Global maps of soil temperature.

Research in global change ecology relies heavily on global climatic grids derived from estimates of air temperature in open areas at around 2 m above the ground. These climatic grids do not reflect conditions below vegetation canopies and near the ground surface, where critical ecosystem functions occur and most terrestrial species reside. Here, we provide global maps of soil temperature and bioclimatic variables at a 1-km <sup>2</sup> resolution for 0-5 and 5-15 cm soil depth. These maps were created by calculating the difference (i.e. offset) between in situ soil temperature measurements, based on time series from over 1200 1-km <sup>2</sup> pixels (summarized from 8519 unique temperature sensors) across all the world's major terrestrial biomes, and coarse-grained air temperature estimates from ERA5-Land (an atmospheric reanalysis by the European Centre for Medium-Range Weather Forecasts). We show that mean annual soil temperature differs markedly from the corresponding gridded air temperature, by up to 10°C (mean = 3.0 ± 2.1°C), with substantial variation across biomes and seasons. Over the year, soils in cold and/or dry biomes are substantially warmer (+3.6 ± 2.3°C) than gridded air temperature, whereas soils in warm and humid environments are on average slightly cooler (-0.7 ± 2.3°C). The observed substantial and biome-specific offsets emphasize that the projected impacts of climate and climate change on near-surface biodiversity and ecosystem functioning are inaccurately assessed when air rather than soil temperature is used, especially in cold environments. The global soil-related bioclimatic variables provided here are an important step forward for any application in ecology and related disciplines. Nevertheless, we highlight the need to fill remaining geographic gaps by collecting more in situ measurements of microclimate conditions to further enhance the spatiotemporal resolution of global soil temperature products for ecological applications

Site And Stereoselectivity Of The Cyclopropanation Of Unsymmetrically Substituted 1,3-dienes By The Simmons-smith Reaction

In the Simmons-Smith reaction, 1,3-dienes are preferentially cyclopropanated at the more electron-rich double bond to afford the trans-vinylcyclopropane; an allylic hydroxyl group increases the reactivity and directs the cyclopropanation to the adjacent double bond.26917931800Simmons, H.E., Cairns, T.L., Vladuchick, S.A., Hoiness, C.M., (1973) Organic Reactions, 20, pp. 1-131. , W. G. Dauben (ed.), John Wiley & Sons, New YorkSchuchardt, U., Nery, J.H.S., Zuiani, M.A., (1991) J. Braz. Chem. Soc., 2, p. 61C. A., 118, pp. 191206jJorgenson, M.J., Leung, T., (1968) J. Am. Chem. Soc., 90, p. 3769Büchel, K.H., Korte, F., (1962) Z. Naturforsch, 17 B, p. 349Overberger, C.G., Halek, G.W., (1963) J. Org. Chem., 28, p. 867Grzybowska, B., Konox, J.H., Trotman-Dickensons, A.F., (1961) J. Chem. Soc., p. 4402Doyle, M.P., (1986) Catalysis of Organic Reactions, p. 47. , R. L. Augustine (ed.), Marcel Dekker, Inc., New YorkLaurent, H., Müller, H., Wiechert, R., (1966) Chem. Ber., 99, p. 3836Bertrand, M., Maurin, R., (1967) Bull. Soc. Chim. Fr., p. 3549Corey, E.J., Yamamoto, H., Herron, D.K., Achiwa, K., (1970) J. Am. Chem. Soc., 92, p. 6635Harrison, I.T., Rawson, P.J., Turnbull, R., Fried, J.H., (1971) J. Org. Chem., 36, p. 3515Schwarz, S., Siemamn, H.J., Ger. Offen, DE 4,239.945, 1994Guerreiro, M.C., (1993), MSc. Thesis, Universidade Estadual de Campinas, Campina

