paper presented at First Chemical Congress of the North American at National Fuels & Lubricants SAE Meeting, Houston,Tex.

,June
Continent, Environment Session, Paper No. 50, Mexico City, Mex.,
Nov. 30-Dec. 5,1975.
(13) Fed. Regist., 34,8186 (April 30,1971).
(14) National Academy of Sciences, “A Critique of the 1975-1976
Federal Automobile Emission Standards for Hydrocarbons and
Oxides of Nitrogen”, May 22,1973.
(15) Heuss, J. M., “PhotochemicalReactivity of Mixtures Simulating
Present and Expected Future Concentrations in the Los Angeles
Atmosphere”, paper presented at 68th Annual APCA Meeting,
Boston, Mass., June 15-20,1975.
(16) Mayrsohn, H., Crabtree, J., “Source Reconciliation of Atmo-
spheric Hydrocarbons”, California Air Resources Board, El Monte,
Calif.,March 1975.
(17) Black, F. M., Bradow, R. L., “Patterns of Hydrocarbon Emis-
sions from 1975 Production Cars”,Paper SAE #750681, presented
3-5,1975.
(18) Dimitriades,B., “An Alternative to the Appendix-J Method for
Calculating Oxidant- and NOZ-Related Control Requirements”,
paper presented at International Conference of Photochemical
Oxidant Pollution and Its Control, Raleigh, N.C., Sept. 12-18, 1976
(ConferenceProceedings in press),U S . EnvironmentalProtection
Agency, Research Triangle Park, N.C.
(19) Dodge, M., “The Combined Use of Modeling Techniques and
Smog Chamber Data to Derive Ozone-PrecursorRelationships”,
paper presented at International Conference of Photochemical
Oxidant Pollution and Its Control, Raleigh, N.C., Sept. 12-17,1976
(ConferenceProceedings in press), US.Environmental Protection
Agency, Research Triangle Park, N.C.
Received for review September IO, 1975. Accepted August 2,1976.

Kinetics of Chemical Degradation of Malathion in Water

N. Lee Wolfe’, Richard G. Zepp, John A. Gordon, George L. Baughman, and David M. Cline
Environmental Research Laboratory, U S . Environmental Protection Agency, Athens, Ga. 30601

