Eaton, and Dr. Alan Maki for contributing helpful information and for encouragement to prepare this document. Literature Cited (1) Atkins, E. L., Greywood, E. A , , Macdonald, R. L., Agricultural Extension. Universitv of California. Riverside. Calif.. unwblished report no. M-16, IL97k. ( 2 ) Batchelder, T. I,., McCartv, W. M., Dow Chemical U.S.A., Midland, Mich., unpublished LC50 studies on Daphnia, 1978. ( 3 ) Heath, R. G., Spann, J. W., Hill, E. F., Kreitzer, J. F., U . S .Fish Wildl. Seru., S p e c Sci. Rep., Wildl., No. 152 (1972). (4) Hill, E. F., Heath, R. G., Spann, J. W., Williams, J. D., ibid., No. 191 (1975). ( 5 ) Kenaga, E. E., Ehd, C. S., 1974. “Commercial and Experimental Organic Insecticides”, Entomological Society of America, Special Publication 74-1. College Park, Md., 77 pp, 1974. (6) Kenaga. E. E., Dou n Earth, 23 (4), 11-4, 16-8 (1968). (7) Macek, K. J., McAllister, W. A,, Trans. Am. Fish. Soc., 99 ( l ) , 20-7 (1970). (8) Pearson, d. G., Crlennon. J . P.. Barkley, J . J., Highfill, J. W., “An Approach to the Toxicological Evaluation of a Complex Industrial IVastewater”, ASTM Second Symposium on Aquatic Toxicology, Cleveland, Ohio, Oct. 31-Nov. 1, 1977. (9) Sanders. H. 0.. J . Water Pollut. Control Fed.. Part 1. 42 (8). 1544-80 (1970). (10) Sanders, H 0 , Tech P a p Bur Sport Fish Wildl C S No. 66, 1-19 (1972). (11) Sanders, H. O., Cope, 0 B., Trans Am Fish Soc , 95 (21,165-9
(1966). (12) Schafer, E. W., Toxicol. Appl. Pharmacol., 21,315-30 (1972). (13) Schafer. E. W.. Jr.. Cunnineham. D. J.. U.S. Fish. Wildl. Seru.. Spec. ~ c ik.e p . , ~ i l d l . NO. , 150 (1972). (14) Tucker, R. K., Crabtree, D. G., Bur. Sport Fish.Wildl.. Resource Publ., No. 84 (1970) (also, private communication from Tucker and Hudson). (15) Tucker, R. K., Haegele, M. A., Toxicol. Appl. Pharrnacol., 20, 50-66 (1971). (16) U.S. Fish Wildl. Seru., Circ., No. 143 (1962). (17) Ibid., No. 167 (1963). (18) Ibid., No. 199 (1964). (19) Ibid., No. 226 (1965). (20) US.Department of Interior, Sport Fishery Research, Quarterly Progress Reports, quarter ending Mar. 31, 1966, pp 24, 33-39, 1966. (21) US.Department of Interior, Report of the Committee on Water Criteria, Federal Water Pollution Control Administration, Washington, D.C., 234 pp, 1968. (22) U S . Department of Interior, Progress in Sport Fishery Research, Resource Publ. No. 106, Washington, D.C., 27 pp, 1970. (23) Fed. Reg., 43 (163), 37336-403 (1978). (24) “Herbicide Handbook of the Weed Science Society of America”, 3rd ed, Weed Science Society of America, Champaign, Ill., 430 pp, 1974. (25) Willford, W. A,, “Toxicity of 22 Therapeutic Compounds to Six Fishes. Investigations in Fish Control”, Resource Publ. No. 35, US. Department of Interior, Washington, D.C., 10 pp, 1966.
