Tong Zhang

Experimental Demonstration of Topological Surface States Protected by Time-Reversal Symmetry

We report direct imaging of standing waves of the nontrivial surface states of topological insulator Bi2Te3 using a scanning tunneling microscope. The interference fringes are caused by the scattering of the topological states off Ag impurities and step edges on the Bi2Te3(111) surface. By studying the voltage-dependent standing wave patterns, we determine the energy dispersion E(k), which confirms the Dirac cone structure of the topological states. We further show that, very different from the conventional surface states, backscattering of the topological states by nonmagnetic impurities is completely suppressed. The absence of backscattering is a spectacular manifestation of the time-reversal symmetry, which offers a direct proof of the topological nature of the surface states.

Mechanisms Regulating Mercury Bioavailability for Methylating Microorganisms in the Aquatic Environment: A Critical Review

Mercury is a potent neurotoxin for humans, particularly if the metal is in the form of methylmercury. Mercury is widely distributed in aquatic ecosystems as a result of anthropogenic activities and natural earth processes. A first step toward bioaccumulation of methylmercury in aquatic food webs is the methylation of inorganic forms of the metal, a process that is primarily mediated by anaerobic bacteria. In this Review, we evaluate the current state of knowledge regarding the mechanisms regulating microbial mercury methylation, including the speciation of mercury in environments where methylation occurs and the processes that control mercury bioavailability to these organisms. Methylmercury production rates are generally related to the presence and productivity of methylating bacteria and also the uptake of inorganic mercury to these microorganisms. Our understanding of the mechanisms behind methylation is limited due to fundamental questions related to the geochemical forms of mercury that persist in anoxic settings, the mode of uptake by methylating bacteria, and the biochemical pathway by which these microorganisms produce and degrade methylmercury. In anoxic sediments and water, the geochemical forms of mercury (and subsequent bioavailability) are largely governed by reactions between Hg(II), inorganic sulfides, and natural organic matter. These interactions result in a mixture of dissolved, nanoparticulate, and larger crystalline particles that cannot be adequately represented by conventional chemical equilibrium models for Hg bioavailability. We discuss recent advances in nanogeochemistry and environmental microbiology that can provide new tools and unique perspectives to help us solve the question of how microorganisms methylate mercury. An understanding of the factors that cause the production and degradation of methylmercury in the environment is ultimately needed to inform policy makers and develop long-term strategies for controlling mercury contamination.

Landau quantization of topological surface states in Bi2Se3.

1 Department of Physics, Tsinghua University, Beijing 100084, China 2 Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China 3 Microsoft Research, Station Q, University of California, Santa Barbara, CA 93106, USA 4 Department of Physics, Stanford University, Stanford CA 94305, USA 5 Physikalisches Institut, Universität Würzburg, D-97074 Würzburg, Germany * These authors contributed equally to this work. ¶ To whom correspondence should addressed. Email: xc@mail.tsinghua.edu.cn, xcma@aphy.iphy.ac.cn

Direct observation of nodes and twofold symmetry in FeSe superconductor.

Scanning tunneling spectroscopy suggests an orbital ordering mechanism for electron pairing in an iron-based superconductor. We investigated the electron-pairing mechanism in an iron-based superconductor, iron selenide (FeSe), using scanning tunneling microscopy and spectroscopy. Tunneling conductance spectra of stoichiometric FeSe crystalline films in their superconducting state revealed evidence for a gap function with nodal lines. Electron pairing with twofold symmetry was demonstrated by direct imaging of quasiparticle excitations in the vicinity of magnetic vortex cores, Fe adatoms, and Se vacancies. The twofold pairing symmetry was further supported by the observation of striped electronic nanostructures in the slightly Se-doped samples. The anisotropy can be explained in terms of the orbital-dependent reconstruction of electronic structure in FeSe.

Photolytic degradation of methylmercury enhanced by binding to natural organic ligands.

