Estimating Maximum Concentrations for Open Path Monitoring Along a Fixed Beam Path

ABSTRACT

Researchers have applied open path optical sensing techniques to a variety of workplace and environmental monitoring problems. Usually these data are reported in terms of a path-average (or path-integrated) concentration. When assessing potential human exposures along a beam path, this path-average value is not always informative, since concentrations along the path can vary substantially from the beam average. The focus of this research is to arrive at a method for estimating the upper-bound in contaminant concentrations over a fixed open beam path. The approach taken here uses a statistical model to estimate an upper-bound concentration based on a combination of the path-average and a measure of the spatial variability computed from point samples along the beam path. Results of computer simulations and experimental testing in a controlled ventilation chamber indicate that the model produced conservative estimates for the maximum concentration along the beam path. This approach may have many applications for open path monitoring in workplaces or wherever maximum concentrations are a concern.     

Predicting and Managing the Health Risks of Sour-Gas Wells

The development of sour-gas resources in Canada and the United States has prompted concerns about the public health risks of accidental releases of gas contaminated with hydrogen sulfide (H₂S) from wells. This paper focuses on methods for improving the prediction and management of those risks. Data associated with the health effects of hydrogen sulfide are examined, and it is suggested that sublethal effects should be addressed in risk assessments of sour-gas wells along with the life-threatening effects normally considered. The demarcation of hazard zones around wells can be improved by using a statistical approach for estimating an upper-bound H₂S release rate; this rate can then be used in an atmospheric dispersion model to estimate maximum distances to downwind concentrations for lethal (300 ppmv) and sublethal (50 ppmv) effects resulting from an accidental release. A vertical release is found to have little impact, especially under stable atmospheric conditions; horizontal releases, on the other hand, result in the greatest downwind distances for health impacts. Management of health risks depends on a mix of safety technologies and contingency actions, such as well-ignition options and provision for post-release monitoring and assessment of ambient H₂S concentrations.     

Evaluation of Virtual Source Beam Configurations for Rapid Tomographic Reconstruction of Gas and Vapor Concentrations in Workplaces

Abstract

Beam path average data from an Open Path Fourier Transform Infrared (OP-FTIR) spectrometer can be used to reconstruct two-dimensional concentration maps of the gas and vapor contaminants in workplaces and the environment using computed tomographic (CT) techniques. However, a practical limitation arises because in the past, multiple-source and detector units were required to produce a sufficient number of intersecting beam paths in order to reconstruct concentration maps. Such a system can be applied to actual field monitoring situations only with great expense and difficulty. A single monostatic OP-FTIR system capable of rapid beam movement can eliminate this deficiency. Instead of many source and detector units, a virtual source arrangement has been proposed using a number of flat mirrors and retroreflectors to obtain intersecting folded beam paths.

Three virtual source beam configurations generated for a single-beam steerable FTIR system were tested using 54 flat mirrors and four retroreflectors or 54 flat mirrors and 56 retroreflectors mounted along the perimeter walls of a typical 24- x 21-ft test room. The virtual source CT configurations were numerically evaluated using concentration maps created from tracer gas concentration distributions measured experimentally in a test chamber. Synthetic beam path integral data were calculated from the test maps and beam configurations. Computer simulations of different beam configurations were used to determine the effects of beam geometry. The effects of noise and peak-reducing artifacts were evaluated. The performance of the tomographic reconstruction strategy was tested as a function of concentration and concentration gradients.     

The Odor Impact Model

Abstract

This paper presents the simulation and field evaluation results of two approaches to localize pollutant emission sources with open-path Fourier transform infrared (OPFTIR) spectroscopy. The first approach combined the plume’s peak location information reconstructed from the Smooth Basis Function Minimization (SBFM) algorithm and the wind direction data to calculate source projection lines. In the second approach, the plume’s peak location was determined with the Monte Carlo methodology by randomly sampling within the beam segment having the largest path-integrated concentration. We first conducted a series of simulation studies to investigate the sensitivity of using different basis functions in the SBFM algorithm. It was found that fitting with the beta and Weibull basis functions generally gave better estimates of the peak locations than with the normal basis function when the plumes were mainly within the OP-FTIR’s monitoring line. However, for plumes that were symmetric to the peak position or spread over the OP-FTIR, fitting with the normal basis function gave better performance. In the field experiment, two tracer gases were released simultaneously from two locations and the OP-FTIR collected data downwind from the sources with a maximum beam path length of 97 m. For the first approach, the release locations were within the 0.25- to 0.5-probability area only after the uncertainty of the peak locations was included in the calculation process. The second approach was easy to implement and still performed as satisfactorily as the first approach. The distances from the sources to the best-fit lines (i.e., the regression lines) of the estimated locations were smaller than 10 m.     

