Amendments and Feed ThroughAmendments and Feed‐Through Additive for Gas and Odor Emission
Reduction from Dairy ManureEileen Fabian WheelerEileen Fabian Wheeler
Professor of Agricultural Engineering
Pennsylvania State University, USA
American Chemical Society 242nd National Meeting & ExpoAGRO Division
Denver Colorado 2011
The SituationThe Situation
• An inexpensive and popular air qualityAn inexpensive and popular air quality mitigation strategy in the USA is the use of manure amendmentsmanure amendments
• Additives in dairy diets to modulate rumen fermentation and subsequent gas formationfermentation and subsequent gas formation
The ProblemThe Problem
• Evaluations of manure amendments underEvaluations of manure amendments under controlled conditions often indicate limited effectiveness despite on‐farm testimonials ofeffectiveness despite on farm testimonials of success
• A need for simultaneous• A need for simultaneous assessment of odor and pollutant gasand pollutant gas
Objective 1Objective 1
To evaluate performance of dairy manureTo evaluate performance of dairy manure amendments in reducing odor, ammonia, hydrogen sulfide and/or greenhouse gashydrogen sulfide and/or greenhouse gas emissions after short, medium and long storage periodsstorage periods.
Objective 2Objective 2
To evaluate different amendment modes ofTo evaluate different amendment modes of action on emissions
Digestive / Microbial
Di i f iDisinfecting
Oxidizing
Adsorbents
Masking
Chemical (pH)
Objective 3Objective 3
To characterize odor descriptors using humanTo characterize odor descriptors using human panel observations
MethodMethodScreening Study
Twenty‐Two Manure Amendments (n=1)7 i bi l/di t7 microbial/digest6 oxidizing/chemical3 di i f3 disinfectants6 masking agents1 adsorbentOdor and gas evaluations at 3 d and 30 dStorage at 20oC
Method 1/2Method 1/2Main Study
• Seven Manure Amendments (n=2 to 4)
2 microbial/digest‐MBR liquid & MPG powder/ g q p
oxidizing‐ Abandoned (acid) mine drainage
chemical CGE liquid chemical‐ CGE liquid
disinfectant‐ oxychlorine liquid
2 masking essential oils‐ peppermint & Hyssopus
Method 2/2Method 2/2Main Study
Plus one feed‐through essential oil additiveeugenol (28%) + cinnamaldehyde (17%) @ 525 mg/cow/d
Odor and gas evaluations at 3 d, 30 d and 94 dStorage at 10oC and 20oCg
MethodMethodManure Preparation
Manure collected during a Feed Additive trial
Urine: feces collected & combined 1:1 7Urine: feces collected & combined 1:1.7
MethodMethodManure Preparation
Stored @ 4oC for at least 2 wk to stabilize feedstock
Average pH 7.86
total solids 12 0%total solids 12.0%
total N 50.6 g kg‐1
No bedding
MethodMethodManure Storage & Study
2 kg Dairy Manure into 3.8L glass jars with d ( l)amendment (or Control)
5 batches with Control
Walk‐in incubator
MethodMethodGas Measurement
Multi‐chamber steady‐state gas emission h i i f d i ( )Photoacoustic infrared gas monitor (Innova)Ammonia
b d dCarbon dioxideNitrous oxideM thMethane
Pulsed fluorescence (TEI) H d lfidHydrogen sulfide
Methodsl l d lCalculate Steady‐State Flux
)(sf CiCo )(A
f CiCo
f = gas flux (mg cm‐2 min‐1)s = sweep air flow rate (m min‐1)s = sweep air flow rate (m min )Co = exhaust gas concentration (mg/m3)Ci = ambient gas concentration (mg/m3)iA = surface area of manure each chamber (cm2)
MethodOdor Emission
Olfactometer with qualified human panelists using Triangular Forced Choice method‐Detection threshold
‐Recognition threshold
Plus Odor QualityHedonic toneIntensityCharacter
CEN.2003. Air quality – Determination of odour concentration by dynamic olfactometry. EN. 13725 European Committee for Standardization (CEN), Management Centre: Rue de Stassart 36, B‐1050 Brussels.
