How well can aerosol instruments measure particulate mass and solid particle number in engine exhaust?

Aerosol instruments provide more informative engine exhaust particulate matter (PM) data than the gravimetric filter and solid particle number methods prescribed by regulations. Yet their lack of conformity to the regulatory methods can limit their acceptance for vehicle development. This article examines the ability of the Dekati Mass Monitor (DMM), Engine Exhaust Particle Sizer (EEPS), and Micro Soot Sensor (MSS) to measure PM_2.5 mass and solid particle number relative to current motor vehicle PM emissions standards. Simultaneous PM measurements are made by these three instruments and the two regulatory methods for 50 tests of six gasoline direct injection and two port fuel injection vehicles over the U.S. Federal Test Procedure. DMM and EEPS determinations of PM mass correlate well to gravimetric values (regression slopes of 1.06 ± 0.04 and 0.98 ± 0.08) down to a few mg/mile, below which filter weighing variability becomes problematic. The MSS exhibits a lower slope of 0.79 ± 0.03 consistent with it measuring the soot fraction, rather than total PM. At emissions rates above ～10¹³ particles/mile, solid particle number determined from DMM and EEPS data correlates respectably with, but overestimates the regulatory method (regression slopes are 1.7 ± 0.1 and 1.4 ± 0.15, respectively). Below this emissions rate, the correlation degrades. EEPS estimates of PM mass are significantly improved with the recent soot optimized inversion algorithm (slope improves from 0.45 to 0.98). While they cannot replace filters and solid particle counting, the present study suggests that these instruments can be used as more informative surrogates during motor vehicle development.

© 2016 Ford Motor Company     

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     

Using a new inversion matrix for a fast-sizing spectrometer and a photo-acoustic instrument to determine suspended particulate mass over a transient cycle for light-duty vehicles

Integrated particle size distribution (IPSD) is a promising alternative method for estimating particulate matter (PM) emissions at low levels. However, a recent light-duty vehicle (LDV) emissions study showed that particle mass estimated using IPSD (M_IPSD) with the TSI Engine Exhaust Particle Sizer (EEPS) Default Matrix was 56–75% lower than mass derived using the reference gravimetric method (M_Grav) over the Federal Test Procedure (FTP). In this study, M_IPSD calculated with a new inversion matrix, the Soot Matrix, is compared with M_Grav and also photoacoustic soot mass (M_Soot), to evaluate potential improvement of the IPSD method for estimating PM mass emissions from LDVs. In addition, an aerodynamic particle sizer (APS) was used to estimate mass emission rates attributed to larger particles (0.54–2.5 µm in aerodynamic diameter) that are not measured by the EEPS. Based on testing of 10 light-duty vehicles over the FTP cycle, the Soot Matrix significantly improved agreement between M_IPSD and M_Grav by increasing slopes of M_IPSD/M_Grav from 0.45–0.57 to 0.76–1.01 for gasoline direct injected (GDI) vehicles; however, for port-fuel injection (PFI) gasoline vehicles, a significant discrepancy still existed between M_IPSD and M_Grav, with M_IPSD accounting for 34 ± 37% of M_Grav. For all vehicles, strong correlations between M_IPSD and M_Soot were obtained, indicating the IPSD method is capable of capturing mass of soot particles. The discrepancy between the M_IPSD and M_Grav for PFI vehicles, which have relatively low PM emissions (0.22 to 1.83 mg/mile), could be partially due to limited size range of the EEPS by not capturing larger particles (0.54–2.5 µm) that accounts for ～0.08 mg/mile of PM emission, uncertainties of particle effective density, and/or gas-phase adsorption onto filters that is not detected by in situ aerosol instrumentation.

