Superhydrophobic and superoleophilic micro-wrinkled reduced graphene oxide as a highly portable and recyclable oil sorbent.

The potential of superhydrophobic and superoleophilic microwrinkled reduced graphene oxide (MWrGO) structures is here demonstrated for oil spill cleanup. The impact of the thickness of MWrGO films on the sorption performance of three different oils was investigated. Water contact angles across the MWrGO surfaces were found to exceed 150°, while oil could be easily absorbed by the microwrinkled structures of MWrGO within seconds after contact. Although the oil surface diffusion rate was not found to be dependent on the thickness of the graphene oxide films, the oil sorption capacity was the largest with the thinner MWrGO films due to the high surface area resulting from their fine surface texture. Furthermore, the composite films can be repeatedly used for at least 20 oil sorption-removal cycles without any notable loss in selectivity and uptake capacity. These MWrGO/elastomer composite films could be applied as a potential candidate material for future oil spill cleanup.

The Effect of Iron Oxide Nanoparticles on the Fate and Transformation of Arsenic in Aquatic Environments

Iron oxides and arsenic are prevalent in the environment. With the increase interest in the use of iron oxide nanoparticles (IONPs) for contaminant remediation and the high toxicity of arsenic, it is crucial that we evaluate the interactions between IONPs and arsenic. The goal was to understand the environmental behavior of IONPs in regards to their particle size, aggregation and stability, and to determine how this behavior influences IONPs-arsenic interactions. A variety of dispersion techniques were investigated to disperse bare commercial IONPs. Vortex was able to disperse commercial hematite nanoparticles into unstable dispersions with particles in the micrometer size range while probe ultrasonication dispersed the particles into stable dispersions of nanometer size ranges for a prolonged period of time. Using probe ultrasonication and vortex to prepare IONPs suspensions of different particle sizes, the adsorption of arsenite and arsenate to bare hematite nanoparticles and hematite aggregates were investigated. To understand the difference in the adsorptive behavior, adsorption kinetics and isotherm parameters were determined. Both arsenite and arsenate were capable of adsorbing to hematite nanoparticles and hematite aggregates but the rate and capacity of adsorption is dependent upon the hematite particle size, the stability of the dispersion and the type of sorbed arsenic species. Once arsenic was adsorbed onto the hematite surface, both iron and arsenic can undergo redox transformation both microbially and photochemically and these processes can be intertwined. Arsenic speciation studies in the presence of hematite particles were performed and the effect of light on the redox process was preliminary quantified. The redox behavior of arsenite and arsenate were different depending on the hematite particle size, the stability of the suspension and the presence of environmental factors such as microbes and light. The results from this study are important and have significant environmental implications as arsenic mobility and bioavailability can be affected by its adsorption to hematite particles and by its surface mediated redox transformation. Moreover, this study furthers our understanding on how the particle size influences the interactions between IONPs and arsenic thereby clarifying the role of IONPs in the biogeochemical cycling of arsenic.

The Performance and Service Life Prediction of High Performance Concrete in Sulfate and Acidic Environments

Concrete substructures are often subjected to environmental deterioration, such as sulfate and acid attack, which leads to severe damage and causes structure degradation or even failure. In order to improve the durability of concrete, the High Performance Concrete (HPC) has become widely used by partially replacing cement with pozzolanic materials. However, HPC degradation mechanisms in sulfate and acidic environments are not completely understood. It is therefore important to evaluate the performance of the HPC in such conditions and predict concrete service life by establishing degradation models. This study began with a review of available environmental data in the State of Florida. A total of seven bridges have been inspected. Concrete cores were taken from these bridge piles and were subjected for microstructural analysis using Scanning Electron Microscope (SEM). Ettringite is found to be the products of sulfate attack in sulfate and acidic condition. In order to quantitatively analyze concrete deterioration level, an image processing program is designed using Matlab to obtain quantitative data. Crack percentage (Acrack/Asurface) is used to evaluate concrete deterioration. Thereafter, correlation analysis was performed to find the correlation between five related variables and concrete deterioration. Environmental sulfate concentration and bridge age were found to be positively correlated, while environmental pH level was found to be negatively correlated. Besides environmental conditions, concrete property factor was also included in the equation. It was derived from laboratory testing data. Experimental tests were carried out implementing accelerated expansion test under controlled environment. Specimens of eight different mix designs were prepared. The effect of pozzolanic replacement rate was taken into consideration in the empirical equation. And the empirical equation was validated with existing bridges. Results show that the proposed equations compared well with field test results with a maximum deviation of ± 20%. Two examples showing how to use the proposed equations are provided to guide the practical implementation. In conclusion, the proposed approach of relating microcracks to deterioration is a better method than existing diffusion and sorption models since sulfate attack cause cracking in concrete. Imaging technique provided in this study can also be used to quantitatively analyze concrete samples.

