JOURNAL OF

GEOCNEMCAl
ELSEVIER
EAPLORATION
Journal of Geochemical Exploration 52 ( 1995) 303-33 I

Petrology and mass-balance constraints on major-,

trace-, and rare-earth-element mobility in porphyry-
greisen alteration associated with the epizonal True
Hill granite, southwestern New Brunswick, Canada
David R. Lentz a, Conrad Gregoire b
’ New Brunswick Geological Surveys Branch, P.O. Box 50, Bathurst, N.B. E2A 321, Canada
h Geological Survey of Canada, 601 Booth Street, Ottawa, Ont. KIA OE8, Canada

Received 11May 1994; accepted after revision 25 October 1994

Abstract

Endogreisen and exogreisen weakly mineralized with Bi, Sn, and MO are associated with two of
three granite porphyry (granite) cupolas hosted in Silurian metasedimentary rocks at True Hill,
southwestern New Brunswick. The epizonal, weakly peraluminous and compositionally evolved True
Hill granite is quartz and K-feldspar porphyritic; groundmass textures, such as granophyric patches,
miarolitic cavities, and pegmatite pods, are indicative of rapid cooling and vapor saturation.
The greisen mineralization in cupolas B and C is overprinted by various types of alteration, reflecting
multi-stage devolatilization of the magma. The most intense topaz-bearing greisen is confined mainly
to the apical parts of the granite. In places, fluorite is associated with silicification, sericitization, and
chloritization, which is common to greisen-type alteration. The alteration types reflect the physical
and chemical changes in the hydrothermal fluid that was derived principally by second boiling of the
magma. Al-normalized, mass-balanced geochemical data supported by petrographic observations
show that in the greisenized True Hill granite, Fe, Mn and Mg enrichment corresponds to chlorite
and/or Fe-muscovite alteration and are coincident with leaching of Na and K and deposition of SiO?.
Ca was remobilized in the greisen environment, but erratically deposited as fluorite. Minor P and
LREE enrichment are reflected by the presence of monazite in the greisen. The HFSE are mobile to
a minor degree, based on correlations with elements known to be hydrothermally mobile. The base
metals correlate with S and other ore-forming elements. The distribution of many of the trace elements
is related to alteration, including the leaching of alkalis, which leads to the stabilization of aluminos-
ilicates, principally muscovite and topaz. The distribution of trace elements reflects their relative
mobility during greisenization, with high-field-strength elements (Zr and Ti) the most immobile and
the lithophile and chalcophile elements the most mobile. Breccias and greisen alteration in cupola C
at True Hill are similar to those at the base of the W-Mo-Bi porphyry-greisen in the Fire Tower zone
above the Mount Pleasant fine-grained granite.

0375-6742/95/$09.50 0 1995 Elsevier Science B.V. All rights reserved

.SSDIO375-6742(94)00059-X
304 D.R. L.entz, C. Gregoire / Journal of Geochemical Exploration 52 (1995) 303-331

1. Introduction

True Hill is located just north of the northern margin of the Saint George Batholith in
southwestern New Brunswick, about 3 km west of the Mount Pleasant W-Mo-Bi-Sn
deposits (Fig. 1) . It is underlain by a subvolcanic porphyritic microgranite that is genetically
related to the Beech Hill, Sorrel Ridge, and Mount Pleasant granites, based on age and
chemical composition (Dagger, 1972; Butt, 1976; Fyffe et al., 1981a, b). At True Hill,
three cupolas, designated A, B, and C, form a linear array trending southwest to northeast
(Fig. 1) . The Bi-Sn-Mo mineralized zones at True Hill have many aspects in common
with the W-Mo-Bi porphyry deposits within the Mount Pleasant Fire Tower zone (Lentz
et al., 1988; Lentz, 1994). The True Hill Sn-Zn lodes that crosscut the B cupola granite
porphyry have structural and mineralogical characteristics similar to the Sn lodes of the
North Zone at Mount Pleasant (Lentz and McAllister, 1990; Figs. 2,3). A number of Sn-
W-Mo-Bi deposits were formed in association with the Sorrel Ridge, Beech Hill, and
Mount Pleasant granites mentioned above (Ruitenberg and Fyffe, 1982), of which the
largest is the W-Mo-Bi deposit at Mount Pleasant.
This paper describes the weakly mineralized Bi-Sn-MO-W porphyry-greisen alteration
zone that is concentrated in two cupolas (B and C) at True Hill. The paper also describes
a mass-balance and statistical method that can be applied to porphyry-greisen systems that
can considerably enhance description of the geochemical and alteration and aid interpreta-
tion of critical factors controlling mineralization. This technique is applied to the geochem-
ical data from two drill holes (DDH 80-3 and 80-6) that intersect cupola B and cupola C
at True Hill, respectively, and penetrate into fresh granite at depth (Fig. 3) to illustrate the
method.

... LoI*
0..
Ordovician slal~r Devonian votcanics
.. :
CoolrronFm. . Mount Pleasant coldara

Fig. I. Geological map of the Mount Pleasant area, southwestern New Brunswick (after Taylor et al., 1985). True
Hill cupolas A, B, and C are shown from southwest to northeast, respectively.
 D.R. Lentz, C. Grqoire / Journal oj’Geochemical Exploration 52 (1995) 303-331 305

LEGEND

d Sulfide lodes

El I Gn~senued
” granite porphyry

I”v”,y Granite porphyry

m Metosedimentary rocks

Geological contact

Om 200m

Fig. 2. Geological plan of True Hill cupola B and C with the location of diamond drill holes (DDH) and trenches.

2. Geological setting

The Mount Pleasant, True Hill, Beech Hill, Pleasant Ridge, and Sorrel Ridge granites,
the “Beech Hill series” of Dagger (1972), intruded Ordovician to Silurian feldspathic
graywackes and shales along the northern margin of the Saint George Batholith (Ruitenberg
and Fyffe, 1982). During the Acadian Orogeny, these rocks were folded and metamorphosed
to lower greenschist grade and, proximal to intrusions, to andalusite-cordierite hornfels
facies (Ruitenberg and Fyffe, 1982). The Mount Pleasant deposit is located along the
southwestern margin of the Mount Pleasant caldera, which consists of shallowly dipping,
dominantly felsic volcanic and sedimentary rocks (Ruitenberg and Fyffe, 1982). The Late
Devonian Mount Douglas Granite, part of the eastern Saint George Batholith ( McLeod et
al., 1988) is compositionally similar to the Beech Hill series (Butt, 1976; Ruitenberg and
Fyffe, 1982). Recent 4”Ar/39Ar step heating of mineralized samples from the Mount Doug-
306 D.R. Lentz, C. Gregoire / Journal of Geochemical Exploration 52 (1995) 303-331

LEGEND

Sulfide lodes

Greieenized granite porphyry

Granite porphyry

Metasedimentary rocks

Geological contact

J” 1
‘h
” ” Y ” ” ” ” ,” ” ” ” ” Y ” ” ” ” ” ” 1f m;~md$/ip~
” ” “““V v yzde”vyv v v v v Y v v v v Y v
“““V
” 150m” ” ” ” ““““Y””

1”“” ““““““““““Y”“”

Fig. 3. Geological cross section of the True Hill cupolas B and C with the location of diamond drill holes. See
Fig. 2 for location.

las Granite yielded ages of 360 and 370 Ma consistent with the 366 f 1 and 367 + 1 Ma U-
Pb ages from the same intrusion (McLeod, 1990). An age of 36 1 k 9 Ma from hornfels
associated the Mount Pleasant caldera (Hunt and Roddick, 1990) suggests a similar history
for the Mount Pleasant deposits, although less reliable younger ages have been obtained.
The True Hill granite is compositionally similar to the Mount Pleasant fine-grained granite
and the other intrusions in the Beech Hill series, which are peraluminous and characterized
by high SiO,, K,O/Na,O, Rb/Sr, “Sr/?ri and low CaO, TiO,, and Zr (Dagger, 1972;
Butt, 1976; Ruitenberg and Fyffe, 1982; Kooiman et al., 1986; Lentz et al., 1988). The
True Hill and Beech Hill granites, as well as the Mount Douglas Granite, are interpreted to
have crystallized near the granite thermal minimum (730°C) at P( H20) = 100 + 50 MPa
(Butt, 1976; Lentz et al., 1988; McLeod, 1990). The transition zone between the W-Mo-
Bi mineralized system and the source microgranite at Mount Pleasant is comparable to the
weakly mineralized breccias and greisenized granite in the apical parts of the True Hill
granite.
 D.R. Lentz, C. Greg&e I Journey of Geochemical Exploration 52 (19% j 303-33 I 307

Fig. 5. Photomicrographs of primary and secondary features in the True Hill granite and greisen. f A) least-altered
granite with microperthitic K-feldspar, oligoclase, quartz, and weakly chloritized green biotite (sample 80-6-
391.7m; crossed nichols); (B) sericitized microgranophyri~ inter~owth of quartz (white) with sericite (grey )
after K-feldspar and fluorite is isotropic (sample 80-3-I 20.1 m; crossed nichols); (C) weakly ~hlo~tized hydro-
thermal red-brown pieochroic biotite along the margin of a sericitic greisen (light) and weakly altered granite
with dark turbid K-feldspar (sample 80-6-892; ptane-polarized light); (D) sericitic greisenized granite (grey l
with quartz-topaz greisen vein (sample 80-3-160.3m; plane-polarized light); (E) fluorite+ptartz-muscovite vein
in greisenized granite (sample 80-3-163.3m; crossed nichols); (F) chlorite-pyrite veins in greisenized granite
(80-S I06.7m; plane-polarized light).

