occupational beryllium exposure in primary aluminium production

34
OCCUPATIONAL BERYLLIUM EXPOSURE IN PRIMARY ALUMINIUM PRODUCTION Y. Thomassen 1 , D.G. Ellingsen 1 , K. Dahl 1 , I. Martinsen 2 , N.P. Skaugset 1 and P.A. Drabløs 3 1 National Institute of Occupational Health, OSLO, Norway. 2 Amersham Health, Oslo, Norway 3 Norsk Hydro, Karmøy Plant, Håvik, Norway E-mail:[email protected]

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Page 1: Occupational Beryllium Exposure in Primary Aluminium Production

OCCUPATIONAL BERYLLIUM EXPOSURE IN PRIMARY ALUMINIUM PRODUCTION

Y. Thomassen1, D.G. Ellingsen1, K. Dahl1, I. Martinsen2, N.P. Skaugset1 and P.A. Drabløs3

1National Institute of Occupational Health, OSLO, Norway.2Amersham Health, Oslo, Norway3Norsk Hydro, Karmøy Plant, Håvik, Norway

E-mail:[email protected]

Page 2: Occupational Beryllium Exposure in Primary Aluminium Production

AL industryIncreased risk of asthma have been

shown to be associated with

exposures in potrooms.

Site of deposition in the respiratory tract

and hence size, may be important.

Page 3: Occupational Beryllium Exposure in Primary Aluminium Production

Potroom asthma:Hypothesis

! Potroom asthma is caused by contaminants penetrating below the larynx.

! Mixed fluoride phases(vapour-particles, PIP’s ?)

! HF and SO2 are transported to the alveolar region adsorbedto particles.

Page 4: Occupational Beryllium Exposure in Primary Aluminium Production

Chemistry:HF, F-

sSO2

PAHs”Total” dust

Temporalexposure

Health related aerosol fractions:

particle size distribution

Spatialexposure:stationary,personal

Morphology:Al2O3

Na3AlF6Cryolite fibers

”New”pollutants ?

”New”pollutants ?

Be COF2SOF4

Page 5: Occupational Beryllium Exposure in Primary Aluminium Production

Be in Alumina:0.01 – 4 ppm

Bath temperature: 960 0CSublimation temperature of BeF2: 800 0C

Page 6: Occupational Beryllium Exposure in Primary Aluminium Production

A recent study found that 9% of workers exposed to Be in a machiningplant were sensitised after lifetime weighted average exposures between 24 - 600 ng Be/m3.

A possible ACGIH new TLV recommendation : 20 ng inhalable Be/m3

PC. Kelleher et al.: J Occup Environ Med, 43:231-237 (2001)

Page 7: Occupational Beryllium Exposure in Primary Aluminium Production

Health Related Aerosol Fractions

Page 8: Occupational Beryllium Exposure in Primary Aluminium Production

Hund/TSI - Respicon

Page 9: Occupational Beryllium Exposure in Primary Aluminium Production

Participating plants

Sampling at:! Lista ! January 2003! Mosjøen ! February 2003!SØRAL ! March 2003!Karmøy ! March/April 2003!Årdal ! September 2003!Høyanger ! November 2003 !Lista ! March 2004

ParticipatingAl-smelters

Page 10: Occupational Beryllium Exposure in Primary Aluminium Production

Sampling equipment

Photo: D. Kroslid, EA Lista

Respicon

SO2 sensor

IOM Split 2direct readingspectrometer

Gas filter

3 Pumps

Page 11: Occupational Beryllium Exposure in Primary Aluminium Production

Variability of exposure

Anode worker - Prebake Cell operator - Søderberg

Direct reading Respicon

Page 12: Occupational Beryllium Exposure in Primary Aluminium Production

Screw cap

Sample chamberhousing

Centrifuge tube

10 ml reagent

Air filter

0.2 µm PVDF membrane

Centrifuge Tube with Filter Cup Insert

Page 13: Occupational Beryllium Exposure in Primary Aluminium Production

Inductively coupled plasma optical emission spectrometry

(ICP-OES)

Detection limits in ng/m3

(sample volum:1 m3)3x SD of blank filters (n=89)

