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At least 775 records · Page 43

Limits to the Indirect Aerosol Forcing in Stratocumulus

The indirect radiative forcing of aerosols is poorly constrained by the observational data underlying the simple cloud parameterizations in GCMs. signal of cloud response to increased aerosol concentrations from meteorological noise. Recent satellite observations indicate a significant decrease of cloud water in ship tracks, in contrast to an ensemble of in situ measurements showing no average change in cloud water relative to the surrounding clouds. Both results contradict the expectation of cloud water increasing in polluted clouds. We find through large-eddy simulations of stratocumulus that the trend in the satellite data is likely an artifact of sampling only overcast clouds. The simulations instead show cloud cover increasing with droplet concentrations. The simulations also show that increases in cloud water from suppressing drizzle by increased droplet concentrations are favored at night or at extremely low droplet concentrations. At typical droplet concentrations we find that the Twomey effect on cloud albedo is amplified very little by the secondary indirect effect of drizzle suppression, largely because the absorption of solar radiation by cloud water reduces boundary-layer mixing in the daytime and thereby restricts any possible increase in cloud water from drizzle suppression. The cloud and boundary layer respond to radiative heating variations on a time scale of hours, and on longer time scales respond to imbalances between large-scale horizontal advection and the entrainment of inversion air. We analyze the co-varying response of cloud water, cloud thickness, width of droplet size distributions, and dispersion of the optical depth, as well as the overall response of cloud albedo, to changes in droplet concentrations. We also dissect the underlying physical mechanisms through sensitivity studies. Ship tracks represent an ideal natural laboratory to extricate the

Ackerman, Andrew↗

Estuarine Dissolved Organic Carbon Flux from Space: With Application to Chesapeake and Delaware Bays

This study uses a neural network model trained with in situ data, combined with satellite data and hydrodynamic model products, to compute the daily estuarine export of dissolved organic carbon (DOC) at the mouths of Chesapeake Bay (CB) and Delaware Bay (DB) from 2007 to 2011. Both bays show large flux variability with highest fluxes in spring and lowest in fall as well as interannual flux variability (0.18 and 0.27 Tg C/year in 2008 and 2010 for CB; 0.04 and 0.09 Tg C/year in 2008 and 2011 for DB). Based on previous estimates of total organic carbon (TOCexp) exported by all Mid-Atlantic Bight estuaries (1.2 Tg C/year), the DOC export (CB + DB) of 0.3 Tg C/year estimated here corresponds to 25% of the TOCexp. Spatial and temporal covariations of velocity and DOC concentration provide contributions to the flux, with larger spatial influence. Differences in the discharge of fresh water into the bays (74 billion m(exp3)/year for CB and 21 billion m9exp3)/year for DB) and their geomorphologies are major drivers of the differences in DOC fluxes for these two systems. Terrestrial DOC inputs are similar to the export of DOC at the bay mouths at annual and longer time scales but diverge significantly at shorter time scales (days to months). Future efforts will expand to the Mid-Atlantic Bight and Gulf of Maine, and its major rivers and estuaries, in combination with coupled terrestrial-estuarine-ocean biogeochemical models that include effects of climate change, such as warming and CO2 increase.

Signorini, Sergio↗

Estuarine Dissolved Organic Carbon Flux From Space: With Application to Chesapeake and Delaware Bays

This study uses a neural network model trained with in situ data, combined with satellite data and hydrodynamic model products, to compute the daily estuarine export of dissolved organic carbon (DOC) at the mouths of Chesapeake Bay (CB) and Delaware Bay (DB) from 2007 to 2011. Both bays show large flux variability with highest fluxes in spring and lowest in fall as well as interannual flux variability (0.18 and 0.27 Tg C/year in 2008 and 2010 for CB; 0.04 and 0.09 Tg C/year in 2008 and 2011 for DB). Based on previous estimates of total organic carbon (TOCexp) exported by all Mid-Atlantic Bight estuaries (1.2 Tg C/year), the DOC export (CB + DB) of 0.3 Tg C/year estimated here corresponds to 25% of the TOCexp. Spatial and temporal covariations of velocity and DOC concentration provide contributions to the flux, with larger spatial influence. Differences in the discharge of fresh water into the bays (74 billion cu. m/year for CB and 21 billion cu. m/year for DB) and their geomorphologies are major drivers of the differences in DOC fluxes for these two systems. Terrestrial DOC inputs are similar to the export of DOC at the bay mouths at annual and longer time scales but diverge significantly at shorter time scales (days to months). Future efforts will expand to the Mid-Atlantic Bight and Gulf of Maine, and its major rivers and estuaries, in combination with coupled terrestrial-estuarine-ocean biogeochemical models that include effects of climate change, such as warming and CO2 increase.

