The solar spectral irradiance and its action in the atmospheric photodissociation processes

A critical analysis has been made of solar irradiance in the spectral region covering wavelengths from 100 nm upwards; the absorption characteristics of molecules of oxygen and ozone have been taken into account with a view to the direct application of the results to atmospheric photochemistry. The absorption of radiation by these molecules results in the photodissociation of both of them in the homosphere, and it also makes possible the penetration of solar radiation from the thermosphere, through the mesosphere and the stratosphere, down to the troposphere.Special attention has been given to each of the following spectral regions: Lyman-alpha radiation at 121.6 nm, the O₂ Schumann-Runge continuum at wavelengths less than 175 nm, the O₂ Schumann-Runge band system from 200 to 175 nm, and the O₂ Herzberg continuum at 242.4 nm. For absorption by ozone, the solar spectrum has been analysed in the following regions: the Hartley band at wavelengths less than 310 nm, the Huggins bands at wavelengths above 310 nm and the visible Chappuis bands. Finally, for the photodissociation of O₃, particular attention has been given to the transition region (300–320 nm) in which there is a change-over from the production of the excited atom O(¹D) to that of the atom in its ground state O(³p).     

Tracing of variabilities within a geological barrier by molecular organic geochemistry.: Case of the Callovo-Oxfordian sedimentary series in the East of the Paris Basin (France)

The Callovo-Oxfordian claystones located at 500 m depth at Bure (Meuse, France) are currently being investigated by Andra (the French National Radioactive Waste Management Agency) for testing the feasibility of long-term and deep geological nuclear waste disposal. In order to evaluate its potential as a geological barrier, it is very important to study, assess and describe its physico-chemical variability. The molecular biomarker composition of 150 samples of these claystones and their surrounding limestones carry diverse information on the sources of the sedimentary organic matter, the chemistry of the depositional environment, the preservation and diagenesis conditions. It also allows assessing the degree of lateral and vertical variability of the organic matter within these sedimentary series. The abundance of unsaturated biomarkers, the distribution of steroids and hopanoids and CPI values >2 prove the thermal immaturity of the organic matter. The co-occurrence of plankton, bacteria and land plant biomarkers indicate that the organic matter is a mixture of marine and continental contributions. The data also reveal that the organic matter was deposited under oxic and open-sea conditions except for a brief event of photic zone anoxia at the beginning of the Middle Callovian. In the claystones, the geosynthesis of diasterenes is favored to the detriment of the formation of steranes, especially in smectite-rich levels, and the organic matter is rapidly isolated from oxidizing then reducing conditions after the deposition due to the protective effect of clays. On the scale investigated, the claystones are characterized by a unique molecular facies and are thus homogenous from their organic content point of view. Yet, detailed investigation of specific molecular families indicates changes related to major claystone–limestone transitions. The homogeneity of these claystones can be explained by the paleogeographic position of their depositional setting and the plane and sub-horizontal paleotopography on which they were deposited. This study demonstrates the efficiency of organic geochemistry in the assessment of the variability of geological barriers.     

Laboratory sulfurisation of the marine microalga Nannochloropsis salina

To understand more fully the mode of preservation of organic matter in marine sediments, laboratory sulfurisation of intact cells of the cultured microalga Nannochloropsis salina was performed using inorganic polysulfides in seawater at 50°C. Solvent extractable and non-extractable materials were analysed by GC–MS and Py–GC–MS, respectively, to study the incorporation of sulfur into the microalgal organic matter. No GC-amenable sulfur-containing compounds were found in the extracts apart from some minor thiophenes with a phytanyl carbon skeleton. The residue after extraction and hydrolysis contained abundant macromolecular sulfur-containing moieties as revealed by the presence of dominant C₂₈–C₃₂ thiols, thiophenes, thianes and thiolanes in the flash pyrolysates. These products are thought to be formed from moieties derived from sulfurisation of C₂₈–C₃₂ diols and alkenols, characteristic lipids of N. salina. C₁–C₂ alkylated thiophenes were also found in the pyrolysates and probably result from moieties formed upon sulfurisation of carbohydrates. The highly resistant biomacromolecule (algaenan) synthesised by N. salina remains unaffected by sulfurisation. The non-hydrolysable residue isolated from the sulfurised N. salina thus comprises algaenan and (poly)sulfide-bound long alkyl chains. The sulfurisation experiments show that both selective preservation of algaenans and lipid and carbohydrate “vulcanisation” can be involved in the preservation of algal organic matter in marine environments.     

