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This report contains the collective views of an in- ternational group of expertsand doesnot necessarily represent the decisions or the stated policy of the United Nations Environment Programme, the Interna- tional Labour Organisation, or the World Health Organization.

Environmental Health Cnteria ll2

TRI.n.BUTYL PHOSPHATE

Publishedunder the joint sponsorshipof the United Nations Environment Programme, the International Labour Organisation, and the World Health Organization

First draft prepared by Dr A. Nakamura, National Institute for Hygienic Sciences,Japan

World Health Organization

Geneva,1991

The

International

Progranne

on

Chemical

Safety

(IPCS)

is

a

joint

venture of the United Nations Environment Programme, the International Labour Organisation, and the World Health Organization. The main objec- tive of the IPCS is to carry out and disseminate evaluations of the effects of chemicals on human health and the quality of the environ- ment. Supporting activities include the development of epidemiological,

experimental laboratory, and risk-assessment methods that could produce internationally comparable results, and the development of manpower in the field of toxicology. Other activities carried out by the IPCS include the development of know-how for coping with chemical accidents, coordination of laboratory testing and epidemiological studies, and

promotion

chemicals.

of research on the mechanisms of the biological action of

WHO Library

Cataloguing in Publication Data

Tri-n-butyl

phosphate.

(Environmental health criteria ; l12)

l. Phosphoric acid esters -

adverse effects

2. Phosphoric acid esters - toxicity

I. Series

rsBN924 r57rr28

rssN0250-863X

(NLM

Classification: QV 627)

@World Health Organization l99l

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or

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The

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Printed in Finland

DHSS-Vammala-5000

GONTENTS

EI.IVIRONIV{ENTAL

EHC 112:Tti-wWI

HEALTH

CRITERIA

FOR

Pmpnate

TRI-r-BUTYL

PHOSPHATE

 

l.

SUMMARY

ll

l.l

ldentity, physical and chemical properties, analytical methods

ll

1.2

Sourcesof human and environmental exposure

ll

1.3

Environmental transport, distribution, and transformation

ll

1.4

Environmental levels and human exposure

t2

1.5

Effects on organismsin the environment

t2

1.6

Kinetics and metabolism

t2

1.7 Effects

on experimental animals and

 

in vitro test systems

 

l3

1.8

Effects on humans

l3

2.

IDENTITY,

PHYSICAL AND CHEMICAL

PROPERTIES,

ANALYTICAL

METHODS

t4

2.1 Identity

l4

2.2 Physicaland chemical properties

l5

2.3 Conversion factor

l6

2.4 Analytical methods

r6

2.4.1 Extraction and concentration

r6

 

2.4.2 Clean-up procedure

l9

2.4.3 Gas chromatographyand massspectrometry

l9

2.4.4 Contamination of analytical reagents

20

2.4.5 Other analytical methods

20

J .

SOURCESOF HUMAN EXPOSURE

AND ENYIRONMENTAL

22

3.1 Production and processes

22

3.2 Uses

22

4. ENVIRONMENTAL

TRANSPORT, DISTRIBUTION,

AND TRANSFORMATION

23

4.1

Transport and transformation in the environment

z)

4.1.1

Releaseto the environment

ZJ

4.1.3

Biodegradation

24

 

4.1.4

Watertreatment

25

4.2

Bioaccumulationand biomagnification

26

5. ENYIRONMENTAL LEYELS AND HUMAN EXPOSURE 27

 

5.1 Environmentallevels

 

J

J

5.1.1 Air

J

J

5.1.2 Water

33

5.1.3 Sediment

33

5.1.4 Fish,shbllfish,andbirds

33

5.2 Generalpopulationexposure

34

5.2.1

Food

34

5.2.2

Drinking-water

35

5,2.3

Humantissues

35

5.3 Occupationalexposure

 

35

6. EFFECTSON ORGANISMSIN THE ENYIRONMENT

36

 

6.1 Unicellular algae, protozoa, and bacteria

36

6.2 Aquatic organisms

 

36

6.3 Plants

40

6.4 Arachnids

 

40

7. KINETICS

AND

METABOLISM

4l

 

7.1 Absorption

 

4l

7.2 Distribution

4l

7.3 Metabolism

42

7.4 Excretion

43

8.

EFFECTS ON EXPERIMENTAL ANIMALS AND IN VITRO TEST SYSTEMS

44

8.1 Single exposure

 

44

8.2 Short-term exposure

45

8.3 Skin and eye irritation;

skin sensitization

47

8.4 Teratogenicity

47

8.5 Mutagenicity and carcinogenicity

47

8.6 Neurotoxicity

 

49

IO. EVALUATION OF HUMAN HEALTH RISKSAND EFFECTSON THE ENVTF.ONMENT

l0.l

Evaluationof humanhealthrisks

l0.l.l

Exposurelevols

10.1.2

Toxic effects

10.2 Evaluationof effectslonthe environment

10.2.1 Exposurelevdls

10.2.2 Toxic effects

I I.