Estuarine DOC export↗

On the Relationship between Regional Ocean Heat Content and Sea Surface Height

Abstract An accurate diagnosis of ocean heat content (OHC) is essential for interpreting climate variability and change, as evidenced for example by the broad range of hypotheses that exists for explaining the recent hiatus in global mean surface warming. Potential insights are explored here by examining relationships between OHC and sea surface height (SSH) in observations and two recently available large ensembles of climate model simulations from the mid-twentieth century to 2100. It is found that in decadal-length observations and a model control simulation with constant forcing, strong ties between OHC and SSH exist, with little temporal or spatial complexity. Agreement is particularly strong on monthly to interannual time scales. In contrast, in forced transient warming simulations, important dependencies in the relationship exist as a function of region and time scale. Near Antarctica, low-frequency SSH variability is driven mainly by changes in the circumpolar current associated with intensified surface winds, leading to correlations between OHC and SSH that are weak and sometimes negative. In subtropical regions, and near other coastal boundaries, negative correlations are also evident on long time scales and are associated with the accumulated effects of changes in the water cycle and ocean dynamics that underlie complexity in the OHC relationship to SSH. Low-frequency variability in observations is found to exhibit similar negative correlations. Combined with altimeter data, these results provide evidence that SSH increases in the Indian and western Pacific Oceans during the hiatus are suggestive of substantial OHC increases. Methods for developing the applicability of altimetry as a constraint on OHC more generally are also discussed.

54 ENVIRONMENTAL SCIENCES↗

Relativistic electron precipitation enhancements near the outer edge of the radiation belt

Characteristics of relativistic electron precipitation bursts observed by the Heavy Ion Large Telescope (HILT) experiment onboard the Solar, Anomalous, and Magnetospheric Partical Explorer (SAMPEX) satellite were examined. Relatively narrow, persitent, latitudinal bands of precipitation with time scales of 10 to approximately 30 sec near the outer edge of the radiation belt which develop and decay with a time scale of a few hours are reported. Acceleration processes more effective than the usual radial diffusion process or scattering process would be needed to explain this strong precipitation band phenomenon. Another prominent signature is microbursts with a time scale down to a few hundred milliseconds. It is suggested that these microbursts are due to wave-particle interaction involving a relaxation-oscillator type of mechanism.

Nakamura, R.↗

The root-zone soil moisture spectrum in a mediterranean ecosystem

Storage of water within soil pores of the root zone introduce memory effects in the dynamics of soil moisture that are considerably longer than the integral timescale of many atmospheric processes. Thus, hydro-climatic states can be “sustained” through land-surface heat and water vapor fluxes primarily because they can “feed off” on this long-term soil moisture memory. Root-zone soil moisture memory is only but one feature characterizing the spectrum of soil moisture dynamics, which is analyzed here using a combination of long-term measurements and models. In particular, the spectrum of root-zone soil moisture content in a Mediterranean ecosystem is examined using 14-years of half-hourly measurements. A distinguishing hydro-climatic feature in such ecosystems is that sources (mainly rainfall) and sinks (mainly evapotranspiration) of soil moisture are roughly out of phase with each other. For over 4 decades of time scales and 7 decades of energy, the canonical shape of the measured soil moisture spectrum is shown to be approximately Lorentzian determined by the soil moisture variance and its memory but with two exceptions: the occurrences of a peak at diurnal-to-daily time scales and a weaker peak at near annual time scales. Model calculations and spectral analysis demonstrate that diurnal and seasonal variations in hydroclimate forcing responsible for variability in evapotranspiration had minor impact on the normalized shape of the soil moisture spectrum. However, their impact was captured by adjustments in the temporal variance. These findings indicate that precipitation and not evapotranspiration variability dominates the multi-scaling properties of soil moisture variability consistent with prior climate model simulations. Furthermore, the soil moisture memory inferred by the annual peak of soil moisture (340 d) is consistent with climate model simulations, while the memory evaluated from the loss function of a linearized mass balance approach leads to a smaller value (50 d), highlighting the effect of weak non-stationarity on soil moisture variability.

