Amanda Cole

How does climate change influence arctic mercury

Recent studies have shown that climate change is already having significant impacts on many aspects of transport pathways, speciation and cycling of mercury within Arctic ecosystems. For example, the extensive loss of sea-ice in the Arctic Ocean and the concurrent shift from greater proportions of perennial to annual types have been shown to promote changes in primary productivity, shift foodweb structures, alter mercury methylation and demethylation rates, and influence mercury distribution and transport across the ocean-sea-ice-atmosphere interface (bottom-up processes). In addition, changes in animal social behavior associated with changing sea-ice regimes can affect dietary exposure to mercury (top-down processes). In this review, we address these and other possible ramifications of climate variability on mercury cycling, processes and exposure by applying recent literature to the following nine questions; 1) What impact has climate change had on Arctic physical characteristics and processes? 2) How do rising temperatures affect atmospheric mercury chemistry? 3) Will a decrease in sea-ice coverage have an impact on the amount of atmospheric mercury deposited to or emitted from the Arctic Ocean, and if so, how? 4) Does climate affect air-surface mercury flux, and riverine mercury fluxes, in Arctic freshwater and terrestrial systems, and if so, how? 5) How does climate change affect mercury methylation/demethylation in different compartments in the Arctic Ocean and freshwater systems? 6) How will climate change alter the structure and dynamics of freshwater food webs, and thereby affect the bioaccumulation of mercury? 7) How will climate change alter the structure and dynamics of marine food webs, and thereby affect the bioaccumulation of marine mercury? 8) What are the likely mercury emissions from melting glaciers and thawing permafrost under climate change scenarios? and 9) What can be learned from current mass balance inventories of mercury in the Arctic? The review finishes with several conclusions and recommendations.

Observations of the anomalous oxygen isotopic composition of carbon dioxide in the lower stratosphere and the flux of the anomaly to the troposphere

[1] Measurements of the triple oxygen isotopic composition of stratospheric CO 2 in whole air samples from the NASA ER-2 aircraft show anomalous enrichments in 17 O and 18 O. The compact correlation of the isotope anomaly (defined as Δ 17 O = δ 17 O - 0.516 x δ 18 O) with simultaneous N 2 O measurements demonstrates that Δ 17 O CO2 is a long-lived tracer with a stratospheric source. These characteristics, and an isotopic link to O 3 production, make Δ 17 O CO2 potentially useful as a tracer of integrated stratospheric chemistry and transport. The Δ 17 O CO2 :N 2 O correlation is also used to estimate a net Δ 17 O CO2 flux to the troposphere of 3.6 ± 0.9 x 10 15 ‰ mol CO 2 yr -1 . This flux is required to predict and understand the CO 2 and O 2 isotope anomalies in the troposphere and their use as tracers of gross carbon exchanges between the atmosphere and biosphere on interannual to glacial-interglacial time scales.

Atmospheric mercury in the Canadian Arctic. Part I: A review of recent field measurements

Long-range atmospheric transport and deposition are important sources of mercury (Hg) to Arctic aquatic and terrestrial ecosystems. We review here recent progress made in the study of the transport, transformation, deposition and reemission of atmospheric Hg in the Canadian Arctic, focusing on field measurements (see Dastoor et al., this issue for a review of modeling studies on the same topics). Redox processes control the speciation of atmospheric Hg, and thus impart an important influence on Hg deposition, particularly during atmospheric mercury depletion events (AMDEs). Bromine radicals were identified as the primary oxidant of atmospheric Hg during AMDEs. Since the start of monitoring at Alert (NU) in 1995, the timing of peak AMDE occurrence has shifted to earlier times in the spring (from May to April) in recent years, and while AMDE frequency and GEM concentrations are correlated with local meteorological conditions, the reasons for this timing-shift are not understood. Mercury is subject to various post-depositional processes in snowpacks and a large portion of deposited oxidized Hg can be reemitted following photoreduction; how much Hg is deposited and reemitted depends on geographical location, meteorological, vegetative and sea-ice conditions, as well as snow chemistry. Halide anions in the snow can stabilize Hg, therefore it is expected that a smaller fraction of deposited Hg will be reemitted from coastal snowpacks. Atmospheric gaseous Hg concentrations have decreased in some parts of the Arctic (e.g., Alert) from 2000 to 2009 but at a rate that was less than that at lower latitudes. Despite numerous recent advances, a number of knowledge gaps remain, including uncertainties in the identification of oxidized Hg species in the air (and how this relates to dry vs. wet deposition), physical-chemical processes in air, snow and water-especially over sea ice-and the relationship between these processes and climate change.

