K.R.R. Mahanama

Use of volatile tracers to determine the contribution of environmental tobacco smoke to concentrations of volatile organic compounds in smoking environments

Three volatile nitrogen-containing compounds, 3-ethenylpyridine (3-EP), pyridine and pyrrole, were investigated as potential tracers for determining the contribution of environmental tobacco smoke (ETS) to concentrations of volatile organic compounds (VOCs) in indoor environments with smoking. The source emission rates of the three tracers and ten selected VOCs in ETS were first measured in a room-size environmental chamber for a market-weighted selection of six commercial cigarettes. The ratios of the emission rates of the tracers to the emission rates of the selected VOCs were calculated and compared among the six brands. The utility of the tracers was then evaluated in a field study conducted in five office buildings. Samples for VOCs were collected in designated smoking areas and adjoining non-smoking areas, air change rates were measured, and smoking rates were documented. Concentrations of the three tracers in the smoking areas were calculated using a mass-balance model and compared to their measured concentrations. Based on this comparison, 3-EP was selected as the most suitable tracer for the volatile components of ETS, although pyrrole is also potentially useful. Using 3-EP as the tracer, the contributions of ETS to the measured concentrations of the selected VOCs in the smoking areas were estimated by apportionment. ETS was estimated to contribute 57 to 84 percent (4.1 to 26 pg m{sup -3}) of the formaldehyde concentrations, 44 to 69 percent (0.9 to 5.8 pg m{sup -3}) of the 2-butanone concentrations, 37 to 58 percent (1.3 to 8.2 pg m{sup -3}) of the benzene concentrations, and 20 to 69 percent (0.5 to 3.0 pg m{sup -3}) of the styrene concentrations. The fractional contributions of ETS to the concentrations of acetone, toluene, ethylbenzene, xylene isomers and d-limonene were all less than 50 percent.

Cyclohexane oxidation and carbon deposition over metal oxide catalysts

Catalytic activity of V, Mn, Ni, Cu, Zn, Mo, Zr and Ce oxides over an alpha-alumina support was evaluated for cyclohexane oxidation under oxygen deficient conditions in order to understand the relation between carbon deposition and catalytic activity/selectivity. Carbon formation over the catalysts during the oxidation reaction was measured by means of Fourier transformed infrared spectroscopy (FTIR). Catalysts Mn/Al2O3 and Ce/Al2O3, which are selective for deep oxidation of cyclohexane, possessed relatively carbon free surfaces. The catalysts with relatively high carbon deposition (V, Ni, Cu, Zn, Mo and Zr) produced CO in addition to CO2. Traces of formaldehyde were produced over the catalysts Mo and V.

Toxic volatile organic compounds in environmental tobacco smoke: emission factors for modeling exposures of California populations.

e Lawrence Berkeley Laboratory UNIVERSITY OF CALIFORNIA ENERGY & ENVIRONMENT Toxic Volatile Organic Compounds in Environmental Tobacco Smoke: Emission Factors for Modeling Exposures of California Populations J.M. Daisey, K.R.R. Mahanama, and A.T. Hodgson October 1994 E E G & ENVIRONMENT N R Y DIVISION Prepared for the U.S. Department of Energy under Contract Number DE-AC03-76SF00098

Fractionation of polar organic extracts of airborne particulate matter using cyanopropyl-bonded silica in solid-phase extraction

A mg-scale fractionation method has been developed for polar organic matter in airborne particles. The method give reproducibly good recoveries of mass while avoiding the use of water or salts. Cyanopropyl-bonded silica solid-phase extraction (SPE) columns were used to fractionate a mixture of standard compounds and acetone-soluble extracts from particles collected in Elizabeth, NJ, USA and from National Institute of Standards and Technology Standard Material 1649 (urban air particles). Critical factors proved to be reducing the polarity of the extract before its application to the column and pre-wetting the column with n-hexane. Ten fractions were eluted with solvent mixtures of increasing polarity, ranging from n-hexane to methanol. Blank-corrected mass recoveries were 95 and 98% for the Elizabeth, NJ, USA and SRM 1649 extracts, respectively.

