Orthit in den Gesteinen der Sonnblickgruppe (Hohe Tauern)

Summary Some types of Allanite (Orthite) are here described. They are found as assessory minerals in the rocks of the Hohe Tauern (penninic zone of the Eastern Alps) and in the hercynian foreland (Bohemian Massif). We distinguish Allanite I, II and III.The Allanite I (Hohe Tauern) is not isotropisized, but currently idiomorphic, with a xenomorphic rim of Clinozoisite. Where Allanite I is bordering Quartz or Potassium feldspar there is generally no rim of Clinozoisite. In the tectonites one observes granulated Allanite I and transformation of Allanite I to finegranied aggregates of Clinozoisite.Allanite II (Hohe Tauern) is found in intensely radioactive rocks. It is currently isotropisized, xenomorphic and surrounded by xenomorphic rims of Pistacite.Allanite III (Bohemian Massif) may be the oldest one and it is mostly isotropisized.The problems of the genesis and the age of crystallisation of Allanite during the history of our polymetamorphic rocks are shortly touched.

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Progressive development of s-type flanking folds in simple shear

Flanking structures are deflections of planar or linear fabric elements in a rock alongside a crosscutting element (CE), e.g. a vein or fault. This study provides new results from analogue experiments, which test and extend recent numerical models of flanking structures. A linear viscous matrix material (PDMS) was deformed in a ring shear rig that allows continuous observation to large values of shear strain. Rotational behaviour, offset and deflection of marker lines around a predefined, lubricated CE were monitored for different initial orientations of the fault with respect to the shear zone boundary, and the results were compared with numerical results and natural examples. At high initial angles to the shear zone boundary (>135°), a structure previously described as an ‘s-type flanking fold’ develops. During progressive deformation, an initially straight marker line passing through the centre of the CE is offset in a sense synthetic with the bulk sense of shear and shows a shortening displacement across the CE. Simultaneously, this central marker line is deflected and forms symmetrical folds, which are convex in the direction of shear along the CE (i.e. normal drag). Both offset and deflection of the marker lines decrease towards the tips of the fault. Natural examples of s-type flanking folds, directly comparable with the model results, are more common than is generally appreciated.     

Absolute OH quantum yields in the laser photolysis of nitrate,nitrite and dissolved H2O2 at 308 and 351 nm in the temperature range 278–353 K

Absolute quantum yields for the formation of OH radicals in the laser photolysis of aqueous solutions of NO₃ ^-, NO₂ ^- and H₂O₂ at 308 and 351 nm and as a function of pH and temperature have been measured. A scavenging technique involving the reaction between OH and SCN^- ions and the time resolved detection by visible absorption of the (SCN)₂ ^- radical ion was used to determine the absolute OH yields. The following results were obtained:

1. NO ₃ ^- -photolysis:% MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGceaqabeaacaaIWa% GaaGioaGGaaiab-bcaGiaab6gacaqGTbGaaeOoaiab-bcaGiabfA6a% gnaaBaaaleaacqWFFoWtcqWFxoasaeqaaOGaaiikaiaaikdacaaI5a% GaaGioaiab-bcaGiab-P5aljaacMcacqGH9aqpcqWFGaaicqWFWaam% cqWFUaGlcqWFWaamcqWFXaqmcqWF3aWncqWFGaaicqGHXcqScqWFGa% aicqWFWaamcqWFUaGlcqWFWaamcqWFWaamcqWFZaWmcqWFGaaicaqG% MbGaae4BaiaabkhacaqGGaGaaeinaiaabccacqGHKjYOcaqGGaGaam% iCaiaabIeacaqGGaGaeyizImQaaeiiaiaabMdaaeaacqWFGaaicqWF% GaaicqWFGaaicqWFGaaicqWFGaaicqWFGaaicqWFGaaicqWFGaaicq% WFGaaicqWFGaaicqWFGaaicqWFGaaicqWFGaaicqWFGaaicqqHMoGr% daWgaaWcbaGae83Nd8Kae83LdGeabeaakiaacIcacaWGubGaaiykai% abg2da9iabfA6agnaaBaaaleaacqWFFoWtcqWFxoasaeqaaOGaaiik% aiaaikdacaaI5aGaaGioaiab-bcaGiab-P5aljaacMcacqWFGaaica% qGLbGaaeiEaiaabchacaqGGaWaamWaaeaacaqGOaGaaeymaiaabIda% caqGWaGaaeimaiaabccacqGHXcqScaaI0aGaaGioaiaaicdacaqGPa% GaaeikamaalaaabaGaaeymaaqaaiaabkdacaqG5aGaaeioaaaacaqG% GaGaeyOeI0IaaeiiamaalaaabaGaaeymaaqaaiaadsfaaaGaaeykaa% Gaay5waiaaw2faaiaac6caaaaa!9673!\[\begin{gathered}08 {\text{nm:}} \Phi _{{\rm O}{\rm H}} (298 {\rm K}) = 0.017 \pm 0.003 {\text{for 4 }} \leqslant {\text{ }}p{\text{H }} \leqslant {\text{ 9}} \hfill \\\Phi _{{\rm O}{\rm H}} (T) = \Phi _{{\rm O}{\rm H}} (298 {\rm K}) {\text{exp }}\left[ {{\text{(1800 }} \pm 480{\text{)(}}\frac{{\text{1}}}{{{\text{298}}}}{\text{ }} - {\text{ }}\frac{{\text{1}}}{T}{\text{)}}} \right]. \hfill \\\end{gathered}\] Selected experiments at 351 nm indicate that these results are essentially unchanged.
