Professional Documents
Culture Documents
NOTICE: The project that is the subject of this report was approved
by the Governing Board of the National Research Council, whose members
are drawn from the councils of the National Academy of Sciences, the
National Academy of Engineering, and the Institute of Medicine. The
members of the Committee responsible for the report were chosen for
their special competences and with regard for appropriate balance.
This report has been reviewed by a group other than the authors
according to procedures approved by a Report Review Committee
consisting of members of the National Academy of Sciences, the
National Academy of Engineering, and the Institute of Medicine.
Available from:
NATIONAL ACADEMY PRESS
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t_ ,?
^
*
Printed in the United States of America
V
COMMITTEE ON ALDEHYDES
*Early in the preparation of this report, Dr. Liu was with SRI
International, Menlo Park, California.
111
BOARD ON TOXICOLOGY AND ENVIRONMENTAL HEALTH HAZARDS
IV
ACKNOWLEDGMENTS
v
Dr. Eric R. Allen, Atmospnenc Sciences Research Center,
State University of New York, Albany, New York
Mr. Douglas Anthon, Lawrence-Berkeley Laboratory, University
of California, Berkeley, California
Dr. Charlotte Auerbach, University of Edinburgh, Edinburgh,
Scotland
Mr. W. L. Benning, Manufactured Housing Institute, Arlington,
Virginia
Mr. Charles A. Campbell, Aerolite SPE Corporation, Florence,
Kentucky
Dr. T. Cooke, Textile Research Institute, Princeton, New
Jersey
Mr. Maynard Curry, U.S. Department of Housing and Urban
Development, Washington, D.C.
Dr. John W. Drake, National Institute of Environmental Health
Sciences, Research Triangle Park, North Carolina
Dr. Julius Fabricant, New York State College of Veterinary
Medicine, Ithaca, New York
Ms. Mary Leah Fanning, Lawrence-Berkeley Laboratory,
University of California, Berkeley, California
Mr. Robert B. Faoro, U.S. Environmental Protection Agency,
Research Triangle Park, North Carolina
Mr. R. David Flesh, Del Green Associates, Foster City,
California
Dr. Alfred L. Frechette, Massachusetts State
Department of
Public Health, Boston, Massachusetts
Dr. A. Myrick Freeman II, Department of Economics, Bowdoin
College, Brunswick, Maine
Mr. Ernest Freeman, Department of
Energy, Washington, D.C.
Dr. Thomas E. Graedel, Bell
Laboratories, Murray Hill, New
Jersey
Mr. Serge Gratch, Ford Motor
Company, Dearborn, Michigan
Mr. William Groah, Hardwood
Plywood Manufacturers
Association, Arlington, Virginia
Dr. Daniel Grosjean, Environmental Research and
Technology,
Inc., West Lake Village, California
Mr. Jan Heuss, General Motors Research
Laboratory, Warren,
Michigan
Mr. Richard C. Holmquist, American
Mining Congress,
Washington, D.C.
Dr. Nelson S. irey, Armed Forces
Institute of Pathology.
Washington, D.C.
Dr. Howard Johnson, SRI
International, Menlo Park, California
VI
Dr. Geoffrey Meadows, E. I. du Pont de Nemours and Company,
Wilmington, Delaware
Mr. Andrew Micula, New Jersey Department of Environment
Protection, Trenton, New Jersey
Dr. Dominick J. Mormile, Consolidated Edison, New York, New
York
Mr. Charles Morschauset, National Particle Board Association,
Silver Spring, Maryland
Dr. Demetrios J. Moschandreas, GEOMET Technologies, Inc.,
Gaithersburg, Maryland
Mr. John F. Murray, Formaldehyde Institute, Scarsdale, New
York
Ms. Laura A. Oatman, Minnesota Department of Health,
Minneapolis, Minnesota
Mr. Edward Owens, Aberdeen Proving Grounds, Maryland
Mr. James Paine, Texas Air Control Board, Austin, Texas
Dr. G. J. Piet, National Institute for Water Supply,
Voorburg, The Netherlands
Dr. James M. Ramey, Celanese Corporation, New York, New York
Dr. Yuko Sasaki, Tokyo Metropolitan Research Institute for
Environmental Protection, Tokyo, Japan
Dr. Eugene N. Skiest, Borden, Inc., Columbus, Ohio
Dr. Ronald J. Spanggord, SRI International, Menlo Park,
California
Dr. Karl J. Springer, Southwest Research Institute,
San Antonio, Texas
Dr. Edgar R. Stevens, California Statewide Air Pollution
Research Center, Riverside, California
Mr. William Stockwell, Department of Chemistry, Ohio State
University, Columbus, Ohio
Mr. John G. Tritsch, American Textile Manufacturers
Institute, Washington, D.C.
Dr. Michael P. Walsh, U.S. Environmental Protection Agency,
Washington, D.C.
Mr. Frank Walter, Manufactured Housing Institute,
Arlington, Virginia
Mr. Ralph C. Wands, Mitre Corporation, McLean, Virginia
Dr. Jonas Weiss, CIBA-GEIGY Corporation, Ardsley, New York
Dr. Rather me W. Wilson, Pacific Environmental Services,
Santa Monica, California
Ms. Mary Ann Woodbury, Wisconsin State Department of Health
and Social Services, Madison, Wisconsin
VI 1
CONTENTS
1 Introduction 1
2 Summary 3
3 Recommendations 11
ix
CHAPTER 1
INTRODUCTION
SUMMARY
RECOMMENDATIONS
11
12
R-C-H
MONOMERIC FORMALDEHYDE
20
21
H
=
>
H
TRIOXANE
CH 2 CH 2
PARAFORMALDEHYDE
FORMALIN
2HCHO + CH 3 OH + CO (1)
Cannizzaro Reaction
H 2 + HCHO(aq) + CH 3 OH
Tischenko Reaction
Polymerization Reactions
is often not clear which is followed, and both may play a part in some
instances. Recent evidence indicates that the formation of
urea- formaldehyde resins, which used to be regarded as a simple
polycondensation of methylol ureas, may actually involve the primary
formation of a methylene urea that then polymerizes to give a cyclic
trimethylenetriamine whose methylol derivatives are finally
cross-linked by condensation.
Thermoplastic resins are the result of simple linear
condensations, whereas the production of thermosetting resins involves
the formation of methylene cross-linkage between linear chains. Both
types may be produced from the same raw materials by variations in the
relative amounts of formaldehyde used, the conditions of catalysts,
and the temperature. However, with compounds whose molecules present
only two reactive hydrogen atoms, only thermoplastic resins can be
obtained.
A diverse group of organic compounds including alcohols, amines,
amides, proteins, phenols, and hydrocarbons form resins with
formaldehyde.
FORMALDEHYDE
Production
Ag
Mo,Fe
OXlde
CH 3 OH + 2
^ HCHO + H 2
The capital costs of the silver-catalyst process are higher, but its
operating costs are lower. The ratio of formaldehyde to methanol in
26
Uses
2 *
Major uses for formaldehyde have been reported elsewhere.
9
ACETALDEHYDE (CH-jCHO)
Production
C 2 H4 + 0.502 + CH 3 CHO
Almost all the ethylene reacts in a single pass through the reactor in
the two-step version; hence, recovery and recycling of ethylene are
not critical as a rule.
In both versions of the process, acetaldehyde is separated from
the exit gas stream from the reactor by water absorption, and an
aqueous solution of acetaldehyde is produced. Unreacted ethylene, if
any, is recycled to the reactor. There is always a need for a vent
stream, to remove chlorinated byproducts. This vent stream contains
some ethylene and low amounts of acetaldehyde; the exact
concentrations of these materials in the vent stream apparently have
never been reported for any specific industrial plant. If necessary,
however, an absorber could be designed and operated to remove
essentially all acetaldehyde from the vent stream. To prevent most of
the combustible hydrocarbons, including acetaldehyde, from escaping to
the surroundings, it is generally more economical to send the vent
stream to a flare or to the furnace. In the one-step process, the
vent stream has a substantial fuel value.
Before development of the Wacker technology, the following two
processes were of major importance:
Hydration of acetylene. This process was commercialized in
Germany during World War I. Several modifications have been reported,
but the process has not been competitive with the Wacker-Hoechst
process, because of the relatively high price of acetylene, compared
with ethylene.
Dehydrogenation of ethanol. In many respects, this process
is similar to the one for production of formaldehyde from methanol.
To make its use feasible in the future, the required ethanol reactant
must be available at a much lower cost than ethylene.
Although these two process are still used to a limited extent, it
is unlikely that they will be used in any new plants in the near
future.
In transporting or storing acetaldehyde, extensive precautions
must be taken to prevent leaks and ensure safe conditions, because
this aldehyde boils at room temperature. When mixed with air, it is
highly flammable and reacts to form acetic acid, highly explosive
peroxides, and other products. It is transported in drums or
insulated trucks or tank cars. Specific information was not found on
acetaldehyde concentrations in the atmosphere in or near acetaldehyde
plants.
28
Uses
Production
Uses
Production
CH 2 =CH 2 + CO + H 2 -
CH 3 CH 2 CHO
Uses
BENZALDEHYDE (C 6 H 5 CHO)
Uses
FURFURAL
EC' ^C-CHO
II II
HC CH
Production
FORMALDEHYDE RESINS
H-N-H H-N-CH 2 OH
C= +HCHO -- C=
I I
H-N-H H-N-H
urea
C= *- C= O C=O + H2
H-N-H H-N-H H-N-H
32
Eventually:
r~ -~
H-N-CH 2 OH H N-CH2 OH
C= *- C= +
n (n-l)H 2
H-N-H H-i-H
REFERENCES
36
37
URBAN ATMOSPHERES
30
r
20-
10-
1 i i
\n
6
10 10 7 10
8
lfl9 ifllO
LOCAL TIME
60-
o 40 - HCHO
I
CJ
I
I
o 20 -
o
o
12
WORKDAY
a 10-
Z ^
O
SUNDAY
] I
12 16 20 24
HOUR OF DAY
C T) fl
3 a,
H Q 4J 0) 4J O 3
42 CO -H H
4J 4J Q 43 S
?>
&
cu
c2
cu >
o
;
r **
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x co H w o
J-J
0)
CO
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U
f3
O >
'H<
cU
ON
CN
III
II I
QJ Qu rH
tO
QJ
S
4J
CO
o
o <!
>>H BUM m o -a
,3^-1
(DO
MC(3
OOcd o
|
rH
I
o
^
I II!
i i i
>, .
4J U
$ s -g 5
W ool MD-OrH-H?
,
TI in co
agucoo
-HtocirJC
43CU r-iCOOH-HO
fXM
O.eO
oo
CO
oo
CM
34JbpU>Hu
-d 43 -rf
M M iM O
QJ-QJ O 00
H
<U-*iHOOa
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Tjt2> CO rH
>,O<3
O-HM-HO*
COcfl>4-lUO>>
4JCO>4J
o o
COO 60 CO
4Ja a H
O O cd o m
EH O M CO
IJ-J
c i-i co a i-i o
i fl tfl 4J
42 OJ (U M C
o
-
QJ O<
M CD
^
^ 5 S a S>
CUediHrHO<;
U 4J
4J J-l H
O rt tU 3 M-i H
O T3 T3 CQ O
CO H
tn m
CM
i
CM
CM
CO
CM 0) QJ
CO
4-1 4J
4J
CO
4J
(2
TJ T3 4J fl TJ O
00 00 QJ >^ CO T3 O O
p> 43 TJ S CO
H O C
O H
Q) -H CO fl
cu rH 00 i-l 00
vO
-d- m rH 43 rH
QJ X O
Q)
vO r*. OJ (0
4-1
co CTi o\ Q < > O H 4J
a
43
44
>r impurity derived from the Bay town industry, to aldehydes through
jspheric reactions.
In 1973, the aldehyde concentrations in the Deer Park area of
ston were very high rather consistently aoove those in any
ghboring areas. There are several major refineries and
cochemical plants in this area. In 1974 and in 1975, aldehyde
centrations in Deer Park were similar to those in the remainder of
Houston area. The reason for the large reduction in 1974 and 1975
unknown .
Aldehyde concentrations at or near Houston's and Cincinnati's
or airports were similar to those in neighboring areas,
'sumably, airports and planes contribute only a small fraction of
>
direct emission of aldehyde in metropolitan areas.
It is clear that transport of the air masses, the height of the
:ing layer, and other meteorologic factors can be important in
:ermining ambient aldehyde concentrations.