Developing and evaluating techniques for localizing pollutant emission sources with open-path Fourier transform infrared measurements and wind data

This paper presents the simulation and field evaluation results of two approaches to localize pollutant emission sources with open-path Fourier transform infrared (OP-FTIR) spectroscopy. The first approach combined the plume's peak location information reconstructed from the Smooth Basis Function Minimization (SBFM) algorithm and the wind direction data to calculate source projection lines. In the second approach, the plume's peak location was determined with the Monte Carlo methodology by randomly sampling within the beam segment having the largest path-integrated concentration. We first conducted a series of simulation studies to investigate the sensitivity of using different basis functions in the SBFM algorithm. It was found that fitting with the beta and Weibull basis functions generally gave better estimates of the peak locations than with the normal basis function when the plumes were mainly within the OP-FTIR's monitoring line. However, for plumes that were symmetric to the peak position or spread over the OP-FTIR, fitting with the normal basis function gave better performance. In the field experiment, two tracer gases were released simultaneously from two locations and the OP-FTIR collected data downwind from the sources with a maximum beam path length of 97 m. For the first approach, the release locations were within the 0.25- to 0.5-probability area only after the uncertainty of the peak locations was included in the calculation process. The second approach was easy to implement and still performed as satisfactorily as the first approach. The distances from the sources to the best-fit lines (i.e., the regression lines) of the estimated locations were smaller than 10 m.     

Innovative approach for estimating fugitive gaseous fluxes using computed tomography and remote optical sensing techniques.

This paper presents a new approach to quantify emissions from fugitive gaseous air pollution sources. The authors combine Computed Tomography (CT) with Path-Integrated Optical Remote Sensing (PI-ORS) concentration data in a new field beam geometry. Path-integrated concentrations are sampled in a vertical plane downwind from the source along several radial beam paths. An innovative CT technique, which applies the Smooth Basis Function Minimization method to the beam data in conjunction with measured wind data, is used to estimate the total flux from the fugitive source. The authors conducted a synthetic data study to evaluate the proposed methodology under different meteorological conditions, beam geometry configurations, and simulated measurement errors. The measurement errors were simulated based on data collected with an Open-Path Fourier Transform Infra-Red system. This approach was found to be robust for the simulated errors and for a wide range of fluctuating wind directions. In the very sparse beam geometry examined (eight beam paths), successful emission rates were retrieved over a 70 degrees range of wind directions under extremely large measurement error conditions.     

Localizing gaseous fugitive emission sources by combining real-time optical remote sensing and wind data

This paper presents a new approach to localize point emissions from ground-level fugitive gaseous air pollution sources. We estimate the crosswind plume's ground-level peak location downwind from the source by combining smooth basis functions minimization (SBFM) with pathintegrated optical remote sensing concentration data acquired along the crosswind direction in alternating beam path lengths. Peak location estimates, in conjunction with real-time measured wind direction data, are used to reconstruct the fugitive source location. We conducted a synthetic data study to evaluate the proposed peak location SBFM reconstruction. Furthermore, the methodology was validated with open-path Fourier transform infrared concentration data collected with wind direction data downwind from a controlled point source. This approach was found to provide reasonable estimates of point source location. The field study reconstructed source location was within several meters of the real source location.     

The potential inhalation hazard posed by dioxin contaminated soil.

