HREM studies of intergrowths in Sr2[Srn-1TinO3n+1] Ruddlesden-Popper phases synthesized by mechanochemical activation

A mechanochemical activation route has been applied in order to obtain the <i>n</i>=1–4 and ∞ members of the Sr<sub>2</sub>[Sr<sub>n</sub><sub>−1</sub>Ti<sub>n</sub>O<sub>3n+1</sub>] Ruddlesden– Popper series from different (<i>n</i>+1)SrO:nTiO<sub>2</sub> mixtures. The mechanosynthesis of SrTiO<sub>3</sub> and Sr<sub>2</sub>TiO<sub>4</sub> was observed during the milling process from the initial stoichiometric mixture, but in the cases of the <i>n</i>=2–4 members, a subsequent thermal treatment was needed. The synthesis protocol of Sr<sub>3</sub>Ti<sub>2</sub>O<sub>7</sub> has been greatly improved and this compound can be isolated as a single, crystalline phase after annealing at 800°C. In the case of Sr<sub>4</sub>Ti<sub>3</sub>O<sub>10</sub> and Sr<sub>5</sub>Ti<sub>4</sub>O<sub>13</sub>, the formation temperature was also decreased, but members with <i>n</i>=3 and 4 could not be isolated. Detailed investigations using electron microscopy methods (TEM, HREM and SAED) were carried out in the samples corresponding to <i>n</i>=2–4. Although a single ordered Sr<sub>3</sub>Ti<sub>2</sub>O<sub>7</sub> structure is dominant in the sample corresponding to <i>n</i>=2, a few intergrowths of other Ruddlesden–Popper phases were observed. In the cases of <i>n</i>=3 and 4, the intergrowths of Ruddlesden–Popper phases are more frequent than in the <i>n</i>=2 composition and are randomly distributed in the sample. The more frequent occurrence of such stacking faults, with increasing <i>n</i> value, leads to a somewhat disordered layer stacking sequence

Mid-Infrared ultra-high-Q resonators based on fluoride crystalline materials

Decades ago, the losses of glasses in the near infrared (near-IR) were investigated in views of developments for optical telecommunications. Today, properties in the mid-infrared (mid-IR) are of interest for molecular spectroscopy applications. In particular, high-sensitivity spectroscopic techniques based on high-finesse mid-IR cavities hold high promise for medical applications. Due to exceptional purity and low losses, whispering gallery mode microresonators based on polished alkaline earth metal fluoride crystals (i.e the $\mathrm{XF_2}$ family, where X $=$ Ca, Mg, Ba, Sr,...) have attained ultra-high quality (Q) factor resonances (Q$>$10$^{8}$) in the near-IR and visible spectral ranges. Here we report for the first time ultra-high Q factors in the mid-IR using crystalline microresonators. Using an uncoated chalcogenide (ChG) tapered fiber, light from a continuous wave quantum cascade laser (QCL) is efficiently coupled to several crystalline microresonators at 4.4 $\mu$m wavelength. We measure the optical Q factor of fluoride crystals in the mid-IR using cavity ringdown technique. We observe that $\mathrm{MgF_2}$ microresonators feature quality factors that are very close to the fundamental absorption limit, as caused by the crystal's multiphonon absorption (Q$\sim$10$^{7}$), in contrast to near-IR measurements far away from these fundamental limits. Due to lower multiphonon absorption in $\mathrm{BaF_2}$ and $\mathrm{SrF_2}$, we show that ultra-high quality factors of Q $\geqslant$ 1.4 $\times 10^{8}$ can be reached at 4.4 $\mu$m. This corresponds to an optical finesse of $\mathcal{F}>$4$\cdot$ 10$^{4}$, the highest value achieved for any type of mid-IR resonator to date, and a more than 10-fold improvement over the state-of-the-art. Such compact ultra-high Q crystalline microresonators provide a route for narrow linewidth frequency-stabilized QCL or mid-IR Kerr comb generation.Comment: C. Lecaplain and C. Javerzac-Galy contributed equally to this wor

Post-glacial climate forcing of surface processes in the Ganges–Brahmaputra river basin and implications for carbon sequestration

