Delayed build-up of Arctic ice sheets during 400,000-year minima in insolation variability.

Knowledge of the past variability of climate at high northern latitudes during astronomical analogues of the present interglacial may help to inform our understanding of future climate change. Unfortunately, long-term continuous records of ice-sheet variability in the Northern Hemisphere only are scarce because records of benthic (18)O content represent an integrated signal of changes in ice volume in both polar regions. However, variations in Northern Hemisphere ice sheets influence the Siberian High (an atmospheric pressure system), so variations in the East Asian winter monsoon (EAWM)--as recorded in the aeolian dust deposits on the Chinese Loess Plateau--can serve as a useful proxy of Arctic climate variability before the ice-core record begins. Here we present an EAWM proxy record using grain-size variations in two parallel loess sections representative of sequences across the whole of the Chinese Loess Plateau over the past 900,000 years. The results show that during periods of low eccentricity and precessional variability at approximately 400,000-year intervals, the grain-size-inferred intensity of the EAWM remains weak for up to 20,000 years after the end of the interglacial episode of high summer monsoon activity and strong pedogenesis. In contrast, there is a rapid increase in the EAWM after the end of most other interglacials. We conclude that, for both the 400,000-year interglacials, the weak EAWM winds maintain a mild, non-glacial climate at high northern latitudes for much longer than expected from the conventional loess and marine oxygen isotope records. During these times, the less-severe summer insolation minima at 65° N (ref. 4) would have suppressed ice and snow accumulation, leading to a weak Siberian High and, consequently, weak EAWM winds.

Changes in monsoon precipitation in East Asia under a 2°C interglacial warming.

Past intervals of warming provide the unique opportunity to observe how the East Asia monsoon precipitation response happened in a warming world. However, the available evaluations are primarily limited to the last glacial-to-interglacial warming, which has fundamental differences from the current interglacial warming, particularly in changes in ice volume. Comparative paleoclimate studies of earlier warm interglacial periods can provide more realistic analogs. Here, we present high-resolution quantitative reconstructions of temperature and precipitation from north-central China over the past 800 thousand years. We found that the average precipitation increase, estimated by the interglacial data, was only around one-half of that estimated for the glacial-to-interglacial data, which is attributed to the amplification of climate change by ice volume variations. Analysis of the interglacial data suggests an increase in monsoon precipitation of ~100 mm for a warming level of 2°C on the Chinese Loess Plateau.

East Asian winter monsoon intensification over the Northwest Pacific Ocean driven by late Miocene atmospheric CO2 decline.

East Asian winter monsoon (EAWM) activity has had profound effects on environmental change throughout East Asia and the western Pacific. Much attention has been paid to Quaternary EAWM evolution, while long-term EAWM fluctuation characteristics and drivers remain unclear, particularly during the late Miocene when marked global climate and Asian paleogeographic changes occurred. To clarify understanding of late Miocene EAWM evolution, we developed a high-precision 9-million-year-long stacked EAWM record from Northwest Pacific Ocean abyssal sediments based on environmental magnetism, sedimentology, and geochemistry, which reveals a strengthened late Miocene EAWM. Our paleoclimate simulations also indicate that atmospheric CO2 decline played a vital role in this EAWM intensification over the Northwest Pacific Ocean compared to other factors, including central Asian orogenic belt and northeastern Tibetan Plateau uplift and Antarctic ice-sheet expansion. Our results expand understanding of EAWM evolution from inland areas to the open ocean and indicate the importance of atmospheric CO2 fluctuations on past EAWM variability over large spatial scales.

Large-Scale Fabrication of Three-Dimensional Surface Patterns Using Template-Defined Electrochemical Deposition.

