Variation of the Relative Humidity of Air Released from Canisters after Ambient Sampling

ABSTRACT

Dalton's law of partial pressures and the hypothesis that water vapor equilibrium in a canister is identical to that established above liquid water are used to predict the variation of the percent relative humidity (%RH) of air released from canisters used in ambient air sampling, typically 6-L canisters pressurized with 18 L of air. When (and if) the water vapor partial pressure in a canister exceeds its saturation vapor pressure, water vapor condensation begins and the condensation rate equals the sampling rate of water vapor into the canister. Under constant temperature conditions, the air subsequently released from the canister is less humid than the original sample, following the relationship %RH = 100% (6 L/V_s) for V_s> V_r, where V_s is the residual air volume (referenced to atmospheric pressure), and V_r is shown to depend on the %RH of the ambient air sample. V_r is the residual air volume at which water is completely removed (except for adsorbed water vapor) from the canister wall. For V_s < V_r, the predicted %RH is constant and equal to its value at V_r. Experimental values agree reasonably well with predictions at both high (90%) and low (34%) RH. However, experimental values are often slightly displaced (usually towards lower values of %RH) for mid-range %RH (61%) and variations in %RH near V_r change from canister to canister.     

Estimates of Particle Hygroscopicity during the Southeastern Aerosol and Visibility Study

ABSTRACT

Aerosol water content was determined from relative humidity controlled optical particle counter (ASASP-X) size distribution measurements made during the Southeastern Aerosol and Visibility Study (SEAVS) in the Great Smoky Mountains National Park during summer 1995. Since the scattering response function of the ASASP-X is sensitive to particle refractive index, a technique for calibrating the ASASP-X for any real refractive index was developed. A new iterative process was employed to calculate water mass concentration and wet refractive index as functions of relative humidity. Experimental water mass concentrations were compared to theoretically predicted values assuming only ammonium sulfate compounds were hygroscopic. These comparisons agreed within experimental uncertainty. Estimates of particle hygroscopicity using a rural aerosol model of refractive index as a function of relative humidity demonstrated no significant differences from those made with daily varying refractive index estimates. Although aerosol size parameters were affected by the assumed chemical composition, forming ratios of these parameters nearly canceled these effects.     

Characterization of Fine Particulate Matter Produced by Combustion of Residual Fuel Oil

ABSTRACT

Combustion experiments were carried out on four different residual fuel oils in a 732-kW boiler. PM emission samples were separated aerodynamically by a cyclone into fractions that were nominally less than and greater than 2.5 |j.m in diameter. However, examination of several of the samples by computer-controlled scanning electron microscopy (CCSEM) revealed that part of the PM_2.5 fraction consists of carbonaceous cenospheres and vesicular particles that range up to 10 |j.m in diameter. X-ray absorption fine structure (XAFS) spectroscopy data were obtained at the S, V, Ni, Fe, Cu, Zn, and As K-edges and at the Pb L-edge. Deconvolution of the X-ray absorption near edge structure (XANES) region of the S spectra established that the dominant molecular forms of S present were sulfate (26-84% of total S) and thiophene (13-39% of total S). Sulfate was greater in the PM_2.5 samples than in the PM₂₅₊ samples. Inorganic sulfides and elemental sulfur were present in lower percentages. The Ni XANES spectra from all of the samples agreed fairly well with that of NiSO₄, while most of the V spectra closely resembled that of vanadyl sulfate (VO?SO₄?xH₂O). The other metals investigated (i.e., Fe, Cu, Zn, and Pb) also were present predominantly as sulfates. Arsenic was present as an arsen-ate (As⁺⁵). X-ray diffraction patterns of the PM_2.5 fraction exhibit sharp lines due to sulfate compounds (Zn, V, Ni, Ca, etc.) superimposed on broad peaks due to amorphous carbons. All of the samples contain a significant organic component, with the loss on ignition (LOI) ranging from 64 to 87% for the PM_2.5 fraction and from 88 to 97% for the PM_2.5+ fraction. Based on ¹³C nuclear magnetic resonance (NMR) analysis, the carbon is predominantly condensed in graphitic structures. Aliphatic structure was detected in only one of seven samples examined.     

