CO MMUNICAT1ONS
Occurrence of Beryllium as a Trace Element in Environmental Materials William R. Meehan and Lloyd E. Smythe Australian Atomic Energy Commission, Private Mail Bag, Sutherland, New South Wales, Australia
Trace levels of beryllium were determined in a variety of environmental materials. Values for foodstuffs generally were low and were on the order of 0.01 to 0.10 p.p.m. Oyster flesh and mushrooms had the highest values. The highest values for human organs were found for lung. There was little evidence for any beryllium concentration mechanism in plants. Values generally were lower for soils than those previously reported. Water from the Indian Ocean showed the lowest value for sea waters. Rain water and river water contents were comparable. The beryllium content of fish samples showed that the gut of fishes had significantly higher levels than the flesh, and the levels were somewhat related to feeding habits.
B
eryllium metal and its compounds now have extensive applications in atomic energy, space research, and in the chemical and metallurgical industries. The recognition that minute quantities of beryllium and its compounds, particularly beryllium oxide, can cause respiratory disease (White and Burke, 1955) led to the need for careful health control of factory and laboratory workers handling these materials. As a result of regular beryllium surveys resulting from such control, the analytical chemist has been called on t o determine submicrogram quantities of beryllium in such diverse samples as paper smears, urine, grass, soil, effluent, rain water, river water, marine life, and air samples. In addition, the distribution of beryllium has been the subject of a number of geochemical and medical investigations. Recent reviews of the now extensive literature on the subject have been undertaken by Smythe and Whittem (1961) and Smythe and Florence (1963). Everest (1964) reviewed the general chemistry of berylli um. A significant proportion of the earlier work on environmental trace element levels of beryllium used methods which
lacked the sensitivity and precision of those developed within the past four to five years. A knowledge of the environmental distribution and occurrence of beryllium is particularly useful to biologists, geochemists, medical research workers, and others involved in studies of the role of trace elements. Very few results of surveys for traces of beryllium find their way into the literature where they can be used by research workers. Also, gaps exist in the range of materials covered, little work having been done. for example, on human organs and marine life. Method
This study reports results for a wide range of materials using a reliable method for the determination of beryllium a t sub parts per million levels (Cosgrove, Morgan, et a/., 1961). The method is based on the fluorimetric determination of beryllium in alkaline solution with morin (2’,4’,3,5,7pentahydroxyflavone) following the work of Sill and coworkers (Sill and Willis, 1959; Sill, Willis, et al., 1961). The morin method for beryllium constitutes the most sensitive chemical method known for this element, with a practical limit of 2 X 10-j pg. Be per ml. Details of preparation, digestion, and ashing of the solid samples have been described (Cosgrove, Morgan, et a/., 1961). The beryllium in aqueous samples was coprecipitated with ferric hydroxide, digested with perchloric acid, and extracted with acetyl acetone prior t o the morin determination (Cosgrove, Morgan, et a/., 1961). Results A survey of the literature revealed a number of values for natural levels of beryllium in various samples (Table I). The results of the present study are summarized in Table 11. The choice of materials was governed by the gaps in the literature and the ready availability of samples. The main classes of materials examined were foodstuffs, human organs, plants, soils, waters, and marine life. Volume 1, Number 10, October 1967 839
Table I. Levels of Beryllium from Previous Analysis Be Content, P.P.M." Talc 6 . 5 X lo+ Asbestos 2 . 4 X 10-1 Kaolin 7.4 Monazite 5 . 9 x 10-2 Clays and coals of the Moscow basin 7 . 1 Stream sediments-Oslo region, 2.3 Norway, from 146 stream basins Seawater lo2to 10-3 pg. per liter Honey Spectrographically present Blood cells of Ascidiella aspersa 60 pg. per liter Be was detected in a few samples Bottom muds of Indian Ocean Alkaline rocks of the Ditrau massif Be was present in very small amounts, and its content did not depend on the nature of the rocks Proteozoic and Paleozoic granite, rocks: 1 . 2 to 7 , 6 Granite rocks of the eastern Vitem highland (northwestern TransRocks of Mesozoic Intrusive Complex: 40 to 82 baikal) region Igneous rocks Mafic: 10 to 30 Coal ash 300 Earth's crust 6 Oilfield waters 20 to 200 pg. per liter Urine 0.05 pg. per liter (limit) Ocean water 5 x pg, per liter Igneous rocks 2 Meteorites (including chondrites and 0.038 achondrites) (except U.S.A.) Silicic volcanic glasses (western 7.4 United States, southern Idaho), or Pearlette ash (member of the Sappa formation) Cascade Range 4.4 Be Determined by Method Indicated Direct Reading Chem. Analysis Spectrograph Source of Sample
Beryl concentrate Medium grade beryl ore Low grade beryl ore Tailing waste HumansSuspected berylliosis
4.0 X 4 . 0 4 x 104 1 . 9 9 x 104 1.90 x 0 . 5 0 x 104 0.42 x 0.094 X lo4 0.086 X Be demonstrable in 20 of 58 cases Min. Av. Max.
