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Landcare Research Manaaki Whenua, Riddet Road, Palmerston North, New Zealand
University of Victoria, BC, Canada
a r t i c l e
i n f o
Article history:
Received 31 July 2011
Received in revised form 14 February 2012
Accepted 16 February 2012
Keywords:
Biolters
Dairy farms
Efuent ponds
Methane
a b s t r a c t
Dairy farm efuent ponds are a source of methane (CH4 ), a potent greenhouse gas. Bioltration, whereby
CH4 is oxidised by methanotrophic bacteria, is a potentially cost-effective CH4 mitigation technology. We
report on the performance of a eld-scale biolter treating dairy farm efuent pond CH4 emissions for 16
months. This study is the rst to report on the feasibility of using bioltration to mitigate dairy waste CH4
emissions. The 70-L lter comprised a 1:1 volumetric mixture of volcanic soil from a landll and perlite.
Biogas collected in a oating cover on a 4-m2 section of the pond was directed through the biolters
base. Air was pumped through the lter to supply oxygen to the methanotrophs. The lters maximum
CH4 removal rate was 16 g m3 h1 (or 53 g g1 h1 ), which is high compared with literature landll
soil oxidation rates (typically <1 to 40 g g1 h1 ). At the trials conclusion, the lter experienced acid
accumulation, due to oxidation of H2 S in the inlet biogas (evidenced by low pH [3.9] and high sulphate-S
[1079 mg1 kg1 ] at the base of the lter compared with the top [pH = 4.6, sulphate-S = 369 mg1 kg1 ]).
Nonetheless, the lters oxidation rate peaked at the end of the experiment indicating negligible H2 S
impact on overall performance over the 16-month period. The results showed that a 50-m3 lter would be
needed to offset CH4 emissions (approximately 720 g h1 ) from a typical 1000-m2 dairy efuent pond. As
this calculation is based on the efciency of a single experimental lter, eld testing of replicate biolters
is needed to accurately establish full-scale lter sizing. Nonetheless, this study has shown that biolter
technology is feasible to mitigate dairy efuent pond CH4 emissions. Current research is underway to
make the lter more economically viable through design optimisation.
2012 Elsevier B.V. All rights reserved.
1. Introduction
Methane (CH4 ) is a greenhouse gas (GHG) with a global warming potential at least 23 times greater than that of carbon dioxide
(CO2 ) (Shindell et al., 2009). Agriculture is the main contributor of
anthropogenic CH4 to the atmosphere, accounting for over 60% of
total emissions (Mosier et al., 1998). Within the agricultural sector, dairy farming is one of the principal sources of CH4 . Enteric
fermentation is the major on-farm CH4 source typically accounting for about 95% of total farm emissions (Mosier et al., 1998;
MfE, 2010). However, enteric CH4 emissions rapidly diffuse into
the atmosphere and, hence, are difcult to intercept.
Another signicant farm CH4 source is waste storage ponds.
These structures are being increasingly adopted on New Zealand
dairy farms to address nutrient, pathogen and organic (i.e., chemical
oxygen demand/biological oxygen demand) loading from efuent
Corresponding author. Tel.: +64 6353 4996; fax: +64 6353 4801.
E-mail address: prattC@landcareresearch.co.nz (C. Pratt).
1
Deceased.
0167-8809/$ see front matter 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.agee.2012.02.011
34
oating cover (Fig. 1). Methane emissions from the pond surface
were recorded using a purpose-built volumetric ow meter, based
on a design described by Smith and Stckle (2008). Flow rates were
measured continuously by a datalogger and half-hourly averages
were recorded. The lter was sealed, oxygen was supplied to the
lter by an air pump and an outlet hose was inserted into the top
of the lter.
The biogas and air ow rates fed into the lter were continuously monitored and adjusted so that there was always sufcient
O2 to achieve complete CH4 oxidation (i.e. 2 molecules of O2 to
every molecule of CH4 ). Methane/O2 ratios in the gas mixture fed
into the lter were determined by taking the average measured
biogas composition of 80%CH4 /20%CO2 , and an O2 concentration
in air of 20%. The empty bed residence time (i.e. the lter volume
divided by the ow rate, Nikiema et al., 2007) of the gas mixture
in the lter was kept at >2 h (by manually adjusting the air or
biogas ow) to ensure sufcient contact time for CH4 transfer to
the methanotrophs. Gas samples were collected periodically from
the headspace of the closed lter and from the biogas inlet pipe.
Samples were collected in duplicate and sampling times covered
working hours between 9:00 a.m. and 5:00 p.m. In order to assess
if CH4 oxidation rates varied outside of these hours, sampling was
conducted hourly over two full-day periods (from 15 to 17 March
2010). Local air temperature and the temperature in the top 5 cm of
the biolter were monitored half-hourly over the experiment. The
eld lter trial was set up as shown in Fig. 1, and run for 16 months.
