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Using aircraft measurements to determine the refractive index of Saharan dust during the DODO Experiments
Much uncertainty in the value of the imaginary part of the refractive index of mineral dust contributes to uncertainty in the radiative effect of mineral dust in the atmosphere. A synthesis of optical, chemical and physical in-situ aircraft measurements from the DODO experiments during February and August 2006 are used to calculate the refractive index mineral dust encountered over West Africa. Radiative transfer modeling and measurements of broadband shortwave irradiance at a range of altitudes are used to test and validate these calculations for a specific dust event on 23 August 2006 over Mauritania. Two techniques are used to determine the refractive index: firstly a method combining measurements of scattering, absorption, size distributions and Mie code simulations, and secondly a method using composition measured on filter samples to apportion the content of internally mixed quartz, calcite and iron oxide-clay aggregates, where the iron oxide is represented by either hematite or goethite and clay by either illite or kaolinite. The imaginary part of the refractive index at 550 nm (ni550) is found to range between 0.0001 i to 0.0046 i, and where filter samples are available, agreement between methods is found depending on mineral combination assumed. The refractive indices are also found to agree well with AERONET data where comparisons are possible. ni550 is found to vary with dust source, which is investigated with the NAME model for each case. The relationship between both size distribution and ni550 on the accumulation mode single scattering albedo at 550 nm (ω0550) are examined and size distribution is found to have no correlation to ω0550, while ni550 shows a strong linear relationship with ω0550. Radiative transfer modeling was performed with different models (Mie-derived refractive indices, but also filter sampling composition assuming both internal and external mixing). Our calculations indicate that Mie-derived values of ni550 and the externally mixed dust where the iron oxide-clay aggregate corresponds to the goethite-kaolinite combination result in the best agreement with irradiance measurements. The radiative effect of the dust is found to be very sensitive to the mineral combination (and hence refractive index) assumed, and to whether the dust is assumed to be internally or externally mixed
Some considerations related to the use of the Scherrer equation in powder X-ray diffraction as applied to heterogeneous catalysts
This short overview summarises some of the basic considerations which should be undertaken when the Scherrer equation is applied to reflection widths in X-ray diffraction patterns of heterogeneous catalysts in order to extract meaningful information. Frequently, little account has been taken of the apparent complications arising from the presence of microstructural strain and disorder such as that which can be introduced upon doping or of anisotropic effects and such considerations are highlighted.
Scanning electron micrograph showing the highly anisotropic nature of biogenic iron oxide found in a natural iron ochre source
Green rust formation and reactivity with arsenic species
Elevated levels of arsenic (As) in soils and groundwaters remain a pressing global challenge due to its widespread occurrence and distribution, high toxicity and mobility. In oxygen-limited subsurface conditions, redox-active mineral phases can be important substrates in controlling the fate and mobility of As in the environment. Among these redox-active minerals, green rust (GR) phases, an Fe(II)-Fe(III)-bearing layered double hydroxide, have been shown to be able to sequester a wide range of toxic metals and metalloids, including As. However, very little is known regarding how GR phases interact with As species and what is the fate of the immobilized As under dynamic geochemical conditions. GR phases are suggested to form through the transformation of metastable iron mineral phases in non-sulfidic, reducing environments. However, the exact mechanism and pathway of this transformation, as well as the fate of mineral-associated As (i.e. whether it is re-released back into the groundwater by desorption, dissolution or redox transformation) is not yet known but critically needed for modelling As cycling in contaminated environments.
To address these knowledge gaps, I conducted a series of experimental geochemical studies and combined them with various laboratory- and synchrotron-based solid and liquid phase characterization methods to examine the interaction between GR sulfate (GRSO4) and As species [As(III) and As(V)]. Specifically, I performed several batch experiments under anoxic and near-neutral pH conditions to determine As-GR interaction mechanisms during GR formation and transformation. Moreover, I also quantified how these transformation reactions affect the toxicity and mobility of As species in contaminated environments.
From the batch adsorption experiments, I showed that synthetic GRSO4 can adsorb up to 160 and 105 mg of As(III) and As(V) per g of solid, respectively. These adsorption capacities are among the highest reported for iron (oxyhydr)oxides that form in soils and groundwaters. Results from this study also show that As removal by GRSO4 can be inhibited by several geochemical parameters such as pH, high ionic strength, presence of co-existing inorganic ions (e.g., Mg2+, PO43-, Si) and low temperature.
