nitrogen-dioxide and triethanolamine

Aqueous triethanolamine (TEA) solutions are widely used as sorption medium for passive sampling of ambient NO(2), with NO(2) trapped and accumulated as nitrite ion. The results of test measurements of ambient NO(2) concentrations using passive sampling method showed that the simple approach commonly used to describe passive sampling process might lead to substantial systematic errors. Presented in the article is a new physicochemical model of the process of passive sampling of gaseous NO(2), with aqueous TEA solution used as a trapping medium. The model is based on the available results of experimental studies of interaction of gaseous NO(2) with TEA/water solutions. The key principles underlying the model are: (1) when absorbed by a trapping solution, NO(2) forms nitrite ion only on the condition that TEA is hydrated; (2) coefficient of conversion of NO(2) to NO(2)(-) is equal to one when reacting with hydrated TEA; and (3) the fraction of hydrated TEA molecules depends on air humidity at the moment of measurement. Validation of the model was made using the data of the field measurements carried out in the Middle Urals in 2007-2009. The new model was used to calculate average NO(2) concentrations. Concentrations calculated agreed well with the results obtained by reference methods. The difference between the datasets was statistically insignificant.

Topics: Adsorption; Air Pollutants; Environmental Monitoring; Ethanolamines; Humidity; Models, Chemical; Nitrogen Dioxide

We have previously introduced a new type of rotatable flow-through directional passive air sampler (DPAS) for monitoring trace air pollutants in ambient air. In wind tunnel tests, the sampler turns into the prevailing wind direction and retains NO(2) (used as a test pollutant) on an internal sampling medium ring of triethanolamine (TEA)-coated meshes to indicate the source of pollution. However, these meshes can become saturated, after exposure times of tens of hours or a few days, due to the relatively small masses of TEA which can be coated onto them. This paper outlines the saturation problem and presents a possible redesign of the DPAS sampling approach, to allow longer-term (weeks-months) deployments, where air passes over larger volumes of TEA retained in a compartmentalised carousel. Investigations varying the volume, depth and mixing of TEA in sampling compartments suggested that the limiting step of NO(2) uptake was its rate of supply from the atmosphere. In wind tunnel trials, NO(2) uptake into TEA continued linearly in response to a stable air concentration over periods of tens of days, showing no signs of saturation. Uptake was wind velocity dependent across the range of 0.50, 2.00, 5.00 and 8.00 m s(-1). Results indicate that the total sampling time and storage capacity of the TEA for NO(2) can be varied to meet deployment time requirements, indicating that long-term, cheap, directional passive air sampling is achievable.

Topics: Air Pollutants; Environmental Monitoring; Equipment Design; Ethanolamines; Nitrogen Dioxide

This study describes the field evaluation of a tailor-made new glass passive sampler developed for the determination of NO(2), based on the collection on triethanolemine (TEA)-coated fibre filter paper. The sampler has been derived from a Palmes design. The overall uncertainty of the sampler was determined by using Griess-Saltzman ASTM D 1607 standard test method as a reference method. The agreement between the results of the passive sampler and the reference method was +/-7.90% with the correlation coefficient of 0.90. Method precision in terms of coefficient of variance (CV) for three simultaneously applied passive samplers was 8.80%. The uptake rate of NO(2) was found to be 2.49 ml/min in a very good agreement with the value calculated from theory (2.63 ml/min). Sampler detection limit was 1.99 microg/m(3) for an exposure period of 1 week and the sampler can be stored safely for a period of up to 6 weeks before exposure. A comparison of the sampler performance was conducted against a commercially available diffusion tube (Gradko diffusion tube). The results from the applied statistical paired t test indicated that there was no significant difference between the performances of two passive samplers (R (2) > 0.90). Also, another statistical comparison was carried out between the dark and transparent glass passive samplers. The results from the dark-colour sampler were higher than that from the transparent sampler (approximately 25%) during the summer season because of the possible photodegradation of NO(2)-TEA complex.