Receiced for reciew March 2, 1978. Accepted August 14, 1978
NOTES
Composition of Particles Emitted from the Nicosia Municipal Incinerator Robert R. Greenberg’, Glen E. Gordon*, and William H. Zoller Department of Chemistry, University of Maryland, College Park, Md. 20742
Robert 6. Jacko, David W. Neuendorf, and Kenneth J. Yost Department of Civil Engineering and School of Pharmacy, Purdue University, West Lafayette, Ind. 47907
Concentrations of 28 elements in suspended particulate material from the Nicosia incinerator are measured, as well as size distributions of particles bearing four elements, Zn, Pb, Cu, and Cd. Despite the fact that this incinerator serves a highly industrialized and commercial area, the compositions and size distributions of emitted particles are very similar to those from two incinerators in the Washington, D.C., area that serve residential and commercial areas. Previous studies of two municipal incinerators in the Washington, D.C.. area ( 1 ) have indicated that the incineration of urban refuse may be responsible for major fractions of the masses of Zn, Cd, Sb, and possibly Sn, In, and Ag found on aerosols in many U.S. cities. This conclusion, however, is subject to the criticism that, as the composition of input refuse may vary considerably from one incinerator to another, there may also be wide variations in the composition of emitted particles. T o provide additional information on the variations
from one incinerator to another, we determined the composition of suspended particles and the size distributions of particles bearing several important metals from a third incinerator. This incinerator serves a mixed industrial, commercia1,residential area in East Chicago and Hammond, Ind., whereas the other two incinerators studied served largely residential, lightly commercial areas around Washington, D.C. The question of emissions from refuse incineration is especially important in view of the fact that there is much interest by communities in the U S . in the use of refuse-derived fuel as an energy source and a means of disposal of refuse. Plant Description
Present address, Center l o r Analytical Chemislry, National Bureau of Standards, Washington, D.C. 20234. 0013-936X/78/0912~-1329$01.OO/O
@ 1978 American Chemical Society
The John D. Nicosia Municipal Incinerator in East Chicago, Ind., has two furnace trains, each designed to incinerate 204 metric tons of refuse daily (Figure 1).The furnaces are selfsustaining after initial start-up. The emission-control system consists of a spray chamber followed by a three-stage, horizontal, plate-type scrubbing tower. Suspended particles removed from the gas stream by the scrubbers are recovered from the closed-loop water system by disposable filters (2). Volume 12, Number 12, November 1978
1329
Table 1. Concentrations of Elements Observed in Nicosia Municipal Incinerator Suspended Particles element
Na ( % ) cs Mg (Yo) Ba CI (%) Br AI ( % ) Ti ( % ) Cr Mn Fe(%) co Ni cu Zn (YO) As Se Ag Cd In Sn (YO) Sb La Sm Th
w Au Pb (Yo)
av
concn (pglg unless SD'
*
8.2 f 1.3 8.5 f 3.3 2.8 f 0.8 220 f 130 27 f 3 880 f 390 e0.5 %0.05b 105 f 17 270 f 80 0.33 f 0.15 2.3 f 0.5 79 f 29 1700 f 300 11.4 f 2.8 200 f 90 49 f 37 110 f 80 1500 f 400 6.5 f 3.6 1.29 f 0.16 1600 & 800 2.9 k 0.6 0.40 f 0.20 0.37 f 0.28 =8 0.43 f 0.18 6.9 f 1.0
Oh
indicated) range
5.1-9.5 4.0-15.7 1.7-4.0 40-470 22-33 490-1600
67- 128 170-380 0.17-0.63 1.8-3.3 42-130 1200-2 100 8.3-17.8 81-330 24-122 43-300 950-2200 3.7-15.8 1.09-1.51 850-3700 0.92-5.6 0.15-0.73 0.15-0.84
because of high filter blanks.
