The dehydration process in the zeolite laumontite: a real-time synchrotron X-ray powder diffraction study

The dehydration process of the natural zeolite laumontite Ca₄Si₁₆Al₈O₄₈ · 18 H₂O has been studied in situ by means of powder diffraction and X-ray synchrotron radiation. Powder diffraction profiles suitable for Rietveld refinements were accumulated in time intervals of 5 minutes using a position sensitive detector (CPS-120 by INEL), while the temperature increased in steps of about 5 K. The synchronization of accumulation time and temperature plateau allowed collection of 62 temperature-resolved powder patterns in the range 310–584 K, whose analysis produced a dynamic picture of the laumontite structure response to dehydration. The first zeolitic water molecules diffusing out of the channels are those not bonded to the Ca cations and located in the W(1) site, whose occupancy drops smoothly to 10% during heating to 349 K, while the sample in the capillary is still submerged in water. The remaining W(1) and 60% of W(5) water molecules are expelled rather sharply at about 370 K. At this temperature all remaining water submerging the powder crystallites is lost, the structure contains about 13 water molecules/cell, and the crystal structure is that of leonhardite. On continued heating 80% of the water molecules from the W(2) site are lost between 420 and 480 K, while a small amount of the diffusing water is reinserted in the W(5) site. The occupancy factor of the W(8) site decreases starting at 480 K, and reaches a maximum loss of 20% at 584 K. The combined occupancy of the Ca-coordinated W (2) and W (8) water sites never falls much below two, so that the Ca cations in the channels, which are bonded to four framework oxygen atoms, are nearly six-coordinated in the explored temperature range. The water loss is accompanied by large changes in the unit cell dimensions. Except at 367 K, where the excess surrounding water is leaving, all changes in cell dimensions are gradual. The loss of the hydrogen bonded W(1) and W(5) water molecules is related to most of the unit cell volume reduction below 370 K, as shown by the contraction of the a-, b- and c-axes and the increase in the monoclinic angle. Loss of the Ca-coordinated W(2) and W(8) water molecules has a small effect on the unit cell volume as the continued contraction of the a- and c-axes is counter-balanced by a large expansion in the b-axis and a decrease in the monoclinic β angle.     

Loess record of the Pleistocene–Holocene transition on the northern and central Great Plains, USA

Various lines of evidence support conflicting interpretations of the timing, abruptness, and nature of climate change in the Great Plains during the Pleistocene–Holocene transition. Loess deposits and paleosols on both the central and northern Great Plains provide a valuable record that can help address these issues. A synthesis of new and previously reported optical and radiocarbon ages indicates that the Brady Soil, which marks the boundary between late Pleistocene Peoria Loess and Holocene Bignell Loess, began forming after a reduction in the rate of Peoria Loess accumulation that most likely occurred between 13.5 and 15 cal ka. Brady Soil formation spanned all or part of the Bølling-Allerød episode (approximately 14.7–12.9 cal ka) and all of the Younger Dryas episode (12.9–11.5 cal ka) and extended at least 1000 years beyond the end of the Younger Dryas. The Brady Soil was buried by Bignell Loess sedimentation beginning around 10.5–9 cal ka, and continuing episodically through the Holocene. Evidence for a brief increase in loess influx during the Younger Dryas is noteworthy but very limited. Most late Quaternary loess accumulation in the central Great Plains was nonglacigenic and was under relatively direct climatic control. Thus, Brady Soil formation records climatic conditions that minimized eolian activity and allowed effective pedogenesis, probably through relatively high effective moisture.Optical dating of loess in North Dakota supports correlation of the Leonard Paleosol on the northern Great Plains with the Brady Soil. Thick loess in North Dakota was primarily derived from the Missouri River floodplain; thus, its stratigraphy may in part reflect glacial influence on the Missouri River. Nonetheless, the persistence of minimal loess accumulation and soil formation until 10 cal ka at our North Dakota study site is best explained by a prolonged interval of high effective moisture correlative with the conditions that favored Brady Soil formation. Burial of both the Brady Soil and the Leonard Paleosol by renewed loess influx probably represents eolian system response that occurred when gradual change toward a drier climate eventually crossed the threshold for eolian activity. Overall, the loess–paleosol sequences of the central and northern Great Plains record a broad peak of high effective moisture across the late Pleistocene to Holocene boundary, rather than well-defined climatic episodes corresponding to the Bølling-Allerød and Younger Dryas episodes in the North Atlantic region.     