Topics: Air Pollutants; Environmental Monitoring; Ethanolamines; Nitrogen Dioxide; Turkey

We propose the use of lab-on-a-chip technology for measuring gaseous chemical pollutants, and describe the development of a microchip for the detection of nitrogen dioxide (NO2) in air. A microchip fabricated from quartz glass has been developed for handling the following three functions, gas absorption, chemical reaction and fluorescence detection. Channels constructed in the microchip were covered with porous glass plates, allowing nitrogen dioxide to penetrate into the triethanolamine (TEA) flowing within the microchannel beneath. The nitrogen dioxide was then mixed with TEA and reacted with a suitable fluorescence reagent in the chemical reaction chamber in the microchip. The reacted solution was then allowed to flow into the fluorescence detection area to be excited by an ultraviolet light-emitting diode (UV-LED), and the fluorescence was detected using a photomultiplier tube (PMT). The reaction time, reagent concentration, pH, flow rate and other measurement conditions were optimised for analysis of nitrogen dioxide in air. Preliminary studies with standardized test solutions revealed quantitative measurements of nitrite ion (NO2-), which corresponded to atmospheric nitrogen dioxide in the range of 10-80 ppbv.

Topics: Air Pollutants; Environmental Monitoring; Equipment Design; Ethanolamines; Humans; Lab-On-A-Chip Devices; Microchip Analytical Procedures; Nitrogen Dioxide

A personalized, miniaturized air sampling system was evaluated to estimate the daily exposure of pediatric asthmatics to nitrogen dioxide (NO2). The lightweight device (170 g) uses a sampling pump connected to a solid sorbent tube containing triethanolamine (TEA)-impregnated molecular sieve. The pump is powered by a 9 V battery and samples air over a 24 h period at a collection rate of 0.100 L/min. After exposure, the solid sorbent is removed from the tubes for spectrophotometric analysis (Griess Assay). The lower detection limit of the overall method for NO2 is 11 microg/m3. The linearity, precision and accuracy of the sampler was evaluated. Different NO2 concentrations generated in the laboratory (range: 50 to 340 microg/m3) were simultaneously measured by the TEA tube samplers and colocated continuous chemiluminescent NO(x) analyzers (reference method). The coefficient of determination for the laboratory test derived from ordinary linear regression (OLR) was r2 = 0.99 (y(OLR) = 0.94 x -4.58) and the precision 3.6%. Further, ambient NO2 concentrations in the field (range: 10-120 microg/m3) were verified with continuous chemiluminescent monitors next to the active samplers. Re-weighted least squares analysis (RLS) based on the least median squares procedure (LMS) resulted in a correlation of r2 = 0.68 for a field comparison in Riverside, CA (y(RLS) = 1.01 x -0.94) and r2 = 0.92 in Los Angeles, CA (y(RLS) = 1.31 x -7.12). The precision of the TEA tube devices was 7.4% (at 20-60 microg/m3 NO2) under outdoor conditions. Data show that the performance of this small active sampling system was satisfactory for measuring environmental concentrations of NO2 under laboratory and field conditions. It is useful for personal monitoring of NO2 in environmental epidemiology studies where daily measurements are desired.

Topics: Air Pollutants; Child; Child, Preschool; Environmental Monitoring; Ethanolamines; Humans; Los Angeles; Miniaturization; Nitrogen Dioxide

This study was carried out in response to suggestions that the measurement of NO(2) by Palmes-type passive diffusion tubes (PDT) is affected by the method of preparation of the triethanolamine (TEA) absorbent coating on the grids. The following combinations of factors were investigated: TEA solvent (acetone or water), volume composition of TEA in solvent (50% or 20%), and grid coating method (dipping in solution prior to assembly or pipetting solution on after assembly). Duplicate PDTs prepared by each of the 8 methods were exposed in parallel, in urban air, for a total of 80 separate 1 week exposures. NO(2) concentrations derived from PDTs prepared by pipetting methods were significantly less precise than concentrations from dipping methods, with mean RSDs for duplicate measurements of 13.8% and 8.5%, respectively (n= 316 each category). Pipetting methods using solutions of 50% TEA composition were particularly imprecise (mean RSD 17.2%). Data from PDTs prepared by pipetting methods were systematically more poorly correlated with each other and with data from co-located chemiluminescence analysers, than corresponding data from PDTs prepared by dipping methods, indicating that more consistent accuracy was also obtained by the latter PDTs. The statistical evidence suggested that PDTs prepared by pipetting 50% TEA in water generally gave lower NO(2) concentrations. Although this is in agreement with a previous study, it is also possible that such an observation here may be a statistical artefact given the demonstrably poorer precision of this method. The general tendency of PDTs to show positive bias in NO(2) measurement in urban air in 1 week exposures was again evident in this study (mean biases at roadside and urban centre locations of +35% (n= 475) and +18% (n= 112), respectively) consistent with augmentation of within-tube NO(2) flux by chemical reaction between co-diffusing NO and O(3). Overall, it is recommended that the pipetting method of PDT grid preparation is avoided, or at least investigated further, because of the apparent degradation in precision and accuracy of NO(2) measurement. Potential reasons for the effect are discussed.

