Planning A State-Wide Air Pollution Advisory Service

An investigation of high volume particle sampling and sample handling procedures was undertaken to evaluate variations of protocols being used by the U.S. Environmental Protection Agency. These protocols are used in urban ambient air studies which collect ambient and source samples for subsequent mutagenicity analysis of the organic extracts of the aerosol fraction. Specific protocol issues investigated include: (a) duration of sampling period, (b) type of filter media used to collect air particles, (c) necessity for cryogenic field site storage and dry ice shipping of filter samples, and (d) sample handling at the receiving laboratory. Six PM₁₀ Hi-Vol samplers were collocated at an urban site in downtown Durham, North Carolina and operated simultaneously to evaluate 12 h versus 24 h collection periods and filter media choices of glass fiber, Teflon® impregnated glass fiber (TIGF), and quartz fiber. Filters from the samplers plus field blanks were collected during each of 25 sampling periods. TIGF filters from two samplers were immediately placed on dry ice in the field and transported directly to cryogenic storage. TIGF, quartz, and glass fiber filters from three samplers were transported at ambient and maintained at room temperature for three to six days prior to cryogenic storage. One TIGF sample, which was collected on a previously tared filter, was subjected to controlled environment equilibration (40 percent relative humidity, 22°C) for 8 to 24 h and weighed prior to cryogenic storage. All filters were subsequently stored at ?70°C to ?80°C prior to a one-time extraction and Salmonella (Ames) mutagenicity bioassay of the entire sample set. Results indicate that the sample handling variations and collection period variables had no significant effect on recovery of organics or mutagens. However, a filter type difference was observed. The sonication extraction of organics and mutagens was significantly greater for TIGF filters than for glass fiber or quartz. Results from a second phase of study indicated differences in extracted organics and mutagens for these filter types.     

Evaluation of high volume particle sampling and sample handling protocols for ambient urban air mutagenicity determinations.

An investigation of high volume particle sampling and sample handling procedures was undertaken to evaluate variations of protocols being used by the U.S. Environmental Protection Agency. These protocols are used in urban ambient air studies which collect ambient and source samples for subsequent mutagenicity analysis of the organic extracts of the aerosol fraction. Specific protocol issues investigated include: (a) duration of sampling period, (b) type of filter media used to collect air particles, (c) necessity for cryogenic field site storage and dry ice shipping of filter samples, and (d) sample handling at the receiving laboratory. Six PM10 Hi-Vol samplers were collocated at an urban site in downtown Durham, North Carolina and operated simultaneously to evaluate 12 h versus 24 h collection periods and filter media choices of glass fiber, Teflon impregnated glass fiber (TIGF), and quartz fiber. Filters from the samplers plus field blanks were collected during each of 25 sampling periods. TIGF filters from two samplers were immediately placed on dry ice in the field and transported directly to cryogenic storage. TIGF, quartz, and glass fiber filters from three samplers were transported at ambient and maintained at room temperature for three to six days prior to cryogenic storage. One TIGF sample, which was collected on a previously tared filter, was subjected to controlled environment equilibration (40 percent relative humidity, 22 degrees C) for 8 to 24 h and weighed prior to cryogenic storage. All filters were subsequently stored at -70 degrees C to -80 degrees C prior to a one-time extraction and Salmonella (Ames) mutagenicity bioassay of the entire sample set.(ABSTRACT TRUNCATED AT 250 WORDS)     

Characterisation of fresh particulate vehicular exhausts near a Paris high flow road

