Evaluation of an Ion Selective Electrode Monitor for Total Oxidants

The iodide ion selective electrode has potential use for continuous monitoring of total oxidants in ambient air. Total oxidants are measured coulometrically or colorimetrically after oxidation of neutral buffered Kl solution (0.6-1.2M) to free iodine. On the other hand, the iodide electrode can measure much more dilute solutions (<10^-4M). The iodide electrode measures the disappearance of iodide from the absorbing solution. The detector is made from an iodide electrode, reference electrode, an expanded scale pH meter, and millivolt recorder. The iodide electrode shows a constant Nernstian —59 mv change per decade over a dilute solution range although the absolute voltage shows a drift of 1 mv/day. A continuous iodide electrode air monitor was set up and investigated for ambient monitoring. Operational parameters as air and solution flow rates and electrode parameters as response time at different iodide concentrations were investigated. Statistical comparison was made with a Beekman colorimetric total oxidant monitor and a prototype REM chemiluminescent ozone monitor. The iodide electrode monitor was shown capable of continuously monitoring oxidants in the atmosphere being sensitive to changes in ambient concentrations.     

Criteria for Certification of Motor Vehicle Pollution Control Devices in California

This investigation used an acid medium for sampling atmospheric oxidants. The acid iodide oxidant procedure was unaffected by air or oxygen, temperature variance, and reducing gases (sulfur dioxide and hydrogen sulfide.) The method possessed good color stability. The method also agreed favorably with the 1 or 2% neutral buffered iodide method when a chromium trioxide scrubber was required to remove the reducing gases from the latter procedure.

The acid oxidant absorption solution of 1 3 ml in a midget impinger contained 10 ml of 1.5% potassium iodide in a 0.1 N sodium hydroxide solution and 3 ml of acetic acid (1:5) which produced a solution of approximately 3.8 pH. Particulate matter was removed by a glass wool attachment to the midget impinger. The air was sampled with a Gelman Sequential Sampler at the rate of 1.41 liters per minute. After the oxidant sample was collected, the absorbing solution was transferred to a graduated cylinder and the volume was adjusted to 25 ml with distilled water. The absorbance was read at 355 millimicrons wavelength by a spectrophotometer in a 1 cm cell. The acid oxidant method was effective between 1 to 70 pphm of ozone.     

An Analysis of Ozone Generation in Irradiated Houston Air

Ambient ozone measurements in the United States and many other countries are traceable to a National Institute of Standards and Technology Standard Reference Photometer (NIST SRP). The NIST SRP serves as the highest level ozone reference standard in the United States, with NIST SRPs located at NIST and at many U.S. Environmental Protection Agency (EPA) laboratories. The International Bureau of Weights and Measures (BIPM) maintains a NIST SRP as the reference standard for international measurement comparability through the International Committee of Weights and Measures (CIPM). In total, there are currently NIST SRPs located in 20 countries for use as an ozone reference standard. A detailed examination of the NIST SRP by the BIPM and NIST has revealed a temperature gradient and optical path-length bias inherent in all NIST SRPs. A temperature gradient along the absorption cells causes incorrect temperature measurements by as much as 2 °C. Additionally, the temperature probe used for temperature measurements was found to inaccurately measure the temperature of the sample gas due to a self-heating effect. Multiple internal reflections within the absorption cells produce an actual path length longer than the measured fixed length used in the calculations for ozone mole fractions. Reflections from optical filters located at the exit of the absorption cells add to this effect. Because all NIST SRPs are essentially identical, the temperature and path-length biases exist on all units by varying amounts dependent upon instrument settings, laboratory conditions, and absorption cell window alignment. This paper will discuss the cause of, and physical modifications for, reducing these measurement biases in NIST SRPs. Results from actual NIST SRP bias upgrades quantifying the effects of these measurement biases on ozone measurements are summarized.

Implications: NIST SRPs are maintained in laboratories around the world underpinning ozone measurement calibration and traceability within and between countries. The work described in this paper quantifies and shows the reduction of instrument biases in NIST SRPs improving their overall agreement. This improved agreement in all NIST SRPs provides a more stable baseline for ozone measurements worldwide.     