2. NO ₂ ^- -photolysis:% MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGceaqabeaacaaIWa% GaaGioaGGaaiab-bcaGiaab6gacaqGTbGaaeOoaiab-bcaGiabfA6a% gnaaBaaaleaacqWFFoWtcqWFxoasaeqaaOGaaiikaiaaikdacaaI5a% GaaGioaiab-bcaGiab-P5aljaacMcacqGH9aqpcqWFGaaicqWFOaak% cqWFWaamcqWFUaGlcqWFWaamcqWFXaqmcqWF3aWncqWFGaaicqGHXc% qScqWFGaaicqWFWaamcqWFUaGlcqWFWaamcqWFWaamcqWFXaqmcqWF% PaqkcqWFGaaicaqGMbGaae4BaiaabkhacaqGGaGaaeinaiaabccacq% GHKjYOcaqGGaGaamiCaiaabIeacaqGGaGaeyizImQaaeiiaiaabMda% caqGSaaabaGae8hiaaIae8hiaaIae8hiaaIae8hiaaIae8hiaaIae8% hiaaIae8hiaaIae8hiaaIae8hiaaIae8hiaaIae8hiaaIae8hiaaIa% e8hiaaIae8hiaaIaeuOPdy0aaSbaaSqaaiab-95apjab-D5aibqaba% GccaGGOaGaamivaiaacMcacqGH9aqpcqqHMoGrdaWgaaWcbaGae83N% d8Kae83LdGeabeaakiaacIcacaaIYaGaaGyoaiaaiIdacqWFGaaicq% WFAoWscaGGPaGae8hiaaIaaeyzaiaabIhacaqGWbGaaeiiamaadmaa% baGaaeikaiaabgdacaqG1aGaaeOnaiaabcdacaqGGaGaeyySaeRaae% iiaiaabodacaqG2aGaaeimaiaabMcacaqGOaWaaSaaaeaacaqGXaaa% baGaaeOmaiaabMdacaqG4aaaaiaabccacqGHsislcaqGGaWaaSaaae% aacaqGXaaabaGaamivaaaacaqGPaaacaGLBbGaayzxaaGaaiilaaqa% aiaaiodacaaI1aGaaGymaiaabccacaqGUbGaaeyBaiaabQdacqWFGa% aicqqHMoGrdaWgaaWcbaGae83Nd8Kae83LdGeabeaakiaacIcacaaI% YaGaaGyoaiaaiIdacqWFGaaicqWFAoWscaGGPaGaeyypa0Jae8hiaa% Iae8hkaGIae8hmaaJae8Nla4Iae8hmaaJae8hnaqJae8NnayJae8hi% aaIaeyySaeRae8hiaaIae8hmaaJae8Nla4Iae8hmaaJae8hmaaJae8% xoaKJae8xkaKIae8hiaaIaaeOzaiaab+gacaqGYbGaaeiiaiaabsda% caqGGaGaeyizImQaaeiiaiaadchacaqGibGaaeiiaiaab2dacaqGGa% GaaeioaiaabYcaaeaacqWFGaaicqWFGaaicqWFGaaicqWFGaaicqWF% GaaicqWFGaaicqWFGaaicqWFGaaicqWFGaaicqWFGaaicqWFGaaicq% WFGaaicqWFGaaicqWFGaaicqqHMoGrdaWgaaWcbaGae83Nd8Kae83L% dGeabeaakiaacIcacaWGubGaaiykaiabg2da9iabfA6agnaaBaaale% aacqWFFoWtcqWFxoasaeqaaOGaaiikaiaaikdacaaI5aGaaGioaiab% -bcaGiab-P5aljaacMcacqWFGaaicaqGLbGaaeiEaiaabchacaqGGa% WaamWaaeaacaqGOaGaaeymaiaabIdacaqGWaGaaeimaiaabccacqGH% XcqScaqGGaGaaeinaiaabcdacaqGWaGaaeykaiaabIcadaWcaaqaai% aabgdaaeaacaqGYaGaaeyoaiaabIdaaaGaaeiiaiabgkHiTiaabcca% daWcaaqaaiaabgdaaeaacaWGubaaaiaabMcaaiaawUfacaGLDbaaca% GGUaaaaaa!FC61!