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Article history:
Received 2 November 2009
Accepted 22 April 2010
Available online 3 June 2010
Keywords:
Skarn
Geochemical halo
Carbonate
Copper
a b s t r a c t
The presence of geochemical anomalies, dening haloes around hydrothermal ore deposits, can be used to
vector towards mineralization, or identify ore bodies buried at depth. Several important types of ore
deposits, including skarn deposits, are often hosted within carbonate-rich sedimentary rocks. Identifying
anomalous trace-element concentrations in carbonate rocks is complicated by variable lithology (i.e.
siliciclastic component) and volume loss during hydrothermal alteration. In this study of the world-class
Antamina skarn deposit in Peru, we use the ratio of metals:immobile elements (e.g. La, Al2O3) to differentiate
genuine and false geochemical anomalies in limestones and marbles surrounding the skarn deposit.
Unaltered limestones are used to dene threshold values for metal:immobile element ratios (through use of
the median value 2 median absolute deviations). Genuine anomalies are identied when metal
concentrations exceed those predicted using median + 2 median absolute deviations. In addition,
comparison of four acid and lithium-borate fusion analytical techniques reveals that the lower cost fouracid techniques give reliable results. Our approach can be used to identify geochemical anomalies and halos
related to hydrothermal alteration of carbonate-rich rocks, which have direct application to skarn deposits.
2010 Elsevier B.V. All rights reserved.
1. Introduction
Geochemical anomalies, or haloes around hydrothermal ore
deposits, formed as a result of metasomatism of host rocks by
hydrothermal uids, have been extensively used as an exploration
tool for the discovery of economic ore deposits (Boyle, 1967;
Korzhinskii, 1968; Rose et al., 1979). The detection of trace-element
anomalies is dependent on accurate characterization of the range of
values for the particular trace element(s) or metal(s) of interest (e.g.
Cu, As, and Au) in unaltered rocks, thus allowing trace-element haloes
(i.e. statistical outliers; Barnett and Lewis, 1994) to be distinguished
from background variations.
Skarn deposits form when magmas, intruded into carbonate-rich
host rocks, generate a hydrothermal system. Subsequent thermal
metamorphism and hydrothermal alteration convert carbonate-rich
host rocks into skarn, marble and diopside. In this study, we describe a
method for distinguishing trace-element metasomatism related to
hydrothermal mineralization in impure carbonate rocks. This technique has applications for both regional and local exploration of ore
deposits in carbonate rocks (e.g. skarns, Carlin-type gold deposits).
Impure carbonate rocks contain ne clastic material that may
generate a broad range of trace-element and metal concentrations. In
addition, volume loss (commonly caused by carbonate dissolution)
Corresponding author.
E-mail address: gdipple@eos.ubc.ca (G.M. Dipple).
0375-6742/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.gexplo.2010.04.011
118
Fig. 1. Simplied geology map of the AntaminaCondorcocha skarn systems, showing the visible alteration zoning and the sampling areas and transects used in this study. Modied
from Compania Minera Antamina, 2002.
119
120
Table 1
Averages and range of compositions of host rocks from Antamina (major elements and REE). Database obtained by XRF and ICP-MS analysis of samples previously fused with lithium
borate.
XRF
wt.%
Limit of detection
Marble (n = 32)
(wt.%)
Mean
SiO2
Al2O3
Fe2O3
CaO
MgO
Na2O
K2O
Cr2O3
TiO2
MnO
P2O5
SrO
BaO
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
ICP-MS
ppm
Ce
Cs
Dy
Er
Eu
Gd
Ho
La
Lu
Nd
Pr
Rb
Sm
Sr
Tb
Tm
Yb
LaN/YbN
Ce/Ce*
Eu/Eu*
0.5
0.1
0.1
0.1
0.1
0.1
0.1
0.5
0.1
0.5
0.1
0.2
0.1
0.1
0.1
0.1
0.1
S.D.
Limestone (n = 38)
Range
Mean
S.D.
Hornfels (n = 27)
Range
Mean
S.D.