RECOMMENDATIONS

ll.l

Recommendationsfof further research

REFERENCES

RESUME

RESUMEN

EN EL MEDIO

AMBIENTE

RECOMENDACIONES

5l

5l

5l

5r

52

52

53

54

54

55

65

69

72

t 5

77

80

WHO TASK GROUP ON ENYIRONMENTAL HEALTH CRITERIA FOR TRI-N-BUTYL PHOSPHATE

Members

Dr S. Dobson, Institute of Terrestrial Ecology, Monks Wood Experimental Station, Abbots Ripton, Huntingdon, Cambridgeshire,England (Chairman)

Dr S. Fairhurst, Medical Division, Health and Safety Executive, Bootle, Merseyside, England ( Joint Rapporteur )

MsN. Kanoh, Division of Information on Chemical Safety, National Institute of Hygienic Sciences,Setagaya-ku, Tokyo, Japan

Dr A. Nakamura, Division of Medical Devices,National Institute of Hygienic Sciences,Setagaya-ku,Tokyo, Japan

Dr M. Tasheva,Department of Toxicology, Institute of Hygiene and OccupationalHealth, Sofia, Bulgaria

Dr B. Veronesi, Neurotoxicology Division, US Environmental Protection Agency, ResearchTriangle Park, North Carolina, USA

MrW.D. Wagner,Division of StandardsDevelopmentand Technology Transfer, National Institute for Occu- pational Safety and Health, Cincinnati, Ohio, USA

Dr

R. Wallentowicz, ExposureAssessmentApplication Branch, US Environmental Protection Agency, Washington, DC, USA (Joint Rapporteur)

Dr Shen-Zhi Zhang, Beijing Municipal Centre for Hygiene and Epidemic Control, Beijing, China

Observers

Dr M. Beth, Berufsgenossenschaftder ChemischenIndustrie (BG Chemie), Heidelberg, Federal Republic of Germany

EHC 112: Tti-rvb@,

Phosptnb

Dr R. Kleinstiick, Bayer of Germany

Secretariat

Leverkusen, Federal Republic

Dr M. Gilbert, Interna Division of En

I Programmeon Chemical Safety, tal Health, World Health Organiz-

ation, Switzerland ( ary)

NOTE TO READERS

OF THE CRITERIA

DOCUMENTS

Every effort has been made to present information in the criteria documents as accurately as possible without unduly delaying their publication. In the interest of all users of the environmental health criteria documents, readers are kindly requested to communicate any errors

that may have occurred to the Manager of the International Programme on Chemical Safety, World Health Organization, Geneva, Switzerland, in order that they may be included in

corrigenda, which will

appear in subsequentvolumes.

**

be

obtained from the International Register of Potentially

Toxic Chemicals, Palais des Nations, l2ll Geneva 10, Switzerland (TelephoneNo. 7988400or 7985850).

A

detailed

data

profile

and

a

legal

file

can

HIC 112: Tri-nfinyl ntryme

ENYIRONMENTAL

TRI-n-BUTYL

TH CRITERIA

TE

FOR

A WHO TaskGroup

ng on Environmental Health Cri-

teria for Tri-n-butyl

Industrial Biological

Carshalton, United Ki , from 9 to 13 october 1989.Dr

S.D. Gangolli, Director, BIBRA, welcomed the participants

was

held

at

the

British

Research Association (BIBRA),

on behalf of

the meeting on behalf of the three cooperating organiz-

the host

titution

and Dr

M.

Gilbert

opened

ations of the IPcs ( reviewed and revised

an evaluation of the environment from exposu

,

UNEP,

WHO).

The

Task

Group

draft

criteria

document and made

isks

for

human

health

and the

to tri-n-butyl

phosphate.

 

The first

draft

of

th

document was prepared by

Dr

A.

Nakamura. National

I

tute

for

Hygienic

Sciences,

Japan.

Dr

M.

Gilbert

and Dr

.G. Jenkins. both members

of

the

IPCS

Central

Unit,

responsible

for

the

overall

scientific contentand edi

, resPectively.