3. True Hill granite

At True Hill, three granite cupolas (A, B, and C) (Figs. 2,3), occur within greenschist-
grade, sedimentary rocks as noted above. The north and south contacts of the cupolas dip
shallowly (O-45”), whereas the east and west contacts are steep (subvertical). The proximal
homfels contains biotite, andalusite, and cordierite index minerals with ~dalusite porphy-
308 D.R. Lentz, C. Gregoire / Journal ofGeochemical Exploration 52 (1995) 303-331

Table 1
Major- and trace-element compositional data on True Hill granite and greisens from diamond drill holes TH80-3 and THSO-6 in
southwestern New Brunswick

DDH 80-3 80-3 80-3 80-3 80.3 so-3 80.3 SO-3 80-3 80-3
ft 314 332 350 394 465 526 537 573 690 970
S.G. _ _ _ _ _ _ _ _ _
Alt/L.Alt Alt Alt Alt Alt L.Alt Alt Alt Alt L.Alt L.Alt
-
302 77.85 77.1 75.9 82.3 76.4 78.1 76.3 76.4 77.7 76.3
TiOz 0.09 0.06 0.10 0.05 0.09 0.08 0.06 0.09 0.08 0.08
Al,O, 11.96 12.41 I I .74 13.17 12.39 12.59 12.12 12.15 12.81 12.53
Pe$?v 2.49 1.75 6.06 0.18 I.63 1.32 4.01 1.15 I
.59 0.93
M&J 0.49 0.24 0.38 0.48 0.28 0.23 0.13 0.16 0.80 0.13
MnO 0.27 0.01 0 14 0.01 008 0.06 0.06 0.05 0.08 003
cao 0.18 0.77 0.12 1.17 0.52 0.43 0.94 0.60 0.63 0.48
Na20 0.30 2.96 0.08 n.00 2.67 0.30 1.42 2.5X I.71 2.49
K,O 4.40 4.26 3.42 0.12 5.29 4.19 3.66 4.89 5.18 5.33
P,O, 0.04 0.01 0.06 0.01 0.03 0.06 0.01 0.00 0.01 0.01
LO1 1.87 0.91 2.18 2.79 1.0x 2.23 1.7Y O.Y4 1.40 0.5’)
Total 99.9 100.5 100.1 loo.2 100.4 99.6 100.5 99.0 102.0 98.9

F ppm 2400 3200 1900 10600 3000 8400 8800 4300 3600 2900
s 1400 I no 2800 1300 1900 400 <SO I(N) inn Inn
Ba 187 170 290 28 145 IS3 204 113 134 144
Sr 9 19 4 6 21 I6 23 I6 8 IS
Rb 680 575 496 22 523 544 626 552 559 584
Li _ _ _ _ _
CS 12 8.3 11 9.7 6.7 5.6 9.3 IS 23 9.0
TI 7.0 5.2 12 7.1 4.1 5.2 6.2 x.7 I5 9.1
K/Rb 54 61 57 45 x4 64 4’) 74 77 76
Rb/Ba 3.6 3.4 1.7 0.8 3.6 3.6 3.1 4.9 4.2 4. I
Rb/Sr 76 30 124 3.7 25 34 27 35 70 39
Rb/Cs 57 69 45 2.3 78 97 67 36 24 65
TIlRb 97 III 41 3.1 122 105 101 63 37 64

Zr pprn 140 140 140 Iso I40 I40 130 130 130 140
Hf 6.6 6.8 7.X 6.4 7.2 6.9 6.1 7.0 7.8 7.7
Y 110 110 62 91 150 85 100 91 140 120
Nb 78 66 Y3 SY X6 Y2 62 82 89 87
Bi 35 2.2 210 16 2.8 1.4 28 13 6.4 3.7
MO <2 5 < 2 <I 52 <2 6 <2 <2 <2
S” 14 32 16 12 38 43 17 19 13 56
Ga 20 22 26 21 24 21 22 24 28 26
Ta II X.7 II 8.3 IO 9.8 8.0 I0 13 I.5
Th 53 SO 61 51 54 62 52 54 57 s4
U 30 27 32 25 32 33 26 28 34 33
Nb/Ta 71 7.6 X.5 7.1 8.6 9.4 78 x7 6X 58
Th/U I .77 1.85 1.91 2.04 I.69 I.8X 2.00 1.93 I
.68 1.64

La ppm 42 43 33 45 38 40 46 30 35 33
Ce 92 97 87 99 87 88 100 67 83 7Y
Pr 11 12 II 12 II IO 12 8.2 IO 9.7
Nd 36 40 39 40 37 35 41 28 35 32
Sm 8.8 IO 8.4 9.6 9.9 7.9 IO 67 94 83
E” 0.15 0.13 0.18 0.13 0.09 0.09 0.13 0.1 I 0.16 0.2 I
Gd 90 10 6 0 95 II 70 97 70 I0 x3
Tb 2.0 2.2 I .4 2.0 2.5 1.6 2.0 1.5 2.3 I.Y
DY 15 IS 9.3 13 18 II 14 II 16 14
HO 3.5 3.5 2.0 2.Y 4.3 2.5 3.0 2.4 3.8 x2
El 12 12 7.2 9.5 IS 8.6 9.9 8.2 13 II
Tm 2.3 2.2 I .4 I.8 2.9 I .7 1.9 I6 2.6 2.3
Yb 17 16 II I3 22 12 14 I2 20 18
LU 25 2.5 1.5 19 3.2 18 21 1.9 2.9 27

Aa ppm 11 8 14 II 24 8 II IX 7 20
Sb 4 <3 16 <3 <3 <3 <3 < 3 <. 3 c3
ZII 1317 62 49 31 135 271 80 63 62 46
In 0. I7 0.03 0.57 0.11 0 IO 0 04 0.12 0.09 0.8 I 0.40
Cr <5 <5 29 39 <5 <5 <5 <5 <5 <5
Ni 40 22 15 23 23 39 21 IO IS 13
V <5 <5 <:S <5 <5 <5 <5 <5 c5 c5

Alt ~ altered, L.Alt ~ least-altered. Major-element and TiO,. I’,&, Ba, Rb, Sr, Cr, NI, V. Zn contents were determmed by X-
ray fluorescence(Phillips PW140) “~1 fused disks in the Geochemical Laboratory at the University of Ottawa. Loss on ignition
(LOI) analyses represent the weight loss after heating in a muffle furnace (1050°C) for 2 hours. Sulfur and fluorine ufere
dctermincd by Dioncx High Prcssurc Liquid Chromatography (HPLC) at the Geological Survey of Canada. Lithium was deter-
80-6 80.6 80-6 SO-6 80-6 80-6 80-h 80-6 80-6 80-6
45 IO0 I81 336 371 415 471 480 667 728
2.50 2.58 2.73
AlI Alt Al1 Ah Alt AIt Ah Ah AlI AlI

7x 5 75 2 75.1 78.5 XI.7 77. I 76.5 75. I a.7 Xl.7

0.06 0.05 0.05 0.06 0.06 0. I3 0.05 0.06 0.09 0.09
I I .76 I I.59 12.85 12.66 II.21 12.52 12.24 12.70 10.20 12.48
0.82 7.79 4.61 2.81 I .65 2.28 I.81 3.12 1.60 1.57
0.25 0.45 0.25 0.21 0.03 0.26 0.14 0.10 0.2 1 0.03
0.02 0. I7 0.16 0.09 0.16 0.16 0,s 0.05 il.06 0.06
0.73 0.42 0.99 1.08 0.92 I .63 0.76 0.87 1.17 0.56
0.06 0.10 0.00 3.1 I 0.07 0.0.5 2.66 I.21 0.35 0.20
5.18 2.85 3.83 2.15 2.09 4.07 4.23 5.18 0.29 0.49
0.00 0.04 0.01 0.00 003 002 001 0.01 0.03 0 02
I.91 0.12 2.61 1.87 I .‘>9 I .46 I.16 I .46 3.14 I .4’f
99.3 98.X loo.5 102.5 loo.0 99.7 YYh 99.9 103.9 9x 7

5300 3900 7200 8000 ‘KxKJ I9600 6700 7500 13900 28900
I 00 5600 600 200 2w 200 I 00 < 50 100 IO0
207 II3 I71 97 156 209 I45 I74 60 X8
I3 9 I6 35 IO I3 lb 23 22 3
611 564 775 461 448 701 564 811 53 II3
_ 46 I06 91 _ _ _ _
0.93 II 27 23 I6 16 3.2 I6 24 2.3
0.49 6.6 8.9 I0 12 I0 2.3 54 I4 0.89
70 42 40 39 39 48 62 I? 45 34
3.0 5.0 4.5 4.8 2.9 3.4 3.9 4.7 0 9 13
4-l 63 4x 13 4s 54 35 35 2.4 38
656 51 29 20 28 44 176 50 2.2 49
1247 85 87 46 37 70 245 I50 38 127