Simultaneous continuous measurements of PM_2.5, PM₁₀, black carbon mass (BCae), Black smoke (BS) and particle number density (N) were conducted in the close vicinity of a high traffic road around Paris during a three-month period beginning in August 1997. In parallel some aerosol collection was performed on filters in order to assess the black carbon (BC), organic carbon (OC) and water soluble organic fractions (WSOC) of the freshly emitted traffic aerosols. The high hourly concentrations of PM_2.5 (39±20 μg m⁻³), BCae (14±7 μg m⁻³), and N (220,000±115,000 cm⁻³), were found to be well correlated with each other. On average PM_2.5 represented 66±13% of PM₁₀ and appears to be composed primarily of BC (43±20%). On the contrary no correlation was found between PM_2.5 and the coarse (PM₁₀–PM_2.5) mass fractions which was attributed to resuspension processes by vehicles. Black carbon mass concentrations obtained from both filter analyses (BC) and Aethalometre data (BCae) show a good agreement suggesting that the Aethalometre calibration based on a black carbon specific attenuation coefficient (σ) of 19 m² g⁻¹ is well adapted to nearby roadside measurements. Daily BC (used as a surrogate for fine particles) concentrations and wind speed were found to be anti-correlated. Average daily variations of BC could be related to traffic intensity and regime as well as to the boundary layer height. As expected for freshly emitted traffic aerosols, filter analyses indicated a high BC/TC ratio (29±5%) and a low mean WSOC/OC ratio (12.5±5%) for the bulk aerosol. For these two ratios no day/night differences were observed, the sampling station being probably too close to traffic to evidence photochemical modification of the aerosol phase. Finally, a linear relationship was found between BC and BS hourly concentrations (BC=0.10×BS+1.18; r²=0.93) which offers interesting perspectives to retrieve BC concentrations from existing BS archives.     

The Magnitude of Bias in the Measurement of PM25 Arising from Volatilization of Particulate Nitrate from Teflon Filters

ABSTRACT

Because the Federal Reference Method for PM₂₅ specifies the collection of ambient particles on Teflon filters, we have examined the loss of a known volatile species, particulate nitrate, during sampling. Data are presented from two studies in southern California for which parallel samples were collected by different methods. Differences in collected nitrate are modeled using an evaporation model based on the work of Zhang and McMurry. The average nitrate obtained from sampling with Teflon filters was 28% lower on average than that measured by denuded nylon filters. In contrast, cascade impactor samples were within 5% of the denuded nylon filter on average. A simple model is presented that accounts for the particulate nitrate loss from Teflon filters either by scavenging nitric acid and ammonia in the sampler inlet or by heating the filter substrate during sampling. The observed magnitude of loss is explained by any of the following situations: (1) 100% nitric acid and ammonia vapor loss in the inlet, (2) 5 °C heating of the filter substrate above ambient temperature during sampling, or (3) a combination of these factors, such as 50% vapor loss in the inlet and 3 °C heating of the filter.     

Quantification of elemental and total carbon in combustion particulate matter using thermal-oxidative analysis

The use of a two-step thermal-oxidative analysis (TOA) technique for quantification of the mass of total carbon (TC) and elemental carbon (EC) of turbine engine-borne particulate matter (PM) has been evaluated. This approach could be used in lieu of analysis methods which were developed to characterize diluted PM. This effort is of particular interest as turbine engine PM emissions typically have a higher EC content than ambient aerosols, and filter sample mass loadings can be significantly greater than recommended for existing analysis techniques. Analyses were performed under a pure oxygen environment using a two-step temperature profile; reference carbon and actual PM samples were used to identify appropriate analysis conditions. Thermal gravimetric analysis (TGA) methods were used to provide guidance on the nature of the carbon in several of the materials. This was necessary as a standard reference material does not exist for determination of the EC fraction in PM. The TGA also assisted in identifying an appropriate temperature range for the first-stage of the TOA method. Quantification of TC and EC for turbine engine PM samples using TOA was compared to results obtained using the NIOSH 5040 thermal-optical method. For first-stage TOA temperatures of 350°C and 400°C, excellent agreement between the techniques was observed in both the quantified TC and EC, supporting the viability for using TOA for analysis of turbine engine PM samples. A primary benefit of using TOA for these types of PM samples is that filters with relatively high PM mass loadings (sampled at the emission source) can be readily analyzed. In addition, an entire filter sample can be evaluated, as compared to the use of a filter punch sample for the NIOSH technique. While the feasibility of using a TOA method for engine PM samples has been demonstrated, future studies to estimate potential OC charring and oxidation of EC-type material may provide additional data to assess its impact on the OC/EC fractions for other carbon-type measurements.

