Experimental design and batch experiments for optimization of Cr(VI) removal from aqueous solutions by hydrous cerium oxide nanoparticles

Hydrous cerium oxide (HCO) was synthesized by intercalation of solutions of cerium(III) nitrate and sodium hydroxide and evaluated as an adsorbent for the removal of hexavalent chromium from aqueous solutions. Simple batch experiments and a 2⁵ factorial experimental design were employed to screen the variables affecting Cr(VI) removal efficiency. The effects of the process variables; solution pH, initial Cr(VI) concentration, temperature, adsorbent dose and ionic strength were examined. Using the experimental results, a linear mathematical model representing the influence of the different variables and their interactions was obtained. Analysis of variance (ANOVA) demonstrated that Cr(VI) adsorption significantly increases with decreased solution pH, initial concentration and amount of adsorbent used (dose), but slightly decreased with an increase in temperature and ionic strength. The optimization study indicates 99% as the maximum removal at pH 2, 20 °C, 1.923 mM of metal concentration and a sorbent dose of 4 g/dm³. At these optimal conditions, Langmuir, Freundlich and Redlich–Peterson isotherm models were obtained. The maximum adsorption capacity of Cr(VI) adsorbed by HCO was 0.828 mmol/g, calculated by the Langmuir isotherm model. Desorption of chromium indicated that the HCO adsorbent can be regenerated using NaOH solution 0.1 M (up to 85%). The adsorption interactions between the surface sites of HCO and the Cr(VI) ions were found to be a combined effect of both anion exchange and surface complexation with the formation of an inner-sphere complex.

Distribution of Uranium and Thorium in Dolomitic Gravel Fill and Shale Saprolite

The objectives of this study were to examine (1) the distribution of U and Th in dolomitic gravel fill and shale saprolite, and (2) the removal of uranium from acidic groundwater by dolomitic gravel through precipitation with amorphous basaluminite at the U.S. DOE Oak Ridge Integrated Field Research Challenge (ORIFRC) field site west of the Oak Ridge Y-12 National Security Complex in East Tennessee. Media reactivity and sustainability are a technical concern with the deployment of any subsurface reactive media. Because the gravel was placed in the subsurface and exposed to contaminated groundwater for over 20 years, it provided a unique opportunity to study the solid and water phase geochemical conditions within the media after this length of exposure. This study illustrates that dolomite gravel can remove U from acidic contaminated groundwater with high levels of Al3+, Ca2+, NO3−, and SO42− over the long term. As the groundwater flows through high pH carbonate gravel, U containing amorphous basaluminite precipitates as the pH increases. This is due to an increase in groundwater pH from 3.2 to ∼6.5 as it comes in contact with the gravel. Therefore, carbonate gravel could be considered as a possible treatment medium for removal and sequestration of U and other pH sensitive metals from acidic contaminated groundwater. Thorium concentrations are also high in the carbonate gravel. Thorium generally shows an inverse relationship with U from the surface down into the deeper saprolite. Barite precipitated in the shallow saprolite directly below the dolomitic gravel from barium present in the acidic contaminated groundwater.

Two-dimensional images of dissolved sulfide and metals in anoxic sediments by a novel diffusive gradients in thin film probe and optical scanning techniques

A novel diffusive gradients in thin film probe developed comprises diffusive gel layer of silver iodide (AgI) and a back-up Microchelex resin gel layer. 2D high-resolution images of sulfide and trace metals were determined respectively on the AgI gel by densitometric analysis and on the Microchelex resin layer with laser-ablation-inductively-coupled plasma mass spectrometry (LA-ICP-MS).We investigated the validity of the analytical procedures used for the determination of sulfide and trace metals. We found low relative standard deviations on replicate measurements, linear trace-metal calibration curves between the LA-ICP-MS signal and the true trace-metal concentration in the resin gel, and a good agreement of the sulfide results obtained with the AgI resin gel and with other analytical methods. The method was applied on anoxic sediment pore waters in an estuarine and marine system. Simultaneous remobilization of sulfide and trace metals was observed in the marine sediment.

Tunable thermomorphism and applications of ionic liquid analogues of Girard's reagents

A series of ionic liquids based on Girard's reagents was synthesised. Their tunable thermomorphic behaviour with water was demonstrated, and slight modifications in the cationic structure led to drastic changes in their water miscibility. Their phase behaviour, involving monophasic–biphasic transitions, drove a number of practical applications, including scavenging water-soluble dyes and the extraction of metals from water.

An ionic liquid process for mercury removal from natural gas

Efficient scrubbing of mercury vapour from natural gas streams has been demonstrated both in the laboratory and on an industrial scale, using chlorocuprate(ii) ionic liquids impregnated on high surface area porous solid supports, resulting in the effective removal of mercury vapour from natural gas streams. This material has been commercialised for use within the petroleum gas production industry, and has currently been running continuously for three years on a natural gas plant in Malaysia. Here we report on the chemistry underlying this process, and demonstrate the transfer of this technology from gram to ton scale.

