CHARACTERIZATION OF LEAD AND CADMIUM SPECIES IN EMISSIONS FROMMUNITIONS DEACTIVATION FURNACE

Veera M. Boddu* and K. James HayU.S. Army Engineer Research and Development Center

Construction Engineering Research Laboratory (ERDC-CERL)P.O. Box 9005, Champaign, IL 61826-9005

Larry CottoneCCI Environmental Consultants, Inc.

3855 South 500 West, Suite I, Salt Lake City, Utah 84115

ABSTRACT

Information on the chemical species, and phase and ERDC-CERL has conducted a sampling study on theparticle size distribution of lead and cadmium species is conventional demilitarization furnace APE 1236 at therequired for developing strategies for pollution Tooele Army Depot.prevention, environmental compliance, and mitigationstrategies for controlling hazardous air pollutantemissions from Army munitions deactivation furnaces. 2. EXPERIMENTAL APPROACHEmissions samples were collected from the furnaceexhaust system on a small arms deactivation furnace at A schematic of the deactivation furnace is shown inTooele Army Depot, Tooele, Utah. The samples Figure 1. The samples were collected at near isokineticcollected were analyzed using standard U.S. conditions in a temperature range of 400 to 1600 'F.Environmental Protection Agency methods and other Samples were collected at three different locations [(1)laboratory chemical and physical methods to obtain after the cyclone, (2) on the duct before the ceramic filterparticulate size distribution and to identify lead and house, and (3) on the stack after the ceramic filter house]cadmium species. Results show that lead is a major on the furnace exhaust system. Due to the regulatorycomponent of the particulate matter while antimony is a importance of the semi-volatile metals, an emphasis wasdistant second. Lead oxides and carbonates are the placed on characterizing the lead and cadmium species,dominant species. Cadmium is not a major component which are expected to be in the form of aerosols orin the emissions for the two munitions deactivated. The particulates after combustion. Emissions sampling wasresults showed that nearly 45-58% of the particulate conducted while two types of munitions were deactivatedemissions are of particulate matter PM2.5. to determine composition, phase distribution, and particle

size distributions.

1. INTRODUCTION

The Army releases hazardous air pollutants into theatmosphere from its weapons demilitarization andtraining activities. Of significant concern is the fineparticulate material (PM2.5) containing lead andcadmium that is generated by demilitarization furnaces.The Army currently uses ceramic baghouses to controlthese emissions from its demilitarization furnaces. Themaintenance of these baghouses can be expensive whenthe candle filters become plugged. ERDC-CERL isdeveloping new control technologies to lessen themaintenance requirements and to reduce the overall Fig. 1: Schematic of a conventional small armsmetal emissions to surroundings. Knowledge of the deactivation furnace.various metal species present in the emissions may helpwith development of effective emission controltechnologies designs, efficient means of operation of thefurnace, and pollution prevention strategies. Thus,

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1. REPORT DATE 2. REPORT TYPE 3. DATES COVERED

00 DEC 2004 N/A

4. TITLE AND SUBTITLE 5a. CONTRACT NUMBER

Characterization Of Lead And Cadmium Species In Emissions From 5b. GRANT NUMBER

Munitions Deactivation Furnace5c. PROGRAM ELEMENT NUMBER

6. AUTHOR(S) 5d. PROJECT NUMBER

5e. TASK NUMBER

5f. WORK UNIT NUMBER

7. PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES) 8. PERFORMING ORGANIZATION

U.S. Army Engineer Research and Development Center Construction REPORT NUMBER

Engineering Research Laboratory (ERDC-CERL) P.O. Box 9005,Champaign, IL 61826-9005; CCI Environmental Consultants, Inc. 3855South 500 West, Suite I, Salt Lake City, Utah 84115

9. SPONSORING/MONITORING AGENCY NAME(S) AND ADDRESS(ES) 10. SPONSOR/MONITOR'S ACRONYM(S)

11. SPONSOR/MONITOR'S REPORT

NUMBER(S)

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Approved for public release, distribution unlimited

13. SUPPLEMENTARY NOTES

See also ADM001736, Proceedings for the Army Science Conference (24th) Held on 29 November - 2December 2005 in Orlando, Florida., The original document contains color images.

