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Case 2:13-cv-04762-JTM-ALC Document 1-3 Filed 06/10/13 Page 1 of 6

Case 908-cv-00084-TH

Document 122-8

Filed 05108/09

Page 10 of 56

API TOXiCOLOGICAL

REVIEW

BENZENE

SEPTEMBER

1945

Moat This review swnmauzcs the best available infonnaw

Lion

on the properties

characteristics

and tcSwdogy

of

bnpsene

It offers suggestions

and

tentative neonnnenda

lions

pertaining

examine-
lions and precautionary measures for workers who are ex

treatments medial

to mr4icsl

posed

to beuzene

of Public Htb Boston Mass under

It was prepared at

the Harvard

School

the direction of

Professor hillp Drinker

The review has been accepted

for

publication

by

the Medkai Advisory Committee

of

the

American Petroleum Institute Anyone desiring to submit
or proposed changes for ecosidon
to send

sddithrnai
lion prior to re-issuance of Lids review is requested
theta to the American Petroleum Institute

information

This review was prepared by Marshall Clinton

AMERICAN PETROLEUM INSTITUTE

DEPMmSIU.rr

or SAFElY

30 Wesr SUm Smrtr

NEW Ywot 20

Exhibit B

0001

Case 2:13-cv-04762-JTM-ALC Document 1-3 Filed 06/10/13 Page 2 of 6

Case 908-cv-00084-TH

Document 122-8

Filed 05/08/09

Page 11 of 56

tOXICOLOO3CAI

Brnzzzqz

TOXICOLOGICAL

REVIEW ON DENZENE

Stsbnancc

1enzene

Formulat CH1
$tructural fonmila

vfoleoiJar wdgbtrra78.1

$yaonyrns

benzol

phenc

IL Propcrtts and Ckaracitrisde

Boiling poInt 40.1 deg

176.2

deg

Melting

point

deg

41s deg

Vapor pressure 74.6 mm of

mercury

at 20 deg

68 deg

jjqkldcnsity cnos99gpermilliliteratodcgC

32.dcgp

Specific

gravity

0.8181 at 15 deg

deg

Refractiveindau1.5016

at 20 deg

GB degfl

rug per

liter 313 ppm 100 ppm0319 tug per

l3enzenc

is

dear culotss lipid with

din

actl2istiC

pleasant odor at

low concentrations and

blended

into motor gasolines

Some is used

as

solvent

in commercial

processes

such as the beazene

methyl etbyl4cetone

asuon

used

dewazing process whereas minor
to

in pilot plants and laboratories

solvent or

reagent

purposes

Bxposurc

to beazene

is usually limited

to vapor exposure although

skin

contact may occur

IV TizxicoIogy

Anus Macti

Acute beazene

poisoning generally

results

from

the inhalAtion of

reWively

high concentrations

of

the vapor

bposntc

to air containing bemiene in

concentrations of 19000
mgperliterofak causesdeathwithinafew
minute whereas

concentrations of 7500 ppm 23

ppm 61 to 65

to 20000

mgperiitcr
lhe snasisnuna concentration which can be tolerated

nedangermsstolifelntnlboar

for

hour withceut

serious

disturbances is estimated

at from 3000 to 4700 ppm41D to 15 rag pet liter
MUd

to

exposure

symptoms supervene following
to 3000 ppm

to 10 nag per
several hows Theikint4ng

period of

liter for

of beozene

produces

symptoms similar

to those

following

halation of like amounts of

the substanc4

plus local

evidences

of acute irritation

of

the mouth throat

disagreeable

odor at higher koncentrations

It fonts

1500

4ialy $nflarnrnabk and explosLve.miztuxe with$r
ranging from IA to 6.8 per ant
burns with ye