Range
12.27
3.53
1.31
46.03
1.69
0.20
0.83
0.01
0.21
0.05
0.08
0.09
0.01
10.56
3.40
1.01
9.45
0.86
0.19
1.59
0.01
0.17
0.04
0.05
0.05
0.01
1.5446.81
0.3514.59
0.253.66
12.1754.1
0.853.72
0.010.83
0.029.08
b 0.010.04
0.040.76
0.020.19
0.020.21
0.040.26
b 0.010.04
17.55
4.98
2.01
39.29
2.20
0.24
1.01
0.01
0.29
0.06
0.10
0.08
0.01
8.02
2.36
0.76
7.09
0.65
0.22
0.65
0.00
0.14
0.04
0.04
0.02
0.01
2.4537.28
0.6510.79
0.443.47
21.8252.71
0.913.93
0.020.77
0.063.13
b 0.010.03
0.040.65
0.020.31
0.030.19
0.030.11
b 0.010.03
36.61
11.24
3.21
25.25
2.83
0.66
3.83
0.01
0.57
0.08
0.15
0.06
0.03
10.66
3.01
0.85
9.18
0.49
0.41
2.76
0.01
0.16
0.08
0.03
0.02
0.02
11.5758.71
3.0215.29
1.174.98
6.7947.21
1.734.16
0.061.48
0.6510.78
b 0.010.02
0.180.8
0.020.44
0.10.24
0.030.09
0.010.09
30.7
2.49
1.56
0.96
0.44
2.04
0.32
13.7
0.14
10.5
3.08
41.6
2.13
765
0.27
0.13
0.89
9.79
1.23
0.87
31.7
2.60
1.58
0.96
0.40
2.07
0.33
15.9
0.13
11.7
3.50
63.5
2.17
416
0.30
0.14
0.88
2.39
0.19
0.80
4.7131
0.410.9
0.36.59
0.24.02
b 0.11.36
0.38.58
b 0.11.28
1.770
b 0.10.55
1.951.4
0.515.2
2.4332
0.39.13
3542130
b 0.11.25
b 0.10.59
0.23.77
5.4313.93
0.961.62
0.0483.41
38.1
4.70
2.15
1.31
0.64
2.63
0.42
16.5
0.16
13.5
3.96
57.0
2.91
640
0.34
0.16
1.20
9.54
1.19
0.74
22.6
3.84
1.15
0.72
0.42
1.39
0.22
9.5
0.08
7.6
2.36
30.8
1.61
152
0.19
0.08
0.67
1.60
0.17
0.39
5.6122
0.219.6
0.35.6
0.23.4
0.141.4
0.47.4
b0.11
2.352.5
b0.10.4
1.941.3
0.512.8
4.5129.5
0.48.3
367999
b0.10.9
b0.10.4
0.23.1
6.9614.27
0.791.61
0.232.29
76.8
3.46
4.53
2.81
1.04
5.42
0.88
39.2
0.38
29.7
8.62
135.6
5.62
629
0.80
0.39
2.62
10.36
1.04
0.57
25.6
2.77
1.26
0.79
0.34
1.45
0.25
13.0
0.13
9.3
2.81
76.5
1.54
154
0.24
0.13
0.78
2.25
0.10
0.15
26121
0.410.25
1.46.8
0.84.4
b0.11.8
1.87.83
0.21.21
11.863.4
b0.10.56
8.348.1
2.414.3
18.8302
28.2
274880
0.11.16
b0.10.58
0.74.3
2.5313.20
0.951.37
0.081.02
Ce/Ce* = CeN/((LaN)0.667 (NdN)0.333); Eu/Eu* = EuN/(SmN GdN)0.5; N = chondrite-normalized (data from McDonough, W.F. and Sun, S.S., 1995).
121
Table 2
Averages and range of compositions of host rocks from Antamina (trace elements) Database obtained by ICP-MS analysis of samples previously dissolved by four acids.
