Article

pubs.acs.org/est

Contribution of Liquid/Gas Mass-Transfer Limitations to Dissolved

Methane Oversaturation in Anaerobic Treatment of Dilute
Wastewater
Hyeongu Yeo,† Junyeong An,† Robertson Reid,† Bruce E. Rittmann,‡ and Hyung-Sool Lee*,†
†
Department of Civil and Environmental Engineering, University of Waterloo, 200 University Avenue West, Waterloo, Ontario
Canada, N2L3G1
‡
Swette Center for Environmental Biotechnology, The Biodesign Institute at Arizona State University, P.O. Box 875701, Tempe,
Arizona 85287-5701, United States
*
S Supporting Information

ABSTRACT: The mechanisms controlling the accumulation of dissolved

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methane in anaerobic membrane bioreactors (AnMBRs) treating a synthetic

dilute wastewater (a glucose medium) were assessed experimentally and
theoretically. The AnMBR was maintained at a temperature of 24−26 °C as
the organic loading rate increased from 0.39 to 1.1 kg COD/m3-d. The
measured concentration of dissolved methane was consistently 2.2- to 2.5-
fold larger than the concentration of dissolved methane at thermodynamic
equilibrium with the measured CH4 partial pressure, and the fraction of
dissolved methane was as high as 76% of the total methane produced. The
low gas production rate in the AnMBR significantly slowed the mass
transport of dissolved methane to the gas phase. Although the production
rate of total methane increased linearly with the COD loading rate, the
concentration of dissolved methane only slightly increased with an increasing
organic loading rate, because the mass-transfer rate increased by almost 5-fold
as the COD loading increased from 0.39 to 1.1 kg COD/m3-d. Thus, slow mass transport kinetics exacerbated the situation in
which dissolved methane accounted for a substantial fraction of the total methane generated from the AnMBR.

■ INTRODUCTION
Energy-efficient wastewater treatment is gaining attention for
lowering costs and the carbon footprint. Municipal wastewater
treatment plants (WWTPs) mainly have used the activated
sludge process for almost a century.1 However, activated sludge
is expensive due to the large operations and maintenance
(O&M) costs of aeration and sludge disposal, and it has a large
carbon footprint.2 To reduce O&M costs and improve
sustainability, anaerobic biotechnologies are being considered
as alternatives to activated sludge.3 Furthermore, anaerobic
biotechnologies allow the recovery of substrate electron
equivalents as valuable products, such as methane, hydrogen,
H2O2, or electric power.4−7 These merits already have driven
the growth of anaerobic treatment of high strength organic
wastes and wastewaters (e.g., animal manure, industrial
wastewater, and primary and waste activated sludge), for
which achieving a low effluent concentration of biochemical
oxygen demand (BOD) is not a constraint, since anaerobic
treatment often is used as pretreatment, not for meeting
effluent standards.8,9
In contrast, anaerobic treatment of dilute wastewater, such as
domestic sewage, is rarely used due to deficiencies in effluent
quality and process reliability. However, combining membrane
separation with anaerobic treatment (called anaerobic mem-
brane bioreactors (AnMBRs)) can improve effluent quality and
reliability due to the perfect separation of suspended
solids.3,10,11 For example, membrane separation can lower the
effluent concentration of BOD enough (<7 mg BOD/L) to
make discharge feasible in many settings.11−13
AnMBRs present limitations that need to be addressed
before they can be put into widespread use: The main
challenges are lack of nutrient removal and dissolved methane
in the effluent.3,12,13 The focus of this work is on dissolved
methane. Dissolved methane in the effluent should be avoided
as much as possible because, on the one hand, methane is a
potent greenhouse gas,14 and, on the other hand, the energy
benefit from methane gas recovery is lost.13,15,16 Recent
literature has shown supersaturation of dissolved methane in
steady-state AnMBR permeate, as well as other anaerobic
processes. For example, Bandara et al.17,18 reported dissolved
methane concentrations of 11 to 15 mg CH4/L in upflow
anaerobic sludge blanket reactors, while dissolved methane of
16 to 26 mg CH4/L (the saturated concentration of dissolved
Received: November 10, 2014
Revised: July 24, 2015
Accepted: August 4, 2015
Published: August 4, 2015

