Using Rock‐Eval 6 pyrolysis for tracking fossil organic carbon in modern environments: implications for the roles of erosion and weathering

This work relates to the debate on the fossil organic carbon (FOC) input in modern environments and its possible implication for the carbon cycle, and suggests the use of Rock‐Eval 6 pyrolysis as a relevant tool for tracking FOC in such environments. Considering that such a delivery is mainly due to supergene processes affecting the continental surface, we studied organic matter in different reservoirs such as bedrocks, alterites, soils and rivers in two experimental catchments at Draix (Alpes de Haute Provence, France). Samples were subjected to geochemical (Rock‐Eval 6 pyrolysis) investigations and artificial bacterial degradations. After comparing the geochemical fingerprint of samples, geochemical markers of FOC were defined and tracked in the different reservoirs. Our results confirm the contribution of FOC in modern soils and rivers and display the various influences of weathering and erosional processes on the fate of FOC during its exchange between these pools. In addition, the contrasting behaviour of these markers upon the supergene processes has also highlighted the refractory or labile characters of the fossil organic matter (FOM). Bedrock to river fluxes, controlled by gully erosion, are characterized by a qualitative and quantitative preservation of FOM. Bedrock to alterite fluxes, governed by chemical weathering, are characterized by FOC mineralization without qualitative changes in deeper alterites. Alterite to soils fluxes, controlled by (bio)chemical weathering, are characterized by strong FOC mineralization and qualitative changes of FOM. Thus weathering and erosional processes induce different FOM evolution and affect the fate of FOC towards the global carbon cycle. In this study, gully erosion would involve maintenance of an ancient sink for the global carbon cycle, while (bio)chemical processes provide a source of CO₂. Finally, this study suggests that Rock‐Eval 6 pyrolysis can be considered as a relevant tool for tracking FOC in modern environments. Copyright © 2006 John Wiley & Sons, Ltd.     

Carbon Capture and Storage From Fossil Fuels and Biomass – Costs and Potential Role in Stabilizing the Atmosphere

The capture and storage of CO₂ from combustion of fossil fuels is gaining attraction as a means to deal with climate change. CO₂ emissions from biomass conversion processes can also be captured. If that is done, biomass energy with CO₂ capture and storage (BECS) would become a technology that removes CO₂ from the atmosphere and at the same time deliver CO₂-neutral energy carriers (heat, electricity or hydrogen) to society. Here we present estimates of the costs and conversion efficiency of electricity, hydrogen and heat generation from fossil fuels and biomass with CO₂ capture and storage. We then insert these technology characteristics into a global energy and transportation model (GET 5.0), and calculate costs of stabilizing atmospheric CO₂ concentration at 350 and 450 ppm. We find that carbon capture and storage technologies applied to fossil fuels have the potential to reduce the cost of meeting the 350 ppm stabilisation targets by 50% compared to a case where these technologies are not available and by 80% when BECS is allowed. For the 450 ppm scenario, the reduction in costs is 40 and 42%, respectively. Thus, the difference in costs between cases where BECS technologies are allowed and where they are not is marginal for the 450 ppm stabilization target. It is for very low stabilization targets that negative emissions become warranted, and this makes BECS more valuable than in cases with higher stabilization targets. Systematic and stochastic sensitivity analysis is performed. Finally, BECS opens up the possibility to remove CO₂ from the atmosphere. But this option should not be seen as an argument in favour of doing nothing about the climate problem now and then switching on this technology if climate change turns out to be a significant problem. It is not likely that BECS can be initiated sufficiently rapidly at a sufficient scale to follow this path to avoiding abrupt and serious climate changes if that would happen.     

X-Ray Emission from Comet McNaught-Hartley (C/1999 T1)