© The Author(s), 2017. This is the author's version of the work. It is posted here under a nonexclusive, irrevocable, paid-up, worldwide license granted to WHOI. It is made available for personal use, not for redistribution. The definitive version was published in Earth and Planetary Science Letters 478 (2017): 89-101, doi:10.1016/j.epsl.2017.08.013.Climate has been proposed to control both the rate of terrestrial silicate weathering and the export rate of associated sediments and terrestrial organic carbon to river-dominated margins – and thus the rate of sequestration of atmospheric CO2 in the coastal ocean – over glacial-interglacial timescales. Focused on the Ganges-Brahmaputra rivers, this study presents records of post-glacial changes in basin-scale Indian summer monsoon intensity and vegetation composition based on stable hydrogen (δD) and carbon (δ13C) isotopic compositions of terrestrial plant wax compounds preserved in the channel-levee system of the Bengal Fan. It then explores the role of these changes in controlling the provenance and degree of chemical weathering of sediments exported by these rivers, and the potential climate feedbacks through organic-carbon burial in the Bengal Fan. An observed 40‰ shift in δD and a 3–4‰ shift in both bulk organic-carbon and plant-wax δ13C values between the late glacial and mid-Holocene, followed by a return to more intermediate values during the late Holocene, correlates well with regional post-glacial paleoclimate records. Sediment provenance proxies (Sr, Nd isotopic compositions) reveal that these changes likely coincided with a subtle focusing of erosion on the southern flank of the Himalayan range during periods of greater monsoon strength and enhanced sediment discharge. However, grain-size-normalized organic-carbon concentrations in the Bengal Fan remained constant through time, despite order-of-magnitude level changes in catchment-scale monsoon precipitation and enhanced chemical weathering (recorded as a gradual increase in K/Si* and detrital carbonate content, and decrease in H2O+/Si*, proxies) throughout the study period. These findings demonstrate a partial decoupling of climate change and silicate weathering during the Holocene and that marine organic-carbon sequestration rates primary reflect rates of physical erosion and sediment export as modulated by climatic changes. Together, these results reveal the magnitude of climate changes within the Ganges-Brahmaputra basin following deglaciation and a closer coupling of monsoon strength with OC burial than with silicate weathering on millennial timescales.This work was supported by the National Science Foundation [grant numbers OCE-1333826 and OCE-1333387]

Sustained wood burial in the Bengal Fan over the last 19 My

Author Posting. © National Academy of Sciences, 2019. This article is posted here by permission of National Academy of Sciences for personal use, not for redistribution. The definitive version was published in Proceedings of the National Academy of Sciences 116(45), (2019): 22518-22525, doi:10.1073/pnas.1913714116.The Ganges–Brahmaputra (G-B) River system transports over a billion tons of sediment every year from the Himalayan Mountains to the Bay of Bengal and has built the world’s largest active sedimentary deposit, the Bengal Fan. High sedimentation rates drive exceptional organic matter preservation that represents a long-term sink for atmospheric CO2. While much attention has been paid to organic-rich fine sediments, coarse sediments have generally been overlooked as a locus of organic carbon (OC) burial. However, International Ocean Discovery Program Expedition 354 recently discovered abundant woody debris (millimeter- to centimeter-sized fragments) preserved within the coarse sediment layers of turbidite beds recovered from 6 marine drill sites along a transect across the Bengal Fan (∼8°N, ∼3,700-m water depth) with recovery spanning 19 My. Analysis of bulk wood and lignin finds mostly lowland origins of wood delivered episodically. In the last 5 My, export included C4 plants, implying that coarse woody, lowland export continued after C4 grassland expansion, albeit in reduced amounts. Substantial export of coarse woody debris in the last 1 My included one wood-rich deposit (∼0.05 Ma) that encompassed coniferous wood transported from the headwaters. In coarse layers, we found on average 0.16 weight % OC, which is half the typical biospheric OC content of sediments exported by the modern G-B Rivers. Wood burial estimates are hampered by poor drilling recovery of sands. However, high-magnitude, low-frequency wood export events are shown to be a key mechanism for C burial in turbidites.This work was funded by National Science Foundation Grants OCE-1401217 and COL-T354A55 to S.J.F. and OCE-1400805 to V.G. Graduate student participation in the project received support from University of Southern California Provost’s Fellowship to H.L. Samples were provided by the International Ocean Discovery Program. We are grateful for the efforts of the Expedition 354 Science Party, Carl Johnson, and Zongguang Liu. C.F.-L. and A.G. were supported by IODP-France. We thank Colin Osborne and Maria Vorontsova for helpful discussions.2020-04-2