\[\begin{gathered}08 {\text{nm:}} \Phi _{{\rm O}{\rm H}} (298 {\rm K}) = (0.017 \pm 0.001) {\text{for 4 }} \leqslant {\text{ }}p{\text{H }} \leqslant {\text{ 9,}} \hfill \\\Phi _{{\rm O}{\rm H}} (T) = \Phi _{{\rm O}{\rm H}} (298 {\rm K}) {\text{exp }}\left[ {{\text{(1560 }} \pm {\text{ 360)(}}\frac{{\text{1}}}{{{\text{298}}}}{\text{ }} - {\text{ }}\frac{{\text{1}}}{T}{\text{)}}} \right], \hfill \\351{\text{ nm:}} \Phi _{{\rm O}{\rm H}} (298 {\rm K}) = (0.046 \pm 0.009) {\text{for 4 }} \leqslant {\text{ }}p{\text{H = 8,}} \hfill \\\Phi _{{\rm O}{\rm H}} (T) = \Phi _{{\rm O}{\rm H}} (298 {\rm K}) {\text{exp }}\left[ {{\text{(1800 }} \pm {\text{ 400)(}}\frac{{\text{1}}}{{{\text{298}}}}{\text{ }} - {\text{ }}\frac{{\text{1}}}{T}{\text{)}}} \right]. \hfill \\\end{gathered}\]
3. H₂O₂-photolysis:% MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGceaqabeaacaaIWa% GaaGioaGGaaiab-bcaGiaab6gacaqGTbGaaeOoaiab-bcaGiabfA6a% gnaaBaaaleaacqWFFoWtcqWFxoasaeqaaOGaaiikaiaaikdacaaI5a% GaaGioaiab-bcaGiab-P5aljaacMcacqGH9aqpcqWFGaaicqWFOaak% cqWFWaamcqWFUaGlcqWF5aqocqWF4aaocqWFGaaicqGHXcqScqWFGa% aicqWFWaamcqWFUaGlcqWFWaamcqWFZaWmcqWFPaqkcqWFGaaicaqG% MbGaae4BaiaabkhacaqGGaGaamiCaiaabIeacaqGGaGaeyizImQaae% iiaiaabEdacaqGSaaabaGae8hiaaIae8hiaaIae8hiaaIae8hiaaIa% e8hiaaIae8hiaaIae8hiaaIae8hiaaIae8hiaaIae8hiaaIae8hiaa% Iae8hiaaIae8hiaaIae8hiaaIaeuOPdy0aaSbaaSqaaiab-95apjab% -D5aibqabaGccaGGOaGaamivaiaacMcacqGH9aqpcqqHMoGrdaWgaa% WcbaGae83Nd8Kae83LdGeabeaakiaacIcacaaIYaGaaGyoaiaaiIda% cqWFGaaicqWFAoWscaGGPaGae8hiaaIaaeyzaiaabIhacaqGWbGaae% iiamaadmaabaGaaeikaiaabAdacaqG2aGaaeimaiaabccacqGHXcqS% caqGGaGaaeymaiaabMdacaqGWaGaaeykaiaabIcadaWcaaqaaiaabg% daaeaacaqGYaGaaeyoaiaabIdaaaGaaeiiaiabgkHiTiaabccadaWc% aaqaaiaabgdaaeaacaWGubaaaiaabMcaaiaawUfacaGLDbaacaGGSa% aabaGaaG4maiaaiwdacaaIXaGaaeiiaiaab6gacaqGTbGaaeOoaiab% -bcaGiabfA6agnaaBaaaleaacqWFFoWtcqWFxoasaeqaaOGaaiikai% aaikdacaaI5aGaaGioaiab-bcaGiab-P5aljaacMcacqGH9aqpcqWF% GaaicqWFOaakcqWFWaamcqWFUaGlcqWF5aqocqWF2aGncqWFGaaicq% GHXcqScqWFGaaicqWFWaamcqWFUaGlcqWFWaamcqWF0aancqWFPaqk% cqWFGaaicaqGMbGaae4BaiaabkhacaqGGaGaaeinaiaabccacqGHKj% YOcaqGGaGaamiCaiaabIeacaqGGaGaaeypaiaabccacaqG3aGaaeil% aaqaaiab-bcaGiab-bcaGiab-bcaGiab-bcaGiab-bcaGiab-bcaGi% ab-bcaGiab-bcaGiab-bcaGiab-bcaGiab-bcaGiab-bcaGiab-bca% Giab-bcaGiabfA6agnaaBaaaleaacqWFFoWtcqWFxoasaeqaaOGaai% ikaiaadsfacaGGPaGaeyypa0JaeuOPdy0aaSbaaSqaaiab-95apjab% -D5aibqabaGccaGGOaGaaGOmaiaaiMdacaaI4aGae8hiaaIae8NMdS% Kaaiykaiab-bcaGiaabwgacaqG4bGaaeiCaiaabccadaWadaqaaiaa% bIcacaqG1aGaaeioaiaabcdacaqGGaGaeyySaeRaaeiiaiaabgdaca% qG2aGaaeimaiaabMcacaqGOaWaaSaaaeaacaqGXaaabaGaaeOmaiaa% bMdacaqG4aaaaiaabccacqGHsislcaqGGaWaaSaaaeaacaqGXaaaba% GaamivaaaacaqGPaaacaGLBbGaayzxaaGaaiOlaaaaaa!F3D0!\[\begin{gathered}08 {\text{nm:}} \Phi _{{\rm O}{\rm H}} (298 {\rm K}) = (0.98 \pm 0.03) {\text{for }}p{\text{H }} \leqslant {\text{ 7,}} \hfill \\\Phi _{{\rm O}{\rm H}} (T) = \Phi _{{\rm O}{\rm H}} (298 {\rm K}) {\text{exp }}\left[ {{\text{(660 }} \pm {\text{ 190)(}}\frac{{\text{1}}}{{{\text{298}}}}{\text{ }} - {\text{ }}\frac{{\text{1}}}{T}{\text{)}}} \right], \hfill \\351{\text{ nm:}} \Phi _{{\rm O}{\rm H}} (298 {\rm K}) = (0.96 \pm 0.04) {\text{for 4 }} \leqslant {\text{ }}p{\text{H = 7,}} \hfill \\\Phi _{{\rm O}{\rm H}} (T) = \Phi _{{\rm O}{\rm H}} (298 {\rm K}) {\text{exp }}\left[ {{\text{(580 }} \pm {\text{ 160)(}}\frac{{\text{1}}}{{{\text{298}}}}{\text{ }} - {\text{ }}\frac{{\text{1}}}{T}{\text{)}}} \right]. \hfill \\\end{gathered}\] Together with the absorption coefficients and an assumed actinic flux within atmospheric droplets of twice the clear air value, the partial photolytic lifetimes (τ_OH) of these molecules at 298 K are estimated as 10.5 d, 5.4 h and 30.3 h for NO₃ ^-, NO₂ ^- and H₂O₂, respectively. These lifetimes will increase by a factor of two (NO₃ ^-, NO₂ ^-) and by 15% (H₂O₂) at T=278 K. Using average ambient concentrations in tropospheric aqueous droplets, the photolytic OH source strengths from these species are calculated to be 2.8×10^-11, 1.3×10^-11 and 1.4×10^-11 mol 1^-1 s^-1 for NO₃ ^-, NO₂ ^- and H₂O₂ respectively.