I 20 I60 I IO 120 120 130 120 120 170 t IO

6.6 6.7 5.3 7.1 5.8 7.4 5.4 7.0 6.5 6. I
I20 79 68 130 90 170 90 I5 78 750
76 60 55 77 66 84 50 91 47 59
500 I.9 YO 210 I 00 81 7x 45 62 2 10
I6 <2 <2 <2 12 4 <2 39 <2 -i-2
87 29 23 39 I9 36 17 I7 II 55
5.0 21 21 SO 41 29 12 33 27 I7
x7 8.1 x.5 I2 8.3 II II I4 5.5 IO
44 52 39 49 51 52 47 54 46 lo0
30 25 I8 35 24 35 21 31 18 29
8.7 7.4 6.4 6.4 8.0 7.6 4.5 6.5 x.5 5.‘)
I .47 2.08 2.17 I .4 2.13 1.49 2.24 I .74 2.56 3.45

41 51 36 33 16 44 30 29 70 82
tOO II0 x1 7x 3x 100 68 73 I IO I X0
I2 I2 9.6 9.1 4.2 I3 8.2 Y.3 I7 25
41 39 31 30 I4 42 29 34 54 89
9.3 7.8 6.3 7.9 4.1 II 7.1 8.8 IO II
0.13 0.13 0.08 0.40 0.10 0.1 I 0. IO 0.08 0.26 0.36
x.3 6.X 5.4 9.0 6.2 II 7.2 7.8 7.7 ?I
2.0 1.3 1.1 2.2 I.5 2.6 1.6 I.6 I.5 4. I
IS 9.3 8.2 16 I2 I9 II II IO 29
3.5 2.1 1.9 3.8 2.8 4.5 2.7 2.6 2.2 7. I
I‘? 7.1 6.5 I4 9.7 I6 9.1 9.4 7.2 24
2.5 1.3 1.3 2.7 1.8 3.3 1.7 2.0 I .4 4.5
I8 9.8 9.4 20 13 25 I2 I5 9.6 32
2.7 1.6 1.5 3.1 2.0 3.8 1.8 2.4 1.5 5.0

4 IO IO 46 24 8 x 12 7 52
20 I7 24 13 17 4 8 3 -c 3 lb
39 I56 165 87 2Y 83 50 I13 61 Sh
0.04 0.13 0.64 I.3 I.9 0.3 I 0.2 I 0.23 0.76 0. IO
6 in 0 8 24 <5 c-5 c5 45 26
34 2.5 36 39 22 99 L2 30 45 17
<s <5 9 <5 <5 <S 5 <5 11 5

mined by Atomic Absorption Spectroscopy in the Geochemical Laboratory at the University of New Bmnswck. As, Sb, Sn, and
MO were detemxned by pressed pellet XRF at X-Ray Assay Labs, Don Mdls, Ontum. The remainmg trace-elements were
determined by Inductively Coupled Plasma Mass Spectroscopy (ICP-MS) in Geochemical Laboratory at the Geological Survey
of Canada. “Fresh” True Hill granite is an average of least-altered (L.Alt.) granite compositions.
 310 D.R. Len@., C. Gregoire / Journal of Geochemical Exploration 52 (1995) 303-331

Table 1(continued)
DDH 80-6 80-6 X0-6 80-6 SO-6 80-6 X0-6 80-6 fresh
ft 739 845 870 892 925 937 1011 1285 x Is
S.G. _ 2.61 _ _ _ _ 2.59 2.54
Alt/L.Alt Alt L.Alt L.Alt L.Alt L.Alt Alt L.Alt L.Alt

SiO, 76.8 76.5 76.0 77.7 77.2 79.1 77.8 76.3 76.9 0.7
TiO, 0.09 0.07 0.1 I 0. IO 0.10 0.09 0.08 0.07 0.09 0.01
Al,@ 12.01 12.76 12.37 12.35 12.44 I I.43 12.83 12.61 12.57 0.19
k% 3.64 0.79 0.57 1.37 1.39 2.02 1.06 1.16 1.17 0.36
M@ 0.35 0.11 0.04 0.07 0.28 0.27 0.20 0.1 I 0.22 0.23
MnO 0.07 0.03 0.03 0.05 0.08 0.16 0.04 0.04 0.05 0.02
cao I .73 0.53 0.72 0.64 0.54 0.60 0.57 0.54 0.57 0.08
Na,O 0.00 2.78 1.70 2.64 2.90 0.11 3.00 3.19 2.56 0.53
KzO 3.23 5.39 5.18 5.15 5.22 3.71 4.56 5.48 5.20 0.26
P,O, 0.01 0.00 0.01 0.03 0.01 0.01 0.01 0.02 0.01 0.01
LO1 2.42 0.99 I .50 0.79 0.94 2.25 1.04 0.99 1.04 0.28
Total 100.3 99.9 98.3 100.8 101.1 loo.4 100.8 100.5 100.3

F wm 16100 4600 4400 6300 3400 4400 2900 3000 3790 1140
s 200 <50 100 <50 100 2100 <50 100 275 610
Ba 118 III 141 110 191 IOil 125 95 133 28
Sr 31 15 23 14 21 9 13 17 16 5
Rb 782 636 613 622 572 718 588 620 591 36
Li _ 34 _ _ _ 61 3x _ _
CS 8.8 9.9 27 9.3 31 9.2 12 12 15.5 9.0
Tl 8.2 7.1 3.7 6.4 II 5.9 7.1 4.4 7.6 3.7
K/Rb 34 70 70 69 76 43 64 73 73 6
RblBa 6.6 5.7 4.3 5.7 3.0 7.2 4.7 6.5 4.6 1.1
RblSr 25 42 27 44 27 80 45 36 40 14
RbiCs 89 64 23 67 18 78 49 52 49 22
TIlRb 95 90 166 97 52 122 83 141

Zr PPm 120 130 140 180 130 130 140 120 139 17
Hf 6.8 7.4 5.9 7.6 5.8 6.1 6.6 7.2 7.0 0.8
Y 150 110 77 110 95 72 78 130 112 26
Nb 89 85 60 56 53 83 71 90 75 15
Bi 12 21 6.6 18 32 8.1 4.6 210 34 67
MO <2 <2 <2 6 II <2 6 <2 9 17
Sn 28 91 22 122 28 65 22 48 46 38
Ga 25 25 21 16 34 21 22 17 24 6
Ta 13 13 7.4 7.7 5.5 x.1 7.2 13 10.2 3.4
Th 54 52 49 53 43 57 53 46 51 4
U 35 38 21 23 22 30 28 38 30 7
NblTa 6.8 6.5 8.1 7.3 9.6 10.2 9.9 6.9 7.7 1.4
Th/U I .54 I .37 2.33 2.30 1.96 1.90 I .89 1.21 I .79 0.38

La PPm 39 32 40 50 41 38 33 88 43 I8
Cc 92 77 91 110 90 88 72 180 97 33
Pr 11 9.4 II 13 IO 10 8.2 24 11.8 4.8
Nd 38 33 36 45 36 35 27 79 40 15
Sm 9.9 8.5 8.4 II 8.3 8.0 6.0 17 9.6 3.1
EU 0.09 0.08 0.18 0.19 0.20 0.11 0.10 0.52 0.19 0.13
Gd IO 7.9 7.6 10 8.7 7.0 5.5 12 9.0 2.0
Tb 2.4 1.7 1.6 2.0 1.8 1.5 1.2 2.6 2.0 0.5
DY 18 13 II 14 13 IO 8.8 19 14.1 3.2
HO 4.2 3.0 2.4 3.3 2.8 2.2 2.1 4. I 3.2 0.7
Er 15 II 8.2 II 9.5 7.5 7.2 14 11.1 2.6
Tltl 3.0 2.2 1.6 2.1 1.7 1.5 1.4 2.8 2.2 0.5
Yb 22 17 II 15 12 11 IO 21 16.2 4.5
LU 3.4 2.6 1.7 2.3 1.8 1.6 1.6 3.1 2.4 0.6

As wm 13 14 9 32 <3 12 11 9 14 IO
Sb <3 II 9 I8 21 46 15 16 IO 8
Zll 75 6X 39 15 72 91 65 48 61 33
In 0.16 0.21 1.6 0.04 0.14 0.04 0.10 0.39 0.42 0.50
Cr 4 <5 <5 8 <5 15 5 <5 _
Ni 20 19 20 106 14 32 11 31 28 30
V 0 4 15 <5 9 <5 <5 15 _ _
 D.R. Lentz, C. Gregoire /Journal of Geochemical Exploration 52 (1995) 303-331 31 I

