Gas-phase ammonia and water-soluble ions in particulate matter analysis in an urban vehicular tunnel.

Ammonia is a key alkaline species, playing an important role by neutralizing atmospheric acidity and inorganic secondary aerosol production. On the other hand, the NH3/NH4 (+) increases the acidity and eutrophication in natural ecosystems, being NH3 classified as toxic atmospheric pollutant. The present study aims to give a better comprehension of the nitrogen content species distribution in fine and coarse particulate matter (PM2.5 and PM2.5-10) and to quantify ammonia vehicular emissions from an urban vehicular tunnel experiment in the metropolitan area of São Paulo (MASP). MASP is the largest megacity in South America, with over 20 million inhabitants spread over 2000 km(2) of urbanized area, which faces serious environmental problems. The PM2.5 and PM2.5-10 median mass concentrations were 44.5 and 66.6 µg m(-3), respectively, during weekdays. In the PM2.5, sulfate showed the highest concentration, 3.27 ± 1.76 µg m(-3), followed by ammonium, 1.14 ± 0.71 µg m(-3), and nitrate, 0.80 ± 0.52 µg m(-3). Likewise, the dominance (30 % of total PM2.5) of solid species, mainly the ammonium salts, NH4HSO4, (NH4)2SO4, and NH4NO3, resulted from simulation of inorganic species. The ISORROPIA simulation was relevant to show the importance of environment conditions for the ammonium phase distribution (solid/aqueous), which was solely aqueous at outside and almost entirely solid at inside tunnel. Regarding gaseous ammonia concentrations, the value measured inside the tunnel (46.5 ± 17.5 µg m(-3)) was 3-fold higher than that outside (15.2 ± 11.3 µg m(-3)). The NH3 vehicular emission factor (EF) estimated by carbon balance for urban tunnel was 44 ± 22 mg km(-1). From this EF value and considering the MASP traffic characteristics, it was possible to estimate more than 7 Gg NH3 year(-1) emissions that along with NOx are likely to cause rather serious problems to natural ecosystems in the region.

Versatile microanalytical system with porous polypropylene capillary membrane for calibration gas generation and trace gaseous pollutants sampling applied to the analysis of formaldehyde, formic acid, acetic acid and ammonia in outdoor air.

The analytical determination of atmospheric pollutants still presents challenges due to the low-level concentrations (frequently in the µg m(-3) range) and their variations with sampling site and time. In this work, a capillary membrane diffusion scrubber (CMDS) was scaled down to match with capillary electrophoresis (CE), a quick separation technique that requires nothing more than some nanoliters of sample and, when combined with capacitively coupled contactless conductometric detection (C(4)D), is particularly favorable for ionic species that do not absorb in the UV-vis region, like the target analytes formaldehyde, formic acid, acetic acid and ammonium. The CMDS was coaxially assembled inside a PTFE tube and fed with acceptor phase (deionized water for species with a high Henry's constant such as formaldehyde and carboxylic acids, or acidic solution for ammonia sampling with equilibrium displacement to the non-volatile ammonium ion) at a low flow rate (8.3 nL s(-1)), while the sample was aspirated through the annular gap of the concentric tubes at 2.5 mL s(-1). A second unit, in all similar to the CMDS, was operated as a capillary membrane diffusion emitter (CMDE), generating a gas flow with know concentrations of ammonia for the evaluation of the CMDS. The fluids of the system were driven with inexpensive aquarium air pumps, and the collected samples were stored in vials cooled by a Peltier element. Complete protocols were developed for the analysis, in air, of NH(3), CH(3)COOH, HCOOH and, with a derivatization setup, CH(2)O, by associating the CMDS collection with the determination by CE-C(4)D. The ammonia concentrations obtained by electrophoresis were checked against the reference spectrophotometric method based on Berthelot's reaction. Sensitivity enhancements of this reference method were achieved by using a modified Berthelot reaction, solenoid micro-pumps for liquid propulsion and a long optical path cell based on a liquid core waveguide (LCW). All techniques and methods of this work are in line with the green analytical chemistry trends.

