Plutonium, 90Sr and 241Am in human bones from southern and northeastern parts of Poland

Kamil Brudecki; Jerzy W. Mietelski; Robert Anczkiewicz; Edward B. Golec; Ewa Tomankiewicz; Konstanty Kuźma; Paweł Zagrodzki; Joanna Golec; Sebastian Nowak; Elżbieta Szczygieł; Zbigniew Dudkiewicz

doi:10.1007/s10967-013-2850-y

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Journal of Radioanalytical and Nuclear Chemistry

March 2014, Volume 299, Issue 3, pp 1379–1388

Plutonium, ⁹⁰Sr and ²⁴¹Am in human bones from southern and northeastern parts of Poland

Authors
Authors and affiliations

Kamil Brudecki
Jerzy W. MietelskiEmail author
Robert Anczkiewicz
Edward B. Golec
Ewa Tomankiewicz
Konstanty Kuźma
Paweł Zagrodzki
Joanna Golec
Sebastian Nowak
Elżbieta Szczygieł
Zbigniew Dudkiewicz

Open Access

Article

First Online:: 27 November 2013

Received:: 06 August 2013

DOI: 10.1007/s10967-013-2850-y

Cite this article as:: Brudecki, K., Mietelski, J.W., Anczkiewicz, R. et al. J Radioanal Nucl Chem (2014) 299: 1379. doi:10.1007/s10967-013-2850-y

Abstract

The paper presents the results of our study on ²³⁸Pu, ²³⁹Pu, ²⁴⁰Pu, ²⁴¹Am and ⁹⁰Sr concentration in human bones carried out on a set of 88 individual samples of central Europe origin. Bone tissue samples were retrieved under surgery while introducing hip joint implants. The conducted surgeries tend to cover either southern or northeastern parts of Poland. While for the southern samples only global fallout was expected to be seen, a mixed global and Chernobyl fallout were to be reflected in the others. Alpha spectrometry was applied to obtain activity concentration for ²³⁸Pu, ^239+240Pu, ²⁴¹Am, while liquid scintillation spectrometry for ⁹⁰Sr and mass spectrometry to receive ²⁴⁰Pu/²³⁹Pu mass ratio. Surprisingly enough, and to the contrary to our expectations we could not see any significant differences in either Pu activity or Pu mass ratio between the studied populations. In both populations Chernobyl fraction proved marginal. The results on ⁹⁰Sr and ²⁴¹Am confirm similarities between the two examined groups.

Keywords

Plutonium Americium Strontium Chernobyl Mass spectrometry Pu isotopic ratios Human bones

Introduction

Plutonium isotopes present in Polish environment are of two sources. The first is Global Fallout (GF), a radioactive contamination formed as a result of nuclear weapons tests carried out in the last century. Among the effects of such tests, a spread in atmosphere of about 4.5 t of ²³⁹Pu, 1 t of ²⁴⁰Pu, 200 kg of ²⁴²Pu, 95 kg of ²⁴¹Pu and 1 kg of ²³⁸Pu was observed [1]. As the result, for example, the average annual air concentration of ^239+240Pu in Finland in 1963 reached 20,000 nBq m⁻³ [2]. At present, Pu in air concentration falls usually below 10 nBq m⁻³ [3]. The second source of Pu in air is Chernobyl. Due to the reactor explosion on the night of 25 April 1986 (23:23 GMT, or 1:23 on 26 April in Moscow time) Pu in the amounts much smaller than in GF were released to the atmosphere. Namely, 14 kg of ²³⁹Pu, 4 kg of ²⁴⁰Pu, 48 g of ²³⁸Pu and 1.4 kg of ²⁴¹Pu [4]. Most of this mass settled near the damaged reactor, but some of them migrated over long distances. Just after the accident a radioactive cloud migrated onto the northern-east part of Poland, contaminating this region with Chernobyl ^239+240Pu, deposited in a form of small hot particles [5]. The maximum of ^239+240Pu deposition from Chernobyl within this region reached 24 Bqm⁻². Geographical distribution of plutonium contamination is shown in Fig. 1 [6, 7]. Much higher Pu cumulated deposition, even slightly exceeding 200 Bqm⁻² for ^239+240Pu, were noticed in High Tatra Mountains in the southern Poland, though it was pure global fallout [8]. The average deposition of ^239+240Pu for the latitude belt of Poland from GF is believed to be 58 Bqm⁻² [9].

Fig. 1
Approximate map of ^239+240Pu deposition from Chernobyl fallout in Poland left: first approximation [6] et al. right result of more detailed study [7]

The main exposure pathway for plutonium is inhalation. Plutonium deposition in the respiratory system mainly depends on aerosols diameter, individual’s age, sex, and lifestyle, reaching from 11 to 99 % of the inhaled plutonium from the air [10, 11]. Subsequently, a part of plutonium is transferred from the respiratory to gastro–intestine system, where almost all Pu is excreted (f₁ for plutonium is only 0.0005) and the rest is transferred to blood. Plutonium from blood is accumulated mainly in liver and bones, where it remains for many years [12].

The study has been driven by our search to estimate and compare plutonium internal contamination in humans living in southern and north-eastern parts of Poland. For the southern Poland we expected to find only global fallout tracers, while for northeastern Poland a mixed global and Chernobyl fallout was likely to be detected. Besides plutonium isotopes, we estimated also internal contamination with ²⁴¹Am and ⁹⁰Sr.