Sample Collection Sampling was performed using two 7.6-cm ports a t 90-deg to each other in the stack a t a point 8 m above the roof line, more than six stack diameters beyond any perturbations. Thus, the velocity profile across the stack was quite smooth as shown by pitot-tube measurements a t eight points along each of two perpendicular traverses of the stack. The probe with the pitot tube was also used for sampling according to EPA methods specified for incinerators ( 3 ) ,except that 1M "03 was substituted for water in the impingers and these solutions were saved for analysis. Particulate samples were collected isokinetically on 12.5-cm diam Reeve Angel Grade 900 AF glass-fiber filters a t each of the eight points on the two perpendicular traverses. In the first four runs, particles were sampled for 5 min a t each point and, in the remaining seven experiments, for 10 min a t each point. In two additional experiments, an Andersen fractionating sampler was used to separate the particles into different size groups. The sampler was attached to the nozzle end of the probe and inserted directly into the stack. Collection surfaces of the Andersen sampler were acetone-washed stainless steel, and the back-up filter was cut from the same glass-fiber material as used for whole-filter collections. For more details on the collection of samples, see ref. 4 . Analytical Techniques The whole-filter, suspended-particle samples were analyzed mainly by instrumental neutron activation analysis (INAA) a t the National Bureau of Standards (NBS) reactor using Environmental Science & Technology
Y
RECEIVING AREA
I00
, , ,
I
4
I
I
I
I 1 1 / 1
Size Distributions
,
Y
1
-
Nicosia Incinerator
I;'
15 pm; last stage (back-upfilter) collected particles < O X ,um
techniques previously described ( 5 ) .The accuracy of these analyses was checked by analyzing NBS Standard Reference Material #1633 (Fly Ash) and obtaining results in good agreement with those previously given ( 5 ) .Lead, Ni, and Cu were measured by atomic absorption spectrophotometry (AAS) of material leached from the filters with "03. Cadmium and Zn were measured by both techniques ( I ) . The size-fractionated, suspended-particle samples and the "03 solutions from the impingers were analyzed by AAS for Cu, Cd, P b , and Zn. Since the nuclear analyses were performed on the filters plus collected material, it was necessary to analyze clean filters from the same lot to determine corrections for filter blanks. The filter blanks for many elements normally measurable ( 1 ) by INAA were too large to permit measurements of these elements in the filter deposits (Ca, Sc, V, Ce, Eu, Lu, Yb, Hf, and Ta). The blanks for W, Al, and Ti were so high that we are able to report only approximate values for those elements below in Table I. For all other elements reported, the estimated analytical error, including uncertainty in blank corrections is comparable to or, usually, less than the observed sampleto-sample variation. Results and Discussion From the masses of material deposited on the filters per unit
Table II. Comparison of Suspended Particles from Three Municipal Incinerators element
Na (YO)
cs Mg ( % I
Ba CI (Yo) Br AI ( % ) Ti
Cr Mn Fe
co Ni
cu Zn ( % ) As Se Ag
Cd
In Sn (YO)
Sb La Sm Th
w
Alexandria
9.8 f 2.aa 3.1 f 1.7 0.68 f 0.25 ago f 570 20 f 5 2600 f 1400 1.6 f 0.8 2900 f 1400 490 f 350 1500 f 1400 9000 f 3300 12f7 200 f ao 2000 f 1200 12f6 210 f 100 23 f 21 390 f 360 1100 f 400 6.5 f 5.4 1.07 f 0.15 2400 f 2400 3.8 f 2.6 -0.8
1.8 f 1.4 1 7 f 11 0.71 f 0.77 9.7 f 2.6
concn ( p g l g unless % indicated) SWRC #1 Nicosia
6.5 f 1.3a 5.5 f 2.2 0.36 f 0.07 990 f 410 14f3 920 f 520 2.1 f 1.0 3600 f 2000 a70 f 370 410 f 110 7100 f 1400 5.4 f 2.5 170 f 70 1500 f 500 13f5 310 f 160 39 f 29 1000 rt aoo 1900 f 700 3.6 f 0.7 1.08 f 0.11 2400 f 1100 4.6 f 1.1 0.62 f 0.15 -3 22 f a 0.70 f 0.06 7.7 f 1.1
8.2 f i.3a 8.5 f 3.3 2.8 f 0.8 220 f 130 27 f 3 a80 f 390 -O.!jc
~ 5 0 0 ~
105 f 17 270 ao 3300 f 1500 2.3 f 0.5 79 f 29 1700 f 300 11 f 3 200 f 90 49 f 37 i i o f ao 1500 f 400 6.5 f 0.7 1.29 f 0.16 1600 aoo 2.9 f 1.6 0.40 f 0.20 0.37 f 0.28
=a
av
8.2 f 1.76 5.7 f 2.7 1.3 f 1.3 700 f 420 20 f 7 1500 f 1000 1.4 f 0.8 2400 f 1600 490 f 380 730 f 670 6500 f 2900 6.6 f 5.0 150 f 60 1700 f 300 12f 1 240 f 60 37 f 13 500 f 460 1500 f 400 5.5 f 1.7 1.15 f 0.12 2100 f 500 3.7 f 0.7 0.6 f 0.2 16f7
0.43 f 0.18 0.61 f 0.16 Au 8.1 f 1.1 6.9 f 1.0 Pb (%) a Uncertainties are standard deviations. Uncertainties are standard deviations of the averages from three incinerators. High blank values allow for only approximations.
