Document pmdp8e09djm0z07Bx6xjm4N7B

R e p r i n t e d f r o m t t }(<A r c h i v e s o f E n v t r o n m e n t a i H e a lt h May 1973, Volum e 26 C opyright 1973, Am erican Medical Association Lead in New-Fallen Snow Near a Lead Smelter Zarka Kerin. MSc, Belgrade. Yugoslavia In a m ountai nous ar ea of Yu g osl avi a, where a lead mine and smelter have been in operation for some 300 years, samples of new-fallen snow were obtained within t hr ee zon es si tuated at i nc r easi ng dis tances in different directions from the two centrally located stacks of the smelter, and wer e anal yzed fo r t hei r l ead c ont ent . The lead content of new snow would be a factor of the quantities of lead in the air through which precipitation of moisture has qcc ur r ed. The resul ts confi r m ed the exp ec t a ti on t h at , wi th i ncr easi ng di stanc e fr om $he source of lead emission, the snow con tained consistently decreasing quaptities of lead. Mor eover , 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 distance of the sampling sites from the stacks. At Zerjav, Yugoslavia, in the up per valley o f `the Meza River, 542 meters above sea level, in an Al pine area not far from the Austrian border, a lead mine and smelter have processed a rich lead-zinc ore for some 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 452191Dr. Kehoei. 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 the removal from the air of particu 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. Methods Sampling Sites. --Sites in three areas fanning out along three different axes from the central position of `ne stacks (actually along.the courses of the Meza River and two of its tributariesi were se lected to examine any quantitative differ ences in lead content of snow as variables in distance from the stacks and compara tive altitude with respect to the stacks. The three areas were that nearest the stacks, extending outward for about 700 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 ;transferred with a vinyl spatula 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 iwhich comprised the sample for further handlings, was mea sured and found to be usually 160 ml. To it were added 0.5 ml of 0.0IN H,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 Heaith/Vl 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 ithat 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 ai.'! by Jaworowski,-* and by Picciotto et al.J 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-H-YUG. S a m p le N o .. 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 C ontent of New-Fallen Snow P la c e Zerjav Zerjav Zerjav Zerjav 26 Musentk Rudarjevo Musenik Orna Orna Zerjav 13 Sp. Javorje Sp. Javorje Plat 5 Pristava Prlstava 14 Skrnbej Podpeca 75 Polena Mezica Topla Poljana Prevalje Prevalje-Ravne Ravne A ltitu d e Above (+ ) or B e lo w ( - ) Top of S ta ck . M e te rs S ta ck 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 C o n tro l Zone D is ta n c e (L a te ra lly ) From S ta c k , M e te rs 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 C o n c e n tra tio n of L ead (P b - ) In M e lte d S n o w , m g /L ite r 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, in fossil ice and bones. Nature 'Land) 217:152-^3. 