Modeling contaminant behavior in Lake Superior : a comparison of PCBs, PBDEs, and mercury

A mass‐balance model for Lake Superior was applied to polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and mercury to determine the major routes of entry and the major mechanisms of loss from this ecosystem as well as the time required for each contaminant class to approach steady state. A two‐box model (water column, surface sediments) incorporating seasonally adjusted environmental parameters was used. Both numerical (forward Euler) and analytical solutions were employed and compared. For validation, the model was compared with current and historical concentrations and fluxes in the lake and sediments. Results for PCBs were similar to prior work showing that air‐water exchange is the most rapid input and loss process. The model indicates that mercury behaves similarly to a moderately‐chlorinated PCB, with air‐water exchange being a relatively rapid input and loss process. Modeled accumulation fluxes of PBDEs in sediments agreed with measured values reported in the literature. Wet deposition rates were about three times greater than dry particulate deposition rates for PBDEs. Gas deposition was an important process for tri‐ and tetra‐BDEs (BDEs 28 and 47), but not for higher‐brominated BDEs. Sediment burial was the dominant loss mechanism for most of the PBDE congeners while volatilization was still significant for tri‐ and tetra‐BDEs. Because volatilization is a relatively rapid loss process for both mercury and the most abundant PCBs (tri‐ through penta‐), the model predicts that similar times (from 2 ‐ 10 yr) are required for the compounds to approach steady state in the lake. The model predicts that if inputs of Hg(II) to the lake decrease in the future then concentrations of mercury in the lake will decrease at a rate similar to the historical decline in PCB concentrations following the ban on production and most uses in the U.S. In contrast, PBDEs are likely to respond more slowly if atmospheric concentrations are reduced in the future because loss by volatilization is a much slower process for PBDEs, leading to lesser overall loss rates for PBDEs in comparison to PCBs and mercury. Uncertainties in the chemical degradation rates and partitioning constants of PBDEs are the largest source of uncertainty in the modeled times to steady‐state for this class of chemicals. The modeled organic PBT loading rates are sensitive to uncertainties in scavenging efficiencies by rain and snow, dry deposition velocity, watershed runoff concentrations, and uncertainties in air‐water exchange such as the effect of atmospheric stability

Development of measurement and modeling techniques to quantify atmospheric deposition of persistent, bioaccumulative and toxic chemicals in the Great Lakes

Measurement and modeling techniques were developed to improve over-water gaseous air-water exchange measurements for persistent bioaccumulative and toxic chemicals (PBTs). Analytical methods were applied to atmospheric measurements of hexachlorobenzene (HCB), polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs). Additionally, the sampling and analytical methods are well suited to study semivolatile organic compounds (SOCs) in air with applications related to secondary organic aerosol formation, urban, and indoor air quality. A novel gas-phase cleanup method is described for use with thermal desorption methods for analysis of atmospheric SOCs using multicapillary denuders. The cleanup selectively removed hydrogen-bonding chemicals from samples, including much of the background matrix of oxidized organic compounds in ambient air, and thereby improved precision and method detection limits for nonpolar analytes. A model is presented that predicts gas collection efficiency and particle collection artifact for SOCs in multicapillary denuders using polydimethylsiloxane (PDMS) sorbent. An approach is presented to estimate the equilibrium PDMS-gas partition coefficient (Kpdms) from an Abraham solvation parameter model for any SOC. A high flow rate (300 L min-1) multicapillary denuder was designed for measurement of trace atmospheric SOCs. Overall method precision and detection limits were determined using field duplicates and compared to the conventional high-volume sampler method. The high-flow denuder is an alternative to high-volume or passive samplers when separation of gas and particle-associated SOCs upstream of a filter and short sample collection time are advantageous. A Lagrangian internal boundary layer transport exchange (IBLTE) Model is described. The model predicts the near-surface variation in several quantities with fetch in coastal, offshore flow: 1) modification in potential temperature and gas mixing ratio, 2) surface fluxes of sensible heat, water vapor, and trace gases using the NOAA COARE Bulk Algorithm and Gas Transfer Model, 3) vertical gradients in potential temperature and mixing ratio. The model was applied to interpret micrometeorological measurements of air-water exchange flux of HCB and several PCB congeners in Lake Superior. The IBLTE Model can be applied to any scalar, including water vapor, carbon dioxide, dimethyl sulfide, and other scalar quantities of interest with respect to hydrology, climate, and ecosystem science

Rapid rotation of micron and submicron dielectric particles measured using optical tweezers

We demonstrate the use of a laser trap (‘optical tweezers’) and back-focal-plane position detector to measure rapid rotation in aqueous solution of single particles with sizes in the vicinity of 1 μm. Two types of rotation were measured: electrorotation of polystyrene microspheres and rotation of the flagellar motor of the bacterium Vibrio alginolyticus. In both cases, speeds in excess of 1000 Hz (rev s−1) were measured. Polystyrene beads of diameter about 1 μm labelled with smaller beads were held at the centre of a microelectrode array by the optical tweezers. Electrorotation of the labelled beads was induced by applying a rotating electric field to the solution using microelectrodes. Electrorotation spectra were obtained by varying the frequency of the applied field and analysed to obtain the surface conductance of the beads. Single cells of V. alginolyticus were trapped and rotation of the polar sodium-driven flagellar motor was measured. Cells rotated more rapidly in media containing higher concentrations of Na+, and photodamage caused by the trap was considerably less when the suspending medium did not contain oxygen. The technique allows single-speed measurements to be made in less than a second and separate particles can be measured at a rate of several per minute

