United States
                    Environmental Protection
                    Agency
Industrial Environmental
Research Laboratory
Cincinnati OH 45268
                    Research and Development
EPA-600/S2'83-119  July 1984
&ER&         Project  Summary

                    Management  of Industrial
                    Pollutants  by Anaerobic
                    Processes
                    Alan W. Obayashi and Joseph M. Gorgan
                      A study was made of the anaerobic
                    degradation  of  organic   matter  to
                    methane, a  byproduct which  could
                    recommend wider use of the anaerobic
                    waste  treatment  as  a   short-term
                    solution for lessening U.S. demand for
                    oil in an  energy crisis. The anaerobic
                    process requires less energy than does
                    the aerobic biological process which
                    does not produce a usable byproduct.
                      The study  investigated  two  major
                    aspects of anaerobic treatment: devel-
                    opment of the process, and process
                    control parameters.  Other areas  of
                    study   included  biodegradation  of
                    organic compounds,  toxicity effects,
                    and microbial sulfur recovery.
                      This Project Summary was developed
                    by  EPA's Industrial Environmental
                    Research  Laboratory. Cincinnati, OH,
                    to announce key findings of the research
                    project that is fully documented in a
                    separate report of the same title (see
                    Project Report ordering information at
                    back).

                    Anaerobic Treatment Processes
                      The anaerobic degradation of organic
                    matter  to methane   is  a  complex
                    interaction of three groups  of bacteria
                    (illustrated in the full report).  The first
                    group of bacteria are the fermentative
                    bacteria which  hydrolize the  complex
                    long chain organics and ferment them to
                    fatty acids, alcohols and other soluble
                    organics. The second group of bacteria
                    are the  acetogenic  bacteria which
                    degrade propionate and longer chain fatty
                    acids to acetate,  H2 and C02- Presently
                    this is the only known pathway for long
                    chain fatty acids and alcohols, since there
are  no  documented  cases  of a
methogenic  bacteria being  isolated
which can degrade these organics di-
rectly to methane. For the third group of
bacteria, the methanogens, the
substrates for growth determined to date
are H2, acetate, formate and methanol.
  A review of the literature suggests that
the  rate  limiting  step  in  anaerobic
digestion  may  be  the  conversion  of
propionic and acetic acid to methane gas.
However, one reference indicated that at
high solids retention times (greater than
10 days)  the rate limiting  step in the
digestion of sewage sludge at 35°C is the
hydrolysis of organic solids. The same
study reports that cellulose hydrolysis is
the rate limiting step in the digestion of
municipal solid wastes.
  In  spite of their present significance
and future potential, anaerobic waste
treatment processes have not enjoyed a
favorable reputation. This lack of popular-
ity stems from the many misconceptions
held by design engineers  concerning the
microbiological  and  biochemical
fundamentals of the anaerobic digestion
process. Anaerobic waste treatment is
thought of by many as a sensitive process
which is  easily upset and  difficult to
control. The anaerobic digestion process
also  has a reputation  for producing
obnoxious odors and requiring long initial
startup periods  and high temperatures
(35°C) for effective waste stabilization.
Another  reason may  be  that  direct
treatment processes have  yet to  be
proven on specific industrial effluents.
  Nevertheless,  anaerobic  waste
treatment does have several fundamen-
tal advantages  over aerobic biological
treatment processes. First, anaerobic

-------
treatment attains a high degree of waste
stabilization  with very little sludge pro-
duction (less than 5% of the biodegrad-
able organic matter is converted to cell
material) which reduces  the  nutrient
requirement  in  the  influent  waste
stream.  A   second advantage  of  the
anaerobic process is  that 90%  of the
biodegradable fraction can be converted
to a usable  end-product in the form of
methane (CH4) gas which can be used to
heat the waste stream to give a  higher
rate of  stabilization  or to  supplement
inplant power requirements. Using direct
anaerobic  digestion  processes,high
organic  loadings  along with  short hy-
draulic retention times (three hours and
greater) can be achieved.
  Because of the current energy situation
throughout the country and the need for
energy conservation,  use  of anaerobic
processes by industry will undoubtedly
increase. Many researchers see energy
conservation as the only practical short-
term solution for the U.S. to become self-
sufficient in energy production. More and
more interest  is being evinced by the
anaerobic processes which require little
energy  and supply a valuable  power
source,  methane  gas.  Anaerobic
biological processes on the other hand,
require a high energy input and produce
no  usable byproduct.
  In the final report, two major aspects of
anaerobic treatment are reported in detail:
the development of the processes and the
process  control  parameters.  In  the
development  aspect,  the   anaerobic
processes are reviewed in a chronologi-
cal order, i.e., from the simplest to the
higher rate processes, e.g.,  anaerobic
sludge blanket  process. The final report
also  summarizes  the  application of
anaerobic processes to a variety of waste-
waters. In  the process control aspect,
three areas  are covered (1) pH and alka-
linity, (2) nutrient requirements, and (3)
temperature   effects  on  biological
processes.
Biodegradation of Organic
Compounds by Anaerobic
Processes
  Recent advances  in technology have
led to the production  of many new and
potentially dangerous  compounds, some
of  which  eventually turn  up  as  a
constituent in wastewater. Each of these
new substances, representing a wide
array  of  compounds  ranging  from
phenols to pesticides,  presents problems
for its  ultimate  disposal.  Wastewater
treatment plants are experiencing many
problems and challenges in dealing with
these hazardous wastes. Many new and
innovative techniques for their treatment,
including anaerobic processes, are being
investigated. As is the case in any waste
treatment method, anaerobic processes
will  not  breakdown  all  organic
compounds. In the final report, complete
details are presented on how anaerobic
processes function to breakdown large
numbers of organic  wastes. Also, the
applicability of  anaerobic  processes  to
new wastes are evaluated in a three-step
evaluation: (1) formulation of  a definition
of the term biodegradation and setting of
standards for the degree of biodegrada-
tion; (2) a comparison of tests on aerobic
and  anaerobic processes to determine
relative  biodegradabilrty;  and  (3)  a
summary of previous work involving the
biodegradation of organic  by anaerobic
processes.

