Water Air Soil Pollut (2007) 183:177–186
DOI 10.1007/s11270-007-9367-3
Evaluation of Biodegradability and Biodegradation Kinetics
for Anionic, Nonionic, and Amphoteric Surfactants
Sybil Sharvelle & Rebecca Lattyak &
M. Katherine Banks
Received: 27 October 2006 / Accepted: 9 February 2007 / Published online: 20 April 2007
# Springer Science + Business Media B.V. 2007
Abstract The biodegradation kinetics of anionic
(sodium laureth sulfate – SLES), amphoteric (diso-
dium cocoamphodiacetate – DSCADA), and nonion-
ic surfactants (polyalcohol ethoxylate – PAE) were
assessed in this laboratory study. Similar degradation
behavior was observed for all surfactants with only a
fraction of the parent compound readily biodegradable.
Biodegradation, as estimated by COD removal, was
initially (i.e., within 24 h) rapid, however only 40–70%
of the surfactant molecules were readily biodegradable.
Intrinsic kinetic parameters were successfully quanti-
fied for the readily biodegradable component of the
surfactant. Inhibition was not observed and microbial
kinetics of SLES, DSCADA, and PAE degradation fit
the Monod model well. Average μ-S curves were
generated for each surfactant. Based on these results,
complete degradation of the target surfactants using
biological waste treatment would be limited.
Keywords Surfactants . Biodegradation . Bacteria .
Kinetics . Metabolism . Growth
S. Sharvelle (*) : R. Lattyak : M. K. Banks
School of Civil Engineering, Purdue University,
West Lafayette, IN 47907, USA
e-mail: ssharvel@purdue.edu
1 Introduction
Surfactants are present as active constituents in
detergents, personal hygiene products, and industrial
solvents. Due to their widespread use, surfactants are
commonly encountered in domestic and industrial
wastewaters. Most surfactants are reported to be at
least partially biodegradable. However, surfactants are
characterized by high molecular weight and complex
structures and thus biodegradation pathways are often
multi-step processes (Jimenez et al. 1991; van Ginkel
1996). Metabolites formed during surfactant biodeg-
radation may degrade more slowly than the parent
compound (Griffiths et al. 1986; van Ginkel 1996;
Bokern and Harms 1997; Bennie 1999; Itrich and
Federle 2004). The fate of surfactants in biological
treatment systems is becoming increasingly important
as water reuse systems become more common and
regulations for trace contaminant release by wastewa-
ter treatment plants are more stringent. Contaminants
present in wastewater effluent may have the potential to
accumulate in the environment. In order to design bio-
logical treatment systems for removal of both surfac-
tants and their relevant degradation byproducts,
biokinetics of surfactant degradation must be well defined.
The most commonly used models for microbial
growth kinetics are the Monod equation for a non-
inhibitory substrate:
b Ss
m
m¼ ð1Þ
Ks þ Ss
178
and the Andrews equation for a substrate that is
inhibitory to biodegradation:
b Ss
m itates during surfactant degradation.
m¼ ð2Þ
Ks þ Ss þ Ks2 =KI
b is the maximum
where μ is the specific growth rate, m
specific growth rate, Ss is the soluble substrate
concentration, Ks is the half saturation constant, and
KI is an inhibition coefficient. Determination of
substrate specific kinetic parameters in these models
(mb, Ks, and KI) enables prediction of removal rates
from biological waste treatment systems, thus sup-
porting design decisions. Several approaches have
been applied to determine biokinetic parameters for
specific substrates including measurement of substrate
removal, microbial growth, or oxygen consumption
over time. Measurement of oxygen consumption by
respirometry has been found to be more reliable than
other methods for kinetic parameter estimation
(Grady et al. 1989).
Although extensive research exists regarding bio-
degradation extent of surfactants (Balson and Felix
1995; Domsch 1995; Steber and Berger 1995),
biokinetic parameters have not been well character-
ized for most surfactants. There are three types of
surfactants commonly present in personal cleansing
products and detergents; anionic, nonionic, and
amphoteric. Anionic surfactants are characterized by
the presence of an anion as the hydrophilic moiety
whereas nonionic surfactants are not ionized in
solution (Lange 1999). Amphoteric surfactants are
characterized by zwitterionic properties, that is, the
molecules are capable of possessing either a positive
or negative charge. Some researchers have investigat-
ed simple kinetics of surfactant biodegradation.
Biokinetics were determined for two anionic and
two nonionic surfactants based on microbial growth
data (Zhang et al. 1999). Others have examined
microbial growth kinetics using an anionic surfactant,
linear alklybenzene sulfate (Perales et al. 1999).
Several bacterial populations capable of degrading
octylphenolpolyethoxylate, a nonionic surfactant,
were identified and biokinetics quantified (Chen
et al. 2005). Kinetic parameters determined by Perales
et al. (1999) and Chen et al. (2005) can not be applied
to broad design scenarios due to the conditions under
which experiments were conducted. Zhang et al.
(1999) developed kinetic parameter estimations that
Water Air Soil Pollut (2007) 183:177–186
can be applied in a more general sense. However, the
researchers did note interference with biological
growth data resulting from the formation of precip-
The objective of this research is to examine the
biodegradability of and determine biokinetic parame-
ters for representative surfactants from each group
(anionic, nonionic, and amphoteric) with the goal that
parameter estimates can be applied to biological waste
treatment design decisions for graywater treatment
and water reuse applications. In terms of anionic
surfactants, sufficient work has been done to charac-
terize microbial kinetics for linear alkylbenzene
sulfonate (Perales et al. 1999; Zhang et al. 1999).
Therefore, another commonly used anionic surfactant,
sodium laureth sulfate (SLES), was chosen for this
study. SLES is commonly found as a component in
personal care products (Raney 1999). Polyalcohol
ethoxylates (PAEs) are the most widely used nonionic
surfactants and are present in most dishwashing and
laundry detergents (Raney 1999). Therefore, a repre-
sentative PAE was chosen for this study. Very little
research exists on amphoteric surfactants because
they have only recently gained widespread accep-
tance. The use of amphoteric surfactants in personal
care products is projected to grow by 3% annually
(Uphues 1998). Disodium cocoamphodiacetate
(DSCADA) was chosen as a representative ampho-
teric surfactant. Respirometry methods were used to
monitor oxygen uptake for estimation of biokinetic
parameters for these surfactants.
2 Materials and Methods
2.1 Surfactants
The chemical structures of the surfactants used in this
study (SLES, DSCADA, and PAE) are shown in
Fig. 1. SLES is a member of the alcohol ether sulfate
group of anionic surfactants and was purchased from
Stepan Co. in the form of STEOL CS-330 (28.8%
SLES). STEOL CS-330 contains SLES that is
ethoxylated to an average of 3 moles. DSCADA is a
mixture of the compounds depicted in Fig. 1b and c
and is a member of the alkylamphoacetate group of
amphoteric surfactants. This surfactant was purchased
from Rhodia Inc. in the form of Miranol (38.5%
DSCADA). Neodol 23-5 ® (Shell Co.) is 100% pure
Water Air Soil Pollut (2007) 183:177–186 179

