Development of a fast capillary electrophoresis method to determine inorganic cations in biodiesel samples

The aim of this study was to develop a fast capillary electrophoresis method for the determination of inorganic cations (Na(+), K(+), Ca(2+), Mg(2+)) in biodiesel samples, using barium (Ba(2+)) as the internal standard. The running electrolyte was optimized through effective mobility curves in order to select the co-ion and Peakmaster software was used to determine electromigration dispersion and buffer capacity. The optimum background electrolyte was composed of 10 mmol L(-1) imidazole and 40 mmol L(-1) of acetic acid. Separation was conducted in a fused-silica capillary (32 cm total length and 23.5 cm effective length, 50 mu m I.D.), with indirect UV detection at 214 nm. The migration time was only 36 s. In order to obtain the optimized conditions for extraction, a fractional factorial experimental design was used. The variables investigated were biodiesel mass, pH, extractant volume, agitation and sonication time. The optimum conditions were: biodiesel mass of 200 mg, extractant volume of 200 mu L. and agitation of 20 min. The method is characterized by good linearity in the concentration range of 0.5-20 mg kg(-1) (r > 0.999), limit of detection was equal to 0.3 mg kg(-1), inter-day precision was equal to 1.88% and recovery in the range of 88.0-120%. The developed method was successfully applied to the determination of cations in biodiesel samples. (c) 2010 Elsevier B.V. All rights reserved.

Pendimethalin determination in natural water, baby food and river sediment samples using electroanalytical methods

This work describes the electroanalytical determination of pendimethalin herbicide levels in natural waters, river sediment and baby food samples, based on the electro-reduction of herbicide on the hanging mercury drop electrode using square wave voltammetry (SWV). A number of experimental and voltammetric conditions were evaluated and the best responses were achieved in Britton-Robinson buffer solutions at pH 8.0, using a frequency of 500 s(-1). a scan increment of 10 mV and a square wave amplitude of 50 mV. Under these conditions, the pendimethalin is reduced in an irreversible process, with two reduction peaks at -0.60 V and -0.71 V. using a Ag/AgCl reference system. Analytical curves were constructed and the detection limit values were calculated to be 7.79 mu g L(-1) and 4.88 mu g L(-1), for peak 1 and peak 2, respectively. The precision and accuracy were determinate as a function of experimental repeatability and reproducibility, which showed standard relative deviation values that were lower than 2% for both voltammetric peaks. The applicability of the proposed methodology was evaluated in natural water, river sediments and baby food samples. The calculated recovery efficiencies demonstrate that the proposed methodology is suitable for determining any contamination by pendimethalin in these samples. Additionally, adsorption isotherms were used to evaluate information about the behavior of pendimethalin in river sediment samples. (C) 2010 Elsevier B.V. All rights reserved.

Anodic stripping voltammetric determination of copper(II) using a functionalized carbon nanotubes paste electrode modified with crosslinked chitosan

The development and application of a functionalized carbon nanotubes paste electrode (CNPE) modified with crosslinked chitosan for determination of Cu(II) in industrial wastewater, natural water and human urine samples by linear scan anodic stripping voltammetry (LSASV) are described. Different electrodes were constructed using chitosan and chitosan crosslinked with glutaraldehyde (CTS-GA) and epichlorohydrin (CTS-ECH). The best voltammetric response for Cu(II) was obtained with a paste composition of 65% (m/m) of functionalized carbon nanotubes, 15% (m/m) of CTS-ECH, and 20% (m/m) of mineral oil using a solution of 0.05 mol L(-1) KNO(3) with pH adjusted to 2.25 with HNO(3), an accumulation potential of 0.3V vs. Ag/AgCl (3.0 mol L(-1) KCl) for 300 s and a scan rate of 100 mV s(-1). Under these optimal experimental conditions, the voltammetric response was linearly dependent on the Cu(II) concentration in the range from 7.90 x 10(-8) to 1.60 x 10(-5) mol L(-1) with a detection limit of 1.00 x 10(-8) mol L(-1). The samples analyses were evaluated using the proposed sensor and a good recovery of Cu(II) was obtained with results in the range from 98.0% to 104%. The analysis of industrial wastewater, natural water and human urine samples obtained using the proposed CNPE modified with CTS-ECH electrode and those obtained using a comparative method are in agreement at the 95% confidence level. (C) 2009 Elsevier B. V. All rights reserved.

