Origin and Pathway of Equatorial 13 degrees C Water in the Pacific Identified by a Simulated Passive Tracer and Its Adjoint

The origin and pathway of the thermostad water in the eastern equatorial Pacific Ocean, often referred to as the equatorial 13 degrees C Water, are investigated using a simulated passive tracer and its adjoint, based on circulation estimates of a global general circulation model. Results demonstrate that the source region of the 13 degrees C Water lies well outside the tropics. In the South Pacific, some 13 degrees C Water is formed northeast of New Zealand, confirming an earlier hypothesis on the water's origin. The South Pacific origin of the 13 degrees C Water is also related to the formation of the Eastern Subtropical Mode Water (ESTMW) and the Sub-Antarctic Mode Water (SAMW). The portion of the ESTMW and SAMW that eventually enters the density range of the 13 degrees C Water (25.8 < sigma(theta) < 26.6 kg m(-3)) does so largely by mixing. Water formed in the subtropics enters the equatorial region predominantly through the western boundary, while its interior transport is relatively small. The fresher North Pacific ESTMW and Central Mode Water (CMW) are also important sources of the 13 degrees C Water. The ratio of the southern versus the northern origins of the water mass is about 2 to 1 and tends to increase with time elapsed from its origin. Of the total volume of initially tracer-tagged water in the eastern equatorial Pacific, approximately 47.5% originates from depths above sigma(theta) = 25.8 kg m(-3) and 34.6% from depths below sigma(theta) = 26.6 kg m(-3), indicative of a dramatic impact of mixing on the route of subtropical water to becoming the 13 degrees C Water. Still only a small portion of the water formed in the subtropics reaches the equatorial region, because most of the water is trapped and recirculates in the subtropical gyre.

植物营养元素的含量和δ~(13)C值随海拔而变化的特征及营养元素相互作用对碳同位素分馏作用的影响

为了研究植物营养元素的含量和δ~(13)C值随海拔而变化的相关关系,沿着海拔450 m的贵州茂兰至海拔1330 m的贵州安顺一线,采集和分析研究了C_3植物——小果蔷薇(R.cymosa Tratt)的叶片。分析结果表明,植物叶片中营养元素含量随着海拔的上升而产生的变化是:氮、磷和钾的含量会在增高,而钙和镁的含量却会降低。植物叶片的δ~(13)C值会增大,其变幅为+2.4‰/1000m。

The stability of nanosized HZSM-5 zeolite: a high-resolution solid-state NMR study

The thermal and hydrothermal stabilities of HZSM-5 zeolites with crystal sizes less than 100 nm have been studied by multinuclear solid-state NMR, combined with BET and XRD. As evidenced by Al-27 and Si-29 MAS as well as their corresponding cross-polarization/MAS NMR investigations, the thermal stability of nanosized HZSM-5 is not so good as that of microsized HZSM-5. This is due to two processes concerning dealumination and desilicification involved in the calcination of nanosized HZSM-5, while only the dealumination process is conducted in microsized HZSM-5 under the similar calcination process. The hydrothermal stability of nanosized HZSM-5 is, contrary to what was expected, not so bad as that of the microsized HZSM-5 in the course of steam treatment. The actual resistance of the hydrothermal stability to the crystal size of HZSM-5 can be ascribed to an active reconstruction of zeolitic framework through an effective filling of amorphous Si species into nanosized HZSM-5 during hydrothermal treatment. (C) 2001 Published by Elsevier Science B.V.

