Industrial-era decline in Arctic methanesulfonic acid is offset by increased biogenic sulfate aerosol.

Marine phytoplankton are primary producers in ocean ecosystems and emit dimethyl sulfide (DMS) into the atmosphere. DMS emissions are the largest biological source of atmospheric sulfur and are one of the largest uncertainties in global climate modeling. DMS is oxidized to methanesulfonic acid (MSA), sulfur dioxide, and hydroperoxymethyl thioformate, all of which can be oxidized to sulfate. Ice core records of MSA are used to investigate past DMS emissions but rely on the implicit assumption that the relative yield of oxidation products from DMS remains constant. However, this assumption is uncertain because there are no long-term records that compare MSA to other DMS oxidation products. Here, we share the first long-term record of both MSA and DMS-derived biogenic sulfate concentration in Greenland ice core samples from 1200 to 2006 CE. While MSA declines on average by 0.2 µg S kg-1 over the industrial era, biogenic sulfate from DMS increases by 0.8 µg S kg-1. This increasing biogenic sulfate contradicts previous assertions of declining North Atlantic primary productivity inferred from decreasing MSA concentrations in Greenland ice cores over the industrial era. The changing ratio of MSA to biogenic sulfate suggests that trends in MSA could be caused by time-varying atmospheric chemistry and that MSA concentrations alone should not be used to infer past primary productivity.

Geochemical ice-core constraints on the timing and climatic impact of Aniakchak II (1628 BCE) and Thera (Minoan) volcanic eruptions.

Decades of research have focused on establishing the exact year and climatic impact of the Minoan eruption of Thera, Greece (c.1680 to 1500 BCE). Ice cores offer key evidence to resolve this controversy, but attempts have been hampered by a lack of multivolcanic event synchronization between records. In this study, Antarctic and Greenland ice-core records are synchronized using a double bipolar sulfate marker, and calendar dates are assigned to each eruption revealed within the 'Thera period'. From this global-scale sequence of volcanic sulfate loading, we derive indications toward each eruption's latitude and potential to disrupt the climate system. Ultrafine sampling for sulfur isotopes and tephra conclusively demonstrate a colossal eruption of Alaska's Aniakchak II as the source of stratospheric sulfate in the now precisely dated 1628 BCE ice layer. These findings end decades of speculation that Thera was responsible for the 1628 BCE event, and place Aniakchak II (52 ± 17 Tg S) and an unknown volcano at 1654 BCE (50 ± 13 Tg S) as two of the largest Northern Hemisphere sulfur injections in the last 4,000 years. This opens possibilities to explore widespread climatic impacts for contemporary societies and, in pinpointing Aniakchak II, confirms that stratospheric sulfate can be globally distributed from eruptions outside the tropics. Dating options for Thera are reduced to a series of precisely dated, constrained stratospheric sulfur injection events at 1611 BCE, 1561/1558/1555BCE, and c.1538 BCE, which are all below 14 ± 5 Tg S, indicating a climatic forcing potential for Thera well below that of Tambora (1815 CE).

Occurrence, latitudinal gradient and potential sources of perchlorate in the atmosphere across the hemispheres (31°N to 80°S).

Perchlorate (ClO4-) is harmful to human health, and knowledge on the levels and sources of natural ClO4- in different environments remains rather limited. Here, we investigate ClO4- in aerosol samples collected along a cross-hemisphere ship cruise between China and Antarctica and on a traverse between coastal East Antarctica and the ice sheet summit (Dome Argus). Perchlorate concentrations range from a few to a few hundred pg m-3. A clear latitudinal trend is found, with elevated ClO4- concentrations near populated areas and in the southern mid-high latitudes. Spatial patterns of atmospheric ClO4- over oceans near the landmasses support that terrestrial ClO4- is not transported efficiently over long distances. In the southern mid-latitudes, higher ClO4- concentrations in March than in November-December may be caused by significant stratospheric inputs in March. Perchlorate concentrations appear to be higher in the warm half than in the cold half of the year in the southern high latitudes, suggesting seasonal difference in main atmospheric sources. ClO4- may be formed in the reactions between chlorine free radical (Cl·) and ozone (O3) in the stratosphere when Antarctic ozone hole occurs during September-October. And the stratosphere-produced ClO4- is moved to the boundary layer in several months and may be responsible for the high ClO4- concentrations in the warm half of the year. Perchlorate produced by photochemical reactions between O3 and Cl· in the Antarctic stratosphere is likely responsible for the higher ClO4- concentrations in Antarctica than in Arctic.

Evidence of Influence of Human Activities and Volcanic Eruptions on Environmental Perchlorate from a 300-Year Greenland Ice Core Record.

A 300-year (1700-2007) chronological record of environmental perchlorate, reconstructed from high-resolution analysis of a central Greenland ice core, shows that perchlorate levels in the post-1980 atm were two-to-three times those of the pre-1980 environment. While this confirms recent reports of increased perchlorate in Arctic snow since 1980 compared with the levels for the prior decades (1930-1980), the longer Greenland record demonstrates that the Industrial Revolution and other human activities, which emitted large quantities of pollutants and contaminants, did not significantly impact environmental perchlorate, as perchlorate levels remained stable throughout the 18th, 19th, and much of the 20th centuries. The increased levels since 1980 likely result from enhanced atmospheric perchlorate production, rather than from direct release from perchlorate manufacturing and applications. The enhancement is probably influenced by the emission of organic chlorine compounds in the last several decades. Prior to 1980, no significant long-term temporal trends in perchlorate concentration are observed. Brief (a few years) high-concentration episodes appear frequently over an apparently stable and low background (∼1 ng kg-1). Several such episodes coincide in time with large explosive volcanic eruptions including the 1912 Novarupta/Katmai eruption in Alaska. It appears that atmospheric perchlorate production is impacted by large eruptions in both high- and low-latitudes, but not by small eruptions and nonexplosive degassing.