Origin of Archean lamprophyre dykes,Superior Province,Canada: rare earth element and Nd−Sr isotopic evidence

Hornblende- and clinopyroxene-phyric lamprophyre dykes exposed in the Roaring River Complex, Superior Province are alkaline, nepheline-normative, basaltic compositions (>50 wt% SiO₂), that range from primitive to fractionated [Mg/(Mg + total Fe)=0.66–0.40; Ni=200–35 ppm], and which have high abundances of light rare earth elements (REE) [(Ce/Yb)_n=16–26, Ce_n=60–300; n = chondrite normalized], Sr (870–1,800 ppm), P₂O₅ (0.4–1.3 wt%), and Ba (150–900 ppm). Crystal fractionation of the lamprophyres produced coeval gabbro and clinopyroxenite cumulate bodies. A whole-rock Sm–Nd isochron for lamprophyres and gabbro-pyroxenite yields a crystallization age of 2,667±51 Ma Ma (I=0.50929±0.0004; _Nd = + 2.3 0.7). Whole-rock Sr isotope data are scattered, but suggest an initial ⁸⁷Sr/⁸⁶Sr ratio of 0.7012, similar to bulk Earth. The elevated levels of light REEs and Sr in the lamprophyres were not due to crustal contamination or mixing with contemporaneous monzodioritic magmas, but a result of partial melting of a mantle source which was enriched in these and other large-ion-lithophile elements (LILEs) shortly before melting. The lamprophyres were contemporaneous with mantle-derived, high-Mg, LILE-enriched monzodiorite to granodiorite of the Archean sanukitoid suite. Both suites have concave-downward light REE profiles, suggesting that depleted mantle was common to their source regions, but the higher light REE abundances, higher Ba/La ratios, and lower _Nd values (+1.3±0.3) of the parental monzodiorites suggest a more enriched source. The lamprophyres and high-Mg monzodiorites were derived from a mineralogically and compositionally heterogeneous, LILE-enriched mantle lithosphere that may have been part of a mantle wedge above a subducting plate in an arc environment.     

Assessment of elemental contamination in estuarine and coastal environments based on geochemical and statistical modeling of sediments

Sediment of variable mineralogical, textural and metal contaminant composition was collected from 38 estuaries along the Atlantic and Gulf of Mexico coasts of the United States and analyzed for total Al, Ag, As, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Se, Si, Sn, Tl and Zn concentrations. Based on observed covariation of elements at 15 estuaries remote from contaminant inputs, linear regressions of metals on Al were used to model the metal content in baseline sediments. A geochemical model for the covariation was developed, verified and used to guide the statistical modelling approach. Comparison of metal concentrations predicted by the models with those occurring in uncontaminated geological materials suggests that baseline relationships are valid for the entire region sampled. Using these baseline relationships, sediment metal concentrations can be partitioned into natural and anthropogenic fractions. Models improve the comparability of metal levels in sediments by correcting for variable background concentrations that, if left uncorrected, only serve to increase total data variability and reduce detection of spatial and temporal differences.Examples of the application of baseline models to pollution studies are provided. A continuing decline in Pb concentrations in Mississippi River delta sediments is observed consistent with the declining use of Pb additives in gasoline since 1970. Major spatial trends in contaminant metals in sediments along the Atlantic and Gulf of Mexico coasts are noted.     