The Assessment of Emission Analysis Accuracy

An assessment of the accuracy of emission measurements is fundamental to an understanding of the ability of an organization to comply with emission regulations. Without a knowledge of the measurement accuracy, the significance of observed differences cannot be assessed. In addition, the average emission level that a group of engines must achieve for compliance is a function of the accuracy of the measurement of the exhaust constituents; i.e., the less accurate the measurement, the lower the average level must be to assure that essentially all engines pass the compliance tests. The accuracy assessment specifically included: 1) test instrument precision, 2) calibration gas accuracy and 3) sample error due to the distribution of data resulting from gas concentrations that are spatially non-uniform. In addition, the accuracy assessment required the consideration of the following general topics: the propagation of errors in a calibration hierarchy, the proper choice of error units, surveys of instrument precision, the evaluation of the significance of various instrument errors, the assessment of the significance of sampling error, and the consideration of methods for demonstrating representative samples and improving instrument precision. An accuracy assessment considering those factors resulted in the following conclusions: 1) Emission instrument precision is best expressed as percent of full scale. 2) The proper units for bias errors are percent of point. 3) Calibration-to-calibration repeatability may be utilized to estimate instrument precision. 4) Instrument precision shows wide variations from day to day. 5) Correcting past data by post-test calibration adjustments will not, in general, improve emission data altered by instrument drift. 6) Sampling error due to the distribution of emission concentrations in space is the single largest source of uncertainty in gas turbine emission measurements.     

Dynamic Calibration of an Acid Aerosol Analyzer

A method is described for dynamic calibration of an acid aerosol analyzer based on a commercial modification of the Thomas Autometer and manufactured by the Instrument Development Company. This automated instrument removes acid aerosol from an air stream by sonic impaction, and the sulfuric acid collected is determined conductometrically. An all-glass aerosol generator based on the reaction of water vapor with sulfur trioxide vapor released from fuming sulfuric acid was built for the calibration. Air samples were withdrawn for instrument calibration before and after the concentration of the acid aerosol was determined by titration. The apparent particle size as determined by an Andersen sampler ranged from 2.0 microns to less than 0.68 micron and exhibited a sharp peak with mass median diameter at 1.3 microns in the distribution curve. The size of the aerosol, within certain limits, could be controlled by humidity. Data indicated a linear response with an aerosol collection efficiency of 80 percent in the important respirable size range.     

The Effects of Photochemical Oxidants on Materials

The excessive cracking of rubber products was one of the earliest indicators of the presence of atmospheric photochemical oxidants. It has been demonstrated that this excessive cracking of rubber is caused by atmospheric ozone formed in the photochemical smog formation process. Depending on the formulation of the rubber, cracking under stress can readily be detected within 3/4 hr when atmospheric oxidant levels are as low as 0.03 ppm. Natural and certain synthetic rubbers are particularly vulnerable. These rubbers when stressed show cracking when exposed to 0.02 ppm laboratory ozone for about 1 hr. Other materials known to deteriorate under atmospheric photochemical smog conditions are textiles and certain dyed fabrics, particularly under conditions of high humidity. Loss of tensile strength of cotton textiles when wet or moist, and similar fading of these dyed fabrics, particularly under high humidity, can be also produced by laboratory exposure of these textiles to pure ozone. Ozone effects on asphaltic materials ate also reported.     

Design of Afterburners for Varnish Cookers

Currently, outdoor ozone levels in many U.S. cities exceed the primary health-based national ambient air quality standard. While outdoor ozone levels are an important measure of the severity of those exceedances, people typically spend more than 80 percent of their time Indoors, where ozone levels are lower. Indoor ozone levels range from 10 to 80 percent of outdoor levels, with many people receiving a substantial portion of their ozone exposure while indoors. This paper uses an Indoor air quality model (IAQM) to estimate indoor ozone levels by mlcroenvlronment type (home, office, and vehicle) and configuration (windows open, windows closed, older construction, weatherized, and air conditioned). The formulation of IAQM is discussed, along with specification of model parameters for ozone. The multicompartment version of IAQM is described, with a single-compartment version used for the analyses. IAQM-calculated ozone indoor-outdoor ratios compare well with research-reported values. Results indicate that ozone peak-concentration indoor-outdoor ratios range as follows: home—0.65 (windows open), 0.36 (air conditioned), 0.23 (typical construction, windows closed), and 0.05 (energy-efficient construction, windows closed); office—0.82 (heat-Ing, ventilation and air conditioning systems supplying 100 percent outdoor air), 0.60 (typical HVAC), and 0.32 (energy-efficient HVAC); and vehicle—0.41 (85 mph), 0.33 (55 mph), and 0.21 (10 mph). Analysis results are presented to characterize IAQM’s sensitivity to assumed model parameters.     

