Article

pubs.acs.org/est

Use and Legacy of Mercury in the Andes

Colin A. Cooke,*,, Holger Hintelmann, Jay J. Ague, Richard Burger, Harald Biester, Julian P. Sachs,#
and Daniel R. Engstrom

Department of Geology and Geophysics, Yale University, New Haven, Connecticut 06520, United States

Department of Anthropology, Yale University, New Haven, Connecticut 06520, United States

Department of Chemistry, Trent University, Peterborough, Ontario K9J 7B8, Canada

Institute for Geoecology, Technical University-Braunschweig, Langer Kamp 19c, 38106 Braunschweig, Germany
#
School of Oceanography, University of Washington, Seattle, Washington 98195, United States

St . Croix Watershed Research Station, Science Museum of Minnesota, Marine-on-St. Croix, Minnesota 55047, United States
*
S Supporting Information

ABSTRACT: Both cinnabar (HgS) and metallic mercury (Hg0) were

important resources throughout Andean prehistory. Cinnabar was used
for millennia to make vermillion, a red pigment that was highly valued in
pre-Hispanic Peru; metallic Hg0 has been used since the mid-16th
century to conduct mercury amalgamation, an ecient process of
extracting precious metals from ores. However, little is known about
which cinnabar deposits were exploited by pre-Hispanic cultures, and the
environmental consequences of Hg mining and amalgamation remain
enigmatic. Here we use Hg isotopes to source archeological cinnabar and
to ngerprint Hg pollution preserved in lake sediment cores from Peru
and the Galapagos Islands. Both pre-Inca (pre-1400 AD) and Colonial
(15321821 AD) archeological artifacts contain cinnabar that matches
isotopically with cinnabar ores from Huancavelica, Peru, the largest
cinnabar-bearing district in Central and South America. In contrast, the Inca (14001532 AD) artifacts sampled are characterized
by a unique Hg isotopic composition. In addition, preindustrial (i.e., pre-1900 AD) Hg pollution preserved in lake sediments
matches closely the isotopic composition of cinnabar from the Peruvian Andes. Industrial-era Hg pollution, in contrast, is distinct
isotopically from preindustrial emissions, suggesting that pre- and postindustrial Hg emissions may be distinguished isotopically
in lake sediment cores.

INTRODUCTION
Cinnabar (HgS) forms a bright red pigment (vermillion) when
powdered. In the South American Andes, vermillion is found in
graves of high-status individuals and as a paint covering
funerary masks and adorning ceremonial artifacts (Figure 1A).
Vermillion has been recovered in association with a range of
archeological artifacts spanning one of the rst (Chav n) to the
last (Inca) pre-Hispanic Andean civilizations. Deposits of
cinnabar are known from a range of hydrothermal ore deposits
located across Central and South America,1 the largest of which
is the Huancavelica quicksilver district in central Peru (Figure
1B).2,3 It has been suggested that Huancavelica cinnabar was
mined and traded for in pre-Hispanic times,4 but clear
conrmation is lacking, as is information regarding other
possible cinnabar sources.
A renewed interest in cinnabar, this time as a source of
metallic mercury (Hg0), occurred after Spanish conquest of the
Andes in 1532 AD. By 1570 AD, metallic Hg0 was relied upon
across Central and South America to conduct mercury
amalgamation, a technological development that allowed for
the extraction of silver and gold from even low-grade ores.5,6
The rapid adoption of mercury amalgamation across the
Americas stimulated cinnabar mining on an unprecedented
scale, and the cinnabar mines within the Huancavelica
quicksilver district, the largest of which was the Santa Barbara
mine,2,3 supplied much of the metallic Hg 0 used for
amalgamation. Mercury amalgamation dominated silver
production globally until 1900 AD,7 and it is estimated to
have emitted >100 Gg of gaseous Hg0 to the global
atmosphere.6,8 Resolving the geographic scope and biogeo-
chemical impact of preindustrial mercury mining and emissions
is important because mercury can be recycled repeatedly
between various earth-surface compartments9 and may persist
for centuries in biogeochemically active pools before being
sequestered in soils or sediments.10,11
High-precision measurements of Hg isotopes have aorded
new insight into source apportionment and the biogeochemical
Received: November 26, 2012
Revised: April 1, 2013
Accepted: April 3, 2013
Published: April 18, 2013

