United States
Environmental Protection
Agency
National Risk Management
Research Laboratory
Research Triangle Park, NC 27711
Research and Development
EPA/600/SR-97/094  January 1998
Project  Summary

Field  Measurement of
Greenhouse Gas Emission
Rates  and  Development of
Emission  Factors for Wastewater
Treatment
Bart Eklund and Jeffrey LaCosse
  A research project was conducted to
measure emissions  of greenhouse
gases (GHGs) from wastewater treat-
ment (WWT) and disposal facilities. The
overall objective of the research under
the  base statement of work area for
this contract is to develop more reli-
able estimates of GHG emissions from
industrial and domestic WWT systems.
Most previous  research for  these
sources has  used a mass balance ap-
proach to estimate potential methane
(CH4) emissions, but in this study emis-
sions of CH4 and other GHGs were mea-
sured under field conditions,  which
should  improve the reliability of the
emission estimates.
  Field sampling was performed at five
sites, including WWT systems  in the
beef and chicken processing industries
and two publicly owned  treatment
works (POTWs). Ambient air was mea-
sured immediately downwind of the la-
goons using a Fourier Transform Infra-
red  (FTIR) approach. The FTIR light
beam was directed along a path of sev-
eral hundred feet and the absorbance
of gases was  measured.  The  target
compounds of interest included CH4,
carbon  dioxide  (CO2), nitrous  oxide
(N2O), carbon monoxide (CO), ammo-
nia  (NH3), and certain volatile organic
compounds (VOCs). The source term
(i.e., emission rate) can be determined
from information about the average
downwind ambient concentration (mea-
sured by the FTIR method) and the
atmospheric dispersion characteristics
at the time of sampling. In addition,
samples of influent and effluent waste-
water and sludge were collected. Emis-
 sion factors were developed in terms
 of grams of species emitted per gram
 of precursor in the influent wastewa-
 ter; e.g., g CH4/g biological oxygen de-
 mand (BOD). The emission factors will
 be combined with  activity factor data
 to develop national and global  emis-
 sions inventories.
  This Project Summary was developed
 by  EPA's National Risk Management
 Research Laboratory's Air Pollution
 Prevention and  Control Division, Re-
 search  Triangle Park, NC, 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.)

 Introduction
  A GHG generally can be defined as any
 molecule which absorbs  infrared light in
 the spectral region of 5 to 20 |jm These
 molecules include water vapor (H2O), CO2,
 CO,  CH4, certain VOCs,  and N2O. Rea-
 sonably accurate global balances of GHGs
 are needed as input to climatic models for
 estimating long-term global temperature
 changes.
  A large number of natural and anthropic
 activities produce or release GHGs. The
 emphasis of this  program was on emis-
 sions from WWT facilities. The decomposi-
 tion of organic waste may occur aerobi-
 cally (i.e.,  with oxygen) or anaerobically
 (i.e., without oxygen). Aerobic decomposi-
 tion of organic carbon  results in the pro-
 duction  of CO2, while anaerobic decompo-
 sition results in the production of CH4and
 CO2. Given a sufficient amount of time,
 essentially every atom of carbon in waste
 streams is converted to either CO2 or CH4.

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In terms of their ability to retain heat in the
atmosphere, however, CO2 and CH4 are
not equivalent. A given mass of CH4 is 58
times stronger a GHG than the same mass
of  CO2 (it is 21 times  stronger on a mo-
lecular  basis). Therefore, the  relative
amount of anaerobic versus aerobic de-
composition  is of interest.
  The  overall  objective of the  research
under the  base statement of work area for
this contract was to develop more reliable
estimates  of GHG emissions from indus-
trial and domestic WWT systems. National
and  global inventories of CH4 emissions
from WWT facilities have been published.
These estimates, however, are based on
various assumptions and very limited data.
Most previous  research for these sources
has  used  a mass balance approach to
estimate potential CH4 emissions, but  in
this  study emissions  of CH4 and  other
GHGs were measured  under field condi-
tions, which  should improve the  reliability
of the emission estimates.
  The overall objectives of this study were:
1)  Identify industries and WWT processes
that  have  the greatest potential  for mea-
surable  emissions of CH4; 2) Select the
most promising sites for testing in those
industries; 3) Perform ambient  air mea-
surements using an open path monitoring
(OPM)  approach with a FTIR spectros-
copy instrument; 4) Collect and  process
data and characterize the  influent and ef-
fluent wastewater quality at the field sites;
and 5) Use the field data to develop emis-
sion factors for each  target compound.
The target compounds of interest included
CH4, CO2, N2O, CO,  NH3,  and certain
VOCs.
  A subset of WWT systems that employ
anaerobic treatment processes  was se-
lected  for testing.  Within this  subset,
anaerobic lagoons were given priority over
anaerobic digesters, tanks, and sludge dis-
posal units because lagoons offered the
fewest  logistical constraints to testing. Al-
though anaerobic lagoons  are not exten-
sively used to treat industrial and domes-
tic waste in the U.S., other countries use
anaerobic lagoons to treat  wastewater.
Because of difficulties associated with iden-
tifying sites and the expense of conduct-
ing field measurements in foreign coun-
tries, sites in the U.S. that are representa-
tive of treatment conditions in developing
countries were selected for testing.

