United States
                                    Environmental Protection
                                    Agency
                                                           EPA/540/F-94/504
                                                           May 1994
  &EPA
                                     SUPERFUND  INNOVATIVE
                                     TECHNOLOGY EVALUATION
                      Emerging   Technology   Bulletin

                                       Institute of Gas  Technology
                                    (Chemical and Biological Treatment)
  Technology Description: The institute of Gas Technology's
  (IGT)  Chemical and Biological Treatment  (CBT) process
  remediates sludges and soils contaminated with organic pollut-
  ants,  such  as polyaromatic hydrocarbons (PAHs) and polychlori-
  nated  biphenyls (PCBs).  The treatment system combines two
  remedial techniques: (1) chemical oxidation as pretreatment, and
  (2) biological treatment using aerobic and anaerobic biosystems
  either  in sequence or alone, depending on the  waste.  The CBT
  process  uses mild chemical treatment to produce  intermediates
  that are biologically  degraded,  reducing both the  cost and  risk
  associated  with more severe treatment process, such as incin-
  eration.

  The figure below shows some of the options available for applica-
  tion. The contaminated  material is treated with a  chemical re-
  agent that degrades the organopollutants to carbon dioxide, water,
  and more  biodegradable partially-oxidized  intermediates. In  the
  second stage of the CBT process, biological systems are used to
  degrade the hazardous  residual materials  and  the partially-oxi-
  dized  material  from the first stage. Chemically-treated  wastes
  are subject to cycles of aerobic  and anaerobic degradation  if
  aerobic or  anaerobic treatment  alone is not sufficient. Also, sev-
  eral cycles of chemical and biological treatment  are used for
  extremely recalcitrant contaminates.

  Waste Applicability: The CBT process can  be applied to soils
  and sludges containing high waste concentrations that would
             For TCE, PAHs
                           \
CO, CH4 C02
t T
Aerobic
^

Anaerobic
Clean
— — 1,,
product
Contaminated
 soil/sludge
Chemical
oxidation
,
AriMroijic
!

w

Aerobic
r I
CH4 CO2 C02
                                                     Cleat
                                                     product
  Figure l  Chemical and biological treatment (CBT Process).
typically inhibit bioremediation and low waste concentrations when
bioremediation alone is too  slow.  The process is  not adversely
affected  by radionuclides or heavy metals. Depending on the
types of  heavy  metals present, these metals  will  either
bioaccumulate in the biomass,  complex with organic or inorganic
material  in the soil  slurries,  or solubilize in the recycled water.
The  CBT  process  can be applied to a wide range of organic
pollutants,  including  alkenes, chlorinated alkenes, aromatics, sub-
stituted aromatics,  and complex  aromatics. Applicable matrices
include soil, sludge,  groundwater, and surface water.

Test Results:  IGT has completed two yr of evaluation of the
CBT process  within the SITE Emerging Technology Program.
This  evaluation has included  bench-scale  studies of  important
operational parameters for applying the  CBT technology to soils
and  sludges contaminated with PCBs. Table 1 shows the PCS
degradation for a  single-cycle of  the chemical/biological  treat-
ment process. Results indicate that this  technology can treat
various  PCB-contaminated  matrices with  modifications to the
original treatment protocol that increases the availability of the
PCBs.

During the evaluation of the CBT process, a nonstandard GC/
ECD method for PCS analyses was developed at IGT for quanti-
fication of  individual PCS  congeners.  Although there are several
EPA methods for  analyses of PCBs,  no method  is currently
approved  for  quantitative analyses of  PCBs which have been
chemically altered  by chemical, biological,  or thermal reaction.
Protocol development and verification was  necessary before  be-
ginning experiments with PCS  contaminated soils.

Initial studies  indicated that 30-40% of 2,2',4,4' tetrachlorinated-
14C—biphenyl could  be  mineralized to 14CO2 by chemical oxida-
tion.   Equally   as  important,  30-35%  of  2,2',4,4'
tetrachlorinated-biphenyl is  modified  to a  water  soluble,  more
easily degradable product. As expected the higher the chlorina-
tion  of the biphenyl,  the lower  the amount of  mineralization.
Chlorine groups in  the 3-position inhibited mineralization by 50%
when compared with the  2-position. Chlorines in the 4-position
appear to  be  sightly more susceptible (=8%) to chemical degra-
dation than chlorines in the 2-position. This difference is statisti-
cally significant as  measured by  ± the  standard  deviation. This
study indicated that the majority of the chemical mineralization of
PCBs occurs in the  first 45-60  min of the reaction.

