Stabilization of Fe/Cu nanoparticles by starch and efficiency of arsenic adsorption from aqueous solutions

Due to the severity of arsenic contamination of soil and water resources around the world, finding new adsorbents for arsenic removal from the water is of high importance. The present study investigates the possible use and effectiveness of starch-stabilized Fe/Cu nanoparticles for adsorption of arsenic from aqueous solutions. First, Fe/Cu nanoparticles at various starch concentrations of 0, 0.02, 0.04 and 0.06 wt% were synthesized and characterized by X-ray diffraction, transmission electron microscopy and zeta potential/particle size analyzer. Then 0.04 wt% stabilized Fe/Cu nanoparticles were tested for the sorption of As(III) and As(V) from synthetic arsenic-contaminated water. To have an understanding about the arsenic adsorption mechanism of nanoparticles, X-ray photoelectron spectroscopy (XPS) was performed before and after adsorption. The results showed that starch provides nanoparticles with a neutral surface and stabilization of nanoparticles is possible with 0.04 wt% or higher concentrations of starch. For 0.04 wt% starch-stabilized Fe/Cu nanoparticles, the adsorption isotherms fit well within the Langmuir equation, with maximum sorption capacities of 90.1 mg/g for As(III) and 126.58 mg/g for As(V) at a pH of 7.0 from the aqueous arsenic solutions. Examining the XPS spectra of nanoparticles before and after adsorption showed that arsenic adsorption by this nanoparticle can be due to the formation of inner-sphere arsenic complexes on the particle surface, and the surface oxygen-containing functional groups involved in adsorption. The high sorption capacity suggests the potential for applying starch-stabilized Fe/Cu nanoparticles to the contaminated waters for removal of arsenic.     

Authigenic carbonates from active methane seeps offshore southwest Africa

The southwest African continental margin is well known for occurrences of active methane-rich fluid seeps associated with seafloor pockmarks at water depths ranging broadly from the shelf to the deep basins, as well as with high gas flares in the water column, gas hydrate accumulations, diagenetic carbonate crusts and highly diverse benthic faunal communities. During the M76/3a expedition of R/V METEOR in 2008, gravity cores recovered abundant authigenic carbonate concretions from three known pockmark sites—Hydrate Hole, Worm Hole, the Regab pockmark—and two sites newly discovered during that cruise, the so-called Deep Hole and Baboon Cluster. The carbonate concretions were commonly associated with seep-benthic macrofauna and occurred within sediments bearing shallow gas hydrates. This study presents selected results from a comprehensive analysis of the mineralogy and isotope geochemistry of diagenetic carbonates sampled at these five pockmark sites. The oxygen isotope stratigraphy obtained from three cores of 2–5?m length indicates a maximum age of about 60,000–80,000?years for these sediments. The authigenic carbonates comprise mostly magnesian calcite and aragonite, associated occasionally with dolomite. Their very low carbon isotopic compositions (–61.0?<?δ¹³C ‰ V-PDB?<?–40.1) suggest anaerobic oxidation of methane (AOM) as the main process controlling carbonate precipitation. The oxygen isotopic signatures (+2.4?<?δ¹⁸O ‰ V-PDB?<?+6.2) lie within the range in equilibrium under present-day/interglacial to glacial conditions of bottom seawater; alternatively, the most positive δ¹⁸O values might reflect the contribution of ¹⁸O-rich water from gas hydrate decomposition. The frequent occurrence of diagenetic gypsum crystals suggests that reduced sulphur (hydrogen sulphide, pyrite) from sub-seafloor sediments has been oxidized by oxygenated bottom water. The acidity released during this process can potentially induce the dissolution of carbonate, thereby providing enough Ca²⁺ ions for pore solutions to reach gypsum saturation; this is thought to be promoted by the bio-irrigation and burrowing activity of benthic fauna. The δ¹⁸O–δ¹³C patterns identified in the authigenic carbonates are interpreted to reflect variations in the rate of AOM during the last glacial–interglacial cycle, in turn controlled by variably strong methane fluxes through the pockmarks. These results complement the conclusions of Kasten et al. in this special issue, based on authigenic barite trends at the Hydrate Hole and Worm Hole pockmarks which were interpreted to reflect spatiotemporal variations in AOM related to subsurface gas hydrate formation–decomposition.     

Biological and Temporal Variations of Trace Element Concentrations in the Moss Species Scleropodium purum (Hedw.) Limpr.