a O
ONa
O S
O O
n O

OH
OH
b c
ONa

O O

NH N O
R N R N
H H

ONa
O O ONa

d
OH
O
n
Fig. 1 Structure of a SLES, b and c DSCADA, and d PAE

PAE and is a mixture of 12 and 13 carbon length alkyl
chains with an average of 5 moles ethylene oxide per
mole of alcohol ethoxylate (Fig. 1d).
2.2 Experiment Setup
A detailed description of respirometry techniques
applied to determine biokinetic parameters has been
published previously (Brown et al. 1990; Grady et al.
1989). For this experiment, a respirometer (Columbus
Instruments, Columbus, OH) was used to quantify
oxygen consumption during microbial metabolism of
the surfactants of interest. Samples were automatical-
ly collected from the headspace of 300 ml closed
bottles and supplied to an oxygen sensor. Gas samples
were passed through the oxygen sensor and recircu-
lated back to sample bottles. The instrument is
capable of detecting leaks in sample bottles and it
was ensured that all bottles were completely sealed at
the beginning of the experiment. The concentration of
oxygen in the headspace was automatically recorded
by computer. Sample bottles were placed on stir
plates and mixed throughout the experiment to ensure
adequate oxygen transfer between the liquid and gas
phases. The respirometer was programmed to auto-
matically refresh air in the headspace of bottles if
oxygen became limiting. However, this was not
necessary during any of the experiments.
To ensure that oxygen consumption is solely a
result of biodegradation of the substrate of interest
and that the inoculum consists primarily of bacteria
that utilize the target substrate, it is necessary to
acclimate bacteria to the surfactant prior to the
experiment (Grady et al. 1989). This acclimation
period also alleviates a lag phase in the oxygen
consumption curve, facilitating straightforward data
analysis. Three separate flasks were used to acclimate
bacteria to SLES, DSCADA and PAE for at least two
weeks prior to the start of experiments. Activated
sludge samples were collected from the recycle line of
180
the activated sludge tank at the West Lafayette
Wastewater Treatment Plant (West Lafayette, IN)
and used as an inoculum. Each flask contained 5 ml
activated sludge and 95 ml minimal salts media
(MSM) solution with a surfactant concentration of
50 mg/l. The following constituents were dissolved in
1 l of distilled deionized (DDI) water to prepare the
MSM solution: 0.68 g potassium phosphate, 1.73 g
potassium phosphate dibasic, 0.10 g magnesium
sulfate, 1.00 g ammonium nitrate, and 0.1 ml of trace
elements per liter of MSM. The chemicals used to
prepare the trace elements solution were as follows:
2.00 g magnesium oxide, 0.40 g calcium carbonate,
1.08 g iron (III) chloride, 0.288 g zinc sulfate, 0.05 g
cupric sulfate, 0.0056 g cobaltous sulfate, 0.0124 g
boric acid, and 0.0098 g sodium molybdate. These
constituents were dissolved in 190 ml DDI water and
10 ml of hydrochloric acid. 50 mg/l surfactant was
supplied to the flasks twice per week over the
acclimation period.
For each respirometer run, three 100 ml samples
containing acclimated bacteria, MSM, and surfactant
were tested. In addition, two controls were used, one
containing acclimated bacteria in MSM solution (no
surfactant or carbon source added) and another
containing MSM solution with no bacteria added.
The first control bottle was used to ensure that
microbial degradation of carbon present in the
acclimated bacteria inoculum did not contribute
substantially to oxygen demand. The second control
was conducted to account for any minor abiotic shifts
in oxygen composition in the bottle headspace. The
surfactant concentrations were 73 mg/l SLES, 62 mg/l
DSCADA, and 80 mg/l PAE, or in COD units 150,
100, and 200 mg/l, respectively. Each substrate was
tested at only one concentration because the method to
determine kinetic parameters has been shown to be
independent of substrate concentration (Grady et al.
1989). This study focused on determination of
intrinsic kinetics. Intrinsic kinetics do not reflect the
growth history of bacteria because substrate levels are
kept high enough to allow for changes in microbial
community structure (Grady et al. 1996). The recom-
mended ratio of substrate COD to biomass COD for
determination of intrinsic kinetics is 20:1 (Grady et al.
1989). Therefore, biomass COD concentration was
determined for acclimated bacteria solutions prior to
the experiment and a volume of acclimated bacteria
was added to achieve the appropriate ratio of substrate
Water Air Soil Pollut (2007) 183:177–186
to biomass COD. Two respirometer runs were
performed for each surfactant with three replicate
solutions tested in each run for a total of six replicate
data sets for each surfactant. Brown et al. (1990)
reported that microbial growth kinetics can be highly
variable and recommended that a large number of
replicates be used to accurately characterize kinetic
parameters for growth on a specific substrate. Samples
were collected at the start of experiments for analysis
of initial soluble chemical oxygen demand (Ssom) and
initial biomass COD (Xo). Additionally, after a plateau
was observed in oxygen consumption, data samples
were collected and analyzed for soluble COD. The
dichromate colorimetric method outlined in Standard
Methods (Greenberg et al. 1992) was used to
determine COD of each sample with Hach Co. (Love-
land, CO) high range test kits. The detection range for
this test kit is 20–1,500 mg/l COD, which was adequate
for all samples analyzed.
2.3 Batch COD Removal Assays
For all surfactants tested, the COD concentrations at
the oxygen uptake plateau were higher than expected.
The COD removal was less than 70% in all cases.
However, if ultimate degradation of the surfactant had
occurred, one would expect to observe nearly 90%
removal of COD. Limited COD removal at the
oxygen uptake plateau was noted by other researchers
examining degradation of PAE (Godsey 1997). To
better understand COD removal over the course of
experiments, batch studies were conducted to evaluate
COD removal for each surfactant. Surfactant was
added to a solution containing 5% acclimated bacteria
by volume in MSM. Three replicate flasks were tested
for each surfactant. The initial surfactant concentra-
tion for each test was 248 mg/l SLES, 218 mg/l
DSCADA, and 80 mg/l PAE. Batch experiments
were terminated when a plateau was observed for
COD removal. For all surfactants tested, the rate of
COD removal substantially decreased after an initial
phase of rapid degradation. It was hypothesized that
the respirometer was not capable of detecting further
oxygen consumption due to lack of sensitivity. The
head space in the bottles was approximately 280 ml
compared to a sample volume of 100 ml and minor
fluctuations in oxygen due to slow degradation could
not be observed with this setup. Therefore, the
fraction of readily biodegradable COD ( fB) was
Water Air Soil Pollut (2007) 183:177–186 181