Using degraded music quality to encourage a health improving walking pace : BeatClearWalker

Meeting the target of 8000 steps/day, as recommended by many national governments and health authorities, can provide considerable physical and mental health benefits and is seen as a key target for reducing obesity levels and improving public health. However, to optimize the health benefits, walking should be performed at a “moderate” intensity. While there are numerous mobile fitness applications that monitor distance walked, none directly support walking at this cadence nor has there been any research into live feedback for walking cadence. We present a smartphone fitness application to help users learn how to walk at a moderate cadence and maintain that cadence. We apply real-time audio effects that diminish the audio quality of music when the target walking cadence is not being reached. This provides an immersive and intuitive application that can easily be integrated into everyday life as allows users to walk while listening to their own music and encourages eyes-free interaction. In this paper, we introduce our approach, design, initial lab evaluation and a controlled outdoor study. Results show that using music degradation decreases the number of below-cadence steps, that users felt they worked harder with our player and would use it while exercise walking

Using degraded music quality to encourage a health improving walking pace : BeatClearWalker

Meeting the target of 8000 steps/day, as recommended by many national governments and health authorities, can provide considerable physical and mental health benefits and is seen as a key target for reducing obesity levels and improving public health. However, to optimize the health benefits, walking should be performed at a "moderate" intensity. While there are numerous mobile fitness applications that monitor distance walked, none directly support walking at this cadence nor has there been any research into live feedback for walking cadence. We present a smartphone fitness application to help users learn how to walk at a moderate cadence and maintain that cadence. We apply real-time audio effects that diminish the audio quality of music when the target walking cadence is not being reached. This provides an immersive and intuitive application that can easily be integrated into everyday life as allows users to walk while listening to their own music and encourages eyes-free interaction. In this paper, we introduce our approach, design, initial lab evaluation and a controlled outdoor study. Results show that using music degradation decreases the number of below-cadence steps, that users felt they worked harder with our player and would use it while exercise walking

Crystal Field Splitting and Charge Flow in the Buckled-Dimer Reconstruction of Si(100)—2× 1

The effect of the 2×1 reconstruction on the core-electron binding energies of the outermost Si(100) layers has been determined using high-resolution photoemission data. A previously unobserved 190-meV crystal-field splitting is resolved for the up-atoms of the asymmetric surface dimers, whose average core-level shift is -400 meV. The signal from the down-atoms is clearly identified and has a shift of +220 meV. These new findings indicate a charge flow of ∼0.05e from the subsurface to the surface layers, with a substantially larger difference of ∼0.34e between the up-atoms and down-atoms in the dimer

Photoemission Measurement of Equilibrium Segregation at GeSi Surfaces

Photoemission spectroscopy is used to demonstrate that Ge segregates to the first atomic layer of Ge0.5Si0.5(100)2×1 and that the second layer is predominantly Si. Comparison of the resolved signals from the dimer atoms of the reconstructed (100)2×1 surfaces of Ge, Si, and equiatomic Ge‐Si alloy shows that the surface layer of the alloy is extremely Ge rich and the second layer is occupied mainly by Si atoms. This result is in good agreement with theoretical predictions

A Class of Eccentric Binaries with Dynamic Tidal Distortions Discovered with Kepler

We have discovered a class of eccentric binary systems within the Kepler data archive that have dynamic tidal distortions and tidally-induced pulsations. Each has a uniquely shaped light curve that is characterized by periodic brightening or variability at time scales of 4-20 days, frequently accompanied by shorter period oscillations. We can explain the dominant features of the entire class with orbitally-varying tidal forces that occur in close, eccentric binary systems. The large variety of light curve shapes arises from viewing systems at different angles. This hypothesis is supported by spectroscopic radial velocity measurements for five systems, each showing evidence of being in an eccentric binary system. Prior to the discovery of these 17 new systems, only four stars, where KOI-54 is the best example, were known to have evidence of these dynamic tides and tidally-induced oscillations. We perform preliminary fits to the light curves and radial velocity data, present the overall properties of this class and discuss the work required to accurately model these systems.Comment: 13 pages, submitted to Ap

Solution structure of a bacterial microcompartment targeting peptide and its application in the construction of an ethanol bioreactor

Targeting of proteins to bacterial microcompartments (BMCs) is mediated by an 18-amino-acid peptide sequence. Herein, we report the solution structure of the N-terminal targeting peptide (P18) of PduP, the aldehyde dehydrogenase associated with the 1,2-propanediol utilization metabolosome from Citrobacter freundii. The solution structure reveals the peptide to have a well-defined helical conformation along its whole length. Saturation transfer difference and transferred NOE NMR has highlighted the observed interaction surface on the peptide with its main interacting shell protein, PduK. By tagging both a pyruvate decarboxylase and an alcohol dehydrogenase with targeting peptides, it has been possible to direct these enzymes to empty BMCs in vivo and to generate an ethanol bioreactor. Not only are the purified, redesigned BMCs able to transform pyruvate into ethanol efficiently, but the strains containing the modified BMCs produce elevated levels of alcohol