Can the carbon isotopic composition of methane be reconstructed from multi-site firn air measurements?

Methane is a strong greenhouse gas and large uncertainties exist concerning the future evolution of its atmospheric abundance. Analyzing methane atmospheric mixing and stable isotope ratios in air trapped in polar ice sheets helps in reconstructing the evolution of its sources and sinks in the past. This is important to improve predictions of atmospheric CH4 mixing ratios in the future under the influence of a changing climate. The aim of this study is to assess whether past atmospheric δ13C(CH4) variations can be reliably reconstructed from firn air measurements. Isotope reconstructions obtained with a state of the art firn model from different individual sites show unexpectedly large discrepancies and are mutually inconsistent. We show that small changes in the diffusivity profiles at individual sites lead to strong differences in the firn fractionation, which can explain a large part of these discrepancies. Using slightly modified diffusivities for some sites, and neglecting samples for which the firn fractionation signals are strongest, a combined multi-site inversion can be performed, which returns an isotope reconstruction that is consistent with firn data. However, the isotope trends are lower than what has been concluded from Southern Hemisphere (SH) archived air samples and high-accumulation ice core data. We conclude that with the current datasets and understanding of firn air transport, a high precision reconstruction of δ13C of CH4 from firn air samples is not possible, because reconstructed atmospheric trends over the last 50 yr of 0.3–1.5 ‰ are of the same magnitude as inherent uncertainties in the method, which are the firn fractionation correction (up to ~2 ‰ at individual sites), the Kr isobaric interference (up to ~0.8 ‰, system dependent), inter-laboratory calibration offsets (~0.2 ‰) and uncertainties in past CH4 levels (~0.5 ‰).

Gas transport in firn: multiple-tracer characterisation and model intercomparison for NEEM, Northern Greenland

Air was sampled from the porous firn layer at the NEEM site in Northern Greenland. We use an ensemble of ten reference tracers of known atmospheric history to characterise the transport properties of the site. By analysing uncertainties in both data and the reference gas atmospheric histories, we can objectively assign weights to each of the gases used for the depth-diffusivity reconstruction. We define an objective root mean square criterion that is minimised in the model tuning procedure. Each tracer constrains the firn profile differently through its unique atmospheric history and free air diffusivity, making our multiple-tracer characterisation method a clear improvement over the commonly used single-tracer tuning. Six firn air transport models are tuned to the NEEM site; all models successfully reproduce the data within a 1σ Gaussian distribution. A comparison between two replicate boreholes drilled 64 m apart shows differences in measured mixing ratio profiles that exceed the experimental error. We find evidence that diffusivity does not vanish completely in the lock-in zone, as is commonly assumed. The ice age- gas age difference (1 age) at the firn-ice transition is calculated to be 182+3−9 yr. We further present the first intercomparison study of firn air models, where we introduce diagnostic scenarios designed to probe specific aspects of the model physics. Our results show that there are major differences in the way the models handle advective transport. Furthermore, diffusive fractionation of isotopes in the firn is poorly constrained by the models, which has consequences for attempts to reconstruct the isotopic composition of trace gases back in time using firn air and ice core records.

The Decrease in Summer Surface Water Temperature with Altitude in Swiss Alpine Lakes: A Comparison with Air Temperature Lapse Rates

Using miniature thermistors with integrated data loggers, the decrease in summer lake surface water temperature (LSWT) with increasing altitude a.s.l. was investigated in 10 Swiss Alpine lakes located between 613 m a.s.l. and 2339 m a.s.l. The LSWTs exhibit essentially the same short-term structure as regional air temperature, but are about 3 to 5°C higher than the air temperature at the altitude of the lake. LSWTs decrease approximately linearly with increasing altitude at a rate slightly greater than the surface air temperature lapse rate. Diel variations in LSWT are large, implying that single water temperature measurements are un- likely to be representative of the mean. Local factors will affect LSWT more than they affect air temperature, possibly resulting in severe distortion of the empirical relationship between the two. Several implications for paleoclimate reconstruction studies result. (1) Paleolimnologically reconstructed LSWTs are likely to be higher than the air temperatures prevailing at the altitude of the lake. (2) Lakes used for paleoclimate reconstruction should be selected to minimize local effects on LSWT. (3) The calibration of organism-specific quantitative paleotemperature inference models should not be based on single water temperature measurements. (4) Consideration should be given to calibrating such models directly against air temperature rather than water temperature. (5) The primary climate effect on the aquatic biota of high-altitude lakes may be mediated by the timing of the ice cover.

