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Environmental Processes
Evidence of Influence of Human Activities and Volcanic Eruptions on Environmental Perchlorate from a 300-Year Greenland Ice Core Record Jihong Cole-Dai, Kari Marie Peterson, Joshua Andrew Kennedy, Thomas S. Cox, and David G. Ferris Environ. Sci. Technol., Just Accepted Manuscript • DOI: 10.1021/acs.est.8b01890 • Publication Date (Web): 26 Jun 2018 Downloaded from http://pubs.acs.org on June 28, 2018
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Environmental Science & Technology
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Evidence of Influence of Human Activities and Volcanic Eruptions on Environmental
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Perchlorate from a 300-Year Greenland Ice Core Record
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Jihong Cole-Dai1, Kari M. Peterson1, Joshua A. Kennedy1*, Thomas S. Cox2, and David G.
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Ferris3
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1: Department of Chemistry and Biochemistry, South Dakota State University, Box 2202, Avera Health and Science Center, Brookings, SD 57007, USA
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2: Department of Physical Sciences, Butte College, Oroville, CA 95965, USA
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3: Department of Earth Sciences, Dartmouth College, Hanover, NH 03755, USA
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*Corresponding author:
[email protected] ACS Paragon Plus Environment
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ABSTRACT A 300-year (1700-2007) chronological record of environmental perchlorate,
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reconstructed from high-resolution analysis of a central Greenland ice core, shows that
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perchlorate levels in the post-1980 atmosphere were two-to-three times those of the pre-1980
14
environment. While this confirms recent reports of increased perchlorate in Arctic snow since
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1980 compared with the levels for the prior decades (1930-1980), the longer Greenland record
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demonstrates that the Industrial Revolution and other human activities, which emitted large
17
quantities of pollutants and contaminants, did not significantly impact environmental perchlorate,
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as perchlorate levels remained stable throughout the eighteenth, nineteenth, and much of the
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twentieth centuries. The increased levels since 1980 likely result from enhanced atmospheric
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perchlorate production, rather than from direct release from perchlorate manufacturing and
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applications. The enhancement is probably influenced by the emission of organic chlorine
22
compounds in the last several decades. Prior to 1980, no significant long-term temporal trends in
23
perchlorate concentration are observed. Brief (a few years) high concentration episodes appear
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frequently over an apparently stable and low background (~1 ng kg‒1). Several such episodes
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coincide in time with large explosive volcanic eruptions including the 1912 Novarupta/Katmai
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eruption in Alaska. It appears that atmospheric perchlorate production is impacted by large
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eruptions in both high and low latitudes, but not by small eruptions and non-explosive degassing.
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TOC Art
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INTRODUCTION Perchlorate (ClO4-) is water soluble, kinetically stable, and ubiquitous in the environment.
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It has been found to be widespread in both terrestrial soil and water systems.1-8 Environmental
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perchlorate may be a significant health risk to vulnerable populations, due to its inhibition of
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iodine uptake in the thyroid, disrupting normal thyroid function.9-10 Ammonium and potassium
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perchlorate are produced and used in rocket propellant, munitions, fireworks, and road flares,
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among many applications. During production and use, perchlorate may be disbursed into the
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environment. In the southwestern United States, for example, manufacture of perchlorate salts
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and associated waste releases are believed to have elevated perchlorate levels in the lower
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Colorado River.11 In the United States, however, perchlorate is not designated a pollutant, and
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no nationwide enforceable limits have been established for perchlorate in drinking water,
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although several states regulate perchlorate for public health.12
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Perchlorate is found at trace levels in many areas of the world. Terrestrial areas where
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perchlorate has been detected include arid regions such as Chile, the southwestern United States,
