Metal Stimulation and Municipal Digester Thermophilic/Mesophilic Activity
Metal Stimulation and Municipal Digester Thermophilic/Mesophilic Activity
Metal Stimulation and Municipal Digester Thermophilic/Mesophilic Activity
Thermophilic/Mesophilic Activity
Daniel H. Zitomer1; Carlan C. Johnson2; and Richard E. Speece3
Abstract: Biomass from thermophilic and mesophilic digesters 共four temperature-phased anaerobic digesters and one phased thermo-
philic digester兲 was assayed for potential methane production rate increases resulting from nutrient 共Ni, Co, and Fe兲 addition. Further-
more, digester operations and biomass activities were compared. The majority 共77%兲 of biomass samples benefited from nutrients, with
propionate and acetate utilization rates increasing as much as 50 and 35%, respectively, after nutrient addition. Propionate utilization rates
were more frequently stimulated by nutrient addition, demonstrating increased methane production rates of from 14 to 50% upon nutrient
amendment. Others have observed difficulty achieving low propionate concentrations in municipal thermophilic digesters, especially at
lower retention times. Trace nutrient supplementation is one method to increase propionate and acetate utilization in some municipal
thermophilic as well as mesophilic digesters.
DOI: 10.1061/共ASCE兲0733-9372共2008兲134:1共42兲
CE Database subject headings: Biomass; Digestion; Nutrients; Metals; Municipal wastes.
3.5, 0.40, 0.45, and 2.0 mg/ L, respectively. These concentrations 共Speece 1996兲, are not toxic to anaerobic biomass, and are sig-
are ten times greater than those determined for mesophilic meth- nificantly higher than the Monod half-saturation constant values.
ane fermentation from acetate 共Takashima and Speece 1989兲, Therefore, systems were not substrate limited during the initial
indicating a possible decrease in bioavailability or increase in testing period. For each group, five metal-dosed systems were
nutrient requirements at thermophilic temperatures. prepared, with each system receiving either NiCl2, CoCl2, FeCl3,
In this study, the stimulatory effect of trace metals 共Ni, Co, or all three salts so as to result in added Ni, Co, and Fe concen-
and Fe兲 on methanogenesis using biomass from thermophilic, and trations of 25 mg/ L each in the systems. A control receiving no
TPAD municipal anaerobic digesters was quantified. The purpose nutrient amendment was also prepared.
of the study was to determine if trace metal supplementation for Sixteen of the 126 nutrient assay systems were run in triplicate
full-scale municipal thermophilic, and TPAD systems would be for statistical analysis. The average coefficient of variation 共CV兲
advantageous. The increase in propionate and acetate utilization value for maximum methane production rates of triplicate sys-
rates due to trace metal addition was determined. In addition, a tems was 2.5% when one high outlier was disregarded 共i.e.,
survey of operations for digesters from which biomass was as- 24.7% for the Greater Vancouver Regional District-Annacis
sayed was performed. Island Wastewater Treatment Plant, 共WWTP兲, thermophilic bio-
mass with calcium propionate control system receiving no nutri-
ent dose兲. This average CV value is comparable to the value of
Methods less than 3% reported by Vogel 共2003兲 for similar mesophilic and
thermophilic anaerobic serum bottle activity testing. An estimated
Municipal wastewater treatment plants with thermophilic anaero- CV value of 4.6% was used herein to compare mean values of
bic digesters were identified in North America through literature systems not run in triplicate. This value represents the upper 95%
共e.g., Schafer et al. 2003兲, internet research, and discussion with confidence limit of the CV values measured during this study.
practicing engineers 共Johnson 2006兲. Five plants were chosen for Average results from each of the biomass samples assayed were
study based upon availability of quasi-steady-state biomass and compared using student’s t-test to determine whether results were
willingness of plant managers to participate in the study. Some statistically different.
plants were not included since they were in start up or were not
operating thermophilic digesters at the time of the study. The
participating treatment plants are listed in Table 1. A treatment Biochemical Methane Potential Testing
plant survey instrument was created and completed by personnel
at all participating plants. The purpose of the survey was to pro- Biochemical methane potential 共BMP兲 is a measure of the meth-
vide information regarding digester type/configuration, digester ane that can be produced biologically from a given waste, sludge,
volume, type of material fed 共i.e., primary sludge, secondary or substrate, and is often reported in units of methane volume per
sludge, mixture兲, raw sludge feed rate, solids retention time, vola- mass of chemical oxygen demand 共COD兲 or per volume of ma-
tile solids destruction, biogas production, digester temperature, terial. The BMP protocol of Owen et al. 共1979兲 was used to de-
digester pH and alkalinity, volatile acids concentration, and am- termine the methane generation potential of each biomass. For
monia nitrogen concentration. BMP testing, a biomass sample 共50 ml兲 was placed in a 160 mL
Biomass samples were transported to the laboratory from all serum bottle, and biogas production was measured as described
participating plants for diagnostic assays. Tests performed in- below. The BMP was calculated by dividing the cumulative vol-
cluded: 共1兲 maximum potential acetate utilization rate 共MPAUR兲 ume of methane produced by the volume of biomass added to the
and maximum potential propionate utilization rate 共MPPUR兲 as- bottle.