Results‐Screening ExampleResults Screening Example Ammonia Measurement
A0.20
PAIRS of Treated manure + Control
m-2
hr-1
0.120.140.160.180.20
Treated with Microbial digestTreated with ChemicalTreated with DisinfectantTreated with Masking AgentTreated with AdsorbentControl
30D***
*** *** ***
NH
3 mg
cm
0 020.040.060.080.10
****** ************ ** *** **
Digestive MBR
Digestive MUN
Digestive MAE
Digestive MAC
Digestive MAF
Chemical CSE
ainage sediment
Chemical CBP
Chemical CBS
Chemical CGE
Chemical CAS
Chemical CPRBorax
drogen peroxide
chlorine solution
rvacrol + pineneEugenol
Glycerol
cimum basilicum
t black mitcham
Hyssopus oilZeolite
0.000.02
D D D
Acid mine drain CHydro
OxychlCarv Ocim
Peppermint b
Results‐Screening ExampleResults Screening Example Ammonia Measurement
A0.20
Reduction in Treated manure pH explains much of the improvementCircled amendments significantly reduced NH3 at 3 d and 30 d.
m-2
hr-1
0.120.140.160.180.20
Treated with Microbial digestTreated with ChemicalTreated with DisinfectantTreated with Masking AgentTreated with AdsorbentControl
30D***
*** *** ***
NH
3 mg
cm
0 020.040.060.080.10
****** ************ ** *** **
Digestive MBR
Digestive MUN
Digestive MAE
Digestive MAC
Digestive MAF
Chemical CSE
ainage sediment
Chemical CBP
Chemical CBS
Chemical CGE
Chemical CAS
Chemical CPRBorax
drogen peroxide
chlorine solution
rvacrol + pineneEugenol
Glycerol
cimum basilicum
t black mitcham
Hyssopus oilZeolite
0.000.02
D D D
Acid mine drain CHydro
OxychlCarv Ocim
Peppermint b
Results‐Screening Example Ammonia Measurement
• Products that reduced ammonia flux by atProducts that reduced ammonia flux by at least 10% for both 3 d and 30 d storage at 20oC included:– MBR, proprietary aerobic/facultative microbes– Acid mind drainage,– CAS, a Chemical proprietary liquid mix– Glycerol– Hyssopus oil– Peppermint black mitcham oil– Zeolite clinoptilolite
Full Results‐Screening: 2010 ASABE American Society of
Agricultural & Biological EngineersAgricultural & Biological Engineers
Wheeler, E.F., M.A.A. Adviento‐Borbe, R.C. Brandt, P. A. Topper, D. A. Topper H A Elliott R E Graves A N Hristov V A Ishler and M ATopper, H. A. Elliott, R. E. Graves, A. N. Hristov, V. A. Ishler and M.A. Bruns. 2010. Amendments for mitigation of dairy manure ammonia and greenhouse gas emissions: Preliminary screening. ASABE Paper No. 1008662. ASABE, St. Joseph, MI.00866 . S , St. Josep , .
Wheeler, E.F., M.A.A. Adviento‐Borbe, R.C. Brandt, P. A. Topper, D. A. Topper, H. A. Elliott, R. E. Graves, A. N. Hristov, V. A. Ishler and M.A. Bruns. 2010. Amendments for mitigation of odor emissions from dairy manure: Preliminary screening. ASABE Paper No. 1008658. ASABE, St. Joseph, MI.
