M. Ali Awan

Determination of biogenic diamines with a vaporisation derivatisation approach using solid-phase microextraction gas chromatography-mass spectrometry.

A gas-phase on-fibre derivatisation method for the determination of putrescine and cadaverine by gas chromatography/mass spectrometry using trifluoroacetylacetone (TFAA) has been studied and optimised. Small amounts (2μl) of putrescine, cadaverine and TFAA standards were vaporised at high temperature in a 20cm(3) closed SPME vial. The subsequent derivatives were recovered from the headspace of the vial using a PDMS/DVB fibre. The optimised mole ratio for [TFAA]/[Putrescine+Cadaverine] reaction was 22.3/1 with a derivatisation and extraction temperature of 120(o)C and an extraction time of 20min. The retention times for the derivatised putrescine and cadaverine were 20.5 and 22.2min, respectively on a capillary column, CP-Sil 8CB; 30m length×0.25mmi.d.×0.25μm film thickness. The correlation coefficients (R(2)) of calibration curves for putrescine and cadaverine were 0.999 and 0.997, respectively over a range of sample masses of 20-350ng, using nonadecane as an internal standard. Putrescine and cadaverine recoveries were determined to be 93.9% and 103.3%, respectively. The method was found to be a straightforward single step procedure that was unaffected by complex sample matrices and was successfully tested on samples of meat, vegetables and cheese.

Removal of Fluoride from Drinking Water Using Modified Immobilized Activated Alumina

The study describes the removal of fluoride from drinking water using modified immobilized activated alumina (MIAA) prepared by sol-gel method. The modification was done by adding a specific amount of alum during the sol formation step. The fluoride removal efficiency of MIAA was 1.35 times higher as compared to normal immobilized activated alumina. A batch adsorption study was performed as a function of adsorbent dose, contact time, stirring rate, and initial fluoride concentration. More than 90% removal of fluoride was achieved within 60 minutes of contact time. The adsorption potential of MIAA was compared with activated charcoal which showed that the removal efficiency was about 10% more than the activated charcoal. Both the Langmuir and Freundlich adsorption isotherms fitted well for the fluoride adsorption on MIAA with the regression coefficient R2 of 0.99 and 0.98, respectively. MIAA can both be regenerated thermally and chemically. Adsorption experiments using MIAA were employed on real drinking water samples from a fluoride affected area. The study showed that modified immobilized activated alumina is an effective adsorbent for fluoride removal.

Cancer and non-cancer risk assessment of trihalomethanes in urban drinking water supplies of Pakistan.

This study aims at monitoring and risk assessment of trihalomethanes (THMs) such as chloroform, bromodichloromethane, dibromochloromethane and bromoform, in the drinking water supplies of Rawalpindi and Islamabad. THMs were monitored at twenty locations in these twin cities using solid phase micro extraction-gas chromatography (SPME-GC). Total concentration of THMs was ranged between 21 and 373μg/L, whereas both cities had an average total THMs concentration of 142 and 260μg/L, respectively. Chloroform was found as one the major contributor to the THMs concentration (>85%). The occurrence of THMs followed the given order: chloroform, bromodichloromethane>dibromochloromethane>bromoform. Lifetime cancer risk assessment of THMs was carried out using prediction models via different exposure routes (ingestion, inhalation and dermal). An average lifetime cancer risk was found to be 0.74×10(-4) and 1.24×10(-4) for Rawalpindi and Islamabad, respectively. The number of expected cancer cases per year could reach two cases for each city. Hazard index values were found below unity for both the cities implying that there would be no considerable non-cancer risk. Oral ingestion was found to be one of the main routes of exposure for both types of risk which was followed by inhalation and dermal routes.

