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Fluid inclusion LA-ICP-MS and whole rock geochemical investigation of

possible magmatic contributions to the giant Windy Craggy Besshi-type VMS
deposit

Technical Report · March 2019

DOI: 10.4095/313651

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 Fluid inclusion LA-ICP-MS and whole rock geochemical
investigation of possible magmatic contributions to the
giant Windy Craggy Besshi-type VMS deposit
M.A. Schmidt1, M.I. Leybourne1, J.M. Peter2, D. Petts2 and D. Layton-Matthews1
1
Department of Geological Sciences and Geological Engineering, Queen’s University,
36 Union Street, Kingston, Ontario K7L 3N6
2
Geological Survey of Canada, 601 Booth Street, Ottawa, Ontario K1A 0E8

Abstract
The world-class Windy Craggy Cu-Co-Au deposit, northwestern British Columbia, is investigated to assess potential
magmatic contributions to mineralizing fluids in volcanogenic massive sulphide (VMS) deposits. Windy Craggy is of
particular interest for two reasons: 1) its atypically large size and high-grade; and 2) the observation of fluid inclu-
sions with anomalously high salinities. The deposit has recorded fluids with salinities up to 17 weight % equivalent
NaCl (most 6–16 weight % equivalent). The Ca/Na values in fluid inclusions determined by laser ablation-
inductively coupled plasma-mass spectrometry (LA-ICP-MS) are greater than seawater and similar to values from
other mafic-dominated VMS systems. The fluid inclusions have variable metal and metalloid concentrations, with
positive correlations between Cu, Mn, Zn, Sb, Sn and Bi. Also analyzed are Windy Craggy host lithologies, including
footwall argillites, relatively fresh to highly altered footwall mafic volcanic rocks and stringer and massive sulphides.
These inclusions show similar trends and overlap the host rocks in Fe versus Mn and Cu versus Zn, but show clear
excesses over host rocks in antimony, tin, bismuth and similar elements that are commonly ascribed as indicative of
magmatic input. We suggest that these excess values strongly point to direct magmatic contributions to the Windy
Craggy ore-forming fluids, as opposed to simply reflecting leaching of metals from the footwall sedimentary and
igneous rocks.

Introduction There is evidence of magmatic contribution in some mod-

ern seafloor hydrothermal systems at arcs, back-arcs and mid-
In the currently accepted genetic model for volcanogenic
ocean ridges. An example of direct magmatic contribution to a
massive sulphide (VMS) deposits, there is a geochemical dis-
seafloor hydrothermal system in a modern arc/back-arc envi-
connect between the magmatic heat source present at depth and
ronment is Brothers Volcano located on the Kermadec arc
the circulating hydrothermal fluid system responsible for the
northeast of New Zealand. Indications of magmatic contribu-
mineralization (Shanks and Thurston, 2012). The mineralizing
tion to a back-arc hydrothermal system ( i.e. magmatic hydro-
fluids are generally accepted to be modified seawater with a
thermal) includes the following: 1) hydrothermal discharge
salinity typically close to that of seawater (3.2 weight % NaCl;
significantly more acidic than typically found at mid-ocean
Bischoff and Rosenbauer, 1985) and falling within the range of
ridges (de Ronde et al., 2001; Leybourne et al., 2012; Massoth
2 to 6 weight % NaCl equivalent (Bodnar et al., 2014). VMS
et al., 2003); 2) presence of 3He anomalies in modern vent flu-
deposits form at or near the seafloor from rising metal-bearing
ids and ancient fluid inclusions (Leybourne et al., 2012;
hydrothermal fluids that are quenched by mixing with cold
Lupton, 1983); 3) elemental S precipitate (Giggenbach, 1996;
seawater to precipitate sulphide minerals (Hannington, 2013;
Lyon, 1974); 4) high total dissolved copper and iron in the vent
Tornos et al., 2015). However, there is continued debate as to
fluids (de Ronde et al., 2001) and 5) high Fe/Mn values in the
the source of metals in seafloor hydrothermal systems and the
vent fluids (Massoth et al., 2003). Although there are clear in-
role of magmatic volatiles in the formation of ore deposits
dications of magmatic volatile contributions to seafloor mas-
(Beaudoin et al., 2007; de Ronde, 1995; Huston et al., 2001;
sive sulphide systems, the extent to which metals and metal-
Leybourne et al., 2012; Timm et al., 2012; Wysoczanski et al.,
loids of economic interest are also contributed from exsolving
2012; Yang and Scott, 1996; Yang and Scott, 2006). In this
magmas driving hydrothermal circulation is still widely debat-
standard model for the formation of VMS deposits, metals are
ed (Agangi et al., 2018; Chen et al., 2015; de Ronde et al.,
leached from proximal volcanic rocks, with the magma cham-
2005; Huston et al., 2011; Yang and Scott, 2006).
ber primarily providing heat to drive hydrothermal circulation
of seawater (Galley et al., 2007). The Windy Craggy Cu-Co-Au deposit in northwestern Brit-

Corresponding author: Madison Schmidt ([email protected])

Schmidt, M.A., Leybourne, M.I., Peter, J.M., Petts, D., and Layton-Matthews, D., 2019. Fluid inclusion LA-ICP-MS and whole rock geochemical investigation of
possible magmatic contributions to the giant Windy Craggy Besshi-type VMS deposit; in Targeted Geoscience Initiative: 2018 report of activities, (ed.) N.
Rogers; Geological Survey of Canada, Open File 8549, p. 189–204. https://doi.org/10.4095/313651

