beryllium in environmental air, water and soil

B E R Y L L I U M IN E N V I R O N M E N T A L AIR, WATER AND SOIL

E N. BHAT and K. C. PILLAI* Health Physics Division, Bhabha Atomic Research Centre, Trombay, Bombay-400 085

(Received 21 February, 1995; accepted 15 February, 1996)

Abstract. The study was specifically aimed to obtain concentration of beryllium in various environmental matrices such as air, water and soil in the vicinity of the Beryllium Metal Plant situated at Turbhe, New Bombay. Two analytical techniques - Morin fluorescence method and Atomic Absorp- tion Spectrophotometry using graphite furnace were standardised for beryllium estimation. The beryllium concentration in the natural matrices studied - air, water and soil were in the range of 0.41-0.43 ng m -3, 0.01-0.02 ng mL-J and 325-767 ng g-~ respectively.

Key words: beryllium, environment, air, water, soil

1. Introduction

In view of unique properties of metal beryllium (Be) it has got number of appli- cations in nuclear, electronic and space industries (Darwin and Buddery, 1960; Narayan and Ramamurthy, 1980; White and Burke, 1955, WHO, 1990). The ever increasing demand of metal beryllium and its alloys in the country necessitated setting up of the beryllium processing plant at Turbhe, New Bombay. The metal is extracted from the ore beryl of composition (3BeO, A120?, 6SIO2) for preparation of its alloys such as copper-beryllium and aluminium-beryllium.

Literature survey indicates that data on concentration of beryllium in environmental matrices like air, water, soil etc. are very scarce. It is reported that non- metallurgical processes such as combustion of coal and oil are the major sources of emission of beryllium into the environment (Kabata-Pendias and Pendias, 1984; Kaplan et al., 1990; Zubovic, 1969). Extraction processes of beryllium, accidental leakage, disposal of toxic waste etc. are potential sources. In the context of the setting up of the Beryllium Plant at New-Bombay, the background concentration of beryll ium in environmental matrices in the area is required to assess the change in environmental quality due to operations of the beryllium production facility. The present study was undertaken to obtain data on beryllium concentration in air, water and soil in the area of New Bombay.

* Former Head, Health Physics Division.

Water. Air, and Soil Pollution 95: 133-146, 1997. @ 1997 Kluwer Academic Publishers. Printed in the Netherlands.

134 a N. BHAT AND K. C. PILLAI

2. Materials and Methods

2.1. STANDARDISATION OF ANALYTICAL METHOD

Two analytical techniques for determination of beryllium in environmental samples were standardised in the present study. Air samples were analysed by morin fluorescence method, water and soil samples were analysed by atomic absorption spectrophotometry (Graphite furnace attachment) method.

2.1.1. Morin Fluorescence Method In fluorometric method (Sill and Willis, 1959, Sill et al., 1961; Fusheng et al., 1990), Beryllium-morin chelates complex is formed which gives the fuorescence in alkaline medium which is proportional to the concentration of the analyte in the solution. The complex was excited at 365 nm and fluorescence were measured at 550 nm wavelength. The fluorometer made by Health Physics Division, B.A.R.C. was used for the study.

2.1.2. Atomic Absorption Method Water and soil samples were analysed by A.A.S. (APHA, 1985). Optimum tem- perature parameters were selected for dehydration, ashing and atomisation steps. Absorbance was measured at 234.9 nm wavelength. A Varion Techtron atomic absorption spectrophotometer, model AA-1475, fitted with Graphite Tube Atom- iser (GTA-95) was used in the present study. A beryllium hollow cathode lamp was used as light source. The standard addition method was followed for water and soil samples.

2.2. REAGENTS

All reagents used were Analar grade. All solutions were prepared in distilled water. (i) 0.1 N sulfuric acid solution: 3.6 mL of concentrated sulfuric acid diluted to

1000 mL with distilled water. (ii) 1 N, 4 N sodium hydroxide solution: 40.0 and 160 g sodium-hydroxide pellets

were dissolved in half liter distilled water separately and finally made upto one liter to give 1 N, 4 N solution respectively.

