Observed Secular Variations in the Metallogeny of Volcanic-Hosted Massive Sulfide Deposits

We have described above the possible changes in the carcter of the Earth and consequent
changes in Earth processes.
To assess how these temporal changes have affected VHMS deposits and to assess additional
constraints provided by these deposits on Earth processes, we have compiled data for VHMS
deposits into the StratDB and DateView online databases (Eglington et al., 2009) from existing
compilations (Godwin et al., 1988; Franklin et al., 2005; Thorpe, 2008; Geological Survey of
Canada, 2009; Mosier et al., 2009), supplemented by recent discoveries and additional data from
literatura reviews. Data exist in the database for more than 1,650 occurrences; however, we
have used a subset of nearly 800 for which we have verified the available data and updated
information in the previous datasets. In addition, sulfur isotope (updated from Huston, 1999),
lead isotope (stored in the DateView database), and fluid inclusion data have been compiled.
We have also used the >26,000 igneous crystallization ages stored in DateView (Eglington et al.,
2009) to assess posible links between VHMS formation and magmatic events. In our analysis of
secular trends in VHMS deposits, we have used the deposit association classification of Franklin
et al. (2005, Table 1), which is based on the character of the footwall succession of the deposit,
in preference to a tectonic classification. This classification is relatively objective and is broadly
linked to tectonic setting (Table 1), whereas tectonic classifications tend to be less definitive and
can be contentious. Quantities of ore and metal The temporal distribution of VHMS deposits
in terms of the amount of mineralized rock (ore; see also Barrie and Hannington, 1999) is
shown in Figure 3. Although it is also posible to determine the distribution according to the
number of deposits, such an analysis biases the distribution to minor deposits and also to
deposits for which data are presented by orebody. However, the distribution of total ore also
biases the data to large tonnage, low-grade deposits, although such deposits can contain less
metal than medium, or even small, tonnage, high-grade deposits. As a consequence, we also
show the temporal distribution for total copper, zinc, lead, and gold (Fig. 3B-E). Comparison of
secular trends of metals highlights changes in the metallogenic makeup of the ores.
The total ore curve (Fig. 3A) indicates that VHMS formation was episodic throughout Earth
history but that episodes were more scattered or less well preserved in the Archean and
Proterozoic. Although there are a few smaller peaks, prominent episodes of mineralization at
2740 to 2680, 1900 to 1840, and ~750 Ma dominate the Precambrian. The ~2700 Ma peak,
although dominated by large tonnage deposits in the Abitibi subprovince, also contains deposits
in the Slave and Yilgarn cratons. The second peak is dominated by 1890 to 1880 Ma deposits in
several major districts in the North American Trans-Hudson province and the Svecokarelian
craton, although it also contains younger, small deposits in the North Australian craton. The
~750 Ma peak, which has a poorly constrained age, consists of a single Zn-Pbrich deposit, the
Kholodina deposit in Russia, which alternatively has been interpreted as a clastic-dominated
sediment-hosted deposit (Leach et al., 2010).
The distribution of global igneous activity determined using age and uncertainty data from
DateView is also shown in Figure 3A. This methodology is affected by selective preservation and
sampling bias, with the bias toward very young ages seen in the distribution or to felsic rocks
that contain datable minerals, such as zircon, rather than mafic lithologic units that generally
lack such material. Nevertheless, it provides a first-order indication of periods of intense igneous
activity. Comparison of this distribution with the ore distribution highlights a close relationship
between the ~2700 and ~1880 Ma peaks with global igneous activity. These peaks coincide with

intervals that have previously been suggested to reflect major juvenile additions to the crust
(Condie, 1998, 2000; Hawkesworth and Kemp, 2006a, b). In contrast to VHMS deposits in the
Precambrian, the Phaner ozoic is characterized by more consistent mineralization events, with
major peaks at 510 to 460 and 390 to 355 Ma. The smaller 510 to 460 Ma peak is a composite
of two major metallogenic provinces, the ~500 Ma Mount Read, Tasmania, and the ~470 Ma
Canadian Appalachian, including the New Brunswick and Newfoundland districts, and the 390
to 355 Ma peak includes deposits in the Urals and in the Iberian Pyrite Belt.