Cassava wastewater as a substrate for the simultaneous production of rhamnolipids and polyhydroxyalkanoates by Pseudomonas aeruginosa

Glycerol, cassava wastewater (CW), waste cooking oil and CW with waste frying oils were evaluated as alternative low-cost carbon substrates for the production of rhamnolipids and polyhydroxyalkanoates (PHAs) by various Pseudomonas aeruginosa strains. The polymers and surfactants produced were characterized by gas chromatography-mass spectrophotometry (MS) and by high-performance liquid chromatography-MS, and their composition was found to vary with the carbon source and the strain used in the fermentation. The best overall production of rhamnolipids and PHAs was obtained with CW with frying oil as the carbon source, with PHA production corresponding to 39% of the cell dry weight and rhamnolipid production being 660 mg l(-1). Under these conditions, the surface tension of the culture decreased to 30 mN m(-1), and the critical micelle concentration was 26.5 mg l(-1). It would appear that CW with frying oil has the highest potential as an alternative substrate, and its use may contribute to a reduction in the overall environmental impact generated by discarding such residues.

Biocompatible in-tube solid phase microextraction coupled with liquid chromatography-fluorescence detection for determination of interferon alpha in plasma samples

The present work demonstrates the successful application of automated biocompatible in-tube solid-phase microextraction coupled with liquid chromatography (in-tube SPME/LC) for determination of interferon alpha(2a) (IFN alpha(2a)) in plasma samples for therapeutic drug monitoring. A restricted access material (RAM, protein-coated silica) was employed for preparation of a lab-made biocompatible in-tube SPME capillary that enables the direct injection of biological fluids as well as the simultaneous exclusion of macromolecules by chemical diffusion barrier and drug pre-concentration. The in-tube SPME variables, such as sample volume, draw/eject volume, number of draw-eject cycles, and desorption mode were optimized, to improve the sensitivity of the proposed method. The IFN alpha(2a) analyses in plasma sample were carried out within 25 min (sample preparation and LC analyses). The response of the proposed method was linear over a dynamic range, from 0.06 to 3.0 MIU mL(-1), with correlation coefficient equal to 0.998. The interday precision of the method presented coefficient of variation lower than 8%. The proposed automated method has adequate analytical sensitivity and selectivity for determination of IFN alpha(2a) in plasma samples for therapeutic drug monitoring. (C) 2010 Elsevier B.V. All rights reserved.

Anodic oxidation of wastewater containing the Reactive Orange 16 Dye using heavily boron-doped diamond electrodes

Boron-doped diamond (BDD) films grown on the titanium substrate were used to study the electrochemical degradation of Reactive Orange (RO) 16 Dye. The films were produced by hot filament chemical vapor deposition (HFCVD) technique using two different boron concentrations. The growth parameters were controlled to obtain heavily doped diamond films. They were named as E1 and E2 electrodes, with acceptor concentrations of 4.0 and 8.0 x 10(21) atoms cm(-3), respectively. The boron levels were evaluated from Mott-Schottky plots also corroborated by Raman`s spectra, which characterized the film quality as well as its physical property. Scanning Electron Microscopy showed well-defined microcrystalline grain morphologies with crystal orientation mixtures of (1 1 1) and (1 00). The electrode efficiencies were studied from the advanced oxidation process (AOP) to degrade electrochemically the Reactive Orange 16 azo-dye (RO16). The results were analyzed by UV/VIS spectroscopy, total organic carbon (TOC) and high-performance liquid chromatography (HPLC) techniques. From UV/VIS spectra the highest doped electrode (E2) showed the best efficiency for both, the aromaticity reduction and the azo group fracture. These tendencies were confirmed by the TOC and chromatographic measurements. Besides, the results showed a direct relationship among the BDD morphology, physical property, and its performance during the degradation process. (C) 2011 Elsevier B.V. All rights reserved.