The second round of Critical Assessment of Automated Structure Determination of Proteins by NMR: CASD-NMR-2013

The second round of the community-wide initiative Critical Assessment of automated Structure Determination of Proteins by NMR (CASD-NMR-2013) comprised ten blind target datasets, consisting of unprocessed spectral data, assigned chemical shift lists and unassigned NOESY peak and RDC lists, that were made available in both curated (i.e. manually refined) or un-curated (i.e. automatically generated) form. Ten structure calculation programs, using fully automated protocols only, generated a total of 164 three-dimensional structures (entries) for the ten targets, sometimes using both curated and un-curated lists to generate multiple entries for a single target. The accuracy of the entries could be established by comparing them to the corresponding manually solved structure of each target, which was not available at the time the data were provided. Across the entire data set, 71 % of all entries submitted achieved an accuracy relative to the reference NMR structure better than 1.5 Å. Methods based on NOESY peak lists achieved even better results with up to 100 % of the entries within the 1.5 Å threshold for some programs. However, some methods did not converge for some targets using un-curated NOESY peak lists. Over 90 % of the entries achieved an accuracy better than the more relaxed threshold of 2.5 Å that was used in the previous CASD-NMR-2010 round. Comparisons between entries generated with un-curated versus curated peaks show only marginal improvements for the latter in those cases where both calculations converged.

Dinámica del carbono en sistemas agrícolas bajo siembra directa : nuevas evidencias obtenidas mediante el uso de 13 C sobre la importancia de las raíces, la calidad de los residuos y el laboreo

El carbono orgánico del suelo (COS) es uno de los principales determinantes de la productividad de los ecosistemas, afectando la fertilidad del suelo y su capacidad de secuestrar CO2. La agricultura es uno de los principales cambios de uso del suelo que afecta significativamente el COS. En esta tesis se examinan, mediante experimentos de campo y usando al 13C como trazador isotópico, tres aspectos de la dinámica de C en sistemas agrícolas: 1) la importancia de las raíces en la formación de COS, 2) los efectos de la cantidad y calidad de los residuos sobre la tasa de descomposición y humificación del COS y 3) la dinámica del COS en sistemas de agricultura continua iniciados sobre pastizales naturales nunca laboreados. Los resultados obtenidos muestran que 1) en cultivos de soja y maíz, la formación de COS se deriva principalmente de la biomasa subterránea y en menor medida de los residuos aéreos, al menos en la fracción de la materia orgánica particulada (MOP). También, se observó 2) que el agregado de residuos de maíz con alta relación C:N aumentó la tasa de descomposición de la MOAM (materia orgánica asociada a los minerales) cuando se la compara con el agregado de residuos de soja (baja relación C:N), efecto conocido como priming. Sin embargo, también existió una mayor formación de materia orgánica bajo cultivos de maíz, y por ende se conservaron las reservas de COS, pero su ciclado fue más rápido. Finalmente, 3) los cultivos en sistemas de siembra directa establecidos sobre suelos nunca laboreados presentaron niveles de COS similares a los de los pastizales naturales remplazados. Estos resultados cuestionan parte de nuestro conocimiento sobre los sistemas agrícolas bajo siembra directa, aportando nuevas evidencias experimentales y destacando el uso de marcadores isotópicos de 13C para comprender el flujo de C en los agroecosistemas.

Dinámica del carbono en sistemas agrícolas bajo siembra directa : nuevas evidencias obtenidas mediante el uso de 13 C sobre la importancia de las raíces, la calidad de los residuos y el laboreo

El carbono orgánico del suelo (COS) es uno de los principales determinantes de la productividad de los ecosistemas, afectando la fertilidad del suelo y su capacidad de secuestrar CO2. La agricultura es uno de los principales cambios de uso del suelo que afecta significativamente el COS. En esta tesis se examinan, mediante experimentos de campo y usando al 13C como trazador isotópico, tres aspectos de la dinámica de C en sistemas agrícolas: 1) la importancia de las raíces en la formación de COS, 2) los efectos de la cantidad y calidad de los residuos sobre la tasa de descomposición y humificación del COS y 3) la dinámica del COS en sistemas de agricultura continua iniciados sobre pastizales naturales nunca laboreados. Los resultados obtenidos muestran que 1) en cultivos de soja y maíz, la formación de COS se deriva principalmente de la biomasa subterránea y en menor medida de los residuos aéreos, al menos en la fracción de la materia orgánica particulada (MOP). También, se observó 2) que el agregado de residuos de maíz con alta relación C:N aumentó la tasa de descomposición de la MOAM (materia orgánica asociada a los minerales) cuando se la compara con el agregado de residuos de soja (baja relación C:N), efecto conocido como priming. Sin embargo, también existió una mayor formación de materia orgánica bajo cultivos de maíz, y por ende se conservaron las reservas de COS, pero su ciclado fue más rápido. Finalmente, 3) los cultivos en sistemas de siembra directa establecidos sobre suelos nunca laboreados presentaron niveles de COS similares a los de los pastizales naturales remplazados. Estos resultados cuestionan parte de nuestro conocimiento sobre los sistemas agrícolas bajo siembra directa, aportando nuevas evidencias experimentales y destacando el uso de marcadores isotópicos de 13C para comprender el flujo de C en los agroecosistemas.