0.6240.51.96.41.6

Be ax 313.107

Be ax313.042

Be ax 234.861

Be 313.107

Be 313.042

Be 234.861

ax : axial reading

Page 14: Occupational Beryllium Exposure in Primary Aluminium Production

Beryllium exposure in ng/m3: Respicon: All plants

<0,5 - 2084,010,2Respirable

0,7 - 2556,818,1Thoracic

1,3 - 33719,642,1 Inhalable

Min - MaxGM(n=274)

Mean(n=274)

Page 15: Occupational Beryllium Exposure in Primary Aluminium Production

1,0 2,0 3,0 4,0 5,0 6,0 7,0 8,0 9,0 10,0

1=Plant1 Prebake,2=Plant 2 Prebake,3=Plant 3, 4=Plant 4,5=Plant 5 1,6=Plant 5 2,7=Plant 6 Søderberg,8=Plant 6 Prebake, 9=Plant 1 Søderberg, 10=Plant 2 Søderberg

0,00

50,00

100,00

150,00

200,00

250,00

300,00

Beinh

ng/m

3

65

126187

46

125170

165

155

200

17

104

Page 16: Occupational Beryllium Exposure in Primary Aluminium Production

1,0 2,0 3,0 4,0 5,0 6,0 7,0 8,0 9,0 10,0

Prebake, 9=Plant 1 Søderberg, 10=Plant 2 Søderberg

0,00

50,00

100,00

150,00

200,00

250,00

300,00

Bet

h in

ng/

m3

4

125 165

35

62

65

170

155

200

46

17 104

1=Plant1 Prebake,2=Plant 2 Prebake,3=Plant 3, 4=Plant 4,5=Plant 5 1,6=Plant 5 2,7=Plant 6 Søderberg,8=Plant 6

Page 17: Occupational Beryllium Exposure in Primary Aluminium Production

1,0 2,0 3,0 4,0 5,0 6,0 7,0 8,0 9,0 10,0

1=Plant 1 Prebake,2=Plant 2 Prebake,3=Plant 3,4=Plant 4,5=Plant 5 1,6=Plant 5 2,7=Plant 6 Søderberg,8=Plant 6

Prebake, 9=Plant 1 Søderberg, 10=Plant 2 Søderberg

0,00

50,00

100,00

150,00

200,00

250,00

Bea

lv in

ng/

m3

61

139

35

4

62

170

155104

Page 18: Occupational Beryllium Exposure in Primary Aluminium Production

Water Soluble Inhalable Be and Al Plant 1 - Prebake

y = 0,90x + 36,6R2 = 0,8331

0,0

50,0

100,0

150,0

200,0

250,0

300,0

0,0 50,0 100,0 150,0 200,0 250,0 300,0

Be ng/m3

Al u

g/m

3

Page 19: Occupational Beryllium Exposure in Primary Aluminium Production

Water Soluble Thoracic Be and Al Plant 1 - Prebake

y = 1,01x + 22R2 = 0,8846

0,020,040,060,080,0

100,0120,0140,0160,0180,0

0,0 50,0 100,0 150,0 200,0

Be ng/m3

Al u

g/m

3

Page 20: Occupational Beryllium Exposure in Primary Aluminium Production

Water Soluble Respirable Be and AlPlant 1 Prebake

y = 0,83x + 13,6R2 = 0,8818

0,0

20,0

40,0

60,0

80,0

100,0

120,0

0,0 20,0 40,0 60,0 80,0 100,0 120,0 140,0

Be ng/m3

Al u

g/m

3

Page 21: Occupational Beryllium Exposure in Primary Aluminium Production

Water Soluble Respirable Be and Al Plant 2 Prebake

y = 1,25x + 3,9R2 = 0,8659

0,0

5,0

10,0

15,0

20,0

25,0

30,0

35,0

40,0

0,0 5,0 10,0 15,0 20,0 25,0 30,0Be ng/m3

Al u

g/m

3

Page 22: Occupational Beryllium Exposure in Primary Aluminium Production

Water Soluble Respirable Be and Al Plant 5 Søderberg

y = 5,38 + 0,17R2 = 0,8616

0,0

10,0

20,0

30,0

40,0

50,0

60,0

0,0 2,0 4,0 6,0 8,0 10,0Be ng/m3

Al u

g/m

3

Page 23: Occupational Beryllium Exposure in Primary Aluminium Production

Water soluble Be in % of total

0 20 40 60 80 100 120

1

6

11

16

21

26

Mean: 81 % (n=28)