3 WORKPLACE
TABLE 5-2
Concentration, ppm
Sampling Site Range Mean Method of Analysis
TABLE 5-3
Concentration, ppm
Sampling Site Range Mean Method of Analysis
8 1.8 (peak)
Danish residences Unspecified
a
Formaldehyde, unless otherwise indicated.
b Total
aliphatic aldehydes.
rH
cd
t-l
O
O
H
'
Pi
H
O
H
4-1
H
O
in
g
t-
c=
49
50
TABLE 5-4
a
Reprinted from Moschandreas et al.
5-16
52
Outdoor
C a - HCHO-
93 B Indoor-
HCHO
5 - Outdoor
g ^
!
aldehydes ! Wndoor
I
f aldehydes
Si ru~ _n
ro 240
Concentration
to
4= 4=
>f O ON
co
r-
ex cu CM
H T3
< < >-?
r-.
O
rH CO
+ 1 + 1 + 1
+ 1
o en
CM
o
20
CO E CM
V-i bQ
O 3,
r
T| x^
g,
m C.
S B
(U
m
I
W
CO -H
E-
co
4J
C
M-l CU
B
CU
CU 3
43 CO
1 CO
cu
4-1
4=
4J
H
4-1 " C
^ Lj
CU 4-> CU 3
H 3 tH *4-l T3
CX CU CU
5 3 4= H H
U 4- O 4J CX ex
O H O -H
o O 3 3 o
o
C3
o oo
53
54
Although use of the Danish studies may not be appropriate for U.S.
9
homes, the treatment of Andersen ejt al_. illustrates the many
variables with which one must oe concerned. He formulated a
mathematical model that estimates the indoor air concentration of
9
formaldehyde. In climate-chamber experiments, Andersen et al.
found the equilibrium concentration of formaldehyde from particleboard
to be related to temperature, water-vapor concentration in the air,
ventilation, and the amount of particleboard present. From this work,
a mathematical model was established for room air concentration of
formaldehyde.
When the mathematical formulation was applied to the room-sampling
results, a correlation coefficient of 0.33 was found between the
observed and predicted concentration not a particularly good
predictive ability. The authors then modified the value for the
adjustable constants by calculating them for each room on the basis of
monitoring results. The modified values led to a correlation
coefficient of 0.88 a considerable improvement in predictability.
Formaldehyde release from interior particleboard occurs at a
decreasing rate with an increase in product age. Eventually, the rate
of formaldehyde evolution decreases to an imperceptible point. The
length of time necessary for the phenomenon to occur (several years)
depends on the atmospheric conditions to which the board has been
subjected, as well as the degree of cure of the resin. The more
unstable groups degrade first, and then the more stable free methylol
lo l
groups.
Field tests and a mathematical model were used in 1977 to
determine the half-life of formaldehyde in particleboard typically
used in Scandinavian home construction; it was about 2 yr when the
ventilation rate in the home was 0.3 ach (C.D. Hollowell, personal
communication). Suta 171 has analyzed the effect of home age on
*
cities (L. Hanrahan, personal communication), and less than 0.03 ppm
in Raleigh, North Carolina, and Pasadena, California. 79
Formaldehyde concentrations at four Swiss locations ranged from 0.007
to 0.014 ppm; these concentrations are about one-fifth the
corresponding indoor Swiss concentration. 189 In 1951, a mean value
of 0.004 ppm was reported for mainland Europe. 3**
TABLE 5-6
Concentration,
Aldehyde Body of Water and Location
c
Mesitaldehyde Holston River, Kingsport, Tenn. 3
59a
2-Methylpropionaldehyde Delaware River, Torresdale, Pa. 1
62 NR
Paraldehyde Lake Zurich, Switzerland
62
Vanillin Lake Superior, Ontario, Canada NR
1
NR, not reported.
3
G. J. Piet, personal communication.
TABLE 5-7
Concentration,
Aldehyde Location of Water Plant
47 NR
Acetaldehyde Cincinnati, Ohio
Miami, Fla. NR
Ottumwa, Iowa NR
100 0.1
Philadelphia, Pa,
Seattle, Wash. 0.1
126 NR
Durham, No. Car.
100
Chloral Cincinnati, Ohio 2
Grand Forks, No. Dak. 100 0.01
100
Philadelphia, Pa. 5
10 3.5
Seattle, Wash. ?
New York, N.Y. 100 0.02
100
Terrebonne Parish, 1
Kansas City, Kans. NR
158 NR
Crotonaldehyde Unspecified
Concentration
Aldehyde Location of Water Plant
.47
I sovaler aldehyde Cincinnati, Ohio NR
47 NR
Miami, Fla.
Ottumwa, Iowa NR
47
Philadelphia, Pa, NR
47
Seattle, Wash. NR
47
Durham, No. Car. NR
New Orleans, La. 184 NR
158 NR
Methacrolein Unspecified
47
2-Methylpropionaldehyde Cincinnati, Ohio NR
47
Miami, Fla. NR
Ottumwa, Iowa NR
47
Philadelphia, Pa NR
47
Seattle, Wash. NR
126
Durham, No. Car. NR
100
3-Methylvaleraldehyde Ottumwa, Iowa 1
.47 NR
Propionaldehyde Cincinnati, Ohio
47
Miami, Fla. NR
Ottumwa, Iowa NR
47
Philadelphia, NR
Seattle, Wash. NR
126 NR
Durham, No. Car.
100 0.5
Valeraldehyde Ottumwa, Iowa
INDUSTRIAL OPERATIONS
The vent stream from the water absorber used for the recove
of formaldehyde and methanol usually contains carbon dioxide, carbon
monoxide, hydrogen, water vapor, nitrogen (if air is used), and trac
amounts of formaldehyde, methanol, and some byproducts. The absorbe
can be built and operated to recover formaldehyde so effectively tha
the exit gas stream is sometimes exhausted directly into the
atmosphere. Other formaldehyde producers use slightly less efficien
and cheaper absorbers with lower operating costs and use the exhaust
streams as supplemental fuel in the furnaces of their power stations
because the streams often have appreciable fuel values. In another
alternative, the vent stream from the absorber can be sent to a
flare. Almost complete oxidation of formaldehyde, methanol, and
carbon monoxide occurs in both a furnace and a flare, so the exhaust
gas stream from the formaldehyde unit contains little formaldehyde.
The vent stream from the top of the product fractionator us
to prepare specification-grade product solution can be sent as neede
to a flare, a furnace, or an absorber to reduce the formaldehyde
content.
Intermittent gaseous emission that occurs during plant
startup or shutdown is sometimes sent to a flare, the furnace, or a
small water absorber to reduce the formaldehyde content.
Intermittent losses that occur at pump seals, from storage
tanks, or at valves are sometimes controlled with portable gas blowe
used in connection with small absorbers.
Combustion
TABLE 5-8
3
Reported Aldehyde Emission from Various Sources
Aldehyde Emission
Source __ (as formaldehyde)
Amberglass manufacture
3
Brakeshoe debonding
Core ovens
Meat smokehouses
Aldehyde Emission
Source (as formaldehyde)
Curing ovens
3
Wool coolers 32 ug/m
3
Litho oven inlet 120 Mg/m
3
Litho oven outlet 32,880 ug/m
3
Litho oven outlet 4, 680 ug/m
Atmospheric burner
Premix burner
3
Phthalic acid plant 135,600 ug/m
63
Aldehyde Emissic
Source (as formaldehyde
Multijet burner
Locomotive, 113 hp
HRT, 150 hp
Aldehyde Emission
Source (as formaldehyde)
Inspirator burner
360 pg/m 3
3
480 ;ig/ni
3
1,920 jig/nT
a 168
Reprinted from Stahl.
65
Transportation Vehicles
O
O
CO
1-1
JO
u
cfl
m O
O
4J
CO
-n
Cfl
o
U 3 o
cd
o
JS
o
ON CO
m
4J
CO
-n
3 XI
cti
fl
<U
a
H CM 30
CO
O
CO
cd Q
o v,
C!
O m
CM
B
O
H
4J
H C
CO
O CO
O H
1
4J
cd o
B 1-1
O 4J
C.3
CUS
O O CM
ro O
O
t
aus
JC
4(
CU
o
-o H
H tH
fl 3 Cu
*J
QQ
c
M O H
> >
u E-i
y a CU O
ij og =q t- o
67
TABLE 5-10
Concentration, mole %
a j. M.
Heuss, personal communication.
e !975
Plymouth Fury.
68
the
Age, condition, and degree of tuning or adjustment of
engine engines require tuning and maintenance, if they are to have
low emission rates.
Converter replacement catalytic converters age and must
eventually be replaced, if they are to maintain sufficiently low
emission rates.
Design of engine engine types in different cars sometimes
result in quite different emission rates.
Temperature of ambient air 75 F was found to result in lower
aldehyde emission for some engines, compared with 25F or 95F; and
starting a cold engine generally results in high aldehyde emission
rates.
methanol can be obtained from natural gas, petroleum/ coal, and wood;
it is now used as a fuel for some racing vehicles.
Methyl-tert-butyl ether (MTBE) MTBE is being blended with
gasoline at 5-20% by several oil companies; it results in
substantially higher octane ratings and is thought by many persons
knowledgeable about gasoline to have a bright future.
Sill
W
OOO
X
"x IS
I
O
"it
I
O
I
O
*K
oo
x "x
p^eatooiv IM M oo X MS V CO
I O CM - 10 a in
CO
4-J
CO
CU
CO
o
H
-o
in
H
CO
s
TJ
cu
H
"O
co
C0|
4->
(U
U
CO
JQ
4-1
o
o
o
o
G
O
H
CO
CO
1 CO
CU cu
(X rH
U
H
4-J
g CO
a,
-a
cu
tx
cu
71
72
amount and type of such emission vary greatly between plants, but the
lowest rates of formaldehyde emission occurred in some coal-burning
plants. In 1978, Natusch 137 reported rather limited data from power
plants using coal, oil, and natural gas. Coal-fired furnaces emitted
the most particles, the most carbon monoxide, and the least aldehyde
(reported as formaldehyde). Aldehyde emission by coal-, oil-, and
natural-gas-fired furnaces was reported to be 0.002, 0.1, and 0.2 Ib
from 1,000 Ib of fuel. If the results of Natusch are average values
and if the consumption data of the U.S. Department of Energy for coal,
oil, and natural-gas consumption in power plants are used, the amount
of aldehyde emitted from power plants in the United States is
estimated to be approximately 50 million pounds per year (see Table
5-12) . The unburned hydrocarbon emitted may lead to the eventual
formation of 10-20 times more aldehyde. Large changes have occurred
in the last 10-20 yr in the design and operation of fossil-fueled
power plants. As a general rule, the major emphasis has been on
increased energy efficiency. The results probably produce more
complete combustion and decreased aldehyde concentrations, although
specific data to support this hypothesis are not available.
Sulfur dioxide is considered by many to be a more obnoxious
emission from oil- and coal-burning plans than aldehyde. Natusch 137
pointed out that the polycyclic organic materials formed to a small
extent, particularly from coal-fired furnaces, were especially
critical, in that such materials are generally considered to be
carcinogens.
A variety of aldehydes have been identified as products of forest
fires (Table 5-13) . Bonfires and garbage fires also produce aldehydes
and other undesirable byproducts. The amounts emitted obviously
depend on the size of the fire, i.e., the amount of material burned
(Table 5-14) . In most cases, detrimental effects of such fires are
limited to the immediate area of the fire.
The combustion of tobacco in the process of cigarette-smoking also
generates a variety of aldehydes. This is an important source of
aldehydes only in the indoor environment, and it is discussed in more
detail later in this chapter.
VEGETATION
73
74
TABLE 5-13
a
Aldehydes Emitted by Forest Fires
Aliphatic Aromatic
Formaldehyde Vanillin
Propanal Syringaldehyde
Sinapaldehyde
Is o but anal
Olefinic Cyclic
Acrolein Furfural
5-Methylfurfural
a 73
l)ata from Graedel.
75
TABLE 5-14
a 70
Reprinted with permission from Gerstle and Keranitz.
and pear have an especially high aldehyde content 13-18 rag/kg. Some
species contain three carbonyl compounds f others as many as 20 (Table
5-15); 2-trans-hexenal (2TH) is the most common. Schauenstein et al.
speculated that the unusually wide distribution of 2TH indicates that
it probably is formed during the processing of the fruit. According
to their interpretation, some aldehyde in apple and fruit ^uices is
formed biogenically in the fruit/ and some of the remainder is
produced by enzymatic and nonenzymatic reactions during processing.
Vegetables are not without their share of aldehydes. 167
Acetaldehyde, propionaldehyde , isobutyraldehyde, and butyraldehyde
have been detected in beans, broccoli, brussels sprout, cabbage,
carrot, cauliflower, celery, cucumber, lettuce, onion, potato and,
soybean .
