Biological Treatability Studies:

New Regulations Require a New Approach

W. Wesley Eckenfelder, Jr.
227 French Landing Drive, Nashville, TN 37228

In the past, biological treatability studies were directed toward defining effluent
BOD and TSS. Recent regulations now require effluent limitations on volatile
organic carbon, specific priority pollutants, aquatic toxicity and in many cases
nitrogen for complex wastewaters. This, in turn, has changed the focus of
biological treatability studies.
It is assumed that a screening protocol has been employed to define biological treatment as
a candidate process [ I ] .
(a) Priority Pollutants-If one or more priority pollutants are a permit issue, a fed batch
reactor (FBR) is run using acclimated biosolids to determine the maximum degradation
rate, q,, and the half velocity constant, K,. From these data, the required SRT to meet
effluent limitations can be computed.
(b) Aquatic Toxicity-If the wastewater exhibits aquatic toxicity in addition to priority
pollutant requirements, bioassays are run on the biological units. Effluent toxicity and COD
are tracked with time. Since effluent toxicity is frequently associated with soluble microbial
products (SMP), the SMP is estimatedfiom the effluent COD over time of aeration.
(c) Nitrogen-Many organics including SMP are inhibitoiy to nitrification. The nitrification
rate should be determined on the efluents using seeded NH,Cl as a control. From these
data, the required SRT can be computed.
This paper reviews the required protocols and presents several case histories from the
chemical and pharmaceutical industry.

VOLATILE ORGANIC CARBON (VOC)
The prescnt emphasis on volatile emissions from wastewa-
ter treatment plants requires that stripping be considered in
activated biosolids process design where volatiles are prescnt
in the influent wastewater. There are several factors to be
considered in the experimental design.
Both thc power level in the aeration basin and the type
of acrator (i.e., diffused or mechanical) significantly in-
fluence stripping. The pilot reactor should therefore use
the type of aerator to be considered and operate at the
design power level.
The maximum concentration of each particular volatile
should be employed. The degradation rate of specific
volatiles will be related both to the composite wastewa-
ter composition and process operating conditions such as
SRT. Therefore, these variables must be fixed prior to
volatile stripping and degradation studies.
It has been shown that gas recirculation will significantly
enhance biodegradation [ 21. Therefore, this should be in
the pilot studies if it is to be considered in the final
design.
Covered aeration basins may result in a significant tem-
perature rise due to the exothermic reaction with high
strength wastewaters. Basin temperatures in excess of
38°C will result in floc dispersion. In these cases, it is
therefore necessary to monitor the reactor temperature