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and the Dry Valleys of Antarctica, locations far from known pollution sources.2, 13-15 Perchlorate 2 ACS Paragon Plus Environment
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has also been detected in subsurface waters with no possible input from pollution or direct
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atmospheric deposition.6 These findings demonstrate that perchlorate either is or has been
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formed naturally. Available evidence suggests that natural sources of perchlorate are likely to be
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atmospheric in origin.16 The most likely initial precursor is chloride, the most common form of
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chlorine in the surface environment. In several proposed perchlorate formation mechanisms1, 17-
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21
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phenomena (e.g., lightning and volcanic eruptions) are believed to play a significant role.17, 22 It
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has been suggested that at least some perchlorate may be formed in the stratosphere.23-24
, important atmospheric oxidants (e.g., ozone) are suggested to be involved and natural
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Knowledge of the natural background and variability of perchlorate in the environment
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not only is valuable to the effort to establish regulatory limits and thresholds for environmental
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perchlorate to protect public health, it can also provide insight into important aspects (e.g.,
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oxidants and oxidation kinetics) of atmospheric chemistry and of large-scale environmental and
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natural processes. Such knowledge can be obtained from records of perchlorate in the
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environment. Snow carries chemical substances from the atmosphere and accumulates
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continuously in polar regions such as Greenland and Antarctica, and on high-elevation mountain
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glaciers. Thus, chronological records of chemical substances in the environment can be obtained
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from ice core chemical measurements. Polar ice cores have yielded valuable records that
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provide insight into the climate system25 and chemical characteristics26-28 of the atmosphere.
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Extended and detailed records can be used to assess the relative contributions of natural and
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anthropogenic sources of a pollutant, and to investigate atmospheric processes and conditions
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impacting variations of the chemical species over time. Several ice core studies have
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investigated perchlorate specifically.23, 29-32 However, the brief and/or discontinuous records in
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those studies make it difficult to assess natural variability, long-term trends, and relative source
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contributions. We have constructed a 300-year, high-resolution record of perchlorate from a
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2007 central Greenland ice core, and shorter records from other Greenland ice cores. We use the
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records to (1) discern major trends of environmental perchlorate in the recent past and over the
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last three centuries, (2) assess possible anthropogenic impact on environmental perchlorate, and
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(3) identify important factors affecting variability of perchlorate in the environment.
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MATERIALS AND METHODS
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Ice Core Collection
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Several shallow ice cores were drilled during June and July, 2007 near Summit Station,
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Greenland (73.6° N, 38.5° W). The top 97.98 meters of one core (SM07C2, 211 m) was
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analyzed for perchlorate and used for this study, except for a few short intervals (19.29-20.28,
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27.405-28.42, 67.45-69.48, 76.49-76.84, 83.35-84.32, and 86.19-87.14 m) where ice had been
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consumed for other purposes. Perchlorate was also measured in a 1996 ice core from TUNU in
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northern Greenland (78.1° N, 34.0° W), and a 2002 core from Basin 4 in southern Greenland
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(62.3° N, 46.3° W). All ice core sections were wrapped in clean plastic lay-flat tubings and kept
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frozen during transport from the field to the laboratory, where they were maintained at or below
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‒20° C until chemical analysis.