Oxidation With The "o2-h2o2-vo3 --pyrazine-2-carboxylic Acid" Reagent: 6. * Oxidation Of N-heptane And Cyclohexane. Direct Determination Of Alkyl Hydroperoxides By Gas-liquid Chromatography

n-Heptane is readily oxidized in acetonitrile under the action of H2O2 with a "vanadate anion-pyrazine-2-carboxylic acid" system as the catalyst in air to form isomeric heptyl hydroperoxides (detected by GLC) along with isomeric heptanols and heptanones. Heptyl hydroperoxides slowly decompose at low temperature yielding the corresponding alcohols and ketones (aldehyde). The values of the parameter of the relative normalized reactivity of the H atoms at the carbon atoms in positions 1, 2, 3, and 4 depend on the reaction time and concentrations of the reagents. The value of the parameter of selectivity C(1) : C(2) : C(3) : C(4) varies in the range from 1.0 : 2.8 : 2.9 : 1.8 to 1.0 : 5.6 : 5.9 : 5.3. The low selectivity of the reaction shows that the key role is played by the attack of highly reactive radical particles on the C-H bond of the alkane molecule.464749754Shul'pin, G.B., Drago, R.S., Gonzalez, M., (1996) Izv. Akad. Nauk, Ser. Khim., p. 2514(1996) Russ. Chem. Bull., 45, p. 2386. , Engl. TranslShul'pin, G.B., Attanasio, D., Suber, L., (1993) Izv. Akad. Nauk. Ser. Khim., p. 64(1993) Russ. Chem. Bull., 42, p. 55. , Engl. TranslShul'pin, G.B., Attanasio, D., Suber, L., (1993) J. Catal., 142, p. 147Shul'pin, G.B., Druzhinina, A.N., Nizova, G.V., (1993) Izv. Akad. Nauk, Ser. Khim., p. 1394(1993) Russ. Chem. Bull., 42, p. 1326. , Engl. TranslNizova, G.V., Shul'pin, G.B., (1994) Izv. Akad. Nauk, Ser. Khim., p. 1212(1994) Russ. Chem. Bull., 43, p. 1146. , Engl. TranslShul'pin, G.B., Süss-Fink, G., (1995) J. Chem. Soc., Perkin Trans. 2, p. 1459Shul'pin, G.B., Guerreiro, M.C., Schuchardt, U., (1996) Tetrahedron, 52, p. 13051Emanuel', N.M., Gal, D., (1984) Okislenie Etilbenzola [Oxidation of Ethylbenzene], , Nauka, Moscow, 280 pp. (in Russian)Shul'pin, G.B., Bochkova, M.M., Nizova, G.V., (1995) J. Chem. Soc., Perkin Trans. 2, p. 1465Shul'pin, G.B., Nizova, G.V., Kozlov, Yu.N., (1996) New J. Chem., 20, p. 1243Nizova, G.V., Süss-Fink, G., Shul'pin, G.B., (1997) J. Chem. Soc., Chem. Commun., p. 397Nizova, G.V., Süss-Fink, G., Shul'pin, G.B., (1997) Tetrahedron, 53, p. 3603Aveline, B.A., Kochevar, I.E., Redmond, R.W., (1996) J. Am. Chem. Soc., 118, p. 289Sheu, C., Richert, S.A., Cofré, P., Ross B., Jr., Sobkowiak, A., Sawyer, D.T., Kanofsky, J.R., (1990) J. Am. Chem. Soc., 112, p. 1936Sheu, C., Sobkowiak, A., Zhang, L., Ozbalik, N., Barton, D.H.R., Sawyer, D.T., (1989) J. Am. Chem. Soc., 111, p. 8030Ellis P.E., Jr., Lyons, J.E., (1990) Coord. Chem. Rev., 105, p. 181Schuchardt, U., Krähembühl, C.E.Z., Carvalho, W.A., (1991) New J. Chem., 15, p. 955Goldstein, A.S., Drago, R.S., (1991) J. Chem. Soc., Chem Commun., p. 21Kao, L.-C., Hutson, A.C., Sen, A., (1991) J. Am. Chem. Soc., 113, p. 700Lin, M., Sen, A., (1992) J. Am. Chem. Soc., 114, p. 7307Sen, A., Lin, M., (1992) J. Chem. Soc., Chem. Commun., p. 508Sen, A., Lin, M., Kao, L.-C., Hutson, A.C., (1992) J. Am. Chem. Soc., 114, p. 6385Schuchardt, U., Carvalho, W.A., Spinacé, E.V., (1993) Synlett, p. 713Labinger, J.A., (1994) Catal. Lett., 26, p. 95Grinstaff, M.W., Hill, M.G., Labinger, J.A., Gray, H.B., (1994) Science, 264, p. 1311Nakata, K., Yamaoka, Y., Miyata, T., Taniguchi, Y., Takaki, K., Fujiwara, Y., (1994) J. Organomet. Chem., 473, p. 329Goldstein, A.S., Beer, R.H., Drago, R.S., (1994) J. Am. Chem. Soc., 116, p. 2424Lin, M., Sen, A., (1994) Nature, 368, p. 613Kurioka, M., Nakata, K., Jintoku, T., Taniguchi, Y., Takaki, K., Fujiwara, Y., (1995) Chem. Lett., p. 244Barton, D.H.R., Taylor, D.K., (1995) Izv. Akad. Nauk, Ser. Khim., p. 595(1995) Russ. Chem. Bull., 44, p. 575. , Engl. TranslBirnbaum, E.R., Grinstaff, M.W., Labinger, J.A., Bercaw, J.E., Gray, H.B., (1995) J. Mol. Catal., A: Chem., 104, pp. L119Shilov, A.E., Shul'pin, G.B., (1995) Aktivatsiya i Kataliticheskie Reaktsii Uglevodorodov [Activation and Catalytic Reactions of Hydrocarbons], , Nauka, Moscow, 400 pp. (in Russian