(iii) Morin reagent solution: Stock morin solution was prepared by dissolving 4.0 g morin in 100 mL of absolute alcohol. Working solution of strength 0.5 x 10-3% was prepared fresh with appropriate dilutions.

(iv) Quinine sulfate solution: 0.1% quinine sulfate solution was prepared in 0.1 N H2804 solution. Working solution of concentration 0.5 x 10-3% was prepared in 0.1 N acid solution by diluting stock solution.

(v) Beryllium standard stock solution: Beryllium stock solution was prepared by dissolving 1.9638 g BeSO4, 4H20 crystals in 0.1 N H2SO4 to give final concentration 1 mg Be mL- I. The required beryllium solution of concentration 1000 ng Be mL -1 and 20 ng Be mL 1 were prepared in 0.1 N H2SO4 freshly.

135

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Q

LU

L~

Z ld 0

LU O~ 0 -I

2.3.1. Morin Method Three sets of beryllium standards in the range of 0.4 to 4.0 ng Be mL-1 were prepared in 25 mL capacity standard flask containing 5 mL of 0.1 N H2SO4 solution. After beryllium addition, volume was equalised to 10 mL by adding 0.1 N acid solution.

The solution was neutralised by adding 1 N NaOH solution. At the neutral pH, 2 mL of disodium EDTA solution was added to each and final pH of the solution was raised to 11.5 using 1 N NaOH solution. Morin solution of strength 0.5 x 10-3% was added to each before making the final volume and immediately fluorescence were measured using fluorometer. Standard calibration graph of Be in ng mL 1 against fluorometric reading (Blank corrected) was plotted, which is linear passing through origin. (Refer Figure 1).

50.0

40.0

30.0

20.0

tO.{]

0 . 0 . . . . i . . . . i . . . . I . . . . ! . . . .

-o.o 1.o 2.o a.o 4.o BERYLLIUM CONCENTRATION (ngBe/mt)

CALIBI~TION CURVE,

BERYLLIUM IN ENVIRONMENTAL AIR, WATER AND SOIL

2 .3 . CALIBRATION

5 . 0

MORIN METHO[] (Range 0.4-4.0 ngBe/m[l

Figure I. Calibration curve, morin method (Range 0.44.0 ng Be mL-l).

Similarly standard calibration for the range 10-100 ng Be m g -1 in 50 mL, following the same procedure, was also carried out using morin solution of 1 x 10-3%. (Refer Figure 2).

136 p.N. BHAT AND K. C. PILLAI

100.0

80.0

Z

O < 60.0 L.m.l (DIC

W (..J Z

u 4 0 . 0 Co L~ CK C~

_J

" 20.0

0.0 . . . . I . . . . I . . . . t . . . . I . . . .

0.0 20.0 40.0 130.0 80.0 I00.0

BERI'I_LIUN CONCENTRATION ( ng Be / rml ) CALIBRATION CURVE (MORIN METHOD) Ronge 10:-100 ngBe/ml).

Figure 2. Calibration curve, morin method (Range 10-100 ng Be mL-m).

2.3.2. Analytical Reproducibility Since the reagent blank containing morin also exhibits fluorescence, the sensitivity of the method was assessed with respect to the blank and the lowest detectable concentration was found to be 0.4 ng Be mL- I. Ten sets of standards in the range of 0.4 4.0 ng Be mL-I and equal number of blanks were prepared. The relative standard deviation was better than +4% at the lowest concentration of 0.4 ng Be m L - l and at higher concentrations it was +2.6%.

2.3.3. Atomic Absorption Spectrophotometric Method Stock beryllium and final sample solution were prepared in 2% HNO3solution and analysis was carried out at the beryllium resonance wavelength line 234.9 nm with deuterium background facility.

