116/D Zbigniew Jaworowakl Prepared in Oooperation with Andrzej

Ze port л*. OLOR - 116/D

INFLUENCE OP INDUSTRY ON POLLUTION OP THB ENVIRONMENT AND HUMAN POPULATION WITH NATURAL RADIONUCLIEBS AID HEAVY HBTALS

Zbigniew Jaworowakl prepared in oooperation with Andrzej Barana4i Jan Bilkiewios Maria Byeiek Danuta Grzybowskm Ludwika Kownacke Maria Snplinaka

and with technical aid of Adam Adancsyk Małgorzata Baranoweka Bdward Chrzanowaki Stanisława Desbinska Zbigniew Kryaa jjech Świtał Krystyna Trscialkowaka

Central Laboratory for Radiological Prot*oti*n Department of Radiation Hygle-e 03-194 WARSAW, Konwaliowa 7 Poland July 1982 Report Ho.OLOH - 116/D

IHPLUENC2 OP IBDUSTRY ON PGLLUTIOH OP THE EHVIROTHBH? ABD HTJMAF POPULATION WITH NATURAL RADIOBUCLUES AID ЫЕА7Т HETALS

Zbigniew Jaworowski prepared is oooperatlon with Andrzej Barana4i Jan Bilkiewio» Maria Дуе1ек Danuta Grsybowek* J.udwlka Kownacka Baria Suplińeka

and with teehnloal aid of Adas Adamcsyk Hałgorsata Baranowsk» Edward Chrzanowski Stanisława Desbirfska Zbigniew Xrysa ъесЬ Świtał Krystyna TrzoiałkowBka

Central Laboratory for Radiological Proteotlea Department of Radiation Hygiene 03-194 9ARSAW, Eonwaliowa 7 Poland July 1982 Table of content5 Page

Preface

Part 1. Local effects и 1.1. Introduction и 1.2. Dispersion of pollutants from industrial emissions 7

226 21O 1.2.1. Content of Rav Pb,U,,ThtCci, Pb, and Za in the coal fly ash 7 1.2.2. Radium-226 in snow and dry fallout in relation to distance fron emission sources 1С 1.3. Temporal changes of *"*" Ra concentrations in glacier ice and of U, Th, and Pb in pine trees in Poland Ł2 1.4. Concentrations of pollutants in soil from industrial and rural regions 2Ъ 1.5. Concentrations of natural radionuclides and stable lead in plants **fc 1.6. Radionuclides and stable heavy metals in human bones ьг 1.7. Vertical distribution of pollutants in the atmosphere 79 1.8. Conclusions ^1 1.9. References 97 1.10. Appendix 102 Part 2. Global effects 109 2.1. Introduction 109 2.2. Glacier pollution study 11? 2.2.1. Sampling and analysis of ice 115 2.2.2. Concentrations of metals in ice 11U 2.3. Estimates of flows of metals in the global atmosphere 12C 2.4. References 125 2.5. Tables 134 151 Тле interest in observing the levels of pollutants ax local and regional levels stems from the important health effects whicn may be expected from localized emissions into the lower troposphere. The apparent lack of threshold for health effects due to some of tne pollutants, suggests that minor increase in their global concentrations might be hazardous to the world population. Observation of the global distribution of these pollutants ana rt long-term changes in their concentrations supplies information for assesa- "aent of this hazard. For the study of local effects of industrial pollution, Poland is a suitable place, as a typical Industrialized country, where more trian 80 per cent of the energy supply comes from coal. With approximately 140 million tons of coal burned in 197b, and its world "first" in coal production per сер ~, Poland may be regarded as an example of the possible future situation in other regions where energy production nay become dominated by coal burning. For observing global distribution and temporal change-} of airborne pollutants, glaciers are excellent object of study. They are the cleanest parts of the surface of the earth on which changes of levels of pollutants may be more readily observed than for example in soil or sea water. Their annual stratification allows one to collect ice samples representing precipitation from the paat.

Between 1972 and 1979, the Central Laboratory for Radiological Protection in Warsaw, supported in part by the US idivlronmental Protection Agency, has studied pollution of the environment by Ha, Pb, uranium, thorium, radioactive fifiaion products and - 2 - by stable lead, cadmium, vanadium and mercury, on local and global scales. In the course of this study, we have succesively oublished the preliminary results of our investigations (refe- rencas 1-14}. This report contains detailed information from the orevious^y published reports, along with new data. It is based en tne unpublished Final Report to the United States Environ- mental Protection Agency concerning Research Contract No. 5-536-1 ana on the material published in Geochlmica et Cosmochimica Acta ub: 2183-2199, 1981.

The study of local effects was confirmed to observation of dispersion patterns for airborne pollutant, and of their concentrations in soil, plants, and human bones as a function of distance from various emission sources in Polar.a. Temporal changes in concentrations of stable lead and natural radionuclides in trees and glacier ice were observed in the regions exposed to local or regional industrial emissions in Poland. We have also observed the vertical distribution of these substances and of fission products in the troposphere and stratosphere up to a height of 12 Km ever Poiand. To observe the global effects we organised rune expeditions to 1u glaciers in Northern and Southern Hemisphere, irom which we collected samples of snow deposited during the past гпгее decades and also in the pre-inaustrial period. Using virtually the same sampling and analytical methods we determined in these samples the concentrations of Cs, U, Ra, Pb, Pb, Cd, V and Hg.

tfe found that depending on weather conditions the points of maximum 22oRa fallout from industrial sources of emission were situated appr. 1 tc 17.5 km from the source; the soil and aeropby- tic clar.ts in industrial reeisns were more contamined with heavy - 3 - metals and natural radionuclides than the rural soils? a draaa- tic increase of pollutants in glacier ice from deposited during the last 100 years in Southern Poland was acconDanied by a much smaller increase in the concentrations 01 pollutants in th« pine trees and by a decrease of their levels in human bones from the same region; the levels of pollutants in himan bones were related ratner to the geological bacKgrouna than to the industrial emissions of pollutants; vertical distribution of pollutants in the atmosphere indicate that there exists a quiescent upward transport ?f these substances from the surface of the earth into tne stratosphere.

The principal aim of the glacier stuay was to estimate the flows of natural radionuclides and heavy metals intfc the global atmosphere. We were also interested ic finding their tenporal and geographical distribution in the global precipitation. Ve found that with exception of V, the natural flows of these nucliats are by orders of magnitude higher than the anthropogenic ilows; we were unable to detect any significant difference between the present and pre-industrial flows; and we found that the high concentration of metals in ice from remote glaciers is related to the presence of local or regional aer^sits of their ores. - 4 -

Pmrt 1. LOCAL EFFECTS

1.1. INTRODUCTION Coal burning is the main source of industrial air pollution in Poland. Of about 140x10 tone of coal burned in 1976 in Poland, approximately 90x10 ton* were used for heating purposes and electric power generation (15) and SOxlO tons for other industrial and household uses. Assuming that 3 per cent of burned coal escapes as particulatcs from stacks, this corresponds to 4,2x10 tons of fly ash transferred to the atmosphere. This corresponds to about 1Э tons of dust fall per square kilometer per annum in Poland.

This is approximately half of the actual dust fallout from industrial sources in Poland which was assessed to be 22 tons per square kilometer in 1973 and is in agreement with the 52 per cent contribution to the total industrial dust omission estimated for this source in Poland (16). Por comparison, tho man maoe dust em.' ssions from coal burning in the United States in 1968 were 19.8x10* tons (17) or approximately 2.1 tons per square kilometer, a value about one tenth that in Poland. This comparison suggests that some local effects of man-mado emission svay probably now be detected in Poland, even though not - 5 - yet detectable in regions with lore.- density of industry and coal consumption per capita. Our study of the local effects was concentrated on four types of studies г 1. Dispersion and accumulation of pollutants in the vicinity of coal fueled power stations and other sources of industrial emission for comparison with less exposed rural regions. In the particular situation of Poland, these rural regions can not be regarded as free from the influence of regional industrial fallout, however, the rate of this influence is lower there than in the industrialized areas.

2.Geographical distribution of 226Ra, 2l0Pb, 90Sr, Cd.Zn and Pb concentrations in human bones in Poland.

3. Temporal changes of Ra and Pb in glacier ice and human bones, and of U„ Th, and Pb in pine trees in Poland.

4, Vertical distribution of pollutants in the atmosphere over Poland.

The sampling sites for collection of industrial dust, soil, plants, glacier ice and human bones in Poland are presented in Figure 1. Z»ron WARSZAWA Si»ki»rki

Kozienic» «^ Puławy

FIGURE 1. MTTATRA MTMS. Sampling sites for collection of inaustrial dust = Q, soil = Д, plants = Ot glacier ice = 4 and human bones = in Poland . -7 -

1.2. DISPERSION OF POLLUTANTS FROM INDUSTRIAL EMISSIONS 1.2.1. CONTENT OF 226Ra, Pb,U,Th,Cd,Pb, AND Zn IN COAL FLY ASH 1.2.1.1. Materials and methods We determined the concentrations of four natural radionuelides and three heavy metals in fly ash samples from electrostatic precipitators of the lignite coal power plant, Adamów, in Western Poland and of the bituminous coal power plant,Siersza, in Silesia, -and from the top of the stack of i:he bituminous coal power plant,Zcran, in Warsaw. From each location, three separate samples were pooled. After dissolving the samples in г mixture of nitric, perchloric and hydrofluoric acids the content of Ra 2lOPb,U,Th,Cd,Zn and Pb were determined using the methods listed in Table A of the Appendix and described in detail in ref. l.The minimum detectable concentrations of the elements in fly ash ere presented in Table В of the Appen- dix. Exchangeable 226Re,leached by fM ammonium acetate, was determined by Piper's method(l8) and the detailed chemical procedure of this analysis is described in ref.l. Solubility of 226Ra in hydrochloric acid and in water were also determined. - 8 -

1.2.1.2. Results end discussion 226 The Re concentrations of 0.41 to 4.2 pCi/g found in fly esh Teble I ere higher than the concentrations in Polish coals which renge from 0.048-0.94 pCi/g21j. Similar 226 concentrations of Re in coal and fly esh were found by Coles et el. (49 end Kaakinen et al.(20}.In our samples 0.7 to 5 p«r cent of fta was in en exchangeable form which might be assumed accessable to plants.Its solubility in 6M hydrochloric acid ranged froro 50 to 72 per cent,but in lM hydrochloric acid end in distilled water was less than 1 per cent. 210 Pb concentrations in fly ash from 3 Polish plants ranged from 1.7 to 6.7 pCi/g in comparison with reported concentrations of 1.4 to 17 pCi/g in the United States(l9,20). The 2lOPb/226Re ratio in fly ash from the top of stack of the Żeren plant was 10.7,whereas from the electrostatic precipitetor only 3. For two other plants,Siersze and Ada- mów, the latter was 1.6 end 1.9. In power plants in the United States Ll9,2O},this ratio ranged from 1.3 to 42.8 for stack fly esh,and 0.61 to 12.8 for fly ash from electrostatic precipitatore. Uranium and thorium concentrations in fly ash froa the Żerań and Siersze plants were similar to those found In samples *rom north Aeierican power plants (l9,22jl. Concentrations of cadmium in fly ash ranged from •5.5 to 6.5/дд/д, zinc from 164 to 530 /ug/g and lead ^.rom 23 to 265 /uy/g* These concentrations are similar to those found in the United States f20,22. With the exception of Ra, the concentrations of natural radio-

and heavy metals in fly ash from the lignite Adamów power plant were lower than from two other bituminous coal power stations. The results of *-.his study also indicate that coal power stations may differ greatly in the n О С amounts of Ra emitted. i . 2 . 2 . ^£IL^__^__ Ц_y_^ TO DIST^NCE_F_HOK_ 1>"ЛЯS 7_ON_SOURCES 1.2.2.1. Material:, and methods To study the dispersion range of industrial omissions from plants using coal for production of energy, we usud radium-226 as a tracer. This radionuclide is present in the ccal fly ash and can be detected with sufficient accu- racy in samples of dust collected in snow and dry fallout. The other important source of Ra in these samples may be airborne soil particles. To diminish this last contribution, we collected samples of snow freshly fallen on the old snow cover which blanketed the soil surface. We also collected dry fallout samples in the suTimer, when most fields were covered by vegetation.

Snow and dry fallout samples were collected at different distances under the visible plume. Snow was collected around two bituminous coal power stations in: Warsaw,Zeran in February,1970 and Siekierki in March,1971, and around the lignite coal power station Konin in Konin, in March,1971. Dry fallout was collected around the Nowa Huta iron mills near Krakow in June,1972 and around the Adamów (lignite) power station in Turek in July,1973. The Nowa Huta mills may be considered as an area source of emissions, whereas the three power stations are point sources. -11 _

Characteristics of these omission sources are given in Taole 2. Around the Konin power station, samples of freshly fallen snow, weighing 6-12 kg each, were collected from a polyethylene foil sheet of 2 square meters area, exposed 24 hours before collection at ground level. Arcund the Zeran and Siekierki stations snow samples were taken from snow deposited during 24 hours upon the old more compact layer. The samples were evaporated,dry-ashed and dissolved in hydrochloric acid. Dry fallout was collected for 24 hours on gummed polyester films of 2 square meters area, placed 1 meter above the ground. After removing injects and fragments of plants collected occasionally, the dust was washed out with methanol together with a mixture of castor oil and rosin used as adhesive agents. After evaporation of methanol, the residue was dry-ashed and dissolved in hydrochloric acid. The weight of a~h was assumed to represent the content of mineral matter of the sample.In these eanples 226Ra wee determined by the radon emenation method(l).The lower limit of detection of the method and the corresponding minimum datectable concentro- tion of 226Ra in enow and dry fallout are presented in Teble A and В of the Appendix. - 12 -

1.2.2.2. Results and discussion Natural sources of Ka in the atmosphere are volcanic eruptions, wind transfer of sea water and soil, forest fires and meteoric dust. From estimates of the amount of inorganic matter entering the atrr.ocphcre from these 226 sources, one might infer the natural Ra content in ground level air. This type of estimate, however, is sub- ject to uncertainty because of scarcity f reliable information on the rates of solids transfer into the atrr.os- 226 phere from particular natur.il sources and the Ra concentration in each. These natural transfer rates are now difficult to estimate, because in some localities they are overhelmed by the man's activities. This is illustrated by 226 temporal changes of dust and Ra contents in fossil ice deposited over years of increasing industrialization in a small glacier in the Tatra Mtns. in Southern Poland (para 1.3), from which it may be inferred thafc only a small frac- 226 tion of Ra in our snow and dry fallout samples collected around industrial sources of emission, is of natural origin. In freshly fallen snow collected under the plume emitted from the Zeran power station, the highest concentration

* location of the plume was determinated by visual siting _ 13 -

of radium-226 was found near the station and the concentration decreased with distance up to 45 km. (Table 3). Collecting was done during a very dense snow fall, when the cloud ceiling was low, the wind was slight and its direction stable. During collection of snow samples in the vicinity of the Siekierki power station (Table 4), the mean wind speed was about 5.0 m/s and in the Konin station (Table 5) 1.8 m/s. In both of these localities, the highest concentrations of radium-226 in snow were found not in the vicinity of emission sources but many kilometers away in' the wind direction. In these localities where the snow was deposited at higher wind speeds, the radium-226 concentration in snow was found to increase with distance from the source of emission up to 14 and 20.7 kilometers, and then to decrease again with greater distance (Table 4 and 5). A similar relationship was observed in the case of dry fallout near the Adamów power station in Turek, where the maximum radium-226 deposition was found it 7.5 km under the plume, at a wind speed of 1.7 m/s (Table 6). This was not found in the vicinity of the Nowa Huta iron mills, where sampling was performed at a wind speed of 2.0 m/s and limited to a km from the boundary of this area source of emission (Table7). The distances of maximum surface deposition of -14-

Re and of maximum Ra concentrations in ŁHCW and : n particulates run more or lc-ss parallel in the localities studied. The relatively low concentration of 226 Ra in particulates found near the point sources of emission suggests that radium is enriched in the snajlcr fly ash particles that travel longer distances than in the bigger ones deposited near emission sources. This is in agreement vith the findings of Coles et al. who found concentrations in the fly ash that increased with decreasing particle size in four sized-fractions of fly ash studied (19).,

using the method of Byzova et al. (23), we have calculated the theoretical distribution of particles deposited in various distances from the Adair.ow coal power station in relation to the diameter of j-articles. The height of stack of the Adamów station-h, is 150 гг., its ciair.eter-d is 10 m, temperature of outgoing gases-t^, is 110°C, average ambient air temperature-t was 28°C, the nean speed of outgoing substances-w is 21m/s and the mean wind speed-u was 1.7m/s. The height of the thermal transport, <Д h, was calcu-

lated using Davidson Brayant formula: -15, -

£,h = d ( —-)1'4 (1 + ) ъд The total height of emission source i.e. h+Ah was calculated as 740 rri. The size distribution of the outgoing particles was determined by the Air Pollution Control Laboratory of the Adamów power station, at the same time as dry fallout sampling (Table 8), i.e. on the 4th and 5th of July,1973. The experimental Richardson factor,B, was calculated from the formula given by Byzova et al.(23):

xo u where: g is accelaration of gravity of 981cms , H is height of wind speed measurements of 2 ą At, i.e. the difference between the temperatures at 2H and —^—, is -1°C, and T i.e. average ambient air temperature^is 24S°K.

The value of this factor on July 4,1973 was -0.028? what corresponds according to Byzova et al. (23) to the horizontal turbulent diffusion coefficients near the ground level of 0.13 and to the vertical one of 0.06. These coefficients characterize the В weather category of Pasquill(24).

Using these turbulent diffusion coefficients and values -16 -

of avtnirjc wind cpc-t-r] .ir.d f.;11 velocity giv<-n in Tabl# 8, and with the data on total i-ni csion height , froa thr- no».c- grams given by Byzova et al.(23) we can find the width of the deposition area and the distances of the maximum

ground-level deposition of the particles (Table 8^ . Com-

paring these calculated distances of maximum deposition with the results of our dry fallout measurements given in 'у у с Table С, one may sec that the maximum Ra deposition of

O.CC pCi m day" found at the distance of 7.5 krr., corresponds to the particle size fraction if about 40/jr, diameter.

This point is close to the distance of maximum mass depo-

sition of 0.91 giri~2 day" found at 5.8 km.

Ti.cse data indicate th.\t the range of local ccvitri- mir.ation of the environment by radium, and ргоЬг.Ыу .i)so by other constituents of fly ash escaping from cor. 1 burning emission sources, is at least on the order of seve- *) "J f ral tens of kilometers. The relatively high fta concentration in the 1970 ice from a glacier in the Tatra Mtns.

(Hi) suggests that the local range of airborne pollutants may be from 100 to 150 kilometers in the direction of prevailing winds (see para 1.3). - 17-

Table 1 226Ra, 210Pb, U. Th, Cd, Pb, and Zn in fly ash from three coal-fueled power stations

Adamów Zcran Siersza lignite. Bituminous coal BiLuminous Substance electrostatic coal,ele- precipitators top of electro- ctrostatic stack static precipita- precipi- tors tators

226 Ra pCi/g 0.9 0.4 0.8 4.2

"~Ra pCi/g extracted by:

6N HCL 0.5

IN HCL 0.00-

IN NH4 Ac 0.02

0.00.4 н2о

П0?Ь PCi/g 1.7 4.4 2.4 6.7

U /ug/g 1.9 8.5 - 17.3

Th /ig/g 11.0 18.0 - 22.0

Cd /ig/g - 4.5 6.5 6.5

РЬ л»д/д 23.0 112.0 158.0 265.0

Zn /ug/g 164.0 340.0 500.0 580.0 _ 18 .

Table 2 Characteristic» of emission source» an4 meteorological conditions

Power Height of Number of Emission Wind Mean tempe- station the stack sources speed raturc Ira) (ton/ at 2 m PC) year) (m/s) In 4m

Zeran 100 Siekier- ki 120 1 15 ,780 s.0 -3 -3.9S Konin 150 2 83 ,360 1.8 -4.7 -5.8 Adamów 150 1 23 ,000 1.7 28.2 27.2 Nowa Hu- ta 4-100 486 83 ,000 2.0 20.6 20.8

Tablet 3 Concentration of Ra in «now around the Zeran power station in Warsaw,February 1970. 226 Distance from source, km Ra, snow

0,6 0.98 1.0 0.63 2.0 0.45 4.0 0.076 30.0 0.073 45.0 0.019 -19 -

Table 4 Concentrations of Ra and particulatcs in snow around the Siekierki power station, Warsaw,March,1971

Distance from source, Km pCiAg pCi, g par- particula •now ticulatcs tee g/Jcg snow •

1.0 0.03 0.13 0.21 7.0 0.07 0.88 0.10 8.5 0.21 4.17 O.OC 14.0 0.48 9.89 0.05 26.0 0.02 1.26 0.02

Table 5 Fallout of Ra in snow around the Konin power station, March,19"1

Distance from pCi/ra /day pCi/kg pCi/g par- g parti- source, km snow ticulates eulates/ kg snow

3.5 0.08 0.32 12.0 0.05 0.08 0.97 0.08 17.5 • 0.25 0.34 0.27 1.26 20.7 0.06 1.74 5.40 0.32 21.3 0.05 0.51 4.40 0.11 21.5 0.03 - 3.50 - 30.0 0.09 0.045 3.90 0.01 31.Q 0.008 0.019 0.39 0.04 20° .