© 2015 American Chemical Society 10366 DOI: 10.1021/acs.est.5b02560

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Figure 1. Schematic diagram of the laboratory-scale AnMBR. An ultrafiltration membrane module was immersed in the middle of the AnMBR. pH
and temperature probes and pressure transducers were installed in the AnMBR to continuously monitor pH, temperature, transmembrane pressure,
and the pressure inside the AnMBR. The effluent flow was monitored by weight on a scale. All sensors and the scale were connected to a personal
computer.
methane ∼12 mg CH4/L at 0.5 atm CH4 partial pressure and
25 °C) was measured in AnMBR permeates.13,19
Dissolved methane can be recovered from the effluent by
using gas-permeable membranes or gas-separation reactors as
post-treatment.17,18 High-efficiency recovery of dissolved
methane was obtained (77 to 98%), but the post-treatment
adds energy and O&M costs. A better strategy would be to
minimize the concentration of dissolved methane in the
effluent of AnMBRs by manipulating operating parameters,
such as the hydraulic retention time (HRT). However,
parameters affecting dissolved methane have not been
quantified due to the lack of understanding of how dissolved
methane behaves in steady-state AnMBRs.
This study addresses the mechanisms that lead to dissolved
methane accumulation in the effluent of steady-state AnMBRs
treating dilute wastewater, such as domestic sewage or low-
strength industrial wastewater. First, we build a mass-balance
model for dissolved methane in a steady-state AnMBR to
illuminate the main mechanisms affecting the fate of methane
for non-steady-state conditions: substrate-utilization rate to
generate methane, HRT to control loss of dissolved methane,
and mass transfer of methane to the gas phase. Second, we
experimentally determine key parameters for the dissolved
methane model (substrate-utilization rate, mass transfer
coefficient KLa, and dissolved methane concentration) in the
AnMBR operated at different organic loading rates and evaluate
the ability of the model to represent the effluent concentration
of dissolved methane. Finally, we build COD balances including
dissolved methane and document the role of oversaturation of
dissolved methane for causing poor recovery of methane gas
when the volumetric loading rate of chemical oxygen demand
(COD) and influent COD concentration are low.
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■ MATERIALS AND METHODS
Mass Balance for Dissolved Methane. The mass balance
for dissolved methane in the AnMBR is
d(CH4,L)
V = Q · CH4,L,in − Q · CH4,L,out + methanogenesis
dt
− KLa(CH4,L − CH4,eq)V (1)
where V is the volume of reactor (L), t is the time (h), Q is the
flow rate to the AnMBR (L/h), CH4,L,in is the concentration of
dissolved methane in the feed liquid (mg CH4/L), CH4,L,out is
the concentration of dissolved methane in permeate (mg CH4/
L), methanogenesis is the the mg/h rate of methane production
by methanogens, KLa is the mass-transfer coefficient (1/h),
CH4,L is the concentration of dissolved methane in the AnMBR
(mg/L), and CH4,eq is the concentration of dissolved methane
at thermodynamic equilibrium (mg/L) with the gas-phase CH4
partial pressure.
Dissolved methane typically is not present in the AnMBR
influent, and, hence, the input term in eq 1 becomes zero
(CH4,L,in = 0). In completely mixed bioreactors, CH4,L,out is
equal to CH4,L; we confirmed experimentally that the dissolved
methane concentrations in the bioreactor (mixed liquor) and in
the permeate were not significantly different (see the
Supporting Information). At steady state, application of those
simplifications and division by V converts eq 1 to
⎛ 1⎞ ⎛ dS ⎞
CH4,L ·⎜KLa + ⎟ = αfe ⎜ − ⎟ + KLa ·kH·PCH4
⎝ θ⎠ ⎝ dt ⎠ M (2)
where θ is the HRT (h) = V/Q, α is the conversion factor from
substrate removal to CH4 generation (mg CH4/CODglucose), fe
is the fraction of substrate electrons transferred to electron
acceptor ( fe = 1−fs), fs is the fraction of substrate electrons used
for biomass growth, (−dS/dt)M is the substrate-utilization rate
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 Environmental Science & Technology
by the methanogens (mg CODglucose/L-h), kH is Henry’s law
constant for methane (25.6 mg CH4/L-atm at 25 °C), and PCH4
is the partial pressure of methane in the AnMBR (atm).
Finally, the dissolved methane concentration at steady state
can be expressed as
( dS )M + KLa·kH·PCH
αfe − dt 4
CH4,L =