Mathematical models and field data were used to estimate the airborne concentrations of 2,3,7,8 tetrachlorodibenzo-p-dioxin (TCDD) vapor and particulates which could originate from soil containing 100 ppb TCDD. The model of Jury et al. (1983) and the box approach were used to predict the concentration of TCDD vapor from soil. The daily soil temperature was assumed to vary between 20 degrees C and 40 degrees C for six months of the year to account for diurnal warming and cooling of the soil. The depth of contamination was 50 mm. The model predicted average vapor flux rate for TCDD from soil for this temperature profile was 1.5 x 10(-14) mg/sec-cm2. The upper-bound estimates of the TCDD vapor concentration on-site at 40 degrees C and 20 degrees C were 2.5 pg/m3 and 1.8 pg/m3, respectively. Using a recently proposed unit risk value (URV) of 2.9 x 10(-6) (pg/m3)-1 [slope factor = 1.0 x 10(-14) (mg/kg-day)-1], the maximum plausible cancer risk is about 1 x 10(-5). If one accepts the EPA URV of 3.3 x 10(-5) (pg/m3)-1 (slope factor = 1.2 x 10(-13) (mg/kg-day)-1), then the risk is no greater than 1 x 10(4). A maximum TCDD vapor concentration of 0.21 pg/m3 was predicted 100 meters downwind (for summer days). The on-site concentration of TCDD in suspended particulate was estimated to be 1.4 pg/m3 (based on a TSP level of 0.07 mg/m3 from site soil). For persons exposed to vapors and particulates about 100 meters off-site, the exposure was about 10-fold less.(ABSTRACT TRUNCATED AT 250 WORDS)     

Localizing Gaseous Fugitive Emission Sources by Combining Real-Time Optical Remote Sensing and Wind Data

ABSTRACT

This paper presents a new approach to localize point emissions from ground-level fugitive gaseous air pollution sources. We estimate the crosswind plume's ground-level peak location downwind from the source by combining smooth basis functions minimization (SBFM) with path-integrated optical remote sensing concentration data acquired along the crosswind direction in alternating beam path lengths. Peak location estimates, in conjunction with real-time measured wind direction data, are used to reconstruct the fugitive source location. We conducted a synthetic data study to evaluate the proposed peak location SBFM reconstruction. Furthermore, the methodology was validated with open-path Fourier transform infrared concentration data collected with wind direction data downwind from a controlled point source. This approach was found to provide reasonable estimates of point source location. The field study reconstructed source location was within several meters of the real source location.     

Innovative Approach for Estimating Fugitive Gaseous Fluxes Using Computed Tomography and Remote Optical Sensing Techniques

ABSTRACT

This paper presents a new approach to quantify emissions from fugitive gaseous air pollution sources. The authors combine Computed Tomography (CT) with Path-Integrated Optical Remote Sensing (PI-ORS) concentration data in a new field beam geometry. Path-integrated concentrations are sampled in a vertical plane downwind from the source along several radial beam paths. An innovative CT technique, which applies the Smooth Basis Function Minimization method to the beam data in conjunction with measured wind data, is used to estimate the total flux from the fugitive source. The authors conducted a synthetic data study to evaluate the proposed methodology under different meteorological conditions, beam geometry configurations, and simulated measurement errors. The measurement errors were simulated based on data collected with an Open-Path Fourier Transform Infra-Red system. This approach was found to be robust for the simulated errors and for a wide range of fluctuating wind directions. In the very sparse beam geometry examined (eight beam paths), successful emission rates were retrieved over a 70° range of wind directions under extremely large measurement error conditions.     

Abundance and sources of ambient dioxins in Hong Kong: a review of dioxin measurements from 1997 to 2001