Continuous measurements of methane mixing ratios from ice cores

This work presents a new, field-deployable technique for continuous, high-resolution measurements of methane mixing ratios from ice cores. The technique is based on a continuous flow analysis system, where ice core samples cut along the long axis of an ice core are melted continuously. The past atmospheric air contained in the ice is separated from the melt water stream via a system for continuous gas extraction. The extracted gas is dehumidified and then analyzed by a Wavelength Scanned-Cavity Ring Down Spectrometer for methane mixing ratios. We assess the performance of the new measurement technique in terms of precision (±0.8 ppbv, 1σ), accuracy (±8 ppbv), temporal (ca. 100 s), and spatial resolution (ca. 5 cm). Using a firn air transport model, we compare the resolution of the measurement technique to the resolution of the atmospheric methane signal as preserved in ice cores in Greenland. We conclude that our measurement technique can resolve all climatically relevant variations as preserved in the ice down to an ice depth of at least 1980 m (66 000 yr before present) in the North Greenland Eemian Ice Drilling ice core. Furthermore, we describe the modifications, which are necessary to make a commercially available spectrometer suitable for continuous methane mixing ratio measurements from ice cores.

Effects of prolonged endotoxemia on liver, skeletal muscle and kidney mitochondrial function

INTRODUCTION: Sepsis may impair mitochondrial utilization of oxygen. Since hepatic dysfunction is a hallmark of sepsis, we hypothesized that the liver is more susceptible to mitochondrial dysfunction than the peripheral tissues, such as the skeletal muscle. We studied the effect of prolonged endotoxin infusion on liver, muscle and kidney mitochondrial respiration and on hepatosplanchnic oxygen transport and microcirculation in pigs. METHODS: 20 anesthetized pigs were randomized to receive endotoxin or saline infusion for 24 hours. Muscle, liver and kidney mitochondrial respiration was assessed. Cardiac output (thermodilution), carotid, superior mesenteric and kidney arterial, portal venous (ultrasound Doppler) and microcirculatory blood flow (laser Doppler) were measured, and systemic and regional oxygen transport and lactate exchange were calculated. RESULTS: Endotoxin infusion induced hyperdynamic shock and impaired the glutamate- and succinate-dependent mitochondrial respiratory control ratio (RCR) in the liver (glutamate: endotoxemia: median [range] 2.8 [2.3-3.8] vs. controls: 5.3 [3.8-7.0]; p<0.001; succinate: endotoxemia: 2.9 [1.9-4.3] vs. controls: 3.9 [2.6-6.3] p=0.003). While the ADP:O ratio was reduced with both substrates, maximal ATP production was impaired only in the succinate-dependent respiration. Hepatic oxygen consumption and extraction, and liver surface laser Doppler blood flow remained unchanged. Glutamate-dependent respiration in the muscle and kidney was unaffected. CONCLUSIONS: Endotoxemia reduces the efficiency of hepatic but neither skeletal muscle nor kidney mitochondrial respiration, independent of regional and microcirculatory blood flow changes.

GATS and the Regulation of Trade in Services

This collection of essays takes stock of the key challenges that have arisen since the entry into force of the General Agreement on Trade in Services in the mid-1990s and situates them in the context of the WTO's Doha Development Agenda and the proliferation of preferential agreements addressing services today. The multidisciplinary approach provides an opportunity for many of the world's leading experts and a number of new analytical voices to exchange ideas on the future of services trade and regulation. Cosmopolitan approaches to the treatment of labour mobility, the shape of services trade disciplines in the digital age and pro-competitive regulation in air transport are explored with a view to helping readers gain a better understanding of the forces shaping the changes. An essential read for all those concerned with the evolution of the rules-based trading system and its impact on the service economy.

Is there a common pattern of future gas-phase air pollution in Europe under diverse climate change scenarios?

Climate change alone influences future levels of tropospheric ozone and their precursors through modifications of gas-phase chemistry, transport, removal, and natural emissions. The goal of this study is to determine at what extent the modes of variability of gas-phase pollutants respond to different climate change scenarios over Europe. The methodology includes the use of the regional modeling system MM5 (regional climate model version)-CHIMERE for a target domain covering Europe. Two full-transient simulations covering from 1991–2050 under the SRES A2 and B2 scenarios driven by ECHO-G global circulation model have been compared. The results indicate that the spatial patterns of variability for tropospheric ozone are similar for both scenarios, but the magnitude of the change signal significantly differs for A2 and B2. The 1991–2050 simulations share common characteristics for their chemical behavior. As observed from the NO2 and α-pinene modes of variability, our simulations suggest that the enhanced ozone chemical activity is driven by a number of parameters, such as the warming-induced increase in biogenic emissions and, to a lesser extent, by the variation in nitrogen dioxide levels. For gas-phase pollutants, the general increasing trend for ozone found under A2 and B2 forcing is due to a multiplicity of climate factors, such as increased temperature, decreased wet removal associated with an overall decrease of precipitation in southern Europe, increased photolysis of primary and secondary pollutants as a consequence of lower cloudiness and increased biogenic emissions fueled by higher temperatures.