Oxidations By The Reagent O2-h2o2-vanadium Complex - Pyrazine-2-carboxylic Acid. Part 7. Hydroperoxidation Of Higher Alkanes

Alkanes (n-heptane, 2- and 3-methylhexane, cis- and trans-decalin) are readily oxidized under air in acetonitrile by the O2-H2O2-PCA-VO3 - reagent at room temperature to produce alkyl hydroperoxides as main products as well as minor amounts of the corresponding alcohols and carbonyl compounds. The site selectivities of the reactions are very similar to those observed with hydroxylation of the alkanes with hydrogen peroxide under UV irradiation. The proposed mechanism involves the catalytic formation of hydroxyl radicals from hydrogen peroxide which abstract hydrogen atoms from the alkanes. The alkyl radicals react rapidly with molecular oxygen to produce peroxyl radicals which are transformed mainly into the hydroperoxides.52411305113062Patai, S., (1983) The Chemistry of Peroxides, , Wiley: ChichesterDrauz, K., Waldmann, H., (1995) Enzyme Catalysis in Organic Synthesis, , VCH: New York-WeinheimJefford, C.W., (1993) Chem. Soc. Rev., p. 59Shul'pin, G.B., (1988) Organic Reactions Catalyzed by Metal Complexes, , Nauka: MoscowDrago, R.S., (1992) Coord. Chem. Rev., 117, p. 185Barton, D.H.R., Doller, D., (1992) Acc. Chem. Res., 25, p. 504Strukul, G., (1992) Catalytic Oxidations with Hydrogen Peroxide as Oxidant, , Kluwer: DordrechtBarton, D.H.R., Martell, A.E., Sawyer, D.T., (1993) The Activation of Dioxygen and Homogeneous Catalytic Oxidation, , Plenum: New YorkSchuchardt, U., Carvalho, W.A., Spinacé, E.V., (1993) Synlett, p. 713Oyama, S.T., Hightower, J.W., (1993) Catalytic Selective Oxidation, , ACS: WashingtonCrabtree, R.H., (1995) Chem. Rev., 95, p. 987Shilov, A.E., Shul'pin, G.B., (1995) Activation and Catalytic Reactions of Hydrocarbons, , Nauka: MoscowShul'pin, G.B., Attanasio, D., Suber, L., (1993) Russ. Chem. Bull., 42, p. 55Shul'pin, G.B., Druzhinina, A.N., Nizova, G.V., (1993) Russ. Chem. Bull., 42, p. 1326Nizova, G.V., Shul'pin, G.B., (1994) Russ. Chem. Bull., 43, p. 1146Shul'pin, G.B., Süss-Fink, G., (1995) J. Chem. Soc., Perkin Trans. 2, 2, p. 1459Shul'pin, G.B., Drago, R.S., Gonzalez, M., (1996) Russ. Chem. Bull, 45, p. 10Guerreiro, M.C., Schuchardt, U., Shul'pin, G.B., Russ. Chem. Bull., , submitted for publicationNizova, G.V., Süss-Fink, G., Shul'pin, G.B., unpublished resultsGalimova, L.G., Maslennikov, S.I., Nikolaev, A.I., (1980) Bull. Acad. Sci. USSR, Div. Chem. Sci., 29, p. 1731Baxendale, J.H., Wilson, J.A., (1957) Trans. Faraday Soc., 53, p. 344Sawyer, D.T., (1991) Oxygen Chemistry, p. 126. , Oxford University Press: New York, cap. 5, 128Russel, G.A.J., (1957) J. Am. Chem. Soc., 79, p. 3871Reid, I.D., Rhodes, C.J., Roduner, E., (1992) Tetrahedron Lett., 33, p. 561