beazetic by voluint

Pure bcnzene

tzncrnuatiozs

Pt

low luminous smoky

flame

Bentene

Is relatively

insoluble in water

0.08

esophagus and stomach

in lOGin water

at 22 deg

but

is readily miscible

Acute

exposure

to bcnzene

produces

rajMly in

Au

proportions

with alcohol

ether

acetic

acid

creasing symptoms of

tightening

of

leg muscles

ddbivfonn

carbon

sulfrde carbon

tctrathloridc

dizziness excitation

and pallor

followed

by flab-

and sintilar organic

solvents

Commercial

bentene

log weakness

headach breathlessness apprehen

is

practically

utter pure and usually contains vary

rylcuc

phenol

and

tolucne

also

ing 4n000t3 of
carbon

of

disuiSde 0.2 to 1.0 per cent4

traces
tI$cpbene o.i to 0.2 per cent olefios naplithalene
anc similar substances

Chemically benzeoe

is the siniplcst

of

the aromatic

and coristdctiutr

sion of death
pulse becomes rapid and the color bloc Visual dis
are en

weakness

isv

the chest

The

turbances

tremors and muscular
The victim may

lose consciousness

and

coma or may dnelop acute mania and
Death

Convulsions

fairly frequent

are

countered

pass

into

delirhun

hy4rocaxhous

It is relatively

stable but

is capable

may occur almost at once or several

hours

to several

of

variety of substitution

reactions such as cWoritut

days following

exposure.5

tint nitraton sulfonithon

and aBtylation

Recovery

from acute beozene

poisoning

Eequires

is an excellent

solvent

for most organIc

substances

from to

weeks

lxnniediatdy alter

exposure

there

IL Probabic

Sources of Contact

arc temporary

symptoms of

shortness of breath

giddineis

chest

and

bead

pain.
nausea and loss of

$eqzene is used extensively in the petroleum

in

dusgtry 13y far the greatest

amounts of bcztrcnr

are

rm zdcr

io biUaosrn.hr

p.

appetitc

tability

Evidences

of unsteady gait

nervous

iS-

and breathlessness stray persist

or

or

weeks whereas cardiac distress and

peculiar

Case 2:13-cv-04762-JTM-ALC Document 1-3 Filed 06/10/13 Page 3 of 6

Case 908-cv-00084-TH

Document 122-8

Filed 05/08/09

Page 12 of 56

-J

ft

.2

t_.__.

ft_.___J

s__s

_a

L._

s__ __ s.._.

API

tOCtICOJAXflCAL VIEWS

pallor

to the skin may last for as

long as month

proacho within

few minutes

after exposnrc

is

Rtcovcry

from acute poisoning

generally complete

begun and practlcallr

complete

elimination

of hen

ahe

zene

this period although

Sdences

of chronic ben

zenefrorn the blood

occurs within

few minutes after

poisoning may be encountered

later

The acute effects of beozene

exposure

result

from

its

pressaut

action on the central

nervous

systeth

In addition

to its general

rzncotk act benrene

apparently

has

characteristic

neuro-irritant

effect

the

is terminated

exposure

f0fSmthwitht

higher concentrations

and

dlixnlnaticn

axe more

content

and

saturation

Mont the beuzene

absorbed

by tbe.body is

which accounts

for the

bypertonkfty

excitement

and

metabolized

to

variety

of substances

the principal

convulsions

which

arc encountered

Benatne also

oven which

is phenol Minor aznoimts

of pyro

sensitizes

the heart

rnusck

to the action

of epi

catedsol hydroquinone muccinic

acid and similar

instant death

nephrine so that
fibrillation may occur Muscular activity
rate nnd severity of acute

beuzene

due to ventricular

substances

are also produced Whether

the tenticity

increases

the

of heiSt is due to one of these metabolites or to

poisoning

Per

unaltered beraene

is not known

These

substances

sons dying of acne benzene

poisoning generally show

are all tlimintted in the urine alter combination with

absence

of dotting

of

the blood

and

widespread

sulfate

and glycumnic

add

petetbial hemorrhages

in the brain

pleura

Practically

all of

the chronic effects

cardisun urinary tract

intestinal

tract mucous melt

are

result of

the influence

of benrene

-\

of exposure

or its oxida

brasses and skin There axe no

specific

lesions

of

diagnostic import

tion products on the blood-forming

of

reaSons may be encountered

system
and there is littlt

varIety

Skin contact with beenene

results

in defaffing

of

correlation

between the degree

and duration

of

the skin and leads to the

development

of ezytbeina

posuresud the severity

or nature of

the findings in

dry scaling and in some
vesicular papt Prolonged-ezposurrnay produce
lesions resembling first- or second-degree

the formation

burns

cases

of

the blood on microscopic

rnuhination There is no

single change

in the blood or blood4onning organs

which is universally

present

in beazene poisoning.0

The produthoa of

systemic benzene

poisoning

The bone marrow where blood

is fotrncd may be

by skin absorption has received scant attention in the

literature

and definitive

information

on this

is not available.