Unexpected variations in the triple oxygen isotope composition of stratospheric carbon dioxide

We report observations of stratospheric CO2 that reveal surprisingly large anomalous enrichments in 17O that vary systematically with latitude, altitude, and season. The triple isotope slopes reached 1.95 ± 0.05(1σ) in the middle stratosphere and 2.22 ± 0.07 in the Arctic vortex versus 1.71 ± 0.03 from previous observations and a remarkable factor of 4 larger than the mass-dependent value of 0.52. Kinetics modeling of laboratory measurements of photochemical ozone–CO2 isotope exchange demonstrates that non–mass-dependent isotope effects in ozone formation alone quantitatively account for the 17O anomaly in CO2 in the laboratory, resolving long-standing discrepancies between models and laboratory measurements. Model sensitivities to hypothetical mass-dependent isotope effects in reactions involving O3, O(1D), or CO2 and to an empirically derived temperature dependence of the anomalous kinetic isotope effects in ozone formation then provide a conceptual framework for understanding the differences in the isotopic composition and the triple isotope slopes between the laboratory and the stratosphere and between different regions of the stratosphere. This understanding in turn provides a firmer foundation for the diverse biogeochemical and paleoclimate applications of 17O anomalies in tropospheric CO2, O2, mineral sulfates, and fossil bones and teeth, which all derive from stratospheric CO2.

Exploration of robust operating conditions in inductively coupled plasma mass spectrometry

Abstract ‘Robust’ conditions, as defined by Mermet and co-workers for inductively coupled plasma (ICP)-atomic emission spectrometry, minimize matrix effects on analyte signals, and are obtained by increasing power and reducing nebulizer gas flow. In ICP-mass spectrometry (MS), it is known that reduced nebulizer gas flow usually leads to more robust conditions such that matrix effects are reduced. In this work, robust conditions for ICP-MS have been determined by optimizing for accuracy in the determination of analytes in a multi-element solution with various interferents (Al, Ba, Cs, K, Na), by varying power, nebulizer gas flow, sample introduction rate and ion lens voltage. The goal of the work was to determine which operating parameters were the most important in reducing matrix effects, and whether different interferents yielded the same robust conditions. Reduction in nebulizer gas flow and in sample input rate led to a significantly decreased interference, while an increase in power seemed to have a lesser effect. Once the other parameters had been adjusted to their robust values, there was no additional improvement in accuracy attainable by adjusting the ion lens voltage. The robust conditions were universal, since, for all the interferents and analytes studied, the optimum was found at the same operating conditions. One drawback to the use of robust conditions was the slightly reduced sensitivity; however, in the context of ‘intelligent’ instruments, the concept of ‘robust conditions’ is useful in many cases.

