In this study we describe the mobility and fractionation of REEs in two deep (up to 30m) tropical weathering profiles developed on two granites from the Kuala Lumpur pluton, Malaysia, sampled at ...Cheras and Rawang. On the basis of Na2O and K2O both are S-type granites, but Rawang has higher CaO, MgO and FeO than Cheras and lower SiO2. With respect to Al-saturation Rawang is I-type and Cheras is S-type. We compared the two profiles in terms of total REEs, magnitude and changes in Ce and Eu anomalies, REE mobility and LREE/HREE fractionation. Rawang profiles have higher REE contents, display lower mobility for most except the heaviest REEs and show higher LREE/HREE fractionation than those from Cheras. These differences can be linked to differences in primary mineralogy and degree of weathering, the latter controlling the type and volume of secondary minerals. Specifically, bowl-shaped parent-rock-normalised patterns in the Cheras saprolites appear to be a result of apatite dissolution. Moreover, moderate weathering evident in lower Mineralogical Indices of Alteration (MIA) at Cheras has conserved parent rock REE patterns and fractionation factors in the saprolites. By contrast, more intense weathering observed in Rawang profiles has produced abundant kaolinite group minerals that have preferentially retained LREE, which consequently display high LREE/HREE fractionation. This study provides important insights into the factors controlling REE mobility during tropical weathering, and its potential as an indicator of weathering intensity.
•We study the mobility and fractionation of lanthanides in weathered profiles.•Lanthanides (including Y) behave as a coherent group in nature.•We use lanthanides to (a) compare the mobility of the elements.•We use lanthanides to (b) assess fractionation during weathering.•REE fractionation is potentially a good indicator of the degree of weathering.
Intracrystal microtextures formed by a process of mutual replacement in alkali feldspars record fluid–rock reactions that have affected large volumes of the Earth’s crust. Regular, ≤1 μm-scale ...‘strain-controlled’ perthitic microtextures coarsen, by up to 10
3
, by a dissolution–reprecipitation process, producing microporous patch or vein perthites on scales >100 μm. We have developed earlier studies of such reactions in alkali feldspar cm-scale primocrysts in layered syenites from the Klokken intrusion, South Greenland. We present new hyperspectral CL, SEM images, and laser ICPMS analytical data, and discuss the mechanism of such replacement reactions. The feldspars grew as homogeneous sodic sanidines which unmixed and ordered by volume diffusion during cooling into the microcline field at ~450°C, giving regular, fully coherent ‘braid’ cryptoperthite. At ≤450°C the crystals reacted with a circulating post-magmatic aqueous fluid. The braid perthite behaved as a single reactant ‘phase’ which was replaced by two product phases, incoherent subgrains of low albite and microcline, with micropores at their boundaries. The driving force for the reactions was coherency strain energy, which was greater than the surface energy in the subgrain mosaic. The external euhedral crystal shapes and bulk major element composition of the primocrysts were unchanged but they became largely pseudomorphs composed of subgrains usually with the ‘pericline’ and ‘adularia’ habits (dominant {110} and subordinate {010} morphology) characteristic of low
T
growth. The subgrains have an epitactic relationship with parent braid perthite. Individual subgrains show oscillatory zoning in CL intensity, mainly at blue wavelengths, which correlates with tetrahedral Ti. Regular zoning is sometimes truncated by irregular, discordant surfaces suggesting dissolution, followed by resumption of growth giving regular zoning. Zones can be traced through touching subgrains, of both albite and microcline, for distances up to ~500 μm. At ≤340°C, the microcline subgrains underwent a third stage of unmixing to give straight lamellar film perthites with periodicities of ~1 μm, which with further cooling became semicoherent by the development of spaced misfit dislocations. Sub-grain growth occurred in fluid films that advanced through the elastically strained braid perthite crystals, which dissolved irreversibly. Braid perthite was more soluble than the strain-free subgrain mosaics which precipitated from the supersaturated solution. Some volumes of braid texture have sharp surfaces that suggest rapid dissolution along planes with low surface energies. Others have complex, diffuse boundaries that indicate a phase of coherent lamellar straightening by volume diffusion in response to strain relief close to a slowly advancing interface. Nucleation of strain-free subgrains was the overall rate-limiting step. To minimise surface energy subgrains grew with low energy morphologies and coarsened by grain growth, in fluid films whose trace element load (reflected in the oscillatory zoning) was dictated by the competitive advance of subgrains over a range of a few tens of mm. The cross-cutting dissolution surfaces suggest influxes of fresh fluid. Removal of feldspar to give 2 vol% porosity would require a feldspar:fluid ratio of ~1:26 (by wt). The late reversion to strain-controlled exsolution in microcline subgrains is consistent with loss of fluid above 340°C following depressurization of the intrusion. A second paper (Part II) describes trace element partitioning between the albite and microcline subgrains, and discusses the potential of trace elements as a low-
T
geothermometer.