volume of stack gas samples, the stack cross-sectional area, and velocity profile, we found that the particulate loading in the stack varied from 210 to 410 mg/ms under normal operating conditions (corrected to 294 K, 1 atm, dry gases). The total mass emission rate varied from 16 to about 30 kg/h for one of the twin furnaces, corresponding to an average output of 4 kg/tonne of refuse consumed. The latter figure is to be compared to the values of 2.8 and 0.46 kg/tonne of refuse from the Washington-area incinerators a t Alexandria, Va., and Solid Waste Reduction Center # 1 (SWRC) in Washington, D.C., respectively ( I ) . The Andersen sampler results indicated particulate loadings comparable with those from whole filters, but with lower accuracy. The average elemental concentrations, standard deviations, and ranges observed in the suspended particles from the Nicosia incinerator are listed in Table I. The observed sampleto-sample variation is quite small in view of the variable nature of urban refuse. The average elemental concentrations observed in the suspended particles from the Nicosia incinerator are compared in Table I1 with those of the Alexandria incinerator and SWRC ( I ) . Quite good agreement is observed among the three incinerators. Greater variability is observed among coal-fired power plants even after normalizing to the composition of coal burned (6, 7). Predominantly small-particle distributions were observed for Cu, Cd, Zn, and P b (Figure 2 ) a t the Nicosia incinerator. Of particular interest in Figure 2 is the sharp increase in stack-gas elemental concentrations with decreasing diameter (between 6 and 0.6 fim) of the particles bearing the elements. Note that the increase was a factor of>400 for Pb, 75 for Zn,
50 for Cd, and >40 for Cu. Similar predominantly smallparticle distributions were observed for these elements at the Alexandria incinerator and the SWRC # 1 ( I ) . Less than 1%of the masses of Pb, Zn, Cd, and Cu collected solutions from the impingers. This were found in the "03 indicates that only negligible amounts of these elements are in the gas phase in the stack. A total mass balance for these elements reported elsewhere ( 2 ) indicated that about 90% or more of the Cd, Pb, and Zn and 38% of the Cu entering the plant leaves via the stack. The good agreement in the composition of the suspended particles from the three incinerators shows that municipal incinerators in different geographic regions of the U. S.serving quite different types of communities can have very similar emissions. A comparison of these three incinerators is useful also because they have different pollution control devices. As noted above, the Nicosia incinerator has a spray chamber followed by plate-type scrubbing tower. The Alexandria incinerator has only a water-spray baffle, and the SWRC # 1 has both mechanical separators and electrostatic precipitators. Although each incinerator releases a different amount of suspended particles per unit mass of refuse burned (see above), the compositions of these emissions are similar. S u m m a r y and Conclusions
The particle emissions of the Nicosia incinerators are very similar to two other municipal incinerators despite differences in geographic location and pollution control devices. Although this result does not prove that all incinerators emit particles of the same composition, it supports the conclusion ( I ) that municipal incinerators can be major sources of Cd, Zn, Sb and Volume 12, Number 12, November 1978 1331
possibly Sn, Ag, and In in many urban areas. Furthermore, these results confirm the earlier finding that many of the trace metals are borne predominantly by small (