Skin

absorption is difficult

subject

to dii

ingsiith as jubilation of beuzenc

vapor

would

ac

it and confuse

company
was worn However

the picture

unless

mask

reputable authorities

have stated

vethally that skin

absorption Is extensive and should

be avoided

uoaaht Elan

Ironic beazene poisoning results

from repeated

or continuous

exposure

to

relatively

low conrentra-

tSr of

benzcne

vapor

The

level

and degrec

of

aposure

necessary

to produce

poisoning apparently

vary widely There as? at

lea-u two well authenticated

cases of poisoning
75 ppm yet many dsexnists

by repeated

exposures

of only

repeatedly expose

them

bypoplastk

fairly

normal

in appearance

or byper

plastic

Aboonriat

forms or young cells may abound

and

reasonably well documented

instAnces

of

the

development

of

leukemia as

result of chronic hen

acne

exposure

have

been cited

lieved

that various individuals

It is generally be
in their bone

differ

marrow response

to henzeneSome

showing

no

essential change

some showing decreased cellularity

and others

increased

cellularity

and even

evidences

of malignant changes

Cases with symptoms fairly

soon

after

exposure

usually

have fewer cells

in the

whereas

bone marrow
more apt to have an increased
is believed that

marrow It

cases developitig

later are

number of cells in the

this represents

an nrty

weeding

out of

those who

develop

hypoplastic

changes rather

than

gradual shift

from one

of

typc

selves

to far higher concentrations over periods of

response

to the other

many years with no apparent

01 effects

The findings

on microscopic

examination

of

the

Rename is

relatively

insoluble in body fluids and

blood

are as variable as the bone-snarjoW

response

tissues therefore

only small amounts are absorbed

by

They may consist

of

reduction

in red-cell white

the body Equilibrium between

blood

and air

is ap

cell or platelet

levelsin any two of these or in all

Case 2:13-cv-04762-JTM-ALC Document 1-3 Filed 06/10/13 Page 4 of 6

Case 908-cv-00084-TH

Document 122-5

Filed 05/08/09

Page 13 of 56

Afl 7oX1LOWCAL

$EUZZNE

three

These

thanges

can develop

denly The Mood usually

shows

raduaJ.iy orsuci
moderate Sue

variation

in Individual

susceptlbility

it

is generally

considered

that

the only absolutely safe concentration

don

in red cells below Si million white cells

for bcnzcue

is zero.3

The inadequacy

of

limit of

below 4jOG and
blood

platelets

Examination

of

the

for evidences of Lenient

poisoning

should

i0Opp is indicated by well authenticated
of at

cases of bentene p isdning fotlowing

least

reports

never beluxutcd

to

single determination auth nsa

exposuretoonly75pp

Alimitof5oppmorlets

rid- or white-cell

count but should
plate study of the red wbitc and

consist

of

corn

is

strongly

recommended

particularly

where cx

platelet

fractions

posm are recurrent Slain contact should be avoided

Progressive changes

are of more significance

thai

Uje absolute alteration

Treatment of Bentene Poisnning2

Bensene

is eliminated from the body In

part via

tlelungs and in

part tia the kidneys

Theratfoof

xcwl

to lung wccre4on

is not known

That portion

excreted

in the urine is in combination

with sulfate

ovdth gincutonic add The combination

of beazene

wftb sulfate alters the organic-inorganic

sulfate ratio

sO that

an estimation

of

the ratio of orgar$c

to in

sulfate may provide

of

absorption

of benxene

useful guide
by the body

to the

There is

speculation

in the literature on the oomr

rence of

latent bone-marrow injury due to benzene

wfrjrnut any immedIate

alteration

in blood æadings

followed

by the development

of

obvious

blood

changes

years later under

the stress of

intercurrent

illnesses

or

the general wear and tear of everyday

Ifli Conclusive proof

is lathing but the occuneace

of delayed toxic effects

appears

likely

The iride individual

variation in