A new strategy to achieve large-scale, three-dimensional (3D) micro- and nanostructured surface patterns through selective electrochemical growth on monolayer colloidal crystal (MCC) templates is reported. This method can effectively create large-area (>1 cm2), 3D surface patterns with well-defined structures in a cost-effective and time-saving manner (<30 min). A variety of 3D surface patterns, including semishells, Janus particles, microcups, and mushroom-like clusters, is generated. Most importantly, our method can be used to prepare surface patterns with prescribed compositions, such as metals, metal oxides, organic materials, or composites (e.g., metal/metal oxide, metal/polymer). The 3D surface patterns produced by our method can be valuable in a wide range of applications, such as biosensing, data storage, and plasmonics. In a proof-of-concept study, we investigated, both experimentally and theoretically, the surface-enhanced Raman scattering (SERS) performance of the fabricated silver 3D semishell arrays.

Seasonal climatic instability in the western Chinese Loess Plateau during Marine Isotope Stages 12-10.

Because of similar astronomical background, Marine Isotope Stage (MIS) 11 is viewed as an analogue of the Holocene, but the evolution of seasonal climatic instability during MIS 11 has not been well investigated. Here we present a time series of land-snail eggs-a recently-developed proxy of seasonal cooling events-from the Chinese Loess Plateau (CLP) to investigate seasonal climatic instability during MIS 11 and adjacent glacials. Due to the impact of low temperatures on egg hatching, egg-abundance peaks document seasonal cooling events. A total of five egg-abundance peaks were recorded in the CLP during MIS 12, MIS 11 and MIS 10. Three peaks are strong and occur close to glacial inception or interglacial-to-glacial transition; two weaker peaks occur during MIS11. These peaks imply seasonal climatic instability intensifies mainly during glacial initiation or transition. All these events correspond to ice-sheet growth and the loss of ice-rafted debris at high northern latitudes. Moreover, they occurred at the minima of local spring insolation during the MIS 12 and MIS 10 glacials, but at the maxima during the MIS 11 interglacial. This may contribute to the difference in the intensity of seasonal cooling events between low-eccentricity glacials and interglacials. Our results provide new evidence for understanding low-eccentricity interglacial-glacial evolution.

Assessment of Common Cyanotoxins in Cyanobacteria of Biological Loess Crusts.

Cyanotoxins are a diverse group of bioactive compounds produced by cyanobacteria that have adverse effects on human and animal health. While the phenomenon of cyanotoxin production in aquatic environments is well studied, research on cyanotoxins in terrestrial environments, where cyanobacteria abundantly occur in biocrusts, is still in its infancy. Here, we investigated the potential cyanotoxin production in cyanobacteria-dominated biological loess crusts (BLCs) from three different regions (China, Iran, and Serbia) and in cyanobacterial cultures isolated from the BLCs. The presence of cyanotoxins microcystins, cylindrospermopsin, saxitoxins, and ß-N-methylamino-L-alanine was analyzed by liquid chromatography-tandem mass spectrometry (LC-MS/MS) method, while the presence of cyanotoxin-encoding genes (mcyE, cyrJ, sxtA, sxtG, sxtS, and anaC) was investigated by polymerase chain reaction (PCR) method. We could not detect any of the targeted cyanotoxins in the biocrusts or the cyanobacterial cultures, nor could we amplify any cyanotoxin-encoding genes in the cyanobacterial strains. The results are discussed in terms of the biological role of cyanotoxins, the application of cyanobacteria in land restoration programs, and the use of cyanotoxins as biosignatures of cyanobacterial populations in loess research. The article highlights the need to extend the field of research on cyanobacteria and cyanotoxin production to terrestrial environments.

Milankovitch theory and monsoon.

