VOC Emission Factor for SJV Dairies · Considerations (2 of 3) Absence of Evidence is NOT Evidence...

VOC Emission Factor for VOC Emission Factor for SJV DairiesSJV Dairies

Argument for DPAG Viewpoint 2Argument for DPAG Viewpoint 2a mida mid--range positionrange position

May 31, 2005May 31, 2005

David A. David A. GrantzGrantz

Personal IntroductionPersonal Introduction

David A. David A. GrantzGrantz, Ph.D., Ph.D.University of California at RiversideUniversity of California at Riverside

Department of Botany and Plant SciencesDepartment of Botany and Plant SciencesAir Pollution Research CenterAir Pollution Research Center

Plant PhysiologistPlant PhysiologistExtension Air Quality SpecialistExtension Air Quality SpecialistDirector, Kearney Agricultural CenterDirector, Kearney Agricultural Center

Considerations (Considerations (11 of 3)of 3)

Perfect, Complete Data Not Available NowPerfect, Complete Data Not Available NowNever Will Be AvailableNever Will Be Available

Weather, location, management all differWeather, location, management all differDPAG had to generalize from few test dairies DPAG had to generalize from few test dairies and few studiesand few studies

Considerations (Considerations (22 of 3)of 3)

Absence of Evidence is Absence of Evidence is NOTNOTEvidence of AbsenceEvidence of Absence

All studies have limitationsAll studies have limitationsOnly some dairy processes were measuredOnly some dairy processes were measuredOnly some days (time of year) were measuredOnly some days (time of year) were measuredOnly some chemical classes of VOCs were measuredOnly some chemical classes of VOCs were measuredDPAG considered data from many studies (in DPAG considered data from many studies (in California and in the scientific literature) to evaluate California and in the scientific literature) to evaluate as many processes, time periods and chemical classes as many processes, time periods and chemical classes as possibleas possible

Considerations (Considerations (33 of 3)of 3)Despite data limitations, DPAG was required Despite data limitations, DPAG was required

to use best available science to determine: to use best available science to determine:

“…“…VOC emissions from individual dairies, VOC emissions from individual dairies, including the development of a Dairy including the development of a Dairy Emission Factor or Dairy Emission Factors Emission Factor or Dairy Emission Factors for the dairy facility as a whole and, to the for the dairy facility as a whole and, to the extent possible, for individual units that extent possible, for individual units that may be part of individual dairy operations.may be part of individual dairy operations.””

Methods UsedMethods Usedto Measure VOCsto Measure VOCs

Partial VOCsPartial VOCs if standards in mixif standards in mix----Method TOMethod TO--15 15 Oxygenated VOCsOxygenated VOCs----PTRMS PTRMS –– (e.g., methanol)(e.g., methanol)Volatile Fatty AcidsVolatile Fatty Acids----GC/MS GC/MS ThermodesorptionThermodesorption ––AminesAmines----NIOSH Method 2010 NIOSH Method 2010 (ion chromatography)(ion chromatography)

PhenolsPhenols----Not tested Not tested

Emission Sources at a Dairy/Emission Sources at a Dairy/(Sources Not Measured)(Sources Not Measured)

Milking ParlorMilking ParlorCow Holding AreaCow Holding AreaEnteric EmissionsEnteric EmissionsFeed LanesFeed LanesSilage PilesSilage PilesMechanical SeparatorMechanical SeparatorSettling Basin(s)Settling Basin(s)Lagoon(s)Lagoon(s)Storage Pond(s)Storage Pond(s)Land ApplicationLand ApplicationProcessing PitProcessing Pit

Flush LanesFlush LanesFreestallsFreestallsOpen CorralsOpen CorralsCalf HutchesCalf HutchesBedding MaterialBedding MaterialManure PilesManure PilesManure DisturbanceManure DisturbanceCompostingCompostingSeparated SolidsSeparated Solids

Process Based Emission FactorsProcess Based Emission Factors3 Viewpoints (slide 3 Viewpoints (slide 11 of 3)of 3)

1.21.2(lb/(lb/hdhd/yr)/yr)



33VOCs Var.VOCs Var.




22Amines Var.Amines Var.




11Cows/FeedCows/Feed

EmissionEmissionFactorFactor

Viewpoint 3Viewpoint 3





Process or Process or ConstituentConstituent



0 or NA0 or NA0.00.0(lb/(lb/hdhd/yr)/yr)

66Phenols Var.Phenols Var.




