Characterization of Indoor Particle Sources Using Continuous Mass and Size Monitors

ABSTRACT

A comprehensive indoor particle characterization study was conducted in nine Boston-area homes in 1998 in order to characterize sources of PM in indoor environments. State-of-the-art sampling methodologies were used to obtain continuous PM_2.5 concentration and size distribution particulate data for both indoor and outdoor air. Study homes, five of which were sampled during two seasons, were monitored over week-long periods. Among other data collected during the extensive monitoring efforts were 24hr elemental/organic carbon (EC/OC) particulate data as well as semi-continuous air exchange rates and time-activity information.

This rich data set shows that indoor particle events tend to be brief, intermittent, and highly variable, thus requiring the use of continuous instrumentation for their characterization. In addition to dramatically increasing indoor PM₂₅ concentrations, these data demonstrate that indoor particle events can significantly alter the size distribution and composition of indoor particles. Source event data demonstrate that the impacts of indoor activities are especially pronounced in the ultrafine (d_a < 0.1 um) and coarse (2.5 < d_a < 10 |um) modes. Among the sources of ultrafine particles characterized in this study are indoor ozone/terpene reactions. Furthermore, EC/OC data suggest that organic carbon is a major constituent of particles emitted during indoor source events. Whether exposures to indoor-generated particles, particularly from large short-term peak events, may be associated with adverse health effects will become clearer when biological mechanisms are better known.     

Transient and Frequency Response of Air Quality Monitors

Results of dynamic or transient tests and steady state calibration of carbon monoxide and sulfur dioxide continuous air quality monitors are reported. Standard gases and permeation tubes were used to establish low level concentrations bpth for the steady-state calibration and the dynamic testing. The steady-state calibration was in excellent agreement with results obtained from grab samples of the calibration gas stream taken with standard gas bubblers and analyzed by the West and Gaeke procedure. Such tests have been carried out by other investigators with similar results. The important contribution of this paper lies in the application of dynamic testing techniques developed by the senior author and co-workers to determine the transient and frequency response characteristics of these air quality monitors.     

Calibration of Sharp Cut Impactors for Indoor and Outdoor Particle Sampling

ABSTRACT

A low-flow rate, sharp cut point inertial impaction sampler was developed in 1986 that has been widely used in PM exposure studies in the United States and several other countries. Although sold commercially as the MS&T Area Sampler, this sampler is widely referred to as the Harvard Impactor, since the initial use was at the Harvard School of Public Health. Impactor nozzles for this sampler have been designed and characterized for flows of 4,10, 20, and 23 L/min and cut points of 1, 2, 5, and 10 |im. An improved method for determining the actual collecting efficiency curve was developed and used for the recent impactor calibrations reported here. It consists of placing a multiplet reduction impactor inline just downstream of the vibrating orifice aerosol generator to remove the multiplets, thus allowing only the singlet particle s to penetrate through to the impactor being calibrated.

This paper documents the techniques and results of recent nozzle calibrations for this sampler and compares it with other size-selective inertial impactors. In general, the impactors were found to have sharp cutoff characteristics. Particle interstage losses for all of the impactors were very low, with the exception of the 10-|im cut size 20 L/ min impactor, which had greater losses due to the higher flow rate. All of the cut nozzle laboratory calibrations compare favorably to the U.S. Environmental Protection Agency (EPA) WINS-96 fine particle mass (PM_{2 5}) impactor calibration data.     

Modeling Inorganic Aerosols and Their Response to Changes in Precursor Concentration in Mexico City

Abstract

Based on data from the 1997 Investigación sobre Materia Particulada y Deterioro Atmosférico-Aerosol and Visibility Evaluation Research (IMADA-EVER) campaign and the inorganic aerosol model ISORROPIA, the response of inorganic aerosols to changes in precursor concentrations was calculated. The aerosol behavior is dominated by the abundance of ammonia and thus, changes in ammonia concentration are expected to have a small effect on particle concentrations. Changes in sulfate and nitrate are expected to lead to proportional reductions in inorganic fine particulate matter (PM_2.5). Comparing the predictions of ISORROPIA with the observations, the lowest bias and error are achieved when the aerosols are assumed to be in the efflorescence branch. Including crustal species reduces the bias and error for nitrate but does not improve overall model performance. The estimated response of inorganic PM_2.5 to changes in precursor concentrations is affected by the inclusion of crustal species in some cases, although average responses are comparable with and without crustal species. Observed concentrations of particle chloride suggest that gas phase concentrations of hydrogen chloride may not be negligible, and future measurement campaigns should include observations to test this hypothesis. Our ability to model aerosol behavior in Mexico City and, thus, design control strategies, is constrained primarily by a lack of observations of gas phase precursors. Future campaigns should focus in particular on better understanding the temporal and spatial distribution of ammonia concentrations. In addition, gas phase observations of nitric acid are needed, and a measure of particle water content will allow stable versus metastable aerosol behavior to be distinguished.     

