Chemosphere 53 (2003) 809–818

www.elsevier.com/locate/chemosphere
Review
Diphenylamine and derivatives in the environment: a review
Oliver Drzyzga *

Department of Marine Microbiology, Center for Environmental Research and Environmental Technology (UFT),
University of Bremen, Leobener Strasse, 28359 Bremen, Germany
Received 3 May 2002; received in revised form 31 March 2003; accepted 12 June 2003

Abstract

Diphenylamine (DPA) is a compound from the third European Union (EU) list of priority pollutants. It was as-
signed by the EU to Germany to assess and control its environmental risks. DPA and derivatives are most commonly
used as stabilizers in nitrocellulose-containing explosives and propellants, in the perfumery, and as antioxidants in the
rubber and elastomer industry. DPA is also widely used to prevent post-harvest deterioration of apple and pear crops.
DPA is a parent compound of many derivatives, which are used for the production of dyes, pharmaceuticals, pho-
tography chemicals and further small-scale applications. Diphenylamines are still produced worldwide by the chemical
industries. First reports showed that DPA was found in soil and groundwater. Some ecotoxicological studies dem-
onstrated the potential hazard of various diphenylamines to the aquatic environment and to bacteria and animals.
Studies on the biodegradability of DPA and its derivatives are very sparse. Therefore, further investigation is required
to determine the complete dimension of the potential environmental hazard and to introduce possible (bio)remediation
techniques for sites that are contaminated with this class of compounds. This is the first detailed review on DPA and
some derivatives summarizing their environmental relevance as it is published in the literature so far and this review will
recommend conducting further research in the future.
Ó 2003 Elsevier Ltd. All rights reserved.

Keywords: Diphenylamine; Nitrodiphenylamine; Aminodiphenylamine; Stabilizer; Toxicity; Microbial degradation; Bioremediation

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .................. . . . . . 810

2. Application and occurrence of DPA and derivatives. . . . . . .................. . . . . . 810
3. Chemistry and toxicity of DPA and derivatives . . . . . . . . . .................. . . . . . 811
4. Environmental fate, microbial degradation, and metabolism of DPA and derivatives . . . . . 812
5. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .................. . . . . . 813
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .................. . . . . . 815
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .................. . . . . . 815

*
Tel.: +49-421-218-7234; fax: +49-421-218-7222.
E-mail address: drzyzga@biotec.uni-bremen.de (O. Drzyzga).