2.3. Assessing the effect of H2 S on biolter performance
Hydrogen sulphide in biogas oxidises in the presence of water
and air to produce sulphuric acid. A pH reduction, caused by H2 S
oxidation, can inhibit methanotroph growth and activity (Nikiema
et al., 2007). Hence, the pH of the lter media was analysed at the
completion of the experiment in order to determine whether pH
had decreased in the lter over time. Approximately 300 mL of
soil/perlite mixture was collected from the top 20 cm, middle 20 cm
and bottom 20 cm portions of the lter and the pH and sulphate-S
in each layer were measured. Laboratory batch tests were conducted on media from each layer to determine CH4 consumption
rates. In the batch tests, 200 mL of soil/perlite mixture from each
depth layer of the lter was placed into a 1.8 L air-tight glass jar
and 4 mL (2.7 mg at 20 C and 1 atmosphere pressure) of CH4 was
injected into each jar. Samples were drawn from each jar every
half hour over a 2.5 h period and their CH4 and CO2 concentrations
were measured. Methane oxidation rates were determined using
the changing gas concentration proles over time.
35
Fig. 2. CH4 oxidation rates in the eld lter over the 16 month trial. All duplicate
values for CH4 removal are shown in the dataset.
lter. The highest CO2 concentration in the biolter exit gas was
6.4% on 21 February 2011. The theoretical CO2 concentration (i.e.
only biogas-CO2 , with no contribution from the lter medium) in
the same gas sample was 1.4%. By comparison, the observed CH4
concentration in the biolter exit gas at this interval was <0.01%
and the theoretical CH4 value was 4.4%. Hence, the CO2 produced
corresponded very closely with the reduction in CH4 , suggesting
that CH4 oxidation was the principal biological process occurring
in the lter by the end of the trial. The concentration of N2 O in the
undiluted biogas was below the method detection limit (0.1 ppmv)
while the N2 O contents measured in the gas exiting the lter were
consistently negligible, being in the range of atmospheric levels
(0.32 ppmv).
Leading up to November 2010, O2 concentrations were more
than double CH4 concentrations in the biolter exit gas (data
not shown), indicating sufcient O2 for complete CH4 oxidation.
However, on 1 November 2010 O2 concentrations (15.7%) were
commensurate with CH4 values (12.7%) in the exit gas, due to
increased biogas production. This lower O2 :CH4 ratio may have limited CH4 oxidation rates in the lter, which were only 22% on that
day. Hence, the air ow fed through the lter was increased and for
the remainder of the trial O2 values in the biolter exit gas were
adequate to facilitate complete CH4 oxidation.
Diurnal variations in CH4 inux and oxidation rates in the lter
were recorded in March 2010 for 2 days (Fig. 3). The data show
that CH4 inux rates uctuate over the course of a day. This is
not unexpected, as intermittent and irregular biogas eruptions are
frequently observed on dairy efuent pond surfaces. The CH4 oxidation rates responded to this emission variability with higher
oxidation observed at times of higher inux rates (Fig. 3). This
Fig. 3. Hourly variations in CH4 inux and oxidation rates in eld lter over two
day period (1517 March 2010).
36
Fig. 4. pH, sulphate-S and CH4 oxidation rates in different depth horizons of eld
lter. Mean of duplicate values and ranges shown.
concentrations decreased considerably, probably indicating incorporation into the soil microbial pool. Olsen-P levels decreased
marginally in the lter media during the trial (Table 1) again likely
due to incorporation into the microbial pool, but these diminishing
P concentrations did not appear to adversely affect methanotroph
activity. Overall, the lters physical and chemical parameters were
favourable for high microbial activity and, in general, appeared to
remain in the ideal range over 16 months in the eld-scale biolter
without any need for intervention.
In contrast to the other physicochemical parameters which were
optimal for CH4 oxidation, the pH decreased throughout the entire
lter over the course of the trial (Table 1), which could be inhibitory
for methanotroph activity (Nikiema et al., 2007). This pH decrease
was likely due to oxidation of H2 S within the biogas. Measurements taken in March 2010 revealed a mean H2 S concentration
of 443 ppmv in the biogas, which is high compared with values
reported by Rasi et al. (2007) (maximum H2 S values of 427 ppmv in
landll biogas and 20170 ppmv for sewage and farm biogas). The
H2 S concentration in the biolter exit gas was 0 ppmv, indicating
effective H2 S oxidation by the lter. In order to establish whether
CH4 oxidation was affected by H2 S oxidation, CH4 oxidation rates
at various depth horizons in the lter were measured (Fig. 4).
Results in Fig. 4 indicate increasing H2 S oxidation rates down the
lter prole, evidenced by decreasing pH and increasing sulphateS values. Methane oxidation rates diminished with depth down
the lter apparently suggesting that H2 S oxidation had an adverse
impact on methanotrophy. However, our research revealed that
substrate moisture also strongly inuences CH4 oxidation; the
studied soil oxidised CH4 twice as efciently at 40% moisture
(wt/dry wt) than at 85% moisture (wt/dry wt). Hence, the difference in CH4 oxidation rates between the top and base of the lter
could also be accounted for by moisture content alone (Table 1).