189
 Schmidt et al., 2019

ish Columbia is the largest Besshi-type VMS deposit in the Geology

world (Peter and Scott, 1999). Windy Craggy is the focus of
The Windy Craggy deposit (Peter and Scott, 1999) is locat-
the present study due to its atypically large size, relatively high
ed in extreme northwestern British Columbia, within rocks of
salinity fluids compared to other VMS deposits and its back-
the Alexander Terrane, one of the largest accreted terranes in
arc setting (Peter et al., 2014). A previous study suggested that
the North American Cordillera (Coney et al., 1980) (Fig. 1).
the impressive metal endowment and anomalous salinity of the
The terrane is comprised of a thick succession of weakly meta-
fluids could be explained by a direct magmatic contribution to
morphosed, complexly deformed, Precambrian to Permian
the mineralizing fluids (Peter and Scott, 1993). Through better
basinal and platformal carbonate and clastic rocks with a minor
understanding of world-class deposits such as Windy Craggy
volcanic component. This succession is unconformably over-
we can further refine and improve exploration models. A more
lain by Upper Triassic calcareous, proximal to distal, turbidites
refined and detailed model could allow for the targeting of
and a bimodal volcanic suite (Campbell and Dodds, 1979,
atypically large deposits as well as those containing atypically
1983; MacIntyre, 1984).
high grades and specific metals or trace elements of interest.
1) The Windy Craggy deposit is hosted in the Late Triassic
To investigate potential magmatic contributions to large section commonly referred to as the Tats Volcanic Com-
VMS systems, we have conducted a laser ablation inductively plex. The complex has been subdivided into five major
coupled plasma-mass spectrometry (LA-ICP-MS) study of units described in order, moving down through stratigraphy.
fluid inclusions from the Windy Craggy deposit (Schmidt et
al., 2018). We have also obtained ultra-trace ICP-MS analyses 2) The upper most unit is an approximately 1500 m-thick sec-
of the volcanic and sedimentary host rocks, together with min- tion dominated by Upper Triassic pillow basalts referred to
eralization at Windy Craggy in order to characterize their bulk as the Upper Tats.
geochemical composition and extend the element suite previ- 3) An approximately 2000 m thick section of interbedded gra-
ously analyzed by Peter and Scott (1993). The application of phitic and calcareous argillites, pillowed and massive mafic
LA-ICP-MS to the analysis of major and trace elements in ore flows, tuff, agglomerate and limestone referred to as the
deposits has proven to be an effective tool for microanalysis of Middle Tats. Conodont assemblages in the limestone are
major and trace elements in minerals (Bodnar et al., 2014; Gag- Upper Triassic (ca. 225 Ma) (Orchard, 1986).
non et al., 2003). Further application of this method to fluid 4) An approximately 1000 m thick section of Upper Triassic
inclusions has allowed for in situ, multi-element analysis of mafic flows and sills referred to as the Lower Tats.
single fluid inclusions (Audétat et al., 1998; Batchelor and 5) A lower sedimentary unit, part of the Tats group, divided
Mcdonald, 1992; Hennings et al., 2017). into a section of interlayered calcareous and graphitic shale,
Analysis of individual fluid inclusions by LA-ICP-MS pro- argillite and limestone of undefined age and overlying a
vides a more detailed understanding of the fluid history without gray limestone unit, possibly Siluro-Devonian.
the errors and lack of resolution that accompanied the previ- The Windy Craggy deposit is hosted in the lower portion of
ously used methods such as grinding/crushing the sample under the Middle Tats group. The deposit consists of several lenses of
vacuum (Roedder, 1972); decrepitation by stepwise heating Cu-Co-Au mineralization, each with a discrete stockwork zone
(Piperov and Penchev, 1973); and decrepitation under vacuum (Peter and Scott, 1999). Collectively, these lenses contain over
(Welhan, 1988). Previous applications of LA-ICP-MS to fluid 300 million tonnes grading 2.12 weight % Cu, 0.083 weight %
inclusion studies have generally focused on high salinity fluids Co, 0.16 g/t Au, and 3.30 g/t Ag (Downing et al., 1990). Felsic
(e.g. magmatic-hydrothermal deposits). High salinity fluids volcanic rocks are not present in the immediate area of the
contain a higher concentration of total dissolved solids and, Windy Craggy deposit. However, other parts of the Alexander
given the already small sample size presented by fluid inclu- Terrane do contain felsic volcanic rocks or their metamor-
sions, this results in a more reliable analysis (Audétat et al., phosed equivalents, and their presence indicates volcanism was
1998). The relative lower salinity of the fluid inclusions in our bimodal at the regional scale (Taylor et al., 2008).
study, however, necessitated further method development to
optimize the process and provide the best possible results.
Methods
Herein, we detail refined LA-ICP-MS methods for the anal-
ysis of single, low salinity fluid inclusions typical of VMS de- Fluid inclusions
posits. We show that LA-ICP-MS analyses of fluid inclusions Doubly polished thin rock chips were prepared from the
in VMS deposits can provide metal and metalloid abundances feeder/stockwork zone of the deposit. This study focused only
that may reflect direct magmatic contributions to the Windy on quartz-hosted fluid inclusions. Photomicrographs were tak-
Craggy hydrothermal system. Finally, we compare the trace en of each sample to allow for careful mapping of each fluid
element geochemical compositions of host rocks (i.e. footwall inclusion to be analyzed. Fluid inclusions were classified using
and hanging wall sedimentary and volcanic rocks, and sulphide the criteria of Roedder (1984). Microthermometric measure-
-rich samples) against fluid inclusions to demonstrate the po- ments were made on 46 inclusions and include first melting
tential magmatic origin of metals and metalloids. temperature (Tf), final melting temperature (Tm), and tempera-

190
 Fluid inclusion LA-ICP-MS and whole rock geochemical
investigation Windy Craggy Besshi-type VMS deposit

Figure 1. Location map of the Windy Craggy deposit in northwestern British Columbia (from Peter et. al., 2014).

191
 Schmidt et al., 2019

ture of homogenization (Th). The percentage of vapour and that was then placed in the sample chamber. The sample was
liquid, and the size of each inclusion were also recorded. The observed using 100% magnification of the LA-ICP-MS optical
measurements were made using a Linkham THMSG600 heat- system and the fluid inclusions were located using chip photo-
ing freezing stage coupled to an automated controller unit and micrographs obtained during the preliminary stages of the
Nikon Optiphot microscope. The system was calibrated using study. The laser spot size was chosen to be the smallest that
synthetic fluid inclusion standards for CO2 (-56.6°C), the freez- encompassed the entire fluid inclusion, typically between 10
ing point of H2O (0°C) and the critical point of H2O (374.1°C). and 15 mm. The laser optics was then set to 50% magnification
The salinity of each fluid inclusion was calculated using the and focused on the surface of the chip. The data collection pro-
H2O-NaCl system based on Bodnar (1994). gram was set to collect 40 seconds of gas blank (no ablation),
ablate the sample for 20 seconds and then continue to collect
Laser ablation-inductively coupled plasma-mass spec- until a total count of 100 seconds. A small mixing chamber was
trometry added to the line to allow for the monitoring of all the elements
The LA-ICP-MS analyses of the fluid inclusions were per- of interest (109Ag, 75As, 11B, 137Ba, 209Bi, 79Br, 42Ca, 111Cd,
140
formed at the Geological Survey of Canada, Ottawa, using a Ce, 35Cl, 59Co, 133Cs, 65Cu, 57Fe, 202Hg, 115In, 39K, 7Li, 25Mg,
55
Teledyne Photon Machines Analyte G2 excimer laser ablation Mn, 95Mo, 23Na, 208Pb, 85Rb, 34S, 121Sb, 77Se, 29Si, 118Sr, 125Te,
205
system (l = 193 nm) with a HelEx ablation cell coupled to an Ti, 182W and 66Zn).
Agilent 7700x ICP-MS equipped with a second rotary vacuum For session 2, an in-house aqueous solution standard
pump that improves instrument sensitivity across the mass (SOL2018) was used in addition to synthetic glass standard
range by 2 or 3 times (Cabri and Jackson, 2011). Data were reference material NIST 610 (Norman et al., 1996) and the
collected over two multi-day sessions. The instrumental param- previously prepared in-house aqueous solution (SOL2017).
eters for session 1 (March 2017) and session 2 (July 2018) are The in-house aqueous solutions were contained within borosili-
presented in Table 1. cate capillary tubes. The capillary was rinsed with the solution
For session 1, an in-house aqueous solution standard 3 times before the sample was loaded and positioned in the
(SOL2017) was used in addition to two standard reference ma- centre of the tube. The ends were sealed using hot glue to pre-
terials (SRM), synthetic glass SRM NIST 610 (Norman et al., vent leakage and the capillary was affixed to the slide using
1996), and pyrrhotite SRM Po689 (Mungall et al., 2005). The double sided tape.
in-house solution was contained within wells constructed of The fluid inclusion chips were positioned on a slide and
pipette tips, which were sealed on the bottom and top with Par- held in place using double-sided tape. The sample chips were
afilm. This was intended to limit the evaporation of the solu- cleaned prior to placement in the sample chamber using a solu-
tion within the ablation chamber. Prior to analysis, the wells tion of 2% nitric acid and a precision tip cotton swab. This was
were opened by ablation of a hole through the Parafilm using a intended to remove any surface contamination due to polishing
40 mm spot size. The solution was then ablated directly using a and atmospheric exposure. The sample was observed using the
30 mm spot size. 100% magnification of the LA-ICP-MS optical system and the
The fluid inclusion chips were positioned on a thin circular fluid inclusions were located using chip photomicrographs ob-
(cross-sectional) slice of a pipette tip resting on a glass slide tained during the preliminary stages of the study. The laser spot