Approach
  Site  selection focused  on U.S. WWT
systems that employ open,  anaerobic pro-
cesses to achieve high levels of BOD or
chemical oxygen demand (COD) removal.
First, industries that treat large volumes of
wastewater and remove large amounts of
BOD/COD were identified. Approximately
a dozen industries were identified as po-
tential candidates for testing. Second, a
telephone survey was  conducted of in-
dustry representatives, experts in the WWT
area, and regulatory personnel to identify
industries most likely to treat wastewater
to remove  high  levels of BOD/COD  in
open, anaerobic lagoons. The most prom-
ising candidates  were  beef  and poultry
processing  plants, and  pulp and paper
mills. POTWs also were of  interest be-
cause they are used to treat  a significant
fraction of wastewater both nationally and
globally  and,  also, are thought to  be a
potentially significant source of N2O emis-
sions.
  Five sites were selected for testing. The
selection intentionally included sites from
several different industries: two beef pro-
cessing  plants, one  chicken processing
plant, and  two POTWs. Two sites from
certain  industries  were included  to help
determine the variability in emissions within
a given industry.
  The field  work involved being on site for
about 5  days at each facility. Ambient air
was  measured immediately  upwind  and
downwind of the  lagoons  using an OPM-
transect method (OPM-TM) approach with
detection by FTIR spectroscopy. The FTIR
light  beam  was directed along a path  of
several hundred feet and the absorbance
of gases was measured.  Emission  rates
were determined from measurements  of
the downwind ambient concentration and
the atmospheric dispersion characteristics
at the time of sampling.  In  addition,  a
limited  number of influent and  effluent
wastewater and sludge samples were col-
lected.
  Emission  factors  were developed  in
terms of grams of GHG species emitted
per gram of precursor in the influent waste-
water (e.g., g CH4/g  BOD). The emission
factors will  be combined with activity fac-
tor data to develop national and global
emission estimates.

Results
  OPM-TM using the  FTIR was used  to
determine emission  rates. A very  large
data  set was  generated,  and up to  300
separate valid, 5-minute  average emis-
sion  rate determinations were made at a
given site. The air measurement data were
reviewed to identify  compounds found  in
significantly greater concentrations in the
downwind air versus  the  upwind air  at
each site. Any such compounds were likely
to have been emitted from  the lagoons
being tested.  Many of the target analytes
were found at the same concentration lev-
els upwind  and downwind of  the lagoons;
i.e., they had no quantifiable emission rate.
Only CH4, NH3, and the sulfur hexafluo-
ride  (SF6) tracer gas  generally  were
present in greater amounts in the down-
wind air.
  The minimum quantifiable emission rate
varied from site to site and from one 5-
minute period  to  another.  The detection
limit  for a given compound, in terms of
grams  per second, is dependent on the
smallest difference between downwind and
upwind concentrations that could be iden-
tified apart from the measurement vari-
ability within each of the upwind and down-
wind data  sets. For each increment of 0.5
ppmv (500 ppbv)  that  a given compound
was  present in  greater  concentrations
downwind  than upwind, its emission rate
was about 1  g/sec (depending on the mo-
lecular weight  of the compound).  Typical
detection limits were  about 0.1 g/sec for
most compounds, except for CO2, which
had  a  minimum  detection limit of about
150  g/sec. The  high  detection  limit for
CO2 was due to the high background con-
centrations (e.g., 500 ppmv) and the mea-
surement coefficient of variability (e.g., CV
= 7.5%, or 37.5 ppmv).
  At all three meat processing plants, large
amounts of CH4 were detected downwind
of the  WWT system.  For the  two beef
processing plants, the concentration of CH4
(and NH3) exhibited an exponential rela-
tionship with wind speed. The downwind
CH4 concentration at the chicken process-
ing plant did not show  a clear relationship
between concentration and wind speed.
At the chicken  processing plant, however,
the range  of  wind speeds was much
smaller than for the meat processing plants
and the number of valid measurement pe-
riods also was much  smaller, making it
more difficult to identify trends and rela-
tionships. There also was a thick grease
layer present on top of the  lagoon which
would tend to  diminish the  effect of sur-
face winds on air emissions.
  The  emission rates  measured at each
site for CH4, NH3, and other selected com-
pounds are given  in Table 1. Surprisingly,
no emissions  were  detected  from the
POTWs. It was expected that either CH4
or CO2 would be detected. The dissolved
oxygen (DO) level in the lagoons exceeds
2  mg/L, indicating that BOD removal  is
taking place  under aerobic conditions. So
it  is  highly probable that CO2 is being
generated, but the levels were too  small
to detect given the very high background
levels of CO2 and the  measurement vari-
ability.  In  general, anaerobic degradation
can be expected to produce a mixture of
CH4 and CO2 (somewhere between a 50:50
and a 70:30 ratio). Therefore, emissions
of CO2 would be expected wherever quan-
tifiable  emission rates of CH4 were found.