ABBREYIATIONS

BCF

bioconcentrationfactor

BUN

blood urea nitrogen

EC

effective concentration

FPD

flame photometric detector

GC

gas chromatography

GPC

gel permeation chromatography

HPLC

high performance liquid chromatography

LC

lethal concentration

LD

lethal dose

MS

massspectrometry

NADPH

reduced nicotinamide adeninedinucleotide phosphate

NPD

nitrogen-phosphorussensitivedetector

OPIDN

organophosphate-induceddelayedneuropathy

TAP

trialkyl/aryl phosphate

TBP

tri-n-butyl

phosphate

TCP

tricresyl phosphate

TLC

thin-layer chromatography

TPP

triphenyl phosphate

EHC 112: Tn-n-buty,Ptlns@e

1. SUMMARY

1.1 ldentity, physical and chemical properties, analytical methods

Tri-n-butyl phosphate (TBP) is a non-flammable, non-

explosive, colourless, odourless liquid. However, it is thermally unstable and begins to decomposeat temperatures below its boiling point. By analogy with the known chemi- cal properties of trimethyl phosphate, TBP is thought to hydrolyse readily in either acidic, neutral, or alkaline

solutions.

partition coefficient between octanol and water (log

Po*) is 3.99-4.01.

The analytical method of choice is gas-liquid chroma- tography with a nitrogen-phosphorus sensitive or flame photometric detector. The detection limit in water is about 50 ng/litre. Contamination of analytical reagents with TBP has been frequently reported; therefore, care must be taken in order to obtain reliable data in trace analysisof TBP.

It

behaves as

a

weak

alkylating

agent.

The

1.2 Sourcesof humanandenvironmentalexposure

TBP is manufactured by the reaction of n-butanol with

phosphorus oxychloride. It is used as a solvent for cellu-

lose esters, lacquers, and

plasticizer in the manufacture of plastics and vinyl

resins, as a

formulation of fire-resistant aircraft

and as an antifoaming agent. During

the

ution

primary

natural

as

gums,

a

as

a

metal

of

extractant,

TBP

conventional

an

as

base stock

in

the

hydraulic

fluids,

the

past few

years,

in

the

dissol-

reprocessing

utilization

extractant

nuclear

process in

fuel

has increasedconsiderably.

Exposure of

the general population through normal use

can be regardedas minimal.

1.3 Environmentaltansport,distribution,andtransformation

When used as an

extraction reagent, solvent, or

anti-

foaming

agent, TBP

is

continuously

lost

to

the

air

and

Sunmary

aquatic environment. The biodegradation of TBP is moderate or slow depending on the ratio of TBP to active biomass. It involves stepwise enzymatic hydrolysis to orthophos- phate and n-butanol, which undergoes further degradation. The concentration of TBP in water is not decreased bv standard techniquesfor drinking-water treatment.

Bioconcentration

factors

(BCF)

measured

for

two

species of fish (killifish

and

goldfish)

range

from

6

to

49. The depuration half-life

was 1.25 h.

 

1.4 Erwironmentallevelsandhumanexposure

TBP has been found frequently in air, water, sediment, and aquatic organisms, but levels in environment samples are low. Higher concentrations of TBP have been detected

in air, water, and fish samples collected near paper manu-

facturing

plants in

Japan: 13.4 nglm3 in air; 25 200 ng

per litre

in

river

water;

I l1

nglg

in fish organs. Total

diet-studies in the United Kingdom and the USA indicate averagedaily TBP intakes of approximately 0.02-0.08 t g per kg body weight per day.

1.5 Effectson organismsinthe environment

The inhibitory concentrations(ECo, ECb', EC100)of TBP for the multiplication of unicellular algae, protozoa, and bacteria have been estimated to lie within the range of 3.2-100 mgllitre. The acute toxicity fish (LCso) ranges from 4.2 to l l.8 mg/litre. TBP increases the drying rate of plant leaves, which results in rapid and complete inhi- bition of leaf respiration.

l-G Kineticsand metabolism

In

experimental animals, oral

or

intraperitoneally

in-

jected TBP is readily transformed by the liver, and pre- sumably by the kidney, to yield hydroxylated products as butyl moieties. TBP is excreted mainly as dibutyl hydrogen phosphate, butyl dihydrogen phosphate, and butyl bis- (3-hydroxybutyl) phosphate. Alkyl moieties hydroxylated as alkyl chains are removed and excreted partly as N-acetylalkyl cysteineand partly as carbon dioxide.

EHC 112:ni-rvbdyl Pnarylnte

1-7 Effectson experimentalanimalsandin vito test systems

Oral LDuo values for TBP in mice and reported to range from about I to 3 glkg, tively low acutetoxicity.

rats have been indicating rela-

In

subchronic toxicity

studies with

TBP,

dose-depend-

ent depression of body weight gain and increases in liver,

kidney,

the subchronic studies indicafe that the kidney may be a target organ of TBP.

and

testis weights

were

reported. The

results of

Primary

skin

irritation

caused by

TBP

in

albino

rab-

bits may be as seriousas that causedby morpholine.

TBP

is reported to be slightly teratogenic at high

dose levels. The mutagenicity of TBP has been inadequately

investigated. Negative results have been reported in bac- terial tests and in a recessive lethal mutation test with Drosophila melanogaster.