0045-6535/$ - see front matter Ó 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/S0045-6535(03)00613-1
810 O. Drzyzga / Chemosphere 53 (2003) 809–818
1. Introduction
Diphenylamine (DPA; structure see Fig. 1A) is a
chemical compound of the third European Union list of
priority pollutants. The elaboration of recommenda-
tions to assess and control the environmental risks
originating from this compound was assigned to Ger-
many by the Commission of the European Communities
(Kommission der Europ€aischen Gemeinschaften, 1997).
While for aniline (the simplest primary amine of pure
aromatic structure) numerous studies concerning toxi-
city and degradability are known since many years, the
simplest secondary amine of pure aromatic structure,
DPA, has been entered into the list of priority pollutants
quite recently. Because of its antioxidative property,
DPA is a stabilizing compound predominantly included
in mono-, di-, and tri-base propellants of missiles and
nitrocellulose-containing explosives. The mostly utilized
stabilizers are diphenylamine and its urea-substituted
derivatives, the so-called ‘‘acardites’’ and ‘‘centralites’’
(see example given in Fig. 1D). They can be distin-
guished in: acardite I (unsymmetrical diphenyl urea),
acardite II (methyldiphenyl urea), acardite III (ethyldi-
phenyl urea); centralite I (symmetrical diethyldiphenyl
urea), centralite II (symmetrical dimethyldiphenyl urea),
and centralite III (methylethyldiphenyl urea) (Meyer,
1977). Some of these stabilizers have the additional
function to be gelatinizing compounds, an advantage
for manufacturing processes of multi-base, solvent-free
gunpowders and propellants (Meyer, 1977).
Apart from military utilization, diphenylamines were
and are still used in numerous further industrial appli-
H DPA is predominantly used as stabilizer for single- or
N N
Diphenylamine Diphenylamidogen
(A) (B)
CH3
O NH
A
H
D C
N N
B CE F Thornton, 1994). If DPA from ammunition waste causes
Diphenylamine derivatives Acardite II
(C) (D)
Fig. 1. Molecular structures of diphenylamine and derivatives.
Panel 1B shows the radical structure of DPA. The substituents
A–F in panel 1C are variable (see description in the text) or
covered by hydrogen atoms. Arcardite II (methyldiphenyl urea)
is one example for urea-substituted derivatives of DPA (panel
1D).
cations (see next section). DPA-containing stabilizers
usually have not been taken into consideration in ana-
lytical investigations of ammunition-contaminated sites.
The contamination of soils of former ammunition plants
with nitro- and amino-substituted compounds as well as
other additives (e.g., stabilizers) is a constant source of
hazard for the human health, especially if these sub-
stances pass into underground and surface waters (Haas
et al., 1990; Gorontzy et al., 1994; Blotevogel and
Gorontzy, 2000). Many of these substances own muta-
genic properties and carcinogenic potential, which has
been confirmed by animal experiments for a large
number of such compounds (Dieter, 1994; Greim et al.,
1998; Lachance et al., 1999). It is known from nitro-
aromatic compounds that they can cause toxications in
humans connected with haemato- and hepatotoxical
alterations. Because of the multitude of substances
contained within ammunition wastes and because of their
even larger number of metabolites, a toxicological eval-
uation of the total contamination is often very difficult
to realize (Dieter, 1994; Greim et al., 1998).
2. Application and occurrence of DPA and derivatives
The worldwide annual production of DPA in the
1980s was about 40 000 t of which nearly 4000 t were
produced in Germany (BUA, 1993; Rippen, 1997). The
compound still has an industrial significance, so that the
todayÕs annual production amount may be even higher.
This is especially supported by published values showing
high production rates for this compound in the eastern
countries of Europe (for example, the Slovak Republic
producing more than 10 000 t/year (M urin et al., 1997)).
multi-base propellants and nitrocellulose-containing
explosives. It has the function of binding degradation
products, which develop during long-term storage (e.g.,
NO, NO2 , HNO3 ) in order to prolong storage times.
Otherwise, the nitric degradation products would en-
hance further decomposition so that finally the powder
becomes useless (Espinoza, 1988; Espinoza and Thorn-
ton, 1994). During its stabilizing reaction, DPA is
transformed to its nitrated derivatives (above all to
mono-, di- and trinitro-DPA) (Curtis and Rogasch,
1987; Espinoza, 1988; Haas et al., 1990; Espinoza and
soil and water contamination, it always will be accom-
panied by nitrated DPA derivatives. For example, at a
site of a former ammunition plant in Lower Saxony
(Germany), in which nitrocellulose had been produced
and mixed with DPA as stabilizer during the second
world war, Haas et al. (1990) could detect large fractions
of contaminated material. Gunpowder plates or discs
were found at this site, which showed high concentra-
tions of DPA (1.4–2.9 g/kg), 2-nitro-DPA (0.5–1.25
 O. Drzyzga / Chemosphere 53 (2003) 809–818
g/kg), and 4-nitro-DPA (0.4–1.2 g/kg). In another study,
Entenmann and Sch€acke (1994) reported on a former
military air base area in Lower Saxony (Germany) on