determined for each surfactant based on batch COD representation of readily biodegradable COD. The
removal assays. Plots were generated of COD versus following modified equations were applied:
time (Fig. 2) and when the slope changed by more  
than 50%, the fraction of COD removed was Ssom fB  Ssom  Sp
YP ¼ ð3Þ
determined to be fB. The point at which fB was Ssom fB
determined for each surfactant is indicated by an
arrow. Initial concentrations of SLES and DSCADA Ssom fB  OUP
(248 and 218 mg/l, respectively) were different than Y ¼  YP ð4Þ
Ssom fB
the initial concentrations used for respirometer studies
 
(73 and 62 mg/l, respectively). Observation of results OUH
from several batch COD removal studies for these Ks ¼ Ssom fB  ð5Þ
1  Yp  Y
surfactants indicated that fB was the same regardless
of initial surfactant concentration (data not shown). where Sp is the measured soluble COD at the oxygen
For purposes of assessing biokinetic parameters, the uptake plateau, OUP is oxygen uptake at the plateau,
initial soluble substrate (Ssom) was multiplied by fB to and OUH is the oxygen uptake at half the estimated
represent readily degradable soluble substrate. This maximum growth rate. Estimation methods for m b and
technique was also utilized by Godsey (1997); b were not modified from Brown et al. (1990). To
however, a theoretical fraction of readily degradable estimate mb, a plot was generated of μ vs. oxygen
surfactant was applied. Of note is that kinetic uptake (OU) and m b was assumed to be the value of μ
parameters reported in this paper are representative at the plateau of the curve. The values of μ for time t
of kinetics for primary surfactant degradation, not were obtained from:
ultimate degradation.
 dOU 
μ¼  Xo  dt t
ð6Þ
2.4 Parameter Estimation  ð1  YP  Y Þ þ ðOU Þt
Y
A method for preliminary estimation of kinetic
parameters mb, Ks, Yield (Y ), product yield (YP), and An estimate for b was made by fitting Eq. 7 to the
decay rate (b) was utilized and is described in detail oxygen uptake data using a nonlinear curve fitting
elsewhere (Brown et al. 1990). The equations used for routine in MATLAB:
preliminary estimates for YP, Y, and Ks were slightly    
modified from the methods used by Brown et al. OU  OUP ¼ Xp 1  exp b t  tp ð7Þ
(1990) due to the need to multiply Ssom by fB for
where tp and Xp are the time and biomass concentra-
tion associated with OUP. All units were expressed as
COD units. Final estimates for each parameter were
500
PAE not varied by more than 50% from the estimated
400 SLES values. Utilization of this method to make preliminary
DSCADA estimates for biokinetic parameters provides more
COD (mg/L)