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Perchlorate Measurement
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The procedures to prepare decontaminated Greenland ice core samples for measurement
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of perchlorate and other species have been described by Peterson et al.33 Samples (2174 for
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SM07C2, 445 for TUNU, and 410 for Basin 4) and procedural blanks were analyzed for
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perchlorate using ion chromatography-tandem mass spectrometry with electrospray ionization 4 ACS Paragon Plus Environment
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(IC-ESI-MS/MS). As described previously,33 perchlorate was eluted from a Dionex IonPac®
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AS16 (2 x 250 mm) analytical column with 60 mM NaOH at 0.3 mL min‒1. The effluent from
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the ion chromatograph was mixed with an acetonitrile/water solution (90/10% v/v at 0.3 mL
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min‒1). This mixture was delivered to the ionization/nebulization inlet of an AB SCIEX QTRAP
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5500 triple quadrupole mass spectrometer. Negative ion mode was used to detect 35ClO4‒ and
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37
101
transitions, respectively. Quantification was performed using the 35ClO4‒ peak area with external
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calibration. The limit of detection and lower limit of quantification of the method were 0.1 and
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0.3 ng kg‒1, respectively.33
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Ice Core Dating
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ClO4‒ using multiple reaction monitoring of the m/z 99.0 to 83.0 and m/z 101.0 to 85.0
Ice cores can be dated with the technique of annual layer counting (ALC), in which
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annual peak-valley-peak oscillations in concentrations of certain chemical species are counted to
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develop a depth-age relationship. Concentrations of major ions (Na+, K+, Mg2+, Ca2+, Cl‒, NO3‒,
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SO42‒) in the top 97.98 m (except for 19.27-20.28 m, which was consumed in a previous study)
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of the SM07C2 core (3259 samples) were measured with ion chromatography.34 The maximum
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concentration of calcium (Ca2+) during a year in Greenland snow occurs in early spring, and
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minimum concentration in autumn.34 At Summit, the chloride-to-sodium (Cl‒/Na+) mass ratio in
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snow fluctuates seasonally and reaches an annual minimum during winter and a maximum
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during summer (see data in Supporting Information). Oscillations in Ca2+ concentration and
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Cl‒/Na+ ratio (SI Figure S1) were identified and used as primary annual layer markers to yield
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307 years (1700-2007) in the SM07C2 core (0-97.98 m). Concentrations of Na+ and SO42‒,
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which tend to reach maxima in summer and early spring, respectively,35 were used for auxiliary
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confirmation of annual layers. For the depth interval of 19.27-20.28 m where no major ion data 5 ACS Paragon Plus Environment
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are available, two years (mid-1964 to mid-1966) were assigned, based on the average annual
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accumulation rate for the depth interval of 15-25 m. The depth where the annual Cl‒/Na+ ratio
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minimum occurs is assigned the month of January of each year. Therefore, an ice core year
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corresponds to a calendar year in this 300-year chronology. No major ions were measured for the
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TUNU and Basin 4 cores; these were dated using the average annual accumulation rate for each
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site36-37 with the assumption of constant accumulation over the time covered by the length of
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those core sections.
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The dating uncertainty for the SM07C2 core at 100 years (~43 m) is less than 1 year and
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is ±3 years at 300 years (~100 m). This is consistent with the uncertainty reported by Cole-Dai
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et al. in an 800-year chronology of the 2007 Summit cores.34 The uncertainty in the dating of the
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TUNU and Basin 4 cores was not determined but is expected to be slightly higher than the ALC-
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dated Summit cores as a result of variations in accumulation rate.
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Annual layer depth interval (thickness) was measured and presented as annual snow
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accumulation (cm) in water equivalent. The amount of perchlorate (or other ions) in snow is
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expressed in units of concentration (ng kg‒1 or µg kg‒1) when the analytical measurement is
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presented, or in units of flux (µg m‒2 yr‒1 or mg m‒2 yr‒1) when discussing air-to-ground
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deposition. For each year, annual flux was calculated by summing mass deposition of all samples
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in the year. Since snow accumulation rates at Summit, Greenland have remained relatively stable
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in recent centuries34, trends in concentration are similar to those in deposition flux.30
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RESULTS AND DISCUSSION
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Long-term Trend of Environmental Perchlorate 6 ACS Paragon Plus Environment
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Perchlorate concentrations in the Summit core (Figure 1) are extremely low, with an
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average concentration (±standard deviation) of 1.6±2.8 ng kg‒1. Prior to 1980, the relatively
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stable concentration is punctuated by brief spikes of up to a few years in duration. The average
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perchlorate concentration (Table 1) in the period from mid-nineteenth century to late twentieth
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century (1850-1979, 1.2±1.2 ng kg‒1, excluding samples in 1912 and 1913 when perchlorate
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concentration was drastically impacted by an explosive volcanic eruption, to be discussed later)
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shows no significant change from that in the pre-industrial time (1700-1849, 1.2±1.0 ng kg‒1).