NOTE: Both articles “in press” for Agricultural Engineering International: CIGR Journal
Results‐Replicated Main Experiment Methane 3 d Storage
0.5
0.6Treated; 10oCControl; 10oCTreated; 20oCControl; 20oC
3D
d‐1 No significant improvements
0.3
0.4
Control; 20 C
**
H4cm
‐2d
0.1
0.2
mg CH
0.0
Digestive MBRDigestive MPG
id mine drainage sedimentChemical CGE
Oxychlorine solutionHyssopus oil
Peppermint black mitchamFeed additive
0.0
Acid min Peppe
Results Methane 94 d Storage
C
0.6 94DTreated; 10oCControl; 10oC No significant improvements
0 3
0.4
0.5
cm‐2d‐
1
Control; 10 CTreated; 20oCControl; 20oC
No significant improvements
0 1
0.2
0.3
**
mg CH
4c
igestive MBRigestive MPG
e sedimentChemical CGE
ine solutionHyssopus oil
ck mitchamFeed additive
0.0
0.1*** ******
m
Digestiv Digestiv
Acid mine drainage sedChemic
Oxychlorine so Hyssop
Peppermint black mi Feed a
Results 0.5
0.6Treated; 10oCControl; 10oCTreated; 20oCControl; 20oC
3D
Methane0 1
0.2
0.3
0.4
**
0.0
0.1
CH
4 cm
-2 d
-1
0 4
0.5
0.6 30D
emis
sion
s, m
g C0.1
0.2
0.3
0.4
** ** *** *
Reduced CH with
CH
4 e
0.0
0 4
0.5
0.6 94D
*** ** * *
Reduced CH4 with longer storage
0.1
0.2
0.3
0.4
**
*** ******
Digestive MBRDigestive MPG
Acid mine drainage sedimentChemical CGE
Oxychlorine solutionHyssopus oil
Peppermint black mitchamFeed additive
0.0
Results d dOdor Emission 3 d Storage
140 3DTreated; 10oCC t l 10oC1 Acid mine drainage reduced odor
80
100
120Control; 10oCTreated; 20oCControl; 20oC
cm‐2d‐
1 gemission at 20oC
40
60
80
*OUE
0
20
1
i e MBRi e MPG diment
al CGEolution pus oil
itcham dditive0.0
Digestive MBDigestive MP
Acid mine drainage sedimeChemical CG
Oxychlorine solutioHyssopus o
Peppermint black mitchaFeed additi
Results Odor Emission 94 d Storage
140 94D
1 Treated; 10oC Significant reduction but generally
80
100
120
cm‐2d‐
1 ;Control; 10oCTreated; 20oCControl; 20oC
Significant reduction but generally small improvements
40
60
80
***
OUE
MBR MPG iment l CGE lution us oil t ham dditive0
20 ** *** ****** * **
Digestive MBRDigestive MPG
Acid mine drainage sedimentChemical CGE
Oxychlorine solutionHyssopus oi
Peppermint black mitchamFeed additive
Results 100
120
140 3DTreated; 10oCControl; 10oCTreated; 20oCControl; 20oC
Odor Emission 20
40
60
80
100 ;
*
Emission0
20
OU
E cm
-2 d
-1
100
120
140 30D
or e
mis
sion
s, O
20
40
60
80
** ***
*
Odor emission was
Odo
0
0
100
120
140 94D
reduced with longer storage time
20
40
60
80
** *** ******
*** * **
Digestive MBRDigestive MPG
Acid mine drainage sedimentChemical CGE
Oxychlorine solutionHyssopus oil
Peppermint black mitchamFeed additive
0
Results Ammonia 3 d Storage
2.8 Treated; 10oC 3D
d‐1
2.0
2.4Control; 10oCTreated; 20oCControl; 20oC
H3cm
‐2d
No significant reductions
0.8
1.2
1.6
mg NH
0 0
0.4
MBR MPG ent CGE tion s oil ham ditive0.0
Digestive MBRDigestive MPG
Acid mine drainage sedimentChemical CGE
Oxychlorine solutionHyssopus oil
Peppermint black mitchamFeed additive
Results Ammonia 94 d Storage
Treated; 10oC
N 0.02.8 94D
**
Several amendments and the feed additive reduced emissions
Treated; 10 CControl; 10oCTreated; 20oCControl; 20oC
2.0
2.4 **
m‐2d‐
1
0.8
1.2
1.6
*** *****
*