roblasts observed up to 120 m from the inferred contact of the granite. The contact between
granite porphyry and metasedimentary rocks is commonly marked by various stages of
brecciation associated with greisen alteration in the cupola (Lentz, 1994).
The True Hill granite is hiatal porphyritic, with equal proportions of quartz and K-feldspar
phenocrysts and variable amounts of biotite and plagioclase (Fig. 4). Quartz and K-feldspar
phenocrysts range in size from 1 mm to 2 mm on average and have euhedral to subhedral
morphology. The K-feldspar contains various styles of string and patch perthite reflecting
albite exsolution and/or replacement by plagioclase. Plagioclase also forms euhedral phe-
nocrysts that are commonly finer grained than the dominant phases. Biotite is fine grained
(0.5 mm) and contains zircon, sphene, opaque phases, and rare cassiterite and is commonly
variably chloritized (Fig. 5A). Granophyric quartz and K-feldspar intergrowths (Fig. 5B)
occur in the groundmass near miarolitic cavities and pegmatite pods.
The True Hill granite has high Si02 (76.9 wt.%), K,O (5.20 wt.%), and K,O/Na,O
(2.2) with low MgO (0.22 wt.%), Fe,O,, (1.44 wt.%), CaO (0.57 wt.%), TiOz (0.09
wt.%), and P205 (0.01 wt.%) (“fresh”; Table 1) . Rb, Ba, and Sr contents indicate the
granite is highly evolved (Lentz et al., 1988). The granite is also weakly peraluminous
( A/CNK = 1.16). Lentz et al. ( 1988) showed that the normative mineralogy corresponds
closely to the thermal minimum (730°C) for H,O-saturated granitic liquid (3 wt.% norm.
anorthite) at the 100 MPa ( 1 kbar) eutectic of James and Hamilton ( 1969). The petrography
and composition of the granite and greisen at True Hill indicate that F was present; this
could account for some of the apparent deviation from the thermal minimum ( see Manning,
198 1) .The granite has high total REE, little fractionation of LREE relative to HREE, and
a pronounced negative Eu anomaly. The REE distribution is typical of high-silica granites,
reflecting their highly evolved nature and high fluorine content (Cullers and Graf, 1984).
The large negative Eu anomaly, as well as low CaO, Ba, and Sr, reflects extensive fraction-
ation of feldspars. The True Hill granite has characteristics of A-type granites found else-
where in southwestern New Brunswick (Taylor et al., 1985; Whalen, 1986) with high SiO,,
K20, Na,O, Fe/Mg, F, Nb, Y, Zr, Ga, and REE and low TiO,, FeO, MgO, CaO, Sr, and
Eu. On the Rb, Nb, Y, Yb, and Ta empirical discrimination plots of Pearce et al. ( 1984),
True Hill falls in the within-plate field as do the Mount Douglas Granite ( McLeod et al..
1988; McLeod, 1990) and the Mount Pleasant microgranite (Kooiman et al., 1986).

4. Alteration and mineralization

At True Hill, endogranitic alteration and mineralization principally occur in cupolas B

and C (Lentz et al., 1988) and are similar to other porphyry-greisen systems (cf., Scherba,
1970; Taylor, 1979; White et al., 1981), although not as extensively developed. Detailed
investigation of alteration zones, including thin section and whole-rock chemical analyses,
was done on diamond drill holes (DDH) 80-3 and DDH 80-6. These two holes explored
cupola B and C, respectively (Figs. 2,3) and represent a section through the altered granite
carapace into unaltered granite. Two types of alteration are recognized: alkalic ( feldspathic )
alteration characterizes the deepest, weakly altered rocks, whereas greisen (phyllic) alter-
ation is more prominent at higher levels in the cupola.
312 D.R. Lentz, C. Gregoire/Journal of Geochemical Exploration 52 (1995) 303-331

The alkalic alteration is generally cryptic but can be recognized locally in the deeper
weakly altered parts of the True Hill granite. For instance, chessboard albite alteration,
though not pervasive, is evident petrographically within veins. Secondary albite replaces
primary K-feldspar and oligoclase. Some of this secondary albite (An,) contains abundant
inclusions of secondary mica. K-feldspathization is suspected to have occurred but is minor
because the K-feldspar is microperthitic in most instances, indicative of crystallization above
the solvus (i.e. igneous origin). Dagger ( 1972) and Pouliot et al. ( 1978) have described
similar types of alkalic alteration at depth beneath the Mount Pleasant Fire Tower W-Mo-
Bi ore zone.
Greisen (phyllic) alteration is pervasive and fracture controlled both within and outside
cupolas B and C. Greisen veins and their alteration envelopes commonly overprint each
other and thus indicate progressive episodes of volatile saturation from the crystallizing
magma. Three types of endogreisen, probably reflecting variations in the hydrothermal
fluid, are developed at True Hill; ( 1) fluorite-bearing, quartz-sericite greisen, (2) fluorite-
bearing, quartz-chlorite-sericite greisen, and (3) fluorite-bearing, quartz-topaz-sericite
greisen. The first and third types of greisen host most of the bismuthinite, molybdenite, and
wolframite, whereas the chlorite-bearing assemblage hosts sphalerite, chalcopyrite, and
galena and is enriched in tin.
Pervasive greisen alteration is commonly manifested by the replacement of feldspar by
white mica with minimal dissolution of quartz, as shown by the preservation of granophyric
textures (Fig. 5B). Feldspar hydrolysis and alkali metasomatism are the main factors
responsible for sericitization, the most common type of alteration associated with greisen
veins in cupolas B and C. Quartz-topaz-sericite greisen alteration is mainly confined to
cupola C. Topaz and quartz commonly form the center of veins with selvages of secondary
sericite and both secondary and residual quartz. Rhythmically-banded, quartz-sericite and
quartz-topaz greisen in the upper parts of cupola C is interpreted to have been produced by
changes in the acidity and salinity of the greisenizing fluids, possibly resulting from boiling
(see Burt, 198 1) . It is identical to banded greisen at the Mount Pleasant W-Mo-Bi deposit
and at the Climax MO deposit (White et al., 198 1) . Hydrothermal muscovite (phengitic)
and topaz were produced by hydrogen metasomatism, causing the release of alkalis and
silica. Hydrothermal pleochroic red-brown biotite may occur along the reaction interface
between weakly altered granite and greisen with dark turbid microcline and pervasive or
vein-controlled silicification (Fig. 5C). Topaz occurs with fluorite- and quartz-rich greisen
assemblages that are vein-controlled and are usually hosted within sericitic greisen (Fig.
5D). Coarse-grained fluorite, muscovite, and quartz occur in the core of veins in various
proportions (Fig. 5E). Sulfide-bearing, Fe-rich chloritic veins also are evident within the
upper parts of the greisen alteration zone and are commonly hosted by sericitic greisen to
which it may or may not be related (Fig. 5F).
Two styles of chloritization occur during greisen alteration; chloritic alteration of biotite
during weak alteration probably under moderately acidic conditions (low Kt /H+ ) or by
the introduction of Fe (higher uFrz + ) to stabilize chlorite associated with sericitic alteration
(Fig. 5F). Chloritic alteration occurs to some degree in all biotite in the True Hill granite
and may be responsible for the enrichment of ferromagnesian components (Fe, Mn, Mg,
and Sn; Tischendorfet al., 197 1) in the hydrothermal fluid if it represents a partial dissolution
and/or exchange reaction. The enrichment of these components (Fe, Mn, and Mg) in the
 D.R. Lentz, C. Gregoire / Journal of Geochetnical Exploration 52 (I 995) 303-331 313

Table 2
Phyllosilicate compositions from granites and greisens from True Hill, New Brunswick

Sample 6-100 6-100 3-350 3-350 6-336 6-411 6-480 6- I285 6- 1299
Mineral Chl Mus Chl Mus Mus Mus Mus Chl Bt

SiOz wt.% 23.1 45.8 22.4 45.9 46.7 48.9 44.65 22.4 35.17
TiO, _ _ _ - 0.1 I 0.00 0.00 0.20 2.88
Al,01 23.12 28.84 23.85 33.23 28.50 30.01 29.73 20.10 17.99
Fe0 36.7 1 5.66 37.15 4.96 5.80 4.58 5.17 41.46 25.69
MgO 1.25 1.55 0.77 0.20 0.00 0.45 0.25 0.96 0.93
MnO 0.98 0.34 4.11 0.24 0.00 0.00 0.00 I .50 0.87
CaO 0.00 0.00 0.10 0.00 0.09 0.16 0.00 0.10 0.13
NazO 0.00 2.08 0.00 0.53 0.42 0.18 0.38 0.19 0.43
KLO 1.16 10.12 0.38 10.47 IO.20 9.90 10.23 0.00 8.89
HZ0 * 10.74 4.35 10.61 4.43 4.42 4.48 4.42 10.44 3.84
Total 97. I 98.7 99.4 99.9 96.2 98.7 94.8 97.4 96.8

Chl - chlorite, Mus - muscovite/sericite/phengite, Bt - biotite. The samples were analysed by Dr. Douglas
Hall at the Electron Microscopy, University of New Brunswick on a JEOL JSM-6400 Digital SEM at 15 kV
accelerating voltage and a 2.5 nA beam current equipped with a 4 crystal wavelength dispersive spectrometer and
a LINK Pentafet Energy Dispersive Spectrometer with 100 set integration time and 40 set counting on Na. Silicate.
oxide, and metallic standards were used to quantify the instrument. Hz0 * calculated based on formula.