2.4. REAGENTS

Beryllium stock solution was prepared by dissolving 1.9638 g BeSO4, 4H20 crystals in 2% HNO3 solution. The working beryllium solution of concentration 1-5 ng Be mL- l were prepared daily with appropriate dilutions. Final volume was made

BERYLLIUM IN ENVIRONMENTAL AIR, WATER AND SOIL 137

LIJ r,.J Z CD O~ 0

OQ

2.0

1.6

1.2

0.8

0.4

0.0 . . . . I . . . . I , , I , , , I . . . . -0.0 1.0 2.0 3.0 4.0

BERYLLIUM CONCENTRATION (ngBe/ml) CALIBRKi[ON CURVE (A.A.S.METHOID).

Figure 3. Calibration curve, A.A.S. method.

5.0

upto 25 mL. Standard calibration graph is shown in Figure 3; which is linear upto 3.0 ng Be mL - I .

2 .5 . SAMPLE COLLECTION AND PROCESSING

2.5.1. Air Air samples were collected at five stations near the beryllium processing plant. Sampling locations are shown in Figure 4. High volume samplers of capacity 600 L rain-I were arranged at the height of five meters from ground level. Whatman 41 circle of dia 11 cm was used as sampling media. Sampling was carried out during eight hours of working days. Sampled filters were removed and stored in 10 x 7.5 cm envelope to avoid any cross contamination before processing. Total sampling time and sampled volume was in the range of 139-269 rain and 78- 145.6 m 3 respectively.

2.5.2. Water Sampling locations for water and soil samples are shown in Figures 4 and 5. Water samples from the wells and pond from New Bombay area, near beryllium processing plant, were collected in five liter capacity plastic containers. After

138 P.N. B H A T A N D K. C. PILLAI

2 5 0 M

\

B

~[~ A I R S A M P L I N G STATION ] - 5 )

O SO,L (1 -~)

S A M P L I N G STAq'ION A R O U N D L~ERYLLIUM M E T A L P L A N T

Figure 4. Sampling stations around Beryllium Metal Plant.

sampling, immediately samples were made acidic to pH 1.0 by adding concentrated nitric acid to avoid absorption by the sample container.


~@ VA SHI

/ -- lU RBH E

/ SAi'I PADA

5 SOHEHAR [

, o l

' l(0 sO(/i 6 i f @ , r

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, ~ B E R Y L L I U M METAL P LAi'I J //4 / ~ .~.

0 SOIL ( POND ~ ~,ARAVE /

@ WELL

KURSHET

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S A M P L I H G STATIOHS AROUHD BERYLLIUM METAL PL-, ;J-

Figure 5. Sampling stations around Beryllium Metal Plant.

2,5.3. Soil Sampling site selected was nearby the beryllium plant and five km away from the plant in New Bombay area. A one sq.m. area was cleared off by removing vegetation, stones etc. Area was dug up to 15 cm depth and entire soil was mixed thoroughly. From this 2 kg soil was taken in a plastic bag and brought to the laboratory. Soil was crushed and made homogeneous using mortar and pastel and passed through 500 mesh (32 micron) sieve. Soil samples were dried at 120 ~ and was taken for analysis.

140 P.N. BHAT AND K. C. PILLA!

2.6. SAMPLE PREPARATION

2.6.1. Air Air filters were treated with 10 mL of 0.1 N H2804 solution in a beaker for two hours. This step was repeated for three hours with 5 mL of 0.1 N sulfuric acid. Both leachates were transferred to the standard flask of 25 mL. Further, after leaching, same filters were digested in concentrated HNO3 and H2SO4 acid mixture. Both leachate and acid extract were analysed fluorometrically following the standard procedure.

Leachate and acid extract both were neutralised using 1N and 4 N sodium- hydroxide solution respectively. 2 mL of 10% disodium- EDTA was added as a masking agent and final pH of the solution was made to 11.5 by adding 1 N NaOH solution. Before making the final volume to 25 mL, 1 mL working morin solution of strength 0.5 x 10-3% was added to each flask before making up to final volume with distilled water. A set of standard beryllium solution of concentration 0.4-4.0 ng Be mL -1 was also processed simultaneously and calibration graph was made. Two sets of reagents and filter+reagent were also measured along with the samples. Concentrations were read out from standard calibration graph. Total beryllium in filter was estimated by the sum of beryllium obtained in 0.1 N acid extract and strong acid digest. Results are presented in Table I. Average beryllium concentration at each location were computed and is given in Table II.