172 August, 1995 Environmental Progress (Vol. 14, No. 3)

 and make appropriate temperature adjustments as re-
quired.
Once the degradation rate is defined, the calculations to de-
termhe the fraction of the volatile stripped can be made [ I ] .
PRIORITY POLLUTANTS
It has been shown that specific organics such as phenol are
removed in a biological process in accordance with Monod
kinctics. For a complcte mix reactor o r multistage reactors,
the effluent quality is defined by the relationship:
in which:
s = effluent concentrations, mg/L
8,. = S R r , days
(I = biological biosolids yield coefficient
h = endogenous coefficient, days-'
X, = degradable fraction of the biological volatile suspended
solids
q,n = maximum degradation rate, g/g VSS . day
K , = substrate concentration when the concentration is
one-half the maximum rate, mg/L
The coefficients a, h, and X, are determined from con-
ventional treatability studies or plant operating data. The
coefficients q, and must be determined for the specific
operating conditions. Several investigators have shown that
the history of the biomass and the wastewater composition
will influence the value of the coefficients in Equation (1) [3 ,
41.
It is therefore important to determine the coefficients with
a biomass cultured at the appropriate biosolids age with the
appropriate substrate. In order to maintain the integrity of
the results, a short term test such as the FBR should be used
in order not to change the population dynamics.
The modified FBR test would appear to be most applica-
ble to the determination of the kinetic coefficients q,, and
K,, under appropriate operating conditions. In the test,
biomass produced under field condition is used. The com-
pound in question is added at a constant rate. In order to
determine q",, the addition rate must exceed the degradation
rate as shown in Figure 1. When testing wastewater samples,
r /
v
m Acclimation
* Feed
.
n I
0 30 60 90 120
TIME (min)
Xv = 1,500 m g L
- -
29640 19472 = 0.78 rng Plmg VSS day
qm - 1,500
FIGURE 1. FBR test for determination of g, and K,.
Environmental Progress (Vol. 14, No. 3)
the priority organic levels may be too low, requiring that the
concentration be supplemented to provide a sufficient con-
centration to meet the conditions of the test. The data arc
only relevant so long as levels achieved i n
the test reactor are below the threshold, This can
be determined from the shape of the concentration-time
curve. The maximum degradation rate q,, is computed as the
difference in slope of the addition rate and the residual accu-
mulation.
A second FBR test is then conducted with the addition
rate of the compound equal to one-half the maximum dcgra-
dation rate (q,J determined in the first test. As shown in
Figure I , the steady state concentration observed in the reac-
tor during this test will be K , in mg/L. Since these coeffi-
cients have been observed to vary with SRT, it may be desir-
able to repeat the test with biosolids acclimated to a range o f
SRTs if available or relevant.
As previously mentioned, these parameters are influenced
by changes in wastewater composition and process operating
variables so that in many cases require statistical evaluation.
Three continuous units arc then run, one at the S R T dcter-
mined by the FBR, one at a SO percent higher S R T and one
at a SO percent lower SRT. Multi-stage operation should be
considered in order to reduce volumetric requirements.
TOXICITY REDUCTION
Aquatic toxicity is now a parameter on virtually all efflucnt
discharge permits. Toxicity can bc generated by organics
which are biodegradable, non-biodegradable, or generated
within the process as soluble microbial products (SMP). One
of the first steps in a treatability study therefore is to deter-
mine the applicability of biological treatment to the wastewa-
ter stream in question.
Two cases will be considered. In the first, there is a known
toxic compound which is biodegradable. A series of reactors
at varying SRT are run in order to determine the rcquircd
S R T to meet permit requirements. An example of this using
nonylphenol from a surfactant manufacturing wastewater is
shown in Figure 2. In the second more common case. toxicity
is caused by an unknown mixture of organics or generated o r
enhanced by the production of SMP during biooxidation. A
protocol has been developed to define treatment options in
this case [ 5 ] .The biodegradability of the wastewater in ques-
tion is determined through a Fed Batch Reactor (FBR) test
4-
2B -
v -
Feed Rate l/2 qm
4
0
g2-
2 -
Ks = 0379 mg/L
0 I
August, 1995 173
 lo r
c 8G
SRT = 4.5 days
d

0
0 1 2 3 4

-
Nonylphenyl Mono and Diethoxylate, mg/L
SO ld, 150 2b, 2lO 3bo d 0 4dO 450 560
PAC Dosage (mg/L)
FIGURE 2. Effect of SRT on toxicity reduction for FIGURE 4. Toxicity reduction in an organic chemi-
nonyl phenolics. cals wastewater using PAC.

procedure. It is important that the biological biosolids used

in the test is fully acclimated to the wastewater in question. If
the wastewater proves to be nondegradable and toxic, it is
then considered for pre or source treatment. The primary
objective of pretreatment would be detoxification and en-
hanced biodegradability. If the wastewater is degradable as
defined by the FBR procedure, then a long-term oxidation,
usually 48 hours aeration follows. The objective is to degrade
all degradable components. This effluent is then subjected to
an appropriate bioassay. If this effluent is still toxic, then
pretreatment or tertiary treatment should be considered.
Since it is not possible to distinguish between wastewater
component toxicity and SMP toxicity, the wastewater should
be pretreated for detoxification. A subsequent long-term oxi-
dation test should determine the source of the toxicity.
If the toxicity is caused by SMP, tertiary treatment with
carbon should be evaluated. In most cases, powdered acti-
vated carbon (PAC) will be the cost-effective technology of
choice. It has been shown that while laboratory adsorption
isotherms will establish the applicability of carbon, they can-
not be used for process design as shown in Figure 3 [I]. A
series of reactors should be run at various carbon dosages. It
should be noted that the SRT of the system is defined by that
required to remove degradable organics and/or priority pol-
lutants. Each reactor should be preloaded with carbon which
has been brought into equilibrium with the effluent. The
carbon concentration in the reactor is calculated from the
relationship:
in which:
<
X = equilibrium PAC concentration
= PAC dosage
Oc = SRT
HHT = hydraulic retention time
A relationship between PAC dosage and effluent toxicity
will be defined as shown in Figure 4.