300 accurate final estimates for Monod parameters than

f B (DSCADA)
making random initial guesses for parameters (Brown
200 et al. 1990), particularly because estimates are based
on measured data collected during experiments.
100
f B (SLES) f B (PAE)
Additionally, the method results in reduced problems
0 associated with parameter identifiability, or multiple
0 5 10 15 20 25 30 35 40 45 50 55 solutions for the same data set.
Time (hours) Plots of μ vs. OU were utilized to confirm that
Fig. 2 COD removal in shaker flasks containing SLES,
DSCADA, and PAE. Points where fraction of readily biode- inhibition kinetics were not observed as described by
gradable surfactant ( fB) were determined are indicated Brown et al. (1990). Inhibition kinetics did not occur
182
and, therefore, it was determined that all surfactants in
this study could be modeled using Monod kinetics. To
ensure that the OU observed was solely the result of
substrate consumption, plots were generated for dO U
dt
vs. OU (Brown et al. 1990). These plots were
evaluated based on the criteria that a constant positive
slope should be observed. Two data sets from PAE
experiments were discarded based on observation of
these curves, so there are four replicate data sets for
PAE rather than six.
A standard fourth order Runge-Kutta routine in
MATLAB software was applied to solve the set of
three differential equations (Eqs. 8–10) described by
Grady et al. (1989) that predict oxygen uptake (11)
over time based on kinetic parameters.
 