Page 24: Occupational Beryllium Exposure in Primary Aluminium Production

Characterization of individual aerosol particles in workroom air of aluminium smelter potroomsBurkard L.W. Höflich1, Stephan Weinbruch2*, Ralf Theissmann1, Hauke Gorzawski2, Martin Ebert2, Hugo M. Ortner1, Asbjørn Skogstad3, Dag G. Ellingsen3, Per A. Drabløs4, and Yngvar Thomassen3,5

1Institute of Materials Science, Technical University of Darmstadt, Petersenstr. 23, D-64287 Darmstadt, Germany2Institute of Applied Geosciences, Technical University of Darmstadt, Schnittspahnstr. 9, D-64287 Darmstadt, Germany3National Institute of Occupational Health, P.O. Box 8149 DEP, N-0033 Oslo, Norway4Karmøy Plant-Norsk Hydro, N-4265 Håvik, Norway5Department of Plant and Environmental Sciences, Agricultural University of Norway, N-1432 Ås, Norway

Submitted to: Journal of Environmental MonitoringDecember 2004

Page 25: Occupational Beryllium Exposure in Primary Aluminium Production

Theoretical aspects of fluoride air contaminantformation in aluminium smelter potrooms

Boris V. L’Vova, Leonid K. Polzika, Stephan Weinbruchb, Dag G. Ellingsenc

and Yngvar Thomassenc,d

aDepartment of Analytical Chemistry, St. Petersburg State Polytechnic University, Politekhnicheskaya ul. 29, 195251 St. Petersburg, Russia bInstitute of Applied Geosciences, Technical University of Darmstadt, Schnittspahnstr. 9, D-64287 Darmstadt, GermanycNational Institute of Occupational Health, P.O. Box 8149 DEP, N-0033 Oslo, Norway dDepartment of Plant and Environmental Sciences, Agricultural University of Norway,N-1432 Ås, Norway.

Submitted to : Journal of Environmental Monitoring January 2005

Page 26: Occupational Beryllium Exposure in Primary Aluminium Production

Ultrafine particles at workplaces of a primary aluminium smelter

Yngvar Thomassen1,2, Wolfgang Koch3, Wilhelm Dunkhurst3, Dag Ellingsen1, Nils-Petter Skaugset1, Lars Jordbekken1 and Per Arne Drabløs4

1 National Institute of Occupational Health, P.O. Box 8149 DEP, N-0033 Oslo, Norway2 Department of Plant and Environmental Sciences, Agricultural University of Norway, N-1432 Ås, Norway

3 Fraunhofer Institute of Toxicology and Experimental Medicine, Nikolai- Fuchs-Str. 1,D-30625 Hannover, Germany

4 Karmøy Plant Norsk Hydro, N- 4265 Håvik, Norway

To be submitted to : Journal of Environmental Monitoring

Page 27: Occupational Beryllium Exposure in Primary Aluminium Production
Page 28: Occupational Beryllium Exposure in Primary Aluminium Production
Page 29: Occupational Beryllium Exposure in Primary Aluminium Production

0 1 2 3 4 50

100

200

300

num

ber o

f par

ticle

s

µm

For particles below 100 nm only electrostatic sampling procedures can be applied and their size classification is performed by scanning mobility particle sizing.

Histogram of the measured particle sizes with diameters ≤ 5 µm from all of the particles investigated from the Prebake hall

Page 30: Occupational Beryllium Exposure in Primary Aluminium Production
Page 31: Occupational Beryllium Exposure in Primary Aluminium Production

3-d plot of the mobility size distribution during anode change operations

Page 32: Occupational Beryllium Exposure in Primary Aluminium Production

Formation route of ultrafine particles

960 °C

Al

Anode

CryoliteNa3AlF6 Decomposition, evaporation

Reaction, nucleation, condensation

Fluorides of Al and Na (Be)Na5Al3F14

AluminaAl2O3

Cathode

Page 33: Occupational Beryllium Exposure in Primary Aluminium Production

Conclusions:" Be is present in workroom aerosols in

potrooms of Al-primary smelters

" Ultrafines contain Be

" Be is mostly water soluble

" Water soluble fluorides are present in high excess

" High variability in exposure is experienced

Page 34: Occupational Beryllium Exposure in Primary Aluminium Production

Acknowledgements:

Financial support is gratefully acknowledged from:

Confederation of Norwegian Businessand Industry (NHO)

AMS

Norsk Hydro