During the Phanerozoic, the link between VHMS formation and igneous activity appears to break
down. Major VHMS deposition in the Mount Read district, the Bathurst district, the Iberian
Pyrite Belt, and the Urals is not matched by major peaks in global igneous activity, whereas major
igneous activity at ~50 Ma does not have significant associated VHMS deposits. It must be noted
that the igneous activity curve (Fig. 3A) does not differentiate between subaerial and
subaqueous magmatism, nor does it distinguish between subduction- or arc-related magmatism
and collisional or plumerelated activity, so certain yet unrecognized, more specific relationships
may nevertheless exist. The secular distribution of ore according to the classification of
Franklin et al. (2005) is shown in Figure 4. Inspection of this diagram, which groups the deposit
associations of Franklin et al. (2005) into felsic- and mafic-dominated associations, indicates that
these deposit associations did not occur equally through time, an observation also made by
Barrie and Hannington (1999). Mafic-dominated associations, particularly the bimodal-mafic
association, dominate the Archean and Proterozoic, whereas felsic-dominated associations are
much more abundant in the Phanerozoic. Deposits of the bimodal- mafic association reappear
as a major peak in the late Phanerozoic. In detail, within mafic-dominated associations, deposits
of the pelitic-mafic association are mostly restricted to rocks younger than 1000 Ma, and
deposits of the mafic association are mostly restricted the Phanerozoic, although small peaks of
mafic-dominated deposits are noted at ~2000 and 1910 to 1880 Ma. The younger peak also
includes deposits of the pelitic-mafic association, and this broad age range corresponds with the
age of the oldest known ophiolites (Maxeiner et al., 2005).
Metal content: Although, in general, metal content peaks closely follow ore peaks, important
differences are present (Fig. 3). These differences are best reflected by changes in the relative
peak heights between metals. Although relative peak heights of copper and gold mainly mirror
those of ore, significant differences are apparent when comparing the peak heights of zinc and
lead to ore. Although the period between 510 and 460 Ma is a subsidiary peak in terms of
tonnage of ore (and copper), it is the third largest peak in terms of zinc and the second largest
in terms of lead, consistent with the observation that these deposits have significantly higher
grades of zinc and lead, and reflecting biases in using total tonnages as a measure of
productivity. Of genetic significance, however, is the change in the amount of lead in comparison
with zinc; lead is significantly more abundant in the Phanerozoic than in the Proterozoic or
Archean, as discussed below.
Metal ratios
Temporal variations in 100Zn/(Zn+Pb) and 100Cu/(Cu+ Zn) can describe the metallogeny of
VHMS deposits (Fig. 5). Of these two ratios, the most striking variation is the overall decrease in
the minimum value for 100Zn/(Zn+Pb), which is also reflected in changes in the relative peak
heights of zinc and lead, as described above showing an increase in the proportion of deposits
with lower Zn/(Zn+Pb). The increasing importance of felsic-dominated associations with time
relative to mafic-dominated associations appears to be the main control on this trend. As
indicated by the data in Table 2, deposits of felsic-dominated associations have significantly

lower 100Zn/(Zn+Pb) and, as discussed above, these associations become increasingly

important with decreasing age. However, this main trend hides a second trend where for both
felsic-and mafic-dominated associations, 100Zn/(Zn+ Pb) both decreases and becomes more
variable with time (Table 3). An important exception to this trend is Paleoarchean deposits that
are characterized by enrichment in lead (i.e., lower 100Zn/(Zn+Pb): mean = 80.7 11.2 (1); n =
8) relative to Mesoarchean and Neoarchean deposits.
The 100Cu/(Cu+Zn) ratio, which probably varies with ore fluid temperature, does not show a
clear pattern. There is, however, a tendency for deposits in felsic-dominated associations to
have lower values than deposits in mafic-dominated associations (Table 3), perhaps suggesting
that deposits of felsic- dominated associations formed from cooler fluids.
Lead isotope ratios
Lead isotopes are sensitive indicators of metal sources in rock and hydrothermal systems. In
particular, mantle, upper crustal, and lower crustal regimes may be effectively distinguished
(Doe and Zartman, 1979). Modern VHMS deposits in a variety of oceanic settings, particularly
along mid-ocean ridges, have a range in lead isotope composition, consistent with variable
contributions of lead from the mantle, seawater, and sediments (Fouquet and Marcoux, 1995;
Stuart et al., 1999; Hannington et al., 2005). More radiogenic lead isotope ratios occur where
sedimentary contributions are greatest, in some cases derived by weathering of crustal lithologic
units, and lower values occur at faster spreading centers or where there is little sediment
accumulation. The uranogenic (Fig. 6) and thorogenic (not shown) lead isotope systems
demonstrate distinct scatter about the Stacey and Kramers (1975) evolution line and also further
emphasize the intermittent nature of VHMS formation through Earth history. Because the
curvature in the Pb-Pb isotope evolution curve (Fig. 6) partially obscures variations in source
composition, all data for which reasonable age information are available were recalculated to
derive model source 238U/204Pb () values. This variable allows simple comparison of
variations in initial uranogenic lead isotope composition (both 206Pb/204Pb and 207Pb/204Pb)
relative to age of mineralization (Fig. 7) and provides a single variable that acts as a proxy for
combinations of age, 206Pb/204Pb and 207Pb/204Pb. We have chosen to use the Stacey and
Kramers (1975) model because it is a reasonable approximation to the general evolution of
orogene-type lead since at least 3700 Ma. It should be emphasized, though, that the specific
model used is not important because the calculations merely illustrate relative changes and are
not meant to imply specific U/Pb ratios.