Oxidation With The "o2 - H2o2 - Vauauium Complex - Pyrazine-2-carboxylic Acid" Reagent 9. Oxidation Of Cyclohexene And Decalin

The oxidation of cyclohexene with hydrogen peroxide catalyzed by a vanadium complex and pyrazine-2-carboxylic acid (PCA) in air results in the formation of cyclohex-2-enyl hydroperoxide as the main product and cyclohex-2-enol, cyclohex-2-enone, cyclohex-3-enyl hydroperoxide, cyclohex-3-enol, cyclohexanol, cyclohexane, and 1,2-epoxycyclohexane in lesser amounts. The composition of the products of oxidation of decalin isomers with the system in question is similar to those obtained in the photochemical oxidation with hydrogen peroxide in air and in the oxidation with air in the presence of anthraquinone. A proposed mechanism for the oxidation includes the initiation by hydroxyl radicals generated from hydrogen peroxide under the action of the V - PCA system.472247252Nizova, G.V., Süss-Fink, G., Shul'pin, G.B., (1997) Tetrahedron, 53, p. 3603Shilov, A.E., Shul'pin, G.B., (1995) Aktivatsiya i Kataliticheskie Reaktsii Uglevodorodov [Activation and Catalytic Reactions of Hydrocarbons], , Nauka, Moscow, 400 pp. (in Russian)Shilov, A.E., Shul'pin, G.B., (1997) Chem. Rev., , in pressShul'pin, G.B., Attanasio, D., Suber, L., (1993) Izv. Akad. Nauk, Ser. Khim., p. 64(1993) Russ. Chem. Bull., 42, p. 55. , Engl. TranslShul'pin, G.B., Druzhinina, A.N., Nizova, G.V., (1993) Izv. Akad. Nauk, Ser. Khim., p. 1394(1993) Russ. Chem. Bull., 42, p. 1326. , Engl. TranslNizova, G.V., Shul'pin, G.B., (1994) Izv. Akad. Nauk, Ser. Khim., p. 1212(1994) Russ. Chem. Bull., 43, p. 1146. , Engl. TranslShul'pin, G.B., Süss-Fink, G., (1995) J. Chem. Soc., Perkin Trans., 2, p. 1459Shul'pin, G.B., Drago, R.S., Gonzalez, M., (1996) Izv. Akad. Nauk, Ser. Khim., p. 2514(1996) Russ. Chem. Bull., 45, p. 2386. , Engl. TranslGuerreiro, M.C., Schuchardt, U., Shul'pin, G.B., (1997) Izv. Akad. Nauk, Ser. Khim., p. 780(1997) Russ. Chem. Bull., 46, p. 749. , Engl. TranslShul'pin, G.B., Guerreiro, M.C., Schuchardt, U., (1996) Tetrahedron, 52, p. 13051Shul'pin, G.B., Attanasio, D., Suber, L., (1993) J. Catal., 142, p. 147Shul'pin, G.B., Nizova, G.V., (1992) React. Kinet. Catal. Lett., 48, p. 333Nizova, G.V., Süss-Fink, G., Shul'pin, G.B., (1997) Chem. Commun., p. 397Day, V.W., Klemperer, W.G., Yagasaki, A., (1990) Chem. Lett., p. 1267Baxendale, J.H., Wilson, J.A., (1957) Trans. Faraday Soc., 53, p. 344Rontani, J.-F., Giusti, G., (1990) J. Photochem. Photobiol., A: Chem., 53, p. 69Mimoun, H., Saussine, L., Daire, E., Postel, M., Fischer, J., Weiss, R., (1983) J. Am. Chem. Soc., 105, p. 3101Barton, D.H.R., Hu, B., Li, T., MacKinnon, J., (1996) Tetrahedron Lett., 37, p. 8329Shul'pin, G.B., Druzhinina, A.N., (1992) React. Kinet. Catal. Lett., 47, p. 207Shul'pin, G.B., Nizova, G.V., (1995) Mendeleev Commun., p. 143Shul'pin, G.B., Nizova, G.V., Kozlov, Yu.N., (1996) New J. Chem., 20, p. 1243Barton, D.H.R., Béviére, S.D., Chavasiri, W., Csuhai, E., Doller, D., (1992) Tetrahedron, 48, p. 2895Barton, D.H.R., Béviére, S.D., Chavasiri, W., Csuhai, E., Doller, D., Liu, W.-G., (1992) J. Am. Chem. Soc., 114, p. 2147Bateman, L., Gee, G., (1951) Trans. Faraday Soc., 47, p. 155Russel, G.A., (1957) J. Am. Chem. Soc., 79, p. 3871Mimoun, H., Chaumette, P., Mignard, M., Saussine, L., (1983) Nouv. J. Chim., 7, p. 467Mimoun, H., Mignard, M., Brechot, P., Saussine, L., (1986) J. Am. Chem. Soc., 108, p. 3711Mimoun, H., (1983) Isr. J. Chem., 23, p. 451Butler, A., Clague, M.J., Meister, G.E., (1994) Chem. Rev., 94, p. 625Neumann, R., De La Vega, M., (1993) J. Mol. Cat., 84, p. 93Bonchio, M., Conte, V., Di Furia, F., Modena, G., Moro, S., (1994) J. Org. Chem., 59, p. 626