Table 1. Instrumental and analytical parameters for LA-ICP-MS analyses comparing session 1 and session 2.
Session 1 (March 2017) Session 2 (July 2018)
Teledyne Photon Machines Analyte G2 Teledyne Photon Machines Analyte G2
Laser system type
Excimer Excimer
Wavelength 193 nm 193 nm
Energy density for pre cleaning N/A 1.09 J/cm2
Repetition rate for pre cleaning N/A 1
Energy density for quartz ablation 4.54 J/cm2 4.54 J/cm2
Repetition rate for quartz ablation 8 hz 8 hz
Crater size for Standard analysis NIST610 40 μm, Po689 40 μm, SOL2017 30
Consistent at 20 μm
μm
Crater size for FI analysis Varied from 10 μm to 20 μm Consistent at 20 μm
ICP-MS Agilent 7700x Agilent 7700x
Carrier gas flow 1.00 L/min He 1.00 L/min He
Rf power 1550 W 1550 W
Dwell time per isotope 5 ms seconds with the exception of Na, K, 5 ms seconds with the exception of Na, K,
Si, at 2.5 ms & Au at 10 ms Si, at 2.5 ms & Au at 10 ms

192
 Fluid inclusion LA-ICP-MS and whole rock geochemical
investigation Windy Craggy Besshi-type VMS deposit

size was kept constant at 20 mm for samples and standards. metaborate fusion (method ME-MS81) to include elements
The laser optics was set to 50% magnification and focused on within phases resistant to acid digestion (zircon, chromite,
the surface of the chip. A pre-ablation cleaning sequence con- monazite); 3) trace and some major elements (Ag, Al, As, Ba,
sisted of single low energy pulse (see Table 1 for laser set- Be, Bi, Ca, Cd, Ce, Co, Cr, Cs, Cu, Fe, Ga, Ge, Hf, In, K, La,
tings). The data collection sequence was the same as session 1: Li, Mg, Mn, Mo, Na, Nb, Ni, P, Pb, Rb, Re, S, Sb, Sc, Se, Sn,
40 seconds of gas blank, ablation of the sample for 20 seconds, Sr, Ta, Te, Ti, Tl, U, V, W, Y, Zn, Zr) determinations by an
and data collection for 100 seconds. ultra-trace four-acid digestion (HF, HClO4, HCl, HNO3; meth-
The LA-ICP-MS tests were performed using a signal ex- od ME-MS61L) followed by a mixture of ICP-AES and ICP-
tender (Squid) added to the line. The element list outlined MS analysis, to allow lower detection limits on elements not
above for session 1 was reduced from the original list of 33 incorporated in resistant phases; 4) lead oxide fire assay was
elements to 109Ag, 75As, 137Ba, 209Bi, 79Br, 42Ca, 111Cd, 140Ce, used to preconcentrate and collect Au, prior to analysis by ICP-
35
Cl, 59Co, 65Cu, 57Fe, 115In, 39K, 25Mg, 55Mn, 95Mo, 88Sr, 23Na, MS (method Au-MS23L). The Pb isotopes were also deter-
206
Pb, 207Pb, 208Pb, 85Rb, 121Sb, 77Se, 29Si, 118Sn, 205Ti, 182W, mined on the 4-acid digestions with analysis by quadrupole
181
Ta, 197Au and 66Zn. The reasons for this are detailed below. ICP-MS. A proprietary ALS method is used to eliminate inter-
ferences of 204Hg on 204Pb.
Data reduction
The data were processed using SILLS, a Matlab computer Results
program designed for the reduction of LA-ICP-MS data ob- Fluid Inclusions
tained from both mineral grains and fluid inclusions (Guillong
et al., 2008). SILLS is designed to allow for the isolation of the Both primary and secondary inclusions are present in the
fluid inclusion signal from that of the host mineral. This is samples, with the latter predominating over the former. Sec-
achieved through the use of an internal defined standard and ondary inclusions are defined predominantly by their occur-
the manual selection of various peaks and time spans by the rence along fractures and planes crossing growth features in the
user. Sodium was defined as the internal standard for these quartz. Secondary inclusions range in size from 1 to 16 mm,
reductions in this study. The internal standard was determined are oval and circular in cross section. The secondary inclusions
for each inclusion prior to ablation using fluid inclusion mi- have varying liquid/vapour (L/V) values ranging from 5 to
crothermometric ice melting temperatures. The size of the in- 100% (monophase liquid). The primary inclusions are defined
clusion and matrix signal varied by inclusion as does salinity by the negative crystal structure or occurrences along growth
(internal standard). For this reason, SILLS allowed each varia- planes of the quartz. They range in size from 5 to 24 mm and
ble to be defined independently for each fluid inclusion. are circular, oval or hexagonal in cross section. The primary
inclusions display consistent L/V values indicating that the
Back calculations were performed to verify the validity of
fluids did not boil at the time of entrapment, consistent with the
the SILLS corrections, by converting the concentrations of the
observations of Peter and Scott (1993). There is also a large
cations (Na, K, Ca, Mg) to weight % NaCl equivalent and then
abundance of monophase inclusions present in the samples.
calculating the required Cl assuming all of the cations are pre-
The monophase inclusions are not useful for salinity measure-
sent as salt. The sum of these values equates the calculated
ments; however, rare two-phase (liquid-vapour) inclusions oc-
salinity. The calculated weight % equivalent salinities were
cur within particular clusters of monophase inclusions. No
compared to the salinities determined by the microthermomet-
daughter minerals were observed within any of the inclusions.
ric measurements. The veracity of data processing in SILLS for
session 2 was also verified using the SOL2017 solution. This Forty-six additional microthermometric measurements have
was accomplished by ablating SOL2017 as a standard and been made beyond those of Peter and Scott (1993). The salini-
treating it as an unknown in SILLS. The weight % NaCl equiv- ties range from 3.2 to 13.1 weight % equivalent NaCl (Fig. 2).
alent (0.38) for SOL2017 was calculated from the known con- The homogenization temperatures range from 101.4 to 414.4°C
centrations of Ca, K, Na, Mg and Fe to be used as the internal (Fig. 3). The first melting temperatures (eutectic melting) range
standard required for SILLS. The known concentrations were from -39.6 to -4.8°C (Fig. 4). The microthermometric observa-
then compared to the SILLS output. tions of the L-V inclusions agree closely with the ice melting in
the monophase inclusions. Therefore, salinity data for these
Whole rock geochemistry monophase liquid inclusions are deemed to be representative of
Pulverized samples were analyzed at ALS Geochemistry, this population of inclusions as a whole.
Vancouver, for whole rock geochemical composition. The fol- Development of LA-ICP-MS technique
lowing analyses were performed: 1) major element determina-
tions by inductively coupled plasma atomic emission spectros- The methods developed during the present study have led to
copy (ICP-AES) following lithium metaborate fusion (method an effective methodology and work flow for performing LA-
ME-ICP06); 2) trace elements (Ba, Cr, Cs, Ga, Hf, Nb, Rb, Sr, ICP-MS analysis of low salinity fluid inclusions (3.2–13.1
Ta, Th, U, V, Y, Zr and rare earth elements (REE)) determina- weight % NaCl equivalent). The method allows for the reliable
tions by ICP mass spectrometry (ICP-MS) following lithium analysis of more than 30 isotopes. Several issues that arose in