Limit of
detection
a
Au
Ag
Al %
As
Ba
Be
Bi
Ca %
Cd
Ce
Co
Cr
Cs
Cu
Fe %
Ga
Ge
Hf
Hg
In
K%
La
Li
Mg %
Mn
Mo
Na %
Nb
Ni
P
Pb
Rb
Re
S%
Sb
Se
Sn
Sr
Ta
Te
Th
Ti %
Tl
U
V
W
Y
Zn
Zr
0.005
0.01
1.00%
0.2
10
0.05
0.01
0.01
0.02
0.01
0.1
1
0.05
0.2
0.01
0.05
0.05
0.1
0.01
0.005
0.01
0.5
0.2
0.01
5
0.05
0.01
0.1
0.2
10
0.5
0.1
0.002
0.01
0.05
1
0.2
0.2
0.05
0.05
0.2
0.005
0.02
0.1
1
0.1
0.1
2
0.5
Marble (n = 32)
Limestone (n = 38)
Hornfels (n = 28)
Mean
S.D.
Range
Mean
S.D.
Range
Mean
S.D.
Range
0.003
0.68
2.13
14.6
65.9
0.66
2.41
29.44
0.41
25.58
3.3
17
2.96
58.6
0.90
5.22
0.12
0.4
0.01
0.033
0.71
12.9
9.1
1.05
289
1.11
0.16
5.1
7.6
365
56.5
38.4
0.002
0.43
0.77
1
0.9
878
0.37
0.23
4.0
0.102
0.33
1.5
34
1.1
8.2
126
12.7
0.001
1.98
1.97
23.3
72.1
0.62
5.71
5.70
0.49
27.06
2.5
12
3.14
69.9
0.73
4.91
0.04
0.4
0.00
0.027
1.00
13.2
8.3
0.55
263
0.80
0.15
5.4
6.1
229
161.4
58.6
0.002
0.39
1.10
1
0.8
446
0.40
0.21
4.4
0.100
0.36
0.7
35
1.9
6.8
166
12.3
b 0.0050.008
0.0511.3
0.248.09
b 5128
10330
b0.052.38
0.0430.5
9.0536
b0.021.6
4.45123.5
1.210
452
0.4513.75
6.6222
0.172.68
0.6921.4
0.050.21
0.11.6
b0.010.01
b 0.0050.116
0.035.56
2.356.3
1.339.9
0.482.41
991280
0.213.5
0.010.65
0.525.1
b 0.221.6
801010
2.9915
1.8325
b 0.0020.011
0.031.67
0.15.97
b 13
0.14
3612330
b0.051.81
0.081.03
0.320.4
0.0090.416
0.031.68
0.53.3
5118
0.19
1.828.9
5610
1.448.3
0.006
0.19
3.04
17.8
85.0
0.91
0.11
25.39
0.48
34.60
5.4
25
5.76
9.2
1.37
7.25
0.16
0.8
0.01
0.026
1.01
17.6
19.8
1.38
404
0.86
0.19
6.5
12.5
467
14.9
52.8
0.001
0.49
0.70
1
1.0
741
0.47
0.10
5.2
0.145
0.54
1.5
71
0.7
12.0
78
27.7
0.017
0.32
1.43
28.4
49.3
0.49
0.11
4.58
0.41
21.14
2.0
26
4.77
4.7
0.53
3.39
0.06
0.3
0.01
0.013
0.61
10.4
9.8
0.41
324
0.37
0.18
3.8
4.9
174
28.9
27.6
0.001
0.21
0.89
1
0.6
165
0.30
0.05
3.3
0.074
0.32
0.4
32
0.5
5.3
74
10.6
b 0.0050.105
b 0.011.91
0.46.63
b5143
10210
0.172.11
0.010.67
14.835.3
0.021.89
4.86112
1.49.3
6174
0.3123.6
2.531.5
0.332.45
1.0115.9
0.050.31
0.21.5
b 0.010.06
b 0.0050.071
0.093.12
2.855.9
3.441.2
0.562.46
1542240
0.131.78
0.010.62
0.917.5
b 0.219.7
120860
1.1180.5
4119
b 0.0020.004
0.0061.06
0.053.56
b13
b 0.22.2
4371090
0.051.32
b 0.050.25
0.614.7
0.0160.344
0.051.84
0.72.5
5133
0.12.2
226.1
15436
549.3
0.006
0.61
6.46
47.1
305.0
2.20
1.02
17.21
0.55
73.77
9.6
42
3.79
71.6
2.23
16.49
0.16
1.1
0.02
0.064
3.10
38.2
16.9
1.69
601
1.39
0.50
16.4
18.0
735
108.0
131.0
0.001
0.83
1.30
3
2.4
662
1.18
0.32
12.9
0.335
0.78
2.0
110
2.4
23.0
151
30.4
0.007
1.05
1.59
54.5
192.8
0.80
1.76
5.97
1.25
23.56
4.4
18
3.06
173.5
0.58
6.77
0.05
0.3
0.06
0.058
1.72
14.2
12.2
0.28
563
0.89
0.33
5.2
4.0
168
338.4
66.8
0.001
0.44
1.16
1
0.7
164