There are no adequate data to assess the carcino- genicity of TBP, and the effects on reproduction have not been investigated.

The ability of TBP to produce delayed neuropathy has been inadequately investigated. Effects seen following

oral administration of a high dose (0.42 ml/kg per day for

14 days) suggested delayed neuropathy, but no axonal de-

generation was seen and no definite conclusions could be

drawn. This same high dose (0.42 ml/ke

days) caused a significant reduction in conduction vet- ocity of the caudal nerve and morphological alteration of unmyelinated fibres in rats. These results indicate that TBP has a neurotoxic effect on the peripheral nerve.

14

per

day

for

1-8 Effectson humans

In

an

in

ritro

study, TBP has been reported to have a

slight inhibitory effect on human plasmacholinesterase.

There are no case reports of

has

poisoning.

been

observed

in

cases of

delayed neurotoxicity, as

tri-o-cresyl

phosphate

lderw,

P@cal and Chsfical Proryrlies,AnalyticalMe./inods

2. IDENTffY,PHYSICALANDCHEMICALPROPERTIES, ANALYTICALMETHODS

2.1 ldernity

ChemicalStructure:

HsC -(CHz)r

-

O-

o

tl

P

I

o

-

(CH2)s

CHs

O-

Molecular formula: C .",H*TA4P

Relative molecular mass: 266.3

(CHr)s -

CHs

CAS chemical name:Phosphoricacid, tributyl ester

CAS registry number: 126-73-8

RTECS registry number: TC7700000

Synonyms: TBP;

ester

tri-n-butyl

tri-n-butyl

phosphate; phosphoric

acid,

Trade name: Phosflex 4Q Skydrol t O-4@;Celluphos 4Q Disphamol I TBP@

Manufacturers and suppliers (Modern 1975;Parker, 1980;Laham et al., 1984):

Plastics Encyclopedia,

Albright & Wilson Ltd.;

A & K PetroleumInd. Ltd. (Laham et al., 1984);

Ashland Chemical Co.; Bayer AG; Commercial Solvent Corp.; East CoastChemicalsCo.; FMC Corporation; McKesson Chemical Co.;

EHC 112: Tn-*buUI Pharyhate

Mobay Chemical Co.; Mobil Chemical Co.; Monsanto Chemical Co.; Rhone-PoulencCo.; Protex (SA) Stauffer Chemical Co.; Tenneco Organics Daihachi Chemical Ind. Co.; Nippon Chemical Ind. Co. Ltd.

2.2 Physicalandchemicalproperties

The

physical

properties

of

(TBP) are listed in Table l.

tri-n-butyl

phosphate

Table1. Physicalproperties oftri{t-buv phosphate

Physicalstate colourless,odourlessliquid

Meltingpoint ('C)

Boilingpoint("C)

€04

289(with decomp.)b'd;177-178(3.6 kPQo'a;

150(1.33kPa)D

Flashpoint("C)

Relativedensty 0.973{.983(25 'go; 0.978(20

Relractiveindex 1.4226(25'C)b;1.4215(25

Viscosity(cst)

Surfacetension 2gdynes/cm(20

Vapourpressure 66.7kPa(200

'C)

Solubilltyinorganicsolvents misclblewithorganicsolvents

Solubilityinwater(mg/litre)

193b:166P:146d

3.5-12.2Di3.74

'ga

'C)d

'C)

'C)a:973 Pa(150 'C)a

133Pa(100 "C)c;9 Pa(25

1012(4'C\e ; 9.422 125 "67e'

2.85x 10.4(50

.c)e

Octanol-waterpartition coefficient 0og Po*)

4.Od;9.99s;4.01n

a

D

c

o

6

r

s

t

laham etal. (1984)

ModernPlasticsEncyclopedia(1975)

Parker(1980)

Windholz(1983)

Hlgginsetal. (1959)

Saegeretal.(1979)

Sasakietal. (1981)

Kenmotsuetal. (1980b)

TBP is non-flammable and non-explosive. However, it

is thermally unstable and begins to decompose at temper- atures below its boiling point (Paciorex et &1., 1978; Bruneau et al., I98l). The weak bond of the molecule is the C-O bond, and its primary splitting leads to butene and phosphoric acid (Bruneau et al., l98l). With an

excess of oxygen, complete

and water occurs at about 700 'C

combustion to

carbon dioxide

(Bruneau et al., l98l).

HerloTy,Physi@l aN Chsial

Prqertie.s, Amlylial

Metlds

hydrolyse

readily in either acidic, neutral, or alkaline solution,

based on the known chemical properties of trimethyl phosphate(Barnard et al., 196l).

