Document 70e7g0VZYxkJGMBR09z70wGma

Copyright 1973, American Medical Association Lead in New-Fallen Snow Near a Lead Smelter Zarka Kerin. MSc, Belgrade. Yugoslavia In a mountainous area of Yugoslavia, where a lead mine and smelter have been in operation for some 300 years, samples of new-fallen snow were obtained within three zones situated at increasing dis tances in different directions from the two centrally located stacks of the smelter, and were analyzed for their lead content. The lead content of new snow would be a factor of the quantities of lead in the air through which precipitation of moisture has qc- 300 years. Until January 1969, when a Lurgi filter was installed, 200 to 300 tons of metallic lead and lead oxide per year were discharged into the air from two stacks in the plant area at a level of 623 meters above sea level. Determinations of the lead content of new-fallen snow (during or shortly after its fall) were made to establish curred. The results confirmed the expecta the removal from the air of particu tion that, with increasing distance from $he source of lead emission, the snow con tained consistently decreasing quaptities of lead. Moreover, samples of new-fallen snow collected at altitudes that differed from that of the stacks yielded results that deviated from each other to such an extent as to alter significantly the negative cor relation of the results with an increasing late metallic lead and its compounds, as well as the extent and the variabil ity of these phenomena, at upland and lowland points located at various distances and in various directions along the courses of the rivers and streams that drain this mountainous region. distance of the sampling sites from the stacks. Methods Sampling Sites. --Sites in three areas fanning out along three different axes t Zerjav, Yugoslavia, in the up from the central position of `ne stacks A per valley of`the Meza River, (actually along.the courses of the Meza River and two of its tributariesi were se 542 meters above sea level, in an Al lected to examine any quantitative differ pine area not far from the Austrian ences in lead content of snow as variables border, a lead mine and smelter have in distance from the stacks and compara processed a rich lead-zinc ore for some tive altitude with respect to the stacks. The three areas were that nearest the stacks, extending outward for about 700 Submitted for publication March 30, 1972; accepted Jan 10. 1973. From the Institute of Occupational and Ra diological Health. Belgrade. Yugoslavia. Reprint requests to Department of Environ mental Health. Kettering Laboratory. Universi ty of Cincinnati Medical Center, 3223 Eden Ave, Cincinnati 452191 Dr. Kehoei. meters, designated as the stack zone: that extending outward from the stacks from 700 to 7,000 meters, designated as zone A; that expected to be a transition area from slight to negligible contamination by effluents from the stacks, extending from 7.000 to 17.000 meters, zone B. An addi- 256 Arch Environ Health/Vol 26, May 1973 Lead in New-Fallen Snow/Kerin izontallv over its base. The enclosed snow was transferred with a vinyfspatula into a wide plastic dish fitted with a lid of the same material. Two samples were collect ed. side by side, and both iwere emptied into the same dish. The volume of the two samples of snow from each site, when melted in the dish i which comprised the sample for further handlings, was mea sured and found to be usually 160 ml. To it were added 0.5 ml of'O.OlN JT.SO, and 1 to 2 ml of concentrated HNO;,, after which the liquid was evaporated toldryness. The quantity of lead ini the prepared sample was determined by a micromethod described elsewhere.' The results of the analyses are expressed in terms of the con centration of lead in milligrams per liter of liquid, and are presented in the Table, according to the designated zones of sam pling. The identification of each sample, except the two samples taken in the con trol zone, is indicated by its number on the map (Fig 2), and by a local place name, together with the difference between its altitude and that of the top of the stacks, and the horizontal distance of its position from that of the stacks, as well as the lead content of each sample. Results and Comment The outstanding feature of the data in the Table is the sharp decrease in the quantities of lead found in the freshly fallen snow, as the distance between the sampling sites and the stacks increased. The quantities of lead found in the samples did not fall in sequence in strict accordance with their distances from the stack, but as the Table indicates clearly, the magnitude of the values decreases so nearly regularly from above downward (with increasing