With the exception of pelitic and/or mafic association mineralization, and ocean back-arc, ocean
ridge, and intracontinental rift situations where insufficient data are available, all VHMS deposit
associations exhibit a distinct decrease in the variability in model source with time. Model
source values for the Phanerozoic deposits range from ~9.0 to ~10.0, for
Proterozoic from ~8.7 to ~12.0, and for Archean from ~7.5 to ~12.2. When only Phanerozoic
deposits are considered, there is a broad systematic variation in according to deposit association
(Fig. 7). Deposits underlain by mafic-dominated successions (mafic, pelitic-mafic, bimodal-mafic,
and mid-ocean ridge) do not exhibit the higher values evident in deposits underlain by felsicdominated successions (bimodal-felsic and siliciclastic-felsic). The range in values for
Phanerozoic deposits is similar to that in modern MORB-hosted mineralization affected by
variable contributions of sediment (Fig. 7).
For older deposits, no consistent pattern was observed according to the deposit associations of
Franklin et al. (2005).

The abundance of sulfate minerals

Primary sulfate minerals, such as anhydrite, gypsum, and, most importantly, barite, have a very
distinctive temporal distribution. Although VHMS deposits formed during the Paleoarchean are
relatively uncommon, the majority of these deposits contain barite: all six deposits older than
3200 Ma for which mineral resources have been estimated contain barite. Only two poorly
understood prospects are not known to contain barite or other sulfate minerals (Huston et al.,
2007; D. Huston, unpub. data). In addition to these deposits, Huston and Logan (2004) showed
that stratiform barite deposits of this age are also common and are present in all major
Paleoarchean terranes. The geologically oldest ore economic deposit is the ~3481 Ma (Van
Kranendonk et al., 2008) Dresser barite deposit in the Pilbara craton, which produced 0.130 Mt
barite (Abeysinghe and Fetherstone, 1997).
The abundance of barite in Paleoarchean volcanic-hosted massive sulfide and sulfate deposits
contrasts with the virtual absence of hypogene sulfate minerals in deposits with ages between
3200 and 2400 Ma. Despite being one of the most highly mineralized periods with respect to
volcanic-hosted massive sulfate deposits, hypogene sulfates have been observed in only the
Geco deposit from the Wawa subprovince of the Superior craton (Franklin et al., 1981).
After 2400 Ma, however, barite and other sulfate minerals become increasingly important. The
~2195 Ma Perkoa deposit in Burkino Faso contains significant quantities of barite (Schwartz and
Melcher, 2003), and the 1900 to 1850 Ma deposits in the Skellefte and Bergslagen districts in
Sweden and the Snow Lake district in Manitoba contain minor barite (Gavelin et al., 1960;
Rickard et al., 1979; Walford and Franklin, 1982). In addition, during the Proterozoic, sulfate
minerals increasingly become a more important component of the overall rock record (Huston
and Logan, 2004).
In the Phanerozoic, barite, anhydrite, and gypsum are relatively common, known to be present
in the majority of VHMS deposits and districts (Franklin et al., 1981; Huston, 1999). Similarly,
sulfate minerals are common constituents of currently forming black smoker deposits
(Hannington et al., 2005).
Variations in 34S and 33S
Sulfur isotope values in VHMS deposits also change with time, both in sulfide and sulfate
minerals. As discussed by Franklin et al. (1981) and Huston (1999), ore-related sulfide minerals
in Archean and Proterozoic VHMS deposits are characterized by 34S values near zero per mil
and by limited variability within deposits (Fig. 2B). In contrast, 34S values of sulfide minerals
from Phanerozoic deposits are highly variable, both within and between deposits. As first
observed by Sangster (1968), 34S values of ore sulfide minerals mimic the seawater sulfate
34S curve (Fig. 2B), with values on average ~16 per mil more depleted than the coexisting
seawater (Huston, 1999).