The widely accepted "Milankovitch theory" explains insolation-induced waxing and waning of the ice sheets and their effect on the global climate on orbital timescales. In the past half century, however, the theory has often come under scrutiny, especially regarding its "100-ka problem." Another drawback, but the one that has received less attention, is the "monsoon problem," which pertains to the exclusion of monsoon dynamics in classic Milankovitch theory even though the monsoon prevails over the vast low-latitude (∼30° N to ∼30° S) region that covers half of the Earth's surface and receives the bulk of solar radiation. In this review, we discuss the major issues with the current form of Milankovitch theory and the progress made at the research forefront. We suggest shifting the emphasis from the ultimate outcomes of the ice volume to the causal relationship between changes in northern high-latitude insolation and ice age termination events (or ice sheet melting rate) to help reconcile the classic "100-ka problem." We discuss the discrepancies associated with the characterization of monsoon dynamics, particularly the so-called "sea-land precession-phase paradox" and the "Chinese 100-ka problem." We suggest that many of these discrepancies are superficial and can be resolved by applying a holistic "monsoon system science" approach. Finally, we propose blending the conventional Kutzbach orbital monsoon hypothesis, which calls for summer insolation forcing of monsoons, with Milankovitch theory to formulate a combined "Milankovitch-Kutzbach hypothesis" that can potentially explain the dual nature of orbital hydrodynamics of the ice sheet and monsoon systems, as well as their interplays and respective relationships with the northern high-latitude insolation and inter-tropical insolation differential.

Polarization-independent dual-band infrared perfect absorber based on a metal-dielectric-metal elliptical nanodisk array.

We have designed and fabricated a dual-band plasmonic absorber in the near-infrared by employing a three-layer structure comprised of an elliptical nanodisk array on top of thin dielectric and metallic films. finite difference time domain (FDTD) simulations indicate that absorption efficiencies greater than 99% can be achieved for both resonance frequencies at normal incidence and the tunable range of the resonant frequency was modeled up to 700 nm by varying the dimensions of the three-layer, elliptical nanodisk array. The symmetry in our two-dimensional nanodisk array eliminates any polarization dependence within the structure, and the near-perfect absorption efficiency is only slightly affected by large incidence angles up to 50 degrees. Experimental measurements demonstrate good agreement with our simulation results.

High contrast modulation of plasmonic signals using nanoscale dual-frequency liquid crystals.

We have designed and simulated a dual-frequency liquid crystal (DFLC) based plasmonic signal modulator capable of achieving over 15 dB modulation depth. The voltage-controlled DFLC is combined with a groove and slit configuration and its operation is discussed. Using the finite-difference time domain (FDTD) method, simulations were conducted to discover the groove-slit separation distance that enabled a practically useful modulation depth for the two states of the DFLC. Moreover, we have shown that significant improvement in modulation depth can be achieved by addition of a second groove to the design structure. Additionally, a performance analysis indicates a switching energy on the order of femtojoules and a switching speed on the order of 100 microseconds. Results of this investigation can be useful for the future design, simulation, and fabrication of DFLC-based plasmonic signal modulating devices, which have application in electro-optical and all-optical information systems.

Beam bending via plasmonic lenses.

We have designed and characterized three different types of plasmonic lenses that cannot only focus, but can also bend electromagnetic (EM) waves. The bending effect is achieved by constructing an asymmetric phase front caused by varying phase retardations in EM waves as they pass through a plasmonic lens. With an incident wave normal to the lens surface, light bends up to 8° off the axial direction. The optical wave propagation was numerically investigated using the finite-difference time-domain (FDTD) method. Simulation results show that the proposed plasmonic lenses allow effective beam bending under both normal and tilted incidence. With their relatively large bending range and capability to perform in the far field, the plamsonic lenses described in this article could be valuable in applications such as photonic communication and plasmonic circuits.

Phased uplift of the northeastern Tibetan Plateau inferred from a pollen record from Yinchuan Basin, northwestern China.