2.6.2. Water Since very low concentration was expected in the matrix, pre-concentration of water samples were made by evaporation method following concentrated acid digestion. Acidified water sample was divided in 100 mL quantity in four beakers of capacity 250 mL. Known standard beryllium solution in the range 0-40 ng be was added in container serially.

The addition of 10 mL concentrated HNO3 was repeated to remove all organic matter. Sample was further digested with 3 mL of acid perchloric (72%) and final residue was dissolved in 2% HNO3 and filtered. Filtrate volume made upto 50 mL and absorbance was measured at 234.9 nm resonance wavelength.

The beryllium concentration in water samples are presented in Table III. A typical graph of standard addition technique followed for water samples is also presented in Figure 6.

2.6.3. Soil Beryllium occurs in soil as its oxide form and hence (Kabata-Pendias and Pendias, 1984) acid digestion method was followed. 0.5 g soil sample, from each, was weighed in separate four beakers of 250 mL capacity. Concentrated HNO3, H2SO4, 5 mL and 2 mL respectively was added to each sample after addition of 0, 250, 500, 750 ng Be standard solution serially and subjected to digestion on hot plate. Addition of concentrated HNO3 was repeated thrice and finally 2 mL perchloric acid


Table I

Beryllium concentration in environmental air

Total In 25 mL sample solution Total Be

Sample vol air in 0.1 N H2SO4 in acid in air Be conc.

No. sampled extract digestion filter in air

m 3 ng ng ng ng m -~

Location: 1 Front side of BPP (Sampling period: October 1985).

1 103.6 32.0 10.0 42.0 0.405

2 120.4 45.0 7.0 52.0 0.432

3 117.6 45.0 5.0 50.0 0.425

4 100.8 37.0 4.0 41.0 0.407

5 95.2 35.0 5.0 40.0 0.420

6 106.4 39.0 4.0 43.0 0.404

7 112.0 35.0 9.0 44.0 0.393

8 126.0 45.0 13.0 58.0 0.460

9 92.4 32.0 6.0 38.0 0.411

10 114.8 40.0 8.0 48.0 0.418

filter

blank - 10.0 19.0 - -

l_z~cation: 2 Fivnt side of BMFI (Sampling period: November 1985).

1 112.0 36.0 12.0 48.0 0.429

2 120.4 44.0 7.0 51.0 0.424

3 145.6 47.0 12.0 59.0 0.405

4 120.4 45.0 7.0 52.0 0.432

5 134.4 44.0 9.0 53.0 0.394

6 134.4 44.0 9.0 53.0 0.394

7 78.4 32.0 4.0 36.0 0.459

8 123.2 38.0 10.0 48.0 0.390

filter

blank - 10.0 20.0 - -

Location: 3 Back side of BMF (Sampling period: December 1985).

1 78.4 30.0 5.0 35.0 0.446

2 114.8 38.0 7.0 45.0 0.392

3 95.2 35.0 5.0 40.0 0.420

4 92.4 30.0 8.0 38.0 0.411

5 109.2 37.0 8.0 45.0 0.412

6 106.4 35.0 9.0 44.0 0.414

7 95.2 35.0 4.0 39.0 0,410

8 92.4 32.0 6.0 38.0 0.411

142 R N. BHAT AND K. C. PILLAI

Table I

Continued.

Total In 25 mL sample solution Total Be

Sample vol air in 0.1 N H2SO4 in acid in air Be conc.

No. sampled extract digestion filter in air m 3 ng ng ng ng m -3

Location: 3 Back side of BMF (Sampling period: December 1985).

9 103.6 30.0 12.0 42.0 0.405

10 109.2 30.0 15.0 45.0 0.412

1 I I 17.6 35.0 13.0 48.0 0.408

filter

blank - 10.0 19.0 - -

Location: 4 Front side of RPL (Sampling period: January 1986).