Implications: This work presents results and procedures of an analytical method for the determination of total and elemental carbon, i.e., TC and EC present in combustion source particulate matter samples. In general, it is shown that the LECO TOA methodology is as reliable and comprehensive as NIOSH 5040 for determining TC and EC carbon types in particulate matter present in turbine emission sources, and should be considered as an alternative. Principles of the methodology, differences, and corresponding agreement with the standard NIOSH 5040 method and TGA analysis are discussed.     

Variability of total ozone over India and its adjoining regions during 1997–2008

Total Ozone Concentration (TOC) data over nineteen stations around India (fifteen stations) and its adjoining regions (three stations in Pakistan and one station in Bangladesh) are investigated in the present analysis. The overpass satellite data for these nineteen stations, distributed in the latitude range from 8.48°N to 35.83°N and altitude range from 6 m to 2718 m are available from FTP Site. TOC data pertaining to the last twelve years from 1997 to 2008 were obtained from two different instruments: Total Ozone Mapping Spectrometer (TOMS) and Ozone Monitoring Instrument (OMI) on Earth Probe and AURA satellites respectively. The analysis is divided into two phases, each of six years duration; from 1997 to 2002 and from 2003 to 2008. Seasonal average values of TOC are calculated for the two phases and compared to study the spatial distribution (latitude, longitude and station altitude) and the trends of TOC variation. In general a decreasing tendency in ozone concentration was found everywhere. The average yearly rate of the TOC decrease was ?0.363 DU over the entire region during the period 1997–2008. The trends in the TOC distribution and its decrease with latitude were found parabolic, with a deep near 14.7°N and 12.1°N for the two phases respectively. The decrease was maximum at lower latitude (?1.87%) and minimum (?0.25%) at higher latitude. Weak oscillatory trends in the TOC distribution and its decrease with longitude were found. A deep in the longitudinal variation was observed in each phase, at 77.4°E during 1997–2002 and at 78.2°E during 2003–2008. The minimum centre of the ozone distribution is therefore shifted from 14.7°N, 77.4°E to 12.1°N, 78.2°E over the last twelve years, and in general a meridional line near 78°E appears to divide symmetrically the TOC distribution over this region. Strong oscillatory trends in the seasonal average of TOC distribution and its decrease with station altitude are observed during the two phases. The inversion of high correlation coefficients between the seasonal average TOC and station altitude in the range 6 m to 2718 m indicate the existence of four transition layers aloft, near 200, 740, 1670, and 2400 m in the lower troposphere. Emission of precursor pollutants together with complex wind pattern around the marine boundary appears to have strong potentials to modulate tropospheric ozone and the observed spatial distribution of TOC may be expected.     

Study on dissolved organic carbon in precipitation in Northern China

Dissolved organic carbon (DOC) was measured in 483 precipitation samples collected at 10 sites in Northern China from December 2007 to November 2008. The annual volume-weighted mean (VWM) concentrations and wet deposition fluxes of DOC for 10 sites ranged from 2.4 to 3.9 mg C/L and 1.4 to 2.7 g C m^?2 yr^?1, respectively. The proportion of DOC to total organic carbon (TOC) was 79% on average, suggesting that a significant fraction of TOC was present as insoluble particulate organic carbon. Due to intensive domestic coal use for house heating and smaller dilution of scavenged organic carbon, higher VWM concentrations of DOC were observed during winter and spring than during summer and autumn. When precipitation events were classified via air mass back-trajectories, the mixed trajectories from SE and NW always corresponded to significantly higher DOC than those from SE or NW alone, coinciding with the centre of a low pressure system moved eastward and the wind direction changed from southeast to northwest. The results also showed that each site had a similar seasonal variation for DOC wet deposition flux. The largest flux occurred during the rainy season, and the lowest flux appeared during winter months. The product of the TC/DOC ratio and the DOC flux yielded an average TC wet deposition flux of 3.2 g C m^?2 yr^?1 in Northern China, accounting for 8.6% and 22% of the carbon sink magnitude (37 g C m^?2 yr^?1) in terrestrial ecosystems and anthropogenic carbon emissions (14 g C m^?2 yr^?1), respectively. This indicates that atmospheric wet deposition of TC is a significant carbon flux that cannot be neglected in regional models of the carbon cycle, and should be considered along with dry deposition in the removal mechanism for carbon from regional atmosphere.     