says using nickel, cobalt, and iron; 共2兲 5- and 30-day biochemical
methane potential 共BMP兲 tests; and 共3兲 MPAUR and MPPUR
assays without nutrient supplementation. All these assays have MPAUR and MPPUR Testing
previously been used by Speece 共1988兲 to investigate over 30
conventional mesophilic digesters. MPAUR and MPPUR testing was performed without nutrient
supplementation to determine the thermophilic and mesophilic
maximum biomass utilization rates of acetate and propionate
Nutrient Assays
under nonsubstrate-limited conditions. These tests have been de-
Biomass aliquots 共50 mL兲 were placed in multiple, 160 mL scribed by Speece 共1988兲 as assays to characterize the rate that a
serum bottles. Two serum bottle groups were prepared for each given biomass can utilize the anaerobic digestion intermediates,
biomass sample used in nutrient assays. To one group, 7.5 g / L acetate, and propionate. Briefly, 50 mL biomass aliquots were
calcium acetate was added, whereas 3 g / L calcium propionate placed in 160 mL serum bottles and either 7.5 g / L calcium ac-
was added to the other group. These substrate concentrations are etate or 3 g / L calcium propionate was added for MPAUR and
typically employed for acetate and propionate utilization testing MPPUR tests, respectively. Bottles were incubated and the
MPAUR and MPPUR values were determined as the maximum tive methane volume produced versus time was plotted, and the
slope of the plot of cumulative methane produced versus time, as initial maximum methane production rate was quantified by linear
described below. regression of appropriate initial plot points, giving biomass activ-
ity for MPAUR and MPPUR values.
Total solids, volatile solids and alkalinity concentrations as
Analytical Testing well as pH were determined by standard methods 共APHA,
AWWA, and WEF 1998兲. Soluble phosphate concentrations were
After adding biomass and any substrate or metal dose, the head-
determined by centrifuging samples at 5,600 rpm for 1 h, and
space of all serum bottles was gassed with 70/ 30 v / v N2 / CO2,
then filtering the supernatant through 0.45 m opening cellulose
sealed with butyl rubber septa, and placed on an incubator shaker
at 35° C or 55° C 共C25KC, New Brunswick Scientific, Edison, nitrate membrane filters. The filtrate was then analyzed for ortho-
N.J.兲 for mesophilic and thermophilic samples, respectively. Bio- phosphate via the vanadomolybdophosphoric acid colorimetric
gas production was measured over time using a glass syringe with method, as described elsewhere 共APHA, AWWA, and WEF 1998;
wetted barrel inserted through the bottle septa. For ease of com- Johnson 2006兲. Biogas methane content was determined by gas
parison, thermophilic biogas measurements were converted to chromatography using a flame ionization detector 共APHA,
equivalent volumes at 35° C assuming an ideal gas. The cumula- AWWA, and WEF 1998; Johnson 2006兲.
Plant name 共 兲
MG
MGD 共1,000 GPD
MGD 兲 共1,000 CFD
MGD 兲 共 兲
CFD
CF 共 兲
CF
CF
Results and Discussion more complete biosolids stabilization. This more complete stabi-
lization may be a result of both thermophilic temperatures and
larger total digester size.
Treatment Plant Survey
Four TPAD systems and one, four-stage thermophilic system
Nutrient Assays
were chosen for study. The four-stage system 共Annacis Island
Wastewater Treatment Plant兲 was comprised of four initial ther- The majority of biomass samples tested 共77%兲 benefited from
mophilic digesters in parallel with a solids retention time 共SRT兲 nutrient supplementation, with seven of the nine biomass samples
of approximately 18 days followed by three smaller thermophilic 共four mesophilic and three thermophilic兲 exhibiting statistically
digesters in series. The overall SRT of the three smaller digesters significant increased acetate and/or propionate utilization rates
was approximately three days. The operating data provided by upon supplementation with either nickel, cobalt, iron, or all three
personnel from each are presented in Table 2. Four plants di- nutrients. Table 4 summarizes the thermophilic and mesophilic
gested a mixture of primary and waste-activated sludge, whereas biomass samples that demonstrated a statistically significant in-
one digested waste-activated sludge only. Total average system crease in biogas production with acetate and propionate sub-
SRTs were between seven and 30 days, with an average of ap- strates, respectively. In some cases, supplementation of a single
proximately 19 days. nutrient caused an increase in methane production rate, whereas
In general, all plants were operating well, with pH values supplementation with all three nutrients together did not. The rea-
greater than 7 and VFA concentrations ⬍1,000 mg/ L as acetic son for this is unknown.
acid 共see Table 2兲. VSR was generally very good, and averaged Propionate utilization rate was more frequently increased by
53%. However, the relatively low value of VSR for the Western nutrients than acetate utilization. In this regard, six out of seven
Lake Superior Sanitary District 共WLSSD兲 was an outlier. propionate-fed, nutrient-amended biomass samples 共86%兲 demon-
Normalized data are presented in Table 3, along with average strated increased biogas production rates, whereas only three out
results for mesophilic systems as reported by Speece 共1988兲. For of nine acetate-fed samples 共33%兲 demonstrated an increase.