which a widely scattered, diffuse contamination with
DPA, 2-nitro-DPA, and 4-nitro-DPA in soil and in
groundwater had been detected.
In general, the detection of DPA and derivatives has
not found analytical consideration in most cases until
now, although the analytical techniques are established
(see references below).
DPA is also widely used to prevent post-harvest de-
terioration (storage scald) of apple and pear crops (Olek,
1988; Gutenmann et al., 1990; Ingle et al., 1990; Johnson
et al., 1997; Kim-Kang et al., 1998; Mir and Beaudry,
1999). Another important application of DPA is its use
as an antioxidant for various polymers and elastomers
and as condensates for the insulation of rubber. Some
further applications include: (i) DPA as precursor for
the chemical synthesis of (azo-)dyes such as Metanil
Yellow and Orange IV (Layer and Kehe, 1981; Shao and
Young, 1994; Lye and Freeman, 1999), (ii) DPA as
stabilizer in perfumery products (Calnan, 1978; Bazin
et al., 1986), (iii) its use for the detection of oxidizers
(Sugihara et al., 1993), (iv) its use for the detection
of DNA (Decallonne and Weyns, 1976; Gendimenico
et al., 1988; Thompson and Dvorak, 1989; Hauser and
Karamata, 1992), (v) its use as a biozid against body
louse, chiggers and housefly (Layer and Kehe, 1981),
and (vi) its use as a precursor of non-steroidal anti-
inflammatory drugs (Shaw et al., 1995; Masubuchi et al.,
1999).
4-Amino-DPA (4A-DPA; see Fig. 1C with B ¼ –NH2 )
is used in the production of hair dyes and other dyes
(Singh et al., 1986, 1992), is a precursor and intermediate
for the synthesis of various chemicals for photography
and for pharmaceutical products (Layer and Kehe, 1981;
Srivastava et al., 1982; Lye and Freeman, 1999), and is
used in rubber compound manufacture (Layer and Kehe,
1981). Additionally, 4-amino-DPA is an azo reduction
metabolite of the widely used food dye Metanil Yellow
(Raza et al., 1982, 1983; Singh et al., 1986).
2-Nitro-DPA (2N-DPA; see Fig. 1C with A ¼ –NO2 ),
4-nitro-DPA (4N-DPA; see Fig. 1C with B ¼ –NO2 ), and
2,4-dinitro-DPA (24diN-DPA; see Fig. 1C with A and
B ¼ –NO2 ) are used in different dispersion colors and are
components of several azo dyes (Burkinshaw and Lu,
1993; Lye and Freeman, 1999). 4-Nitro-DPA is also used
as intermediate for the production of antioxidant ad-
ditives for rubber products (Layer and Kehe, 1981).
2-Nitro-DPA is a component of Otto Fuel II used by the
US Navy as fuel for torpedoes and other weapon systems
(Powell et al., 1998). 2,20 ,4,40 ,6,60 -Hexanitro-DPA (hexyl;
see Fig. 1C with A, B, C, D, E, and F ¼ –NO2 ) was
used by Navy military forces as underwater explosive
(marine bombs, marine mines, and torpedoes) in mix-
tures together with TNT (trinitrotoluene) and aluminium
811
powder and therefore represents a hazard for the aquatic
marine environment (Meyer, 1977; Urbanski, 1985;
Schreiber, 1990). Nevertheless, hexyl-containing explo-
sives have not been produced anymore for military ap-
plications.
2,20 ,4,40 -Tetrahalo-DPA (see Fig. 1C with A, B, D
and F ¼ –Br or –Cl) are used in biocidal reagents (Layer
and Kehe, 1981) and 2-carboxy-DPA (also known as
DPC; see Fig. 1C with A ¼ –COOH) is used as a non-
specific Cl channel blocker (open pore inhibitor) for
physiological studies (Leung and Wong, 2000; Fortner
et al., 2001; Fortuna et al., 2001; Kogan et al., 2001;
Trout et al., 2001).
Because of the manifold utilization of DPA and de-
rivatives there is a lot of literature available for the
analytical detection of these compounds. Spectropho-
tometric, voltametric and amperometric, colorimetric as
well as numerous chromatographic methods have been
applied (TLC, HPLC, GC, and GC/MS) (Piorr and
Toth, 1967; Allen and Hall, 1980; Luke and Cossens,
1980; Ryder and Knowlton, 1983; Curtis and Rogasch,
1987; De Jong and Verweij, 1988; Espinoza, 1988; Olek,
1988; Ho et al., 1990; Wigfield and McLenaghan, 1990;
Bergens, 1995; Bergens and Danielsson, 1995; Drzyzga,
1996; Drzyzga and Blotevogel, 1997; Yu et al., 1997;
Tong et al., 2001).
DPA is also described as a naturally occurring
compound in onions (Karawya et al., 1984), in leaves of
black and green tea and further plants (Nose et al., 1971;
Karawya et al., 1984; Wang et al., 2001) as well as in the
peel of citrus fruits (Piorr and Toth, 1967). Therefore,
the development of microbial degradation strategies for
this compound could have occurred during microbial
evolution.
3. Chemistry and toxicity of DPA and derivatives
DPA is a very reactive compound. This is due to the
imine hydrogen atom, which can easily be replaced
electrophilically. For example, it can be replaced by al-
kali metals, a reaction which can be used for the detec-
tion of potassium (as N -potassium-DPA). Also metals
(e.g., aluminum) are able to displace the hydrogen under
formation of metal (e.g., aluminum) diphenylamide. Nu-
merous other derivatives are known which are formed
when the N-hydrogen is replaced by alkyl-, aryl-, or
acyl-groups. A transformation to carbazole can happen
via dehydrogenation of the two carbon atoms in ortho-
position. The reaction with nitric compounds (as men-
tioned above) leads rapidly to N -nitroso-DPA, followed
by complete nitration to various nitrodiphenylamines.
Espinoza and Thornton (1994) summarized some plau-