susceptibility

to

beuzene

has already beets mentioned

Cestain factors

h4ve

been

noted to influence this to

limited

do

gree Overwcigbt

individuals

are more commonly

nEcctcd but no difference

in

susceptibility

has been

rg$ed

between

young men and womcn.tt.l

low

prptein high-fat

diet

is said to promote the disease
the presence of hang disease bent disease

Whereas
ar liver or kidney

daznsge

are believed to predis

to the conditit

Pregnant

women may be

more prone

to Lenient poisoning than others.tm

Acute

poisoning by bentene

should

be considered

as an node cmexgency

Irons

the contaminated

The victim most be removed

atrssospbem at once and kept

at camp/ne

rest

subsequently

Care roust

be

taken

that

the rescuers are not also

overcome

by the fumes

Frequently

rescuers who ant themselves will sub

sequaty die whereas

the inactive

victim recovers

Artihcial

respiration should be administered if natural

breathing has beers interrupted

and oxygen may be

administered aswellliitii

available Theuseof

adrenin should be avoided

because

of

the danger of

inducing ventricular

fibrillation

There are poorly

substantiated reports of benefit

from the intravenous

injection

of

lecithin but

such measures

should

be

considered with skepticism at present

Inasmuch

as bentene

is excreted

rapidly rio speciflc measures

to promote its removal from the body

are necessary

Chronic

beniene poisoning

is atremely

refractory

to

treatment

PraØtically

all

therapeutic

measures

attempted

have

aBed although

transfusions

arc

at

least

temporarily

useful

in combatting

severe

aueinij

The aaministrafion

of

fairly large doses

of ascorbic add LO0 mg per day may
and should

be carried outP It

is most

be of value

important

however

that

the condition be diagnosed

early

and

the individual withdrawn Irons all contact with the

affecting

agent

for the rest of his life

.3 StIr Quilt

VL Enxuinations

The American Stndards Association Jt and most

The

pre-etriploytnetit

examination

should

indnde

states

have

set

an arbitrary

limit of 100 ppm as

the maximum permissible beniene

concentration for

workers

erposed

to this substance

during an 8-bow

day Massathuseits
limits of
75ppsn whereas New York considers 50 ppras the
highest permissible level

and Oregon have

inasmuch as

the body

set

tie-

vdops no tolerance

to bentenc and as

the e

is wide

detailed history physical

examination

that X-ray

and complete blood count All workers with organic

disease of the heart lungs liver or kidneys

should be

eliminated

us

should

those with toy

history

previous beuzene intoxication

or any evidence

of

of

abnormality

anism.tti

ii

of

the blood

or

blood-clotting

mccli

0004

Case 2:13-cv-04762-JTM-ALC Document 1-3 Filed 06/10/13 Page 5 of 6

Case 908-cv-00084-TH

Document 122-8

Filed 05108109

Page 14 of 56

TOXJCOLocgCAi

REVIEWS

Periodic cxamiuadoos

should

be carried

out

ascorbic acid

vitamin

daily

to

individuals

regularly

their

frepiency

hem3 determined

by the

unavoidably

exposed

to bairenc

vapor might welt

severity of

the

exposure

Individuals

exposed

to cone

be of value

although

it would be diThcult

to prove

ceutsations approachfn8

should

be examined atinontbly

the accepted safe limits
at Least1-

intervals

its effectiveness

or to justify its cost

The concentration of benrene

vapor

in the air

The examination

should

include

brief

interval his

should

be checked

regularly in situations

where cx

tory and physical

inspection

together with

corn

ccssie exposures are apt

to be encountered

.This

plete blood

study including white and differential

can

be done by

counts and an estimation of the platelet

levels

The

of which axe

ratio of inorganic to total urinary sulfates

should

be

acne

is nitrated

variety of methods among the best
the butanone method irs which bent
to form mdtbenzenc which is
wid the aid