Despite

a

lack

of

data,

TBP

is

thought

to

2.3 Gowersionfactor

Tributyl

phosphate

2.4 Anatyticalmeffiods

I ppm = 10.89 mglms

Analytical methods for determining TBP in air, water, sediment, fish, and biological tissues are summarized in Table 2. The methods of choice are gas chromatography (GC) equipped with a nitrogen-phosphorus sensitive detector (GC/NPD) or flame photometric detector (GCIFPD), and gas chromatography plus massspectrometry (GC/MS). The detec-

tion limit

in water by GC/NPD

or GCIFPD is approximately

50 ngllitre.

TBP

and

other

trialkyl/aryl

phosphates

(TAPs),

.8.,

triphenyl

phosphate (TPP),

trioctyl

phate,

and

tricresyl

phosphate

(TCP),

can

be

phos-

simul-

taneously determined by GC. Thin-layer chromatography (TLC) is sometimes used for determining TBP but is not widely applicable.

2-4-t E

TBP

is

easily

extracted

from

aqueous solution

with

methylene chloride or benzene (Kenmotsu et &1., 1980a;

Kurosaki et al., 1983; Ishikawa

of TBP in water are successfully concentrated on Amberlite

xAD-2

(Hutchins et al., 1983), or a mixed resin of XAD-4 and

XAD-8 (Rossum & Webb, 1978).The purge-trap

charcoal filter for ng/litre levels of TBP was reported by Grob & Grob (1974), but the percentage recovery was not

calculated.

et

al.,

1985). Low

xAD-4

levels

resin

resin

(Lebel

et

al.,

1979, l98l),

method with

TBP may be extracted from

sediment with

polar solvents

such as acetonitrile (Kenmotsu et al., 1980a) or acetone

(Ishikawa et al., 1985).

Acetonitrile and methylene chloride (Kenmotsu et al., 1980a) or acetone-hexane (Lebel & Williams, 1983; EAJ, 1984) have been used for extracting TBP from fish or

EHC 112:Tri-rYAtV Pharylm,te

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EHC 112:Tti-*Wttyt Prps@e

adipose tissues. Gas-phase and particulate TBP in the atmosphere have been simultaneously collected on glycerol- coated Florisil@ columns (Yasuda, 1980).

and

concentrating

1988).The sample was passedthrough the column from which

TBP was eluted with

litre was more than 900/oof the TBP added to the column.

An

octadecyl column

TBP

in

has been used for

extracting

blood

plasma preparations

The recovery of

(Pfeiffer,

50

FE per

chloroform.

2.4-2 CieelrFrygdure

Florisil column chromatography has been used for clean-up (Kenmotsu, et al., 1980a; Lebel & Williams, 1983; EAJ, 1984). This method allows the separation of TBP from

other

phosphate esters, 0.9., TPP,

and

from

organophos-

phorus

pesticides, .8.,

parathion

Sulfur-containing com-

pounds, which often exist in sediment samples and inter- fere with the analysis of TBP by GC/FPD, are easily separ- ated by elution with hexane from the Florisil column. Re- extraction with sulfuric acid from the hexane layer is a useful technique to avoid interference by sulfur-contain- ing compounds (Kenmotsu et al., 1980a). However, it is

difficult to separate TBP from lipids by Florisil column

chromatography because of

(Kenmotsu et al., 1980a). In such cases, gel permeation chromatography (GPC) is useful (where the elution volume varies depending on the type of phosphate ester, i.e. trialkyl, triaryl, or tri(haloalkyl) phosphates) (Lebel & Williams, 1983). Partitioning between acetonitrile and petroleum ether is an effective way of separating TBP from adipose tissue (Kenmotsu et al., 1980a; EAJ, 1984). Actir vated charcoal column chromatography has also been used to separate TBP from co-extractives of sediment samples (Kenmotsuet al., 1980a)

their

similar

polarities

2.4.3 Gas chron atograptryand rms

spxtotnety

To identify TBP in environmental samples by packed column GLC, a comparison of each retention time using two types of liquid phase of different polarity is desirable. As a low polarity liquid phase,3o/oor 100/oOV-l (Kenmotsu et ol., 1980a; Ramsey & Lee, 1980), 2o/o or 3o/oSE-30 (Ramsey& Lee, 1980;EAJ, 1984),2o/oor 30/oOV-17 (Lebel et

Idqtfu, PWel

aN CtlenlcrtlPtWfies,Amlyricrll MMs

ol.,

l98l;

EAJ,

1984), 3% or

7Vo OY-l0l

(Sasaki et

al.,

l98t;

Lebel et al., l98l),

SP-2100(Rossum &

Webb, 1978.),

2VoOY-225 (Yasuda, 1980), 2% DC-200 (EAJ, 1984), aind296

OV-17

used. For

(Bloom,

al.,

Thermon-3000 (Kenmotsu et al., 1980a, 1982) have been

used. When a non-polar

column GC, the reproducibility of the phosphate ester chromatogram is often poor. High loading of the liquid phase generally gives a good reproducibility (Kenmotsu et al., 1980q Nakamura et al., 1980).