54 ENVIRONMENTAL SCIENCES↗

Protein Conformational Populations and Functionally Relevant Substates

Functioning proteins do not remain fixed in a unique structure, rather they sample a range of conformations facilitated by motions within the protein. Even in the native state, a protein exists as a collection of interconverting conformations driven by thermodynamic fluctuations. Motions on the fast time scale allow a protein to sample conformations in the nearby area of its conformational landscape, while motions on slower time scales give it access to conformations in distal areas of the landscape. Emerging evidence indicates that protein landscapes contain conformational substates with dynamic and structural features that support the designated function of the protein. Nuclear magnetic resonance (NMR) experiments provide information about conformational ensembles of proteins. X-ray crystallography allows researchers to identify the most populated states along the landscape, and computational simulations give atom-level information about the conformational substates of different proteins. This ability to characterize and obtain quantitative information about the conformational substates and the populations of proteins within them is allowing researchers to better understand the relationship between protein structure and dynamics and the mechanisms of protein function. In this Account, we discuss recent developments and challenges in the characterization of functionally relevant conformational populations and substates of proteins. In some enzymes, the sampling of functionally relevant conformational substates is connected to promoting the overall mechanism of catalysis. For example, the conformational landscape of the enzyme dihydrofolate reductase hasmultiple substates, which facilitate the binding and the release of the cofactor and substrate and catalyze the hydride transfer. For the enzyme cyclophilin A, computational simulations reveal that the long time scale conformational fluctuations enable the enzyme to access conformational substates that allow it to attain the transition state, therefore promoting the reaction mechanism. Long-term, this emerging view of proteins with conformational substates has broad implications for improving our understanding of enzymes, enzyme engineering, and better drug design. Researchers have already used photoactivation to modulate protein conformations as a strategy to develop a hypercatalytic enzyme. Furthermore, the alteration of the conformational substates through binding of ligands at locations other than the active site provides the basis for the design of new medicines through allosteric modulation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Protein Conformational Populations and Functionally Relevant Sub-states

Functioning proteins do not remain fixed in a unique structure, but instead they sample a range of conformations facilitated by motions within the protein. Even in the native state, a protein exists as a collection of interconverting conformations driven by thermodynamic fluctuations. Motions on the fast time scale allow a protein to sample conformations in the nearby area of its conformational landscape, while motions on slower time scales give it access to conformations in distal areas of the landscape. Emerging evidence indicates that protein landscapes contain conformational substates with dynamic and structural features that support the designated function of the protein. Nuclear magnetic resonance (NMR) experiments provide information about conformational ensembles of proteins. X-ray crystallography allows researchers to identify the most populated states along the landscape, and computational simulations give atom-level information about the conformational substates of different proteins. This ability to characterize and obtain quantitative information about the conformational substates and the populations of proteins within them is allowing researchers to better understand the relationship between protein structure and dynamics and the mechanisms of protein function. In this Account, we discuss recent developments and challenges in the characterization of functionally relevant conformational populations and substates of proteins. In some enzymes, the sampling of functionally relevant conformational substates is connected to promoting the overall mechanism of catalysis. For example, the conformational landscape of the enzyme dihydrofolate reductase has multiple substates, which facilitate the binding and the release of the cofactor and substrate and catalyze the hydride transfer. For the enzyme cyclophilin A, computational simulations reveal that the long time scale conformational fluctuations enable the enzyme to access conformational substates that allow it to attain the transition state, therefore promoting the reaction mechanism. In the long term, this emerging view of proteins with conformational substates has broad implications for improving our understanding of enzymes, enzyme engineering, and better drug design. Researchers have already used photoactivation to modulate protein conformations as a strategy to develop a hypercatalytic enzyme. In addition, the alteration of the conformational substates through binding of ligands at locations other than the active site provides the basis for the design of new medicines through allosteric modulation.

