Kusakabe, M., Hori, M., and Matsuhisa, Y., 1990, Primary mineralization of the El Teniente and

1072 Rio Blanco porphyry copper deposits, Chile: Stable isotopes, fluid inclusions, and

1073 Mg2+/Fe2+/Fe3+ ratios of hydrothermal biotite: in Herbert, H.K., and Ho, S.E., eds., Stable

1074 isotopes and fluid processes in mineralization. Perth, University of Western Australia,

1075 Geology Department Publication 23, p. 244259.

1076 Mancano, D.P., and Campbell, A.R., 1995, Microthermometry of enargite-hosted fluid inclusions

1077 from the Lepanto, Philippines, high-sulfidation Cu-Au deposit: Geochimica et Cosmochimica

1078 Acta, v. 59, p. 3909-3916.

1079 Pontual, S., Merry, N., and Gamson, P., 1997, Spectral Interpretation Field Manual, G MEX, v. 1,

1080 AusSpec International Pty. Ltd., 168 p. Unpublished.

1081 Ransome, F.L., 1907, The association of alunite with gold in the Goldfield district, Nevada:

1082 Economic Geology, v. 2, p. 667692.

1083 Ringenbach, J.C., Stephan, J.F., Maleterre, P., and Bellon, H., 1990, Structure and geological

1084 history of the Lepanto-Cervantes releasing bend on the Abra River Fault, Luzon Central

1085 Cordillera, Philippines: Tectonophysics, v. 183, p. 225-241.

1086 Rye, R.O., 1993, The evolution of magmatic fluids in the epithermal environment; the stable

1087 isotope perspective: Economic Geology, v. 88, p.733-752.

1088 Sajona, F. G., Izawa, E., Claveria, R.J.R., Motomura, Y., Imai, A., Sakakibara, H., and Watanabe,

1089 K., 2001, The Victoria gold deposit of the Mankayan district, Luzon, Philippines: in Izawa, E.,

43
1090 Watanabe, K., and Taguchi, S. (eds.), Proceedings of the International Symposium on Gold

1091 and Hydrothermal Systems, November 4, 2001, Kyushu University, Fukuoka, Japan, p. 25-36.

1092 Sajona, F. G., Izawa, E., Motomura, Y., Imai, A., Sakakibara, H., and Watanabe, K., 2002, Victoria

1093 carbonate-base metal gold deposit and its significance in the Mankayan mineral district,

1094 Luzon, Philippines: Resource Geology, v. 52, p. 315-328.

1095 Sakakibara, F., Sajona, F.F., Cuncan, R.A., Watanabe, K., and Izawa, E., 2001, Hydrothermal

1096 alteration and mineralization age of the Victoria gold deposit, Mankayan mineral district,

1097 Philippines: in Izawa, E., Watanabe, K., and Taguchi, S. (eds.), Proceedings of the

1098 International Symposium on Gold and Hydrothermal Systems, November 4, 2001, Kyushu

1099 University, Fukuoka, Japan, p. 71-76.

1100 Shinohara, H., and Hedenquist, J.W., 1997, Constraints on magma degassing beneath the Far

1101 Southeast porphyry Cu-Au deposit, Philippines: Journal of Petrology, v. 38, p. 1741-1752.

1102 Sillitoe, R.H., 1983, Enargite-bearing massive sulfide deposits high in porphyry copper systems:

1103 Economic Geology, v. 78, p. 348-352.

1104 Sillitoe, R.H., 1993, Epithermal models: Genetic types, geometrical controls and shallow features:

1105 in Kirkham, R.V., Sinclair, W.D., Thorpe, R.I. and Duke, J.M., eds., Geological Association

1106 of Canada Special Paper 40, p. 403-417.

1107 Sillitoe, R.H., 1995a, Exploration of porphyry copper lithocaps: Publication Series - Australasian

1108 Institute of Mining and Metallurgy, v.9/95, p. 527-532.

1109 Sillitoe, R.H., 1995b, Exploration and discovery of base- and precious-metal deposits in the

1110 Circum-Pacific region during the last 25 years: Resource Geology, Special issue 19, 119 p.

1111 Sillitoe, R.H., 1999, Styles of high-sulphidation gold, silver and copper mineralization in the

1112 porphyry and epithermal environments: in Australian Institute of Mining and Metallurgy,

1113 PacRim 99, Bali, Indonesia, 10- 13 October, Proceedings, p. 29-44.

1114 Sillitoe, R.H., Porphyry copper systems: Economic Geology, v. 106, in press.

44
1115 Sillitoe, R.H., and Angeles, C.A., Jr., 1985, Geological characteristics and evolution of a gold-rich

1116 porphyry copper deposit at Guinaoang, Luzon, Philippines: in Asian Mining '85, Manila,

1117 Philippines, February 11-14, Institute of Mining and Metallurgy, London, p. 15-26.

1118 Sillitoe, R.H., and Gappe, I.M. Jr., 1984, Philippine porphyry copper deposits: Geologic setting and

1119 characteristics: Bangkok, United Nations ESCAP, CCOP Technical Publication 14, 89 p.

1120 Sillitoe, R.H., and Hedenquist, J.W., 2003, Linkages between volcanotectonic settings, ore-fluid

1121 compositions, and epithermal precious-metal deposits: in Simmons, S.F., and Graham, I.J.,

1122 (eds.), Volcanic, geothermal and ore-forming fluids: Rulers and witnesses of processes within

1123 the Earth: Society of Economic Geologists and Geochemical Society, Special Publication 10,

1124 Chapter 16, p. 315-343.

1125 Steven, T.A., and Ratt, J.C., 1960, Geology and ore deposits of the Summitville District, San Juan

1126 Mountains, Colorado: U. S. Geological Survey Professional Paper 343, 70 p.

1127 Stoffregen, R.E., and Cygan, G.L., 1990, An experimental study of Na-K exchange between alunite

1128 and aqueous sulfate solutions: American Mineralogist, v. 75, p. 209-220.

1129 Tejada, M.L.G., 1989, Characteristics of paragenesis of luzonite in the Lepanto copper-gold

1130 deposit, Mankayan, Benguet, Philippines: Unpublished M.Sc. thesis, National Institute of

1131 Geological Sciences, University of the Philippines, 89 p.

1132 Thompson, A.J.B., Hauff, P.L., and Robitaille, A.J., 1999, Alteration mapping in exploration:

1133 application of short-wave infrared (SWIR) spectroscopy: SEG Newsletter, v. 39, p. 1627.

1134 Trudu, A.G., 1992, The Tirad porphyry copper-gold prospect (Guinaoang, NW Luzon, Philippines),

1135 with a special study on tellurian sulfides: PhD dissertation. Monash University, 6 parts.

1136 White, N.C., 1991, High sulfidation epithermal gold deposits: Characteristics and a model for their

1137 origin: Geological Survey of Japan Report, No. 277, p. 9-20.

1138

45
1138 Captions:

1139

1140 Fig. 1. Geologic map of the Mankayan district (modified from Garcia, 1991, Garcia, unpublished,

1141 and this study, plus Sillitoe and Angeles, 1985, for Guinaoang). The alteration mineral zones shown

1142 are for surface outcrops. Position of Lepanto high-sulfidation deposit (red outline), Far Southeast

1143 porphyry mineralization (brown), Victoria-Teresa ore veins (thin red and brown lines), and

1144 Guinaoang, Buaki, and Palidan porphyry mineralization (brown outlines) are surface projections of

1145 largely underground orebodies (the barren core of Guinaoang is shown). Suyoc is off the map area,

1146 ~1 km southeast of Palidan. There is only one area of enargite-luzonite-Au mineralization that

1147 outcrops along the Lepanto fault trace at the Spanish workings. The elongated, roughly E-W high-

1148 sulfidation orebodies to the south of the main Lepanto body and to the west of Far Southeast are

1149 called Branch Veins. The quartz-alunite zone includes traces of pyrophyllite, as well as dickite

1150 kaolinite. The dickite kaolinite zone locally includes pyrophyllite or diaspore over the Teresa

1151 vein. White mica is illite or muscovite, but also has been mapped using the field term sericite

1152 prior to this study. The two breccias are the diatreme breccia with porphyry-style alteration and

1153 mineralized lithic fragments above the Lepanto orebody and the hydrothermal breccia above the

1154 northeast portion of the Far Southeast deposit. Dashed line shows the positions of schematic long

1155 section (Fig. 3) and the dotted line shows the position of cross section through Lepanto orebody and

1156 lithocap (Fig. 4); locations of Figs. 6a, 6b, and 8a are also shown.