Material and method

In our study bone tissue samples obtained during routine surgeries, namely implanting hip joint replacements, were studied. Patients of general population, were in no special way exposed to radioactive contamination. Surgeries were conducted at the 5th Military Hospital in Kraków (in Southern Poland) and at the General Hospital of Bielsk Podlaski (Northeastern Poland). As the patients originated broadly from the vicinity of the hospitals, Pu only from GF was expected for Kraków, while mixed GF and Chernobyl fallout was expected for Bielsk Podlaski. Both hospital studies were granted approval by the appropriate council for ethics in medical research.

To extract plutonium isotopes we applied the method described in details elsewhere [13, 14, 15]. The samples were ashed at 600 °C for 2 days. Tracers such as ²⁴²Pu, ²⁴³Am and ⁸⁵Sr were added. The ashes were gently soaked with 6 M HCl, then heated, evaporated to nearly dryness. Hydrogen peroxide was added to each sample to destroy carbon traces. Next, the samples were dissolved in 1 M HNO₃. For each sample precipitation of calcium oxalates at pH = 3 was completed to obtain the transuranic (Pu + Am) fraction. Calcium oxalates were dissolved with 1 M HNO₃. The oxidation state of Pu was adjusted to +4 by means of hydrazine and NaNO₂ [16], and after conversion into 8 M HNO₃ the fraction was passed through Dowex-1 × 8 column. Th was washed out with 12 M HCl. Pu retained on the column was eluted with 50 mL of 0.1 M HF–0.1 M HCl. Alpha spectrometric Pu sources were prepared directly in the solutions by means of NdF₃ method [17]. Pu sources were measured with Silena AlphaQuattro spectrometer equipped with four Canberra PIPS detectors. A typical measurement time was about 600 000 s. We also took the opportunity to extract and measure ²⁴¹Am and ⁹⁰Sr following procedures described previously [13].

Later, all alpha spectrometric plutonium sources were dissolved and prepared for measurement on the mass spectrometry. The NdF₃ source with a plastic filter was dissolved in a solution of concentrated HCl and HNO₃ with a dish of boric acid added. The solution was evaporated several times to reach near dryness. To make sure that the source was dissolved, we used also HClO₄ [18]. Then, we purified the samples from uranium and thorium tracers. The Pu oxidation state was again adjusted to +4 (as described above) and converted into 4 M HNO₃. The solutions were passed through Triskem International TEVA Resin. This was performed to remove traces of uranium, which passes the column without retention. Thorium, which together with Pu remains in the column, was eluted with the concentrated HCl and then Pu was eluted with 15 mL of 0.1 M HF–0.1 M HCl. The last step was to converse samples into 300 μL of 2 % HNO₃—0.1 % HF and to measure with mass spectrometer MC ICPMS Neptune by Thermoelectron Finningan.

Along with the samples two reference material (RM) were analysed. The first one, NIST 4356 [19] was used to check alpha spectrometry results. Ashed animal bones provided the matrix for this reference material. In the course of the study, we measured RM four times. The comparison between the received and the reference values are presented in Table 1. The second RM was NIST 947 [20] and we used it to check mass spectrometer results. Over the 4 days when mass spectrometer was used the second RM material was measured 8 times. The comparison between the received and reference values are presented in Table 2.

Table 1

Comparison between the received and reference values for the standard reference material NIST 4356 [19]

Isotopes	Sample number	Received value	Certified value	Tolerance limit
²³⁸Pu (mBq g⁻¹)	1	0.82 ± 0.12	0.86 ± 0.01	0.73–1.00
	2	0.84 ± 0.12
	3	0.88 ± 0.07
	4	0.90 ± 0.10
^239+240Pu (mBq g⁻¹)	1	1.10 ± 0.13	1.26 ± 0.03	1.09–1.65
	2	1.10 ± 0.12
	3	1.24 ± 0.09
	4	1.14 ± 0.12
²⁴¹Am (mBq g⁻¹)	1	12.2 ± 0.7	9.98	8.76–13.6
	2	10.6 ± 1.1
	3	10.5 ± 1.4
	4	10.2 ± 0.9
⁹⁰Sr (mBq g⁻¹)	1	41 ± 9	42.6 ± 0.9	36.4–49.5
	2	–
	3	37 ± 3
	4	40 ± 2

Table 2

Comparison between the received and reference values for the standard reference material NIST 947 [20]

Day	Received value	Certified value
04.08.2011	0.241 ± 0.004	0.241
04.08.2011	0.240 ± 0.005
06.09.2011	0.249 ± 0.001
07.09.2011	0.251 ± 0.001
07.09.2011	0.250 ± 0.001
08.09.2011	0.246 ± 0.002
	0.253 ± 0.001
	0.244 ± 0.001