Acid degradation of malathion is too slow to be important
under environmental reaction conditions. However, alkaline
degradation is fast enough to be a competitive degradation
pathway in the environment. The products of alkaline deg-
radation are temperature dependent. Oxidation by molecular
oxygen is too slow under acidic conditions to be a degradation pH = 6 a t 70’); on the other hand, Goldberg e t al. (12)found
pathway. Photolysis is slow in distilled water but may be im-
portant in natural waters.
Malathion [O,O-dimethyl-S-(1,2-dicarbethoxy)ethyl
phosphorodithioate] is a widely used nonsystemic insecticide
and acaricide that exhibits low mammalian toxicity. Its
widespread use is indicated by a steady rise in production,
reaching 35 million lb in 1971 ( I ) . With increasing emphasis will be used in models being developed to predict the fate of
on nonpersistent pesticides, this organophosphorus compound
is anticipated to receive even greater usage in the future.
The breakdown of malathion in soils has received limited
investigation. Degradation by organisms isolated from soils
was reported by Walker (2). Konrad et al. (3) studied the
degradation of malathion in soils and reported that the rate
of malathion degradation was directly related to malathion
adsorption. The authors concluded that degradation occurred
by a chemical mechanism that was catalyzed by adsorption.
Studies of malathion in relation to aquatic ecosystems have ter.
dealt primarily with the toxicity of malathion and its break-
down products to aquatic life. Algal growth was reported to
be inhibited by malathion ( 4 ) .Sanders and Cope ( 5 )reported flame ionization detector and fitted with a 6 ft X ‘14 in. column
malathion to be toxic to two species of daphnids. Macek and
McAllister (6) found that malathion toxicity to fish differed
with the species, coho salmon having the highest susceptibility port, column, and detector temperatures were 235, 210, and
(96 TLso = 0.101 ppm). Bender (7),in studies with the fathead
minnow, found malathion breakdown products to be more
toxic than the parent pesticide. He also noted a toxic syner-
gistic effect for certain of these compounds.
Data pertaining to the breakdown of malathion in the
aquatic environment are not generally available. Paris et al.
(8) isolated a heterogeneous bacterial population capable of
utilizing malathion as a carbon source. At low concentrations
of malathion and bacteria, the rate of bacterial degradation
was described mathematically by a second-order rate ex-
pression. The major metabolite was malathion @monoacid.
Muhlmann and Schrader (9) reported that malathion un-
derwent acid breakdown to give diethyl thiosuccinate and
0,O-dimethyl phosphorothionic acid. Cowart et al. (10)
studied the rates of hydrolysis of seven organophosphorus
pesticides (pHabout 6). The malathion half-life was reported
to be between one and two weeks. Ruzicka et al. ( 1 1 )reported
that malathion had a half-life of 7-8 h (20% ethanol-water,
that malathion did not react under alkaline or acidic condi-
tions.
We have investigated in detail some potential chemical and
photochemical pathways for the degradation of malathion in
laboratory experiments. These experiments have been de-
signed with emphasis on kinetics and products. Chemical
degradation may then be compared with other degradative
pathways, and its role in the environment evaluated. The data
malathion in aquatic ecosystems. The products will be in-
vestigated to determine their impact on aquatic life.
Experimental
Instrumental.All melting points were obtained on a Fisher
Johns melting point apparatus and are uncorrected. Infrared
(IR) spectra were obtained with a Perkin-Elmer 621 grating
infrared spectrophotometer, and ultraviolet (UV) spectra were
recorded on a Perkin-Elmer 602 recording spectrophotome-
Gas-liquid chromatography (GLC) was carried out on a
Tracor MT-220 gas chromatograph equipped with a hydrogen
packed with 4% SE-30 on Chromosorb W or a 3 ft X IJ4in.
column packed with 4% FFAP on Chromosorb W. Injection
250 “C, respectively, and the flow rate was 60 cc/min. Peak
area integrations were obtained employing an Autolab 6300
digital integrator.
Liquid chromatographic (LC) analyses were performed on
a Du Pont Model 820 liquid chromatograph equipped with
an ultraviolet photometric detector (254 nm). The column was
a Micropak SL-10,50 cm X 2.2 mm i.d. The mobile phase was
5% methanol in methylene chloride a t a pressure of 1000 psi
a t a 1 ml/min flow.
Proton nuclear magnetic resonance (NMR) spectra were
obtained on a Varian Associates HA-100 spectrometer oper-
ating in the frequency sweep mode with a probe temperature
of 30 “C. Tetramethylsilane (TMS) was used as an internal

88 EnvironmentalScience & Technology

reference and lock signal source. A sweep width of 100 Hz with
a sweep time of 500 s was used to record the spectra. The
spectra were calibrated utilizing the frequency difference
network.
Gas-liquid chromatography-mass spectrometry (GLC-MS)
analyses were performed with a Varian Aerograph Model 1400
gas liquid chromatograph and a Finnigan 1015SL quadrupole
mass spectrometer having a gas jet separator and a Systems
Industries 150 digital computer.
Thin-layer chromatography (TLC) techniques employed
have been described in the literature (13,14).
Chemicals. Malathion (98.5% purity) was obtained as a gift
from American Cyanamide. Further purification was achieved
by dissolving the compound in chloroform and washing the
organic mixture with dilute aqueous base. The organic layer
was separated and dried (Na*S04), and the solvent was
evaporated, leaving malathion as a colorless viscous oil.
The synthesis and structure determination of malathion
cy- and @-monoacids,malathion diacid, and 0,O-dimethyl
Several kinetic studies dealt with the formation and dis-
appearance of malathion acid products. In these studies di-
phenylacetic acid was added to the reaction solution as an
internal standard. Aliquots were removed, acidified to pH 2
with 10% hydrochloric acid, and extracted with ether. The
ether extracts were methylated with diazomethane and ana-
lyzed by GLC. Malathion acid concentrations were then cal-
culated based on the internal standard malathion peak area
ratios.
The rate constants for formation of malathion monoacids
( k m h ) ,malathion diacids ( k m d ) , and 0,O-dimethyl phospho-
rodithioic acid ( k m e )were obtained by computer curve fitting
techniques employing MLAB ( I 7). The malathion disap-
pearance rate constant (hd)was calculated as described above.
Pseudo-first-order rate constants were assumed for formation
of malathion acids and 0,O-dimethyl phosphorodithioic acid.
The following constraints were used.
kd = kmh f hme