1157

1158 Fig. 2. Contours (blue) of the elevation of the unconformity between the basement and the

1159 Imbanguila units (from Garcia, 1991), from drill hole information. Two likely vents of the

1160 Imbanguila units can be seen. Outcrops of the quartz-alunite lithocap are also shown, with the

1161 elevation labeled (green).

1162

46
1163 Fig. 3. Schematic long section (northwest-southeast dashed line, Fig. 1) along the plane of the

1164 Lepanto fault, showing the location of the Lepanto enargite-Au orebody. The position of the FSE

1165 porphyry mineralization is projected from the northeast, about 250 m away. Section turns south at

1166 the southeast end of the Lepanto deposit and cross the Victoria veins. Modified from Hedenquist et

1167 al. (2001).

1168

1169 Fig. 4. Cross section through the Lepanto fault (location shown in Fig 1), illustrating the mushroom

1170 nature of the silicic and advanced argillic altered zones at the unconformity between basement and

1171 Imbanguila units (modified from Gonzalez, 1956; Garcia, 1991). The main orebody constitutes ~70

1172 percent of the Lepanto enargite-Au ore and is hosted by the Lepanto fault. The rest of the mined ore

1173 was from stratabound bodies located at the unconformity, as well as above and below this contact

1174 and in subsidiary east-west structures, adjacent to the Lepanto fault (Garcia, 1991). Where the

1175 unconformity is intersected by erosion to the southwest, approximately parallel to the trace of the

1176 Lepanto fault, quartz-alunite alteration zone is exposed (Fig. 1), commonly forming cliffs (e.g.,

1177 shown here to the southwest of the Lepanto fault). Over and beneath the quartz-alunite zone, the

1178 alteration is characteristically dickite kaolinite, e.g., where exposed at the northwest end of the

1179 airstrip (Fig. 6a).

1180

1181 Fig. 5. Photographs showing the cross-cutting relationship between alteration related to high- and

1182 intermediate-sulfidation epithermal mineralization. a) Quartz-pyrite vein cuts quartz-alunite-

1183 pyrophyllite-pyrite assemblage. b) Anhydrite + pyrite veins cut massive quartz + diaspore + pyrite

1184 assemblage.

1185

1186 Fig. 6. a) Northwest end of the airstrip, ~4 km northwest of the surface projection of the Far

1187 Southeast porphyry deposit, showing the quartz-alunite cliff outcrops and dickite + kaolinite

1188 alteration over and beneath them. Looking to the north. b) Mohong Hill lithocap of quartz + alunite,

47
1189 forming cliffs above the exposed sericite alteration zone of the Palidan porphyry, in the valley to the

1190 right. Looking to the north.

1191

1192 Fig. 7. Cathodoluminescence (CL) image shows that massive silicic rocks contain vugs that have

1193 been filled with quartz. The CL texture of the infilling quartz indicates that they have grown in open

1194 space. The rest of the rock, i.e., the matrix of the vugs, consists of micron-size quartz and trace

1195 rutile. The observation indicates that this massive silicic rock was originally vuggy in texture.

1196

1197 Fig. 8a. Detailed mapping of surface alteration above the Victoria intermediate-sulfidation

1198 epithermal veins, with illite and smectite zones distinguished by PIMA and XRD. Previous

1199 alteration mapping, outside the dashed line, is also shown with same color for the same units but a

1200 lighter shade. Lepanto ore plus Victoria-Teresa veins are projected to the surface. The quartz-

1201 alunite alteration is associated with limited silicic alteration, and can also contain trace pyrophyllite

1202 or dickite kaolinite; the dickite kaolinite zone can also contain traces of pyrophyllite. Halloysite

1203 smectite zone without pyrite is interpreted to be largely due to weathering, since igneous-rock

1204 magnetite is still present.

1205

1206 Fig. 8b. Pseudo-cross section from quartz-alunite alteration in distal Branch vein area, southeast to

1207 the Victoria veins, then north to the Far Southeast area (Fig. 8a), with alteration zoning from surface

1208 as well as subsurface workings (locations of subsurface samples from 1150 mL crosscut shown).

1209 Approximate upper limits of the veins from underground workings plus drill hole information.

1210 Areas where there is only halloysite smectite and fresh-rock magnetite are interpreted to have

1211 suffered weathering (or at most very weak alteration), supported by the lack of pyrite; this unaltered

1212 zone must extend to some depth. Subtle alteration zone of smectite + pyrite appears to be a halo at

1213 the surface, up to a few 100s m over the tops of the veins; there is no control on its depth extent or

1214 distribution. Illite crystallinity (IC) determined by PIMA; values
1.0 are dominantly illite, whereas

48
1215 values
0.5 are dominantly smectite (surface samples); illite/smectite refers to interlayered clays.

1216 Some of the zones noted as silicic quartz-alunite contain quartz-alunite at the surface; dickite

1217 kaolinite locally includes pyrophyllite.

1218

1219 Fig. 9. a) Alunite absorption feature at ~1480 nm shifts to higher SWIR wavelength position

1220 towards intrusive center. b) Wavelength position of alunite ~1480 nm feature (average; at least 3

1221 measurements per sample) has positive correlation with alunite Na/(Na+K) mole ratio (microprobe

1222 data; average of 7 to 11 analyses). The error bars are 1 sigma for both variables. c) The Ca content

1223 of alunite is higher closer to intrusive center, with huangite observed close to the surface projection

1224 of the Far Southeast porphyry (blue stars); samples from surface lithocap, plus three from

1225 underground, with multiple analyses of each sample. d) Alunite Pb content measured by LA-ICP-

1226 MS, with multiple analyses for each sample. Intra-sample variation is much smaller than the total

1227 range of the whole dataset. 1 - MK04-08B; 2 - 816829; 3 - MK04-04A; 4 - MK04-39a; 5 - U89-34-

1228 630; 6 - U91-42-156; 7 - 816803; 8 - MK04-01A; 9 - MK04-03B; 10 - MK04-100; 11 - 816813; 12

1229 - MK04-87E; 13 - MK04-107; 14 - 816831; 15 - MK04-65A; 16 - 816811; 17 - 817010; 18 -

1230 MK04-92c

1231

1232 Fig. 10. a) Alunite Pb content decreases towards intrusive center. Samples of alunite from surface

1233 lithocap, plus two from underground, analyzed by LA-ICP-MS, with multiple analyses for each

1234 sample. b-d) Whole-rock Pb concentrations of non-mineralized samples (Cu<0.1 wt% and Au <100

1235 ppb): b) Only alunite-bearing samples are plotted; whole rock Pb concentration decreases towards

1236 intrusive center. c) All the non-mineralized samples are plotted without the mineralogical

1237 discrimination; the trend is less clear. d) For samples containing alunite, the molar Pb/(Na + K)

1238 ratio of whole rock data has the same trend as alunite Pb content (Fig. 10a), indicating the Pb is

1239 mostly in alunite, and the ratio can be used as a proxy of alunite Pb content.

1240

49
1241 Fig. 11. Gold content of surface lithocap samples. Dashed lines show outcrops with silicic and/or

1242 advanced argillic alteration, including dickite kaolinite pyrite zones. Mineral deposits on the

1243 map are surface projections. Surface samples from the Mankayan lithocap, even a few hundred

1244 meters from the ore body, have low gold anomalies of 1 to 46 ppb, averaging 12 ppb (n = 25).

1245 Exception to these values are for samples collected along structures with silicic alteration, most of

1246 which contain visible enargite; in these cases, gold values were >1 g/t.

1247

1248 Fig. 12. Surface and underground non-mineralized samples (Cu > 0.1 wt% and Au >100 ppb). a)

1249 Only alunite-bearing samples plotted; whole rock Hg concentration decreases towards intrusive

1250 center. b) All the non-mineralized samples are plotted without the mineralogical discrimination; the

1251 trend is less clear.

1252

1253 Fig. 13. Surface geochemical anomalies over the Victoria and Teresa veins (alteration results in Fig.

1254 8a). a) Arsenic concentrations, with >8 ppm As being anomalous in the white mica + pyrite zone,

1255 250 to 350 m above the tops of veins in the main Victoria zone. The least-altered rocks contain ~0.2

1256 ppm As. b) Se concentrations, with >0.5 ppm Se being anomalous; least-altered rock values ~0.1

1257 ppm Se.

1258

1259 Fig. 14. Image showing magnetic data after RTP transformation by World Geoscience, overlain by

1260 the positions of ore deposits and surface alteration. The dashed lines show areas of silicic and/or

1261 advanced argillic alteration. Red=magnetic high, blue=low.