Use of an indoor air quality model (IAQM) to estimate indoor ozone levels

Currently, outdoor ozone levels in many U.S. cities exceed the primary health-based national ambient air quality standard. While outdoor ozone levels are an important measure of the severity of those exceedances, people typically spend more than 80 percent of their time indoors, where ozone levels are lower. Indoor ozone levels range from 10 to 80 percent of outdoor levels, with many people receiving a substantial portion of their ozone exposure while indoors. This paper uses an indoor air quality model (IAQM) to estimate indoor ozone levels by microenvironment type (home, office, and vehicle) and configuration (windows open, windows closed, older construction, weatherized, and air conditioned). The formulation of IAQM is discussed, along with specification of model parameters for ozone. The multicompartment version of IAQM is described, with a single-compartment version used for the analyses. IAQM-calculated ozone indoor-outdoor ratios compare well with research-reported values. Results indicate that ozone peak-concentration indoor-outdoor ratios range as follows: home--0.65 (windows open), 0.36 (air conditioned), 0.23 (typical construction, windows closed), and 0.05 (energy-efficient construction, windows closed); office--0.82 (heating, ventilation and air conditioning systems supplying 100 percent outdoor air), 0.60 (typical HVAC), and 0.32 (energy-efficient HVAC); and vehicle--0.41 (85 mph), 0.33 (55 mph), and 0.21 (10 mph). Analysis results are presented to characterize IAQM's sensitivity to assumed model parameters.     

Impact of ozone mini-holes on the heterogeneous destruction of stratospheric ozone

A comprehensive study of ozone mini-holes over the mid-latitudes of both hemispheres is presented, based on model simulations with the coupled climate-chemistry model ECHAM4.L39(DLR)/CHEM representing atmospheric conditions in 1960, 1980, 1990 and 2015. Ozone mini-holes are synoptic-scale regions of strongly reduced total ozone, directly associated with tropospheric weather systems. Mini-holes are supposed to have chemical and dynamical impacts on ozone levels. Since ozone levels over northern mid-latitudes show a negative trend of approximately -4%/decade and since it exists a negative correlation between total column ozone and erythemally active solar UV-radiation reaching the surface it is important to understand and assess the processes leading to the observed ozone decline. The simulated mini-hole events are validated with a mini-hole climatology based on daily ozone measurements with the TOMS (total ozone mapping spectrometer) instrument on the satellite Nimbus-7 between 1979 and 1993. Furthermore, possible trends in the event frequency and intensity over the simulation period are assessed. In the northern hemisphere the number of mini-hole events in early winter decreases between 1960 and 1990 and increases towards 2015. In the southern hemisphere a positive trend in mini-hole event frequency is detected between 1960 and 2015 in spring associated with the increasing Antarctic Ozone Hole. Finally, the impact of mini-holes on the stratospheric heterogeneous ozone chemistry is investigated. For this purpose, a computer-based detection routine for mini-holes was developed for the use in ECHAM4.L39(DLR)/CHEM. This method prevents polar stratospheric cloud formation and therefore heterogeneous ozone depletion inside mini-holes. Heterogeneous processes inside mini-holes amount to one third of heterogeneous ozone destruction in general over northern mid- and high-latitudes during winter (January-April) in the simulation.     