dSs b
m Ss
¼ X ð8Þ
dt Y Ks þ Ss
 
dSpr dSs
¼ Yp  ð9Þ
dt dt
   
dX Ss Ks
b
¼m X bX ð10Þ
dt Ks þ Ss Ks þ Ss
 
OU ¼ ðSsom  Ss Þ  ðX  Xo Þ  Spr  Spro ð11Þ
Ss is substrate COD, Spr is soluble product, Spro is
initial soluble product and X is biomass concentration.
Parameters were modified from original estimates
until the residual sum of squared error (RSSE)
between the predicted oxygen uptake curve and
experimentally determined oxygen uptake curve was
minimized. A nonlinear curve fitting routine in
MATLAB was utilized. Research has shown that
estimation of mb and Ks by taking the simple arithmetic
mean of parameter estimates from multiple data sets is
not accurate, particularly when high variability in the
data is observed (Magbanua et al. 1998). Because the
data collected was characterized by high variability,
the method for determining parameters representing
the average μ-S response (PRAMUS) (Magbanua
et al. 1998) was applied to quantify the mean m b and
Ks values for SLES, DSCADA, and PAE. The
function for nonlinear curve fitting in MATLAB was
utilized to determine PRAMUS values, minimizing
the RSSE between the predicted and experimentally
Water Air Soil Pollut (2007) 183:177–186
determined μ-S curves. The standard deviation from
the PRAMUS values (SP) was defined as follows:
rffiffiffiffiffiffiffiffiffiffiffiffiffi
P ffi
i dPi
SP ¼ ð12Þ
n1
where n is the number of samples and dPi ¼
jy P  y i j where ψ is the parameter of interest.
3 Results & Discussion
3.1 Batch COD Removal Assays
COD removal in batch reactors was tracked over time
for each surfactant and results are presented in Fig. 2.
Error bars indicate +/− one standard deviation for
three replicate flasks. For each surfactant, a point
could be observed where the rate of COD removal
clearly decreased with a change in slope of greater
than 50%. Based on these curves, fB was identified for
each surfactant as shown in Fig. 2. Empirically
determined values for fB are listed in Table 1. Other
researchers have observed that the degradation of
PAE became very slow or nonexistent after an initial
rapid biodegradation period for Neodol 45-7 ® and
Neodol 23-6.5 ® (Godsey 1997). Most researchers
agree that the most predominant pathway of PAE
biodegradation is an initial cleavage at the ether group
with the resulting byproducts of an alkyl chain and
polyethylene glycol (PEG) (Steber and Wierich 1985;
van Ginkel 1996). The degradation of PEGs occurs
more slowly than other degradation byproducts
formed during PAE degradation (van Ginkel 1996).
It is likely that the COD remaining after primary
biodegradation in shaker flasks and respirometer tests
consists primarily of PEGs. The most common
degradation pathway for SLES is similar to PAE and
involves an initial scission at the ether group by the
etherase enzyme. The resultant degradation products
Table 1 Empirically determined fraction of readily biodegrad-
able surfactant ( fB)
Surfactant fB
SLES 0.7+/−0.03
DSCADA 0.6+/−0.01
PAE 0.4+/−0.05
Water Air Soil Pollut (2007) 183:177–186 183

are mono-, di-, and tri-ethylene glycol sulfates and DSCADA (Domsch 1995; Bokern and Harms
depending on the location of the initial cut (Hales 1997). In fact, some research has shown less than 70%
et al. 1982; Griffiths et al. 1986). Glycol based removal of COD in closed bottle tests where DSCADA
metabolites have been found to persist longer than was the test compound (Domsch 1995), indicating
other products (Griffiths et al. 1986), consistent with potential for accumulation in the environment.
observations from this study. The significant decrease
in slope of the SLES COD removal curve likely 3.2 Monod Kinetic Parameter Estimates