Woody species also contain aldehydes, but there is disagreement as
to whether they occur in healthy, as well as in injured, tissue.
According to Schauenstein et: a!L. , 153 one report stated that 2TH was
emitted by Robin ia pseudoacacia in the absence of injury when the
plant was enclosed within a plastic bag for 12 h. More numerous
reports cite the capacity for formation of 2TH in injured trees, such
as Ginkgo biloba, Albizia julibrissin, and Ailanthus glandulosa. It
has been suggested that the biosynthesis of aldehydes is a defense
against biologic attack, for example, in the resistance shown by
ginkgo to fungi. 123
In the course of inquiry into the possible etiologic factors of
nasopharyngeal tumors among the Chinese and Kenyans, Gibbard and
Schoenthal 71 made a semiquantitative measurement of sinapylaldehyde
and related aldehydes in the wood of eight angiosperms and two
gymnosperras. The aldehyde content varied according to species, with
Eucalyptus sp. and Fagus sylvatica having the highest and Juniperus
procera and Larix decidua the lowest content (Table 5-16).
There is some information on the location of aldehydes in plant
tissue. 1S3 A report by Lamberton and Redcliffe established that the
long-chain aldehydes occur in cuticular plant waxes. On measuring the
aldehyde content as a percentage of total lipids, they found a range
from 0.2% in purple loosestrife (Lythrum salicaria) to 14.3% in
cranberry (Table 5-17) . Apparently, the distribution pattern of
aldehydes is so characteristic for a species that it may have value in
taxonomic studies.
Aldehydes emanating from vegetation have been detected in ambient
air. 73 Thirty-six plant volatiles including aliphatic, olefinic,
aromatic, and cyclic aldehydes have been cited by Graedel (Table 5-18).
When plant material is burned either deliberately for disposal of
agricultural waste or unintentionally as in forest fires, the increase
in aldehyde emission may become significant. Because the nature of
the plant material and the conditions of the burning can vary widely,
it is difficult to characterize the emission. In a special experiment
with a tower that simulated field conditions, Darley et al. 51
compared emission from the three principal types of agricultural waste
in the San Francisco Bay area. The number of pounds of total
hydrocarbon emitted per ton of plant material was 9.7 for fruit
prunings, 14.5 for barley straw, and 4.4 for native brush. Aldehydes
77
TABLE 5-15
3
Carbonyl Compounds in Various Fruits
Pineapple Pear Orange
acetaldehyde
benzaldehyde
furfural
C C
24> 26
C aldehydes
a
Reprinted with permission from Schauenstein et al.
1 ^ Unless otherwise stated,
alkenals have 2-trans configuration.
78
TABLE 5-16
.a
Yields of Aldehydes in Wood of Various Tree Species'
f"** QO ON
04 m
rt 00
6 o
o ao <N irt
S -
cfl
CO
u
H IS O
rt o* OO O
-d
fi
m
t^
oo -n
Hn
^1
SI
^o n rn oo
LO
cd
J=i
a
V3
C/3
m^
s
H PI
o
CO H
0) CO
CO
01
-d OJ
Pu
x:
4-1
d
ai
4J
c
H
^
P-
cu
od
cd
80
TABLE 5-18
3
Aldehydes Emitted from Natural Plant Sources
Alipnatic Aromatic
Formaldehyde Be nz aldehyde
Acetaldehyde Cuminaldehyde
Propanal Dihydrocuminaldehyde
i- But anal Phenylpropanal
Isobutanal Cinnamaldenyde
ji-Pentanal _p_-Hydroxybenzaldehyde
Isopentanal Anisaldehyde
Hexanal j)-Me thoxycinnamaldehyde
He pt anal Piperonal
Octanal Vanillin
Nonanal Veratraldehyde
Decanal Conifer aldehyde
Unde canal Eve rnic aldehyde
Te trade canal
Olefinic Cyclic
l-Hexen-2-al Furfural
trans-2-Hexenal Safranal
3, 7-Dimethyl-2, b-octadien-1-al
3 , 7-Dimethyl-b-octen-l-al
4-Hydroxy- 3 7-dimethyl-6-octen-l-al
,
2, b-Nonaldien-1-al
a Data
from Graedel. 73
\
81
Building Materials
Insulation
Combustion Appliances
25,000 yg/h and 15,000 yg/h for the oven and each top burner,
respectively (Traynor, personal communication).
Tobacco Smoke
TABLE 5-19
3
Aldehydes Identified in Tobacco Smoke
Aromatic Aromatic
Formaldehyde Benzaldehyde
Acetaldehyde
Glyoxylic Acid
Propanal Cyclic
2-Oxopropanal
n-Butanal Furfural
Jsobutanal 5-Hydroxymethylf urf ural
Galactose
Olefinic
Acrolein
Crotonaldehyde
a
Data from Graedel.
TABLE 5-20
Amount in
Cigarette Smoke,
85
fabrics.
from the earth, tree and plant emission, etc. The reaction of these
naturally occurring hydrocarbons with photochemically generated HO
radicals is the major natural source of formaldehyde in the clean
lower troposphere. The HO-radical is formed through a variety of
reactions. One important reaction sequence is initiated by the
photodissociation of ozone, 3 , at the short wavelengths present in
sunlight:
+ 1 + 1 3
3 + hv(X < 3200 A) O^D) + 2 ( Z
g , A
g,
or Z
g ") (1)
HO + CH 4 + H 2 + CH 3 (4)
CH 3 + 2 (+ N 2 or 2) + CH 3 2 (+ N 2 or 2) (5)
CH 3 2 + NO * CH 3 + N0 2 (6)
CH 3 2 + CH 3 2 * CH 3 + CH 3 + 2 (7)
-
CH 3 OH + HCHO + 2 (8)
CH 3 + 2 * HCHO + H0 2 (9)
CH 3 CH 2 CH 2 CH 3 + HO - CH 3 CH 2 CH 2 CH 2 + H2 (10)
-
CH 3 CHCH 2 CH 3 + H 2 O (11)
(0,) (NO)
CH 3 CH 2 CH 2 CH 2 *- CH 3 CH 2 CH 2 CH 2 - - CH 3 CH 2 CH 2 CH 2 0- +N0 2
2
CH 2 CH 2 CHO
JCH 3
3 CH 2 CH 2 C00 2
(NO)
|
CH 3 CH 2 CH 2 C0 2 +N0 2
CH 3 CH 2 CH 2 -+C0 2
(0 2 ) HCHO
CH 2 CH 2 2
-
(NO)
|
CH 3 CH 2 CH 2 0- +N0 2
X
CH 3 CH2 CHO + H0 2
X
I3 CH 2 C00 2 -
,(NO)
CH 3 CH 2 C0 2 +N0 2
CH 3 CH 2 -+HCO CH 3 C TT '
XCH CH
3 2 HCHO
,(NO)
CH 3 CH 2 0-+N0 2
CH 3 CHO
HCHO
CH 3 CH = CH 2 + HO -> CH 3 CHCH2 OH ( 12 )
OH
-*CH 3 CHCHj
90
00-
- CH 3 CHCH 2 OH + O 2 ->CH 3 CHCH2 OH
6
CH 3 CHCH2 QH + NO 2
2)
J(0
II
H0 2 + CH 3 CCH 2 OH CH 2 OH
+ HO,
0-0-0
3 + CH 3 CH = CH2 -> CH 3 CH CH (14)
CH 2 2 +NO (18)
CH 2 O 2 +SO 2 (19)
HCHO + hv -
HCHO* - H + HCO (I)
+ H2 + CO (II)
H + 2 (+ N 2 or 2) + H0 2 (+ N2 or 2 ) (22)
HCO + 02 * H0 2 + CO (23)
I I I I I
2000 2200 2400 2600 2800 3000 3200 3400 3600 3800
Wavelength, A
1 -
CH 2 +hv HCO(I)
02-
o
2700
'
3000
WAVELENGTH. A
3300
\0 i t l
3600
CH 2 +hv (E)
08-
6-
04-
I I I I
20
till 40 60 80
SOLAR ZENITH ANGLE
^
(0 2 )\ CH 4 + CO (IV)
\
products 9
+ hy->(CH 3 CH 2
CHO)* ->C 2 H 5 +HCO (V)
(VI)
products?
(0 2 )\ C 2 KU + CH 2 = CHOH 00
T
CH 3 GHO
9
products
Although many studies related to these processes have been made, the
atm remains
quantum efficiency of each for molecules in air at 1
unclear. Thus, Demer^ian t al. 5S have reviewed the present
information on acetaldehyde primary quantum yields, and they could
III
suggest only a large range of values that may apply for processes
and IV. From the data of Table 5-21, it can be seen that the
98
TABLE 5-21
Rate Constant, s
-1
CH 3 + O2 > CH 3 2 (5)
C 2H5 + 2 + C 2 H5 2 (24
n-C 3 H 7 + O 2 -
n-C 3 H 7 2 (25
HCO + O2 *
HO2 + CO (23
TABLE 5-22
5
C H
2 5
CHO + hv >C 2 H 5 + HCO ( V) (4.2-2.0) x 10"
5
n-C 3 H7 CHO + hv > JT C 3 H7 + HCO (VII) (3.2-2.2) x 10"
6
> C H
3 8
+ CO (IX) 1.0 x 10"
5
> C H
2 4
+ CH CHO
3 (X) 1.0 x 10~
a
Reprinted with permission from Demerjian et al.
101
TABLE 5-23
C H CHO
2 5 (2.1 + 0.1) x 10~U 142
11
C H6 CHO
6 (1.3 + 0.1) x 10" 142
3 3
0( P) HCHO (1.5 + 0.5) x 10"]- 84
(1.5 +0.2) x ICT^ 121
1.64 x 10~ 13 138
(1.50 + 0.10) x 10"" 106
(1.61 + 0.17) x 1Q~ 1J 105
13
(1.9 + 0.4) x 10~ 44
3 162
C 9 H,-CHO 7.0 x I0~;j-
25 2.3 x 10'
13 30
3 162
-n-CoH CHO 9.5 x 10" ?-
3 77 13 92
2.5 x ID'
12 162
iso-C 3 H 7 CHO 1.2 x 10~
3 30
CH Z9 =CHCHO 2.7 x 10~?-
1J 65
4.9 x 10"
0.83 x 10'^ 30
CUoCH-CHCHO
J 1Z 65
1.09 x 10~
15 131
N0 3 CH 3 CHO 1.2 x 10"
14 172
H0 2 HCHO l.OxlO'
24 24
HCHO <2.1 x 10"
3
102
TABLE 5-24
Approximate
Typical Concentrations Rate Constant, Relative Rate
a
Rate of addition; net rate is lower as result of reverse reaction.
b
Taken as equal to that for NO^ + CH 3 CHO measured by Morris and Niki. 131
103
formaldehyde; the CHO radical formed here will react primarily to form
HC>2and carbon monoxide:
HCO + 2 + H0 2 + CO (23)
For the HC^-radical reaction, recent studies show that the addition
of the radical to formaldehyde, rather than H-atom abstraction, is the
l 7 l 172
major step:
H02 + HCHO -
(H0 2 CH 2 0) -
O 2 CH 2 OH (28)
O 2 CH 2 OH -
(H0 2 CH 2 O) + H0 2 + HCHO (29)
H0 2 + O 2 CH 2 OH + H0 2 CH 2 OH + O 2 (30)
2O 2 CH 2 OH + 20CH 2 OH + 2 (31)
HO 2 CH 2 OH + HCO 2 H + H 2 (32)
TABLE 5-25
Relative Rate
Reaction (approximate)
etc.) will probably act as a permanent sink as well and also compete
with the dissociation reaction (Reaction 29).
If the processes considered here alone describe the removal of
formaldehyde in the lower atmosphere, then the half-life of
formaldehyde for these conditions, typical of the highly polluted
atmosphere, would be somewhat less than 2.6 h. Ill-defined
heterogeneous reaction pathways involving rainout of formaldehyde and
removal by surface water, rock, and soil must also occur and shorten
the lifetime of formaldehyde. Thus, O.C. Zafiriou and A.M. Thompson
(personal communication, 1979) estimated that in the vicinity of Woods
Hole, Massachusetts, formaldehyde enters the ocean from the atmosphere
at the rate of 6 yg/cm 2 per year. The flux of gaseous
formaldehyde into the sea at a remote, marine site in the equatorial
Pacific was measured by Zafiriou et^ al^. 9 7 at 5 yg/cm 2 per year;
1
show very
Benzaldehyde , 2-methylbenzaldehyde, and 3-methylbenzaldehyde
N0-N0 2 mixtures in air
low reactivity when photooxidized in dilute
57 In contrast, 1-methylbenzaldehyde
in smog-chamber experiments.
shows a high reactivity characteristic of the aliphatic aldehydes.
of the half-lives of
Present data do not allow quantitative estimates
or other possible
the aromatic aldehydes toward photodecomposition
to be somewhat longer than
light-induced reactions, but they appear
those observed for the aliphatic aldehydes in most cases.