fluid must eventually lead to a higher abundance of chlorite, which happens to be more
commonly found in the upper parts of the cupola. The abundance of Fe in the fluid must
also affect the saturation of pyrite, and more rarely magnetite in the greisen, and together
with accessory chlorite, results in the formation of sulfide-bearing, quartz-chlorite-sericite
greisen zones. Of course, saturation of pyrite or magnetite is also a function of the absolute
and relative activities of S2 and 0,.
Several analyses indicate that micas are very Fe-rich (Table 2). Hydrothermal chlorite
replacing biotite is slightly more Fe-rich [Fe/ (Fe + Mg) = 0.98, sample 80-6- 128.5; Table
21 than the probably original biotite composition [Fe/ (Fe + Mg) = 0.96, sample 80-6-
1299; Table 21. The hydrothermal chlorite (daphnite or Fe chamosite) associated with
chloritic greisen and chlorite veins are also very Fe-rich [Fe/ (Fe + Mg) > 0.951 similar to
septachlorite associated with tin-base-metal lodes that are genetically related to these gran-
ites (Lentz and McAllister, 1990). The associated phengitic micas have Fe/ (Fe + Mg)
from 0.75 to 1 and so seem to be in equilibrium with coexisting chlorite. The pyrite-bearing
chlorite vein (Fig. 5F) has relatively high Mn contents. The compositional evolution of
chlorites from high Fe/ (Fe + Mg) to very high Fe/ (Fe + Mg) is indicative of conductive
cooling of fluids (cf. Saccocia et al., 1994) and that sulphide saturation has not substantially
decreased the Fe/Mg of the fluid. Application of the chlorite geothermometer (Jowett,
I99 1; De Caritat et al., 1993) to the chlorites that coexist with muscovite and quartz indicates
temperatures between 380 and 390°C just beyond the calibration range suggested by Jowett
(1991).
Within intense and pervasive greisen alteration, dissolution of igneous quartz is evident
with the rounded anhedral (defaceted) quartz hosted within sericite (Fig. 5F). The silica
that is mobilized is involved with silicification elsewhere, although the superposition of
silica dissolution and precipitation in veins during the entire evolution of the hydrothermal
314 D.R. Lentz, C. Gregoire /Journal ofGeochemica1 Exploration 52 (1995) 303-331

systems makes it difficult to resolve these problems chemically. Silicic alteration is asso-
ciated with all types of greisenization. Seriate quartz grain boundaries (dissolution of
quartz) and replacement of feldspar by mica and topaz by incongruent dissolution of
feldspars during pervasive hydrolysis reactions increased the dissolved silica in solution. In
the vein-controlled greisens, quartz and quartz-cored greisen veins indicate local saturation
of quartz within veins in both the endogranitic and exogranitic environments. The present
distribution of the most siliceous alteration (vein cores, fracture filling, and pervasive
silicification in the cupola) suggests a decrease in silica solubility, perhaps due to a decrease
in the fluid pressure during hydrofracturing and vein formation (see Foumier, 1984).
At True Hill, greisen alteration is only weakly mineralized with up to 100 ppm MO and
W as molybdenite and wolframite, and an average of 295 ppm Bi manifested as bismuthinite.
The quartz-chlorite-sericite greisen typically has low tin (ave. 30 ppm Sn) but locally has
values up to 300 ppm. The distribution of Zn and Pb are irregular but are as much as 500
ppm locally (Lentz et al., 1988).

5. Mass-balance analysis

5. I. Introduction

Mass-balance techniques have commonly been used in the analysis of hydrothermal

alteration systems in lode gold deposits and volcanogenic massive-sulfide settings
(MacLean and Barrett, 1993) but have rarely been applied to porphyry-greisen systems
(Leitch and Lentz, 1994). Using equations presented by Gresens ( 1967) and Grant ( 1986))
net mass change can justifiably be calculated by using a component that remains relatively
unchanged during the alteration process. Mass balance may be evaluated from Eq. 1 using
A&O, as the unchanged (immobile) component for illustrative purposes (Eq. 1; cf. Grant,
1986):

(1)
where X, is net mass change, WA is weight of least-altered sample, W, is recalculated weight
of altered sample, X, = WA is weight of least-altered sample, X, is weight of altered sample,
and X&,7/X&,3is RAjB (correction factor - CF; see the Appendix for further definitions).
In this study, the mass-change is expressed as a percentage (X,/X, * 100) to illustrate
the relative change of components.

5.2. Immobile-element selection criteria

Gresens’ mass-volume-balance technique compares volume factors (F,; Appendix) for

each element analysed to identify coincident F, values that can be used as a correction
factor; the reasoning is that coincidence of F, values indicates coherent element behaviour
and thus immobility. However, this may not work in some hydrothermal systems, particu-
larly those that contain fluorine because many elements are more mobile than in fluorine-
absent systems. Correlative statistics to determine conserved-element behaviour (Leitch
and Lentz, 1994) do not work if the mass variations are small because the natural trace-
 D.R. Lentz, C. Gregoire / Journul of Geochemical Exploration 52 (1995) 303-331 71.5

element variance may be much higher than the mass changes taking place particularly if
the mass changes are small ( < 15%). Alternatively, experimental and empirical solubility
data may be used to determine relative element immobility. Unfortunately however, few
element/mineral solubility studies have been done, even under restricted hydrothermal
conditions. In many studies, aluminum is considered relatively immobile under low- to
moderate-temperature hydrothermal, and greenschist-grade metamorphic conditions (cf.
Barton et al., 199 1) . In albite-paragonite-quartz and microcline-muscovite-quartz assem-
blages, Woodland and Walther ( 1987) and Walther and Woodland ( 1993) determined that
Al solubility in Hz0 was prograde with temperature and pressure but at 450°C and 1 kbar
( 100 MPa) the Al solubility is about 12 ppm. This is similar to measured Al contents from
vent fluids from the TAG submarine hydrothermal system (Campbell et al., 1988) and
from the East Pacific Rise submarine hydrothermal system (Bowers et al., 1988).
Aluminum solubility relative to Al abundance in the host rocks is critical; the higher the
abundance of a particular element in a rock, the higher the fluid-rock ratios must be to
transform it. Solubility relative to rock abundance is important because in a mass-balance
analysis, the ratio the immobile-element contents of the least-altered parent (A) and altered
rock (B) is used to determine the correction factor ( RA”) ( simplified F,) . For example,
a ratio of approximately 9 X lo-’ (Al,,/Al,,,,) for aluminum (immobile) in comparison
to 3 X lop3 (Si,,/Si,,,,,) for silicon (mobile) can be calculated using the solubility data of
Woodland and Walther ( 1987) and Walther and Woodland ( 1993), which is similar to
experimental data presented by May et al. ( 1986) and Sokolava and Khodakowsky ( 1978).
The lower this dimensionless number (relative solubility index; RSI), the lower the relative
solubility. The presence of muscovite/sericite with most of the alteration assemblages
indicates the fluid pH did not drop below the muscovite-aluminosilicate buffer at a given
aK + except in a few instances so that Al solubility should remain relatively low. With this
inmind, Al was used to calculate the RA’B (Table 1), which was applied as a correction
factor to each of the samples. The mass-balanced data were derived by the difference
between the average True Hill granite (y1= 9) and the particular sample with the raw data
presented in Table 1. The mass-balanced major- and trace-element data were plotted down
each of the drill holes to illustrate the compositional changes between the greisen and least-
altered granite samples spatially (Fig. 6a,b). The variance of the least-altered data is shown
using different symbols for altered and least-altered samples, and should be considered
when evaluating the mobility of any particular element. It is evident that some of the
traditionally immobile elements (e.g., TiO, or Zr) have a high variance because of frac-
tionation within the parent granite, thus making them unsuitable for deriving RA’B factors
or determining their mobility.

5.3. Mass-balance systematics

Description of the compositional changes resulting from alteration within the granite will
involve only the calculated mass-change data. Trace- and major-element behaviour may be
discerned from a statistical analysis of the mass-balanced data. Both parametric (Pearson
Product; r) and non-parametric (Spearman’s Rank; r' ) correlation coefficients and their
95% confidence levels (Davis, 1986) were derived from the net mass-change data because
some of the data have both normal (parametric) and skewed (non-parametric) distribution.
316 D.R. Lentz, C. Gregoire / Journal of Geochemical Exploration 52 (1995) 303-331

s 3
(ml wdaa
D.R. kntz, C. Gregoire /Journal of Geochemical Exploration 52 (1995) 303-331 317

(4 @aa
318 D.R. Lent,-, C. Gregoire /Journal of Geochemical Exploration 52 (1995) 303-331

40
20 .-

0 -.
c
. AIMi”lml
l.
. .A
.
.
900

700
--

--
D

.
M”scovil~
Tww
+

. illl
- . o,rnlu
G,.lsa”

A% NE@ -20 ..

_4o v
j

-60 -- I . 0.49
1

l
(Irmti.

bhn . , /
AA A%F
500

300 ..
--

I’/ .

,>*
Fbx.*e

- 8mcmcdmt 100 .. . :$a= ’ I r 0.61

-80 .. . ToDui*“h seh8”tbn i J
l

. . . .-
-1w.o : . ?:=%. t -100 7
-100 80 -m -40 -20 0 20 ~100 0 100 203 3w
A% K,O A% CaO

Fig. 7. Mass-balance variation diagrams with correlations for data distribution. (A) A% F versus A % SOL, (B)
A % K,O versus A % Si02, (C ) A % Na,O versus A % K,O, (D) A % F versus A % CaO. Vectors illustrate general
alteration trends. r = Pearson Product correlation coefficient for the data.

