Laboratory study of the rates and products of the phototransformations of naphthalene adsorbed on samples of titanium dioxide,ferric oxide,muscovite, and fly ash

The photodegradation of naphthalene (NPH), chosen as a model of polynuclear aromatic pollutants, has been studied in the presence of a layer of four water-insoluble inorganic solids which can be found in the troposphere (TiO₂, Fe₂O₃, muscovite, and a fly ash sample). Direct photolysis of NPH is negligible at >340 nm. Dark adsorption of NPH on TiO₂ (mainly anatase, nonporous, 50 m² g^–1) at 293 K corresponds to a surface coverage ofca. 50% at equilibrium. Under these conditions (saturated surface), the stationary-state photocatalytic degradation reaches 0.4 molecule nm^–2 h^–1 (>340 nm, radiant fluxca. 22 mW cm^–2). Dioxygen is required and its partial pressure in air is such that the degradation is zero order in O₂. Water vapor markedly increases the rate. The other particulates have also an effect, less important than that of TiO₂, however quite noticeable with respect to surface area unit for the fly ash sample which contains 3.2% Fe₂O₃. Apart from 1,4-naphthoquinone, which is the main intermediate product in all cases, 2-naphthol, phthalide, phthaldialdehyde, phthalic acid, acetophenone, benzaldehyde, benzoic acid are also formed on dry TiO₂. Depending on their volatility, these compounds are transferred to the gas phase or remain principally adsorbed on the solid particles where they are further transformed. For instance, phthalic acid (or anhydride) and benzoic acid are generated from 1,4-naphthoquinone. Degradation mechanisms are briefly discussed.     

Geoarchaeological Investigations in Mesoamerica Move into the 21st Century: A Review

Over the past thirty years, geoarchaeology has moved from the fringe to mainstream status within Mesoamerican archaeological investigations. This review focuses on works published since the year 2000. Five themes are identified as central to recent studies: (1) the correlation of environmental change and cultural history; (2) anthropogenic environmental impacts; (3) ancient land cover, land use, and diet; (4) archaeological prospection; and (5) provenance studies. These themes are often interwoven in the application of complex systems approaches that allow scientists to more accurately model the intricacies of ancient human–environment interactions.     

Abrupt climate change as an important agent of ecological change in the Northeast U.S. throughout the past 15,000 years

We use a series of tests to evaluate two competing hypotheses about the association of climate and vegetation trends in the northeastern United States over the past 15 kyrs. First, that abrupt climate changes on the scale of centuries had little influence on long-term vegetation trends, and second, that abrupt climate changes interacted with slower climate trends to determine the regional sequence of vegetation phases. Our results support the second. Large dissimilarity between temporally close fossil pollen samples indicates large vegetation changes within 500 years across >4° of latitude at ca 13.25–12.75, 12.0–11.5, 10.5, 8.25, and 5.25 ka. The evidence of vegetation change coincides with independent isotopic and sedimentary indicators of rapid shifts in temperature and moisture balance. In several cases, abrupt changes reversed long-term vegetation trends, such as when spruce (Picea) and pine (Pinus) pollen percentages rapidly declined to the north and increased to the south at ca 13.25–12.75 and 8.25 ka respectively. Abrupt events accelerated other long-term trends, such as a regional increase in beech (Fagus) pollen percentages at 8.5–8.0 ka. The regional hemlock (Tsuga) decline at ca 5.25 ka is unique among the abrupt events, and may have been induced by high climatic variability (i.e., repeated severe droughts from 5.7 to 2.0 ka); autoregressive ecological and evolutionary processes could have maintained low hemlock abundance until ca 2.0 ka. Delayed increases in chestnut (Castanea) pollen abundance after 5.8 and 2.5 ka also illustrate the potential for multi-century climate variability to influence species' recruitment as well as mortality. Future climate changes will probably also rapidly initiate persistent vegetation change, particularly by acting as broad, regional-scale disturbances.     