g NH3cm
MBR MPG nt CGE tion oil m itive0.0
0.4***
mg
Digestive MBRDigestive MPG
Acid mine drainage sedimentChemical CGE
Oxychlorine solutionHyssopus oil
Peppermint black mitchamFeed additive
Results 2.4
2.8 Treated; 10oCControl; 10oCTreated; 20oC
3D
Ammonia0.8
1.2
1.6
2.0
;Control; 20oC
Long‐term storage, promising results:
0.0
0.4
H3 c
m-2
d-1
2.4
2.8 30D
(Digestive MPG) Digestive MBR A id i i em
issi
ons,
mg
N0 4
0.8
1.2
1.6
2.0
** *
Acid Mine Drainage Hyssopus oil
(Feed additive)
NH
3 e0.0
0.4
2.0
2.4
2.8 94D
****
(Feed additive)
Longer storage did not reduce NH3
0.4
0.8
1.2
1.6
***
*** *****
*
not reduce NH3emission
Digestive MBRDigestive MPG
Acid mine drainage sedimentChemical CGE
Oxychlorine solutionHyssopus oil
Peppermint black mitchamFeed additive
0.0 ***
Overall Correlations dGas & Odor Emissions
Odor/ Gas Odor Ammonia Methane Carbon
dioxideNitrous oxide
Hydrogen sulfide
coeff1 P coeff P coeff P coeff P coeff P coeff P
NH3 -0.43 **CH4 0.76 ** -0.22 **CO2 0.18 * 0.42 ** 0.35 **N2O 0.08 ns 0.21 ** 0.26 ** 0.53 **H2S 0.54 ** -0.25 * 0.20 * 0.25 * 0.08 ns
Odor 0.16 * 0.18 * 0.26 ** 0.29 ** 0.07 ns -0.05 ns
1Coefficient of Correlation*P< 0.05**P<=0.001ns = not significant
Conclusionsd d lManure Amendment Odor Control
Essential oils, Hyssopus and Peppermint black mitcham,Essential oils, Hyssopus and Peppermint black mitcham, were effective for long‐term odor control.
They reduced odor emission by 25 to 50% and H2S by y y 2 y80% (20oC after 94 d). However, at 10oC after 30 d they increased odor and H2S.
Under long‐term cool (10oC) conditions, typical of storage, digest MBR and chemical CGE were effective
d d lin odor and H2S control.
Acid mine drainage was effective in short‐term odor t l (20oC) ff i l d li ti t ti lcontrol (20oC) offering pre‐land‐application potential
Conclusionsd lManure Amendment Gas Control
Storing manure, treated or not, reduced greenhouseStoring manure, treated or not, reduced greenhouse gas (and odor) emissions about 90%
Acid mine drainage reduced ammonia emission by 40‐g y80% after medium and long‐term storage under both cool and warm conditions
Two digestive amendments significantly reduced ammonia emissions at 30 d & 94 d storage
Feed‐through additive not efficient method for odor emission control, but showed promise for ammonia
t l t 20oCcontrol at 20oC.
Co‐Authorsl l l lAgricultural & Biological Engineering
• Patrick Topper – Senior Research Technologist
• Robin Brandt – Lecturer– Director Penn State Odor Assessment Laboratory
• Arlene Adviento‐Borbe – Post‐Doctorate Scholar
• Deborah Topper – Research Technologist
• Hershel “Chip” Elliottp– Professor
• Robert Graves – Professor
• Roderick Thomas– Instrumentation Instructor
Co‐AuthorslDairy & Animal Science
• Virginia IshlerVirginia Ishler– Nutrient Management Extension Specialist
– Manager Penn State Dairy Production Research and Teaching Center
• Alex Hristov– Associate Professor
G b i ll V• Gabriella Varga– Professor
C d S il S iCrop and Soil Science• Mary Ann Bruns
– Associate Professor
FundingFunding
• USDA Special GrantUSDA Special Grant– Improved Dairy Management Practices
