Andrey Khlystov

Chemical and Biological Applications of Digital-Microfluidic Devices

Digital-microfluidic lab-on-a chip (LoC) technology offers a platform for developing diagnostic applications with the advantages of portability, sample and reagent volume reduction, faster analysis, increased automation, low power consumption, compatibility with mass manufacturing, and high throughput. In addition to diagnostics, digital microfluidics is finding use in airborne chemical detection, DNA sequencing by synthesis, and tissue engineering. In this article, we review efforts to develop various LoC applications using electrowetting-based digital microfluidics. We describe these applications, their implementation, and associated design issues.

Nucleation events during the Pittsburgh air quality study: Description and relation to key meteorological, gas phase, and aerosol parameters

During the Pittsburgh Air Quality Study (PAQS) aerosol size distributions between 3 nm and 680 nm were measured between July 2001 and June 2002. These distributions have been analyzed to assess the importance of nucleation as a source of ultrafine particles in Pittsburgh and the surrounding areas. The analysis shows nucleation on 50% of the study days and regional-scale formation of ultrafine particles on 30% of the days. Nucleation occurred during all seasons, but it was most frequent in fall and spring and least frequent in winter. Regional nucleation was most common on sunny days with below average PM2.5 concentrations. Local nucleation events were usually associated with elevated SO2 concentrations. The observed nucleation events ranged from weak events with only a slight increase in the particle number to relatively intense events with increases of total particle counts between 50,000 cm−3 up to 150,000 cm−3. Averaging all days of the study, days with nucleation events had number concentrations peaking at around noon at about 45,000 cm−3. This is compared to work days without nucleation, when the daily maximum was 8 am at 23,000 cm−3, and to weekends without nucleation, when the daily maximum was at noon at 16,000 cm−3. Twenty-four-hour average number concentrations were approximately 40% higher on days with nucleation compared to those without. Nucleation was typically observed starting around 9 am EST, although the start of nucleation events was later in winter and earlier in summer. The nucleation events are fairly well correlated with the product of [UV intensity * SO2 concentration] and also depend on the effective area available for condensation. This indicates that H2SO4 is a component of the new particles. Published correlations for nucleation by binary H2SO4—H2O cannot explain the observed nucleation frequency and intensity, suggesting that an additional component (perhaps ammonia) is participating in the particle formation.

The steam-jet aerosol collector

Abstract A new principle of sampling aerosol particles by means of steam injection with the consequent collection of grown droplets has been established. An air stream free of water-soluble gases is rapidly mixed with steam. The resulting supersaturation causes aerosol particles to grow into droplets. The droplets containing dissolved aerosol species are then collected by two cyclones in series. The solution collected in the cyclones is constantly pumped out and can be on- or off-line analysed by means of ion chromatography or flow injection analysis. On the basis of the new sampling principle a prototype of an aerosol sampler was designed which is capable of sampling particles quantitatively down to several nanometres in diameter. The mass sampling efficiency of the instrument was found to be 99%. The detection limit of the sampler for ammonium, sulphate, nitrate and chloride ions is below 0.7 μg m−3. By reduction of an already identified source of contamination, much lower detection limits can be achieved. During measurements the sampler proved to be stable, working without any assistance for extended periods of time. Comparison of the sampler with filter packs during measurements of ambient air aerosols showed that the sampler gives good results.

Positive and Negative Artifacts in Particulate Organic Carbon Measurements with Denuded and Undenuded Sampler Configurations Special Issue of Aerosol Science and Technology on Findings from the Fine Particulate Matter Supersites Program

Measurement of ambient particulate organic carbon (POC) with quartz filters is prone to positive and negative sampling artifacts. One approach for estimating these artifacts is to sample with a backup quartz filter placed behind either the main quartz filter or a Teflon filter in a parallel line. Another approach is to use a denuder to reduce the positive artifact in combination with a highly adsorbent backup filter to capture any negative artifact. Results obtained using both of these approaches in parallel for over one year in Pittsburgh, PA are presented in this article. A sampler using an activated carbon monolith denuder has been developed and tested extensively. Transmission losses were found to be negligible, and the denuder is on average 94% efficient at removing gas-phase organics. Denuder breakthrough is corrected for each run using a dynamic blank in parallel with the sample line. Comparisons with the dynamic blank indicate that the denuder almost eliminates the positive artifact on the quartz filter. Negative artifact from the denuded quartz filter is quantified using a carbon-impregnated glass fiber (CIG) backup filter and was found to be small, typically less than 10% of the ambient POC. Compared to the denuded sampler POC, 24 h bare quartz samples showed an almost constant positive artifact of 0.5 μg-C/m3 for samples taken throughout the year-long study period. Sampling for shorter durations (4–6 h) resulted in a larger positive artifact. A quartz filter behind a Teflon filter (QBT) provides a consistent estimate of the positive artifact on the bare quartz filter irrespective of sample duration, though it overcorrects for the positive artifact by 16–20% (attributed to particulate matter volatilizing off the upstream Teflon filter). The quartz behind quartz (QBQ) approach provides a reasonable estimate of the positive artifact on the bare quartz filter for the 24 h samples but not for the shorter samples. A slight seasonal variation is observed in the absolute value of the positive artifact, with higher values observed during the summer months.