Apparatus for Simultaneous Size-Differentiated Sampling of Optical and Suboptical Aerosols: Application to Analysis of Nitrates and Sulfates

In recent years, the EPA has moved toward a risk assessment/risk reduction framework for making regulatory decisions. The Agency has taken a number of steps to assure the quality and consistency of the risk assessment component of those decisions. The first, and perhaps most important of these steps, is the development of Agency-wide risk assessment guidelines. Five guidelines have been published. They are: carcinogenicity, mutagenicity, developmental toxicity, chemical mixtures, and exposure. The provisions of the five guidelines are discussed in the context of the four components of risk assessment. Other activities designed to assure quality and consistency in risk assessments, reduce uncertainty in risk assessment, ensure a more efficient information exchange about risk and risk assessment, and develop the appropriate oversight mechanisms are also discussed. These include additional guidelines, the Risk Assessment Forum, risk assessment research, the Integrated Risk Information System, the Hazard Assessment Notification System, and the Risk Assessment Council.     

Development of Models for Predicting the Distribution of Indoor Nitrogen Dioxide Concentrations

Extensive data on residential indoor and outdoor NO₂ levels have been collected in a limited number of U.S. locations. To date, researchers have analyzed these data sets individually, but have not analyzed them in the aggregate. Results have not, therefore, been suitable for application in a nationwide exposure assessment. This paper presents an analysis of indoor and outdoor NO₂ field measurements from five U.S. metropolitan areas for homes with gas-fueled ranges and discusses potential applications of the results. Using linear regression analysis, the relationship between indoor NO₂ and various predictor variables was explored. Results indicated that ambient NO2 levels alone explain an estimated 37 percent of the variability in indoor NO₂ levels, that the relationship between indoor and outdoor NO₂ concentrations differs significantly from summer to winter months, and that homes with range pilot lights have indoor levels approximately 7 ppb greater than homes without pilot lights. A logistic regression model which predicts the distribution of indoor NO₂ levels based on ambient NO₂ concentrations was developed. Estimation and testing of the logistic model indicated good model performance. The model is particularly useful for addressing policy-oriented questions that involve the concept of "acceptable" threshold levels for human exposure to NO₂.     

A High-Volume Sampler for the Determination of Particle Size Distributions in Ambient Air

A size selective particle sampler has been developed for continuous sampling of the urban aerosol over periods ranging from hours to weeks, providing relatively large sample weights. The system, which is now operating in New York City, uses a parallel array of two-stage samplers. The cyclones used as the first stage collectors have 50% particle retention at 3.5,2.5,1.5 and 0.5 µm aerodynamic diameter, respectively. Undersize particles which pass through the cyclones are captured on glass fiber filters. Equal intake velocities are assured by using flow equalizers on the inlets to the cyclones. Accurate control of the flow through the cyclones is obtained by the use of an integrated circuit pressure transducer in conjunction with a specially designed feedback control circuit. The collection efficiencies of the cyclone were calibrated using monodisperse ferric oxide test aerosols tagged with Tc-99m. Mass balances of the par-ticulates collected on the cyclones and filters are obtained for the five sampling stages. Preliminary results show the distributions of the total suspended particulates in New York City to be bimodal. The distributions of lead, copper, and manganese with particle size are also discussed.     

A New Method for the Rapid Determination of Volatile Organic Compound Breakthrough Times for a Sorbent at Concentrations Relevant to Indoor Air Quality

Abstract

The use of sorbents has been proposed to remove volatile organic compounds (VOCs) present in ambient air at concentrations in the parts-per-billion (ppb) range, which is typical of indoor air quality applications. Sorbent materials, such as granular activated carbon and molecular sieves, are used to remove VOCs from gas streams in industrial applications, where VOC concentrations are typically in the parts-per-million range. A method for evaluating the VOC removal performance of sorbent materials using toluene concentrations in the ppb range is described. Breakthrough times for toluene at concentrations from 2 to 7500 ppb are presented for a hydrophobic molecular sieve at 25% relative humidity. By increasing the ratio of challenge gas flow rate to the mass of the sorbent bed and decreasing both the mass of sorbent in the bed and the sorbent particle size, this method reduces the required experimental times by a factor of up to several hundred compared with the proposed American Society of Heating, Refrigerating, and Air-Conditioning Engineers method, ASHRAE 145P, making sorbent performance evaluation for ppb-range VOC removal more convenient. The method can be applied to screen sorbent materials for application in the removal of VOCs from indoor air.     

