Development of a Technology for Online Measurement of Total and Water-Soluble Copper (Cu) in PM2.5

A novel monitor for online, in situ measurement of copper (Cu) in ambient fine and ultrafine particulate matter (PM) was developed based on a recent published high flow rate aerosol-into-liquid collector. This aerosol-into-liquid collector operates at 200 L/min flow and collects particles directly as highly concentrated slurry samples. The Cu concentration in slurry samples is subsequently determined by a cupric ion selective electrode (ISE). Laboratory tests were conducted to evaluate the performance of the cupric ISE. The calibration curve of the cupric ISE was determined using Cu(NO₃)₂ standard solutions prepared by serial dilution. As part of the evaluation, the effects of ionic strength, temperature and pH of the aerosol slurry sample on the cupric ISE measurement were also evaluated. The Cu measurement system performance was evaluated by collecting and measuring samples of lab-generated Cu(NO₃)₂ aerosols with known mass concentration. Overall, very good agreement between the theoretical and measured Cu concentrations was obtained, corroborating the excellent high overall collection efficiency and measurement accuracy of the Cu measurement system. Field evaluations of the online Cu monitor demonstrated very good agreement for total and water-soluble Cu concentrations with measurements performed by inductively coupled plasma mass spectrometry (ICP-MS), suggesting that interferences from other components of particulate matter are minimal under real world sampling conditions. Moreover, the field tests indicated that the new online Cu monitor could achieve near-continuous collection and measurements (at 2–4 h intervals) for at least 4 to 7 days without any obvious shortcomings in its operation. Both laboratory and field evaluations of the online Cu monitor indicate that it is an effective and valuable technology for PM collection and characterization of Cu in ambient aerosols and provides the foundation for the wider use of ISE for metal analysis and speciation of aerosols.

Copyright 2014 American Association for Aerosol Research     

Mixing and sink effects of air purifiers on indoor PM2.5 concentrations: A pilot study of eight residential homes in Fresno,California

We measured real-time and integrated PM2.5 inside eight occupied single-family homes in Fresno, California to evaluate how turbulent air mixing and pollutant removal caused by a filter-based air purifier influences the levels of fine particles in everyday indoor environments. In each home, we used a real-time monitor to log PM2.5 levels every 5 min over 12 weeks during which air purifiers were operating, except for a designed 3-day shutdown period for baseline measurements. We assessed how the operation of air purifiers changed the patterns of the frequency distributions for short-term (5 min) concentrations, which included spikes produced by sporadic indoor activities or emissions. This allowed us to examine the reduction effectiveness of air purifiers on concentrations of both recently emitted and well-mixed background aerosols. We observed a systematic change in the 5-min PM2.5 distributions in different homes—while air purifiers reduced 96% of the 5-min concentrations, they increased the magnitudes of the top 4%, representing transient concentration peaks. This phenomenon is consistent with what would be theoretically expected based on passive scalar turbulence in fluid physics. We also collected gravimetric filter samples for PM2.5 composition, finding mean reductions of the long-term (2–5 days) concentrations of 29%–37% for indoor PM2.5 and endotoxin. A less significant reduction (19%–26%) was seen for Pb (Lead).

© 2016 American Association for Aerosol Research     

Hydroxyl radical formation and soluble trace metal content in particulate matter from renewable diesel and ultra low sulfur diesel in at-sea operations of a research vessel

Reactive oxygen species, including hydroxyl radicals generated by particles, play a role in both aerosol aging and PM2.5 mediated health effects. We assess the impacts of switching marine vessels from conventional diesel to renewable fuel on the ability of particles to generate hydroxyl radical when extracted in a simulated lung lining fluid or in water at pH 3.5, for samples of engine emissions from a research vessel when operating on ultra-low sulfur diesel (ULSD) and hydrogenation-derived renewable diesel (HDRD). Samples were collected during dedicated cruises in 2014 and 2015, including aged samples collected by re-intercepting the ship plume. After normalizing to particle mass, particles generated from HDRD combustion had slightly to significantly (5–50%) higher OH generation activity than those from ULSD, a difference that was statistically significant for some permutations of year/fuel/engine speed. Water soluble trace metal concentrations and fuel metal concentrations were similar, and compared to urban Los Angeles samples lower in soluble iron and manganese, but similar for most other trace metals. Because PM mass emissions were higher for HDRD, normalizing to fuel increased this difference. Freshly emitted PM had lower activity than the “plume chase” samples, and samples collected on the ship had lower activity than the urban reference. The differences in OH production correlated reasonably well with redox-active transition metals, most strongly with soluble manganese, with roles for vanadium and likely copper and iron. The results also suggest that atmospheric processing of fresh combustion particles rapidly increases metal solubility, which in turn increases OH production.

