Iodine speciation in rain, snow and aerosols and possible transfer of organically bound iodine species from aerosol to droplet phases

International audienceIodine oxides, such as iodate, should theoretically be the only stable sink species for iodine in the troposphere. However, field observations have increasingly found very little iodate and significant amounts of iodide and organically bound iodine in precipitation and aerosols. The aim of this study was to investigate iodine speciation, including the organic fraction, in rain, snow, and aerosols in an attempt to further clarify aqueous phase iodine chemistry. Diurnal aerosol samples were taken with a 5 stage cascade impactor and a virtual impactor (PM2.5) from the Mace Head research station, Ireland, during summer 2006. Rain was collected from Australia, New Zealand, Patagonia, Germany, Ireland, and Switzerland while snow was obtained from Greenland, Germany, Switzerland, and New Zealand. All samples were analysed for total iodine by inductively coupled plasma mass spectrometry (ICP-MS) and speciation was determined by coupling an ion chromatography unit to the ICP-MS. Total iodine in the aerosols from Mace Head gave a median concentration of 50 pmol m?3 of which the majority was associated with the organic fraction (median day: 91±7%, night: 94±6% of total iodine). Iodide exhibited higher concentrations than iodate (median 5% vs. 0.8% of total iodine), and displayed significant enrichment during the day compared to the night. Interestingly, up to 5 additional, presumably anionic organic peaks were observed in all IC-ICP-MS chromatograms, composing up to 15% of the total iodine. Organically bound iodine was also the dominant fraction in all rain and snow samples, with lesser amounts of iodide and iodate (iodate was particularly low in snow). Two of the same unidentified peaks found in aerosols were also observed in precipitation from both Southern and Northern Hemispheres, suggesting that these species are transferred from the aerosol phase into precipitation. It is suggested that organo-I is formed by reactions between HOI and organic matter derived from the ocean surface layer. This may then photolytically decompose to give iodide and the unidentified species. The data in this study show that iodine oxides are the least abundant species in rain, snow, and aerosols and therefore considerably more effort is required on aqueous phase iodine chemistry for a holistic understanding of the iodine cycle

Low hydrological connectivity after summer drought inhibits DOC export in a forested headwater catchment

Understanding the controls on event-driven dissolved organic carbon (DOC) export is crucial as DOC is an important link between the terrestrial and the aquatic carbon cycles. We hypothesized that topography is a key driver of DOC export in headwater catchments because it influences hydrological connectivity, which can inhibit or facilitate DOC mobilization. To test this hypothesis, we studied the mechanisms controlling DOC mobilization and export in the Große Ohe catchment, a forested headwater in a mid-elevation mountainous region in southeastern Germany. Discharge and stream DOC concentrations were measured at an interval of 15 min using in situ UV-Vis (ultraviolet–visible) spectrometry from June 2018 until October 2020 at two topographically contrasting subcatchments of the same stream. At the upper location (888 m above sea level, a.s.l.), the stream drains steep hillslopes, whereas, at the lower location (771 m a.s.l.), it drains a larger area, including a flat and wide riparian zone. We focus on four events with contrasting antecedent wetness conditions and event size. During the events, in-stream DOC concentrations increased up to 19 mg L−1 in comparison to 2–3 mg L−1 during baseflow. The concentration–discharge relationships exhibited pronounced but almost exclusively counterclockwise hysteresis loops which were generally wider in the lower catchment than in the upper catchment due to a delayed DOC mobilization in the flat riparian zone. The riparian zone released considerable amounts of DOC, which led to a DOC load up to 7.4 kg h−1. The DOC load increased with the total catchment wetness. We found a disproportionally high contribution to the total DOC export of the upper catchment during events following a long dry period. We attribute this to the low hydrological connectivity in the lower catchment during drought, which inhibited DOC mobilization, especially at the beginning of the events. Our data show that not only event size but also antecedent wetness conditions strongly influence the hydrological connectivity during events, leading to a varying contribution to DOC export of subcatchments, depending on topography. As the frequency of prolonged drought periods is predicted to increase, the relative contribution of different subcatchments to DOC export may change in the future when hydrological connectivity will be reduced more often.</p

The importance of calcium and amorphous silica for arctic soil CO₂ production

Future warming of the Arctic not only threatens to destabilize the enormous pool of organic carbon accumulated in permafrost soils but may also mobilize elements such as calcium (Ca) or silicon (Si). While for Greenlandic soils, it was recently shown that both elements may have a strong effect on carbon dioxide (CO2) production with Ca strongly decreasing and Si increasing CO2 production, little is known about the effects of Si and Ca on carbon cycle processes in soils from Siberia, the Canadian Shield, or Alaska. In this study, we incubated five different soils (rich organic soil from the Canadian Shield and from Siberia (one from the top and one from the deeper soil layer) and one acidic and one non-acidic soil from Alaska) for 6 months under both drained and waterlogged conditions and at different Ca and amorphous Si (ASi) concentrations. Our results show a strong decrease in soil CO2 production for all soils under both drained and waterlogged conditions with increasing Ca concentrations. The ASi effect was not clear across the different soils used, with soil CO2 production increasing, decreasing, or not being significantly affected depending on the soil type and if the soils were initially drained or waterlogged. We found no methane production in any of the soils regardless of treatment. Taking into account the predicted change in Si and Ca availability under a future warmer Arctic climate, the associated fertilization effects would imply potentially lower greenhouse gas production from Siberia and slightly increased greenhouse gas emissions from the Canadian Shield. Including Ca as a controlling factor for Arctic soil CO2 production rates may, therefore, reduces uncertainties in modeling future scenarios on how Arctic regions may respond to climate change

Surface water numerical modelling for the Clarence-Moreton bioregion. Product 2.6.1 from the Clarence-Moreton Bioregional Assessment