estimated cotothnetricatly

determined

in order

to detect

the

ccssive

absorption

and

excretion

of

presence
of bcnaene

Any change

in the blood

picture or the

presence

subsequently

of butarione the ndlinltzoberizene

reduction methodt

of

in which mdlnitrobenzeoe

formed from benzene

Is

an inorganic total sulfate ratio of

cent

is case for withdrawal

less than

50 per
of the worker ftcni any

separated horn nitrating

acids by steam distillation

reduced

by an excess

of standard

titanous

chloride

further exposure4

Due to the delayed

character of

solution and the excess titanous chloride back-titrated

benrene

poisoning

it would

be well

to continue

with

standard

ferric-alum solution

the use of the

perIodic blood

counts

for several months after ex

basic inator which depends

on an indirect

inca

posure las ceased

VII Precautionary Measures

stremeut of the beat produced by oxidation of bennol

and finally

the cotorimetric

determination

of hen-

rent

by oxidation with hydrogen peroxide hi

the

The safety measures

necessary

for the prevention

presence

beazene

poisoning are primarily those designed

to

prcvent

tire Irshalathu of berntne

vapor Ventilation

either by dilution

or local exhaust

should

be so do

cently

duced

than

of

ferrous sulfate solution.t

More re

method has been intro

an absorptiornetric
in England which is said to be more specific
bensen
other methods

In this procedure

signed

as to prevaiL

toxIc concentrations of

the

vapors

from reaching

the breathing zone

of

the

workers All

apparatus

and piping should

be in

spected

rcgnla4y and systematically

for the

presence

of

leaks Workers who must be

exposed

to bcnzene

vapor

should

be

rotated in dada

to reduce

their

exposure

time to miulmonc When excessive con

centrations are unavoidably

encountaed

in opera

tions such

as the cleaning of

tank

cars vats or

storage tanks air masks
The concentration of

should

be employed.3

Ienzen vapor on equipment

previously

exposed

to the liquid should

be reduced

by cleaning

with steam if

possible or by cooling

Apparatus

to be cleaned

in bcnzenc

should

be cold

itt order

to reduce

evaporation

and

stopcocks

or

joints should

be smeared with glycerin which

being

msoluble

in benzene keeps

thean

ajrtight

Skin contact

and

possible dermatitis from

bentrac

should

be 4voidcd

entirely

if possible

but

if the

bands mast contact

the solvent

then neorene gloves

zylen and totuene

vapors

axe absorbed

in

bead

bubbler

charged with

nitration mixture diluted

and .neutraliaed

The nitro derivatives

are extracted

with butanone and the yellow color

imparted

to the

butanone

by the nitro

derivatives

of

toluene

and

zylene is measured The wixture is then made alka
Mn and color
to proceed The
solution is then acidified with disappearance