Synchronous volcanic eruptions and abrupt climate change ∼17.7 ka plausibly linked by stratospheric ozone depletion.

Glacial-state greenhouse gas concentrations and Southern Hemisphere climate conditions persisted until ∼17.7 ka, when a nearly synchronous acceleration in deglaciation was recorded in paleoclimate proxies in large parts of the Southern Hemisphere, with many changes ascribed to a sudden poleward shift in the Southern Hemisphere westerlies and subsequent climate impacts. We used high-resolution chemical measurements in the West Antarctic Ice Sheet Divide, Byrd, and other ice cores to document a unique, ∼192-y series of halogen-rich volcanic eruptions exactly at the start of accelerated deglaciation, with tephra identifying the nearby Mount Takahe volcano as the source. Extensive fallout from these massive eruptions has been found >2,800 km from Mount Takahe. Sulfur isotope anomalies and marked decreases in ice core bromine consistent with increased surface UV radiation indicate that the eruptions led to stratospheric ozone depletion. Rather than a highly improbable coincidence, circulation and climate changes extending from the Antarctic Peninsula to the subtropics-similar to those associated with modern stratospheric ozone depletion over Antarctica-plausibly link the Mount Takahe eruptions to the onset of accelerated Southern Hemisphere deglaciation ∼17.7 ka.

Rapid measurement of perchlorate in polar ice cores down to sub-ng L(-1) levels without pre-concentration.

An ion chromatography-electrospray ionization-tandem mass spectrometry (IC-ESI-MS/MS) method has been developed for rapid and accurate measurement of perchlorate in polar snow and ice core samples in which perchlorate concentrations are expected to be as low as 0.1 ng L(-1). Separation of perchlorate from major inorganic species in snow is achieved with an ion chromatography system interfaced to an AB SCIEX triple quadrupole mass spectrometer operating in multiple reaction monitoring mode. Under optimized conditions, the limit of detection and lower limit of quantification without pre-concentration have been determined to be 0.1 and 0.3 ng L(-1), respectively, with a linear dynamic range of 0.3-10.0 ng L(-1) in routine measurement. These represent improvements over previously reported methods using similar analytical techniques. The improved method allows fast, accurate, and reproducible perchlorate quantification down to the sub-ng L(-1) level and will facilitate perchlorate measurement in the study of natural perchlorate production with polar ice cores in which perchlorate concentrations are anticipated to vary in the low and sub-ng L(-1) range. Initial measurements of perchlorate in ice core samples from central Greenland show that typical perchlorate concentrations in snow dated prior to the Industrial Revolution are about 0.8 ng L(-1), while perchlorate concentrations are significantly higher in recent (post-1980) snow, suggesting that anthropogenic sources are a significant contributor to perchlorate in the current environment.

Nitrogen isotopes in ice core nitrate linked to anthropogenic atmospheric acidity change.

Nitrogen stable isotope ratio (δ(15)N) in Greenland snow nitrate and in North American remote lake sediments has decreased gradually beginning as early as ∼1850 Christian Era. This decrease was attributed to increasing atmospheric deposition of anthropogenic nitrate, reflecting an anthropogenic impact on the global nitrogen cycle, and the impact was thought to be amplified ∼1970. However, our subannually resolved ice core records of δ(15)N and major ions (e.g., NO3(-), SO4(2-)) over the last ∼200 y show that the decrease in δ(15)N is not always associated with increasing NO3(-) concentrations, and the decreasing trend actually leveled off ∼1970. Correlation of δ(15)N with H(+), NO3(-), and HNO3 concentrations, combined with nitrogen isotope fractionation models, suggests that the δ(15)N decrease from ∼1850-1970 was mainly caused by an anthropogenic-driven increase in atmospheric acidity through alteration of the gas-particle partitioning of atmospheric nitrate. The concentrations of NO3(-) and SO4(2-) also leveled off ∼1970, reflecting the effect of air pollution mitigation strategies in North America on anthropogenic NO(x) and SO2 emissions. The consequent atmospheric acidity change, as reflected in the ice core record of H(+) concentrations, is likely responsible for the leveling off of δ(15)N ∼1970, which, together with the leveling off of NO3(-) concentrations, suggests a regional mitigation of anthropogenic impact on the nitrogen cycle. Our results highlight the importance of atmospheric processes in controlling δ(15)N of nitrate and should be considered when using δ(15)N as a source indicator to study atmospheric flux of nitrate to land surface/ecosystems.

High speed, high resolution, and continuous chemical analysis of ice cores using a melter and ion chromatography.

Measurement of trace chemical impurities in ice cores contributes to the reconstruction of records of the atmospheric environment and of the climate system. Ion chromatography (IC) is an effective analytical technique for ionic species in ice cores but has been used on discretely prepared ice samples, resulting in extensive and slow sample preparation and potential for contamination. A new technique has been developed that utilizes IC as the online detection technique in a melter-based continuous flow system for quantitative determination of major ionic chemical impurities. The system, called CFA-IC for continuous flow analysis with ion chromatography detection, consists of an ice core melter, several ion chromatographs, and an interface that distributes meltwater to the IC instruments. The CFA-IC technique combines the accuracy, precision, and ease of use of IC measurement with the enhanced speed and depth resolution of continuous melting systems and is capable of virtually continuous, high-speed and high-resolution chemical analysis of long ice cores. The new technique and operating procedures have been tested and validated with the analysis of over 100 m of ice cores from Antarctica. The current CFA-IC system provides an all-major-ion analysis speed of up to 8 m a day at a depth resolution of approximately 2 cm.