Topics: Adsorption; Air Pollutants; Diffusion; Environmental Monitoring; Ethanolamines; Nitrogen Dioxide

Factors concerning NO2 uptake by the absorbent triethanolamine (TEA) in NO2 diffusion tubes are examined. Although the nominal freezing point of TEA is 17.9-21.2 degrees C, we show that, for a range of aqueous TEA solutions (0-20%, H2O), no freezing occurs even at -10 degrees C. Therefore NO2 collection efficiency is unlikely to be impaired by low temperature exposure. The recovery of TEA from the meshes of exposed samplers is determined as approximately 98%, even after 42 days, showing that the stability in situ of TEA is unaffected by long-term exposure. A model of a diffusion tube sampling array for simultaneous exposures, with a 0.1 m sampler spacing, shows that NO2 uptake by individual samplers is not affected by the presence of neighbouring tubes in the array. This is confirmed by sampler precision at two Cambridge sites. Four sampler preparation methods are compared for differences in NO2 uptake of exposed samplers. All methods employ TEA as absorbent, transferred by either dipping meshes in a TEA-acetone solution or pipetting aliquots of a TEA-H2O solution onto the meshes. For samplers prepared by three of the methods, no difference in NO2 uptake is found, but for samplers prepared using a 50% v/v TEA-H2O solution, a mean reduction of 18% is found. Student's t-tests show that the difference is highly significant (P < or = 0.001). Reasons for the difference are discussed.

Topics: Absorption; Diffusion; Environmental Monitoring; Ethanolamines; Freezing; Nitrogen Dioxide; Reproducibility of Results; Sensitivity and Specificity; Specimen Handling

When nitrogen dioxide (NO2) samplers were exposed at several reduced pressures, it was found that the sampling rate was correspondingly decreased; that finding did not agree with accepted diffusional theory. When the experiments were repeated using water vapor as the gas and molecular sieve as the sorbent, the observed sampling rates were in very good agreement with diffusional theory. These findings demonstrated that the pressure effect was not common to all diffusional samplers and suggested that there might be an alternate explanation for the results with NO2-triethanolamine (TEA). The best possibility appeared to be the dehydration of TEA that takes place at reduced pressures. That this is a very significant factor was demonstrated by simultaneous exposure to identical concentrations of NO2 at 1 atm and 50% or 0% relative humidity. In dry air the sampling rate was equivalent to that found previously at about 1/10 atm. The earlier results can be satisfactorily explained as indirect rather than direct effects of reduced pressure.

Topics: Diffusion; Ethanolamines; Humidity; Nitrogen Dioxide; Pressure; Water

Nitrogen dioxide (NO2) and sulphur dioxide (SO2) in air were sampled by the use of a Sep-Pak C18 cartridge impregnated with triethanolamine-potassium hydroxide. The trapped NO2 and SO2 were eluted with a 8 mM sodium carbonate-3 mM sodium hydrogencarbonate solution and simultaneously determined by ion chromatography. In the active sampling mode, NO2 was determined with 5.2% relative standard deviation at 95 ppb and SO2 was determined with 2.4-5.3% relative standard deviation at 54-184 ppb. The recoveries were 85-98% for NO2 and 91-105% for SO2. In the passive sampling mode, the average concentrations of NO2 and SO2 were determined with 2.4-6.8 and 2.8-7.9% relative standard deviation, respectively, at atmospheric levels for 6-24 days.

Topics: Air Pollutants, Occupational; Chromatography, Ion Exchange; Ethanolamines; Humidity; Hydroxides; Nitrogen Dioxide; Nitrous Oxide; Potassium; Potassium Compounds; Sulfur Dioxide