The  standard reagent  concentration of 2.5% H2O2  and ferrous
sulfate,  10mM, resulted in the greatest degradation  in both the
                                                                                                Printed on Recycled Paper

-------
Table 1.  PCS Degradation by IGTs Chemical and Biological Treatment
        Process

                         Single-Cycle
Treatment*
Biological
(Aerobic)
Water
30%
Sludge
<5%
Soil
0%
    Chemical

    Chemical/
    Biological
    (Aerobic)
90%

100%
65%

65%
50%

30%
. Chemical Treatment = 5% H2O2 for 1 hr.
  Biological (Aerobic)  Treatment = 10% inoculum of a mixed
  consortium for approximately 15 Days

lower and higher chlorinated compounds. When compared to the
control,  40% of total PCBs  were removed  by chemical degrada-
tion and as much as 90% of some PCB congeners were  removed.
As the reagent concentration increases the degradation of PCBs
increases;  however, the PCBs with less than 5 chlorine groups
are  more susceptible than  PCBs with  greater than 5 chlorine
groups. This  pattern complements the anaerobic and  aerobic
biodegradation of PCBs in that it aggressively attacks the interme-
diate biphenyl compounds  with  3-5  chlorine groups,  anaerobic
biodegradation effectively  reduces the  concentration  of  higher
chlorinated biphenyls (4-8 chlorine groups) by 44-70% and aero-
bic biodegradation  efficiently  removes  mono- and  di-chlorinated
biphenyls. Experiments conducted using actual contaminated soil
demonstrated  greater than  50% of all congeners were  removed
with a single cycle  of the integrated chemical/biological  degrada-
tion.

 IGT's CBT technology continues to  be successfully applied  to
 PAH-contaminated  soils. The CBT process  consistently outper-
forms  conventional bioremediation,  especially with  multi-ring
(4-6)  PAH  compounds.  The  CBT  process increases  both  the
rate and extent of removal of contamination from various types of
soils.  Two successful field tests,  one solid-phase  land treatment
and one in  the soil slurry mode, have  been conducted under
other  gas industry  supported programs. The  field  experiment
showed that the integrated treatment system resulted in  about
50% greater  removal of total PAHs  and 90% greater removal of
carcinogenic PAHs than those of conventional biotreatment. The
integrated system's results exceed  the  treatment goals which
had been established  and were  reached in 42 days. This field
study  verified the effectiveness of the integrated biological-chemi-
cal treatment process on a large- scale demonstration.  Also,  the
field  data show that the integrated process results in higher
cleanup levels and  at faster  rates  as compared  with  biological
treatment alone.

The CBT technology has  been admitted into the SITE  Demon-
stration Program and IGT is evaluating possible sites for a full-
scale  demonstration.

For Further  Information:
                                         EPA Project Manager   .  -L__._li_J,___1_j
                                          Naomi Berkley
                                          U.S.   EPA
                                          Risk Reduction Engineering Laboratory
                                         26 West Martin Luther King Drive
                                         Cincinnati, OH 45268
                                         513-569-7854

                                         Technology  Developer Contact:

                                          Robert Kelley
                                          Institute  of Gas Technology
                                         3424 South State Street
                                          Chicago, IL 60616-3896
                                         312-949-3809
                                          Fax: 312-949-3700
                                                                                       'U.S. Government Priming Office: 1994 -550-067/80250
    United States
    Environmental Protection  Agency
    Center for  Environmental  Research  Information
    Cincinnati,  OH  45268

    Official  Business
    Penalty for Private Use
    $300
                                                                              BULK  RATE
                                                                        POSTAGES FEES PAID
                                                                                 EPA
                                                                           PERMIT No. G-35
    EPA/540/F-94/504

-------