Heterogeneous Fe(II) oxidation and zeta potential

The determination of electrophoretic mobility and zeta potential was used as a diagnostic tool, alongside kinetic experiments, to delineate between three plausible mechanisms for the heterogeneous oxidation of Fe(II) by dissolved oxygen. One of these mechanisms is dependant on the positive surface charge that exists on Fe(III) (oxy)hydroxide surfaces at pH values below the Iso-Electric Point (IEP). However, this mechanism can be disputed as catalysis is observed on Fe(III) (oxy)hydroxide surfaces above the IEP despite a negative zeta potential. As well as an IEP shift an overall reduction of the magnitude of the zeta potential is observed in samples of field Fe(III) (oxy)hydroxide collected from the Taff Merthyr mine water treatment site in South Wales, UK. Low zeta potentials determined in mine water treatment systems will have beneficial effects for particle coagulation and settling in passive mine water treatment systems.     

Zinc surface complexes on birnessite: A density functional theory study

Biogeochemical cycling of zinc is strongly influenced by sorption on birnessite minerals (layer-type MnO₂), which are found in diverse terrestrial and aquatic environments. Zinc has been observed to form both tetrahedral (Zn^IV) and octahedral (Zn^VI) triple-corner-sharing surface complexes (TCS) at Mn(IV) vacancy sites in hexagonal birnessite. The octahedral complex is expected to be similar to that of Zn in the Mn oxide mineral, chalcophanite (ZnMn₃O₇·3H₂O), but the reason for the occurrence of the four-coordinate Zn surface species remains unclear. We address this issue computationally using spin-polarized density functional theory (DFT) to examine the Zn^IV-TCS and Zn^VI-TCS species. Structural parameters obtained by DFT geometry optimization were in excellent agreement with available experimental data on Zn-birnessites. Total energy, magnetic moments, and electron overlap populations obtained by DFT for isolated Zn^IV-TCS revealed that this species is stable in birnessite without a need for Mn(III) substitution in the octahedral sheet and that it is more effective in reducing undersaturation of surface O at a Mn vacancy than is Zn^VI-TCS. Comparison between geometry-optimized ZnMn₃O₇·3H₂O (chalcophanite) and the hypothetical monohydrate mineral, ZnMn₃O₇·H₂O, which contains only tetrahedral Zn, showed that the hydration state of Zn significantly affects birnessite structural stability. Finally, our study also revealed that, relative to their positions in an ideal vacancy-free MnO₂, Mn nearest to Zn in a TCS surface complex move toward the vacancy by 0.08-0.11 Å, while surface O bordering the vacancy move away from it by 0.16-0.21 Å, in agreement with recent X-ray absorption spectroscopic analyses.     

Map making in small field modulated CMB polarization experiments: approximating the maximum likelihood method

Map making presents a significant computational challenge to the next generation of kilopixel cosmic microwave background polarization experiments. Years worth of time ordered data (TOD) from thousands of detectors will need to be compressed into maps of the T , Q and U Stokes parameters. Fundamental to the science goal of these experiments, the observation of B modes, is the ability to control noise and systematics. In this paper, we consider an alternative to the maximum likelihood method, called destriping , where the noise is modelled as a set of discrete offset functions and then subtracted from the time stream. We compare our destriping code (Descart: the DEStriping CARTographer) to a full maximum likelihood mapmaker, applying them to 200 Monte Carlo simulations of TOD from a ground-based, partial-sky polarization modulation experiment. In these simulations, the noise is dominated by either detector or atmospheric  1/ f   noise. Using prior information of the power spectrum of this noise, we produce destriped maps of T , Q and U which are negligibly different from optimal. The method does not filter the signal or bias the E- or B-mode power spectra. Depending on the length of the destriping baseline, the method delivers between five and 22 times improvement in computation time over the maximum likelihood algorithm. We find that, for the specific case of single detector maps, it is essential to destripe the atmospheric  1/ f   in order to detect B modes, even though the Q and U signals are modulated by a half-wave plate spinning at 5 Hz.     