2013 American Chemical Society 4181 dx.doi.org/10.1021/es3048027 | Environ. Sci. Technol. 2013, 47, 41814188
Environmental Science & Technology
Figure 1. Artifact photos and sample locations. (A) Photographs of
some of the artifacts included in this study; the red pigment on each
item is cinnabar. Details about the provenance, cultural aliation, and
age of each artifact are provided in Table 2; photographs of the
artifacts not shown here (samples A78, A10, A1213, and A1516)
are included in the Supporting Information. (B) Map showing the
locations of cinnabar samples (C#; white squares), archeological
artifacts (A#; gray squares), and lake sediment cores (red stars). Also
indicated is the approximate extent of the Inca Empire at the time of
Spanish conquest (1532 AD), which extended across much of
modern-day Peru and Ecuador, and parts of Colombia, Bolivia,
Chile, and Argentina. Sample labels in both panels correspond to
Tables 1 and 2.
cycling of Hg.1214 There are seven stable isotopes of Hg
(196204 amu), and mass-dependent fractionation (MDF) of
Hg isotopes is expressed as 202Hg, which is derived using
standard delta notation: xHg () = ([(xHg/198Hg)unknown/
(xHg/198Hg)NIST SRM 3133] 1) 1000, where
(xHg/198Hg)NIST SRM 3133 is the average Hg isotope ratio of
bracketing standards.15 MDF of Hg is known to occur during
reductionoxidation transformations, biological cycling, and
volatilization of Hg. Hg isotopes can also undergo mass-
independent fractionation (MIF) in which the even- and odd-
mass-number isotopes fractionate from each other.12 MIF of
Hg isotopes is reported as the deviation of a measured 202Hg
value from that theoretically predicted on the basis of MDF.
MIF is thus reported as 199Hg and 201Hg in per mil (),
and for variations 5 can be calculated using the following:
199Hg = 199Hg (202Hg 0.252) and 201Hg = 201Hg
(202Hg 0.752);15 we use 199Hg as the default value to
report MIF. MIF of Hg is largely produced by photochemical
reactions and remains unchanged by most dark and biological
transformations.12,16
Here we present the results of an interdisciplinary study
using Hg isotopes to link resource exploitation, the
archeological record, and environmental pollution. Our new
Hg isotope data oer unprecedented insight into artisanal
cinnabar mining and exchange and the environmental legacy of
mercury mining in the Andes.
MATERIALS AND METHODS
Mercury Stable Isotopes. Hg isotopic compositions were
measured using Thermo-Finnigan Neptune continuous-ow
cold vapor generation MC-ICP/MS at Trent University and in
Article
accordance with published methodologies.17,18 Additional
details are provided in the Supporting Information. Analytical
uncertainty was evaluated using replicate analyses of both the
UM-Almaden standard and the certied standard reference
materials (CRM) MESS-3 (marine sediment) and NIST 1944
(New York/New Jersey waterway sediment); the CRM were
processed and analyzed in the same manner as our samples.
The results for these standards (Table S1) were indistinguish-
able (within uncertainty ranges) from published values.15,17,19,20
We estimate a typical analytical uncertainty of a given isotope
ratio as 2 SD of the measurement of the ratio in procedural
standards (e.g., 202Hg uncertainty = 0.09). Digestion
duplicates yielded 202Hg values with 2 SD uncertainty ranges
spanning 0.02 to 0.56 (202Hg); 0.02 to 0.09
(199Hg) and 0.01 to 0.09 (201Hg) (Table S1). While
we cannot readily explain the relatively large 202 Hg
heterogeneity observed in sample H5, it seems likely that this
reects heterogeneity within the original deposit (discussed
below).
Cinnabar Ores and Archeological Artifacts. To
constrain the Hg isotopic signature of cinnabar sources across
the South American Andes, we obtained 12 samples of cinnabar
ore from eight deposits (Table 1; Figure 1B). Our samples,
Table 1. List of Cinnabar Ores, with Sample IDs
Corresponding to Labels in Figures 1 and 2
sample ID location
H15 Huancavelica, Peru
C1 Jalaca, Honduras
C2 Antioquia, Colombia
C3 Quindio, Colombia
C4 Chonta, Peru
C5 Cerro Colorado, Bolivia
C6 Mina de Pedernal, Bolivia
C7 Algarrobo Mine, Chile
which were obtained from museum mineral collections, are by
no means a complete sampling of Andean cinnabar
occurrences. But they oer an initial evaluation of Hg isotope
heterogeneity across the Andes and include the only two
deposits (Huancavelica and Chonta, Peru) mined historically
(i.e., since 1532 AD).1
We hypothesized that Hg isotopes might be used to
provenance archeological cinnabar. To test this hypothesis,
we obtained samples of cinnabar found either as an oering
(samples A17) or as a pigment covering ceramic (sample A8),
metal (sample A9), or wooden (samples A1017) artifacts
(Table 2; Figure 1). A complete list of the objects sampled,
including information about the archeological site, cultural
aliation, and age, is provided in Table 2; additional details
about each item are provided in the Supporting Information.
The artifacts sampled include a number of pre-Inca (i.e., pre-
1400 AD), Inca (ca. 14001532 AD), and Colonial (1532
1821 AD) objects.
Lake Sediment Core Mercury Content. To reconstruct
the history of Hg deposition, we collected sediment cores from
two lakes, one located in the Peruvian Andes (Laguna Negrilla:
13 09 S, 72 58 W; 4125 masl) and one located on San
Cristobal Island, Galapagos archipelago, Ecuador (El Junco
Lake: 0 53 S, 89 28 W; 660 masl) (Figure 1B). Details
about the recovery, chronology, and Hg measurements of the
Laguna Negrilla sediment core have been published pre-
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Table 2. List of Archaeological Cinnabar Samples: Sample IDs Correspond to Labels in Figures 1 and 2a
archaeological site or
sample id object region cultural aliation age estimate
Pre-Inca
Artifacts
Al2 cinnabar in grave Kuntur Wasi Chav n Early Horiozn (800300 BC)
A36 funerary oering Chongoyape Chav n Early Horizon (800300 BC)
A7 cinnabar in ceremonial Las Huacas Cupisnique Initial Period (1200800 BC)
oering
A8 bottle rim Cerro Blanco Chav n Early Horiozn (800300 BC)
A9 gold funerary mask Northern Peruvian Lambayeque Late Intermediate Period (10001250 AD)
coast (Sican)
A1011 wooden mummy bundle Central Peruvian coast unknown A10: 10201150 AD All: 8901020 AD
masks
Colonial Artifacts
A1214 wooden drinking vessels Cusco Colonial A12: 16701890 ADA13: 16701950 AD A14: 15201790 AD
(qeros)
Inca Artifacts
A1517 wooden digging boards Southern Peruvian Inca A15: 14001440 AD A16: 14601630 AD
coast
a
Archaeological samples occur either as pure cinnabar entombed within a burial or oering (A17) or as a decorative pigment (A817). Samples
A1017 were radiocarbon dated, and the calibrated 2 age ranges are also provided. More details about each artifact and the radiocarbon results are
provided in the Supporting Information.

