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Long-term time series of the atmospheric composition are essential for environmental research and thus require compatible, multi-decadal monitoring activities. The current data quality objectives of the World Meteorological Organization (WMO) for carbon monoxide (CO) in the atmosphere are very challenging to meet with the measurement techniques that have been used until recently. During the past few years, new spectroscopic techniques came to market with promising properties for trace gas analytics. The current study compares three instruments that have recently become commercially available (since 2011) with the best currently available technique (Vacuum UV Fluorescence) and provides a link to previous comparison studies. The instruments were investigated for their performance regarding repeatability, reproducibility, drift, temperature dependence, water vapour interference and linearity. Finally, all instruments were examined during a short measurement campaign to assess their applicability for long-term field measurements. It could be shown that the new techniques perform considerably better compared to previous techniques, although some issues, such as temperature influence and cross sensitivities, need further attention.

The goal of the GHG-CCI project (http://www.esa-ghg-cci.org/) of ESA's Climate Change Initiative (CCI) is to generate global atmospheric satellite-derived carbon dioxide (CO2) and methane (CH4) data sets as needed to improve our understanding of the regional sources and sinks of these important greenhouse gases (GHG). Here we present an overview about the latest data set called Climate Research Data Package No. 3 (CRDP3). We focus on the GHG-CCI project core data products, which are near-surface-sensitive column-averaged dry air mole fractions of CO2 and CH4, denoted XCO2 (in ppm) and XCH4 (in ppb) retrieved from SCIAMACHY/ENVISAT (2002-2012) and TANSO-FTS/GOSAT (2009-today) nadir mode radiance observations in the near-infrared/shortwave-infrared spectral region. The GHG-CCI products are primarily individual sensor Level 2 products. However, we also generate merged Level 2 products ("EMMA products"). Here we also present a first GHG-CCI Level 3 product, namely XCO2 and XCH4 in Obs4MIPs format (monthly, 5°×5°).

Since 2004, atmospheric carbon dioxide (CO2) is being measured at the High Altitude Research Station Jungfraujoch by the division of Climate and Environmental Physics at the University of Bern (KUP) using a nondispersive infrared gas analyzer (NDIR) in combination with a paramagnetic O2 analyzer. In January 2010, CO2 measurements based on cavity ring-down spectroscopy (CRDS) as part of the Swiss National Air Pollution Monitoring Network were added by the Swiss Federal Laboratories for Materials Science and Technology (Empa). To ensure a smooth transition – a prerequisite when merging two data sets, e.g., for trend determinations – the two measurement systems run in parallel for several years. Such a long-term intercomparison also allows the identification of potential offsets between the two data sets and the collection of information about the compatibility of the two systems on different time scales. A good agreement of the seasonality, short-term variations and, to a lesser extent mainly due to the short common period, trend calculations is observed. However, the comparison reveals some issues related to the stability of the calibration gases of the KUP system and their assigned CO2 mole fraction. It is possible to adapt an improved calibration strategy based on standard gas determinations, which leads to better agreement between the two data sets. By excluding periods with technical problems and bad calibration gas cylinders, the average hourly difference (CRDS – NDIR) of the two systems is −0.03 ppm ± 0.25 ppm. Although the difference of the two data sets is in line with the compatibility goal of ±0.1 ppm of the World Meteorological Organization (WMO), the standard deviation is still too high. A significant part of this uncertainty originates from the necessity to switch the KUP system frequently (every 12 min) for 6 min from ambient air to a working gas in order to correct short-term variations of the O2 measurement system. Allowing additional time for signal stabilization after switching the sample, an effective data coverage of only one-sixth for the KUP system is achieved while the Empa system has a nearly complete data coverage. Additionally, different internal volumes and flow rates may affect observed differences.