0.20

0.15
Carbon A

0.10

0.05

0
0 10 20 30 40 50 60

EFFLUENT TOC, mg/L

FIGURE 3. Performance comparison between continuous PAC reactors and their adsorption isotherms.

174 August, 1995 Environmental Progress (Vol. 14, No. 3)


Time, hours
FIGURE 5. Batch nitrification results.
NITRIFICATION
Many organics and in some cases, inorganics, are inhibitory
to nitrifiers. Therefore, when treating industrial wastewaters,
it is essential to determine the nitrification rate and in turn
the required S R T to achieve nitrification under field operat-
ing conditions. This can be accomplished in one of two ways.
Batch Oxidation
A wastewater sample is aerated with a nitrifying biosolids
(this can be biosolids obtained from an actively nitrifying
plant or ii commercial culture of nitrifiers. The initial NH,-N
concentration should be between 20 and 50 mg/L.
If the wastewater contains organic nitrogen, then TKN
should be measured instead of NH,-N since some of the
organic nitrogen may convert to NH,-N during the test.
T h e alkalinity should b e adjusted to 7.15 mg
alkalinity/mg NH,-N plus 50 mg/L.
If the wastewater contains high organics then the NH,-N
removal must be corrected for synthesis, based on the
C O D removed during the test run. NH,-N,,, =
0.04ACOD
A batch test run is shown in Figure 5. The initial
wastewater had an NH,-N of 48 mg/L and a COD of
310 mg/L. At the end of the batch test, both the NH,-N
and the COD were essentially removed. Over 24 hours
38 mg/L NH,-N was removed. The amount nitrified was
38 - 0.04 (310) = 26 mg/L. The nitrification rate is
therefore:
-
26 mg/L day
= 0.022 mg NH,-N/mg -
MLVSS day
1,200 mg/L VSS
The fraction of nitrifiers is estimated as:
-
0.15 26
fN = -
0.5 .310 + 0.15 26 = 0’0245
Environmental Progress (Vol. 14, No. 3)
tNH3-N Added
tNH3-N Measured
VSS N = 250 mg/L
RN = 1.15 mg NH3-Nlmg VSS * day
I I I 1
100 150 200 250
Time (mint
FIGURE 6. FBR determination of nitrification rate.
The nitrification rate is therefore:
0.022
o.0245
~- - 0.9mgNH3-N/mgVSS, - day
and the growth rate is 0.9 * 0.15 = 0.135 days-’.
The required SRT is therefore:
A control test should be run using the same nitrifier
biosolids with ammonium chloride at the same concentra-
tions. The growth rate for the control at 20°C should be in
the order of 0.34 days-’.
The second procedure is to use the FBR as previously
described. In this case, the wastewater, spiked with NH,-N if
required is added at a constant rate to the reactor. The am-
monia concentration is intermittently measured and the con-
centration added calculated as shown in Figure 6. COD or
T O C is also measured during the course of the test. The
nitrification rate and required SRT is calculated in a manner
similar to the batch test.
LITERATURE CITED
1. Lankford, P. W., and Eckenfelder, W. W., Toxicity Reduc-
tion in Industrial EfJluents, Van Nostrand Reinhold, New
York (1990).
2. Argaman, Y., and Musterman, J. L., “Off-Gas Recycle
for VOC Emission Control, Conceptual Model,” Journal
of Enoironmental Engineering ASCE, 120, 3, May/June
(1994).
3. Philbrook, D. M., and Grady, C. P., “Evaluation of
Biodegradation Kinetics for Priority Pollutants,” Pro-
ceedings 40th Industrial Waste Conference (1985).
4. Templeton, L. L., and Grady, C. P., “Effect of Culturc
History on the Determination of Biodegradation Kinetics
by Batch and Fed Batch Techniques,” J . Water Pollution
Control Federation, 60(5), 65 1 (1988).
5. Eckenfelder, W. W., and Lankford, P. W., “Protocol for
Source Toxicity Evaluation,” Water Science and Technol-
ogy, 25, 3 (1992).
August, 1995 175