Table g 226 Dry fallout of Ra under the plume from the Adamów power station in Turek,July,1973

Distance from pCi/w2/ pCl/g par- с particular •ource, ka day tieulstea tes/n /day

0.05 0.31 1=5 0.21 0.5 0.23 0.95 0.26 1.0 0.24 i.. 6 0., 16 1.2 6.17 0.96 0,18 1.4 0.20 e.69 0.2* 1.6 0.22 0.57 0.39 3.6 0.24 0.31 fi.77 5.8 6.3$ 0.94 6.91 7.5 0.66 1 06 0.62 11.8 0o25 «.63 0.46 14.1 0.35 1.2 0.30 16.2 0Л2 i.9 0.0? 16.5 0.24 l.S ел? 19.0 0.64 в.5» 0.67 21.0 0.06 0.54 0.11 25.7 0.09 1.» 0.06 26.0 0.06 1.1 0.05 28.9 0.05 . 0.42 0Л2 36.8 ОоОЗ 0.42 0.0*

Table 7 Dry fallout of -""Ra under the plume from tho Nowa Huta iroa mills, near Krakow, JUT>C/1»72

Distance from the pCi/«2/day pCi/a. par- g of parti- boundary of the ticulates eulates/m^/ source, km day

0.8 1.24 1.19 1.05 1.1 1.08 1.31 •0.83 4.3 0.22 2.14 0.11 8.0х 0.11 .l.LS 0.09 8.0х 0.06 0.73 0.07 8.0х 0.02 0.43 0.04

ж Samples collected along 2 km line across the plume 21

Table в

Theoretical distribution of particles deposited under the plus* from the Adataow power station,July 4,1973

Range of fraction at Average fall Width of Distan- particle particles velocity depoei~ ce of diameter bxst) (per cent) (я/в) tion maximum •rea deposi- (km) tion of particles (M0

6-10 41.5 0.003 1.30 10.0 10-20 24.5 0.010 20=28 14.2 e.oi7 Iol7 9.0 30=411 6.0 0.041 1.04 8,0 40-56 5.f в.090 0.91 7.0 «0-10D 2.1 0.200 0.84 6.5 >ioe 5.1 >в.ЗОО •=• - 22 -

1.3. TEMPORAL CHANGES OF *°Ra AND Pb CONCENTRATIONS IN GLACIER ICE AND OF 22SRa,U,Th АГ'Р Pb IN PINE TREES IN POLAND 1.3.1-Material» end methods Four ice samples weighing 14 to 18 kg each were collected at a miniature glacier in the Great Mieguszo- wiocki Cirque,Tatra Mtns.,Poland, from the annual strata deposited in the years 1888,1900,1910 and 1970. The error in age determination of the first three samples is assessed as - 5 years. After evaporation o£ the samples, the residue was dry ashed, weighed and dissolved in hydrochloric acid. Then the 226Ra content was determined by the radon emanation method (1). The weight of ash was accepted as mineral dust content of the ice samples. For the determination of lead, ice samples were collected from the same glacier and from glacier in the cave Grota Lodowa located about 15 km west in the Tatra Mtns.(25). Eighteenth century pine tree samples were collected in an excellent state of preservation from the old Wielicz- ka salt mine near Krakow. Contemporary pine samples were collected in the Puszcza Nicpolomnicka forest, close to the salt mine and exposed to the dust fallout from Kra- kow and the Nowa Huta iron mills.Samples were also collected in another industrial region near Katowice and in - 23 -

rural areas. The samples of tree rings or -Whole crocs- sections of the trunk were dry ashed and 5 yram sampler. of ash мг| taken for analyele.The nudldee in pin* trees «ere determined ее in ref.l.Fcr ehort information on the enalyticel aethode eee Teblee A and В of the Appendix.

1.3.2. Reeulte and diecueeion

As may bo seen in Figure 2, the concentration of mineral dust in the precipitation deposited in a glacier in the Tatra Ktns. increased 160 times durii.g t^c last century and the concentration of Ra about 50 tiroes '. Between 1861 and 1965 the average stable lead rcntent increased appr. 15 tiroes in this glacier (Figu- re 3).

The majority of the ^"Ra and particulates found in the 1970 ice (Tatra Mtns.) probably originates front the industrial regions, 100 to 150 kilometers to the west, north-west and north of the Tatra Mtns. aid from use of coal heating in resorts situated several tens of kilometers around, the glacier. Also during the past century, great industrial centers developed in the Oetrawa-Karwina region in Czechoslovakia, in Upper Si- lesia and in Krakow which are supposedly responsible for the observed increase in pollution of this glacier in the Tatras. Part of this pollution, however, might be a re-

*/ 226 Ra values not corrected for decay 24

cional effect, i.e. the result of emissions from other European industrial centers. The concentrations of Ra and participates, 0.004 pCi and 3.4 mg per kg of ice respectively, found in the 18S3 ice layer (21) should not be- rc-gr rded as nutur.il levels in prc-cipitation for this part of Poland. Indus- trial and other activities, such as agricultural ounu- dution of land, started to increase th^dust joad in atmospheric air in this area much earlier. In the 18th century pine trees fron. the Wieliczka salt ir.ine, the mean concentration of Ra was 0.03 6 pCi/ a of ash. This may be compared with a mean concentration of this nuclide which is approxin^tely 10 times higher than i л contemporary pines from tbe Niepołomice forest (Table 9). This forest is situated near the Wieliczka salt mine and was in all probability the main source of timber for the 18th century exploitation of the mine. In 19th century pines from the Kieliczka mine the "°Ra content vas higher than in the lfith century -and in contemporary pines from Niepołomice forest, but approximately one third of the mean content in three rural regions of Poland. This is astonishing as the Niepołomice forest is under the influence of large industrial dust emi-ssions from the nearby Nowa Huta iron mills which is apparently less important Cor contamination of pine timber than natural or probably some other man-made factors. Thorium and lead concentrations in 19th century pines frem Wieliczka were lower than in contemporary trees. This difference was not statistically significant in the case of uranium.- Comparing Figure 8 and Table 9, one can see that the dramatic increase of airborne pollutants observed in Southern Poland in fossil precipitations deposited during the past century was accompanied by a much smaller increase in the concentration of pollutants in pine trees. Table 5 Mean content of "RajUjTh, and Pb in the ash of pre-industrial and contemporary pine trees.

226 Age and origin of samples RBa U Th Pb pCi/g wg/g Aig/g

18th century ь>/ Wieliczka salt mine U) , o.oie .*/ ../

19th century Wieliczka salt mine {8} (9.30 5.42 i.3 50 ' S 1960-1971 Niepołomice Hi 0.17 -./ ../ .-/

1960-1971 Three rural districts - 0.46 3.6 • 4 in Poland 16)

a/ No measurements made b/ In paienthesls number of samples - 27 -

FIGURE 2. 226 RQ and 5h ice from a glacier in Ore szowiecki Cirque in Tatra Poland (ref.21.)

226 Mineral dust pCi/kg

100

I "j — • | ii • 1880 1900 1920 1940 1970 years 28

ie lead in two lers m TotrQ Mtns. [ref.JU'.3 C^2 represent averages for the period covered.

•- '•'••'•• ft -T-JCTŁ. о ("j

tsa

а э

?1D0

< но p

а. ( >•

••••в a -SB TT a

•> a a 20 а э а i° О О о о ( ) a р 1900 20 40 S0 60 years - 29 -

1.4. CONCENTRATIONS OF POLLUTANTS IN SOIL FROM INDUSTRIAL AND RURAL REGIONS 1.4.1. Introduction The Influence of coal power plants and other sources of industrial emissions on the contamination of soils by natural radionuclides and heavy roetals has no*- been extensively studied, Their presence in coal fly ash (para 1.2.1.) suggests that they may accumulate in soils exposed to industrial emissions. Martin et.al.(27) found 226 that the specific activity of Ra in the soil around an American power plant was similar to that in the fly ash and therefore concluded that increased levels of this nuclide in soil would not be expected from operations of this plant* However? this may not necessarilly be the case with other power plarts or types of coal and we therefore believe more information is needed for an evaluation of this problem» Here we present the results of a study on the contamination", of soils with Ra, Pb,U,Th, stable Pb,Zn and Cd in the vicinity of four coal power plants, a largo iron mill center and a heavily industrialized region of Silesia and compare them with predominantly agricultural regions of Poland. The decreasing concentrations of stable heavy metals versus depth in soil around several smelter sites suggests that the origin of this contamination is aerial (28) • Presumably natural rvidioisotopes and heavy met.ils dispersed in the air from industrial sources of emission are accumulated ot the surface of the soil rather thón in the lower layers. If this assumption is correct , then the diffcrer.ee encountered between concentrations iji the surface and lower layers of the soil would reflect the effect of long term fallout of these nuclides accumulating above their naturally occuring levels in the soil.

Information on the vertical distribution and migration of these natural radionuclides in soil is scarce. Sc- veral authors have studied the relationship between 22 6Ra 210 oi* •''i-s Pb daughter in soil to a depth of about 40 cm (29»3O,3t)• The vertical distribution of Ra in various types of soil was studied by Rusanova (32) to a depth of 100 cm and that of Ra and thorium by Baranov et a\. ( 31) to a depth of 300 cm. Here we present the results of our study on the vertical distribution of several natural radionuclides and stable heavy metals in three types of soil down to depths of 160 cm.

1.4.2. Material» and Methods

The soil sarr.ples were collected in 23 locations at various distances downwind from three bituminous coal power plants: the 5i^rs-a in Silesia, the Zeran arid the 31 -

Sl*kl*T0kl in Warsaw, the lignite coal power plant -Ada- mow in Western Poland, a large iron mill center - Nowa Huta near Krakow, and in the industrial region of Silc- ' sia. In rural regions, 10 samples were collected from coastal locations situated up to 25 km from the Baltic shore, and 10 samples in inland districts of Poland. Soil samples were taken from level, grass covered fields that h^d not been cultivated for many years and were not sheltered by buildings or trees.Three samples were pooled together from each location. At each site samples were collected from an area 15x15 cm., and se- parated into two layers one between 0 and 5 cm and the second between 5 and 10 cm from the surface. For the study of vertical distribution^» of r.uclides the samples were collected from undisturbed profiles at three sites in agricultural areas in Kazimierz,Osiny and Kronow in central Poland. Three types of soil were studied: brown soil formed from loess, podsolic soil formed from loess and podsolic soil formed from loamy sands. The thic- kness of the sampling layers ranged from 5 to 20 cm, depending on the soil horizons, and were utually separa'-cd by 5 to 10 cm layers of soil not collected. After removing plant Material and stone* the samples were air dried, crushed, mixed and aieved through a 1.02 an meeh.Frcs this powder portions were teken and prepareJ - 32 -

for analysis. 226Ra, 2l0Pb, U, Th, Cd, Zn and Pb concentrations in soil were determined according to procedures described in ref.l. Lower limits of detection and sensitivities of the methods used and the corresponding minimum detectable concentrations of the nuclides in soil ere presented in Tables A and В of the Appendix. Exchangeable 226Ra. which night be accessable to plants, was also determined. For this purpose the air-dried soil samples were extracted with Ц ammonium acetate solution. The detailed procedure, baaed on Piper's method C*8) « ie given in ref. 1.

1.4.3. Results

1.4.3.1. Natural radionuclides

In industrial regions wo found a mean concentratioi for raciur.-22G of 1.0 pCi/o oi soil in the upper 5 его layer and 0.73 pCi/g in the 5-10 cm. layer. In the rural coastal recjions the concentration in both the upper and lower layers was 0.71 pCi/g (Table 10). The difference between the upper and lower layers in industrial regions was statistically significant at the 0.95 level of confidence and between the upper layers of industrial and rural regions at the 0.85 level of confidence.

The small increase of radium-22f; content in the upper layer of industrial soils may be caused by the fallout of - 33 -

fly ash from coal combustion and probably also by othor industrial dust emissions. On the other hand, in rural regions, no statistically significant difference in concentration of radiura-226 was found between the two soil layers studied. The mean content of exchangeable radium-226 in soil was usually similar in both layers in industrial and rural regions. In all samples the mean concentration of this form of radium-226, which is probably easily accessible to plants, was only 0.023 pCi/g, i.e. about 3 per cent of the total content of this nuclide in soil. However, it is interesting to see in Table 11 that the concentrations of exchangeable raoium-226 in soil around the Siersza power plant цг< several times higher than at other sites. This is probably caused by differences in the types of coil or ir, combustion technology, leading to higher exchangeabili- ty of radium-226 in the Siersza fly ash (Tcble'1 ).

The distribution of thorium in soil was similar to that of radium-226, i.e. in industrial regions a higher mean concentration was found in the upper layers os compared with the lower ones. This difference is statistically significant at the 0.98 level of confidence. This difference was not observed in rural regions. Also the concentration of thorium in *-.he upper soil layer- was higher in industrial than in rural reci.;nb (0.95 confidence level). - 34 -

Concentrations of uranium d.id not reveal such patterns; although we four.d higher levels of this nuclide in industrial than in rural regions, no significant difference was observed between the upper and lower layers of the soil which may reflect a higher mobility of this pollutant in the soil as compared with radium and thorium. In all the regions studied we found higher mean concentrations of lead-210 in upper than in the lover soil layer. This difference, which in industrial regions was statistically significant at the 0.99 lovel of confidence, might not be caused by the industrial emissions of le.id- 210. In the rural inland regions, the lead-210 concentrations in soil were similar to those in industrial ones, but in coastal areas we found lower concentrations, 'i'iie effect is probably caused by natural fallout of lrad-210, the concentrations of which are higher in continental air masses than in those coming from above the sea 33 )•

As may be seen in Table 11, the highest concentrations of natural radionuclidss in the upper soil layer wore not usually found close to emission sources but several kilometers distant. This is in agreement with the results of our study on dry fallout and snow deposition of radiurr.-226 around the same power plants, in which we - 35 -

found that the points of_ maximum particle deposition in

average meteorological conditions were located between

1 and 20 kilometers ггэт the stations.

We were able to detect the increases in soil concentrations of radium-226, uranium and thorium in indu-

strial regions only after collecting the samples in lar-

ger number of locations. The increase is small and does

not at present cause an environmental hazard. However,

it indicates that there is a trend caused by contem-

porary technology, whicli m;.y becone important in the

future in view of the imlnfinite time ouriinj which

t hor.e nnclidc:; may aci'iimu) .il.e лпЛ reside in soi).

During the study of the vertical distribution

of natura] rauionuclides in soil, we found that the

concentrations of radiuir,-22G, lead-210, uranium and

thorium in the deeper layers of three types of soil

studied (Table 12) are similar to those found in 20

other rural locations in coastal and inland regions

of Poland (Table 10).

In all three types of soil the concentrations of

thorium were similar. In the pseudopodsolic soil from

Osiny the mean concentrations of uranium, radium and

lead-210 were lower than in the two other soil types.

No correlation was found between the concentra- - 36 -

tions of radionuclides and the acidity of soil and type of horizon.

The vertical distribution of natural radicnucli- ucs in the three types of soil is rather random. No correlation was found between the concentrations of iV,c four radionuclides at particular depth levels.' The rrie.T.bers of the uranium family do not seem to be in the state of radioactive equilibrium in the particular soil layers. This suggests that their concentrations

in soil do not represent their oraoinai cor, tor.t in th.'

Kiinerals froir, which the noil originated. Son.e of these rod ionuclides rr.icht be selectively Teachod out from the

soil; on the other hand, soil reicht also be enriched in

some of thcrr. fro.T, percolating ground water. In the climatic conditions of Poland the first process probably

•.-rcvai Is.

1.4.3 2. Stable heavy aetala Cadmiun

Concentrations of cadmium found in fly ash ranged

frorr, 4.S to 6.5 ддд/с (Table 1) and are higher than those

in undisturbed soil profiles in rural districts, which

ranged from 1.0 to 4.0/uc;/g (Table 13). This suggests

that coal burning may contribute to the cadmium content

in soil exposed to the fly ash fallout for long times. - 37 -

As may be seen in Table 14, no simple correlation was

found between the distance from coal power stations and cadmium cc.icentrations in the top 5 cm layer of soil.

In industrial regions, however, the highest concentra-

tions of this natal were found in the same locations as those of lead and zinc, which suggests a common origin.

In these particular locations the concentrations of cadmium in the top layers of soil were higher than in the

lower ones, except for the vicinity of the lignite fue-

led Adamów piano. However, the mean concentrations found in industrial regions differ only slightly in both layers (Table 15).

In the rural regions these conci-.iti ations u.-e Li,-- same in both layers and about half the concentrations in the industrial regions. In the vicinity of the h-ocvy metals smelter in Szopienice, Upper Silesia, the soil concentrations of cadmium are *bout one order of magnitude higher than they are near other sources of industrial emissions.

It does not seem that the contamination of soil with cadmium depends directly on the mass of dust falling out in industrial regions. For example, in Halenba.an Upper

Silesian location with a_ dust deposition of more than

1,000 m /km /year (34), che soil concentration of cadmium was similar to Swierklaniec, a site located about - 38 -

5 km north from the boundary of the large area omission Gourcc in Bytom,Upper Silesia, where the deposition of of oust is lower than 2&0m /km /year (32) . In the case of lead and zinc, however, the contamination of soil with these metals is higher in Halemba than in Swierkla-

Lead The lead content found in fly ash from three power plants ranged from 23»6to 265 /ug/c (Table 1) which was several tir.es higher thin the mean concentrations in three types of soil, which ranged from 28.1 to 38.9 /ug/g (Table 13). This suggests that coal £]y ash may contribute to the kić content in soils exposed to emissions frox power piants.

As г.ау be seen in Table 14, the upper soil layors usually contain n.ore lead than the lower ones, with >-hc exception of the lignite coal Adamów plant, where this effect was not observed. The content of lead in the fly ash from the Adamów plant is lower than in other power stations (Table 1). This plant is situated in a typica- lly rural district and it started to operate only about seven years before collection of soil samples. This probably resulted in a lower accumulation of lead in soil in the vicinity of the Adamów plant, as compared with the three bituminous coal power plants studied which are - 39 -

situated in industrialized regions and have been in operation for several decades. Extremely high lead concentrations in soil were found in the samples collected in the vicinity of the Szopienice heavy metals smelter. The hignest concentration of lead at this .location was contained in the top 5 cm layer of soil. Apart from this sampling point, the mean concentration of lead in the top soil layers of industrial regions was similar to that in the lower layers. As may be seen in Table 15, down to 10 с n, the mean lead concentrations in soil in industrial and rural regions were also similar. Zinc Concentrations of zinc in the fly ash from three power stations ranyed between 164 ond 580 Aig/g (Table 1) which were several times higher than in the undisturbed soil profiles. The influence of the fly ash fallout on soil contamination with zinc is reflected in the higher content of this metal in the soil samples collected near bituminous coal power plants. The soil around the Nowa Huta iron mill Complex are rather less contaminated with zinc than those in the vicinity of the coal power plants. We found the highest concentrations of zinc in the soil samples collected necr - 40 -

the Szopienice smelter. Excluding this locality, in industrial regions the mean concentration of zinc in the top soil laver was about 3.5 times higher than in the rural regions (Table 15 and Table 16).