The 34S values of sulfate minerals also show significant changes with geologic time. During the
Paleoarchean, barite 34S values are generally restricted, with all deposits, except the Big
Stubby deposit (34S ~12), having barite 34S values of about 5 per mil (Fig. 2B: Huston and
Logan, 2004). In addition, this barite is characterized by mass-independent fractionation of 33S
relative to 32S (i.e., 33S <0; Farquhar et al., 2000). In contrast, after 2400 Ma, 34S values
of sulfate minerals become more variable and generally more enriched (Fig. 2B), with sulfate
minerals having similar 34S values to coexisting seawater during the Phanerozoic. When
compared with coexisting sulfide minerals, 34Ssulfate-sulfide during the Phanerozoic was

between 15 and 32 per mil, in contrast to values of between 3 and 15 per mil during the Archean
and Proterozoic (Fig. 8).
Variations in fluid salinity
Fluid inclusion studies, from which salinities of VHMS ore fluids are determined, are limited,
particularly for Precambrian deposits. Given this limitation and uncertainties in interpreting fluid
inclusion data (Roedder, 1984), Archean and Proterozoic ore fluids appear to have higher
salinities (624 wt % NaCl equiv) than Phanerozoic fluids (113 wt % NaCl equiv). Moreover, in
all cases, the measured salinities appear to be greater than that of coexisting seawater.
Changes in Volcanic-Hosted Massive Sulfide Metallogeny through Time: Linkages to Secular
Changes in Earth Evolution
Over the length of geologic time, as described above, there has been significant variation in the
character and mechanisms of plate tectonics and in the composition of the hydrosphere and
atmosphere. Moreover, using an extensive dataset containing grade and tonnage data, the
lithologic characteristics of successions underlying ore positions, mineralogical data, lead and
sulfur isotope data, and fluid inclusin data, there appears to be systematic variations in the
distribution and character of VHMS deposits with time. In this section, we discuss how these
metallogenic changes are linked to secular changes in Earth evolution.
Variations related to changes in the evolution of tectonic processes
Our analysis of trends in the metallogeny of VHMS deposits, in comparison with global tectonic
trends, suggests that several features of these deposits may be related to the evolution of the
crust and tectonic processes. These include the following: (1) an increase in the proportion of
deposits of felsic-dominated associations, (2) an increase in the average lead content of the ores,
(3) changes in the variability of values through time and, for Phanerozoic deposits, subtle
changes in values according to the character of the rock package underlying ore, and (4) the
episodicity of ore formation.
Increase in the proportion of deposits of felsic-dominated associations: There is a marked
increase in VHMS deposits underlain by felsic-dominated successions through time, a trend
noted here in tonnages and also in overall numbers of deposits (Franklin et al., 2005). The two
major deposit associations in the felsic grouping, bimodal-felsic and siliclasticfelsic, typically
form in continental settings, mainly in local extensional settings within contractional
(epicontinental back-arcs and continental margin-arcs) settings, and, to a lesser extent,
divergent (submarine continental rifts) settings.
An explanation for this trend could lie in a greater subductability of tectonic settings that host
mafic associations (submarine arc rifts, juvenile back arcs, and nascent arcs) due to increasingly
dense oceanic lithosphere through time. Another possible explanation lies in an inferred
increase in plate size and speed through time and the less erratic movement of larger plates
(Phillips and Bunge, 2005). Persistence of
Archean lithosphere and Archean-Paleoproterozoic cratons through time, and larger overall
plate size with slower, stable plate movement in the Phanerozoic, could favor establishment of
longer, more continuous continental margins, such as the modern-day North American
Cordilleran margin. This would lead to a predominance of continental-related felsic associations.

A corollary would be decreased preservation of the bimodal-mafic association, which dominates

the Archean, when smaller plates, with transient and smaller continental masses, were
common.
This increase in VHMS deposits underlain by felsic-dominated successions is the case for the
Gondwana assembly at ca. 550 to 500 and 50 Ma to present (Fig. 4B), but there is a spike in
bimodal-mafic preservation associated with Euramerica amalgamation, beginning at 440 Ma.
This may be the exception that proves the rule, as these deposits are related to intraoceanic arcs
and pericratonic arcs in the Iapetus
Ocean that are interpreted to relate to complex, small-plate geometry (van Staal et al., 1998;
van Staal, 2007). Thus settings and periods where pericratonic arcs, small plates, and small
margin lengths dominate, such as the Trans-Hudson (Pehrsson et al., 2007), Fennoscandian,
(Lahtinen et al., 2009) and Baie-Verte (Rambler-Ming; van Staal, 2007) districts, could favor
preservation of bimodal-mafic types despite the overall trend. In the modern oceans, such a
setting would be the southwest Pacific after the Pacific Ocean closes.