If the Pearson Product and Spearman’s Rank correlation coefficients are similar, the data
are probably close to a normal distribution and the parametric statistics (r) should be used.
If they are different, i.e. typical of skewed distributions, the non-parametric correlation
coefficient (r’) is probably the more relevant. Using similar reasoning, MacDonald and
Clarke ( 199 1) use nonparametric ranking statistics to characterize magmatic versus post-
magmatic element mobility.
Statistical analysis of selected mass-balanced data helps to reveal elemental associations
that are indicative of mineralogy and processes occurring in the alteration zone (Table 1) .
The inference is that those samples falling farthest from the point of zero change for that
element are the most altered with respect to parent granite. Note that the most silicified
sample (80-6-203.3m) ( + 40% SiO,) has the largest mass increase ( + 23%). Hydrother-
mal alteration is concentrated in the upper parts of B and C cupolas, which is evident from
the mass-change data going down each of the holes (Fig. 6a,b). SiO,, FeO, MnO, CaO,
and S are enriched, whereas K,O and Na,O are depleted, in most greisen samples.
Moderate positive correlations between SiO, and F (Fig. 7A) and CaO and F (Fig. 7D)
indicate that fluorite is erratically associated with silicification, whereas the inverse corre-
lation of alkali elements and Si02 is typical of alkali element leaching during greisen
alteration (Fig. 7B). For the most part, K20 and Na,O are leached during feldspar hydrolysis
with Na decreasing more markedly than K20 because of formation of muscovite/sericite
in the greisen assemblage (Fig. 7C). However, one sample contains secondary albite (80-
6- 102.4m), that replaces K-feldspar.
Sulfur is enriched in only a few samples, particularly near the upper part of the cupolas,
and correlates with Fe (Fig. 8A), perhaps indicating the presence of pyrite. Fe correlates
inversely with the major alkali elements but positively with MnO (Fig. 8B,C) consistent
with the formation of hydrothermal chlorite and pyrite. Si02 correlates inversely with major
 D.R. Len@. C. Gregoire/Journal of Geochemical Exploration 52 (1995) 303-331 319

A% SiO,

‘a,
i .
: .+
0;
0
..
i .
e .
d .
.,m,- . . ..t- .
.* :*. *.
r = 0.48
r’ = 0.49

A% K,O

.
.
.
.’ .
. .

Fig. 8. Mass-balance variation diagrams illustrating the differences between least-altered granites ( v) and gre-
isenized granite (0) with correlations for data distribution. I= Pearson Product correlation coefficient.
r’ = Spearman’s Rank correlation coefficient for the data (see Davis, 1986).

alkali elements (Fig. 8D,E), indicating that silicification coincides with the hydrolysis of
feldspar to micas. P,O, increases with Fe, S, Mn, Th, SiO,, Ti02, and La and other LREE
enrichment indicative of hydrothennal monazite and possibly titanite with silicic chlorite-
pyrite alteration. There is an inverse correlation between F and K20 but a positive correlation
between K20 and Rb (Fig. 8H,I). Moderate positive correlations between SiO,, CaO, and
F and Y and F demonstrate the association of fluorite and silicic alteration (Fig. SJ,K,L) .
As expected, the decrease in alkalis resulting from feldspar hydrolysis and increase in
SiO, and F are the major characteristics of greisen alteration because of the formation of
fluorine-rich muscovites and local saturation of quartz and fluorite. Compared to the average
composition of each cupola, the average greisen cupola is slightly enriched in SiOl (Fig.
6a; Fig. 9A) indicating silicification and to a greater degree enrichment in Fe20Zt, MnO,
and MgO, due to the formation of hydrothermal chlorites and sulfides (Fig. 9A). CaO and
320 D.R. Lentz, C. Gregoire / Journal of Geochemical Exploration 52 (1995) 303-331

4.00
3.50
3.00
g 2.50

i
B 2.00

5 1.50
_n

E 1.00

0.50

0.00

-0.50
SO.2 TiO2 A1203 Fe203 MS0 M”0 CaO N&Z0 K20 P205

1.80

1.60

1 .A0

g 1.20

0i! 1.00

2 0.80

f
(1 0.60

0.40

0.20

0.00 4 I
Ba Sr Rb es Tl Zr Y Nb Ta Th ”

LOO

1 .a0

1.60

0.00
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

Fig. 9. Average greisen/average granite from cupola B and C at True Hill (cupola B: 7 greisen and 3 granite
samples; cupola C: 12 greisen and 6 granite samples). (A) Major- and minor-element, (B) trace-element, and
(C) rare-earth-element distribution in the average cupola B and C greisen relative to the associated True Hill
average granite.

P,O, are also enriched because of the presence of fluorite and monazite in the greisen,
whereas NazO and K20 are leached due to hydrolysis of feldspars (Fig. 9A). The Al,O,
content of the average greisen is usually slightly lower than the associated granite indicative
of small mass-volume gains associated with the alteration process. In general, the intensity
of greisen alteration is greater in cupola C than cupola B, based on the major-element data,
consistent with the description of the alteration.
 D.R. Lentz, C. Gregoire /Journal of Geochemical Exploration 52 (1995) 303-331 321

In general, Cs, Rb, Sr, and Eu decrease, whereas Ba increases, during alteration (Fig.
9B). Ba, Rb, Cs, and Tl contents are very irregular, particularly in the greisen samples. Ba
correlates weakly with Rb (r= + 0.48), whereas Rb covaries most strongly with K,O
( r= + 0.62). Cs correlates strongly with Tl ( r = + 0.66) and Ga ( r = + 0.59)) but not with
either Ba or Rb (Table 1) , which explains the similarity in their downhole profiles. Although
Ba, Rb, Cs, and Tl principally substitute into muscovite, their behaviour is more varied in
the hydrothermal system compared to K20. Zr, Hf, Nb, and Ta variations in greisens are
minor compared to the high variance for these elements in the least-altered granites, keeping
in mind that variations in the granite samples probably do not result from alteration and,
therefore, are not real from a mass-balance perspective. Although weak, Sr correlates most
strongly with CaO and Na,O, indicating that it is partially leached due to alteration but
locally enriched, probably in fluorite. The elements Ga, Th, U, Bi, MO, Sn, As, and Sb are
variable in the greisen samples compared to the granite samples. Ga correlates strongly with
Cs, Tl, and In indicating that it is mobile during alteration. Th covaries with the middle
REE (MREE) , SiOz, and TiO,, whereas U covaries with Nb, Ta, and MREE. Bismuth is
the main mineralizing element within the True Hill system but does not correlate signifi-
cantly with any other elements except Sb. MO was not included in the statistical analysis
because of the large number of samples below the detection limit. Tin correlates inversely
with Cs, In, and Tl, but has positive correlations with K20, HREE, and more weakly with
As. Arsenic correlates most strongly with the HREE. Antimony correlates with Bi, S, and
Sn. The LREE have a strong positive correlation with the MREE and HREE, and a weak
positive correlation with P,05 and SiO,. Eu correlates most strongly with the LREE but not
with Ca. The MREE and Y may be substituting in fluorite and/or monazite, which would
account for the moderate positive correlation with F. The HREE correlate with MREE and
LREE and to a lesser extent with Ta and Th. There are weak positive correlations between
CaO and F and HREE.

+z Granit

-(3- Granite C

A Greisen B

-I
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

Fig. 10. Rare-earth-element distribution in the average granite and greisen from cupolas B and C at True Hill.
Chondrite-normalized True Hill granite and greisen using the recommended average chondrite of Henderson
(1984).
322 D.R. Lentz. C. Gregoire /Journal of Geochemical Exploration 52 (1995) 303-331

The granite-normalized greisen REE spectra are different for the cupola B and C granites
(Fig. SC) resulting from different alteration intensities and types in the two cupolas. The
overall REE patterns of the True Hill granite and greisen (Fig. 10) mimic the patterns from
the Mount Pleasant fine-grained granite and several other highly evolved granites in south-
western New Brunswick (see Taylor et al., 1985 and Lentz et al., 1988). The low L%/Lu,
and CeJYb,, characteristic of these highly evolved granites, is typical of F-bearing granitic
melts (Taylor and Fryer, 1984).

6. Discussion and conclusions

The elemental associations within the granite-greisen system are a function of several
processes operating within the granite; ( 1) primary igneous variations, ( 2) fluid saturation
of the granite, including the effects of partitioning of elements into the fluid phase, and (3)
the high- to low-temperature subsolidus hydrothermal reactions between the buoyant hydro-
thermal fluid and the host crystalline granite and metasedimentary rocks.
Interestingly, the HFSE variations are different between the two cupolas; for instance,
the HREE are enriched in cupola C compared to its granite, whereas the cupola B greisen
is depleted in HREE with respect to its granite. This phenomena may be due to high-level
fractionation (primary), high-temperature alkaline alteration (e.g., albitization), or greisen
alteration within the cupola. The cupola C greisen has higher Fe, Mg, Ca, P, and F than the
cupola B greisen indicating that alteration was most intense in cupola C.
The distribution of alteration in each instance is focused predominantly into local cupolas
in the irregular roof of these granites. The hornfels assemblages related to the intrusion are
preserved in most cases except in the stockwork zone above the granite cupola. This evidence
together with the general absence of pervasive and minimal proportion of vein related
alteration in the deepest parts of the granite intersected by drilling indicate that meteoric
water was probably not involved in the main stage greisen alteration process dominated by
deuteric fluids.
As previously mentioned, the True Hill granite has many geochemical similarities to the
haplogranite system with estimated eutectic conditions of 730°C and 100 MPa ( 1 kbar)
(Lentz et al., 1988). In each case, the granites have undergone vapor-phase separation
resulting in the formation of pegmatitic zones, aplite dikes, and locally miarolitic cavities.
These fluids have produced variable degrees of alteration and host-rock preparation for the
migration of fluids including spectacular evidence of multiple brecciation (Lentz et al.,
1988; Lentz, 1994). The partitioning of elements into a fluid-phase, evolving from a
saturated crystallizing melt may account for the enrichment of some elements above that
melt in the endogranitic and exogranitic carapace that is undergoing metasomatic fluid/
rock reactions. Element partitioning and solubility studies (e.g., Holland, 1972; Candela
and Holland, 1984; Eugster, 1985; Urabe, 1985; Webster et al., 1989; Keppler and Wyllie,
199 1) suggest that pressure, temperature, ligand concentration, and bulk-melt composition
are critical factors in the solubility and partitioning of elements from a melt and into a fluid.
The anomalous Sn, MO, W, and selected base-metals may be attributed to vapor-phase
separation under these crystallization conditions. Like the base-metals, Sn was probably
complexed by Cl under moderately acidic conditions during vapor saturation (Eugster,
 D.R. Lentz, C. Gregoire /Journal of Geochemical Exploration 52 (1995) 303-331 323