Ambient measurements of seventeen 2,3,7,8-polychlorinated dibenzo-p-dioxin/dibenzofuran congeners (2,3,7,8-PCDD/Fs) have been taken in a number of monitoring programs or ad-hoc studies in Hong Kong. The longest monitoring program started at two locations in the territory in July 1997. The other monitoring efforts are ad-hoc studies, varying from a few coordinated sampling events at multiple sites to a year-long monitoring project that targeted suspected local dioxin sources. In this paper, we examined these measurements to understand the ambient levels, temporal and spatial variation, and possible sources of the 2,3,7,8-PCDD/Fs in Hong Kong. The territory-wide annual average concentration of the dioxins was 0.052 pg I-TEQ/m3 measured at the regular monitoring stations in the most recent annual cycle of 2000/2001. This level fell at the lower end of the range of dioxin concentrations measured at other urban locations around the world. The dioxin levels showed a clear seasonality in that elevated concentrations were observed in the winter and lower concentrations in the summer at all monitoring sites with one year or more regular measurements. The measurements indicated that the few known local dioxin sources, including a major chemical waste incinerator facility, landfill sites, and vehicular traffic, are not important contributors to ambient dioxins in Hong Kong. On days of high dioxin concentrations, the 2,3,7,8-PCDD/F congeners were observed to have almost identical compositions with a north-northwest to south-southeast spatial gradient in concentrations at different sampling locations in Hong Kong. This observation, along with other collaborative evidence, established a strong link between high dioxin concentration days in Hong Kong and regional transport of the polluted air masses from the north.     

Workplace and Environmental Air Contaminant Concentrations Measured by Open Path Fourier Transform Infrared Spectroscopy: A Statistical Process Control Technique to Detect Changes from Normal Operating Conditions

Open path Fourier transform infrared (OP-FTIR) spectroscopy is a new air monitoring technique that can be used to measure concentrations of air contaminants in real or near-real time. OP-FTIR spectroscopy has been used to monitor workplace gas and vapor exposures, emissions from hazardous waste sites, and to track emissions along fence lines. This paper discusses a statistical process control technique that can be used with air monitoring data collected with an OP-FTIR spectrometer to detect departures from normal operating conditions in the workplace or along a fence line. Time series data, produced by plotting consecutive air sample concentrations in time, were analyzed. Autocorrelation in the time series data was removed by fitting dynamic models. Control charts were used with the residuals of the model fit data to determine if departures from defined normal operating conditions could be rapidly detected. Shewhart and exponentially weighted moving average (EWMA) control charts were evaluated for use with data collected under different room air flow and mixing conditions.

Under rapidly changing conditions the Shewhart control chart was able to detect a leak in a simulated process area. The EWMA control chart was found to be more sensitive to drifts and slowly changing concentrations in air monitoring data. The time series and statistical process control techniques were also applied to data obtained during a field study at a chemical plant. A production area of an acrylonitrile, 1,3-butadiene, and styrene (ABS) polymer process was monitored in near-real time. Decision logics based on the time series and statistical process control technique introduced suggest several applications in workplace and environmental monitoring. These applications might include signaling of an alarm or warning, increasing levels of worker respiratory protection, or evacuation of a community, when gas and vapor concentrations are determined to be out-of-control.     

Comparison of line– and point–source releases of tracer gases

Field measurements were made of greenhouse gas emissions from a wastewater treatment system using open path monitoring with detection by FTIR spectroscopy. Emission rates were determined by the ratio technique using a sulfur hexafluoride tracer gas released from a line source. As a quality control check, a second tracer gas – ethylene – was released from various single point locations. This paper presents a comparison of the line-source and point-source tracer releases for approximating emissions from the area source. The two types of tracer release showed excellent agreement when both release points were two hundred meters from the FTIR beam path. Data for other release points also were comparable, once differences in vertical dispersion as a function of distance are taken into account.     

Experimental investigation of outdoor and indoor mean concentrations and concentration fluctuations of pollutants

Tracer gas was released upwind of a two-compartment complex shaped building under unstable atmospheric conditions. The mean wind direction was normal to or at 45° to the long face of the building. The general patterns of concentration distribution on the building external walls and inside the building were analysed and the influence of natural and mechanical ventilation on indoor concentration distributions was discussed. Mean concentration levels, as well as the concentration fluctuation intensity, were higher on the windward walls of the building, although concentration levels varied along each wall. Concentration fluctuations measured inside the building were lower than those measured outside. Inside the two compartments of the building, the time series of concentrations had a similar general behaviour; however, gas concentrations took approximately 1.5 times longer to reach the mean maximum concentration value at the downwind compartment 02 while they also decreased more rapidly in the upwind compartment 01 after the source was turned off. The highest indoor concentration and concentration fluctuation values were observed at the detectors located close to the windward walls, especially when the building windows were open. Experiments with and without natural ventilation suggested that infiltration and exfiltration of contaminants is much faster when the building windows are open, resulting to higher indoor concentration levels. Furthermore, mechanical ventilation tends to homogenize concentrations and suppress concentration fluctuations, leading to lower maximum concentration values.     