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This is strong evidence that the large-scale human activities of the Industrial Revolution
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beginning in the early-to-mid-nineteenth century did not increase the level of perchlorate in
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Greenland snow and in the atmospheric environment. It has been speculated38-39 that the
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widespread use of Chilean nitrate throughout North America and Europe in the nineteenth
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century and the first half of the twentieth century may have introduced significant amounts of
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perchlorate, an impurity in Chilean nitrate, to the environment; the Summit ice core record
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suggests that the impact of Chilean nitrate use on environmental perchlorate was minimal.
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Perchlorate Increase since 1980
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A remarkable change in perchlorate concentration is observed in Summit snow since
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1980 (Figure 1). The average perchlorate concentration during 1980-2007 (2.7±2.1 ng kg‒1) is
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more than double the pre-1980 average (1.2±1.2 ng kg‒1) and more than three times that (0.8±0.6
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ng kg‒1) during the immediately preceding 30 years (1950-1979, Table 1), when rockets in early
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space exploration could have introduced perchlorate into the environment. This observation was
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initially reported in Peterson et al.30 using a shorter and discontinuous part of the SM07C2 core
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dataset. The increase of environmental perchlorate since 1980 was first discovered by Rao et al.31
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who found that perchlorate concentration in post-1980 snow samples from Eclipse Icefield in 7 ACS Paragon Plus Environment
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Canada increased to over 2.2 ng kg‒1 from the pre-1980 level (0.6 ng kg‒1 during 1973-1976).
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Those findings are unambiguously confirmed in this much longer (300-year) and continuous
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record with preindustrial background. Moreover, similar post-1980 increases are found in ice
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cores from the other Greenland locations, TUNU and Basin 4 (Table 2, SI Figures S2 and S3).
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The change in perchlorate concentrations in North America and Greenland snow after 1980 is
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also similar to increases observed in snow samples and ice cores (Table 2) from several other
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Arctic locations (Nunavut, Canada; Yukon Territory, Canada). For example, Furdui et al.32
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recently reported that annual perchlorate deposition flux on the Agassiz Ice Cap in Nunavut
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increased from 0.42 µg m‒2 during the 1936-1979 period to 1.14 µg m‒2 during 1980-2007.
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Possible or probable causes of the apparent increase of environmental perchlorate since
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1980 in the Arctic, and probably North America, as documented in the recent studies (Table 2),
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need to be investigated. The additional perchlorate may be released during industrial perchlorate
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production or large-scale applications. Available data suggest that industrial production of
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perchlorate salts in the United States began to increase in the late 1950s and a substantial
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production increase may have occurred during the 1980s.38 Perchlorate pollution stemming from
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release during production or disposal of unused perchlorate salts is likely to be confined to only
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local or regional surface environments and groundwater. Perchlorate in localized pollution may
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become airborne and possibly be transported to remote areas via atmospheric circulation. In the
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atmosphere, however, the non-volatile perchlorate is likely associated with dust,40 which is
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generally not transported efficiently over long distances,41 and therefore unlikely to be recorded
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in Arctic snow. In addition, industrial production of perchlorate in the United States is estimated
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to have peaked during the late 1980s,38 whereas the perchlorate concentrations in Greenland
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snow are highest in the early and mid-1990s (Figure 2). The difference in timing provides
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further evidence that perchlorate release during production or disposal is unlikely to be
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responsible for the observed increase of perchlorate in the Arctic and North America since 1980.
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It was speculated30 that perchlorate residues in solid fuels during frequent rocket launches
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(e.g., the United States Space Shuttle program, 1981-2005) may be dispersed over the Northern
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Hemisphere and the High Arctic. However, analyses of space shuttle launch plumes and
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highway road flares have shown that essentially no perchlorate residue remains when
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perchlorate-containing explosives are used as intended.38 Therefore, no significant amount of
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perchlorate would be expected to be released into the environment by major applications; this is
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supported by the fact that the average perchlorate concentration during the early rocket-age
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period of 1950-1979 (Table 1) is no higher than during the previous 250 years.