Normal lung tissueCincinnati Chicago a
P.p.m., unless otherwise noted.
840 Environmental Science and Technolog)
= =
Reference Sill, Willis, et al., 1961
Volkov, 1962 Brinck and Hofmann, 1964 Lal, Arnold, et al., 1964 Makerochkin and Udenich, 1960 Rezaeva, 1964 Katchenkov and Flegentova, 1964 Ianovici and Ionescu, 1964
Zilov, Kusnetsova, et al., 1963
Shawe and Bernold, 1964
Aleksandrov and Reznikov, 1964 Mason, 1952 Collins and Pearson, 1964 Sutton, 1963 Merrill, Lyden, et al., 1960 Rankama, 1956 Sill and Willis. 1962 Griffitts and Powers, 1963
lo4 104 104
lo4
Helz and Annell. 1961
2821
8 y per gram of dried lung wt. 1925
0.00033 y per gram 0.324 y per gram
Schepers, 1962
~~~~
Sample
N. D. = not detected.
~
~
_____~______
z
N.D. to 0.01
~~
No. of
Samples
0.01 0.03
0.65 0.78
3 1
0.01 0.006 0.014
1.75 1.01 77.44
1 1 1
0.02 0.02 0.02
0.83 0.81 0.86
50 17 33
0.12
1.32
1
0.02 0.47 0.01 0.01 0.02 0.02 N.D.
2.6 2.5 2.9 2.9 1.05 1.62
2 2 1 1 1 1 1
0 . 0 5 to 0.34 0.05 to 0.10 0.06 to 0.07 0 . 0 5 to 0.09 0.03 to 0 . 0 6 0.01 to 0 . 0 6 0.01 to 0.11 0.01 to 0.06
0.21 0.08 0.07 0.07 0.04 0.04 0.04 0.03 0.02
0.6 1.3 0.06 0.07 1.1 0.4 9.1 1.4 9.5
0.61 to 1.20
0.93
2.7
5
0.81 to 1 . 5 6 0.25 to 0.56
1.22 0.48
2.6 4.3
3 6
0.10to 1.06 0.15 to 2 . 0 0
0.46 0.69 0.02
2.0 3.7 2.9
6 5 1
0.01 to 0.96 0 . 0 6 to 0.56 0 . 0 1 to 0.96
0.32 0.26 0.35
4.6 4.5 4.7
96 18 78
0.24 to 0.26
0.25 0.24 0.25
11 . o 11.1 13.1
1 1 2
0.01 to 0.01 to 0 . 0 8 to 0 . 0 1 to
0.28 0.16 0.32 0.32
+
a
~
Table 11. Levels of Beryllium in Environmental Materials Survey Figures (P.P.M. Ash Wt.) Beryllium Level. Ash, Fresh Range Average Wt.,
Foodstuffs Beans (Lucas Heights area) Cabbage (Lucas Heights area) Hen eggs Yolk Yolk whites Shells Milk All samples Lucas Heights area Hawkesbury and Campbelltown Mushrooms Lucas Heights area Nuts Peanut kernels Peanut shells Almond kernels Almond shells Tomatoes (Lucas Heights area) Yeast (bakers) Aluminum (cooking saucepans) Human Organs Lung Brain Kidney Spleen Liver Muscle Vertebrae Heart Bone Hair-( head) Lucas Heights, composite Lucas Heights active areas (including Be working areas) Away from Lucas Heights Plants, etc. Acacia Angiosperms Sydney area Field lupine seeds Grass All samples Lucas Heights Away from Lucas Heights Tobacco Cigarette tobacco Pipe tobacco Cigarettes (manufactured) Soil All samples Lucas Heights Lucas Heights (disposal ground) Non-Lucas Heights
1
~
N.D. to 0.09 N.D. to 0 , 0 4 N.D. to 0.09
0.01 to 0 . 0 3 0.41 to 0.52
1.69 0.30 0.75 1.69
. . .