1.4.4. Discussion

In Poland, where the majority of energy is produced by coal burning, fly ash seems to be the main cause of the increased content of cadmium and zinc in soils of industrial regions. Even larger local contributions wore observed in the vicinity of a heavy metals smelter. On the other hand the difference between le&d content in surface soils in industrial and rural regions is too small to indicate contributions from fly ash. The concentrations of dust, radium-226 and stable lead in atmospheric precipitations increased in a non- industrialized part of Poland 160, 50 and 15 times,respectively, during the past hundred years (para 1.3). It is reassuring to see that such an intensive rise in atmospheric pollution, resulted in rather small contamination of soils, limited mainly in industrial regions. Table 10 The mean contents and range of natural radionuclides in industrial and rural soils (No. of samples and standard deviations in parenthesis)

RadIonuc11de Depth Industrial Rural regions (cm) regions (22) Inland (10) Coastal (10)

226 RBa 0-5 1.0(0.7) 0.7(0.5) 0.7(0.4) (pCi/g) 0.1-4.1 0.2-1.5 0.3-1.6 5-10 0.7(0.4) 0.8(0.2) 0.7(0.3) 0.2-2.3 0.4-1.1 0.3-1.1

226Ra 0-5 2.4 (2.1) 3(3.8) exchangeable 0.3-8.1 0.4-11.8 (pCi/100g) 5-10 2.1(2.0) 2.6(2.4) - 0.3-7.1 0.5-6.2

2ioPb 0-5 1.2(0.6) 1.2(1.2) 0.9(0.5) (PCi/g) 0.2-2.6 0.6-4.5 0.3-2.1 5-10 0.7(0.5) 0.7 (0.5) 0.6(0.3) 0.03-1.9 0.3-1.9 0.3-1.1

U 0-5 1.2 (0.9) 0.9(0.4) 0.5(0.4) fug/g) 0.3-4.2 0.5-1.6 0.1-1.3 5-10 1.1(1.2) 1.0(0.6) 0.7(0.6) 0.2-6.9 0.4-2.3 0.2-1.8

Th 0-5 4.8(3.4) 3.4(2.7) 3.4(1.5) 0.5-15.9 1.4-6.4 1.7-5.9 5-10 4.4(3.1) 3.6(2.0) 3.4(1.5) 1.5-10.9 1.4-7.2 1.9-6.6 Table 11 Natural radionuclides in two layers of soil around industrial emission sources

226 226 210 Source of Ra Ra exchan- Pb U Th emission anc1 (PCi/g) geable (pCiAOOg) (PCi/g) {ug/g ) fug/g)

O-Scro 5-10an 0-5cm 5-10cm 0-5cra 5-IOCT 0-5cm 5-10cm 0-5cm 5-IOOT

Zeran Power 0.3 0.7 0.2 1.5 1.0 0.5 0.3 0.6 0.6 3.1 2.7 Plant 1.0 0.1 0.ч 1.3 1.1 0.7 0.6 0.6 0.7 1.9 Л.9 15.0 2.3 0.5 1.9 0.6 1.9 0.5 4.0 0.4 4.0 1.6 60.0 1.1 0.9 1.5 1.3 1.2 1.4 0.9 1.2 3.8 2.7

Adanew Po- 0.5 0.3 0.4 0.9 1.0 0.3 0.3 0.9 0.8 2.4 2.3 wer Plant 4.0 1.2 0.8 * 2.8 0.9 0.6 0.2 1.1 0.4- 1.7 2.8 10.0 0.5 0.6 0.6 0.6 0.6 0.7 0.5 0.7 1.6 1.8 20.0 0.7 0.2 0.7 0.5 0.2 0.7 0.7 0.5 2.4 1.7 i IM Siekierki 0.3 0.7 0.5 0.6 0.5 1.2 0.2 0.9 0.6 5.2 4.6 Power Plant 1.0 0.6 0.4 1.4 0.5 0.8 0.03 0.9 0.2 2.5 2.1 i 15.0 4.1 0.7 0.3 0.3 0.6 0.4 0.6 0.4 2.2 1.8

Siersza Po- 0.5 1.9 2.3 2.6 2.4 2.9 1.6 4.2 6.9 7.9 10.9 wer Plant 5.0 0.6 0.8 2.4 1.7 0.8 ' 0.8 0.5 0.2 0.5 4.3 10.0 0.9 0.7 7.3 7.9 1.4 0.5 1.6 1.7 8.6 9.3 15.0 0.9 0.8 7.6 5.8 0.9 ? .4 1.2 1.1 15.9 5.7 15.0 1.2 1.0 8.1 7.6 1.6 0.6 1.3 1.4 8.2 9.1 20.0 0.8 0.5 4.4 3.8 2.6 1.1 1.3 0.9 5.8 5.8

Nowa Huta 0.2 1.2 0.8 5.4 1.2 1.2 0.5 1.9 1.4 5.9 6.1 lion Hills 7.0 1.3 1.2 2.2 3.5 1.5 1.3 1.3 1.7 8.8 8.9 12.0 1.1 1.2 1.8 1.9 0.8 0.6 0.9 1.2 7.9 9.6 16.0 0.9 0.9 2.4 3.4 1.3 0.9 1.5 1.2 8.1 5.9 . 25.0 1.8 1.1 1.9 3.0 1.5 1.9 1.2 1.7 8.9 7.9 - 43 - Table 12 Vertical distribution of Ra, Pb,U. and Th in three types of soil frcm agricultural region in central Poland

210 Location Depth Hori- р» Orga- Ra Pb U Th and type (an) zon in nic p=i/g FCi/g /*з/д of soil a/ matter н2о

Kazimierz 5-10 A 6.6 1.6 1.0 0.4 0.7 4.2 (brcvn 10-20 A 7.0 1.7 0.8 0.4 1.1 4.9 soil,lo- 25-35 В 7.0 0.4 0.7 1.9 1.2 3.2 ess) 40-50 В 5.5 0.2 0.8 0.3' 3.8 60-70 В/С 5.5 0.2 0.9 1.2 1.4 5.2 80-90 В/С . 6.3 0.9 2.9 0.8 3.9 100-110 В/С 6.9 0.9 1.9 1.6 3.4 115-125 с 8.5 0.9 1.1 1.7 6.9 130-140 8.7 1.1 1.7 9.9 150-160 с 8.6 0.2 0.7 1.5 10.4 Mean 0.8 1.2 .1.5 5.8 S.D. ±0.2 ±0.8 to. 9 ±2.7 Wronow 5-15 А 5.9 1.6 0.4 0.9 2.4 1.9 (podsolic 20-30 Аз 5.7 0.3 0.9 1.1 1.0 6.4 sandy loam) 25-30 Aj/Bi S.9 0.2 0.7 0.9 1.2 2.6 35-45 Bi 5.8 0.2 1.1 1.0 0.8 2.9 50-70 Bl 5.9 O.i 0.7 0.6 1.7 3.9 80-90 в/с 6.0 0.7 0.9 1.6 6.9 100-110 в/С 6.2 3.4 0.9 1.2 1.9 125-135 с 6.9 1.0 0.6 0.5 3.1 140-150 с 7.3 0.5 1.2 2.1 3.9 150-160 с .7.5 0.5 1.9 • 0.8 3.1 tean 1.0 1.0 1.3 .3.7 S.D. ±0.9 ±0.4 ±0.6 ±1.7

Osiny 5-15 к 6.6 1.7 0.8 0.5 0.5 3.3 (pseudo- 20-30 •Ч 6.6 1.4 0.6 1.4 0.2 3.3 podsolic, 40-50 • 5.5 0.6 0.7 0.4 0.2 4.3 loony 60-70 в3 6.0 0.4 1.3 i\2 5.9 sand) 70-80 в 6.0 0.5 0.7 0.6 5.3 80-90 вл: 6.5 0.6 0.2 0.8 5.2 90-100 с 6.7 0.7 0.5 0.5 5.2 110-120 с 6.5 0.5 0.6 0.2 5.2 130-140 с 6.8 0.7 0.4 0.2 4.5 140-150 с 6.7 0.4 0.8 0.5 4.9 Kaon 0.6 0.7 .0.4 4.7 S.D. ±0.1 ±0.4 ±0.2 ±0.9

S.D. - standard deviation . a/ soil horizons were determined according to ref 35. Table 13 Vertical distributicn of cadmium, lead and zinc in the three types of soil frora agricultural region in central Poland

Location and Depth Horizon Cd РЬ 7л type of soil (on) /ug/g лч/д т/д

Kazimierz 5-10 A 4.0 30.4 108 (brown 10-20 A 2.5 43.0 49 soil, loess) 25-35 В 2.0 26.4 67 40-50 В 36.8 60-70 ь/с 20.0 80-90 в/с 40.0 100-110 В/С 36.8 115-125 с 74.0 130-140 с 42.4 150-160 с 31.2 Mrvm 2.8 34.6 75 S.D. 4.0 iu.7 *30 Wronow 5-15 А 2.0 32.0 90 (podsolic 20-30 Аз .3.0 23.0 90 sandy 25-30 1 3.0 24.8 loam) 35-45 в 27.2 50-70 в 17.6 80-90 В/С 40.0 100-110 В/С 36.8 125-135 с 27.6 140-150 с 22.0 150-160 с 30.4 28.1 )fcan +2.7 90 S.D. V.8

Osiny 5-15 А1 2.0 17.6 50 (psejdo- 20-30 А 2.0 21.6 66 podsolic 40-50 Аз 1.0 41.6 38 loary sand) 60-70 в3 36.0 70-80 в 28.0 80-90 В/С 21.6 90-100 с 54.4 110-120 с 54.4 130-140 с 66.4 140-150 с 48.0 Mnan 1.7 33.9 51 S.O. *0.6 -18.8 *14

S.D. - standard deviation Table 14. Cadmium,lead and zinc in two top layers of soil around Industrial sources of emission

Source of emission and Cd (ug/g) Pb Zn distance of sarrpllng site (km) 0-5 an 5-10" cm 0-5 cm 5-10 cm 0-5 cm 5-10 cm Fewer Plant Zeran 0.3 2.6 5.0 51 47 3 (Diturunous coal) 1.0 2.0 1.0 39 29 79 - 15.0 7.0 2.0 172 37 470 25 60.0 1.0 2.0 36 39 5 12 Adajnow Power Plant . 0.5. 2.4 3.0 35 43 — •• (Lignite) 4.0 1.0 3.0 35 32 - - 10.0 1.0 3.0 36 36 - - 20.0 1.0 2.0 36 63 - - Siekierki Power 0.3 4.0 3.6 65 52 570 590 Plant 1.0 2.0 1.6 64 29 , 88 63 (Bituminous coal) 15.0 1.0 1.0 64 33 13 17 t Siersza Power Plant 0.5 8.0 4.0 117 65 410 207 pp. (Bituminous coal) 5.0 3.0 3.0 22 39 104 46 10.0 7.0 3.0 94 83 136 83 15.0 , 1.0 3.0 66 70 29 58 1 15.0 8.0 5.0 214 19b 224 195 20.0 2.0 5.0 117 51 65 111 "Nowa Huta I^rcri Mill* " 2.0 6.0 4.6 74 57 T5l ' 131 7.0 2.6 2.6 92 83 112 40 12.0 3.0 2.0 62 57 IB 14 16.0 2.0 2.0 50 144 102 97 25.0 2.6 ?.6 77 49 76 98 Heavy metal smelter Szopic-uce 0.1 53.0 10.6 1243 186 4076 770 Iron Mill Hal«nba 0.2 4.0 3.2 181 177 116 ' 189 Dytcm area emission source Świerkianiec 5.0 4.0 5.6 67 67 34 104 Table 15. Mean concentrations and range of cadmium, lead and zinc in soil* of industrial and rural regions tyug/g). (Standard deviations and number of samples in paronthesis)

Region • Cadmium Lead ' Zinc

0-5 on* 5-10 cm 0-5 cm 5-10 cm 0-5 cm 5-10 cm

Industrial 3.2 (±2.4) 2.9 (4.2) 73 61 (*40> 149 <*165) 105 (П38) (Vicinity of coal (22) (22) (22) (21) (18) (17) pow»--r stations) 1.0-8. 0 1.0 - 5.0 22 -213 29 -195 5 - 570 3 - 590

Rural 1.7 (*2.6) 1.7 (-0.8) 63 (±41) 57 (±43) 43 (±24) 58 (±42) (17) (17) (17) (17) (17) (17) 1.0-3. 0 1.0 - 3.0 28 -177 24 -194 2 - 88 3 - 157 - 47 -

16 Ratio of mean concentrations of heavy metals in industrial soils to that in rural soils

Top soil layer Lower soil layer

Cd 1.9 1.7 Pb 1.2 1.1 Xn 3.5 1.9 -48-

1.5. CONCENTRATIONS OF NATURAL RADIONUCLIDES AND STABLE LEAD IN PLANTS 1.5.1. Introduction The surface soils in industrial regions of Poland are more contaminated with natural radionuclidcs and heavy metals than in rural aroas (para 1.4). To, find out whether this difference can be observed also in vegetation, we collected samples of plants in various distances from several sources of industrial dust emission and also in less exposed rural regions. In these samples Ra, U, Th and Pb were measured.

1.5.2. Materials and Methods

Samples of the following plants wore collected arounJ 10 large sources of industrial dust emissions, and in three rural districts of Poland: aerophytic plants i.e. lichens (Cladonia sp.) and moss (Sclero- podiuni sp.) ; pine tree rings from the decade 1962/72, meadow vegetation (mainly grass) and cabbage (Figure 1). In industrial regions the samples were collected at various distances downwind up to 60 km from the following sources of industrial emissions: the bituminous coal power plants Siersza, Zeran, Siekierki, Kozienice, lignite power plant Adamów, copper smelter Lubin-and - 49 -

Nowa Huta iron mills. In addition, samples were collected at three sites in the industrial region of Silesia (Ha- lemba,Swierklaniec and Szopienice) which wore exposed to fallout from heavy metal smelters and fly ash from coal burning industry. The rural region samples were collected in the Bieszczady Mtns. (south eastern Poland), in the Mazury District (north eastern Poland) and in coastal regions of northern Poland.These samples were collected from sites situated more than 60 km from the larger towns and more than 1 km from highways and railways. The plant sample» «fere anallzed with the aethods presented in ref.l and in Table A of the Appendix. The minimum detectable concentration* of the nuclides in plant ash are listed in Table В of the Appendix. * 1.5.3. Results and discussion

As may be seen in Figures 5 to 8 the mean concentrations of 226Ra,U,Th and Pb in plants are rather rjr,- ' domly distributed in relation, to distance from the emission sources, with exception of meadow vegetation, in which these concentrations decreased with distance. We found the highest concentrations in aerophytic plants, i.e. lichens and moss, which obtain their nutriento mainly from the atmosphere. The angiosperm and gymnospcrm - 50 -

plants studied appeared to be less contaminated. This points to an aerial origin of the bulk of these nuclides and tract metals in the plants. The mean concentrations of Ra,U,Th and Pb in lichen, moss and meadow vegetation from industrial regions of Poland are higher than in these plants collected in the rural regions. (Tables 17 to 20). However, in the case of Ra the difference is not statistically significant. The concentrations of U,Th and Pb in industrial regions were up to 3.5, 4.4, and 1.6 tiroes higher respectively, than in the rural regions. This is in agreement with the results of Grodzinska who found that contamination of mosses with heavy metals correlated with

the distribution of industrial centers in Poland (36). 226 On the other hand, the concentrations of Ra and U in pine tree rings and in cabbage as well as the necn concentrations of Pb in internal leaves of cabbage were higher in rural regions than in industrial ones and therefore do not seem to be as good indicators of industrial emissions as atrophytic plants.

Some of the variability of uranium and radium concentrations in plants nay be influenced by the use of phosphate fertilizers which may contain up to 40 and 60 pCi/g of 226Ra and 238U, respectively£37). Also lead con- - 51 - centratiors may be influenced by lead alfcyls fron automobile exhausts. These two factors enhance the levels of natural radionuclióes and stable lead in the er. /iror.n.cnt in addition to industrial e/nissions. Over the whole country, the vegetation of Poland is approximately cr.e cr^~r of magnitude more contr-r-^nated with stable lead (36»38), uranium, and thorium (39), than it is in Scandinavia.

The differences between the contamination of industrial and rural regions with U,Th ani Pb are r.jch more pronounced in acrophytic plants (i.e. lichens and mosr.es) than in coils (sec pnra 1.4). This indicates th.it acrophytic plants may be used as indicators of environmental po-

llution with these nuclidcs. It seems that other types of plants studied discriminate against ~ Ra,U and 7h in soil which contains more of these nuclides than Cc tht- pla.-.ts

(Table 21) . On the other hand the enrichrnent o£ oeropny- tic plants compared to soil clearly indicates the atmospheric source of these pollutants. This atrnospheric scarce is mainly the airborne fly ash which contains more 2 ' Ka,

0 and Th than plants and soil in either type of region.

The bulk of lead content in plants in all probability originates also from an atmospheric source, as ite content in soil is mach lower than in plants. Fly ash may - 52 - contribute only in part to the lead content in aerophytic plants, since it contains about one order of magnitude loss lead than these plants- This indicates that in both industrial and rural regions the main source of environmental pollution with lead is not the fly ash. The lead alkyls frora autorr.ative exhausts nay be a more significant contributor. The extremely high concentration of lead in some samples of cabbage from industrial regions, reaching 63 0/ug/g in ^sh (Table 20) (11.75 год per 1 kg of fresh cabbage) can be compared with 0.30 mq cf Pb, assumed as the daily alimentary intake of this elenent in the United States (25). Table 17 226 Ra concentrations in ash of plants in industrial and rural reoicns (Standard deviations in parenthesis)

Industrial (pCi/g) (IND) . Rural (pCi/g) (RJR) Probability Plant* ЕЛУНЛ , « : С/ No of Mean Range No of Mean Range ' ranp- soap- . . le« les

Lichens (Cla- 14 1.4 (0.8) 0.3-2.3 3 13 (0.5) 0.6-1.5 0.2 donia sp.) Moss (Selen?- 18 1.6 (0.8) 0.5-3.2 5 1.6(0.2) 1.2-1.9 0.1 pediun sp.) . Maadow vegeta- 30 0.6 (0.3) 0.1-1.6 6 0.5(0.3) 0.1-0.9 0.6 ticn (Mainly grass)

Pine ring* 15 0.3 (0.2) 6.06-0.7 6 l.C(0.3) O.?-1.8 0.99 1960-70

Cabbage ** 14 0.3 (0.1) 0.09-0.5 2 0.4. . 0.4-0.5

Cabbage & 15 0.1(0.05) 0.04-0.2 2 0.1 0.09-0.1

?% - external leaves 5> - interrjl leaves ' - calculate: with Student's t-test Table 18 U concentrations in ash of plants in industrial and rural region» (Standard deviations in parenthesis)

Industrial (ug/g) (IND) Riral S/a&/q) (FOR) Probability Plants 1ND/WJR - No of Moan Range No of Mean Range sanp- sanp- les les

Lichens (Cla- 14 4.3 (3.4) 0.5-12 3 2.7 (1.9) 0.6-4.0 0.6 dor la «p.) Moss (Sclero- 18 .4.7 (2.2) 1.1-9 5 2.5 (0.6) 1.6-3.0 0.97 podium sp.) Meadow vegeta- 24 1.1 (0.9) 0.2-3.4 С 0.3 (0.2) 0.2-0.7 0.95 tion (Mainly grass) Pine rings 10 0.3 (0.1) b.2-0.5 6 0.5 (0.4) 0.2-0.5 0.6 1960-70 Cabbage ** 13 0.6 (0.4) 0.2-1.2 2 0.3 0.1-0.4 Cabbage1*' 15 0.2 (0.03) 0.2-0.3 2 0.1 0.1-0.1

- external leaves - internal leaves - calculated with Student*s t-test Table 19 Th concentrations in ash of plants in industrial and rural regions (Standard deviations in parenthesis)

Industrial уде/, (IND) Rural }Юв/д) (PUR) Probability Plants - No of Mean Range No of Mean Range яаяр- sanples les

Lichens (Cla- donia sp.) 11 10.9 (5.1) 4..5-15.5 3 5.8 (3.3) 2.0-8.3 0.8 i Hoes (Sclero- \n podium sp.) 17 10.7 (5.4) 6..3-12.7 5 2.5 (0.6) l.«-3.0 0.99 i Maadow vegetation (Main- ly grass) 29 4.3 (2.3) 1.6-10.0 6 3.4 (1.2) 2.7-4.8 0.6 Pine rings 1960-70 10 4.1 (2.0) 1.0-6.5 6 3.6 (0.9) 2.4-4.8 . 0.5 Cabbage ** 13 5.6 (2.6) 2.4-13.5 2 4.5 •4.5-4.6 -

V Cabbage 15 2.5 U.8) 1.0-8.0 2 1.0 1.0-2.0 -

2/ - external leaves c/ - internal leaves - calculated with Student's t-tert Table 20 Pb concentrations1 in ash of plants in industrial and rural regions (Standard deviations in parenthesis)

Industrial {/Щ/д) (ВЯ)) Rural (^e/g) (BUR) Probability Plants No of Mean Range No of Mean Range samp- earcp- les les

Lichens (Clado- nia sp-) 14 1291(1704) 180-6970 Э 899(676) 192-1540 0.3 Moss (Se.Tero- podium sp-) 17 1738(1564) 115-6220 $ 1529(780) 870-2555 0.4 Meadow vegetation (Mainly grass) 28 264(24) 53-985 6 168(82) 76-293 0.99 Pine rings 1960-70 15 156(74 ) 46-310 5 84(17) 60-99 0.95 Cabbage 14 129(150) 15-630 2 96 79-113 - • Cabbage Ь/ 15 55(20) 19-82 2 129 121-137

- external leaves - internal leaves - calculated with Student's t-test Table 21 Canparison of mean concentration* of Tto,O,Th and Fb in ash of plants in soils and fly ash (Standard deviations in parenthesis).

Region and type of samples и Th Fb KVg т/я т/ч

Aerophytes (Lichens, Mosses) 1.5 (0.8) 4.5 (2.7) 10.8 (S.2) 1515(1600) Other plants (Pines, cabbage, grass, etc.) 0.3 (0.2) 0.6 (0.3) 3.6 (2.3) 158(114) Soil*' 1.0(0.7) 1.2(0.9) 4.8(3.4) 74(47)

Aerophytes (Lichens, Mosses) 1.4 (0.4) 2.6 (1.1) 4.1 (1.9) 1214(691) Other plants (Pines, cabbage, grass, etc) 0.5 (0.4) 0.4 (0.3) 2.7 (0.8) 127(17) Soil */ 0.7 (0.5) 0.7 (0.4) 3.4 (2.6) 63(41)

Fly ash 0.4-4.2 1.9-17.3 10.9-21.5 22.6-265

Tables 10 and IS Table 1 - 58 -

FIGURE A. Mean concentrations of mRa in plants. [ Number of samples in parenthesis ]

PC i/g ash 2.2. го! 1.8. 16. .• \ \ W LICHEN У 1.4. N! MOSS 1.2. i \ -•' 1.0. 0.8, 'm if" 0.6 0.4. -?- -ł MEADOW PLANTS «Я (51 "~S) PINE 0.2. •^, CABBAGE cxt.le f-ns-—If _ 0.0 10 20 30 40 50 km Distance from emission sources - 59 -

FIGURE 5. Mean concentration of U in plants [Number of samples in parenthesis]

/ug/gash

LICHEN •^. ..** MOSS

(sł MEADOW PLANTS jafT"" tu) CABBAGE ext. leove» 10 20 30 АО 50 km Distance from emission sources - 60 -

FIGURE 6. Mean concentration of Th in plants tnumbąr of samples in parenthesis]

15 .

ll] LICHEN

CABBAGE ext. (eaves 5 .