pKa values of aqua ligands of platinum (II) anticancer complexes: [1H, 15N] and 195Pt NMR Studies of cis- and trans- [PtCl2 (NH3) (Cyclohexylamine)]

Syntheses and NMR studies are reported of two 15N-labelled Pt(II) complexes of anticancer interest: cis-PtCl2(15NH3)(c-C6H1115NH2), a metabolite of the orally-active Pt(IV) complex cis,trans,cis-[PtCl2(acetate)2(c-C6H11NH2)(NH3), and trans-[PtCl2(15NH3)(c-C6H1115NH2), a reduction product of the active Pt(IV) complex trans,trans,trans-[PtCl2(OH)2(c-C6H11NH2). For cis-[PtCl2(15NH3)(c-C6H1115NH2), hydrolysis was faster for the chloride ligand trans to cyclohexylamine, and the pKa values determined by [1H, 15N NMR spectroscopy for the two cis monoaqua isomers were the same (6.73). The trans monoaqua complex was a stronger acid with pKa of 5.4 (determined by 195Pt NMR). For the cis diaqua complex, pKa values of 5.68 and 7.68 were determined.

Applications of DNP-NMR for the measurement of heteronuclear T1 relaxation times

Measurement of heteronuclear spin-lattice relaxation times is hampered by both low natural abundance and low detection sensitivity. Combined with typically long relaxation times, this results in extended acquisition times which often renders the experiment impractical. Recently a variant of dynamic nuclear polarisation has been demonstrated in which enhanced nuclear spin polarisation, generated in the cryo-solid state, is transferred to the liquid state for detection. Combining this approach with small flip angle pulse trains, similar to the FLASH-T(1) imaging sequence, allows the rapid determination of spin-lattice relaxation times. In this paper we explore this method and its application to the measurement of T(1) for both carbon-13 and nitrogen-15 at natural abundance. The effects of RF inhomogeneity and the influence of proton decoupling in the context of this experiment are also investigated.

Evolution of Clay Morphology in Polypropylene/Montmorillonite Nanocomposites upon Equi-biaxial Stretching: A Solid-State NMR and TEM Approach

Solid-state NMR and TEM were used to quantitatively examine the evolution of clay morphology upon equibiaxial stretching of polypropylene/montmorillonite (PP-MMT) nanocomposites up to a stretch ratio (?= final length/initial length) of 3.5. 1 H spin-lattice relaxation times were measured by the saturation-recovery sequence. For the nanocomposites, initial portions of the magnetization recovery
curves (e~20 ms) were found to depend on v t, indicative of diffusion-limited relaxation and in agreement with calculations based on estimates of the spin-diffusion barrier radius surrounding the paramagnetic centers in the clay, the electron-nucleus coupling constant, and the spin-diffusion coefficient. Initial slopes of these magnetization recovery curves directly correlated with the fraction of clay/polymer interface. New clay surface was exposed as a near linear function of strain. Long-time portions of the magnetization recovery curves yielded information on the average interparticle separations, which decreased slowly before reaching a plateau at ?=~2.5 as particles aligned. TEM images supported these findings and were used to define and quantify degrees of exfoliation and homogeneity from the NMR data. Exfoliation, defined as (platelets/ stack)-1, increased from 0.38 (unstretched) to 0.80 at ? = 3.5 for PP-MMT nanocomposites stretched at
150 C and 16 s-1. A lower stretch temperature, 145 C, which is slightly below melting onset, led to an exfoliation degree of 0.87 at ?= 2.8, consistent with the ability of higher melt viscosities to allow for higher shear stress transfer. Exposure of new clay surface is attributed to aggregate breakup and orientation at low strains (? e ~2) and to platelets sliding apart at higher strains.