Tomographic reconstruction of tracer gas concentration profiles in a room with the use of a single OP-FTIR and two iterative algorithms: ART and PWLS

Computed tomographic (CT) reconstructions of air contaminant concentration fields were conducted in a room-sized chamber employing a single open-path Fourier transform infrared (OP-FTIR) instrument and a combination of 52 flat mirrors and 4 retroreflectors. A total of 56 beam path data were repeatedly collected for around 1 hr while maintaining a stable concentration gradient. The plane of the room was divided into 195 pixels (13 x 15) for reconstruction. The algebraic reconstruction technique (ART) failed to reconstruct the original concentration gradient patterns for most cases. These poor results were caused by the "highly underdetermined condition" in which the number of unknown values (156 pixels) exceeds that of known data (56 path integral concentrations) in the experimental setting. A new CT algorithm, called the penalized weighted least-squares (PWLS), was applied to remedy this condition. The peak locations were correctly positioned in the PWLS-CT reconstructions. A notable feature of the PWLS-CT reconstructions was a significant reduction of highly irregular noise peaks found in the ART-CT reconstructions. However, the peak heights were slightly reduced in the PWLS-CT reconstructions due to the nature of the PWLS algorithm. PWLS could converge on the original concentration gradient even when a fairly high error was embedded into some experimentally measured path integral concentrations. It was also found in the simulation tests that the PWLS algorithm was very robust with respect to random errors in the path integral concentrations. This beam geometry and the use of a single OP-FTIR scanning system, in combination with the PWLS algorithm, is a system applicable to both environmental and industrial settings.     

Carbon monoxide concentration forecasting in Santiago, Chile

In the city of Santiago, Chile, air quality is defined in terms of particulate matter with an aerodynamic diameter < or = 10 microm (PM10) concentrations. An air quality forecasting model based on past concentrations of PM10 and meteorological conditions currently is used by the metropolitan agency for the environment, which allows restrictions to emissions to be imposed in advance. This model, however, fails to forecast between 40 and 50% of the days considered to be harmful for the inhabitants every year. Given that a high correlation between particulate matter and carbon monoxide (CO) concentrations is observed at monitoring stations in the city, a model for CO concentration forecasting would be a useful tool to complement information about expected air quality in the city. Here, the results of a neural network-based model aimed to forecast maximum values of the 8-hr moving average of CO concentrations for the next day are presented. Forecasts from the neural network model are compared with those produced with linear regressions. The neural network model seems to leave more room to adjust free parameters with 1-yr data to predict the following year's values. We have worked with 3 yr of data measured at the monitoring station located in the zone with the worst air quality in the city of Santiago, Chile.     

Microbial in situ degradation of aromatic hydrocarbons in a contaminated aquifer monitored by carbon isotope fractionation