193
 Schmidt et al., 2019

Figure 2. Histogram of microthermometric data showing the Figure 4. Histogram of microthermometric data showing the
distributions of measured salinities (weight % NaCl equiva- distributions of measured first melts (eutectic melting). Da-
lent). Data from Peter and Scott (1993) and this study. ta from Peter and Scott (1993) and this study.

session 1 (March 2017) were remedied in session 2 set up (July ing and unloading was difficult due to the small size of the
2018). Standard Po689 was used in session 1 to obtain S/Fe samples and their propensity to shift on the slide, with the po-
signal intensity values for calibration of S. This standard was tential for them to slide/bounce off the slide. The use of double
not used in session 2 to eliminate a source of contamination. In -sided tape in session 2 prevented any samples from being lost.
both sessions, the NIST610 glass standard was used to calibrate However, some chips broke during their removal after analysis.
the in-house solution, the primary standard for the data correc- The laser spot size in session 1 was variable and dependent
tion of the fluid inclusion LA-ICP-MS data. In session 1, the in on the size of the fluid inclusion. This was changed in session 2
-house solution contained within wells constructed from pipette to a consistent laser spot size (20 mm) on the unknowns as well
tips and sealed with Parafilm did not provide effective contain- as the standards. This removed potential for variability and
ment, and once the well was opened it continued to leak Cl, Br improved the data confidence for comparison between stand-
and other contaminants into the chamber throughout the fol- ards and unknowns. The initial LA-ICP-MS test analyses were
lowing analyses. This was solved in session 2 through modifi- performed without the use of a signal smoothing device and
cation of the in-house solution containment vessels. The capil- using a dwell time of 4 ms per element. This setup was found
lary action of the capillary tubes contained the solution even to produce a signal that was too transient to obtain data for all
after the wall was breached by the laser. of the elements of interest. To remedy this problem a small
In session 1, the positioning of the chips on a slide without mixing chamber was added to the line. The mixing chamber
the aid of an adhesive resulted in the loss of samples. Although was constructed from a plastic test tube and nylon tubing. This
samples remained stationary inside the vacuum chamber, load- allowed for dwell times to be lengthened to 5 ms with the ex-
ception of Na, K, Si (2.5 ms) and Au (10 ms), which improved
the duty cycle and provided greater accuracy and precision in
the measurements. In session 2, the mixing chamber was re-
placed with a signal extender (Squid), lengthening the signal.
In session 2, the element list was shortened to 109Ag, 75As,
137
Ba, 209Bi, 79Br, 42Ca, 111Cd, 140Ce, 35Cl, 59Co, 65Cu, 57Fe,
115
In, 39K, 25Mg, 55Mn, 95Mo, 88Sr, 23Na, 206Pb, 207Pb, 208Pb,
85
Rb, 121Sb, 77Se, 29Si, 118Sn, 205Ti, 182W, 181Ta, 197Au and 66Zn
from the original list of 33 elements. Elements that were not
detected during the first round, or those that were deemed no
longer of interest to the study, were removed. Anomalously
high Pb concentrations were noted in the data from session 1.
To remove any possible surface contamination, two cleaning
steps were added to the method for session 2. The samples
were manually cleaned using 2% HNO3 and a pre-ablation
cleaning sequence was added to the laser program. The pre-
Figure 3. Histogram of microthermometric data showing the ablation consisted of single low energy pulse that effectively
distributions of measured temperatures of homogenization. removed the Pb anomalies without destroying the underlying
Data from Peter and Scott (1993) and this study. inclusions.

194
 Fluid inclusion LA-ICP-MS and whole rock geochemical
investigation Windy Craggy Besshi-type VMS deposit

Fluid inclusion LA-ICP-MS results of 7.69 ppm to 18 500 ppm. Ranges and averages of all ele-
ments are presented in Table 2.
Laser ablation-ICP-MS was performed on over 130 inclu-
sions, 46 for which there are salinity data collected directly Whole rock geochemistry
from the same inclusion that was analyzed (i.e. not inferred).
This study successfully analyzed 34 elements from relatively Whole rock trace element analyses were performed on 19
low salinity fluid inclusions (3.2–13.1 weight % NaCl) ob- samples from throughout the deposit. Representative samples
tained from a VMS deposit with a complex history of multiple of sulphides, argillite, hanging wall, footwall, altered footwall
fluid events. Out of the 34 elements monitored, Na, Mg, K, Ca, flows and stockwork stringer zones were analyzed to provide a
Mn, Fe, Co, Cu, Zn, Sr, Sn, Ba, Ce, Pb and Bi were detected general understanding of the distribution and sources of all
consistently throughout the analyses. Chlorine, Sb, Cd, Mo, elements (including those of potential magmatic origin) within
Rb, Br, and As were also detected in a significant number of the deposit (Table 3). Detailed interpretations of the geochem-
inclusions. Boron, Ag, In, Ta, Au and Ti were not detected in istry of Windy Craggy lithologies have been presented else-
any of the inclusions. Comparison of the Ca/Na and Mg/Na where (Peter, 1992; Peter et al., 2014). Here, we briefly discuss
values of the inclusions reveals a continuous trend in the data our new geochemical data in the context of understanding po-
population (Fig. 5). The fluids from this study contain higher tential magmatic contributions. As such, we have subdivided
Ca/Na values than seawater. As Ca concentrations increase, the the data into four groups: 1) metasedimentary rocks (argillites);
Pb, Zn, Fe, Mn, As, Se, Br, Sn, Sb and Ba values also show a 2) mafic volcanic and intrusive mafic rocks; 3) hydrothermally
general increasing trend, although most are not statistically altered mafic rocks; and 4) sulphide-rich and stringer zone
relevant. Calcium versus Zn and Ca versus Sn do show statisti- samples.
cally significant correlations (all values based on Spearman The chemical composition for each of the rock groups is
Rank correlations) at r = 0.341 (p = 0.012, n = 47) and r = listed in Table 3. The least altered mafic volcanic samples were
0.357 (p = 0.015, n = 46), respectively. There is large variation differentiated from the altered mafic volcanic rock samples
observed in the metal concentrations obtained from different using a Chlorite-Carbonate-Pyrite Index (CCPI) versus Altera-
fluid inclusions. For example, Cu ranges from below a detec- tion Index (AI) plot of Large et al. (2001) (Fig. 6). The average
tion limit of 0.154 ppm to 39500 ppm, Zn ranges from 0.181 Al2O3 values of the least altered mafic volcanic rock samples
ppm to 3490 ppm and Fe ranges from below a detection limit are 2x that of the altered mafic volcanic rocks (16.76 versus

Figure 5. a) Mg/Na vs. Ca/Na and b) K/Na vs. Ca/Na plot of Windy Craggy fluid inclusions. Also plotted are fluid inclusions
from the Monte Mattoni mafic complex (Hennings et al., 2017), as well as fluid inclusion data from felsic systems including
Brothers Volcano on the modern Kermadec arc (de Ronde et al., 2011), Bajo de la Alumbrera (Ulrich et al., 2001), Butte
(Rusk et al., 2004), El Teniente (Williams-Jones and Heinrich, 2005), modern seawater and Windy Craggy host lithologies.