Agarwal, Pratul K↗

Short- vs . long-range elastic distortion: structural dynamics of a [2 × 2] tetrairon( II ) spin crossover grid complex observed by time-resolved X-Ray crystallography

Spin crossover complexes (SCO) are among the most studied molecular switches due to their potential use in displays, sensors, actuators and memory components. A prerequisite to using these materials is the understanding of the structural changes following the spin transition at out-of-equilibrium conditions. So far, out-of-equilibrium studies in SCO solids have been focused on mononuclear complexes, though a growing number of oligonuclear SCO complexes showing cooperative effects are being reported. Here, we use time-resolved pink Laue crystallography to study the out-of-equilibrium dynamics of a [2 × 2] tetranuclear metallogrid of the form [Fe II 4 L Me 4 ](BF 4 ) 4 ·2MeCN ([L Me ] - = 4-methyl-3,5-bis{6-(2,2'-bipyridyl)}pyrazolate). The out-of-equilibrium spin state switching induced by a ps laser pulse demonstrates that the metallogrid exhibits a multi-step response similar to that reported for mononuclear complexes. Contrary to the mononuclear complexes, the metallogrid shows two types of elastic distortions at different time scales. The first is a short-range distortion that propagates over the entire Fe 4 grid complex during the ps time scale, and it is caused by the rearrangement of the coordination sphere of the photo-switching ion and the constant feedback between strongly linked metal ions. The second is a long-range distortion caused by the anisotropic expansion of the lattice during the ns time scale, observed in mononuclear materials. The structural analysis demonstrates that the long-range prevails over the short-range distortion, inducing the largest deformation of both the entire grid and the coordination sphere of each metal ion. The present study sheds light on the out-of -equilibrium dynamics of a non-cooperative oligonuclear complex.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ultrafast carrier dynamics in the large-magnetoresistance material WTe 2

In this study, ultrafast optical pump-probe spectroscopy is used to track carrier dynamics in the large-magnetoresistance material WTe 2 . Our experiments reveal a fast relaxation process occurring on a subpicosecond time scale that is caused by electron-phonon thermalization, allowing us to extract the electron-phonon coupling constant. An additional slower relaxation process, occurring on a time scale of ~5–15 ps, is attributed to phonon-assisted electron-hole recombination. As the temperature decreases from 300 K, the time scale governing this process increases due to the reduction of the phonon population. However, below ~50 K, an unusual decrease of the recombination time sets in, most likely due to a change in the electronic structure that has been linked to the large magnetoresistance observed in this material.

36 MATERIALS SCIENCE↗

Differential memory in the earth's magnetotail

The process of 'differential memory' in the earth's magnetotail is studied in the framework of the modified Harris magnetotail geometry. It is verified that differential memory can generate non-Maxwellian features in the modified Harris field model. The time scales and the potentially observable distribution functions associated with the process of differential memory are investigated, and it is shown that non-Maxwelllian distributions can evolve as a test particle response to distribution function boundary conditions in a Harris field magnetotail model. The non-Maxwellian features which arise from distribution function mapping have definite time scales associated with them, which are generally shorter than the earthward convection time scale but longer than the typical Alfven crossing time.

Burkhart, G. R.↗

Site Disorder Drives Cyanide Dynamics and Fast Ion Transport in Li 6 PS 5 CN

Halide argyrodite solid-state electrolytes of the general formula Li 6 PS 5 X exhibit complex static and dynamic disorder that plays a crucial role in ion transport processes. Here, we unravel the rich interplay between site disorder and dynamics in the plastic crystal argyrodite Li 6 PS 5 CN and the impact on ion diffusion processes through a suite of experimental and computational methodologies, including temperature-dependent synchrotron powder X-ray diffraction, AC electrochemical impedance spectroscopy, 7 Li solid-state NMR, and machine learning-assisted molecular dynamics simulations. Sulfide and (pseudo)halide site disorder between the two anion sublattices unilaterally improves long-range lithium diffusion irrespective of the (pseudo)halide identity, which demonstrates the importance of site disorder in dictating bulk ionic conductivity in the argyrodite family. Furthermore, we find that anion site disorder modulates the presence and time scales of cyanide rotational dynamics. Ordered configurations of anions enable fast, quasi-free rotations of cyanides that occur on time scales of 10 11 Hz at T = 300 K. In contrast, we find that cyanide dynamics are slow or frozen in Li 6 PS 5 CN when site disorder between the cyanide and sulfide sublattices is present at T = 300 K. We rationalize the observed differences in cyanide dynamics in the context of elastic dipole interactions between neighboring cyanide anions and local strain induced by the configurations of site disorder that may impact the energetic landscape for cyanide rotational dynamics. Through this study, we find that anion disorder plays a decisive role in dictating the extent and time scales of both lithium ion and cyanide dynamics in Li 6 PS 5 CN.