Accounting for the effects of lipids in stable isotope (δ13C and δ15N values) analysis of skin and blubber of balaenopterid whales

RATIONALE Stable isotope values (d¹³C and d¹⁵N) of darted skin and blubber biopsies can shed light on habitat use and diet of cetaceans, which are otherwise difficult to study. Non-dietary factors affect isotopic variability, chiefly the depletion of C due to the presence of C-rich lipids. The efficacy of post hoc lipid-correction models (normalization) must be tested. METHODS For tissues with high natural lipid content (e.g., whale skin and blubber), chemical lipid extraction or normalization is necessary. C:N ratios, d¹³C values and d¹⁵N values were determined for duplicate control and lipid-extracted skin and blubber of fin (Balaenoptera physalus), humpback (Megaptera novaeangliae) and minke whales (B. acutorostrata) by continuous-flow elemental analysis isotope ratio mass spectrometry (CF-EA-IRMS). Six different normalization models were tested to correct d¹³C values for the presence of lipids. RESULTS Following lipid extraction, significant increases in d¹³C values were observed for both tissues in the three species. Significant increases were also found for d¹⁵N values in minke whale skin and fin whale blubber. In fin whale skin, the d¹⁵N values decreased, with no change observed in humpback whale skin. Non-linear models generally out-performed linear models and the suitability of models varied by species and tissue, indicating the need for high model specificity, even among these closely related taxa. CONCLUSIONS Given the poor predictive power of the models to estimate lipid-free d13C values, and the unpredictable changes in d N values due to lipid-extraction, we recommend against arithmetical normalization in accounting for lipid effects on d13C values for balaenopterid skin or blubber samples. Rather, we recommend that duplicate analysis of lipid-extracted (d13C values) and non-treated tissues (d15N values) be used. Copyright © 2012 John Wiley & Sons, Ltd.

Balancing the (carbon) budget: Using linear inverse models to estimate carbon flows and mass-balance 13C:15N labelling experiments in low oxygen sediments.

Over 1 million km² of seafloor experience permanent low-oxygen conditions within oxygen minimum zones (OMZs). OMZs are predicted to grow as a consequence of climate change, potentially affecting oceanic biogeochemical cycles. The Arabian Sea OMZ impinges upon the western Indian continental margin at bathyal depths (150 - 1500 m) producing a strong depth dependent oxygen gradient at the sea floor. The influence of the OMZ upon the short term processing of organic matter by sediment ecosystems was investigated using in situ stable isotope pulse chase experiments. These deployed doses of ¹³C:¹⁵N labeled organic matter onto the sediment surface at four stations from across the OMZ (water depth 540 - 1100 m; [O₂] = 0.35 - 15 μM). In order to prevent experimentally anoxia, the mesocosms were not sealed. ¹³C and ¹⁵N labels were traced into sediment, bacteria, fauna and ¹³C into sediment porewater DIC and DOC. However, the DIC and DOC flux to the water column could not be measured, limiting our capacity to obtain mass-balance for C in each experimental mesocosm. Linear Inverse Modeling (LIM) provides a method to obtain a mass-balanced model of carbon flow that integrates stable-isotope tracer data with community biomass and biogeochemical flux data from a range of sources. Here we present an adaptation of the LIM methodology used to investigate how ecosystem structure influenced carbon flow across the Indian margin OMZ. We demonstrate how oxygen conditions affect food-web complexity, affecting the linkages between the bacteria, foraminifera and metazoan fauna, and their contributions to benthic respiration. The food-web models demonstrate how changes in ecosystem complexity are associated with oxygen availability across the OMZ and allow us to obtain a complete carbon budget for the stationa where stable-isotope labelling experiments were conducted.