No abstract available

Surface water numerical modelling for the Clarence-Moreton bioregion. Product 2.6.1 from the Clarence-Moreton Bioregional Assessment

No abstract available

Modelling to bridge many boundaries: the Colorado and Murray-Darling River basins

Increasing pressure on shared water resources has often been a driver for the development and utilisation of water resource models (WRMs) to inform planning and management decisions. With an increasing emphasis on regional decision-making among competing actors as opposed to top-down and authoritative directives, the need for integrated knowledge and water diplomacy efforts across federal and international rivers provides a test bed for the ability of WRMs to operate within complex historical, social, environmental, institutional and political contexts. This paper draws on theories of sustainability science to examine the role of WRMs to inform transboundary water resource governance in large river basins. We survey designers and users of WRMs in the Colorado River Basin in North America and the Murray-Darling Basin in southeastern Australia. Water governance in such federal rivers challenges inter-governmental and multi-level coordination and we explore these dynamics through the application of WRMs. The development pathways of WRMs are found to influence their uptake and acceptance as decision support tools. Furthermore, we find evidence that WRMs are used as boundary objects and perform the functions of ‘boundary work’ between scientists, decision-makers and stakeholders in the midst of regional environmental changes

Speciation analysis of iodine and bromine at picogram-per-gram levels in polar ice

Iodine and bromine species participate in key atmospheric reactions including the formation of cloud con- densation nuclei and ozone depletion. We present a novel method coupling a high-performance liquid chromatogra- phy with ion chromatography and inductively coupled plas- ma mass spectrometry, which allows the determination of iodine (I) and bromine (Br) species (IO3−, I−, Br−, BrO3−) at the picogram-per-gram levels presents in Antarctic ice. Chromatographic separation was achieved using an ION- PAC® AS16 Analytical Column with NaOH as eluent. Detection limits for I and Br species were 5 to 9 pg g−1 with an uncertainty of less than 2.5% for all considered species. Inorganic iodine and bromine species have been determined in Antarctic ice core samples, with concentrations close to the detection limits for iodine species, and approximately 150 pg g−1 for Br−. Although iodate (IO3−) is the most abundant iodine species in the atmosphere, only the much rarer iodide (I−) species was present in Antarctic Holocene ice. Bromine was found to be present in Antarctic ice as Br−

Disentangling the complexity of groundwater dependent social-ecological systems

Groundwater resources are part of larger social-ecological systems. In this chapter, we review the various dimensions of these complex systems in order to uncover the diversity of elements at stake in the evolution of an aquifer and the loci for possible actions to control its dynamics. Two case studies illustrate how the state of an aquifer is embedded in a web of biophysical and sociopolitical processes. We propose here a holistic view through an IGM-scape that describes the various possible pathways of evolution for a groundwater related social-ecological system. Then we describe the elements of this IGM-scape starting with physical entities and processes, including relations with surface water and quality issues. Interactions with society bring an additional layer of considerations, including decisions on groundwater abstraction, land use changes and even energy related choices. Finally we point out the policy levers for groundwater management and their possible consequences for an aquifer, taking into account the complexity of pathways opened by these levers

Short-Lived Trace Gases in the Surface Ocean and the Atmosphere

The two-way exchange of trace gases between the ocean and the atmosphere is important for both the chemistry and physics of the atmosphere and the biogeochemistry of the oceans, including the global cycling of elements. Here we review these exchanges and their importance for a range of gases whose lifetimes are generally short compared to the main greenhouse gases and which are, in most cases, more reactive than them. Gases considered include sulphur and related compounds, organohalogens, non-methane hydrocarbons, ozone, ammonia and related compounds, hydrogen and carbon monoxide. Finally, we stress the interactivity of the system, the importance of process understanding for modeling, the need for more extensive field measurements and their better seasonal coverage, the importance of inter-calibration exercises and finally the need to show the importance of air-sea exchanges for global cycling and how the field fits into the broader context of Earth System Science

Phospholipid membranes drive abdominal aortic aneurysm development through stimulating coagulation factor activity

Abdominal aortic aneurysm (AAA) is an inflammatory vascular disease with high mortality and limited treatment options. How blood lipids regulate AAA development is unknown. Here lipidomics and genetic models demonstrate a central role for procoagulant enzymatically oxidized phospholipids (eoxPL) in regulating AAA. Specifically, through activating coagulation, eoxPL either promoted or inhibited AAA depending on tissue localization. Ang II administration to ApoE−/− mice increased intravascular coagulation during AAA development. Lipidomics revealed large numbers of eoxPL formed within mouse and human AAA lesions. Deletion of eoxPL-generating enzymes (Alox12 or Alox15) or administration of the factor Xa inhibitor rivaroxaban significantly reduced AAA. Alox-deficient mice displayed constitutively dysregulated hemostasis, including a consumptive coagulopathy, characterized by compensatory increase in prothrombotic aminophospholipids (aPL) in circulating cell membranes. Intravenously administered procoagulant PL caused clotting factor activation and depletion, induced a bleeding defect, and significantly reduced AAA development. These data suggest that Alox deletion reduces AAA through diverting coagulation away from the vessel wall due to eoxPL deficiency, instead activating clotting factor consumption and depletion in the circulation. In mouse whole blood, ∼44 eoxPL molecular species formed within minutes of clot initiation. These were significantly elevated with ApoE−/− deletion, and many were absent in Alox−/− mice, identifying specific eoxPL that modulate AAA. Correlation networks demonstrated eoxPL belonged to subfamilies defined by oxylipin composition. Thus, procoagulant PL regulate AAA development through complex interactions with clotting factors. Modulation of the delicate balance between bleeding and thrombosis within either the vessel wall or circulation was revealed that can either drive or prevent disease development