Characterisation and source apportionment of fine particulate sources at Hanoi from 2001 to 2008

PM_2.5 particulate matter has been collected on Teflon filters every Sunday and Wednesday at Hanoi, Vietnam for nearly eight years from April 2001 to December 2008. These filters have been analysed for over 21 different chemical species from hydrogen to lead by ion beam analysis techniques. This is the first long term PM_2.5 dataset for this region. The average PM_2.5 mass for the study period was (54 ± 33) μg m^?3, well above the current US EPA health goal of 15 μg m^?3. The average PM_2.5 composition was found to be (29 ± 8)% ammonium sulfate, (8.9 ± 3.3)% soil, (28 ± 11)% organic matter, (0.6 ± 1.4)% salt and (9.2 ± 2.8)% black carbon. The remaining missing mass (25%) was mainly nitrates and absorbed water. Positive matrix factorisation techniques identified the major source contributions to the fine mass as automobiles and transport (40 ± 10)%, windblown soil (3.4 ± 2)%, secondary sulfates (7.8 ± 10)%, smoke from biomass burning (13 ± 6)%, ferrous and cement industries (19 ± 8)%, and coal combustion (17 ± 7)% during the 8 year study period.     

Sewage-exposed marine invertebrates: survival rates and microbiological accumulation

A large number of bacteria, including agents responsible for diseases, characterise sewage-polluted seawaters. Apart from standards for bathing waters and bivalve aquaculture waters, there are no general microbiological standards applicable to seawaters to help decide if bacterial pollution is within acceptable ranges. This study represents an attempt towards the issue of comparing the susceptibility of different marine invertebrates subjected to polluted seawater with a high microbial contamination. We explored the survival rates and the microbiological accumulation of mollusc bivalves, echinoderms and crustaceans species exposed to sewage-polluted seawaters. Microbiological analyses were performed on the polluted seawater and on the homogenates of exposed and unexposed specimens. Culturable bacteria (22 °C and 37 °C) and microbial pollution indicators (total coliforms, Escherichia coli and intestinal enterococci) were measured. When exposed to the sewage-polluted seawater, the examined invertebrates showed different survival rates. In the filter feeders, bacterial densities at 22 °C and 37 °C rose after 96 h of exposure to sewage. The highest concentrations of total coliforms and intestinal enterococci were found in exposed bivalve Mytilus galloprovincialis. The concentrations of bacteria growing at 37 °C were lower in the exposed deposit feeders compared to the polluted seawater. Some yeasts were absent in several exposed species although these yeasts were present in the polluted seawater. Our data suggest that the examined filter feeders, given their capability to survive and accumulate bacteria, may counteract the effects of sewage and restore seawater quality.     

The Recovery of Selenious Acid Aerosols on Glass Fiber Filters

Previous workers have shown that selenium is only partially trapped on a filter during air sampling. In some cases, these losses have been attributed to volatilization of selenium dioxide. Our results demonstrate that selenium dioxide, In the presence of moist air, is completely recovered (apparently as selenious acid aerosols) and that the previous shortfalls must be due to other selenium species as yet unidentified. Selenious acid aerosols In our study were formed by volatilizing selenium dioxide (≈3 mg) Into a stream of moist ambient air (relative humidity, >50%), and trapped on glass fiber filters using a high-volume air sampler. Selenium(IV) was ultrasonlcally extracted from the filter with water and analyzed by atomic absorption spectrometry. Selenious acid aerosols were trapped on the filters with high efficiency (105 ± 5 percent) using a 50 minute sampling period. With an extended sampling period (24 hours) the recovery was 103 ± 6 percent.     