29 7 3 19 (continued)
Volume 1, Number 10, October 1967 841
Table 11. Continued Sample Sand, Woronora R. All samples Lucas Heights area Other sites Diatoms Kieselguhr G (from E. Merck, H. G. Darmstadt) Phosphate rock Nauru Marine Crabs Woronora R. Non-Woronora R. Eels Whole fish Woronora R., Mullet Blackfish Non-Woronora R., mullet Fish gut Woronora R., Mullet Blackfish Leather jacket Non-Woronora R., Mullet Blackfish Fish fillets Woronora R., Mullet Blackfish Perch and bream Non-Woronora R., Blackfish Bonita Perch Redfin Mullet Homosira Banks I1 Bubble-weed (coast south of Sydney) Catostylus Mosaicus (jelly blubber) Osyter flesh All samples Woronora R. Hawkesbury R. Oyster liquid All samples Woronora R. Hawkesbury R. Oyster shells All samples Woronora R. Hawkesbury R.
842 Environmental Science and Technology
Survey Figures (P.P.M. Ash Wt.) Ash, Fresh Average Wt.9 72
Beryllium Levela
Range
N.D. to 1.67 0 . 0 4 to 1.67 N.D. to 0.57
0.21 0.39 0.15
No. of Samples
65 16 49
0.31
0.08 to 3.75
1.07
0 . 0 7 to 0.13
0.10 0.17 N.D.
15.4 15.4 5 .O
6 1 1
0 . 0 3 to 0.36 0.08 to 0.39
0.21 0.23 0.01
5.2 4.6
8 4 1
0.42 to 0.71 0 . 4 6 to 1.78 0.48 to 0 . 6 3
0.54 0.99 0.56
9.2 5.6 3.2
6 5 2
0.04 to 1.33 0.80 to 1.25
0.43 1.03
4.2 5.7
4 2
N.D. to 0.07
0.04 0.01 N.D.
3.7 3.6 3.7
2 1 1
0.01
0.01 0.01 0.01 0.01 0.02
4.4 2.4 1.6 5.7 3.3
2 1 1 1 1
0.01 to 0.05
0.03 N.D.
16.5 1.2
5 1
0.01 to 0.27 0.02 to 0.14 0.01 to 0.27
0.03 0.03 0.10
2.0 2.0 2.0
59 41 18
0.01 to 0.03 0.01 to 0.03
0.02 0.02 0.02
2.7 2.5 2.9
2 2 1
0 . 0 1 to 0.08 0.01 to 0.08 0.02 to 0.06
0.04 0.04 0.04
94.9 93.8 96.5
20 14 6
6
Table 11. Continued Sample Plankton preparations Prawns (green) Cunjevoi flesh, Pyura Stoloniferra Mixture from Cronulla and Coalcliff Cronulla Coalcliff Cunjevoi tunics, Pyura Stoloniferra Mixture from Cronulla and Coalcliff Cronulla Coalcliff River Solid Particles Woronora (Discharge Pt.) Woronora (Tolofin) Rockweeds (algae) Cronulla Coalcliff Scallops, Tasmanian Seaweed? Woronora R. Shellfish flesh Mixture from Cronulla and Coalcliff Cronulla Coalcliff Shellfish shells C ron u 11a Coalcliff Starfish, whole, Coalcliff Zostera All samples Woronora R. Hawkesbury R.