0.38
0.46
4.4
0.088
0.67
0.6
19
3.8
5.8
311
8.8
b0.0050.021
0.044.05
1.948.31
5.1243
40850
0.613.89
0.117.38
5.4830.1
b 0.026.47
25.1110.5
3.923.3
1393
0.5812.05
4.8904
0.793.41
4.4344.8
0.110.32
0.41.6
b 0.010.3
0.0170.331
0.656.88
13.180.9
260.3
12.34
2242960
0.655.17
0.041.24
3.624.5
11.427.7
5001210
3.61800
26.2319
b0.0020.004
0.162.56
0.365.48
0.15
0.73.5
298889
0.241.78
b 0.052.29
2.821.4
0.0860.455
0.183.45
0.94.4
58148
0.321.4
8.732.9
141650
12.649
the QFP dikes (N100 m) spans a range of values between Celendin and
Jumasha, which makes it difcult to identify the stratigraphic unit that
host the mineralization at Antamina. In general, SiO2 correlates with
Al2O3, Fe2O3, K2O and La (Fig. 2A to E), which together are taken to
reect variations in the siliciclastic component of limestones. Low
SiO2/Al2O3 ratios for limestone (average 3.63) are consistent with a
detrital source of silica in limestone (Slack et al., 2004). The plot of
SiO2/Al2O3 versus TiO2 (Fig. 2F) for limestone shows that some
samples taken at distances less than 100 m from QFP dikes generally
contain more TiO2 than limestone distal to dikes.
4.1.2. Marble
Five different marble units are recognized in Antamina based on
color: gray, light gray, light green, tan and white. Gray and white
marble have higher CaO and lower Al2O3, SiO2, Fe2O3 and K2O content
than average limestone (Fig. 3A, B and C). Fine-grained marble found
outside the Antamina West zone (tan, light gray and light green)
generally contains more MgO than the gray and white, coarse-grained
marble units. The chemical composition of marble units close to the
skarn front, especially at Antamina West, is very similar to that of the
unaltered Jumasha limestone taken at Yanacancha. The green and tan
marble units are generally richer in most of the major elements (SiO2,
Al2O3, Fe2O3, MgO and La) than other marble units and unaltered
limestone (Fig. 3A, B). The K2O and Na2O contents of the green and tan
marbles are also high with the exception of one sample of tan marble
taken at Antamina West, which contains the lowest value of K2O and
Na2O. The green and tan marbles also contain the lowest values of
calcium. Fig. 3F shows a trend between tan marble with low SiO2/
122
Fig. 2. Plots of representative major elements versus silica (A, B, C) and bivariate plots of relatively insoluble elements for limestone rocks from Antamina (D, E, F). Observe the
relative low silica and titanium content of samples taken at distances greater than 100 m from QFP dikes. Observe also the composition of limestone taken at Antamina is similar to
the Celendin Formation limestone taken at Yanacancha.