The difference between the characteristic plutonium mass ratios (²⁴⁰Pu to ²³⁹Pu) in the global and Chernobyl fallout allowed us to distinguish the two. By solving the equation system given below

$$ \frac{{_{G}^{240} N}}{{_{G}^{239} N}} = \alpha $$

(1)

$$ \frac{{_{Ch}^{240} N}}{{_{Ch}^{239} N}} = \beta $$

(2)

where

²⁴⁰N: stands for the observed number of counts ²⁴⁰Pu
²³⁹N: stands for the observed number of counts ²³⁹Pu
$ _{G}^{240} N $: stands for the observed number of counts ²⁴⁰Pu, come from global fallout
$ _{G}^{239} N $: stands for the observed number of counts ²³⁹Pu, come from global fallout
$ _{Ch}^{240} N $: stands for the observed number of counts ²⁴⁰Pu, come from Chernobyl fallout
$ _{Ch}^{239} N $: stands for the observed number of counts ²³⁹Pu, come from Chernobyl fallout
α: is the model ratio, characteristic for the global fallout (assumed 0.18 [21])
β: is the model ratio, characteristic for Chernobyl fallout (assumed 0.40 [21])

we can prove that the percent of Chernobyl fraction F can be expressed as

$$ F = \left( {\frac{{^{240} N}}{{^{239} N}} - \alpha } \right)*\left( {\beta - \alpha } \right)^{ - 1}\,*\,100\,\% $$

(3)

Results

In total we analysed bone samples of 88 patients. The group of Southern Poland inhabitants contained 60 people, 20 men, 37 women, and 3 person whose gender had not been specified in the questionnaire. The youngest patient was 41 years old, while the oldest 88. For Northeastern Poland bones 28 people were involved, 11 of them were men and 17 women. Their age ranged between 32 and 90. The obtained concentration ranges for the studied isotopes in booth populations are presented in Table 3. In all the samples ²³⁸Pu activity was found to be below the minimum detection activity concentration, that is on the level of a single mBqkg⁻¹. The completed results for booth group are presented in Table 4. It is noticeable that the data presented in Tables 3 and 4 do not show any significant differences for the studied isotopes concentration in bones between the members of both groups.

Table 3

Obtained activity ranged of studied isotopes in both studied populations

Population	Isotopes	Min	Max	Average	Median
Kraków (Southern Poland)	^239+240Pu (mBq kg⁻¹)	<2	42 ± 12	15 ± 9	14 ± 3
	²⁴¹Am (mBq kg⁻¹)	<2	35 ± 12	12 ± 7	11 ± 2
	⁹⁰Sr (Bq kg⁻¹)	1.6 ± 0.3	18 ± 1	6.5 ± 4.1	5.2 ± 0.2
Bielsk Podlaski (North-eastern Poland)	^239+240Pu (mBq kg⁻¹)	<2	50 ± 4	16 ± 10	14 ± 3
	²⁴¹Am (mBq kg⁻¹)	<2	20 ± 4	7 ± 5	6 ± 3
	⁹⁰Sr (Bq kg⁻¹)	1.8 ± 0.4	19 ± 2	6.4 ± 3.9	5.2 ± 3.8

Table 4

Obtained activity for each individual of the studied isotopes in both populations under study