Time-integrated sampling of glyphosate in natural waters

Environmental monitoring of pesticide residues in surface water is often done with time-integrated sampling where a specified volume is sampled each hour during, e.g., a week, thus avoiding at momentary high or low extreme concentrations. However, sampling over an extended period of time can result in losses of easily degradable analytes, why the stability of the target analytes over the timespan of the sampling must be checked. Glyphosate is one of the most widely used herbicides. Because of its chemical complexity, glyphosate binds differently to metals and colloids at different pH, and the degradation may also be affected. Recovery of glyphosate from spiked natural waters after 1 and 3 weeks of storage was higher when the samples were acidified to approximately pH 2 rather than at their natural pH. Keeping the samples refrigerated to 4 °C in darkness also enhanced recovery, while glyphosate losses were substantial from samples kept at their natural pH at 20 °C. Total loss of glyphosate was observed in some samples kept at natural pH, 20 °C, and daylight; a loss partly due to binding to metals or colloids that could only partially be reversed by acidification. For 1-week time-integrated sampling a small amount of hydrochloric acid in a piece of heat-sealed hydrophobic micro-porous tubing is added to the sampling bottles before deployment, a procedure that acidifies the samples during collection keeping them below pH 2 until analysis, thus minimising losses of glyphosate. The method also allows determination of the primary degradation product aminomethylphosphonic acid (AMPA).     

Intercomparison of two different thermal-optical elemental carbons and optical black carbon during ABC-EAREX2005

A formal intercomparison of fine particle elemental (black) carbon is conducted involving three real-time semi-continuous measurement systems. Two-hourly interval time-resolved measurements of organic carbon (OC) and elemental carbon (EC) were performed at the Gosan site, Korea during Atmospheric Brown Clouds–East Asian Regional Experiment 2005 (ABC-EAREX2005) campaign. They were operated by the same semi-continuous field carbon instruments of Sunset Laboratory (thermal optical transmittance) in PM_2.5 particulate. However, their thermal protocols (four and two steps for OC and five and two steps for EC) were different. The co-located 1 min black carbon (BC) concentrations were compared by an Aethalometer for an intercomparison study.As a result, the poor R² of OC between two different temperature protocols suggested that OC can be significantly more biased by the slight differences of maximum temperature (870 and 840 °C) and a number of temperature steps (four steps and two steps) with their hold times. However, EC that is a smaller fraction of total carbon (TC) shows the good agreement between two different protocols, which are under a mixture of 2% O₂ and 98% He in six temperature steps and two temperature steps as max as 900 and 880 °C with the slope of 1.05±0.15 (R² of 0.98). The different slopes between EC and BC, which show the range of 1.23–1.61, demonstrate the variability of the attenuation coefficient of the BC particulate.     

Photooxidation of methylhydroperoxide and ethylhydroperoxide in the aqueous phase under simulated cloud droplet conditions

The photooxidation of methylhydroperoxide (MHP) and ethylhydroperoxide (EHP) was studied in the aqueous phase under simulated cloud droplet conditions. The kinetics and the reaction products of direct photolysis and OH-oxidation were studied for both compounds. The photolysis frequencies obtained were J_MHP=4.5 (±1.0)×10⁻⁵ s⁻¹ and J_EHP=3.8 (±1.0)×10⁻⁵ s⁻¹ for MHP and EHP respectively at 6 °C. The rate constants of OH-oxidation of MHP at 6 °C were 6.3 (±2.6)×10⁸ M⁻¹ s⁻¹ and 5.8 (±1.9)×10⁸ M⁻¹ s⁻¹ relative to ethanol and 2-propanol respectively, and the rate constant of OH-oxidation of EHP was 2.1 (±0.6)×10⁹ M⁻¹ s⁻¹ relative to 2-propanol at 6 °C. The reaction products obtained were not only the corresponding aldehydes, but also the corresponding acids, and hydroxyhydroperoxides as primary reaction products. The yields for these products were sensitive to the pH value. The carbon balance was higher than 85% for all experiments, showing that most reaction products were detected. A chemical mechanism was proposed for each reaction, and the atmospheric implications were discussed.     