55VFA Var.VFA Var.




44Lagoon/PondLagoon/Pond












TOTALTOTALVOCsVOCs


NANAIncluded Included Above orAbove or

InsignificantInsignificant

88Feed, basins, Feed, basins, composting, composting, disturbancedisturbance


NANANANA77Land Land ApplicApplic..








1. Cows and Feed (3.4)1. Cows and Feed (3.4)

OutletInlet

Dr. Mitloehner Emission Chamber-Schematic

TO-15PTRMS

TO-15PTRMS

HEPA Filter

Emission = (Concentration Difference) x (Chamber Flow Factor) x (MW ratio)

Emission = (Out – In) x (CF) x (MW2/MW1)

Feed FreshManure

1. Cows and Feed (3.4)1. Cows and Feed (3.4)From Dr. Mitloehner letter 4/17/05From Dr. Mitloehner letter 4/17/05

PTRMS 3.0 lb/PTRMS 3.0 lb/hdhd/yr/yr--0.3 lb/0.3 lb/hdhd/yr (/yr (--10% due to manure)10% due to manure)

= 2.7 lb/= 2.7 lb/hdhd/yr/yrPTRMS missed ethanol (Dr. Schmidt’s largest) and aromatic PTRMS missed ethanol (Dr. Schmidt’s largest) and aromatic VOCs. No data for VOCs. No data for EtOHEtOH but can add 2 but can add 2 TrimethylTrimethyl--benzenes:benzenes:

0.7 lb/0.7 lb/hdhd/yr/yr(0.104 kg/(0.104 kg/hdhd/yr; 1,2,4 TMB)/yr; 1,2,4 TMB)(0.236 kg/(0.236 kg/hdhd/yr; 1,3,5 TMB)/yr; 1,3,5 TMB)x (2.2 lb/kg)x (2.2 lb/kg)

= 3.4 lb/= 3.4 lb/hdhd/yr/yr

2. Amines (0.2)2. Amines (0.2)Dr. C.E. Schmidt small chamber studies Dr. C.E. Schmidt small chamber studies = 0.2 lb/= 0.2 lb/hdhd/yr/yrDirectly measured on California dairies; Other Directly measured on California dairies; Other Calif. dairy data exist (e.g. Calif. dairy data exist (e.g. RabaudRabaud et al. 2003) et al. 2003) but not used for Viewpoint 2but not used for Viewpoint 2Highly probable this underHighly probable this under--estimateestimate

Chemical classes underChemical classes under--representedrepresented----only ethylamine only ethylamine reported but literature indicates many dairy aminesreported but literature indicates many dairy aminesDairy processes underDairy processes under--sampled (see list)sampled (see list)On other hand, Dr. Schmidt attempted to sample high On other hand, Dr. Schmidt attempted to sample high emitting microemitting micro--sitessites

3. VOCs from misc. dairy operations 3. VOCs from misc. dairy operations (1.2)(1.2)

Consensus among 3 ViewpointsConsensus among 3 Viewpoints= 1.2 lb/= 1.2 lb/hdhd/yr/yr

Dr. C.E. Schmidt small chamber studiesDr. C.E. Schmidt small chamber studiesDirectly measured on California dairies Directly measured on California dairies This is likely to underestimate emissionsThis is likely to underestimate emissions

Includes only some chemical classes and some Includes only some chemical classes and some dairy operations not considered elsewheredairy operations not considered elsewhere

4. VOCs from manure lagoons and 4. VOCs from manure lagoons and storage ponds (1.0)storage ponds (1.0)

Consensus among 3 Viewpoints Consensus among 3 Viewpoints = 1.0 lb/= 1.0 lb/hdhd/yr/yrDr. C.E. Schmidt and Dr. C. Dr. C.E. Schmidt and Dr. C. KrauterKrauter

Synthesis of small chamber studies and Synthesis of small chamber studies and whole dairy (upwindwhole dairy (upwind--downwind) studiesdownwind) studies

Directly measured on California dairiesDirectly measured on California dairiesThis is likely to underestimate emissionsThis is likely to underestimate emissions

Includes only some chemical classes not Includes only some chemical classes not considered elsewhereconsidered elsewhere

5. Volatile Fatty Acids (5. Volatile Fatty Acids (VFAsVFAs; 7.5); 7.5)

5.5. Volatile Fatty Acids (Volatile Fatty Acids (VFAsVFAs; 7.5); 7.5)BackgroundBackground——Why might VFA be important?Why might VFA be important?