phosphorodithioic acid (DPTA) were reported previously (151,
and the same procedures were used in these studies.
Double-distilled deionized water was used in all laboratory
experiments except those carried out with natural waters. The
natural water sample was obtained from the Withlacoochee
River located in southern Georgia.
For basic degradation studies, the following buffer systems
were used: sodium dihydrogen phosphate-disodium hydrogen
phosphate, boric acid-sodium hydroxide, and sodium car-
bonate-sodium bicarbonate. For acid degradation studies,
hydrochloric acid was used. These chemicals were commer-
cially available and used as received.
Kinetic Method. The following kinetic procedure for the
determination of the malathion disappearance rate constant
is representative of the procedures used throughout these
studies. A buffer solution (99 ml) of 0.008 M boric acid and
0.002 M sodium hydroxide was prepared, and the flask was
placed in a constant temperature bath at 27.00 f 0.02 "C and
allowed to equilibrate. One ml of a stock solution of 1.41 X
lo-*M malathion in acetonitrile was added to the buffer so-
lution to give a 1.41 X M malathion solution containing
1%acetonitrile, at a pH of 8.56 as determined with a pH meter
calibrated with standard buffer solutions. A 5-ml aliquot was
removed, the reaction was quenched by extraction of mala-
thion with a 5-ml aliquot of chloroform containing 3,4,6,2',-
5'-pentachlorobiphenyl (PCB) (2.79 X M) as an internal
standard, and the time was recorded. Aliquots were withdrawn
at various time intervals through approximately two mala-
thion disappearance half-lives. At the end of 10 half-lives, an
aliquot was obtained and used as the infinity point. Analysis
of the infinity point showed that greater than 98% malathion
had reacted. The concentration of malathion at each recorded
time was determined by GLC analysis based on the PCB-
malathion peak area ratios.
Pseudo-first-order rate constants were obtained using the
integrated first-order rate equation (16):
1 (Co-C,)
k =-ln
t (C, - C,)
where CO= malathion concentration at zero time, Ct = ma-
lathion concentration at time t , and C, = malathion con-
where kmh and k,, > 0.
The concentration of 0,O-dimethyl phosphorodithioic acid
[ E ]was obtained using the expression:
[El = [Mol - [AI - [MI - PI
where [Mol = initial malathion concentration, [A]= monoacid
concentration, [ D ] = diacid concentration, and [MI = mala-
thion concentration.
The rate of disappearance of malathion and the rate of
formation of monoacids are given by the following three dif-
ferential equations:
d [ M 1- h d [ M ]
dt
--
d [ A 1- k,h[M]
dt
--
d [ E 1- h m e [ M ]
dt
Product Studies. Product studies were carried out at the
end of one half-life. In general, the solution (100 ml) was
acidified to pH 2 with 10% hydrochloric acid and extracted
with three 50-ml portions of ether. The organic fractions were
combined, dried (Na2S04), and concentrated. Thin-layer
chromatography was used for qualitative identification of
malathion, malathion monoacids, malathion dicarboxylic acid,
and 0,O-dimethyl phosphorodithioic acid (14). Quantitative
determinations were carried out by methylation of the ethe-
real extract (diazomethane) foilowed by GLC analysis. Con-
firmation of products was obtained by GLC-MS and NMR.
The relative amounts of malathion cy- and /3-monoacids were
determined by LC. Analysis of the reaction mixture by NMR
and GLC was used to verify the presence of diethyl fumarate,
ethyl hydrogen fumarate, and thiosuccinic acid.
Discussion
There are several potential pathways by which malathion
may be chemically degraded under reaction conditions com-
mon to the aquatic environment (Scheme I).
.%le* I

centration after 10 half-lives.

The rate constant was taken as the slope of the line obtained
S
ICH,OI~PSH I cHcooc~H~ - s
ICH,01,PS-CHCOCC2H, - IICH,OI,P S CHCOOH *
s
'CH,012P 5 CHCOOC2H3

by a linear least-squares analysis of the data. The second-order

0 0 O,m*l*"iPho,
mho?od8m#o.r.c,o
c2H~ooccw
h m r l f"m.rae
/
CHCOOCIH,

M81a'n'on
, M,,.Ih
CH>COOCIHs
D l 0 nonoa<,o M.,Il"#O"
CH,COOH
ir o n D # m

rate constant was obtained by dividing the pseudo-first-order P ,

' S
rate constant by the hydroxide ion concentrations. Thermo- ICH,Ol> P S-CHCOOC,H.
I t ICH,OlrPOH
cn,cooc2~5
dynamic parameters were calculated from reaction rate con- **-ion 3 *,," Ih 0 0 0 3 11.w m o l
JYCC " l n onar0,n 0, c ar d
stants obtained at two temperatures differing by a t least
20°. Carbon-sulfur cleavage proceeding by an elimination reac-