(KLa + θ1 ) (3)
AnMBR System Configuration and Inoculation. A
bench-scale, cylindrical AnMBR (ID 10.2 cm and H 70.0 cm;
total volume 5.72 L; working volume 4.5 L) was equipped with
a submerged ultrafiltration membrane module (ZeeWeed, GE
Water and Technologies, Canada), as shown in Figure 1. The
average pore size and the surface area of the membranes were
0.04 μm and 0.047 m2, respectively; the membrane flux of
ZeeWeed for AnMBRs ranges from 5 to 10 L/m2-h (LMH)
with regular membrane cleaning.20 A pH probe (PHE-1411,
Omega, Canada) and a compact industrial resistance temper-
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ature detector (RTD, Oakton Instruments, USA) were installed
inside the AnMBR to monitor pH and temperature
continuously. A gas flow meter (Ritter MilliGas counter,
Type MGC-1 V3.1 PMMA, Germany) was connected to a gas
port on the top of the AnMBR to measure biogas production.
Pressure transducers (Accuracy pressure transmitter, Cole-
Parmer, Canada) monitored the transmembrane pressure and
the pressure inside the AnMBR.
The AnMBR was inoculated with 2 L of sludge from an
anaerobic digester that had been operated with glucose medium
for over a year. After inoculation, glucose medium (2.5 L) was
added to the AnMBR with continuous nitrogen-gas sparging
(99.9%, PraxAir, Canada) over 20 min. The AnMBR was then
operated in a continuous mode with a HRT of 1 d and with the
glucose medium (alkalinity 4,300 mg/L as CaCO3) described
in the literature;19 refer to the Supporting Information for
medium composition.
Operation. To avoid complexity caused by heterogeneous
wastewater, we used a glucose medium as feed to the AnMBR.
The influent glucose concentration was increased stepwise from
320 to 1,080 mg COD/L at a fixed HRT of 1 d to evaluate how
the COD loading rate affects the concentration of dissolved
methane in the AnMBR permeate: The COD loading rates
were 0.39 ± 0.01, 0.74 ± 0.02, and 1.1 ± 0.03 kg COD/m3-d,
which are within the usual range of COD loading rates for
AnMBRs applied to treat domestic and low-strength industrial
wastewaters.3,10,12,17 Nitrogen and phosphorus concentrations
in the medium were fixed at 45 and 3.8 mg/L for each influent
COD concentration. Relatively long HRT and low membrane
flux allowed us to maintain steady operation of the AnMBR at a
given COD loading rate without having membrane fouling that
required chemical cleaning.
The AnMBR was run at each COD loading rate for 3−4
months, and steady state was confirmed by <5% deviations in
effluent COD concentrations, biomass concentrations, and
methane gas production rates. Influent and permeate flow rates
were controlled with two digital pumps (Masterflex L/S Digital
Drive, Cole-Parmer, USA); variations between feed and
permeate flow rates were less than 5% at all times. The
AnMBR mixed liquor was circulated in and out of the AnMBR
at a flow rate of 1.63 ± 0.11 L/min using a peristaltic pump
(Masterflex Economic Drive, Cole-Parmer, USA).12,19 To
mitigate deposition of biomass on the membrane surface,
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biogas was circulated at a constant flow rate of 0.93 ± 0.06 L/
min from the headspace to a gas diffuser connected to the
bottom of the membrane module (Figure 1). These two
vigorous mixing methods of liquid and gas circulation created
completely mixed conditions in the AnMBR, which allowed us
to focus on the effects of substrate-utilization rate and KLa value
in the steady-state AnMBR on dissolved methane concen-
tration; the information on tubing is described in the
Supporting Information. By avoiding serious membrane
fouling, we eliminated the possibility of adverse effects of
membrane-cleaning chemicals on microbial metabolism in the
AnMBR. The membranes were physically cleaned by permeate
back pulsing conducted for 30 min (1 min back-pulsing and 1
min relaxation in 15 cycles) once every 2 days. The only sludge
withdrawn from the AnMBR was for samples to quantify mixed
liquor suspended solids (MLSS) and mixed liquor volatile
suspended solids (MLVSS) concentrations (sample volumes 20
mL/week). pH, temperature, transmembrane, and the pressure
inside the AnMBR were continuously monitored with the
probes and sensors connected to a personal computer. The pH
in the AnMBR was constant at 7−7.3 during experiments, and
the temperature was stable at 24−26 °C. The permeate
production rate was also monitored using a scale (Adam GBK