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Perchlorate Formation in the Atmosphere
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Since perchlorate is also formed in the atmosphere, the post-1980 increase of perchlorate
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may be caused by enhanced atmospheric production. Among several proposed chemical
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mechanisms of atmospheric perchlorate formation, two appear to be the leading or principal
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pathways. In one process, as has been demonstrated17, 22, 38 in laboratory studies, perchlorate is
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produced from chloride in aerosols subjected to electric discharge simulating lightning. In
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another process, further oxidation of chlorine radicals and oxy-chlorine species generated in
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reactions involving ozone and other oxidants leads to perchlorate formation17, 21, 38, among many
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other reaction products (e.g., chlorate).
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Furdui et.al. proposed32 that, prior to 1960, a significant fraction of perchlorate in Arctic
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snow results from chloride aerosols, based on a strong correlation between chloride and
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perchlorate in an Agassiz (Nunavut, Canada) ice core during 1940-1959. Despite this proposal,
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Furdui et al. did not attribute the post-1980 perchlorate increase in Arctic snow to the source of
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aerosol chloride, for no correlation between chloride and perchlorate is observed in Agassiz
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snow samples after 1980. No significant correlation between chloride and perchlorate is found
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in the Summit, Greenland core for the period of 1940-1959, or during any previous time periods
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in the 300-year record (SI Figures S4-S6). This suggests that, at Summit, perchlorate is not
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dominated by formation from aerosol chloride either before or after 1980. Therefore, the increase
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since 1980 cannot be attributed to elevated levels of either aerosol chloride from sea-salt or HCl
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emitted by volcanic eruptions and degassing. A significantly increased frequency or intensity of
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lightning could enhance perchlorate formation rate; however, there is no evidence that lightning
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frequency has increased since 1980.42-43
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A major source of chlorine radicals and oxy-chlorine species in the atmosphere are
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organic chlorine compounds from both natural and anthropogenic emissions.44 In a recent study,
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Jiang et al.23 found higher perchlorate levels in Antarctic snow since the 1970s than those in
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older snow and suggested that this increase is correlated with stratospheric chlorine, which has
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increased significantly since the 1970s due to anthropogenic emission of organic chlorine
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compounds.45 Because of possible post-depositional change to perchlorate in Antarctic snow23,
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the impact of anthropogenic chlorine on perchlorate was difficult to assess. In exploring possible
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causes of the post-1980 increase in the Arctic, Furdui et al. examined29, 32 the emission records of
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several organic chlorine compounds and suggested that the increased emission of methyl
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chloroform (CH3CCl3) since 1970 and the drastic decrease since the mid-1990s are likely the
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main contributors to the perchlorate trend since 1980. This suggestion is similar to that by Jiang
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et al.23: a substantial increase of perchlorate in polar snow beginning around 1980, followed by a
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leveling-off in the mid-1990s and a slight decrease since that time, likely reflects the trend of
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anthropogenic emissions of organic chlorine compounds.