RCHO + H 2 -
RCH(OH) 2
the
the olefinic and aromatic hydrocarbons in air induced
photooxidation of the hydrocarbons. They expressed concern that these
results could modify current considerations of whether control of the
nitrogen oxides would effectively reduce photochemical air pollution.
Using dilute NO-NC>2-aldehyde and/or -hydrocarbon mixtures in
57 studied the smog-forming reactivities
air, Dimitriades and Wesson
of several aldehydes formaldehyde, acetaldehyde , propionaldehyde,
n_-butyr aldehyde, acrolein, crotonaldehyde
, benzaldehyde,
o-tolualdehyde, m-tolualdehyde, and p_-tolualdehyde. Several criteria
were used to establish the reactivity of the aldehyde or olefin used:
rate of N02 formation; maximal concentrations of ozone,
peroxyacetylnitrate, peroxybenzoylnitrate, and formaldehyde; and the
time-weighted exposures (ppm x rain) for these four products. These
workers concluded that the aldehydes present in auto exhaust as a
exhaust components. The
group should be classified among the reactive
specific reactivity (reactivity per part per million) of formaldehyde,
as measured by the rate of NO-to-NC>2 conversion, was comparable with
that of the average exhaust alkene. However, with respect to oxidant
yield, the specific reactivity of formaldehyde was considerably lower
than that of the average exhaust hydrocarbon. The specific reactivity
of the higher aldehydes was in every respect comparable with that of
the average exhaust alkene. When tested individually, benzaldehyde
and m- and p_-tolualdehyde were unreactive, and o-tolualdehyde was
reactive. In mixtures, benzaldehyde and presumably all the aromatic
aldehydes manifested reactivity as precursors of the strong eye
irritants, the peroxybenzoylnitrates.
Dimitriades and Wesson 57 observed another important effect of
formaldehyde: mixtures containing formaldehyde appeared to have
higher oxidant-yield reactivity than expected from the sum of the
individual effects observed from the specific reactivity and
compositional data alone; the difference increased with increasing
formaldehyde content.
Kopczynski jet aiL. 10B found that the photooxidation of dilute
mixtures of formaldehyde, acetaldehyde, and propionaldehyde in the
presence of nitrogen oxides produces the same products and biologic
effects (eye irritation and plant damage) as does the hydrocarbon
photooxidation. Propionaldehyde was found to be the most reactive,
with respect to highest product yields, eye irritation, and plant
damage. These workers concluded that, inasmuch as aldehydes are both
primary (directly emitted) and secondary (photochemically formed)
products, their substantial reactivities are of special importance.
They may be expected to contribute to photochemical air pollution
problems, not only in the central city, but in the urban, suburban,
and rural areas downwind.
Computer modeling of the complex chemical changes expected to
occur in simulated, sunlight-irradiated, NO-, NO2~r hydrocarbon-,
and aldehyde-polluted atmospheres has confirmed the observed aldehyde
effects and pointed to the specific chemistry responsible for these
effects. " 38 39
1 * 5S SB 7<l 103 12 139 It has shown that the
aldehydes (formaldehyde and acetaldehyde) present initially in
polluted air will decrease the induction period observed for ozone,
109
N0 2 + hy + NO + (34)
+ 2 (+N2 , 2 )
-
3 (+N2 , 2 ) (35)
O 3 + NO -
2 + N0 2 (36)
R + 2
-
R02 (39)
R0 2 + NO RO + N0 2 (40)
H0 2 + NO + HO + NO 2 (41)
110
.500 1 ' ' ' ' ' ' ' ' ' ' ' '
-
I I I I I I I I I I 1 I I
.400 -
E
O.
O.
.300 -
NO
O
01
.200 -
O
z
.100 -
0.332 ppm, urban mix* 2.45 ppmC. Reprinted with permission from
Jeffries and Kamens.
Ill
'
I I
AV NMHC = 2450ppbC
05 AV NO
TIME (hours)
(26)
(23)
(42)
(43)
(44)
(45)
(39)
CH3C002 + N02 -
CH3COO 2 NO2 (PAN) (48)
NO --
CH3C0 2 + N0 2 (49)
HCO + 2
- HO 2 + CO (23)
HCO + 2 (+N 2 or 2 )
-
HCOO 2 (+N 2 or 2 ) (50)
C 2H2 + 3
* CH 2 O 2 + HCHO (52)
0-0
CH 2 2 +HCHO->CH2 OOCH 2 O- CH 2 CH 2 -
(53)
x x
o
OCH 2 OCH 2 O - HOCH 2 OCHO
O
(I II
REFERENCES
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122. Mack, G. P. R. , and B. A. Thrush. Reaction of oxygen atoms with
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123. Major, R. T. The Ginkgo, the most ancient living tree. Science
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127. Mill, T. Structure Reactivity Correlations for Environmental
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128. Miller, B. H., and H. P. Blejer. Report of an Occupational
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126
70:3639-3651, 1979.
130. Morris, E. D., Jr., and H. Niki. Mass spectrometric study of
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132. Morris, E. D., Jr., D. H. Stedman, and H. Niki. Mass
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130
STATIC METHODS
132
133
pH meter.
A second method is the bisulf ite-iodine titration procedure. 10 l
DYNAMIC METHODS
SAMPLING
IR
If the collection
efficiency of the trapping solution is less than
10%, it is desirable to use more than one
impinger in series. A
Apical arrangement for the
sampling of formaldehyde (as recommended
'
NIOSH) us consists of two midget impingers in
series, each
xitaining 10 ml of water. The sample is collected at a flow
rate of 1
137
a 1I
L.J
D
a. Midget Impinger. b. Midget Gas Bubbler
Ace Glass Co. (coarse frit) .
Ace Glass Co.
c. Nitrogen Dioxide Gas Bub
Ace Glass Co.
J*-
m
1
i
FIGURE 6-1 Various types of impingers used to sample air. a-e and g
98 f
reprinted with permission from Pagnotto; from C. D. Hollowell
(personal communication).
138
e
inding several aldehydes in ambient air with this method.
oo
CO43 CTi I
s- rH -O CM CO
CO r* ro m
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sd
O O O O
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d U O
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140
141
Impingers
Solenoid
valves
L _i _1 I
|SAMP!TN(F
TRAIN 1
Pump
Other solid adsorbents also have been used. Molecular sieves have
been used to capture low-molecular-weight aldehydes by physical
entrapment. Samples can be desorbed with water for analysis by
gas-chromatographic or colorimetric techniques. Formaldehyde,
acetaldehyde, and acrolein have all been detected with molecular
sieves, but quantitative data are available only on acrolein. 8 The
**
Continuous Samplers
the best elements of direct and indirect sampling. Air is sampled via
an impinger apparatus to generate a preconcentrated sample that,
instead of being transported to a central laboratory for analysis, is
analyzed in the field.
The continuous analyzer described by Yunghans and Munroe 150 and
Cantor 27 is manufactured by Combustion Engineering Associates
(CEA) . The instrument can use the pararosaniline method to analyze
for formaldehyde, or it can use the Purpald method to measure total
aldehydes. One problem with this instrument is that it is not
thermostated. The color -development rate of pararosaniline is
143
WATER
PLANT MATERIAL
evidence that 2-hexenal content of plant tissue varies with the oxyge
concentration in the atmosphere at the time of crushing. Teranishi e
135 avoided crushing and processing and sampled aromas from fresh
aj..
fruit directly.
Extraction of aldehydes from plant products has been accomplished
either with solvents or with distillation. Purified isopentane has
been used to extract aldehydes from apple and fruit juices; after the
extract is dried, it is washed with propylene glycol to remove
132
alcohols; the remaining oil is ready for aldehyde analysis.
Alternatively, steam distillation has been used to recover aldehydes:
Major et^a]^. 85 steam-distilled fresh Ginkgo biloba leaves, collected
144
FORMALDEHYDE
Chromotropic Acid
145
146
Pararosaniline
Acetylacetone
this property.
The procedure of Belman 19 is as follows: Equal volumes of
formaldehyde solution and a reagent consisting of 2 M ammonium acetate
and 0.02 M acetylacetone (pH, 6) are mixed and incubated at 37C for 1
h. After cooling to room temperature, the fluorescence is determined
* 51 nm Tne standard curve is
(Xexcite = 41 nm ' *emit )
linear with formaldehyde from 0.005 yg/ml to about 0.4 yg/ml and
deviates slightly from linearity from 0.4 \ig/ml to 1.0 yg/ml.
Above 1.0 yg/ml, the formaldehyde can be determined color imetrically.
This method has been particularly chosen by the wood industry in
20 90 Under
determining emission from particleboard and plywood.
controlled conditions in specially designed chambers, the formaldehyde
content of headspace vapor over materials being examined is
determined. This test is being considered for promulgation as a
European standard. 113 Acetylacetone has not been used for sampling
for formaldehyde in ambient air. In this application, possible
interference by oxides of nitrogen, sulfur dioxide, and ozone must be
considered. 9
Other Methods
It has already been mentioned that there are a fairly large number
of spectrophotometric methods for the determination of formaldehyde,
in addition to the two discussed above. In general, these methods
either have not been fully evaluated or suffer from major defects.
Several alternative wet-chemistry spectrophotometric methods of
analysis are listed in Table 6-2. Closely analogous methods, based on
spectrofluorometry, have also been suggested, as shown in Table 6-3.
One final analogous method deserving serious consideration is based on
chemiluminescence. All these methods are discussed below.
An older reagent that has been considered as a candidate for the
colorimetric determination of formaldehyde is phenylhydrazine.
Reaction of this reagent with formaldehyde, followed by oxidation of
the adduct with ferricyanide, leads to the formation of an anionic
88 The essential drawback encountered
species absorbing at 512 nm.
is that color is not stable and fades with time. Under some
procedural conditions, aliphatic aldehydes interfere.
13 * Other
possible interferences have not been investigated.
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150
151
3-Methyl-2-benzothiazolone Hydrazone
Purpald
Other Methods
ACROLEIN
4-Hexylresorcinol
Other Methods
ACETALDEHYDE
SPECTROSCOPIC METHODS
have aJ
Microwave, infrared, and laser-fluorescence spectroscopy
ambient air directls
been used to measure aldehyde concentrations in field
Each of the methods is prohibitively expensive for ordinary
The instrumentation required is often cumbersome and
sampling.
156
CHROMATOGRAPHIC METHODS
detectors (TCDs) are less sensitive and respond only to very high
concentrations of formaldehyde. An electron capture detector (ECD)
has a limited linear response range and is sensitive only to
conjugated carbonyl groups. The photoionization detector (PID) is
reported to be sensitive to formaldehyde (HNU Company, Newton Upper
Falls, Mass.), but appears to have some drawbacks. Specifically, a
high-energy lamp is required to detect formaldehyde; this drastically
reduces both the selectivity and the lifetime of the detector. 96
In principle, it is possible to circumvent the insensitivity of
the FID to formaldehyde by catalytically reducing formaldehyde to
easily detectable methane. 32 Because hydrogen is required for the
operation of the FID, the reduction is easily achieved by passing a
mixture of the column effluent and hydrogen gas over a short bed of
catalyst before introduction into the FID. Deposits of nickel,
thorium, and ruthenium on fine-mesh glass beads have all been used
successfully to reduce formaldehyde to methane. The lack of success
in applying the technique to routine analysis of formaldehyde can be
attributed to problems in choosing proper gas-chromatographic
conditions. Apparently, it is difficult to pass formaldehyde through
any of a variety of column -pack ing materials quantitatively. 26
With the exception of formaldehyde, aldehydes may be analyzed by
direct gas injection if concentrations are high enough. By using a
six-port valve equipped with a 1-ml gas-sampling loop, aldehydes can
be routinely detected with an FID at concentrations as low as 0.03 pp
without preconcentration (Analytical Instrument Development, Inc.,
Avondale, Pa.). It is important to recall, however, that gas
chromatography excels at separation, but provides minimal
identification. Ambient-air samples often contain hydrocarbons, and
their responses may overlap and obscure the aldehydic responses.
Bellar and Sigsby 18 reported a complex automated gas chromatographic
technique to analyze for C 2 -C 5 aldehydes that avoided this
problem. Hydrocarbons and aldehydes from an air sample flowed onto
polar cutter column, where the aldehydes were retained as the
hydrocarbons were passed through and vented. The cutter column was
then backflushed to a cryogenic trap, where the aldehydes were
reconcentrated before introduction onto an analytic column. About ar
hour was required for a complete analysis. The method has not been
used by other workers.