Copyright © 2016 American Association for Aerosol Research     

Raman spectroscopy and TEM characterization of solid particulate matter emitted from soot generators and aircraft turbine engines

To obtain reliable mass concentrations of solid particulate matter (PM) in the exhaust emissions from engines using optical instruments, it is essential that the solid PM used for instrument calibration has similar optical properties to the solid PM emitted from the engines being tested. The solid PM emitted from combustion engines is predominantly soot. The optical properties of soot are dictated by its chemical structure, size, and morphology. In this work, the chemical bond structure, primary-particle diameters, aggregate sizes, and morphological parameters of the soot emitted from two laboratory soot generators, widely used for calibrating instruments, are compared to those of soot emitted from three aircraft turbine engines using Raman spectroscopy and transmission electron microscopy. The Raman spectral properties, size, and morphology of soot emitted from aircraft engines are distinctly different from the properties of soot emitted from the soot generators operating under globally near-stoichiometric and fuel-rich conditions. These differences can be attributed to the variations in the size and orientation of the graphitic crystallites, amorphous-carbon content, amount of polyacetylene compounds, deposition of organic material, and extent of oxidation. Conversely, general agreement is observed between the chemical structure, size, and morphology of soot emitted from aircraft engines and the soot emitted from the soot generators operating at globally fuel-lean conditions. The findings of this investigation can be useful for identifying suitable soot particles for the calibration of instruments to measure the mass concentration of solid PM emissions from engines, and for other types of soot.

Copyright © 2017 Crown Copyright     

Distinguishing fuel and lubricating oil combustion products in diesel engine exhaust particles

The main sources of particulate emissions from engines are fuel and lubricating oil. In this study, particles emitted by a medium speed diesel engine for locomotive use were characterized chemically by using a soot particle aerosol mass spectrometer (SP-AMS). Additionally, positive matrix factorization (PMF) was applied to the SP-AMS data for the separation of fuel from lubricating oil and/or oil additives in diesel engine emissions. The mass spectra of refractory species, i.e., metals and rBC, were included in the PMF input matrix in addition to organics in order to utilize the benefit of the SP-AMS to measure non-refractory and refractory species. In general, particulate matter emitted by the diesel engine was dominated by organics (51%) followed by refractory black carbon (rBC; 48%), trace metals and inorganic species (1%). Regarding the sources of particles, PMF indicated four factors for particle mass of which two were related to lubricating oil-like aerosol (LOA1, 29% and LOA2, 24%) and two others to diesel-like fuel aerosol (DFA1, 35% and DFA2, 12%). The main difference between LOA1 and LOA2 was the presence of soot in LOA1 and metals in LOA2 factors. DFA factors represented burned (DFA1) and unburned fuel (DFA2). The results from the PMF analysis were completed with particle size distributions, volatility measurements and particle morphology analyses.

Copyright © 2019 American Association for Aerosol Research     

Detailed Microphysical Modeling of the Formation of Organic and Sulfuric Acid Coatings on Aircraft Emitted Soot Particles in the Near Field

The development of a detailed microphysical model that describes the complex multicomponent interactions between organic vapors and soot particles emitted from aircraft gas turbine engines is presented. Our model formulation includes both soot surface activation by organic vapors and organic vapor condensation on the activated part of the soot surfaces. To enable this formulation, approaches to estimate chemical and physical properties of aerosols containing complex mixtures of sulfuric acid, water, and organic molecules were developed. Relevant distributions of a list of organic surrogates at the engine exit plane were used to represent complex organic emissions from aircraft engines. A parametric study was performed using this new formulation to understand the effects of ambient conditions, organic emissions levels, and mass accommodation coefficient values on the evolution of near field volatile particulate matter emissions from aircraft engines at ground level.

Copyright 2014 American Association for Aerosol Research     

Collection of soot particles into aqueous suspension using a particle-into-liquid sampler

Steam collection devices collecting aerosol particles into liquid samples are frequently used to analyze water-soluble particulate material. The fate of water-insoluble components is often neglected. In this work, we show that fresh soot particles can be suspended into pure water using a steam collection device, the particle-into-liquid sampler (PILS, Weber et?al. 2001). The overall collection efficiency of freshly generated soot particles was found to be on the order of 20%. This shows that, depending on the analytic technique employed, the presence of insoluble, and/or hydrophobic particles in liquid samples from steam collection cannot be neglected.