An algorithm for combining electrical mobility and aerodynamic size distributions data when measuring ambient aerosol

Ambient aerosol particles vary in size from a few nanometers to several micrometers. No instrument is currently available to cover such a wide size range, and so a combination of several instruments is usually used. One such combination is that of electrical mobility classifiers and an aerodynamic sizer. Because of the differences in measurement principles between the instruments, difficulties arise in the combination of the measurements into a single size distribution. Here we report a simple algorithm that was developed to combine aerosol size distributions measured with commercially available scanning mobility particle sizers (SMPS; TSI Inc.) and an aerodynamic particle sizer (APS; TSI Inc.). This algorithm was tested during July 2001 in the Pittsburgh Air Quality Study. The aerosol during the study had both urban and regional origin and is characteristic of urban atmosphere in the Northeastern U.S. The integrated volume concentrations from the SMPS–APS showed a good correlation with PM2.5 mass concentration measurements using a TEOM. The relation of the aerosol mass to its volume is an “effective” density, a ratio of the bulk aerosol density to the shape factor. As a result of the comparison with the TEOM the ambient aerosol in the Pittsburgh area was found to have an effective density of 1.5 ± 0.3 g cm−3. Given that the aerosol during the study was found to always contain water, the particles are expected to be spherical and thus the shape factor may be assumed to be 1. This assumption has been supported by a comparison with the MOUDI, using the aerosol density of 1.5 g/cm3. It should be noted that the estimated aerosol density and the shape factor are applicable to this study only and may be different in other locations.

Integrated chemical/biochemical sample collection, pre-concentration, and analysis on a digital microfluidic lab-on-a-chip platform

An ideal on-site chemical/biochemical analysis system must be inexpensive, sensitive, fully automated and integrated, reliable, and compatible with a broad range of samples. The advent of digital microfluidic lab-on-a-chip (LoC) technology offers such a detection system due to the advantages in portability, reduction of the volumes of the sample and reagents, faster analysis times, increased automation, low power consumption, compatibility with mass manufacturing, and high throughput. We describe progress towards integrating sample collection onto a digital microfluidic LoC that is a component of a cascade impactor device. The sample collection is performed by impacting airborne particles directly onto the surface of the chip. After the collection phase, the surface of the chip is washed with a micro-droplet of solvent. The droplet will be digitally directed across the impaction surface, dissolving sample constituents. Because of the very small droplet volume used for extraction of the sample from a wide colection area, the resulting solution is realatively concentrated and the analytes can be detected after a very short sampling time (1 min) due to such pre-concentration. After the washing phase, the droplet is mixed with specific reagents that produce colored reaction products. The concentration of the analyte is quantitatively determined by measuring absorption at target wavelengths using a simple light emitting diode and photodiode setup. Specific applications include automatic measurements of major inorganic ions in aerosols, such as sulfate, nitrate and ammonium, with a time resolution of 1 min and a detection limit of 30 nm/m3. We have already demonstrated the detection and quantification of nitroaromatic explosives without integrating the sample collection. Other applications being developed include airborne bioagent detection.

Instrument development and application in studies and monitoring of ambient ammonia

During recent years, it has become clear that ammonia is an important gas in relation to different environmental issues, such as acidification, eutrophication, human health and climate change (through particle formation). Therefore, there is a growing need to develop and apply instrumentation suitable for research into emission, dispersion, conversion and deposition of ammonia and ammonium. Recently, several instruments were developed suitable for measuring concentrations in ambient conditions even at very low levels, such as ammonia sensors suitable for monitoring and research, deposition measuring systems and aerosol samplers for on-line measurement of aerosol composition. These instruments have been tested and applied in a number of field studies. These studies include dry deposition measurements, ammonium nitrate studies in relation to the (in)direct aerosol effect, emission studies and policy evaluation with concentration and deposition monitoring data. The policy evaluation study showed that the measures to reduce ammonia emissions were not as successful as projected beforehand by statistical studies.