sible nitrosation and nitration mechanisms of DPA, in-
cluding the classical explanation of DPA conversion into
its various derivatives by rearrangement reactions of
812 O. Drzyzga / Chemosphere 53 (2003) 809–818
N-nitrosamines to the C-nitroso compounds (the Fisher–
Hepp reaction) and its subsequent oxidation to the cor-
responding nitro compounds. Also halogenations with
chlorine or bromine to produce polyhalogenated DPA
(e.g., 2,20 ,4,40 -tetrahalo-DPA as mentioned above) can
be obtained. A large number of further derivatives is
known, which will not be listed here. Many of these
derivatives are generated from the so-called ‘‘diphenyl-
amidogen’’, the highly reactive radical of the deproto-
nated DPA (Fig. 1B). This unstable radical is developed
during oxidation of DPA with different oxidizing agents
and demonstrates its utilization property as a highly
effective anti-oxidizing agent (Sugihara et al., 1993). For
further information about the chemistry of DPA and
other diarylamines see the review of Layer and Kehe
(1981).
Little is known about the toxicity of DPA and de-
rivatives. The current knowledge is basically limited on
the parent compound DPA and 4-amino-DPA. DPA
can enter humans orally, percutaneously or by inhala-
tion, and accidentally it leads to dermatitis effects
(formation of vesicular and exudative eczemas) when
employees worked with DPA-containing products
(Raith, 1976; Bazin et al., 1986; Hemmer et al., 1997). Ec-
zema formation, hypertension, tachycardia, and bladder
diseases have been observed when humans had been
administered alcoholic DPA solutions (GDCh, 1988).
DPA treatment in short-time studies and during long-
term expositions in animal experiments with dogs, rats,
and mice showed an increase of organ weights, methe-
moglobinemia as well as liver, spleen, and kidney dam-
aging effects (e.g., coagulations, necroses and lesions)
(Alexander et al., 1965; Thomas et al., 1967a,b; Crocker
et al., 1972; Sorrentino et al., 1978; Kronevi and
Holmberg, 1979; Powell et al., 1983, 1984; Alvarez et al.,
1987; GDCh, 1988; Mallon et al., 1988; Lenz and
Carlton, 1990; Das et al., 1992; Rohrbach et al., 1993;
Lenz et al., 1995; Masubuchi et al., 2000). The oral LD50
for rat, mouse, and guinea pig is reported to be 1165–
2000, 1750, and 300 mg/kg, respectively (RTECS, 1995;
GDCh, 1988). Yoshida et al. (1989) reported on a
NOEL on male and female F344 rats of about 111 mg/
kg/day. After oral intake and metabolism (e.g., oxida-
tion to hydroxy-DPA derivatives, glucuronidase reac-
tions), the excretion takes place via urine and faeces
(Das et al., 1992). A direct mutagenic or carcinogenic
effect of DPA could not be detected in diverse Ames
tests with different cultures of Salmonella typhimurium
(TA 98, TA 100, TA 1535, TA 1538; with or without
metabolic activation), in several DNA tests (e.g., DNA
reparation test (SOS repair system), Unscheduled DNA
Synthesis (UDS), point mutation test) as well as in
studies with rats, mice, and dogs (GDCh, 1988; Mallon
et al., 1988; Das et al., 1992; Rippen, 1997). Ardito et al.
(1996) reported on a slight increase of sister chromatid
exchanges after a 48-h influence of DPA on cultured
human lymphocytes. A further study indicated oxidative
DNA injuries within liver cells of rats caused by DPA
(Lodovici et al., 1997).
Contact with 4-amino-DPA leads to skin irritations
(Raza et al., 1983) and shows interaction with gut mu-
cosal epithelium of rats causing alterations (Raza et al.,
1982). Srivastava et al. (1982) reported on binding ca-
pacity of 4A-DPA to proteins of the liver tissue (espe-
cially binding to aspartic and glutamic acid). Binding
affinity of 4A-DPA to serum proteins was also shown by
Raza et al. (1983). These authors showed the covalent
binding of 4A-DPA to aspartic acid, especially to the
globulin fraction. The oral LD50 for 4A-DPA is 464 mg/
kg for rats and about 847 mg/kg for male and female
albino rats (RTECS, 1995). These values are much lower
than the LD50 value measured for 4-nitro-DPA of above
7940 mg/kg for rats (RTECS, 1995), clearly demon-
strating that the aromatic amines in general are more
toxic than the nitrated (parent) compounds.
DPA is hazardous to organisms of the aquatic envi-
ronment as shown by the EC50 values of Kaiser and
Ribo (1988) for the bioluminescent bacterium Photo-
bacterium phosphoreum. After 30 min contact time, a
value of about 4.75 mg/l was determined. This value was
confirmed by Drzyzga et al. (1995a) with Vibrio fischeri
as model organism (5.5 mg/l) and therefore, the au-
thors classified DPA as ‘‘very toxic for aquatic organ-
isms’’ by using a widely accepted classification scheme.
More ecotoxicological effects of various diphenylamines
are summarized in Table 1.
DPA also shows inhibitory effects on the photosyn-
thesis of phototrophic bacteria. Goodwin (1980) re-
ported on the inhibition of the carotenoid synthesis of a
few photosynthetic bacteria by DPA. Another study
demonstrated the negative effect of DPA on the photo-
synthetic apparatus of Rhodopseudomonas sphaeroides.
DPA treatment led to a decrease of the spheroidin
synthesis and to the accumulation of reduced precursors
(Michalski et al., 1985). Sharp et al. (1999a,b) found that
DPA is a binding QO site inhibitor of the cytochrome