Rate of iodine volatilization and accumulation by filamentous fungi through laboratory cultures

Five strains of basidiomycetes (Lentinula edodes, Coprinus phlyctidosporus, Hebeloma vinosophyllum, Pleurotus ostreatus and Agaricus bisporus), one strain of ascomycete (Hormoconis resinae) and six strains of imperfect fungi (Penicillium chrysogenum, Penicillium roquefortii, Cladosporium cladosporioides, Alternaria alternata, Aspergillus niger and Aspergillus oryzae) were cultured in a liquid medium containing a radioactive iodine tracer (¹²⁵I), and were tested for their abilities to volatilize or accumulate iodine. Of the fungal strains tested, 11 strains volatilized a considerable amount of iodine, with L. edodes showing the highest volatilization rate of 3.4%. The volatile organic iodine species emitted from imperfect fungi cultures was identified as methyl iodide (CH₃I). In contrast, six fungal strains in 12 strains accumulated a considerable amount of iodine from the medium with concentration factors of more than 1.0. Among these, Alt. alternata and Cl. cladosporioides accumulated more than 40% of the iodine in their hyphae, and showed high concentration factors of 22 and 18, respectively. These results suggest that filamentous fungi have a potential to influence the mobility and speciation of iodine by volatilization and accumulation. Considering their great biomass in soils, filamentous fungi may contribute to the global circulation of stable iodine and also the long-lived radioiodine, ¹²⁹I (half-life: 1.6 × 10⁷ years), released from nuclear facilities into the environment.     

Field evaluations of newly available “interference-free” monitors for nitrogen dioxide and ozone at near-road and conventional National Ambient Air Quality Standards compliance sites

Long-standing measurement techniques for determining ground-level ozone (O₃) and nitrogen dioxide (NO₂) are known to be biased by interfering compounds that result in overestimates of high O₃ and NO₂ ambient concentrations under conducive conditions. An increasing near-ground O₃ gradient (NGOG) with increasing height above ground level is also known to exist. Both the interference bias and NGOG were investigated by comparing data from a conventional Federal Equivalent Method (FEM) O₃ photometer and an identical monitor upgraded with an “interference-free” nitric oxide O₃ scrubber that alternatively sampled at 2 m and 6.2 m inlet heights above ground level (AGL). Intercomparison was also made between a conventional nitrogen oxide (NO_x) chemiluminescence Federal Reference Method (FRM) monitor and a new “direct-measure” NO₂ NO_x 405 nm photometer at a near-road air quality measurement site. Results indicate that the O₃ monitor with the upgraded scrubber recorded lower regulatory-oriented concentrations than the deployed conventional metal oxide–scrubbed monitor and that O₃ concentrations 6.2 m AGL were higher than concentrations 2.0 m AGL, the nominal nose height of outdoor populations. Also, a new direct-measure NO₂ photometer recorded generally lower NO₂ regulatory-oriented concentrations than the conventional FRM chemiluminescence monitor, reporting lower daily maximum hourly average concentrations than the conventional monitor about 3 of every 5 days.

Implications: Employing bias-prone instruments for measurement of ambient ozone or nitrogen dioxide from inlets at inappropriate heights above ground level may result in collection of positively biased data. This paper discusses tests of new regulatory instruments, recent developments in bias-free ozone and nitrogen dioxide measurement technology, and the presence/extent of a near-ground O₃ gradient (NGOG). Collection of unbiased monitor inlet height–appropriate data is crucial for determining accurate design values and meeting National Ambient Air Quality Standards.     

A rapid spectrophotometric determination of persulfate anion in ISCO

Due to a gradual increase in the use of persulfate as an in situ chemical oxidation (ISCO) oxidant, a simple measurement of persulfate concentration is desirable to analyze persulfate distribution at designated time intervals on/off a site. Such a distribution helps evaluate efficacy of ISCO treatment at a site. This work proposes a spectrophotometric determination of persulfate based on modification of the iodometric titration method. The analysis of absorption spectra of a yellow color solution resulting from the reaction of persulfate and iodide in the presence of sodium bicarbonate reveals an absorbance at 352 nm, without significant interferences from the reagent matrix. The calibration graph was linear in the range of persulfate solution concentration of 0-70 mM at 352 nm. The proposed method is validated by the iodometric titration method. The solution pH was at near neutral and the presence of iron activator does not interfere with the absorption measurement. Also, analysis of persulfate in a groundwater sample using the proposed method indicates a good agreement with measurements by the titration method. This proposed spectrophotometric quantification of persulfate provides a simple and rapid method for evaluation of ISCO effectiveness at a remediation site.     