Monomethylmercury is a neurotoxin that poses significant risks to human health1 due to its bioaccumulation in food webs. Sunlight degradation to inorganic mercury is an important component of the mercury cycle that maintains methylmercury at low concentrations in natural waters. Rates of photodecomposition, however, can vary drastically between surface waters2–5 for reasons that are largely unknown. Here, we show that photodegradation occurs through singlet oxygen, a highly reactive form of dissolved oxygen generated by sunlight irradiation of dissolved natural organic matter. The kinetics of degradation, however, depended on water constituents that bind methylmercury cations. Relatively fast degradation rates (similar to observations in freshwater lakes) applied only to methylmercury species bound to organic sulfur-containing thiol ligands such as glutathione, mercaptoacetate, and humics. In contrast, methylmercury-chloride complexes, which are dominant in marine systems, were unreactive. Binding by thiols lowered the excitation energy of the carbon-mercury bond on the methylmercury molecule6–7 and subsequently increased reactivity towards bond breakage and decomposition. Our results explain methylmercury photodecomposition rates that are relatively rapid in freshwater lakes2–4 and slow in marine waters5.

Widespread production of extracellular superoxide by heterotrophic bacteria.

Sending Out an ROS The global imprint of biological activity in aquatic environments is often considered a consequence of enzyme-mediated redox reactions that support metabolic activity, such as reducing oxygen during respiration. But some organisms also release redox-active reactive oxygen species (ROS) into the environment—to acquire trace metals or to prevent viral infections—which can influence global processes like nutrient availability and contaminant transport. Photosynthetic organisms like phytoplankton are thought to be the primary biological source of ROS in freshwater and marine environments. However, Diaz et al. (p. 1223, published online 2 May; see the Perspective by Shaked and Rose) now show that a broad range of ecologically and phylogenetically diverse heterotrophic bacteria also produce large quantities of superoxide. Production rates vary widely across 30 common bacterial isolates but in some cases were greater than production rates of phytoplankton. Because these bacteria do not require light to grow, they may be the dominant source of ROS in dark environments like the deep ocean, terrestrial soils, or lake sediments. A broad range of bacteria produce substantial amounts of reactive oxygen species in aquatic ecosystems. [Also see Perspective by Shaked and Rose] Superoxide and other reactive oxygen species (ROS) originate from several natural sources and profoundly influence numerous elemental cycles, including carbon and trace metals. In the deep ocean, the permanent absence of light precludes currently known ROS sources, yet ROS production mysteriously occurs. Here, we show that taxonomically and ecologically diverse heterotrophic bacteria from aquatic and terrestrial environments are a vast, unrecognized, and light-independent source of superoxide, and perhaps other ROS derived from superoxide. Superoxide production by a model bacterium within the ubiquitous Roseobacter clade involves an extracellular oxidoreductase that is stimulated by the reduced form of nicotinamide adenine dinucleotide (NADH), suggesting a surprising homology with eukaryotic organisms. The consequences of ROS cycling in immense aphotic zones representing key sites of nutrient regeneration and carbon export must now be considered, including potential control of carbon remineralization and metal bioavailability.

Net Methylation of Mercury in Estuarine Sediment Microcosms Amended with Dissolved, Nanoparticulate, and Microparticulate Mercuric Sulfides

The production of methylmercury (MeHg) by anaerobic microorganisms depends in part on the speciation and bioavailability of inorganic mercury to these organisms. Our previous work with pure cultures of methylating bacteria has demonstrated that the methylation potential of mercury decreased during the aging of mercuric sulfides (from dissolved to nanoparticulate and microcrystalline HgS). The objective of this study was to understand the relationship between mercury sulfide speciation and methylation potential in experiments that more closely simulate the complexity of sediment settings. The study involved sediment slurry microcosms that represented a spectrum of salinities in an estuary and were each amended with different forms of mercuric sulfides: dissolved Hg and sulfide, nanoparticulate HgS (3-4 nm in diameter), and microparticulate HgS (>500 nm). The results indicated that net MeHg production was influenced by both the activity of sulfate-reducing microorganisms (roughly represented by the rate of sulfate loss) and the bioavailability of mercury. In the presence of abundant sulfate and carbon sources (supporting relatively high microbial activity), net MeHg production in the slurries amended with dissolved Hg was greater than in slurries amended with nano-HgS, similar to previous experiments with pure bacterial cultures. In microcosms with minimal microbial activity (indicated by low rates of sulfate loss), the addition of either dissolved Hg or nano-HgS resulted in similar amounts of net MeHg production. For all slurries receiving micro-HgS, MeHg production did not exceed abiotic controls. In slurries amended with dissolved and nano-HgS, mercury was mainly partitioned to bulk-scale mineral particles and colloids, indicating that Hg bioavailability was not simply related to dissolved Hg concentration or speciation. Overall, the results suggest that models for mercury methylation potential in the environment will need to balance the relative contributions of mercury speciation and activity of methylating microorganisms.