A high resolution study of continuous pulsations in the European sector

Complex demodulation has been described in detail and applied to Pi2 pulsations in a previous paper by Beamish et al. (1979). The technique is now extended to demonstrate spatiotemporal variations in the fundamental characteristics of Pc3 and Pc4 pulsations along a meridional profile extending from the U.K. to Iceland. With the exception of a high latitude Pc4 coupled resonance the results are consistent with a ?90° Hughes rotation (introduced by the ionosphere) of magnetospheric toroidal line resonances. Furthermore, the ionosphere appears capable of smoothing away the polarisation reversal which would be expected across such amplitude maxima within the plasmasphere. However, a toroidal line resonance in the Pc3 period range about which a sense of polarisation reversal is clearly observed on the ground is suggested as occurring at the plasmapause. This is accounted for in terms of the width of the resonance structure.     

Mantle heterogeneity and crustal recycling in Archean granite-greenstone belts: Evidence from Nd isotopes and trace elements in the Rainy Lake area, Superior Province, Ontario, Canada

The 2685–2752 Ma old granite-greenstone crust in the Rainy Lake area, Ontario, consists of metaigneous and metasedimentary rocks that range in composition from tholeiite to monzogranite and include anorthosite, trachyandesite, monzodiorite and high-silica rhyodacite. Major element, rare earth and other trace element data are the basis for modelling the formation of the crust by melting of large-ionlithophile element enriched and unenriched mantle, by melting of basalt at mantle to crustal levels and by melting of monzodiorite and tonalite at crustal levels.

All metaigneous rocks lie on a ¹⁴³Nd/¹⁴⁴Nd vs. ¹⁴⁷Sm/¹⁴⁴Nd isochron with an age of 2737 ±42 Ma and an initial ¹⁴³Nd/¹⁴⁴Nd of 0.509178 ±33 (ε_Nd = +1.9). This age is consistent with U-Pb zircon ages, which suggests the Nd isotopic system has been unaffected since the crust-forming events. The positive initial ε_Nd's are further evidence for time-averaged depletion in Sm/Nd relative to CHUR for the Archean mantle. The similarity of the initial Nd isotopic composition for both mantle-derived and crustally-derived rocks suggests rapid recycling of crustal components, which were previously derived from depleted mantle sources.

Initial ¹⁴³Nd/¹⁴⁴Nd ratios on individual rocks range from ε_Nd = +3.3 to ε_Nd = −0.4. Younger granitoids have lower ε_Nd values (+1.5 to −0.1) relative to tholeiites and monzodiorites crystallized from mantle-derived melts (+3.3 to +1.0). Thus, incorporation of slightly older crust (ca. 100–200 Ma) in some of the granitoid source areas is possible. Mantle-derived rocks form an isochron of 2764 ±58 Ma that represents a minimum age for enrichment processes in the mantle sources for the Rainy Lake area. Consideration of data from the Abitibi belt suggests such enrichment processes in the mantle may have preceded crust-forming events in a wide area of the Superior Province, perhaps by as much as 50–70 Ma.     

Kinetics of formation of zeolite Na-A [LTA] from natural kaolinites

 The kinetics and mechanism of hydrothermal formation of zeolite A from natural kaolinites have been studied using as starting materials two international kaolinite standards (KGa-1 and KGa-2 from Georgia, USA) exhibiting a different degree of stacking disorder. Precursors utilized for the synthesis were prepared by heating the kaolinites at 800 °C. Metakaolinite was also prepared from KGa-1 by thermal activation at 600 °C. The hydrothermal syntheses were accomplished by heating the samples in NaOH solutions at temperatures between 70 and 110 °C. The kinetic experiments were performed by time-resolved synchrotron powder diffraction in isothermal mode using a transmission geometry and an Image Plate detector. The results of the kinetic analysis are interpreted in the light of the structural state of the starting kaolinite, and of the temperature of activation of the precursor material. For kaolinite activated at high temperature the nucleation and crystallization of zeolite A is essentially independent of the defect density of the original kaolinite, and the thermal history of the precursor seems to be the main controlling parameter. The formation process of zeolite A from metakaolinite materials obtained at lower activation temperatures shows significantly faster reaction rates and lower apparent activation energies. This is again interpreted in the light of the short range inhomogeneities present in metakaolinite. As the reaction proceeds metastable zeolite A transforms into hydroxy-sodalite. Received April 18, 1996 / Revised, accepted September 27, 1996