viously.21 El Junco Lake occupies an extinct volcanic crater on

the southwest summit San Cristobal Island in the Galapagos
Archipelago. The lake, which is roughly circular with a diameter
of 220 m, lies within a 320-m diameter crater.
Stratocumulus cloudswhich are an ecient scavenger of
atmospheric Hg2+ (ref 22)usually conceal the lake in a dense
fog (locally called garua), and strong surface winds channel air
year round from the southeast. El Junco Lake is thus ideally
situated to record the long-range atmospheric transport of Hg
emitted from the South American mainland.
The sediment cores from both lakes were dated using both
210
Pb (Table S2) and 14C (Table S3) radioisotopes, and age-
depth models for the sediment cores (Figure S2) were
generated using the CLAM software package.23 To quantify
the total sediment Hg content, we freeze-dried and
homogenized 200 mg of sediment from 1-cm intervals and
measured the Hg content using a DMA-80 direct mercury
analyzer. Duplicate analyses and the CRM MESS-3 were
measured after every 10th sample and were always within 5% of Figure 2. Three-isotope plot of 202Hg and 199Hg values for
cinnabar. The sample numbers correspond to the sample ID numbers
each other (for duplicates) and certied values (for CRM). We in Table 1 (for the cinnabar ore) and Table 2 (for the artifacts) but
also measured a suite of other sediment parameters including without the capital letters. A signicant and linear (r2 = 0.99, p =
organic carbon and nitrogen contents (%C and %N), and the 0.001) relationship is noted within cinnabar samples from
concentration of aluminum (Al), titanium (Ti), sodium (Na), Huancavelica (black line). The majority of the pre-Inca (pre-1400
and manganese (Mg) (Figure S3). AD) and Colonial (15321900 AD) archeological cinnabar samples

(circled) plot within the 2 uncertainty ranges for the Huancavelica

RESULTS AND DISCUSSION
Ancient Cinnabar Mining and Exchange. Many of the
cinnabar ores we analyzed exhibit both MDF and MIF of Hg
(Figure 2; Table S1). Cinnabar 202Hg values span 3.5, and
199Hg and 201Hg values span 0.4. There is, furthermore,
greater variability in 202Hg values within the Huancavelica ores
than among the dierent deposits, reecting the heterogeneity
of this district.
Our cinnabar samples were obtained from museum
collections that are largely devoid of information concerning
their geological provenance beyond their general location of
collection. Formation conditions are, therefore, unknown for
the majority of the samples we analyzed, making it dicult to
explain the wide range of isotopic compositions observed
(Figure 2). However, MDF of Hg has been observed previously
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cinnabar ores (gray shading), suggesting Huancavelica was the source
of cinnabar on these objects. In contrast, cinnabar from Inca-era (ca.
14001532 AD) artifacts plot away from the Huancavelica, pre-Inca,
and Colonial cinnabar samples.
within a variety of hydrothermal ores, including cinnabar,2428
and is thought to result from a combination of processes
associated with the emplacement of Hg-bearing minerals.25,26
In contrast, signicant MIF of Hg has not been observed
previously in cinnabar, and we observe a linear relationship
between MDF and MIF within Huancavelica ore (r2 = 0.99, p =
0.001). MIF of Hg is thought to be initiated by either the
nuclear volume eect (NVE) or the magnetic isotope eect
(MIE). The NVE, which generates smaller MIF (0.4) and
a 199/201Hg ratio of 1.601.65, has been observed during
dx.doi.org/10.1021/es3048027 | Environ. Sci. Technol. 2013, 47, 41814188
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liquidvapor Hg0 evaporation, Hg2+ reduction in the absence
of light, and Hg2+thiol complexation.2931 In contrast, the
MIE produces larger MIF with a 199/201Hg ratio between 1.0
and 1.3, and is initiated during photoreduction of Hg2+ or
methyl-Hg (ref 12). Our cinnabar samples are characterized by
a 199/201Hg ratio of 1.23 0.09 (Figure S1), suggesting that
the MIE drives MIF in these samples. While photochemically
initiated reduction of oxidized Hg2+ (to gaseous Hg0) is
thought to be the main driver of MIF of Hg in natural
samples,13,32 it cannot explain the MIF observed within our
cinnabar samples. Instead, the MIF anomalies preserved within
Central and South American cinnabar may indicate isotopic
inheritance from interactions with sedimentary source-rocks,
which, for example, are found in close association with the
cinnabar deposits at Huancavelica.2 Coal, peat, and marine
sediments all exhibit MIF of Hg generated by the MIE,13,32 and
a similar suggestion was made by Sonke et al. to explain
signicant MIF anomalies of trace Hg found within sphalerite
(ZnS).20 We also note that, given our small sample size, we
cannot rule out the existence of other isotopic end-members.
Regardless of the exact cause of MIF within cinnabar, the
relatively high degree of isotopic variability among cinnabar
deposits raises the possibility that Hg isotopes can be used to
source cinnabar preserved as part of the archeological record.
The archeological artifacts we analyzed can be broadly grouped
according to their antiquity and Hg isotopic signatures. The
rst group (samples A111) includes all of the artifacts
predating the Inca Empire (i.e., pre-1400 AD). Most of these
pre-Inca artifacts do not reveal signicant MIF of Hg, and, with
the lone exception of sample A2, plot within the 2 uncertainty
range of the Huancavelica data (gray band) (Figure 2). The
second group of artifacts (samples A1517), which contains all