Volume 11, Number 1, January 1977 89

tion would give 0,O-dimethyl phosphorodithioic acid and
diethyl fumarate as products. Phosphorus-sulfur bond
cleavage would give diethyl thiosuccinate and 0 , O - dimethyl
phosphorothionic acid. However, 0,O- dimethyl phosphoro-
thionic acid would be in equilibrium with its tautomer 0 , O -
dimethyl phosphorothiolic acid. Thermodynamic calculations
(28) predict the equilibrium constant for the tautomerization
reaction to be about one. Carbon-oxygen bond cleavage by
carboxyl ester hydrolysis would result in two possible prod-
ucts, malathion a- and @-monoacids.Continued carboxyl ester
hydrolysis would result in malathion dicarboxylic acid for-
mation. Another possible reaction would be oxidation of the
phosphorus-sulfur double bond to a phosphorus-oxygen
double bond to give malaoxon.
Acid Degradation. The stability of malathion in water a t
acidic pH's was investigated. Malathion was stable in water
a t pH 2.59 for up to 10 days. Therefore, the kinetic studies
were carried out a t elevated temperatures (67 and 87'). The
extrapolated second-order rate constant (kaeX)is (4.8 f 0.2)
X M-I s-l a t 27' (Table I).
Aquatic systems are generally buffered, and as a result, acid
or base concentration is not affected by the reaction. Under
these conditions the convenient half-life expression is given
by
0.693
tu2 =
k[(H+) or (OH-)]
where h is the second-order acid or alkaline rate constant.
Based on the extrapolated acid degradation rate constant
(h,,,), the malathion would have a half-life greater than four
years a t pH 4. A t temperatures and pH's common to the
Alkaline Degradation. The kinetics of alkaline malathion
degradation and the resulting products were also investigated.
Malathion is more susceptible to basic degradation and sig-
nificant chemical breakdown would therefore be anticipated
under certain environmental conditions. Temperature and,
in some cases, chemical species common to aquatic ecosystems
might be expected to influence malathion persistence.
The second-order disappearance rate constant for alkaline
degradation of malathion ( k d ) is 5.5 f 0.3 M-l s-1 a t 27'
(Table 11).Based on this rate constant, malathion would have
a 36-h half-life in water a t pH 8 and 27'. As anticipated, an
increase in temperature results in a decrease in the half-life.
At pH 8 and 40' the half-life is about 1 h, while a t 0' (pH 8)
the half-life is about 40 days. At lower temperatures found in
the environment, although it would be somewhat slower, al-
kaline degradation of malathion could still be significant.
Product studies were carried out (GLC) after one malathion
half-life. The species present, with percentages based on initial
malathion concentration, were malathion (50%),malathion
monoacid (15%),diethyl fumarate and ethyl hydrogen fu-
marate (35%), and 0,O-dimethyl phosphorodithioic acid.
These products indicate that a t 27', malathion undergoes two
competing reactions (Scheme IV).
Scheme / V
H
ICH3Ol,P-S-CHCOOC2H,
S
lCH30i2b\-S-CHCCOH
\ CHCOCC,H,
1I
s
+ ICH,CI,P.SH
C,H,OOCCH