Biogeochemical and hydrographic controls on chromophoric dissolved organic matter distribution in the Pacific Ocean

Recent in situ observations of chromophoric dissolved organic material (CDOM) in the Pacific Ocean reveal the biogeochemical controls on CDOM and indicate predictive potential for open-ocean CDOM in diagnosing particulate organic matter (POM) remineralization rates within ocean basins. Relationships between CDOM and concentrations of dissolved oxygen, nutrients and inorganic carbon in the subthermocline waters of the Pacific reflect the relative influences of water mass ventilation and water-column oxidative remineralization. Apparent in situ oxygen utilization (AOU) accounts for 86% and 61% of variance in CDOM abundance, respectively, in Antarctic Intermediate Water and North Pacific Intermediate Water. In the deep waters of the Pacific below the zone of remineralization, AOU explains 26% of CDOM variability. The AOU–CDOM relationship results from competing biogeochemical and advective processes within the ocean interior. Dissolved organic carbon (DOC) is not statistically linked to the CDOM or AOU distributions, indicating that the majority of CDOM production occurs during the remineralization of sinking POM and thus potentially provides key information about carbon export. Once formed in the ocean interior, CDOM is relatively stable until it reaches the surface ocean where it is destroyed by solar bleaching. Susceptibility to bleaching confers an additional tracer-like quality for CDOM in water masses with active convection, such as mode waters that appear as subsurface CDOM minima. In the surface ocean, atypically low CDOM abundance highlights a region of unusually extreme oligotrophy: the subtropical South Pacific gyre. For these hyper-oligotrophic waters, the present CDOM observations are consistent with analysis of in situ radiometric observations of light attenuation and reflectance, demonstrating the accuracy of the CDOM spectrophotometric observations. Overall, we illustrate how CDOM abundance in the ocean interior can potentially diagnose rates of thermohaline overturning as they affect regional biogeochemistry and export. We further show how relative surface ocean CDOM abundances are driven in large part by processes occurring in the deep layers of the ocean. This is particularly significant for the interpretation of the global surface distribution of CDOM using satellite remote sensing.     

Laser Ablation (U-Th-Sm)/He Dating of Zircons: Analytical Age Bias and its Consequence for Studying Detrital Zircon Populations

The in situ (U-Th-Sm)/He and U/Pb laser-ablation double-dating procedure is a valuable method that can provide a large dataset relatively efficiently in contrast with conventional bulk helium thermochronometry. In this study, we evaluate the potential age error associated with the double ablation procedure and report the in situ (U-Th-Sm)/He double-ablation dating of 249 zircons from the Fish Canyon Tuff locality. With LA-ICP-MS pseudo-depth profiling and 3D numerical modelling, we show that the concentric double-ablation procedure in minerals with U-Th-Sm zoning can generate a significant (U-Th-Sm)/He age error (positive or negative), resulting in over-scattering and/or an offset of the mean age. Pseudo-depth profiling is insufficient to predict the individual age error, partly because of the superimposed ablations. To evaluate the consequence of this inherent bias, we confront a synthetic age distribution to the error expected for U-Th-Sm zoned zircons analysed with double-ablation (U-Th-Sm)/He thermochronometry. As expected, a strong age bias causes the spreading of peak ages, downgrading the original signal. Yet, the throughput of the ablation-based method can allow intra- and inter-sample peak age identification and comparison, and the coupling of (U-Th-Sm)/He and U/Pb ages extends our ability to deconvolute a multimodal age spectrum.     

Extreme ultraviolet flashes of solar flares observed via sudden frequency deviations: Experimental results

Properties of solar-flare EUV flashes measured via a type of ionospheric event, called a sudden frequency deviation (SFD), are presented. SFD's are sensitive to bursts of radiation in the 1–1030 Å wavelength range. He ii 303.8 Å, O v 629.7 Å, HL 972.5 Å and C iii 977.0 Å have essentially the same impulsive time dependence as the 1–1030 Å flash responsible for SFD's. Soft X-rays (2–20 Å) and certain EUV lines have a much slower time dependence than the 1–1030 Å flash. Most SFD's have some fine structure, but marked quasi-periodicity in EUV flashes is quite rare. EUV flashes are closely associated with hard X-ray bursts, white-light emission, microwave radio bursts and small bright impulsive kernels in the H flare. The intensity of EUV flashes depends on the central meridian distance of the H flare location; the intensity decreases at the limb. The total energy radiated in the 10–1030 Å flash for the largest events observed is about 10³¹ ergs.     

Détermination indirecte des limites d'Atterberg par gravimétrie dynamique

This study presents a new method for Atterberg limits measurements using dynamic drying. Indeed, for some polluted clays, or clay mixtures, classical methods cannot be used. The principle of liquid $(W_{\mathrm{L}})$ and plasticity $(W_{\mathrm{P}})$ limits determination by this method is presented. Experimental values for classical clays are close to those obtained with Casagrande's methods, allowing for larger physical mud characterisation. To cite this article: C. Proust et al., C. R. Geoscience 336 (2004).