MEADOW PLANTS PINE MOSS

10 20 30 40 JO km Distance from emission sources FIGURE 7, Mean concentration of Pb in plants [Number of samples in parenthesis)

yug/gosh 2500 J

2000.

1500. MOSS

1000.

^.# LICHEN 500

& MEADOW PLANTS _*W PINE (1) CAB BASE ext. leaves 10 20 30 40 50 km Distance from emission sources 1.6. RADIONUCLIDES AND STABLE HEAVY METALS IN HUMAN BONES 1.6.1.Material* and nethods

Samples of ribs were collected from the bodies of individuals deceased in 1969 and 1970 in four regions of Poland, indicated in Figures 8 and 9v The four sets of samples are more representative for urban populations of the capitals of particular voivodities than for rural areas. In Białystok Voivodity (eastern region) the ribs were collected from 45 bodies, in Gdansk Voivodity (northern region) from 69 bodies, in Krakow Voivodity (southern region) from 41 bodies and in Wroclaw Voivodity (western region) from 47 bodies. Two or three ribs were collected from each body and pooled as one sample. The samples were divided into five age groups: new-boms and infants up to 1 year old, children (2 to 15 years), youths (16 to 25 years), adults (26 to 60 years) and old people ( more than 60 years old). For the study of temporal variations, various types of bones were collected from skeletons of adults living in southern Poland between the 11th and 19th century and buried in graves located in four churches:Mariacki and Reformatów Churches and Bielany and Tyniec Monasteries near Krakow. Most of these bones were preserved in wooden or stone coffins which were stored in dry underground crypts. The bones from Tyniec Monastery were buried directly in the loess beneath the floor of church. Bo- ne samples from the skeletons of adults and children living in the 3rd century were also collected in a cave located in Kroczyce in southern Poland. These bones were lying on a dry floor of limestone rock. Six bone samples were collected from adult Egyptian mummies stored in the Museum Narodowe in Warsaw, the age of which was assessed as 12th century B.C. In various parts of Geor- gia of the Soviet Union, bones were collected from graves located directly in the ground, the age of which ranged from the 10th to 19th century A.O. Samples of femurs of persons deceased between 1700-1800 were also collected from the catacombs under the San Francisco Con- vent in Lima, Peru.

After the external impurities and remains of soft tissues were removed, the bones were dried at 105°C to constant weight and then samples weighing up to 100 grane were placed in quartz beakers and wet-ashed in concentrated nitric and perchloric acid and dissolved in di- luted hydrochloric acid. Allquots Mounting to five per cent of the solution were taken for determination of -64 -

Cd, Са( Zn and Pb. The remaining solution was used for radiocheaical analysis of 226Ra, 2l0Pb and ^sr. The detailed procedures of the analytical methods ar» given ref.1 end are summarized in Table A of the Appendix. The minimum detectable concentrations of the elements in dried bones, calculated on the. basis of Table A, are presented in Table В of the Appen- dix. The radioactivity concentrations were corrected for decay during the period between dearth and analysis.

1.6.2. Results and dieeuealon 1.6.2.1. Contemporary bones

The content of stable heavy metals in the bones of contemporary residents of Poland differs in the four regions studied (Figure в and Table 22). Those differences do not seem to be related to the environmental pollution of particular regions. In the Krakbw Voivodity, a heavily industrialized and polluted region, we observed the lowest mean content of stable lead of 5.5 /ug/g dried bone, whereas in the rural Białystok region, the mean lead content in bone was 2.4 times higher. The highest concentration of all stable metals studied was found in northern Poland (Gdansk Voivodity) which is less industrialized - 65 - than the southern parts of the country and which has the lowest level of heavy roetals in vegetation (36). Across the whole country, the mean concentrations of Pb.Zn and Cd in bones of recent residents of Poland 13.9, 103 and 4.3/ug/g d.w. respectively, do not differ substantially from the values reported from other countries and assumed as typical for "standard mar." (25r 4©) • The highest content of 226Ra in bones was found in western Poland, a region with the highest level of natural terrestrial background radiation in this country (41) lor the whole country, the mean concentration of Ra found in bones of contemporary residents of Poland of 0.OO8 pCi/g d.w., is similar to the world arithmetic irtean of 0.0085 pCi/g in areas of normal radiation background (42) . The content of 2*°Pb was more uniformly distributed in bones of residents of the four regions of Poland. The mean concentration in dried bone of 0.05 pCi/g was slightly lower than the mean value of 0.08 pCi/g assumed as a mean for. the northern latitudes in the recent UNSCREAR report (43•

In 1969 the highest mean content of ^Sr in bones of 2.6 pCi/g was found in northeastern Poland in Białys- tok Voivodity. The mean of 2.2 pCi/g Ca (Table 22) for - 66 - the whole country in that year is similar to that found in the вате period in Czechoslovakia, France and Germany /42/. The age distribution of Pb, Zn and Ra concentra- ?1П tione in bone differs from that of Cd, Pb and 90Sr TPig. 10 and Table 23). The higheBt content of Pb, ZP "26 and *" Ra was found in new-borns and infants to 1 year of age. This effect is most clearly seen with lead and Ra, the concentrations of which are several times higher in the group of oew-borns and infants than in other four age groups. Thi£ effect in case.of Ra was also observed by Ыагеу et al f43 J. The higher concentration of Ra in new-born and infant bones is probably caused by high level of tnis nuclide in their food, which was reported to be significantly higher than in diet of older population group С44,) • This also a case with Pb(45J and probably with other metals. There is a tendency for stable lead concentration to increase with age, what was also observed by others {'46) . A similar trend was found with radioactive lead.

1.6.2.2. Preindustrial bones The concentrations of lead in bones of residents of southern Poland deceased between the 3rd and 20th centu- - 67 - ries reaveal a striking feature. The low concentrations in the 3rd century increased to very high levels in me- dieval ages, remained high until the end of the 19th century and then in the 20th century dropped annin to level only twice as high as 1800 years ago. (Fig. -ц and Table 24).

The mean lead concentration of 2.8/ug per gram of dried bone, found in the 3rd century samples, represents probably the natural level of l^ad in human bones in this region, since metallic lead was not in use in Poland in this period (47). In a bone from the 11th century, be- longing to the first abbot of the Benedictine Monastery in Tyniec near Krakow, who probably was an :mmigrant from Belgium, the le<"»d concentration in dried bone was 92.5/tig/g, i.e. 33 times higher than the mean in the 3rd century samples. Still higher lead concentrations were found in bones from 13th, 17th and 19th centuries reaching the highest level of 373.5 дад/д d.w. in the 17th century.

In the 13th, 19th and 20th century, the range of lead concentrations in bones was much greater than in the 3rd, 17th and 18th century which reflects a uniform distribution in population of the "bad" habits leading to high intake of lead in the 17th and 18th centuries, and of the "better" habits in the 3rd century. This might suggest that 13th and 19th centuries were the transitory periods, changing the - 68 - habits leading to increased intake of lead. Thes,e habits consisted mainly in the use of pewter kitchen utensils and tableware ( 26) which in the 13th century started to be more common among the higher classes. On the other hand in the 19th century the rich classes exchanged the pewter for pottery, leaving the less well-to-do ones with the lead containing pewter.

In the 20th century, with the absence of the pewter as the main source of lead contamination, new sources such as lead from gasoline combustion in cars, have appeared which apparently are not evenly distributed in the society of this country. In the long run they may overwhelm the beneficial influence of household improvements and again enhance the lead level in the population.

The mean lead concentration in th.2 oldest (3rd century) bones from Poland is 2.6 times lower than in the Egy- ptian bones from the 12th century B.C.(Table 25). In this period metallic lead was widely used in Egypt (4J), probably also for household purposes. Relatively low levels of lead were found in the 10th to 19th century bones from Georgia,USSR. These samples were collected in countryside graveyards and probably represent the rural population in contrast to the Polish set of samples from the same period collected in the industrial - 69 -

city of Krakow and in rich monasteries nearby. On the other hand, in 18th century Lima,Peru, the lead concentrations in bones were as high as in Krakow. This probably reflects similarity of methods of food pre- paration and serving in both communities. 226 Contrary to lead, the concentrations of Ra in bones of the Polish population n:<* not change much through 18 centuries (Table 24 and Fig..12). The mean concentration of this nuclide in contemporary bones is 2 to 4 times lower than in the period between the 3rd and 19th centuries. In the old bones from Egypt, Georgie and Peru (Table 25) this concentration was also higher than the contemporary global mean of 0.0085 pCi/g (Ą2). This might reflect a change in nutritional habits. Two factor s might cajee this effect: use of tap water from water treatment systems which removes 70 to 99 per cent of 226Ra contained in raw water ( 4.9./ and decrease in bread and cereals consumption which are dominant sources of Ra intake with Polish diet.( 50, 5.1 ). ТдЫ« 22. . ИРЛП content of Ca, Pb, Zn, Cd, ZZ6Ra, /luPb end *wSr in rlbe of recent residents of four region» of Poland of age < 1 to^> 60 years. (Nunber of pooled samples in parenthesis)

Content in 1 g of dried Ьоле * 3.D. PCi ( я Ca)-1 *S.D. »/

Region 226 90 b/ 226 210 90^ (Voivodity) Ca Pb Zn Cd Ra Sr Ra Pb 9 m m PCi pCi

Białostockie 0.18 13.1 n.d. n.d. . 0.006 0.046 0.56 0.03Э _,_ 0.28 2.6 4 * 0.08 * 14.6 i о.ооб * 0.032 * 0.60 * 0.031 0.21 * 2.8 (45) (45) (45) (22) (45) (45) (22) (45)

Gdańskie . 0.25 . 19.6 0.006 ж 0.051 . 0.18 . 0.026 . 0.24 0.9 - 0.10 - 16.6 i 43 4 5*.3 * 0.003 - 0.029" * 0.08 * 0.019 * 0.19 - 0.5 (51) (51) (47) (51) (50) (51) (3) (51) (51) (3) Krakowskie . 0.18 1.9 0.005 . 0.040 . 0.34 . 0.030 0.21 - 0.06 * 7.4 t 51 * 2.4 * 0.003 - 0.028 - 0.26 - 0.018 * 0.12 - i!e (40) (41) (41) (41) (39) (40) (34) (41) (40) (34) Wrocławskie . 0.17 16.2 89 0.013 0.060- 0.095 0.44 - 0.05 * 25.3 ± 26 * 2Л * 0.012 * 0.044 n.d. * O.UO * 0.46 n.d. (47) (46) (15) (44) (47) (44) (47) Weighted 0.19 . 13.9 . 103 4.3 . 0.008 0.050 . 0.41' 0.047 0.30 2.2 mean с/, ±0.08 -18.0 - 45 * 4.2 - 0.008 - 0.035 -0.43 - 0.064 i 0.29 -2.1 (183) (183) (103) (133) (178) (183) (59) (181) (183) (59)

a/ Calculations based on individual determinations of Ca b/ Sarrples collected in 1969 c/ Weighted according to nunfcer of pooled sanples S.D. - Standard Deviation n.d. - Not determined Table 23. Mean content of Ca, Pb, Zn, Cd, 6Ra, T>b and Sr in ribs of recent resident* of Poland in five age groups. (Number of pooled samples in parenthesis)

Content in ig ofdriea bone* S.D. pCxTg S.p.a/ Age Zn Cd 226^ 210р 90s b/ 226^ 210p 90 b/ (years) Ca Pb Ь r b Sr 9 ли /jg Aig pCi pCi pCi

0.20 42.7 .144 +3.8 . 0.020 . 0.045 0.55 0.139 0.28 1.8 • 4 4 4 0-1 ± 0.07 5.7 - 72 ^6.3 0.017 - 0.063 ± 0.40 0.157 - 0.45 1.0 (19) (21) (6) (12) (16) (21) (5) (18) (21) (5)

0.20 13.9 133 . 0.007 0.043 0.58 0.047 0.30 . 2.9 4 2-15 ± 0.08 17.6 ± 47 * 0.005 ± 0.032 * 0.21 ± 0.038 * 0.43 i 0.8 (36) (39) (23) (30) (38) (39) (7) (39) (39) (6)

0.16 7.0 82 3 8 . 0.007 0.047 0.24 0.043 0.27 3.1 ± ± 4 ' 4 4 16-25 0.08 6.6 ±40 ±3.2 - 0.006 ± 0.027 - o.u 0.029 0.13 ±1.9 (30) (30) (20) (21) (29) (29) (7) (30) (30) (7) 0.21 0.026 0.30 1.5 4 11.5 4.3 . 0.005 . 0.053 0.24 26-60 0.-07 ±10.9 4 34 *4.8 4 0.003 4 0.029 4 0.23 ±0.016 4 0.24 ±1.6 (51) (51) (33) (40) (51) (51) (18) (50) (51) (18)

. 0.19 13.4 2.4 0.007 0.057 0.50 0.037 0.31 2.5 > 60 4 0.04 t 4.0 ±31 *2.9 t 0.006 * 0.028 ± 0.60 t 0.035" t 0.16 t 2.8 (43) (42) (20) (30) (43) (42) (22) (43) (42) (22) a/ Calculations based on individual determinations of Ca b/ Sanples collected in 1969 S.O. - Standard Deviation - 72 .

Table 24 Mean content and range of Pb and 226Ra in human bones in Krakow Voievodity between rhe 3rd and 20th centuries (No. of samples in parenthesis)

Century Pb 22(

/ug/g d.w.*S.D., P=i/g d.w.*S.D. *Ci/gCa tS.D.

3rd 2.8*1.7- (18) 15.6*9.1 0. 029*0. 014(13) 0. 161*0. 074 0.4-7 .5 2.2-40.0 0. 010-0. 051 0. 056-0. 275

11th 92.5 (1) 438.4 - - 13th 67.3*98. 7(11) 342.3*504.1 0,,017*0..011(3) 0. 078*0. 057 5.7-3181.6 18.8-1625.5 0,.008-0.,030 0.,045-0.,144 14th 6.1*1.5 (3) 26.2*5.7 0.022! (2) 0.09: 5.0-7.8 20.4-31.8 0,.014-0.,031 0.,065-0.,126 17th 158.2*128.5(6) 707.6*506.2 0,.013*0,.006(5) 0.,067*0,.028 23.5-373.5 126.9-1441.0 0.005-0,,020 0,,025-0,.103 18th 50.9*23. 0(14) 280.7*178.3 0.010*0,.004(9) 0,.049*0,.021 15.4-88. 4 69.4-616.8 0.003-0,.015 0,.015-0,.079 19th 67.2*61..8(13) 381.6-387.2 0.013*0 .006(9) 0.073*0 .022 3.7-231,.1 •42.1-1491.9 0.006-0 .022 0.042-0 .109. 20th 5.5*7.4 (41) 31.4*32.7 0.005*0.003(39) 0.030*0.018(41) < 0.4-36,.7 <1.8-103.5 <0.001-0.013 <0.010-0.078

- Values corrected for decay .Contribution from precursors not added S.D. - Standard Deviation Table 25 Comparison of the mean concentration* of" Pb and ***Ra in bones of residents of southern Poland, Egypt, Georgia, and Peru. (In parenthesis range of concentrations)

Country Century No. of No. Of •anples /jg/g d.v. * S.D. eanples pci/g d.w. * S.D.

Poland 3rd 18' 2.8 i 1.7 13 0.029 * 0.014 (0.4-7.5) (0.010-0.051) Poland 11th to 18 70.6 ± 79.5 28 0.013 * 0.006 19th (3.7-373.5) (0.003-0.031) Poland 20th 41 5.5 t 7.4 39 0.005 * 0.003 (ct).4-36.7) «0.001-0.013)

Egypt 12th B.C. 6 7.4 ± 4.2 6 . 0.015 * 0.004 (5.9-8.7) (0.010-0.023) Georgia, 10th to 13 3.7 t 2.5 11 0.025 * 0.020 USSR 19th (0.3-8.9) (0.002-0.050) Peru 18th 16 44.0 ± ?3.8 16 0.016 * 0.013 (14.8-101.8) (0.003-0.042)

S.D. - Standard Deviation ui «BIAŁYSTOK

FIGURE 8. Meon content of Pb.Zn and Cd in ribs of recenf residents of four regions of Poland . (in /ug/g of dried bone] Ш>Ь, D-Zn, I

FIGURE 9. Mean content of 226Ra.210Pb and 90Sr in ribs OF recent residents of four regions of Poland. tin pCi/g of dried bone] ra226Ra,EH210Pb,S90Sr FIGURE 10. Mean concentrations of Pb Cd end Zn[A] and 226Ra 210Pb and 90Sr[B] in human bones in relation to age

pCi/g of dried bone 0.6"! В

0-1 2-15 16-25 26-GO >$0 years 0-1 2-15 18-25 2S-60 >60 years - 77 - FIGURE 11. Centennial means and range of Pb concentration in human bones in southern Poland between 3rd and 20th century. [No.of samples in parenthesis. Dashed line shows general long-term trend.]

Pb fjg/g dried bones 103

102

Ю1 .

10° .

ю-1 2 A 6 8 10 12 U 16 18 20 Century FIGURE 12. Centennial means and range of Ra-226 concentration in human bones in southern Poland between the 3rd and 20th century. (No.of samples in parenthesis. Dotted line shows general long-term trend.] 228 Ro. pCi/g dried bone

-4

Ю"2 L

10-3 2 4 6 8 10 12 14 16 18 20 Century - 79-

1.7. VERTICAL DISTRIBUTION OF POLLUTANTS IN THE ATMOSPHERE

1.7.1. Introduction

Tho long-distance migration of pollutants in the atmoophcro is probably enabled by their ascent into higher levels in the troposphere and possibly also into the lower stratosphere. To study this ascent, we collected samples of aerosols from various levels in the atmosphere up to an altitude of 12 kilometers. In these samples we determined naturally occurinc "°Ra and stable lead and also man-made radionuclldos introduced into the stratosphere by nuclear exolos.łons. The sources of 22^Ra ar. i stable lead in the atmosp.iere are situated at the surface of the Earth, whereas the source of nuclear debris is at high altitudes. Comparing the distribution of these two types of pollutants at various altitudes from the ground level up to the lower stratosphere may be helpful in elu- cidating the patterns of vertical transport of particles in the atmosphere. More than a decade ago Junge (J>2.) found that concentration of particles in the stratosphere is greater than in the upper troposphere, and that the main chemical constituents of these particles were ammonium and sodium sul- phates, thought to arise from the aecent of their volatile - 80 -

precursors II2S and SCU (53) • In addition, minute concentrations of Л1, Ca, Cl, Cr, Co, Си, Ag, Fe, Kg, Si, and Ti have also been detected (54,55)/ which, having no volatile precursors, enter the stratosphere as particles. Since the extraterrestrial fraction of these elo- ments in stratospheric aerosols is extremely small (56), their main source seems to be the surface of the Karth, but data available on the nature of such sources, and or. the chemical composition and concentration of stratospheric aerosols are rather scarce- an astonishing fact, in view of their possible climatological impact. Also, the patterns of upward transport of terrestrial matter into the stratosphere are not sufficiently known.

1.7.2. Materials and methods

Between 1973 and 1976 we collected 139 samples of aerosols over Poland, at heights of 6, 3, 10 and 12 km. At each altitude 9 to 12 samples were collected in 1973, 6 to 9 in 1974, 8 to 11 in 1975 and 6 to 11 in 1976. In 1973 we collected samples between July to November, in 1974 between May and October, in 1975 between March and December and in 1976 between January and May. The level of the tropopause for each sampling profile was determined from data on the vertical gradient of temperature, _ 81 -

supplied by the Institute of Meteorology and Watt-r Mana- gement, Warsaw. The mean altitude of the tropopause over Poland is between 10 and 12 km, so that almost all our sample3 from 12 km represent stratospheric air. In five cases the tropopause was below 10 km and in two cases above 12 km. When the tropopause was below 10 km the samples collected at 10 km were not included in the mean of values for other samples at that altioude which normally represent the troposphere. Conversely, when the tropo- pausc was above 12 km, the samples at that altitude \.oro not included in the moan values with other samples representing only stratopheric air. We used 1,600 cm2 PVC fi- bre filters type "PETRIANOV FPP-15-1.7 (Soviet nada), placed in collectors (Fig.13 ) suspended under the wings of LIM-type jet pianos. The details of the collecting de- vice and sampling method are given in ref 1. With an aircraft speed of 74 0 km/h, the volumes of sampled air was ranging from 484 m3 STP at an altitude of 12 km to 913 m3 STP at 6 km. Tho effective velocity of air through

the filter was about 4 m/s. 226 After wet ashing of the filters the contents cf Re. Pb,90Sr.137Cs and 144Co were determined with the methods given in ref.l and listed in Tables A end В of the Appendix. - 82" i.7.3. Results ond discussion

As may be seen in Figures 14 and 15 tho vertical distribution of average annual concentrations of Ua and lead in vertical profiles of the upper troposphere and lower stratosphere is opposite to the vertical distribution of fission products. The bulk of fission products collected on our filters originated from the two Chinese nuclear explosions of Juno 26,1973 and Juno 17, 1974.Contributions from the third Chinese explosion and from French explosions in the Southern Hemisphere are rather negligible (Table 26) .