Code of individual KR—Kraków (Southern Poland) BP—Bielsk Podlaski (Northereastern Poland)	Age	Sex	²³⁸Pu (mBq kg⁻¹)	^239+240Pu (mBq kg⁻¹)	²⁴¹Am (mBq kg⁻¹)	⁹⁰Sr (Bq kg⁻¹)	Mass ratio ²⁴⁰Pu/²³⁹Pu	F (%)
KR1	56	M	<2	6.1 ± 1.1	7.1 ± 2.1	9.3 ± 0.9	0.0839 ± 0.0006	–
KR2	76	M	<3	20.1 ± 2.3	11.1 ± 2.6	12.4 ± 1.5	0.1912 ± 0.0011	5.1 ± 0.5
KR3	59	M	<3	15.3 ± 2.7	4.7 ± 1.6	12.9 ± 1.3	–	–
KR4	76	F	<4	15.5 ± 2.4	7.3 ± 3.5	4.2 ± 0.4	0.1161 ± 0.0008	–
KR5	78	F	<4	7.5 ± 1.6	7.2 ± 3.6	6.2 ± 0.7	0.0983 ± 0.0012	–
KR6	59	M	<3	5.7 ± 1.1	5.5 ± 2.3	3.6 ± 0.5	0.1818 ± 0.0020	0.8 ± 0.9
KR7	–	–	<5	16.1 ± 2.7	2.8 ± 2.4	3.3 ± 0.4	0.1661 ± 0.0014	–
KR8	–	–	<3	22.8 ± 6.2	7.1 ± 4.9	1.9 ± 0.2	0.1925 ± 0.0013	5.7 ± 0.6
KR9	–	–	<2	17.2 ± 2.0	7.3 ± 1.4	13.4 ± 1.9	0.1997 ± 0.0017	9.0 ± 0.8
KR10	64	F	<3	11.9 ± 3.9	23.0 ± 12.0	10.9 ± 0.9	0.1921 ± 0.0017	5.5 ± 0.8
KR11	73	F	<5	16.4 ± 2.7	8.9 ± 3.4	4.7 ± 0.6	0.1902 ± 0.0011	4.6 ± 0.5
KR12	88	F	<10	17.3 ± 3.2	23.0 ± 7.7	1.6 ± 0.3	0.1863 ± 0.0015	2.9 ± 0.7
KR13	62	F	<4	9.5 ± 1.9	3.6 ± 3.1	9.4 ± 1.3	0.1878 ± 0.0019	3.5 ± 0.9
KR14	84	M	<5	14.0 ± 2.6	15.0 ± 12.0	7.7 ± 1.1	0.1842 ± 0.0021	1.9 ± 1.0
KR15	64	M	<2	27.1 ± 5.4	11.4 ± 4.8	8.9 ± 0.7	0.1869 ± 0.0006	3.1 ± 0.3
KR16	63	M	<2	15.7 ± 4.9	5.8 ± 2.1	13.5 ± 1.2	0.1938 ± 0.0010	6.3 ± 0.5
KR17	60	M	<3	10.8 ± 5.6	16.0 ± 4.7	4.9 ± 1.3	0.1964 ± 0.0012	7.5 ± 0.5
KR18	77	F	<6	16.0 ± 2.9	19.8 ± 4.7	7.4 ± 0.9	0.1899 ± 0.0018	4.5 ± 0.8
KR19	76	F	<5	13.7 ± 2.4	8.6 ± 3.9	3.6 ± 0.4	0.1844 ± 0.0010	2.0 ± 0.5
KR 20	75	F	<4	14.0 ± 2.2	7.6 ± 3.9	15.0 ± 2.0	0.1912 ± 0.0017	5.1 ± 0.8
KR 21	73	F	<3	9.3 ± 1.7	2.7 ± 4.7	6.0 ± 0.6	0.1929 ± 0.0015	5.9 ± 0.7
KR 22	71	F	<7	10.4 ± 2.3	12.6 ± 8.8	2.0 ± 0.6	0.1839 ± 0.0030	1.8 ± 1.4
KR 23	78	M	<3	25.0 ± 3.2	20.4 ± 6.7	5.4 ± 0.6	0.1961 ± 0.0011	7.3 ± 0.5
KR 24	42	M	<1	<2	<2	11.9 ± 2.8	0.1291 ± 0.0017	–
KR 25	66	M	<1	24.9 ± 1.9	8.3 ± 2.2	2.7 ± 0.3	0.1899 ± 0.0018	4.5 ± 0.8
KR 26	53	M	<2	12.4 ± 1.7	7.0 ± 2.1	9.9 ± 1.2	0.1876 ± 0.0017	3.5 ± 0.8
KR 27	70	F	<2	15.1 ± 2.4	10.0 ± 3.3	9.7 ± 0.7	0.1923 ± 0.0017	5.6 ± 0.8
KR 28	73	F	<3	12.6 ± 2.2	10.4 ± 3.1	11.6 ± 0.5	0.1910 ± 0.0015	5.0 ± 0.7
KR 29	63	M	<1	16.4 ± 1.9	9.4 ± 1.7	1.9 ± 0.1	0.2022 ± 0.0017	10.1 ± 0.8
KR 30	78	M	<4	15.0 ± 3.0	18.2 ± 5.2	7.5 ± 0.3	0.1916 ± 0.0018	5.3 ± 0.8
KR 31	82	F	<5	17.7 ± 4.4	11.3 ± 6.3	4.2 ± 0.2	0.1974 ± 0.0017	7.9 ± 0.8
KR 32	83	F	<3	9.4 ± 2.0	3.7 ± 2.5	2.05 ± 0.1	0.1903 ± 0.0017	4.7 ± 0.8
KR 33	78	F	<2	4.4 ± 1.4	<2	13.0 ± 4.3	0.2305 ± 0.0037	23.0 ± 1.7
KR 34	67	F	<1	11.1 ± 1.6	6.7 ± 1.5	7.8 ± 0.5	0.1976 ± 0.0015	8.0 ± 0.7
KR 35	78	F	<23	39.6 ± 12.3	<2	6.1 ± 0.4	0.1819 ± 0.0027	0.9 ± 1.2
KR 36	65	F	<2	21.4 ± 1.8	12.6 ± 2.4	9.2 ± 3.0	0.1904 ± 0.0019	4.7 ± 0.9
KR 37	76	F	<3	7.7 ± 1.6	<3	4.6 ± 0.4	0.1772 ± 0.0022	<1.0
KR 38	56	F	<3	10.6 ± 1.4	9.9 ± 3.4	3.6 ± 0.6	0.1760 ± 0.0040	<1.8
KR 39	66	M	<2	17.7 ± 2.4	6.1 ± 1.6	3.4 ± 0.4	0.1919 ± 0.0012	5.4 ± 0.5
KR 40	60	F	<10	7.0 ± 3.2	–	3.1 ± 0.3	0.1735 ± 0.0038	<1.7
KR 41	79	F	<6	36.6 ± 5.1	27.7 ± 11.7	3.7 ± 0.4	0.1999 ± 0.0019	9.0 ± 0.9