of the Colonial era (15321821 AD) samples, is characterized
by 202Hg and 199Hg values that overlap closely with
Huancavelica cinnabar. This is consistent with historical records
that indicate Huancavelica was the only signicant source of
cinnabar exploited by the Spanish.2 The nal group of artifacts
all date to the Inca era (ca. 14001532 AD). The cinnabar
adorning these items is characterized by Hg isotopic
compositions that are signicantly dierent from both the
Huancavelica cinnabar ore and the other artifacts.
The isotopic overlap between the Huancavelica ores and the
majority of the artifacts is consistent with previous suggestions4
that the Huancavelica region was an important prehistoric
source of cinnabar. However, we cannot eliminate the
possibility that some of the archeological cinnabar might have
come from deposits at Chonta in the Department of Huanuco,
Peru (sample C4), Cerro Colorado in the Nor Chicas Province,
Bolivia (sample C5), or other deposits that we did not analyze.
We are also unable to constrain the Hg isotopic heterogeneity
that may be present in these other cinnabar deposits.
Historically, Chonta was exploited only briey (<100 years),
and the Cerro Colorado mine was not utilized at all, despite its
proximity to the huge silver deposit in Potos , which was an
important center of silver mining and mercury amalgamation.
The pre-Inca artifacts we analyzed were recovered from
archeological sites spanning thousands of kilometers and nearly
3000 years of Andean prehistory. The oldest artifacts we
analyzed date either to the Initial Period (ca. 1200800 BC) or
Early Horizon (ca. 800300 BC) cultural periods and were
found in association with the remains of high-status individuals
from Northern Peru (Table 2). For example, samples A1 and
A2 were excavated in secure archeological contexts from two
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dierent burials of elite individuals at the site of Kuntur Wasi in
the upper Jequetepeque drainage (Figure 1A). Artifact
assemblages from Kuntur Wasi indicate that the center engaged
in long-distance trade with Chav n de Huantar and other
centers of the Chav n Horizon, which was the rst pan-regional
cultural phenomenon in the Andes.33 Four jars of dierent
shades of cinnabar (samples A36; Figure 1A) were similarly
recovered from Chongoyape in the Lambayeque drainage of
Perus north coast in association with a large collection of gold
and silver funerary items fashioned in the distinctive Chav n
style.34 Other cinnabar samples from north coast archeological
sites include Las Huacas in the middle Jequetepque Valley
(sample A7) and Cerro Blanco in the lower Nepena Valley
(sample A8). All of these samples show an isotopic signature
consistent with that of the Huancavelica ores. Thus, our isotope
data suggest cinnabar from the Huancavelica district could have
been actively traded from deposits in the south central
highlands of Peru to as far away as the far north coast of
Peru (a distance of over 800 km) almost three thousand years
ago.
Mining and metallurgy along Perus northern coast increased
dramatically during the Late Intermediate Period (ca. 1000
1250 AD) by communities belonging to the Lambayeque (or
Sican) culture.35 Lambayeque burials contain some of the
largest caches of precious metals yet discovered in the Americas
(e.g., sample A5), and cinnabar pigment is often found coating
their gold death masks and other jewelry (Figure 1A). Our Hg
isotope data from a Lambayeque burial mask strongly suggest
that Huancavelica remained an important source of cinnabar
during this period of increased metallurgical production.
The exchange of cinnabar during the late Middle Horizon/
Late Intermediate Period (ca. 8001200 AD) extended to the
central coast of Peru as well. Two wooden burial masks
(samples A10 and A11), which radiocarbon date to 8901150
AD (Table S2), are painted red with cinnabar that matches
closely both Huancavelica ores and the other pre-Inca artifacts
from northern Peru (Figure 2). Thus, it appears that northern
Peruvian cultures did not have exclusive access to Huancavelica
cinnabar.
Cinnabar from Huancavelica was similarly used for
ceremonial objects after conquest of the Inca (in 1532 AD)
as well. Three incised and painted wooden drinking cups called
qeros (samples A1214; Figure 1A), which radiocarbon date to
the 17th and 18th centuries AD (Table S2), have Hg isotopic
compositions that span nearly the full range of isotopic values
observed within the Huancavelica ores (Figure 2). Colonial
cinnabar mining of the Huancavelica quicksilver district
exploited three types of deposits, which are classied according
to their host rock (sandstone, limestone, or igneous rocks).1
The largest of these mines (the Santa Barbara mine) exploited
ore contained within the sandstone; however, all three types of
deposits were mined historically. Thus, the isotopic variability
we observe within these qeros and our samples of Huancavelica
ores may reect Colonial mining of deposits unexploited during
pre-Hispanic times.
A clear exception is noted in the isotopic composition of
cinnabar associated with a series of large and highly decorated
wooden digging boards (samples A1517; Figure 1A). These
items, which are from the south coast of Peru (Figure 1B) and
radiocarbon date to the Inca Empire (Table 2), plot well away
from all of the ores and archeological objects we analyzed
(Figure 2). Our Hg isotope data therefore suggest that the
cinnabar adorning these items was not obtained from
dx.doi.org/10.1021/es3048027 | Environ. Sci. Technol. 2013, 47, 41814188
Environmental Science & Technology Article