I also employed an integrated nano-scale solid-state characterization approach to elucidate As-GRSO4 interactions. Specifically, I combined scanning transmission electron microscopy (STEM) coupled with energy dispersive X-ray (EDX) spectroscopy together with bulk synchrotron-based X-ray techniques including high energy X-ray total scattering, pair distribution function (PDF) analysis and X-ray absorption spectroscopy (XAS). With these, I was able to directly visualize and pinpoint As binding sites at the GR surface sites and to identify the binding mechanism for both As(III) and As(V). In the case of As(III)-reacted GR, STEM-EDX maps showed that As(III) were preferentially adsorbed at the GR crystal edges, primarily as bidentate binuclear (2C) inner-sphere surface complexes based from the differential PDF and As K-edge XAS data. For the As(V)-reacted GR, As(V) was sequestered as a newly-formed As-bearing mineral phase parasymplesite and as adsorbed As(V) species at the GR edges (in 2C geometry).
To assess the fate of As in subsurface environments, I studied As during GR formation and transformation to quantify As uptake and/or its potential release back into solution and the stability of GR and other Fe (oxhydr)oxide phases in this process. During the Fe2+-induced transformation of As(V)-bearing ferrihydrite, I followed the changes in aqueous behavior and speciation of As, as well as the changes in composition of the Fe mineral phases, as a function of varying Fe2+(aq)/Fe(III)solid ratios (0.5, 1 ,2). In all the ratios tested, GRSO4, goethite and lepidocrocite formed in the early stages of transformation (≤ 2h). However, at low ratios (<2), the initially formed GRSo4 and/or lepidocrocite disappeared as the reaction progressed, leaving goethite and unreacted ferrihydrite after 24 h. At an Fe2+(aq)/Fe(III)solid ratio of 2, GRSO4 was formed and remained in the solids until the end of the 24-h transformation, with goethite and unreacted ferrihydrite. The initial As(V) was partially reduced to As(III) by the surface-associated Fe2+-GT redox couple, and extent of reduction increased from 34 to 44% as Fe2+(aq)/Fe(III)solid ratios increased. Despite this reduction to the more mobile and more toxic As(III) species, no significant As release was observed during the mineral transformation reactions.
Finally, I tested the long-term stability and reactivity of GR by aging synthetic GRSO4 in pristine and As-spiked natural groundwater at ambient (25 °C) and low (4 °C) temperatures. The spiked As in the groundwater was completely removed after 120 days at 25 °C while the removal rate was ~2 times slower at 4 °C with only ~66% As removal after 120 days. On the other hand, the stability of synthetic GRSO4 in groundwater was strongly affected by the presence of adsorbed As species and temperature. At ambient temperature, the initial GRSO4 aged in As-free groundwater was converted to GRCO3 by ion exchange within a few days and both GR phases eventually transformed to magnetite after 120 days. Remarkably, both the addition of As species in groundwater and lowering the temperature increased long-term GRSO4 stability through the inhibition of (a) ion exchange in the GRSO4 interlayer (i.e., slower conversion to GRCO3) and (b) transformation of GR to magnetite. Moreover, a synergistic stabilization effect was observed with both As addition and low temperature, significantly enhancing GR stability up to a year.
Overall, the work presented in this thesis clearly emphasizes the potential role of GR phases in controlling the mobility and toxicity of As species in subsurface environments. Specifically, I contributed to the fundamental understanding of the reactions involving As(III) and As(V) at GR surfaces, elucidating the relevant binding mechanisms and visualizing specific binding sites of immobilized As species. This work also identified critical geochemical factors that affect As removal and GR formation and transformation under anoxic and circum-neutral pH conditions. More importantly, I was able to show the enhanced long-term stability of GR in natural groundwaters and its prolonged reactivity for As sequestration
Neodymium recovery by chitosan/iron(III) hydroxide [ChiFer(III)] sorbent material: Batch and column systems
A low cost composite material was synthesized for neodymium recovery from dilute aqueous solutions. The in-situ production of the composite containing chitosan and iron(III) hydroxide (ChiFer(III)) was improved and the results were compared with raw chitosan particles. The sorbent was characterized using Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy-energy dispersive X-ray analyses (SEM-EDX). The equilibrium studies were performed using firstly a batch system, and secondly a continuous system. The sorption isotherms were fitted with the Langmuir, Freundlich, and Sips models; experimental data was better described with the Langmuir equation and the maximum sorption capacity was 13.8 mg g-1 at pH 4. The introduction of iron into the biopolymer matrix increases by four times the sorption uptake of the chitosan; the individual sorption capacity of iron (into the composite) was calculated as 30.9 mg Nd/g Fe. The experimental results of the columns were fitted adequately using the Thomas model. As an approach to Nd-Fe-B permanent magnets effluents, a synthetic dilute effluent was simulated at pH 4, in order to evaluate the selectivity of the sorbent material; the overshooting of boron in the column system confirmed the higher selectivity toward neodymium ions. The elution step was carried out using MilliQ-water with the pH set to 3.5 (dilute HCl solution).Peer ReviewedPostprint (published version