Kinetic analysis of metal uptake by dry and gel alginate particles

The kinetics of metal uptake by gel and dry calcium alginate beads was analysed using solutions of copper or lead ions. Gel beads sorbed metal ions faster than the dry ones and larger diffusivities of metal ions were calculated for gel beads: approximately 10−4 cm2/min vs. 10−6 cm2/min for dry beads. In accordance, scanning electron microscopy and nitrogen adsorption data revealed a low porosity of dry alginate particles. However, dry beads showed higher sorption capacities and a mechanical stability more suitable for large-scale use. Two sorption models were fitted to the kinetic results: the Lagergren pseudo-first order and the Ho and McKay pseudo-second order equations. The former was found to be the most adequate to model metal uptake by dry alginate beads and kinetic constants in the orders of 10−3 and 10−2 min−1 were obtained for lead solutions with concentrations up to 100 g/m3. The pseudo-first order model was also found to be valid to describe biosorbent operation with a real wastewater indicating that it can be used to design processes of metal sorption with alginate-based materials.

Evaluation of dry protonated calcium alginate beads for biosorption applications and studies of lead uptake

Alginate polysaccharide is a promising biosorbent for metal uptake. Dry protonated calcium alginate beads for biosorption applications were prepared, briefly characterized and tested for lead uptake. Several advantages of this biosorbent are reported and discussed in comparison with other alginate-based sorbents. The alginate beads contained 4.7 mmol/g of COOH groups, which suffered hydrolysis near pH 4. The Weber and Morris model, applied to kinetic results of lead uptake, showed that intraparticle diffusion was the rate-controlling step in lead sorption by dry alginate beads. Equilibrium experiments were performed and the data were fitted with different isotherm models. The Langmuir equation was the most adequate to model lead sorption. The maximum uptake capacity (qmax) was estimated as 339 mg/g and the Langmuir constant (b) as 0.84 l/mg. These values were compared with that of other sorbents found in the literature, indicating that dry protonated calcium alginate beads are among the best biosorbents for the treatment and recovery of heavy metals from aqueous streams.

Evaluation of dry protonated calcium alginate beads for biosorption applications and studies of lead uptake

Alginate polysaccharide is a promising biosorbent for metal uptake. Dry protonated calcium alginate beads for biosorption applications were prepared, briefly characterized and tested for lead uptake. Several advantages of this biosorbent are reported and discussed in comparison with other alginate-based sorbents. The alginate beads contained 4.7 mmol/g of COOH groups, which suffered hydrolysis near pH 4. The Weber and Morris model, applied to kinetic results of lead uptake, showed that intraparticle diffusion was the rate-controlling step in lead sorption by dry alginate beads. Equilibrium experiments were performed and the data were fitted with different isotherm models. The Langmuir equation was the most adequate to model lead sorption. The maximum uptake capacity (qmax) was estimated as 339 mg/g and the Langmuir constant (b) as 0.84 l/mg. These values were compared with that of other sorbents found in the literature, indicating that dry protonated calcium alginate beads are among the best biosorbents for the treatment and recovery of heavy metals from aqueous streams.