KR 42	77	M	<2	11.1 ± 1.6	10.6 ± 2.5	2.1 ± 0.1	0.1957 ± 0.0021	7.1 ± 1.0
KR 43	83	M	<5	26.0 ± 3.8	7.1 ± 5.1	3.0 ± 0.1	0.1965 ± 0.0016	7.5 ± 0.7
KR 44	73	F	<3	11.7 ± 2.1	5.1 ± 2.3	5.2 ± 0.2	0.1940 ± 0.0038	6.4 ± 1.7
KR 45	88	F	<4	10.6 ± 3.0	11.9 ± 4.6	17.8 ± 0.9	0.1948 ± 0.0031	6.7 ± 1.4
KR 46	87	F	<18	42.4 ± 11.9	17.9 ± 7.9	2.3 ± 0.5	0.1923 ± 0.0021	5.6 ± 1.0
KR 47	80	F	<8	17.8 ± 4.8	5.1 ± 4.6	3.1 ± 0.7	0.1988 ± 0.0079	8.5 ± 3.6
KR 48	56	F	<4	15.9 ± 3.2	15.0 ± 3.4	6.6 ± 0.7	0.1905 ± 0.0019	4.8 ± 0.9
KR 49	46	F	<5	2.3 ± 1.9	<5	2.7 ± 0.4	0.1541 ± 0.0077	–
KR 50	77	F	<12	27.4 ± 7.5	12.4 ± 4.2	2.2 ± 0.2	0.1689 ± 0.0027	–
KR 51	79	F	<2	11.2 ± 2.0	6.5 ± 2.5	2.9 ± 0.4	0.1747 ± 0.0020	<0.9
KR 52	84	F	<8	26.6 ± 6.9	10.1 ± 5.7	1.6 ± 0.3	0.1915 ± 0.0016	5.2 ± 0.7
KR 53	56	F	<5	20.9 ± 3.0	9.4 ± 4.1	2.3 ± 0.3	0.1978 ± 0.0013	8.1 ± 0.6
KR 54	81	F	<8	5.5 ± 2.8	<5	–	0.1784 ± 0.0014	<0.6
KR 55	69	M	<13	35.4 ± 6.8	<2	6.6 ± 0.8	0.1852 ± 0.0018	2.4 ± 0.8
KR 56	73	F	<8	9.6 ± 2.9	9.4 ± 5.4	4.1 ± 0.4	0.1888 ± 0.0016	4.0 ± 0.7
KR 57	49	F	<2	4.9 ± 1.0	4.3 ± 2.7	6.0 ± 1.8	0.1874 ± 0.0016	3.4 ± 0.7
KR 58	48	M	<4	3.2 ± 1.6	<5	–	0.1866 ± 0.0037	3.0 ± 1.7
KR 59	45	M	<5	2.9 ± 1.2	<5	9.9 ± 1.5	0.1473 ± 0.0036	–
KR 60	41	F	<6	<2	4.0 ± 3.4	3.3 ± 0.4	0.1582 ± 0.0035	–
BP 1	53	M	–	–	5.4 ± 2.6	1.8 ± 0.4	–	–
BP 2	88	F	–	–	9.4 ± 4.1	–	–	–
BP 3	74	F	<3	21.4 ± 3.2	8.8 ± 2.4	–	0.1933 ± 0.0013	6.0 ± 0.6
BP 4	80	F	<2	13.2 ± 2.1	5.1 ± 1.9	7.5 ± 2.7	0.1954 ± 0.0012	7.0 ± 0.5
BP 5	70	F	<4	21.1 ± 3.9	3.1 ± 2.8	2.7 ± 0.5	0.1925 ± 0.0020	5.7 ± 0.9
BP 6	56	M	<3	8.8 ± 2.0	4.0 ± 1.5	3.7 ± 0.8	0.1772 ± 0.0019	<0.9
BP 7	77	F	<3	14.1 ± 2.6	13.4 ± 2.6	3.4 ± 0.8	0.1929 ± 0.0013	5.9 ± 0.6
BP 8	71	F	<2	14.7 ± 2.3	5.0 ± 2.1	9.9 ± 4.3	0.1942 ± 0.0009	6.5 ± 0.4
BP 9	68	M	<4	17.3 ± 3.3	13.9 ± 2.7	4.8 ± 2.4	0.1963 ± 0.0016	7.4 ± 0.7
BP 10	66	M	<3	21.7 ± 3.0	8.9 ± 3.4	–	0.1954 ± 0.0014	7.0 ± 0.6
BP 11	59	F	<2	6.6 ± 1.7	2.1 ± 1.6	3.0 ± 1.7	0.1802 ± 0.0015	0.1 ± 0.7
BP 12	55	F	<3	7.2 ± 1.7	4.6 ± 2.6	4.9 ± 2.6	0.1764 ± 0.0012	<0.5
BP 13	56	M	<3	12.7 ± 2.4	4.6 ± 1.9	5.3 ± 2.8	0.1755 ± 0.0011	<0.5
BP 14	90	M	<2	22.6 ± 2.8	16.3 ± 6.1	9.0 ± 4.6	0.1830 ± 0.0012	1.4 ± 0.5
BP 15	76	F	<5	10.2 ± 2.7	<2	3.8 ± 2.0	0.1787 ± 0.0013	<0.6
BP 16	57	M	<2	15.1 ± 2.0	5.1 ± 1.8	5.1 ± 2.7	0.1140 ± 0.0006	–
BP 17	81	F	<4	22.9 ± 3.6	6.4 ± 3.7	8.1 ± 4.2	0.1837 ± 0.0011	1.7 ± 0.5
BP 18	81	F	<3	15.0 ± 2.9	6.1 ± 3.1	9.3 ± 4.9	0.1840 ± 0.0013	1.8 ± 0.6
BP 19	70	F	<2	12.3 ± 3.7	3.7 ± 2.5	4.5 ± 3.2	0.1903 ± 0.0014	4.7 ± 0.6
BP 20	64	M	<2	10.3 ± 1.7	11.2 ± 5.6	5.5 ± 4.0	0.1856 ± 0.0011	2.5 ± 0.5
BP 21	77	F	<2	26.6 ± 3.2	5.1 ± 3.7	2.4 ± 1.9	0.1892 ± 0.0006	4.2 ± 0.3
BP 22	55	F	<4	10.8 ± 2.5	<4	5.6 ± 4.0	0.1796 ± 0.0013	<0.6
BP 23	70	F	<2	12.3 ± 2.2	<4	5.2 ± 3.8	0.1856 ± 0.0018	2.5 ± 0.8
BP 24	32	M	<8	<2	<4	10.9 ± 16.3	0.1139 ± 0.0064	–
BP 25	68	F	<3	50.1 ± 3.9	8.6 ± 3.5	13.0 ± 1.4	0.0459 ± 0.0004	–
BP 26	64	M	<9	<2	5.8 ± 4.2	6.8 ± 1.0	0.1740 ± 0.0027	<1.2
BP 27	59	F	<6	7.8 ± 2.9	4.2 ± 4.1	19.3 ± 2.3	0.1801 ± 0.0104	<4.7
BP 28	85	F	<5	26.5 ± 4.7	20.5 ± 1.9	4.1 ± 0.4	0.1864 ± 0.0010	2.9 ± 0.5