TPAD systems, digester biogas production values are the sum of There were three thermophilic propionate-fed systems stimulated,
mesophilic and thermophilic digester production. The average with a range of stimulation of from 14% to 51%, but only one
digester volume per unit influent flow of the TPAD and the ther- acetate-fed thermophilic system was stimulated, and the stimula-
mophilic staged system was 50% greater than that previously tion was marginal 共i.e., ⬍5%兲 共see Table 4兲.
reported for conventional mesophilic digesters 共Speece 1988兲;
however, the difference is not statistically significant at 95% con-
MPAUR and MPPUR
fidence. Nevertheless, it is interesting that TPAD and thermo-
philic systems are often cited as requiring less volume to achieve Fig. 1 summarizes the MPAUR and MPPUR results for the me-
a given solids destruction, yet the existing TPAD systems studied sophilic and thermophilic sludge samples taken from each of the
are, on average, larger than conventional mesophilic digesters. On participating municipal wastewater treatment plants. All rate data
the other hand, the average biogas production per volume of raw in Fig. 1 have been normalized as volumes of methane 共at 35° C兲
sludge fed and digester biogas produced per unit plant flow were per g VS in feed sludge 共mL CH4 / g VS day兲.
52 and 32% higher for the TPAD and thermophilic system studied Acetate and propionate utilization rates are important factors
as compared to conventional systems. Although these differences in the digestion process, with difficulties sometimes reported
are not statistically significant at a 95% confidence level, this is when trying to achieve low propionate concentrations in anaero-
an indication that TPAD and thermophilic systems accomplish bically treated effluents, especially at thermophilic temperatures.
All TPAD plants tested with propionate as the substrate showed production rates of 0.29 vol CH4 / vol d 共with an average SRT of
increased propionate utilization rates at thermophilic tempera- approximately 19 days兲. Comparing these values, the average di-
tures. The average specific rate for the thermophilic MPPUR was gested sludge stability increase due to a short additional digestion
statistically higher than the average specific rate for the meso- phase can be estimated. To illustrate, the BMP serum bottle can
philic MPAUR 关see Fig. 1共b兲兴, representing an 84% average rate be considered to simulate a final-phase, complete-mix reactor
increase from mesophilic to thermophilic biomass 共p = 0.05, treating a given mesophilic digester effluent. Daily methane pro-
v = 7兲. The increase in acetate utilization from mesophilic to ther- duction could theoretically increase by 2% with a one-day SRT
mophilic temperatures was even more pronounced and statisti- final phase. Likewise, the data of Speece 共1988兲 indicate a 3.6%
cally significant; the average thermophilic MPAUR was 159% average methane production increase if a final phase having a
greater than the mesophilic value 共p = 0.05, v = 7兲 关see Fig. 1共a兲兴. five-day SRT was implemented 共i.e., estimated using the reported
BMP5 values and plant operating data兲 even after an average of
45 days of digestion.
BMP Testing
Measured mesophilic BMP5 values ranged from 0.18 to
A low BMP value indicates stable sludge, whereas high BMP 0.40 vol CH4 / vol 共see Fig. 2兲. Comparing the average mesophilic
values indicate less stability and an increased potential to produce BMP5 values reported herein for TPAD systems 共Fig. 2兲 with
additional methane. BMP5 values for exclusively mesophilic bio- those reported for conventional mesophilic systems by Speece
mass samples averaged 0.11 vol CH4 / vol d 共see Fig. 2兲, whereas 共1988兲, it is apparent that BMP values were statistically lower for
treatment plant personnel reported average total digester methane TPAD systems 共p = 0.05, v = 34兲. It should be noted, however, that
the TPAD systems also had longer average SRT values than the
Fig. 1. Digester biomass acetate and propionate assay results. Fig. 2. Biochemical methane potential results. Summary of 5-day
Summary of maximum potential acetate utilization rate 共MPAUR兲 共BMP5兲 and 30-day 共BMP30兲 biochemical methane potential testing
and maximum potential propionate utilization rate 共MPPUR兲 assays for biomass from various municipal digesters. SBU⫽Sturgeon Bay
for biomass from various municipal digesters. SBU⫽Sturgeon Bay Utilities, WLSSD⫽Western Lake Superior Sanitary District,
Utilities, WLSSD⫽Western Lake Superior Sanitary District, GVRDAI⫽Greater Vancouver Regional District-Annacis Island,
GVRDAI⫽Greater Vancouver Regional District-Annacis Island, JWWTP⫽Janesville Wastewater Utility WWTP, DH⫽Delafield-
JWWTP⫽Janesville Wastewater Utility WWTP, DH⫽Delafield- Hartland WWTP, and average⫽average value for all biomass
Hartland WWTP, and average⫽average rates for all biomass. samples.