Reactive transport model of the formation of oxide-type Ni-laterite profiles (Punta Gorda, Moa Bay, Cuba)
Oxide-type Ni-laterite deposits are characterized by a dominant limonite zone with goethite as the economically most important Ni ore mineral and a thin zone of hydrous Mg silicate-rich saprolite beneath the magnesium discontinuity. Fe, less soluble, is mainly retained forming goethite, while Ni is redeposited at greater depth in a Fe(III) and Ni-rich serpentine (serpentine II) or in goethite, where it adsorbs or substitutes for Fe in the mineral structure. Here, a 1D reactive transport model, using CrunchFlow, of Punta Gorda oxide-type Ni-laterite deposit (Moa Bay, Cuba) formation is presented. The model reproduces the formation of the different laterite horizons in the profile from an initial, partially serpentinized peridotite, in 10(6) years, validating the conceptual model of the formation of this kind of deposits in which a narrow saprolite horizon rich in Ni-bearing serpentine is formed above peridotite parent rock and a thick limonite horizon is formed over saprolite. Results also confirm that sorption of Ni onto goethite can explain the weight percent of Ni found in the Moa goethite.Sensitivity analyses accounting for the effect of key parameters (composition, dissolution rate, carbonate concentration, quartz precipitation) on the model results are also presented. It is found that aqueous carbonate concentration and quartz precipitation significantly affects the laterization process rate, while the effect of the composition of secondary serpentine or of mineral dissolution rates is minor. The results of this reactive transport modeling have proven useful to validate the conceptual models derived from field observations
Limonite – a weathered residual soil heterogeneous at all scales
Limonite is a residual soil produced by the decomposition of magnesium silicate (olivine) rocks in tropical environments. During weathering most of the original rock is leached away leaving only its iron content, which is precipitated out in the form of iron sesqui-oxides to create a soft and highly porous soil. The predominant mineral present in limonite is goethite, which forms acicular nanoparticles that agglomerate to produce a silty sand with porous particles. The void ratio varies from 2 to 6, with higher values being a consequence of structure-supported voids. An extensive set of laboratory tests have been performed on a limonite soil profile which extends 50 m to rock. These data show that there is no pattern to shear strength with depth, with the shear strength equally likely to be 50 or 200 kPa through much of the profile. It is argued that the shear strength parameters for failure mechanisms, having any significant length, should be based on average values. The letter presents scanning electron microscopy photographs showing the fundamental particles, the results of triaxial tests comparing natural and reconstituted behaviour which show the effects of microstructure on the meso-scale response, and field data to show site variability
Dissolution features of gold particles in a lateritic profile at Dondo Mobi, Gabon
Cet article décrit l'évolution morphologique de particules d'or dans un profil d'altération latéritique sous forêt humide (Dondo Mobi, Gabon). Héritées d'une veine de quartz associée à des amphibolites, les particules d'or sont reconnues dans la saprolite à partir du front d'altération et dans les horizons meubles de surface dans la partie centrale du halo de dispersion de l'or supergène. Les particules d'or montrent des transformations dans les premiers dix mètre
Soil-Saprolite Profiles Derived from Mafic Rocks in the North Carolina Piedmont: II. Association of Free Iron Oxides with Soils and Clays
The association of free Fe oxides with soils and clays from two Enon sandy loam (Ultic Hapludalfs, fine, mixed, thermic) soilsaprolite profiles was studied. Goethite was the dominant Fe oxide identified. Lepidocrocite was detected in trace amounts in some samples. FeCBD/clay ratios were highest in the epipedons of these soils suggesting the concentrating of Fe oxides as a result of aluminosilicate mineral weathering. External (BET-N2) surface area measurements of non-deferrated and deferrated clays were analyzed in conjunction with electron micrographs of selected clay fractions to determine the association of free Fe oxides with aluminosilicate clays as a function of depth in the profile. Free Fe oxides were found to exist mainly as small, discrete clusters in the A and B horizons of both profiles and specific of the clay surface decreased as a result of treatment for Fe removal. However, external surface areas increased for the saprolite (Cr) horizon clays after deferration. One subfraction identified as having an increase in surface area after deferration was fine clay from the Cr2 horizon, Enon (metagabbro) profile. Chemical data and electron micrographs suggest that either partial dissolution of small, poorly crystalline aluminosilicate clays or removal of some Fe or non-Fe oxide aggregating agent results in breakdown of the fine clays into smaller particles of higher net specific surface
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