Influence of storage and release on particle emissions from new and used CRTs

This paper describes the results of three experiments performed with Continuously Regenerating Traps (CRTs^®) in a controlled laboratory setting to elucidate the effects of fuel sulfur content, filter age, and storage and release effects on particle concentration. In the first experiment, a new CRT was tested using near zero sulfur Fischer-Tropsch fuel and low sulfur lubricating oil (420 ppm). The objective was to measure particle emissions from an emission control device that had not previously been exposed to sulfur under a variety of operating and dilution conditions. Next, a used CRT was evaluated using the same fuel and lubricating oil. Finally, the used uncatalyzed Diesel particulate filter (DPF) from the used CRT was replaced with a new, uncatalyzed DPF. The emissions from the used Diesel oxidation catalyst (DOC) + new DPF were evaluated and compared to those of the used CRT.Our laboratory results show that particle number emissions from the new CRTs are 99.9% lower than equivalent used CRT data collected on-road at an exhaust temperature of 370 °C. Even as the new CRT temperature was increased to almost 400 °C, emission levels were still at background levels for roadway aerosol and no nucleation mode was observed. With the used CRT, the nucleation mode particle number concentration increased sharply at an exhaust temperature of about 380 °C and remained high for the duration of the test. Mass emissions were estimated and found to exceed US EPA on-road standards. The used DOC + new DPF led to essentially the same number emissions as the used CRT, suggesting that these emissions arise mainly from release of sulfates stored by the DOC and not the uncatalyzed DPF.     

Transformation of diesel engine exhaust in an environmental chamber

Overnight aging experiments with diesel engine exhaust from a diesel power aggregate, with no or 9 kW load, and from a diesel-fueled vehicle were conducted in an environmental chamber. During a 24 h aging period the volatilities of monodisperse particles at 140, 250 and 360 °C heater temperatures were analyzed with volatility tandem differential mobility analysis (VTDMA). The particulate organic to total carbon ratio and organic carbon subfractions at 120, 250, 450 and 550 °C were analyzed with thermal-optical carbon analysis for samples from fresh, 8 or 18 h aged and 24 h aged aerosol. During the experiment also the particle size distribution, ozone and nitrogen oxide concentration, and temperature, relative humidity and total solar and total ultraviolet radiation in the chamber were monitored.After injection, the geometric mean diameter and number concentration of the particles in the chamber were 66–85 nm and 0.9–4.6×10⁵ cm⁻³, respectively. The particles were seen to grow fast, at a growth rate of 18–47 nm h⁻¹ during the first hour. The fresh particles from the diesel power aggregate contained 37–45% of apparent volume semi-volatile compounds with no load and 10–24% with 9 kW load. The semi-volatile apparent volume fraction at 360 °C for 50 nm particles produced by the diesel power aggregate was 57%. After 24 h of aging, the semi-volatile apparent volume fraction at 360 °C for 100 nm particles was 99%. This suggests that the particles in the 24 h aged aerosol at this size class are no more primary particles but particles that are formed in the chamber through nucleation and subsequent growth.     

Elemental and organic carbon in urban canyon and background environments in Budapest,Hungary

As part of an international research project, aerosol samples were collected by several filter-based devices on Nuclepore polycarbonate membrane, Teflon membrane and quartz fibre filters over separate daylight periods and nights, and on-line aerosol measurements were performed by TEOM and aethalometer within an urban canyon (kerbside) and at a near-city background site in Budapest, Hungary from 23 April–5 May 2002. Aerosol masses in PM2.0, PM10–2.0, PM2.5, PM10 size fractions and of TSP were determined gravimetrically; atmospheric concentrations of organic (OC) and elemental carbon (EC) for PM2.5 (or PM2.0), PM10 fractions and for TSP were measured by thermal–optical transmission method. Repeatability of the mass determination by Nuclepore filters seems to be 5–6%. Collections on Teflon filters yielded smaller mass on average by 8(±12)% than that for the Nuclepore filters. Quartz filters overestimated the PM10 mass in comparison with the Nuclepore filters due primarily to sampling artefacts on average by 10(±16)% at the kerbside. Tandem filter set-ups were utilised for correcting the sampling artefacts for OC by subtraction method. At the kerbside, the aerosol mass was made up on average of 35(±4)% of organic matter (OM) in the PM10 fraction, while the contribution of OM to the PM2.5 mass was 43(±9)%. At the background, OM also accounted for 43(±13)% of the PM2.0 mass. On average, EC made up 14(±6)%, 7(±2)% and 4.5(±1.1)% of the mass in the PM2.5, PM10 fractions and TSP, respectively, at the kerbside; while its contribution was only 2.1(±0.5)% in the PM2.0 fraction in the near-city background. Temporal variability for PM mass, OC and EC concentrations was related to road traffic, local meteorology and long-range transport of air masses. It was concluded that a direct coupling between the atmospheric concentration levels and vehicle circulation can be identified within the urban canyon, nevertheless, the local meteorology in particular and long-range transport of air masses have much more influence on the air quality than changes in the source intensity of road traffic. Concentration ratios of OC/EC were evaluated, and the amount of secondary organic aerosol (SOA) was estimated by using EC as tracer for the primary OC emissions. Mean contribution and standard deviation of the SOA to the OM in the PM2.5 size fraction at the kerbside over daylight periods and nights were of 37(±18) and 46(±16)%, respectively.     