Industrial Scale GBK-35a, Adam Equipment CO. Ltd., USA)
connected to the personal computer.
Chemical Analysis. A gas chromatograph was employed to
quantify the composition of the biogas. It was equipped with a
thermal conductivity detector (TCD) (SRI 310C GC-TCD,
SRI Instruments, USA), and a packed column (PorapakQ, 6 ft
× 1/8 in., 80/100 mesh, Agilent Technologies Inc., USA) was
used to separate gases in the GC. The temperatures of the
column oven and the detector were 41 and 200 °C,
respectively. Helium gas (99.999%, PraxAir, Kitchener, ON,
Canada) was used as a carrier gas at a flow rate of 10 mL/min
and a pressure of 21 psi. The concentration of dissolved
methane in the permeate was measured using a modification of
the method established by Kampbell and Vandegrift.21 10 mL
of permeate was taken with a 10 mL syringe and transferred to
a 20 mL vial that had been already sparged with carbon dioxide
gas (99%, PraxAir, Canada) for 10 min. After the vial was
shaken with a vortex mixer (Maxi-Mix II, Fisher-Scientific,
USA) for 3 min at 3,000 rpm and room temperature (for
building equilibrium between liquid and headspace), headspace
gas was sampled from the vials for quantifying the methane gas
percentage. Using a gastight syringe (Hamilton Gastight High-
Performance Syringe, Hamilton, USA), 500 μL of biogas was
injected to the GC-TCD. We converted the quantified methane
percentage from the headspace method to the concentration of
dissolved methane in liquid sample using Henry’s law, eq S1 in
the Supporting Information. The dissolved methane concen-
tration was measured 15 times for each organic loading rate.
Concentrations of volatile fatty acids (VFAs: acetate,
propionate, n-butyrate, isobutyrate, n-valerate, isovalerate, n-
caproate, and isocaproate) in the permeate were quantified
using a GC equipped with a flame ionization detector (FID)
(Hewlett-Packard HP 5980 Series II, USA) and a Nukol fused-
silica capillary column (15 m × 0.53 mm, Sigma-Aldrich Co.
LLC., USA). The initial temperature of the column oven was
110 °C, and it was increased to 195 °C with a temperature
gradient of 8 °C/min. The temperatures of the injector and the
detector were set at 220 and 280 °C, respectively. Helium gas
(99.999%, PraxAir, Canada) was used as a carrier gas at a
constant pressure of 40 psi. The GC-FID was calibrated using a
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standard solution (PN 46975-U, Sigma-Aldrich, Canada) for
every set of measurements. All samples were acidified with
phosphoric acid (PX0996-6, HPLC grade, EM Science, USA)
and filtrated using a syringe filter (Hydrophilic PTFE Syringe
Filters, 0.2 μm, Cole-Parmer, Canada) prior to analysis. VFAs
were quantified in triplicate for each measurement.
The concentrations of COD, MLSS, and MLVSS were
measured according to Standard Methods.22 A glucose assay kit
(GAGO20-1KT, Sigma-Aldrich, USA) was used to measure
concentrations of glucose in the permeate; the kit’s detection
range was 20 to 80 mg glucose/L.
KLa Determination. We experimentally measured KLa
values for the steady-state AnMBR using eq 423
⎛ Q gPCH4 ⎞⎛ ⎞ Qv
KLa = ⎜ ⎟⎜⎜
1 ⎟⎟ =
⎝ VRT ⎠⎝ CH4,L − CH4,eq ⎠ ⎛ CH ⎞ mg/L for MLVSS. Since no sludge was wasted from the
kHRT ⎜ CH 4,L − 1⎟
⎝ 4,eq ⎠ AnMBR, endogenous decay and/or release of soluble microbial
(4)
where Qg is the gas production rate (L/h), V is the volume of
liquid in the AnMBR (L), Qv (Qg/V) is the volumetric methane
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rates of 0.39 and 0.74 kg COD/m3-d, but it was 88 ± 12 mg
COD/L at 1.1 kg COD/m3-d; the detection limit for glucose
concentration was 24 mg COD/L using the glucose test kit.
High COD concentration, propionate accumulation, and
significant glucose accumulation in the permeate suggest that
a nutrient deficiency (e.g., phosphorus, which was input at only
3.8 mg/L) limited glycolysis and fermentation for the higher
COD loading rate.24,25 The phosphorus requirement for
complete COD removal is estimated at 3.4, 6.5, and 10.1
mg/L for the three OLRs, based on the COD to phosphorus
ratio of 100 g COD:1 g P.9,24
Biomass, Soluble Microbial Products (SMP), and
Membrane Flux. The MLSS and MLVSS concentrations
did not change much for the different loading rates: 2,080 ± 40
to 2,300 ± 110 mg/L for MLSS and 1,850 ± 40 to 1,960 ± 120
products (SMP) minimized the increase in biomass solids. In
fact, the AnMBR permeate accumulated significant SMP,
computed from CODSMPs = CODpermeate − CODglucose −

