Ljubinka V. Rajaković

The sorption of arsenic onto activated carbon impregnated with metallic silver and copper

Abstract The adsorption of arsenic species in aqueous solutions onto activated carbon with and without chemical impregnation has been studied. The ability of activated carbon to adsorb arsenic depends on the arsenic oxidation state, the pH of the water, and the activity of the metal used for the activated carbon impregnation. The results of the investigations have shown that physical adsorption is effective only for the arsenic(V) species in water. Activated carbon adsorbs arsenic(V) with a saturation adsorption capacity of 0.27 mmol/g. The chemisorption process is effective for both arsenic species. By impregnation of activated carbon by copper, the sorption process for the arsenic(III) species is significantly improved. The saturation adsorption capacity of the activated carbon impregnated by copper is 0.41 and 0.23 mmol/g for the arsenic(III) and arsenic(V) species, respectively. The pH values of the water are important for both sorption processes because of the change in the ionic forms of both arseni...

Determination of inorganic arsenic species in natural waters--benefits of separation and preconcentration on ion exchange and hybrid resins.

A simple method for the separation and determination of inorganic arsenic (iAs) species in natural and drinking water was developed. Procedures for sample preparation, separation of As(III) and As(V) species and preconcentration of the total iAs on fixed bed columns were defined. Two resins, a strong base anion exchange (SBAE) resin and a hybrid (HY) resin were utilized. The inductively-coupled plasma-mass spectrometry method was applied as the analytical method for the determination of the arsenic concentration in water. The governing factors for the ion exchange/sorption of arsenic on resins in a batch and a fixed bed flow system were analyzed and compared. Acidity of the water, which plays an important role in the control of the ionic or molecular forms of arsenic species, was beneficial for the separation; by adjusting the pH values to less than 8.00, the SBAE resin separated As(V) from As(III) in water by retaining As(V) and allowing As(III) to pass through. The sorption activity of the hydrated iron oxide particles integrated into the HY resin was beneficial for bonding of all iAs species over a wide range of pH values from 5.00 to 11.00. The resin capacities were calculated according to the breakthrough points in a fixed bed flow system. At pH 7.50, the SBAE resin bound more than 370 microg g(-1) of As(V) while the HY resin bound more than 4150 microg g(-1) of As(III) and more than 3500 microg g(-1) of As(V). The high capacities and selectivity of the resins were considered as advantageous for the development and application of two procedures, one for the separation and determination of As(III) (with SBAE) and the other for the preconcentration and determination of the total arsenic (with HY resin). Methods were established through basic analytical procedures (with external standards, certified reference materials and the standard addition method) and by the parallel analysis of some samples using the atomic absorption spectrometry-hydride generation technique. The analytical properties of both procedures were similar: the limit of detection was 0.24 microg L(-1), the limit of quantification was 0.80 microg L(-1) and the relative standard deviations for samples with a content of arsenic from 10.00 to 300.0 microg L(-1) ranged from 1.1 to 5.8%. The interference effects of anions commonly found in water and some organic species which can be present in water were found to be negligible. Verification with certified reference materials proved that the experimental concentrations found for model solutions and real samples were in agreement with the certified values.

Separation and determination of arsenic species in water by selective exchange and hybrid resins.

A simple and efficient method for separation and determination of inorganic arsenic (iAs) and organic arsenic (oAs) in drinking, natural and wastewater was developed. If arsenic is present in water prevailing forms are inorganic acids of As(III) and As(V). oAs can be found in traces as monomethylarsenic acid, MMA(V), and dimethylarsenic acid, DMAs(V). Three types of resins: a strong base anion exchange (SBAE) and two hybrid (HY) resins: HY-Fe and HY-AgCl, based on the activity of hydrated iron oxides and a silver chloride were investigated. It was found that the sorption processes (ion exchange, adsorption and chemisorptions) of arsenic species on SBAE (ion exchange) and HY resins depend on pH values of water. The quantitative separation of molecular and ionic forms of iAs and oAs was achieved by SBAE and pH adjustment, the molecular form of As(III) that exists in the water at pH <8.0 was not bonded with SBAE, which was convenient for direct determination of As(III) concentration in the effluent. HY-Fe resin retained all arsenic species except DMAs(V), which makes possible direct measurements of this specie in the effluent. HY-AgCl resin retained all iAs which was convenient for direct determination of oAs species concentration in the effluent. The selective bonding of arsenic species on three types of resins makes possible the development of the procedure for measuring and calculation of all arsenic species in water. In order to determine capacity of resins the preliminary investigations were performed in batch system and fixed bed flow system. Resin capacities were calculated according to breakthrough points in a fixed bed flow system which is the first step in designing of solid phase extraction (SPE) module for arsenic speciation separation and determination. Arsenic adsorption behavior in the presence of impurities showed tolerance with the respect to potential interference of anionic compounds commonly found in natural water. Proposed method was established performing standard procedures: with external standard, certified reference material and standard addition method. Two analytical techniques: the inductively coupled plasma mass spectrometry (ICP-MS) and atomic absorption spectroscopy-hydride generation (AAS-GH) were comparatively applied for the determination of arsenic in all arsenic species in water. ICP-MS detection limit was 0.2 μg L(-1) and relative standard deviation (RSD) of all arsenic species investigated was between 3.5 and 5.1%.

Arsenic removal from water by chemisorption filters.