At least some Chinese explosions were reported to introduce radioactive debris into comparatively high altitudes {57). The vertical distribution of concentrations of *"Sr, *37Cs and Ce indicates that the source of these nuclides was in the stratosphere, where the highest concentration» were found (Fig. 15 ). On the other hand, for 22 f\ Ra and lead, comparatively high concentrations found at the altitude of 6 km decreased at higher levels in the troposphere, usually reaching the minimum just below the tropopause, and rising again to higher concentrations in the stratosphere (Fig. 16 ). This type of vertical concentration distribution indicates that the dominant sources - 83 -

of atmospheric duet containing C£ORa and lead in the atmosphere are situated near the suri je of the Earth, and that the stratosphere exhibits a trapping effect on dust entering above the tropopauee. It is also possible that the type of -vertical distribution of lead and radium which we observed is oaueed by a mixture of two processes : an upward transport frost the Earth's surface and high altitude injections by volcanic erruptione» The particles from both types of sources reaching upper tropospheric or stratospheric levels may be enriched in eon» elements beoause of other processes such ae vola- tilization and sublimation* Assuming that the Ra content in stratospheric participates is the ваше as in fly ash or soil, we have calculated that the 1975 concentration of mineral matter bound to Ra would reach 50-250 /ag,/i& STP in stratospheric air at a height of 12 km С 9) • This is rather a high ooncentrat ion"» As may be seen in Figure 17, the concentrations of Ra and lead in tropospheric and stratospheric air showed a tendency to increase between 1973 and 1976. This may be caused by emissions from antropogenic sources or by fluctuation of natural emission** 84 -

In 1976 the average concentration of lead decreased as compared with 1975 but was higher than in 1974. This drop of concentration was not observed in the case of 226 Ra. This, and also the differences in the average annual vertical distribution of both nuclides (Fig. \Ą ), may be related to the difference in the type of particles with which lead and radium are associated. If the upward transport of particulate matter observed in the atmosphere over Poland is not a local but a world-wide phenomenon, than it may be assumed, that it is one of the most important factors in long distance migration of airborne pollutants. -85 -

Table 26 Nuclear weapon tests in the atmosphet* between 1973 and 1976

Dat* Explosion tit* Yield

197^ 6/26 Lop Hor (43oM-90°E) 2-3 HT 7/21 Mururoa (22°S-139°W) 20 KT 7/28 • •- -•- 8/18 • •«. -"- 8/25 »•»

8/29 ""* Ш! в/17 Lop Hor 0.2-1 MT 6/17 Mururoa 5 KT 7/7 »"— 150 XT 7/17 -•» - 7/15 -•- 20 KT 7/29 mm

1976 1/23 Lop ЯОГ 20 XT FIGURE 13 . High altitude aerosol sampler. 1. Control mechanism and power supply . 2. FPP-15-1.7 filter with support. - 87 -

12 10 8 6 1976 U.F.M.A.M) 12 10 8 6 1975 (M.M.J.J.O.D) 12 10 8 Pb 6 1974(M.J,S,O> Ra-226 12 10 8 1973(J,A,S.O.N) 6 20 40 60 80 Pbjug/100m33STP Q02 ' O!K 0.06 O.'O8 Ra-226 pCi/i00m3STP

FIGURE U. Average annual vertical distribution of Ra-226 end Pb in the atmosphere between 1973 and 1976 (In parenthesis months in which samples «we collected) 1976 (OF.HA.M) 12 . 10 a б 1975 (M.M.J.S.O.D)

•• —• ••ŁlC- — i 8 t Cs-137 Sr-90 - — Ce-1U — 1973(J.A.S.O.N)

Ю 20 30 ДО pC«/100m3STP FIGURE 15.. Average annual vertical distribution of fission products between 1973 and 1916 (In parenthesis*-months in which samples were collected). FIGURE 16. Typical profile of concentrations of Pb.Ra-226.Sr-90.Cs-137 and Ce-U4 in the Ctmosphere (Sampling date March 11th 1975]

12 11.03.1975 STRATOSPHERE 10 12J12 GMT_ OC.QC GMT TROPOSPHERE 8 — -226 Ra Pb 6 100 150 200 Pb (jug/IOOn^STP) 0.02 3 aO4 0.06 ade 0.Ю 226Ra (pci/юот STPI 12

STRATOSPHERE

137 90 3 10 20 Cs, Sr {pCi/ЮОп STPl FIGURE 17. Temporal changes of average annual concentrations of 22&Ra and Pb in tropospheric and stratospheric air.

Ra-226 o Pb stable pCi/100m3STP yug/100m3STP 0.06. oAttitude 12 km 60- AAttitude 6 km

004.

0.02. 20

1973 74 75 76 1973 74 75 76 years 1.8.CONCLUSIONS l.The rate of fallout of Ra depends on the distance from industrial emission sources. Depending on weather conditions and type of emission source, the points of maximum RĆI fallout were situated appr. 1 to 17.5 km from the emission source. At the Adamów and Siekierki power stations they were roughly coincided with the maxima of 2^6Ra concentration of soil.

2.With the exception of ?26Ra in the coastal region, contamination of soil with natural radionuclides and with Cd, Pb and 2n is higher in industrial than in rural regions of Poland.

226 3.Concentrations of Ra, u, Th and Pb in ash of aerophytic plants are higher than in soil which may suggest an aerial origin of these pollutants. Concentrations of these nuclides in aerophytic plants in Poland are higher in industrial than in rural regions. This difference is less clearly seen in plants which discriminate against these nuclides compared with soil concentrations. The vegetation in Poland is appr. one order of magnitude more contamined with U, Th and Pb than in Scandi- navia and tlie United States. Both in rural and Indus- - 92 -

trial regions concentrations of ^Ra, U, Th and Pb in aerophytoa are two to a hundred times higher than in pine, cabbage and grass. It seems that aerophytic plants are less sheltered from the adverse influence of airborne industrial pollution than- other species. In fact aerophytes are now becoming extinct in a large part of southern Poland including National Parks ( 59 ). This is also the case with pine trees (59 )> although we have found them less contaminated than the aerophytes.

4.A dramatic increase in airborne pollutants observed during the last 100 years in Southern Poland in fossil precipitation was accompanied by a much smaller increase in the concentration of pollutants in pine trees.

5.The lowest content of lead in human bones was found in 1800 year old samples from southern Poland, i.e. from the time when Polish population had no contact with metallic lead. This content may be accepted as the natural level in this region. Contemporary bones from the same region contain only »,bout 2.5 times more lead than the prehistoric ones. On the other hand, in all the periods between the 11th and the end of 19th - S3 -

century Polish population was highly contaminated by. lead, exhibiting bone levels sometimes hundreds of times higher than in the 3rd century.

6.Paradoxically, at the beginning of the 20th century, when in Poland the lead content in atmospheric precipitation increased dramatically, the lead concentration in human bones decreased to a level not much higher than natural (Fig. 18). The industrial development which caused the increase of lead content in the atmosphere, also improved living and hygienic conditions which resulted in decontamination of the population. This development resulted in replacement of household uses of pewter and lead, which once were sources of common contamination•with non-toxic and inex- pensive porcelain, aluminium and stainless steel.

7.As may be seen in Figure 18 , the level of 6Ra in Polish population had been decreasing steadily through centuries and during the past hundred years was not influenced*by the rise of 226Ra content in precipitation. The question arises whether this optimistic situation will be long-lasting. With the continuation of polluting the environment at the current rate, we may lose in the future what was gained in the recent past. - 94 -

8.Our data on levels of contaminants in various compo-. nents of the environment (precipitation, soil, plants) and in human bones indicate that man - at least his skeleton - is rather well protected by discriminating barriers between him and the environment.In variously contaminated regions of Poland the concentrations of 22ft Ra, Pb, Zn and Cd in human bones were not related to the level of environmental pollution in those particular regions. The influence of the local level of pollutants in soil, plants and air on contamination of urban populations is overwhelmed by other factors, presumably related to the homogenizing effect of the food supply system.This suggests also that, at least in case of Pb and 226Ra, the respiratory route is of minor importance in contamination of the population of the country. This is supported by the his- torical study of Pb and °Ra levels in the population indicating that there existed a decreasing trend in these levels in the same period when their atmospheric levels were dramatically increasing. It seems therefore that the commonly accepted philosophy sta- ting that the effects of pollutants on the health of other species in the biosphere are less significant than the effects on man, and that when nan is protected - 95-

as individual the other species are automatically protected, is rather a product of anthropocentric wishful thinking than of the environmental evidence.

9.Between 1973 and 1976 the concentrations of 226Ra and stable lead were increasing in tropospheric and stratospheric air over Poland.

10.The vertical distribution of 226Ra and stable lead in the atmosphere over Poland indicate that there exists an upward transport in the troposphere and an accuramulation in the lower stratosphere of these elements, associated with mineral dust particles.

11.If the upward transport of particulate matter observed in the atmosphere over Poland is not a local but a world-wide phenomenon then we assume that it is one of the most important factor in the long-distance migration of airborne pollutants. - 96 -

FIGURE 18. Comparison of general trends in centennial mean of 226Ra and Pb in human bones and glacier ice in southern Poland [based on Figures 2, 3,11 and 12 ]

226 Pb Ra 1 3 10 10 •I I I • • Bones Ice Bones Ice Jjg/g /ug/ pCi/g pCi/ kg

10 10 гPb Bones

10 10Г1

10* 8 8 10 12 14 16 18 20 Century - 97 -

1.9. REFERENCES

1. Bilkiewicz, J., M. nvniek, E. Chrzanowski, S. Dombinska, D. Grzybowska, Z. Jaworowski, L. Kownacka, H. hcwandowski, W. Rutkowski, T. WardasHko, S. W^odck and L. Wórtkiewicz. Procedures for radiochomical and chemical analysis of environmental and bioloqical samples. (Ed. J. Bilkiowic^). Report No. CLOR-110/D, 197 8. 2. Jaworowski, %., J. Bilkiewicz, L. Kownacka and S. Wjodek. Artificial sources of natural radionuclides in environment. Proc. Syrap. "Natural radiation environment II", Houston, Texas, 7-11 August 1972. (Ed. J.A.S. Adams, W.M. Lowdcr and T.F. Gesell). U.S. ERDA Report CONP-720805-P2, pp. 809-818, 1972. 3. W^odck, S., Z. Jaworowski anJ W. Rutkowski. Lead pollution of plants in rural and industrial regions of Poland. Pre- sented 1st World Conqress of Environmental Medicine and Bioloqy, Paris, 1-5 July, 1974, Central Laboratory for Radio- loqical Protection, Warsaw, Report CLOR-103/D, 1974.

4. Jaworowski, Z. , L. Kownacka, J. Bilkiewicz, E. Dobosz, D. Grzybowska anć Z. Wroński. Radiation hazards to the population resulting from conventional and nuclear electric power production. In Proc. Symp. "Environmental surveillance around nuclear installations", Vol. 1, IAEA, Vienna, pp. 403- 412, 1974. 5. Jaworowski, Z., L. Kownacka, J. Bilkiewicz and D.T. Oakley. Stable and radioactive pollutants in some Northern Hemisphe- re glaciers. In: Proc. Symp. "Isotopes and impurities in snow and ice", Grenoble, France, August-September, 1975. JAHS Publ. No. 118, pp. 112-115, .1977.

6. Jaworowski, Z., Ł. Kownacka and S. Wjodek. Influence of conventional industry on the pollution of environment with radium-226. (in Russian) In: Proc. of 1st Radioccological Conference, Stary Smokovec/ Czechoslovakia, 16-1S May, 1972, Vol. 1, pp. 128-140, 1972. 7. Jaworowski, Z.. Hazards to population from fossil and nuclear fuels. (In Polish). Postępy Fizyki Medycznej 10: 149-154, 1975.

8. Jaworowski, Z., J. Bilkiewicz and E. Dobosz. Stable and radioactive pollutants in a Scandinavian glacier. Environ.PoHut.9: 305-315, 1975. 9. Jaworowski, Z. and I,. Kovnacka. Lead and radium in the lower stratosphere. Nature 263: 303-304, 197G.

10. Jaworowski, Z., J. Bilkiewicz, M. Dysick, D. firzybowr.kn , L. Kownacka and S. W/odok. The influence on man and the environment of natural rndionuclidcs and heavy motaIs from industrial operations . In: Proc. Svmp. "Bioloqic.il implications of metals in the environment", RichIn ml, Washington, 29 September - 1 October 1975, U.S. ERDA Report CONF-7509-29, pp. 628-647, 1977.

11. Jaworowski, Z.. Miqration of radionuclides and hoavv metals in environment. (In Polish). Kosmos 26: 25-39, 1977. 12. Jaworowski, Z. and D. Grzvbowska. Natural radionuclides in industrial and rural soils. The Sc. Total Environ. 7: 45-52, 1977. 13. Jaworowski, Z., L. Kownacka, K. Grotowski and K. Kwiatkowski. Load-210 from nuclear explosions in the environment. Nuclear Technology 37: 159-166, 1978.

14. Jaworowski, Z., L. Kownacka and M. Bysiek. Global distribution and sources of uranium, radium-226 and lcad-210. In: Proc. Symp. "Natural radiation environment IIIй. (Ed. T.P. Gesell and W.M. Lowder). Report of US Department of Energy, C0NF-78O422, /Vol. 1/, pp. 383-404, ;озо. 15. Rocznik statystyczny - 1977 (in Polish). Główny Urząd Sta- tystyczny, Warszawa, 1977. 16. Kompleksowy program ochrony i kształtowania środowiska w Polsce do roku 1980. Part. I. Ministerstwo Gospodarki Tere- nowej i Ochrony Środowiska, Warszawa, p. 9, 1973. 17. Nationwide inventory of air pollutant emissions, 19IS8. National Air Pollution Central Administration, Publication No. AP-73, Raleigh, N. Carolina, 1970.

18. Piper, C.S. Analysis of soil and plants. (In Polish). PWN, Warszawa, 1957. 19. Coles, D.G., R.C. Ragaini and J.M. Ondov. Behaviour of natural radionuclides in western coal-fired power plant*. Environ. Sci. Technol. 12: 442-446, 1978. 20. Kaakinen, J.W., И. Jorden, M.H. Lawasami and R.E. West. Trace elements in coal-fired power plant. Environ. Sci. Technol. 9: 862-868, 1975. - 99 -

21. Jaworowski, Z., J. nilkiowicz and E. Xyxicz. Ra-22G in contemporary and fossil snow. Health Phys. 20: 449-450,

22. Klein, O.H., A.W. Andren, Э.А. Carter, D.F. Emery, C. Feldman, w. Fulkerson, W.S. Lyon, Э.С. Ogle; Y. Tslmi.R.I. Van Hook and N. Bolton. Pathways of thirty-seven trace elements through cool-fired power plant. Environ. Sci. Technol. 9: 973-979, 1975. 23. Byzova, N.L. and Y.S. Otsipov. Metodika rescheta rasseyaniya osedayushchej primes! ot vyeotnogo tochech- nogo istochnike. Tr. Inst. Ehksp. Met. 15, 155-133, 1970.

24. Pasquill, P.. Atmospheric diffusion. Van Nostrand, London, 1962. 25. Jaworowski, Z.. Stable and radioactive lead in environment and human body. Nuclear Energy Information Center, Raport NEIC-RR-29, Warsaw, 1967.

26. Jaworowski, Z.. Stable lead in fossil ice and bones. Nature 217: 152-153, 1968. 27. Martin, J.E., E.D. Horward, D.T. Oakley, J.M. Smith and P.II. Ucdrosian. RtifHooctivity from fonsil-fuel л ml nuclear l«wnr plant;;. In: Рггхт. Symp. "Knvironmontal asj^octs of nuclear power stations", International Atomic F.ncrqy Agency, Vienna, pp. 325-337, 1971. 28* Lagerwerff, J.V. and D.L. Brower. Effect of a smelter on the agricultural conditions in the surrounding environment. In: Proc. Symp. "Trace substances in environmental health - VIIIй. (Ed. D.D. Hemphill) University of Missouri, Columbia, pp. 203-212, 1974. 29. Wileńskij, W.D. Raspredelenie svintsa-210 v nekotorykh pochvakh. Geokhimiya 12: 1507-1509, 1969. 30. Baltakroens, T. Profiles of lead-210 and radium-226 in four New Zealand soils. N.Z.J. of Science 17: 435-4 39, 1974. 31. Baranov, V.I. and N.G. Morozova. Povedenie estestvennych radionuklidov v pochvakh. Radioekologiya , Atomizdat, Moskva, pp. 13-41, 1971. 32. Rusanova, G.V. Soderzhanie «akonomernosti raspredelcniya radiya-226 w pochvennom pokrove rajona povyshennoj jesteetve- nnojVadiatsii.Materiały radioekologicheskikh issledovanii w prirodnikh biogeotsenozakh, Komi Filial Akademii Nauk SSRR, Syktykvar, pp. 32-65, 1971. - 100 -

33. Jaworowski, Z. Radioactive" lead in the environment and in the human body. At. Energy Rev. 7: 3-45, 1969. 34. Paluch, J.. Private communication, 1973.

35. Musierowicz, Л.. Gleboznawstwo ogólne. (In Polish). Państwowe Wydawnictwo Rolnicze i Leśne, Warszawa, pp. 65-91, 1956. 36. Hrodzińska, K.. Mosses as bioindicators of heavy metal f»ollution in Polifih national parks. Water, Air Soil Pollut. 9: 83-97, 1976. , 37. Radioloqical quality of the environment in the United States, 1977. U.S. Kiwi roniuiMit-.al Protection Aqency, Washington, D.C. Rojwrt No. rj20/l-00(), 1977. 3C. imiillnii, A. and r,, Tvl.-r. Water, Air, Roil PolV.it. 2« 455, 1973, (After геГ. l£) . 39. Holm, K. and B.R.R. Porsson. Radiochcmical and radiocco- loqical studies of natural and artificial alpha emitting radionuclides. Int'Natural radiation environment III", / Ed.O.F.G«sell and w.M.Lotfder/ U.S.Dept. of Energy, CONF-780422 Aol.l/ pp. 560-579 ,1980. , 40< Report of the Task Group of Reference Man. Л report of a Task Group of Committee 2 of ICRP. ICRP Publication 23, Porgamon Press, Oxford, 1975. 41. Nicwiadomski, T. and Ej Ryba. Natural radiation field in Poland. Institute of Nuclear Physics, Kraków, Report No. 960/D, 1977. 42. Sources and effects of ionizing radiation. United Nations, New York, UNSCEAR 1977 Report, 1977.

43. Marey, A.N., V.A. Knizhnikova and A.N. Karmaeva. The2c|fect of'calcium in drinking water on the accumulation of Ra and Sr in the human body. In: "Radioekologi£al concentration processes." (Ed. H. tfbcrcr.and F.P. Hunqate) , Pcrgamon Press, Oxford, pp. 333-336, 1967.

44. Mastinu, G.C. and C.P. Santaroni . 226-Rn levels in Italian drinkinq waters and foods. In: "Natural radiation environment III". (I'd. T.F. Г.0Р0П and W.M. Lowdcr) . U.S. Dept. Of energy, CONF-780422 /Vol. 1/, pp. 810-824!*,1980. \ 45. Tol.in, Л. and С.Л.П. Klton. Lead intake from food. In: "'.'.nvironmontal honlLh ,is|V?cts of load". (Kd. D. Barth, A. borlin, R. Hnnol, P. Rocht and J. Smcets). Commission of the Kuropcan Commuriicies. Centre for Information and Docu- montation-CID, Luxomburn, pp. 77-64, 1973. - 101 -

46» Holtzman, R.B., H.P.-Lucas Jr. and F.H. Ilccwicz. The concentration of lead in human bone. Argonne National Laboratory, Radiological Physics Division, Annual Report, ANL-7615, pp. 43-49, 1969.

47. Dąbrowska, Т.. Private communication, 1967. •48. Friend, J.N.. Mnrt and the chemical elements. Charles Griffin and .Co. Ltd. London, 1951. 49. Samuels, L.D.. A study of environmental exposure to radium in drinking water. In: "The natural radiation environment". (Ed. J.A.S. Adams and W.M. Lowder), The University of Chicago Press, Chicago, pp. 239-251, 1964. 50. Report of UNSCEAR No. 16/A/5216/ United Nations. New York, p. 221, 1962. 51. Biuletyn Statystyki Warunków Bytu Nr 17/64. (In Polish). Główny Urząd Statystyczny, Warszawa, 1964. 52. Junqe, C.E.. /Mr chemistry. Academic Press, New York, 1963.

53. Junoe, C.E. And J.E. M.m^on. Tropospheric aerosol studies. J. Geoph^s. Res. 66: 21G2-2182, 1961.

54. Shcdlovsky, J.P. and S. Paisley. On the meteoritic component of stratospheric aerosols. Tellus 18: 498-503, 1971.

55. Gillette, D.A. and .Т.Н. Clifford Jr.. Composition of tropo- sphcric aerosols as a function of altitude. J. Atroos. Sci. 28: 1199-1210, 1971.

56. Ferry, G.V. and il.Y. Lem. Aerosols in the stratosphere. In: "Climatic impact assessment program". (F.d. A.J. Brodorick and T.M. Hard). U.S. Department of Transportation, Washing- ton D.C. Report No. DOT-TSC-OST-74-15, pp. 310-317, 1974. 57. Tcleqadas, K.. An estimate of maximum credible radioactive i ty concentrations from nuclear tests. U.S. ERDA, Report HASL-328, I, pp. 39-C», 1977. 58. Bysiok, M. end Z. Oaworcnreki. List of nuclear explosions in 1945-1978. Report No. CL0R-113/D, 1979.