Next, we tried to find correlation between the studied isotopes concentration and the patients age. The obtained correlation results are presented in Figs. 2, 3 and 4. For Pu and Am one can see an increasing trend, the older the person was, the higher activity Pu and Am concentration were found. This was observed already for a smaller group of 28 analysed human bone samples [13]. On the contrary, for Sr such a trend could not be observed. As the main pathway of Pu is inhalation, the increasing trend may suggest that the observed Pu was systematically accumulated over the patient‘s life. On the other hand, in Fig. 5 we can see a difference between a child patient at 1970 and the rest of the investigated people. It is generally known that after 1963 the USA, Soviet Union and UK stopped their atmospheric weapon tests, thus Pu concentration in air kept falling down smoothly over the next years by orders of magnitude. This difference can be explained by much less lungs air exchange efficiency in children. Moreover, the increase in the activity concentration with age can be also interpreted in terms of losing bones mass while aging—the bone mass is in the denominator and keeps diminishing. Therefore, the increasing trend is of solely spurious nature as the observed concentration had been accumulated mainly in the fifties and sixties of the last century, when the number of atmospheric tests reached its maximum.

Fig. 2
Patients’ age—^239+240Pu concentration correlation

Fig. 3
Patients’ age and ²⁴¹Am concentration correlation

Fig. 4
Patients’ age and ⁹⁰Sr concentration correlation

Fig. 5
Correlation between the patients’s age at seventies and ^239+240Pu concentration (patients younger than 10 years old in 1970 were excluded from the fit of the *trend line*)

Correlation between Pu and Am concentration was also analysed (Fig. 6). The coefficient of trend line equal to 0.26 is very close to the model ratio between activity of ²⁴¹Am and ^239+240Pu for the global fallout, i.e. 0.33. This may suggest the global fallout to be the main source of contamination in examined humans.

Fig. 6
²⁴¹Am and ^239+240Pu concentration correlation

The mass spectrometry range obtained for Pu ratios in both populations are presented in Table 5. Table 6 shows the range of Chernobyl fraction. The mass ratios and the Chernobyl fraction for each sample are presented in Table 4. Pu mass ratio for each sample are also presented in Figs. 7 and 8. As we can see in both populations the majority of the samples display ratios characteristic for the global fallout. In several samples we also found very unusual relatively low ratios that may suggest nuclear weapon construction materials to have participated into it. We did not manage to formulate a good explanation to it. Chernobyl fraction in both population tends to be marginal. More than a half (56 %) of all the results showed Chernobyl fraction to be below 5 %. Only in two samples Chernobyl fraction above 10 % was detected.

Table 5

The range of Pu mass (²⁴⁰Pu/²³⁹Pu) ratios for both populations

Population	Min	Max	Average	Median
Kraków (Southern Poland)	0.1735 ± 0.0038	0.2305 ± 0.0035	0.1907 ± 0.0175	0.1911 ± 0.0015
Bielsk Podlaski (Northeastern Poland)	0.1740 ± 0.0027	0.1963 ± 0.0016	0.1856 ± 0.0143	0.1856 ± 0.0018

Table 6

Calculated percentage of Chernobyl Pu fraction for both populations

Population	Min	Max	Average	Median
Kraków (Southern Poland)	<0.9	23 ± 1.7	5.0 ± 3.7	5.0 ± 0.7
Bielsk Podlaski (Northereastern Poland)	<0.6	7.4 ± 0.7	2.9 ± 2.8	2.5 ± 0.8

Fig. 7
Pu mass ratio in Krakow (Southern Poland)

Fig. 8
Pu mass ratio in Bielsk Podlaski (Northeastern Poland)

The current results can be compared to the existing data on Pu content in human bones. Table 7 presents such a comparison for activity concentration range of bone-seeking isotopes obtained currently with a set of examples to the data already existing [13, 22, 23, 24, 25, 26, 27, 28]. Apart from cases where bones of accident victims were examined, the obtained results are very similar to the ones reported previously for a worldwide population.