Photo-assisted electrochemical degradation of real textile wastewater

In the present study, photo-assisted electrochemical degradation of real textile wastewater was performed. Degradation assays were performed at constant current (40 mA cm(-2)) in a combined electro/photochemical flow-cell using a Ti/Ru(0.3)Ti(0.7)O(2) DSA(R) type electrode. The results show that the method is capable of removing color and chemical oxygen demand (COD) from the effluent. Additionally, the effect of initial pH and type of supporting electrolyte (Na(2)SO(4) or NaCl) was investigated. The principal figures of merit used in this study were COD removal and color removal (605 nm). The results show that up to 72% color and up to 59% COD removal in 120 min is possible under the operating conditions employed. Studies of the phytotoxicity of the wastewater before and after the photo-assisted degradation assays are also presented and the results demonstrate that the toxicity of the effluent is dependent on the length of electrolysis time and the treatment procedure employed.

Polydimethylsiloxane/polypyrrole stir bar sorptive extraction and liquid chromatography (SBSE/LC-UV) analysis of antidepressants in plasma samples

A new polymeric coating consisting of a dual-phase, polydimethylsiloxane (PDMS) and polypyrrole (PPY) was developed for the stir bar sorptive extraction (SBSE) of antidepressants (mirtazapine, citalopram, paroxetine, duloxetine, fluoxetine and sertraline) from plasma samples, followed by liquid chromatography analysis (SBSE/LC-UV). The extractions were based on both adsorption (PPY) and sorption (PDMS) mechanisms. SBSE variables, such as extraction time, temperature, pH of the matrix, and desorption time were optimized, in order to achieve suitable analytical sensitivity in a short time period. The PDMS/PPY coated stir bar showed high extraction efficiency (sensitivity and selectivity) toward the target analytes. The quantification limits (LOQ) of the SBSE/LC-UV method ranged from 20 ng mL(-1) to 50 ng mL(-1), and the linear range was from LOQ to 500 ng mL(-1), with a determination coefficient higher than 0.99. The inter-day precision of the SBSE/LC-UV method presented a variation coefficient lower than 15%. The efficiency of the SBSE/LC-UV method was proved by analysis of plasma samples from elderly depressed patients. (C) 2008 Elsevier B.V. All rights reserved.

Electrochemical Behavior of Verapamil at Graphite-Polyurethane Composite Electrodes: Determination of Release Profiles in Pharmaceutical Samples

A solid graphite-polyurethane composite electrode has been used to determine release profiles of verapamil, a calcium-channel blocker. The electro-oxidation process was characterized by cyclic voltammetry and electrochemical impedance spectroscopy and showed no adsorption of analyte or oxidation products, unlike at other carbon-based electrodes. Quantification gave linear ranges up to 40molL-1 with cyclic voltammetry and detection limits of 0.7molL-1 by differential pulse and square-wave voltammetry. Commercial product samples were successfully analyzed with results equal to those from spectrophotometry. Because no electrode surface renewal is needed, this electrode material has many advantages.

Microwave-assisted digestion procedures for biological samples with diluted nitric acid: Identification of reaction products

Microwave-assisted sample preparation using diluted nitric acid solutions is an alternative procedure for digesting organic samples. The efficiency of this procedure depends on the chemical properties of the samples and in this work it was evaluated by the determination of crude protein amount. fat and original carbon. Soybeans grains, bovine blood. bovine muscle and bovine viscera were digested in a cavity-microwave oven using oxidant mixtures in different acid concentrations. The digestion efficiency was evaluated based on the determination of residual carbon content and element recoveries using inductively coupled plasma optical emission spectrometry (ICP OES). In order to determine the main residual organic compounds, the digests were characterized by nuclear magnetic resonance (1 H NMR). Subsequently, studies concerning separation of nitrobenzoic acid isomers were performed by ion pair reversed phase liquid chromatography using a C18 stationary phase, water:acetonitrile:methanol (75:20:5, v/v/v) +0.05% (v/v) TFA as mobile phase and ultraviolet detection at 254 nm. Sample preparation based on diluted acids proved to be feasible and a recommendable alternative for organic sample digestion, reducing both the reagent volumes and the variability of the residues as a result of the process of decomposition. It was shown that biological matt-ices containing amino acids, proteins and lipids in their composition produced nitrobenzoic acid isomers and other organic compounds after cleavage of chemical bonds. (C) 2009 Elsevier B.V. All rights reserved.