Preconcentration before direct analysis has also been
investigated. Pellizzari 1 3 101 has reported the collection of some
*
ELECTROCHEMICAL METHODS
AIR
Ambient Air
The MBTH technique has been applied to automobile (gasoline) 1211 12S
and diesel 111 exhaust emission to determine the concentration of
total aliphatic aldehydes. Two titrimetric procedures have also been
used for auto-exhaust measurements. 39
The chromotropic acid method has been used widely for measuring
formaldehyde in automobile *- 6 8 7S 117 125 and diesel " * el 82
1
1
WATER
Most of and perhaps all the methods that have been used to
identify or measure aldehydes in samples of air and biologic tissue
should be applicable to water samples; however, little research has
been performed to determine the relative accuracy, precision, or
sensitivity of the methods for measuring aldehydes in water.
Because of the high toxicity of acrolein to aquatic life, Kissel
and co-workers 70 evaluated several chemical analytical procedures by
comparing the analytical data with data from bioassays on acrolein.
Eight methods three derivatization and five direct were evaluated.
The derivatization methods were the bromide-iodide-thiosulfate
titration method of Pressman and Lucas, 106 the 2,4-dinitrophenyl-
hydrazine colorimetric method of Bowmer and co-workers, 22 and the
aminophenol fluorescence method of Alar con. J Direct measurements
were performed by ultraviolet spectrophotometry, 1 * 9 gas-liquid
chroma tography, 13 nuclear-magnetic-resonance spectroscopy,
differential-pulse polar ogr aphy, 5S and direct fluorescence. The
effect of different buffering systems on the toxicity and chemical
analysis of acrolein was also investigated.
Analytical data produced by the derivatization methods and by
gas-liquid chromatography did not correlate well with the bioassay
data. Often, no biologic responses were observed for test solutions
in which these methods indicated the presence of toxic concentrations
of acrolein. The direct ultraviolet spectrophotometric method was
also judged unsuitable, because it produced extraneous peaks, which
were often more intense than the acrolein peaks and tended to mask
them.
Data producted by nuclear-magnetic-resonance spectroscopy,
differential-pulse polarography, and direct fluorescence correlated
very well with the bioassay data. Assuming that the bioassay provided
a more realistic measure of the concentrations of acrolein in
solution, the authors concluded that these direct methods were
suitable for monitoring acrolein in water. How well these methods
163
P^LANT MATERIAL
REFERENCES
175
176
TABLE 7-1
Formaldehyde reacts with DNA less frequently than with RNA, because
the hydrogen bonds holding DNA in its double helix are more stable. 6 "
172 Reaction of formaldehyde with DNA has been observed, by
spectrophotometry and electron microscopy, to result in irreversible
denaturation. In reactions with transfer RNA, formaldehyde interferes
with amino acid acceptance. 11 172 The equilibrium reaction of
formaldehyde with DNA involves thermally activated opening and closing
of hydrogen bonds between matching base pairs in the helix. 172 If
permanent cross links are formed between DNA reactive sites and
formaldehyde, these links could interfere with the replication of DNA
and may result in mutations. When human fetal lung fibroblasts were
incubated with tracer amounts of -^C-labeled formaldehyde and
acetaldehyde, 55 a pulse of 10 rain with formaldehyde followed by a
l
6-min and 24-h chase showed migration of carbon-14 into the nucleus.
Fractionation of the nucleus revealed that the RNA fraction had the
highest absolute and specific activity, whereas the DNA and protein
fractions had considerably lower activity. All the counts from
formaldehyde were found in the adenine and guanine components of RNA.
The DNA count was distributed among adenine, guanine, and thymine.
EFFECTS IN ANIMALS
MUTAGENIC POTENTIAL
CARCINOGENIC POTENTIAL
EFFECTS IN HUMANS
TABLE 7-2
Approximate
Formaldehyde
Concentration,
iealth Effects Reported ppm References
Lower airway and pulmonary 5-30 68, 71, 85, 86, 107,
effects 151, 152, 167, 173,
198, 204, 215, 218
a
The low concentration (0.01 ppm) was observed in the presence of other pollutant
that may have been acting synergistically.
187
EYE
mg/m3 (0.7 ppm) in a chamber. 9 Sim and Pat tie 175 exposed 12 men
in an exposure chamber at 13.8 ppm for 30 min. There was considerable
nasal and eye irritation when the men first entered the chamber.
However, the eye irritation was reportedly not severe, and the
symptoms wore off after about 10 min in the chamber. Other studies
reported that eye irritation may occur at concentrations below 1
ppm. 133 lse 175 207 217 Marked irritation with watering of the eyes
occurs at a concentration of 20 ppm in air. 198 Eye damage from
formaldehyde vapor at low concentration is thought not to occur,
because of the protective closure of the eye that results from
discomfort. 78 Increased blink rates were noted at concentrations of
0.3-0.5 ppm in persons studied in so-called pure air irradiated in
smog chambers. 16B Blink rate, although used as an objective measure
of eye irritation, appears variable for any given subject. The
irritant effects of formaldehyde seem to be accentuated when it is
mixed with other gases. In 14 smog-chamber tests, there was an
average eye-irritation index of 4.9 1.0 units (on a scale of 0-24;
0-16, none to severe irritation, and over 16, lacrimation in more tha
50% of the subjects) . It was concluded that the human subjects teste>
could readily detect and react to formaldehyde at as low as 0.01 ppm.
188
OLFACTORY SYSTEM
TABLE 7-3
Formaldehyde
Concentration,
ppm Exposure Effects on Eyes Refer
Chamber single :
Chamber repeated :
Occupational :
0.9-2.7 Tearing
itching
Indoor residential:
0.067-4.82 Tearing
0.02-4.15 Irritation
0.03-2.5 Irritation
190
RESPIRATORY TRACT
eye
irritation, some persons seem to tolerate higher concentrations, 16-30
ppm perhaps subjects who developed tolerance.
When 16 healthy young subjects were exposed to formaldehyde at
0.25, 0.42, 0.83, or 1.6 ppm for 5 h/d for 4 d, nasal-mucus flow rate
was decreased at all concentrations except 0.83 ppm. 9 Subjective
responses to formaldehyde included slight conjunctival irritation and
dryness of the throat and the upper third of the nose.
Helwig reported that schoolchildren and teachers developed eye and
respiratory tract irritation, gastrointestinal disturbances, increased
thirst, and apathy after moving into a prefabricated school
81
building.
*
The "new-building odor" was particularly strong after
weekends and holidays. Measurements of airborne formaldehyde made
with Drager tubes revealed concentrations of 5 ppm or more on one
occasion. Mild dysrhythmias were present in 20 children who underwent
EEC studies. No details were given regarding the medical complaints
or the number of children who developed adverse reactions while
attending classes. The author felt that plastic polymers used in
chipboard might also produce similar effects. Children who moved to
another building after graduation no longer had any symptoms.
Eye and upper respiratory tract irritation were noted in some
employees of funeral homes that used formaldehyde and paraformaldehyde
191
.reported exposed^
pe^le
a
to ^aldehyde at high concentrations
Perslnf apprenticed
192
Asthma
Summary
'.KIN
TABLE 7-4
Formaldehyde
Challenge No.
Concentration, Responding
=>
% (n 5)
1 4
0.5 2
0.2 1
0.1 1
0.01 1
I
tyc.
a Data from Marzulli and Maibach.
197
TABLE 7-5
Positive-Response
Species Method Frequency, %
119
Guinea pig Draize intradermal 5
119
Adjuvant (maximization) 80
ALIMENTARY TRACT
BLOOD
TABLE 7-6
Standard
j
Country mg/m ppm Type
United States:
The total number of people who are exposed to formaldehyde and who
manifest adverse health effects is difficult to determine. There is
evidence that such responses may occur in a substantial proportion of
the exposed population in the United States. The variability in
response among exposed persons makes it particularly difficult to
assess the problem.
People are exposed to formaldehyde from occupational sources,
consumer products, outdoor ambient air, and indoor air.
In the occupational setting, about 1.4 million persons are
directly or indirectly exposed to formaldehyde. It is not possible to
determine exactly the exposure in each industry. However, owing to
the irritant nature of formaldehyde, most workplaces probably have
concentrations of less than 3 ppm more often around 1 ppm or less for
an 8-h workday.
Some 11 million persons live in homes that contain either UF foam
insulation or particleboard made with UF resins. When measurements
have been performed, a wide range of formaldehyde concentrations from
0.01 ppm to 10.6 ppm, have been reported. Most homes have shown less
than 0.5 ppm with a range of 0.1-0.2 ppm being more prevalent.
Because people spend up to 70% of their time indoors, the exposure to
formaldehyde released from UF foam or particleboard could be
substantial.
Formaldehyde concentrations measured in ambient air are lower than
in the occupational or indoor residential situation. Outdoor
concentrations vary, but are rarely more than 0.1 ppm and usually less
than 0.05 ppm. However, the probability of high outdoor exposure to
formaldehyde for the 220 million people in the United States does not
appear to be substantial, except for unusual circumstances of traffic,
fuel use, or automobile density. Consumer exposures are
mainly by
direct contact, and contact dermatitis is an important consideration,
as has been discussed.
Little is known about the magnitude of the population that is more
susceptible to the effects of inhaling formaldehyde vapor. Asthmatics
may constitute a segment of the general population that is more
susceptible; inhalation even at low concentrations may precipitate
acute symptoms. Airway hyperactivity may explain the
susceptibility of
asthmatics to formaldehyde at low concentrations. Using data gathered
from over 1,500 methacholine challenge tests, one can estimate the
prevalence of airway hyperreactivity in the population at large. 19
About 9 million people in the United States have bronchial asthma.
Essentially all will react positively to methacholine challenge tests
and thus be considered to have hyper reactive
airways. 190 The degree
of airway reactivity is variable and depends on a number of
205
REFERENCES
134. Mills, J. CPSC warns about health hazard of foam home material.
Washington Post, Real Estate, August 11, 1979.
135. Montgomery, S. Paresthesia following endodontic treatment. J.
Endodon. 2:345-347, 1976.
136. Morgan, G. B., C. Golden, and E. C. Tabor. New and improved
procedures for gas sampling and analysis in the National Air
Sampling Network. J. Air Pollut. Contr. Assoc. 17:300-304, 1967,
137. Morrill, E. E., Jr. Formaldehyde exposure from paper process
solved by air sampling and current studies. Air Cond. Heat.
Vent. 58(7):94-95, 1961.
138. Nagorny, P. A., Z. A. Sudakova, and S. M. Schablenko. On the
general toxic and allergic action of formaldehyde. Gig. Tr.
Prof. Zabol. 1:27-30, 1979.
139. National Research Council, Committee on Toxicology.
Formaldehyde. An Assessment of Its Health Effects. Washington,
D.C.: National Academy of Sciences, 1980. 38 pp.
140. National Research Council, Panel on Air Quality in Manned
Spacecraft. Atmospheric Contaminants in Spacecraft.
Washington, D.C.: National Academy of Sciences, 1972. 11 pp.
14
141. Neely, W. B. The metabolic fate of formaldehyde- C
intraperitoneally administered to the rat. Biochem. Pharmacol.
13:1137-1142, 1964.
142. North American Contact Dermatitis Group. Epidemiology of
contact dermatitis in North America: 1972. Arch. Dermatol.
108:537-540, 1973.
143. Nova, H. , and R. G. Touraine. Asthma from formaldehyde. Arch.
Mai. Prof. 18:293-294, 1957. (in French)
144. Odom, R. B., and H. I. Maibach. Chapter 15. Contact
urticaria: A different contact dermatitis, pp. 441-453. In F.
N. Marzulli and H. I. Maibach, Eds. Advances in Modern
Toxicology. Vol. 4. Derma to toxicology and Pharmacology.
Washington, B.C.: Hemisphere Publishing Corporation, 1977.
145. Orringer, E. P., and w. D. Mattern. Formaldehyde-induced
hemolysis during chronic hemodialysis. New Eng. J. Med.
294:1416-1420, 1976.
146. Palecek, E. Premelting changes in DNA conformation. Prog.
Nucleic Acid Res. Mol. Biol. 18:151-213, 1976.
147. Palese, M. , and T. R. Tephly. Metabolism of formate in the
rat. J. Toxicol. Environ. Health 1:13-24, 1975.
148. Paliard, F., L. Roche, C. Exbrayat, and E. Sprunck. Chronic
asthma due to formaldehyde. Arch. Mai. Prof. 10:528-530, 1949.