occurs when only ethylene glycol sulfates remain and
all other metabolites have been degraded. Unfortu- Monod kinetic parameters were determined for SLES,
nately, a detailed description of biodegradation of DSCADA, and PAE (Table 2). Mean values reported
amphoteric surfactants does not exist in the literature. b and Ks are PRAMUS values while mean values
for m
Although our results clearly indicate that the degra- for Y and b are arithmetic means. RSSE values were
dation of DSCADA follows a similar trend as PAE divided by the number of data points (n) and a mean
and SLES in which biodegradation slows substantial- RSSE/n was calculated for each surfactant. Mean
ly after an initial rapid biodegradation step, it is RSSE/n values ranged from 0.68 to 1.3, indicating
difficult to predict the cause of this reduction or that parameter estimation provided a good fit of data
isolate specific metabolites that may slowly degrade. collected by respirometry to the Monod model. One
The data set presented in Fig. 2 indicates that representative model fit to DSCADA oxygen uptake
although primary biodegradation of surfactants occurs data is shown in Fig. 3 (RSSE/n=0.84). All data
rapidly, secondary byproducts are formed that exhibit collected during these experiments was characterized
slower biodegradation kinetics. In a set of follow-up by substantial variability (see mean deviation values
experiments, samples collected at the termination of in Table 2). Surfactant molecules are highly complex
respirometry experiments were filtered (0.45 μm) and and different degradation pathways are possible for
introduced to a fresh inoculum. Oxygen uptake was any given surfactant. Brown et al. (1990) also noted
not measurable for any samples either by respirometry high variability in kinetic data, particularly when
or by a microtiter-based oxygen sensor system different inoculums were used. When applying kinetic
(Garland et al. 2003) after introduction to a fresh
inoculum (data not shown), further indicating that
Table 2 Kinetic parameters for SLES (mean RSSE/n=0.68+/−
metabolites formed during biodegradation of surfac- 1.20), DSCADA (mean RSSE/n=1.0+/−0.36), and PAE (mean
tants were not readily biodegradable. Complete RSSE/n=1.3+/−1.3)
removal of the studied surfactants in a biological b (h−1)
m
Ks (mg/l) Y b (h−1)
treatment system may be limited or require a large
liquid retention time. Experimental conditions applied SLES:
in this study may have selected for fast growing Meana 13 0.21 0.34 0.015
primary degraders of surfactants and future studies Mean Dev.b 7.3 0.052 0.097 0.015
should be conducted to examine the biodegradability Min 3.9 0.16 0.17 0.0010
Max 24 0.30 0.44 0.040
of SLES, DSCADA, and PAE in biological treatment
DSCADA:
systems with cell recycle. While the fate of some
Meana 2.9 0.092 0.50 0.015
surfactants have been studied in municipal wastewater Mean Dev.b 1.7 0.017 0.13 0.02
treatment plants, such studies have not been con- Min 1.2 0.077 0.26 0.0010
ducted for SLES, DSCADA, and PAE (Domsch 1995; Max 6.2 0.12 0.7 0.06
Steber and Berger 1995; Bokern and Harms 1997). PAE:
The extent of biodegradability of alcohol ether sulfate Meana 6.3 0.19 0.48 0.02
surfactants, the group to which SLES belongs, has Mean Dev.b 1.6 0.078 0.21 0.02
Min 4.54 0.13 0.25 0.0010
been well studied and it has been shown that their
Max 8.0 0.29 0.67 0.05
biodegradation does not result in the formation of
recalcitrant byproducts (Steber and Berger 1995). a
b.
PRAMUS values reported for Ks and m
Similar data is not available in the literature for PAE b
b.
SP reported for Ks and m
184 Water Air Soil Pollut (2007) 183:177–186