aquatic environment, this degradative pathway would be too

slow to be significant.
Product studies were carried out a t the end of one half-life
for the acid degradation of malathion a t 87' (Scheme 11).
Scheme / I
S
s S
(CH30),P-S-CHCOOC2H,
I
CH,COOC,H,
- pH 2.5 (CH,Oi,P-S-CHCOOC,H,
I
CH,COOH
After extraction and methylation (diazomethane), GLC
analysis showed only one product, malathion monoacid. No
malathion diacid was found although it was an anticipated
product a t longer reaction times.
A sample of the diacid was subjected to similar reaction
conditions, extracted, and methylated (diazomethane). Al-
though the reaction was not carried out quantitatively,
GLC-MS analysis showed the presence of methyl 0,O-di-
rnethyl phosphorothionate and dimethyl thiosuccinate. Thus,
malathion diacid undergoes phosphorus-sulfur cleavage to
give 0,O-dimethyl phosphorothionic acid and thiosuccinic
acid (Scheme 111).
Scheme I l l
s
(CH,OJ,P-S-CHCOOH H+
I
CH2COOH
81.(CH,OI,P.OH
This reaction sequence is consistent with the results re-
ported by Muhlmann and Schrader ( 9 ) ,who found malathion
breakdown products in aqueous ethanol solvent a t elevated
temperatures to be 0,O-dimethyl phosphorothionic acid and
diethyl thiosuccinate. Under their reaction conditions, how-
ever, the malathion monoacids, if formed, would have been
esterified in the presence of ethanol.
These results indicate that acid catalyzed degradation of
malathion, malathion monoacid, and malathion diacid would
not be an important environmental degradative pathway.
Product studies as a function of temperature indicated that
the elimination reaction is favored a t elevated temperatures
and carboxyl ester hydrolysis is favored a t low temperatures.
Figure 1 shows a plot of malathion disappearance and mala-
thion monoacid formation vs. time a t 27'. A t 47' after one
half-life, analysis showed only 5% malathion monoacid; a t 67"
ICH301,6-S-CHCOOH
I
CH,COOC,H,
only a trace of monoacid was detected. On the other hand, a t
0' the monoacid product is important (Figure 2).
Second-order rate constants for elimination and carboxyl
ester hydrolysis at 27 and 0' were obtained by following ma-
lathion disappearance and monoacid formation. Table I11
contains the rate data for the individual competing reactions
along with the activation parameters. The rate constant for
elimination (kme) is 3.9 f 0.2 M-' SKI, and for carboxyl ester
hydrolysis ( h m h ) 1.4 f 0.1 M-I s-l at 27'. Based on these rate
constants malathion undergoes 74% elimination and 26% ester
hydrolysis a t this temperature.
Malathion degradation is strongly influenced by tempera-
ture and pH. The effects of these two variables are shown in
Figure 3 where malathion half-life is plotted as a function of
pH at various temperatures. This figure shows that malathion
has a maximum half-life a t pH 4.
Two possible malathion monoacids can result from mala-
thion carboxyl ester hydrolysis. The structures of these iso-
s HSCHCOOH
mers were tentatively assigned by Chen et al. (29) based on
+ 1
CH,COOH proton NMR and confirmed by Wolfe et al. ( 1 5 ) using car-
bon-13 NMR. Qualitative determination of both isomers was
made using thin-layer chromatography (TLC) (13). An esti-
mate of the relative amounts of each isomer present at the end
of one malathion reaction half-life was obtained by liquid
chromatographic analysis. The relative amounts of monoacid
were a-monoacid, 85%,and $-monoacid, 15%.This is in con-
trast to results for microbial degradation of malathion by Paris
et al. (8) in which the @-monoacidwas the major product
(99%).
We found it necessary to analyze (GLC) for diethyl fuma-
rate prior to methylation with diazomethane because diazo-

90 Environmental Science & Technology

Table 1. Malathion Acid Catalyzed Degradation - 2.68 I
Kinetic Data 2- I '-
&\
Temp, OC k , M-' 8-1 AH*, kcallmol AS*, eu A MALATHION
87 (2.88f 0.01)X lo-' 22.3 f 0.1 -4.1 f 0.4
0 DPTA
0 MONOACID
67 (4.36f 0.04)X lo-*

'.
. .
27 a (4.8f 0.20)x 10-5 X I

a Extrapolatedrate constant.
a.
..24 - %

-a
Table 11. Temperature Effect on Malathion Alkaline
Degradation Rate Constant
Temp, ' C kd, P4-l S-'
0 0.067 f 0.003
27
47
5.5 f 0.3
47 f 1 00 0 -. -0-0-