1262

1263 Fig. A1: Sample MKU04-44, Teresa vein, 900 mL; 1-4 micron fraction of illite. This wall rock

1264 sample is in the footwall, 2 m from a ~50 cm wide vein. It contains ~0.6 ppm Au (ACME AA-Litho

1265 Package). Dated by the Oregon State University Ar-Ar laboratory.

1266

50
1267 Fig. A2. Examples of normalized hull quotient Short Wavelength Infra-Red (SWIR) spectra of

1268 alunite, including huangite.

1269

1270 Fig. A3. Surface and underground samples. a) Alunite Ag/Au ratio decreases towards intrusive

1271 center. b) Alunite Ag content not regular. c-d show whole rock geochemistry of selected samples

1272 (Cu < 0.1 wt % and Au < 100 ppb and alunite-bearing). c) Whole-rock Ag/Au ratio decreases

1273 towards intrusive center. d) Whole-rock Ag content decreases towards intrusive center.

1274

1275 Fig. A4. Surface and underground samples. a) Alunite Sr content increases towards intrusive center.

1276 b) Alunite Sr/Pb ratio increases towards intrusive center. c-d show whole rock geochemistry of

1277 selected samples (Cu < 0.1 wt % and Au < 100 ppb and alunite-bearing). c) Whole-rock Sr

1278 concentration has a weak trend of increase towards intrusive center. d) Whole-rock Sr/Pb ratio

1279 increases towards intrusive center.

1280

1281 Fig. A5. Surface and underground samples. a) Alunite La content increases towards intrusive

1282 center. b) Alunite La/Pb ratio increases towards intrusive center. c-d show whole rock geochemistry

1283 of selected samples (Cu < 0.1 wt % and Au < 100 ppb and alunite-bearing). c) Whole-rock La

1284 concentration has a weak trend of increase towards intrusive center. d) Whole-rock La/Pb ratio

1285 increases towards intrusive center.

1286

1287 Table A1 Alunite major elements determined using microprobe

1288 Table A2 Alunite trace elements determined using LA-ICP-MS

1289 Table A3 Whole rock composition analysis protocols (Anglo American package AA group LITHO,

1290 ACME Lab, Vancouver, Canada).

1291 Data repository (Excel file): Whole rock chemistry: surface and underground samples

51
Fig. 1
Fig. 2
Fig. 3

Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8a

Fig. 8b
 Fig. 9a Fig. 9b

Fig. 9c Fig. 9d

Fig. 9
 Fig. 10a Fig. 10b

Fig. 10c Fig. 10d

Fig. 11
 Fig. 12a Fig. 12b

Fig. 12

Fig. 13a Fig. 13b

Fig. 13
Fig. 14
Figures in Appendix

Fig. A1
Fig. A2
 Fig. A3-a Fig. A3-b

Fig. A3-c Fig. A3-d

Fig. A3
 Fig. A4-a Fig. A4-b

Fig. A4-c Fig. A4-d

Fig. A4
 Fig. A5-a Fig. A5-b

Fig. A5-c Fig. A5-d

Fig. A5
Appendix Table A1 Major elements composition of alunite measured using microprobe

Sample Na% Al% P% S% K% Ca% Fe% Sr% Ba% H% O% Sum

816803 2.61 20.15 0.04 15.22 3.28 0.07 0.06 0.06 0.11 1.46 54.08 97.14
816803 1.63 20.19 0.04 14.76 5.67 0.29 0.06 0.06 0.10 1.46 53.67 97.92
816803 1.61 20.08 0.05 14.42 5.43 0.25 0.05 0.06 0.09 1.46 53.01 96.51
816803 1.60 20.17 0.06 15.20 4.94 0.85 0.04 0.13 0.11 1.46 54.43 99.00
816803 1.54 20.25 0.03 15.09 5.50 0.67 0.05 0.19 0.10 1.46 54.32 99.19
816803 1.30 20.05 0.03 14.87 6.26 0.39 0.05 0.13 0.09 1.46 53.77 98.43
816803 1.23 20.01 0.05 14.71 5.98 0.42 0.06 0.15 0.09 1.46 53.44 97.58
816803 1.20 19.93 0.05 14.79 6.60 0.37 0.05 0.12 0.11 1.46 53.59 98.27
816803 1.07 20.12 0.05 14.72 6.88 0.18 0.06 0.06 0.10 1.46 53.57 98.25
816811 2.90 20.13 0.05 15.28 3.83 0.25 0.06 0.06 0.10 1.46 54.47 98.60
816811 1.44 19.96 0.04 15.08 6.48 0.09 0.05 0.06 0.09 1.46 53.96 98.69
816811 0.62 19.46 0.04 15.01 8.01 0.02 0.05 0.06 0.10 1.46 53.43 98.26
816811 0.56 19.27 0.04 14.62 8.14 0.02 0.06 0.17 0.11 1.46 52.71 97.16
816811 0.52 19.75 0.04 14.95 8.23 0.03 0.05 0.06 0.11 1.46 53.60 98.80
816811 0.38 19.77 0.05 14.72 8.59 0.03 0.18 0.19 0.11 1.46 53.39 98.87
816811 0.27 19.80 0.07 14.71 8.62 0.03 0.05 0.06 0.10 1.46 53.31 98.47
816813 2.82 20.21 0.05 14.74 3.55 0.12 0.04 0.25 0.10 1.46 53.63 96.98
816813 2.51 19.91 0.23 15.05 3.03 0.18 0.10 0.24 0.36 1.46 53.91 96.99
816813 2.48 20.18 0.04 15.12 3.22 0.03 0.05 0.16 0.11 1.46 53.92 96.77
816813 2.42 20.02 0.04 14.87 3.56 0.03 0.05 0.30 0.11 1.46 53.47 96.33
816813 2.39 19.87 0.05 14.89 4.52 0.03 0.06 0.15 0.25 1.46 53.56 97.22
816813 2.30 19.78 0.07 14.36 4.11 0.05 0.05 0.29 0.12 1.46 52.61 95.20
816813 2.30 20.05 0.04 14.72 4.53 0.03 0.06 0.19 0.12 1.46 53.42 96.92
816813 1.45 19.36 2.76 11.61 2.48 1.61 0.06 3.92 0.53 1.46 52.30 97.53
816813 1.34 18.89 4.11 10.67 1.96 1.52 0.11 6.16 0.79 1.46 52.51 99.52
816813 0.13 17.89 7.31 6.66 0.16 2.54 0.05 11.66 0.88 1.46 50.35 99.08
816813 0.03 17.73 8.04 6.05 0.03 3.04 0.06 10.60 1.12 1.46 50.21 98.37
816813 0.03 17.85 7.93 5.78 0.03 2.53 0.06 12.61 0.86 1.46 49.90 99.03
817010 2.18 20.11 0.04 15.03 3.81 0.03 0.05 0.06 0.11 1.46 53.72 96.58
817010 2.06 19.97 0.06 15.27 4.48 0.03 0.04 0.18 0.11 1.46 54.10 97.77
817010 2.05 19.99 0.05 15.09 4.46 0.03 0.05 0.12 0.11 1.46 53.82 97.23
817010 1.72 19.68 0.04 14.83 5.39 0.03 0.06 0.06 0.12 1.46 53.20 96.59
817010 1.44 19.73 0.00 14.65 6.52 0.03 0.10 0.16 0.12 1.46 53.10 97.31
817010 1.13 19.78 0.06 14.55 6.90 0.03 0.06 0.15 0.23 1.46 53.03 97.38
817010 1.11 19.64 0.05 14.78 7.12 0.03 0.10 0.13 0.10 1.46 53.27 97.78
817010 0.72 19.35 0.04 14.57 7.40 0.02 0.06 0.15 0.11 1.46 52.60 96.49
950ml 130FZ XC 2.08 20.07 0.05 15.08 4.76 0.03 0.05 0.59 0.12 1.46 54.01 98.29
950ml 130FZ XC 2.00 19.77 0.05 15.01 4.69 0.03 0.05 0.25 0.12 1.46 53.56 96.99
950ml 130FZ XC 1.99 19.86 0.09 14.96 4.69 0.03 0.05 0.26 0.12 1.46 53.62 97.13
950ml 130FZ XC 1.97 19.94 0.04 14.65 3.69 0.16 0.06 0.29 0.12 1.46 53.01 95.39
950ml 130FZ XC 1.88 19.75 0.04 14.85 4.44 0.03 0.06 0.46 0.12 1.46 53.23 96.31
950ml 130FZ XC 1.85 19.89 0.05 14.85 4.76 0.16 0.06 0.53 0.30 1.46 53.51 97.42
950ml 130FZ XC 1.79 19.83 0.04 15.14 5.00 0.03 0.05 0.36 0.12 1.46 53.78 97.59
950ml 130FZ XC 1.69 19.67 0.04 15.29 5.54 0.03 0.05 0.35 0.12 1.46 53.95 98.18
950ml 130FZ XC 1.66 19.64 0.05 15.19 5.13 0.03 0.06 0.45 0.11 1.46 53.72 97.50
MK04-01A 3.00 20.46 0.06 15.41 1.03 0.17 0.44 0.06 0.11 1.46 54.56 96.75
MK04-01A 2.80 20.47 0.05 15.30 1.79 0.10 0.14 0.19 0.12 1.46 54.34 96.76
MK04-01A 2.78 20.45 0.06 15.18 1.09 0.14 0.58 0.13 0.12 1.46 54.20 96.20
MK04-01A 2.67 20.53 0.05 15.33 1.33 0.12 0.15 0.06 0.10 1.46 54.30 96.10
MK04-01A 2.63 20.43 0.05 15.25 1.85 0.11 0.30 0.06 0.12 1.46 54.25 96.51
MK04-01A 2.62 20.44 0.05 15.44 1.78 0.10 0.49 0.12 0.12 1.46 54.60 97.23
Sample Na% Al% W% S% K% Ca% Fe% Sr% Ba% H% O% Sum