Chemical speciation of PM emissions from heavy-duty diesel vehicles equipped with diesel particulate filter (DPF) and selective catalytic reduction (SCR) retrofits

Four heavy-duty diesel vehicles (HDDVs) in six retrofitted configurations (CRT^®, V-SCRT^®, Z-SCRT^®, Horizon, DPX and CCRT^®) and a baseline vehicle operating without after--treatment were tested under cruise (50 mph), transient UDDS and idle driving modes. As a continuation of the work by Biswas et al. [Biswas, S., Hu, S., Verma, V., Herner, J., Robertson, W.J., Ayala, A., Sioutas, C., 2008. Physical properties of particulate matter (PM) from late model heavy-duty diesel vehicles operating with advanced emission control technologies. Atmospheric Environment 42, 5622–5634.] on particle physical parameters, this paper focuses on PM chemical characteristics (Total carbon [TC], Elemental carbon [EC], Organic Carbon [OC], ions and water-soluble organic carbon [WSOC]) for cruise and UDDS cycles only. Size-resolved PM collected by MOUDI–Nano-MOUDI was analyzed for TC, EC and OC and ions (such as sulfate, nitrate, ammonium, potassium, sodium and phosphate), while Teflon coated glass fiber filters from a high volume sampler were extracted to determine WSOC. The introduction of retrofits reduced PM mass emissions over 90% in cruise and 95% in UDDS. Similarly, significant reductions in the emission of major chemical constituents (TC, OC and EC) were achieved. Sulfate dominated PM composition in vehicle configurations (V-SCRT^®-UDDS, Z-SCRT^®-Cruise, CRT^® and DPX) with considerable nucleation mode and TC was predominant for configurations with less (Z-SCRT^®-UDDS) or insignificant (CCRT^®, Horizon) nucleation. The transient operation increases EC emissions, consistent with its higher accumulation PM mode content. In general, solubility of organic carbon is higher (average ～5 times) for retrofitted vehicles than the baseline vehicle. The retrofitted vehicles with catalyzed filters (DPX, CCRT^®) had decreased OC solubility (WSOC/OC: 8–25%) unlike those with uncatalyzed filters (SCRT^®s, Horizon; WSOC/OC ～ 60–100%). Ammonium was present predominantly in the nucleation mode, indicating that ternary nucleation may be the responsible mechanism for formation of these particles.     

Measurement of organic mass to organic carbon ratio in ambient aerosol samples using a gravimetric technique in combination with chemical analysis