Al2O3 white, light gray, green and gray marble with progressively
higher SiO2/Al2O3 values and lower TiO2 content. Plots of La versus
SiO2 and La versus Al2O3 show that some samples of tan marble occur
outside the limestone eld. The near constant SiO2: La and Al2O3: La
ratios between limestone and tan marble and the higher content of
SiO2, La and Al2O3 in tan marble (Fig. 3D and E) require either that
they were derived from a limestone protolith that is not prevalent
outside the area of alteration, or that the value represents chemical
alteration. One way to elevate concentrations at xed ratios is passive
enrichment during mass loss. Therefore, covariations of SiO2, Al2O3
and La are attributed to hydrothermal alteration via carbonate
dissolution.
4.1.3. Hornfels
In general, hornfels silica content is greater than unaltered
limestone. Gray and light gray hornfels show a broad range of values
in SiO2 content, but it is generally similar to those found in limestone
proximal to the QFP dikes (Fig. 4A and B). Tan, white, light green and
green hornfels contain slightly higher Al2O3, SiO2 and K2O values (Fig.
4A and C) and lower CaO and SrO. Average SiO2, Al2O3 and K2O
contents of white hornfels are higher than other hornfels. In general,
there is not a signicant variation in the Fe2O3, MgO, Na2O and MnO
content of all hornfels, which are similar to concentrations in
limestones and marbles. A plot of SiO2/Al2O3 versus TiO2 for hornfels
(Fig. 4F) shows that similar SiO2/Al2O3 ratios between unaltered
limestone and hornfels, but striking higher amounts of TiO2 in
hornfels especially in white, tan, green and light green hornfels. Plots
of La versus SiO2 and Al2O3 for hornfels suggest that elevated
siliciclastic content are the product of carbonate dissolution (Fig. 4D
and E).
4.2. Rare earth elements (REE)
Rare earth element (REE) abundances (see Appendix 1) were
normalized to chondrite (McDonough and Sun, 1995; see Appendix 3).
Chondrite-normalized values were plotted for each rock type, and
compared to limestones, in order to determine REE variations in the
different alteration zones around Antamina (Figs. 5 and 6).
4.2.1. Limestone
Variations in chondrite-normalized variations (1100 chondrite)
for limestones from Antamina (n = 38) are interpreted to represent
123
Fig. 3. Plots of representative major elements versus silica (A, B, C) and bivariate plots of relatively insoluble elements for the different types of marble recognized at Antamina
(D, E, F). Fields of all limestone samples as well as limestone located at distances greater than 100 m from QFP are plotted for reference. Observe the almost linear correlation of
lanthanum with silica and aluminum (D, E) suggesting that tan marble is the product of strong dissolved limestone.
124
Fig. 4. Plots of representative major elements versus silica (A, B, C) and bivariate plots of relatively insoluble elements for the different types of hornfels recognized at Antamina
(D, E, F). Fields of all limestone samples as well as limestone located at distances greater than 100 m from QFP dikes are plotted for reference. The relative high amount of
insoluble elements in hornfels and the linear correlation of lanthanum with silica in limestone and hornfels suggest that hornfels especially white, light green, green and tan
hornfels are the products of limestone dissolution.
125
Fig. 5. CI chondrite-normalized REE diagrams for limestone and marble from Antamina. CI chondrite-normalizing values from McDonough and Sun (1995). (A) Limestone from
Antamina and Yanacancha. Graphs B, C, D, E and F show the REE content of gray, light gray, white, green and tan marble, respectively, in relation to the eld of REE determined for
limestone samples. Gray pattern shows range of REE patterns for limestones.
host rock and the amount of suldes associated with the mineralizing
conduit.
Standard statistical distributions are commonly used to describe
low concentrations of trace elements (Monecke et al., 2005).