The uplift of the Tibetan Plateau (TP) significantly affected both regional and global climates. Although there is evidence that the Tibetan Plateau experienced uplift during the Quaternary, the timing and amplitude are poorly constrained. However, the increased availability of long sedimentary records of vegetation change provides an opportunity to reconstruct the timing of the uplift. Here, we present a well-dated, high-resolution pollen record for the last 2.6 Ma from the Yinchuan Basin, which was incised by the Yellow River with its source in the northeastern Tibetan Plateau. Variations in the Artemisia/Chenopodiaceae (A/C) ratio of the reveal changes in moisture conditions in the Yinchuan Basin during glacial-interglacial cycles, as well as a gradual long-term aridification trend which is consistent with progressive global cooling. However, fluctuations in the percentages of Picea and Abies differ from those of the A/C ratio and we propose that they reflect changes in the vegetation and environment of high elevation areas. The Picea and Abies records reveal two phases of increased representation, at 2.1 and 1.2 Ma, which may indicate phases in the uplift of the northeastern Tibetan Plateau. Thus, they provide independent evidence for the timing of the uplift of the Tibetan Plateau during the Quaternary.

Extra-long interglacial in Northern Hemisphere during MISs 15-13 arising from limited extent of Arctic ice sheets in glacial MIS 14.

Knowledge of the behavior of Northern Hemisphere (NH) ice sheets over the past million years is crucial for understanding the role of orbitally driven insolation changes on glacial/interglacial cycles. Here, based on the demonstrable link between changes in Chinese loess grain-size and NH ice-sheet extent, we use loess grain-size records to confirm that northern ice-sheets were restricted during marine oxygen isotope stage (MIS) 14. Thus, an unusually long NH interglacial climate of over 100 kyr persisted during MISs 15-13, much longer than expected from marine oxygen isotope records. Taking a global view of the paleoclimate records, MIS 14 inception seems to be a response to changes in Antarctic ice-sheets rather than to NH cooling. Orbital configuration in the two Polar regions shows that the onset of MIS 14 was forced by austral insolation changes, rather than by boreal summer insolation, as Milankovitch theory proposes. Our analysis of MIS 14 raises the possibility that southern insolation forcing may have played an important role in the inception of several other glacials. We suggest that the extra-long NH interglacial climate during MISs 15-13 provided favorable conditions for the second major dispersal episode of African hominins into Eurasia.

Tuning surface-enhanced Raman scattering from graphene substrates using the electric field effect and chemical doping.

Graphene recently has been demonstrated to support surface-enhanced Raman scattering. Here, we show that the enhancement of the Raman signal of methylene blue on graphene can be tuned by using either the electric field effect or chemical doping. Both doping experiments show that hole-doped graphene yields a larger enhancement than one which is electron-doped; however, chemical doping leads to a significantly larger modulation of the enhancements. The observed enhancement correlates with the changes in the Fermi level of graphene, indicating that the enhancement is chemical in nature, as electromagnetic enhancement is ruled out by hybrid electrodynamical and quantum mechanical simulations.

Simple fabrication of snowman-like colloids.

Anisotropic colloidal particles consisting of different compositions and geometry are useful for various applications. These include optical biosensing, antireflective coatings and electronic displays. In this work we demonstrate a simple and cost-effective method for fabricating anisotropic colloidal particles bearing a snowman-like shape. This is achieved by first settling the positively-charged polystyrene latex (PSL) colloids and negatively-charged silica colloids in deionized water onto a glass substrate, forming heterodoublets. The temperature is then raised above the glass transition temperature of the polymer. As a result, the silica particle spontaneously rises to the top of the PSL particle forming a snowman like structure. We have extended this method to different sizes and shown that the structure of the hybrid particles can be tuned by adjusting the size ratio between the silica and the PSL colloids. The surface coverage of the PSL, and hence of the snowman particles, on the glass substrate can also be varied by changing the ionic strength of the solution during the adhesion of PSL to the glass.

Surface-Enhanced Raman Scattering Study on Graphene-Coated Metallic Nanostructure Substrates.