Traffic and Meteorological Impacts on Near-Road Air Quality: Summary of Methods and Trends from the Raleigh Near- Road Study

Abstract A growing number of epidemiological studies conducted worldwide suggest an increase in the occurrence of adverse health effects in populations living, working, or going to school near major roadways. A study was designed to assess traffic emissions impacts on air quality and particle toxicity near a heavily traveled highway. In an attempt to describe the complex mixture of pollutants and atmospheric transport mechanisms affecting pollutant dispersion in this near-highway environment, several real-time and time-integrated sampling devices measured air quality concentrations at multiple distances and heights from the road. Pollutants analyzed included U.S. Environmental Protection Agency (EPA)-regulated gases, particulate matter (coarse, fine, and ultrafine), and air toxics. Pollutant measurements were synchronized with real-time traffic and meteorological monitoring devices to provide continuous and integrated assessments of the variation of near-road air pollutant concentrations and particle toxicity with changing traffic and environmental conditions, as well as distance from the road. Measurement results demonstrated the temporal and spatial impact of traffic emissions on near-road air quality. The distribution of mobile source emitted gas and particulate pollutants under all wind and traffic conditions indicated a higher proportion of elevated concentrations near the road, suggesting elevated exposures for populations spending significant amounts of time in this microenvironment. Diurnal variations in pollutant concentrations also demonstrated the impact of traffic activity and meteorology on near-road air quality. Time-resolved measurements of multiple pollutants demonstrated that traffic emissions produced a complex mixture of criteria and air toxic pollutants in this microenvironment. These results provide a foundation for future assessments of these data to identify the relationship of traffic activity and meteorology on air quality concentrations and population exposures.

Effect of Peak Inert-Mode Temperature on Elemental Carbon Measured Using Thermal-Optical Analysis

Thermal-optical analysis is a conventional method for classifying carbonaceous aerosols as organic carbon (OC) and elemental carbon (EC). This article examines the effects of three different temperature protocols on the measured EC. For analyses of parallel punches from the same ambient sample, the protocol with the highest peak helium-mode temperature (870°C) gives the smallest amount of EC, while the protocol with the lowest peak helium-mode temperature (550°C) gives the largest amount of EC. These differences are observed when either sample transmission or reflectance is used to define the OC/EC split. An important issue is the effect of the peak helium-mode temperature on the relative rate at which different types of carbon with different optical properties evolve from the filter. Analyses of solvent-extracted samples are used to demonstrate that high temperatures (870°C) lead to premature EC evolution in the helium-mode. For samples collected in Pittsburgh, this causes the measured EC to be biased low because the attenuation coefficient of pyrolyzed carbon is consistently higher than that of EC. While this problem can be avoided by lowering the peak helium-mode temperature, analyses of wood smoke dominated ambient samples and levoglucosan-spiked filters indicate that too low helium-mode peak temperatures (550°C) allow non-light absorbing carbon to slip into the oxidizing mode of the analysis. If this carbon evolves after the OC/EC split, it biases the EC measurements high. Given the complexity of ambient aerosols, there is unlikely to be a single peak helium-mode temperature at which both of these biases can be avoided. †Now at the Department of Civil and Environmental Engineering, University of Illinois, Urbana, IL 61801, USA

Field investigation of roadside vegetative and structural barrier impact on near-road ultrafine particle concentrations under a variety of wind conditions

Roadside barriers, such as tree stands or noise barriers, are prevalent in many populated areas and have been shown to affect the dispersion of traffic emissions. If roadside noise barriers or tree stands are found to consistently lower ground-level air pollution concentrations in the near-road environment, this may be a practical strategy for reducing exposures to air contaminants along populated traffic corridors. This study measured ultrafine particle (UFP) concentrations using an instrumented mobile measurement approach, collecting data on major roadways and in near-road locations for more than forty sampling sessions at three locations in central North Carolina, USA. Two of the sampling sites had relatively thin tree stands, one evergreen and one deciduous, along a portion of the roadway. The third sampling site had a brick noise wall along a portion of the road. At 10 m from the road, UFPs measured using a mobile sampling platform were lower by approximately 50% behind the brick noise wall relative to a nearby location without a barrier for multiple meteorological conditions. The UFP trends at the vegetative barrier sites were variable and the barrier effect is uncertain. In some cases, higher concentrations were observed behind the vegetative barrier, with respect to the clearing, which may be due to gaps in the thin tree stands allowing the transport of traffic-related air pollution to near-road areas behind the vegetation. On-road sampling revealed no consistent difference in UFP levels in on-road portions of the road with or without a roadside barrier present. These findings support the notion that solid roadside barriers may mitigate near-road impact. Given the co-benefits of vegetative barriers in the urban landscape, research regarding the mitigation potential of vegetative barriers of other configurations (e.g., greater density, wider buffer) is encouraged.