195
 Schmidt et al., 2019

Table 2. Summary table describing the fluids that occur within

the deposit compared to ambient sea water composition.
Fluid inclusions Seawater
Average (n = 123) Range
Temperature of
153.4 101.4–414.1
Homogenization (˚C)
Salinity (wt.% NaCl
9.3 3.2–13.1
Equivalent)

Na 16108 BD–44264 10800

Ca 23647 BD–36012 411
Mg 1986 BD–19733 1290
K 6371 BD–55183 392

Cu 912.1 BD–39508 0.0009

Sn 125.9 BD–882.3 0.00081
Zn 370.7 BD–6534.8 0.000003
Mo 17.24 BD–237.44 0.01
Se 466.4 BD–2667.2 0.00009
Rb 54.88 BD–3674.2 0.12
Cs 9.51 BD–48.381 0.0003
W 11.85 BD–56.486 BD
Br 9074.3 BD–154500 67.3
Sb 85.16 BD–3139.1 0.00033
Ce 66.69 BD–7251.6 0.0000012
Li 123.62 BD–456.56 0.17
Figure 6. Chlorite-carbonate-pyrite index (CCPI) versus altera-
Hg 542.1 BD–999.02 0.00015 tion index (AI) plot (after Large et al., 2001) showing the
Te 28.59 BD–31.39 N/A extent of alteration for the basalt, metasedimentary and
Mn 138.84 BD–2321.1 0.0004 mineralized samples. CCPI = 100(MgO + Fe))/(MgO +
Co 21.09 BD–76513 0.00039
As 221 BD–3643.1 0.0026 FeO + Na2O + K2O). AI = 100(K2O + MgO)/(K2O + MgO
Cd 54.46 BD–410.83 0.00011 + Na2O + CaO).
Ba 87.36 BD–1266.1 0.021
Bi 98.38 BD–191.68 0.00002
Fe 3723.74 BD–44728 0.0034
nized five distinct fluids, which represent a clear chronological
picture of the hydrothermal fluid evolution. Types A, B and C
inclusions are CO2-rich and range from liquid-liquid-vapour to
two-phase inclusions with daughter crystals. Types B and C
8.19 weight %) (Table 3). The altered mafic rocks range from
have high homogenization temperatures of 334 ± 10°C and 310
moderately to strongly silicified (28–71.8 weight % SiO2). The
± 3°C, respectively. Salinities of these inclusions vary from 7.9
Pb isotope compositions for the metasedimentary, least altered
± 0.3, 5.5 ± 0.3, and 3.6 ± 0.4 weight % NaCl equivalent for
basalts, altered basalts and sulphides are listed in Table 3 and
shown in Figure 7. “Massive sulphides” include massive sul-
phide and stringer samples. The new data follows the same
trend as the older data (Peter and Scott, 1999), trending from
non-radiogenic sulphide-rich samples (higher 207P/206Pb and
208
Pb/206Pb values) to more radiogenic host rocks (lower
207 206
P/ Pb and 208Pb/206Pb values) (Fig. 7).

Discussion
Major ion chemistry of Windy Craggy fluid inclusions
Few studies have investigated the LA-ICP-MS major and
trace element composition of fluid inclusions in relatively low
salinity, mafic volcanic (or plutonic) rock-associated hydro-
thermal or magmatic-hydrothermal systems. Hennings et al.
(2017) collected data by LA-ICP-MS on fluid inclusions from
the Monte Mattoni mafic complex in northern Italy. We have
compared the Windy Craggy fluid inclusions to those from
Monte Mattoni as it is one of the few studies of a mafic rock-
Figure 7. 207Pb/206Pb vs. 208Pb/206Pb for Windy Craggy sulphides,
dominated system, with broadly similar inclusion salinities,
basalts and metasedimentary rock groups compared to previ-
and some trace metal and metalloid results. Their study recog-
ous lead isotope data for Windy Craggy from Peter (1992).

196
 Table 3. Major, trace and rare earth element composition of representative samples of the host rocks and mineralization from the Windy Craggy deposit.

Sample No. S131319 S131302 S131317 S131315 S131303 S131304 S131307 S131308 S131310 S131301 S131305 S131316 S131306 S131309 S131311 S131312 S131313 S131314 S131318
Clasification Metasedimentar Metasedimentar Metasedimentar Fresh mafic rock Fresh mafic rock Fresh mafic rock Fresh mafic rock Fresh mafic rock Fresh mafic rock Altered mafic Altered mafic Altered mafic Altered mafic Altered mafic Altered mafic Sulphide Rich Sulphide Rich Sulphide Rich Sulphide Rich
y rock y rock y rock rock rock rock rock rock rock and stringer and stringer and stringer and stringer
(wt. %)
SiO2 56.5 51.2 40.9 54 48.7 51 49.4 46.5 42.4 71.8 67.7 41.5 43.7 42.9 28 28 34.6 0.35 0.43
TiO2 0.21 0.5 0.52 1.14 2.07 1.12 0.87 1.02 0.66 0.08 0.05 0.95 0.85 1.7 0.39 0.9 0.96 0.001 0.001
Al2O3 7.08 9.82 8.23 15.75 18.05 18.1 16.45 15.25 16.95 2.53 1.33 13.15 12.9 13.2 6.08 13.7 14.15 0.09 0.15
Fe2O3 25.8 23.1 27.6 7.56 8.07 6.23 8.56 12.35 9.72 17.6 15.25 27.6 15.6 11.3 18.45 33.2 33.3 62.9 57.9
MnO 0.08 0.07 0.31 0.04 0.12 0.11 0.09 0.22 0.28 0.18 0.05 0.1 0.19 0.16 0.34 0.11 0.19 1.07 1.16
CaO 0.37 0.6 6.75 2.74 8.5 6.92 4.37 6.22 8.91 1.46 0.7 2.21 4.7 5.45 12.15 2.51 0.77 3.91 2.83
MgO 4.07 6.19 2.55 7.5 3.71 5.34 8.85 5.27 4.53 0.88 0.32 6.43 11.15 13.1 12 9.5 6.44 0.57 0.37
Na2O 0.28 0.001 1.21 5.07 3.18 4.54 4.6 4.33 2.39 0.03 0.28 0.03 1.19 1.55 0.01 0.01 0.01 0.01 0.02
K2O 0.45 0.001 0.05 0.02 3.07 1.64 0.47 0.12 2.09 0.07 0.09 0.08 0.01 0.35 0.01 0.04 0.01 0.03 0.09
Cr2O3 0.005 0.011 0.024 0.02 0.001 0.01 0.039 0.022 0.002 0.003 0.002 0.039 0.088 0.064 0.222 0.011 0.018 0.001 0.001
P2O5 0.23 0.42 1.09 0.53 0.98 0.87 0.36 0.6 0.33 0.16 0.09 0.59 0.28 0.42 0.23 0.51 0.58 0.03 0.02
SrO 0.001 0.001 0.02 0.01 0.18 0.13 0.04 0.02 0.04 0.001 0.01 0.01 0.01 0.02 0.05 0.01 0.01 0.04 0.02
BaO 0.02 0.001 0.001 0.001 0.11 0.06 0.03 0.01 0.12 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001
Total 100.47 98.09 94.62 99.17 98.79 98.57 99.26 99.01 97.08 100.37 97.47 99.43 98.19 98 98.13 98.33 98.04 92 89.29
C 0.5 1.12 2.11 0.49 0.04 0.03 0.54 1.24 1.96 0.82 0.13 0.54 0.83 0.81 5.52 0.78 0.5 3.58 3.26
S 1.12 2.79 5.37 0.01 0.001 0.01 0.07 0.1 0.01 5.93 8.29 1.74 0.15 0.04 0.1 6.46 0.89 32.3 34.8
(ppm)
Ba 223 0.001 18.3 15.7 1095 615 317 62.4 1100 9 16.1 4.9 3.4 33.4 3.8 9.1 3.4 5.6 11.2
Ce 16.7 0.001 30.5 80.3 156.5 121.5 43.1 71.1 23.6 1.6 2.4 62.8 42 65.6 26.4 55.9 56.1 0.8 0.9
Cr 40 0.001 180 170 5 80 290 170 10 20 20 300 690 450 1650 90 140 5 5
Cs 3.22 0.001 0.17 0.23 0.46 0.3 0.15 0.14 0.59 0.05 0.05 0.07 0.2 0.69 0.18 0.14 0.1 0.05 0.03
Dy 1.77 0.001 3.16 4.02 4.98 4.14 3.27 3.64 2.96 0.65 0.4 3.44 3.09 3.18 1.76 3.27 2.94 0.05 0
Er 1.12 0.001 1.82 2.53 2.41 2.01 1.84 1.92 1.66 0.32 0.26 2.06 2.06 1.5 0.84 2.04 1.69 0.015 0.06
Eu 0.22 0.001 1.18 0.98 3.02 2.11 0.92 1.56 1.21 0.07 0.31 0.81 1.06 1.62 0.85 0.74 0.7 0.11 0.18
Ga 6.8 0.001 13.3 18.4 21.3 19.3 13.3 14.6 17 12.2 4.2 24.9 13.4 13.6 7.5 36.3 31.2 6.5 9.4
Gd 2.02 0.001 4.21 4.64 7.58 5.74 3.21 4.34 3.59 0.64 0.48 3.45 3.12 4.17 1.87 3.68 3.23 0.07 0.08
Hf 1.3 0.001 1.5 3.6 6 3.9 2 3 1.6 0.5 0.4 2.8 2.1 2.6 1.1 2.6 2.6 0.1 0.1
Ho 0.42 0.001 0.74 0.85 0.95 0.8 0.69 0.68 0.57 0.15 0.12 0.67 0.74 0.63 0.36 0.8 0.69 0.01 0.01
La 11.5 0.001 19 44.2 78.3 66.6 22.6 35.9 10.4 1 1.5 33.4 20.5 29.3 13.7 28.1 27.6 0.7 0.9
Lu 0.22 0.001 0.21 0.42 0.32 0.31 0.23 0.32 0.23 0.09 0.05 0.3 0.25 0.19 0.11 0.33 0.28 0.01 0.01
Nb 2 0.001 9.3 27.8 64.2 37.6 17.7 26.2 3.2 0.8 0.4 24.6 12.8 20.4 9.4 23.8 19.9 0.1 0.1
Nd 11.5 0.001 18.8 31.7 66.6 44.6 17.4 27.7 14.8 2 2 25.3 17.3 28.7 11.1 23.5 22.8 0.3 0.3