Environmental formaldehyde analysis by active diffusive sampling with a bundle of polypropylene porous capillaries followed by capillary zone electrophoretic separation and contactless conductivity detection.

Compared to other volatile carbonylic compounds present in outdoor air, formaldehyde (CH(2)O) is the most toxic, deserving more attention in terms of indoor and outdoor air quality legislation and control. The analytical determination of CH(2)O in air still presents challenges due to the low-level concentration (in the sub-ppb range) and its variation with sampling site and time. Of the many available analytical methods for carbonylic compounds, the most widespread one is the time consuming collection in cartridges impregnated with 2,4-dinitrophenylhydrazine followed by the analysis of the formed hydrazones by HPLC. The present work proposes the use of polypropylene hollow porous capillary fibers to achieve efficient CH(2)O collection. The Oxyphan fiber (designed for blood oxygenation) was chosen for this purpose because it presents good mechanical resistance, high density of very fine pores and high ratio of collection area to volume of the acceptor fluid in the tube, all favorable for the development of air sampling apparatus. The collector device consists of a Teflon pipe inside of which a bundle of polypropylene microporous capillary membranes was introduced. While the acceptor passes at a low flow rate through the capillaries, the sampled air circulates around the fibers, impelled by a low flow membrane pump (of the type used for aquariums ventilation). The coupling of this sampling technique with the selective and quantitative determination of CH(2)O, in the form of hydroxymethanesulfonate (HMS) after derivatization with HSO(3)(-), by capillary electrophoresis with capacitively coupled contactless conductivity detection (CE-C(4)D) enabled the development of a complete analytical protocol for the CH(2)O evaluation in air.

Determination of salbutamol in syrups by capillary electrophoresis with contactless conductivity detection (CE-C(4)D).

This paper describes the separation and quantification of salbutamol in pharmaceutical products (salbutamol syrups) by capillary electrophoresis (CE) with contactless conductivity detection (C(4)D). The system was studied by micellar electrokinetic capillary chromatography (MEKC) and free solution capillary electrophoresis (FSCE), being the latter chosen in function of best resolution and sensitivity in comparison with the MEKC method. CE-C(4)D was applied to analysis of salbutamol in syrups utilizing 1.0 x 10(-2) molL(-1) acetic acid/sodium acetate buffer (pH 4.9) as running electrolyte. Tetraethylammonium (TEA) solution was used as internal standard. The results obtained include a linear dynamic range from 7. x 10(-5) to 3.0 x 10(-4) molL(-1) and good repeatability (R.S.D.=4.7% for n=10 for a 7.0 x 10(-5) molL(-1) salbutamol solution). The detection limit was calculated as 1.0 x 10(-5) molL(-1) and the limit of quantification was estimated as 3.3 x 10(-5) molL(-1). For syrups analysis the reproducibility presented deviations between 1.5% and 2.5% (three different days) obtained for measurements in triplicate.

Trace analysis of acids and bases by conductometric titration with multiparametric non-linear regression.

A chemometric method for analysis of conductometric titration data was introduced to extend its applicability to lower concentrations and more complex acid-base systems. Auxiliary pH measurements were made during the titration to assist the calculation of the distribution of protonable species on base of known or guessed equilibrium constants. Conductivity values of each ionized or ionizable species possibly present in the sample were introduced in a general equation where the only unknown parameters were the total concentrations of (conjugated) bases and of strong electrolytes not involved in acid-base equilibria. All these concentrations were adjusted by a multiparametric nonlinear regression (NLR) method, based on the Levenberg-Marquardt algorithm. This first conductometric titration method with NLR analysis (CT-NLR) was successfully applied to simulated conductometric titration data and to synthetic samples with multiple components at concentrations as low as those found in rainwater (approximately 10 micromol L(-1)). It was possible to resolve and quantify mixtures containing a strong acid, formic acid, acetic acid, ammonium ion, bicarbonate and inert electrolyte with accuracy of 5% or better.