Bimodal magneto-luminescent dysprosium (DyIII)-potassium (KI)-oxalate framework: magnetic switchability with high anisotropic barrier and solvent sensing

We report synthesis, characterization, and properties of a multifunctional oxalate framework, {KDy(C₂O₄)₂(H₂O)₄}_n (1) (C₂O₄^2- = oxalate dianion) composed of two absolutely different metal ions in terms of their size, charge, and electronic configuration. Dehydrated framework (1′) exhibits permanent porosity and interesting solvent (H₂O, MeOH, CH₃CN, and EtOH) vapor sorption characteristics based on specific interactions with unsaturated alkali metal sites on the pore surface. Compound 1 shows solvent responsive bimodal magnetic and luminescence properties related to the DyIII center. Compound 1 exhibits reversible ferromagnetic to antiferromagnetric phase transition upon dehydration and rehydration, hitherto unknown for any lanthanide based coordination polymer or metal-organic frameworks. Both the compounds 1 and 1′ exhibit slow magnetic relaxation with very high anisotropic barrier (417 ± 9 K for 1 and 418 ± 7 K for 1′) which has been ascribed to the single ion magnetic anisotropy of the Dy^III centers. Nevertheless, compound 1 shows a metal based luminescence property in the visible region and H₂O molecules exhibit the strongest quenching effect compared to other solvents MeOH, MeCN, and EtOH, evoking 1′ as a potential H₂O sensor.

Exploring the potential of novel biomixtures and Lentinula edodes fungus for the degradation of selected pesticides. Evaluation for use in biobed systems

An approach to reduce the contamination of water sourceswith pesticides is the use of biopurificaction systems. The active core of these systems is the biomixture. The composition of biomixtures depends on the availability of local agro-industrial wastes and design should be adapted to every region. In Portugal, cork processing is generally regarded as environmentally friendly and would be interesting to find applications for its industry residues. In this work the potential use of different substrates in biomixtures, as cork (CBX); cork and straw, coat pine and LECA (Light Expanded Clay Aggregates), was tested on the degradation of terbuthylazine, difenoconazole, diflufenican and pendimethalin pesticides. Bioaugmentation strategies using the white-rot fungus Lentinula edodes inoculated into the CBX, was also assessed. The results obtained from this study clearly demonstrated the relevance of using natural biosorbents as cork residues to increase the capacity of pesticide dissipation in biomixtures for establishing biobeds. Furthermore, higher degradation of all the pesticides was achieved by use of bioaugmented biomixtures. Indeed, the biomixtures inoculated with L. edodes EL1were able to mineralize the selected xenobiotics, revelling that these white-rot fungi might be a suitable fungus for being used as inoculum sources in on-farm sustainable biopurification system, in order to increase its degradation efficiency. After 120 days, maximum degradation of terbuthylazine, difenoconazole, diflufenican and pendimethalin, of bioaugmented CBX, was 89.9%, 75.0%, 65.0% and 99.4%, respectively. The dominant metabolic route of terbuthylazine in biomixtures inoculated with L. edodes EL1 proceeded mainly via hydroxylation, towards production of terbuthylazine-hydroxy-2 metabolite. Finally, sorption process to cork by pesticides proved to be a reversible process,working cork as a mitigating factor reducing the toxicity to microorganisms in the biomixture, especially in the early stages.

Composition and characteristics of the ferromanganese crusts from the western Arctic Ocean

Layered ferromanganese crusts collected by dredge from a water depth range of 2770 to 2200 m on Mendeleev Ridge, Arctic Ocean,were analyzed formineralogical and chemical compositions and dated using the excess 230Th technique. Comparison with crusts from other oceans reveals that Fe-Mn deposits of Mendeleev Ridge have the highest Fe/Mn ratios, are depleted inMn, Co, and Ni, and enriched in Si and Al aswell as some minor elements, Li, Th, Sc, As and V. However, the upper layer of the crusts shows Mn, Co, and Ni contents comparable to crusts from the Atlantic and Indian Oceans. Growth rates vary from3.03 to 3.97mm/Myr measured on the uppermost 2mm. Mn and Fe oxyhydroxides (vernadite, ferroxyhyte, birnessite, todorokite and goethite) and nonmetalliferous detrital minerals characterize the Arctic crusts. Temporal changes in crust composition reflect changes in the depositional environment. Crust formation was dominated by three main processes: precipitation of Fe-Mn oxyhydroxides from ambient ocean water, sorption of metals by those Fe and Mn phases, and fluctuating but large inputs of terrigenous debris.