197
Pr 2.69 0.001 4.14 8.22 17.4 12.4 4.57 7.48 3.2 0.44 0.5 6.73 4.6 7.87 3.04 6.3 6.32 0.09 0.12
Rb 12.3 0.001 0.7 0.3 49.7 18.8 4.3 1.9 51.1 0.3 1.7 0.2 0.4 8.9 0.3 0.2 0.2 0.1 0.4
Sm 2.23 0.001 3.43 5.55 10.8 7.62 3.56 4.62 3.92 0.48 0.43 4.29 3.34 5.75 2.32 4.05 4.19 0.015 0.09
Sn 1 0.001 1 2 2 1 1 2 1 1 1 1 1 1 1 1 1 4 2
Sr 23.5 0.001 130 106.5 1615 1180 323 198.5 324 35.1 32.1 84.9 105.5 178.5 393 94.5 33 302 140.5
Ta 0.2 0.001 0.6 1.8 3.3 2 1 1.5 0.2 0.1 0.2 1.4 0.7 1.2 0.6 1.3 1.3 0.2 0.3
Tb 0.27 0.001 0.53 0.76 0.92 0.79 0.54 0.67 0.59 0.1 0.09 0.55 0.52 0.65 0.31 0.59 0.52 0.02
Th 0.77 0.001 1.09 4.09 4.84 5.85 2.18 2.9 1.07 0.41 0.25 2.84 1.78 1.18 1.05 3.02 2.97 0.025 0.025
Tm 0.21 0.001 0.29 0.4 0.34 0.33 0.23 0.31 0.24 0.04 0.05 0.28 0.24 0.23 0.11 0.29 0.29 0.01 0.01
U 1.66 0.001 2.38 1.41 1.54 1.82 0.74 0.83 0.61 1.27 1.4 0.94 0.7 0.34 0.3 1.94 1.38 0.58 0.33
V 54 0.001 173 201 228 156 185 206 231 33 40 188 184 206 90 202 199 7 19
W 2 0.001 1 1 1 1 1 3 2 2 3 13 1 1 2 7 2 2 2
Y 12.6 0.001 20.8 23.1 26.1 21.7 17.2 19.9 16.1 5.2 3.5 17.8 18.5 14.8 8.9 21.3 16.7 0.3 0.4
investigation Windy Craggy Besshi-type VMS deposit

Yb 1.56 0.001 1.55 2.71 2.19 2.08 1.58 2.12 1.67 0.39 0.34 2.03 1.88 1.39 0.79 2.31 1.84 0.04 0.03
Fluid inclusion LA-ICP-MS and whole rock geochemical