1 100.8 37.0 5.0 42.0 0.417

2 95.2 35.0 4.0 39.0 0.410

3 106.4 32.0 12.0 44.0 0.414

4 106.4 30.0 13.0 43.0 0.404

5 112.0 35.0 10.0 45.0 0.402

6 92.4 32.0 7.0 39.0 0.422

7 113.7 35.0 13.0 48.0 0.422

filter

blank - 10.0 19.0 - -

Location." 5 Toxic side qf BPP (Sampling period: April 1986).

1 92.4 40.0 4.0 44.0 0.476

2 109.2 35.0 10.0 45.0 0.412

3 106.4 38.0 6.0 44.0 0.414

4 92.4 35.0 4.0 39.0 0.422

5 75.6 35.0 N.D. 35.0 0.463

6 114.8 30.0 18.0 48.0 0.418

7 112.0 35.0 I0.0 45.0 0.402

8 114.8 40.0 7.0 47.0 0.409

9 78.4 35.0 N.D. 35.0 0.446

10 95.2 40.0 N.D. 40.0 0.420

filter

blank - 10.0 19.0 - -

(72%) was added. Perchlorate fumes were cleared off. Final residue was dissolved in 2% HNO3 solution. After cooling the insoluble matter were filtered and filtrate volume made upto 100 mL with washings. Insoluble matter was digested with HF

BERYLLIUM IN ENVIRONMENTAL AIR, WATER AND SOIL

Table II Average beryllium concentration in air at each sampling location

Period of Total no. Beryllium concentration

sampling of samples Maximum Minimum Average

(ng m -3)

Oct. 1985 10 0.460 0.393 0.42 Nov. 1985 8 0.459 0.390 0.42 Dec. 1985 11 0.446 0.392 0.41 Jan. 1986 7 0.422 0.402 0.41 Apr. 1986 l0 0.476 0.402 0.43

143

Table III Beryllium cone levels in water samples

Location Be concentration No. Sample source Avg. of 3 samples

__(ngmL-L) __

1 Tap water 0.010 2 Pond water 0.020 3 Well water (1)~' 0.010 4 Well water (2) ~ 0.015 5 Well water (3) a 0.015 6 Well water (4) a 0.020 7 Drinking water (Nerul) 0.010 8 Drinking water (Turbhe) 0.010

Location of wells are expressed in parenthesis (Figure 5).

in teflon beaker and final solution was analysed by A.A.S. (Zeitschrift and Fur,

1987). The results are given in Table IV.

3. R e s u l t s a n d D i s c u s s i o n

The standard calibration graph of ~br both fluorometric and A.A.S. methods are

presented in Figures l, 2 and 3 respectively. The standard addition p lo t s /o r water

and soil are presented in Figures 6 and 7 respectively. The observed concentration

of beryll ium in each of the matrix estimated (viz. air, water and soil) are presented

in Tables I, Ill and IV. The results of the analysis of air samples at five locations (Table I) indicates

the value in the range of 0 .41-0.43 ng Be m -3 which are similar to those reported

fbr some other countries in the world. The variation in beryllium air concentration

at each of the site studied were within 4-10%. The results compare well with the

44 P.N. BHAT AND K. C. PILLAI

Table IV

Beryllium concentration levels in soil samples

Total Be

St. No." Sampling location concentration

_ ( n g g - I ) _

1 Near security watch tower 396.6

2 Near RPL Stack 325.0

3 Site of solid waste disposal 496.6

4 Near LCLR on road 490.0

5 Sonehar village, Near well 416.6

Thane Belapur road

Sonehar Bus stop

Sonehar village, near school

Bombay Pune highway (near bus stop)

Near Railway bridge

6 553.4

7 660.0

8 693.4

9 766.6

Sampling location number as indicated in Figures 4 and 5.

O. fi:5

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O. 25

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/ / /

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. . . . . . . . . 1 . . . . . . . . . I . . . . . . . . I . . . . . . . . . . .

0.00 12.50 25.00 37.50 2,0.00

SAMPLE (lOOrnl.) + BERYI_L[UM AIIDED (rig)

Figure 6. Standard addition graph for water; A.A.S. method.