Rumen is preRumen is pre--stomachstomachAnoxic or Anaerobic fermentation; WellAnoxic or Anaerobic fermentation; Well--mixed by muscular actionmixed by muscular actionMajor function: Microbial conversion of fiber and carbohydrates Major function: Microbial conversion of fiber and carbohydrates to to VFAsVFAs ––-- 50 to 70% of cow’s energy comes from VFA in rumen50 to 70% of cow’s energy comes from VFA in rumen

Balance of Production/Uptake keeps Balance of Production/Uptake keeps VFAsVFAs above 40 above 40 mmolarmmolarIn dairy cows (In dairy cows (HungateHungate at UCD) 108 at UCD) 108 –– 224 224 mMmM VFAVFA40 40 –– 70% Acetic, 1570% Acetic, 15--40 % 40 % PropionicPropionic, 5 , 5 –– 15 % Butyric Acids15 % Butyric Acids

VFA mostly dissociated; VFA mostly dissociated; pKapKa below rumen pHbelow rumen pHRumen pH 6.2 Rumen pH 6.2 –– 6.8 6.8 VFA VFA pKapKa about 4.8 about 4.8 (Acetic, Butyric, (Acetic, Butyric, PropionicPropionic 4.75, 4.81, 4.87)4.75, 4.81, 4.87)

*Uptake from Rumen is of NON*Uptake from Rumen is of NON--Dissociated VFADissociated VFAVolatilization is also of NONVolatilization is also of NON--Dissociated VFADissociated VFA

Volume of EructationVolume of Eructation——Cow BelchesCow BelchesUp to 50 quarts/Up to 50 quarts/hdhd/hr = 110,000 gal//hr = 110,000 gal/hdhd/yr/yrStripping into gas phase likely to deliver VFA to airStripping into gas phase likely to deliver VFA to air

5. Volatile Fatty Acids (5. Volatile Fatty Acids (VFAsVFAs; 7.5); 7.5)Two peerTwo peer--reviewed estimates of reviewed estimates of EFsEFs for for VFAsVFAs

Hobbs et al. (2004);Hobbs et al. (2004); 11.9 lb/11.9 lb/hdhd/yr from dairy manure slurry /yr from dairy manure slurry studies in Great Britainstudies in Great BritainKozielKoziel et al. (undated);et al. (undated); 1.17 lb/1.17 lb/hdhd/yr from dry manure on beef /yr from dry manure on beef feedlot in Texas (adjusted for dairy feed characteristics as feedlot in Texas (adjusted for dairy feed characteristics as suggested by CARES to DPAG on 4/13/05)suggested by CARES to DPAG on 4/13/05)

Two sets of measurements on California dairiesTwo sets of measurements on California dairiesDr. F. Dr. F. MittleohnerMittleohner; Detected abundant ; Detected abundant VFAsVFAs

DPAG advised to ignore data due to poor quality, variability, anDPAG advised to ignore data due to poor quality, variability, and d absence of inlet VFA concentrationabsence of inlet VFA concentration

Dr. C.E. Schmidt; did not detect Dr. C.E. Schmidt; did not detect VFAsVFAsDPAG advised that sampling used inappropriate long sample tubesDPAG advised that sampling used inappropriate long sample tubesVFAsVFAs would stick to tubing before collecting on sample cartridgeswould stick to tubing before collecting on sample cartridges

VFAsVFAs were not a primary target of either studywere not a primary target of either study

5. Volatile Fatty Acids (5. Volatile Fatty Acids (VFAsVFAs; 7.5); 7.5)

Viewpoint 2 used:Viewpoint 2 used:Hobbs and Hobbs and KozielKoziel data data RWQCB Fact Sheet # 4 “Nutrient & Irrigation Water RWQCB Fact Sheet # 4 “Nutrient & Irrigation Water MgmentMgment Plans” (60% to 80% of dairy manure is handled Plans” (60% to 80% of dairy manure is handled wet, in separators and lagoons)wet, in separators and lagoons)If use low number of 60% for wet then 40% is handled dryIf use low number of 60% for wet then 40% is handled dry