67 730 f 20 ./*-6
.04- 0 I
0 6
Table 111. Rate Constants for Malathion Elimination and 0 133 268
Carboxyl Ester Hydrolysis Reactions TIME, min
Reaction Temp, OC k , h4-l s-l AH*, kcal/mol As*,eu Figure 1. Plot of malathion disappearance and malathion monoacid
Elim (kme) 0 4.0X lo-' formation at 27' and DH 9.10
27 3.9 f 0.2 26.5 f 0.6 30 f 2
47 4.1 X 10'
67 6.6 X 10'
Ester (kmh) 0 2.5 X lo-'
27 1.4f 0.1 21 f 1 11 f 5
a MALATHION
0 DPTA
47 6.7
E: \a 0 MONOACID
67 6.8 X 10' X I I

methane reacts with the carbon-carbon double bond to form

a pyrazoline (Scheme V), which could not be detected under
the GLC conditions employed.
Scheme V

I
H

T o determine if our laboratory data could be extrapolated

to natural waters, the half-life of malathion was determined 0 245 488
in a natural water sample obtained from a south Georgia river, TIME, min
the Withlacoochee River (pH 8.2). The experimentally de-
Figure 2. Malathion disappearance and malathion monoacid formation
termined half-life in Withlacoochee River water was 22 h, in at '
0 and pH 10.79
good agreement with the predicted half-life of 20 h, based on
laboratory rate data obtained in distilled water.
The effect of inorganic species common to the aquatic en-
vironment that might in some way catalyze malathion deg- 106
radation was investigated. Basal salts nutrient medium, which
has a high concentration of inorganic salts ( 8 ) ,did not affect
malathion degradation at pH 6.8 in one week. Sodium chloride
(0.05 M) had no apparent catalytic effect on degradation of
malathion at pH 6.0 as shown by the absence of any detectable
degradation at the end of two weeks.
General base catalysis ( 1 6 ) might be expected to be im-
portant in the elimination pathway. However, there was no
detectable difference in the rate of disappearance of malathion
over nearly a tenfold change in buffer concentration (boric
acid-sodium hydroxide) at constant ionic strength (sodium
chloride). Thus, the general base catalysis contribution would
not be significant in natural waters.
Bender ( 7 )has investigated nine potential malathion deg-
radation products for toxicity to the carp. His data showed 0 2 4 6 8 10
that in some cases the breakdown products were as toxic as
the parent pesticide. However, he did not investigate the PH
toxicity of the malathion monoacids. Because they are an- Figure 3. Temperature effect on malathion degradation

Volume 1 1 , Number 1, January 1977 91

ticipated products, we examined their persistence under al-
Table IV. Alkaline Degradation Rate Constants for
kaline reaction conditions.
The second-order rate constant for malathion monoacid Malathion Monoacids and Malathion Diacid in Water
disappearance ( k a d ) obtained with a mixture of 53% a- at 27'
Rate constant,
monoacid and 47% @-monoacidwas (3.1 f 0.2) X 10-1 M-l s-l M-1 =-I
(Table IV). Assuming no large difference in reactivity for the
kada = (3.1f 0.02)X lo-'
two isomers (Scheme VI), a t p H 8 the monoacids have a
half-life of about 26 days. Thus, malathion monoacids are kahb = (1.3f 0.1)X lo-'
about 18 times more stable than malathion under the same kaeC= (2.0 f 0.1) X 10-'
alkaline conditions. k M d = (1.8f 0.2)X lo-*
a Malathion monoacid disappearance rate constant. Malathion monoacid
Scheme Vi carboxyl ester hydrolysis rate constant. Malathion monoacid elimination rate
constant. Malathion diacid elimination rate constant.
S
ICH,Ol,~.S-CHCOOC,H, +
s
(CH,Ol,P-SCHCOOH
I I
CH,COOH CH,COOC,H,