Leaf wax biomarkers in transit record river catchment composition

Author Posting. © American Geophysical Union, 2014. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geophysical Research Letters 41 (2014): 6420–6427, doi:10.1002/2014GL061328.Rivers carry organic molecules derived from terrestrial vegetation to sedimentary deposits in lakes and oceans, storing information about past climate and erosion, as well as representing a component of the carbon cycle. It is anticipated that sourcing of organic matter may not be uniform across catchments with substantial environmental variability in topography, vegetation zones, and climate. Here we analyze plant leaf wax biomarkers in transit in the Madre de Dios River (Peru), which drains a forested catchment across 4.5 km of elevation from the tropical montane forests of the Andes down into the rainforests of Amazonia. We find that the hydrogen isotopic composition of leaf wax molecules (specifically the C28 n-alkanoic acid) carried by this tropical mountain river largely records the elevation gradient defined by the isotopic composition of precipitation, and this supports the general interpretation of these biomarkers as proxy recorders of catchment conditions. However, we also find that leaf wax isotopic composition varies with river flow regime over storm and seasonal timescales, which could in some cases be quantitatively significant relative to changes in the isotopic composition of precipitation in the past. Our results inform on the sourcing and transport of material by a major tributary of the Amazon River and contribute to the spatial interpretation of sedimentary records of past climate using the leaf wax proxy.This work was supported by funding from the U.S. National Science Foundation award 1227192 to A.J.W. and S.J.F. V.G. was supported by the U.S. National Science Foundation award OCE-0928582.2015-03-2

Magneto-Dielectric Effect in the S = 1/2 Quasi-Two Dimensional Antiferromagnet K2V3O8

We report the optical and magneto-optical properties of K2V3O8, an S=1/2 quasi-two-dimensional Heisenberg antiferromagnet. Local spin density approximation electronic structure calculations are used to assign the observed excitations and analyze the field dependent features. Two large magneto-optical effects, centered at ~1.19 and 2.5 eV, are attributed to field-induced changes in the V 4+ d to d on-site excitations due to modification of the local crystal field environment of the VO5 square pyramids with applied magnetic field. Taken together, the evidence for a soft lattice, the presence of vibrational fine structure on the sharp 1.19 eV magneto-optical feature,and the fact that these optical excitations are due to transitions from a nearly pure spin polarized V d state to hybridized states involving both V and O, suggest that the magneto-dielectric effect in K2V3O8 is driven by strong lattice coupling.Comment: Zipped file containing 8 pages, 12 figures, in press PR

NaV_2O_5 as a quarter-filled ladder compound

A new X-ray diffraction study of the one-dimensional spin-Peierls compound \alpha-NaV_2O_5 reveals a centrosymmetric (Pmmn) crystal structure with one type of V site, contrary to the previously postulated non-centrosymmetric P2_1mn structure with two types of V sites (V^{+4} and V^{+5}). Density functional calculations indicate that NaV_2O_5 is a quarter-filled ladder compound with the spins carried by V-O-V molecular orbitals on the rungs of the ladder. Estimates of the charge-transfer gap and the exchange coupling agree well with experiment and explain the insulating behavior of NaV_2O_5 and its magnetic properties.Comment: Final version for PRL, value of U correcte