Survey Figures (P.P.M. Ash Wt.) Beryllium Levela Ash, Fresh Range Average Wt.9
z
No. of Samples
N.D. 0.03
13.5 3.5
1 1
0.10 to 0.26
0.53 0.18 0.42
3.6 9.1 4.1
1 2 1
0.05 to 0.08
0.30 0.07 0.26
35.4 38.5 33
1 2 1
N.D. N.D.
1 1
0.29 to 1.02
0.01 0.28 0.02 0.66
4.2 5.2 1.7 5.5
1 2 1 3
0.07 to 0.09 0.30to 1.15
0.04 0.08 0.73
8.8 8.1 14.0
1 2 2
N.D. to 0.01 N.D. to 0.01
0.01 0.01 0.02
96.4 96.3 37.1
2 2 1
0 . 2 8 to 1.12 0.28 to 1.12
0.60 0.61 0.41
5.5 5.5 5.5
28 27 1
0.02 to 0 . 5 4
pg. per liter
Waters Rain All samples Lucas Heights Non-Lucas Heights River Lachlan (Forbes) Macquarie (Bathurst) Nepean (Emu Plains) Woronora (Discharge Pt.) Woronora (Tolofin:) Sea Pacific Ocean Indian Ocean Tank Lucas Heights area
0.01 to 0.18 0.01 to 0.07 0.03 to 0.18
0.07 0.05 0.08
20 5 15
0.01 to 0.12 0.01 to 0.08
0.01 0.01 N.D. 0.03 0.02
1 1 1 27 26
0.002 0.001
1 1
0.002
2
0.002
N.D. = not detected.
Volume 1, Number 10, October 1967 843
Locations of sampling sites may be seen in any general map of the state of New South Wales, Australia. Discussion Comparisons between the tables should be made only after considering the preparation and chemical analysis method used for each sample. Results indicate the distribution of beryllium as a trace element in part of the local (Australian) environment. Possibly, samples from other regions in Australia or elsewhere in the world would result in different values. Some general comments on the values in Table I1 are necessary. Foodstuffs (Including Edible Marine Life). Values are generally low and lie in the range 0.01 to 0.10 p.p.m. Oyster flesh and mushrooms have the highest value. Human Organs. The highest values were recorded for human lung. Hair. Since the determinations were carried out on unwashed hair samples, the major part of the beryllium content may result from external contamination such as dust, smog, and hair preparations. The values are among the highest recorded in the survey. Plants. Consistently high values in the range 0.25 to 0.50 p.p.m. give little evidence of any concentration mechanism in plants. Approximately the same levels of beryllium were found in the various forms of tobacco. Soils and Rocks. Values are generally lower for soils than those previously reported. Only two values are reported for other geological materials (phosphate rock and kieselguhr). Water. Seawater from the Indian Ocean showed the lowest value. Rain water and river water contents are comparable, but an exception was found in samples of tank water (collected from roofs of houses and stored in a galvanized iron tank). In tank water, fine sediment would have settled before the sample was taken, whereas suspended material would be present in rain water and river water samples. Marine Samples. The fish samples are of some interest. At first, determinations indicated that different parts of the fish (flesh L’S. organs) had markedly different beryllium contents. The beryllium content of the gut of fishes showed significantly higher levels, and the level was somewhat related to feeding habits of the fish. For example, Girella tricuspidata (blackfish) feeds on Zostera which contains relatively high levels of beryllium. Mugil dobula (mullet) and Pseudomonacanthus ayraudi (leather jackets) do not feed on this material, and consequently showed lower levels of beryllium in the gut. Results for fish flesh showed levels of beryllium comparable with other marine life, The levels of beryllium in cunjevoi and shellfish flesh from the Coalcliff area appeared to be higher than in other areas. This may be related to seepage of ground waters which contact numerous near-surface coal seams. The ground waters enter the tidal zone in this region. 844 Environmental Science and Technology
N o survey of the ber>llium content of these coal seams has been carried out, but it has been reported by Volkov (1962) that some coals hake appreciable levels of beryllium.