5%

plus 2% PZ-179

the higher

(Ishikawa et

liquid

al.,

1985) have been

or 2% QF-l

and

packed

polarity

et

phase, l%

1973; Kurosaki

1983), 5% FFAP,

phase is

used

in

liquid

the

identification

samples. Lebel

used SP-2100 fused silica capillary column (25 m long;

0.22 mm internal diameter) for

water samples. A wide-bore capillary glass column (25 m long) coated with OV-l0l was used by Rogers & Mahood

(1982).

Capillary

column

and

et

GC

has

also

of

been

TBP

in

Hutchins

used

for

determination

al.

environmental

et

al.

(1983)

TBP in

(1981) and

the determination of

Lebel

&

Williams (1983) used GC-MS

for

identifying

TBP.

The

selected ion

monitoring

(SIM)

technique

is

useful

for

the

quantification

of

low

TBP

levels (Lebel

ol.,

l98l;

Lebel

&

Williams,

1983;

Ishikawa

1985).

 

2.4-4 Cm@ntndion

d amlytial

reglg€nts

et

also

et

al.,

The

widespread use of

TBP

in

the plastics and paper

industries may cause contamination of analytical reagents.

Traces of

81., l98l; Karasek et ol., l98l), methylene chloride

(Lebel

(crystalline cellulose) (Kenmotsu et Bl., 1980a). There- fore, care must be taken in order to obtain reliable data in trace analysisof TBP.

TBP have been found

et

81.,

l98l),

in cyclohexane (Bowers et

activated charcoal, and Avicel

2.4.5 Other analytical m&tods

TLC

has been used for

determining TBP. Bloom (1973)

reported good separation of

Ttsp by coupling TLC

with

Komlev

et

al.

(1979)

described

TBP in

waste

water

and

air

an

using

analytical

TLC.

method

Tittarelli

GC.

for

&

EHC112: Tri-tlbuyt P@we

Mascherpa (1981) described a highly specific HPLC detector for TAPs using a graphite furnace atomic absorption spectrometer. In general, TLC and HPLC have not been as widely used as GC. Parker (1980) described the automatic monitoring of air using a flame photometric detector.

futces

d Hmranand Eruironrnenal gryosure

3. SOURCESOFHUMANAND ENVIRONMENTALD(FOSURE

3.1 Productionsandprooesses

TBP does not occur naturally in

the environment. Fig-

ures concerning total world production are not available. In Japan, 230 tonnes were produced in 19844, and 45 tonnes were produced in the USA in 1982 (Schultz et al.,

1984). The

estimated 1985 worldwide

production

capacity

was 2720-4080tonnes per year (US EPA, 1987a).

by

chloride with n-butanol (Windholz, 1983).

TBP

is

prepared

the

reaction

of

phosphorus oxy*

3-2 Uses

TBP

is

used

as

a

solvent

for

cellulose

esters,

lacquers, and natural gums, as a primary plasticizer in the manufacture of plastics and vinyl resins, and as an antifoam agent (Sandmeyer& Kirwin, l98l; Windholz, 1983). In recent years, there has been a considerable increase in the use of TBP as an extractant in the dissolution process in conventional nuclear fuel processing (Parker, 1980;

Laham

preparation

acid method) (Davister & Peeterbroeck, 1982). Some 400/o

to 60% of

as

aircraft hydraulic fluids (US EPA, 1985). In Japan, 140 tonnes was used in 1984 as an antifoaming agent (mainly in paper manufacturing plants), 40 tonnes as a metal extract- ant, and 50 tonnes for miscellaneous purposesa. TBP is

also used as a constituent of cotton defoliants, which act by producing ieaf scorching (Harris & May-Brown, 1976).

et

al.,

of

all

1984; schultz

purified

et

al.,

1984)

(wet

and

in

the

phosphoric

acid

phosphoric

TBP consumed (probably in the USA) is used

stock

in

the

formulation

of

fire-resistant

a

base

a Personalcommunicationto IPCSfromtheAssociationofthe PlasticizerIndustry ot Japan (1985)

EHC 112: Tti-tvtrtilyl Phoqphafe

4. E]WIRONMENTAL TRANSPORT, DISTRIBUTION, AND TRANSFORMATION

Surnntary

TBP has been found widely in environmentalmqdia (air, water, sediment, and biological tissues) but usually at low concentrations.Sources of TBP in the environment include leakage from sftes of production and use (e.g., aircraft trydraulicfluids) and releasefrom plasticsor other products. No figures on the amounts releasedinto the environmentare available.