;*/..;;SF
S S
ICH,O),kCHCOOH (CH,0I2k.SH t CHCOOC,H5
/I
L,COOH C,H,OOCCH

The products of monoacid degradation were investigated

employing GLC analysis. At the end of one alkaline degrad-
ative half-life, the reaction mixture was acidified and extracted
with ether. GLC analysis revealed ethyl hydrogen fumarate
as a product. The ethereal extract was subsequently methyl-
ated (diazomethane), and GLC analysis showed the presence
of malathion monoacid (50%),malathion dicarboxylic acid
(15%), and 0,O-dimethyl phosphorodithioic acid.
Two possible pathways may account for these products.
According to one mechanism, both monoacids may react by
carboxyl ester hydrolysis to give diacid, with a competing
elimination reaction to give 0,O-dimethyl phosphorodithioic
acid. In an alternative mechanism, one monoacid of the
monoacid mixture may react by carboxyl ester hydrolysis and
the other monoacid by the elimination pathway.
Figure 4 is a plot of malathion monoacid disappearance and
dicarboxylic acid formation as a function of time a t 27'. The
monoacid elimination rate constant (kaJ is (2.0 f 0.1) x 10-1
M-l s-l, and the ester hydrolysis rate constant ( k a b ) is (1.3
f 0.1) X lo-' M-I s-l a t 27'. Based on rate constants, the
monoacids undergo about 40% ester hydrolysis and about 60%
elimination.
Temperature effects on the two competing reaction path-
ways for monoacid degradation were not investigated. How-
ever, it is anticipated that malathion dicarboxylic acid for-
mation is favored a t low temperatures, and the elimination
reaction to give 0,O-dimethyl phosphorodithioic acid and
ethyl hydrogen fumarate is operative a t elevated tempera-
tures.
Because malathion diacid is anticipated to be a significant
breakdown product, we determined its stability under alkaline
reaction conditions. The second-order rate constant (kdd) for
disappearance of the diacid is (1.8 f 0.2) X M-l s-l a t
27' (Table IV). Thus, at pH 9 the degradative half-life would
be about a year. Under the same alkaline conditions, mala-
thion diacid is approximately 200 times less reactive than
malathion.
Product studies were carried out a t the end of one half-life.
Extraction and methylation (diazomethane) followed by
GLC-MS analysis showed that 0,O-dimethyl phosphoro-
thionic acid and thiosuccinic acid were products of hydrolysis
(Scheme VII).
Scheme VI1
v-
0 157 313
TIME, min
Figure 4. Malathion monoacid disappearance and malathion diacid
formation at pH 10.39 and 27'.
The overall alkaline degradative reaction scheme for ma-
lathion and its acid derivatives should be considered. The end
products of alkaline degradation are fumaric acid, 0,O-di-
methyl phosphorodithioic acid, thiosuccinic acid, and 0,O-
dimethyl phosphorothionic acid. However, the intermediate
malathion monoacids are degraded a t a slower rate than ma-
lathion and may therefore have an impact on the aquatic en-
vironment themselves. Analysis of environmental samples for
malathion is generally carried out under conditions in which
the malathion acids are not detected and therefore are over-
looked.
A quantitative description of the proposed reaction se-
quence is given graphically in Figure 5 , a plot of malathion
disappearance and malathion derivative formation and dis-
appearance as a function of time. At 27' 0,O-dimethyl
phosphorodithioic acid is the major degradation product.
However, at the lower temperatures common to aquatic eco-
systems, malathion monoacid formation is anticipated to
predominate. Under these conditions, one would expect to see
a buildup of malathion dicarboxylic acid.
Malathion Oxidation. Another potential reaction that
malathion might undergo is oxidation. Malathion is readily
oxidized to malaoxon by a variety of oxidizing reagents in the
laboratory. Therefore, one might anticipate oxidation by
molecular oxygen in the environment. Experiments, however,
showed that malathion was stable in oxygen-saturated water
a t acidic pH's for up to two weeks. Therefore, oxidation by
molecular oxygen does not appear to be environmentally
significant.