Table 7

Comparison of the results obtained currently (the last row) for artificial bone seeking radioisotopes with similar studies conducted all over the world

Site	^239+240Pu (mBq kg⁻¹)	²⁴¹Am (mBq kg⁻¹)	⁹⁰Sr (Bq kg⁻¹)	Remarks	Reference
Marshall Isl.	(8 ± 2) ÷ (46 ± 4)	(8 ± 4) ÷ (19 ± 8)	–		[22]
Nepal	(10.0 ± 3.3) ÷ (73.3 ± 13.3)	–	–		[23]
Australia	<8.3 ÷ (23.3 ± 11.7)	–	–		[23]
Germany	–	–	(7.3 ± 2.2) ÷ (13.7 ± 4.1)	Tooth	[24]
Northwest Ukraine	–	–	(19.7 ± 5.9) ÷ (30.4 ± 9.1)	Tooth	[24]
Belgium	2.9 ÷ 20.2	–	–	Accident	[25]
U.S.A.	25 ÷ 36,036	14 ÷ 2,365,000	–	LANL (incl. accident)	[26]
Southern Poland	(5.7 ± 1.1) ÷ (27.1 ± 5.4)	(2.8 ± 2.4) ÷ (23.4 ± 12.2)	(1.6 ± 0.3) ÷ (15 ± 2)		[13]
Poland	<2 ÷ (50 ± 4)	<2 ÷ (35 ± 12)	(1.6 ± 0.3) ÷ (19 ± 2)		This work

A more complex statistical studies, such as correspondence analysis, were preformed to find any relationship between the observed activity concentration and certain properties, or individual habits reported in the questionnaire. The results were already published elsewhere, in the proceedings of a local conference [29], nevertheless it worth quoting that among different parameters used in correspondence analysis, the strongest relationship between the high levels of activity concentration of ²⁴¹Am and ⁹⁰Sr in bones, and intense cigarette smoking and declared high level mushrooms consumption was found. It is also worth highlighting that higher levels of activity concentration of ²⁴¹Am and ⁹⁰Sr in bones correlated with patients’ age range 61–73 year, which is in accordance with the above hypothesis that these patients incorporated the majority of radioactive contamination during their childhood, i.e. in fifties and sixties of the twentieth century.

Conclusions

We could not see any differences between the studied populations. In both groups the level of internal contamination is comparable, and Chernobyl fraction (if any) seems to be marginal. It is, however, highly probable that the observed concentration for Pu and Am had been accumulated in the fifties and sixties of the last century when the number of nuclear atmospheric explosions had maximum. In both populations the Chernobyl fraction is usually well below 10 %.

The correlation between Pu and Am concentration in human bones, and the age suggested in our previous study [13] carried out on much smaller number of patients has been confirmed; similarly lack of such correlation for ⁹⁰Sr was reported.

Since the examined people were general public and no local, Polish sources for Pu release into environment are available, our results can be treated as background values for Central European population.

Acknowledgments

This study was supported by Polish Ministry of Sciences, research grants NN404318640 and NN404 102837.