1968. J 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 Technol 4:55-58. 1970. Arch Environ Health/Vol 26, May 1973 Lead in New-Fallen Snow/Kerin 259 2:13 '573 -s 25r 61 ana o t n e r t r ac e met al s i n t he a t o t n a " n o r m a l " o n v i ' onmant o f j u c t e c ' n c '' c e r t o v a l i d a t e me t h o d s O the to i n t e r r e l a t e tne consequen e t : . v a n a o', an t u e n as a c e , s e x , ' - , : 1jn i n 0 3 .a t e .o * heal :n. Tn i 5 r e p o r t p r e ! > J '*7 11'. Cr-5 r e 1a t e q t o t h e a r e v a r i a b l e . - . ".A'.V/.l?'0 a t a u t c c s y w i t h t n e c o o p e r a t i o n -r.e^ ' 5 r *' ^5 . St a n o a r o s e c t i o n s r e p r e s e n t i n g I^ 20p 15 h lOh 5F .vere ned from eac n i n d i v i d u a l . An y _ 1 j .11 j- i l u r e s 0 " r o e s c a n c a r o s e c t i o n o r o r c a n w e r e Oh- . :ne lin e o f cpsy and at t ne t i me o f subseauent ;: n : e c r. -0" r . e t a i ana l y s i s . Th e t i s s u e s w e r e a s h e d >, - - - n g 1 a c . n i t r i c j c! i d ano a n a l y ze d f o r l e a d b y t h e IO 20 30 40 30 60 70 80 90 di i;f - ne -er.n.Ou a r c f o r c o o p e r , z i n c , an d c admi um b y AGE (year s) .1ZO-7.' C . ,, ``i o r m o n soecri*!o p n c t c n e t r y . Th e r e s u l t s o f t h e Fi g u r e 1. Re g r e s s i o n l i n e s f o r t i s s u e l e ad c o n c e n t r a - 1GaC ;Mn ; y s e s o f ^2 h i ' e m e n , 2 C- 8 4 y e a r s o f a g e , a r e TTo r f ' f w & t w e i g h t b a s i s ) w i t h a g e. The a s t e r i s k s r e p r e presor,: s e n t s t a t i s t i c a l s i g n i f i c a n c e a t t h e 95% c o n f i d e n c e l evel ^ess; : r ' *nos - o r in ." Yen3 ' " i n s n J ^ iar e snown i n n c u r e i . :n e s e ; i\ ' - e o - e s e n t t ne l e a s t s c u a r e s ' 'i t f o r a a t a p o i n t s 55 r CCM PAR ISON TO iioi- OTHER BONES 'v.ve to nsi cer ap i e s c a t t e r , " o i s s c a t t e r i n c r e a s e s es f o r er a nones and a o r t a { n o t t h e o t n e r ciis-eE s.nr wn m Fi cu r e 2 - o r s x u l l b o n e . Th u s , -6FP4-. 45 4w0r\ L1'r 1 Low Low* Normal Normal CO '1!! 0 7 0 o a s v ; Lnnee oooo nr ..eess md a o r t a s t e n d e d t o i n rr. ... ` n a n a i e -mno s ot 0o *f t h e s o f t t i s s u e s r e m a i n e d a t ne I *7.0' -;ri ' / o o n s t a n t . e v e s ' c f 1 ppm o r l e s s . Th e k i d n e y 35 30 4 Normal -Hi gh High ..no i r nnovfn n - * j r e 1 .r e t wo o f s e ve r a l t i s s u e s ,v n - c n no C.' L' a f .G'J Wi nn n o . " n: i se d e c r e a s e s w e r e g e n e r a l l y n t n o a r .r " .o g i c a :! c n a n q e s i n t n e s e o r g a n s w h i c h pi sc us s e a ' e r e . r o nows ?he o i o t o f i n d i v i d u a l l e a d e p n e e n - . 25 r 20 1h 15!