59. State of vegatation in Poland and trends in its chanqcs induced by man activitv. (In Polish). (Ed. A. Jasicwicz and K. Zarzycki). Report of Botanical Institute, Polish Academy of Sciences, Cracow, 1977. 60. Herley Э.Н. (ed.) . HASL procedures manual. Report HASL-300. Heelth and 8efety Laboratory,U.S. Atoaic Ener- gy Coaalaslon.New York,1972. - 102 -

1 ЛО. APPENDIX; ERRORS AND DETECTABILITY OF THE ANALYTICAL METHODS USED

.l.

.2. Counting error The random nature of the radioactive disintegra- tion process, which is described by the Poisson distribution, causes variations of replicate counting. The quantitative measure of this variability - called statistical counting error - is given by the following e- quation: E= ±z T/-f-+ -t-'

у ts tb where: E - statistical counting error, cpm; Z - the constant associated with a given confidence level; S - gross count rate of the sample and the background, cpm; В - background count rate, cpm; t_ - sample counting time, min; t - background counting time, min. b - юз -

The counting error ~t '.-ho 95 per cent confidence level was calculacuu Tor cacii result from the following equation:

Usually statistical counting error was lower than mean analytical error and was not presented in the report.

.3. Lower limit of detection for redionuclide»

Lower limit of dolectior. (LLD) enn be dcf.inotl, after Herley ( 60 j , as the smallest amount of activity that will yield a net fount for which there is a confidence at & pre-determincd level that radioactivity is present. This definition takes into acco- unt the statistical character of count rate distribution in time.

For the pre-determined confidence level of 95 per cent, that radioactivity is present in a counted sample, the above author deduct the following formula for LLD: 4.66 s LLD - - dpm £f

- standard counting error for background of the system, cpm;

E. • counter efficiency, cpm/apm; - 1СЛ -

В -« background count rate, cpm; t - counting time, min., of the sample. The detection limit of all determined radionuclides was calculated from the above formula and corrected for average chemical recovery. The LLO values are presented in ref.l and put together in Table A.

A. Lower limit of detection for U and Th The lower limit of detection is defined as the lowest content of U and Th which can be read from the calibration curves. The mean analytical errors at these lowest levels are assessed as 25 and 20 per cent .respectively (see ref.l and Table A). I 5. Sensitivity For Cd, Ce. Zn, end Pb the sensitivity of the method le presented instead of the lower limit of detection (see ref. 1 and Table A). -

6. Minimum detectable concentretion, MDC, of elements in sample material The MOC values corresponding to the lower lim.ts of detection ind sensitivities,as well as to the detailed procedures of the analytical methods used, are presented in Table В of the Appendix. Table A.Lower 11(Dlt of detection, LVD, and eanaitivity of analytical aethooa uaed(l). /Mean analytical error, In par cent, of the methods in parenthesis/

Element Analytical aethod LLD or eansltlvity

226R. Radon emanation /10/ 0.02 pCl 2l0Pb 2l0Po electrodeposltion on Ag dlek'/l*/ 0.12 pCi 2l0 Bi electrodepoeltion on N1 dlsk/14/ i 144 C Oxalete precipitation /10/ 0.9 pCl 137, Ce Sorptlon on AMP aat /10/ 0.57 pCl 8 90,Sr Oxalate precipitation /14/ 0.56 pCl U Fluorlaetry /25C/ g Th Araanazo III apeetrophotoaetry /20c/ 10 g in a fused pellet Cd Atoalo Absorption spectrophotoaetry /4/ id per cent in eeaple aatariel Zn /4/ 0.03yug/al per C.0044 ebsorbence unite Ce /2/ 0.05yUg/nl Pb Standard dithizone coloriaetry /5/ O.l5«ug per 0.СЮЗ abaorbance units

*For huaan bonee. For fly ash end soil. rnal/tical errcr et the lower Halt of detection. .т*ы» в.Miniaim detectable concentration*, MOC, of *lM*nta in aaaiple materiel correa- ponding to LLO or aanaitivity of analytical procaduraa uaad / baaed on ref. 1 and Table A /.

Saaple eize Typical ea*pl< ueed for cal- Saaple «aterlal alze culation of Element MDC MOC -f 226, Air dried fly aah 0.5 - i g Re 0.06 pCi/g and ignited aoll Cd 6 /ug/g Zn 6 /"g/g I Pb 1.5 /ug/g 1 210. i g Pb 0.78 pCl/g 8 1 9 U 0.05 / i g Th П.2 /

Snow в -- 12 kg 10 kg 226R. 0.002 pCi/kg

2 26 2 2 Dry fallout of - Re per 2 a per 2 -2 rfv 0.01 pci/m

Gleoler loe 14 -- 18 kg 16 kg 226R. 0.001 pCi/kg 4kflb 4 kg Pb 0.125 Table В, cont.

Plant ash 0.5 - 5 g 2 g 226 Re 0.01 pci/g Pb 7.5 0.5 g U 0.1 г g Th 0.1

226 Huaan bone*.dried at up to 100 g 20 g Ra 0.001 pCl/g 210 iO5°C Pb 0.006 pCl/g 90,Sr 0.03 pCl/g Oa 0.5 i /"g/g Cd 0.3 о

Zn 0.3 i Pb 0.5

Aerosol* in ataoaphe- at 6 ka - 913 oTSTP 700 a^STP 0.003 pCl/100 oTSTP ric air at diffe- 8 ka - 713 a3STP 0.14 pCi/100 m3STP 3 137, 3 rent altitude* 10 k« - 672 a STP Ca 0.086 pCl/100 « STP 12 ka - 484 «3STP 90Sr 0.089 pCi/100 в Pb 0.21 ^g/100 a3STP

"Air dried aoll. According to ref.25.Tne LLD of 0.5

7. Quality control of the analytical procedures Quality control of the procedures «ras baaed on analysis of spiked samples and on participation in interlabora- tory comparison runa W-3 and А-Ю organised by The Inter- national Atonic Agency in Vienna. Results of these tnaly- aes are discussed in ref. 1. - 109 - Part 2. GLOBAL EFFECTS 2.1. INTRODUCTION

Eatiaatea of the annual axehaxiga rata of aetale between tha Earth»* aurfaca and tha ataoaphere ara usually baaed oa global duet flowa (1,2) on concentration* of aetale in oceanio sediaentsO), in rain water (4), ground water, air, aoil (5)e in Greenlaad ice (6)p oa data on weathering processes (7) and on eaiaaiona froa industrial operation* (8, 9)°

Reliability of these estiaate* iB rather aoderate aa the aaapling aitee are of insufficient repreeentativeaeaa for tha whole globe aad saapliag parioda often too abort.

Kspeelally dubioue are eetlaatea baaed oa global duat flowap ее theae flowa theaaelv«s differ by aereral ordere og aagaitude (10) and concentrations of aetala la tha duat are aeauaed to be the aaac aa the eruatal abundance* (8) or to be a «oabiaatloa of eoaeeatra» tioaa in various aaterlal* (1„ 2)» Phyalcal aad cheaioal proceaaea the airborne partiolea undergo duriag their residence ia the ataoapbere lead, hovever» to ehaagea of concentrations of aetala in theae particles ia eoapariaoa to source aateriala aad ia the case of volatile eleaeatae to enrichaenta reaching aereral ordera of aagaitada. High earichaeat factora» relative to tha eruat, vn found ia the early aeventiea for aleaaata ia air partiealatea collected ia reaote (11, 12) aad inhabited areas (12). Later etudlea (13«54) reported the enriebaent of aetala ia aeroaols colleoted at the South Pole, over the Atlantic Ocean, over 8 regioaa of the Soviet Union,ia^areealand and Antarctic glacier lee aad ia duat froa volcanic pluaea. la Antarcticathe enrlcbaent factors for heavy aetala ware found aa high ia snow deposited ia 1914 aa ia 1974, what aeane that the Southern Heaiaphere background eeroeole are - 110 - ratter listed with natural sources tban with anthropoftealtt pollvtlo*

(23). Alao H«rron «t al. (25) found that la Greenland ice Znlt Pb and Cd were highly «arleted in contemporary and In pre-1900 ice aanplea. This suggest* that natural sources otter than continental test are responsible for enrichment of metals In the airboraa dust. In some papers high raluee of concentrations in ice were considered to be eridence of anthropogenic pollution (8, 26) or were disregarded, as the authors supposed that they must hare originated from spurious contamination (8). This approach might lead to the conclusion that increases in lead concentrations by more than a factor of three hundred in Antarctic snows and veil over five hundred in Greenland have occured in recent decades (8). These, and similar statements on mercury increases (6) were challenged by QLckson (27) о and Landy et al., (28), and were not confirmed by later studies» which revealed in both polar regions the absence of an increase in concentrations of trace elements during the past several decades (23, 29, 30, 3D. On the otter hand, in glaciers exposed to local industrial and urban pollution an increase of impurities in ice during the last hundred years may be observed. Such anthropogenic influence is illustrated by a dramatic increase in the concentrations of pollutants in two glaciers in the Tatra Mountains, situated near large European industrial centers. Over the last century, the content of dust in ice has increased there approximately 150 times, of 226Ra 50 times (32) and of Pb 15 times (33). But, with few exceptions, as we shall see later, we did not find evidence of Increase in pollutants in contemporary ice in glaciers remote from industrial centers. - 111 -

Analyses of ice samples collected from polar lee cap* have assumed to be representative of the global background (29). However, for eatlaatlon of global flows of aetala thla aasumptlon does not see» to be correct, aa to other remote parts of the world, -the natural dost and metal loading of the atmosphere is auch greater than In Inland locations In the Arctic and Antarctic (34, 35). Also Zhlgalovskaya et al. (36) found that concentrations of aetals in ground level air in remote continental location (e.g. in Tien-Shan) are up to 3 orders of Magnitude higher them over islands in the Arctic Ocean and 1 to 2 orders higher than near large cities in the Soviet Onion. This ваг be coapared with the ataospheric lead concentrations in reaote areas of the world, eoapiled by ffrlaga(37) which vary by three orders of eagnitirtt. To observe global effects, ice saaples should be collected froa a sufficiently large number of glaciers, situated in the amin geographical regions of the world. Such collections were sampled by Windoa (34) in seven polar and temperate locations. Bis work however, does not provide information on aetals other than ^Tt. The Windom study indicates that the global component in dost fallout differs by several orders of magnitude between polar and temperate regions and suggests that no single region can he taken as representative of the global fallout rate. Other glacier studies have been limited to polar and a few temperate regions, and none of them provided data from a geographical sampling net wide enough for assessment of the global flow of metals into the atmosphere. Between 1972 and 1978, in cooperation with the U.S. Bnvlrooaental Protection Agency, we organised 9 eapedltions to 14 polar ami temperate glaciers from which we collected samples of firm mad - 112 -

ice deposited during the past three decades and also in the pre-industrial peried. The saapling sites cover 9 widely dispersed geographical regions in the Northern and Southern Hemisphere, so that our collection may with some reservation be said to represent the average global precipitation. Using virtually the same sampling cad analytical methods ve determinated the concentrations of ^ Cs,

V, ^^*af ЧРЪ, Pb, Cd, V and Hg. The aim of the study was to estimate the flows of these nuclidee into the global atmosphere. - 113 -

2.2. GLACIER POLLUTION STUDY 2.2.1. Sampling end analysis of ice sample» Samples of snow and ice were collected in nine localities: Spitsbergen, Svartisen and Jotunheimen Htns in Norway, Mt. HcKinley region in Alaska, Oetztal Alps in Austria, Langtanf Hlaal In tb« Nepalese Himalayas, Ruwenzori in Uganda, Cordillera Vilcanota in the Peruvian Andes and Ring George Island in Antarctica (Table 1). The firn and ice samples from the period 1950*1978 were collected into specially cleaned polyethelene bottles and for Hg analysis In glass bottles, froa the vertical faces of natural crevasses in the accumulation zone, after reaoving a 2 m thick external layer, to expoее uncontamlnated ice. We collected as separate samples the whole vertical cross-sections of all particular ice strata in the period studied. Only at East Stanley Glacier, Uganda, layers between 1939 and 1965 were omitted due to technical reasons. Saaples of much older Ice, from the pre-industrlal period, were collected in lower parts of the same glacier or a neighbouring one. At each location 12 to 28 «muni samples of contemporary and 2 to 9 saaples of preindustrlal ice were collected.

The lower limit of detection of 0 and the mean analytical error, Including calibration, were assessed to be 0.1 ug per sample and i 25 per cent for the fluoriaetric method and 0.01 ug and i 25 per cent for alpha epectronetry. The corresponding values for 226Ha were 0.02 pCi and i 10 per cent, for 210РЬ 0.72 pCi and £ 14 per cent, for 137Cs 0.57 pCi and i 10 per cent, for T0.S^gandt2 per cent for Cf 0.15 pg and - 5 per cent for Cd 0.15/Jg and i 5.0 per cent and for Hg 0.5 ng per sample and £ 8%. The detailed procedures for collecting and analytical methods and information on the collection sites and ice dating are given elsewhere (1, 38ł 39). - 114 -

2.2.2. Cencen*retions of metal» in ica The analytical results are presented In Tables 2.10. Cumulative frequency graphs of these results prepared according to a method described by Veltz (40) indicate that the populations of concentrations of radioactive and stable heavy aetals measured in ice samples have lognoraal distribution. Therefor* we present and use In our atmospheric flows of aetals calculations the geometric means and standard deviations. These means were calculated oa the assumption that all values less than the detection limit values are at detection limit. As aay be seen is Tables 2-11 the majority of our pre-lnduetrial samples was contaminated by contemporary 1?7 210 fallout of the relatively short-lived га and Pb. This contamination as indicated by the JIZ% tracer renged from 3% in Alaska to 79* in Peru and as indicated by 210Pb, from k% in Alaska and Nepal to 47* in Austria. The corresponding mean values for all 9 sampling sites were 20 and 21*. The pre-industrial ice In Peru, which was unusually contaminated with -^Cs, was collected froa the ceiling of a cave In cliffs of old ice, surrounding a small lake on the surface of the lower parts of the Jatunjampa glacier. It is possible that the level of the lake fluctuated enough to Inundate the cave with the water aelted froa contemporary snow» which contaminated the old ice in the walls of the cave. The situation in the Peruvian glacier Is clearly not typical, and therefore the unusually high value froa this point, was not Included In the average. We suppose that the contamination of deeper layers of old Ice with 137C* and ^^Pb is due to the transport of impurities. - 115 - collected during long periods on the exposed surface of the older parts of glaciers. Concentrations of 157Cs found in the 0-5 ca thick surface layer of old parts of a Caucasian glacier were about 7 to 44 times higher than in firn fro» the accumulation zone (41), Also concentrations of T*b in the surface layer of old ice that were 50 to 70 tiues higher than in the accumulation zone were found in the sase region (42). The transport of these nuclides from the surface into deeper layers aay be caused by intragranular migration of impurities (43) and also by rein flow processes (44). It is an open question whether the other metals studied hare similar mobility In the old glacier ice as 137Cs and 210Pb. If this were the case, the mean error caused by contemporary contributions in our set of pre-industrial ice sight be about 20 per cent. However, the exposure of our pre-lndustrial ice to the fallout o' stable metals and long-lived U and 6Ra might have been much longer than to that of " Cs. Therefore it is difficult to state unequivocally whether the relatively high concentrations of metals found in old ice sight be caused by this long exposure or represent the original composition of precipitations at the time of their deposition. With this in sind, we nevertheless present the results of analyses of pre-industrial ice, as in all probability they are not an effect of contamination during sampling and analytical procedures, but reflect a real phenomenon. Also the concentrations of impurities found in contemporary snow and ice may not necessarily represent exactly the original chemical composition of precipitation. Changes in this ooaponitlon - 116 -

may be expected ćws to the selective runoff of elements from the upper firn layers in the temperate glaciers (45, 46), by intragranular migration of impurities and self-purification processes at low temperatures (43) by vertical mixing during flrnlficatlon (47), by filtering in snow (48) or by aerosol-snow fractionation during and after snowfall (24). In all glaciers ve observed peaks of Cs concentrations coin- ciding with or close to the periods of greatest nuclear weapon testing in the atmosphere. This is in agreement with other studies of fission products and tritium in Iceland (49)» Alpine (50, 51), Pamir (52), Caucasian and Tien-Shan (46) and Antarctic glaciers (53), in which the vertical profiles of radioactive impurities in ice were foun to correlate with +.heir content in air or precipitation or to coincide with nuclear testing. Comparison of the concentrations of radionuclides and metals in glacier ice samples or in precipitation from various periods and regions of similar latitude may be only tentative, as the world-wide data on fission products in precipitation (54) indicate that their concentrations in neighbouring locations at the same time may differ by a factor of up to two orders of magnitude. In various locations in Greenland, similar differences were also observed in concentrations of heavy metals in ice (27). Our results can be compared with the world-wide fallout of Ce measured in the British global rainwater sampling network (55)• The patterns of temporal and geographical distribution of " Cs concentrations in glacier ice is also similar to that of * Sr in precipitation collected in the Health and Safety Laboratory (54) global sampling network. Aa may be seen in Table 11, except for Hg the geographical die- - 1)7 - tribution of mean concentrations of Rat U and stable heavy metals In contemporary ice is not uniform. The lowest concentrations ve Csund in Northern Norway, Alaska and Antarctica *nd the highest in continental locations at equatorial and middle latitudes. High concentrations of Pb in Peru and Ugand may reflect local or regional Influences. Peruvian Andes are situated in a region rich in lead and other heavy metal deposits» Numerous lead deposits and mines are located in Southern Peru lr the district of Arequipa, Puno and Cusco (56) in a distance 50 to A00 km from ou.* sampling point at Jatunjampa Glacier. In Uganda the lead deposits which appear near Kasese, about 35 km from Stanley Glacier and .Tead deposits in Zaire and Zambia as well as East African ciystallne field enriched in heavy metals (56) may be local and regional source of increased concentrations of metals in Stanley Glacier. Prom the surface of such metal rich regions lead and other heavy metals may be swept up into the atmosphere together with soil and rock dust or may be transported'into the air mass es due to enrichment processes. Ve believe that the latter is rather the case. However, this explanation is tentative, not being based on other experimental evidence than vicinity of glaciers with nigh content of metals and metal rich geological deposits. Other than our measurements, the concentrations of stable heavy metals have been determined in ice from polar regions and from the Alps (Table 12). Concentrations of Cd and V found by us In ice from the Kahiltna Glacier in Alaska are similar to those in snow collected at Barrow, by Weiss et al. (22). The higher concentrations of Hg at Kahiltna Glacier than at Barrow probably reflect the influen- -118 -

се of local mercury deposit* in southwestern Alaska or*seasonal variations, as the samples from Barrow represent only the 1976 mid-win- ter snowfall. In Spitsbergen we found similar concentrations of Hg as in the Kahiltna Glacier, however, in Greenland the concentrations of this metal had a much wider range and reached higher values. The samples from Spitsbergen contained more V, Pb and Cd than those from the Kahiltna Glacier, Barrow and Greenland. Also concentrations 226 of 0 and Ra In Spitsbergen were higher than in the Kanlltna Gla- cier and Svartlsea. Ve have no ready explanation for the higher contents of these неtals in the Spitsbergen glacier than in other polar glaciers. Ore-bearing veins containing Pb and veins of other heavy metals and ore minerals in moraine boulders were found in the same region of Spitsbergen, in a distance of several kilometers from our sampling point (57, 58) and also approximately 200 km north (59). On the other hand the rather high concentrations of 137Cs in Spitsbergen originating from the distant nuclear explosion sites suggest, that the role of the circulation of the global atmosphere in migration of metals to this part of the Arctic might be also significant. In the glacier on King George Island in Antarctica the concentrations of Pb and Cd in ice were similar to those in the Kahiltna Glacier. They were much higher than the values reported from continental Antarctica (8, 23) but lower than the concentrations from the coastal region of Queen Maud Land which were of up to 3*5 and 7.5 /ug kg"1 respectively (48) and from a coastal region near Kir- nyl Station, where Pb concentrations in Ice layers between 1965 and 1971 ranged from 0.4 - 1.2 ,ug kg" (17). Ra and U concentrations in our Antarctic samples are lower than in those from other glaciers. - 119 -

Mean raluee of V and Cd concentrations la a 4 a long ice core from the Jungfraujoch In the Alps and ranges ot У, Pb and Cd in ice from Mt. Blanc in the Alps are lowrr than in our saaplee from an Austrian glacier (Table 12). The measurements from Jungfraujoch, however, are of limited value as the ice core was influenced by severe intrusion of saltwater (60). Concentrations of Ra and 0 of 0.015 and 0.038 ug kg (61) and !n urban regions of the United States froa 30 to 114.9 /Ug kg"1 (63). At various locations in the northern middle latitudes concentrations of fig in rainwater ranged from 0.07 to 0.5 /Ug kg (64). Vith the exception of urban locations in the middle latitudes, the concentrations of heavy aetals in rainwater are similar to those In the glacier ic*. - 120 -