Removal of Zn(2+) from Electroplating Wastewater Using Modified Wood Sawdust and Sugarcane Bagasse

This paper describes the preparation of new adsorbents derived from sugarcane bagasse and wood sawdust (Manilkara sp.) to remove zinc (II) ions from electroplating wastewater. The first part deals with the chemical modification of sugarcane bagasse and wood sawdust, using succinic anhydride to introduce carboxylic acid functions into the material. The obtained materials (modified sugarcane bagasse MB2 and modified wood sawdust MS2) were then characterized by infrared spectroscopy (IR) and used in adsorption experiments. The adsorption experiments evaluates Zn(2+) removal from aqueous single metal solution and real electroplating wastewater on both batch and continuous experiments using fixed-bed columns prepared in laboratorial scale with the obtained adsorbents. Adsorption isotherms were then developed using Langmuir model and the Thomas kinetic model. The calculated Zn(2+) adsorption capacities were found to be 145 mg/g for MS2 and 125 mg/g for MB2 in single metal aqueous solution, whereas for the industrial wastewater these values were 61 mg/g for MS2 and 55 mg/g for MB2.

Application Of Real-Time Control Strategy To Improve Nitrogen Removal In Wastewater Treatment

Biological nitrogen removal is an important task in the wastewater treatment. However, the actual removal of total nitrogen (TN) in the wastewater treatment plant (WWTP) is often unsatisfactory due to several causes, one of which is the insufficient availability of carbon source. One possible approach to improve the nitrogen removal therefore is addition of external carbon source, while the amount of which is directly related to operation cost of a WWTP. It is obviously necessary to determine the accurate amount of addition of external carbon source according to the demand depending on the influent wastewater quality. This study focused on the real-time control of external carbon source addition based on the on-line monitoring of influent wastewater quality. The relationship between the influent wastewater quality (specifically the concentration of COD and ammonia) and the demand of carbon source was investigated through experiments on a pilot-scale A/O reactor (1m3) at the Nanjing WWTP, China. The minimum doses of carbon source addition at different situations of influent wastewater quality were determined to ensure the effluent wastewater quality meets the discharge standard. The obtained relationship is expected to be applied in the full-scale WWTPs. .

City Of Toronto’S Approach On Implementing The New Federal Wastewater Effluent Regulations Using A GIS-Based Hydrologic And Hydraulic Model

Canada releases over 150 billion litres of untreated and undertreated wastewater into the water environment every year1. To clean up urban wastewater, new Federal Wastewater Systems Effluent Regulations (WSER) on establishing national baseline effluent quality standards that are achievable through secondary wastewater treatment were enacted on July 18, 2012. With respect to the wastewater from the combined sewer overflows (CSO), the Regulations require the municipalities to report the annual quantity and frequency of effluent discharges. The City of Toronto currently has about 300 CSO locations within an area of approximately 16,550 hectares. The total sewer length of the CSO area is about 3,450 km and the number of sewer manholes is about 51,100. A system-wide monitoring of all CSO locations has never been undertaken due to the cost and practicality. Instead, the City has relied on estimation methods and modelling approaches in the past to allow funds that would otherwise be used for monitoring to be applied to the reduction of the impacts of the CSOs. To fulfill the WSER requirements, the City is now undertaking a study in which GIS-based hydrologic and hydraulic modelling is the approach. Results show the usefulness of this for 1) determining the flows contributing to the combined sewer system in the local and trunk sewers for dry weather flow, wet weather flow, and snowmelt conditions; 2) assessing hydraulic grade line and surface water depth in all the local and trunk sewers under heavy rain events; 3) analysis of local and trunk sewer capacities for future growth; and 4) reporting of the annual quantity and frequency of CSOs as per the requirements in the new Regulations. This modelling approach has also allowed funds to be applied toward reducing and ultimately eliminating the adverse impacts of CSOs rather than expending resources on unnecessary and costly monitoring.