On the Exchange of NO3 Radicals with Aqueous Solutions: Solubility and Sticking Coefficient

The exchange of NO₃ radicals with the aqueous-phase was investigated at room temperature (293 K) in a series of wetted denuders. From these experiments, the uptake coefficient of NO₃ was determined on 0.1 M NaCl solutions and was found to be (NO₃) 2 × 10^-3 in good agreement with recent studies. The Henry coefficient of NO₃ was estimated to be K_H(NO₃) = 1.8 M · atm^-1, with a (2) uncertainty of ±3 M · atm^-1. From the upper limit for the Henry coefficient (K_H = 5 M · atm^-1) and available thermodynamic data, the redox potential of dissolved NO₃/NO ₃ ^– is estimated to be in the range of 2.3 to 2.5 V. This range is at the lower boundary of earlier estimates. The results are discussed in the light of a recent publication. Based on our data and a model of the transport and chemistry in the liquid film, an upper limit is derived for the product of the Henry coefficient K_H and the rate coefficient k ₁₀ of the potential reaction NO₃ + H₂O HNO₃ + OH. For K_H = 0.6 M · atm^-1, we find k ₁₀ < 0.05 s^-1 · atm^-1, i.e., about 100 times smaller than what was suggested by Rudich and co-workers. Because of its small solubility, heterogeneous removal of NO₃ is only important under conditions where the dissolved NO₃ is removed quickly from equilibrium, for example by reactions with Cl^– or HSO ₃ ^– ions in the liquid-phase. Otherwise, heterogenous removal should mainly proceed via N₂O₅.     

Marine C reservoir ages for 19th century whales and molluscs from the North Atlantic

In order to compare radiocarbon dates on marine and terrestrial samples the former have to be corrected for a reservoir age. We present reservoir ages from dating 21 whales collected 1860–1901 and recalculating dates of 23 molluscs collected 1857–1926. Most of the whales were caught along the coast of Norway, but one is from France and one from Iceland. We assume the former mainly lived in the North and equatorial Atlantic and in the Norwegian Sea. Whales feed only on pelagic organisms and will provide the reservoir age for the open ocean surface water. However, they travel long distances and will integrate the reservoir ages of the different water masses along their way. Molluscs (dated from Norway, Spitsbergen and Arctic Canada) are stationary and monitor the sea water passing their dwelling site, but some also take up carbon from particulate food or sediment pore water. Coastal water also often contains some continental carbon. We present two different views on how to analyze and interpret the data. Mangerud recommends to use reservoir ages based on a combination of the whale and mollusc dates, i.e. 380±30 and 360±30 yr relative to Intcal04 and British oak, respectively, and a ΔR value of 20±30 for the surface water in the N-Atlantic and Norwegian Sea. Bondevik and Gulliksen maintain that the reservoir age—and ΔR—along the Norwegian coast is latitude dependant, with ΔR-values increasing from −3±22 in the South to 105±24 at Spitsbergen. Whales, reflecting North Atlantic open ocean surface water have lower ΔR (7±11) than most molluscs.     

Holocene temperature variations at a high-altitude site in the Eastern Alps: a chironomid record from Schwarzsee ob Sölden, Austria