Application of High Gradient Magnetic Separation to Fine Particle Control

The char produced in the thermolysis of granulated scrap tyres has few market outlets, reducing the economic viability of the thermolytic process. This paper reports the potential of this char as a low-cost precursor of porous carbons. The tyre-derived char was demineralized in either alkaline or acidic media to reduce its ash, zinc, sulfur, and silica contents. The lowest impurity content was achieved with an HNO₃/H₂O treatment. The resulting demineralized char was then subjected to activation by KOH or CO₂. The Brunauer-Emmett-Teller (BET)-specific surface area of the activated carbon produced by the KOH treatment was 242 m²/g, whereas that of the CO₂-activated carbon was 720 m²/g. The textural properties of the latter product were similar to those of some commercial activated carbons. The use of tyre-derived char as a precursor of porous carbons could render the thermolytic treatment of scrap tyres more economically attractive.

Implications: Char produced in thermolysis of granulated scrap tyres has a few market outlets; in this paper an alternative for its use is presented. The char was converted into activated carbon with textural properties similar to those of some commercial activated carbons. This process could render the thermolytic treatment of scrap tyres more economically attractive.     

A Review of Personal/Portable Monitors and Samplers for Airborne Particles

A review of personal and portable particulate monitors and samplers for measuring and sampling airborne particulate matter is presented. These monitors and samplers are proving to be valuable tools for assessing individual exposure to environmental and occupationally generated particulates. The devices are characterized in terms of their sampling characteristics, their monitoring or measurement technique, their particle size separation (50% cut point) capabilities, their sampling flow rate, and their sampling duration per one battery charging cycle. All of the monitors and some of the samplers are commercially available. Commercial sources and originators (in the case of research devices) are made available.     

An Aerosol Sampler for Determination of Particle Concentration as a Function of Size and Time

A high flow rate four-stage impacfor was developed for the determination of aerosol concentration as a function of both particle size and time. The unit is very useful for long-term sampling intervals (24 hr) and for sampling very dusty atmospheres. Gas-borne particulate matter is collected out on four rotating drums, each with a collection surface area of about 10 sq in.; this allows a large quantity of materials to be collected without danger of particle build-up and blow-off. A particle size-collection efficiency calibration for the unit is presented together with experimental data on wall losses, surface coatings, and other important operational considerations.     

Particle Concentrations Inside a Tavern Before and After Prohibition of Smoking: Evaluating the Performance of an Indoor Air Quality Model

Abstract

Measurements were made of respirable suspended particles (RSP) in a large sports tavern on 26 dates over approximately two years in which smoking was allowed, followed by measurements on 50 dates during the year after smoking was prohibited. The smoking prohibition occurred without warning when the city government passed a regulation restricting smoking in local restaurants and taverns. Two follow-up field surveys, consisting of 24 and 26 visits, respectively, were conducted to measure changes in RSP levels after smoking was prohibited. No decrease in tavern attendance was evident after smoking was prohibited. During the smoking period, the average RSP concentration was 56.8 |ig/m3 above the outdoor concentrations, but the average abruptly dropped to 5.9 ug/m3 above outdoor levels—a 90% decrease— on 24 visits in the first two months immediately after smoking was prohibited (first follow-up study). A second set of 26 follow-up visits (matched by time of day, day of the week, and season to the earlier smoking visits) yielded an average concentration of 12.9 jig/m3 above the outdoor levels, or an overall decrease in the average RSP concentration of 77% compared with the smoking period. During the smoking period, RSP concentrations more than 100 ug/m3 above outdoor levels occurred on 30.7% of the visits. During the 50 nonsmoking visits, 92% of the RSP concentrations were less than 20 u,g/m3 above outdoor levels, and no concentration exceeded 100 ug/m3 on any nonsmoking visit. The data show there was a striking decline in indoor RSP concentrations in the tavern after smoking was prohibited. The indoor concentration observed in the nonsmoking periods (9.1 u.g/m3 average for all nonsmoking visits) was attributed to cooking and resuspended dust. A mathematical model based on the mass balance equation was developed that included smoking, cooking, and resuspended dust. Using cigarette emission rates from the literature, the tavern volume of 521 m3, and the air exchange rate measured in the tavern under conditions regarded by the management as "typical," the model predicted 42.5 ug/m3 for an average smoking count of 1.17 cigarettes, which compared favorably with the average concentration of 43.9 ng/m3 observed in the tavern. A regression analysis indicated that the active smoking count explained over 50% of the variation of the RSP concentrations measured on different dates. The mathematical model can be used to estimate RSP concentrations from smoking in other similar taverns under similar conditions.     

