2
The mercuric chloride balance during the described events, shown in the right-hand column of Table IV indi- cates that a total of 4375 gg of mercuric ion was lost to the container. Additional studies, summarized in Figure 1, demon- strate that nearly all of the mercuric chloride that has been lost to the container can be recovered with the aid of NaCl and/or HCI. Chloride ions in aqueous and in acid solution appear to prevent binding of HgZT to the con- tainer. We also examined the sorption of mercuric chloride by glass containers. In typical experiments, the Hg2+ concen- tration of a 12-ppb mercuric chloride solution in a 10-liter glass carboy dropped to 10 ppb after 24 hr. This corre- sponds to a 17% loss or 0.008 gg HgZ+/cmz. Similarly, a 30-ppb mercuric chloride solution in a 1-liter volumetric flask lost about 35% of its Hgz+ after 9 days, correspond- ing to 0.02 +g Hg2+ /cmz. Additional experiments have shown that it is relatively safe to store mercuric chloride in the ppm range, since the total loss falls within the ex- perimental error of the analyses. Precleaning the glassware with 5% to 10% "03, fol- lowed by rinsing of the container with a 0.1N HC1 solution containing IN NaC1, effectively removes any adsorbed mercury from the surface. Similarly, addition of NaCl and/or HC1 to dilute mercuric ion solutions prevents loss of mercury to container. Sorption of mercuric ion on glass has been considered as a source of error in analyses since the eighteen hundreds. However, we have not seen any quantitative studies which show distribution of mercuric ion between plastic or glass containers and the solvent, except for a recent report (Carr and Wilkaiss, 1973) which appeared after this work was completed. Our results show that it is possible to desorb nearly all of the mercuric salt from the container with the aid of chloride ion and hydrochloric acid and that wool effective- ly competes with the container for mercuric ions. This ob- servation is not only of theoretical interest but of obvious practical importance. Literature Cited Carr, R. A,, Wilkaiss, D. E., Enuiron. Sci. Technol., 7,62 (1973). Friedman, M., Waiss, Jr.. A. C., ibid., 6,457 (1972). Masri, M. S., Friedman, M., ibid., 6,745 (1972). Received for reuieu February 20, 1973. Accepted July 16, 1973. Ultraviolet Photography of Sulfur Dioxide Plumes Gary M. Klauber Department of Electrical Engineering, The Johns Hopkins University, Baltimore, Md. 21218 A method to image normally invisible SO2 plumes on photographic film, using the sun's ultraviolet light in the absorption band of SO2 near 300 nm, is described. Design of a primitive SOz plume camera is described, and a sam- ple uv SO2 plume photograph is presented. A knowledge of the geometry and ultimate rise of smoke plumes is necessary to predict the ground level concentra- tions of sulfur dioxide downwind of tall, stationary sources. This has typically been done (Hoult et al., 1969) by shutting off the electrostatic precipitators to release visible particulates and photographing this soot plume. This note describes a novel technique for photographing SO2 plumes using the ultraviolet light of the sun and ex- ploiting the uv absorption properties of SOz. Theory SO2 gas absorbs light in the 232-315-nm wavelength range, with a typical Beer-Lambert law absorption coeffi- cient of 0.013 cm-I torr-I at 304 nm (Warneck et al., 1964). Daytime sunlight typically arrives at the earth's surface only at wavelengths above 295 nm, increasing in intensity with increasing wavelength (Coblentz and Stair, 1936; Knestrick and Curcio, 1970). In principle, if a cam- era body were fitted with a lens which passes uv light and an interference filter which admits only those wavelengths absorbed by SO2, photographs of SO2 plumes are possible. The absorption bands of C02, CO, 02, H20, KzO, "3, and NO fall outside of the SO2 band of interest (Thomp- son et al., 1963). Absorption of NO2 is typically a factor of three lower than that of SO2 near 300 nm (Hall and Bla- cet, 1952). Nitrogen oxides are less than 10% NO2 near the stacks, and the stack exit NO, concentration is typi- cally one third of the SO2 concentration (Cuffe and Gers- tle, 1967). Therefore, NO2 interference is two orders of magnitude below SO:! signals near the stack. In the region of ultimate plume rise in urban atmospheres, NO2 inter- ference may be as much as 107'0, due to rapid oxidation of NO to NO2 in the plume. Apparatus A fused quartz simple lens, with focal length 9.5 cm in the ultraviolet, was mounted on a single lens reflex cam- era body at a lens-to-film distance equal to the focal length. A 10-nm bandwidth interference filter centered at 298 nm was mounted immediately behind the lens. The en- trance aperture was fl6. To estimate exposure and to ad- just the focus, a series of trial exposures was made. Kodak High Contrast Copy Film 5069, processed according to manufacturer's directions, was used. The apparatus was then used to photograph power plant plumes perpendicu- lar to their axes. Resul ts A series of pictures was taken of the H. A. Wagner power plant, southeast of Baltimore, Md., on Monday, April 16, 1973, from 11:05 to 11:lO A.M. EST. The bearing of the stacks from the camera was 285" at a range of 1.1 km. Surface winds 10 min earlier at Friendship Airport, 11 km to the east, were 220" at 4 m sec-I. Skys were part- ly cloudy, with a 40% cirrus cover. Figure 1 shows an ordinary visible light photograph of the scene, taken through a standard 50-mm camera lens, where no smoke is visible above the stacks. Figure 2 is an ultraviolet photograph, exposed for 2 sec, taken about 2 min after Figure 1. Note that one of the stacks, number 1 (left), is not in operation. Superposition of ab- sorption by plumes from units 3 and 4 is apparent. The Volume 7. Number 10, October 1973 953