Huancavelica, making them unique among the archeological

objects analyzed. These Inca-era artifacts are generally
interpreted as digging boards used for agriculture, and elaborate
ones, such as the specimens we analyzed, probably were used in
agricultural rituals associated with these agrarian activities.36
The Hg isotope data indicate the exploitation of a new, perhaps
extra-local, source of cinnabar. One possible source may be
cinnabar deposits in Colombia, two of which we sampled
(samples C2 and C3). While additional assessment Colombian
cinnabar heterogeneity is clearly needed before we can
ngerprint the new source of cinnabar used to decorate these
Inca artifacts, our Hg isotope data oer the potential to reveal
the evolving exchange of mineral resources through time.
Long-Range Transport of Hg Pollution. Cinnabar
mining at Huancavelica left not only a lasting cultural legacy
but an environmental one as well. The geographic impact of
preindustrial Hg emissions would have depended on the Hg
species emitted. For example, emissions of particulate cinnabar
dust associated with early cinnabar mining and processing
would have been characterized by a short atmospheric
residence time (hours to days) and thus would have had a
limited geographic impact. In contrast, emissions of gaseous
Hg0 would have the potential to inuence the global Hg cycle
because of the long atmospheric residence time (0.52 years)
of gaseous Hg0. Preindustrial sources of gaseous Hg0 potentially
included cinnabar retorting, mercury amalgamation, or the
smelting of nonferrous ores containing trace amounts of
mercury.
To assess the potential for long-range atmospheric transport
of preindustrial mercury emissions, we measured the
concentration and isotopic composition of Hg in two sediment
cores from Laguna Negrilla and El Junco Lake (Figure 3). The
Laguna Negrilla Hg data have been published previously21 and
are presented here on an updated age-depth model (Figure S2).
Between about 1000 BC and 1400 AD, Hg concentration and
ux are stable and low in both Laguna Negrilla (Hg
concentration: 178 39 ng g1; Hg ux: 7.1 3.0 g m2
y1) and El Junco Lake (Hg concentration: 76 9 ng g1; Hg
ux: 6.0 0.8 g m2 y1). Increases in both Hg concentration
and ux are noted between 1400 and 1600 AD in both lakes.
These increases in Hg, which are synchronous within the 2
uncertainties of the individual age-depth models (Table S4),
represent clear departures from otherwise steady rates of
atmospheric Hg deposition over the late Holocene. Moreover,
there is no synchronous inux of organic or inorganic material
to either lake or, for El Junco Lake, in the balance of regional
rainfall relative to evaporation.37 Thus, we assert that the
sediment cores from both Laguna Negrilla and El Junco record
preindustrial Hg pollution beginning between 1400 and 1600
AD.
Due to dating uncertainties, we cannot determine if the initial Figure 3. Sediment core Hg results. (A) Sediment core Hg
rise in Hg pollution occurred during the latest stages of the Inca concentration (symbols), Hg ux (lines), 202Hg, and 199Hg proles
Empire or shortly after Hispanic conquest of the Andes in 1532 from Laguna Negrilla and El Junco Lake since 1500 BC (BC dates as
AD. In addition to cinnabar mining for pigment production, negative values). The gray shading spans the interval of preindustrial
Inca metallurgists were highly skilled at smelting a range of Hg pollution (14001900 AD). (B) An expanded plot of Hg ux since
nonferrous ores; both of these activities release Hg to the 1400 AD. Also shown in green is registered metallic Hg0 production at
atmosphere.3840 In 1564 AD, the Spanish assumed control of Huancavelica, Peru since 1564 AD.2 Time periods corresponding to
the Inca Empire (ca. 14001532 AD), the Colonial era (15321900
cinnabar mining at Huancavelica, Peru, in response to the
AD), the Republican era (18211900 AD), and the industrial era
demand for metallic Hg0 for amalgamation. Historical records (1990today) are also indicated. (C) Plot of 1/Hg ux against 202Hg
indicate that, over the next 250 years, metallic Hg0 production for both lake sediment cores in which the data can clearly be separated
gradually declined and eectively ended when Peru achieved into pre- and post-Inca groupings. (D) Plot of 1/Hg ux against
independence in 1821 AD (Figure 3A).3 Regional Hg 199Hg for both lake sediment cores. The sediment cores samples can
deposition appears to have declined concomitantly, as be grouped according to their age.