Changes in the lead content of the ores: One of the most consistent changes with time for VHMS
deposits is an increasing relative amount of lead to zinc, as measured both in absolute quantities
of these metals and as 100Zn/(Zn+Pb), albeit based on a small number of deposits. The only
important exception to this general rule is the lead-rich character of Paleoarchean deposits. In
addition, the deposits underlain by felsic-dominated successions have lower 100Zn/(Zn+Pb) tan
deposits underlain by mafic-dominated successions. In combination with the trend to felsicdominated successions with time, these trends result in a high degree of lead enrichment in
Phanerozoic deposits relative to Precambrian deposits.
As discussed by Huston and Large (1987), variations in 100Zn/(Zn+Pb) are controlled both by the
relative amounts of these elements in the source region and by the temperatura and salinity of
the ore fluids. Temporal variations in total lead and in 100Zn/(Zn+Pb), combined with systematic
differences in these parameters between deposits of mafic- and felsic- dominated associations,
suggest that source rocks exert a major control on lead content. An important control on this
distribution seems to be the increasing importance of deposits of felsic-dominated associations,
which inherently contain more lead, with time. However, the increase in relative lead content
over time for all deposit associations, be it felsicor mafic-dominated successions, suggests,
possibly, that over time lead has preferentially concentrated in the upper crust.
Changes in lead isotope characteristics: One of the most surprising results of the lead isotope
compilation was the decrease in the variability of values through time. This variability includes
values both greater than and less than that of the Stacey and Kramers model ( = 9.74),
requiring contributions to the ore fluid from both time-integrated high and low 238U/204Pb
sources. This result is counterintuitive in that contributions from much older (Archean or
Paleoproterozoic) crust to Phanerozoic deposits should result in greater scatter in the recent
past than early in Earth history. Moreover, in the Archean and Proterozoic, variations in values
do not appear to correlate with the character of the succession underlying the deposits; both
mafic- and felsic-dominated successions exhibit similar variation from high to low values.
These patterns require contributions from both older high values and lower value sources,
which, in turn, require differentiation early in Earth history, well before the major ~2700 Ma
VHMS event and smaller events between 3500 and 3200 Ma. These components had to have
been isolated for sufficient time, hundreds of millions of years, for the lead isotope variations to
become evident, as also previously argued for various Abitibi deposits (Vervoort et al., 1994).

Hence, the trends in lead isotopes from VHMS deposits support proposals for significant
differentiation and crust formation during the Hadean or Eoarchean (Bennett, 2003, and
references therein; Shirey et al., 2009). Depleted, low 207Pb/204Pb crustal contributions are
most prominent in the ~2700 Ma Abitibi subprovince but are also required for some
Paleoproterozoic VHMS formation events. In contrast to Archean and Proterozoic deposits,
Phanerozoic deposits have a more systematic variation in values according to the lithologic
association underlying the ore position.
Deposits overlying felsic-dominated crust tend to have a greater proportion of higher value
examples than deposits overlying mafic-dominated crust. This feature reflects the presence of
evolved, higher values of crustal lead in deposits associated with felsic-dominated successions
versus less evolved, lower values of lead in the mafic-dominated successions.
A final feature of these variations is that deposits with similar lead isotope compositions tend to
be geographically clustered (Thorpe, 1999; Franklin et al., 2005), requiring variations in source
composition within metallogenic provinces but not at the camp or district scale.
Paleoarchean deposits: Limited data were shown above to suggest that Paleoarchen deposits
are unusual in comparison with younger Meso- to Neoarchean deposits in being characterized
by both lower 100Zn/(Zn+Pb) and higher values.
These differences relate to the evolved nature of the Pilbara and possibly Kaapvaal crust at the
time of VHMS deposition.
Champion and Smithies (2007), Smithies et al. (2007), and Van Kranendonk et al. (2007)
demonstrated that granites and volcanic rocks in the Paleoarchean East Pilbara
granitegreenstone terrane, which hosts these old deposits, record a prolonged history involving
extensive continental recycling and large ion lithophile enrichment. Neodymium isotopes
indicate involvement of a major crustal component in generation of the melts, with crustal
residence times as much as 200 m.y. This contrasts with the Abitibi subprovince, which is
characterized by juvenile crust with crustal residence times much less than 100 m.y., based on
two-stage depleted model ages calculated from data in Ayer et al. (2002). Hence the leadenriched and high value character of Paleoarchean deposits reflects the evolved character of
the Pilbara and Kaapvaal crusts.