Power-law decay of standing waves on the surface of topological insulators

We propose a general theory on the standing waves (quasiparticle interference pattern) caused by the scattering of surface states off step edges in topological insulators in which the extremal points on the constant energy contour of surface band play a dominant role. Experimentally, we image the interference patterns on both Bi2Te3 and Bi2Se3 films by measuring the local density of states with a scanning tunneling microscope. The observed decay indices of the standing waves agree excellently with the theoretical prediction: In Bi2Se3, only a single decay index of -3/2 exists, while in Bi2Te3 with strongly warped surface band, it varies from -3/2 to -1/2 and finally to -1 as the energy increases. The -1/2 decay indicates that the suppression of backscattering due to time-reversal symmetry does not necessarily lead to a spatial decay rate faster than that in the conventional two-dimensional electron system. Our formalism can also better explain the characteristic scattering wave vectors of the standing wave caused by nonmagnetic impurities on Bi2Te3.

Photo-degradation of monomethylmercury in the presence of chloride ion

Photo-degradation (PD) of monomethylmercury (MMHg) is recognized as the most important process in mercury cycling that maintains MMHg at low concentration in water systems. Chloride ion (Cl(-)) is present widely in ecosystems and it may have an effect on MMHg PD. In this investigation, MMHg PD with various Cl(-) concentrations under different light radiation intensity and wavelength were performed in a quartz cylinder reactor. Various light radiations were obtained from xenon and ultraviolet (UV) bulbs. The results showed that the first order reaction coefficient decreased (1.35-0.37 h(-1)) with Cl(-) concentrations, and increased (0.14-0.76 h(-1)) with UV-B radiation intensity. The wavelength mediated PD rates varied from 0.29 h(-1) to 0.96 h(-1). The peak emission of Hg(0) was excited by UV-B radiation and Hg(0) flux of the reactions without Cl(-) (94.06 ng) was higher than that with Cl(-) by 1-4 times. All the results suggest that Cl(-) could block MMHg PD and subsequently influence the end products from PD. The wavelength and light intensity have a significant effect on MMHg PD and Hg(0) emission. Calculation of MMHg species (%) at initial and terminal time with various Cl(-) concentrations show that MMHg species changed by Cl(-) complexation and thus result in different PD mechanisms and pathways.

Extensive Dark Biological Production of Reactive Oxygen Species in Brackish and Freshwater Ponds

Within natural waters, photodependent processes are generally considered the predominant source of reactive oxygen species (ROS), a suite of biogeochemically important molecules. However, recent discoveries of dark particle-associated ROS production in aquatic environments and extracellular ROS production by various microorganisms point to biological activity as a significant source of ROS in the absence of light. Thus, the objective of this study was to explore the occurrence of dark biological production of the ROS superoxide (O2(-)) and hydrogen peroxide (H2O2) in brackish and freshwater ponds. Here we show that the ROS superoxide and hydrogen peroxide were present in dark waters at comparable concentrations as in sunlit waters. This suggests that, at least for the short-lived superoxide species, light-independent processes were an important control on ROS levels in these natural waters. Indeed, we demonstrated that dark biological production of ROS extensively occurred in brackish and freshwater environments, with greater dark ROS production rates generally observed in the aphotic relative to the photic zone. Filtering and formaldehyde inhibition confirmed the biological nature of a majority of this dark ROS production, which likely involved phytoplankton, particle-associated heterotrophic bacteria, and NADH-oxidizing enzymes. We conclude that biological ROS production is widespread, including regions devoid of light, thereby expanding the relevance of these reactive molecules to all regions of our oxygenated global habit.