References

1.
Taylor RN, Warneke T, Milton JA, Croudace IW, Warwick PE, Nesbitt RW (2001) Isotope ratio analysis at femtogram to nanogram levels by multicollector ICPMS. J Anal At Spectrom 16:279–284CrossRefGoogle Scholar
2.
Salminen S, Paatero J (2009) Concentrations of ²³⁸Pu, ^239+240Pu and ²⁴¹Pu in the surface air in Finish Lapand in 1963. Boreal Environ Res 14:1797–2469Google Scholar
3.
Kierepko R (2010) Activity concentration of plutonium in atmospheric precipitation. PhD Thesis. Institute of Nuclear Physics, Kraków, Poland (in Polish)
4.
IAEA (1986) Safety series No.75, Vienna 1986
5.
Mietelski JW, Wąs B (1995) Plutonium from Chernobyl in Poland. Appl Radiat Isot 46(11):1203–1211CrossRefGoogle Scholar
6.
Mietelski JW, Baeza AS, Guillen J, Buzinny M, Tsigankov N, Gaca P, Jasińska M, Tomankiewicz E (2002) Plutonium and other alpha emitters in mushrooms from Poland, Spain and Ukraine. Appl Radiat Isot 56(5):717–729CrossRefGoogle Scholar
7.
Brudecki K, Suwaj J, Mietelski JW (2009) Plutonium and ¹³⁷Cs in forest litter: the approximate map of plutonium from Chernobyl deposition in Northeastern and Eastern Poland. Nukleonika 54(3):199–209Google Scholar
8.
Mietelski JW, Kubica B, Gaca P, Tomankiewicz E, Błażej S, Tuteja-Krysa M, Stobiński M (2008) ²³⁸Pu, ^239+240Pu, ²⁴¹Am, ⁹⁰Sr and ¹³⁷Cs in mountain soil samples from the Tatra National Park (Poland). J Radioanal Nucl Chem 275(3):523–533CrossRefGoogle Scholar
9.
UNSCEAR (2000) Sources and effects of ionizing radiation. United Nations Scientific Committee on the Effects of Atomic Radiation Report to the General Assembly, with scientific annexes. UN Press, New York
10.
ICPR (1994) Human respiratory tract model for radiological protection. ICRP Publication 66. The International Commission on Radiological Protection, London
11.
ICPR (2002) Guide for the practical application of the ICRP human respiratory tract model. ICRP Supporting Guidance 3. The International Commission on Radiological Protection, London
12.
ICRP (1986) The metabolism of plutonium and related elements. ICRP Publication 48. The International Commission on Radiological Protection, London
13.
Mietelski JE, Golec E, Tomankiewicz E, Golec J, Nowak S, Szczygiel E, Brudecki K (2011) Human bones obtained from routine joint replacement surgery as a tool for studies of plutonium, americium and ⁹⁰Sr body-burden in general public. J Environ Radioact 102(6):559–565CrossRefGoogle Scholar
14.
Mietelski JW, Kitowski I, Gaca P, Grabowska S, Tomankiewicz E, Szwałko E (2006) Gamma Emitters, ⁹⁰Sr, ^238,239+240Pu and ²⁴¹Am in Bones and Liver of Eagles from Poland. J Radioanal Nucl Chem 270(1):131–135CrossRefGoogle Scholar
15.
Mietelski JW, Gaca P, Jasińska M (2000) Plutonium and other alpha-emitters in bones of wild, herbivorous animals from north-eastern Poland. Appl Radiat Isot 53(1–2):251–257CrossRefGoogle Scholar
16.
LaRosa JJ, Cooper E, Ghods-Esphahani A, Jansta V, Makarewicz M, Shawky S, Vajda N (1992) Radiochemical methods used by the IAEA’s Laboratories at Seibersdorf for the determination of ⁹⁰Sr, ¹⁴⁴Ce and Pu radionuclides in the environment samples collected for the International Chernobyl Project. J. Environ Radioact 17:183–209CrossRefGoogle Scholar
17.
Sill CW (1987) Precipitation of actinides as fluorides or hydroxides for high resolution alpha spectrometry. Nucl Chem Waste Manag 7:201–215CrossRefGoogle Scholar
18.
Moreno J, LaRosa JJ, Danesi PR, Burns K, DeRegge P, Vajda N, Sinojmeri M (1998) Determination of ²⁴¹Pu by liquid scintillation counting in the combined procedure for Pu radionuclides, ²⁴¹Am and ⁹⁰Sr Analyses in Environmental Samples. Radioact Radiochem 9:35Google Scholar
19.
National Institute of Standards and Technology (2000) Certificate standard reference material 4356
20.
National Bureau of Standards (1982) Certificate standard reference material 947
21.
Nassef MH, El-Mongy SA, Diab AM, EL-Tahawy MS (2008) Determination of plutonium isotopes in standard IAEA reference materials by destructive analytical techique. J Nucl Radiat Phys 3(1):21–30Google Scholar
22.
Franke B, Schupfner R, Schuttelkopf H, Spennemann DHR (1995) Transuranics in bone of deceased former residents of Rongelap Atoll, Marshall Islands. Appl Radiat Isot 64(11):1253–1258CrossRefGoogle Scholar
23.
Fisenne IM, Perry PM, Chu NY (1983) Measured ^234,238U and fallout ^239,240Pu in human bone ash from Nepal and Australia: Skeletal Alpha Dose. Health Phys 44:457–467CrossRefGoogle Scholar
24.
Schmitz M, Schitz K, Aumann DC (2003) A simple radiochemical method for determining bone-seeking radionuclides in bone and teeth: ⁹⁰Sr in teeth of children from Ukraine and Germany. J Radioanal Nucl Chem 260(3):451–457CrossRefGoogle Scholar
25.
Culot JP, Blommaert W, Hurtgen C, Minon JP (1997) Radioactivity of teeth in the follow-up old contamination cases. J Radioanal Nucl Chem 226(1–2):139–143CrossRefGoogle Scholar
26.
Kathren RL, McInroy JF, Reichert MM, Swint MJ (1988) Partitioning of ²³⁸Pu, ²³⁹Pu and ²⁴¹Am in skeleton and liver of U.S. transuranium registry autopsy cases. Health Phys 54(2):181–188CrossRefGoogle Scholar
27.
Singh NP (1990) Thorium, uranium and plutonium in human tissues of world-wide general population. J Radioanal Nucl Chem 138(2):347–364CrossRefGoogle Scholar
28.
Taylor DM (1995) Environmental plutonium in humans. Appl Radiat Isot 46(11):1245–1252CrossRefGoogle Scholar
29.
Brudecki K, Zagrodzki P, Mietelski JW, Tomankiewicz E, Golec E, Golec J, Nowak S, Szczygieł E, Marchewka A, Dutkiewicz Z (2013) Application of correspondence analysis for studies of relationship between selected radionuclides activity concentration in human bones and life style. In: Zadora G, Zuba D, Parczewski A (ed) Proceedings of the conference chemometrics—methods and applications. Institute of Forensic Research Publishers, Krakow, in print (in Polish)

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Authors and Affiliations

Kamil Brudecki
- 1
Jerzy W. Mietelski
- 1
Email author
Robert Anczkiewicz
- 2
Edward B. Golec
- 3
- 4
- 5
Ewa Tomankiewicz
- 1
Konstanty Kuźma
- 6
Paweł Zagrodzki
- 1
- 7
Joanna Golec
- 4
- 5
Sebastian Nowak
- 3
Elżbieta Szczygieł
- 4
Zbigniew Dudkiewicz
- 8

1.Institute of Nuclear PhysicsPolish Academy of SciencesKrakówPoland
2.Institute of Geological SciencesPolish Academy of SciencesKrakówPoland
3.5th Military Clinical Hospital with PolyclinicKrakówPoland
4.Faculty of Motor of the Bronislaw Czech University School of Physical EducationKrakówPoland
5.Faculty of Physical TherapyAdministration CollegeBielsko-BiałaPoland
6.General Hospital in Bielsk PodlaskiBielsk PodlaskiPoland
7.Chair of BromathologyJagiellonian University Medical CollegeKrakówPoland
8.Hand Surgery Clinic, Chair of Traumatology and OrthopaedicsMedical University ŁódźLodzPoland