(in French)
149. Parker, C. D., R. E. Bilbo, and C. E. Reed. Methacholine
aerosol as test for bronchial asthma. Arch. Intern. Med.
115:452-458, 1965.
150. Pepys, J., C. A. C. Pickering, A. B. X. Breslin, and D. J.
Terry. Asthma due to inhaled chemical agents tolylene
di-isocyanate. Clin. Allergy 2:225-236 , 1972.
151. Popa, V., D. Teculescu, D. Stanescu, and N. Gavrilescu.
Bronchial asthma and asthmatic bronchitis determined by simple
chemicals. Dis. Chest 56:395-404, 1969.
216
221
222
TABLE 8-1
3
Occupational Exposures to Aldehydes
Acrolein 7,301
Benzaldehyde 15,985
n-Butyraldehyde 1,259
Furfural 15,412
Glyoxal 3,848
Propionaldehyde 1,544
a
Data from NIOSH. 111
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225
226
SENSITIZATION
ANESTHESIA
ORGAN PATHOLOGY
TABLE 8-5
TABLE 8-6
Chamber Duration of
Concentration, Exposure,
Aldehyde ppm min Symptoms
Acrolein 0.80 10 Extremely irritatir
lacrimatory (20 s
1.22 Extremely irritatii
lacrimatory (5s
lacrimatory (30 i
a Data
from Sim and Pattle. 96
ACETALDEHYDE
ACETALDEHYDE IN ANIMALS
Acute Toxicity
TABLE 8-7
Polyaldehydes Sarcoma-180
a
Data from Schauenstein et al. 87
232
Extended Studies
Respiratory-System Effects
Cardiovascular-System Effect
Metabolism
Carcinogenic Potential
Mutagenic Potential
HUMAN INVESTIGATIONS
ACROLEIN
ACROLEIN IN ANIMALS
Acute Toxicology
Extended Studies
Acrolein was added to the drinking water of rats, and that water
was administered as their only source of water for up to 90 d. The
unpalatability of the water was manifest in reduced body weights and
increased kidney weights. The death of animals given water containing
acrolein at 600-1,800 ppm was due to lack of water intake. No adverse
pathologic or hematologic changes were observed (G.W. Newell,
unpublished data; Union Carbide Company, unpublished data) .
Continuous inhalation of acrolein by rats for up to 90 d had
little or no effect at concentrations of 0.06-0.22 ppm. 12
** 60
Respiratory-System Effects
Metabolism/Pharmacokinetics
Carcinogenic Potential
Mutaqenic Potential
ACROLEIN IN HUMANS
TABLE 8-8
Acrolein
Concentration, ppm Response
87
0.33-0.40 a Odor threshold 3 '
6 '
87
0.40-l.U Prolonged deep respiration
6
0.62 Respiratory-response threshold
24.0 Unbearable
a ln a
simulated-smog study, the acrolein eye-irritation threshold (withou
olfaction) for a 30-s exposure was 1.27 ppm, and the odor threshold was
0.08-0.29 ppm. 1 The eye-irritation threshold was the same whether dete
mined by increasing concentrations over a constant period or by increasi
the duration of exposure over a series of concentrations (M. Jones,
H. Buchberg, K. Lindh, and K. Wilson, unpublished data).
240
TABLE 8-9
a. 48
Reprinted with permission from Kane.
241
OTHER ALDEHYDES
Tables 8-2, 8-3, and 8-4 list toxicity information on other common
aldehydes. The eye and respiratory tract irritation caused by
formaldehyde, acrolein, and, to some extent, acetaldehyde is also
caused by propionaldehyde , 9 6 10 butyraldehyde (Sim and Pattle; 96
100 * *
Smyth et^al^; Du Pont Company, unpublished data), and chloral
(Du Pont Company, unpublished data) . Chloral is unique, in that its
inhalation toxicity puts it in the highly toxic category (Du Pont
Company, unpublished data). However, it is widely used as a sedative.
Chloral has also been shown to be mutagenic in the Ames test (Minnich
65
e_t_al_. ; Du Pont Company, unpublished data) and has shown some
110 None of the other
embryotoxic properties. aldehydes have
toxicity values that would be inconsistent with the values typical of
their class.
242
BENZALDEHYDE
CHLORAL HYDRATE
CHLOROACETALDEHYDE
FURFURAL
GLUTARALDEHYDE
GLYOXAL
4 -HYDROXYPENTENAL
KETOALDEHYDES
MALONALDEHYDE
SYNAPALDEHYDE (CINNAMALDEHYDE)
in both male and female A-strain mice was not increased over control
values after intraperitoneal injection at 4.00 or 0.8 g/kg over an
8-wk period. 106
Epidemiologic evidence from a study in Buckinghamshire in
Oxfordshire, England, suggested increased nasal and sinus cancers in
woodworkers of the furniture industry. l Other investigators have
not found a relationship between occupation and nasopharyngeal cancer
in retrospective surveys. 18 56 62 9 * Nasopharyngeal cancers are
16
apparently found in a wide variety of occupations, and Buell,
using occupation as an indicator of economic status, found a twofold
excess of nasopharyngeal cancers among those of lower socioeconomic
status.
As a result of these epidemiologic findings, a number of
constituents of wood are being tested for carcinogenic activity,
including the lignin constituents, methoxy-substituted
cinnamaldehydes, and cinnamalcohols. The latter would yield respective
aldehydes in the course of metabolic oxidation by alcohol
dehydrogenases. Preliminary data indicate that 3,4,5-
246
emesis, and headaches. Although exposures were not measured, the odor
was pronounced, and ambient concentrations may have been high. All
symptoms were reversed within a few days without further consequence.
MISCELLANEOUS
REFERENCES
S. Weil.
99. Smyth, H. F., Jr., C. P. Carpenter, and C.
Ind. Hyg. Toxicol.
Range-finding toxicity data, list III. J.
31:60-62, 1949.
S. Weil.
100. Smyth, H. P., Jr., C. P. Carpenter, and C.
Ind. Hyg. Occup.
Range-finding toxicity data: List IV. Arch.
Med. 4:119-122, 1951.
and U. C.
101. Smyth, H. F., Jr., C. P. Carpenter, C. S. Weil,
Ind. Hyg.
Pozzani. Range-finding toxicity data. List V. Arch.
Occup. Med. 10:61-68, 1954.
U. C. Pozzani,
102. Smyth, H. F., Jr., C. P. Carpenter, C. S. Weil,
VI. Am.
and J. A. Streigel. Range-finding toxicity data. List
Ind. Hyg. Assoc. J. 23:95-108, 1962.
of
103. Sporn, A., I. Dinu, and V. Stanciu. The toxicity
cinnamaldehyde. Igiena 14:339-346, 1965. (in Rumanian; English
abstract in Chem. Abstr. 64:10293a, 1966)
Hazards
104. Stanford Research Institute. Profiles on Occupational
for Criteria Document Priorities, pp. [5-15]. Arlington,
U.S. Department of
Virginia: Stanford Research Institute, for
for
Health, Education, and Welfare, National Institute
Occupational Safety and Health, March 1977.
105. Steiner, P. E. R. Steele, and F. C. Koch. The possible
,
Health
111. U.S. Department of Health, Education, and Welfare, Public
for
Service, Center for Disease Control, National Institute
Hazard
Occupational Safety and Health. National Occupational
data file. 1980.
Survey, conducted 1972-1974. Computerized
112. U.S. Environmental Protection Agency, Office of Water
Criteria for
Regulations and Standards. Ambient Water Quality
Acrolein. U.S. Environmental Protection Agency Report No. EPA
440/5-80-016. Washington, D.C.: U.S. Government Printing
Office, 1980. 100 pp.
255
256
257
DOSE
PRESENCE OF DURATION OF
OTHER POLLUTANTS EACH EXPOSURE
V
CLIMATE SPECIES
PLANT GENETIC
SOIL RECEPTOR ~= VARIABILITY
PATHOGENS AGE
V
MECHANISM OF ACTION
EFFECTS
VISIBLE SUBTLE
4J
s d
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conditions. Radish leaves did not respond until the acrolein exposure
was increased to 6-7 h at 1.5 ppm, and neither geraniums nor tomato
plants were affected even at the greater exposure. Thus, Masaru and
Fukaya demonstrated two principles that have been apparent when air
pollutants have been studied more extensively: species respond
differently to a given exposure to pollutant, and environmental
factors affect plant response.
TABLE 9-3
Butyraldehyde
Propionaldehyde
10000
12.5 11.8 6.3 2.5 1 Severe Severe
Acetaldehyde
Formaldehyde
19
Reprinted with permission from Stephens et al.
b
A, in cell before irradiation; B, in cell after 2 h of irradiation with
black lights in static system; C, at beginning of plant fumigation,
after circulation through plant box; D, at end of fumigation.
264
265
Transpiration
TABLE 9-5
Rate b
Formaldehyde Propionaldehyde
Control Exposure Control Exposure
Unfasted cells
Fasted cells
a
Reprinted with permission from deKoning and Jegier.^
b
For photosynthesis, micromoles of oxygen given off by 6.3 x 10 6 cells
in 10 min; for respiration, micromoles of oxygen absorbed by 6.3 x 10^
cells in 10 min.
267
Pollen Germination
WOODEN CONTAINERS
TABLE 9-6
Pollen-Tube Length, % of
Pollutant control, after Exposure
Concentration, Lasting:
Pollutant Gas ppm
Sulfur dioxide
Nitrogen dioxide
Ozone
Formaldehyde
Acrolein
a 13
Reprinted with permission from Masaru e_t
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269
270
POSTHARVEST TREATMENTS
MAPLE-SYRUP COLLECTION
DISCUSSION
TABLE 9-8
3-Methyl-2-benzothiazolone hydrazone 4
Formaldehyde,
propionaldehyde test
274
REFERENCES
ACROLEIN
276
277
TABLE 10-1
Acetaldehyde X (ESD) X X
Acroleinb X (ESD) X X
Anisaldehyde X (ES) X
Benzaldehyde X (ESD) X
Butyraldehyde X (ESD) X
Capraldehyde X (S)
Caproaldehyde X (SD)
Caprylaldehyde X (S)
Chloral b X (D)
Cinnamaldehyde X (SD)
Citronellal
Crotonaldehyde X (D)
Di~tert-butylhydroxy- X (S)
4-benzaldehyde
Dichlorobenzaldehyde X (S)
Dimethylbenzaldehyde X (SD)
b X (SD)
Enanthaldehyde
Endrin aldehyde
2-Ethylbutyraldehyde X (D)
2-Ethylcaproaldehyde X (S)
Formaldehyde X (E)
b X
Furaldehyde (ED)
Isobutyr aldehyde X (D)
Isopropionaldehyde X (D)
Isovaleraldehyde X (ED)
Mesitaldehyde X (S)
Me thacroleinb X (D)
Met aldehyde
2-Methylpropionaldehyde X (ESD)
3-Me thyl valeraldehyde X (D)
Nonylaldehyde X (S)
Par aldehyde X (ESD)
b
Propionaldehyde X (D)
b X
Sallcylaldehyde (E)
Sorbaldehyde X (E)
Syringaldehyde X (E)
Undecylaldehyde X (S)
Valeraldehyde X (D)
Vanillin5 X (ES)
b X
Veratraldehyde (E)
aE
industrial or sewage treatment plant effluent; S = surface water;
D = drinking water.
b
Evaluated for toxicity.
278
TABLE 10-2
Exposure
Species LC qn , ppm Time, h Reference
(king salmon)
(rainbow trout)
(brown trout)
(longnose killifish)
279
virginica) by 50%. For the water flea (Daphnia magna), Macek and
co-workers 20 reported a 48-h LC5Q of 0.057 mg/L.
Studies by the Shell Development Company l have shown acrolein
to be lethal to various aquatic flora such as Hydrodictyon sp.,
Spirogyra sp. , Potomogeton sp. , Zannichellia sp. , Cladophera sp., and
Ceratophyllum sp. at concentrations ranging from 1.5 to 7.5 ppm.
Macek and co-workers 20 evaluated acrolein for chronic effects in
the water flea (p_. magna) and the fathead minnow (Pimephales promelas)
with the flow-through exposure technique, which provides for
continuous replacement of the test solutions in the exposure tanks.
They also based their toxicity estimates on measured acrolein
concentrations. The water flea was exposed at five concentrations,
from 0.0032 to 0.043 mg/L, for 64 d (three generations). Although the
compound had no statistically significant effect on fecundity at the
concentrations tested, it significantly reduced survival at 0.034 and
.043 mg/L.