Copyright © 2017 American Association for Aerosol Research     

The First Combined Thermal Desorption Aerosol Gas Chromatograph—Aerosol Mass Spectrometer (TAG-AMS)

To address the critical need for improving the chemical characterization of the organic composition of ambient particulate matter, we introduce a combined thermal desorption aerosol gas chromatograph—aerosol mass spectrometer (TAG-AMS). The TAG system provides in-situ speciation of organic chemicals in ambient aerosol particles with hourly time resolution for marker compounds indicative of sources and transformation processes. However, by itself the TAG cannot separate by particle size and it typically speciates and quantifies only a fraction of the organic aerosol (OA) mass. The AMS is a real-time, in-situ instrument that provides quantitative size distributions and mass loadings for ambient fine OA and major inorganic fractions; however, by itself the AMS has limited ability for identification of individual organic compounds due to the electron impact ionization detection scheme used without prior molecular separation.

The combined TAG-AMS system provides real-time detection by AMS followed by semicontinuous analysis of the TAG sample that was acquired during AMS operation, achieving simultaneous and complementary measurements of quantitative organic mass loading and detailed organic speciation. We have employed a high-resolution time-of-flight mass spectrometer (HR-ToF-MS) to enable elemental-level determination of OA oxidation state as measured on the AMS, and to allow improved compound identification and separation of unresolved complex mixtures (UCM) measured on the TAG. The TAG-AMS interface has been developed as an upgrade for existing AMS systems. Such measurements will improve the identification of organic constituents of ambient aerosol and contribute to the ability of atmospheric chemistry models to predict ambient aerosol composition and loadings.

Copyright 2014 American Association for Aerosol Research     

A practical set of miniaturized instruments for vertical profiling of aerosol physical properties

In situ atmospheric aerosol measurements have been performed from a Manta unmanned aircraft system (UAS) using recently developed miniaturized aerosol instruments. Flights were conducted up to an altitude of 3000 m (AMSL) during spring 2015 in Ny-Ålesund, Svalbard, Norway. We use these flights to demonstrate a practical set of miniaturized instruments that can be deployed onboard small UASs and can provide valuable information on ambient aerosol. Measured properties include size-resolved particle number concentrations, aerosol absorption coefficient, relative humidity, and direct sun intensity. From these parameters, it is possible to derive a comprehensive set of aerosol optical properties: aerosol optical depth, single scattering albedo, and asymmetry parameter. The combination of instruments also allows us to determine the aerosol hygroscopicity.

Copyright © 2017 American Association for Aerosol Research     

Shifts in the Gas-Particle Partitioning of Ambient Organics with Transport into the Indoor Environment

Predicting indoor exposures to ambient organic aerosol (OA) is complicated by shifts in the gas-particle partitioning of ambient organics with outdoor-to-indoor transport. This analysis aims to quantify the effect of changes in temperature and OA loading on the gas-particle partitioning of ambient organics transported indoors and explores whether accounting for shifts in partitioning closes the gap between measured indoor ambient OA concentrations and indoor concentrations calculated in a previous analysis using a model that accounts for only physical losses. Changes in the gas-particle partitioning of ambient organics with outdoor-to-indoor transport were calculated for 167 homes using measured temperatures and OA concentrations and published OA volatility distributions. Initially, it was assumed that ambient OA could be represented with a single volatility distribution. We then repeated the analysis treating ambient OA as the sum of distinct components, each with a distinct volatility distribution, derived from factor analysis of aerosol mass spectra (e.g., hydrocarbon-like OA [HOA], oxygenated OA [OOA]). We also evaluated the sensitivity of our calculations to uncertainty in the thermodynamic properties of ambient OA by varying the enthalpy of vaporization. Partitioning shifts were sensitive to enthalpy-of-vaporization assumptions and resulted in changes in indoor ambient OA concentrations of 13–27%. Our calculations indicate that phase changes are important determinants of residential exposure to ambient OA and are of sufficient magnitude to close the gap between measured and modeled indoor concentrations of ambient OA.