30
Ks value observed in wastewater treatment plants of
25
20 mg/l (Grady et al. 1980). Bacteria degrading these
surfactants reach the maximum growth rate at lower
Oxygen Uptake (mg/L)

20 COD concentrations than typical heterotrophic bacte-

15
10
5
0
0 2 4 6 8 10
Time (hours)
Fig. 3 Comparison of oxygen uptake during DSCADA
biodegradation to predicted oxygen uptake based on Monod
kinetic parameter fitting (RSSE/n=0.84)
parameters to models that predict removal rates, a
range of values should be used (Brown et al. 1990).
Therefore, the minimum and maximum parameter
values observed for surfactants have been reported
(Table 2).
Based on the literature, a typical value for mb is
−1
b
0.25 h (Grady et al. 1980). PRAMUS m values for
the surfactants ranged from 0.092 to 0.21 h−1, lower
than reported values. Because surfactant degradation
is complex, it is expected that growth rates will be
lower than observed for simpler organic compounds.
The mb for DSCADA is particularly low in comparison
to the standard value as well as values for other
b of DSCADA should
surfactants (Fig. 4). The slow m
be taken into consideration if complete removal is
required. Ks PRAMUS values for the surfactants
ranged from 2.9 to 13 mg/l, below the average
ria. Values of Y between 0.3 and 0.6 are representative
of heterotrophic growth (Grady et al. 1980) and
estimates of Y for the surfactants fall within this range.
Microbial growth kinetic parameters have not
Model Prediction
previously been determined for SLES, DSCADA, or
Data similar compounds so comparisons can not be made
to literature values. Some researchers have estimated
12 14 16 18 biokinetic parameters for PAE, although not for
Neodol 23-5 ® specifically. Of note is that PAEs
containing different numbers of ethoxylates and alkyl
chain lengths will exhibit different growth kinetics
(Itrich and Federle 2004). Zhang et al. (1999) studied
the growth kinetics of a PAE, Witconol, and deter-
mined that m b was 0.11, lower than 0.19+/−0.078 as
determined for PAE in Neodol 23-5 ®, and Ks was
2,450 mg/l as cobalt active thiocynate substance. Due
to the units in which Ks was expressed, comparisons
are not possible to the Ks determined in our study.
Godsey (1997) reported intrinsic kinetic parameters
for Neodol 23-6.5 ® and Neodol 45-7 ®, both similar
in structure to Neodol 23-5 ®, and PRAMUS values
for mb were 0.39+/−0.043 for Neodol 23-6.5 ® and
0.41+/−0.012 for Neodol 45-7 ®, while Ks values
were 9.85 +/− 1.14 and 2.8 +/− 0.65, respectively.
Although exact comparisons between these values
and those determined in this study are difficult due to
PAE structural differences, kinetic values determined
for PAE in this study seem to be reasonable.
Average μ−S curves for SLES, DSCADA, and
PAE are shown in Fig. 5. The growth curve for
DSCADA is substantially different from those for