Comet McNaught-Hartley was observed in five 1-h exposures on January 8-14 2001 using the advanced CCD imaging spectrometer on board the Chandra X-ray Observatory. The X-ray image of the comet does not show a crescent-like shape. The brightest region is offset from the nucleus between the sunward and comet velocity directions. The comet mean X-ray luminosity is equal to 7.8×10¹⁵ erg s⁻¹ for photon energy E>150 eV and aperture ρ=1.5×10⁵ km where the comet X-ray brightness exceeds 20% of the peak value. Gas production rate was 10²⁹ s⁻¹ during the observations, and the efficiency of X-ray excitation was equal to 4×10⁻¹⁴ erg AU^3/2. Day-to-day variations in X-rays reached a factor of 5. The strongest short-term variation was by a factor of 1.75 for 1600 s. This variation may be explained by a decline in the solar-wind flux by the same factor in ≈800 s. The comet and Earth were seeing different faces of the Sun, and time delay in the solar-wind events on the Earth and the comet was long, equal to 6 days. The best correlation between the comet X-ray luminosity and the solar-wind proton density is for the time delay of 5.5 days and may be explained by the higher velocity of heavy ions.Careful background subtraction made it possible to extract the comet spectrum from 150 to 1000 eV. No signal was detected at E>1000 eV, and a 3σ upper limit to any emission with E>1000 eV is 0.3% of the photon emission at 150-1000 eV. The best χ²-fit model to the spectrum consists of nine narrow emission features. The emission energies and intensities are in good agreement with a charge exchange spectrum calculated by us for the slow solar wind. Using this spectrum, we identify the observed emissions as (Ne⁷⁺+Mg⁷⁺+Mg⁸⁺) at 195 eV, (Mg⁸⁺+Mg⁹⁺+Si⁸⁺) at 250 eV, C⁵⁺ at 370 and 460 eV, O⁶⁺ at 560 eV, O⁷⁺ at 650, 780, and 840 eV, and Ne⁸⁺ at 940 eV. X-ray spectroscopy of comets may be used to diagnose the solar-wind composition and its interaction with comets.     

Environmental changes in an alpine lake (Gossenköllesee, austria) over the last two centuries – the influence of air temperature on biological parameters

Changes in microfossils (diatoms, chrysophytes, chironomids and cladocera remains), geochemistry and deposition of atmospheric pollutants have been investigated in the sediment records of the alpine lake Gossenköllesee (Tyrol, Austria) spanning the last two centuries. The sediment records were compared with seasonal and annual air temperature trends calculated for the elevation (2417 m a.s.l.) and the geographical position (47° 1346N, 11° 0051E) of the lake, and with precipitation records available since 1866 from Innsbruck. Temperature trends followed a 20–30 year oscillation between cold and warm periods. Regarding long-term changes, temperature trends showed a U-shaped trend between 1780 and 1950, followed by a steep increase since 1975.Physical, geochemical, and organic parameters were not controlled by air temperature. Among the biological records only diatoms and chrysophytes reacted to air temperature changes: the relative abundance of planktonic diatoms increased during warm periods and changes in mean annual alpine air temperature explained 36.5% of their variation. The relation between abundance of seasonal stomatocyst types and air temperature varied on two different time scales: while summer stomatocysts were influenced by short term temperature fluctuations, the autumn stomatocysts were affected only by the long term changes. Other biological parameters exhibited a constant species composition (chironomids, pigments) or changes were small and independent of temperature (cladocera). Spheroidal carbonaceous fly-ash particles, and trends in Pb and Cr indicated increasing deposition of atmospheric pollutants but had no detectable effects on the biological parameters either. In respect to temperature variations over the last 200 years, this alpine lake is much less sensitive than expected and has thus to be regarded as a well buffered site. However, temperature alone is not sufficient to understand changes in species composition and other biogeochemical processes with unknown historical patterns might have affected species composition more strongly.     

POPCORN: A Field Study of Photochemistry in North-Eastern Germany

The intensive field study POPCORN (Photo-Oxidant Formation by Plant Emitted Compounds and OH Radicals in North-Eastern Germany) was carried out in a rural area of North-Eastern Germany during August 1994. An overview of the objectives, measurements and major results of this campaign is presented. Measurements of a set of relevant atmospheric trace compounds, including the hydroxyl radical, along with meteorological data were performed to increase the understanding of OH radical chemistry and photo-oxidant formation. Additionally, plant emissions and the exchange of trace gases between a maize field and the atmosphere were investigated. Budgets of selected trace gases were calculated to assess the relative importance of local sources, chemistry or transport. Intercomparisons between measurement techniques were a central issue of POPCORN and included measurements of OH, hydrocarbons, formaldehyde, photolysis frequencies and vertical fluxes. OH radical concentrations were measured simultaneously by LIF (Laser Induced Fluorescence) and DOAS (Differential Optical Absorption Spectroscopy). Both methods showed good agreement. Maximum OH concentrations were around 107 cm–3 and the diurnal cycles closely followed the rate of primary production via ozone photolysis. Generally, the trace gas composition during POPCORN was characterized by relatively low concentrations of most compounds, e.g. CO: 85–200 ppb, ethane: 0.6–2 ppb, and moderate NOx levels: 0.5–5 ppb (at noontime). Concentrations of individual biogenic volatile organic compounds (VOC) were mostly well below 100 ppt. However, formaldehyde and acetaldehyde which partly originate from biological sources were observed at mixing ratios of some ppb.     

Meteorological Aspects, Ozone, and Solar Radiation Measurements During POPCORN 1994

Meteorological data, ozone mixing ratios, and photolysis frequencies for the period August 2 to August 24, 1994, are presented and discussed in support of the field campaign POPCORN (Photochemistry of Plant Emitted Compounds and OH Radicals in Northeastern Germany). Measurements of temperature, ozone, and wind speed at different heights are used to evaluate micro-meteorological parameters. The observations provide information about local influences on the air mass composition. The analysis of radio sonde data of nearby stations provides the height of the planetary boundary layer.     