Copyright 2014 American Association for Aerosol Research     

Comparative study: Correlating extraction efficiency for Hg(II), Cd(II), and Pb(II) metal ions with the chelate stability and total hardness in simple nitrogen donors

Four N-donors (PHDA, ATPH, APHO, and MTAN) containing NH₂ were used to extract Hg(II), Cd(II), and Pb(II). Their extraction capacity was determined by measurement of percentage extraction.

The chelates extract these metals differently: for example, efficiency of ATPH was the highest for Hg(II) compared to PHDA, APHO, and MTAN.

The extraction efficiency was found to depend on: donor atom hardness, chelate total hardness, metal: chelate mole ratio and substituent’s electronic effects. Among all, total hardness and chelate stability are key factors and molecule of small (E_HOMO – E_LUMO) is more reactive, where extraction efficiency increases as molecular stability decreases.     

Using the WIBS-4 (Waveband Integrated Bioaerosol Sensor) Technique for the On-Line Detection of Pollen Grains

Primary biological aerosol particles (PBAP) such as pollen and fungal spores can induce allergenic responses and affect health in general. Conditions such as allergic rhinitis (hay fever) and asthma have been related to pollen concentrations. Likewise some pollen have been shown to induce ice nucleation and cloud condensation at higher temperatures than those associated with some chemical species, thereby affecting planet Earth's albedo and overall radiative balance. Hence, the near real-time (on-line) monitoring of airborne pollen and other PBAP using a variety of spectroscopic and light scattering techniques represents an area of growing development and consequence.

In this study, two separate field campaigns (one at a rural site in Ireland and the other at an urbanized location in Germany) were performed to detect and quantify pollen releases using a novel on-line fluorescence spectrometer (WIBS-4). The results were compared with results obtained using more traditional Hirst-type impactors. Size, “shape,” and fluorescence characteristics of ambient particles were used to determine the concentrations and identity of the PBAP likely to be pollen grains.

The concentration results obtained for both methodologies at both the Irish and German sites correlated very well, with R ² values >0.9 determined for both campaigns. Furthermore, the sizing data available from the WIBS-4 approach employed in Ireland indicated that pollen grains can be identified in appropriate conditions. WIBS-4 measurements of Yew pollen both in the laboratory and at the rural site indicated almost identical size ranges of 25 to 27 μm. Yew pollen is generally reported to be in this range, but the measurements reported here are the first of their type providing data on the size of in-flight Yew pollen.

Copyright 2014 American Association for Aerosol Research     

Laboratory Evaluation of a Microfluidic Electrochemical Sensor for Aerosol Oxidative Load

Human exposure to particulate matter (PM) air pollution is associated with human morbidity and mortality. The mechanisms by which PM impacts human health are unresolved, but evidence suggests that PM intake leads to cellular oxidative stress through the generation of reactive oxygen species (ROS). Therefore, reliable tools are needed for estimating the oxidant generating capacity, or oxidative load, of PM at high temporal resolution (minutes to hours). One of the most widely reported methods for assessing PM oxidative load is the dithiothreitol (DTT) assay. The traditional DTT assay utilizes filter-based PM collection in conjunction with chemical analysis to determine the oxidation rate of reduced DTT in solution with PM. However, the traditional DTT assay suffers from poor time resolution, loss of reactive species during sampling, and high limit of detection. Recently, a new DTT assay was developed that couples a particle-into-liquid-sampler with microfluidic-electrochemical detection. This “on-line” system allows high temporal resolution monitoring of PM reactivity with improved detection limits. This study reports on a laboratory comparison of the traditional and on-line DTT approaches. An urban dust sample was aerosolized in a laboratory test chamber at three atmospherically relevant concentrations. The on-line system gave a stronger correlation between DTT consumption rate and PM mass (R ² = 0.69) than the traditional method (R ² = 0.40) and increased precision at high temporal resolution, compared to the traditional method.