198.5; Heinrich and Eadington, 1986; Heinrich, 1990), whereas W and MO were probably
hydroxyl complexes. Although not investigated in any of the experimental partitioning
studies, bismuth was also probably partitioned into the vapor phase as it evolved from the
granite. At 350°C and weakly acidic pH’s, Bi-hydroxide complexing (Bi( OH),) is impor-
tant, even in saline solutions, as are MO (MoO,( OH),), Sb (Sb( OH),), and W
( WOz( OH) 2) complexing (Wood et al., 1987). The association of Bi with MO and W at
True Hill (Lentz et al., 1988) and in the Fire Tower zone at Mount Pleasant (Dagger, 1972;
Pouliot et al., 1978; Kooiman et al., 1986) supports similar complexing and depositional
mechanisms for these elements. Bi does not correlate well with other elements suggesting
a mechanism for deposition that is independent of the alteration process. Of the element
correlations from East Kempville derived by Chatterjee and Strong ( 1984), only Th, Pb,
and F show significant correlations with MO and W. At True Hill, the minor variations in
Nb and Ta correlate with each other and with the HREE and Th. However, the significant
correlation of %A La, Ce, and Nd with %A SiOz and P,05 suggests that some of the LREE
enrichment is coincident with silicification. The anomalous LREE associated with SiOz and
P205 suggests that the ligand concentration must have been high enough to partition some
LREE into the vapor phase (cf. Flynn and Bumham, 1978; Webster et al., 1989). The
presence of hydrothermal apatite and monazite in the greisen explains the positive corre-
lation between LREE and P*O,, although P is not greatly enriched in the greisen (0.02-
0.03 wt.%). There is also a weak positive correlation between both HREE and Y with F
suggesting that these elements are enriched in the greisen and partially associated with
fluorite, muscovite and topaz alteration. Xenotime has been described in the greisen assem-
blage but HREE and Y may also be substituting partially into fluorite. Flynn and Burnham
( 1978), Taylor and Fryer (1984), and Wood ( 1990) indicate that F preferentially com-
plexes with the HREE, which may account for their weak enrichment. Eu is depleted in
both cupola B and C greisen consistent with the leaching of alkali elements and the break-
down of feldspar, but as it is not correlative with F is probably not preferentially substituting
diadochically for Ca in fluorite. The negative Eu anomaly in the greisen relative to the
granite (Fig. lo), shows that Eu is behaving as a divalent species during greisenization, as
predicted by Sverjensky ( 1984) and Wood ( 1990). Notably, %A Th correlates with %A
P205, SiOz, Nb, and Mn suggesting at least some mobility during alteration. Like the REE,
Th requires F ligands to facilitate partitioning into the vapor phase (Keppler and Wyllie,
1991) consistent with the F associated with the greisen assemblages. Zr correlates strongly
with Pz05 and SiO* also consistent with hydrothermal mobility and deposition within the
zone of greisen alteration. Although extreme fractionation cannot be ruled out in the vari-
ations of some of the HFSE, the small size of the sample area and correlations with known
hydrothermal constituents suggests that much of the variation is related to hydrothermal
activity. The variations in Cs, Rb, and Tl are controlled by the distribution of hydrothermal
muscovite, and show good correlations with K20, although the Cs, and Tl also correlate
with Ga, In, and MnO, which are enriched hydrothermally. Indium does not correlate with
Zn because of the very low abundance of sphalerite. Ga correlates most strongly with In.
Tl, and Cs (Ga, In, and Tl are Group IIIB elements). The coherency of their variation
suggests that these elements are substituting into hydrothermal muscovite.

6.1. Hydrothermal reactions

The compositional changes result from the interaction of the exsolved hydrothermal fluid
with subsolidus granite carapace, which then undergoes metasomatic re-equilibration with
324 D.R. Lentz, C. Gregoire / Journal of Geochemical Exploration 52 (1995) 303-331

0 4 6 -2 0 2 4 6

Log a(K+)/a(H+) Log a(K+)/a(H+)

Fig. 11.Activity-activity diagram illustrating the relative stability of (A) Fe chlorite and biotite relative to other
aluminosilicate phases at 300 and 400°C at 500 bars and (B) intermediate Fe-Mg 14 A chlorite (Chl) and biotite
(Bio) with respect to K-feldspar (Kfs)-Muscovite (Msc)-pyrophyllite (Kaol)-andalusite (And) (topaz) at
300°C and 400°C at 500 bars (see Bowers et al., 1984).

the fluid. The deposition and redistribution of elements is a function of solubilities within
the greisen assemblage under evolving fluid conditions (P, T, pH, ligand cont. etc) . The
distribution of major and trace elements in the greisen-granite system is best interpreted by
the reactions affecting the major components involved in greisenization. The low to mod-
erate pH of the fluid results in partial to complete hydrolysis of primary feldspars to
muscovite, a characteristic of greisen assemblages (Eq. 2; Fig. 11) :
3 KAlSi,O, + 2 HCl + 1 KAl,[ Si3A120L0] (OH), + 6 SiO, + 2 KC1 (2)
K-feldspar muscovite quartz

(K-feldspar= 108.87 cc/mol, muscovite = 140.76 cc/mol, quartz = 22.69 cc/mol).

If silica is already saturated in the fluid during feldspar hydrolysis, there is a net volume
decrease of 15%. It follows, therefore, that the net mass increase realized in most greisen
alteration at True Hill is the result of deposition of other components during the leaching
of alkali elements. The further hydrolysis of muscovite, yielding topaz, involves leaching
of the remaining alkalis from the rock at higher fluid/rock ratios (see Montoya and Hemley,
1975; Rose and Burt, 1979; Bumham and Ohmoto, 1980) or possibly the hydrothermal
mobility of aluminum. The low pH required to break down feldspar to muscovite and/or
topaz at a specific KC activity (K+/H+ ratio) requires further dissociation of the acid
species in the fluid, which is commonly associated with a cooling fluid, or an overall increase
in acid components (e.g., HCl and HF) that may result from boiling or condensation from
a boiling fluid (Burt, 198 1)
The formation of hydrothermal Fe-rich biotite and more commonly Fe-rich chlorite is
indicative of high Fe activities [Fe’+ /(H’)2] (Fig. llA,B) and may be envisaged as
protolysis reactions with muscovite (Eqs. 3 and 4) :
1 KA13Si301,,(OH)2 + 9 FeCl, + 6 Si02 + 2 KC1 + 12 H20
lll”ScO”tte qtZ

= 3 KFe3A1Si,0,,,( OH), + 20 HCl (3)

biotite
 D.R. Lentz, C. Gregoire /Journal of Geochemical Exploration 52 (1995) 303-331 325

2 KAl,Si,OlO( OH), + 15 FeCl, + 3 SiOz + 24 H,O

muscovite qtz

= 3 Fe,Al,Si,O,,( OH), + 2 KC1 + 28 HCl (4)

chlorite

Hydrothermal biotite forms at both higher Kf /Hf and temperatures relative to chlorite.
The predominance of Fe chlorite-muscovite over biotite-muscovite as the hydrothermal
assemblage in the upper parts of the True Hill cupolas supports a low temperature of
formation ( < 350°C) and/or low Kf /H+ ratio ( < 1000; see Beane and Titley, 1981).
The enrichment of Fe, Mn, base metals, and S in the chloritic greisen assemblage, and
the positive correlation between these constituents, indicates that their saturation is a func-
tion of the stabilization of chlorite resulting from increasing FeCl, activities (see Fig.
11A,B) at low pH (low K+ /H+ ) in the upper parts of the cupola. The enrichment in the
Fe, Mn, base-metal constituents and H,S in the fluid is a result of fluid-melt partitioning
(see Holland, 1972; Bumham, 1979; Urabe, 1985) and incongruent dissolution of primary
biotite, titanite, and magnetite in crystalline granite ( see Eugster, 1985). For the most part,
the sulfide assemblage is moderately reducing with magnetite locally present with pyrite.
Earthy hematitic alteration is present but seems to be a later meteoric activity superimposed
on the Fe-rich assemblages.
As previously noted, silica may be oversaturated (deposition?), saturated, or undersa-
turated (dissolution) during feldspar hydrolysis, but the slight increase in silica associated
with the True Hill greisen indicates that Si02 was slightly oversaturated during alteration,
which could account for some of the mass increase. The modest mass increase associated
with greisen alteration at True Hill can, for the most part, be accounted for by the proportion
of quartz-filled cores of greisen veins. The silica solubility during vapor-phase saturation
from the magma at lithostatic conditions should be on the order of 3400 ppm SiO, in
solution, whereas the silica solubility associated with low- to moderate-temperature gre-
isenization (e.g., 300°C) at or above hydrostatic conditions should be just above or on the
boiling curve, and should contain approximately 1000 ppm SiO, in solution, if indeed in
equilibrium (Foumier, 1984). The evidence for quartz dissolution in some of the greisens
indicates that the fluid pressure decreased before temperature dropped resulting in retrograde
quartz solubility in the low-pressure (30 to 60 MPa- 300 to 600 bars) and high-temperature
(400 to 600°C) conditions. The deposition of quartz in veins suggests that at low temper-
atures a decrease in pressure, possibly down to the liquid-vapor boiling curve, may have
resulted in rapid quartz saturation that overcame the sluggish kinetics of quartz deposition.
The distribution of fluorite in the endogranitic greisen is irregular and probably controlled
by the saturation of aqueous CaF,, which is prograde with temperature, pressure, and Ca2+,
Mg2+, and H+ concentrations (Richardson and Holland, 1979). Hence, decreasing tem-
perature and pressure, or increasing pH of the solution in the supercritical region, would
result in fluorite saturation.
The presence of hydrothermal breccias in cupola C (Lentz, 1994) suggests that boiling
was involved in the cupola during the main-stage, fluid saturation/greisenization event. In
addition, fluid inclusion studies in the quartz-topaz assemblages in the Fire Tower Zone at
Mount Pleasant by Davis and Williams-Jones (1985) and Samson (1990) indicate that
fluid boiling was an intergral part of the alteration process. Overall their data seem to favor
326 D.R. Lentz, C. Gregoire / Journal of Geochemical Exploration 52 (1995) 303-331