If O2 is available at circumneutral pH, Fe2+ is rapidly oxidized to Fe3+, which precipitates as FeO(OH). Neutrophilic iron oxidizing bacteria have evolved mechanisms to prevent self-encrustation in iron. Hitherto, no mechanism has been proposed for cyanobacteria from Fe2+-rich environments; these produce O2 but are seldom found encrusted in iron. We used two sets of illuminated reactors connected to two groundwater aquifers with different Fe2+ concentrations (0.9 μM vs. 26 μM) in the Äspö Hard Rock Laboratory (HRL), Sweden. Cyanobacterial biofilms developed in all reactors and were phylogenetically different between the reactors. Unexpectedly, cyanobacteria growing in the Fe2+-poor reactors were encrusted in iron, whereas those in the Fe2+-rich reactors were not. In-situ microsensor measurements showed that O2 concentrations and pH near the surface of the cyanobacterial biofilms from the Fe2+-rich reactors were much higher than in the overlying water. This was not the case for the biofilms growing at low Fe2+ concentrations. Measurements with enrichment cultures showed that cyanobacteria from the Fe2+-rich environment increased their photosynthesis with increasing Fe2+ concentrations, whereas those from the low Fe2+ environment were inhibited at Fe2+ > 5 μM. Modeling based on in-situ O2 and pH profiles showed that cyanobacteria from the Fe2+-rich reactor were not exposed to significant Fe2+ concentrations. We propose that, due to limited mass transfer, high photosynthetic activity in Fe2+-rich environments forms a protective zone where Fe2+ precipitates abiotically at a non-lethal distance from the cyanobacteria. This mechanism sheds new light on the possible role of cyanobacteria in precipitation of banded iron formations.

Surface reflectance is a key parameter in satellite trace gas retrievals in the UV/visible range and in particular for the retrieval of nitrogen dioxide (NO2) vertical tropospheric columns (VTCs). Current operational retrievals rely on coarse-resolution reflectance data and do not account for the generally anisotropic properties of surface reflectance. Here we present a NO2 VTC retrieval that uses MODIS bi-directional reflectance distribution function (BRDF) data at high temporal (8 days) and spatial (1 km × 1 km) resolution in combination with the LIDORT radiative transfer model to account for the dependence of surface reflectance on viewing and illumination geometry. The method was applied to two years of NO2 observations from the Ozone Monitoring Instrument (OMI) over Europe. Due to its wide swath, OMI is particularly sensitive to BRDF effects. Using representative BRDF parameters for various land surfaces, we found that in July (low solar zenith angles) and November (high solar zenith angles) and for typical viewing geometries of OMI, differences between MODIS black-sky albedos and surface bi-directional reflectances are of the order of 0–10% and 0–40%, respectively, depending on the position of the OMI pixel within the swath. In the retrieval, black-sky albedo was treated as a Lambertian (isotropic) reflectance, while for BRDF effects we used the kernel-based approach in the MODIS BRDF product. Air Mass Factors were computed using the LIDORT radiative transfer model based on these surface reflectance conditions. Differences in NO2 VTCs based on the Lambertian and BRDF approaches were found to be of the order of 0–3% in July and 0–20% in November with the extreme values found at large viewing angles. The much larger differences in November are mainly due to stronger BRDF effects at higher solar zenith angles. To a smaller extent, they are also caused by the typically more pronounced maximum of the NO2 a priori profiles in the boundary layer during the cold season, which make the retrieval more sensitive to radiation changes near the surface. However, BRDF impacts vary considerably across Europe due to differences in land surface type and increasing solar zenith angles at higher latitude. Finally, we compare BRDF-based NO2 VTCs with those retrieved using the GOME/TOMS Lambertian equivalent reflectance (LER) data set. The relative differences are mostly below 15% in July but in November the NO2 VTCs from TOMS/GOME are lower by 20–60%. Our results indicate that the specific choice of albedo data set is even more important than accounting for surface BRDF effects, and this again demonstrates the strong requirement for more accurate surface reflectance data sets.

International audience; Hourly measurements of 13 volatile hydrocarbons (C2?C7) were performed at an urban background site in Zurich (Switzerland) in the years 1993?1994 and again in 2005?2006. Changes in hydrocarbon profiles and source strengths were recovered by positive matrix factorization (PMF). Eight and six factors could be related to hydrocarbon sources in 1993?1994 and in 2005?2006, respectively. The modeled source profiles were verified by hydrocarbon profiles reported in the literature. The source strengths were validated by independent measurements, such as inorganic trace gases (NOx, CO, SO2), methane (CH4), oxidized hydrocarbons (OVOCs) and meteorological data (temperature, wind speed etc.). Our analysis suggests that the contribution of most hydrocarbon sources (i.e. road traffic, solvents use, and wood burning) decreased by a factor of about two to three between the early 1990s and 2005?2006. On the other hand, hydrocarbon losses from natural gas leakage remained at relatively constant (?20%) concentration levels. The estimated emission trends are in line with the results from different top-down approaches reported for other European cities. Their discrepancies to national emission inventories are discussed.