Controlled Exposures of Volunteers to Respirable Carbon and Sulf uric Acid Aerosols

Respirable carbon or fly ash particles are suspected to increase the respiratory toxicity of coexisting acidic air pollutants, by concentrating acid on their surfaces and so delivering it efficiently to the lower respiratory tract. To investigate this issue, we exposed 15 healthy and 15 asthmatic volunteers in a controlled- environment chamber (21°C, 50 percent relative humidity) to four test atmospheres: (i) clean air; (ii) 0.5-μm H2SO4 aerosol at =100 μg/m³, generated from water solution; (iii) 0,5-μm carbon aerosol at =250 μg/m³, generated from highly pure carbon black with specific surface area comparable to ambient pollution particles; and (iv) carbon as in (iii) plus =100 μg/m³ of ultrafine H2SO4 aerosol generated from fuming sulfuric acid. Electron microscopy showed that nearly all acid in (iv) became attached to carbon particle surfaces, and that most particles remained in the sub-μm size range. Exposures were performed double-blind, 1 week apart. They lasted 1 hr each, with alternate 10-min periods of heavy exercise (ventilation =50 L/min) and rest. Subjects gargled citrus juice before exposure to suppress airway ammonia. Lung function and symptoms were measured pre-exposure, after initial exercise, and at endexposure. Bronchial reactivity to methacholine was measured after exposure. Statistical analyses tested for effects of H₂SO₄ or carbon, separate or interactive, on health measures. Group data showed no more than small equivocal effects of any exposure on any health measure. One individual's responses were consistent with a clinically significant excess airway constriction from H₂SO₄ plus carbon, and 2-3 others showed slight excess responses to the combined pollutants, but all these observations might have reflected chance variations. We conclude that coexisting carbon aerosol did not increase respiratory irritancy of H₂SO₄, in most healthy and asthmatic subjects exposed for 1 hr under simulated "worst-case" ambient conditions.     

Aerosols formed from the chemical reaction of monoterpenes and ozone

Chamber experiments were conducted to study the aerosol products from the ozonolysis of the major atmospheric monoterpenes; α-pinene, β-pinene and limonene. It was found that the α-pinene-O₃ reaction produced mainly 2′, 2′-dimethyl-3′-acetyl cyclobutyl ethanal (pinonaldehyde), the β-pinene-O₃ reaction, mainly 6,6-dimethyl-bicyclo [3.1.1] heptan-2-one and the limonene-O₃ reaction, several unidentified products. These products were sought in forest aerosols and pinonaldehyde was detected in the atmosphere.     

Aerosols formed from the chemical reaction of monoterpenes and ozone

Chamber experiments were conducted to study the aerosol products from the ozonolysis of the major atmospheric monoterpenes; α-pinene, β-pinene and limonene. It was found that the α-pinend–O₃ reaction produced mainly 2′. 2′-dimethyl-3′-acetyl cyclobutyl ethanal (pinonaldehyde), the β-pinene–O₃ reaction, mainly 6,6-dimethyl-bicyclo [3.1.1] heptan-2-one and the limonene–O₃ reaction, several unidentified products. These products were sought in forest aerosols and pinonaldehyde was detected in the atmosphere.     

Method Development for Determination of Fluroxypyr in Soil

Abstract

Four methods were developed for the analysis of fluroxypyr in soil samples from oil palm plantations. The first method involved the extraction of the herbicide with 0.05 M NaOH in methanol followed by purification using acid base partition. The concentrated material was subjected to derivatization and then cleaning process using a florisil column and finally analyzed by gas chromatography (GC) equipped with electron capture detector (ECD). By this method, the recovery of fluroxypyr from the spiked soil ranged from 70 to 104% with the minimum detection limit at 5 µg/kg. The second method involved solid liquid extraction of fluroxypyr using a horizontal shaker followed by quantification using high performance liquid chromatography (HPLC) equipped with UV detector. The recovery of fluroxypyr using this method, ranged from 80 to 120% when the soil was spiked with fluroxypyr at 0.1–0.2 µg/g soil. In the third method, the recovery of fluroxypyr was determined by solid liquid extraction using an ultrasonic bath. The recovery of fluroxypyr at spiking levels of 4–50 µg/L ranged from 88 to 98% with relative standard deviations of 3.0–5.8% with a minimum detection limit of 4 µg/kg. In the fourth method, fluroxypyr was extracted using the solid liquid extraction method followed by the cleaning up step with OASIS® HLB (polyvinyl dibenzene). The recovery of fluroxypyr was between 91 and 95% with relative standard deviations of 4.2–6.2%, respectively. The limit of detection in method 4 was further improved to 1 µg/kg. When the weight of soil used was increased 4 fold, the recovery of fluroxypyr at spiking level of 1–50 µg/kg ranged from 82–107% with relative standard deviations of 0.5–4.7%.