Copyright © 2018 The Author(s). Published with license by Taylor & Francis Group, LLC     

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     

Effect of ethanol addition in gasoline and gasoline–surrogate on soot formation in turbulent spray flames

The effect of ethanol on soot formation has been studied in turbulent spray flames of gasoline/ethanol and gasoline–surrogate/ethanol mixtures containing 10%, 20% and 30% of alcohol in volume. A hybrid burner specially designed to stabilize different liquid fuels flames with identical hydrodynamic conditions has been used. Spatially resolved measurements of soot volume fraction and of soot precursors concentration have been carried out by coupling Laser-Induced Incandescence (LII) at 1064 nm and Laser-Induced Fluorescence (LIF) at 532 nm. Significant reductions of the concentrations of soot and soot precursors have been observed when adding ethanol to gasoline. A similar behaviour has been obtained with a gasoline–surrogate which has been found to reproduce well the sooting propensity of the unleaded gasoline used in this work. The analysis of the correlation existing between the peak soot volume fraction measured in flames and the Threshold Soot Index (TSI) of the different mixtures tested in this work revealed that the effect of ethanol was not only a dilution one but that the oxygen contained in the alcohol also influence the soot formation. Finally, the comparison of the LII fluence curves and time decays obtained in gasoline/ethanol mixtures showed that soot particles oxidized faster when ethanol is added to the base fuel.     

Response of real-time black carbon mass instruments to mini-CAST soot

Soot is a climate forcer and a dangerous air pollutant that has been increasingly regulated. In aviation, regulatory measurements of soot mass concentration in the exhaust of aircraft turbine engines are to be based on measurements of black carbon (BC) calibrated to elemental carbon (EC) content of diffusion flame soot. The calibration soot must currently meet only one criterion: minimum EC to total carbon (TC) ratio of 0.8. However, not including soot properties other than the EC/TC ratio may potentially lead to discrepancies between different BC measurements. We studied the response of two instruments, the AVL Micro-Soot Sensor (MSS) and the Artium Laser-Induced Incandescence 300 (LII), to soot from two miniature combustion aerosol standard (mini-CAST) burners. By changing the air-fuel ratio, premixing nitrogen into the fuel, and using a catalytic stripper to remove volatile compounds, we produced a wide range of particle morphologies and EC contents. As the EC content decreased, both the instruments underreported the EC mass, but the LII diverged more severely. Upon closer investigation of eight conditions with EC/TC > 0.8, the LII underreporting was found independent of primary particle size, but increased with decreasing geometric mean diameter of the soot agglomerates. As the geometric mean diameter decreased from 160 nm to 50 nm, the differences between the LII and MSS increased from 15% to 50%. The results suggest that in addition to EC content, calibration procedures for the regulatory BC measurements may need to take particle size distributions into account.

© 2016 American Association for Aerosol Research     

The Impact of Ethanol Fuel Blends on PM Emissions from a Light-Duty GDI Vehicle

This study explores the influence of ethanol on particulate matter (PM) emissions from gasoline direct injection (GDI) vehicles, a technology introduced to improve fuel economy and lower CO₂ emissions, but facing challenges to meet next-generation emissions standards. Because PM formation in GDI engines is sensitive to a number of operating parameters, two engine calibrations are examined to gauge the robustness of the results. As the ethanol level in gasoline increases from 0% to 20%, there is possibly a small (<20%) benefit in PM mass and particle number emissions, but this is within test variability. When the ethanol content increases to >30%, there is a statistically significant 30%–45% reduction in PM mass and number emissions observed for both engine calibrations. Particle size is unaffected by ethanol level. PM composition is primarily elemental carbon; the organic fraction increases from ～5% for E0 to 15% for E45 fuel. Engine-out hydrocarbon and NO_x emissions exhibit 10–20% decreases, consistent with oxygenated fuel additives. These results are discussed in the context of the changing commercial fuel and engine technology landscapes.