Frequency distribution of elements was used to observe the shape,
symmetry and modality of each element within the host rocks to
Antamina skarn deposit. Nine metals (Ag, As, Bi, Cu, Mo, Pb, Sb, Tl
and Zn) were selected because of their abundance and strong
association with each other. Frequency histograms were prepared
for these metals for each type of rock. These histograms show the
distribution of 38 samples of limestone, 25 of hornfels and 31 of
marble. Three samples of hornfels (2PAE233, 3PAA121, and
4PAA211) and 1 sample of marble (3PAA134) were excluded from
this analysis because of their extremely high values of Ag, As, Bi, Cu,
Pb and Zn. The histogram bin width was determined using Scott's
formula (Scott, 1979):
1=3
126
Fig. 6. CI chondrite-normalized REE diagrams of hornfels from Antamina. CI chondrite-normalizing values from McDonough and Sun (1995). Most of the hornfels occupy the upper
sector of the limestone eld (C, D, E, F) with the exception of gray and light gray hornfels (A,B), which are similar to the composition of tan marble (Fig. 5F). Gray region shows range
of REE patterns for limestones.
127
128
A. Escalante et al. / Journal of Geochemical Exploration 105 (2010) 117136
Fig. 8. Bivariate plots of selected immobile elements for limestone, marble, hornfels and skarn from Antamina. (A, B, C) SiO2 versus La, Ce and Nd. (D, E, F) Al2O3 versus La, Ce and Nd. G, H, I: TiO2 versus La, Ce and Nd.
65
62
225
90
138
100
15
62
95
177
55
0.6
0.6
0.2
0.6
0.4
0.9
0.2
0.5
0.5
0.1
0.1
0.31
0.31
0.3
0.38
0.47
0.48
0.23
0.37
0.55
0.06
0.05
1.1
0.9
0.4
1.1
0.7
1
0.4
1
1
0.2
0.2
0.37
0.29
0.63
0.35
0.22
1.63
0.14
0.19
0.25
0.05
0.23
8.7
7.6
4.8
15.3
8.4
9.9
3.9
8.9
7.2
1.5
1.1
0.53
0.82
0.63
0.7
0.52
1.59
0.36
0.66
0.47
0.31
0.13
297
363
496
313
303
335
192
249
278
154
172
0.025
0.028
0.017
0.026
0.019
0.026
0.011
0.021
0.025
0.0025
0.0025
0.03
0.005
0.01
0.005
0.005
0.005
0.02
0.03
0.01
0.005
0.005
7
6.1
6.8
10
6.3
10.4
3.3
10.7
10
2.5
2.6
0.49
0.38
1.89
0.56
1.08
0.59
0.14
0.54
0.67
1.25
0.02
0.09
0.08
0.09
0.1
0.07
0.08
0.04
0.08
0.08
0.01
0.02
2.5
8
2.5
6
2.5
40
2.5
15
5
5
2.5
0.005
0.05
0.22
0.11
0.07
0.22
0.04
0.03
0.06
0.005
0.05
100
103
108
132
132
144
162
N 100
N 100
N 100
N 100
Fortuna East
Fortuna East
Fortuna
Fortuna East
Fortuna
Fortuna East
Fortuna
Yanacancha
Yanacancha
Yanacancha
Yanacancha
8946509
8946064
8946098
8946528
8946080
8946044
8946100
8941908
8941606
8941344
8941034
273885
273637
273126
273911
273092
273595
273044
276497
275598
275208
275510
4PAA124
3PAA250
4PAA164
4PAA223
4PAA165
4PAA224
4PAA166
4PAA233
4PAA238
4PAA235
4PAA236
ppm
ppm
ppm
129
70
80
20
90
40
80
40
40
50
30
10
ppm
ppm
Tl
Sn
ppm
ppm
Sb
Pb
ppm
ppm
Mo
Mn
ppm
ppm
ppm
ppm
ppm
ppm
In
ME-MS61
Hg-CV41
Hg
Cu
Cd
Bi
Ba
As
Ag
ME-MS61
Distance
from dike (m)
Locality
Northing
Easting
Sample
no.
Table 3
Samples used to estimate geochemical background.
ppm
Zn
Table 4
Upper background values of metal/La ratios calculated 1 using the median + 2MAD
formula on 11 unaltered samples from Antamina.