Bayesian modelling of clusters of galaxies from multifrequency-pointed Sunyaev–Zel'dovich observations

We present a Bayesian approach to modelling galaxy clusters using multi-frequency pointed observations from telescopes that exploit the Sunyaev–Zel'dovich effect. We use the recently developed multinest technique to explore the high-dimensional parameter spaces and also to calculate the Bayesian evidence. This permits robust parameter estimation as well as model comparison. Tests on simulated Arcminute Microkelvin Imager observations of a cluster, in the presence of primary CMB signal, radio point sources (detected as well as an unresolved background) and receiver noise, show that our algorithm is able to analyse jointly the data from six frequency channels, sample the posterior space of the model and calculate the Bayesian evidence very efficiently on a single processor. We also illustrate the robustness of our detection process by applying it to a field with radio sources and primordial CMB but no cluster, and show that indeed no cluster is identified. The extension of our methodology to the detection and modelling of multiple clusters in multi-frequency SZ survey data will be described in a future work.     

The orbital motion of the Arches cluster: clues on cluster formation near the Galactic Center

We have measured the proper motion of the Arches cluster near the Galactic Center (GC) with respect to the ambient field, using Keck/NIRC2 LGS-AO and VLT/NAOS-CONICA NGS-AO observations spanning a baseline of 4.3 yr. Combined with the radial velocity, we derive a 3D space motion of 232±30 km?s^?1 for the Arches cluster. This motion is exceptionally large compared to molecular cloud orbits at the GC, and places stringent constraints on the formation scenarios for starburst clusters in dense, nuclear environments.     

Evidence for ponding and catastrophic floods in central Valles Marineris, Mars

The Valles Marineris canyon system of Mars is closely related to large flood channels, some of which emerge full born from chaotic terrain in canyon floors. Coprates Chasma, one of the largest Valles Marineris canyons, is connected at its west end to Melas Chasma and on its east end to chaotic terrain-filled Capri and Eos Chasmata. The area from central Melas to Eos Chasmata contains a 1500 km long and about 1 km deep depression in its floor. Despite the large volumes of groundwater that likely discharged from chaotic terrain in this depression, no evidence of related fluvial activity has thus far been reported. We present an analysis of the regional topography which, together with photogeologic interpretation of available imagery, suggests that ponding due to late Hesperian discharge of water possibly produced a lake (mean depth 842 m) spanning parts of the Valles Marineris depression (VMD). Overflow of this lake at its eastern end resulted in delivery of water to downstream chaos regions and outflow channels. Our ponding hypothesis is motivated primarily by the identification of scarp and terrace features which, despite a lateral spread of about 1500 km, have similar elevations. Furthermore, these elevations correspond to the maximum ponding elevation of the region (−3560 m). Simulated ponding in the VMD yields an overflow point at its eastern extremity, in Eos Chasma. The neighborhood of this overflow point contains clear indicators of fluvial erosion in a consistent east-west orientation.     

Radio source calibration for the Very Small Array and other cosmic microwave background instruments at around 30 GHz

Accurate calibration of data is essential for the current generation of cosmic microwave background (CMB) experiments. Using data from the Very Small Array (VSA), we describe procedures which will lead to an accuracy of 1 per cent or better for experiments such as the VSA and CBI. Particular attention is paid to the stability of the receiver systems, the quality of the site and frequent observations of reference sources. At 30 GHz the careful correction for atmospheric emission and absorption is shown to be essential for achieving 1 per cent precision.
The sources for which a 1 per cent relative flux density calibration was achieved included Cas A, Cyg A, Tau A and NGC 7027 and the planets Venus, Jupiter and Saturn. A flux density, or brightness temperature in the case of the planets, was derived at 33 GHz relative to Jupiter which was adopted as the fundamental calibrator. A spectral index at ∼30 GHz is given for each.
Cas A, Tau A, NGC 7027 and Venus were examined for variability. Cas A was found to be decreasing at 0.394 ± 0.019 per cent yr⁻¹ over the period 2001 March to 2004 August. In the same period Tau A was decreasing at 0.22 ± 0.07 per cent yr⁻¹. A survey of the published data showed that the planetary nebula NGC 7027 decreased at 0.16 ± 0.04 per cent yr⁻¹ over the period 1967–2003. Venus showed an insignificant (1.5 ± 1.3 per cent) variation with Venusian illumination. The integrated polarization of Tau A at 33 GHz was found to be 7.8 ± 0.6 per cent at position angle =148°± 3°.     