MK04-01A 2.61 20.01 0.05 14.80 1.84 0.20 0.06 0.25 0.13 1.46 53.16 94.57
MK04-01A 2.57 20.50 0.05 15.33 1.04 0.17 0.13 0.06 0.12 1.46 54.19 95.62
MK04-01A 2.48 20.57 0.04 15.06 1.39 0.16 0.13 0.06 0.11 1.46 53.86 95.32
MK04-01A 2.39 20.14 0.05 15.19 1.78 0.03 0.10 0.06 0.12 1.46 53.67 94.99
MK04-08B 3.39 20.58 0.05 15.19 0.71 0.20 0.06 0.06 0.12 1.46 54.24 96.06
MK04-08B 3.28 20.11 0.05 15.37 1.04 0.42 0.05 0.06 0.12 1.46 54.21 96.17
MK04-08B 3.03 20.57 0.04 14.96 1.35 0.03 0.19 0.06 0.12 1.46 53.87 95.67
MK04-08B 2.62 20.37 0.05 15.27 0.91 0.29 0.20 0.06 0.12 1.46 54.05 95.39
MK04-08B 2.61 20.57 0.05 15.20 0.93 0.29 0.13 0.06 0.11 1.46 54.09 95.49
MK04-08B 2.46 20.59 0.05 15.16 0.54 1.01 0.15 0.12 0.11 1.46 54.21 95.84
MK04-08B 1.96 20.56 0.04 15.55 0.35 3.05 0.14 0.06 0.13 1.46 55.36 98.66
MK04-08B 1.19 20.68 0.04 15.45 0.63 3.41 0.06 0.06 0.12 1.46 55.21 98.32
MK04-08B 0.90 20.74 0.07 15.61 0.52 3.89 0.27 0.06 0.13 1.46 55.69 99.33
MK04-100 2.17 20.12 0.06 15.34 2.56 0.03 0.06 0.18 0.12 1.46 53.98 96.08
MK04-100 0.91 19.79 0.04 14.67 7.31 0.08 0.05 0.13 0.12 1.46 53.20 97.75
MK04-100 0.69 19.75 0.05 14.65 7.44 0.03 0.06 0.06 0.12 1.46 53.07 97.38
MK04-100 0.67 19.78 0.04 14.79 7.66 0.05 0.05 0.13 0.11 1.46 53.35 98.10
MK04-100 0.55 19.68 0.05 14.86 8.13 0.08 0.06 0.16 0.12 1.46 53.44 98.58
MK04-100 0.52 19.89 0.05 14.78 8.01 0.03 0.05 0.16 0.11 1.46 53.45 98.50
MK04-100 0.52 19.64 0.06 14.55 7.94 0.09 0.06 0.16 0.11 1.46 52.92 97.51
MK04-100 0.52 19.62 0.09 14.42 8.41 0.07 0.05 0.15 0.13 1.46 52.84 97.76
MK04-100 0.48 19.86 0.10 14.60 8.25 0.03 0.05 0.16 0.13 1.46 53.26 98.37
MK04-100 0.48 19.47 0.05 14.65 8.20 0.03 0.05 0.20 0.12 1.46 52.93 97.64
MK04-100 0.46 19.66 0.06 14.48 8.16 0.03 0.06 0.17 0.12 1.46 52.82 97.46
MK04-107 2.27 20.04 0.05 15.14 4.50 0.07 0.05 0.14 0.12 1.46 54.03 97.86
MK04-107 2.18 20.40 0.04 15.11 3.66 0.06 0.06 0.13 0.12 1.46 54.09 97.32
MK04-107 2.16 20.19 0.06 14.63 3.74 0.17 0.05 0.06 0.12 1.46 53.26 95.91
MK04-107 1.90 20.05 0.06 14.89 3.96 0.17 0.05 0.06 0.12 1.46 53.46 96.18
MK04-107 1.88 20.14 0.03 15.01 4.20 0.11 0.05 0.16 0.11 1.46 53.73 96.88
MK04-107 1.85 20.12 0.10 15.05 4.35 0.16 0.05 0.24 0.12 1.46 53.92 97.43
MK04-107 1.85 20.06 0.05 15.11 3.76 0.15 0.05 0.19 0.12 1.46 53.77 96.59
MK04-107 1.73 19.96 0.05 15.25 4.66 0.14 0.05 0.22 0.11 1.46 54.02 97.65
MK04-107 1.38 19.70 0.08 14.87 5.72 0.06 0.06 0.18 0.12 1.46 53.30 96.92
MK04-39A 4.92 20.62 0.04 15.59 0.37 0.29 0.06 0.06 0.09 1.46 55.37 98.88
MK04-39A 4.70 20.59 0.06 15.37 0.73 0.26 0.05 0.06 0.11 1.46 55.01 98.38
MK04-39A 4.67 20.91 0.05 15.58 0.60 0.18 0.05 0.06 0.09 1.46 55.54 99.20
MK04-39A 3.36 20.60 0.04 15.67 1.14 1.60 0.06 0.06 0.10 1.46 55.61 99.70
MK04-39A 3.18 20.52 0.05 15.48 0.88 1.63 0.06 0.06 0.10 1.46 55.17 98.60
MK04-39A 2.55 20.77 0.04 15.31 0.69 2.34 0.04 0.06 0.10 1.46 55.12 98.48
MK04-39A 2.19 20.78 0.04 15.80 0.75 2.65 0.06 0.06 0.10 1.46 55.89 99.78
MK04-39A 1.36 20.61 0.04 15.20 0.50 3.44 0.05 0.06 0.11 1.46 54.80 97.61
U89-34-630 3.09 20.40 0.05 15.26 0.63 0.31 0.05 0.18 0.13 1.46 54.14 95.71
U89-34-630 2.76 20.38 0.04 15.12 1.69 0.40 0.05 0.06 0.11 1.46 54.01 96.08
U89-34-630 2.66 20.42 0.05 15.42 1.17 0.20 0.05 0.15 0.11 1.46 54.30 96.01
U89-34-630 2.49 20.24 0.05 15.21 2.70 0.19 0.06 0.21 0.12 1.46 54.09 96.81
U89-34-630 2.47 20.32 0.06 15.36 1.97 0.56 0.05 0.18 0.12 1.46 54.38 96.92
U89-34-630 2.45 20.38 0.05 15.23 2.16 0.39 0.05 0.06 0.11 1.46 54.17 96.52
U89-34-630 2.32 20.30 0.06 15.32 1.75 0.36 0.05 0.12 0.11 1.46 54.10 95.93
U89-34-630 2.15 20.18 0.04 15.52 3.79 0.27 0.06 0.18 0.12 1.46 54.61 98.38
U89-34-630 2.06 20.12 0.04 15.01 4.22 0.13 0.05 0.19 0.11 1.46 53.81 97.20
U89-34-630 1.99 19.90 0.04 15.15 4.53 0.10 0.05 0.26 0.12 1.46 53.85 97.44
 Sample Na% Al% W% S% K% Ca% Fe% Sr% Ba% H% O% Sum