International audience; Hourly measurements of 13 volatile hydrocarbons (C2?C7) were performed at an urban background site in Zurich (Switzerland) in the years 1993?1994 and again in 2005?2006. For the separation of the volatile organic compounds by gas-chromatography (GC), an identical chromatographic column was used in both campaigns. Changes in hydrocarbon profiles and source strengths were recovered by positive matrix factorization (PMF). Eight and six factors could be related to hydrocarbon sources in 1993?1994 and in 2005?2006, respectively. The modeled source profiles were verified by hydrocarbon profiles reported in the literature. The source strengths were validated by independent measurements, such as inorganic trace gases (NOx, CO, SO2), methane (CH4), oxidized hydrocarbons (OVOCs) and meteorological data (temperature, wind speed etc.). Our analysis suggests that the contribution of most hydrocarbon sources (i.e. road traffic, solvents use and wood burning) decreased by a factor of about two to three between the early 1990s and 2005?2006. On the other hand, hydrocarbon losses from natural gas leakage remained at relatively constant levels (?20%). The estimated emission trends are in line with the results from different receptor-based approaches reported for other European cities. Their differences to national emission inventories are discussed.

International audience; This study evaluates NO2 vertical tropospheric column densities (VTCs) retrieved from measurements of the Scanning Imaging Absorption Spectrometer for Atmospheric Chartography (SCIAMACHY) above Switzerland and the Alpine region. The close correlation between pixel averaged NOx emission rates from a spatially and temporally highly resolved inventory and the NO2 VTCs under anticyclonic meteorological conditions demonstrates the general ability of SCIAMACHY to detect sources of NOx pollution in Switzerland. This correlation is further used to infer seasonal mean NOx lifetimes carefully taking into account the influence of the strong diurnal cycle in NOx emissions on these estimates. Lifetimes are estimated to 3.6 (±0.8) hours in summer and 13.1 (±3.8) hours in winter, the winter value being somewhat lower than previous estimates. A comparison between the 2003-2005 mean NO2 VTC distribution over Switzerland and the corresponding 1996?2003 mean from the Global Ozone Monitoring Experiment (GOME) illustrates the much better capability of SCIAMACHY to resolve regional scale pollution features. However, the comparison of seasonal averages over the Swiss Plateau with GOME and ground based in situ observations indicates that SCIAMACHY exhibits a too weak seasonal cycle with comparatively high values in summer and low values in winter. A problem likely contributing to the reduced values in winter (not reported in earlier literature) is the use of inaccurate satellite pixel surface pressures derived from a coarse resolution global model in the retrieval. The marked topography in the Alpine region can lead to deviations of several hundred meters between the model assumed and the real pixel-averaged surface height. A sensitivity study based on selected clear sky SCIAMACHY NO2 VTCs over the Swiss Plateau and two fixed a priori NO2 profile shapes indicates that inaccurate pixel surface pressures affect retrieved NO2 columns over complex terrain by up to 40%. For retrievals in the UV-visible spectral range with a decreasing sensitivity towards the earth's surface, this effect is of major importance when the NO2 resides close to the ground, a situation most frequently observed during winter.

We derive a continuous time approximation of the evolutionary market selection model of Blume & Easley (1992). Conditions on the payoff structure of the assets are identified that guarantee convergence. We show that the continuous time approximation equals the solution of an integral equation in a random environment. For constant asset returns, the integral equation reduces to an autonomous ordinary differential equation. We analyze its long-run asymptotic behavior using techniques related to Lyapunov functions, and compare our results to the benchmark of profit-maximizing investors.

This paper considers the effect of least squares procedures for nearly unstable linear time series with strongly dependent innovations. Under a general framework and appropriate scaling, it is shown that ordinary least squares procedures converge to functionals of fractional Ornstein-Uhlenbeck processes. We use fractional integrated noise as an example to illustrate the important ideas. In this case, the functionals bear only formal analogy to those in the classical framework with uncorrelated innovations, with Wiener processes being replaced by fractional Brownian motions. It is also shown that limit theorems for the functionals involve nonstandard scaling and nonstandard limiting distributions. Results of this paper shed light on the asymptotic behavior of nearly unstable long-memory processes.

We introduce a class of stochastic differential equations driven by fractional Brownian motion (FBM), which allow for a constructive method in order to obtain stationary solutions. This leads to a substantial extention of fractional Ornstein-Uhlenbeck processes. Structural properties of this class of new models are investigated. Their stationary densities are given explicitly.