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Environmental Science & Technology
evidenced by declining Hg burdens in Laguna Negrilla
sediment. However, Hg deposition to El Junco Lake increases
throughout the preindustrial era, rising to over 20 g m2 y1
by 1900 AD (Figure 3A). The steady rise in Hg deposition to
El Junco throughout the preindustrial era suggests the lake
received Hg from a range of activities (e.g., cinnabar mining,
retorting, and mercury amalgamation) occurring at locations
across the South American Andes. Thus, we suggest that
Laguna Negrilla records Hg emissions associated with cinnabar
mining at Huancavelica while El Junco records the long-range
transport of Hg emitted from a range of processes.
Isotopic Legacy of Hg Pollution. The mercuric species
emitted during Colonial and pre-Colonial cinnabar mining,
smelting (retorting), and mercury amalgamation carry
implications for the size of the impacted airshed and the
isotopic composition of the atmospheric Hg pool. Signicant
MDF and MIF of Hg is observed in both the El Junco and
Negrilla sediment cores (Figures 3 and 4; Table S1). Sediment
202Hg values range from 1.7 to 0.4 in Negrilla and from
0.9 to 0.4 in El Junco. Sediment 199Hg values ranged
from 0.13 to 0.30 in Negrilla and from 0.21 to 0.41 in
El Junco.
Both sediment cores are characterized by considerable down-
core variability in 202Hg. This variability implies either the
Figure 4. Three-isotope plot of 202Hg and 199Hg values from the
Laguna Negrilla (circles) and El Junco Lake (diamonds) sediment
cores. Also indicated are the ranges of Huancavelica, pre-Inca, and
Colonial cinnabar data from Figure 2, and published Hg isotopic
values for various terrestrial reservoirs (including soil, peat, lichen, and
snow) and precipitation.19,4550 Lake sediment intervals predating
1400 AD (i.e., pre-Inca) overlap with published values for terrestrial
reservoirs and typically exhibit negative MDF and MIF of Hg.
Preindustrial intervals dating to 14001900 AD, in contrast, typically
exhibit small (<0.2) or no signicant MIF of Hg; these intervals also
tend to overlap with cinnabar ores and artifacts. Industrial-era intervals
(i.e., post-1900 AD) overlap with published precipitation values and
do not overlap with either the cinnabar data or published values for
terrestrial materials.
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input of mercury from multiple sources with dierent Hg
isotopic signatures or varying amounts of in situ Hg isotopic
fractionation through time, or both. Nonetheless, periods of
high Hg delivery to the lakes also tend to be associated with
higher 202 Hg values. For example, peak 202 Hg, Hg
concentration, and Hg ux values co-occur during the Inca
period in Negrilla and during the industrial era in El Junco
(Figure 3). High rates of anthropogenic Hg deposition appear
to have similarly shifted sediment 199Hg signatures. In El
Junco, preindustrial Hg deposition resulted in 199Hg values
shifting from negative values to near 0 (Figure 3). In
Negrilla, no signicant MIF of Hg was detected in preindustrial
sediments. Both lakes record positive 199Hg values in 20th
century sediments.
Comparing the lake sediment Hg isotope data with the
results from both the Huancavelica and archeological cinnabar
provides support for the suggestion that anthropogenic Hg
emissions can be ngerprinted using Hg isotopes. In general,
older (i.e., pre-Inca) sediments within the El Junco Lake and
Laguna Negrilla sediment cores tend to be characterized by
negative MDF and MIF of Hg (Figure 4). This implies that Hg
deposited during pre-Inca times underwent recycling within the
global pool of Hg prior to deposition. In contrast, most of the
Inca, Colonial, and Republican aged (i.e., 14001900 AD)
samples overlap with the isotopic composition of cinnabar from
the Andes, including both the Huancavelica ores and the
archeological artifacts. The preindustrial Hg pollution preserved
within our sediment cores was likely transported to the lakes as
either particulate cinnabar dustemitted during cinnabar
mining and processingor as gaseous Hg0emitted during
the production of metallic Hg0 or during amalgamation. We
expect that emissions of cinnabar dust would preserve the
isotopic composition of the original ore. In contrast, previous
research has demonstrated that roasting cinnabar imparts a
MDF signature that allows for isotopic distinction between
roaster mine waste (calcine) and unroasted ore.27,28,41
However, Yin et al. showed that, even with a substantial
dierence (up to 8) in 202Hg values between calcine and
unroasted cinnabar, an insignicant dierence of only 0.05
in 202Hg values is expected between the released gaseous Hg0
and the unroasted ore.28 Thus, we would not expect a
signicant dierence in 202Hg values between gaseous Hg0 and
the starting cinnabar. We, therefore, cannot use Hg isotopes to
ascertain which species of Hg was emitted during preindustrial
times; emissions of both particulate cinnabar dust and Hg0
would likely closely match the isotopic composition of the
original cinnabar ore. The lack of any signicant MIF of Hg
associated with preindustrial Hg pollution indicates that there
was also relatively little MIF associated with preindustrial Hg
emissions. Nonetheless, the lake sediment data suggest
preindustrial Hg emissions shifted the Hg isotopic composition
of regional lake sediments.
Similar relationships between anthropogenic Hg input and
Hg isotope enrichment have been noted in aquatic sediments
directly impacted by point sources of anthropogenic Hg
pollution, with contaminated sediments commonly character-
ized by 199Hg and 201Hg values near 0.42 In contrast,
mid-Pleistocene marine sediments43 and most terrestrial
reservoirs, including soils,19,44 peat,45 lichen,46 and snow,47
commonly display both negative MDF and MIF (Figure 4).
This suggests that the release of Hg by industrial activities does
not impart MIF into sediments, likely because most crustal and
mantle Hg sources reveal little, if any, MIF of Hg.2528 In
dx.doi.org/10.1021/es3048027 | Environ. Sci. Technol. 2013, 47, 41814188
Environmental Science & Technology
contrast, Hg bound within ancient sediments has likely
experienced signicant recycling within the global pool,
including photochemical reduction, which generates MIF of
Hg. The same would apply to lake sediments that derive most
of their Hg from the erosion of catchment soils.42
The isotopic composition of 20th century sediments within
both the El Junco and Laguna Negrilla sediment cores is
dierent than that at any time previous. In general, preindustrial
intervals are characterized by 199Hg values that are negative or
near 0, while post-1900 AD core intervals are characterized
by positive MIF (Figures 3 and 4). The 199/201Hg slope of