36 MATERIALS SCIENCE↗

The Role of Atmospheric Noise in Decadal SST Variability

Abstract A substantial role for atmospheric noise in simulations of decadal internal variability of SST is demonstrated by a comparison of a multicentury climate model control and a corresponding interactive ensemble (IE) simulation. The IE is designed to reduce atmospheric noise in the heat flux, wind stress, and freshwater flux at the air–sea interface. This comparison suggests that nearly all SST variability on decadal time scales is forced by internal atmospheric variability. The results are examined to determine the relative roles of atmospheric surface heat flux noise and ocean dynamics in the decadal volume-averaged heat budget of the upper ocean. The regional heat budgets in two regions, the South Pacific and the midlatitude North Atlantic, show the net atmospheric surface heat flux to be approximately in equilibrium with the ocean dynamics forcing. The IE and control results are used in the equilibrium heat budget approximation to infer the atmospheric heat flux response to SST, as well as the time series of the control atmospheric noise surface heat flux and ocean dynamics forcings for several regions. The South Pacific region SST is found to be primarily forced by the atmospheric noise surface heat flux and the North Atlantic region SST is forced by the ocean dynamics. Similar strengths for the atmospheric heat flux noise and ocean dynamics forcing, with an interdecadal atmospheric heat flux noise time scale and a centennial ocean dynamics time scale, are found for an Atlantic multidecadal variability region SST.

Meteorology & Atmospheric Sciences↗

Long Period Variations in Tidal and Librational Forcing of Europa

The gravitational field of Jupiter exerts a profound influence on the energy balance, thermal evolution, and stress regime of Europa. It widely appreciated that dissipation associated with the spheroidal tidal deformation is a major source of heat. Another possibly important source of dissipation is the toroidal deformation field associated with forced librations. Both tidal and librational deformations depend on the distance and direction Jupiter, as seen from Europa. These quantities vary with time as a result of the finite values of orbital eccentricity and spin pole obliquity, though the obliquity effects have been ignored in most previous studies. Variations in eccentricity and obliquity of the Galilean satellites occur on a very wide range of time scales, as angular momentum is exchanged among the orbital and rotational components of the coupled system. The orbital periods are only a few days in length, and the secular changes in orbital period associated with tidal and librational dissipation have characteristic time scales of 10-9 years or longer. On intermediate time scales, the satellites perturb each other, and the Sun and Saturn make additional contributions. The present values of satellite orbital inclinations and obliquities are not particularly representative their respective longer term variations. As a result, the tidal stress and dissipation regimes at present may not provide adequate explanation of the sources of surface features seen on the satellites.

Bills, Bruce G.↗

Implications of Wide-Area Geographic Diversity for Short- Term Variability of Solar Power

Worldwide interest in the deployment of photovoltaic generation (PV) is rapidly increasing. Operating experience with large PV plants, however, demonstrates that large, rapid changes in the output of PV plants are possible. Early studies of PV grid impacts suggested that short-term variability could be a potential limiting factor in deploying PV. Many of these early studies, however, lacked high-quality data from multiple sites to assess the costs and impacts of increasing PV penetration. As is well known for wind, accounting for the potential for geographic diversity can significantly reduce the magnitude of extreme changes in aggregated PV output, the resources required to accommodate that variability, and the potential costs of managing variability. We use measured 1-min solar insolation for 23 time-synchronized sites in the Southern Great Plains network of the Atmospheric Radiation Measurement program and wind speed data from 10 sites in the same network to characterize the variability of PV with different degrees of geographic diversity and to compare the variability of PV to the variability of similarly sited wind. The relative aggregate variability of PV plants sited in a dense 10 x 10 array with 20 km spacing is six times less than the variability of a single site for variability on time scales less than 15-min. We find in our analysis of wind and PV plants similarly sited in a 5 x 5 grid with 50 km spacing that the variability of PV is only slightly more than the variability of wind on time scales of 5-15 min. Over shorter and longer time scales the level of variability is nearly identical. Finally, we use a simple approximation method to estimate the cost of carrying additional reserves to manage sub-hourly variability. We conclude that the costs of managing the short-term variability of PV are dramatically reduced by geographic diversity and are not substantially different from the costs for managing the short-term variability of similarly sited wind in this region.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Driving Force Dependent Photoinduced Charge Transfer Dynamics in Polymer-Wrapped Semiconducting Single-Walled Carbon Nanotubes