Once in the environment,it appears that the majority of

TBP finds its way to sediments. Biodegradationin water is

dependenton water quality (1 mg/itre

in River Mr.ssisslppiwater). Lifle or no

in sterile river water or natural sea water. The degradation

pathwaymostprobablyinvolvesstepwiseenzryatic frydrolysis.

was degraded in 7 days

degradation occurs

tn drinking-water treatment, TBP levels do

not decrease

unless powdered activated carbon is used, when very effective

adsorptionoccurs (9F100o/oat a TBPconcentrationof 0.1 g per litre).

The bioaccumulationpotential for TBP in killffish and goldfish is low, the bioconcentrationfactor ranging from 6 to 49. Depurationis rapid (half-lite,1.25h).

fate of TBP in air, but this

does not appear to be an area of concern. ln addition, there areno dataon transportto groundwater.

There is no informationon the

4.1 Transport and transformation in the environment

4.1.1 Relegiseto lheerwironmerfi

A major potential pathway of

entry of TBP into the

environmentis by leakagefrom sitesof production or use,

and leaching from

landfill sites or

aquatic environments.TBP has been foqnd widely in air,

water, sediment, fish, and several biota, but low concentrations.

usually at

plastics disposedin

Envirwnwtul 7anWt

Disribtfron,and Tran$ffiim

Extraction reagents and solvents are continuously lost from solverit extraction processes and may be transferred to aquatic environments. Ashbrook (1973), Ritcey et al. (1974), and Ashbrook et al. (1979) estimated the losses from solvent extraction plants. When recycled acid is used in the dissolution process in a conventional nuclear fuel reprocessing plant, TBP and its phosphate derivatives build up to a level where low concentrations of organo- phosphate vapour are released to the off-gas stream (Parker, 1980). However, no data on TBP levels in air at these plants are available.

TBP used in antifoaming agents may be lost from manu- facturing plants into the environment, but the resultant amounts in the environment have not been measured. High concentrations of TBP have been detected in river water (7.61-25.2 1tg/litre), fish (4.2-ll1.0 nglg), and air over the sea (13.4 nglm3) sampled near Kawanoe City, Japan, where there are many paper manufacturing sites (Yasuda, 1980:Tatsukawaet al., 1975)(Table 5).

4-1-2 Fatein watq aN

sd,imert

in

than I g/litre at ambient temperatures (Table l). Monitor-

ing

and sediment (Suffet et ol.,

Williams & Lebel, l98l; Shinohara et al., l98l; Williams et &1., 1982; Ellis et rl., 1982; Kurosaki et &1., 1983). The difference in TBP concentrations between water and sediment was estimated to be about 3 orders of magnitude (river water, 20-l l0 ng/litre; river sediment, 8-130 nglg; sea water, 6-150 ngllitre; sea sediment, 2-24Q ng/g) (EAJ, l978a,b). The concentration factor of TBP on marine sedi- ment was reported to be 4.3 (Kenmotsu et al., 1980b).

water is considerably less

The

solubility

of

TBP

that

studies have shown

it

is

widely

present in

et

water

1980; Hattori

&1., l98l;

4.1-3 Elidqrdatiott

The

biodegradation

of

TBP

in

river

water

is

slower

than that of triphenyl phosphate and may depend to a con- siderable extent on water quality. Hattori et al. (1981) reported that I mg/litre completely disappeared in 6 days

in Oh River water, Osaka, Japan, after a two-day lag period. Howevere at an initial TBP concentration of 20 mg

EHC 112: Tthll'Ouyt Ptnffie

per litre, only 21.9% was biodegraded in Oh.River water after 14 days (Hattori et al., l98l). In Neya River water, Osaka, Japan, degradation started at 6 days and was com- plete after 9 days. In River Mississippi water (St. Louis waterfront, USA), degradation of TBP (l mgllitre) started

within 7 days (Saeger et

al., 1979). No degradation was observed in sterile river

after 2 days and was complete

water (Saeger et dl., 1979; Hattori

et

Bl.,

l98l)

or in

clear non-sterile sea water after l5

days (Hattori

et al.,

l98l). Primary biodegradation rates from semicontinuous

activated sludge studies (US $ap and Detergent Assoc.,

?1., 1969) generally showed the same

trend in degradation rates as river die-away studies. TBP degradation was 96% complete at a 3-mg per litre, 24-h

feed

feed level (Saeger et al., 1979). The ultimate biodegrad- ability of the phosphate esters was measured by Saeger et

al. (1979) using the apparatus and procedure developed by Thompson & Duthie (1968) and modified by Sturm (19731. Two widely different results were obtained for the degra- dation TBP (20 mgllitre): 3.3% and 90.8% of the theoreti- cal carbon dioxide evolution were measured in two exper-

iments. Such differences are probably due to variations in the composite seed used in the two tests. A difference in the ratio of TBP to active biomass may have resulted in

inhibition

case but not in the second

(Saeger, et al., 1979).