Toxicity Effects in Anaerobic
Processes
  Adequate knowledge of the toxicity of
relevant  toxins  and inhibitors in  any
biological  process is essential for  an
optimal  application  of  the  process.
Despite   the  many  advantages   of
anaerobic treatment, the application  of
methane fermentation is not widely used
in this country for treatment of industrial
wastewaters.
  Much of this  reluctance  to use an-
aerobic processes stems from the belief
that the methane fermentation systems
cannot tolerate the chronic or slug doses
of toxic substances found in industrial
wastewaters. The presence of toxicants
may have caused inhibition which even-
tually led to failure of the process, particu-
larly  in the case of anaerobic  sludge
digestion.  However, it should not be
assumed  that methanogens are more
sensitive  to toxicants  than  facultative
organisms.
  During  the past fifteen years, there
have  been  numerous  documented
studies of the possible  inhibitory effects
on the anaerobic digestion process from
different compounds commonly found in
these  systems.  In  many  instances  in
which digester  performance  had
decreased, the source of the  upset could
be traced to the presence of a compound
that was inhibitory to the microorganisms
involved in the digestion process. These
compounds originate from waste streams
generated  by the  different industrial
processes.
  The control of sulfur pollution is a
widespread problem associated  mainly
with hydrocarbon processing and power
production. For example, the mining of
coal results in  acid mine drainage, the
burning of coal  results in CaSO4 sludges
(SO2   scrubbing)  and  coal  and  oil
desulfurization  results  in  H2S waste
streams.  Of  the two  forms of sulfur
pollution SO24 is a major problem with no
reliable method of control.
Microbial Sulfur Recovery
  The problem with sulfur disposal  are
related  primarily  to  energy  production
and, to  a smaller extent, to the mining
industry. As more emphasis is placed on
the use of hydrocarbons such as oil and
coal for energy production, sulfur control
and disposal become a  more pressing
problem.
  One form of sulfur pollution  is  the
generation  of CaSO4 sludges which is a
result of the scrubbing of flue gases from
coal fired plants. In addition, H2S waste
streams are generated from the desulfur-
ization of coal and oil. This problem is
generally  handled  by using physical-
chemical processes which  convert  the
H2S to  elemental sulfur. Other  more
limited  areas  in  which  high sulfates
(acidic wastes) are a problem include acid
mine drainage (coal mining), acid wastes
from mining operations, and wastes from
ethanol distilleries.
  Currently,  H2S  waste streams  are
handled by physical-chemical processes,
with  the   major   objective  being  the
recovery of elemental sulfur. Presently,
when  high  sulfate  wastewaters  are
neutralized they are either discharged or
stored in lagoons where they continue to
be a problem.
  The   biological   conversion  of high
sulfate wastes or hydrogen sulfide waste
streams to the more desirable form of
elemental sulfur has not been developed
beyond  the laboratory stage. The kinetics
of sulfate reduction and  the kinetics of
hydrogen sulfide conversion to elemental
sulfur have been the subject of very few
published  studies on the applied bio-
process production of elemental  sulfur.
These  studies are discussed in  more
detail in the final report. Also, a brief
summary of the microbiology of sulfur
transformations is presented in the final
report.
Microbiology of Sulfur
Transformations
  All organisms require sulfur with the
major need in the incorporation of sulfur

-------
in proterns. In addition, microorganisms
can use sulfur in a manner similar to the
way that organisms use the various forms
of nitrogen; that  is, as both an energy
source and as an electron acceptor. The
various oxidation states and the forrns in
which  sulfur exists in the environment
are discussed  in the  final report. Of
particular  interest is  the  anaerobic
portion of  the cycle,  the reduction of
sulfate  to  hydrogen  sulfide,  and  the
oxidation of sulfides to elemental sulfur.
Alan  W. Obayashi and Joseph  M. Gorgan are with the Illinois Institute  of
  Technology, Chicago, IL 60616.
William A. Cawley is the EPA Project Officer (see below).
The complete report, entitled "Management of Industrial Pollutants by Anaerobic
  Processes," (Order No. PB84-133 024; Cost: $22.00, subject to change) will be
  available only from:
        National Technical Information Service
        5285 Port Royal Road
        Springfield, VA 22161
        Telephone: 703-487-4650
The EPA Project Officer can be contacted at:
        Industrial Environmental Research Laboratory
        U.S. Environmental Protection Agency
        Cincinnati, OH 45268
                                                                               US'GOVERNMENT PRINTING OFFICE; 1984 — 759-015/7750

-------
United States                       Center for Environmental Research
Environmental Protection              Information
Agency                           Cincinnati OH 45268
Official Business
Penalty for Private Use $300
                                                            AGENCY
                              REtlUN  5  LiBKAKY
                              230  S  DEARtlORN  STREET
                              CHICAGO  IL  60604

-------