CODVFAs: 51 ± 6, 220 ± 10, and 310 ± 10 mg COD/L at

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production rate (L CH4 /L of AnMBR-h), R is the ideal gas law organic loading rates of 0.39, 0.74, and 1.1 kg COD/m3-d,
constant (0.0821 L-atm/mol-K), and T is the temperature (K). respectively. Thus, SMP accounted for 14% to 31% of influent
We measured the methane-gas production rate (Qv) and the
COD, a situation consistent with SMP reported by the
concentration of dissolved methane in the effluent (CH4, L) for
literature.26−28 Nutrients deficiency with a high organic loading
each organic loading rate in the AnMBR; dissolved methane
rate can increase SMP accumulation,29 and SMP is one of the
concentration in membrane permeate was almost equal to that
important membrane foulants.29,30 In our case, however, the
in the AnMBR. To improve data accuracy, we calculated CH4,eq
membrane flux was constant at 4.5 ± 0.3 L/m2-h (Figure S2A),
with the pressure inside the AnMBR measured using the
and the transmembrane pressure was stable at 6.7 to 10.9 kPa
pressure transducers. The temperature was stable at 25 ± 2 °C
(Figure S2B), even though the SMP concentration increased
in the AnMBR during all experiments.
with organic loading rate (Figure S2A). Thus, biogas
COD Balances in the AnMBR. A COD balance was
circulation, regular maintenance cleaning using permeate
established at each steady state to track the distribution of
back-pulse, and maintaining a relatively low MLSS concen-
substrate electron equivalents
tration effectively attenuated membrane fouling in the AnMBR.
CODin = CODpermeate + YgrowthΔCOD + Q methane gas/Q L Methane Gas Production Rate, KLa Value, and
Measured and Estimated Dissolved Methane Concen-
+ CODD‐methane (5) trations. The methane-production rate increased proportion-
ally to the organic loading rate, as shown in Figure 2. The
where CODin is the COD concentration in AnMBR feed (mg measured concentration of dissolved methane increased in
COD/L), CODpermeate is the measured COD concentration in parallel but less than proportionally to the organic loading rate,
AnMBR permeate (mg COD/L), Ygrowth is the observed
biomass yield in the AnMBR (0.14 ± 0.005 mg CODbiomass/mg
COD), ΔCOD (COD in − COD permeate ) is the COD
concentration removed in the AnMBR (mg COD/L),
Qmethane gas is the the production rate of methane gas from the
AnMBR in COD equivalents (mg COD/h), QL is the feed flow
rate (L/h), and CODD‑methane is the dissolved methane
concentration in COD equivalents (mg COD/L). Dissolved
methane in the permeate was readily released to the
atmosphere during COD measurement of the permeate
(CODpermeate); thus, CODpermeate did not include CODD-methane.
We experimentally quantified observed biomass yield with
serum bottle tests (see the Supporting Information).