- vi - s - .u i l - ' e r s u s i c e . T he c o n c e n t r a t i o n s i # w r y i c - i l i r to t n t ;e oot ai n ed fo'r the t i b i a ce v ; e i : , .; 1 t r i or n o n e s a s t o r e l a t i v e l e a d CCS . ' ' i t s ar e snown by a e s i g - i .r e 2 , and ar e based on ?veis 0r - : ; r c o n es v i b , s k u l l , -'..'pare: - i t r .e bon es o f o t n e r m - 10 Ir 5h 0 30 45 60 75 9 0 AGE (year s) Fi g u r e 2 . Sk u l l l e a d c o n c e n t r a t i o n s ( wet w e i g h t b a s i s ) , 7c3 C S10 . Tt e s k u l l s e c t i o n s d i d d e s i r a b l e , i f p os s i b l e , to i n ves t i g at e the exposure h i s :r:an r r r a $s s e e n : n i h e r i b and v e r - t or i es o f these i ndi vi dual s in or der to attempt to rel at e c o n c e r t r at i on s o f the skul l t h e i r exposure wi t h body burdens. In any e v e n t t h e s e t r at i ens of lead in the s t u d i e s p r o v i d e r e l i a b l e b a s e l i n e i n f o r m a t i o n wh i c h may be compared w i t h f u t u r e s t u d i es t o l ook f o r changi ng - . . at e v . -t e oc .i v o - r d e n o f l ead - . v i-~.nr t ne t h i r d aec c c e o f l i f e . ' ' c .t o . c on t i n u ou s i c r eas e i n booy bur den f 0 : ' / I ' f a I' d ) ; a n d o t n u r s c u c c e s t a d e c r e a s e en c f l e a p a f t e r t h e s i x t h dec -i de o f l i f e ( 3 ) . ; p i e s { was a s s u me d t h a t t h e s x e l e t o n c o n t a i n s -c '.t ` ' - v t v ! 1 o f t n e o o d y ' s ` <i ad. . - c m t tne l ead i n sc ul l bone i s a good r e p r e - .. - >.*nvi r o n .' e n t a i e x p o s u r e t o l e a d a n d vt . .' ' t r ~ i n t 1 i c v e - .s o f l e a p d i e n o t c n a n g e a p - 1. . . - v : ' v ; . i - . t / y e a r s ( m e r e s some e v i - . r c a t e t i 1 C n t i r .r .a t i a i r b o r n e - l e a d a c t u a l l y s 1 i ,?.j - Fi g u r e 2 c o u l d i n d i c a t e t h a t 2/ 3 ' 7 t - e t 11 s e c t i o n a t 15 ppm o r l e s s , d o t t e d p a t t e r n s i n man' s bodv bur den o f l e ad w i t h age and e n v i r onmental exposur e. St a n l e y B. Gr o s s , .. ** Em i 1 A. P f i t z e r ' De p a r t m en t o f En v i r o n m e n t a l *Ro b e r t A. Kehoe He a l t h , Co l l e g e o f Me d i c i n e Un i v e r s i t y o f Ci n c i n n a t i **Ho f f m a n l a Ro c h e , I n c . C i n c i n n a t i , Oh i o 4 5 219 Nu t l e y , N. J . 0 7110 ( 1) Ho r i u c h i , K . , Ho r i q u c h i , S . , an d Su e k a n e , M . , Osaka Ci t y Med. J_. , 5 : 4 1- 70 , 19 5 9 . ( 2 ) B a r r y , P . S . I . , and Mos s man , u r i t . J_. I n d . Me d . , 2 7: 3 9 - 5 1 , 1 9 70 . ( 3 ) Sc h r o e d e r , A . , aha T i p t o n , I . H . , Ar c h o f En v i r . H e a l t h , 17: 9 5 5 , 19 5 8 n -e , o p Ua t i c - n was i n a r e a s o n a b l y s t e a d y - s t a t e i -e 1a t i o n v i i n w i r e ] s,w i n - .h e i r e n v i r o n m e n t , f r o m a ge 2 0 . ' S e v e n t y - s e v e n Pe r c e n t o f t h e t i b i a s e c t i o n s w e r e a t 15 ppm o r l e s s . '; Tne o t n e r 1/ 3 s h o w ed v a r y i n g d e g r e e s o f c o n Sou r c e o f Su p p o r t PHS Gr a n t 0 H- 0 0 3 5 9 - 0 1 " Va r i a b l e s A f f e c t i n q t h e Es t i m a t i o n o f Human Body Bu r d en " an d Ce n t e r Gr a n t ES- 0 0 15 9 - 0 6 . t i nuous i ncrease o f body burden tff l eaa wi t h i nc r easi ng ace. Tr e -e ware s c i c e s t i v e r e l a t i o n s h i p s oet ween body bur den and o c c u p a t i o n l i s t e d a t t n e t i m e o f c e a t n . I t w o u l d be Received May 2, 1973.