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Correlation between Atmospheric Chlorine and Perchlorate
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Evidence of the trend of organic chlorine and impact of emissions of organic chlorine
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compounds can be found in atmospheric measurements for the recent decades, and in
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atmospheric concentrations calculated for time periods prior to the measurements. For example,
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tropospheric equivalent chlorine (EC), 80% of which is contributed by organic chlorine,
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increased from approximately 2 ppbv in the 1970s to about 5 ppbv during the 1990s, and has
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decreased slightly (to about 4.5 ppbv) since the mid-1990s.44 Jiang et al. found23 an apparent
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correlation between perchlorate in Antarctic snow and equivalent effective stratospheric chlorine
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(EESC). EESC is calculated from measurements of organic chlorine compounds in the
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troposphere or surface air and represents the ozone-depleting potential of halogens in the
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stratosphere. The trend of EESC lags that of EC by approximately 3 years at the equator and up
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to 7 years at the poles.45 The increase of both EC and EESC in the second half of the twentieth
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century was a result of emissions of chlorofluorocarbons (CFCs) and other long-lived organic
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chlorine compounds (very short-lived chlorine compounds account for a small fraction of EC).45-
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46
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and adjustments to reduce ozone-depleting substances in the atmosphere, tropospheric chlorine
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reached the highest level in the mid-1990s and has been declining gradually, while stratospheric
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chlorine has followed a similar trend. Between 1950 and 1991, tropospheric/surface chlorine
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concentration, estimated from the emission of long-lived organic chlorine compounds45 (CCl4,
251
CH3Cl, CH3CCl3, CFC-12, and CFC-11) summed and scaled for the number of chlorine atoms in
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each compound, shows an increase that accelerated significantly in the 1970s and 1980s (Figure
Because of the implementation of the 1987 Montreal Protocol and subsequent amendments
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3, details in SI Table S1 and Figure S7). Measurements of major organic chlorine species since
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the early 1990s shows a gradual decrease in tropospheric chlorine (Figure 3).47 The increase in
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perchlorate concentration during the 1980s and the slight decrease since the mid-1990s in
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Summit snow appears to largely follow the trend of tropospheric chlorine (Figure 3), indicating
257
that environmental perchlorate may be sensitive to changes in the atmospheric burden of organic
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chlorine. Note that in Figure 3, several brief high-concentration episodes appear to be
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superimposed on the broad trend paralleling that of tropospheric chlorine. The perchlorate
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maxima in the mid-1960s, early 1980s and early 1990s coincide in time with the Agung (1963),
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El Chichón (1982) and Pinatubo (1991) volcanic eruptions, which may have briefly enhanced
262
perchlorate production in the atmosphere (discussed next). Because of the influence of the
263
Pinatubo eruption, it is not possible to determine the exact timing of maximum perchlorate
264
deposition in the 1990s and to use the perchlorate data in Figure 3 to determine if perchlorate in
265
the snow is dominated by tropospheric or stratospheric chlorine.
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The records from North America, Greenland, the Canadian Arctic, and Antarctica
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indicate that the perchlorate increase since 1980 is likely global, rather than regional, and is
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consistent with the global impact of anthropogenic emissions of organic chlorine compounds.
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Volcanic Influence on Episodic Perchlorate Increase
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Numerous relatively short (less than 3 years) episodes of elevated perchlorate
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concentration and deposition flux are observed in the 300-year record (Figure 1). The largest of
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these events occurs in the depth range of 38.3 to 39.2 m (Figure 4) during 1912-1914. The
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highest perchlorate concentrations during this period approach 50 ng kg‒1, compared to the
274
average of approximately 0.9 ng kg‒1 during the periods (about 10 years) immediately before and
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after 1912-1914. The perchlorate flux for 1912 through 1913 (7.7 and 4.9 µg m‒2 yr‒1,
276
respectively) represents the largest deposition in the 300-year record.
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A strong and explosive (VEI 6) eruption of the Novarupta (Katmai) volcano (58.27° N,
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155.16° W) in Alaska occurred on June 6, 1912. It is well established that sulfate in polar snow
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increases significantly following large explosive volcanic eruptions.34-35 The Novarupta eruption
280
is marked in the ice core by substantially increased sulfate concentrations (Figure 4) during 1912
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and 1913, which coincides with the drastically elevated perchlorate concentration and deposition
282
flux (Figure 4). This appears to support previous suggestions that eruptions may increase the
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amount of perchlorate in the environment.29, 31 The extraordinarily high perchlorate
284
concentrations and deposition, along with simultaneous increase of sulfate following the
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Novarupta eruption, were also found in a replicate Summit core (SM07C4, SI Figure S8),
286
demonstrating that the remarkable perchlorate episode is not an artifact from ice core sampling
287
or chemical analysis.