Optimising cell temperature and dispersion field strength for the screening for putrescine and cadaverine with thermal desorption-gas chromatography-differential mobility spectrometry

Biogenic amines, and putrescine and cadaverine in particular, have significant importance in the area of food quality monitoring, and are also potentially important markers of infection, for cancer, diabetes, arthritis and cystic fibrosis. A thermal desorption-gas chromatograph-heated differential mobility spectrometer was constructed and the significant effect of interactions between cell temperature and dispersion field strength on the observed responses studied. The experiment design was a Box-Wilson central composite design (CCD) over the levels of 10-24 kVcm(-1) for dispersion field strength and 100-130 degrees C for cell temperature. The optimum values were estimated to be 16.22 kVcm(-1) and 116 degrees C for putrescine and 14.78 kVcm(-1) and 112 degrees C for cadaverine, respectively with an ammonia dopant at 19 mgm(-3). An amine test atmosphere generator was constructed and produced stable concentrations of putrescine (7 mgm(-3)) and cadaverine (4 mgm(-3)) vapours at 50+/-0.5 degrees C. Tenax TA-Carbotrap adsorbent tubes were used to sample putrescine and cadaverine vapour standards and a linear response function over the range of sample masses 5-20 ng was obtained at 15.0 kVcm(-1) 115 degrees C, with a R(2) of 0.99 for both putrescine and cadaverine. The sample mass at the limit of detection was estimated to be 3 ng for putrescine and cadaverine. Preliminary data from sampling the headspace of chicken meat revealed a 62% increase in the recovered masses of putrescine from 0.84 to 1.36 ng in the sampled air.

Synthesis of silver-doped titanium TiO 2 powder-coated surfaces and its ability to inactivate pseudomonas aeruginosa and bacillus subtilis

Hard, nonporous environmental surfaces in daily life are now receiving due recognition for their role in reducing the spread of several nosocomial infections. In this work, we established the photokilling effects of 1% silver-doped titanium dioxide TiO2. The nanoparticles synthesized by liquid impregnation method were characterized using X-ray diffraction (XRD), energy dispersive spectroscopy (EDS), and scanning electron microscopy (SEM). The Ag-TiO2 nanoparticle coatings that have been applied on glass and venetian blind surfaces were effective in generating a loss of viability of two bacteria (Pseudomonas aeruginosa and Bacillus subtilis) after two hours of illumination under normal light in the visible spectrum. Such surfaces can be applicable to medical and other facilities where the potential for infection should be controlled.

Photocatalytic degradation of nitro and chlorophenols using doped and undoped titanium dioxide nanoparticles

Pure and Ag-TiO2 nanoparticles were synthesized, with the metallic doping being done using the Liquid Impregnation (LI) method. The resulting nanoparticles were characterized by analytical methods such as scanning electron micrographs (SEMs), Energy Dispersive Spectroscopy (EDS), and X-ray diffraction (XRD). XRD analysis indicated that the crystallite size of TiO2 was 27nm to 42nm while the crystallite size of Ag-TiO2 was 11.27nm to 42.52 nm. The photocatalytic activity of pure TiO2 and silver doped TiO2 was tested by photocatalytic degradation of p-nitrophenol as a model compound. Ag-TiO2 nanoparticles exhibited better results (98% degradation) as compared to pure TiO2 nanoparticles (83% degradation) in 1 hour for the degradation of p-nitrophenol. Ag-TiO2 was further used for the photocatalytic degradation of 2, 4-dichlorphenol (99% degradation), 2,5- dichlorophenol (98% degradation), and 2, 4, 6-trichlorophenol (96% degradation) in 1 hour. The degree of mineralization was tested by TOC experiment indicating that 2, 4-DCP was completely mineralized, while 2, 5-DCP was mineralized upto 95 percent and 2, 4, 6-TCP upto 86 percent within a period of 2 hours.