Organic materials make up a significant fraction of ambient particulate mass. It is important to quantify their contributions to the total aerosol mass for the identification of aerosol sources and subsequently formulating effective control measures. The organic carbon (OC) mass can be determined by an aerosol carbon analyzer; however, there is no direct method for the determination of the mass of organic compounds, which also contain N, H, and O atoms in addition to C. The often-adopted approach is to estimate the organic mass (OM) from OC multiplying by a factor. However, this OC-to-OM multiplier was rarely measured for a lack of appropriate methods for OM. We report here a top-down approach to determine OM by coupling thermal gravimetric and chemical analyses. OM is taken to be the mass difference of a filter before and after heating at 550 °C in air for 4 h minus mass losses due to elemental carbon (EC), volatile inorganic compounds (e.g., NH₄NO₃), and loss of aerosol-associated water that arise from the heating treatment. The losses of EC and inorganic compounds are determined through chemical analysis of the filter before and after the heating treatment. We analyzed 37 ambient aerosol samples collected in Hong Kong during the winter of 2003, spring of 2004, and summer of 2005. A value of 2.1±0.3 was found to be the appropriate factor to convert OC to OM in these Hong Kong aerosol samples. If the dominant air mass is classified into two categories, then an OM-to-OC ratio of 2.2 was applicable to aerosols dominated by continent-originated air mass, and 1.9 was applicable to aerosols dominated by marine air mass.     

Comparison among filter-based,impactor-based and continuous techniques for measuring atmospheric fine sulfate and nitrate

Filter-based methods for sampling aerosols are subject to great uncertainty if the gas–particle interactions on filter substrates are not properly handled. Sampling artifacts depend on both meteorological conditions and the chemical mix of the atmosphere. Despite numerous of studies on the subject, very few have evaluated filter-based methods in the Asian environments. This paper reports the results of a comparison of the performances of two filter-based samplers, including a Thermo Anderson Chemical Speciation Monitor (RAAS) and a honeycomb denuder filter-pack system, a Micro Orifice Uniform Deposit Impactor (MOUDI) and a real-time ambient ion monitor (AIM, URG9000B) in measuring atmospheric concentrations of PM_2.5 sulfate and nitrate. Field studies were conducted at an urban site in Jinan, Shandong province, during the winter of 2007 and at a rural site near Beijing in the summer of 2008. The AIM was first compared with the honeycomb denuder filter-pack system which was considered to have minimal sampling artifacts. After some modifications made to it, the AIM showed good performance for both sulfate and nitrate measurement at the two sites and was then used to evaluate other instruments. For the un-denuded RAAS, the extent of sampling artifacts for nitrate on quartz filters was negligible, while that on Teflon filters was also minimal at high nitrate concentrations (>10 μgm^?3); however, loss through evaporation was significant (～75%) at low nitrate concentrations under hot summer conditions. The MOUDI using aluminum substrates suffered a significant loss of nitrate (50–70%) under summer conditions due to evaporation. Considering that the aluminum substrates are still being widely used to obtain size-resolved aerosol compositions because of their low cost and accurate mass weighed, caution should be taken about the potential significant under determination of semi-volatile components such as ammonium nitrate.     

Design of a Cost-Effective Weighing Facility for PM2.5 Quality Assurance

Abstract

The U.S. Environmental Protection Agency (EPA) Quality Assurance (QA) Guidance Document 2.12: Monitoring PM_2.5 in Ambient Air Using Designated Reference or Class I Equivalent Methods¹ (Document 2.12) requires conditioning of PM_2.5 filters at 20-23 °C and 30-40% relative humidity (RH) for 24 hr prior to gravimetric analysis. Variability of temperature and humidity may not exceed ±2 °C and ±5% RH during the conditioning period. The quality assurance team at EPA Region 2’s regional laboratory designed a PM_2.5 weighing facility that operates well within these strict performance requirements.

The traditional approach to meeting the performance requirements of Document 2.12 for PM_2.5 filter analysis is to build a walk-in room, with costs typically exceeding $100,000. The initial one-time capital cost for the laboratory at EPA’s Edison, NJ, facility was approximately $24,000. Annual costs [e.g., National Institute of Standards and Technology (NIST) recertifications and nitrogen replacement cylinders used for humidity control] are approximately $500. The average 24-hr variabilities in temperature and RH in the Region 2 weighing chamber are small, ±0.2 °C and ±0.8% RH, respectively. The mass detection limit for the PM_2.5 weighing system of 47-mm stretched Teflon (lab blank) filters is 6.3 μg. This facility demonstrates an effective and economical example for states and other organizations planning PM_2.5 weighing facilities.