Comparison of methods for analyzing occupational monoterpene exposures

C h e m o s p h e r e , Vol.19, N o s . l O / l l , P r i n t e d in Great B r i t a i n

COMPARISON

OF

METHODS

pp 1483-1488,

1989

FOR

OCCUPATIONAL

ANALYZING

0 0 4 5 - 6 5 3 5 / 8 9 $3.00 + P e r g a m o n Press plc

.OO

MONOTERPENE

EXPOSURES

S. K o n t t i n e n ° , P. Kurttio, University 70211

of Kuopio,

Kuopio,

T. R a u n e m a a

Department

and P. K a l l i o k o s k i

of E n v i r o n m e n t a l

Sciences

P.O.Box

6,

Finland.

ABSTRACT

In this s t u d y t w o d i f f e r e n t m e t h o d s of s a m p l i n g and gas c h r o m a t o g r a p h i c (GC) a n a l y s i s for m o n o t e r p e n e s w e r e compared. C h a r c o a l t u b e s were analyzed by GC a f t e r s o l v e n t extraction, and the c o n t e n t s of T e n a x tubes were d e t e r m i n e d by a GC e q u i p p e d w i t h a cold trap injector. B o t h m e t h o d s were t e s t e d f i r s t in the l a b o r a t o r y and then in a p l y w o o d factory. The Tenax c o l d t r a p m e t h o d was f o u n d to be m u c h more s e n s i t i v e t h a n the charcoal method, g i v i n g a b o u t three t i m e s h i g h e r m o n o t e r p e n e c o n c e n t r a t i o n s .

INTRODUCTION

Terpenes heating

evaporate,

and t i m b e r to

be

much

higher wood

irritation,

(4).

drying

fumes

leukemia

cause

levels

the

Finnish

observed

spruce

reported

or b i r c h

decline

of

to

the

also

The

may

cancer

as

The

fumes

allergic

chronic

from

throat products

exposure

as

or

board

reported

oxidation

that

well

been

coughing,

cause

suggest

sawing

particle

(i).

cause

(2,3).

3-carene,

studies

respiratory

terpenes.

both

previous

collected

on

levels

in p l y w o o d

terpene

exposure

are

have

for

mg/m 3 .

below

the

processing

are,

contact to

wood

lymphatic

of

limit

and spruce 1483

to be high

and p l y w o o d

been

below

and H e a l t h which

no

terpenes,

organic when (i).

in

(i).

Administration) mainly

limits

samples

solvents

this

(ii0-

plants

56 mg/m 3

consists

however,

with

detection

birch

have

Safety

studies

extracted

reported

board

turpentine,

There

hygiene

and

been

In p a r t i c l e

(US O c c u p a t i o n a l

industrial

plants

(7).

concentrations

limits

560

charcoal were

sawmills

sawing

and the O S H A

individual

terpene

from

those

during

(plywood,

from pine w o o d h a v e

been

function

in S w e d i s h pine

terpenes,

the

lung

especially

may

occupational

In

have

woods

industry

emissions

emissions

Epidemiological

mg/m 3 ) during

Finland, The

coniferous wood

(5,6).

Monoterpene 340

than

slight

monoterpenes,

eczema

Terpene

processing

and

from

of the m e c h a n i c a l

production).

mechanical

of

especially

operstions

method

for

have

(1,7). was

of the

been Most

applied

1484

Tenax

adsorption

successfully The

followed

used

suitability

measurements field,

MATERIALS

AND

(30

from

and Tenax

injection

terpene

sorbent

therefore compared

methods

workroom

a reaction

min).

humidity

was

were

trap

lower

polymer

terpenes results

simulated

taken

this

cold

much

method

tested

with

to

levels for

in the

those

a

GC

has

in forests industrial

laboratory

of c h a r c o a l

been

(8,9,10). hygiene

and in the

analysis.

METHODS

The c h a r c o a l that

of

of

and the

by

to a n a l y z e

The

was

in

chamber

temperature

about

were

air

first t e s t e d

a

plywood

after

in

its

the

70 % d u r i n g

in a l a b o r a t o r y

mill

(Figure

internal

chamber

i).

conditions

was

22

°C,

experiment

Samples had

and

were

stabilized

the

relative

sampling.

f

i

REACTION CHAMBER ©

©

AIR IN --IG SS TUBE

o /

#,

WOOD CHIPS

---AIR OUT

SAMPLE Figure

i.

Schematic

heated

in

a

into

stainless

a

system.

Air

a portion

The

the

13-28

factory It w a s

Charcoal

method

Monoterpenes

the

Finnish

sampling h. the

in

The

were

was

tube.

tube)

Terpenes and

carried

22

was

(0.15

out

Samples

°C to

into

i/min,

in

were

Terpene

a

were

26

°C,

charcoal

(ii). and

measured

determined

Spruce

Smoke

chips

fumes

m 3 ) equipped

with

were

were

were

led

a mixing

sampled

from

during

the

by

desorbed with

a

from gas

(I00

in

a central

The temperature

relative

humidity

and

50

mg

chromatograph

rate

sampling

analyzing

the

i).

was

had good ventilation.

by gas flow

plant

head-high

(Table

and

tubes

The the

plywood

taken

work p h a s e s

and d e t e r m i n e d

method

0.2

chamber.