Ultraviolet photography of sulfur dioxide plumes

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Page 1: Ultraviolet photography of sulfur dioxide plumes

The mercuric chloride balance during the described events, shown in the right-hand column of Table IV indi- cates that a total of 4375 gg of mercuric ion was lost to the container.

Additional studies, summarized in Figure 1, demon- strate that nearly all of the mercuric chloride that has been lost to the container can be recovered with the aid of NaCl and/or HCI. Chloride ions in aqueous and in acid solution appear to prevent binding of HgZT to the con- tainer.

We also examined the sorption of mercuric chloride by glass containers. In typical experiments, the Hg2+ concen- tration of a 12-ppb mercuric chloride solution in a 10-liter glass carboy dropped to 10 ppb after 24 hr. This corre- sponds to a 17% loss or 0.008 gg HgZ+/cmz. Similarly, a 30-ppb mercuric chloride solution in a 1-liter volumetric flask lost about 35% of its Hgz+ after 9 days, correspond- ing to 0.02 +g Hg2+ /cmz. Additional experiments have shown that it is relatively safe to store mercuric chloride in the ppm range, since the total loss falls within the ex- perimental error of the analyses.

Precleaning the glassware with 5% to 10% " 0 3 , fol- lowed by rinsing of the container with a 0.1N HC1 solution

containing IN NaC1, effectively removes any adsorbed mercury from the surface. Similarly, addition of NaCl and/or HC1 to dilute mercuric ion solutions prevents loss of mercury to container.

Sorption of mercuric ion on glass has been considered as a source of error in analyses since the eighteen hundreds. However, we have not seen any quantitative studies which show distribution of mercuric ion between plastic or glass containers and the solvent, except for a recent report (Carr and Wilkaiss, 1973) which appeared after this work was completed.

Our results show that it is possible to desorb nearly all of the mercuric salt from the container with the aid of chloride ion and hydrochloric acid and that wool effective- ly competes with the container for mercuric ions. This ob- servation is not only of theoretical interest but of obvious practical importance.

Literature Cited Carr, R. A, , Wilkaiss, D. E., Enuiron. Sci. Technol., 7,62 (1973). Friedman, M., Waiss, Jr.. A. C., ibid., 6,457 (1972). Masri, M. S., Friedman, M., ibid., 6,745 (1972).

Received for reuieu February 20, 1973. Accepted July 16, 1973.

Ultraviolet Photography of Sulfur Dioxide Plumes

Gary M. Klauber Department of Electrical Engineering, The Johns Hopkins University, Baltimore, M d . 21218

A method to image normally invisible SO2 plumes on photographic film, using the sun's ultraviolet light in the absorption band of SO2 near 300 nm, is described. Design of a primitive SOz plume camera is described, and a sam- ple uv SO2 plume photograph is presented.

A knowledge of the geometry and ultimate rise of smoke plumes is necessary to predict the ground level concentra- tions of sulfur dioxide downwind of tall, stationary sources. This has typically been done (Hoult et al., 1969) by shutting off the electrostatic precipitators to release visible particulates and photographing this soot plume. This note describes a novel technique for photographing SO2 plumes using the ultraviolet light of the sun and ex- ploiting the uv absorption properties of SOz .

Theory SO2 gas absorbs light in the 232-315-nm wavelength

range, with a typical Beer-Lambert law absorption coeffi- cient of 0.013 cm-I torr-I a t 304 nm (Warneck et al., 1964). Daytime sunlight typically arrives at the earth's surface only at wavelengths above 295 nm, increasing in intensity with increasing wavelength (Coblentz and Stair, 1936; Knestrick and Curcio, 1970). In principle, if a cam- era body were fitted with a lens which passes uv light and an interference filter which admits only those wavelengths absorbed by SO2, photographs of SO2 plumes are possible.