O. 70.

O. 60

O. 50

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o 0 30 0"1 CO

O. 20

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0.0 2.50.0 500.0 750.0 lO00.O

SAMPLE (O.5g) + BERYLLIUM ADDEO f.ns

Figure 7. Standard addition graph for soil; A.A.S. method.

reported U.S. urban air beryllium concentration of 0.2~).5 ng Be m -3 (Manning and Slavin, 1983; USEPA, 1973a) and are close to the background levels contributed by natural sources.

The well water and pond water studied from the area have shown that the beryllium concentration are in the range of 0.01-0.02 ng Be mL -1 , which is in the same range as reported elsewhere (USEPA, 1973a; Manning and Slavin, 1983). There was no appreciable difference in concentration of beryllium in well water between those in close proximity to the plant and 5 km away from the plant. The calculated daily intake of beryllium for a person using the well water for drinking workout to 30 ng Be per day which is only 7.1% of the daily consumption reported for U.S.A. (USEPA, 1987). Water accounts for 70.9% of the total daily consumption of beryllium in U.S.A.

The analytical results of soil samples could be obtained within 4% variation. In soil samples beryllium content was in the range of 325-767 ng Be g-I with an average value of 5 7 0 i 1 5 9 ng Be mL -I for the area under study. Soil samples collected far away from the processing plant, which have shown values nearly

146 P.N. BHAT AND K. C. PILLAI

twice that of soils close to the plant. In comparison the reported concentration of beryllium in soil varies from 100-1000 ng Be g-I (Kaplan et al. , 1990; Narayan and Ramamurthy, 1980).

The results obtained show that the natural beryllium concentration in environmental matrices air, water and soil in New Bombay area are of the same order as obtained in other areas of the world.

Acknowledgements

We acknowledge the co-operation received from Shri A. Ramamurthy, Head, I.H.S. section, HPD, B.A.R.C., S/Shri G. Subramanium, Officer in charge, HPU, Vashi, S. Narayan, IHSS. during the present study.

Keen interest shown by Shri S. Krishnamony, Head, Health Physics Division is gratefully acknowledged.

References

APHA: I985, "Standard Methods for the Examination of Water and Waste Water', 16th Ed. Wash- ington, D.C.

Darwin, G. E. and Buddery, J. H.: 1960, 'Beryll ium' Butterworth Scientific Publication, London. Fusheng, Wei., Enjiang, Ten. and Zhongxiang, Wu.: 1990, "Enhancement of the Fluorescence of the

Beryll ium-Morin complex by Non-ionic Surfactants', Talanta 3% 947. Kabata-Pendias, A. and Pendias, H.: 1984, Trace Elements in Soils and Plants, CRC Press. Kaplan, D. I., Sajwan, K. S., Adriano, D. C. and Gettier, S. : 1990, Water, Air; and Soil Pollut. 53,

203. Manning, D. C. and Slavin, W.: 1983, APSPA4, Appl. Spectroscopy 37, I. Narayan, S. and Ramamurthy, A.: 1980, 'Beryllium: Hazards and Control', BARC, 1-622, B.A.R.C.,

India. Sill, C. W. and Willis, C. R: 1959, Anal. Chem. 31,598. Sill, C. W., Willis, C. R and Flugare, J. K.: 1961,Anal. Chem. 33, 1671. USEPA: 1973a, 'Control Techniques for Beryllium Air Pollutants', EPA publication, AP-116, Wash-

ington D.C. USEPA.: 1987, 'Health Assessment Document for Beryllium', White, D. W. and Burke, J. E.: 1955, 'The Metal Beryllium' Am. Soc. for Metals, Clevelands. World Health Organisation: 1990, Beryllium: Health and Safety Guide, No. 44. Geneva. Zcitschrift, F. and Fur: 1987, Anafytische cheme, 326, 40. Zubovic, R: 1969, 'Coal Emissions of Beryllium', in Proc. of Beryllium Conference, MIT Press.

beryllium in environmental air, water and soil

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