Over a period of one year, the moss Scleropodium purum was sampled every two weeks in a French rural area to determine the levels of Li, Na, Al, Si, P, Ca, V, Mn, Fe, Zn, Ba, Hg, and Pb. The element distribution in the moss shoot was studied throughout the year. An apical bioconcentration was discovered for Na, P, Ca, Mn, and Zn, whereas higher levels were found in the basal fraction for Li, Al, Si, V, Fe, Ba, Hg, and Pb. A significant variation of element concentrations was observed during the sampling period. In the apical part Li, Al, Si, V, Fe, Ba, and Hg show maximum levels in the summer and minimum in the autumn. The same pattern was found with Ca and Mn in the whole plant, whereas Na showed opposite fluctuations.     

Interpreting the clustering of radio sources

We develop the formalism required to interpret, within a CDM framework, the angular clustering of sources in a deep radio survey. The effect of non-linear evolution of density perturbations is discussed, as is the effect of the assumed redshift distribution of sources. We also investigate what redshift ranges contribute to the clustering signal at different angular scales. Application of the formalism is focused on the clustering detected in the FIRST survey, but measurements made for other radio surveys are also investigated. We comment on the implications for the evolution of clustering.     

Variability in the annual cycle of vertical particulate organic carbon export on Arctic shelves: Contrasting the Laptev Sea,Northern Baffin Bay and the Beaufort Sea

The ongoing regression of sea ice cover is expected to significantly affect the fate of organic carbon over the Arctic continental shelves. Long-term moored sediment traps were deployed in 2005–2006 in the Beaufort Sea, Northern Baffin Bay and the Laptev Sea to compare the annual variability of POC fluxes and to evaluate the factors regulating the annual cycle of carbon export over these continental shelves. Annual POC fluxes at 200 m ranged from 1.6 to 5.9 g C m⁻² yr⁻¹ with the highest export in Northern Baffin Bay and the lowest export over the Mackenzie Shelf in the Beaufort Sea. Each annual cycle exhibited an increase in POC export a few weeks before, during, or immediately following sea ice melt, but showed different patterns over the remainder of the cycle. Enhanced primary production, discharge of the Lena River, and resuspension events contributed to periods of elevated POC export over the Laptev Sea slope. High POC fluxes in Northern Baffin Bay reflected periods of elevated primary production in the North Water polynya. In the Beaufort Sea sediment resuspension contributed to most of the large export events. Our results suggest that the outer shelf of the Laptev Sea will likely sustain the largest increase in POC export in the next few years due to the large reduction in ice cover and the possible increase in the Lena River discharge. The large differences in forcing among the regions investigated reinforce the importance of monitoring POC fluxes in the different oceanographic regimes that characterize the Arctic shelves to assess the response of the Arctic Ocean carbon cycle to interannual variability and climate change.     

An alternative measure of discharge effectiveness

Since 1960, geomorphic effectiveness has been quantified by analytically combining measures of the frequency and the magnitude of geomorphic processes, most often for the case of sediment yield in rivers via the calculation of effective discharge, Q_eff. Here we leverage the Q_eff analysis approach to develop an alternative metric, the functional‐equivalent discharge Q_fed, which is the discharge that will reproduce the magnitude of the sediment load generated by the full hydrologic distribution. Q_fed is intended to be a more representative metric of hydrologic variability than Q_eff: whereas Q_eff provides a measure of the effectiveness of individual flow rates, Q_fed incorporates a measure of the average effectiveness of the entire flow distribution. We develop an analytical approximation of Q_fed based on relatively few parameters, apply the approach to a set of suspended sediment load data and describe how Q_fed varies broadly with sediment and hydrologic conditions. Copyright © 2007 John Wiley & Sons, Ltd.     

In Situ Electromigration as a Method for Removing Sulfate, Metals, and Other Contaminants from Ground Water