Episodicity of ore formation: A comparison of the temporal variation of deposits versus igneous
activity and periods of supercontinent formation and stability (Fig. 3A) shows that peaks in
observed deposit abundance are associated with periods of supercontinent (or supercraton)
assembly, and intervals that lack deposits correlate with times of supercontinent stability and
quiescent magmatic intervals (Fig. 3A). The general pattern is for more intermittent formation
in the Precambrian and more frequent episodes after 0.5 Ga (cf. Groves et al., 2005), mimicking
the pattern of more short-lived supercontinent assembly stability and breakup in the
Phanerozoic.
Intervals with abundant deposits correspond with the known supercontinent assembly,
including the 2740 to 2690 Ma peak corresponding to Kenorland assembly, and the ~1910 to
1840 Ma peak corresponding to the Nuna assembly.
Peaks in VHMS deposits at 510 to 460 and 390 to 355 Ma appear to be associated with the
assembly of Pangea. These intervals reflect ocean closure and major plate reorganization (cf.
Blundell et al., 2002), which can significantly precede final supercontinent amalgamation. They

do not coincide with continental dispersion following supercontinent breakup as has been
proposed (Yakubchuk, 2008), except in cases where such dispersal leads to consumption of
narrow interior oceans.
Intervals that lack deposits include 2500 to 2000, 1700 to 1400, and 1000 to 750 Ma, all of which
correspond to periods of supercontinent stability or breakup. The only supercontinent that does
not appear to have a major peak associated with its assembly is Rodinia. This assembly, between
1400 and 1100 Ma, is marked not only by a lack of VHMS deposits but also an apparent relative
quiescence in magmatic activity.
Possible explanations for this anomaly include underrepresentation of submarine volcanic rocks
during this interval, ineffective or inadequate exploration (Franklin et al., 2005), or the high
metamorphic grade of Rodinian orogens due to uplift and erosion above dense Neoproterozoic
lithosphere (Groves et al., 2005). Of these three alternatives, the first two, particularly the
second, are difficult to assess. The last option seems less likely because at least one-quarter of
global deposits, including major deposits such as Geco, are in amphibolite or higher grade
metamorphic belts, and Rodinia orogens are underrepresented as VHMS deposit hosts, even
when corrected for metamorphic grade. In addition, a number of the major Rodinia orogenic
belts, including the North American Grenville, are actually underlain by thick Archean
lithosphere (van der Lee and Nolet, 1997), which is similar to the basement of the world-class
Paleoproterozoic Trans-Hudson VHMS district (Corrigan et al., 2007). Major areas of low to
medium metamorphic-grade submarine volcanic rocks are also locally associated with Rodinia
(Elzevir and Montauban terranes of the Canadian Grenville: Corriveau et al., 2007) but lack
significant deposits. These terranes formed in continental back-arc settings and have abundant,
possibly shallower water, carbonates. Accordingly, they may not be good prospects for VHMS
deposits, although they are known to be districts that contain clastic sediment-hosted Pb-Zn
deposits.
A fourth alternative is that the assembly of Rodinia was characterized by a different tectonic
style. As noted by Cawood et al. (2009), Rodinia is the only one of the reasonably wellunderstood supercontinents to be dominated by advancing accretionary orogenesis. It is
possible that greater amounts of subduction erosion, associated with this style of accretion,
preferentially removed the most prospective, pericratonic or intraoceanic submarine volcanic
rocks. In addition, the overall contractional upper plate stresses would have inhibited high heat
flow and submarine continental back-arc basins. In this regard, alternative reconstructions of
Rodinia (Evans, 2006) would lengthen its Cordilleran-style oceancontinent margin with
advancing accretion. It is likely that the poor endowment of Rodinia for VHMS deposits is telling
us something fundamental about its paleogeography that has yet to be fully evaluated.
Variations related to changes in the composition of the hydrosphere and atmosphere
Because VHMS-forming ore fluids, at least in part, mixed with seawater to cause ore deposition,
the composition of seawater is an important constraint on the final characteristics of the
deposits. Aspects of seawater chemistry that appear most influential are the redox state, which
not only influences the presence or absence of sulfate gangue minerals and the carcter of
exhalites but also variations in sulfur isotopes; and the salinity, which has a major influence on
the behavior of ore fluids as they vent and a smaller influence on the ability of fluids to transport
metal. The redox state of the hydrosphere is also controlled by the redox state of the
atmosphere.

Changes in the redox state of seawater and implications for sulfur isotopes: One of the most
fundamental changes in the history of the Earth was the oxygenation of the atmosphere and, as
a consequence, the hydrosphere. This concept was first suggested by Cloud (1973), partly based
on observations of secular variations in the abundance of banded iron formation.