Leimavo Revisited: Agrarian Land-Use Change in the Highlands of Madagascar

Describing and explaining land-use change is of critical concern in Madagascar, where land transformations such as deforestation and resulting environmental degradation currently capture widespread attention. While the eastern rain forest recedes in the face of swidden cultivators, the highlands demonstrate more constructive transformations. In this paper I present a case study of land-use change in Leimavo, a small village near Ambositra studied in the 1960s by Jean-Pierre Raison. Here, the twentieth century has seen a gradual reduction in irrigated rice cultivation and cattle husbandry, and a boom in market-oriented orange, vegetable, and grain production. In the long term, a historical landscape of grassy hills has been transformed into a productive cultural landscape with woodlots, anti-erosion benching, rice terraces, fruit groves, and diverse crops. Critical factors determining the trajectory of land-use change include regional population pressure, state policies, market incentives, climate variations, and access to land and water resources. These critical factors, or explanations, are linked in the discussion by the use of a simple heuristic device—the range of choice—as a theoretical framework.     

Nutrients limiting the algal growth potential (AGP) in the Po River plume and an adjacent area, Northwest Adriatic Sea: Enrichment bioassays with the test algaeNitzschia closterium andThalassiosira pseudonana

From April 1993 to March 1994, 135 samples were collected at two sites in the coastal Adriatic Sea, both near (14.5 km) and far (63 km) from the Po River delta. The nutrient(s) limiting algal growth potential (AGP) were estimated by bioassay usingNitzshia closterium (local isolate) andThalassiosira pseudonama (strain 3-H). Estimates were also made by comparing the nutrient molar ratios, ΣN:P and ΣN:Si (whereΣN=NO₃ ^?+NO₂ ^?+NH₄ ⁺+urea), to the Redfield Ratio (16∶1, 1∶1). According to the bioassay results, phosphorus was the sole nutrient limiting AGP in 2% of the samples and was the most limiting nutrient in 69% of the samples; nitrogen was sole limiting nutrient in 18% of the samples. In 11% of samples, nitrogen and phosphorus were equally co-limiting. Omission of phosphorus from spike enrichments allowed, on average, only a 1.6-fold increase in biomass over that in the unenriched controls. Similar omission of nitrogen allowed a 4-fold increase, while silicon, iron, and micronutrients resulted in 14-fold, 18-fold, and >20-fold increases, respectively. In most of the samples, ΣN:P was much greater than 16, indicating a marked phosphorus deficiency, while ΣN:Si values suggested that silicon was the third most limiting nutrient in 35% of samples. In water collected for from the Po delta, the yield ofN. closterium was not limited by any nutrients other than the three major ones: P, N and Si. In these same waters,T. pseudonana was also potentially limited by iron and, to a lesser extent, by vitamins. The role of iron varied. In samples collected near the Po delta, iron acted as the third most limiting nutrient forN. closterium in June and September; it appeared 29 times out of 78 on the list of potentially limiting nutrients forT. pseudonana, including 5 times as the most limiting. Altogether, comparison with published results suggests that the roles of iron and silicon in AGP limitation have increased during the past three decades, and could become even more important if eutrophication in the Adriatic Sea continues to increase.     

Carbonyls and nonmethane hydrocarbons at rural European sites from the mediterranean to the arctic

Results of regular measurements during 1992–1995 of hydrocarbons and carbonyl compounds for a number of rural European monitoring sites are presented. The measurements are part of the EMEP programme for VOC measurements in Europe. In addition, several years of regular measurements are included from the Norwegian stations Birkenes at the south coast, and Zeppelin Mountain on Spitsbergen in the Arctic. The sampling frequency has been about twice per week throughout the years, implying that a substantial amount of measurement data are available. Almost all the chemical analyses have been performed by one laboratory, the EMEP Chemical Co-ordinating Centre located at NILU, which avoids problems of intercomparison and intercalibration among different laboratories. For the measured concentrations both seasonal and geographical variations are shown and discussed. The diurnal cycles of the hydrocarbon concentrations were studied in detail at one site, where the grab samples by EMEP where compared with a parallel continuous sampler, operated by EMPA, Switzerland. Hydrocarbons linked to natural gas and fuel evaporation become well mixed into the Arctic in the winter, whereas combustion products show a latitudinal gradient. The sum of oxygenated species constitutes about 5–15% of the sum of C₂–C₅ hydrocarbons in winter. In summer they are almost equal in magnitude, consistent with an increasing oxidation of hydrocarbons.