Bortezomib N-(2,3-pyrazine)carbonyl-L-phenylalanine-L-leucine boronic acid is a potent first-in-class dipeptidyl boronic acid proteasome inhibitor that was approved in May 2003 in the United States ...for the treatment of patients with relapsed multiple myeloma where the disease is refractory to conventional lines of therapy. Bortezomib binds the proteasome via the boronic acid moiety, and therefore, the presence of this moiety is necessary to achieve proteasome inhibition. Metabolites in plasma obtained from patients receiving a single intravenous dose of bortezomib were identified and characterized by liquid chromatography/mass spectrometry (LC/MS) and liquid chromatography/tandem mass spectrometry (LC/MS/MS). Metabolite standards that were synthesized and characterized by LC/MS/MS and high field nuclear magnetic resonance spectroscopy (NMR) were used to confirm metabolite structures. The principal biotransformation pathway observed was oxidative deboronation, most notably to a pair of diastereomeric carbinolamide metabolites. Further metabolism of the leucine and phenylalanine moieties produced tertiary hydroxylated metabolites and a metabolite hydroxylated at the benzylic position, respectively. Conversion of the carbinolamides to the corresponding amide and carboxylic acid was also observed. Human liver microsomes adequately modeled the in vivo metabolism of bortezomib, as the principal circulating metabolites were observed in vitro. Using cDNA-expressed cytochrome P450 isoenzymes, it was determined that several isoforms contributed to the metabolism of bortezomib, including CYP3A4, CYP2C19, CYP1A2, CYP2D6, and CYP2C9. The development of bortezomib has provided an opportunity to describe the metabolism of a novel boronic acid pharmacophore.
Eight feldspar phases have been distinguished within individual alkali feldspar primocrysts in laminated syenite members of the layered syenite series of the Klokken intrusion. The processes leading ...to the formation of the first four phases have been described previously. The feldspars crystallized as homogeneous sodian sanidine and exsolved by spinodal decomposition, between 750 and 600 °C, depending on bulk composition, to give fully coherent, strain-controlled braid cryptoperthites with sub-μm periodicities. Below ~500 °C, in the microcline field, these underwent a process of partial mutual replacement in a deuteric fluid, producing coarse (up to mm scale), turbid, incoherent patch perthites. We here describe exsolution and replacement processes that occurred after patch perthite formation. Both Or- and Ab-rich patches underwent a new phase of coherent exsolution by volume diffusion. Or-rich patches began to exsolve albite lamellae by coherent nucleation in the range 460–340 °C, depending on patch composition, leading to film perthite with ≤1 μm periodicities. Below ~300 °C, misfit dislocation loops formed, which were subsequently enlarged to nanotunnels. Ab-rich patches (bulk composition ~Ab
91
Or
1
An
8
), in one sample, exsolved giving peristerite, with one strong modulation with a periodicity of ~17 nm and a pervasive tweed microtexture. The Ab-rich patches formed with metastable disorder below the peristerite solvus and intersected the peristerite conditional spinodal at ~450 °C. This is the first time peristerite has been imaged using TEM within any perthite, and the first time peristerite has been found in a relatively rapidly cooled geological environment. The lamellar periodicities of film perthite and peristerite are consistent with experimentally determined diffusion coefficients and a calculated cooling history of the intrusion. All the preceding textures were in places affected by a phase of replacement correlating with regions of extreme optical turbidity. We term this material ultra porous late feldspar (UPLF). It is composed predominantly of regions of microporous very Or-rich feldspar (mean Ab
2.5
Or
97.4
An
0.1
) associated with very pure porous albite (Ab
97.0
Or
1.6
An
1.4
) implying replacement below 170–90 °C, depending on degree of order. In TEM, UPLF has complex, irregular diffraction contrast similar to that previously associated with low-temperature albitization and diagenetic overgrowths. Replacement by UPLF seems to have been piecemeal in character. Ghost-like textural pseudomorphs of both braid and film parents occur. Formation of patch perthite, film perthite and peristerite occurred 10
4
–10
5
year after emplacement, but there are no microtextural constraints on the age of UPLF formation.
Karlheinz Stockhausen created a scandal when he described the 9/11 attacks on the World Trade Center as the greatest work of art, which he attributed to Lucifer, the archetypal rebel of his ...opera-cycle LICHT. In trying to understand Stockhausen's comment, it is useful to examine his conceptualization of Lucifer by drawing on Lacan's psychic register of the Real and Adorno's concept of dissonance, at the same time critiquing the composer's perception and depiction of some of the darker regions of the human psyche. Such an examination suggests that Stockhausen's depiction of Lucifer represents a view of terrorism as a symptom of society's inability to reconcile with its own internal contradictions and dissonance.
Attractive Toxic Sugar Baits (ATSB) deployed outdoors are likely to be particularly effective against outdoor biting mosquitoes and, if they contain insecticides with a different mode of action, ...mosquitoes resistant to pyrethroids. One such ATSB based on the neonicotinoid dinotefuran is currently under evaluation in Africa. As with any insecticide-based intervention, it will be important to monitor for the possible emergence of vector resistance. While methods for detecting resistance to insecticides via tarsal contact are recommended by the World Health Organization (WHO), these may not be applicable for orally ingested insecticides. Here, a new ingestion assay, appropriate for a controlled laboratory setting, is described using fluorescein sodium salt (uranine) as a feeding marker. Conventional topical application bioassays, more appropriate for routine deployment, have also been used to apply dinotefuran to the thorax of adult
mosquitoes with an organic carrier to bypass lipid cuticle barriers. The two methods were compared by establishing lethal doses (LD) in several
strains. The similarity of the ratios of susceptibility to dinotefuran between pairs of pyrethroid susceptible and resistant strains validates topical application as a suitable, more practical and field applicable method for monitoring for the emergence of resistance to orally ingested dinotefuran. A discriminating dose is proposed, which will be further validated against field populations and used to routinely monitor for the emergence of resistance alongside ATSB trials.
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