High ozone levels in the northeast of Portugal: Analysis and characterization

Each summer period extremely high ozone levels are registered at the rural background station of Lamas d'Olo, located in the Northeast of Portugal. In average, 30% of the total alert threshold registered in Portugal is detected at this site. The main purpose of this study is to characterize the atmospheric conditions that lead to the ozone-rich episodes at this site. Synoptic patterns anomalies and back trajectories cluster analysis were performed, for the period between 2004 and 2007, considering 76 days when ozone maximum hourly concentrations were above 200 μg m^?3. The obtained atmospheric anomaly fields suggested that a positive temperature anomaly is visible above the Iberian Peninsula. A strong wind flow pattern from NE is observable in the North of Portugal and Galicia, in Spain. These two features may lead to an enhancement of the photochemical production and to the transport of pollutants from Spain to Portugal. In addition, the 3D mean back trajectories associated to the ozone episode days were analysed. A clustering method has been applied to the obtained back trajectories. Four main clusters of ozone-rich episodes were identified, with different frequencies of occurrence: north-westerly flows (11%); north-easterly flows (45%), southern flow (4%) and westerly flows (40%). Both analyses highlight the NE flow as a dominant pattern over the North of Portugal during summer. The analysis of the ozone concentrations for each selected cluster indicates that this northeast circulation pattern, together with the southern flow, are responsible for the highest ozone peak episodes. This also suggests that long-range transport of atmospheric pollutants is the main contributor to the ozone levels registered at Lamas d'Olo. This is also highlighted by the correlation of the ozone time-series with the meteorological parameters analysed in the frequency domain.     

Evaluation of Contact Columns for Nitrogen Dioxide Absorption

The absorption efficiencies of 6–, 10–, IS–, and 60-turn spiral contact columns for two formulations of Saltzman reagent are evaluated for use in atmospheric nitrogen dioxide analyzers at several air and liquid flow rates. Response times for the several columns as a function of flow rates and absorbing reagent are also given. The recommended column and reagent are indicated. The technique of adjusting instrument parameters for direct readout of NO₂ concentrations is described.     

Aircraft measurement of ozone turbulent flux in the atmospheric boundary layer

In May 1995, the “Chimie-Creil 95” experiment was undertaken in the north of France. The field data are first used to validate the methodology for airborne measurement of ozone flux. A certain number of methodological problems due to the location of the fast ozone sensor inside the airplane are, furthermore discussed. The paper describes the instrumentation of the ARAT (Avion de Recherche Atmosphérique et de Télédétection), an atmospheric research and remote-sensing aircraft used to perform the airborne measurements, the area flown over, the meteorological conditions and boundary layer stability conditions. These aircraft measurements are then used to determine ozone deposition velocity and values are proposed for aerodynamic, bulk transfer coefficients (ozone and momentum). The paper also establishes the relationship between the normalised standard deviation and stability parameters (z/L) for ozone, temperature, humidity and vertical velocity. The laws obtained are then presented.     

Determination of group parameters for organically bound chlorine, bromine and iodine in precipitation

The presence of organically bound halogens in precipitation was studied by first adsorbing organics on activated carbon and then analysing the chloride, bromide and iodide formed during combustion of the carbon. A standard instrument for the group parameter AOX (adsorbable organic halogens) was used for the combustion. The halides formed were trapped in an alkaline solution and analysed by capillary zone electrophoresis. The method described enabled determination of sub-ppb concentrations of the group parameters AOCl, AOBr and AOI (adsorbable organic chlorine, bromine and iodine, respectively). Analysis of rain and snow collected at different sites in Europe showed that organochlorines were responsible for the major part of the AOX content in all samples collected. Organically bound bromine was found in sub-ppb concentrations in all of the samples, whereas organic iodine was detected in only two of the samples.     