sediment Hg remains unchanged (0.92 0.12) across these
transitions (Figure S1), suggesting that the evolution of
atmospheric MIF cannot be explained by a change in the
initiating mechanism of atmospheric Hg MIF. Moreover, this
shift occurs at dierent depths within each core and, therefore,
is not due to the in situ reductionoxidation cycling of
sedimentary Hg. Instead, we hypothesize that this positive shift
in the MIF of atmospheric Hg reects the large-scale industrial
release of gaseous Hg0 into the global atmosphere, initiated by
the global adoption of high-temperature fossil-fuel combustion
or by a large-scale change in the cycling of low-latitude
atmospheric Hg. Measurements of Hg in precipitation, which
today is dominated by anthropogenic sources, are commonly
characterized by positive MDF and MIF.4750 We, therefore,
suggest that, in lakes where the rate of Hg sequestration and
sedimentation exceeds the rate of Hg loss (via Hg2+ reduction
and volatilization of Hg0), sediment cores can faithfully record
the past isotopic composition of atmospheric Hg. In contrast,
the Hg isotopic composition of terrestrial archives, at least
those that are subaerially exposed for long periods of time (e.g.,
peat, lichen, snow, soil), likely incorporates some degree of
photochemical alteration. We, therefore, conclude that while
the magnitude of Hg release from New World metal extraction
was comparable to that from later industrial activities, its impact
on the global mercury cycle was far less signicant and more
local in nature. Additional Hg isotopic records from
atmospherically sensitive archives (e.g., crater lake sediment
cores) are clearly required to better characterize the unique
nature of 20th century Hg emissions.
The cinnabar deposits at Huancavelica, Peru, were among
the most important mercuric deposits ever exploited. The long
and complex history of mining and metallurgy produced an
archeological and environmental legacy that we have delineated
using Hg isotopes. This geochemical ngerprinting provides
new opportunities to decipher the cultural and environmental
legacies of early Hg emissions in this and potentially other
metallogenic provinces.
ASSOCIATED CONTENT
* Supporting Information
S mercury: Present-day versus preindustrial cycles and anthropogenic
Additional experimental details, a list of archaeological materials
included in this study, a table of stable Hg isotope results for
standards and samples, a table of radiocarbon results for
artifacts and lake sediment samples, a table of 210Pb activities
and constant ux/constant supply (cf/cs)-derived ages for the
El Junco sediment core EJ6-MW1, a table of [Hg] and Hg ux
data for the El Junco and Negrilla sediment cores, a plot of
199/201Hg ratio in (A) cinnabar and (B) lake sediment
samples, age-depth models for the Laguna Negrilla and El
Junco sediment cores, and geochemical proles from the El
Junco sediment core. This material is available free of charge via
the Internet at http://pubs.acs.org.
4187
Article
AUTHOR INFORMATION
Corresponding Author
*E-mail: colin.cooke@yale.edu.
Present Address
C.A.C.: Department of Geology and Planetary Science,
University of Pittsburgh, Pittsburgh, PA 15260, USA.
Notes
The authors declare no competing nancial interest.
ACKNOWLEDGMENTS
This eort is dedicated to the memory of our friend and
colleague, Karl Turekian. Karls scientic interests, which did
not adhere to traditional disciplinary boundaries, set the course
of geochemistry that carries forward today and will do so for
decades to come. We thank Ellen Howe, Emily Kaplan, Ramiro
Matos, Yoshio Onuki, Yuji Seki, Koichiro Shibata, Eisei
Tsurumi, Yuichi Matsumoto, William Brooks, Mike Rumsey,
and Jason Nesbitt for contributing samples. Dan Nelson, Will
Hobbs, Alex Wolfe, Joel Blum, and two anonymous reviewers
provided valuable feedback on an earlier draft of this
manuscript. The National Geographic Society and Yale
University provided funding for this project.
REFERENCES
(1) Berry, E. W.; Singewald, J. T., Jr. The geology and paleontology of
the Huancavelica mercury district; Johns Hopkins University Press:
Baltimore, MD, 1922; Vol. 2.
(2) Yates, R. G.; Kent, D. F.; Fernandez Concha, J. Geology of the
Huancavelica quicksilver district, Peru; Geological Survey Bulletin; U.S.
G.P.O.: 1951; p 59
(3) Wise, J. M.; Feraud, J. Historic maps used in new geological and
engineering evaluation of the Santa Barbara Mine, Huancavelica
mercury district, Peru. De Re Metallica 2005, 4, 1524.
(4) Burger, R. L.; Matos, R. Atalla: a center on the periphery of the
Chav n horizon. Lat. Am. Antiq. 2002, 13 (2), 153177.
(5) Nriagu, J. O. Legacy of mercury pollution. Nature 1993, 363, 589.
(6) Nriagu, J. O. Mercury pollution from the past mining of gold and
silver in the Americas. Sci. Total Environ. 1994, 149 (3), 167181.
(7) Hylander, L. D.; Meili, M. 500 years of mercury production:
global annual inventory by region until 2000 and associated emissions.
Sci. Total Environ. 2003, 304 (13), 1327.
(8) Streets, D. G.; Devane, M. K.; Lu, Z.; Bond, T. C.; Sunderland, E.
M.; Jacob, D. J. All-Time releases of mercury to the atmosphere from
human activities. Environ. Sci. Technol. 2011, DOI: org/10.1021/
es202765m.
(9) Selin, N. E. Global biogeochemical cycling of mercury: A review.
Annu. Rev. Environ. Resour. 2009, 34 (1), 4363.
(10) Sunderland, E. M.; Mason, R. P. Human impacts on open ocean
mercury concentrations. Global Biogeochem. Cycles 2007, 21, GB4022
DOI: 10.1029/2006GB002876.
(11) Selin, N. E.; Jacob, D. J.; Yantosca, R. M.; Strode, S.; Jaegle, L.;
Sunderland, E. M. Global 3-D land-ocean-atmosphere model for
enrichment factors for deposition. Global Biogeochem. Cycles 2008, 22,
GB2011 DOI: 10.1029/2007GB003040.
(12) Bergquist, B. A.; Blum, J. D. Mass-dependent and-independent
fractionation of Hg isotopes by photoreduction in aquatic systems.
Science 2007, 318 (5849), 417.
(13) Bergquist, B. A.; Blum, J. D. The odds and evens of mercury
isotopes: applications of mass-dependent and mass-independent
isotope fractionation. ELEMENTS 2009, 5 (6), 353357.
(14) Blum, J. D., Applications of stable mercury isotopes to
biogeochemistry; Springer: Berlin, 2011; pp 229245.
(15) Blum, J. D.; Bergquist, B. A. Reporting of variations in the
natural isotopic composition of mercury. Anal. Bioanal. Chem. 2007,
388 (2), 353359.
dx.doi.org/10.1021/es3048027 | Environ. Sci. Technol. 2013, 47, 41814188
Environmental Science & Technology
(16) Kwon, S. Y.; Blum, J. D.; Carvan, M. J.; Basu, N.; Head, J. A.;
Madenjian, C. P.; David, S. R. Absence of fractionation of mercury
isotopes during trophic transfer of methylmercury to freshwater fish in
captivity. Environ. Sci. Technol. 2012, 46 (14), 75277534.