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Table 1. Measured Emission Rates of Selected Compounds for Each Field Site

Site
Beef Processing Plant
inSWU.S.
Beef Processing Plant
in Midwest U.S.

Compound
CH4
NH3
NH!
Average
Downwind
Cone.
(ppm)
61.9
355 ppb
58.1
1.04
Average
Upwind
Cone.
(ppm)
2.3
0
2.83
0.277
Maximum
Downwind
Cone.
(ppm)
142
609 ppb
200
2.06
Average
Emission
Rate
(g/sec)
280
2.2
230
3.5
Chicken Processing Plant
in SE U.S.
POTWfor Small Town
in SWU.S.3
POTWfor Very Small
Town in SWU.S.3
NH3
N20
CH
NH
C02
NH
CO,
9.80
2.6 ppb
563 ppb
2.20
0.2 ppb
342
2.11
93.3 ppb
528
1.92
2.8 ppb
542 ppb
2.14
0
351
2.16
25.5 ppb
668
29.9
44.1 ppb
586 ppb
2.46
15.4 ppb
384
2.81
21 4 ppb
691
180
0.066
2.6
O.15
O.05
<150
O.15
O.05
<150
aMethane, carbon dioxide, and ammonia values are shown for the POTWs for comparison purposes. No quantifiable emissions of these
 compoundswere detected at either POTW.
The lack of quantifiable CO2 emission rates
may be due to the high detection limit for
CO2 emission rates,  as previously  dis-
cussed. The absence of CO2 emissions
also could  be  due to the  presence of
cyanobacteria (blue-green algae) in  the
anaerobic lagoons.
  The  wastewater data for all three meat
processing plants  are very  similar, with
the two beef processing plants showing
very good agreement. All three WWT sys-
tems have high BOD  removal rates (88-
95%),  as  well as high removal rates for
COD, total organic carbon (TOC), and ni-
trates.  All three  WWT systems at meat
processing plants generated large amounts
of NH3 as  a by-product of the biodegrada-
tion of the wastewater. The  only param-
eter that  showed variable behavior from
system to system was total Kjeldahl nitro-
gen (TKN).
  The  two  POTWs had similar influent
wastewater  and  exhibited similar  perfor-
mance in terms of removal of BOD, COD,
TOC, TKN, and NH3. Both systems gener-
ated nitrates as a by-product of biodegra-
dation.
  Activity factors were developed for each
site based on information provided by the
plant operators and from the wastewater
data. Emission factors were developed for
each site  by dividing  the average  emis-
sion rates by the  activity factors for each
site. The  resulting emission  factors  are
given in Table 2. For CH4, the emission
factor based on COD  should be a  better
predictor of emissions from other facilities
than the emission factor based on BOD.
The 5-day BOD test will not fully degrade
all of the biological  material  in wastewa-
ters  containing proteins and  fatty  acids.
The suspended solids associated with the
wastewaters also are  biodegradable, and
their ultimate BOD would not be exerted
in  the 5 days it takes to run a standard
BOD test. COD data,  however, are not
always available, and estimates based on
other activity factors may be necessary.
Therefore, a variety of  emission  factors
are included in Table 2.
Table 2. Average Emission Factors
Compound
                  Emission Factor
  Average
Range
Methane