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Peterson et al. found30 in a portion of the Summit (SM07C2) perchlorate record that high
289
perchlorate episodes in recent snow coincide in time with the eruptions of Pinatubo (15.14° N,
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120.35° E) in 1991, and El Chichón (17.36° N, 93.23° W) in 1982, two stratospheric eruptions in
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the tropics (Table 3). A few additional instances of elevated perchlorate levels are found to be
292
associated with large volcanic eruptions during the 300-year period. Deposition flux of
293
perchlorate is significantly elevated (Table 3 and Figure 5) following the eruptions of Tambora
294
(1815), Babuyan Claro (1831), Cosigüina (1835), and Krakatoa (1883). Note that, due to lack of
295
ice, no perchlorate measurement was made in the period of 1808-1816 when Tambora and
296
another large eruption occurred; and, therefore, the perchlorate response to Tambora is only
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partially seen in Figure 5. These four, as well as El Chichón and Pinatubo, are known to have 13 ACS Paragon Plus Environment
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been powerful eruptions (VEI 4-7) with probable injection of volcanic ash and gas (e.g., SO2)
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directly into the stratosphere.34 The Summit record suggests that low-latitude stratospheric
300
eruptions are also capable of elevating perchlorate concentrations in the atmosphere leading to
301
increased deposition in Arctic snow. Powerful eruptions that inject SO2 into the stratosphere are
302
associated with short-term (a few years) increases in aerosol optical depth (AOD). The El
303
Chichón and Pinatubo (and the 1963 eruption of Agung in Indonesia) impact on Northern
304
Hemisphere AOD, for instance, is clearly observed (Figure 2), and the perchlorate response in
305
each case is contemporaneous with the increase in stratospheric aerosol; the perchlorate response
306
to Agung is only partially seen (Figures 2 and 3), due to lack of ice for measurement. In the
307
Agassiz ice core, no perchlorate spike was observed to correspond to elevated AOD by El
308
Chichón or Pinatubo;32 however, unusually high perchlorate flux was detected in 1981 and in
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1990, just one year prior to the eruptions of El Chichón and Pinatubo, respectively, and the
310
increase in AOD.
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Furdui et al. investigated32 a possible connection between volcanic eruptions and
312
perchlorate by examining the relationship between perchlorate and chloride in the Agassiz ice
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core, based on the assumption that chlorine (HCl) emission from recent volcanic eruptions in
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Alaska, Aleutian Islands, Kuril Islands and Kamchatka Peninsula may enhance atmospheric
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perchlorate production. No correlation was found during the period of 1970-2007 in that study;
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in addition, no correlation was found between sulfate and perchlorate. It was therefore
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concluded that volcanic activity may not significantly increase perchlorate deposition at Agassiz.
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The Summit record supports the conclusion by Furdui et al. that chlorine emissions from
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volcanic eruptions and non-explosive degassing in mid- and high latitudes have no significant
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impact on atmospheric perchlorate production.
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The 300-year Summit record provides strong evidence of impact on perchlorate by
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volcanic eruptions that inject a substantial amount of gas and aerosols directly into the
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stratosphere. It is apparent that this impact is not limited to high latitude volcanic eruptions (e.g.,
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Novarupta), and that injections to the stratosphere from a low latitude eruption (e.g., Pinatubo
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and Tambora) could significantly enhance perchlorate production for one or two years
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immediately following the eruption. Although it is not clear how these large eruptions increase
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perchlorate levels for brief time periods following the eruptions, it appears that direct injection of
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volcanic aerosols into the stratosphere is necessary. However, a comprehensive examination of
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the volcanic impact on atmospheric perchlorate formation is beyond the scope of this study. The
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specific processes and possible reaction mechanisms by which volcanic eruptions impact
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perchlorate will be investigated in future work.
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The Summit data show that many small perchlorate episodes in the 300-year record are
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not associated with known large volcanic eruptions. This suggests that perchlorate production
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may be impacted by factors other than large, stratospheric volcanic eruptions, and the emission
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of organic chlorine compounds.
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ASSOCIATED CONTENT
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The following content is presented in Supporting Information: (1) Summit ice core
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dating; (2) Perchlorate in other Greenland ice cores; (3) Correlation analysis between perchlorate
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and chloride; (4) Estimating tropospheric chlorine concentration; and (5) Perchlorate response to
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the 1912 Novarupta/Katmai eruption in two central Greenland ice cores.