second boiling of a low-volatile melt followed by first boiling of the supercritical fluid,
which is consistent with the deposition of W, MO, and Bi by destabilization of their com-
plexes as a result of first boiling (Drummond and Ohmoto, 1985), and abundant pervasive
silicification due to a decrease in geostatic pressure (Holland and Malinin, 1979; Dagger,
1972; Parrish and Tully, 1978; Pouliot et al., 1978). Like Mount Pleasant, wolframite,
molybdenite, and bismuthinite occur in the cores of quartz veins and disseminated in greisen
at True Hill. The intense greisen alteration usually confined to vein networks also indicates
that first boiling may be responsible for the decrease in K+ /H+ ratio (low pH) associated
with the quartz-topaz and quartz-sericite-topaz alteration zones (Burnham and Ohmoto,
1980; Burt, 1981). Large changes in geostatic pressure from lithostatic to hydrostatic
conditions are characteristic of this environment (Burnham and Ohmoto, 1980).
The saturation of Sn in the hydrothermal fluid to form cassiterite is related to the desta-
bilization of divalent Sn-chloride complexes (SnCl,), which is principally related to
decreasing temperatures below 350°C ( Sn2+ + Sn4+ ), and increasing pH due to hydrolysis
reactions (cf. Jackson and Helgeson, 1985; Eugster, 1985; Heimich and Eadington, 1986;
Heinrich, 1990) both of which are involved in this system.
Several factors affect the variation in intensity of mineralization at True Hill versus
Mount Pleasant including abundance of volatiles, depth of intrusion, composition of volatile
phase, efficiency of partitioning, incongruent and congruent dissolution of minerals hosting
ore-forming elements during intergranular and vein infiltration of deuteric fluids, and the
efficiency of the depositional mechanisms. The mechanisms responsible for the distribution
of cupola mineralization and alteration at True Hill and the Fire Tower W-Mo-Bi porphyry-
greisen deposit at Mount Pleasant are analogous to those responsible for the formation of
the Climax MO deposit (cf. White et al., 198 1)

6.2. Comparison with other porphyry-greisen systems

The limitation of using this example for a mass-balance calculation in a porphyry-greisen

system is the weakly developed mineralization; therefore, the geochemical factors that
control mineralization are probably not as discernible as in more mineralized systems. Few
studies have incorporated mass-balance techniques in the analysis of porphyry-greisen
alteration systems, except Taylor and Fryer ( 1980), Baker ( 1985), Kretz et al. ( 1989))
Merceron et al. ( 1992)) and Kontak ( 1994).
In a detailed comparison of two porphyry Cu alteration systems in Turkey, Taylor and
Fryer (1980) used Gresens’ mass-balance techniques to show that volume changes in
potassic and propylitic alteration zones were minor ( < 10 volume %) based on Al immo-
bility. In the potassic zone, Si02 and K,O increased whereas the remainder of the majors
elements decreased consistent with the observed mineralogy. LREE, Rb, Pb, and Cu were
slightly enriched but Sr, Ba, Zn, and HREE were depleted with Y, Th, and Zr relatively
unchanged. In the propylitic alteration that overprints the potassic alteration, the elemental
variations were more irregular with obvious decreasing Si02, K,O, and REE with increases
in Fe, P, Sr, and Ba, as well as irregular base-metal distributions. At East Kempville Nova
Scotia, Kontak ( 1994) found that in two zoned Sn-bearing greisen veins the isocon diagram
is best defined by Zr, U, Si, Al, Th, and Ta (remained relatively immobile), which indicates
that the alteration products were close to isovolumetric ( + 10%) (cf. Boyle, 1990). HOW-
 D.R. Lentz, C. Gregoire / Journal of Geochemical Exploration 52 (1995) 303-331 321

ever, these element systematics seem to break down in the most intense greisen alteration
(quartz-topaz greisen) possibly because the fluid pH is below the muscovite-
aluminosilicate buffer. In addition, the HF activity (hard acid) is relatively high with topaz
stable over andalusite thus affecting high-field-strength-element (HFSE) mobility, but the
general principle of the relative solubility versus abundance should still apply. Chatterjee
and Strong ( 1984) noted similar chemical changes associated with greisenization of the
East Kempville granite and, as in this study, used the correlation statistics to help decipher
the chemical relationships. Merceron et al. ( 1992) used mass-balance techniques to describe
muscovite and donbassite alteration in a granite cupola in the Massif Central. The muscovite
alteration zone had a 14% decrease in volume (F, = 0.86)) as did most other components,
but showed a slight enrichment in K,O, whereas the donbassite alteration involved 3% mass
addition and involved the addition of FeO, MgO, CaO, K,O, P,O,, and Li. Baker ( 1985)
described the geochemical systematics associated with albitization of a peraluminous granite
and noted that, although it resulted in the depletion of most elements, increases in Ga, Zn
and Ni were noted. As the density and A&O, variations were negligible so then were the
volume changes; the LREE were leached substantially, whereas the HREE and Y were
unchanged. Taking into consideration variance of immobile components, Kretz et al. ( 1989)
noted increases in P,O, and H,O and decreases in K20, Ba, and Sr in the muscovite alteration
selvage in a granitic host rock marginal to a pegmatitic vein. MnO, Li, Zn, Rb, and Zr were
also slightly enriched in the micaceous selvage to the pegmatite.
In each of these cases, the actual compositional variations produced by hydrothermal
alteration were discerned and, in some instances, are similar to the compositional variations
observed in the greisen-altered assemblages at True Hill. Using the mass-balance method
will enable direct comparison of alteration types, processes, and fluid evolution in porphyry
deposits of different composition. If properly applied, this could distill the important vari-
ables and alteration indicies controlling mineralization.

7. Recommendations

Although mass-balance analysis has only been rarely applied to porphyry systems, it has
the potential to outline hydrothermal alteration zones, the extent and intensity of alteration,
and the real association with related mineralization, if proper statistical analysis is applied
to the mass-balanced data set. Standard spreadsheet programs can easily perform the mass-
balance calculations and plotting manipulations enabling very easy application of these
techniques to exploration. Statistical characterization of the composition of the least-altered
protolith is critical to mass-balance analysis in porphyry systems because the spatial asso-
ciation between altered and parent porphyry may not be ideal resulting in a less precise but
still useful mass-balance analysis. Elements such as Zr, Ti, Y, Yb, and Nb, traditionally
considered immobile, are known to be mobile in porphyry systems, particularly if fluorine
is present in the volatile phase. It is also critical to consider element concentration in the
rock when selecting elements for determining the mass-correction factor (CF or RA’B)
because greater fluid/rock ratios are required to change the rock concentration of a high
abundance versus a low abundance element. Obviously, the precision of chemical analysis
is also critical. Therefore, although it is known to be somewhat mobile in F-bearing hydro-
328 D.R. Lentz, C. Gregoire / Journal of Geochemical Exploration 52 (1995) 303-331

thermal systems, it is suggested that Al be considered the least-mobile element in porphyry

systems for mass-balance calculations.

Acknowledgements

This contribution represents a part of a M.Sc. thesis by the first author at the University
of New Brunswick, which was supervised by Dr. Arnie McAllister. We wish to thank John
Langton, Steve McCutcheon, and Dave Sinclair, as well as two anonymous journal referrees
for their incisive reviews of the manuscript. Geological Survey of Canada Contribution No.
19994.

Appendix

Mass-balance definitions and abbreviations

X” net mass change
W‘4 weight of least-altered sample
W, recalculated weight of altered sample
FV volume factor
x,= w, weight of least-altered sample
Xl3 weight of altered sample
SA specific gravity of least-altered sample
St3 specific gravity of altered sample
x,=w,-w*=w*{[(F,)*(SB/S*)*(XB)]-X*} .
smce Fv=VB/VA=MBIMA*SA/
SB, where V B/ V * is the total volume ratio, MB/MA is the total mass ratio, and SB/SA is the
density ratio.
MB/MA may be estimated with an inverse immobile-element weight ratio:

MB/MA = X&, /Xt,,,, or RAIB

x,,= wB - wA = loo{ [ (x:,,O,ix&,,> cxB) 1 -xA)

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