U91-42-156 2.90 20.47 0.05 14.98 3.34 0.16 0.06 0.22 0.10 1.46 54.20 97.93
U91-42-156 2.55 20.11 0.04 15.16 3.69 0.16 0.06 0.16 0.11 1.46 54.08 97.57
U91-42-156 2.50 20.34 0.05 14.89 3.43 0.17 0.27 0.19 0.11 1.46 53.93 97.34
U91-42-156 2.29 20.51 0.04 15.03 3.04 0.18 0.40 0.21 0.11 1.46 54.18 97.45
U91-42-156 2.19 20.16 0.05 14.59 4.85 0.03 0.19 0.48 0.11 1.46 53.47 97.59
U91-42-156 2.09 20.41 0.07 14.85 3.74 0.12 0.05 0.28 0.10 1.46 53.79 96.96
U91-42-156 1.78 20.17 0.04 14.99 4.37 0.09 0.15 0.39 0.11 1.46 53.81 97.35
U91-42-156 1.47 19.91 0.05 14.81 5.84 0.06 0.05 0.18 0.10 1.46 53.42 97.35
U91-42-156 1.40 20.11 0.03 15.06 6.34 0.03 0.06 0.26 0.11 1.46 54.03 98.87

Beam size = 15
, Voltage = 15 kV, Current = 10 nA

Appendix Table A2 Trace elements composition (ppm) of alunite measured using LA-ICP-MS

Sample Mn Fe Cu As Se Sr Zr Ag Sb Ba La Ce Nd Sm Eu Gd Dy Er Yb Lu Au Pb Bi

U91-42-156 0.6 681 0.9 0.8 1.9 3565 0.2 0.1 0.1 573 3.8 6.7 0.8 0.1 0.1 0.1 0.0 0.0 0.0 0.0 0.1 262 0.4
U91-42-156 1.1 443 3.2 1.2 0.6 3619 1.1 0.1 0.0 612 3.5 5.4 0.6 0.1 0.1 0.0 0.0 0.0 0.0 0.0 0.0 139 0.2
U91-42-156 0.5 287 0.6 1.2 1.2 2582 0.0 0.1 0.1 379 2.6 4.0 0.5 0.0 0.1 0.0 0.0 0.0 0.0 0.0 0.1 129 0.2
U91-42-156 0.4 429 1.4 0.9 0.9 3895 0.8 0.1 0.0 621 2.7 3.9 0.6 0.0 0.1 0.1 0.0 0.0 0.0 0.0 0.0 96 0.1
U91-42-156 0.4 985 1.8 1.4 1.3 4356 0.0 0.1 0.0 713 3.0 4.4 0.6 0.0 0.1 0.1 0.0 0.0 0.0 0.0 0.0 148 0.2
U91-42-156 1.1 3172 10.3 6.7 1.0 2913 0.5 0.1 0.1 887 4.0 6.7 1.1 0.1 0.1 0.2 0.1 0.1 0.0 0.0 0.0 112 0.3
U91-42-156 0.9 1327 5.3 3.7 0.8 2101 0.2 0.1 0.1 475 2.2 3.3 0.4 0.1 0.1 0.0 0.1 0.0 0.0 0.0 0.1 91 0.2
U91-42-156 1.2 514 0.5 2.0 0.8 3264 0.4 0.1 0.1 597 3.4 5.4 0.8 0.1 0.1 0.1 0.0 0.0 0.0 0.0 0.0 160 0.6
U89-34-630 0.7 36 1.1 0.8 1.0 740 2.2 0.1 0.1 355 3.3 6.6 2.0 0.2 0.2 0.0 0.0 0.0 0.0 0.0 0.0 103 0.0
U89-34-630 0.4 43 0.5 1.0 1.2 938 0.0 0.1 0.1 494 4.5 9.4 2.4 0.4 0.3 0.1 0.0 0.0 0.0 0.0 0.1 86 0.0
U89-34-630 0.7 13 440.3 1.7 2.3 531 0.0 0.2 0.1 381 2.3 4.9 1.6 0.1 0.2 0.1 0.1 0.0 0.1 0.0 0.1 72 0.0
U89-34-630 1.2 105 0.6 1.6 1.1 1230 0.0 0.1 0.0 459 4.9 9.8 2.8 0.3 0.3 0.1 0.0 0.0 0.0 0.0 0.1 110 0.0
U89-34-630 1.0 138 1.5 0.8 1.4 3072 1.0 0.1 0.1 874 11.9 26.2 7.8 0.5 0.3 0.2 0.0 0.0 0.0 0.0 0.1 194 0.1
U89-34-630 1.9 195 1.5 1.8 2.2 2433 83.9 0.2 0.1 726 7.4 20.0 4.9 0.3 0.1 0.1 0.4 0.1 0.3 0.0 0.1 173 0.0
U89-34-630 0.4 157 0.7 1.1 1.3 925 0.0 0.1 0.1 1506 2.2 5.0 2.2 0.4 0.4 0.1 0.1 0.0 0.0 0.0 0.1 38 0.0
U89-34-630 1.4 20 2.3 3.6 3.1 235 0.1 0.3 0.2 188 1.4 2.8 1.0 0.1 0.0 0.1 0.1 0.0 0.1 0.0 0.2 35 0.0
816803 0.8 685 0.6 0.4 0.7 666 5.3 1.9 0.0 137 7.6 14.3 2.8 0.2 0.9 0.1 0.1 0.1 0.1 0.0 0.0 204 0.2
816803 1.2 8 0.5 0.4 0.8 535 33.9 10.1 0.1 78 5.8 11.0 1.8 0.1 0.7 0.4 0.6 0.3 0.4 0.1 0.1 101 0.8
816803 1.0 2188 0.6 2.3 1.1 339 5.2 2.9 0.2 204 2.9 7.2 4.5 1.1 0.4 0.4 0.2 0.1 0.0 0.0 0.1 79 0.5
816803 0.7 129 0.8 0.7 1.7 839 2.6 3.1 0.1 210 7.6 15.8 3.8 0.4 0.8 0.1 0.2 0.1 0.1 0.0 0.1 207 0.5
816803 1.1 3651 2.5 5.8 1.1 470 34.0 3.1 0.4 642 1.2 3.2 1.3 0.2 0.1 0.3 0.4 0.2 0.4 0.0 0.1 305 0.2
816803 0.4 7 0.8 1.2 1.1 1487 56.9 1.3 0.1 2361 14.5 38.9 24.4 4.8 1.9 2.9 1.7 0.7 0.7 0.1 0.0 386 0.4
816803 1.1 6481 0.7 13.9 1.0 638 8.4 7.2 0.1 165 6.1 12.2 3.0 0.4 0.6 0.1 0.3 0.1 0.0 0.0 0.1 179 0.9
816803 0.9 29 0.5 0.4 0.8 586 2.8 1.9 0.0 110 4.0 8.6 2.9 0.4 0.6 0.2 0.1 0.1 0.1 0.0 0.1 109 0.3
816811 1.8 359 10.4 8.2 27.4 624 0.2 0.8 0.2 750 18.8 10.8 4.3 0.3 0.1 0.1 0.1 0.0 0.0 0.0 0.0 1428 0.7
816811 3.1 3850 29.6 5.9 5.0 855 0.3 0.6 0.6 767 13.2 4.7 2.8 0.2 0.0 0.1 0.1 0.0 0.1 0.0 0.1 2709 0.8
816811 2.9 9532 76.1 7.1 3.8 693 0.3 0.1 0.7 759 15.9 5.5 3.1 0.3 0.1 0.0 0.0 0.0 0.0 0.0 0.1 1408 1.7
816811 2.3 550 4.4 1.3 1.3 741 0.2 0.2 0.4 394 8.9 3.5 1.8 0.1 0.0 0.1 0.0 0.0 0.0 0.0 0.1 2719 0.2
816811 21.0 4727 59.2 16.4 26.6 319 1.9 1.6 1.1 581 17.6 5.3 3.1 0.2 0.1 0.1 0.1 0.1 0.0 0.0 0.1 1267 4.8
816811 2.7 5635 49.7 6.2 1.6 631 2.3 0.6 0.4 914 10.1 4.5 2.6 0.3 0.1 0.1 0.1 0.0 0.0 0.0 0.1 871 0.5
816811 0.5 7 0.7 0.5 1.3 370 0.1 0.1 1.6 587 5.8 3.8 1.3 0.1 0.0 0.1 0.0 0.0 0.0 0.0 0.1 539 0.1
816813 0.9 73 1.5 13.3 1.8 1003 0.1 0.6 0.1 1427 2.5 5.4 1.6 0.2 0.2 0.0 0.0 0.0 0.0 0.0 0.0 229 0.1
816813 0.4 49 1.1 5.4 1.3 1003 0.0 0.1 0.2 1486 3.0 7.0 1.9 0.2 0.3 0.0 0.0 0.0 0.0 0.0 0.1 109 0.0
816813 0.7 108 2.2 49.8 3.4 1498 0.2 0.2 0.1 1163 4.0 6.4 1.8 0.1 0.1 0.0 0.1 0.0 0.0 0.0 0.1 720 0.1
816813 1.1 102 1.9 9.5 1.1 1679 68.9 0.1 0.1 2026 3.0 8.0 3.5 0.7 0.4 0.3 0.2 0.1 0.2 0.1 0.0 330 0.2
816813 0.5 104 1.5 8.7 1.9 1467 42.7 0.1 0.1 1483 2.4 6.7 2.8 0.5 0.3 0.3 0.1 0.1 0.2 0.0 0.1 334 0.1
816813 0.5 153 1.4 10.2 1.5 1988 0.1 0.1 0.1 2602 2.9 7.7 3.0 0.8 0.4 0.6 0.4 0.0 0.0 0.0 0.1 362 0.2
816813 0.4 67 1.0 8.3 1.4 1485 8.4 0.1 0.7 719 1.6 3.2 1.2 0.2 0.2 0.2 0.2 0.0 0.0 0.0 0.0 221 0.2
816829 0.4 137 3.7 0.9 1.3 326 0.0 0.1 0.0 54 0.0 0.1 0.1 0.1 0.1 0.1 0.1 0.0 0.0 0.0 0.0 9 0.0
816829 1.5 1800 3.4 1.2 1.6 277 0.3 0.1 0.1 40 1.9 7.5 18.6 6.8 2.4 6.9 1.7 0.2 0.0 0.0 0.1 24 0.3
816829 0.9 17 3.9 1.0 1.4 208 0.2 0.1 0.1 47 0.0 0.1 0.2 0.1 0.3 0.0 0.0 0.0 0.0 0.0 0.0 6 0.0
816829 0.6 1149 8.0 1.4 7.4 173 0.3 0.2 0.1 33 0.1 0.2 0.4 0.2 0.4 0.3 0.1 0.0 0.0 0.0 0.0 11 0.1
816829 1.5 265 2.2 1.0 1.3 386 42.4 0.1 0.1 63 1.2 6.4 14.6 7.2 2.5 8.7 1.7 0.3 0.6 0.1 0.0 18 0.1
816831 0.4 24 1.1 1.1 1.6 863 0.0 0.1 0.1 785 0.8 1.1 0.1 0.0 0.0 0.1 0.0 0.0 0.0 0.0 0.1 704 0.0
816831 2.5 28 78.0 9.7 1.2 1221 1.3 0.1 0.1 746 3.8 5.6 0.9 0.1 0.0 0.1 0.0 0.0 0.0 0.0 0.1 858 0.0
816831 4.7 711 50.7 9.9 0.9 737 0.4 0.1 0.0 566 3.5 5.4 1.1 0.1 0.0 0.0 0.1 0.0 0.0 0.0 0.1 646 0.0
816831 6.4 50 50.6 6.2 1.0 1005 0.3 0.1 0.1 630 4.7 6.5 1.4 0.1 0.0 0.0 0.0 0.0 0.0 0.0 0.1 695 0.0
816831 7.8 44 50.8 7.7 1.2 1104 0.6 0.2 0.2 684 3.7 5.6 1.3 0.2 0.0 0.1 0.1 0.0 0.0 0.0 0.1 571 0.0
816831 16.0 83 244.3 16.6 1.6 1012 0.2 0.1 0.1 722 4.4 6.3 1.4 0.1 0.0 0.1 0.0 0.0 0.0 0.0 0.0 923 0.0
816831 2.8 208 44.3 16.4 1.2 1321 0.9 0.1 0.1 1000 6.7 10.2 2.3 0.2 0.1 0.1 0.2 0.1 0.0 0.0 0.0 1249 0.0
816831 3.4 198 61.7 18.0 1.4 1361 0.1 0.1 0.1 962 8.3 12.6 2.8 0.2 0.0 0.0 0.0 0.0 0.0 0.0 0.0 1153 0.0
817010 1.1 428 78.8 171.4 1.0 202 0.8 5.0 0.7 765 0.9 1.8 1.2 0.1 0.0 0.2 0.1 0.0 0.0 0.0 0.1 2289 0.3
Sample Mn Fe Cu As Se Sr Zr Ag Sb Ba La Ce Nd Sm Eu Gd Dy Er Yb Lu Au Pb Bi