Ammonia





Nitrous Oxide




g CH4/head of cattle
g CH4/chicken
g CH4/kg meat
g CH4/L of wastewater
g CH4/g influent BOD
g CH4/g BOD removed
g CH4/g COD removed
g NH3/head of cattle
g NH3/chicken
g NH3/kg meat
g NH3/L of wastewater
g NH3/g influent BOD
g NH3/g NH3 in effluent
g N2O/chicken
g N2O/kg meat
g N2O/L of wastewater
g N2O/g BOD removed
g TKN removed
4,200
120
37
2.7
1.5
1.6
0.96
46
0.046
0.14
0.014
0.40
0.072
1.8
1.1
0.067
0.051
1.7
3,500 - 4,800
N/A
15-74
1.6-4.6
0.40 - 3.2
0.43 - 3.4
0.26 - 2.0
37-54
N/A
0.027 - 0.24
0.0017-0.028
0.0031 - 1.2
0.020-0.13
N/A
N/A
N/A
N/A
N/A
N/A = Not applicable.

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  An  estimate of the uncertainty  of  the
emission  factors  was  developed through
standard  error propagation methods. The
derived emission  factors  all  appear  to be
reliable to within  a factor of 2, based on
random  error in  the  measurements, and
assuming that the sites and  samples
accurately represent the population of interest.
  It is possible that the lagoons are a sink
for suspended and colloidal material (i.e.,
insoluble BOD) and this material builds up
over time in the  lagoon  sediments.  If so,
sediments may degrade during  summer
months or whenever the sediment  is re-
suspended,  thereby increasing  the CH4
(and CO2) emissions.  However, no sea-
sonal trend is evident in  the BOD effluent
levels in  the long-term  wastewater data
provided  by the plants.
  A number of previously published stud-
ies contain estimated or  measured values
for the emission fluxes of CH4 from liquid
surfaces  or slurries. The key comparison
is the emission flux (i.e., emission rate per
unit surface area). The average CH4 emis-
sion  flux for the  three  meat  processing
plants ranged from 6,100 to  23,000 \ig
CH4/sec-m2. Results for livestock lagoons
in previous studies (1,400 to 9,400), were
within an  order  of magnitude,  as were
measurements at a manure tank (1,300 to
3,800). The emission flux from municipal
WWT systems, industrial WWT  systems,
and rice paddies was substantially lower,
as expected given the  much  lower BOD
and COD levels in such waters.
   Very few published  emission  factors
can be compared with  the emission fac-
tors developed in  this  study. The most
widely reported emission factor for CH4 is
0.22 g CH4/g BOD. The reference for this
factor does not provide information about
how it was developed.  It is very  close to
the theoretical value for the anaerobic deg-
radation of glucose. The emission factors
determined in this study are substantially
higher than those based on  glucose deg-
radation.  Glucose is a  simple sugar and
its biodegradation  over short periods  of
time cannot be directly compared with the
microbial degradation of complex mixtures
of amino  and fatty acids,  such  as are
present  in  the wastewaters at the meat
processing  plants.
Conclusions
  Several conclusions can be drawn from
the study:

  • The  FTIR  measurement  approach
    used in this study was successful for
    the simultaneous collection of large
    amounts of ambient concentration
    data for CH4 and NH3;
  • The  use of the OPM-TM approach
    using FTIR for estimating emission
    rates has insufficient sensitivity for cer-
    tain  compounds,  such as hydrogen
    sulfide and total non-methane hydro-
    carbons, due to limitations in the FTIR
    analysis.  For most of the sites,  the
    sensitivity for CO2 was limited by the
    high background concentrations and
    the variability in the background con-
    centrations;
  • Anaerobic WWT lagoons are a sig-
    nificant source of CH
    sions; and
  • Lagoons  at POTWs are  not a signifi-
    cant source of any  GHG,  with  the
    possible exception of CO2.
and NH3 emis-

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 Bark Eklund and Jeffrey LaCosse are with Radian Corporation, Austin, TX 78720.
 Susan A. Thorneloe is the EPA Project Officer (see below).
 The complete report, entitled "Field Measurement of Greenhouse Gas Emission
   Rates and Development of Emission Factors for Wastewater Treatment," (Order
   No. PB98-117898; Cost: $67.00, 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:
         Air Pollution Prevention and Control Division
         National Risk Management Research Laboratory
         U.S. Environmental Protection Agency
         Research Triangle Park, NC 27711
United States
Environmental Protection Agency
Center for Environmental Research Information
Cincinnati, OH 45268

Official Business
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         EPA
   PERMIT NO. G-35
EPA/600/SR-97/094

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