92 Environmental Science & Technology


MALATHION
+ -.-.I
z
50
---
- -- DPTA
MONOACID
DIACID
- in Pesticide Manufacturing”, EPA Report # TS-00-72-04, 1972.
W
a (3) Konrad, J. G., Chesters, G., Armstrong, D. E., Soil Sci. Soc. Am.,
---- --- ----
L
0 (1957).
11.6 23.1
TIhIE, days
Figure 5. Product formation and disappearance vs. time at 27’ and pH
8.0
Photolysis. Malathion photolysis was also investigated.
The photolysis half-life is 990 h in distilled water (pH 6) with
wavelengths greater than 290 nm. However, in a natural water
sample (Suwannee River), which contained a large amount
of colored materials, malathion was 50% degraded by sunlight
in 16 h.
Summary
Acid-catalyzed degradation of malathion is not likely to be
important a t most pH’s found in the aquatic environment.
Oxidation by molecular oxygen to give malaoxon is not an-
ticipated to occur a t a rate fast enough to be significant. At
NOTES
Sampling Device for Monitoring Biodegradation of Oil
and Other Pollutants in Aquatic Environments
John D. Walker’ and Rita R. Colwell‘
Department of Microbiology, University of Maryland, College Park, Md. 20742
The fate of petroleum and related pollutants in the aquatic
environment, particularly in estuaries and coastal regions, is
of great importance if the environmental impact of oil spills
and other such accidents arising from both natural causes and
human error is to be properly assessed. The actual processes
of oil biodegradation, as well as the extent of biodegradation,
occurring in the natural environment remain to be deter-
mined. A sampling device suitable for monitoring biodeg-
radation under field conditions has been devised and con-
structed in our laboratory. The sampler has been successfully
employed in monitoring biodegradation of petroleum in situ
a t a marshland site in the Chesapeake Bay.
Present address, Environmental Technology Center, Martin-
Marietta Corp., 1450 South Rolling Road, Baltimore, Md. 21227.
acidic pH’s, photolysis and microbial degradation may be
important pathways. Under alkaline pH’s, chemical trans-
formation is a competitive pathway. Malathion monoacids are
formed and a t lower temperatures are anticipated to be sig-
nificant chemical reaction products.
Literature Cited
(1) U S . Environmental Protection Agency, “The Pollution Potential
(2) Walker, W. W., PhD thesis, Mississippi State University, State
College, Miss., 1972.
Proc., 33, 259 (1969).
(4) Moore, R., Bull. Enuiron. Contam. Toricol., 5, 226 (1970).
(5) Sanders, H. O., Cope, 0. B., Trans. Am. Fish. Soc., 95, 165
(1966).
(6) Macek, K. J., McAllister, W. A., ibid., 99,20 (1970).
(7) Bender, M. E., Water Res., 3,571 (1969).
(8) Paris, D. F., Lewis, D. L., Wolfe, N. L., Environ. Sei. Technol.,
9,135 (1975).
(9) Muhlmann, R., Schrader, G., Z. Naturforsch., Teil B, 12, 196
(10) Cowart. R. P.. Bonner. F. L.. E .. . A,. Jr.. Bull. Enuiron.
~ o s E.
Contam. Toricol , 6,231 (1971).
(11) Ruzicka. J. H., ThomDson, J., Wheals, B. B., J. Chromatogr., 31,
37 (1967).
(12) Goldberg, M. C., Babad, H., Groothius, D., Christianson, H. R.,
Geological Survey Prof. Paper 600 D 20, 1968.
(13) Welling, W., Blackmeer, P. T.,Copier, H., J. Chrornatogr., 47,
281 (1970).
(14) Kadoum, A. M., J Agric Food Chem , 18,542 (1970).
(15) Wolfe, N. L., Cox, R. H., Gordon, J. A., ibid., 23,1212 (1975).
(16) Frost, A. A., Pearson, R. G., “Kinetics and Mechanisms”, 2nd
ed., Wiley, New York, N.Y., 1961.
(17) Knott, G. D., Shrager, R. I., Proceedings of SIGGRAPH Com-
puters in Medicine Symposium,Vol 6, p 138, ACM, SIGGRAPH
Notices, Winter 1972.
(18) Kabachnik, M. I., Mastrukova, T. A,, Shipov, A. E., Melentyeva,
T. A., Tetrahedron, 9,lO (1960).
(19) Chen, P. R., Tucker, W.P., Dauterman, W. C., J Agric Food
Chem , 17,86 (1969).
Received for rellieu:January 12, 1976. Accepted August 5 , 1976.
Experimental
Sampling Device. The design of the sampling apparatus
is given in Figure 1. Lexan (polycarbonate) cylindrical tubes,
3 X 12 in., were inserted into plastic buckets. Holes for the
tubes were cut in the plastic buckets with a hot metal-pointed
pipe. In addition, holes were drilled in the lexan to connect the
tubes to the lexan strips. A disc of lexan was placed on top of
each bucket to present water from entering the bucket and
affecting its buoyancy. Four such buckets were connected by
1 X 48 in. strips of lexan secured to the bottom of the tube in
each bucket. Galvanized li, X :yS in. bolts secured the lexan
strips and tubes. A polyethylene line, y4 in. o.d., connected the
lexan strips to a chain anchor which, in turn, was secured by
a weight consisting of a bucket filled with concrete. Ten-ml
glass pipets were mounted to the walls of the lexan tubes, so
that the tips of the pipets protruded 1in. below the water level.
Tygon tubing and pinch clamps closed off the pipets.
Volume ll., Number 1, January 1977 93