Methylmercury Bioaccumulation in an Urban Estuary: Delaware River,USA

Spatial variation in mercury (Hg) and methylmercury (MeHg) bioaccumulation in urban coastal watersheds reflects complex interactions between Hg sources, land use, and environmental gradients. We examined MeHg concentrations in fauna from the Delaware River estuary, and related these measurements to environmental parameters and human impacts on the waterway. The sampling sites followed a north to south gradient of increasing salinity, decreasing urban influence, and increasing marsh cover. Although mean total Hg in surface sediments (top 4 cm) peaked in the urban estuarine turbidity maximum and generally decreased downstream, surface sediment MeHg concentrations showed no spatial patterns consistent with the examined environmental gradients, indicating urban influence on Hg loading to the sediment but not subsequent methylation. Surface water particulate MeHg concentration showed a positive correlation with marsh cover whereas dissolved MeHg concentrations were slightly elevated in the estuarine turbidity maximum region. Spatial patterns of MeHg bioaccumulation in resident fauna varied across taxa. Small fish showed increased MeHg concentrations in the more urban/industrial sites upstream, with concentrations generally decreasing farther downstream. Invertebrates either showed no clear spatial patterns in MeHg concentrations (blue crabs, fiddler crabs) or increasing concentrations further downstream (grass shrimp). Best-supported linear mixed models relating tissue concentration to environmental variables reflected these complex patterns, with species specific model results dominated by random site effects with a combination of particulate MeHg and landscape variables influencing bioaccumulation in some species. The data strengthen accumulating evidence that bioaccumulation in estuaries can be decoupled from sediment MeHg concentration, and that drivers of MeHg production and fate may vary within a small region.     

Magnetic susceptibility as a proxy for coal ash pollution within riverbed sediments in a watershed with complex geology (southeastern USA)

A study of near surface sediments from the Dan River (southeastern USA) was conducted to assess the use of magnetic properties as proxies of coal ash after a recent spill. The watershed geology is diverse and potentially contributes magnetic minerals to riverbed sediment from diabase dikes in the Dan River Triassic Basin and from granitic gneiss outside the basin. Coal ash is heterogeneous, including aluminosilicate spheres, amorphous particles and carbonaceous rods and lacy particles. The magnetic fraction of ash from the failed storage pond is up to 17 wt% and is mostly composed of black spheres with maghemite and magnetite. Ash was detected in riverbed sediment from quiet water settings such as inside of meander bends, the confluence of tributary streams and near islands between the spill site and 20 miles downstream in the Schoolfield Reservoir, Danville, VA. The strong magnetic signal is detected above background in riverbed samples and is strongly positively correlated with total ash; elevated low field magnetic susceptibility (χ _LF) is evident in samples with ≥ 12% ash content. Anhysteretic remanent magnetization and hysteresis parameters delineate native sediment, ash-bearing sediment, and diabase dikes. Between 20 and 70 miles downstream of the spill site, ash concentrations were either buried or too low due to dilution with native sediment to be detected with χ _LF in riverbed samples.     

A simple model to account for regional inequalities in the effectiveness of solar radiation management

We present a simple model to account for the potential effectiveness of solar radiation management (SRM) in compensating for anthropogenic climate change. This method provides a parsimonious way to account for regional inequality in the assessment of SRM effectiveness and allows policy and decision makers to examine the linear climate response to different SRM configurations. To illustrate how the model works, we use data from an ensemble of modeling experiments conducted with a general circulation model (GCM). We find that an SRM scheme optimized to restore population-weighted temperature changes to their baseline compensates for 99% of these changes while an SRM scheme optimized for population-weighted precipitation changes compensates for 97% of these changes. Hence, while inequalities in the effectiveness of SRM are important, they may not be as severe as it is often assumed.