On discrimination between carbonate and silicate inputs to Himalayan rivers

We review new and published analyses of river waters, bedloads and their constituent minerals from the Dhauli Ganga and Alaknanda, headwaters of the Ganges in Garhwal, and the Marsyandi in Nepal and their tributaries. These data are used to discriminate between the inputs of major cations and Sr from silicate and carbonate sources. Methods of estimating the proportion of the carbonate and silicate inputs to river waters using mixing arrays in Sr-Ca-Mg-Na-K 87Sr/86Sr space are shown to suffer from systematic correlations between the magnitude of the precipitation of secondary calcite and the fraction of the silicate component. This results in factor-of two overestimates of the fractions of silicate-derived Ca, Mg and Sr. To correct for this the magnitude of secondary calcite precipitated and relative fractions of silicate and carbonate-derived cations are instead calculated by modeling the displacement of water compositions from the compositions of the carbonate and silicate components of the bedload in subsets of Sr-Ca-Mg-Na-K 87Sr/86Sr space. The compositions of the carbonate and silicate end-members in the bedload are determined by sequential leaching. The results of this modeling are compared with modeling of the modal mineral inputs to waters where mineral compositions are derived from electronmicroprobe analyses of the minerals in the bedload. In the upper Marsyandi catchment, which drains low-grade Tethyan Sedimentary Series formations, a set of mainstem samples collected over a two-year period define tight correlations in Sr-Ca-Mg-Na-K- 87Sr/86Sr space. Modeling of the magnitude of secondary carbonate precipitation and fractions of silicate-derived Ca, Mg and Sr in Sr-Ca-Mg 87Sr/86Sr space gives selfconsistent results that are compatible with both the calculations of mineral modes and published Mg-isotopic compositions, if the ratio of chlorite to biotite weathering is high or if there is another silicate source of Mg. These calculations imply that between 12 and 31 percent of the Sr and 44 and 72 percent of the Mg is derived from silicate minerals where the range reflects the seasonal change in the ratio of silicate-derived to carbonate-derived cations. Modeling in Sr-Ca-Na and/or K space is inconsistent with the Sr-isotopic and Mg-isotopic constraints and we conclude that in this catchment dissolution of Na and K are incongruent relative to Sr-Ca-Mg. Potassium is preferentially retained in micas whereas the controls on Na are unclear. Modeling of the catchments underlain by High Himalayan Crystalline and Lesser Himalayan Series in Garhwal is complicated by the presence of dolomite as well as calcite in the carbonate and the results imply that dolomite dissolves faster in the acetic acid leaches than in nature. Up to 60 percent of the Sr in the catchment on High Himalayan Crystalline Series and 20 to 30 percent of Sr in the catchments on Lesser Himalayan Series are estimated to be derived from silicates. However it should be noted that the element budgets are not all self-consistent and the use of bedrock-element ratios to model the sources of chemical inputs to river waters remains subject to uncertainties

Crystal structure of LaTiO_3.41 under pressure

The crystal structure of the layered, perovskite-related LaTiO_3.41 (La_5Ti_5O_{17+\delta}) has been studied by synchrotron powder x-ray diffraction under hydrostatic pressure up to 27 GPa (T = 295 K). The ambient-pressure phase was found to remain stable up to 18 GPa. A sluggish, but reversible phase transition occurs in the range 18--24 GPa. The structural changes of the low-pressure phase are characterized by a pronounced anisotropy in the axis compressibilities, which are at a ratio of approximately 1:2:3 for the a, b, and c axes. Possible effects of pressure on the electronic properties of LaTiO_3.41 are discussed.Comment: 5 pages, 6 figure

Quaternary climate modulation of Pb isotopes in the deep Indian Ocean linked to the Himalayan chemical weathering

We use reductive sediment leaching to extract lead (Pb) from the authigenic fraction of marine sediments and reconstruct the Pb isotope evolution of the deep central Indian Ocean over the past 250 thousand years at ∼3 kyr resolution. Temporal variations define a binary mixing line that is consistent with data from ferromanganese nodules and which records mixing between two well-defined endmembers through time. The unradiogenic endmember appears to represent a widely-distributed Pb source, from mid-ocean ridges or possibly volcanic aerosols, while the radiogenic endmember coincides with the composition of Ganges–Brahmaputra river sediments that are indicative of the Himalayan weathering inputs. Glacial–interglacial Pb isotope variations are striking and can be explained by an enhancement of Himalayan contributions by two to three times during interglacial periods, indicating that climate modulates the supply of dissolved elements to the ocean. While these changes could accurately record variations in the continental chemical weathering flux in response to warmer and wetter conditions during interglacials, the relative proportions of Pb derived from the Ganges and Brahmaputra appear to have been constant through time. This observation may point towards particulate-dissolved interactions in the estuary or pro-delta as a buffer of short timescale variability in the composition (and potentially flux) of the fluvial inputs. In addition, the changes are recorded at 3800 m water depth, and with the lack of deep water formation in the Bay of Bengal, a mechanism to transfer such a signature into the deep ocean could either be reversible scavenging of dissolved Pb inputs and/or boundary exchange on the deep sea fan. Unless the mechanism transferring the Pb isotope signature into the deep ocean was itself highly sensitive to global climate cycles, and with the absence of a precessional signal in our Pb isotope data, we suggest that the Indian climate and its influence on basin-scale chemical weathering were strongly modulated by glacial versus interglacial boundary conditions