(170°C).

that the p l y w o o d mill

sampled

standard

pumps

from

observed

a glass

chamber

four d i f f e r e n t

varied

breakthrough

formamide

and

during

oven

the chamber.

spruce.

%.

charcoal

leaving

of

birch

reaction

the system was 20 i/min.

were

location

the

a moving

reaction

through flow

of

with

measurements

processing

in

diagram tube

steel

flow

of t h e

field

plant

glass

of

time both

charcoal

the was

with

of to

battery-operated either

sections

chromatograph

sections according

5

0.5

h or 1

of charcoal ml

of

in

dimethyl

(Perkin-Elmer,

Sigma

1485

2000) m

equipped

long

with

DP-5

Nitrogen

was

used

(6

and

was

min)

study

the

12-1

samples)

method

Tenax

tube

sampling. of

(mesh

hours.

The

sample

Tenax

before

Samples

were

with

thermal

a

column vm).

was

14

was

then

into was

min

was and

the

detection

as

a gas

a

200

°C i n

column.

charcoal was

tube

0.i

was

a 30-

0.250

240

pm).

was °C.

(0.2

50

°C

In

our

mg/m 3

for

87

ng

of

gas.

carrier a few

ng/sample

1 in

150

tubes

at

least

I/min.

the

was

(Carlo

Erba

The

factory. added

the

substances

was

2150)

(Chrompack)

sample

into

mm, was

pg/m 3

desorbed

FID.

at

The

250

samples

6

of

as

°C/min. 1

°C

trap

instantly

programmed of

The 0.25

cold

terpenes

was

increase for

equipped

a

thickness

trap.

introducing

an

and

film

a cold

temperature

with

(0.i

for

individual

The

seconds,

analysis,

sorbent

to 0 . 3

1.0

tube

with

tube.

0.257

GC-oven

the

methanol)

i.d.

gas

filled

ml/min

i/min

and

in

injector

(30 m,

80

from 0.05

charcoal

were use,

of

chromatograph

The

to

with

6 mm)

laboratory

trap

carrier by

°C/min

Before

breakthrough

cold

temperature

2 ~g/sample

flow

Tenax-filled

Scientific)

used

to

limit

dissolved

for

with

G C R.

helium

the

The

oven 6

o.d.

rate varied

a second

column

thickness

i)

it The

for

all

terpenes.

Calibration

way.

(J&W

analytical

for

measured

of

transferred

heated

the

a

1 in

sampling.

of

to b e

3 mm,

(l-chloro-octane,

desorption

DB-5

rate

Tenax

with

0.7

initial

The

film

simultaneously

i.d.

sorbent

flow

was

analyzed

Helium

for

mm,

°C

(FID).

mm,

measured.

performed

sampling

by means

a

was

250

standard

tube

determined

at

(160

polymer at

The

determined

all m o n o t e r p e n e s

volume

internal

was

detector 0.313

gas.

increased

limit

35/60)

five total

then

tubes

regenerated

i.d.

e carrier

sampling

were

An

as

for

Glass

ionization

Scientific;

detection

Tenax

mg

s flame

(J&W

was in

Because all

performed

methanol of the

these

by applying

on

a

linear

Tenax

a known

tube

response

and

of t h e

amount

of reference

analyzing FID,

the

the

tube

response

compounds

in

the

factor

same

was

one

compounds.

RESULTS

The

terpene

concentrations

of

the

concentrations

of

the

results

was

measured

measured

equal

for

The

highest

total

and

3-carene

concentrations)

peeling

(1.9

respectively), similarly

0.9

and and and

terpene

5.7 the 2.7

with

the

were

average mg/m 3 .

the

the

Tenax

laboratory

levels

mg/m 3 ,

with

the

terpene The

method

and

the

method (Table

plywood

( c o m b i n e d c<-pinene, measured

for

charcoal

main

in t h e

charcoal levels

component

the

the of

i). mill

8-pinene,

plywood and

in

were

plant

the

The

%

ratio

samples.

camphene, during

Tenax

plywood

30-50

log

methods, mill

terpenes

were

w a s c~-

1486

plnene

(Figure

1:2:10:24. were

2.).

With

over

The

the

ratio

of 3-carene:

charcoal

the d e t e c t i o n

method,

camphene:

only ~ -

and

B - p l n e n e : o<-plnene was 8-pinene

concentrations

limit.