Graphene, which has a linear electronic band structure, is widely considered as a semimetal. In the present study, we combine graphene with conventional metallic surface-enhanced Raman scattering (SERS) substrates to achieve higher sensitivity of SERS detection. We synthesize high-quality, single-layer graphene sheets by chemical vapor deposition (CVD) and transfer them from copper foils to gold nanostructures, i.e., nanoparticle or nanohole arrays. SERS measurements are carried out on methylene blue (MB) molecules. The combined graphene nanostructure substrates show about threefold or ninefold enhancement in the Raman signal of MB, compared with the bare nanohole or nanoparticle substrates, respectively. The difference in the enhancement factors is explained by the different morphologies of graphene on the two substrates with the aid of numerical simulations. Our study indicates that applying graphene to SERS substrates can be an effective way to improve the sensitivity of conventional metallic SERS substrates.

Shifts in plasmon resonance due to charging of a nanodisk array in argon plasma.

A method for generating charge-induced plasmonic shifts, using argon plasma to charge nanoparticle arrays, is presented. Particles develop a negative charge, due to enhanced collisions with high-temperature electrons, in low-temperature plasmas. The negative charge generated causes a blue shift in the localized surface plasmon resonance. The dynamics of the shift were recorded and discussed. This effect could be used as a real-time method for studying the dynamics for charging in plasma.

Nitrogen-doped graphene: beyond single substitution and enhanced molecular sensing.

Graphene is a two-dimensional network in which sp(2)-hybridized carbon atoms are arranged in two different triangular sub-lattices (A and B). By incorporating nitrogen atoms into graphene, its physico-chemical properties could be significantly altered depending on the doping configuration within the sub-lattices. Here, we describe the synthesis of large-area, highly-crystalline monolayer N-doped graphene (NG) sheets via atmospheric-pressure chemical vapor deposition, yielding a unique N-doping site composed of two quasi-adjacent substitutional nitrogen atoms within the same graphene sub-lattice (N(2)(AA)). Scanning tunneling microscopy and spectroscopy (STM and STS) of NG revealed the presence of localized states in the conduction band induced by N(2)(AA)-doping, which was confirmed by ab initio calculations. Furthermore, we demonstrated for the first time that NG could be used to efficiently probe organic molecules via a highly improved graphene enhanced Raman scattering.

Scalable manufacturing of plasmonic nanodisk dimers and cusp nanostructures using salting-out quenching method and colloidal lithography.

Localization of large electric fields in plasmonic nanostructures enables various processes such as single-molecule detection, higher harmonic light generation, and control of molecular fluorescence and absorption. High-throughput, simple nanofabrication techniques are essential for implementing plasmonic nanostructures with large electric fields for practical applications. In this article we demonstrate a scalable, rapid, and inexpensive fabrication method based on the salting-out quenching technique and colloidal lithography for the fabrication of two types of nanostructures with large electric field: nanodisk dimers and cusp nanostructures. Our technique relies on fabricating polystyrene doublets from single beads by controlled aggregation and later using them as soft masks to fabricate metal nanodisk dimers and nanocusp structures. Both of these structures have a well-defined geometry for the localization of large electric fields comparable to structures fabricated by conventional nanofabrication techniques. We also show that various parameters in the fabrication process can be adjusted to tune the geometry of the final structures and control their plasmonic properties. With advantages in throughput, cost, and geometric tunability, our fabrication method can be valuable in many applications that require plasmonic nanostructures with large electric fields.

Metallic membranes with subwavelength complementary patterns: distinct substrates for surface-enhanced Raman scattering.

We present a detailed comparison of surface-enhanced Raman spectroscopy (SERS) signals from metallic nanoparticle arrays and their complementary hole arrays. Using an analytical model for local field enhancement, we show that the SERS enhancements of the hole arrays are closely related to their transmission spectra. This trend is experimentally confirmed and characterized by a cos(4 )θ dependence of the SERS signal on the excitation polarization angle θ. The particle arrays, on the other hand, exhibit quite different behavior because of the existence of considerable evanescent modes in the near field. Their maximal local field gains appear at wavelengths generally much larger than their localized surface plasmonic resonant wavelengths.