Contribution of dissolved sulfates and sulfites in hydrogen sulfide emission from stagnant water bodies in Sri Lanka

Accumulation of sulfur-containing compounds and their bacterial mediated reductions have led to the emission of pungent odors from stagnant water bodies. This study is focused on the contribution of inorganic sulfur compounds in the emission of hydrogen sulfide. The measured dissolved oxygen levels have demonstrated good negative correlations with the dissolved sulfide levels implying the oxygen deficiency is the key for the reduction of sulfate ion and sulfite ion to sulfide ion. Particularly, the dissolved molar fractions of sulfide from the total dissolved sulfur compounds (sulfates, sulfites and sulfides) have a very good correlation with the dissolved oxygen for the stagnant water bodies except the artificially aerated prawn farms. For the stagnant water bodies with significant correlations, linear regressions are reported for them to be utilized in estimating one component of the regression from the measurement of the other. The measured data were further utilized to estimate the levels of hydrogen sulfide gas. The pH of the water bodies has confined much of the dissolved sulfides in the form of bisulfide ion and they can be easily escaped to the atmosphere upon acidification due to industrial discharges and/or acidic precipitations. The estimated levels of hydrogen sulfide just above the water surface were plotted for the most polluted stagnant water body in Sri Lanka for the pH range of 5-10 and temperature range of 25-35 degrees C.

Validation of a reversed-phase high-performance liquid chromatographic method for the determination of free amino acids in rice using l-theanine as the internal standard

The study presents the validation results of the method carried out for analysis of free amino acids (FAAs) in rice using l-theanine as the internal standard (IS) with o-phthalaldehyde (OPA) reagent using high-performance liquid chromatography-fluorescence detection. The detection and quantification limits of the method were in the range 2-16μmol/kg and 3-19μmol/kg respectively. The method had a wide working range from 25 to 600μmol/kg for each individual amino acid, and good linearity with regression coefficients greater than 0.999. Precision measured in terms of repeatability and reproducibility, expressed as percentage relative standard deviation (% RSD) was below 9% for all the amino acids analyzed. The recoveries obtained after fortification at three concentration levels were in the range 75-105%. In comparison to l-norvaline, findings revealed that l-theanine is suitable as an IS and the validated method can be used for FAA determination in rice.

Development and validation of a method for direct, underivatized analysis of free amino acids in rice using liquid chromatography–tandem mass spectrometry

Inspired by the apparent relationship of free amino acids (FAAs) which are present in minute quantities with the organoleptic characteristics of food, there is an increased demand for analytical methods sensitive in trace level detection. This study presents the validation results of a simple and rapid method developed for direct, underivatized analysis of FAAs in rice using liquid chromatography-tandem mass spectrometry (LC-MS/MS) with electrospray ionization (ESI). The method demonstrated satisfactory selectivity for twenty FAAs with minimum matrix effect. The recoveries obtained for samples fortified at three concentration levels: low mid and high, covering the working range of the method were in the range 80%-110%. The precision measured in terms of repeatability and reproducibility of the method expressed as percentage relative standard deviation (% RSD) were below 10% for the amino acids analyzed. The detection limits (LODs) and quantification limits (LOQs) of the method were in the range 0.4-1.0 mg/kg and 0.6-1.2 mg/kg respectively. Method had a wide linear range between 1.25-100 mg/kg with regression coefficients greater than 0.999 obtained over seven calibration levels. The method was also found robust over other cereals including corn, wheat and finger millet with satisfactory recoveries and precision values. The percentage expanded uncertainties calculated with the coverage factor of 2 (k = 2), were below 14% for the analyzed amino acids. The developed, simple and rapid LC-MS/MS method is accurate and reproducible, allowing determination of underivatized FAAs in rice and comply with the international method validation guideline requirements.