817010 0.5 192 15.5 127.6 0.9 230 2.7 4.3 0.2 644 0.9 2.1 1.2 0.1 0.0 0.1 0.1 0.0 0.0 0.0 0.1 2119 0.3
817010 3.3 8071 71.0 983.0 110.4 427 17.3 3.7 28.2 392 1.9 3.9 3.0 0.2 0.1 0.3 0.2 0.1 0.2 0.1 0.4 1885 7.3
817010 1.3 163 4.8 109.8 1.0 275 4.1 1.2 0.2 642 1.3 2.9 2.4 0.2 0.0 0.1 0.1 0.0 0.0 0.0 0.1 1867 0.3
817010 1.5 2052 139.2 255.8 2.0 198 3.6 12.5 4.2 277 1.3 2.8 1.9 0.1 0.0 0.3 0.3 0.0 0.0 0.0 0.1 1119 0.7
817010 0.6 638 49.8 158.7 1.4 258 0.3 4.3 0.9 508 1.2 2.8 1.6 0.1 0.0 0.2 0.1 0.0 0.0 0.0 0.1 1687 0.4
817010 0.9 8082 43.7 456.9 31.6 356 3.1 1.4 8.4 358 1.5 2.4 1.5 0.1 0.0 0.1 0.1 0.0 0.1 0.0 0.1 1827 3.5
817010 1.9 2646 16.6 95.3 107.5 352 1.7 1.3 1.5 364 0.7 1.3 0.7 0.1 0.0 0.1 0.1 0.0 0.1 0.0 0.1 1516 0.8
817010 1.1 3005 19.5 212.6 13.3 242 14.5 0.8 6.1 390 0.5 1.2 0.5 0.0 0.0 0.1 0.0 0.1 0.0 0.0 0.1 1636 2.8
817010 1.8 1419 12.2 97.9 5.2 240 4.6 1.0 1.6 534 0.3 0.7 0.3 0.1 0.0 0.0 0.1 0.0 0.0 0.0 0.1 1859 0.9
MK04-01A 0.8 127 0.9 2.0 1.1 1006 3.7 0.2 0.7 733 5.9 11.9 1.4 0.2 0.1 0.1 0.1 0.0 0.1 0.0 0.1 208 0.5
MK04-01A 1.2 1860 43.7 10.8 1.2 2015 19.3 0.1 0.4 1631 121.8 250.6 124.1 20.1 4.4 11.1 3.6 0.6 0.2 0.0 0.1 245 0.8
MK04-01A 0.9 512 10.6 3.8 1.6 2077 4.2 0.2 0.3 1072 15.7 26.2 4.8 0.5 0.2 0.3 0.2 0.1 0.1 0.0 0.1 209 0.5
MK04-03B 4.1 251 5.2 5.4 2.0 6570 0.5 0.1 0.4 4068 31.3 71.9 25.5 4.3 2.1 3.4 2.6 0.6 0.5 0.1 0.0 1207 0.1
MK04-03B 1.0 20 0.8 1.1 1.7 2172 0.0 0.1 0.1 2057 7.9 18.3 6.7 1.2 0.6 0.6 0.4 0.1 0.1 0.0 0.1 161 0.0
MK04-03B 2.4 31 0.9 3.9 2.0 2170 0.0 0.1 0.1 1249 9.5 20.2 6.0 1.0 0.6 0.8 0.9 0.2 0.1 0.0 0.1 115 0.0
MK04-03B 1.0 41 3.8 14.5 0.9 502 1.3 0.1 0.6 332 2.4 5.1 1.4 0.2 0.1 0.0 0.1 0.0 0.0 0.0 0.0 38 0.0
MK04-03B 0.6 52 1.2 3.8 2.0 1870 2.8 0.1 0.1 1297 5.4 10.6 2.6 0.3 0.3 0.3 1.3 0.2 0.1 0.0 0.1 131 0.0
MK04-03B 0.6 10 1.3 1.3 1.6 2325 0.1 0.1 0.1 1343 7.3 16.4 5.7 0.7 0.6 1.0 1.2 0.2 0.0 0.0 0.1 107 0.0
MK04-04A 0.4 30 13.3 3.9 39.0 301 0.5 0.1 0.2 145 1.2 3.0 1.0 0.2 0.1 0.2 0.2 0.2 0.1 0.0 0.1 56 0.3
MK04-04A 0.9 14 1.6 7.7 3.2 823 2.5 0.2 0.2 225 2.7 6.3 2.8 0.5 0.2 0.6 0.5 0.2 0.2 0.0 0.1 39 0.8
MK04-04A 0.4 9 0.7 3.6 1.7 170 0.5 0.1 0.1 78 1.0 2.5 0.9 0.2 0.1 0.1 0.1 0.1 0.1 0.0 0.1 24 0.2
MK04-04A 0.4 21 1.5 3.0 1.5 179 0.4 0.1 0.1 79 1.2 3.0 1.1 0.2 0.1 0.1 0.2 0.2 0.1 0.0 0.0 42 0.1
MK04-04A 0.7 16 1.5 2.2 2.9 278 0.1 0.2 0.1 126 1.5 4.2 1.1 0.3 0.1 0.1 0.2 0.1 0.0 0.0 0.2 32 0.5
MK04-04A 0.7 14 1.4 4.0 3.2 177 0.6 0.1 0.1 43 0.9 2.2 1.1 0.1 0.1 0.1 0.0 0.0 0.0 0.0 0.1 23 0.1
MK04-04A 0.5 7 0.9 1.3 1.8 199 4.0 0.1 0.1 69 1.1 2.5 1.2 0.5 0.1 0.1 0.2 0.1 0.1 0.0 0.1 9 0.4
MK04-04A 1.8 810 2.9 4.9 111.4 266 1.0 0.2 0.1 129 1.3 3.0 1.0 0.1 0.1 0.2 0.2 0.2 0.3 0.0 0.1 49 0.1
MK04-08B 2.2 6356 11.7 20.9 5.6 51 0.1 0.3 0.2 433 1.1 2.5 0.8 0.1 0.1 0.1 0.1 0.0 0.0 0.0 0.1 6 0.0
MK04-08B 0.8 33 0.9 2.4 1.4 34 0.1 0.2 0.1 162 0.3 0.6 0.5 0.1 0.3 0.1 0.0 0.0 0.0 0.0 0.1 4 0.6
MK04-08B 0.5 31 0.5 0.5 1.1 17 0.0 0.1 0.1 56 0.1 0.2 0.2 0.1 0.2 0.0 0.0 0.0 0.0 0.0 0.1 1 0.1
MK04-39A 0.7 147 2.9 2.5 1.0 1547 34.0 0.1 0.1 322 18.8 40.3 8.4 0.8 0.3 0.4 0.3 0.1 0.2 0.0 0.1 114 0.0
MK04-39A 0.5 153 414.8 2.3 1.2 1807 0.0 0.1 0.1 358 10.9 24.3 4.4 0.3 0.2 0.1 0.1 0.1 0.1 0.0 0.1 117 0.0
MK04-39A 0.4 35 0.5 1.3 0.8 794 0.0 0.1 0.0 220 10.5 19.8 3.5 0.2 0.2 0.1 0.0 0.0 0.0 0.0 0.1 65 0.0
MK04-39A 0.5 39 1.3 2.3 0.8 1124 0.3 0.1 0.0 283 12.9 24.1 4.0 0.2 0.2 0.1 0.0 0.0 0.0 0.0 0.1 96 0.0
MK04-39A 0.6 26 0.7 1.9 1.3 706 0.5 0.1 0.2 186 9.6 18.7 2.9 0.2 0.1 0.1 0.0 0.0 0.0 0.0 0.0 62 0.0
MK04-39A 0.8 284 0.5 0.5 1.0 209 0.2 0.1 0.5 48 8.9 17.5 2.2 0.1 0.0 0.1 0.0 0.0 0.0 0.0 0.1 16 0.1
MK04-39A 1.8 221 2.3 2.2 4.2 464 0.1 0.4 0.8 124 10.3 27.8 2.7 0.1 0.1 0.1 0.1 0.1 0.1 0.0 0.2 70 0.1
MK04-39A 2.4 359 2.8 2.2 4.4 396 0.2 0.4 1.6 100 8.3 21.0 1.8 0.2 0.1 0.2 0.2 0.1 0.2 0.0 0.2 44 0.1
MK04-65A 0.5 112 3.1 102.6 1.5 2125 0.0 0.1 3.3 1006 3.1 4.4 0.6 0.0 0.1 0.0 0.1 0.0 0.0 0.0 0.0 1946 1.3
MK04-65A 0.7 203 9.8 197.9 3.9 2418 0.5 0.2 6.4 948 3.8 6.0 0.8 0.1 0.0 0.1 0.0 0.0 0.0 0.0 0.1 2655 2.5
MK04-65A 0.6 48 1.1 53.2 2.3 1385 0.0 0.4 1.7 619 2.3 3.6 0.4 0.1 0.1 0.1 0.0 0.0 0.0 0.0 0.1 809 0.8
MK04-65A 0.4 103 2.9 32.8 1.6 1606 0.0 0.1 0.3 633 2.6 3.8 0.8 0.1 0.0 0.1 0.1 0.0 0.0 0.0 0.1 854 0.1
MK04-65A 0.4 50 3.2 35.6 1.9 1193 0.0 0.1 1.3 514 1.5 2.2 0.2 0.1 0.0 0.1 0.0 0.0 0.0 0.0 0.1 813 0.4
MK04-65A 0.4 118 4.5 94.2 2.7 2304 0.1 0.1 2.9 874 3.6 5.4 0.8 0.1 0.1 0.1 0.0 0.0 0.0 0.0 0.1 1693 1.1
MK04-87E 11.0 634 55.9 10.5 1.5 67 0.3 1.9 1.0 117 0.2 0.6 0.2 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 91 0.0
MK04-87E 0.8 24 4.8 6.8 6.3 545 0.6 0.4 0.3 553 1.6 3.0 0.4 0.1 0.1 0.1 0.0 0.0 0.0 0.0 0.1 526 0.2
MK04-87E 1.0 49 3.2 6.7 30.8 691 2.3 1.0 0.4 598 1.5 3.5 0.5 0.1 0.0 0.1 0.0 0.0 0.1 0.0 0.1 610 0.1
MK04-87E 12.0 852 58.9 21.8 11.4 404 0.9 2.4 2.1 430 0.4 6.0 0.3 0.1 0.0 0.1 0.1 0.0 0.1 0.0 0.1 259 0.0
MK04-92C 0.5 254 0.5 13.3 1.3 425 18.8 0.1 1.4 1436 2.2 5.0 4.1 1.3 0.4 0.5 0.1 0.0 0.1 0.0 0.1 6441 0.4
MK04-92C 0.9 574 1.3 17.5 1.8 772 1.8 0.1 2.6 1833 8.2 24.9 22.1 5.2 1.0 1.6 0.3 0.0 0.0 0.0 0.1 6928 0.6
MK04-92C 1.2 402 0.6 16.8 0.9 553 2.9 0.1 1.1 2241 5.8 19.2 15.4 4.1 1.2 2.3 0.5 0.1 0.0 0.0 0.1 4316 0.2
MK04-92C 0.5 469 1.8 18.3 1.4 469 67.5 0.1 1.8 1314 1.8 4.9 3.3 0.8 0.2 0.3 0.1 0.2 0.4 0.1 0.1 7560 0.3
MK04-92C 0.7 545 2.0 27.2 1.6 922 29.4 0.1 1.9 1650 31.9 103.5 68.2 16.6 2.8 5.1 0.6 0.0 0.0 0.0 0.1 7868 0.4
Sample Mn Fe Cu As Se Sr Zr Ag Sb Ba La Ce Nd Sm Eu Gd Dy Er Yb Lu Au Pb Bi