We present an approach for characterizing in situ microbial degradation using the 13C/12C isotope fractionation of contaminants as an indicator of biodegradation. The 13C/12C isotope fractionation of aromatic hydrocarbons was studied in anoxic laboratory soil percolation columns with toluene or o-xylene as the sole carbon and electron source, and sulfate as electron acceptor. After approximately 2 months' of incubation, the soil microbial community degraded 32 mg toluene l(-1) and 44 mg o-xylene l(-1) to less than 0.05 mg l(-1), generating a stable concentration gradient in the column. The 13C/12C isotope ratio in the residual non-degraded fraction of toluene and o-xylene increased significantly, corresponding to isotope fractionation factors (alphaC) of 1.0015 and 1.0011, respectively. When the extent of biodegradation in the soil column was calculated based on the measured isotope ratios (R(t)) and an isotope fractionation factor (alphaC=1.0017) obtained from a sulfate-reducing batch culture the theoretical residual substrate concentrations (C(t)) matched the measured toluene concentrations in the column. This indicated that a calculation of biodegradation based on isotope fractionation could work in systems like soil columns. In a field study, a polluted, anoxic aquifer was analyzed for BTEX and PAH contaminants. These compounds were found to exhibit a significant concentration gradient along an 800-m groundwater flow path downstream of the source of contamination. A distinct increase in the carbon isotope ratio (delta13C) was observed for the residual non-degraded toluene (7.2 per thousand ), o-xylene (8.1 per thousand ) and naphthalene fractions (1.2 per thousand ). Based on the isotope values and the laboratory-derived isotope fractionation factors for toluene and o-xylene, the extent to which the residual substrate fraction in the monitoring wells had been degraded by microorganisms was calculated. The results revealed significant biodegradation along the groundwater flow path. In the wells at the end of the plume, the bioavailable toluene and o-xylene fractions had been almost completely reduced by in situ microbial degradation. Although indane and indene showed decreasing concentrations downstream of the groundwater flow path, suggesting microbial degradation, their carbon isotope ratios remained constant. As the physical properties of these compounds are similar to those of BTEX compounds, the constant isotope values of indane and indene indicated that microbial degradation did not lead to isotope fractionation of all aromatic hydrocarbons. In addition, physical interaction with the aquifer material during the groundwater passage did not significantly alter the carbon isotope composition of aromatic hydrocarbons.     

A model for the maximum credible hourly impact on any ground receptor from point sources with thermal plume rise

A pollutant dispersion model is developed, allowing fast evaluation of the maximum credible 1-h average concentration on any given ground-level receptor, along with the corresponding critical meteorological conditions (wind speed and stability class) for stacks with buoyant plumes in urban or rural areas. Site-specific meteorological data are not required, as the computed concentrations are maximized against all credible combinations of wind speed, stability class, and mixing height. The analysis is based on the dispersion relations of Pasquill-Gifford and Briggs for rural and urban settings, respectively, the buoyancy induced dispersion correlation of Pasquill, the wind profile exponent values suggested by Irwin, the buoyant plume rise relations of Briggs, as well as the Benkley and Schulman's model for the minimum mixing heights. The model is particularly suited for air pollution management studies, as it allows fast screening of the maximum impact on any selected receptor and evaluation of the ways to have this impact reduced. It is also suited for regulatory purposes, as it can be used to define the minimum stack size requirements for a given source as a function of the exit gas volume and temperature, the pollutant emission rates and their hourly concentration standards, as well as the source location relative to sensitive receptors.     

Analysis of Sampling Strategies for Estimating Annual Average Indoor NO2 Concentrations in Residences with Gas Ranges

Abstract

Range gas consumption in households tends to follow an annual cycle resembling a sinusoid, with peak consumption during the winter. When outdoor NO2 concentrations have a constant or small impact, the resulting indoor NO2 concentrations also tend to resemble an annual sinusoid. Optimal monitoring strategies can be designed to take advantage of this knowledge to obtain a better estimate of the true annual average gas consumption or indoor NO2 concentration. Gas consumption data, together with measured outdoor concentrations, house volumes, sampled emission rates, air exchange rates, and NO2 decay rates, are used to model weekly indoor NO2 concentrations throughout the year. Based on the modeling results, various monitoring strategies are evaluated for their accuracy in estimating the annual mean. Analysis of the results indicates that greater accuracy is attained using samples equally spaced throughout the year. In addition, the expected error for various monitoring strategies and various numbers of equally spaced samples is quantified, and their ability to classify homes into correct concentration categories is assessed.     

Carbon monoxide modeling from transportation sources.

Street canyon module and gaussian line source module of a regional-scale dispersion model Indic Airviro were used to simulate ambient carbon monoxide (CO) concentrations due to traffic flow at two roadside monitoring locations in Singapore. The fleet average emission factors for each vehicle category was estimated from US EPA MOBILE 5 A guidelines as a function of speed, vehicle deterioration rates and model years. 1-h CO concentrations and worst case 8-h levels have been simulated and compared with measured readings. This study used model-simulated rooftop concentration levels from non-localized sources as background levels at the two sites. The resulting CO concentrations correlate well with actual measured levels and provide a unique approach to predict the impact of CO from transportation.