Metal Geochemical
background
Metal Geochemical
background
Metal Geochemical
background
Ag
As
Ba
Bi
Cd
Cu
Hg
In
Mn
Mo
Pb
Sb
Sn
Tl
V
W
Zn
0.01701
0.7829
6.7045
0.0085
0.0609
0.8939
0.0023
0.0021
38.97
0.0738
0.706
0.0330
0.0864
0.0375
6.646
0.0465
14.453
130
Fig. 9. Copper content versus lanthanum graphs for (A) limestone, (B) marble and (C) hornfels from Antamina. Observe the distribution of samples in relation to the upper and lower
threshold lines, to the mean and median of Cu/La, and relative to the visual cut-off obtained by construction of the graph of metal content versus distance to a dike. Threshold values
of these graphs have been estimated by using the median 2MAD of the Cu/La ratios.
131
Table 6
Alteration halos to the skarn front at Antamina West determined by analytical and
empirical methods.
Fig. 10. Plots of Cu abundance in marble versus distance to the skarn front at Antamina
West. Graphs A and B show the distribution of individual threshold values calculated by
using the median + 2MAD of Cu/La values multiplied by the La content of each sample.
Lanthanum values used in gure A come from lithium metaborate fusion + ICP-MS
analysis (ME-MS81), whereas La values used in gure B come from four acid digestion
+ ICP-MS analysis (ME-MS61). Figure C shows the geochemical halo obtained by
comparison of the measured data with a visual cut-off line and with a threshold line
estimated by the mean + 2SDEV () of unnormalized data.
Element
Lithium-borate
fusion
Four acid
digestion
Median +
2MAD
Mean +
2SDEV
Visual
cut-off
Ag
As
Ba
Bi
Cd
Cu
In
Mn
Mo
Pb
Sb
Sn
Sr
Tl
V
W
Zn
147
68
0
145
29
247
29
29
157
147
147
18
247
0
0
125
118
147
68
0
145
29
247
29
29
157
147
147
22
247
0
0
125
118
147
0
0
98
0
71
29
0
98
0
0
0
0
0
0
27
98
98
0
0
98
0
71
27
0
0
0
0
0
0
0
0
27
70
147
0
0
98
0
71
29
0
98
0
0
0
0
0
0
27
98
ppm
Element
ppm
Element
ppm
Au
Ag
As
Ba
Bi
Cd
0.01
0.1
10
100
0.1
1
Cu
Hg
In
Mn
Mo
Pb
10
0.01
0.03
800
1
25
Sb
Sn
Tl
V
W
Zn
1
2
1
150
1
100
132
A. Escalante et al. / Journal of Geochemical Exploration 105 (2010) 117136
Fig. 11. Anomalous halos of Cu, As, Pb and Tl to the paleo uid escape conduits of the Antamina skarn deposit. Observe the wide halos at depth and almost no halos at shallow levels for Cu.
133
Fig. 12. Trace-element halo with depth proximal and distal to the CuZn Antamina skarn deposit. Observe the progressive thinner halos of Cu, Sb and Pb as we move away from the
skarn front (4250 m). Also, notice moderate to low temperature indicator elements (Tl) dene halos at shallow levels but not close to the skarn.
134
Fig. 13. Synthesis of geochemical halos proximal and distal to the CuZn Antamina skarn deposit.
(N100 m) that diminish in extension at intermediate levels disappearing at shallower levels. Cadmium and Sn form the second group of
elements with small halos only at deeper levels. Prevalent deep to
shallow halos characterize the third group of elements, which consists
of Ag, As, Pb, Sb, In, Mn and W. These elements form halos that range
between 30 and 150 m at depth, and average 35 m in width at shallow
levels. Thallium and barium form the fourth group of elements with
moderate (60 m) to thin halos (5 m) from shallow to intermediate
levels. No halos are recognized for Hg and V.