In the chronic test with minnows, the test concentrations ranged
from 0.0046 to 0.042 mg/L, and the test was begun with 27-d-old fish.
None of the tested concentrations affected the growth, survival, or
reproductive capacity of these fish; however, at 0.042 mg/L, the
compound significantly reduced the survival of their offspring.
The EPA has determined that acrolein has acute and chronic toxic
effects on freshwater aquatic organisms at concentrations as low as
0.068 and 0.021 mg/L, respectively, and acute toxic effects on marine
32
organisms down to 0.055 mg/L. There are no data on chronic
toxicity in sensitive marine organisms. Toxic effects would occur at
lower concentrations among species that are more sensitive than those
tested.
FORMALDEHYDE
OTHER ALDEHYDES
TABLE 10-3
Concentration,
Species Statistic mg/L Reference
53 8
Lepomis macrochirus 9b-h LC^Q
(bluegill sunfish)
(alga)
EC 5Q (growth) 239 28
Navicula seminulum
(alga)
282
22
LC5QS to be 31 and 23 ppm, respectively. Mattson and co-workers
reported a 96-h LC 50 of 32 ppm for the fathead minnow (P.
promelas) . With the bluegill sunfish (L. macrochirus), Turnbull and
co-workers 31 determined the 24- and 48-h ^598 of furaldehyde to
be 32 and 24 mg/L, respectively. In very turbid water, the 24-h
LC5Q for bluegills has been reported as 44 mg/L, and the 48- and
96-h LC 50 s both have been determined to be 24 mg/L. 31
*
The
lowest reported 96-h LC 50 of furaldehyde is 1.2 ppm, 35 for
bluegills.
Dawson and co-workers 9 tested crotonaldehyde and propionaldehyde
with bluegill sunfish (L. macrochirus) and tidewater silversides
(Menidia beryllina) . The 96-h LCsQS of crotonaldehyde for the
bluegill and silversides were 3.5 and 1.3 mg/L, respectively. The
96-h LC5QS of propionaldehyde were 130 mg/L for the bluegill and 100
mg/L for the silversides.
22
According to Mattson and co-workers, the 96-h 1^59 of
vanillin for fathead minnows is 112-121 mg/L, on the basis of two
27
tests. Palmer and Maloney determined the toxicity of vanillin to
six species of algae with concentrations up to 2 mg/L. This
concentration slightly inhibited the growth of Gomphonema sp., but had
no effect on the other species. In a search for a chemical agent that
would selectively kill the Oregon squawfish (Ptychocheilus
21 screened nearly 1,900 compounds,
oregonensis) MacPhee and Ruelle
,
Other fish included in the study were the rainbow trout (Salmo
gairdnerii) and the bluegill sunfish (Lepomis macrochirus). With some
of the compounds, tests with the trout and bluegill were deleted. The
test concentrations were 0.1, 1.0, and 5.0 ppm, and the maximal
exposure time was 24 h. At 5 ppm, acrolein had no effect on any of
the species. This result is not in agreement with those presented
earlier. Other aldehydes that had no effect on any of the species at
5 ppm were anisaldehyde, benzaldehyde, butyraldehyde (polymer),
chloral, dichlorobenzaldehyde, enanthaldehyde, isobutyraldehyde,
metacrolein, propionaldehyde, salicylaldehyde, and veratraldehyde. Of
the aldehydes tested, only mesitaldehyde was toxic to the lamprey at 5
ppm; it was not tested with the other fish species.
283
BIOCONCENTRATION
chapter, acrolein is the only one for which a BCF has been
experimentally derived. The value was 344, and it was determined with
the bluegill sunfish (S. Petrocelli, personal communication).
An indirect method of determining the propensity of a chemical to
accumulate in tissues is to determine its octanol-water partition
coefficient, which is an experimentally derived ratio of the
concentrations of a compound in N-octanol and in water after N-octanol
is mixed with water that contains the compound. The logarithms of the
octanol-water partition coefficients for the 36 aldehydes are shown in
Table 10-4. The log P values were calculated by the method of Hansch
and Leo, 13 except that for acrolein, which was determined
experimentally (Petrocelli, personal communication) . Hydration will
reduce the calculated log P values of the aliphatic aldehydes by 0.38
and will increase the values of the aromatic aldehydes by 0.39. Of
the log P values shown, capraldehyde, caprylaldehyde,
3 , 5-di-tert-butyl- 4-hydroxybenzaldehyde, mesitaldehyde,
nonylaldehyde and undecylaldehyde have values over 3.0. These may
,
TABLE 10-4
Coefficients
Logarithms of Octanol-Water Partition
3
for 36 Aldehydes
L 8 P
Aldehyde
-0.21
Acetaldehyde
- 9
Acrolein
1 '
^
54
Anis aldehyde
1 - 48
Benzaldehyde
0.87
Butyr aldehyde
4 ' 1;L
Capraldehyde
1.95
Caproaldehyde
3 * 03
Caprylaldehyde
Chloral ' 51
1<92
Cinnaraaldehyde
' 55
Crotonaldehyde
3 5-Di-tert-butyl-A-hydr oxybenzaldehyde
4.75
,
Dichlorobenzaldehyde 2.00
2.82
Dimethylbenzaldehyde
2>49
Enanthaldehyde
2 -Ethyl but yr aldehyde 1 73
2.81
2-Ethylcaproaldehyde
-0.87
Formaldehyde
- 88
Furaldehyde
0.65
Isobutyr aldehyde
1.82
Tsopropionaldehyde
Is ovaler aldehyde 1.28
3 - 48
Mesitaldehyde
- 33
Methacrolein
2-Methylpropionaldehyde 0.65
1 82
3-Methylvaleraldehyde
3.57
Nonylaldehyde
Paraldehyde 1.15
0.33
Propionaldehyde
I- 89
Salicylaldehyde
i- 08
Sorbaldehyde
Syringaldehyde 2.15
4 65
Undecylaldehyde
Valeraldehyde 1.41
Vanillin - 89
Veratr aldehyde ! 61
a Calculated 13
by the method of Hansch and Leo, except the value
for acrolein, which was experimentally derived (S. Petrocelli,
personal communication).
285
REFERENCES
289
290
carboxaldehyde (1,1-Dinethylethyl)-
_t-Butylfonnaldehyde PROPANAL, 2,2-Dimethyl-
4-tert-Butylhexahydro- CYCLOHEXANECARBOXALDEHYDE 4- .
Capraldehyde DECANAL
Capric aldehyde DECANAL
Caprinaldehyde DECANAL
Caprinic aldehyde DECANAL
Caproaldehyde HEXANAL
n-Caproaldehyde HEXANAL
Caproic aldehyde HEXANAL
Capronaldehyde HEXANAL
Caprylaldehyde OCTANAL
ii-Caprylaldehyde OCTANAL
Caprylic aldehyde OCTANAL
Carbomethene ETHENONE
Cassia aldehyde 2-PROPENAL, 3~Phenyl-
Chloral ACETALDEHYDE Trichloro-
,
ethyl)benzene-
Cyclamen aldehyde PROPANAL, a-Methyl-4-(l-methyl-
ethyl)benzene-
3-Cyclohexen-l-aldehyde 3-CYCLOHEXENE-l-CARBOXALDEHYDE
Cyclohexene-4-carboxaldehyde 3- C YCLOHEXE NE-1 -C ARBO XALDEHY DE
Cyclosia OCTANAL, 7-Hydroxy-3,7-dimethyl-
p-Cymene-7-carboxaldehyde ACETALDEHYDE 4-(l-Methylethyl)-
,
benzene-
Decaldehyde DE CANAL
n-Decaldehyde DECANAL
n-De canal DECANAL
Decanal de hyde DECANAL
Decyl aldehyde DECANAL
n-Decyl aldehyde DECANAL
Decylic aldehyde DECANAL
-2-Deoxy-2-(methylamino)-a-l-gluco- STREPTOMYCIN
pyranosyl-(l-4)-N,N/-bis(amino-
iminome thyl ) D-s tr ep tamine
Diethylacetaldehyde BUT ANAL, 2-Ethyl-
292
( 1 3-Dihydro-l 3 3-triraethyl-2H-
, , , ACETALDEHYDE, 1 , 3, 3-Trimethyl-A-
indol-2-ylidene)-acetaldehyde (2,ot)-indoline-
3 , 4-Dihydroxybenzaldehyde 1 3-BENZODTOXOLE-5-CARBOX-
,
ALDEHYDE
2 , 6-Dimethyl-5-hepten-l-al HEPTENAL, 2,6-Dimethyl-5-
3 , 7-Dimethyl-7-hydroxyoctanal OCTANAL, 7-Hydroxy-3,7-diraethyl-
3 , 7-Dimethyl-6-octenal CITRONELLAL (d_ isomer)
3 , 7-Dimethyl-6-octenyl-oxy- ACETALDEHYDE, 3, 7 -Dimethyl -6-
acetaldehyde octenyl-oxy-
6 , 10-Dimethyl-3-oxa-9-undecanal ACETALDEHYDE, 3,7-Dimethyl-6-
octenyl-oxy-
a, a-Dimethylpropanal PROPANAL, 2,2-Dimethyl-
a, a-Dimethylpropionaldehyde PROPANAL, 2,2-Dimethyl-
2 , 2-Dimethylpropionaldehyde PROPANAL, 2,2-Diraethyl-
2 , 4 -Disulf obenz aldehyde BENZALDEHYDE , 4-Formyl-l 3- ,
benzenedisulfonic acid
^i-Dode canal DECANAL, DO-
1 -Do dec anal DECANAL, Do-
Dodecanaldehyde DECMAL, DO-
Dodecyl aldehyde DECANAL, DO-
ja-Dodecyl aldehyde DECANAL, DO-
Dodecylic aldehyde DECANAL, Do-
Enanthal n-HEPTANAL
E nan thai dehyde n-HEPTANAL
Enanthic aldehyde n-HEPTANAL
Enanthole n-HEPTANAL
Epihydrinaldehyde OXIRANECARBOXALDEHYDE
2 , 3-Epoxypropanal OXIRANECARBOXALDE HYDE
2 3-Epoxypropionaldehyde
,
OXIRANECARBOXALDEHYDE
Ethanal ACETALDEHYDE
Ethanedione ETHANEDIAL
1 , 2-Ethanedione ETHANEDIAL
293
Fannofonn FORMALDEHYDE
Ferul aldehyde 2-PROPENAL, 3-(4-Hydroxy-3-
me thoxyphenyl )-
Fisher's aldehyde ACETALDEHYDE 1,3,3-Tnraethyl-A-
,
(2,a)-indoline-
Fixol OCTANAL, 7-Hydroxy-3,7-dimethyl-
Flomine HEPTANAL, 2-(Phenylraethylene)-
Flo-Mor FORMALDEHYDE , Para-
Formaldehyde solution FORMALDEHYDE
Formaldehyde trimer FORMALDEHYDE, 1 ,3,5-Trioxane
Formalin FORMALDEHYDE