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Changes in stream water quality due to logging of the boreal forest in the Montmorency Forest,Québec

Summer stream water quality was monitored before and following the logging of 50% of the boreal forest within three small watersheds (<50 ha) nested in the ‘Ruisseau des Eaux‐Volées’ Experimental Watershed, Montmorency Forest (Québec, Canada). Logging was conducted in winter, on snow cover according to recommended best management practices (BMPs) to minimize soil disturbance and protect advance growth. A 20‐m forest buffer was maintained along perennial streams. In watershed 7·2, cut‐blocks were located near the stream network and logging was partially allowed within the riparian buffer zone. In watersheds 7·5 and 7·7, logging occurred farther away from the stream network. Observations were also made for watershed 7·3 that collected the runoff from watersheds 7·2 and 7·5, and watershed 7·6, the uproad portion of watershed 7·7. The control watershed 0·2 was contiguous to the impacted watersheds and remained undisturbed. Following clearcutting, changes in summer daily maximum and minimum stream temperatures remained within ± 1 °C while changes in diurnal variation did not decrease by more than 0·5 °C. Concentrations of NO₃^? greatly increased by up to 6000% and concentrations of K⁺ increased by up to 300% during the second summer after logging. Smaller increases were observed for Fe_total (up to 71%), specific conductance (up to 26%), and Mg²⁺ (up to 19%). Post‐logging pH decreased slightly by no more than 7% while PO₄^3? concentration remained relatively constant. Suspended sediment concentrations appeared to increase during post‐logging, but there was not enough pre‐logging data to statistically confirm this result. Logging of moderate intensity and respecting established BMPs may account for the limited changes of water quality parameters and the low exceedances of the criteria for the protection of aquatic life. The proximity of the cutover to the stream network and logging within the riparian zone did not appear to affect water quality. Copyright © 2008 John Wiley & Sons, Ltd.     

Analysis of Cassini/CIRS limb spectra of Titan acquired during the nominal mission II: Aerosol extinction profiles in the 600–1420 cm spectral range

We have analyzed the continuum emission of limb spectra acquired by the Cassini/CIRS infrared spectrometer in order to derive information on haze extinction in the 3–0.02 mbar range (∼150–350 km). We focused on the 600–1420 cm⁻¹ spectral range and studied nine different limb observations acquired during the Cassini nominal mission at 55°S, 20°S, 5°N, 30°N, 40°N, 45°N, 55°N, 70°N and 80°N. By means of an inversion algorithm solving the radiative transfer equation, we derived the vertical profiles of haze extinction coefficients from 17 spectral ranges of 20-cm⁻¹ wide at each of the nine latitudes. At a given latitude, all extinction vertical profiles retrieved from various spectral intervals between 600 and 1120 cm⁻¹ display similar vertical slopes implying similar spectral characteristics of the material at all altitudes. We calculated a mean vertical extinction profile for each latitude and derived the ratio of the haze scale height (H_haze) to the pressure scale height (H_gas) as a function of altitude. We inferred H_haze/H_gas values varying from 0.8 to 2.4. The aerosol scale height varies with altitude and also with latitude. Overall, the haze extinction does not show strong latitudinal variations but, at 1 mbar, an increase by a factor of 1.5 is observed at the north pole compared to high southern latitudes. The vertical optical depths at 0.5 and 1.7 mbar increase from 55°S to 5°N, remain constant between 5°N and 30°N and display little variation at higher latitudes, except the presence of a slight local maximum at 45°N. The spectral dependence of the haze vertical optical depth is uniform with latitude and displays three main spectral features centered at 630 cm⁻¹, 745 cm⁻¹ and 1390 cm⁻¹, the latter showing a wide tail extending down to ∼1000 cm⁻¹. From 600 to 750 cm⁻¹, the optical depth increases by a factor of 3 in contrast with the absorbance of laboratory tholins, which is generally constant. We derived the mass mixing ratio profiles of haze at the nine latitudes. Below the 0.4-mbar level all mass mixing ratio profiles increase with height. Above this pressure level, the profiles at 40°N, 45°N, 55°N, at the edge of the polar vortex, display a decrease-with-height whereas the other profiles increase. The global increase with height of the haze mass mixing ratio suggest a source at high altitudes and a sink at low altitudes. An enrichment of haze is observed at 0.1 mbar around the equator, which could be due to a more efficient photochemistry because of the strongest insolation there or an accumulation of haze due to a balance between sedimentation and upward vertical drag.     