EF = (0.60 x 11.9 lb/EF = (0.60 x 11.9 lb/hdhd/yr) + (0.40 x 1.17 lb//yr) + (0.40 x 1.17 lb/hdhd/yr)/yr)= 7.5 lb/= 7.5 lb/hdhd/yr/yr

IIgnores any enteric emissions and emissions from feedgnores any enteric emissions and emissions from feed

5. Volatile Fatty Acids (5. Volatile Fatty Acids (VFAsVFAs; 7.5); 7.5)Alternative Calculation MethodsAlternative Calculation Methods

1. Whole Dairy Approach (DPAG report p. 15)1. Whole Dairy Approach (DPAG report p. 15)= 7.0 lb/= 7.0 lb/hdhd/yr/yr,, from Miller et al. and from Miller et al. and KozielKoziel & & VarelVarel

2. Dr. 2. Dr. MittleohnerMittleohner chamber approachchamber approachUsing acetone flux data from Figure on page 10 of Using acetone flux data from Figure on page 10 of 4/4/05 report 4/4/05 report = 7.1 lb/= 7.1 lb/hdhd/yr/yrUsing methanol flux data from Table on page 11 of Using methanol flux data from Table on page 11 of 4/4/05 report 4/4/05 report = 6.6 lb/= 6.6 lb/hdhd/yr/yr

OutletInlet

Dr. Mittleohner Emission Chamber-Schematic

?

HEPA Filter

Flux= (Concentration Difference) x (Chamber Flow Factor) x (MW ratio)

F = (Out – In) x (CF) x (MW2/MW1)

Feed FreshManure

AdsorptionCartridge/GC/MS TD

5. Volatile Fatty Acids (5. Volatile Fatty Acids (VFAsVFAs; 7.5); 7.5)Acetone approach using Dr. Acetone approach using Dr. MittleohnerMittleohner datadata

Recirculation and contamination of the inlet is about 30% for Recirculation and contamination of the inlet is about 30% for acetone. Likely to be nearacetone. Likely to be near--zero for zero for VFAsVFAs

dusty conditions, HEPA filterdusty conditions, HEPA filterFlux of Acetone = (Out Flux of Acetone = (Out –– In) x CFIn) x CF

0.6 lb/0.6 lb/hdhd/yr = (23.3 ppb /yr = (23.3 ppb –– 7.2 ppb) x CF7.2 ppb) x CFCF for acetone = 0.037 lb/CF for acetone = 0.037 lb/hdhd/yr/ppb/yr/ppbOutlet VFA 185 to 515 ppb, no zeroes, average = 350 ppbOutlet VFA 185 to 515 ppb, no zeroes, average = 350 ppbFlux of acetic acid = (185 Flux of acetic acid = (185 –– 0) x (0.037) x 1.0340) x (0.037) x 1.034

= = 7.1 lb/7.1 lb/hdhd/yr/yror = or = 13.413.4 lb/lb/hdhd/yr/yr if use 350 ppbif use 350 ppbor or =9.4 lb/=9.4 lb/hdhd/yr /yr if 30% inlet contaminationif 30% inlet contamination

5. Volatile Fatty Acids (5. Volatile Fatty Acids (VFAsVFAs; 7.5); 7.5)Methanol approach using Dr. Methanol approach using Dr. MittleohnerMittleohner datadata

Recirculation and contamination of the inlet is about 25% for Recirculation and contamination of the inlet is about 25% for methanol. Likely to be nearmethanol. Likely to be near--zero for zero for VFAsVFAs

dusty conditions, HEPA filterdusty conditions, HEPA filterFlux of Methanol = (Out Flux of Methanol = (Out –– In) x CFIn) x CF

1.35 lb/1.35 lb/hdhd/yr = (94 ppb /yr = (94 ppb –– 24 ppb) x CF24 ppb) x CFCF for acetone = 0.019 lb/CF for acetone = 0.019 lb/hdhd/yr/ppb/yr/ppbOutlet VFA 185 to 515 ppb, no zeroes, average = 350 ppbOutlet VFA 185 to 515 ppb, no zeroes, average = 350 ppbFlux of acetic acid = (185 Flux of acetic acid = (185 –– 0) x (0.019) x 1.8750) x (0.019) x 1.875