bc1 of Rhodobacter capsulatus.
Additional toxicological data of DPA are summa-
rized in the data compilation of Rippen (1997).
4. Environmental fate, microbial degradation, and meta-
bolism of DPA and derivatives
The water solubility of a compound is decisive for its
bioavailability and eventual toxic effects. Depending on
the temperature, DPA shows a water solubility of
around 35–45 mg/l (Meyer, 1977; Layer and Kehe, 1981;
GDCh, 1988; Drzyzga, 1996; USEPA, 1998). DPA has
been classified in Germany as strongly water endanger-
ing (water endangering class 3) (Rippen, 1997). The
available data indicate that DPA is stable towards hy-
 O. Drzyzga / Chemosphere 53 (2003) 809–818
Table 1
EC values of DPA and some derivatives
Compound EC (effective concentration) values
DPA EC50 and EC100 Daphnia magna: 2.3 and 7.0 mg/l, respectively
EC50 Photobacterium phosphoreum: 4.75 mg/l
EC50 Vibrio fischeri: 5.5 mg/l
4A-DPA EC50 Photobacterium phosphoreum: 0.33 mg/l
EC50 Vibrio fischeri: 1.1 mg/l
2A-DPA EC50 Vibrio fischeri: 1.5 mg/l
4N-DPA EC50 Vibrio fischeri: 1 mg/l
2N-DPA EC50 Vibrio fischeri: 7.7 mg/l
24diN-DPA EC50 Vibrio fischeri: 5.3 mg/l
Hexyl EC50 Vibrio fischeri: 6.3 mg/l
drolysis at pH values of 5, 7, and 9 (USEPA, 1998).
DPA appears as a lipophilic substance with a distribu-
tion coefficient (n-octanol/water) log Pow of 3.42 (Rip-
pen, 1997). The vapor pressure of DPA was determined
to be around 6.39  104 Torr (USEPA, 1998). In ex-
periments with the fathead minnow (Pimephales prom-
elas), a bioconcentration factor (BCF) of 30–70 was
found (GDCh, 1988; Rippen, 1997). Also plants are able
to enrich DPA, as for example barley with an enrich-
ment factor of 4 (Mallon et al., 1988). According to
adsorption/desorption effects, the mobility of DPA
ranges from slightly mobile (Kads ¼ 151:57 in clay soil)
to mobile (Kads ¼ 21:43 for loamy sand, Kads ¼ 13:79 for
loam, Kads ¼ 4:92 for silt loam, and Kads ¼ 16:44 for silty
clay loam sediment (USEPA, 1998)).
The physico-chemical and biological degradation of
DPA has only been investigated to a little extend. Thus,
photolytical half-life times of DPA in water during solar
radiation of about 2–33 h (depending on the season)
were determined (BUA, 1993). An irradiation of an
aqueous DPA solution with a wavelength of 313 nm at
pH 7 and 25 °C led to a photolytic (oxidative) trans-
formation to carbazole, and under oxygen exclusion to a
disproportionation to carbazole and tetrahydrocarb-
azole (GDCh, 1988; Mallon et al., 1988).
The biological degradability of DPA and substituted
diphenylamines (nitrated, aminated, methylated, halo-
genated, etc.) has scarcely been investigated until today.
A former publication of Gardner et al. (1982) refers to
an aerobic metabolism of 14 C-labelled diphenylamine.
After incubation of 14 C-DPA in a sewage sludge exper-
iment, the radioactivity was recovered within the me-
tabolites 4-hydroxy-DPA, an unknown isomer, aniline,
and indole. These compounds were identified also in
studies on the microbial degradation and metabolism of
DPA and some derivatives under anoxic conditions
(Drzyzga, 1996; Drzyzga et al., 1996; Drzyzga and
Blotevogel, 1997). The few existing data about products
813
References
GDCh (1988)
Kaiser and Ribo (1988)
Drzyzga et al. (1995a)
Kaiser and Ribo (1988)
Drzyzga et al. (1995a)
Drzyzga et al. (1995a)
Drzyzga et al. (1995a)
Drzyzga et al. (1995a)
Drzyzga et al. (1995a)
Drzyzga et al. (1995a)
and metabolites of the biological degradation of DPA
and derivatives are summarized in Table 2. In nearly all
studies not all metabolites have been extracted or
chromatographically identified. Gardner et al. (1982)
showed that more than 35% of the initial concentration
of 14 C-labelled DPA remained as a residual concentra-
tion after 6 h of incubation in a model sewage sludge
experiment. Consequently, a retention time of DPA-
containing waste water of 2–6 h within the aerobic
treatment complex of a sewage plant is in any case too
short, if the complete degradation of DPA in waste
water will be guaranteed (Gardner et al., 1982).
Nevertheless, the data obtained from the available
literature allow the conclusion that a complex mixed
culture should be able to mineralize DPA and DPA
derivatives. As shown in Table 2 and in Figs. 2 and 3,
the central main product of the anaerobically, microbi-
ally mediated DPA degradation is always aniline, a
compound which is completely degradable under oxic
and anoxic conditions (e.g., Aoki et al., 1983; Schnell
and Schink, 1991; Zissi and Lyberatos, 1999; Kahng
et al., 2000). Also the aerobically, microbially mediated
DPA degradation seems to proceed via aniline (Gardner
et al., 1982) and can therefore lead to total mineraliza-
tion to CO2 , NHþ 4 and H2 O. In addition to complete
mineralization of DPA and derivatives, side reactions
leading to more complex condensation products (e.g.,
carbazole, phenazines, acridines, and benzothiazoles)
have been observed (Table 2).
5. Conclusions
DPA and derivatives still enter the environment and
these compounds represent a group of problematic
substances from the ecotoxicological point of view. For
this reason, their integration into a controlling ana-
lytic at suspicious sites with DPA contamination is
814 O. Drzyzga / Chemosphere 53 (2003) 809–818