Closing Remarks

Considerable attention has been paid in recent years to photochemical smog pollution close to the earth's surface and to stratospheric ozone depletion. There is reason to suspect that the next round of scientific concern will be devoted to the perturbations in the “free troposphere.” Tropospheric ozone has been building up in many regions of the northern hemisphere. Ozone changes in the upper troposphere will exert a considerable impact on global warming. This could affect moisture levels, cloud amount and distribution, precipitation, and atmospheric dynamics on different scales.

This paper analyzes: (1) the physical and chemical processes contributing to changes in tropospheric ozone concentration; (2) the observational evidence of previous ozone change; and (3) results drawn from computer modelling of past and future radiative forcing caused by rising ozone concentrations in the upper troposphere.

The solar and longwave radiative model developed by Wang et al. (1991) was used for calculating the change in radiative forcing to the troposphere-surface system that can be ascribed to changing concentrations in ozone and other greenhouse gases. Nitric oxide emission from aircraft are a prime suspect for the observed increases in upper tropospheric ozone. The inference can be drawn that a radiative forcing of 0.2 to 0.35 Wm^-2 will result from a doubling of aircraft emissions over the next two decades. This will amount to 10 to 25 percent of the radiative forcing attributable to CO₂ alone for the same period. The effect of doubling aircraft emissions will increase as stratospheric ozone concentrations recover from the recent buildup of harmful chlorofluorocarbons. A large fraction of the radiative forcing that occurred during the 1970 to 1990 period can be attributed to increases in tropospheric ozone as opposed to increases in other greenhouse gases.     

Indoor Ozone Exposures

Indoor and outdoor ozone concentrations were measured from late May through October at three office buildings with very different ventilation rates. The indoor values closely tracked the outdoor values, and, depending on the ventilation rate, were 20 to 80 percent of those outdoors. The Indoor/outdoor data are adequately described with a mass balance model. The model can also be coupled with reported air exchange rates to estimate indoor/outdoor ratios for other structures. The results from this and previous studies indicate that Indoor concentrations are frequently a significant fraction of outdoor values. These observations, and the fact that most people spend greater than 90 percent of their time indoors, indicate that indoor ozone exposure (concentration × time) is greater than outdoor exposure for many people. Relatively Inexpensive strategies exist to reduce indoor ozone levels, and these could be implemented to reduce the public’s total ozone exposure.     

The long range transport of ozone within Europe and its control

It is widely accepted that the ozone concentrations experienced during photochemical episodes over large areas of Europe may exceed levels at which adverse environmental effects could be expected. These peak ozone concentrations can be reduced by controlling atmospheric emissions of the hydrocarbon and nitrogen oxide precursors. For ozone control to be successful over the spatial scale of Europe, long term international cooperation is required in the formulation of emission abatement strategies. A significant barrier to rapid progress has been the complexity of the processes that describe ozone formation. Highly sophisticated computer models of chemistry and transport have, up to now, been the only means to study the impact of abatement strategies. An alternative approach has been adopted here involving the development of a simplified long range transport model for ozone based on the analysis of over 60 experimental runs of a photochemical trajectory model applied to a wide range of hydrocarbon-nitrogen oxide emission combinations. Using the ozone-precursor relationship obtained, it has been possible to examine various policy options in the European context. Although taken together, three illustrative emission control scenarios reduce NO(x) and hydrocarbon emissions substantially through controls on motor vehicle exhaust, large combustion plant and solvent usage, a significant potential for photochemical ozone formation and long range transport may still remain after their implementation. The extents of precursor emission abatement that will be required, if the potential for ozone formation is to be reduced below published air quality criteria guidelines or critical levels, have been determined for each European country. The implied reductions in NO(x) and hydrocarbons relative to current levels amount to between 50 and 90%.     

Performance Characteristics of Instrumental Methods for Monitoring Sulfur Dioxide

The performance characteristics of commercially available continuous sulfur dioxide monitors were determined. Conductimetric, colorimetric, and coulometric analyzers were investigated. The study was conducted to develop information on such instrument characteristics as stability, sensitivity, response time, collection efficiency, and response to interfering substances. The methodology and apparatus used to determine each operational parameter are described. The instrument performance data developed in this study should be useful to those involved in selection of instrumental methods for monitoring atmospheric sulfur dioxide.