= = 6.6 lb/6.6 lb/hdhd/yr/yror = or = 12.512.5 lb/lb/hdhd/yr/yr if use 350 ppbif use 350 ppbor or =9.4 lb/=9.4 lb/hdhd/yr /yr if 25% inlet contaminationif 25% inlet contamination

5.5. Volatile Fatty Acids (Volatile Fatty Acids (VFAsVFAs; 7.5) ; 7.5) Comparison of Alternative MethodsComparison of Alternative Methods

--------7.57.5Viewpoint 2Viewpoint 2

--------Hobbs/Hobbs/KozielKoziel(wet/dry manure)(wet/dry manure)

13.413.412.512.5

Inlet Zero,Inlet Zero,Ave. VFAAve. VFA

7.17.16.66.6

Inlet Zero,Inlet Zero,Low VFALow VFA

9.49.4 (Acetone)(Acetone)9.49.4 (Methanol)(Methanol)Inlet NonInlet Non--ZeroZeroAve. VFAAve. VFA

Dr. Dr. MitloehnerMitloehner(cow plus fresh (cow plus fresh

manure)manure)

--------7.07.0 lb/lb/hdhd/yr/yr--------Whole Dairy Whole Dairy

(Miller, (Miller, KozielKoziel & & VarelVarel))

6. Phenols (0 or NA)6. Phenols (0 or NA)Literature data (Hobbs, Literature data (Hobbs, McGinnMcGinn) suggest ) suggest phenol emissions from dairiesphenol emissions from dairiesBut Viewpoint 2 concludes just not enough But Viewpoint 2 concludes just not enough data to estimate, thus data to estimate, thus = 0 or NA= 0 or NAZero is clearly an underestimate which can Zero is clearly an underestimate which can be corrected with further researchbe corrected with further research

7. Land Application (NA)7. Land Application (NA)Literature data (Literature data (McGinnMcGinn) suggest large VOC ) suggest large VOC emissions following land applicationemissions following land applicationBut Viewpoint 2 concludes just not enough But Viewpoint 2 concludes just not enough data to estimate, thus data to estimate, thus = 0 or NA= 0 or NAZero is clearly an underestimate which can Zero is clearly an underestimate which can be corrected with further researchbe corrected with further research

8. 8. Feed Storage, Settling Basins, Feed Storage, Settling Basins, Composting, Manure Disturbance (NA)Composting, Manure Disturbance (NA)Little information available on these processes Little information available on these processes that can be used to calculate Emission Factorsthat can be used to calculate Emission FactorsViewpoint 2 concludes just not enough data to Viewpoint 2 concludes just not enough data to estimate, thus estimate, thus = 0 or NA= 0 or NAThis appears to be an underestimate which can This appears to be an underestimate which can be corrected with further researchbe corrected with further research

Feed storage on a dairy may be a significant sourceFeed storage on a dairy may be a significant sourceDr. Dr. Mittleohner’sMittleohner’s data demonstrated abundant data demonstrated abundant methanol, suggested to be from feed methanol, suggested to be from feed Dr. Schmidt’s data, specifically from feed lanes, Dr. Schmidt’s data, specifically from feed lanes, demonstrated abundant ethanoldemonstrated abundant ethanol

Composting in nonComposting in non--dairy situations is a substantial dairy situations is a substantial source of source of VOCsVOCs

TOTALTOTAL——Viewpoint 2Viewpoint 213.3 lb/13.3 lb/hdhd/yr/yr

My suggestions to APCOMy suggestions to APCOThe 0.1 lb/The 0.1 lb/hdhd/yr precision is technically /yr precision is technically unsupportableunsupportableRounding to a multiple of 5 may be more Rounding to a multiple of 5 may be more reasonablereasonableAll DPAG members have agreed that averaging All DPAG members have agreed that averaging viewpoint TOTALS is NOT appropriate viewpoint TOTALS is NOT appropriate Selecting component estimates from different Selecting component estimates from different Viewpoints to create a new synthesis is reasonable Viewpoints to create a new synthesis is reasonable

And Good LuckAnd Good Luck

13.3 lb/13.3 lb/hdhd/yr/yr

Thank You

VOC Emission Factor for SJV Dairies · Considerations (2 of 3) Absence of Evidence is NOT Evidence...

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