Table i. C o m p a r i s o n of l a b o r a t o r y (reaction chamber) and p l y w o o d mill m o n o t e r p e n e c o n c e n t r a t i o n s o b t a i n e d with the c h a r c o a l and T e n a x cold trap methods. M e a n v a l u e s w i t h s t a n d a r d d e v i a t i o n s and n u m b e r of s a m p l e s are shown, n.d. = not d e t e c t e d . Charcoal mg/m ~ mean REACTION

method range

n

Tenax m e t h o d mg/m 3 mean range

0.84 0.29 n.d. n.d.

0.49-1.18 0.24-0.35

2 2 2 2

1.60 0.74 0.12 0.06

1.31-1.88 0.62-0.85 0.08-0.16 0.06-0.07

2 2 2

1.22 0.64 n.d. n.d.

0.93-1.73 0.52-0.81

3 3 3 3

3.84 1.51 0.16 0.19

3.19-5.00 1.22-2.10 0.14-0.19 0.14-0.29

4 4 4 4

0.60 0.24* n.d. n.d.

0.36-0.73 <0.2-0.38

6 6 6 6

1.47 0.65 0.07 0.06

1.07-1.78 0.40-0.84 0.06-0.09 0.04-0.09

3 3 3 3

0.17" n.d n.d. n.d.

<0.2-0.24

2 2 2 2

0.67 0.27 0.03 0.03

0.54-0.96 0.18-0.38 0.02-0.03 0.02-0.04

6 6 6 6

0.64 n.d. n.d. n.d.

0.60-0.68

2 2 2 2

1.03 0.35 0.03 0.03

0.80-1.35 0.27-0.46 0.02-0.04 0.02-0.04

4 4 4 4

limit

have

replaced

by

CHAMBER

O~-pinene B-pinene camphene 3-carene

2

PLYWOOD MILL PEELING

~-pinene B-pinene camphene 3-carene DRYING

~-pinene B-pinene camphene 3-carene SORTING

AND

~-pinene 8-pinene camphene 3-carene

SCARFING

ASSEMBLING

~-pinene 8-pinene camphene 3-carene

"Results under mg/l (12).

the

No b r e a k t h r o u g h

was o b s e r v e d

Tenax

was

average the

highest

with

breakthrough

samples

taken

detection

from the charcoal

camphene

was

7

been

%.

tubes.

(16 %) and lowest No

at the p l y w o o d

breakthrough

mill.

value

of

The b r e a k t h r o u g h

with

from

a

3-carene

Tenax

was

(0 %). measured

0.i

from The in

1487

3

5

10

15

Time (min) Figure

2.

during

the

A

B-pinene,

gas

chromatogram

peeling 4.

of

of

spruce

3-carene,

a Tenax

and

birch

and 5. internal

sample logs.

taken

at

a plywood

i. ~ - p i n e n e ,

2.

factory

camphene,

3.

standard.

DISCUSSION

Reliable toxic

measurement

effects

method

has

and been

measurements

of m o n o t e r p e n e s

reaction

successfully

during

the

frequently

used

woods

Monoterpene

measurement

in

have

been

(i).

cold

trap

The

Tenax

more

sensitive

were

low.

The

when

concentrations

higher

than

those

measurements. relatively sample

volume

be d o u b l e d

The

low

limiting

should

for e a c h

two

the

with

factor

volume.

plywood

wood.

has

the

been

Tenax

the

Tenax

of To

here

method in

avoid safe

the

were

of t e m p e r a t u r e

because

charcoal

terpene

about

method

is,

and

emissions

times

and

field

however,

its

breakthrough

the

volumes

(13).

the

method

three

laboratory

significant sampling

most

spruce.

was more p r e c i s e

and

both

terpene the

and

difficult

of the

charcoal

plant

birch

of

processed

method

The

However,

are

limit

employed

were

1 i. The

°C d e c r e a s e

for

pine

because

compounds.

production

method

woods

important

these

detection

charcoal

be u n d e r i0

of

factories the

analysis

obtained

sampling

such

of

earlier

plywood

under

these

with

used

processing for

concentrations

is e s p e c i a l l y

capabilities

may,

however,

1488

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Kauppinen

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Effects

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R,

chemical

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Exposition

samt m e l l a n

f~r

exposition

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4.

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V,

Kilpi6

nature

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leukemia

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eczematogens

Fredriksson

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Hakulinen

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ET.

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och

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MM,

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f~r

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13.

Nurminen

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12.

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Environ

mellan

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fresh wood,

industry:

Exposition

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JOttner

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ii.

plywood

27 (1979).

oil

TJ,

EI,

wood

a t m o s p h e r e of forest.

17

the

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i0.

Ros~n Occup

samband

Piril~

Persson

exhausts,

Partanen

terpenkomponenter.

9.

in

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B r i t i s h Journal of I n d u s t r i a l M e d i c i n e 45 (1988), 6.

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5.

to

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191-198.

Lindberg

besv~r

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the

mean

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79-90.

(Received in G e r m a n y 22 June 1989; a c c e p t e d 30 July 1989)

vapor

adsorbent