Copyright 2014 American Association for Aerosol Research     

Recent Advances in Flame Retardancy of Polymeric Materials (Materials,Applications, Industry Developments,Markets)

The Fifth Annual Conference on Flame Retardancy was held May 24–26, 1994, at the Ramada Plaza Hotel, Stamford, Connecticut, USA. The conference was organized by Business Communications Company, Inc., Norwalk, Connecticut (Company President, Mr. Louis Naturman; Conference Coordinator, Mrs. Sharon D. Faust). New materials (polymers, blends, composites), their applications, industry developments, and markets were considered. Specifically, the most important topics were:

Introduction of new technological achievements and development in the field of flame retardancy (FR)

Review of the current state of science and technology in FR

Review of applications and markets for FR products

Presentation of recent developments in local and global standardization and in testing technology

Discussion of toxicity and environmental issues

Provision of a unique opportunity for newcomers to FR research technology and marketing to become acquainted with the FR field in all its aspects

Discussion of halogen-based and non-halogen-based flame retardant chemicals, syngergism, intumescence, FR mechanisms, modeling, flame parameters, inherently FR polymers, and polymer blends     

Emission measurements with gravimetric impactors and electrical devices: An aerosol instrument comparison

Particulate matter in the atmosphere is known to affect Earth’s climate and to be harmful to human health. Accurately measuring particles from emission sources is important, as the results are used to inform policies and climate models. This study compares the results of two ELPI?+?devices, two PM10 cascade impactors and an eFilter, in combustion emission measurements. The comparison of the instruments in a realistic setting shows what types of challenges arise from measuring an emission aerosol with unknown particle morphologies and densities, different particle concentrations and high temperature. Our results show that the PM10 cascade impactors have very good intercorrelation when the collected mass is greater than 150?µg, but below that, the uncertainty of the results increases with decreasing mass. The raw signals of two ELPI?+?devices were nearly identical in most samples, as well as the particle number concentrations and size distributions calculated from raw signals; however, transforming the current distributions into mass distributions showed variation in the mass concentration of particles larger than 1?µm. The real-time time signal measured by eFilter was similar to the total current measured by ELPI+. The eFilter and PM10 cascade impactors showed similar particle mass concentrations, whereas ELPI?+?showed clearly higher ones in most cases. We concluded that the difference is at least partially due to volatile components being measured by ELPI+, but not by the mass collection measurements.

Copyright © 2019 American Association for Aerosol Research     

Intercomparison of a portable and two stationary mobility particle sizers for nanoscale aerosol measurements

During occupational exposure studies, the use of conventional scanning mobility particle sizers (SMPS) provides high quality data but may convey transport and application limitations. New instruments aiming to overcome these limitations are being currently developed. The purpose of the present study was to compare the performance of the novel portable NanoScan SMPS TSI 3910 with that of two stationary SMPS instruments and one ultrafine condensation particle counter (UCPC) in a controlled atmosphere and for different particle types and concentrations.

The results show that NanoScan tends to overestimate particle number concentrations with regard to the UCPC, particularly for agglomerated particles (ZnO, spark generated soot and diesel soot particles) with relative differences >20%. The best agreements between the internal reference values and measured number concentrations were obtained when measuring compact and spherical particles (NaCl and DEHS particles). With regard to particle diameter (modal size), results from NanoScan were comparable < [± 20%] to those measured by SMPSs for most of the aerosols measured.

The findings of this study show that mobility particle sizers using unipolar and bipolar charging may be affected differently by particle size, morphologies, particle composition and concentration. While the sizing accuracy of the NanoScan SMPS was mostly within ±25%, it may miscount total particle number concentration by more than 50% (especially for agglomerated particles), thus making it unsuitable for occupational exposure assessments where high degree of accuracy is required (e.g., in tier 3). However, can be a useful instrument to obtain an estimate of the aerosol size distribution in indoor and workplace air, e.g., in tier 2.     

