Advanced removal of Reactive Yellow 84 azo dye using functionalised amorphous calcium carbonates as adsorbent.

Two environmentally friendly organics (ethylenediaminetetraacetic acid, EDTA and its easier biodegradabe isomer, ethylenediamine-N, N'-disuccinic acid, EDDS) were used to dope calcium carbonate (CC) nanoparticles intending to increase their adsorptive properties and evaluate adsorption performance (uptake capacity and removal efficiency) for the persistent Reactive Yellow 84 azo dye. Easily synthesized nanomaterials were fully characterized (morphology and size, mineralogy, organic content, surface area, pore size and hydrodynamic diameter). RY84 removal was performed using two consecutive processes: photodegradation after adsorption. The CC-EDTA particles were most efficient for dye removal as compared to the plain and CC-EDDS particles. Adsorption kinetics and isotherms were considered for the CC-EDTA system. 99% removal occurred via adsorption on 1 g/L of adsorbent at 5 mg/L dye concentration and pH of 8 and it decreased to 48% at 60 mg/L. Maximum uptake capacity as described by Langmuir is 39.53 mg/g. As post-adsorption, under UVA irradiation, in the presence of 40 mmol/L H2O2, at dye concentration of 10 mg/L the highest degradation was 49.11%. Substantial decrease of adsorption (ca. 4 times) and photodegradation (ca. 5 times) efficiencies were observed in wastewater effluent as compared to distilled water. The results have important implications to wastewater treatments and appropriate decisions making for the choice of treatment process, process optimization and scaling up to pilot and industrial levels.

Surface Coverage Simulation and 3D Plotting of Main Process Parameters for Molybdenum and Vanadium Adsorption onto Ferrihydrite.

Ferrihydrite, FHY, was synthesized and characterized for morphology, mineralogy, surface area, hydrodynamic diameter and surface charge properties before molybdenum (Mo) and vanadium (V) adsorption. The potentiometric titration results showed first direct evidence that CO2 affects FHY surface sites at pH 6-9. Beside CO2, particles concentration may affect surface properties with an impact on adsorption performance. Additional new adsorption simulation results on theoretical surface coverage vs. experimental results obtained at varying particles concentration help theoreticians and experimentalists to better estimate and apply anion adsorption processes to real environments and suggest that simulation may not always be entirely reliable. Uptake capacities obtained experimentally, varying pH, particles and metals concentrations, were plotted to assess their synergetic effect and derive trends for future process optimization. Adsorption kinetics and isotherms were also considered. Experimentally derived values for maximum uptake capacities (0.43 and 1.20 mmol g-1, for Mo and V, respectively) and partitioning coefficients have applications, such as in making decisions for anions removal from wastewaters to achieve depollution efficiency or concentration required for effluents discharge and also implications in elements cycling from a geochemical perspective. In this work, the 3D plotting of the main adsorption process parameters obtained experimentally showed inter-correlations between significant process parameters that influence the adsorption process, and provides guidelines for its optimization and indicates that laboratory data can be transposed to real systems.

Geochemical investigations of noble metal-bearing ores: Synchrotron-based micro-analyses and microcosm bioleaching studies.