A synthesis of the geochemical halos distal to the Antamina skarn
deposit is shown in Fig. 13. Large geochemical halos (150 m)
characterize the zone of coarse-grained white and gray marble
adjacent to the skarn (Antamina West), which include the presence
of anomalous values of Cu, Ag, Bi, Mo, Zn, Pb, Sb, Cd, Sn and W. Halos
up to 85 m of Cu, Pb and In are distinguished in the aureole of negrained marble and hornfels zone (Quarry Bench). Geochemical halos
vary in extension from less than 1 m up to 66 m within the sequence
of thin-layered limestone that surrounds Antamina. At intermediate
levels (4450 m to 4550 m) these halos are formed by Pb, Sb, Cu, Mo,
As, Tl and Ba, whereas at shallow levels (4700 m) they consist of As, Tl,
Pb, Sb, In, Mn, Ag, W and Ba. Halos in limestone correlate with the
presence of sulde veins along dikes, suggesting a leakage from these
mineralized structures.
In summary, high temperature indicator elements (Cu, Bi and Mo)
form large geochemical halos close to the skarn deposit, whereas
moderate to low temperature indicator elements, such as Tl dene
halos at higher and more distal levels.
7. Discussion
Major and trace element as well as REE values of most of the
country rocks to the Antamina skarn deposit indicate an important
siliciclastic component of these rocks. Linear correlation observed in
the bivariate diagrams of major elements versus silica (Figs. 24) and
versus immobile elements for limestone, marble and hornfels (Fig. 8)
indicates a progressive siliciclastic enrichment of limestone closer to
the QFP dikes, as well as tan, green, light green, white marble and
hornfels. The progressive reduction in the CaO and LOI content of
these rocks suggests strong carbonate dissolution by acidic uids and
permeability enhancement due to volume change (Lentz, 2005). The
trend between tan marble with low SiO2/Al2O3, white, light gray,
green and gray marble with progressively higher SiO2/Al2O3 (Fig. 3F)
supports this hypothesis.
The high volume of mineralized skarn (endo- and exoskarn) at
Antamina suggests the production of high amounts of carbonic acid
and CO2 that apparently got trapped in the skarn area by the coarsegrained marble envelope. Fluid escape through more permeable
fractures and certain sedimentary layers explains the heterogeneous
distribution of marble and hornfels around Antamina. The presence of
quartz and calcite + sulde veins adjacent to the QFP dikes from the
deep to shallow levels at Antamina indicates they were the preferred
pathways of the spent mineralizing uids. However, low SiO2/Al2O3
ratios of limestone indicate no addition of silica in these rocks even in
samples proximal to the dikes, conrming a passive trace-element
enrichment of the rocks close to the dikes mainly due to processes of
carbonate dissolution.
Constraints on the recognition of geochemical halos in heterogeneous carbonate rocks distal to a skarn deposit are based on three
observations. Firstly, the identication of the large-scale uid escape
pathways to these deposits. Secondly, the recognition of the traceelement enrichment processes on the country rocks and, thirdly, the
systematic selection of anomalous values relative to a geochemical
threshold determined for each sample. The identication of the
longest uid escape conduits is important to track the lateral and
vertical zonation of the spent mineralizing uids. Mineralogy, traceelement composition and stable isotope analysis on veins associated
with large structures (dikes, faults) can be used to determine the link
between proximal and distal expressions of an intrusive-centered ore
deposit such as Antamina. Trace-element halos to the QFP dikes
extend farther than the thermal aureole of the Antamina skarn.
However, these halos can be linked to the Antamina deposit, because
they reect the interaction of progressively lower temperature uids
with carbonate rocks (as suggested by the metal zonation).
It is demonstrated in this study that the relative enrichment of
major and trace elements in marble and hornfels around the skarn,
and limestone adjacent to the QFP dikes is due to processes of
carbonate dissolution. Therefore, metal concentrations normalized
against a least-mobile element (e.g. La) avoid the inuence of the
inherited siliciclastic material and allow the recognition of true
anomalous values.
Determination of anomalous values demands the appropriate
estimation of background and threshold values besides the proper
selection of representative samples. Drawbacks in the selection of the
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