MK04-92C 1.0 1059 1.6 7.6 1.9 424 5.3 0.3 4.3 1697 2.0 6.2 4.2 0.9 0.3 0.7 0.1 0.0 0.1 0.0 0.1 4631 0.1
MK04-92C 0.5 309 2.1 3.5 1.1 594 7.1 0.1 2.6 1763 3.4 9.4 5.5 1.8 0.5 1.4 0.4 0.1 0.1 0.0 0.1 7749 0.3
MK04-92C 1.2 252 1.5 4.7 0.9 390 4.4 0.1 2.1 1458 1.6 3.9 2.7 0.9 0.2 0.3 0.0 0.0 0.1 0.0 0.1 6848 0.2
MK04-92C 1.0 339 2.0 5.3 0.9 485 10.4 0.1 2.3 1682 2.5 6.8 5.8 1.6 0.3 0.6 0.1 0.0 0.1 0.0 0.1 7373 0.2
MK04-100 0.5 40 0.8 31.6 1.8 208 0.1 0.1 2.4 434 2.0 3.4 0.9 0.3 0.2 0.5 0.2 0.0 0.0 0.0 0.1 315 0.3
MK04-100 0.4 45 2.4 28.2 1.3 314 0.1 0.1 1.5 474 3.1 4.7 0.9 0.2 0.2 0.6 0.2 0.0 0.0 0.0 0.1 329 0.3
MK04-100 2.2 31 2.5 40.4 2.5 156 0.0 0.2 1.8 527 2.5 3.9 0.7 0.2 0.2 0.5 0.2 0.0 0.0 0.0 0.1 363 0.4
MK04-100 0.6 10 0.8 5.7 1.7 228 0.0 0.1 0.1 600 0.5 1.0 0.2 0.1 0.1 0.3 0.1 0.0 0.0 0.0 0.1 165 0.1
MK04-100 0.4 18 0.7 20.3 1.8 121 81.6 0.1 0.5 419 1.7 3.0 0.7 0.2 0.1 0.3 0.3 0.1 0.3 0.1 0.1 209 0.2
MK04-100 0.5 9 0.7 23.5 1.8 113 45.7 0.1 2.7 501 1.8 3.0 0.7 0.1 0.1 0.3 0.2 0.0 0.2 0.0 0.1 188 0.2
MK04-100 0.4 40 1.6 57.5 1.3 270 7.1 0.1 8.4 305 2.7 4.2 0.9 0.1 0.1 0.2 0.1 0.0 0.0 0.0 0.0 548 0.4
MK04-107 1.2 722 2.9 4.4 1.0 409 0.0 0.2 0.5 627 3.5 6.7 2.0 0.3 0.2 0.2 0.0 0.0 0.0 0.0 0.1 585 0.0
MK04-107 0.5 59 1.3 8.2 1.2 558 0.1 0.1 0.5 693 4.9 10.1 4.2 0.9 0.3 0.5 0.2 0.1 0.0 0.0 0.1 683 0.0
MK04-107 0.5 35 0.8 5.9 1.4 383 0.0 0.1 0.1 669 3.0 6.1 1.7 0.4 0.2 0.2 0.0 0.0 0.0 0.0 0.4 471 0.0
MK04-107 0.5 465 2.0 10.7 12.5 466 0.1 0.1 1.4 619 3.1 6.2 2.2 0.4 0.1 0.1 0.1 0.0 0.0 0.0 0.1 651 0.0
MK04-107 0.4 131 3.1 7.6 4.1 640 0.0 0.1 0.5 792 4.2 9.1 2.8 0.4 0.2 0.2 0.1 0.0 0.0 0.0 0.8 879 0.0
MK04-107 0.5 64 0.8 5.2 2.0 494 0.0 0.1 0.3 778 3.6 6.8 2.0 0.4 0.2 0.2 0.1 0.0 0.0 0.0 0.1 426 0.0
MK04-107 0.5 96 0.8 3.4 1.8 326 0.0 0.1 0.1 686 2.2 3.8 1.4 0.2 0.1 0.0 0.0 0.0 0.0 0.0 0.1 258 0.0
Ca content is not shown. Please refer to the microprobe analyses (Table A1).
Appendix Table A3 Whole rock composition analysis protocols (Anglo American package AA group
LITHO, ACME Lab, Vancouver, Canada)
Unit Detec. Method Unit Detec. Method Unit Detec. Method
Limit code Limit code Limit code
SiO2 % 0.02 G4A Cs ppm 0.1 G4B Mo ppm 0.01 G1F-MS
Al2O3 % 0.03 G4A Ga ppm 0.5 G4B Cu ppm 0.01 G1F-MS
Fe2O3 % 0.04 G4A Hf ppm 0.5 G4B Pb ppm 0.01 G1F-MS
MgO % 0.01 G4A Nb ppm 0.5 G4B Zn ppm 0.1 G1F-MS
CaO % 0.01 G4A Rb ppm 0.5 G4B Ag ppb 2 G1F-MS
Na2O % 0.01 G4A Sn ppm 1 G4B Ni ppm 0.1 G1F-MS
K2O % 0.04 G4A Sr ppm 0.5 G4B Co ppm 0.1 G1F-MS
TiO2 % 0.01 G4A Ta ppm 0.1 G4B Mn ppm 1 G1F-MS
P2 O 5 % 0.01 G4A Th ppm 0.1 G4B As ppm 0.1 G1F-MS
MnO % 0.01 G4A U ppm 0.1 G4B Au ppb 0.2 G1F-MS
Cr2O3 % 0.001 G4A V ppm 5 G4B Cd ppm 0.01 G1F-MS
Ba ppm 0.5 G4A W ppm 0.1 G4B Sb ppm 0.02 G1F-MS
Ni ppm 10 G7TD Zr ppm 0.5 G4B Bi ppm 0.02 G1F-MS
Sc ppm 0.1 G4A Y ppm 0.1 G4B Cr ppm 0.5 G1F-MS
LOI % 0.1 G4A La ppm 0.5 G4B B ppm 1 G1F-MS
Total C % 0.02 G4A Ce ppm 0.5 G4B Tl ppm 0.02 G1F-MS
Total S % 0.02 G4A Pr ppm 0.02 G4B Hg ppb 5 G1F-MS
Nd ppm 0.4 G4B Se ppm 0.1 G1F-MS
Sm ppm 0.1 G4B Te ppm 0.02 G1F-MS
Eu ppm 0.05 G4B Ge ppm 0.1 G1F-MS
Au_G3B ppb 2 G3B Gd ppm 0.05 G4B In ppm 0.02 G1F-MS
Pt_G3B ppb 3 G3B Tb ppm 0.1 G4B Re ppb 1 G1F-MS
Pd_G3B ppb 2 G3B Dy ppm 0.05 G4B Be ppm 0.1 G1F-MS
Ho ppm 0.05 G4B Li ppm 0.1 G1F-MS
Er ppm 0.05 G4B Pd ppb 10 G1F-MS
Tm ppm 0.05 G4B Pt ppb 2 G1F-MS
Yb ppm 0.05 G4B
Lu ppm 0.01 G4B