■ RESULTS AND DISCUSION

COD and Specific Organics in the AnMBR Permeate.
The COD concentration in the AnMBR permeate increased
more than proportionally with the organic loading rate: 73 ± 8,
260 ± 20, and 480 ± 30 mg/L, respectively, for 0.39, 0.74, and
1.1 kg COD/m3-d. Acetate was 21 ± 3, 56 ± 2, and 60 ± 5 mg
COD/L for the three organic loading rates. Propionate was
detected only for the highest loading rate (18 ± 5 mg COD/L).
Glucose was undetected in the permeate for the organic loading
Figure 2. Trends of dissolved methane concentrations, methane gas
production rate, and KLa with increasing organic loading rate. D-
methane,eq is the dissolved methane concentration at equilibrium
computed with Henry’s law constant (KH = 25.6 mg CH4/L-atm at 25
°C) and the partial pressure of methane monitored in the AnMBR.

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Table 1. COD Balances and Output Fractions of Influent COD at Different Organic Loading Rates in the AnMBR
organic loading rate (kg COD/m3-d)
0.39
COD (mg/L) fraction (%) COD (mg/L)
influent 335 ± 10 100
permeate 73 ± 8 22
methane gas 38 ± 8 11
D-methanea 117 ± 4 35
biomass growth 36.7 11
unknown 70 21
a
D-methane: dissolved methane.
and the measured CH4 concentration always was 2.2- to 2.5-
fold larger than the dissolved methane concentration at
thermodynamic equilibrium with the measured CH4 partial
pressure (CH4,eq), clearly showing that the dissolved methane
was supersaturated. This level of supersaturation is consistent
with the recent literature for AnMBRs.13,15,19 Because the
temperature was held in the narrow range of 24−26 °C during
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AnMBR operation, any slight change of temperature did not
lead to supersaturation of dissolved methane. High ionic
strength can decrease the solubility of a dissolved gas due to the
salting-out effect,31,32 but the effect becomes significant only for
ionic strength greater than about 0.6−1 M.32 The ionic strength
was close to 0.09 M in our glucose medium; hence, the salting-
out effect on dissolved methane was negligible in our study.
Figure 2 shows how Qv, the oversaturation ratio (CH4,measured
to CH4,eq), and KLa values (experimentally determined using
the QgPCH4 side of eq 4) varied with the organic loading rate.
The KLa values increased from 0.018 ± 0.003/h at the lowest
organic loading to 0.088 ± 0.017/h at the highest organic
loading rate. The factor most affecting KLa was Qv, as described
by the right side of eq 4; other important influencing factors for
KLa (viscosity, gassing rate, liquid circulation, and temperature)
were constant during the experiments. Experimentally, Qv
increased with organic loading rate, but the increase of
dissolved methane to organic loading rate was less than the
Qv increase because the increased KLa with higher Qv allowed
more CH4 to escape to the gas phase.
The dissolved methane concentration estimated from eq 3
plus experimentally determined values of (−dS/dt), KLa, θ, and
PCH4 corresponded well to the measured concentration of
dissolved methane (error of 1−5% (Figure S3)). This validates
the mass balance for dissolved methane and further confirms
the negligible effect of salting-out.
Distributions of Methane Electrons in the AnMBR.
Table 1 summarizes the COD balances in the AnMBR. COD
mass closure was from 79% to 88%. The missing COD (12% to
21%) may have been due to CH4 gas loss from or O2 intrusion
to gas-permeable tubes used in the AnMBR (liquid circulation,
biogas circulation, and permeate collection), which has been
observed in relatively large continuous bioreactors.13,19 We
could not fully track other electron sinks accounting for 12−
21% of COD loss in the AnMBR, but the amount of O2
permeating through tubing was less than 1% of input COD.
Total methane (dissolved methane + methane gas) comprised
33% to 46% of influent COD, with the remaining COD being
mostly soluble COD in the permeate. The dissolved methane
fraction was 14% to 35% of the influent COD, and Figure 3