The Application of Semiconductor Photocatalysis for the Removal of Cyanotoxins from Water and Design Concepts for Solar Photocatalytic Reactors for Large Scale Water Treatment

There has been a significant increase in the occurrence of cyanobacterial blooms in freshwaters over the past few decades due to escalating nutrient levels. These cyanobacteria release a range of toxins, for example microcystins which are chemically very stable. Many cyanotoxins are consequently very difficult to remove from water using existing treatment technologies. Semiconductor photocatalysis, however, has proven to be a very effective process for the removal of these compounds from water. In this chapter we consider the application of this highly versatile and exciting technology for the decomposition of cyanotoxins. Furthermore design concepts for solar photocatalytic reactors that could be utilized for the removal of these toxins are also considered

Hand-held voltammetric analyser for real-time monitoring of heavy metals in situ

This paper presents a novel hand-held instrument capable of real-time in situ detection and identification of heavy metals. The proposed system provides the facilities found in a traditional lab-based instrument in a hand held a design. In contrast to existing commercial systems, it can stand alone without the need of an associated computer. The electrochemical instrument uses anodic stripping voltammetry which is a precise and sensitive analytical method with excellent limits of detection. The sensors comprise disposable screen-printed (solid working) electrodes rather than the more common hanging mercury drop electrodes. The system is reliable, easy to use, safe, avoids expensive and time-consuming procedures and may be used in a variety of situations to help in the fields of environmental assessment and control.

Removal of microorganisms and their chemical metabolites from water using semiconductor photocatalysis

Semiconductor photocatalysis has been applied to the remediation of an extensive range of chemical pollutants in water over the past 30 years. The application of this versatile technology for removal of micro-organisms and cyanotoxins has recently become an area that has also been the subject of extensive research particularly over the past decade. This paper considers recent research in the application of semiconductor photocatalysis for the treatment of water contaminated with pathogenic micro-organisms and cyanotoxins. The basic processes involved in photocatalysis are described and examples of recent research into the use of photocatalysis for the removal of a range of microorganisms are detailed. The paper concludes with a review of the key research on the application of this process for the removal of chemical metabolites generated from cyanobacteria.

Novel photocatalytic reactor development for removal of hydrocarbons from water

Hydrocarbons contamination of the marine environment generated by the offshore oil and gas industry is generated from a number of sources including oil contaminated drill cuttings and produced waters. The removal of hydrocarbons from both these sources is one of the most significant challenges facing this sector as it moves towards zero emissions. The application of a number of techniques which have been used to successfully destroy hydrocarbons in produced water and waste water effluents has previously been reported. This paper reports the application of semiconductor photocatalysis as a final polishing step for the removal of hydrocarbons from two waste effluent sources. Two reactor concepts were considered: a simple flat plate immobilised film unit, and a new rotating drum photocatalytic reactor. Both units proved to be effective in removing residual hydrocarbons from the effluent with the drum reactor reducing the hydrocarbon content by 90% under 10 minutes. 

Voltammetric in situ measurements of heavy metals in soil using a portable electrochemical instrument

This paper presents a portable electrochemical instrument capable of detecting and identifying heavy metals in soil, in situ. The instrument has been developed for use in a variety of situations to facilitate contaminated land surveys, avoiding expensive and time-consuming procedures. The system uses differential pulse anodic stripping voltammetry which is a precise and sensitive analytical method with excellent limits of detection. The identification of metals is based on a statistical microprocessor-based method. The instrument is capable of detecting six different toxic metals (lead, cadmium, zinc, nickel, mercury and copper) with good sensitivity

Acidity compensation of electrochemical measurements for on-site monitoring of heavy metals

This paper presents an electrochemical instrumentation system capable of real-time in situ detection of heavy metals. A practical approach to introduce acidity compensation against changes in amplitude of the peak currents is also presented. The compensated amplitudes can then be used to predict the concentration level of heavy metals. The system uses differential pulse anodic stripping voltammetry, which is a precise and sensitive analytical method with excellent limits of detection. The instrument is capable of detecting lead, cadmium, zinc, nickel and copper with good sensitivity and precision. The system avoids expensive and time-consuming procedures and may be used in a variety of situations to help environmental assessment and control. 

On-site monitoring and cartographical mapping of heavy metals

This paper presents a portable electrochemical instrument capable of real-time in situ detection and automatic identification of heavy metals. The instrument is equipped with an embedded Geographical Position System and is capable of storing the geographical position of the sample under test. Software has been developed to combine pollutant results with geographical position, in order to produce a cartographical presentation of the pollution of an area. The electrochemical instrument provides the facilities found in a traditional lab based instrument in a portable design for on-site measurements. The instrument is capable of detecting lead, cadmium, zinc, nickel, mercury, and copper with good sensitivity and precision. The system is reliable, easy to use, safe, and it may be used in a variety of situations to help environmental assessment and control.

Intelligent potentiostat for identification of heavy metals in situ

This article presents a low-cost portable electrochemical instrument capable of on-site identification of heavy metals. The instrument acquires metal-specific voltage and current signals by the application of differential pulse anodic stripping voltammetry. This technique enhances the analytical current and rejects the background current, resulting in a higher signal-to-noise ratio for a better detection limit. The identification of heavy metals is based on an intelligent machine-based method using a multilayer perceptron neural network consisting of three layers of neurons. The neural network is implemented using a 16 bit microcontroller. The system is developed for use in the field in order to avoid expensive and time-consuming procedures and can be used in a variety of situations to help environmental assessment and control.