Electromigration is proposed as an in situ method for preconcentrating contaminants in ground water prior to pumping and treating. In earlier investigations by the senior author and co-workers, it was found that Cu in synthetic ground water migrated strongly to a Pt cathode and plated out as metallic copper. In the present study, carbon electrodes were inserted into a laboratory column of fine quartz sand that was saturated with a lower concentration of CuSO₄ solution. A fixed potential of 2.5 V was applied, causing dissolved Cu and SO₄ to accumulate strongly at the cathode and anode, respectively. Only minor plating-out of Cu took place on the carbon electrodes. In addition to the use of carbon electrodes, the present research also investigated the effects of a lower concentration of metal, accumulation of SO₄ adjacent to the anodes, adsorption of Cu on the sand, and competition by moving ground water.
At an imposed voltage of 2.5 V and in the presence of 65 mg/L of dissolved Cu and 96 mg/L of SO₄ (0.001 M CuSO₄ solution), electrolysis of water caused large changes in the pH and speciation of the aqueous components, as well as precipitation of solid Cu-hydroxides. Significant retardation of Cu occurred in the presence of ground water flowing at an average intergranular velocity of 0.2 m/day, but only minor retardation at water velocities of 1.9 and 2.9 m/day.
Sulfate tends to migrate strongly to the anodes, suggesting that in situ electromigration may offer a useful new method for preconcentrating such highly soluble ions as SO₄, NO₃, and CI that are difficult to remove by conventional pump-and-treat methods. A number of potential problems exist that should be addressed in a field test.     

Evolution of oceanic gabbros from DSDP Leg 82: influence of the fluid phase on metamorphic crystallizations

Gabbro breccias were recovered from an anomalously shallow level of the ocean crust during DSDP Leg 82. The rocks display evidence of metamorphic crystallization related either to localized deformation or to hydrothermal circulation of a seawater-derived fluid under static conditions. Secondary phases consist of plagioclase, amphibole and minor clinopyroxene, ilmenite, sphene and chlorite. Petrological study indicates that deformation took place at high temperature, under anhydrous conditions, and was followed by hydrothermal circulation. The compositions of secondary minerals (i.e. strong zonations, presence of chlorine in amphiboles, varying compositions of secondary plagioclase) indicate that reactions of the gabbros with the fluids occurred at a low water/rock ratio. Relations between Cl, Na and K in amphiboles suggest penetration of at least two distinct fluids of different compositions. Metamorphic crystallization stopped when greenschist facies conditions were reached( 350°C), probably because hydrothermal circulation faded out.     

Olivine‐dominated asteroids and meteorites: Distinguishing nebular and igneous histories

Abstract— Melting models indicate that the composition and abundance of olivine systematically co‐vary and are therefore excellent petrologic indicators. However, heliocentric distance, and thus surface temperature, has a significant effect on the spectra of olivine‐rich asteroids. We show that composition and temperature complexly interact spectrally, and must be simultaneously taken into account in order to infer olivine composition accurately. We find that most (7/9) of the olivine‐dominated asteroids are magnesian and thus likely sampled mantles differentiated from ordinary chondrite sources (e.g., pallasites). However, two other olivine‐rich asteroids (289 Nenetta and 246 Asporina) are found to be more ferroan. Melting models show that partial melting cannot produce olivine‐rich residues that are more ferroan than the chondrite precursor from which they formed. Thus, even moderately ferroan olivine must have non‐ordinary chondrite origins, and therefore likely originate from oxidized R chondrites or melts thereof, which reflect variations in nebular composition within the asteroid belt. This is consistent with the meteoritic record in which R chondrites and brachinites are rare relative to pallasites.     

‘Paleoenvironmental study of modern charcoal making activity on forest soils in the Northern Vosges Mountains (Bitche,France): A multidisciplinary study of two remaining charcoal platforms and associated soils sequences’

This multidisciplinary study aims to decipher the impact of ancient charcoal production on past and present-day soils in the northern Vosges Mountains. Soil observations in the field and laboratory were complemented by charcoal and phytolith studies on large thin sections, molecular analyses of organic pollutants, and phytolith analysis on bulk samples. The complex technosol platform records an ancient natural soil sequence buried by a human-made platform on which charcoal accumulated. The current upslope soil is an entic Podzol. Palaeoecological data collected in the buried soil are reliable owing to low bioactivity due to soil acidity. Podzolisation predated the platform construction. The presence of ashes induced low soil alkalisation developed in the charcoal hearth remains and appears to have generated the migration of subsequent iron/clay/organic bands throughout the platform sediment and the buried soil. Charcoal studied in thin sections revealed mainly Quercus and Fagus taxa. Phytolith studies suggest that a less dense or degraded forest preceded platform construction, probably due to former woodland coppicing or earlier disorganised wood gathering. The specific distribution of polycyclic aromatic hydrocarbons sorbed on charcoal has persisted in soils throughout centuries, but we have no evidence that charcoal-making activities contributed to diffuse global pollution.