Zr 48 0.001 68 174 264 205 85 134 59 23 16 130 88 104 50 114 127 1 1

As 0.2 0.3 0.7 0.2 0.5 0.1 0.5 1.4 18.4 13.8 28.6 20.6 0.3 0.1 76.8 59.3 7.6 250 250
Bi 0.08 0.68 0.15 0.01 0.01 0.01 0.01 0.02 0.01 1.39 4.08 0.47 0.02 0.01 0.04 0.6 0.21 6.01 16.95
Hg 0.001 0.001 0.001 0.001 0.013 0.001 0.001 0.001 0.001 0.047 0.047 0.001 0.001 0.001 0.005 0.105 0.019 1.035 0.394
In 0.1 0.03 0.106 0.018 0.012 0.006 0.025 0.055 0.019 0.033 0.4 0.025 0.061 0.049 0.069 0.094 0.057 1.18 1.755
Re 0.016 0.019 0.018 0.001 0.001 0.001 0.001 0.001 0.001 0.007 0.006 0.001 0.001 0.001 0.001 0.001 0.001 0.017 0.005
Sb 0.08 0.13 0.21 0.29 0.025 0.025 0.025 0.09 0.025 2.59 0.61 0.76 0.07 0.05 0.08 1.66 0.22 27.6 24.8
Se 1.9 3.2 13.1 0.1 0.1 0.1 0.5 0.1 0.3 3.2 21.8 1.3 0.2 0.3 0.2 6.3 1.6 24.1 27
Te 0.04 0.35 0.15 0.01 0.01 0.01 0.01 0.01 0.01 0.63 2.67 0.96 0.03 0.01 0.02 1.5 0.32 7.33 11.75
Tl 0.21 0.02 0.02 0.01 0.06 0.02 0.01 0.08 1.34 0.07 0.19 0.05 0.02 0.16 0.15 0.37 0.04 4.16 1.33
Au 0.007 0.015 0.011 0.002 0.004 0.005 0.001 0.001 0.001 0.007 0.081 0.039 0.001 0.001 0.005 0.025 0.003 0.542 0.742
Ag 0.03 0.001 0.372 0.026 0.04 0.04 0.007 0.018 0.029 0.299 3.84 0.575 0.009 0.013 0.007 0.577 0.493 15.5 14
Cd 0.016 0.001 0.068 0.08 0.14 0.083 0.005 0.001 0.009 5.44 0.236 0.073 0.009 0.015 0.038 0.05 0.399 34.8 5.52
Co 17.05 0.001 58.5 14.1 19.9 19.3 29.5 20.4 27.8 188 141 51 44.1 54.8 62.9 184.5 42.7 531 363
Cu 188 0.001 607 12 45.2 28.6 25 54.4 86.9 1285 23400 575 25 40 15.95 2150 2970 16950 44600
Li 2 0.001 3.9 6.3 8.9 11 11 8.2 17.3 1 1.2 12.5 4.5 8.7 1.5 5.8 4.5 0.2 0.3
Mo 1.19 0.001 5.23 1.5 0.81 0.47 1.58 0.79 0.39 3.97 2.64 1.11 0.76 0.52 0.45 1.21 1.7 24.1 7.06
Ni 7.89 0.001 57.1 69.9 18 56.1 101 61.3 15.5 6.33 1.91 92.6 293 225 858 67.5 17 4.67 5.09
Pb 1.04 0.001 5.04 0.75 4.06 4.22 0.35 1.22 1.63 11.6 2.96 3.12 0.83 0.42 1.12 3.7 1.29 392 429
Sc 5.48 0.001 14.25 19.9 20.4 18.9 31.1 30.2 22.2 2.71 1.27 26 29.9 23.5 15.05 25.4 27.4 0.07 0.22
Zn 28.3 0.001 149.5 31.7 76.9 65.5 20.3 84.1 70.3 1370 61.8 73.3 45.1 81.6 62.2 61.9 323 13050 1665
204
Pb 0.02 0.001 0.07 0.01 0.05 0.06 0.01 0.02 0.02 0.15 0.04 0.04 0.01 0.01 0.01 0.05 0.02 5.32 5.9
206
Pb 0.36 0.001 1.37 0.28 1.08 1.11 0.1 0.33 0.43 2.94 0.78 0.85 0.22 0.11 0.29 1 0.35 101.5 113
207
Pb 0.26 0.001 1.07 0.2 0.85 0.87 0.05 0.25 0.33 2.42 0.62 0.68 0.16 0.07 0.22 0.77 0.26 86 94
208
Pb 0.69 0.001 2.72 0.56 2.18 2.26 0.19 0.67 0.87 6.04 1.56 1.74 0.44 0.22 0.59 1.95 0.69 213 237
 Schmidt et al., 2019

types A, B and C, respectively (Hennings et al., 2017). Types seawater in the reaction zone overlying the magmatic system
D and E are two phase (L-V) inclusions, like those at Windy driving the hydrothermal circulation in the formation of chlo-
Craggy, with homogenization temperatures of 353 ± 11°C and rite, actinolite and amphibole (e.g. Alt et al., 1986; Goodfellow
approximately 179°C, respectively but have higher salinities and Peter, 1994). However, recent studies of modern arc and
than types A, B and C at 9.5 ± 1 and 27.1 ± 0.9 weight % NaCl back-arc settings have suggested that end-member vent fluids
equivalent, respectively. We have compared the major ion in these environments may contain significant amounts of mag-
chemistry of the Windy Craggy inclusions with those of the nesium (and SO4) owing to the lower pH, higher magmatic gas
Monte Mattoni inclusions, as well as fluid inclusion data from concentrations (H2S, CO2, SO2) and consequently, greater wa-
felsic systems including Brothers Volcano on the modern Ker- ter-rock interaction in the hydrothermal upflow zones (e.g.
madec arc (de Ronde et al., 2011), Bajo de la Alumbrera Leybourne et al., 2012; Reeves et al., 2011). Thus, the elevated
(Ulrich et al., 2001), Butte (Rusk et al., 2004), El Teniente magnesium concentrations and high Mg/Na values in the
(Williams-Jones and Heinrich, 2005), modern seawater and Windy Craggy inclusions likely reflects hydrothermal fluids
host lithologies from Windy Craggy (Fig. 5). We have included that have stripped magnesium through water-rock reactions by
the results from more mafic systems as these are associated fluids similar to magmatic-hydrothermal fluids observed at arcs
with copper-rich mineralization and are recognized as magmat- and back-arcs.
ic-hydrothermal systems; one of the goals of this study is to Windy Craggy fluid inclusions have K/Na values that are
determine the extent, if any, of the magmatic contributions to generally higher and have a wider range than the ones at Monte
the Windy Craggy ore-forming fluids. Fluid inclusions from Mattoni (Fig. 5). Some inclusions at Windy Craggy have K/Na
Windy Craggy display generally similar Ca/Na values to inclu- values greater than sea water. The high K/Na values of the
sions from Monte Mattoni, although Windy Craggy inclusions Windy Craggy fluid inclusions are most likely the result of
extend to higher Ca/Na values. Both Windy Craggy and Monte contributions from footwall sedimentary rocks and from water-
Mattoni inclusions Ca/Na values are elevated in comparison to rock reactions with the footwall mafic rocks; at Windy Craggy,
those from the felsic systems noted above and seawater (Fig. the footwall flows and sills/dykes are alkalic (Peter et al.,
5). Host lithologies at Windy Craggy have Ca/Na values that 2014), compared to the calc-alkalic host rocks at Monte Matto-
overlap those at the upper range of the Windy Craggy inclu- ni and the felsic rocks represented on Figure 5. However, Na/
sions and extend to more elevated Ca/Na values in more altered Kmolar values for Windy Craggy fluid inclusions range from
mafic volcanic rocks and semi-massive and stockwork sulphide approximately 1 to 400 (average = 17, median = 6, excluding
-rich samples. The elevated Ca/Na in the altered Windy Craggy one outlier at 1043). These Na/Kmolar values are more varied
rocks is in part due to addition of carbonate via hydrothermal and generally elevated compared to Na/Kmolar values for the
or metamorphic fluids, but may also be associated with high more felsic porphyry copper-associated fluid inclusions from
temperature calcic alteration, as observed in the core of the Butte (Rusk et al., 2004). The mafic compositions of the
hydrothermal upflow zone in Middle Valley on the Juan de Windy Craggy lithologies, lack of primary potassium feldspar
Fuca Ridge (Leybourne and Goodfellow, 1994). The calcium- and common white mica (sericite) alteration of plagioclase
rich nature of the fluid inclusions is likely related to high tem- (Peter, 1992; Peter et al., 2014), results in lower Na/Kmolar val-
perature alteration of the mafic rocks in the footwall to the de- ues than at Butte, where fluid reactions with potassium and
posit; conversion of calcic plagioclase to albite will produce plagioclase feldspar, at least in part, buffer the range in Na/
more calcium-rich hydrothermal fluids. Hennings et al. (2017) Kmolar (Rusk et al., 2004).
noted that the highest Ca/Na values for the inclusion fluids at
Monte Mattoni were observed in the later, higher salinity types Trace metals and metalloids in Windy Craggy fluid inclu-
D and E inclusions, consistent with water-rock interaction, as sions
also observed for calcic groundwaters in crystalline rocks else-
Late-stage inclusions (types D, E) of magmatic-
where (Leybourne and Goodfellow, 2007).
hydrothermal fluids from Monte Mattoni have salinities be-
Windy Craggy fluid inclusions have generally higher Mg/ tween 9.5 and 27.1 weight % equivalent NaCl, high Ca/Na
Na values compared to those from Monte Mattoni (Fig. 5). The values (Fig. 5), lower S and Cu and higher Pb, Zn, Fe and Mn
Monte Mattoni inclusions are characterized by Mg concentra- concentrations than type A, B or C fluids (Hennings et al.,
tions less than 350 ppm (one outlier, type E = 1714 ppm), with 2017). These trends were attributed to fluid-melt partitioning of
most below 65 ppm (27 of 31 analyses). By contrast, Windy volatiles in the crystalizing magma followed by fluid-rock in-
Craggy inclusions vary from approximately 6 to 20 000 ppm teraction with the host lithologies (Hennings et al., 2017). The
Mg, with a median of 920 ppm Mg. Hydrothermal fluids recov- Windy Craggy fluid inclusions are similar to the late-stage flu-
ered from active vents on the seafloor are typically modelled to ids from Monte Mattoni in that they also have high salinities
have end-member fluid compositions with no magnesium (e.g. 3.2 to 13.1, average 9.20 weight % equivalent NaCl, and high
Humphris and Klein, 2018). Magnesium that is recovered in Ca/Na values (Fig. 5). Calcium shows statistically significant
hydrothermal fluids is interpreted to represent mixing with positive correlations with zinc, lead and tine, but not with cop-
entrained seawater during collection or in the shallow subsur- per, iron or manganese. Calcium is also positively correlated
face; magnesium is assumed to be removed from downwelling with salinity, with r = 0.424 (p = 0.0010, n = 57). Conversely,