The concept of multiple separation by chemisorptive filters was applied and investigated in the process of arsenic removal from water. Chemisorption filters were made by the paper manufacturing method and consisted of cellulose, cationic and anionic ion exchangers, activated carbon and a corresponding chemical agent. In this work chemisorption filters were activated with Ag+, Mg2+, Cu2+, Al3+ and Fe3+ ions, and their chemical contribution to total arsenic removal from the water was analyzed. It was concluded that Cu2+ ions exhibited the best removal effect. Using a chromatographic continuous system with multifunctional filters, which combines the effects of adsorption, ion exchange and filtration, a decrease in the arsenic concentration was determined; for an active layer of 8 mm and a contact time of 2 s it was more than 1000-fold. All processes were performed in batch and chromatographic continuous systems under equilibrium or dynamic conditions. The results of the investigations have shown that arsenic removal is valence dependent (the removal of pentavalent arsenic was more effective). The initial concentration, pH and pollutants in anionic forms, which affected the selectivity, were important for all the processes investigated. The mechanisms of pollutant removal were determined on the basis of measurements of active Cu2+ ion propagation inside the filter structure. By correlating the front propagation of active ions and the pollutant output concentration a more exact model for the removal process was obtained.

Evaluation of coating materials used on piezoelectric sensors for the detection of organophosphorus compounds in the vapour phase

Abstract Several materials were evaluated as possible coatings for a sensitive, reversible and reproducible piezoelectric sensor for organophosphorus compounds (diisoproplmethyl phosphonate and O,O -dimethyl-2,2-dichlorovinyl phosphate). A few experiments were also done with malathion. The effects of coating material, concentration and type of compound on sensitivity, reversibility and reproducibility were investigated. Mechanisms for the interaction between target vapour and coatings are proposed and briefly discussed.

Review: the approaches for estimation of limit of detection for ICP-MS trace analysis of arsenic.

The analytical properties of an analytical method must be evaluated through validation protocols. Beside specificity and/or selectivity, linearity of calibration, repeatability and accuracy, the most important parameters are: LOD (limit of detection) and LOQ (limit of quantification). Through these limits, it is possible to define the smallest concentration of analyte that can be reliably detected and quantified. To establish these limits, an analyst should apply several estimation methods and test a large number of sample replicates. It is difficult to make a compromise between complex statistical programs and the simple analytical demand to have reliable analytical parameters. The differences and equivalency of estimation methods and approaches for analytical limits could be overcome by an experimental comparison. In this paper, the focus is the LOD of inductively coupled plasma-mass spectrometry (ICP-MS) measurements employed for the determination of arsenic. The current approaches for the calculation of the LOD are summarized and critically discussed.

Enhanced Arsenic Removal from Water by Activated Red Mud Based on Hydrated Iron(III) and Titan(IV) Oxides

In this study, acid heat–activated neutralized red mud (AB) was promoted as an efficient sorbent for the removal of inorganic arsenic from water. Three sorbents: neutralized red mud (Bauxsol), acid-treated Bauxsol (aBauxsol), and AB were investigated for arsenic removal. The sorption of arsenic on these adsorbents was studied as a function of contact time, initial arsenic concentration, and adsorbent dosage. The Langmuir isotherm was the best-fit adsorption isotherm model for the experimental data. The adsorption capacity of the activated red mud for As(V) was found to be 1.49 mg g−1 at a pH of water of 7.0. It was observed that AB at a dose of 6.0 g L−1 could effectively remove As(III) and As(V) from water. Anion interference on a molar basis was found to follow the order: phosphate interference was higher than sulfate interference, which was higher than bicarbonate interference.

Surface morphology and the response of piezoelectric gas sensors

The surface morphology of gold electrodes on piezoelectric quartz crystals was characterized by scanning electron microscopy and scanning tunnelling microscopy. Sensors with various coating materials as polymers, liquid crystal and nitrocompounds have been employed to demonstrate the importance of surface properties in determining the response of the device. The sensors were evaluated for detection of organophosphorus and nitroaromatic vapours in air.

Improved methodology for testing and characterization of piezodelectric gas sensors

Abstract An apparatus used for generating test vapours, exposing coated piezoelectric crystals and recording the responses in real time is described. In designing the apparatus, special care was taken to prevent any changes in crystal resonant frequency that could be caused by factors other than the presence of chemical stimulus. Two three-way solenoid valves were used to enable the sensor to be exposed alternatively to clean carrier gas and carrier gas containing sample vapour, while keeping the sensor operating conditions as constant as possible. The experimental data were collected automatically and, simultaneously, stored in a computer memory and sent to a recorder. The described methodology provides sensor response curves that are convenient for display and analysing sensor behaviour. Organophosphorus compounds were used for testing.

Arsenic Removal from Water Using Industrial By-Products

In this study, removal of arsenic ions using two industrial by-products as adsorbents is represented. Removal of As(III) and As(V) from water was carried out with industrial by-products: residual from the groundwater treatment process, iron-manganese oxide coated sand (IMOCS), and blast furnace slag from steel production (BFS), both inexpensive and locally available. In addition, the BFS was modified in order to minimise its deteriorating impact on the initial water quality. Kinetic and equilibrium studies were carried out using batch and fixed-bed column adsorption techniques under the conditions that are likely to occur in real water treatment systems. To evaluate the application for real groundwater treatment, the capacities of the selected materials were further compared to those exhibited by commercial sorbents, which were examined under the same experimental conditions. IMOCS was found to be a good and inexpensive sorbent for arsenic, while BFS and modified slag showed the highest affinity towards arsenic. All examined waste materials exhibited better sorption performances for As(V). The maximum sorption capacity in the batch reactor was obtained for blast furnace slag, 4040 μgAs(V)/g.