development

allowed

of

the

blue-green color

due

to xylene

and

toluene but

persistence of

the color due to benzene This color

is then measured

The individual

method chases must depend Qfl

circumstances

The

ndinitrobenzene

reduction

method and

the absoaptiometric

method are accurate

but

rather

cumbersome

The butanone

pn4 oxida

tion in

presence

of hydrogen-peroxide

and icon-salts

methods are simpler and more rapid

but

are

less

accurate

The use of the beazol

indicator is probably

the simplest but the

presence

of other hydrocarbons

will interfere

seriously as they are also oxidized

or protective creams

should

be used

Viii Elbilography

The pmpylactic

administration

100

of

tog

owniog

Toxicity

of

industrial

0005
Organic So

Case 2:13-cv-04762-JTM-ALC Document 1-3 Filed 06/10/13 Page 6 of 6

Case 908-cv-00084-TH

Document 122-8

Filed 05/08/09

Page 15 of 56

-tip

hIS IOXICOLOGXCAl

REVIEWS

vnts 1n1awd4 flt4th Rnt.ntk Board Ripen No
80 London 1937
14

Jacobs The An4yifrd Chm suy

of mdxnri4
MUsh-

Ilaa4 and Son014

Pohogn
en Inc New York 399 1944

Leteacience

Hodgwan

and

It flolipes Rand3ooh

of

Chmhy and bpkr 25th Sn Chemic
Publishing Co flertland

1941

Rnbbcr

Letter

dgted

tuna Humble Oil and Edning Co houston
June 21 1946
IL

Noxion Ctres

and

Haggard

Beradenon

13

16

lndt4ry in New York City

Pdodng
TceeJroI 21 39 1939

Rod Hyg

13

Jeplscott

arid

IL It Bahner

Sulfate

Test

ha the Lupereision

of WOtSS

Udnasy

Exposed

tO Bcsszanc

End .lfyg Tonicol 21 132 1939
14 aasW.P.YdLB.SqersANew

for Ure

3enzce Exposure

4s MW 4uoc 111 849 1936
Pail La benoilsme
129 1Q33

psotasioneL

Pane mid 41

Winslow Summnasy of

the National

Satvtj

Council Study of Beard OIsOaIn

And Ityg

1927

17 ALt Z37.4

TMAmerfran

Standard

caIro/ion

Bnnene/

Amscan

411thc41t Con
Standarda Man

NewYosk 1941

is

Cook Maximum

Ailoinble Concentrations

Industrial Mtnospberic Courasthnants

of
14flG 1945

End Med

19

20

and Pranice

PrinripIn

Wainpler

of lndaturid
Medlrhn1 Williams and Wilkins Co Baltimore 239
1943
Nick

under

tore of Acute Benani Poisoning
Emulsion Kiln Vo-cb t

Vienna

Lecithin

68 1942

21

I.

Goldwater

and It

Following Exposure to Beazene
23217 1941

Tewcsbuq

Eecovemy

7. lad Hg Toxicol

22

Llbowitrity

and IL scrni-d

of Vita

miss

for Workers

Exposed

to Bezszcne

Kiln

Wo.ebsclr

Vienna

53 343 1940

23

ICammer

lsenberg and 14

Supervision

of Benxene.Plant
Aztec 1.11 1452 1Q38

Workrms

Borg Medical
Am Med

24 Ocist/ation

and Hdth

Encyclopedia

Hygiene

and Soda

rd/an international

Pesboiqy
Office Canon 1226 1930
XL MIlton Absozptiocetric Method tot Estimation
of Zylene

in Presence

Beneene

Atmospheric

labor

of

and

23

and

Abe

PrIncifin

Cbcmjc4

`

pf hi/frolics laflianrin

Their
Catdog Co New York 164 1943
J.LSvisbdyLCDunnandW.F.vonOctfingoo
The Acne Toxicity of

Vapors of Certain Soinos
Mnounu

Beuzese

of

Containing

Appreciable

Tolutn
and The Chronic Toxicity

and
lcd hlyg ro4tol 25 366 1943
of Modetge Coocatrz

tiozis of Btnxcne and

Idlxtres

of

flenzne and

Its

for Eats and Dogs 7.2nd Hg Toxitoi

Hoinologuci
26 37 1944
14 Bowditch

and

Ekirn Chronic

to Benrrae-.-I

ToxkoL2i3fl

The industrial MpCCIS
1939

Pxpcsthe
Xci It yg

53 Scbrenk Vt

Yarn

Parc .F

and

It

Sayers Ahsdrptioo

Distribution

Patty

arid

Ei.th on

of Bcsnenc

Dogs Sposed to Benzene Vapor
eel 23 21 1941

by Body Tinner and fluids at
2nd If71 Toni

Ext and

Rhoads

tnt of

ilcuzene

Poisoning

Hanatological

El
hid Hg Toxicot

21 421 1939
11
Major7

ft

GaB and

Bdddcy

Chronic

cal

Itaufts7

Hunter

Exposure to Bewcnc-3fl

The Patbologi
And flyg Toxkoi 21 356 W45
The
Em .FEyg Tezical 21 331 1939

throok Exposure to BeastUt

Clinui4 BErets

Gnznbur

IL Meyers

Goldwater

arid

Smith

Benrene

Poisoning

in

the Rotognnsre

Tulurne

.Urnith

End Jilt

36 1945

000C