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ACKNOWLEDGEMENTS Funding for this work was provided by U.S. National Science Foundation (Awards
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1203533, 1443663; Major Research Instrumentation Award 0922816 for the acquisition of a
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tandem mass spectrometer). The U.S. National Ice Core Laboratory provided the TUNU and
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Basin 4 ice cores. The South Dakota State University Campus Core Mass Spectrometry Facility
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and Linhong Jing are acknowledged for providing technical support and maintenance of the mass
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spectrometer. Erica Manandhar, Scott Splett, Alexandria Kub, and T. Zack Crawford assisted
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with the laboratory analysis.
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Figure 1. Concentration of perchlorate (smoothed with a 3-sample running mean) in the Summit (SM07C2) core from 0 to 97.98 meters depth, covering the period from 2007 to 1700.
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Figure 2. Aerosol optical depth (a), annual perchlorate flux (b), and annual chloride flux (c) in the period 1940-2006 in the Summit (SM07C2) core.
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Figure 3. Measured surface chlorine concentrations (thick line) from Montzka et al.47; the total atmospheric chlorine (dashed line, scaled for number of chlorine atoms) is the sum of estimates of CCl4, CH3Cl, CFC-12, CFC-11, and CH3CCl3 surface concentrations adapted from data in Newman et al.45, and annual perchlorate flux (3-year running mean, histogram) in the Summit core. See Supporting Information for description of estimating surface chlorine concentrations.
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Figure 4. Perchlorate (a) and sulfate (b) concentrations in the Summit core impacted by the 1912 Novarupta/Katmai eruption (dashed vertical line); data smoothed with a 3-sample running mean.
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Figure 5. Perchlorate (a) and sulfate (b) annual flux in the period of 1800-1900 are impacted by the eruptions of Tambora (1815), Babuyan Claro (1831), Cosigüina (1835), and Krakatoa (1883). Dashed vertical lines indicate the eruption years. Perchlorate data are not available for 18091816, when Tambora and an unidentified volcano erupted (1809), because of lack of ice for perchlorate measurement.
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Table 1. Average perchlorate concentrations in the Summit core during several time periods since 1700. Perchlorate concentrations in samples in the 1912-1913 period are excluded from average calculations, due to unusually high concentrations influenced by a volcanic eruption. Averages and sample numbers including the 1912-1913 samples are given in parentheses. Depth (m) 0-97.98 0-13.84 13.84-25.90 25.90-58.49 58.49-97.98
Years 1700-2007 1980-2007 1950-1979 1850-1979 1700-1849
Average Concentration (ng kg-1) 1.4 (1.6) th Late 20 Century 2.7 Early Rocket Age 0.8 Industrial Age 1.2 (1.6) Pre-Industrial 1.2 Period
Number of Samples 2147 (2174) 264 250 1024 (1051) 859
385 386 387 388 389 390 391
Table 2. Annual snow accumulation rates (in water equivalent) and perchlorate concentrations at sites in the Arctic and North America. Ice cores cover the time periods of 1700-2007 (Summit), 1918-1996 (TUNU), 1972-2002 (Basin 4), 1996-2005 (Devon Island), 1936-2007 (Agassiz Ice Cap, estimated median concentration), 1970-1973 and 1982-1986 (Eclipse Icefield), and 1726-1993 (Fremont Glacier, Wyoming, United States). Location
Greenland Summit34 TUNU36 Basin 4 (ref. 27) Canadian Arctic Devon Island48 Agassiz Ice Cap29, 32, 49 Eclipse Icefield31 North America Fremont Glacier, U.S.A.31
Annual Accumulation (cm)
Average Concentration (ng kg-1) Pre-1980
Post-1980
22.6 12.5 41.1
1.2 1.0 0.9
2.7 3.6 2.8
24.1 10.0 130
N/A 4.2 0.6
5.5 11.4 2.3
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