Development of a volatility and polarity separator (VAPS) for volatility- and polarity-resolved organic aerosol measurement

Discrepancies between modeled and measured atmospheric organic aerosol (OA) have highlighted the need for in situ instrumentation to better characterize the sources, formation mechanisms, and atmospheric evolution of ambient OA. We have developed the Volatility and Polarity Separator (VAPS) for hourly measurements of volatility- and polarity-resolved OA detected using high-resolution time-of-flight mass spectrometry (HR-ToF-MS). Here, atmospheric OA is inertially impacted onto a collection cell, material is transferred onto a short transfer line located inside a gas chromatography (GC) oven, the oven is heated to provide a first-dimension separation of volatility, then thermally pulsed through a short polar GC column for a second-dimension polarity separation, and finally detected by HR-ToF-MS. This novel instrument increases the mass throughput of ambient OA in comparison to traditional GC due to shorter transfer paths and passivated coatings. Molecular separation resolution is partially sacrificed for this increased mass recovery, but the high-resolution mass spectral data recovers information such as chemical classes and even some individual compounds along with elemental composition to determine aerosol oxidation states. Different techniques for interpreting and representing VAPS data are considered and its applicability to positive matrix factorization (PMF) analysis is demonstrated.

Copyright © 2016 American Association for Aerosol Research     

Development of an aerosol mass spectrometer lens system for PM2.5

The aerodynamic lens system of the Aerodyne Aerosol Mass Spectrometer (AMS) was analyzed using the Aerodynamic Lens Calculator. Using this tool, key loss mechanisms were identified, and a new lens design that can extend the transmission of particulate matter up to 2.5 μm in diameter (PM2.5) was proposed. The new lens was fabricated and experimentally characterized. Test results indicate that this modification to the AMS lens can significantly improve the transmission of large sized particles, successfully achieving a high transmission efficiency up to PM2.5 range.

© 2016 American Association for Aerosol Research     

Cu-Sn binary metal particle generation by spray pyrolysis

Cu-Sn binary particles were generated via spray pyrolysis from metal salt precursors with ethylene glycol as the co-solvent and reducing agent. The morphology, crystallinity, and elemental distribution of particles were tunable by changing the reaction temperature, residence time, and quench gas flow rate. Hollow porous particles were fabricated with a higher Sn concentration on the particle surface when the furnace set point was 500°C, while solid particles with a lower surface Sn concentration were generated when the furnace set point was 1000°C. Particles with spherical morphologies were obtained at long residence time conditions (4.5 s). Cu-Sn binary particles with irregular structures (e.g., pores on the particle surface, fragmented spherical particles, and lamellar fragments) were formed at short residence time conditions (0.92 s). A possible spray pyrolysis mechanism was proposed that incorporates chemical reaction steps and structural progression. By this mechanism, the metal salts are believed to sequentially undergo hydrolysis to metal hydroxides, decomposition to metal oxides, reduction to metals, and finally diffusion of Sn into the Cu matrix to generate the Cu-Sn solid solution.

Copyright © 2017 American Association for Aerosol Research     

Modeling of nonstationary processes during separation of multicomponent isotope mixtures

The article presents a mathematical model for calculation of nonstationary hydraulic and separation processes in a gas centrifuge (GC) cascade for separation of multicomponent isotope mixtures. The model has been applied to calculate the parameters of nonstationary processes in a GC cascade for separation of krypton, germanium and tungsten isotopes. As a result, the specifics of the excess holdup distribution along the cascade stages has been identified, and variations of the isotope concentrations in a nonstationary process have been revealed. The data obtained show that the proposed mathematical model is able to adequately describe nonstationary hydraulic processes in GC cascades for separation of multicomponent isotope mixtures.

Highlights:

Mathematical model of cascade for separation of multicomponent isotope mixture has been developed.

The model verification has been done.

The isotope transient regularities into cascade during nonstationary processes has been identified.     