Auriferous sulphide ores often incorporate micro-fine (or invisible) gold and silver particles in a manner making their extraction difficult. Nobel metals are lost in the tailings due to the refractory nature of these ores. Bioleaching is an environment-friendly alternative to the commonly used and toxic cyanidation protocols for gold extraction from refractory ores. In this paper, we investigate gold and silver bioleaching from porphyry and epithermal mineralisation systems, using iron-oxidizing bacteria Acidithiobacillus ferrooxidans. The invisible Au, sequestered in refractory ores, was characterised in situ by synchrotron micro X-Ray Fluorescence (SR-µ-XRF) and X-ray Absorption Spectroscopy (XAS), offering information on Au unaltered speciation at the atomistic level within the ore matrices and at a micro-scale spatial resolution. The SR-µ-XRF and XAS results showed that 10-20 µm sized elemental Au(0) nuggets are sequestered in pyrite, chalcopyrite, arsenopyrite matrices and at the interface of a mixture of pyrite and chalcopyrite. Moreover, the preliminary bioleaching experiments of the two types of ores, showed that Acidithiobacillus ferrooxidans can catalyse the dissolution of natural heterogeneous Fe-rich geo-matrices, sequestering Au and Ag and releasing particulate phases or partially solubilising them within 60 days. These results provide an understanding of noble metal sequestration and speciation within natural ores and a demonstration of the application of synchrotron-based micro-analysis in characterizing economic trace metals in major mineral structures. This work is a contribution to the ongoing efforts towards finding feasible and greener solutions of noble metal extraction protocols.

Iron phthalocyanine-sensitized magnetic catalysts for BPA photodegradation.

The catalytic behavior of iron phthalocyanine (FePc)-sensitized magnetic nanocatalysts was evaluated for their application in the oxidative treatment of Bisphenol A (BPA) under mild environmental conditions. Two types of FePc (Fe(II)Pc and Fe(III)Pc), which are highly photosensitive compounds, were immobilized on the surface of functionalized magnetite. The nanomaterials were characterized by high resolution transmission electron microscopy (HR-TEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analyses (TGA). The generation of singlet oxygen by nanomaterials was also investigated. In the presence of UVA light exposure (365 nm) and 15 mM H2O2, the M@Fe(III)Pc photocatalyst gave the best results; for a catalyst concentration of 2.0 g L - 1, around 60% BPA was removed after 120 min of reaction. These experimental conditions were further tested under natural solar light exposure, for which also M@Fe(III)Pc exhibited enhanced oxidative catalytic activity, being able to remove 83% of BPA in solution. The water samples were less cytotoxic after treatment, this being confirmed by the MCF-7 cell viability assay.

Baltic Fucus vesiculosus as potential bio-sorbent for Zn removal: Mechanism insight.

This research aimed to find the best phenotype of the brown algae Fucus vesiculosus (kelp) which has the greater potential to become a sorption byproduct for Zn removal from contaminated waters. Thus, the Zn uptake capacity and sorption mechanisms of the kelp collected from the Baltic Sea shore was, for the first time, investigated under various conditions, and compared to the phenotype habiting on the Irish Sea shore. Sorption studies were performed investigating the effect of algal dosage, Zn sources as well as algal harvesting time of the year on Zn uptake capacity. The results suggested that the Baltic algae is a better bio-sorbent for Zn uptake. Sorption mechanisms were studied by employing various indirect and direct approaches, more importantly, including high resolution synchrotron X-Ray Fluorescence and X-Ray Absorption Spectroscopy (XAS) and molecular modelling (MM). The results revealed that alginate and cellulose are among the main polysaccharide bonding Zn at algal surface, via coordination with O atoms from carboxyl and hydroxyl groups. XAS results giving direct measurements of Zn bonding environment on algal surface are supported by MM outputs and suggested that Zn is surrounded by ca. 5 O atoms at interatomic distances varying from 1.94 to 2.02 Å. The results contribute to understanding sorption mechanisms which can further lead to finding the best eluent for Zn desorption from the used biomass, bio sorbent reconditioning and reuse in multiple sorption desorption cycles as well as process optimization before industrial scaling up.

Experimental and simulation results of the adsorption of Mo and V onto ferrihydrite.

This study aims to highlight discrepancies between experimental and simulation linked to the mechanisms of Mo and V adsorption onto ferrihydrite (FHY) nanoparticles. We have measured adsorption capacities and uptake efficiencies and then fitted and compared these with outputs from various geochemical and adsorption models that were run as a function of pH, surface area (SA) and ferrihydrite particles size distributions. Our results revealed that the experimental data for the Mo system could be fitted very well, but this was not the case for the V system, when a model default value for the SA of FHY of 600 m2 g-1 was used. The discrepancy in the results for the V system can be explained by the lack of specific V species and/or associated constants in databases and variation in software versions, which change the outputted chemical species. Our comparative results also confirm that any experimental variables used as modelling inputs need to be checked carefully prior to any modelling exercises.