Sammlung der Vortraege anlaesslich des Statusberichtes 1986 des Projekttraegers Stillegung von Nuklearanlagen in Hannover am 22. und 23. November 1986

The publication presents ten selected papers reporting on the progress and status of R and D activities carried out within the project, for establishing and demonstrating processes and methods for application to the decommissioning of nuclear installations at the end of their serviceable life, or to backfitting work in existing nuclear installations. Further tasks reported include studies and experiments relating to the treatment and conditioning of radioactive wastes from decommissioning work and the preparation of specified waste forms for emplacement in a repository, or the development of a novel method for surface decontamination of structural members made of concrete, or possibilities of preparing radioactive or contaminated metallic materials from nuclear installations for recycling and safe re-use, or for the production of components for use in nuclear installations. (orig.)Berichtet wird in 10 ausgewaehlten Fachvortraegen ueber Vorhaben zum Forschungsschwerpunkt Entwicklung und Demonstration von Techniken und Verfahren, die bei der Demontage von kerntechnischen Anlagen nach Ende ihres bestimmungsgemaessen Gebrauchs aber evtl. auch im Rahmen von Backfitting-Massnahmen zur Anwendung kommen koennen. Es wird in dieser Vortragsreihe auch ueber Untersuchungen und durchgefuehrte Versuche zur Behandlung, Konditionierung und endlagergerechten Verpackung von radioaktiven Abfallstoffen aus der Stillegung berichtet, des weiteren ueber den derzeitigen Stand der Entwicklung eines neuartigen Verfahrens zur Oberflaechendekontamination von Baukoerpern aus Beton und ferner ueber Moeglichkeiten der Rezyklierung von radioaktiv kontaminierten/aktivierten metallischen Werkstoffen aus kerntechnischen Anlagen mit dem Ziel einer schadlosen Wiederverwertung oder fuer die Fertigung von Komponenten zum Wiedereinsatz im kerntechnischen Bereich. (orig.)SIGLEAvailable from TIB Hannover: RO 8936(1) / FIZ - Fachinformationszzentrum Karlsruhe / TIB - Technische InformationsbibliothekBundesministerium fuer Forschung und Technologie (BMFT), Bonn (Germany)DEGerman