A New Laser Induced Incandescence–Mass Spectrometric Analyzer (LII-MS) for Online Measurement of Aerosol Composition Classified by Black Carbon Mixing State

We developed a laser induced incandescence–mass spectrometric analyzer (LII-MS) for online measurements quantifying the aerosol chemical compositions with respect to the mixing state of black carbon (BC). The LII-MS is developed as a tandem series comprising an LII chamber to detect and vaporize BC-containing particles and a particle trap laser desorption mass spectrometer (PT-LDMS: Takegawa et al. 2012). The PT-LDMS collects aerosol particles transferred from the LII chamber and quantifies the chemical compositions. A newly designed collection probe, coupled with the sheath-air inlet nozzle of the LII chamber, enables a high throughput of aerosol particles without significant dilution. Total aerosol particles can be analyzed in the PT-LDMS by turning off the laser (MS mode), and the aerosol particles externally mixed with BC can be analyzed by turning on the laser (LII-MS mode). The difference in the PT-LDMS signals between the MS and LII-MS modes yields the chemical composition of materials internally mixed with BC. Performance of the developed instrument was evaluated in the laboratory by generating BC particles internally-mixed with oleic acid (OL) and BC particles externally mixed with ammonium sulfate particles. Preliminary results from ambient measurements are also presented and discussed.

Copyright 2014 American Association for Aerosol Research     

An artifact-minimizing method for total dust sampling and chemical characterization of industrial high-temperature aerosols

Conventional methods for total dust sampling from industrial high-temperature aerosols containing condensable species, e.g., in boilers of municipal solid waste incinerators (MSWI), are always influenced by condensation artifacts. Therefore, we extended the scope of a previously developed probe intended for size-fractionated aerosol sampling with reduced artifacts and employed it for total dust measurements. The dust is collected on quartz fiber filters, which are gravimetrically evaluated and chemically analyzed by energy dispersive X-ray spectroscopy and wet-chemical methods. First measurements in the boiler of an MSWI confirm that the probe is also suitable for artifact-minimized total dust sampling. The data are consistent with results from measurements with the size-fractionating method conducted in parallel. By combining the results of both sampling methods, we reveal the average chemical composition of the submicron particles in the aerosol, which is not accessible by one of the two methods alone.

© 2017 American Association for Aerosol Research     

Using partial flow dilution to measure PM mass emissions from light-duty vehicles

Partial flow dilution (PFD) offers a number of benefits relative to conventional full flow dilution tunnels for motor vehicle PM emissions measurement in terms of measurement variability, footprint, and cost. Its implementation into automotive emissions test cells depends on its ability to record PM mass emissions equivalent to the current constant volume sampling (CVS) dilution tunnel approach. The present work examines factors critical to successful application of PFD sampling and compares vehicle PM emissions measured simultaneously by PFD and CVS tunnel. The combination of a current technology commercial PFD system and ultrasonic flow meter fulfill the two principal requirements of accurate exhaust flow measurement and fast time response for proportional sampling. PM mass emissions measured by PFD versus CVS systems satisfy a 1.03 ± 0.03 regression for the regulatory FTP test cycle, and comparably good agreement for the supplemental US06 drive cycle. Both dilution approaches are amenable to the single filter approach newly allowed under EPA regulations; however, the PFD sample weighted approach has the capability to provide a roughly 35% lower variability relative to the flow weighted approach used in the CVS method. Whereas partial flow dilution has seen application in heavy duty engine measurements, the present work demonstrates its feasibility for light duty chassis dynamometer testing.

Copyright © 2018 Ford Motor Company     

Biosorption of cadmium(II) and lead(II) from aqueous solutions using Pleurotus ostreatus immobilized on bentonite

The purpose of this work was to evaluate the potential of a white rot fungi (P. ostreatus) immobilized on bentonite, in a continuous flow removal of trace heavy metals. The procedure is based on the biosorption of Cd(II) and Pb(II) ions on a column of bentonite loaded with dried, dead fungi components prior to their determination by atomic absorption spectroscopy (AAS). Cd(II) and Pb(II) were determined with a relative error of less than 5%. Various parameters such as “pH, amount of adsorbent, eluent type and volume, flow rate of the solution and matrix interference effect” on the retention of the metal ions were investigated. This procedure was applied to Cd(II) and Pb(II) determination in aqueous solutions, including tap water system. The optimum experimental parameters were determined to be pH 5, concentration of 10 mg/L, contact time of 30 min and 0.2 g of adsorbent for a quantitative adsorption of the metals. The optimum flow rate was found to be 2.5 mL/min for all metal ions. Each column can be used up to 20 successive analyses without considerable change in recoveries of metal ions.

The proposed method is excellent as regards simplicity, sensitivity, selectivity, precision, accuracy and column stability.