distances) as to yield striking evidence of the trend. In view of the topography of the terrain in the entire area, and the likelihood of air currents of varied di rection and velocity, the slight incon gruities in the results are not remark able. The degrees of the correlation between the concentration of lead in the samples of snow (z) and their dis tances (x) from the source of the emis sions is shown by the correlation coefficient V'zx) which turns out to be --0.50 for the total number of 24 sam ples and P= .05. When, however, the differences in the altitude at which the samples were obtained from the altitude of the top of the stacks are eliminated, the partial correlation coefficient rz.t-y becomes --0.62 and P=. 01. Thus, the sampling of freshly fallen snow presents a consistent pattern which derives from the fact that the snow, in falling through an atmos phere that contains considerable quantities of lead at its lower levels, removes lead from the air as it falls, but is not subject to important subse quent fallout of lead upon its surface, if it is sampled promptly after falling. Whether it cleanses the air complete ly and reveals the total lead content of the air, under a variety of condi tions associated with variations in the density and the duration of the snowfall, and more particularly, of the degree of dispersion of the lead compounds is another matter. Cer tainly, some very small particles of lead escape snow showers, as they do rain showers, and remain airborne.As a means of sampling the air for lead in a given locality, involving comparable effluents, falling or newfallen snow, in considerable volume, in relatively quiet air, can be a useful means of measuring change in the lead content of the air. as, for exam- 258 Arch Environ Health/VoI 26, May 1973 Lead in New-Fallen Snow/Kerin pie. before and after a counteracting or remedial procedure. Such a conclu sion is justified by the data in the Table. There is little doubt That in any situation involving high tempera tures of the combustion of materials containing lead, as ores or painted surfaces, particles of minute dimen sions are emitted and remain in the atmosphere for long periods of time, to be depleted by conglomer ation, precipitation, and by removal through entrainment in rainfall or snowfall even at great distance from the point or origin. That wide disper sal occurs is indicated by The accumu lations of lead in polar ice as reported by Murozumi et al.;! by JaworowskiT and by Picciotto et al.5 A more local dispersal is shown by the data pres ented here, in that the quantities of lead found in snow in the control area, w'hile minute, never go down to the very low levels found in snow or rainfall in areas remote from human habitation.* The evidence indicates that the control area was not entirely free from local contamination with lead. This investigation was supported by Public Health Service contract BSS-Ofi-YUG. Sample No.. Fig 2 6 1 2 7 10 3 14 18 19 8 28 38 13 31 34 35a 35 23 16 45 41 48 49a (Not in Fig 2) (Not in Fig 2) Lead Content of New-Fallen Snow Place Zerjav Zerjav Zerjav Zerjav 26 Musentk Rudarjevo Musenik Crna Crna Zerjav 13 Sp. Javorje Sp. Javorje Plat 5 Pristava Pristava 14 Skrnbej Podpeca 75 Polena Mezica Topla Poljana Prevalje Prevalje-Ravne Ravne Altitude Above (+) or Below (-) Too of Stack. Meters Stack Zone -82 -80 -82 Zone A -82 -32 -8 -78 -22 -22 -82 -28 -8 -92 -42 +78 -78 -78 -122 -142 -35 Zone B -172 -172 -172 -222 Control Zone Distance (Laterally) From Stack, Meters 400 650 680 1.050 1,100 1,260 1.350 1.400 1,450 1,450 1.670 1.900 2.000 2,700 3,180 3,620 3.900 4,020 4,850 4,920 7.450 7,600 7,800 9,750 Maribor 62,500 Concentration of Lead (Pb in Melted Snow, mg/Liter 15.76 23.50 17.40 4.20 3.65 2.67 4.01 1.29 1.79 1.49 0.74 0.75 1.08 0.90 0.32 0.48 0.61 0.23 0.22 0.27 0.08 0.13 0.09 0.04 0.02 0.04 References ,1. Kerin Z: Bestimmung von Mikromengen Blei in pflanziichem Material, Mikrochim Acta 1968. pp 927-933. 2. Atkins PR. Kruger P: The Natural Removal ofLead Pollutants from a Suburban Atmosphere. Department of Civil Engineering. Stanford Uni versity, technical report no. 98. 1968. 3. Murozumi M, Chow TJ. Patterson C: Con centrations of common lead in Greenland snows, in Marine Geochemistry. US Atomic Energy Commission document NYO-3450-1. 1965, pp 213-215. ' 4. Javvorowski Z: Stable lead, la fossil ice and bones. Nature 'Land) 217:152-^53. 1968. ) 5. Picciotto E. et al: Determination of rate of snow accumulation at the poie of relative inac cessibility. Eastern Antarctica. J Glacial 7 2732S7. 1968. 6. Lazrus AL. Lorange E. Lodge JP Jr: Lead and other ions in United States precipitation. Environ Sci Technot 4:55-58. 