14. ABSTRACT

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3. ANALYTICAL METHODS Carbon is prevalent in the combustion gas as well asin the propellant. However, the organic carbon and

Analytical procedures/methods were established for elemental carbon analyses of the filter catches indicatedidentification and quantification of the major chemical that an average of less than 1% of the filter mass wasspecies (lead and cadmium oxides, sulfides, sulfates, composed of carbon, almost all of which was organicnitrates, nitrites, chlorides, and metals of lead and carbon. An average of less than 0.04% of the filtercadmium), and particle size and distribution of the weight gain was identified as inorganic carbon. Hydro-particles. Gaseous fractions and particulate fractions were cerrusite (Pb3(CO3) 2(OH)2) was positively identified as acollected in solutions and quartz filters. These fractions minor component of the filter catch by the XRD analyses.were subjected to further solubilization and extractions toidentify anions and cations apart from identification of Sulfur was not found on the filters in significantmetals. Filterable particulate matter samples were quantities by XRF. Sulfate was measured by ioncollected on quartz fiber filters for analyses using X-ray chromatography in the water-soluble fraction of the filterfluorescence (XRF), X-ray diffraction (XRD), atomic catch as the third highest component on the filter. PbS,absorption spectroscopy, ion chromatography (IC), PbSO 4, PbSO 4.PbO, Pb(HS0 4)2 .H 20, PbS2O8 .3H 20, andinductively coupled argon-plasma spectroscopy (ICP) and PbSO 3 are the possible sulphur-lead compounds.for elemental and organic carbon (EC/OC) analyses.

Figure 2 is a typical particle size analysis datacollected from a filter immediately after the after burner.

4. RESULTS Nearly 45% of the mass on the filter is in the form ofPM2.5. The fraction of PM2.5 increases to 58% for the

The results show that lead is by far the predominant sample collected after the baghouse.component of the particulate matter. Antimony is a distantsecond, with lead oxides and carbonates being the Curnrrulative Percent by Mass versus Parde Darreer.

dominant species. An estimated 40% of the total filter 100

mass was quantitatively identified. The XRD analysesindicated that a large fraction of the weight gain (> 25%) 80 -

was of a crystalline form that could not be identified. Anadditional large fraction (>30% of the weight) was non- - _o

crystalline and was suspected to be lead-bearing. Therewas a major contribution by lead mono-oxide (litharge) .and a minor contribution of lead carbonate hydroxide. 40 •

Other expected contributing lead oxides include Pb 20 3, C "Pb30 4, PbO2, and Pb 20. The oxygen in these compounds U 20

can account only for up to 4% of the unidentified filtermass. These observations may be interpreted to infer that 0< 45% of the total filter weight gain was in the form of 0.1 0. 1 5 10 50 10

lead oxide. Lead nitrates (Pb(N0 3)2 and Pb(OH)NO3) and • ...........nitrites (3PbO.N 20 3.H 20) could account at most for an Fig. 2. Cumulative Percent by Mass vs. Particle

additional 15% of the total unidentified mass collected on Diameter (sample collected after the afterburner, for

the filters. A few components that are expected to 20-millimeter ammunition)

significantly contribute to the remaining 60% of the masscaptured on the filters were not analyzed. Oxygen,nitrogen, silica, and water (hydrating other molecules) are CONCLUSIONthe primary components of concern. The lead and cadmium emissions from the

Off-gases from the natural gas combustion, combustion processes are generally believed to be

combined with excess air fed to the burners and in- predominantly in the form of aerosols or particulates.

leakage to the exhaust system, will generally include The results show that lead is by far the predominant

fairly large amounts of the following gases: oxygen (15 component of the particulate matter. Antimony is a

to 16% in the stack gas), carbon dioxide (3.5 to 4.5% in distant second, with lead oxides and carbonates being the

the stack gas), nitrogen (approximately 80% in the stack dominant species. This information can be used to

gas), nitrogen oxide, nitrogen dioxide, water (approxi- design intervening processes to enhance particle growth

mately 5% in the stack gas), and carbon monoxide or agglomeration or introduce other chemical species to

(approximately I to 2 ppm in the stack gas). form environmentally benign species to reduce overallimpact of the hazardous air pollutants released frommunitions deactivation furnaces.

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