Here, we investigate the thermodynamic driving-force dependences of photoinduced charge separation (CS) and subsequent charge transfer dynamics in single-walled carbon nanotube (SWNT)–perylenediimide (PDI) donor–acceptor (D–A) superstructures. Pump–probe spectroscopy reveals that [SWNT (•+)n ]-(PDI –• ) n CS states form on an ∼100 fs time scale following photoexcitation; these dynamics are invariant across an ∼400 mV driving force range, indicating that SWNT hole polaron formation time scales are determined by nanotube lattice and solvent relaxation. These CS states feature SWNT hole polarons adjacent to (geminate) and nearby (nongeminate) PDI radical anions. Analysis of the free energy dependence for charge recombination (CR) of [SWNT •+ ] geminate -(PDI –• ) CS states highlights an ∼2 meV value for D–A electronic coupling (HAB) and ∼0.93 eV for the total reorganization energy (λ T ). A corresponding driving force dependence of the CR dynamics for [SWNT •+ ] nongeminate -(PDI –• ) CS states indicates a diminished H AB value (∼0.6 meV) and a larger λ T (∼1.1 eV), consistent with larger transfer distances. SWNT excitons that persist following photoinduced CS drive photooxidation of PDI –• components of [SWNT (•+)n ]-(PDI –• ) n CS states ( 1 SWNT* + PDI •– → PDI + SWNT •– ); this reaction manifests a significantly reduced λ T value (∼0.67 eV) as the initially prepared SWNT reduced state bears the character of a conduction band injected electron ([SWNT •– ] CB ). This reaction thus gives rise to relaxed, nongeminate SWNT electron and hole polarons on the same nanotube; these polarons react on a 10 2 ps time scale independent of the electronic structure of these SWNT-PDI superstructures.

anions↗

Modification of near-wall coherent structures by inertial particles

Direct numerical simulations are combined with two-way coupled Lagrangian point particles to study the effect of Reynolds number on particle-turbulence interaction. Turbulent planar Couette flow is simulated at a constant dispersed phase mass loading of ϕ{sub m} = 0.25 for particle Stokes numbers of St{sub K} = [O(1), O(10), O(100)] (based on the Stokes time scale of the particle and the Kolmogorov time scale of the flow) and bulk Reynolds numbers of Re{sub b} = [8100, 24000, 72000] (based on the plate velocity difference and separation distance). Statistics of swirling strength |λ{sub ci}| are used to evaluate the impact of particles on near-wall motions which are responsible for turbulent, wall-normal momentum transport. Instantaneously, the number of high-strength swirling motions near the wall decreases significantly in the presence of particles, and this trend is enhanced with increasing Re{sub b}. Conditional averages are computed using linear stochastic estimation, providing the average structures responsible for ejection events near the wall. These conditional eddies are weakened substantially by the presence of the dispersed phase, and this effect is again enhanced with increasing Re{sub b}. We propose a mechanism where particles, by interfering with the hairpin regeneration process near the wall, can influence turbulent fluxes in a way that increases with Re{sub b} despite only having direct interaction with scales on the same order as their small physical size. At the same time, turbulent momentum flux concentrated at higher wavenumbers with increasing Re{sub b} allows small particles to be effective agents for altering turbulent transport.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Stream lamination and rapid mixing in a microfluidic jet for X-ray spectroscopy studies

Microfluidic mixers offer new possibilities for the study of fast reaction kinetics down to the microsecond time scale, and methods such as soft X-ray absorption spectroscopy are powerful analysis techniques. These systems impose challenging constraints on mixing time scales, sample volume, detection region size and component materials. The current work presents a novel micromixer and jet device which aims to address these limitations. The system uses a so-called ‘theta’ mixer consisting of two sintered and fused glass capillaries. Sample and carrier fluids are injected separately into the inlets of the adjacent capillaries. At the downstream end, the two streams exit two micron-scale adjoining nozzles and form a single free-standing jet. The flow-rate difference between the two streams results in the rapid acceleration and lamination of the sample stream. This creates a small transverse dimension and induces diffusive mixing of the sample and carrier stream solutions within a time scale of 0.9 microseconds. The reaction occurs at or very near a free surface so that reactants and products are more directly accessible to interrogation using soft X-ray. We use a simple diffusion model and quantitative measurements of fluorescence quenching (of fluorescein with potassium iodide) to characterize the mixing dynamics across flow-rate ratios.

Huyke, Diego A. (ORCID:0000000283356613)↗