Method G4A-G4B: A 0.2g sample split is fused at 1000C with 1.5g of a 80:20 lithium metaborate/tetraborate mix. The
cooled bead is digested in 100 mL of 5% HNO3. ICP-ES analysis determines major element concentrations reported as
the common oxides. Loss on Ignition (LOI) is report as % weight loss on a 1g split is ignited at 1000C. LECO analysis
determines total C and S on a 0.2g sample split. The same whole rock fusion solution is analysed by ICP-MS (Perkin
Elmer Elan 6000) to determine absolute concentrations of these trace elements.

Method 1F-MS: A 1g subsample is digested in 6 mL of hot (95C) modified Aqua Regia (1:1:1 HCl:HNO3:H2O) for 1
hour, cooled and made to 20 mL volume with 5% HCl. Solution is analysed by ICP-MS (Perkin Elmer Elan 6000 or
9000). *Some minerals of these elements may be only partly attacked. This method is effective in dissolving sulfides
and other minerals soluble is strong acid such as alunite and carbonates but it may only dissolve silicates partially.
Comparing with a granitic standard (TASGRAN), a basaltic standard (TASBAS), a soil power standard (GXR-2), and a
copper mill-head powder standard (GXR-4) reveals that the ACME results are 0-70% lower than accepted values. In
particular, Pb is 18-69% lower, but if Pb is mostly in alunite, then the error should be smaller as alunite will dissolve;
Mercury is 1-10% lower.

Method G3B: A 30g sample split is custom mixed with PbO fire assay fluxes and fired for 45 minutes at 1050C.
Molten Pb + slag is poured into an iron mold, cooled and Pb button recovered. Heating at 950C in a MgO cupel
renders a Ag Au, Pt, Pd dore bead. The bead is parted in hot HNO3, digested by adding HCl and aspirated into a Jarrel
Ash Atomcomp 875 ICP-ES to determine Au, Pt and Pd. Upper limits = 10 ppm.

Method G7TD - A 0.5g sample split is digested in 20 mL of 4-Acid solution (HNO3:HClO4:HF:H2O) at 200C and
taken to dryness. Residue is dissolved in 16 mL of 50% HCl at ~95C for 1 hour then made to volume in a 100 mL
volumetric flask with 5% HCl. ICP-ES analysis determines total Ni.