0.30
0.25
0.25 SLES
DSCADA
0.20 0.2 PAE

0.15 0.15
µ ( hr − 1 )

0.10 0.1

0.05 0.05

0.00
0
SLES DSCADA PAE 0 50 100 150 200
S (mg/L)
Fig. 4 PRAMUS values of for SLES, DSCADA, and PAE.
Error bars indicate +/− one standard deviation Fig. 5 Average μ-S curves for studied surfactants
Water Air Soil Pollut (2007) 183:177–186
SLES and PAE due to the low m b for DSCADA. PAE
and SLES have similar m b values, but since Ks is
higher for SLES than PAE, the slope of the PAE curve
is higher.
4 Conclusions
Intrinsic biokinetic parameters were successfully
determined for SLES, DSCADA, and a representative
PAE, Neodol 23-5 ®. These parameters can be used
for biological waste processors designed to remove
these surfactants. Of note, is that the kinetic param-
eters quantified in this study are representative of pri-
mary degradation of these surfactants. Future research
should focus on determination of kinetic parameters
for degradation of metabolites so that a complete
kinetic model for ultimate degradation of the surfac-
tants can be developed. For all surfactants studied,
only a fraction of the organic carbon was found to be
readily biodegradable. Results from this study indi-
cate that complete removal of these surfactants may
be difficult due to formation of by-products that are
slowly degraded compared to the parent compound. If
complete removal of surfactants is a treatment goal,
hydraulic residence time in biological processing
operations should be increased and cell wasting rates
should be lower than m b to achieve adequate removal
of these compounds. Future research should examine
the fate of SLES, DSCADA, and PAE in biological
treatment processes.
Nomenclature
b decay rate (h−1)
fB fraction of readily degradable COD (−)
Ks half saturation constant (mg COD/l)
OU oxygen uptake (mg O2/l)
OUH b (mg O2/l)
oxygen uptake at half estimated m
OUP oxygen uptake at plateau (mg O2/l)
Sp soluble COD at oxygen uptake plateau (mg
COD/l)
Spr soluble product (mg COD/l)
Spro initial soluble product (mg COD/l)
SP standard deviation from PRAMUS value for
estimate
Ss soluble substrate (mg COD/l)
Ssom initial soluble substrate (mg COD/l)
tp time associated with OUP (h)
185
X biomass concentration (mg COD/l)
Xo initial Biomass concentration (mg COD/l)
Xp biomass associated with OUP (mg COD/l)
Y growth yield (mg biomass COD formed/mg
substrate COD)
YP product yield (mg product COD formed/mg
substrate COD consumed)
Greek Symbols
μ specific growth rate (h−1)
b
m maximum growth rate (h−1)
Acknowledgments Funding for this project was provided by
the NASA ALS NSCORT. We would like to thank Jay Garland,
Eric McLamore, Karen Pickering, and C.P. Leslie Grady for
their contributions to this work.
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