Selected topics in arctic atmosphere and climate

This paper summarizes the main elements of four IPY projects that examine the Arctic Atmosphere. All four projects focus on present conditions with a view to anticipating possible climate change. All four investigate the Arctic atmosphere, ocean, ice, and land interfacial surfaces. One project uses computer models to simulate the dynamics of the Arctic atmosphere, storms, and their interactions with the ocean and ice interface. Another project uses statistical methods to infer transports of pollutants as simulated in large-scale global atmospheric and oceanic models verifying results with available observations. A third project focuses on measurements of pollutants at the ice-ocean–atmosphere interface, with reference to model estimates. The fourth project is concerned with multiple, high accuracy measurements at Eureka in the Canadian Archipelago. While these projects are distinctly different, led by different teams and interdisciplinary collaborators, with different technical approaches and methodologies, and differing objectives, they all strive to understand the processes of the Arctic atmosphere and climate, and to lay the basis for projections of future changes. Key findings include:• Decreased sea ice leads to more intense storms, higher winds, reduced surface albedo, increased surface air temperature, and enhanced vertical mixing in the upper ocean.• Arctic warming may affect toxic chemicals by remobilizing persistent organic pollutants and augmenting mercury deposition/retention in the environment.• Changes in sea ice can dramatically change processes in and at the ice surface related to ozone, mercury and bromine oxide and related chemical/physical properties.• Structure and properties of the Arctic atmospheric—troposphere to stratosphere—and tracking of transport of pollution and smoke plumes from mid-latitudes to the poles.

Estimates of Exceedances of Critical Loads for Acidifying Deposition in Alberta and Saskatchewan

Estimates of potential harmful effects to ecosystems in the Canadian provinces of Alberta and Saskatchewan due to acidifying deposition were calculated, using a one year simulation of a high resolution implementation of the Global Environmental Multiscale – Modelling Air-quality and Chemistry (GEM-MACH) model, and estimates of aquatic and terrestrial ecosystem critical loads. The model simulation was evaluated against two different sources of deposition data; 20 total deposition in precipitation and total deposition to snowpack in the vicinity of the Athabasca oil sands. The model captured much of the variability of observed ions in wet deposition in precipitation (observed versus model sulphur, nitrogen and base cation R 2 values of 0.90, 0.76 and 0.72, respectively), while being biased high for sulphur deposition, and low for nitrogen and base cations (slopes 2.2, 0.89 and 0.40, respectively). Aircraft-observation-based estimates of fugitive dust emissions, shown to be a factor of ten higher than reported values (Zhang et al.., 2017), were used to estimate the impact of 25 increased levels of fugitive dust on model results. Model comparisons to open snowpack observations were shown to be biased high, but in reasonable agreement for sulphur deposition when observations were corrected to account for throughfall in needleleaf forests. The model-observation relationships for precipitation deposition data, along with the expected effects of increased (unreported) base cation emissions, were used to provide a simple observation-based correction to model deposition fields. Base cation deposition was estimated using published observations of base cation fractions in surface 30 collected particles (Wang et al.., 2015). Both original and observation-corrected model estimates of sulphur, nitrogen and base cation deposition were used in conjunction with critical load data created using the NEG-ECP (2001) and CLRTAP (2004, 2016, 2017) protocols for critical loads, using variations on the Simple Mass Balance model for forest and terrestrial ecosystems, and the Steady State Atmos. Chem. Phys. Discuss., https://doi.org/10.5194/acp-2017-1094 Manuscript under review for journal Atmos. Chem. Phys. Discussion started: 26 February 2018 c

Prediction of Multiple Matrix Interferences in Inductively Coupled Plasma Mass Spectrometry

Matrix effects for pairs of interferents (Al, Na, K, Ba, and Cs) were investigated and compared to predictions of the amount of interference determined by single interferent experiments in order to test a model called the total interference level (TIL), which assumes that the effects of different interferents add linearly. The TIL model is part of an Autonomous Instrument and is designed to indicate when a simple default calibration, such as external calibration or internal standardization, is inadequate for the desired accuracy of analysis. The performance of the TIL model was examined in terms of a daily calibration basis, which should be more accurate, and an occasional calibration basis, which is more convenient, considering simple external standardization and internal standardization as the techniques to be tested for desired accuracy. The results are encouraging for multiple interferences and show that the TIL model can serve a useful function in predicting calibration errors, even given the presence of instrument drift on ICP-MS.