Most workers agree that the major oxygenation happened in the Paleoproterozoic, probably as
a gradual process.
The most recent, and possibly the most effective, method to track the redox state of the
atmosphere is mass-independent fractionation of 33S relative to 34S (Mojzsis et al., 2003).
Massindependent 33S fractionation is interpreted to be the consequence of photolytic
breakdown of atmospheric SO2 to produce reduced and oxidized (e.g., sulfate) sulfur species
(Farquhar et al., 2000) that are rained-out of the atmosphere into the hydrosphere (Pavlov
and Kasting, 2002). The observations that mass independent fractionation of 33S declined
between 2450 and 2090 Ma has been used to suggest that initial oxidation of the atmosphere
occurred at this time (Farquhar et al., 2000; Mojzsis et al., 2003).
The abundance of barite in Paleoarchean VHMS deposits with mass-independent 33S
fractionation suggests that the sulfate was sourced from disequilibrium photolytic
decomposition of SO2 in the atmosphere and hence was out of equilibrium with the atmosphere
and ocean as a whole. Huston and
Logan (2004) suggested that this sulfate was restricted to an upper sulfate-rich layer. The lower
part of the seawater column was interpreted to be reduced, with high concentrations of ferrous
iron and low concentrations of sulfur as H2S. They suggested that during the Mesoarchean to
Paleoarchean, oceans became uniformly ferrous iron rich and sulfur poor. As a consequence,
seawater that was drawn down into sea-floor hydrothermal systems did not contribute
significant amounts of sulfur to the evolving hydrothermal fluids. Rather, the sulfur was leached
from country rocks and inherited the isotopic signatures of the volcanic rock pile. This resulted
in very uniform 34S values near 0 per mil for Archean and Paleoproterozoic VHMS deposits
(Fig. 2B). Relatively uniform 34S values of 5 to 10 per mil for barite in Paleoarchean deposits
probably reflect fractionation of an isotopically uniform atmospheric source of SO2 during
photolytic reactions.
Slack et al. (2009) suggested that in the late Paleoproterozoic, the oceans had become suboxic,
possibly caused by an oceanic mixing event resulting from the Sudbury impact at ~1850 Ma
(Slack and Cannon, 2009). Slack and Cannon (2009) interpreted this event to have caused a
change from earlier sulfidic exhalites to magnetite-bearing exhalites associated with VHMS
deposits. Because these deposits are not common in the Mesoproterozoic and Neoproterozoic,
Little can be inferred about oceanic conditions from VHMS deposits until the Phanerozoic.
Phanerozoic deposits have super ficial similarities with Paleoarchean deposits in having
reasonably abundant sulfate, particularly barite, gangue.
However, isotopically, both the sulfate and sulfide minerals are different (Figs. 2B, 8). Sulfur
isotope fractionation between these minerals is much smaller in the Precambrian, and 34S
values of both sulfate and sulfide minerals are more variable in the Phanerozoic. The 34Ssulfate
mimics the sea - water sulfate evolution curve of Claypool et al. (1980), and 34Ssulfide parallels
this curve, with values ~15 per mil lower (Fig. 2B), as first noted by Sangster (1968). These
relationships suggest that the sulfate was derived directly from seawater during mixing and that
a large fraction of the sulfur in the ore fluids was derived from reduction of seawater sulfate.

Because total sulfur concentrations are not buffered by ferrous iron, as in the Paleoproterozoic
and earlier, total sulfur contents of seawater increased such that this sulfur became an
important component of fluids that formed VHMS deposits.
Secular changes in salinity: The limited fluid inclusion data mentioned above suggest that
Archean through Paleoproterozoic seawater was significantly more saline, by a factor of two or
more, than modern seawater, consistent with inferences made by Knauth (2005) based on the
temporal distribution of halite deposits. As the fluids that formed VHMS deposits are, in most
cases, evolved seawater, these fluids should have higher salinities in the Precambrian, an
inference also supported by limited data (Fig. 2A). Higher salinities have implications both for
the genesis of these deposits and for arguments used to infer genesis.
More saline ore fluids are more effective for dissolving and transporting metals (Huston and
Large, 1987). Hence,
Archean to Paleoproterozoic VHMS ore fluids may have been more effective ore formers.
Secondly, as the ambient seawater through most of the Precambrian and possibly into the early
Paleozoic was more saline, much higher salinities are required to form brine pools. Finally, use
of salinities greater than that of modern seawater as evidence for a magmatic-hydrothermal
input to VHMS ore fluids must be questioned, particularly as a number of other processes, such
as deep phase separation, have been documented to enhance the salinity of hydrothermal
systems in modern systems (cf. Hannington et al., 2005).