Relative chronology of crust formation on asteroid Vesta: Insights from the geochemistry of diogenites

The eucrites and diogenites are meteorites that probably originate from asteroid 4-Vesta. The upper part of the crust of this body is certainly composed of eucrites which are basaltic or gabbroic rocks. Diogenites are ultramafic cumulates whose relationships with eucritic lithologies are unknown. Here, we show that the orthopyroxenes of some diogenites display very deep negative Eu anomalies (Eu/Eu∗ close to 0.1 or lower). The contamination of the parental magmas of diogenites by melts derived by partial melting of the eucritic crust can satisfactorily explain the range of the Eu anomalies displayed by diogenites. Thus, these anomalies are the first firm indication that parental melts of diogenites have intruded the eucritic crust, and consequently are younger than eucrites.     

Enhancing the relevance of Shared Socioeconomic Pathways for climate change impacts,adaptation and vulnerability research

This paper discusses the role and relevance of the shared socioeconomic pathways (SSPs) and the new scenarios that combine SSPs with representative concentration pathways (RCPs) for climate change impacts, adaptation, and vulnerability (IAV) research. It first provides an overview of uses of social–environmental scenarios in IAV studies and identifies the main shortcomings of earlier such scenarios. Second, the paper elaborates on two aspects of the SSPs and new scenarios that would improve their usefulness for IAV studies compared to earlier scenario sets: (i) enhancing their applicability while retaining coherence across spatial scales, and (ii) adding indicators of importance for projecting vulnerability. The paper therefore presents an agenda for future research, recommending that SSPs incorporate not only the standard variables of population and gross domestic product, but also indicators such as income distribution, spatial population, human health and governance.     

Oxygen compounds in Titan's stratosphere as observed by Cassini CIRS

We have investigated the abundances of Titan's stratospheric oxygen compounds using 0.5 cm⁻¹ resolution spectra from the Composite Infrared Spectrometer on the Cassini orbiter. The CO abundance was derived for several observations of far-infrared nadir spectra, taken at a range of latitudes (75° S-35° N) and emission angles (0°-60°), using rotational lines that have not been analysed before the arrival of Cassini at Saturn. The derived volume mixing ratios for the different observations are mutually consistent regardless of latitude. The weighted mean CO volume mixing ratio is 47±8 ppm if CO is assumed to be uniform with latitude. H₂O could not be detected and an upper limit of 0.9 ppb was determined. CO₂ abundances derived from mid-infrared nadir spectra show no significant latitudinal variations, with typical values of 16±2 ppb. Mid-infrared limb spectra at 55° S were used to constrain the vertical profile of CO₂ for the first time. A vertical CO₂ profile that is constant above the condensation level at a volume mixing ratio of 15 ppb reproduces the limb spectra very well below 200 km. This is consistent with the long chemical lifetime of CO₂ in Titan's stratosphere. Above 200 km the CO₂ volume mixing ratio is not well constrained and an increase with altitude cannot be ruled out there.