Table 2
Microbial degradation and transformation of DPA and some derivatives
Compound Products and metabolites References
DPA 4-Hydroxy-DPA, aniline, indole (and some unidentified metabolites Gardner et al. (1982)
resulting from the oxidative cleavage of the aromatic ring system)
Aniline as product of DPA cleavage under anoxic conditions (by Drzyzga (1996), Drzyzga and
anaerobic enrichments and sulfate-reducing bacteria) Blotevogel (1997)
Decrease of DPA concentration without identification of intermediates Christodoulatos et al. (1997)
and degradation products (DPA was used aerobically as carbon source by
three Pseudomonas species and by activated sewage sludge)
Biological and abiotic transformation of DPA to 2-OH-, 3-OH-, 4-OH- Kim-Kang et al. (1998)
and 2,40 -diOH-DPA and to glycosyl conjugates of the hydroxylated
intermediates
99.6% decrease of DPA from water in an enzymatic system with horse Verschueren (1996)
radish peroxidase (HRP)

4N-DPA 4A-DPA as product of reduction under anoxic conditions (4-OH-DPA Drzyzga et al. (1995b, 1996)
also found)
2N-DPA 2A-DPA as product of reduction under anoxic conditions Drzyzga et al. (1995b, 1996)
Decrease of 2N-DPA concentration (no identification of intermediates Powell et al. (1998)
and degradation products; cometabolic degradation by Clostridium
species)
4A-DPA Aniline as main product after cleavage; no condensation products Drzyzga et al. (1996)
2A-DPA Aniline as main product after cleavage; further products: phenazine, Drzyzga et al. (1996)
4-aminoacridine, indole, and methylaniline
24diN-DPA 2A4N-DPA as primary and 24diA-DPA as final product of reduction Drzyzga et al. (1995b)
under anoxic conditions
Aniline as main product after cleavage; further products: 2-aminophen- Drzyzga et al. (1996)
azine and three benzothiazole derivates
Hexyl Rapid decrease of hexyl concentration (no identification of intermediates Drzyzga (1996)
or degradation products)