Acknowledgment
Thanks are due to John Loewenthal, G. M . Watson, and F. B. Bartholomew for the provision of some samples. Literature Cited
Aleksandrov, A. R., Reznikov, A. P.. Okeanologiya 4 (4), 651-3 (1964) ( C A 62.362~). Brinck, J. W.,‘ Hofmann, A., Econ. Geol. 59 (1). 79-96 (1964) ( C A 60, 13053h). Collins, A. G., Pearson, C. A,, A n d . Chem. 36 (4), 787-9 (1964). Cosgrove, J. D., Morgan, J., Pakalns. P., Australian At. Energy Comm. Rept. TM87 (1961). Everest, D. A., “The Chemistry of BerylliLim.” Elsevier, New York, 1964. Griffitts, W. R., Powers, H. A., U. S . Geol. Sirrr. Projess. Papers, 475-B, 18-19 (1963). Helz. A. W., Annell. C. S., U. S. Geol. Surc. Profess. Papers, . . 424-C,3862 (1961). . Ianovici. V.. Ionescu. J.. Akad. Nauk S S S R 77. Geokhim Konf, 2, 341-8 (1964) ( C A 62, 8883g). Katchenkov, S. M., Flegentova, E. I., Tr Vses. Nauchn. Issled. Geologorazced. Inst. 1964 (227). 202-11 ( C A 62, 5096e). Lal, D., Arnold, J. R., Somoyajube, B. L. K., Geochim. Cosmochim. Acta. 28 (7), 1111-17 (1964) ( C A 61, 11756~). Makerochkin, B. A., Udenich, D. M., Pchelocodstco 37 ( l l ) , 34 (1960) ( C A 61,99626). Mason, B., “Principles of Geochemistr) .’* Wile!. New York, 1952. Merrill, J. R., Lyden, J. F., Honda, M., Arnold. J. R., Geochim. Cosmochim. Acta. 18,108 (1960). Rankama, T., “Isotope Geology,” Pergamon Press, New York, 1956. Rezaeva, L. T.. Zh. Obshch. Biol. 25 ( 5 ) . 347-56 (1964) ( C A 62, 3129h). Schemrs. G. W. H.. Diseases Chest 42. 60&7 (1962). ShaGe, D. R., Bernold, S., U. S. Geoi. Surc. Profess. Papers, NO.501, B100-B104 (1964) ( C A , 62,3646). Sill, C. W., Willis, C. P., Anal. Chem. 31, 598-608 (1959). Sill, C. W., Willis, C. P., Hygare, J. K.. Anal. Chem. 33 (12), 1671-84 (1961). Sill, C. W., Willis, C. P., Geochim. Cosmochim. Acta 26, (14) 1209 (1962). Smythe, L. E., Whittem, R. N., Analyst 86,83-94 (1961). Smythe, L. E., Florence, T. M., Progr. Nucl. Energy, Ser. I X , Vol. 3, Chapt. 5, Pergamon Press, New York, 1963. Sutton, D. C., U. S. At. Energy Comm. HASL, 134 (1963). Volkov, K . Y., Materialy PO Geol. i Polezn. Iskopaernym Tsentr. Raionoc Ecroneiskoi Chasti S S S R . Moscow, S b 1962 (5), 183-4 ( C A 59; 8492h). White, D. W., Burke, J. E., Eds., “The Metal Beryllium,” The American Society for Metals, Cleveland, Ohio, 1955. Zilov, A. R., KusnetsoGa, A. l.,Cherenko, A. I., Akad. Nauk. S S S R Sibersk. Otd. 1963 (13), 145-52 ( C A 62,7534h). ’
Receiced for reciew July I O , 1967. Accepted October I , 1967.