Copyright 2012 American Association for Aerosol Research     

Conceptual model-based design and environmental evaluation of waste solvent technologies: Application to the separation of the mixture acetone-water

In this paper, two waste solvent technologies are presented as alternatives to the disposal of spent acetone-water mixtures.

In the first alternative, a batch rectifier is used to concentrate the waste in order to obtain a distillate with a higher calorific value, which is then sent to off-site incineration either in a cement kiln or in a conventional waste solvent incinerator. The second alternative is a hybrid process composed by a batch rectifier and a pervaporation unit that processes in batchwise mode the first cut from the distillation task to obtain a dehydrated solvent. Here, four scenarios are considered, comprising two kinds of membrane materials and two different vacuum systems.

For each alternative, the conceptual design was carried out with the aid of conceptual models of the unit operations involved. Quasi-optimal values for design and operation variables were used as input data to perform an economical and an environmental assessment of each alternative. The economic analysis suggests that the hybrid process is the best alternative given that the replacement cost of fresh solvent (about 850 U$S/ton) is considered as a credit value.

From the environmental analysis with life cycle assessment, two main conclusions can be drawn: i) the use of the distillate as an alternative fuel in a cement kiln leads to a reduction in emissions that is relevant for the categories related to human health and ecosystem quality; and ii) in terms of resource depletion, the hybrid process distillation/pervaporation with the ceramic membrane HybSi (Pervatech) shows the lowest impact due to the solvent recovery.     

Characterization of a new miniCAST with diffusion flame and premixed flame options: Generation of particles with high EC content in the size range 30 nm to 200 nm

Flame-generated soot from miniCAST burners is increasingly being used in academia and industry as engine exhaust soot surrogate for atmospheric studies and instrument calibration. Previous studies have found that elemental carbon (EC) content of miniCAST soot is proportional to the mean particle size. Here, the characterization of a prototype miniCAST generator (5201 Type BC), which was designed to decouple the soot composition from the particle size and produce soot particles with high EC and BC content in a large size range, is reported. This prototype may operate either in a diffusion-flame or a partially premixed-flame mode, an option that was not available in former models. It was confirmed that soot properties, such as EC content and Ångström absorption exponent (AAE), were linked to the overall flame composition. In particular, combustion under fuel-rich conditions provided particles with size coupled to the EC fraction and AAE, i.e. smaller particles exhibited a lower EC fraction and higher AAE. In contrast, with fuel-lean diffusion flames and especially with premixed flames under near overall stoichiometric conditions small particles (down to 30?nm) with high EC/TC ratios (>60%) and low AAE (≈1.4) could be generated even without any thermal after-treatment. This new source might thus serve in the future as a useful surrogate for engine exhaust emissions and help to improve calibration procedures of common aerosol instruments.

Copyright © 2018 The Author(s). Published with license by Taylor & Francis Group, LLC     

Effect of potassium on a model soot combustion: Raman and HRTEM evidences

The effect of potassium on the oxidation of a model carbonaceous material (Printex U, namely, soot for brevity) has been investigated under isothermal conditions. For this purpose, Raman spectroscopy, Transmission Electron Microscopy (TEM), and Brunaure, Emmet, Teller surface area characterization have been applied to investigate structural changes occurring during soot oxidation both in the presence and in the absence of potassium. The Raman spectra of the model soot during combustion showed that oxidation preferentially involves the amorphous carbon fraction of the soot and only subsequently it affects the more ordered sp² domains. However, in the K-doped Printex U the oxidation of both the amorphous and more ordered sp² structures occurs concurrently. These findings have been confirmed by TEM analysis and explain the observed higher combustion activity of K-containing sample.