1970. Arch Environ Health/Vol 26, May 1973 Printed and Published m the United Scares of America W a n 1715 Lead in New-Fallen Snow/Kerin 259 I ,x i ERFAC E, 2 :1 o , '973 7RDEM; 0" LEAD: PRELIMINARY THE RELATIONSHIP VilT'ri A&E cf odd ana otner trace metals in the . ars exposed to tne "normal " environment of i cc'-nuccoc ' i o-cer to validate methods . ;.m .no',-.set the to interrelate tne consequen- - tot j.'-e t'i;. .'jrnF;; cucr, as ace, sex, , an ana state, o* heal to. Tils report pre- I ' > ette'-itf crs re t a tee to tne ace variable. ' . i .-.ere ootaisea at autopsy with tne cooperation re'"' 5 te. Stanoarc sections reoresenting ,,i - ' t-.et^as were detained from each individual. Any a,5: matures 0* tne s cancan section or orcan were r;:t.?t it me time or eutepsy and at the time of subseauent cistecro' for r.etai analysis. The tissues were ashed wt*. mo i-i }* nitric acid and analyzed for lead by the di vti tf-ne etr.od and for cooper, zinc, and cadmium by AGE (years) .-.tone .-somcion soectroonotcmetry. The results of the Figure 1. Regression lines for tissue lead concentra- lead in,-lyses of 42 ..nice fen, 20-84 years of age, are TTo'n (w'6t weight basis) with age. The asterisks repre preset a.:'-. mm. sent statistical significance at the 95% confidence level. mims m;'' ; -~j$ for see ana tne concentrations of 'eei 'i lies;,as are snown in ricure 1. These ; \ lines --ec-esent tne least scuares '-'it for data points v.nisfi idiii cerapi e scatter. ~ni s scatter increases as me -I'l'-eiises for c m ,iqr.as and aorta {not the otner 55 r iiOi45 j- COMPARISON TO OTHER BONES Low Low-Normal tiis.es .0 's s.-rwn m Ti-.;re 2 -'or sxull bone. Thus, 40 j- Normal on in tvt: ii tasls tne pones ird aortas tended to in crease -n ore will a cost of tr.e soft tissues remained at 4 Normol-High 35r High relaf v k m / constant eve!s of 1 npm or less. The kidney 30 .no ii-. -r -.-.own in -i -yre 1, .re two of several tissues ..r>icm .:oc.-t;af.e-j Wi.in no. "hese decreases were generally cor--e. -.*a: with .oaimogioaii changes in tnese organs which -c ' i ii sussed 'ere. /- ' nr - 2 now s ? r,e 0f individual lead cqncen- 25 201i 15 L ; - r ' -T ' ' ' ie mu m -anus tie. "he concentrations ipi -v inry s .r.i'or to tntte ootamed fo'r the tibia ;i-j :o"-e ite well < t.-.er rones as to relative le^d :Mc?r,ns. Tati cor-qia .'or.s are snown by aesig- 1'iv i ' 1 -c V; veil' in ' ids 2, and are based on "i" ive- 'evels or cones i>ib, skull, t i-i. ' ve-i-c - :e , -m.-pare: m tie bones of otner in 10 r * 5h * oL 30 i ` , 1 ' 45 60 AGE (years) 75 90 Figure 2. Skull lead concentrations (wet weight basis), ti v-c -i - : "e ire c-c-io. Tie skull sections did desirable, if possible, to investigate the exposure his -f cianrn as seen in -.he rib and ver- tones of these individuals in order to attempt to relate r tie .- to concentrations of the skull . v t ic: cc-itrati'MS of lead in the their exposure with body burdens. In any eventthese studies provide reliable baseline information which may be compared with future studies to look for changing tie ..ie pc -.;v o.rcen of lead patterns in man's bodv burden of lead with age and envir -- . re" fin tne third oec-tce of life onmental exposure. 'i.te . co.irin.,tus -ncrease in booy burden Stanley 3. Gross I'M 7); and otnurs .incest a decrease , .. **Emi1 A. Pfitzer o: '/ t .t - .m uf leaa after the sixth decide of life (3). s' net i-: was assumed that the skeleton contains ' ' Oil) or tne oody's 7>ad. ' i .mi tne lead in scull bone is a good repre- ' Department of Environmental *Robert A. Kehoe Health, College of Medicine University of Cincinnati **Hoffman laRoche, Inc. Cincinnati, Ohio 45219 Nutley, N. J. 07110 r - i'"i-:.c-i ,;nviron.'ental exposure to lead and v -oii-er,11 liven if loan din not mange ap- ; ' -v: n-.t/ years .ys<iere 's some evi- -'Tir.c ' op i C ntinnati ai rborne -lead actually mim -m-i , i ita 'Figure 2 could indicate that 2/3 ' - -or- . -i t-e 11 section at 15 ppm or less, dotted (1) Horiuchi, K., Horiquchi, S., and Suekane, M., Osaka City Med. J_. , 5:41-70, 1959. (2) Barry, P.S.I., and Moss man, uri t. J_. Ind. Med., 27:39-51 , 1 970. (3) Schroeder, A., arid Tipton, I.H., Arch of Envir. Health. 17:955, 1968 n-e, ,f opilari-n was in a reasonably steady-state reiaiin.isnip wi in m.j .u m -.heir environment, from age 20. 'Seventy-seven percent of the tibia sections were at 15 ppm or less. '; Tne otner 1/3 showed varyinq degrees of con- Source of Support PHS Grant 0H-00359-01 "Variables Af- fectinq the Estimation of Human Body Burden" and Center Grant ES-00159-06. tTMOuS increase of body burden Of lead with increasing ace. Tre-e wane uncestive relationships oetween body burden and occupation listed at tne time of deatn. It would be Received May 2, 1973. 7 j 1O