In-situ, satellite measurement and model evidence on the dominant regional contribution to fine particulate matter levels in the Paris Megacity

A detailed characterization of air quality in the megacity of Paris (France) during two 1-month intensive campaigns and from additional 1-year observations revealed that about 70% of the urban background fine particulate matter (PM) is transported on average into the megacity from upwind regions. This dominant influence of regional sources was confirmed by in situ measurements during short intensive and longer-term campaigns, aerosol optical depth (AOD) measurements from ENVISAT, and modeling results from PMCAMx and CHIMERE chemistry transport models. While advection of sulfate is well documented for other megacities, there was surprisingly high contribution from long-range transport for both nitrate and organic aerosol. The origin of organic PM was investigated by comprehensive analysis of aerosol mass spectrometer (AMS), radiocarbon and tracer measurements during two intensive campaigns. Primary fossil fuel combustion emissions constituted less than 20%in winter and 40%in summer of carbonaceous fine PM, unexpectedly small for a megacity. Cooking activities and, during winter, residential wood burning are the major primary organic PM sources. This analysis suggests that the major part of secondary organic aerosol is of modern origin, i.e., from biogenic precursors and from wood burning. Black carbon concentrations are on the lower end of values encountered in megacities worldwide, but still represent an issue for air quality. These comparatively low air pollution levels are due to a combination of low emissions per inhabitant, flat terrain, and a meteorology that is in general not conducive to local pollution build-up. This revised picture of a megacity only being partially responsible for its own average and peak PM levels has important implications for air pollution regulation policies.

Cerium oxide nanoparticle uptake kinetics from the gas-phase into lung cells in vitro is transport limited

Nowadays, aerosol processes are widely used for the manufacture of nanoparticles (NPs), creating an increased occupational exposure risk of workers, laboratory personnel and scientists to airborne particles. There is evidence that possible adverse effects are linked with the accumulation of NPs in target cells, pointing out the importance of understanding the kinetics of particle internalization. In this context, the uptake kinetics of representative airborne NPs over 30 min and their internalization after 24 h post-exposure were investigated by the use of a recently established exposure system. This system combines the production of aerosolized cerium oxide (CeO(2)) NPs by flame spray synthesis with its simultaneous particle deposition from the gas-phase onto A549 lung cells, cultivated at the air-liquid interface. Particle uptake was quantified by mass spectrometry after several exposure times (0, 5, 10, 20 and 30 min). Over 35% of the deposited mass was found internalized after 10 min exposure, a value that increased to 60% after 30 min exposure. Following an additional 24 h post-incubation, a time span, after which adverse biological effects were observed in previous experiments, over 80% of total CeO(2) could be detected intracellularly. On the ultrastructural level, focal cerium aggregates were present on the apical surface of A549 cells and could also be localized intracellularly in vesicular structures. The uptake behaviour of aerosolized CeO(2) is in line with observations on cerium suspensions, where particle mass transport was identified as the rate-limiting factor for NP internalization.

Late Holocene air temperature variability reconstructed from the sediments of Laguna Escondida, Patagonia, Chile (45 degrees 30 ' S)

Climate and environmental reconstructions from natural archives are important for the interpretation of current climatic change. Few quantitative high-resolution reconstructions exist for South America which is the only land mass extending from the tropics to the southern high latitudes at 56°S. We analyzed sediment cores from two adjacent lakes in Northern Chilean Patagonia, Lago Castor (45°36′S, 71°47′W) and Laguna Escondida (45°31′S, 71°49′W). Radiometric dating (210Pb, 137Cs, 14C-AMS) suggests that the cores reach back to c. 900 BC (Laguna Escondida) and c. 1900 BC (Lago Castor). Both lakes show similarities and reproducibility in sedimentation rate changes and tephra layer deposition. We found eight macroscopic tephras (0.2–5.5 cm thick) dated at 1950 BC, 1700 BC, at 300 BC, 50 BC, 90 AD, 160 AD, 400 AD and at 900 AD. These can be used as regional time-synchronous stratigraphic markers. The two thickest tephras represent known well-dated explosive eruptions of Hudson volcano around 1950 and 300 BC. Biogenic silica flux revealed in both lakes a climate signal and correlation with annual temperature reanalysis data (calibration 1900–2006 AD; Lago Castor r = 0.37; Laguna Escondida r = 0.42, seven years filtered data). We used a linear inverse regression plus scaling model for calibration and leave-one-out cross-validation (RMSEv = 0.56 °C) to reconstruct sub decadal-scale temperature variability for Laguna Escondida back to AD 400. The lower part of the core from Laguna Escondida prior to AD 400 and the core of Lago Castor are strongly influenced by primary and secondary tephras and, therefore, not used for the temperature reconstruction. The temperature reconstruction from Laguna Escondida shows cold conditions in the 5th century (relative to the 20th century mean), warmer temperatures from AD 600 to AD 1150 and colder temperatures from AD 1200 to AD 1450. From AD 1450 to AD 1700 our reconstruction shows a period with stronger variability and on average higher values than the 20th century mean. Until AD 1900 the temperature values decrease but stay slightly above the 20th century mean. Most of the centennial-scale features are reproduced in the few other natural climate archives in the region. The early onset of cool conditions from c. AD 1200 onward seems to be confirmed for this region.