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.     

Behavior of an MBT waste in monotonic triaxial shear tests

Legislation in some parts of the world now requires municipal solid waste (MSW) to be processed prior to landfilling to reduce its biodegradability and hence its polluting potential through leachate and fugitive emission of greenhouse gases. This pre-processing may be achieved through what is generically termed mechanical–biological-treatment (MBT). One of the major concerns relating to MBT wastes is that the strength of the material may be less than for raw MSW, owing to the removal of sheet, stick and string-like reinforcing elements during processing. Also, the gradual increase in mobilized strength over strains of 30% or so commonly associated with unprocessed municipal solid waste may not occur with treated wastes. This paper describes a series of triaxial tests carried out to investigate the stress–strain–strength characteristics of an MBT waste, using a novel digital image analysis technique for the determination of detailed displacement fields over the whole specimen. New insights gained into the mechanical behavior of MBT waste include the effect of density on the stress–strain response, the initial 1-D compression of lightly consolidated specimens, and the likely reinforcing effect of small sheet like particles remaining in the waste.     

Author’s Reply

A technique is developed to compute precision requirements for component parts of an emissions inventory to ensure (at a given confidence level) an overall acceptable precision in the estimate of total emissions. Since the emissions inventory is a basic requirement of air quality control implementation plans and provides a valuable management tool for planning air pollution control activities, it isi appropriate to state in quantitative terms the confidence that can be associated with each inventory. The approach reported here uses weighted sensitivity analysis methods to distribute both percentage and physical errors in source class emissions according to their contribution to the total emissions, and utilizes Chebyshev’s inequality to establish confidence levels for total emissions. The analysis has been extended to cover the case where one or more of the error components in a given inventory source class can be fixed by the analyst. The utility of the technique is manifold and several practical applications are reported. In particular, it serves to establish percentage error requirements for source categories to satisfy given error bounds for the overall emissions inventory at a given level of statistical confidence. The weighted sensitivity analysis technique possesses a high degree of generality, being applicable to compute component error requirements for any kind of data inventory which exhibits a hierarchical (tree-like) structure, as exemplified by NEDS Emissions Summary Reports. This work should be of interest to air pollution control planners at all levels of government and to anyone responsible for the air pollution portion of environmental impact statements.     

Rotating Concentric “Homogeneous Turbulence” Gas Scrubber

A device which utilizes the Couette (secondary) flow patterns, which are developed in a fluid between rotating concentric cylinders, is proposed for use in particle collection. The gas being cleaned is dispersed in the scrubbing liquid within the annular space between cylinders. The device was untested at the time of presentation of the paper.     

interpretation of air quality data with respect to the national ambient air quality standards

San Diego Gas &; Electric has developed a quality assurance program for continuous emission monitors (CEM). Extractive, rather than in situ, monitors were selected as a result of an in-house evaluation program. Two extractive systems have been certified and a good operating and maintenance record has been established on these systems. A successful program requires the involvement and support of all affected personnel. It is desirable to have one or two key personnel coordinate the development of the program. It is also highly desirable to have good in-house source testing capabilities.     

Solid Absorbent Method for Sampling and Analysis of Nitrogen Dioxide in Ambient Air

A sampling and analysis system was developed for measuring concentrations of nitrogen dioxide in ambient air. Copper shot was found to be an effective absorbent for collecting samples at ambient levels. The analytical system was based on the desorption of the sample from the copper by heating in a hydrogen carrier stream. The desorbed sample was then determined by a combination of catalytic pyrolysis, which converted it to ammonia, and a Coulson Conductivity Detector. Data are presented showing overall recovery, effects of storage of collected samples, results for 24-hour sampling and interferences. Studies indicated the feasibility of the method for short time sampling as well as for 24-hour sampling periods. The detection limit was shown to be as little as 100 ng NO₂ in laboratory studies. This solid absorbent method provides a simple, convenient, and compact means for air sampling.