Copyright © 2016 American Association for Aerosol Research     

Cloud condensation nuclei from the activation with ozone of soot particles sampled from a kerosene diffusion flame

Due to the exponential increase in aircraft traffic in recent decades, the role of soot particles emitted by aircraft engines on the radiative forcing needs to be addressed, and especially their interaction with clouds has to be better understood and quantified. In this work, we investigate the hygroscopic properties of fresh and aged soot sampled on line in a kerosene flame. The activated fraction (F_a) of size selected soot is measured by means of a variable supersaturation condensation nucleus counter at several heights above the burner (HAB), thereby probing soot particles with different residence times in the flame, i.e., different degrees of maturity. In order to simulate atmospheric aging, the activity of soot as cloud condensation nuclei is measured as a function of ozone exposure. We show that fresh soot is hydrophobic (F_a～0), while F_a increases when soot is exposed to ozone. The measurements depend on the HAB at which soot particles are sampled showing that activation of soot particles is related to their chemical composition. This study brings new results on the link between atmospheric aging of soot and its hygroscopic properties, which is of great interest for understanding the role of soot in the cloud formation.

Copyright © 2018 American Association for Aerosol Research     

Economics of Treating Waste Gases from an Air Stripping Tower Using Photochemically Generated Ozone

Air stripping towers have been recommended for the removal of volatile organic compounds (VOCs) in drinking water supply and industrial waste treatment systems. This technique removes VOCs economically in the liquid phase. It can, however, create adverse secondary environmental impacts by removing VOCs from the water and discharging them to the air.

A commonly proposed method for controlling .VOC emissions is filtration of the off-gas through adsorption of the stripped organics in the off-gas by granular activated carbon. The high incremental cost of this alternative has produced an interest in alternative control technologies.

One alternative currently available is based on short wavelength ultraviolet (UV) radiation. This technique combines the effects of ozone generation, free radical formation and photolysis of the contaminants to effectively control the VOC emissions. This technique is known as Advanced Photo Oxidation (APO)^R.

The cost for APO is $0.27/m³ for a 3.8 m³/hr contaminated water system. A system of this size is adequate for a groundwater decontamination project where a moderate length of time is available for restoration of the site. The cost of a conventional air stripping tower with Granular Activated Carbon (GAC) adsorption emissions control in this size range would be $0.40 to $0.45/m³ (J.M. Montgomery, 1986).

Additional testing will be required to fully develop design guidelines for different contaminants and larger systems. Another area for additional technical documentation is the application of this technique to the liquid phase oxidation of VOCs.     

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     

Filtration efficiency analysis of fibrous filters: Experimental and theoretical study on the sampling of agglomerate particles emitted from a GDI engine

Fibrous filters are commonly used for aerosol purification and sampling. The filtration efficiency has been extensively studied using standard aerosol generators, yet the literature on experimental data and theoretical study concerning the filtration of agglomerates from real engines remains scarce. A filtration efficiency test system was developed to determine the filtration efficiency of two types of filters (uncoated and fluorocarbon coated) loaded by particulate matter (PM) emissions from a gasoline direct injection (GDI) engine. The experimental results showed that the filtration efficiency in terms of PM mass and number increased over time for both types of filters. The fractional efficiency (penetration efficiency) curves for the test fibrous filters rendered a U-shaped curve for particle sizes from 70 to 500 nm, and the most penetrating particulate size (MPPS) decreased over time. A small fraction of accumulation mode particles with the size between 70 nm to 500 nm penetrated the filters while almost all nucleation mode particles with the size below 50 nm were captured by the filters. The filtration efficiency derived from an empirical model based on classical single-fiber theory for laden filters generally agreed with the experimental data for the first 500 s, but suffered a significant deviation by approximately one order of magnitude at 948 s. A better estimate of the filtration efficiency trend with the maximum deviation of about 20% (except for large particles at the high end of the measurement spectra) was obtained by using a revised model which incorporates the effects of the increase in filter solidity, local velocity, dynamic shape factor and effective total length of fibers during the filtration process.

© 2017 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.