(17) Foucher, D.; Hintelmann, H. High-precision measurement of
mercury isotope ratios in sediments using cold-vapor generation multi-
collector inductively coupled plasma mass spectrometry. Anal. Bioanal.
Chem. 2006, 384 (7), 14701478.
(18) Ma, J.; Hintelmann, H.; Kirk, J. L.; Muir, D. C. G. Mercury
concentrations and mercury isotope composition in lake sediment
cores from the vicinity of a metal smelting facility in Flin Flon,
Manitoba. Chem. Geol. 2013, 336 (0), 96102.
(19) Biswas, A.; Blum, J. D.; Bergquist, B. A.; Keeler, G. J.; Xie, Z.
Natural mercury isotope variation in coal deposits and organic soils.
Environ. Sci. Technol. 2008, 42 (22), 83038309.
(20) Sonke, J. E.; Schafer, J.; Chmeleff, J.; Audry, S.; Blanc, G.;
Dupre, B. Sedimentary mercury stable isotope records of atmospheric
and riverine pollution from two major European heavy metal
refineries. Chem. Geol. 2010, 279 (3), 90100.
(21) Cooke, C. A.; Balcom, P. H.; Biester, H.; Wolfe, A. P. Over three
millennia of mercury pollution in the Peruvian Andes. Proc. Natl. Acad.
Sci. 2009, 106, 88308834.
(22) Weiss-Penzias, P. S.; Ortiz, C., Jr.; Acosta, R. P.; Heim, W.;
Ryan, J. P.; Fernandez, D.; Collett, J. L., Jr.; Flegal, A. R. Total and
monomethyl mercury in fog water from the central California coast.
Geophys. Res. Lett. 2012, 39 (3), L03804.
(23) Blaauw, M. Methods and code for classical age-modelling of
radiocarbon sequences. Quatern. Geochron. 2010, 5 (5), 512518.
(24) Hintelmann, H.; Lu, S. Y. High precision isotope ratio
measurements of mercury isotopes in cinnabar ores using multi-
collector inductively coupled plasma mass spectrometry. The Analyst
2003, 128 (6), 635639.
(25) Smith, C. N.; Kesler, S. E.; Klaue, B.; Blum, J. D. Mercury
isotope fractionation in fossil hydrothermal systems. Geology 2005, 33
(10), 825828.
(26) Smith, C. N.; Kesler, S. E.; Blum, J. D.; Rytuba, J. J. Isotope
geochemistry of mercury in source rocks, mineral deposits and spring
deposits of the California Coast Ranges, USA. Earth. Planet. Sci. Lett.
2008, 269 (34), 399407.
(27) Stetson, S. J.; Gray, J. E.; Wanty, R. B.; Macalady, D. L. Isotopic
variability of mercury in ore, mine-waste calcine, and leachates of
mine-waste calcine from Areas mined for mercury. Environ. Sci.
Technol. 2009, 43 (19), 73317336.
(28) Yin, R.; Feng, X.; Wang, J.; Li, P.; Liu, J.; Zhang, Y.; Chen, J.;
Zheng, L.; Hu, T. Mercury speciation and mercury isotope
fractionation during ore roasting process and their implication to
source identification of downstream sediment in the Wanshan mercury
mining area, SW China. Chem. Geol. 2013, 336 (0), 7279.
(29) Estrade, N.; Carignan, J.; Sonke, J. E.; Donard, O. F. X. Mercury
isotope fractionation during liquid-vapor evaporation experiments.
Geochim. Cosmochim. Acta 2009, 73 (10), 26932711.
(30) Zheng, W.; Hintelmann, H. Nuclear field shift effect in isotope
fractionation of mercury during abiotic reduction in the absence of
light. J. Phys. Chem. A 2010, 114 (12), 42384245.
(31) Wiederhold, J. G.; Cramer, C. J.; Daniel, K.; Infante, I.;
Bourdon, B.; Kretzschmar, R. Equilibrium mercury isotope fractiona-
tion between dissolved Hg(II) species and thiol-bound Hg. Environ.
Sci. Technol. 2010, 44 (11), 41914197.
(32) Sonke, J. E. A global model of mass independent mercury stable
isotope fractionation. Geochim. Cosmochim. Acta 2011, 75 (16), 4577
4590.
(33) Burger, R. L., Chav n de Huantar and its sphere of inuence. In
Handbook of South American Archaeology; Silverman, H.; Isbell, W.,
Eds.; Springer: New York, 2008; pp 681703.
(34) Lothrop, S. K. Gold Ornaments of the Chav n Style from
Chongoyape, Peru. Amer. Antiq. 1941, 6, 25062.
(35) Shimada, I.; Epstein, S.; Craig, A. K. Batan Grande: a prehistoric
metallurgical center in Peru. Science 1982, 216 (4549), 952959.
4188
Article
(36) Kvietok, D. P. Digging sticks or daggerboards? A functional
analysis of wooden boards from the Ica region. Andean Past 1987, 1,
247274.
(37) Sachs, J. P.; Sachse, D.; Smittenberg, R. H.; Zhang, Z.; Battisti,
D. S.; Golubic, S. Southward movement of the Pacific intertropical
convergence zone AD 14001850. Nature Geosci. 2009, 2 (7), 519
525.
(38) Cooke, C. A.; Wolfe, A. P.; Hobbs, W. O. Lake-sediment
geochemistry reveals 1400 years of evolving extractive metallurgy at
Cerro de Pasco, Peruvian Andes. Geology 2009, 37 (11), 10191022.
(39) Cooke, C. A.; Balcom, P. H.; Kerfoot, C.; Abbott, M. B.; Wolfe,
A. P. Pre-Colombian mercury pollution associated with the smelting of
argentiferous ores in the Bolivian Andes. Ambio: J. Human Environ.
2011, 40 (1), 1825.
(40) Hylander, L. D.; Herbert, R. B. Global Emission and Production
of Mercury during the Pyrometallurgical Extraction of Nonferrous
Sulfide Ores. Environ. Sci. Technol. 2008, 42 (16), 59715977.
(41) Gehrke, G. E.; Blum, J. D.; Marvin-DiPasquale, M. Sources of
mercury to San Francisco Bay surface sediment as revealed by mercury
stable isotopes. Geochim. Cosmochim. Acta 2011, 75 (3), 691705.
(42) Feng, X.; Foucher, D.; Hintelmann, H.; Yan, H.; He, T.; Qiu, G.
Tracing mercury contamination sources in sediments using mercury
isotope compositions. Environ. Sci. Technol. 2010, 44 (9), 33633368.
(43) Gehrke, G. E.; Blum, J. D.; Meyers, P. A. The geochemical
behavior and isotopic composition of Hg in a mid-Pleistocene western
Mediterranean sapropel. Geochim. Cosmochim. Acta 2009, 73 (6),
16511665.
(44) Estrade, N.; Carignan, J.; Donard, O. F. X. Isotope tracing of
atmospheric mercury sources in an urban area of northeastern France.
Environ. Sci. Technol. 2010, 44 (16), 60626067.
(45) Ghosh, S.; Xu, Y.; Humayun, M.; Odom, L. Mass-independent
fractionation of mercury isotopes in the environment. Geochem.
Geophys. Geosyst. 2008, 9 (3), Q03004.
(46) Carignan, J.; Estrade, N.; Sonke, J. E.; Donard, O. F. X. Odd
isotope deficits in atmospheric Hg measured in lichens. Environ. Sci.
Technol. 2009, 43 (15), 56605664.
(47) Sherman, L. S.; Blum, J. D.; Johnson, K. P.; Keeler, G. J.; Barres,
J. A.; Douglas, T. A. Mass-independent fractionation of mercury
isotopes in Arctic snow driven by sunlight. Nature Geosci 2010, 3 (3),
173177.
(48) Gratz, L. E.; Keeler, G. J.; Blum, J. D.; Sherman, L. S. Isotopic
composition and fractionation of mercury in Great Lakes precipitation
and ambient air. Environ. Sci. Technol. 2010, 44 (20), 77647770.
(49) Sherman, L. S.; Blum, J. D.; Keeler, G. J.; Demers, J. D.;
Dvonch, J. T. Investigation of Local Mercury Deposition from a Coal-
Fired Power Plant Using Mercury Isotopes. Environ. Sci. Technol. 2011,
46 (1), 382390.
(50) Chen, J.; Hintelmann, H.; Feng, X.; Dimock, B. Unusual
fractionation of both odd and even mercury isotopes in precipitation
from Peterborough, ON, Canada. Geochim. Cosmochim. Acta 2012, 90
(0), 3346.
dx.doi.org/10.1021/es3048027 | Environ. Sci. Technol. 2013, 47, 41814188