2.3. ESTIMATES OF FLOWS OF METALS IN THE GLOBAL ATMOSPHERE In Table 11 vt present the "global" geometric mean concentrations of 137Ce, 210Pb, 226Ra, U, V, Cd and Hg found in 139 samples of con- traporary ice and in 34 pre-indu«trial samples collected in nine geographical regions. We should be cautious in treating these average concentrations as "global", as they do not represent all glaciers on Earth, nor even the whole latitudinal cross-section. Our sampling sites are located mainly in the Northern Hemisphere, with one site on the Equator and only two in the Southern Hemisphere, and they do not include the especially "clean" regions of continental Antarctica and the Arctic. At most they can be regarded as "Incomplete global" concentrations. Bearing in mind the reservations expressed in this paper, we assume that these concentrations represent the average content of nuclidesin total precipitation i.e. the nuclides washed out with snow and rain water and deposited as dry fallout. These concentrations can be used to calculate the average flows of the nuclides studied into the global atmosphere in the period 1950*1978, assuming that they are equivalent to their deposition on the Earth surface. The global annual flows of majority of these ouclldes are unknown, but those of Pb and Sr were assessed by UHSCEAR (65, 66, 67). Probably the mcst reliable assessments are those of ^Sr, cased on its global annual depositions. For the purpose of this calculation we assumed after UNSCEAR (66) that the activity ratio 137Cs/90Sr Is 1.6. Using this factor we calculated the annual global flows of 137Cs between the years 1957 and 1978. flows in th# years 1950 to 1956 were calculated proportionally to the fission yield of atmospheric explosions in particular years (67) fro» the total 90Sr deposition in the pre-1958 perioa. So obta- - 121 -

ined annual global flows of 1'7Cs, which ranged 60 to 4688 kCi, fit the lognormal distribution with a geometric man and standard deviation of 495*2^° kCi. The annual global 137Ce depoaition or flow, F, of 495 kCl correeponde to our global average ''Ce concentration in glacier ice, C, of 0.52^°j[ pCi kg"1, and the value F 17 of the ratio £ is 9.5 x 10" kg. This value represent* the average mass of the carrier, i.e. the wet end dry precipitation with which the airborne -"Ce was deposited on the surface of the Earth and, regarding the largely dispersed values of the flows and concentrations, is close to the global annual wet precipitation, wLlch ranges from 4.5 x 1017 kg(68) to 5.11 x 1017 kg (69). If we assume that the ваше removal and migration processes in the atmosphere ar in the glaciers influenced a?l nuclides studied, their annual contemporary flows can be deduced froa the foraula 17 P - 9.5 x 10 kg x C, where С is the "incomplete global" concentration of the nuclide under consideration. The average animal flows of 226Ra and 2^°Pb estimated with this procedure are 6.6 and 489 kCl, and of U, Pb, Cd, V and Hg 12, 4870, 590, 180 and 190 kt, respectively* These estimates of global annual atmospheric flows of D, T and Hg are in agreement with other types of estimates not baaed on emission of particulatев (Table 13)* inferreAlsod thfroe mmea thne ratannuae olf globaflow lcalculate surfaced depositiofroa ourn glacie of Pbr (Tabldata eo 14f ) 2 1 0.9 5 /Ug cm у is similar to the estimates of background Pb deposition in three Eastern Pacific sites, based on an analysis of marine sediments, which ranged froa 0.24 to 1.0 /ug cm j" (70) and to the deposition in rural and remote regions of North America - 122 -

and Europe ranging from 0.5 to 2.0 /Ug си у"1 (37). Our assessments of average global surface deposition of Pb and Hg (Table 14) accord with those based on other measurements. The atmospheric flows of aetals calculated froa glacier ice con- oentratlons are orders of magnitude higher than those estimated from particulate emissions both in this paper (Table 13) and by jfriagu (2). The discrepancy between the two types of estimates, is roughly related to the melting point of the metals (Table 15), which may support suggestion of Duce et al. (15) and of Goldberg (71) that sublimation from rocks at ?ow temperature could be an Important factor in their emission into the global atmosphere. The large discrepancy in the case of ЧГЬ is obviously caused by emission of its gaseous Rn parent. These discrepancies are also similar to the enrichments of metals in airborne dust and precipitation given in Table 16. As may be seen in Table 16 the enrichment factors which we calculated for average global ice concentrations are similar to those "found by others in gLacier ice and STOW from Greenland, Antarctica and Alaska. The values of these factors differ from one region to another and probably reflect local influences (Table 16). This may be compared with enrichment factors for 13 elements in atmospheric particulates, compiled by O'Brlen and Coleman (9) which range over two orders of magnitude in different geographical regions.

Our glacier data indicate that the flow of metals into the global atmosphere is dominated by processes leading to enrichment of metals in airborne dust much higher than the enrichments assumed in flow estimates based on particulate emission (Table 13 and Hrlagu (2). The natural processes which were suggested as potential sources of - 123 -

enriched metals in the atmosphere are volcanln (16}» vapour phase» either from a high - or low-temperature source (1$, 71). biological mobilization from the land (72) and sea (73» 22, 74) and chemical fractionation during production of atmospheric sea salt particles (15)* Part of the atmospheric emissions of metals may be in form of halides or hydroxides which are volatile at the temperature of volcanic effluents (16). Chlorine and fluorine were reported as the common constituents of these effluents (75, 18). Kethylation during biological processes as a source for the enriched elements w^s proposed by Duce et al. » (15)? this is supported by the results of experiments on microbiological and chemical alkylation of lead in aquatic systems (76 and 77) and by finding abnormally high alkyllead/total lead ratios in atmospheric samples attributed to natural processes (78). The elucidation of enrichment sources and processes needs further studies. With the exception of V the contribution of the known natural particulate emissions to the contemporary atmospheric flows of metals is rather snail, ranging between 7.9 and 8.8 per cent in the less-volatile group and from 0.04 to 1.1 per cent in the volatile group (Table 17). In the case of the least volatile V its contemporary atmospheric flow seems to be associated with known particulate emissions. About 10 per cent of world production of Pb enters the atmosphere contributing 7.8 per cent to the total contemporary annual flow of this metal into the global atmosphere. Corresponding values for Cd and Hg are probably 15 and 0.4 and 15 and 0.8 per cent respectively. The natural flows of U, Tla, Pb, Cd and Hg clearly overhelm the anthropogenic inputs. Only the industrial production of Pb - 124 - and U is similar to their contemporary atmospheric flows from all sources, but the input from this production is of minor importance for the pollution of the atmosphere on a global scale. - 125 - 2.4. REFERENCES

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Region and year Glacier Alti- Age of collecting tude,

Spitsbergen Korberbreen 400 1951-1973 76302'4 Hąnsbreen 100 100a 16°07*E 1974

Norway East Svartisen 1310 19S2-1977 Svartisen Austerdalsisen 380 500a 66 02'N 14°12'E 1978

Alaska Kahiltna 2450 1950-1977 Mt.McKinley Ruth 550 400a 63°02'M 131°10'W 1977

Norway Storbreen 17S0 1954-1972 Jotunheimen 1400 100-700a

S°2O'E 1972

Austria Gurgler Ferner 3180 1950-1974 Alas :97o 200* 46^30'N 11э0'Е 1974

Nepal Cherku 5350 1957-1972 Langtang Hiaal. Langtang 4500- 700a Hiaa lavas IS^IO'S

1973

Uganda East Stanley 47S5 1960-1974 Ruwenzori Elena 4511 100a

295S3'E 1975

Peru Jatunjampa 53SO 19S5-197S Cordillera Vil- 30S0 250* canota

1976

Antarctica Znosko 300 1958-1978 King George Is.

19"9

aga in years Table 2. Radlonuolides and hetovy metals in ice rrom Kflrber G.Lacier vcontempor»ry; and Нале Glacier (pre-industrial) in Spitsbergen.

137 210 226 Ce Pb Ra U V Pb Cd Hg Age pCl/kg pCl/kg pCl/kg .-"«/kg /"g/kg /g/kg

1973 0.55 0.95 0.005 0.01.1, О.И5 5.51 0.97 CIO 1972 0.05 <0.04 0.004 0.015 0.44 2.98 0.38 0.07 1971 0.30 0.30- 0.005 0.011 1.59 2.69 0.81 0.14 1970 0.14 0.29 G.008 0.011 0.40 2.98 0.51 <0.11 1969 0.22 0.013 0.111 0.35 . 2.03 0.58 0.12 o.o.-» - 1968 0.12 0.11 0.005 0.025 1.71 2.38 0.45 0.15 1967 0.35 0.31 0.008 0.014 0.33 2.35 0.79 0.05 1966 0.17 0.15 0.0Ó3 0.030 0.30 2.42 1.07 0.17 1965 15.41 7.63 0.019 0.117 2.90 9.45 4.77 0.13 1964 5.05 0.28 0.006 0.037 2.18 8.11 1.83 0.11 1963 3,82 0.39 0.011 0.035 <0.15 3.99 2.3.5 0.30 1962 0.97 0.26 0.006 <0.009 0.38 4.40 V.24 0.10 1961 2.47 0.28 0.007 0.005 <0.15 3.15 0.94 v 0.08 8 1960 3.58 0.76 ,0.005 0.018 0.88 3.7- 1.12 0.12 1959 5.57 0.81 -0.006 0.022 1.00 5.58 1.08 0 11 1958 18.53 3.56 0.012 0.041 2.88 5.69 2.21 0.J3 I 1957 3.11 0.80 0.008 <0.002 8.98 4.64 1.79 0.11 1956 4.56 2.36 0.027 0.033 2.03 9.18 1.12 0.07 1955 6.70 3.04 0.004 0.010 1.98 4.53 4.07 0.09 1954 1.75 0.55 0.006 0.011 0.45 2.70 2.73 0.04 1953 1.88 0.33 0.017 0.061 <0.21 6.97 2.97 <0.08 1952 i. 37 O.bO C.006 0.013 1.12 5.80 8.16 0.14 1951 2.30 0.70 0.003 0.005 0.8b 4.69 2.60 CIO 06 33*5.50 1 27 0029 2*1.«6 !••. I) 0.47* - o7 00# L C17* 1 •"-1.07 -0.34 °-° !j:oo3 -0.011 ' 03 Рге-in- duatrlal 0.18 0.06 0.009 0.025 1.39 2.22 2.55 0.46 0.12 0.38 0.008 0.037 1.60 1Л2 0.68 0.30 П.24 0.16

0 001 14 2 e,*0,30 j j2*2.O3 13*0.0S| 0Ll00e ООН* " «••• 3, -0.00! -0.26 -O.tfO :o Table 3» Radlonuclldaa and heavy aetala in ice from East Svartiaen Glacier (contemporary) and Austerdalalsen Glacier (pre-industrlal) in Northern Norway

2J0 226 pb Ra и V Hg Age ptM/kg pCJ/k* MR/kg

1977 0.72 0.16 0.006 0.048 0.50 1976 0.10 0.18 0.003 0.006 0.26 0.48 1975 0.12 0.40 0.010 0.112 0.57 0.17 1474 0.07 0.18 0.003 0.001 0.37 0.30 1973 0.23 0.24 0.007 0.004 1.19 0.50 1972 0.06 0.12 0.003 0.002 0.97 0.10 1971 0.06 0.16 0.003 0.003 0.96 0.14 1970 0.32 0.52 0.004 0.004 1.12 0.22 1969 0.10 0.14 0.002 0.005 0.10 0.89 0.46 19Ь8 0.08 0.16 0.003 0.005 av. in 21 0.97 О.-33 1967 0.06 0.10 0.002 0.007 pooled 0.13 0.17 1966 0.09 0.19 0.003 0.005 samples 0.81 0.33 1965 0.07 0.18 0.004 0.005 1.13 0.27 1964 1.26 0.82 0.007 0.005 0.88' 0.24 1963 0.19 0.24 0.003 0.005 1.00 0.52 1962 0.27 0.33 0.002 0.004 0.39 0.48 1961 0.07 0.18 0.004 0.003 0.52 0.15 19h0 0.06 0.20 0.006 0.005 0.71 6.16 1959 0.40 0.28 0.006 0.00? 0.70 0.44 1958 0.65 1.15 0.002 0.001 0.76 0.23 1957 * 0.23 1956 0.24 0.23 0.002 0.003 0.50 0.44 1955 6.37 5.87 0.011 0.008 2.29 1.23 0.17 1954 0.53 0.86 0,006 0.002 0.20 0.19 1953 0.30 0.35 0.004 0.004 0.59 •0.30 1952 0.42 0.74 0.002 0.002 0.61 0.12 „•0.49 оо 0 005 0Л0 . „,„•0.48 g.m. о. Л ЛП/t* ' 0 1Z12* 64 гб 2 -0.16 °- «-2:?о1 °- -0.06 °' -0.28 °- !?:!о l&Stftai 0.19 0.15 0.006 0.006 0.40 0.08 0.15 0.04 0.004 0.003 0.19 0.15 0.25 0.7? 0.060 0.004 0.40 0.21 0.05 0.0'j 0.006 0.2'. 0.42 g«m. о.! -0.07 0 -*-0.03 7 Table 4. Radionuclldei and heavy metal» In Ice fro» Kahiltna Glacier (contemporary) and Ruth Glacier (pre-industrial)

137 210 226 Ag* pClVfcg >s^g ^h 1977 0.23 0.84 0.012 0.018 Ą «9.3 0.23 0.28 1976 0.17 0.55 0.002 0,005 3.02 0.20 0.32 1975 0.15 0.51 0.005 0.002 Ą .35 0.17 CO.04 1974 0.20 0.28 0.004 0.003 1.10 0.22 <0.22 1973 ,0.55 0.45 0.006 0.002 1.09 0.15 0.35 1972 0.18 0.10 0.009 0.004 ĄJffi 0.11 0.21 1971 1.03 2.04 0.007 0.013 1.38 0.05 0.25 1970 0.70 0.82 0.007 0.006 0.89 0.15 0.28 1969 0.36 0.28 0.005 0.001 1.07 0.12 0.15 1968 0.32 0.24 0.017 0.001 1.08 0.15 0.18 1967 0.33 0.31 0.010 0.004 0.07 0.97 0.12 0.20 1966 0.83 1.49 0.006 0.005 •т. in 28 0.86 O.%? <0.22 1965 1.Э6 2.17 0.004 0.003 pooled 0-6 0.12 0.13 1964 1.63 1.31 0.009 0.004 eaaole* 0.81 0.15 0.13 I 1963 2.35 0.50 0.010 0.003 0.80 0.13 0.10 1962 3.31 0.34 0.004 0.005 0.85 0.16 0.11 VU 1961 3.82 0.58 0.004 0.005 1.44 0.19 0.24 1960 2.24 0.98 0.005 0.004 1.51 0.22 0.13 I 1959 1.10 0.23 0.008 • 0.006 0.16 1958 0.87 0.39 0.010 0.003 1.36 0.21 1957 3.95 0.42 0.016 0.007 1.12 0.19 1956 4.18 0.71 0.013 0.008 0.63 0.19 . 1955 2.49 0.42 0.004 0.002 0.55 0.15 1954 1.71 0.14 0.006 0.005 0.63 0.12 1953 2.07 0.35 0.012 0.004 0.15 1952 1.79 0.37 0.009 0.002 0.21 1951 1.73 0.94 0.012 0.009 0,15 1950 1.12 0.50 J.011 0.005 oso 0 12 lo01 IB* * ••••: °'"-0.60 *o'M ' -0.003 o.o*«£J2£ 0.0/ ,.*£«{ "-0.0l Pro-in- 6.Ó2 Ol 0.001 6.002 ' ' 0.13 <0.14 dustrial 0.03 0.01 0.002 0.006 0.14 0.17 0.04 0.04 0.013 0.003 0,15 0.26

fc.-.l »о.оов OWJ M OO5 °* -0.0l •••4» •••US •°* -0.CO2 -o.eoi Table 5. Radlonucllden and heavy metal* in lc« from Storbreen Glacier In Southern Norway

137 226 Cg Pb Cd Аве R« и pCl/bg Pr 'kg A*/kg jug/kg

1972 0.31 0.002 0.162 13.93 15.72 . o.n 1969 0.59 0.004 0.110 9.44 5.89 0.10 1968 t 0.003 1.62 4.76 1967 4. }0 0.004 0.026 18.21 35.36 0.13 1966 0.11 — 0.011 3.74 2.15 0.11 1965 1.29 0.002 0.044 11.67 7.88 0.10 1964 1.78 0.002 0.090 5.46 1.35 0.12 1963 0.71 0.078 0.089, 13.97 2.36 0.14 1962 3.86 0.002 о.on1 6.48 1.65 0.21 1961 0.38 0.030 0.039 11.55 5.45 0.19 1960 0.61 0.002 O.OIS 9.35 2.92 0.10 1959 ) .61 0.002 0.016 19.96 2.5a 0.14 1958 0.56 0.002 0.550 10.22 1.95 0.11 1957 0.31 0.002 0.027 6.13 2.88 0.23 1956 0.35 0.002 0.098 6.15 1.25 0.16 1955 3.23 0.002 0.880 10.18 2.69 0.23 1954 0,31 0.002 0.018 9.91 1.46 0.11

76 8 5S*7.53 +SU 33l 4 47 5 *;"• °- -o:s} ••«:::K -2.07 «•

Pre-in-. 0.28 0.002 0,080 . 7.67 2.29 0.32 dustrlal 0.14 0.004 6.43 0.75 0.36 0.09 0.009 0~ 006 3.49 0.52 0.70 0.06 0.005 0.090 6.30 1.33 0.18 0.26 0.002 0.026 9.02 0.58 0.18 0.39 0.002 0.016 3.56 0.52 0.44 0.32 0.006 0.007 1.03 0.40 0.03 0.002 0.005 2.30 0.81 0.40 0.51 0.002 0.035 3.11 0.36 0.42 0.16 0.031 2.09 0.87 0.58

l7 3 63 +0 56 0 00 3•Q00X 3 74* - 0.77 ' ° -o:i5 ( ' -0.53 °-":!лз Table 6. Radionuclldes and heavy metals In Ice from Gurgler Ferner In Austria

137 210 226 Age Cs Pb Ra U V Pb Cd Hg pCi/kg pCi/kg pCi/kg >Ug/kg /tfAg //g/kg /Jg/kg

1974 "1.01 - 0.19 0.006 0.009 0.45 1.58 1.26 0.16 1973 2.94 22.96 0.013 0.040 0.94 15.54 2.01 19 72 3.47 0.29 0.003 0.002 0.06 10.33 0.67 0.12 1971 1.42 .1.21 0.003 0.007 0.51 11.19 0.78 0.13 1970 1.03 0.15 0.003 0.003 0.61 11.64 1.20 1969 0.69 0.16 0.008 0.023 3.51 16.98 1.32 1968 1.01 0.04 0.003 0.002 0.57 6.23 0.69 1967 1.23 0.17 0.004 0.002 0.11 6.65 0.88 0,22 1966 5.59 0.54 0.002 0.016 0.44 10.65 1.68 1965 5.50 1.03 0.011 0.021 0.06 12.73 1.68 0.13 1964 0.70 0.36 0.006 0.016 1.62 7.21 18.40 0.17 1963,1962 2.75 0.73 0.004 0.015 2.40 7.99 1.99 0.23 1961 2.06 0.20 0.004 0.008 1.74 8.14 2.55 0.16 1960 1.80 0.38 0.002 0.043 1.97 6.01 10.19 0.20 1959 5.84 0.08 0.009 0.002 3.03 6.51 0.88 0.11 I 1958 1.86 0.27 0.004 0.006 3.75 6.49 1.02 0.13 -1 1957 1.88 5.36 0.007 0.008 0.63 5.30 0.67 0.14 KM 1956 2.14 0.69 0.002 0.007 0.06 10.60 1.48 0.17 1,955 3.56 2.41 0.003 0.023 1.02 16.55 2.04 0.16 1954 0.78 4.34 0.004 0.011 0.40 14.21 5.96 0.19 1953 0.91 3.34 0.006 0.007 0.93 10.47 4.86 1952 1.71 0.48 0.006 0.006 0.58 6.54 2.83 , 0.13 19S1 1.08 0.18 0.007 0.017 5.21 11.57 0.67 1950 J.17 1.31 0.003 0.012 0.94 12.24 2.91

013 j 79+2.43 •0.04 g.a. 1 78 O>57 ш 8 78 • -0.8S -0.44 °' -о'.шO.O09*jJ" 90S l ' -3.42 Pre-in- 0.46 0.27 0.019 0.055 0.11 15.54 0.75 0.11 dusrtUL 0.18 0.32 0.021 0,006 0.57 11.80 2.01 0.12 0.14 0.22 0/D09 0.011 0.06 12.12 0.79 0.15 0.47 0S „ „,,+0.009 ,033 / f.a. с Q0 2727*°- Ol5 o.oisrj; ' -0.0S °- -O.OO5 aid «•«US '•"111 Table 7. Radlonucliden and heavy metals in ice from Cherku Glacier (contemporary) and Langtang Glacier (pre-lndustrial) in Nepal.

n7 210 226 A«* c Pb RO a U V Vb Cd "g pCl/kg pCl/kR pCl/kR ^AfC/kg JJLt/4 Ug/kg

1971 0.070 049 1.75 0.22 0.29 1970 0.38 1.06 0.163" 0.223 0.11 3.63 0.36 0.26 1969 0.36 1.72 0.048 0.080 0.09 3.08 0.44 0.22 • 196Я 1.54 4.32 0.147 0.529 0.27 5.71 0.42 0.20 1467 4.95 0.496 0.32 5.50 •).63 0.23 1966 7.12 5.24 0.135 0.305 0.27 4.29 0.H6 0.27 1965 2.59 6.64 0.092 0.069 0.04 3.38 0.27 0.23 1964 0.79 0.70 0.027 0.044 0.12 3.06 0.86 0.24 1961 1.04 4.49 0.0)5 0.915 0.13 1.75 0.57 0.24 1Ч62 1.42 4.35 0.038 0.022 0.07 3.16 0.38 0.17 1961 ?.85 2.95 0.076 0.145 0.31 4.20 1.46 0.24 1960 1.59 0.87 0.024 0.043 0,11 2.44 0.61 0.28 1959 Я.61 5.29 0.126 0.347 0.30 7.25 0 72 0.15 1958 11.67 3.36 0.014 0.034 0.06 2.74 2.12 1957 2.30 0.59 0.040 0.165 0.24 7.95 0.91

j O57*0.06S .13 ,,•2.09 +005 g.m. U JJ 0 23 »-«r?:2 ••«.1:2 ' 1 - --0.090 .08 * " -1.32

Pre-»n- 0.07 0.04 0.032 0.163 0.17 4,22 1.20 0.13 dustrlal 0.20 0.08 0.073 0.168 0.48 4.81 1.32 0.21 0.12 0.15 0.104 0.330 0.42 6.37 8.58 0.23 1.15 0.30 0.П6 0.640 0.17 t 4.96 3.36 0.36 0,80 0.04 0.021 0.066 0.18 2.56 4.30 0,53 + 1 0.80 , . O.O72 . ,„.'0.278 .18 . 3 72 g.m. O<27 0•09 * С O57 .-•1.76 2#872 B7* - -o!l9 .10 32 "*0 • 05 -1.26 -1.62 °' -0 16 Table 8. Radlonuclides and heavy metals in ice from East Stanley Glacier (contemporary) and Elena Glacier (pre-Jndustrial) in Uganda.