198
 Fluid inclusion LA-ICP-MS and whole rock geochemical
investigation Windy Craggy Besshi-type VMS deposit

manganese shows statistically significant correlations with centrations (Fig. 8). The positive correlation between cerium
copper (Log Cu versus Log Mn, r = 0.632, p = < 0.0001, n = and barium is not shown by the host lithologies at Windy Crag-
79), zinc (Log Zn versus Log Mn, r = 0.671, p = < 0.0001, n = gy, except for the most altered of the mafic rocks (Fig. 8b),
70), iron (Log Fe versus Log Mn, r = 0.434, p = < 0.0009, n = suggesting that cerium and barium were mobilized into the
55; Fig. 8), tin (Log Sn versus Log Mn, r = 0.646, p = < hydrothermal fluids through water-rock reaction. Cerium is
0.0001, n = 53), antimony (Log S versus Log Mn, r = 0.457, p generally considered immobile, but in these fluids it appears to
= < 0.0018, n = 44), and barium (Log Ba versus Log Mn, r = have been transported by the hydrothermal fluids. This is con-
0.423, p = 0.0002, n = 73). Other positive correlations of note sistent with the altered mafic rocks and massive sulphide sam-
include barium versus cerium (r = 0.520, p = < 0.0001, n = 58), ples from Windy Craggy having lost barium, cerium and stron-
copper versus strontium (Log Cu versus Log Sr, r = 0.331, p = tium (Fig. 8).
0.0001, n = 128) and copper versus barium (Log Cu versus Log Figure 7 plots 207Pb/206Pb versus 208Pb/206Pb for Windy
Ba, r = 0.420, p = < 0.0001, n = 101) (Fig. 8). Compared to the Craggy sulphides, basalts and metasedimentary rock groups
Monte Mattoni fluid inclusions, those from Windy Craggy dif- compared to historical lead isotope data for Windy Craggy
fer in having generally lower manganese and higher iron con- (Peter, 1992). The Pb isotope data collected from this study

Figure 8. Plots of a) Fe vs. Mn, b) Ba vs. Ce, c) Cu vs. Sr, and d) Cu vs. Ba for Windy Craggy fluid inclusions compared to the
host rocks. Also shown is Fe and Mn data for fluid inclusions from the Monte Mattoni mafic complex (Hennings et al., 2017).

199
 Schmidt et al., 2019

follows the same trend as that seen previously (Peter, 1992). isotope data obtained from the whole rock analyses of the dif-
The linear trend of the sulphide isotope data was previously ferent rock groups within the deposit reveal a mixing trend
described as a reflection of mixing of mantle lead with crustal between mantle derived lead and crustal lead. Although we
lead, contributed from the footwall basalts and footwall sedi- were unable to distinguish primary and secondary fluid inclu-
ments, respectively (Peter, 1992; Peter and Scott, 1999). sions on a geochemical basis, the excess of some metals/
metalloids in the fluid inclusions over copper, zinc, maganese
Magmatic-hydrothermal fluids and metal contributions to and iron compared to the host rocks, and in particular the sul-
VMS phide-rich samples, is consistent with the fluids trapped in the
Although there has been some debate as to the relative con- inclusions representing magmatic-hydrothermal fluids rather
tributions of leaching versus metal-rich magmatic volatiles to than reflecting simple hydrothermal leaching of the host rocks.
seafloor ore-forming systems (Agangi et al., 2018; Chen et al.,
2015; de Ronde et al., 2005; Huston et al., 2011; Yang and Acknowledgments
Scott, 2006), there is to some extent, a circularity to the argu-
ment; the footwall rocks from which metals are interpreted to This report is a contribution to NRCan’s Targeted Geosci-
be leached by modified seawater were themselves the products ence Initiative Program (TGI). Support for this study was pro-
of crystallization of magmas similar to those interpreted to be vided through the Volcanic and Sedimentary Hosted Base Met-
the exsolved source of metals. Perhaps one approach to parti- al Mineralization Project’s ‘Activity VS-2.4: Fingerprinting
tion contributions from magmatic fluids over hydrothermal fluid source regions and pathways of volcanogenic massive
fluids, in the absence of available gas chemistry (i.e. on mod- sulphide deposits’.
ern systems on arcs, magmatic contributions are evident from Madison Schmidt is conducting a TGI supported M.Sc. at
4
He, gas chemistry and isotopic compositions; de Ronde et al., Queen’s University, Kingston, Ontario. This report benefited
2005), would be to determine if there is an excess in metals and from the reviews of Alain Plouffe and Neil Rogers.
metalloids commonly interpreted to be magmatic in other ore-
forming systems such as epithermal and porphyry copper. Met- References
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In, W, Te, Tl and Se. For the fluid inclusions investigated here, LaFlamme, C., Jeon, H., Martin, L., Nozaki, T., Takaya, Y.,
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(n = 76), antimony (n = 58), bismuth (n = 52) and arsenic (n = massive sulphide underneath a Palaeoproterozoic seafloor
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investigation Windy Craggy Besshi-type VMS deposit

Figure 9. Plots of a) Zn vs. Cu, b) Sn vs. Cu, c) Sb vs. Cu, d) Bi vs. Fe, e) Sb vs. Fe and f) Sn vs. Fe for Windy Craggy fluid in-
clusions compared to the host rocks. Also shown is Zn and Cu data for fluid inclusions from the Monte Mattoni mafic com-
plex (Hennings et al., 2017).

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