The absorption bands of C02, CO, 0 2 , H20, KzO, "3,

and NO fall outside of the SO2 band of interest (Thomp- son et al., 1963). Absorption of NO2 is typically a factor of three lower than that of SO2 near 300 nm (Hall and Bla- cet, 1952). Nitrogen oxides are less than 10% NO2 near the stacks, and the stack exit NO, concentration is typi- cally one third of the SO2 concentration (Cuffe and Gers-

tle, 1967). Therefore, NO2 interference is two orders of magnitude below SO:! signals near the stack. In the region of ultimate plume rise in urban atmospheres, NO2 inter- ference may be as much as 107'0, due to rapid oxidation of NO to NO2 in the plume.

Apparatus

A fused quartz simple lens, with focal length 9.5 cm in the ultraviolet, was mounted on a single lens reflex cam- era body at a lens-to-film distance equal to the focal length. A 10-nm bandwidth interference filter centered a t 298 nm was mounted immediately behind the lens. The en- trance aperture was fl6. To estimate exposure and to ad- just the focus, a series of trial exposures was made. Kodak High Contrast Copy Film 5069, processed according to manufacturer's directions, was used. The apparatus was then used to photograph power plant plumes perpendicu- lar to their axes.

Resul t s A series of pictures was taken of the H. A. Wagner

power plant, southeast of Baltimore, Md., on Monday, April 16, 1973, from 11:05 to 11:lO A.M. EST. The bearing of the stacks from the camera was 285" a t a range of 1.1 km. Surface winds 10 min earlier a t Friendship Airport, 11 km to the east, were 220" a t 4 m sec-I. Skys were part- ly cloudy, with a 40% cirrus cover.

Figure 1 shows an ordinary visible light photograph of the scene, taken through a standard 50-mm camera lens, where no smoke is visible above the stacks. Figure 2 is an ultraviolet photograph, exposed for 2 sec, taken about 2 min after Figure 1. Note that one of the stacks, number 1 (left), is not in operation. Superposition of ab- sorption by plumes from units 3 and 4 is apparent. The

Volume 7. Number 10, October 1973 953

Page 2: Ultraviolet photography of sulfur dioxide plumes

i

I

' - - . . /

Figure 1. Ordinaryvisibie-light photograph of Wagner power plant Stacks. Baltimore. Md.. April 16. 1973. 11:05 A M ESl

Figure 2. Ultravi olet photograph of v\i lagner,power plant stacks. Baltimore, Md., April 16, 1973, 11~07 A M EST

plume from stack 4 bends over sooner than that from Acknowledgments stack 3, presumably due to a difference in stack exit con- ditions.

Fuzziness near the edge of the picture is caused hy ah- erration in the lens. White spots on the photo are caused

I wish to thank

of this

G. Fastie and Peter E, for their support and encouragement throughout the

by scratches in the interference filter, and other flaws were generated in photographic processing.

~i~~~~~~~~ ci ted

Coblentz, W. W., Stair, R., J. Res. Not1 Bur. Standards, 17, 1 Conclusions

Ultraviolet photography of SOz plumes has great poten- tial in characterizing plume geometry. Attempts to quan- tify SO2 flux from photographs by densitometry will he complicated hy the nonlinearity of the photographic pro- cess and by variation in films and processing from hatch to hatch. A calibrated absorption cell of SO2 interposed in the optical path to calibrate the system may eliminate some of these problems. In oxidizing urban atmospheres, however, rapid conversion of NO to NO2 in the plume may cause up to about 10% interference from NO2 absorp- tion.

(1936). Cuffe, S. T., Gerstle, R. W., "Emissions From Coal-Fired Power

Plants: A Comprehensive Summary," U.S. Department of Health, Education, and Welfare, Public Health Service Pub. 999-AP-35, Durham, N.C., 1967.

Hall, T. C., Blacet, F. E., J. Chem. Phys., 20,1745 (1952). Hoult, D. P., Far, J. A., Fourney, L. J., J. Air Pollut. Contr. Ass.,

Knestrick, G. L., Curcio, J. A.,Appl. Opt., 9, 1574 (1970). Thompson, B. A., Harteck, P., Reeves, R. R., J. Geaphys. Res.,

Warneck, P., Manna, F. F., Sullivan, J. 0.. J. Chem. Phys., 40,

19,585 (1969).

68,6431 (1963).

1132 (1964).

Receiuedforreuiew June 27, 1973. Accepted July 18, 1973

954 Environmental Science 8 Technology