The degradation pathway for stepwise enzymatic hydrolysis to

cohol moieties (Pickard, et al., 1975). The alcohol would

then be expectedto undergo further degradation.

1965; Mausner et

level, but only 56% (x 2lo/o) at a l3-mg/litre, 24-h

in

the

first

TBP most likely

involves

al-

orthophosphate and

4-'l-4 Watert&nent

Fukushimaand Kawai (1986)reported that 0.105-21.2

(geometric mean: 0.543 pg/litre)

reduced

to

0.018-3.80

1tg/litre

ttg

TBP/litre

was

0.156 p,g/litre) by conventional wastewater treatment.

Piet et al. (1981) investigated the behaviour of or- ganic compounds in dune infiltration: no change of concen- tration of TBP was observed. Sheldon & Hites (1979) re- ported that a TBP level of 400 ngllitre was not decreased by standard techniques for drinking-water treatment.

in untreated water

(geometric mean:

Erruironmenhl TranWG

Disffbutiol,

and Truts/ionnaitiot

However, TBP is effectively adsorbed to powdered activated carbon (90-100% at a TBP concentration of 0.1 g/litre). The adsorption coefficient (Freundlich equation) obtained from an experiment using 0.01 to l0 mg TBP/litre at 25 "C was 190 (Ishikawa et al., 1985).

4.2 Bioaccumulationandbiomagniftcation

Data reported on the bioaccumulation and depuration of TBP in killifish and goldfish are given in Table 3. No data for other fish species are available. Calculations of bioconcentration factors (BCF) for other species have been made on the basis of physico-chemical properties (Sasaki et al., 1981, 1982). However, these must be con- sidered less reliable than the low values actually measuredin killifish and goldfish.

TaUs 3. Bioaccumulationard dearancoof TBPby fish

Specles

Temp.

fc)

Killifish

25

(Oryzlas

,atipes)

25

Goldtish

25

(Caiassrlrs

auftltrrs)

no{/

Bloconcen-

E)eosure

Oopuration

$at

tratlon

oonc.

halllile

Reference

tactort

(r€/itrd

(h)

etat

11-49

0.2{.06

Sasakl€tal. (1982)

f,ow

16-27

0.84{.1

slat

30-35

3'{

Sasakletal. (1981)

stat

elt

34

Sasaklst al. (1982)

a

DetermlnedbyGGFPD

EHC 112: Tti-tubuty, Pt'Alpl'E,te

5. ENVIRONMENTAL LEVELS AND HUMAN D(POSURE

Summary

TBP has been found frequently in environmentalsarnp/es (air, water, sediment,and fish) but usually at low levels. Measuredambientair concentratlonsrange trom non-detectable to 41.4 ng/m3; the higher levels occurring near manutacturing sifes. Sudace water levels up to 25 200 ng/itre have been reported, but no groundwater sampling data are available. Levelsin sedimentrangefrom1to 350ng/g.

TBP /evels in

biological

samples, including

fish and

shellfish,of up to 111ng/g have been measured./t has a/so

beendetectedin blrd populations.

Human adipose tissues obtained from the

autopsy of

individualswith no known occupationalexposureto TBP showed onepositivesample(9.0ng TBP/g)outof 16.

Exposureof the general population can occur by several

routes, including the ingestion of

shellfish, and other

fourtd average

(levels up

foodstu,Ts. US FDA total-diet studies

intake levelsof 38.9,27.7,and 2.7-6.2ng/kg body weightper

daytor lntants,toddlers,and adults,respectively.

contaminateddrinking-water

have

to

29.5ng/litre), fish and

Occupationalexposurecan occur in severalindustries,and

especlallywhere aircraft malntenanceworkers handle trydraulic

fluids.

production is

because the various processes have been automated to a considerableesient.

Exposureduring the synthesrisof TBP and in plastics

unlikely if protective measuresare taken aN

Although productionamountsare lower than for other

triaryl/alkyl phosphates,TBP has been found frequently

environmentalsamples(water, sediment,and fish), whereas other triaryl/alkyl phosphatesoccur more rarely. However,

the measuredconcentrationsare usuallv low. These are listedin Tables4-6.

,in

EwironrnenblLeuelsandHurmnfryosre

o

a

o

!

o

o

o

z

=

o

E

o

;

o

-

o

o

G

F

o

o

E

o

E

a

o

U)

9 o

3g

g E

= 5

6

9

-@G

> F

.

:

E

:'

-

{

cj

o

F

6

F

o