In the eld lter, the low pH values certainly did not affect overall CH4 oxidation rates. In fact, the greatest CH4 consumption was
observed during the nal days of monitoring (Fig. 2), suggesting the
effects of sulphur oxidation and subsequent acid generation take a
long time (>16 months) to impact signicantly on methanotroph
activity in engineered biolters. It is possible that over longer periods, sulphide oxidation could inhibit methanotrophy within the
eld lter. This could be overcome by liming the lter to maintain
near-neutral pH, scrubbing H2 S from the biogas using iron chips
37
Table 1
Physicochemical parameters of eld lter media.
Start
Top 20 cm
Middle 20 cm
Bottom 20 cm
Porosity (%)
Bulk density
(kg1 m3 )
Moisture (%)
pH
Total C (%)
Total N (%)
NH4 + -N
(mg1 kg1 )
NO3 -N
(mg1 kg1 )
Olsen P
(mg1 kg1 )
84
84
84
84
310
310
310
310
5.5
4.6
4.5
3.9
2.8
5.1
4.9
5.2
0.24
0.39
0.35
0.39
9.2
6.8
1.2
2.5
5.6
0.1
0.1
0.1
17
9
8
13
(29.6) 38.1
43.9
65.3
85.3
Figure in brackets is initial moisture content of soil, adjacent gure is moisture content of soil after wetting to 60% WHC.
(Scott et al., 2006), or inoculating the lter with acidophilic methanotroph strains which have been detected in peat soils (Dedysh et al.,
2001).
While the lter generally performed well overall, it is clear that
CH4 oxidation rates varied seasonally over the trial (Fig. 2). Oxidation, both as a proportion of the inlet CH4 removed and total
CH4 oxidised, was highest in summer and lowest over winter (e.g.,
<5 g m3 h1 ). Occasionally, over winter, no oxidation was observed
in the lter. Seasonal variation in CH4 oxidation rates has previously been reported (Melse and Van Der Werf, 2005; Tate et al.,
2007; Scheutz et al., 2009). The main factors causing this seasonal
variation appear to be CH4 inux rates and temperature. Methane
inux rates and CH4 oxidation rates were strongly positively
correlated (r2 = 0.42, p[two-tailed] 0.001). Biolter temperature
and CH4 oxidation rates also showed strong positive correlation
(r2 = 0.46, p[two-tailed] 0.001). These correlations are pertinent
at a practical-scale because seasonal variations in biogas production and wide temperature uctuations are common features of
many dairy efuent ponds. In the Manawatu region, where the trial
was performed, summer temperatures often reach 25 C, and occasionally up to 30 C. By contrast, winter temperatures approaching
0 C are not uncommon: a low of 1 C was recorded during the
trial. Diminished methanotroph activity and growth at these cold
temperatures can be a signicant limitation for biolter performance. For example, Scheutz et al. (2009) noted that oxidation
rates can drop to zero over winter. Insulating the lter may retain
internal heat produced by biological activity which may overcome
reduced CH4 removal rates over winter, but this will likely be
expensive, compromising the low-cost/low-maintenance aspect of
this technology. However, the reduction in biolter performance
over winter appears to be offset by the lower CH4 emissions from
the less active methanogen community in the waste pond (Fig. 5).
Winter CH4 production rates were only about 25% of summer,
spring and autumn generation rates (Fig. 5), similar to the CH4 produced from a dairy efuent pond in northern New Zealand (Craggs
et al., 2008). Sommer et al. (2009) also reported that CH4 emissions increased almost 10-fold in summer compared with winter
for cow manure stored in dairy housing in Italy. Therefore, even if
Fig. 5. Average seasonal biogas production by efuent pond. *Note that for
the study location in the Southern Hemisphere, Summer = DecemberFebruary
inclusive, Autumn = MarchMay inclusive, Winter = JuneAugust inclusive and
Spring = SeptemberNovember inclusive.
38
4. Conclusions
We have demonstrated effective and sustained CH4 oxidation
(up to 16 g m3 h1 ) by a eld-scale biolter treating emissions
from a dairy efuent pond. Our results conrm that CH4 emissions
can be reduced substantially using bioltration, and monitoring
over 16 months showed no evidence of reduced performance:
although testing of more biolters in the eld is recommended.
To make bioltration of dairy efuent pond CH4 emissions attractive economically, the lter design could be modied to incorporate
the pond cover and lter as a single structure overlying the ponds
surface.
Acknowledgements
Thanks to Taupo District Council for access to soils, New Zealand
Ministry for Agriculture and Forestry for funding, University of
Victoria (British Columbia, Canada) for gas chromatography equipment, Massey University for access to their dairy farm, and Ted
Pinkney for technical contributions.
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