Few well-dated, quantitative Holocene temperature reconstructions exist from high-altitude sites in the Central Eastern Alps. Here, we present a chironomid-based quantitative reconstruction of mean July air temperatures (T_July) throughout the Holocene for a remote high-mountain lake, Schwarzsee ob Sölden, situated above the treeline at 2796 m a.s.l. in the Austrian Alps. Applying a chironomid-temperature inference model developed from lakes of the Alpine region to a high-resolution chironomid record from the lake provides evidence for early Holocene (ca 10000–8600 cal yr BP) T_July of up to 8.5 °C, i.e. >4 °C above the modern (1977–2006) mean July temperature. The reconstruction reveals the so-called ‘8.2-ka cold event’ centered at ca 8250–8000 cal yr BP with temperatures ca 3 °C below the early-Holocene thermal maximum. Rather warm (ca 6 °C) and productive conditions prevailed during ca 7900–4500 cal yr BP. The chironomid record suggests a climate transition between ca 5200 and 4500 cal yr BP to cooler T_July. A distinct cooling trend is evident from ca 4500 until ca 2500 cal yr BP. Thereafter, the study site experienced its coldest conditions (around 4 °C or less) throughout the rest of the Holocene, with the exception of the warming trend during the late 20th century. Beside other factors, the Northern Hemisphere summer insolation seems to be the major driving force for the long-term trends in T_July at high altitudes in the Eastern Alps. Due to the extreme location of the lake and the limited temperature range represented by the applied calibration data set, the chironomid-based temperature reconstruction fails to track phases of the late-Holocene climatic history with T_July cooler than 4 °C. Further chironomid-based palaeoclimate model and down-core studies are required to address this problem, provide more realistic T_July estimates from undisturbed high-altitude lakes in the Alps, and extract a reliable regional temperature signal.     

An International Relations perspective on the global politics of carbon dioxide capture and storage

With the publication of the IPCC Special Report on Carbon dioxide Capture and Storage (CCS), CCS has emerged as a focal issue in international climate diplomacy and energy collaboration. This paper has two goals. The first goal is to map CCS activities in and among various types of intergovernmental organisations; the second goal is to apply International Relations (IR) theories to explain the growing diversity, overlap and fragmentation of international organisations dealing with CCS. Which international organisations embrace CCS, and which refrain from discussing it at all? What role do these institutions play in bringing CCS forward? Why is international collaboration on CCS so fragmented and weak? We utilise realism, liberal institutionalism and constructivism to provide three different interpretations of the complex global landscape of CCS governance in the context of the similarly complicated architecture of global climate policy. A realist account of CCS's fragmented international politics is power driven. International fossil fuel and energy organisations, dominated by major emitter states, take an active role in CCS. An interest-based approach, such as liberal institutionalism, claims that CCS is part of a “regime complex” rather than an integrated, hierarchical, comprehensive and international regime. Such a regime complex is exemplified by the plethora of international organisations with a role in CCS. Finally, constructivism moves beyond material and interest-based interpretations of the evolution of the institutionally fragmented architecture of global CCS governance. The 2005 IPCC Special Report on CCS demonstrates the pivotal role that ideas, norms and scientific knowledge have played in transforming the preferences of the international climate-change policy community.     

Scientific detector workshop 2022 on-sky performance verification of near-infrared e−APD technology for wavefront sensing and demonstration of e−APD pixel performance to improve the sensitivity of large science focal planes

Near-infrared adaptive optics as well as fringe tracking for coherent beam combination in optical interferometry require the development of high-speed sensors. Because of the high speed, a large analog bandwidth is required. The short exposure times result in small signal levels which require noiseless detection. Both requirements cannot be met by state-of-the-art conventional CMOS technology of near-infrared arrays as has been attempted previously. A total of five near-infrared SAPHIRA 320 × 256 pixel HgCdTe e⁻APD arrays have been deployed in the wavefront sensors and in the fringe tracker of the VLTI instrument GRAVITY. The current limiting magnitude for coherent exposures with GRAVITY is m_k = 19, which is made possible with ADP technology. New avalanche photo-diode array (APD) developments since GRAVITY include the extension of the spectral sensitivity to the wavelength range from 0.8 to 2.5 μm. After GRAVITY a larger format array with 512 × 512 pixels has been developed for both AO applications at the ELT and for long integration times. Since dark currents of <10⁻³ e⁻/s have been demonstrated with 1Kx1K e⁻APD arrays and 2Kx2K e⁻APD arrays have already been developed, the possibilities and adaptations of e⁻APD technology to provide noiseless large-format science-grade arrays for long integration times are also discussed.