Zn adsorption onto Irish Fucus vesiculosus: Biosorbent uptake capacity and atomistic mechanism insights.

This study presents a multifaceted approach of Zn adsorption onto dry Fucus vesiculosus originating from the Irish Sea. Metal chemistry as well as algae surface charge properties were characterized before adsorption. Zn adsorption tests were run as function of: pH, algae concentration and metal source. A comparison with Co, Cd, and Cu adsorption - in mono-ion solutions was also performed. Adsorption kinetics, fitted with pseudo-first order (PFO) and pseudo-second order (PSO) kinetic model, allowed the uptake parameters to be found and a comparison of kinetic rates. Synchrotron X-Ray-Florescence and X-Ray Absorption Spectroscopy measurements of Zn on algae after exposure permitted the extraction of direct information about Zn spatial distribution and bonding environment. The results showed that the carboxylic groups are the ones involved in the heterogeneously distributed Zn adsorption at low pH, Zn being coordinated with 5-6 O at bond distances varying from 1.98 to 2.03 Å - as in Zn alginate. Synchrotron results provide confirmation that, relative to Zn, alginate is one of the main algae components responsible for metal binding.

Combining µXANES and µXRD mapping to analyse the heterogeneity in calcium carbonate granules excreted by the earthworm Lumbricus terrestris.

The use of fluorescence full spectral micro-X-ray absorption near-edge structure (µXANES) mapping is becoming more widespread in the hard energy regime. This experimental method using the Ca K-edge combined with micro-X-ray diffraction (µXRD) mapping of the same sample has been enabled on beamline I18 at Diamond Light Source. This combined approach has been used to probe both long- and short-range order in calcium carbonate granules produced by the earthworm Lumbricus terrestris. In granules produced by earthworms cultured in a control artificial soil, calcite and vaterite are observed in the granules. However, granules produced by earthworms cultivated in the same artificial soil amended with 500 p.p.m. Mg also contain an aragonite. The two techniques, µXRD and µXANES, probe different sample volumes but there is good agreement in the phase maps produced.

Cadmium tolerance and adsorption by the marine brown alga Fucus vesiculosus from the Irish Sea and the Bothnian Sea.

Cadmium (Cd) uptake capacities and Cd tolerance of the marine alga Fucus vesiculosus from the Irish Sea (salinity 35 psu) and from the Bothnian Sea (northern Baltic, 5 psu) were quantified. These data were complemented by measurements of changes in maximal photosynthetic rate (P(max)), dark respiration rate and variable fluorescence vs. maximal fluorescence (F(v):F(m)). At concentrations between 0.01 and 1 mmol Cd l(-1), F. vesiculosus from the Bothnian Sea adsorbed significantly more (about 98%) Cd compared with F. vesiculosus from the Irish Sea. The photosynthetic measurements showed that the Bothnian Sea F. vesiculosus were more sensitive to Cd exposure than the Irish Sea algae. The algae from the Irish Sea showed negative photosynthetic effects only at 1 mmol Cd l(-1), which was expressed as a decreased P(max) (-12.3%) and F(v):F(m) (-4.6%). On the contrary, the algae from the Bothnian Sea were negatively affected already at Cd concentrations as low at 0.1 mmol Cd l(-1). They exhibited increased dark respiration (+11.1%) and decreased F(v):F(m) (-13.9%). The results show that F. vesiculosus from the Bothnian Sea may be an efficient sorption substrate for Cd removal from Cd contaminated seawater and this algae type may also have applications for wastewater treatment.