Conclusions
Analysis of the characteristics of VHMS deposits through time suggests significant secular
variations in distribution and metallogenesis, which appear to be related to changes in tectonic
processes, tectonic cycles, and changes in the composition of the hydrosphere. The most striking
observation is that VHMS deposits are not uniformly distributed in time, an observation also
made by others (e.g., Franklin et al., 2005; Groves et al., 2005). The Archean and Proterozoic are
characterized by two major peaks of deposit formation, at 2740 to 2680 and 1910 to 1840 Ma,
respectively, with only minor deposits having formed outside of these peak intervals. The
Phanerozoic differs in that there appears to be continuous formation of deposits but with a
major peak at 390 to 355 Ma and a smaller peak at 510 to 460 Ma. These major peaks for VHMS
formation through geologic time appear to be associated with the assembly of large continental
masses: the 2740 to 2680 Ma peak corresponds to amalgamation of Kenorland, the 1910 to 1840
Ma peak corresponds to the assembly of
Nuna, and the 510 to 460 and 390 to 355 Ma peaks correspond to the assembly initially of
Gondwana and Euramerica and then final assembly of Pangea. The lack of deposits associated
with the assembly of Rodinia (14001100 Ma) may be related to this amalgamation being
dominated by advancing accretionary orogenesis (Cawood et al., 2009), which was less favorable
for the formation and/or preservation of VHMS deposits.
Other intervals that lack VHMS formation correspond to periods of stability or breakup of major
continental land masses. The close association with land mass amalgamation contrasts with
clastic-dominated, sediment-hosted zinc-lead deposits because these latter deposits appear to
develop during the breakup of the major land masses (Leach et al., 2010).
The VHMS deposits become increasingly enriched in lead with time, a pattern that is partly
related to the greater abundance of felsic-dominated host successions for younger deposits and

partly related to an apparent increase in the average content of lead in the crust. Lead isotopes
also display systematic patterns. Archean intervals are characterized by large variations in
values, reflecting the presence of sources with quite different 238U/204Pb values. These results
support proposals for significant differentiation and crust formation during the Hadean or
Eoarchaen (Bennett, 2003). With time, the variability in values decreased, suggesting mixing
and homogenization of these originally quite different sources. In the younger deposits, the ore
lead reflects the host succession, with mafic-dominated successions producing lead with
values than felsic-dominated successions.
Some characteristics of VHMS deposits are related to the composition of coexisting seawater.
The presence of barite is related to the amount of sulfate in oceans, although the mechanism of
sulfate formation differed through geologic time. Barite is common in deposits from the
Paleoarchean, virtually absent in deposits from the Mesoarchean and
Neoarchean, and becomes increasingly common in the Proterozoic, and is very common again
in the Phanerozoic. The trend from the Neoarchean to the Phanerozoic probably relates to the
progressive oxidation of the atmosphere and hydrosphere, which resulted in increasing
concentrations of oceanic sulfate. However, sulfate in the Paleoarchean seawater was probably
produced by photolytic decomposition of SO2 in a reduced atmosphere.
Because the Archean and Paleoproterozoic oceans had high concentrations of dissolved ferric
iron, the sulfur content of the oceans was low and most sulfur in ore fluids that formed VHMS
deposits was derived from leaching of underlying volcanic rocks. This resulted in the
characteristic near-zero per mil signature of Archean and Paleoproterozoic deposits. An increase
in sulfate contents of seawater in the Phanerozoic resulted in seawater providing more sulfur to
the ore fluids and a more variable sulfur isotope pattern for ore sulfides.
Archean and Proterozoic seawater was significantly more saline than that in the Phanerozoic,
particularly late Phanerozoic seawater. Ore fluids that formed VHMS deposits reflect this, being
typically more saline in Archean and Proterozoic deposits. This variability introduces uncertainty
into genetic models advocating brine pools or magmatic-hydrothermal contributions based on
high-salinity ore fluids. The higher salinities will also enhance the metal-carrying capacity of the
ore fluids, explaining higher grade or larger deposits on the earlier Earth.
Acknowledgments
This contribution is published with permission of the Chief Executive Officer, Geoscience
Australia. It is a contribution to the Geological Survey of Canadas Targeted Geoscience Initiative3 Flin Flon project. Neil Rogers and Alex Zagorevski are thanked for providing geochronological
information about Appalachian deposits. It has benefited from very constructive and thought
provoking reviews by Mark Hannington, Graham Logan, Russell Korsch, and Steve Piercey.