137 210 226 V Cd Hg Age ce Pb R. и t>b k pCi/kg pCl/kg pCi/kg /Ig/kg M8/k8 >Ug/kg Mg/ 8

1974 1.25 7.52 0.026 0.113 1.94 27.92 1.22 0.27 1973 2.16 19.79 0.029 0.167 4.09 23.36 1.87 0.21 1972 1.35 • 0.95 Э.018 0.024 1.61 32.20 1.08 0.12 1971 0.67 1.73 0.044 0.121 0.71 32.83 7.53 0.17 1970 0.38 1.89 0.014 0.025 0.98 15.83 8.46 0.22 1969 0.08 0.43 0.013 0.006 0.69 10.81 3.31 0.22 1965 0.14 0.67 0.021 0.045 1.52 9.06 1.55 0.17 1964 0.07 0.34 0.013 0.007 1.32 8.45 1.48 0.08 1963 0.05 0.36 0,007 0.026 0.74 16.08 0.30 0.09 1962 0.10 0.40 О.О'З 0.006 1.08 31.79 1.24 0.28 1961 0.09 0.83 0.012 0.122 0.95 28.86 0.81 0.17 1960 1.04 0.009 0.002 1.06 24.19 1.48 0.17

0 8 2 91 - «*0.086 ,-•0.76 0 1 21* - ll69 f.a. 0. 1 15* ' 1 °'026-0.020 1 -0.48 19'6- 7.8 -l!02

Pre-1n- 0.02 0.11 0.011 0.004 0.98 20.02 1.32 0.11 duetrial 0.04 0.04 0.015 0.004 0.70 54.60 1.27 0.11 0.02 0.33 0.017 0.105 1.46 12.84 0.91 0.20 0.13 0.09 0.007 0.007 1.46 14.68 0.67 0.27

OI2 , ,^0.47 197 0 38 009 f.a. o. 1! 2211 6 ft* 1 o* * 0016 16* «• *0'07 ,»- -*!:SS5 ' -10.2 -0.06 Table 9. Radionuclide* and heavy metals in ice froa Jatun,}ampa Glacier in Peru*

137 210 226 Ce 0 V Pb Cd A*. Pb R8 Hg pCl/kg pCi/kg pCi/kg jUg/*g /*8 Р&/Ч /«/kg

1975 0.14 0.45 0.016 0.050 29.75 0.92 1.96 1974 0.24 3.16 0.041 0.220 14.91 1.04 0.43 1973 0.47 12.48 0.042 0.270 15.59 1.68 0.96 1972 0.27 4.24 0.030 0.009 12.27 0.46 1971 0.47 4.94 0.020 0.180 14.14 0.71 0.29 1970 0.16 8.11 0.033 0.220 12.92 1.80 1.22 1969 0.21 0.62 0.018 0.170 15.19 0.89 0.38 1968 0.65 0.88 0.032 0.180 11.70 0.98 0.25 1967 1.29 8.63 0.030 0.300 22.85 1.08 0.33 1966 0.20 0.25 0.007 0.100 JO. 16 1.40 0.25 1965 0.42 1.11 0.010 0.006 11.91 1.01 1.53 1964 0.26 0.42 0.029 0.005 у 8.36 0.89 0.3J 1963 0.07 0.32 0.009 0.050 <0 12.77 0.75 1962 0.05 0.21 0.002 0.005 8.61 0.45 0.3T 1S61 0.10 0.11 0.014 0.005 6.94 0.7ft 0.36 1960 0.53 2.89 0.011 0.050 10.88 1.43 0.47 1959 0.34 0.40 0.016 0.190 10.57 1.32 0.52 1958 - 0.24- 0.59 0.014 0.070 11.97 0.98 0.52 1957 0.47 1.07 0.015 0.100 12.87 1.65 0.56 1956 0.43 0.53 0.010 0.120 29.25 1.28 0.67 1955 0.91 3.38 0.015 0.100 26.10 0.74

g.m. +0 36 } ot6 ' 0 О61*0'197

*-*nch individual result under the detection limit. Table 10. Radionuclides and heavy metals in Ice from Znoeko Glacier In Antarctica.

226„ Age 137CS 210Pb Ra V Pb cd pCl/kg pCl/kg PCl/kg jug/kg

1978 0.02 0.12 0.003 . 0.002 2.31 0.008 0.32 1977 0.02 0.11 0.005 0.004 2.12 0.008 0.18 1976 0.01 0.08 0.002 0.004 0.96 0.008 0.25 1975 0.10 0.08 0.002 0.002 2.98 0.008 0.09 1974 0.04 0.06 0.004 0.004 0.06 2.03 0.008 1973 0.03 0.07 0.006 0.002 av. in 19 2.39 0.008 0.35 1972 0.01 0.12 0.022 0.001 pooled 2.55 0.060 0.17 1971 0.04 0.06 0.004 0.001 samples 2.02 0.008 0.17 1970 0.01 0.07 0.007 0.001 3.69 0.2-28 0.15 1969 0.04 0.03 0.002 0.001 1.27 0.008 0.22 1968 0.04 0.06 0.001 0.001 2.22 0.214 -CO. 12 1967 0.07 0.04 0.002 0.001 1.59 0.008 0.24 1966 0.04 0.09 0.002 0.002 2.01 0.008 <0.12 1965 0.08 0.18 0.001 0.001 1.82 0..112 0.11 1964 0.10 0.06 0.001 0.001 1.27 0..217 0.19 1963 СЮ 0.05 0.001 0.004 0..329 0.24 1962 0.01 0.11 0.001 0.008 0.233 <0.18 1961 0.10 0.13 0.002 0.004 1.10 0.008 0.18 1960 0.08 0.11 0.001 0.001 0.008 0.27 1959 0.001 0.001 0.008 <0.25

g.a. o. 97*0.82 0 9 " -0.57 -0.04

Рте-industrial 40.15 0.2

7*0-04 Table 11. "Global" geometric mean concentrations of metals in glacier ice (based on Tables 1-9)

137Cs 21°Pb 226R* U V Pb Cd Hg

Contemporary •,•2.07 Q И.51 л +0.013 ,+0.058 +0.56 +9.1б *2.38 , +0.17 «••• °*5-0.42 * ЧП5 -0.38 O* OO7Ofy7 -Ó.6Ó5 o *O15-6.6i1 o °*1Q19-0.1 4 ч 51ч* э-3.2 9 n °*ft2bZ-0.4 9 0 n Range 0.01-18.5 0.03-23.0 0.001-0.16 0.001-0.92 0.04-9.0 0.55-32.8 0.008-35.4 0.04-2 No 183 167 183 185 167 151 186 162 Pre-industrlal +11 8 +1 22 +0 _ _ n -,+0.27 n 1П+0.21 n fv^Q+0.02 n n5.+0.081 n ,.,+0,87 y n * n тл » п э* « g.m. °*13-0.08 °'10-0.06 ^^^-О.ООЗ 0#02^-0.018 °*31-0.23 7*°- 4.4 °*76-0.43 °'25-0. Range 0.02-1.2 0.04-0.5 0.001-0.14 0.002-0.64 0.06-1.6 1.03-54.6 0ИЭ-8.6 0.08-0.8

No 35 25 34 33 16 28 ' 34 39

g.m. - geometric mean and standard deviation. No - number of samples analized. ^

i Tnble12'-l)l|iParison of ranges of V.I'b.Cd and Ilg concentrations ( ^кЦ in contemporary glacier ice and Snow at corresponding latitudes This work Other works Hugion Pb Cd Ilg Region _Pb_ Cd J1Ł. 78°N,Spitsbergen1" 7-48P 7d N.Spitsbergen 0.15- 2.03- 0.38- .0.04- 65-77°N,Greenland 0.008-. O.OOlr , 0.001г. 0.002- 8.98 10.S9 8.16 .0.3 0.022b 0.42bcd 1.38bdo 0.88a€ 68°N,Harrow.Alaskas 0.04- 0.02-. 0.005- i i 0.26 0.221 0.026 66 N, Svartiscn " 0.1- - 0. 13- 0.12- 2.29 1.23 0.52 63°N. Alaska 0.07 0.55- 0. 05- 0.04- 3.02 0 .23 0.35 61 N.iotunbeimon 1.62- 1.25- 0.1- 19.96 35.36 0.23 40 N.Alps O.Oo- 1.58- 0.67- 0.11- 46°N,Jungfraujoch-) 0.014 0.086* 5.21 16.98 18.4 0.23 46°N,Steingletscherr 9-1804 45 N,Mont Blanc 0.05- 0.04- 0.05- 0.6'n 9.0" 0.25" 28 N.Himalayas 0.04т 1.75- 0.22- 0.15- 0.32 7.95 2.12 0.29 O°,ltuwenzori 0.69- 8.45- 0.30- 0.08- 4.09 32.83 8.46 0.28 П°Р. Amies 0.06 6.94- 0.45- 0.25- 29.75 1.8 1.96 62"s,King George Is. 0.06- 1.27-- 0.008- 0.09- 1.1 3.69 0.33 0.35 66-80 S.Antarctica 0.001г. 0.001- 3<0cklT 7>5*n

1 1 bHerron etal., (79). »* ^ et al.. (3D. °Wyttenbach «t al., (60). "Herron et al., (25). et al., (22). PFderdingetad et al. (82). dMurozumi et al., (8). Уmean value ffro m 18 samplel * ^Fjerdingstad and Kemp (83). .Cragln and Langwąy (80). ^Boutron and Lorius (23). two samples of meltwater Z*9ias et al.t ft7J. „Zhlgalovakaya et »1., (17). from the surface of red snow *Carr and Wilkniee (30). ^ing (48) containing Chlamydomonas san- «Wei»* »t al., (6). (81). guinea algae. "surface snow. TabledEstimates ofjjlobal annual flows Into atmosphere of Ra, Pb (kCi) and of U.Pb^d.V and Hg (kt).

210 Basis of estimation 226Ra Pb U Pb Cd , V He Glacier ice concentration contemporary 1950-1978 6.6 485 12 4870 S90 180 190 Primary particulates flows3 and concentrations in . sea salt 0.003 0.003 0.08 0.09 0.0017 0.009 0.006 soil dust . 0.35 0.6 0.49 31 0.85 SO 0.035 forest fires,volcanic and cosmic dust 0.27 0.16 0.38 23 0.65 38 0.03 industrial and other human activities 0.23 0.62 1.43 358m 0.66 111 li.ois" Total с85 1.68 2.38 412 2.16 199 11.09 Other estimates ?,- exhalation of Rn 715f 600* h Greenland ice 1 ł 25-lSO dust emission 474* 8.1* river discharge 11' 110* 0.5* 280* 2.5* . volcanic emissions 0.3k 0.007 dry and wet deposition 100-2001

vMitchell (84) ^Nrlagu (1). clXtrsma (85) and Bovdltch (86)., j^Bertine and Goldberg (7). Jaworowski and Grzybovska (87) and Vinogra- pUklishanski,} et al., (20). ddov (88). ^ mBengts3on and Tyler (91). eAssuaed. the same as in soil. Contributioa, fron lead in automobile exhausts Assumed the same as in coal fly ash after nof 3tó kt y"'(9) included. United States Senate (89) and Jaworówski Contribution from 11 kt of Hg contained in and Grzybowska (87). Contribution from pro- 3300 million t of coal burned in 1976 (92) eduction of particular metals not incited. with 3.3 /ug g-т average Hg concentration Jaworowski et al. (90). f (93) included. &JNSCEAR (66). ''Weiss et al., (6). - 147 -

Table ЗД^Меап annual deposition on the Earth's surface of 226Ra, 210Pb (pCi on'2) V. U, Pb, Cd and Hg(yug on"2)

This work Other estimates Nuclide Global Global or Local oceanic V 0.035 0.37-1.05*

226Ra 0.013 -

210Pb 0.095 0.16b 0.05* 0.11C 0.071. O.OO23 U 0.002 - -

Pb 0.95 0.24-1.0d 2.2-8.0* 0.5-2.0* 0.5» Cd 0.12 - 0.0005-0.029f Hg 0 037 • 0.02е a. ooi-o.033* ' 0.002-0.004* fin Copenhagen, Denmark, (94). Global, based on rainwater analysis, (4). cInsoluble Pb in sediments of equatorial Atlantic Ocean, (3). лTin sediments of Pacific Ocean, (70). jGlobŁl, based on rainwater analysis, (5). „In Greenland (27). eIn Warsaw, Poland in 1978, M. BYSIEK un- ablished. Greenland, (34). Kt.Olympus, Washington, (34). gin Antarctica, (34). In rural areas of N.America and Europe, ЛУГ). In remote areas «f N.America and Europe, (37). table 15*atio of contemporary atmospheric flows of metals estimated from glacier ice concentration and from total primary parti culates flow (see ^ Table 13.) V 226Ra U Pb 210Pb Cd hg B.p.a 1720 960 1150 327 327 320.9 -38.9 Ratio 0.9 7.8 5 12. 288 273 17 'S? 2111е

Melting point of the metals in °C, after

bHANDBOOK OF CHEMISTRY (95). Contribution from lead smelting and automobile exhausts not included. Contribution from coal burning not included. Table 16. Enrichment factors for V,226R«,U,l»b.Cd and Hg in contemporary glacier ice .snow and air.

Spits- N.Nor- Alaska Austria Nepal Uganda Peru Antar- Global Glacier ice Snow Air tic иеап bergen way:c » : 2 Sn 1.0" 1.1* 17g If . 2.4-140^ 0.8-1.7* 226 'Ra 1.8 6.7 20 77 3 SS 5.9 U 1.2 1.2 2.8 0.6 45 1.1 SO 1.5 .be 130 180 (2470 300 290 50-250 2500* Pb 6S 160 130 g 22OO . 390-130,000J 10-810-844* е 1270 3560 1400. 17070 2670 930 11470 200 2200 320-1000 730 730? Cd 5000 i 190P-33,000,000J 58U 760* 1 212d 14000е 170 3730 4410 340 2540 170 14400 4580 1700 2470 ? 212? 14000 . 5300J1 430е 13000-120,000J . ^Ln this work the enrichment factor Is defined as a concentration ratio of an element to in ice, relative to this ratio in the Earth's crust,calculated from crustal abundances compiled by Vinogradov (88) and Taylor (96). Other estimates are based on Al or Mn. "Relative to Al.in Greenland (29). ^Relative to Al.in Antarctica (23).. TRelative to Mn,in Greenland and at Barrow,Alaska (22). ^Relative to Al.at Barrow.Alaska (24). iRelative to Al, at .the South Pole (11). {Relative to Al.over North Atlantic (15). ^Relative t" Al,Atlantic Westerlies (14). ^Relative to Al.in Greenland (79). Relative to Al.ln Mount Etna pluses (19). "Relative to Al.in Augustine Volcano,Alaska.pluses (97). Table 17.Relative contemporary flows into the global atmospheres and world industrial production of U,226Ra,V,21OPb,Pb,Cd and Hg (in per cent) , 1

Less-volatile • Volatile U - 226Ra V 210Pb Pb Cd Hg Flows from all sources 100 100 100 100 100 100 100 with primary particulates natural 7.9 8.8 49 0.22 1 1.1 0.3 0.04 anthropogenic 11.9 3.5 62 0.12 • 7.3 0.11 5.8 input from world production 0.07 ld - 7.8f 0.4» 0.88 World production 25Oc 10.5е - 82f 2.6е 5.5е fBased on glacier ice concentrations, see Table 13. ZFrom Table 13. , Excluding military operations and assuming a world uranium requirement of _» 30000 t for nuclear power in 1977, of which 5.9 t were released into the u> ..atmosphere (98). ° ~Ve assume a 10 per cent release into the atmosphere. • • The 1973 world production of V was 18950 t, of Cd 15490 t and of Hg 10540 t f(99) From 4,000,000 t of Pb produced in 1970, 380,000 t (9.5 per cent),entered the atmosphere, of which about 90 per cent from gasoline consumption (9). •15 per cent of Cd is released into the atmosphere during its production (100) We assume the same for Hg. 151 -

ACKNOWLEDGEMałTS

Our thanks are due Co the United States Environmental Pro- tection Agency which sponsored a major part of this study through the research Contract No. 5-536-1. During the years 1972-1975 Dr. D.T. Oakley, Director, Interna- tional Technology Division, US. EPA, Washington, D.C. supervised the Research Contract No. 5-536-1 as a Project Officer. Mr. R.H. Johnson Jr., Chief, Surveillance Branch of Radiation Programs, US EPA, Washington, D.C., was the Project Officer for the same Research Contract. The personal contribution of both Project Officers to this study and their assistance and advice is gratefully acknowledged. Critical review of the manuscript of the Final Report concerning this Contract by Dr. T.F. Cesell, Dr. P. Hahn, Dr. J.H. Harley, Dr. T. Hinkley, Dr. R. Leifer, Dr. L. Machta, Prof. V.W. Mayneord and Dr. D.T. Vruble is acknowledged and appreciated. The present report is based in a 1» ^ part on this unpublished Final Report. A part of the _^acier study, i.e. the Antarctic expedition, was financed from the budget of the Research Contract No. A.01.05.01. with Institute of Ecology, Polish Academy of Sciences. We acknowled- ge with thanks this financial support. The Part 2 of this report is based on the material published in Geochimica et Cosmochimica Acta kbt 2165-2199, 1981. 152

We are greatly indebted to Pergamon Press Ltd., Oxford, for the kind permission to reprint this material. IT. 0. Liest^l, Polar Institute, Oslo, Norway; Dr. p.R. Sharma, Dean of the Faculty of Nepalese and Asiatic Studies, Tribhuvan University, Kathmandu, Nepal; №. P. Dumba, National Research Council, Kampala, Uganda; Or. C. Guzman Acevedo, Institute of Nuclear Research, Lisa, Peru; Dr. C. Zuniga Roca, University of San Antonio Abad, Cusco, Peru; Dr. J. Pohl-Rflling, Lehrkanzel Tbr Physik, Salzburg University, Austria, and №. R. Cunther, Anchora- ge, Alaska, helped in organizing the glacier studies.

Dr. J.Chroboczek, №. K.Cielecki, Mr.M.Jaworowski, Mr.A.Glerych, £ng. M.Kuczyr.ski, Dr. K.Haikówski. Dr. Z.Węgrzynowicz, all of Warsaw,Poland, uig. S.Biel, Prof.K.Birkenmayer, Prof.K.Crotowski, Eag. J.Honowski, Dr. W.Maczek., all of Kraków, Poland, Dr. A.Zyzak, Katowice, Poland, Dr. J.Piaseckl, Wroclaw, Poland, №. E.Mlranowski, Zakopane, Poland, Dr. A. Halpern, Jfllich, F.R.C., №. K.B. Thapa, Kathmandu, Nepal, №. J.Arenas-Carrasco, Lima, Peru, Dr. T. Hlnkley, Denver, Colorado, №. R.H. Johnson,Jr., Dr. D.T. Oakley, Washin- gton, D.C., and №. N.SpJeldnaes, Aarhus, Denmark, took part in collecting the Ice samples.

The late Prof. L.T. Davitashvili and Dr. I.G. Tseretelli, Insti- tute of Paleontology of the Georgian Academy of Sciences, Tbilisi, USSR, Prof. K. Kowalski, Institute of Systematic and Experimental Zoology, Polish Academy of Sciences, Kraków, Metropolitan Curia of Warsaw and the Diocesan Curia of Krakow helped in collecting the human bone samples.

Wo would like to express our thanks v,o all these persons and institutions.