(A) H (B) H
not problematic, if the DPA is totally removed when the
N N fruits are washed before consumption, so that it will not
pose a direct danger for the human health. Nevertheless,
the cleaning of the fruits shifts the environmental threat
of DPA and derivatives to the wastewater side. Because
+ 2[H] + H2O
of the lack of toxicity data for diphenylamines especially
NH2 NH2 with regard to human toxicology, it becomes obvious
that there is still a need for research, particularly since
HO these compounds have already been detected in soil and
Aniline Benzene Aniline Phenol groundwater. Various remediation techniques have al-
ready been applied for several xenobiotic compounds
and should be investigated and tested in more detail also
for DPA and its derivatives in future studies.
Aromatic amines are known to be mutagenic and
mineralization carcinogenic and their detection as well as their con-
trolling in the environment has found an increasing at-
Fig. 2. Microbially mediated hydrolytic cleavage (B) and re-
tention during the last years (Schmidt et al., 1998; Rao
ductive cleavage (A) of DPA in anaerobic enrichments and by
et al., 1999, 2001). Because of the manifold application
bacterial pure cultures (adopted and changed from Drzyzga,
1996, 1999). of diphenylamines and the worldwide diffusion into the
environment, the ecotoxicological evaluation of this
group of compounds should not be ignored. As an
recommendable. The application of DPA to help control antioxidant and therefore with the function as a stabi-
apple and pear scald and to prolong their storability is lizer, DPA will open up new fields of application in the
 O. Drzyzga / Chemosphere 53 (2003) 809–818 815

NO2 NO2 Alvarez, F., Diaz-Alferez, F.J., Perez-Munoz, P.J., Arteaga-

H H H
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