Comparative solid phase photocatalytic degradation of polythene films with doped and undoped TiO 2 nanoparticles

Comparative photocatalytic degradation of polythene films was investigated with undoped and metal (Fe, Ag, and Fe/Ag mix) doped TiO2 nanoparticles under three different conditions such as UV radiation, artificial light, and darkness. Prepared photocatalysts were characterized by XRD, SEM, and EDS techniques. Photocatalytic degradation of the polythene films was determined by monitoring their weight reduction, SEM analysis, and FTIR spectroscopy. Weight of PE films steadily decreased and led to maximum of 14.34% reduction under UV irradiation with Fe/Ag mix doped TiO2 nanoparticles and maximum of 14.28% reduction under artificial light with Ag doped TiO2 nanoparticles in 300 hrs. No weight reduction was observed under darkness. Results reveal that polythene-TiO2 compositing with metal doping has the potential to degrade the polythene waste under irradiation without any pollution.

Arsenic removal from aqueous solution using pure and metal-doped titania nanoparticles coated on glass beads: adsorption and column studies

Nanosizedmetal oxide, Titania, provides high surface area and specific affinity for the adsorption of heavymetals, including arsenic (As), which is posing a great threat to the world population due to its carcinogenic nature. In this study, As(III) adsorption was studied on pure and metal- (Ag- and Fe-) doped Titania nanoparticles. The nanoparticles were synthesized by liquid impregnation method with some modifications, with crystallite size in the range of 30 to 40 nm. Band gap analysis, using Kubelka-Munk function showed a shift of absorption band from UV to visible region for themetal-doped Titania. Effect of operational parameters like dose of nanoparticles, initial As(III) concentration, and pH was evaluated at 25°C. The data obtained gave a good fit with Langmuir and Freundlich isotherms and the adsorption was found to conform to pseudo-second-order kinetics. In batch studies, over 90% of arsenic removal was observed for both types of metal-doped Titania nanoparticles from a solution containing up to 2 ppm of the heavy metal. Fixed bed columns of nanoparticles, coated on glass beads, were used for As(III) removal under different operating conditions. Thomas and Yoon-Nelson models were applied to predict the breakthrough curves and to find the characteristic column parameters useful for process design. The columns were regenerated using 10% NaOH solution.

Development of a Method for the Determination of Chromium and Cadmium in Tannery Wastewater Using Laser-Induced Breakdown Spectroscopy

This paper illustrates systematic development of a convenient analytical method for the determination of chromium and cadmium in tannery wastewater using laser-induced breakdown spectroscopy (LIBS). A new approach was developed by which liquid was converted into solid phase sample surface using absorption paper for subsequent LIBS analysis. The optimized values of LIBS parameters were 146.7 mJ for chromium and 89.5 mJ for cadmium (laser pulse energy), 4.5 μs (delay time), 70 mm (lens to sample surface distance), and 7 mm (light collection system to sample surface distance). Optimized values of LIBS parameters demonstrated strong spectrum lines for each metal keeping the background noise at minimum level. The new method of preparing metal standards on absorption papers exhibited calibration curves with good linearity with correlation coefficients, R2 in the range of 0.992 to 0.998. The developed method was tested on real tannery wastewater samples for determination of chromium and cadmium.

DEGRADATION AND INACTIVATION OF CIPROFLOXACIN BY PHOTOCATALYSIS USING TIO2NANOPARTICLES

To compare Ciprofloxacin attenuation efficiency, Ciprofloxacin solutions mixed with TiO2nanoparticles were irradiated with two different light sources: a UV lamp and ordinary electric bulb. Insignificant degradation was witnessed when irradiations were made in absence of TiO2. In contrast, prominent Ciprofloxacin degradation was detected in the presence of 0.01 mg/ml of TiO2. Close to 90 % and 70 % of its original concentration was eradicated in 120 minutes when the irradiation basis used was a UV lamp and Ordinary electric bulb respectively. Without the use of TiO2 nanoparticles, irradiation by UV lamp sources was also significant. The antibactacterial activity of chosen microorganisms was radically inhibited when exposed to Ciprofloxacin solution treated with photocatalyst for the short periods of irradiation.