Formalith FORMALDEHYDE
Formic aldehyde FORMALDEHYDE
Formol FORMALDEHYDE
-Formylanisole BENZALDEHYDE, 4-Methoxy-
-Formylbenzaldehyde BE NZENED ICARBOXALDEHYDE 1,4-
,
4-Eormylbenzaldehyde 1 ,4-BENZENEDICARBOXALDEHYDE
ALDEHYDE
2 Formyl butane BUTANAL (dl), 2-Methyl-
1 Formyl-3-cyclohexene 3-CYCLOHEXE NE-1 -C ARBOXALDEHYDE
4 -Fo rmyl eye lohexene 3-CYCLOHEXENE-l-CARBOXALDEHYDE
-Formyl-N;,N-diethylaniline BENZALDEHYDE, 4-(Diethylamino)-
294
Geliotropin 1 3-BENZODIOXOLE-5-
,
CARBOXALDEHYDE
Geranial 2,6-OCTADIENAL, 3, 7 -Dime thy 1-
Ge rani aldehyde 2,6-OCTADIENAL, 3,7-Dimethyl-
Glutaral 1,5 -PENT ANEDIAL
Glut ar aldehyde 1,5-PENTANEDIAL
Glutardialdehyde 1,5-PENTANEDIAL
Glutaric dialdehyde 1,5-PENTANEDIAL
Glycidal OXIRANECARBOXALDEHYDE
Glyc id aldehyde OXI RANECARBOXALDE HYDE
Glyoxal ETHANE DIAL
Glyoxal aldehyde ETHANEDIAL
Glyoxylaldehyde ETHANE DIAL
Heliotropin 1 3-BENZODIOXOLE-5-CARBOX-
,
ALDEHYDE
Heliotr opine 1 3-BENZODIOXDLE-5-CARBOX-
,
ALDEHYDE
Hende canal UNDE CANAL
Hendecanaldehyde UNDE CANAL
Heptaldehyde _n-HEPTANAL
n-Hept aldehyde n-HEPTANAL
Heptanal ri-HEPTANAL
Heptanaldehyde n-HEPTANAL
_n-Heptylaldehyde n-HEPTANAL
2,4-Hexadien-l-al 2,4-HEXADIENAL
Hexaldehyde HEXANAL
n-Hexanal HEXANAL
(E)-2-Hexenal HEXENAL, 2-
trans-Hex-2-enal HEXENAL, 2-
2- 1 r an s -Hexen al HEXENAL, 2-
t:r ans- 2-Hexenal HEXENAL, 2-
trans-2-Hexen-l-al HEXENAL, 2-
a-n-Hexyl cinnam al dehyd e OCTANAL, 2-(Phenylmethylene)-
Hexyl cinnatnic aldehyde OCTANAL, 2-(Phenylmethylene)-
Hexylenic aldehyde HEXENAL
a-n-Hexyl- 3-phenylacrolein OCTANAL, 2-(Phenylmethylene)-
Hospex 1,5-PENTANEDIAL
Hyacinthal ACETALDEHYDE, ot-Methylbenzene-
Hyacinthin ACETALDEHYDE, Benzene
Hydratropa aldehyde ACETALDEHYDE, ct-Methylbenzene-
Hydratropaldehyde ACKTALDEHYDE, ot-Methylbenzene-
Hydratropic aldehyde ACETALDEHYDE, ct-Methylbenzene-
Hydrocinnamaldehyde PROPANAL, Benzene-
Hydrocinnamic aldehyde PROPANAL, Benzene-
2-Hydroxy-m-anisaldehyde BENZ ALDEHYDE, 2-Hydroxy-3-
methoxy-
3 -Hydr oxy--anis aldehyde BENZ ALDEHYDE, 3-Hydroxy-4-
methoxy-
296
Ketene ETHENONE
Kethoxal BUTANAL, 3-Ethoxy-2-oxo-
a-Ketopropionaldehyde PROPANAL, 2-Oxo-
2-Ketoproplonaldehyde PROPANAL, 2-Oxo-
a-methylbenzene-
Lilyal PROPANAL, 4-(l,l-Dimethylethyl)-
a-methylbenzene-
Lilyl OCTANAL, 7-Hydroxy-3,7-dimethyl-
Lioxin BENZ ALDEHYDE, 4-Hydroxy-3-
methoxy-
Lyral 3-CYCLOHEXEHE-l-CARBOXALDEHYDE ,
4-( 4-Hydroxy-4-methylpentyl)-
Lysoform FORMALDEHYDE
Malonaldehyde PROPANEDTAL
Malondi aldehyde PROPANEDIAL
Malonic di aldehyde PROPANEDIAL
Malonyldialdehyde PROPANEDIAL
Metaformaldehyde FORMALDEHYDE 1,3, 5-Tr ioxane
,
2-Methoxybenzenecarboxaldehyde BE NZ ALDEHYDE,
2-Methoxy-
2 -PRO PENAL,
jD-Me t boxy c innamal deh yd e 3-(2-Methoxyphenyl)-
2-Methoxycinnamaldehyde 2-PROPENAL, 3-(2-Methoxyphenyl)-
jD-Methoxycinnamic aldehyde 2-PROPEMAL, 3-(2-Methoxyphenyl)-
2-Methoxy-4-formylphenol BENZALDEHYDE, 4-Hydroxy-3-
methoxy-
3 -Me t hoxy-2-hydr oxybenz aldehyde BENZALDEHYDE, 2-hydroxy-3-
methoxy-
3-Methoxy-4-hydroxybenzaldehyde BENZALDEHYDE, 4-Hydroxy-3-
inethoxy-
3-Methoxysalicylaldehyde BENZ ALDEHYDE, 2-Hydroxy-3-
methoxy-
Me thylacet aldehyde PROPANAL
a-Methylacrolein 2-PROPENAL, 2-Methyl-
3-Methylacrolein 2-BUTENAL
2-Methylacrolein 2-PROPENAL, 2-Methyl-
Me thy lac r yl aldehyde 2-PROPENAL, 2-Methyl-
Methyl aldehyde FORMALDEHYDE
in-Methylbenzaldehyde BENZALDEHYDE, 3-Methyl-
o>-Methylbenzaldehyde BENZALDEHYDE, 2-Methyl-
jv-Methylbenz aldehyde BENZALDEHYDE 4-Methyl-
,
ALDEHYDE
Methylene oxide FORMALDEHYDE
Methylethylacetaldehyde BUTANAL (dl), 2-Methyl-
Methylf o rmaldehyde ACETALDEHYDE
2-Methyl-3-formylindole INDOLE-3-CARBOXALDEHYDE, 2-
Methyl-lH-
Methylglyoxal PROPANAL, 2-Oxo-
j>-Me thy Ihydratr opal dehyde ACETALDEHYDE a 4-Dimethyl-
, ,
benzene-
j>-Methylhydratropicaldehyde ACETALDEHYDE, a , 4-Dimethyl-
benzene-
2-Methylindole-3-carboxaldehyde INDOLE-3-CARBOXALDEHYDE, 2-
Methyl-lH-
l-Methyl-4-isohexylcyclohexane-l- BENZALDEHYDE, l-Methyl-4-iso-
carboxaldehyde hexylhexahydro-
299
3-Naphthol-l-aldehyde 2-iiydroxy-l-NAPHTHALENECARBOX-
ALDEHYDE
2-Naphthol-l-carboxaldehyde 2-Hydroxy- 1-NAPHTHALENECARBOX-
ALDEHYDE
Neopentanal PROPANAL, 2,2-Diraethyl-
^-Nlcotinaldehyde 2-P YR1D INECARBOXALDEHYDE
_m-Nitrobenzaldehyde BENZ ALDEHYDE, 3-Nitro-
Nonaldehyde NONANAL
n-Nonaldehyde NONANAL
Nonanoic aldehyde NONAI'JAL
n-Nonylaldehyde NONANAL
Nonylic aldehyde NONANAL
NSC 8819 2-PROPENAL
300
Pelargonaldehyde NONANAL
Pelargonic aldehyde NONANAL
1 , 3-Pentadiene-l-carboxaldehyde 2,4-HEXADIENAL
ii-Pentanal PhNTANAL
1 , 5-Pentanedione 1,5-PENTANEDIAL
a-Pent ylcinnaraalde hyde HEPTANAL, 2-(Phenylmethylene.)-
Phenylacetaldehyde ACETALDEHYDE, Benzene
Phenylacetic aldehyde ACETALDEHYDE, Benzene
3-Phenylacrolein 2-PROPENAL, 3-Phenyl-
3-Phenylacrolein L -PRO PENAL, 3-Phenyl-
Phenylethanal ACETALDEHYDE, Benzene
Phenylf o rmaldehyde BENZ ALDEHYDE
Phenylme thanal BENZ ALDEHYDE
l-Phenyl-l-octene-2-carboxaldehyde OCTANAL, 2-(Phenylmethylene)-
2-Phenylpropanal ACETALDEHYDE, a-Methylbenzene-
3 -Phe ny 1 pr opanal PROPANAL, Benzene-
3-Phenyl-l-propanal PROPANAL, Benzene-
3-Phenylpropenal 2-PROPENAL, 3-Phenyl-
QKPhenylpropionaldehyde ACETALDEHYDE a-Methylbenzene-
,
2-Picolinaldehyde 2-PYRIDINECARBOXALDEHYDE
2-Picolinealdehyde 2-PYRIDINECARBOXALDEHYDE
PIcolinic aldehyde 2-PYRIDINECARBOXALDEHYDE
1 , 3-BENZODIOXOLE-5-CARBOX-
Piperonal
ALDEHYDE
1 , 3-BENZODIOXOLE-5-CARBOX-
Piperonaldehyde
AL DEHYDE
1 , 3-BENZODIOXOLE-5-CARBOX-
Piperonylaldehyde
ALDEHYDE
Pivalaldehyde PROPANAL, 2,2-Oimethyl-
Pivalic aldehyde PROPANAL, 2,2-Diraethyl-
Propaldehyde PROPANAL
1 , 3-Propanedialdehyde PROFANED IAL
1 3-Propanedione
,
PROPANEDIAL
Propenal 2-PROPENAL
Prop-2-en-l-al 2 -PRO PENAL
2-Propen-l-one 2-PROPENAL
Propional PROPANAL
Propionaldehyde PROPANAL
Propionic aldehyde PROPANAL
Propylaldehyde PROPANAL
Propylic aldehyde PROPANAL
Protocatechualdehyde dimethyl ether BENZALDEHYDE, 3,4-Diinethoxy-
Protocatechuic aldehyde dimethyl BENZALDEHYDE, 3,4-Dimethoxy-
ether
Protocatechuic aldehyde ethyl ether BENZALDEHYDE, 3-Ethoxy-4-
hydroxy-
Protocatechuic aldehyde methylene 1 , 3-BENZODIOXOLE-5-CARBOX-
ether ALDEHYDE
2-Pyridaldehyde 2-PYRIDINECARBOXALDEHYDE
Pyr id ine-2-al dehyde 2-P YR I D T.NECARBOXALDE HYDE
2-Pyridylcarboxaldehyde 2-PYRIDINECARBOXALDEHYDE
Pyromucic aldehyde 2-FURANC ARBOXALDE HYDE
Pyroracemic aldehyde PROPANAL, 2-Oxo-
Pyruval dehyde PROPANAL, 2-Oxo-
Pyruvic aldehyde PROPANAL, 2-Oxo-
dimethoxy-
Syringic aldehyde BENZALDEHYDE, 4-Hydroxy-3, 5-
dimethoxy-
Syringylaldehyde BENZALDEHYDE , 4-Hydroxy-3 5- ,
dimethoxy-
Terephthal aldehyde BENZENEDICARBOXALDEHYDE, 1,4-
Terephthalic aldehyde BENZENEDICARBOXALDEHYDE, 1,4-
Tgtradecyl aldehyde DECANAL, Tetra-
A -Tetrahydrobenzaldehyde 3-CYCLOHEXENE-l-CMBOXALDEHYDE
1, 2,3,6-Tetrahydrobenzaldehyde 3-CYCLOHEXENE-l-CARBOXALDEHYDE
Tiglaldehyde 2-BUTENAL (E), 2-Methyl-
Tig lie acid aldehyde 2-BUTENAL (E), 2-Methyl-
Tiglic aldehyde 2-BUTENAL (E), 2-Methyl-
m-Tolualdehyde BENZ ALDE HYDE , 3-Me thyl-
_p_-Tolualdehyde BENZALDEHYDE, 2-Methyl-
jg-To lual dehyd e BENZ ALDEHYDE , 4-Methyl-
a-Tolualdehyde ACETALDEHYDE, Benzene
2-Tolualdehyde BEl'IZ ALDE HYDE, 2-Methyl-
4 -Tolualdehyde BENZ ALDEHYDE, 4-Methyl-
^-Toluic aldehyde 3ENZ ALDEHYDE, 2-Methyl-
a-Toluic aldehyde ACETALDEHYDE, Benzene
-To luyl al dehyd e B ENZ ALDE HYDE
, 2-Me thyl -
-Toluyl aldehyde BENZALDEHYDE, 4 -Me thyl-
303
UNDE CANAL
ja-Unde canal
Undecenoic aldehyde UNDECENAL, 9-
Undecyl aldehyde UNDE CANAL
9-Undecylene aldehyde UNDECENAL, 9-
UNDECENAL, 10-
10-Undecylene aldehyde
UNDECENAL, 10-
Undecylenic aldehyde
n-Undecylic aldehyde UNDE CANAL
Valeral PENTANAL
Valeraldehyde PENTANAL
n-Valeraldehyde PENTANAL
Valerianic aldehyde PENTANAL
Valeric acid aldehyde PENTANAL
Valeric aldehyde PENTANAL
Valerylaldehyde PENTANAL
Vanillal BENZALDEHYDE, 3-Ethoxy-4-
hydroxy-
Vanillic aldehyde BENZ ALDEHYDE, 4-Hydroxy-3-
methoxy-
Vanillin BENZ ALDEHYDE, 4-Hydroxy-3-
methoxy-
_o-Vanillin BENZALDEHYDE, 2-Hydroxy-3-
methoxy-
Vanillin ethyl ether BENZ ALDEHYDE, 4-Ethoxy-3-
methoxy-
Vanillin methyl ether BENZALDEHYDE, 3,4-Dimethoxy-
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REFERENCES