shows that only 24% to 58% of the total methane generated
was captured as methane gas in the AnMBR. Others have seen
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0.74 1.1
fraction (%) COD (mg/L) fraction (%)
654 ± 16 100 1010 ± 120 100
256 ± 19 39 478 ± 33 47
99 ± 18 15 192 ± 32 19
132 ± 23 20 140 ± 21 14
55.7 8.5 74.3 7.3
111 17 124 12
Figure 3. Fractions of methane gas and dissolved methane of total
methane and influent COD. Total methane is the sum of methane gas
and dissolved methane (D-methane). Inf COD represents influent
COD concentration. Methane is converted to COD using a methane
half reaction (1 mg COD = 0.25 mg CH4).
similar trends, with dissolved methane ranging from 40 to 63%
of the total methane.13,15
A key trend from Figure 3 is that the fraction as CH4 gas was
lowest for the smallest COD loading rate. Certain AnMBR or
anaerobic-digestion literature has shown CH4 gas yields close to
the theoretical maximum value of 0.38 L CH4/g CODremoved at
25 °C,33−35 but they had high volumetric loading rates (5 to 20
kg COD/m3-d) and high influent COD concentrations (10 to
50 g COD/L), compared to our study: low volumetric loading
rate (0.39 to 1.1 kg COD/m3-d) and low influent COD
concentration (0.32 to 1.08 g COD/L). Our work demon-
strates that dissolved methane became significant because of a
combination of mass transfer and biological factors. First, the
small KLa value associated with a low Qg did not allow dissolved
CH4 to escape to the gas phase, leading to significant
supersaturation. The Qg term mainly depended on the influent
COD concentration, which controlled the organic-loading rate.
Second, the biological production rate of CH4 was faster than
the rate at which saturated CH4 could be removed in the
permeate. Thus, the permeate had to become supersaturated in
CH4 in order to allow a steady-state mass balance. This two-
part interpretation explains why our study gave only 15−36%
COD conversion to CH4 gas, while typical anaerobic digesters
run with high organic loading rate and influent COD show
>90% COD conversion to methane gas.36 AnMBRs treating
dilute wastewater are promising due to energy neutrality and
less sludge production. However, our study clearly shows that
the AnMBRs cannot avoid significant accumulation of dissolved
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 Environmental Science & Technology
methane in the membrane permeate, and methane accumu-
lation becomes more significant with low-strength wastewater,
which normally leads to a low OLR. Thus, success with
AnMBRs demands post-treatment to capture dissolved
methane. The dissolved methane concentration in the
AnMBR was successfully simulated with the mass balance
model in eq 3 when the observed substrate-utilization rate was
used for computing the methane-production rate. Future
research is needed to elucidate and validate microbial reaction
kinetics that underlie the methane-production rate. This
information is essential to understand and mitigate super-
saturation of dissolved methane in AnMBRs.
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.est.5b02560.
Quantification of dissolved methane concentration;
effects of shaking intensity and incubation time on
dissolved methane quantification, glucose medium
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Publication Date (Web): August 13, 2015 | doi: 10.1021/acs.est.5b02560
composition, tubing information, observed biomass
yield, the evolutions of transmembrane pressure, and
membrane flux in the AnMBR; estimation of dissolved
methane concentrations with a developed model; and
computation of COD loss by O2 permeation through
tubing (PDF)
■ AUTHOR INFORMATION
Corresponding Author
*Phone: 1-519-888-4567 Ext. 31095. Fax: 1-519-888-4349. E-
mail: hyungsool@uwaterloo.ca.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This work was financially supported by Canadian Water
Network (CWN) entitled “Recovering the energy in municipal
wastewater with membrane-centered processes” (#2011-26-
845).
■
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