Workshop TopicsOdour Emission MeasurementSwine Odour and EmissionsPoultry Odour and EmissionsNationwide Emissions Project

Odor/Odorous Gases

Typical livestock odorants Sulfides (H2S)

Volatile fatty acids (VFAs)

Mercaptans

Ammonia (NH3) & amines

Alcohols

Aldehydes

Esters

Carbonyls

Source: J. Sweeten, et al. 2/14/02

Tedlar bag

Odor Sample

Collection

Overnight expressto odor lab

Bag Sampling New 10-L Tedlar

bags flushed with N2

checked for odorlessness

Pre-conditioned Simultaneous

with gas measurements

Odor Sampling Use gas sampling system Freeze fans during sampling 2-3 replications Flush and precondition bags Include background

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12

9:00 9:30 10:00 10:30 11:00 11:30 12:00

Time of Day, h:mm

Air flow

rate, m3/s

Odor sampling

30 15

0

5

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15

20

25

30

8/24 9/7 9/21 10/5 10/19 11/2 11/16 11/30Day of Test, mm:dd

Em

issi

on

Rat

e, O

U/m

3-A

U

Control

Treated

Odor Emissions

Odor Measurements Field olfactometer

For evaluating ambient airDetermines odor concentrations with human noseSix dilution ratios

Dynamic, forced-choice olfactometerFor evaluating source samplesUtilizes human olfactometric senses (4-8 people)Odor threshold where 50% of panel is correct

Gas chromatography, mass spectrometry (GC-MS)Separates gasesMeasures presence and concentration

Hydrogen sulfide (popular surrogate gas for odor)

Sensor arrays (electronic nose)

Odor Emission Descriptors

1. Concentration = mass/vol., g/m3 OU/m3

2. Emission rate = concentration x airflow rate = mass/unit time (kg/day) = OU/sec

3. Flux = mass/unit time/unit area (kg/sec/m2); OU/sec/m2

Example (Smith & Watts, 1994 cited by Sweeten et al., 2002

Dry pad/manure surface: 5 OU/s-m2

Wet pad/manure surface: 100 OU/s-m2

4. Emission factor = emission rate/process descriptor

= mass/unit time/capacity,

= kg/day/head; OU/sec/head.

Panelist Rules (BMPs): Be free of physical conditions affecting sense of smell

(colds, pregnancy, etc.) Not smoke or use smokeless tobacco Not eat, drink or chew gun 1 h before session Not eat spicy food prior to session Be fragrance free Not consume alcohol for 3 h prior Not discuss or comment on odors with others Keep odor work confidential Not have been fasting or involved in substance abuse Arrive at least 5 minutes before session begins.

Reference Odorant n-butanol cal gas

C = 40 to 60 ppm ODCb = 1000 Cb/ODTb

prEN 13725 standard (CEN, 2001) Panelist performance criteria (n=10):

20 < mean ODCb < 80 ppb Standard deviation of log ODCb < 2.3

Panel performance criteria (n=10): 31 < mean ODCb < 51 ppb A < 0.213 R < 0.477

Purdue interim criteria for panelists (n=5) 10 < mean ODCb < 160 ppb Needed only about two months

Results for 57.5 ppm n-butanol reference odor

Assessor Step 1 2 3 4 5 Log D A 1 1 6 6 8 3.42A 1 1 6 8 3.42B 2 1 6 6 8 3.42B 2 2 1 6 8 3.13C 1 1 1 6 8 3.13C 2 5 6 6 8 3.42D 1 1 2 6 8 3.13D 1 1 6 8 3.42E 1 1 1 6 8 3.13E 2 1 1 8 8 3.13

Final Results:Response Key: D 1 = Incorrect Guess Avg. Log Value 3.192 = Correct Guess 5 = Incorrect Detection Dilutions to threshold 1,544 6 = Correct Detection 8 = Correct Recognition

Odor detection concentration = 57,500 ppb / 1,544 = 37 ppbcompared to CEN requirements of 20 to 80 ppb

Study Ratings (Watts,1999)

5: prEN 13725 olfactometry 4: NVN2820 olfactometry, report ODCb

3: Nonstandard olfactometry, no ODCb

2: Scentometer 1: Casual sniffing

Repeatability

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1

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100

1000

10000

9/11 10/23 12/4 1/15 2/26 4/8 5/20 7/1 8/12 9/23 11/4 12/16

Date (9/11/99 - 12/16/00)

OD

Cb,

pp

b (

n=

10

)

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1

2

3

4

Re

pe

ata

bili

ty, r

3/98 - 8/99

Mean ODCb (n=10)

Repeatability (n=10)

r=0.477

Accuracy

0

1

10

100

1000

10000

9/11 10/23 12/4 1/15 2/26 4/8 5/20 7/1 8/12 9/23 11/4 12/16

Date (9/11/99 - 12/16/00)

OD

Cb,

pp

b (

n=

10

)

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

Acc

ura

cy, A

3/98 - 8/99

Mean ODCb (n=10)

Accuracy, A (n=10)

A=0.217

Date Method changes 1 Oct. 1999 Original method:

Teflon sample tube length = 90 cm Prime time = 6 s Purge time = 45 s No uniform starting scale step determination Panelist screening subjectively based on retrospective screening

19 April 2000 Olfactometer upgrade Added mass flow controller Improved cabinet ventilation Implemented uniform warm-up

23 May 2000 Teflon sample tube length reduced from 90 to 30 cm Prime time = 30 s Purge time = 60 s

24 May 2000 Panelists not meeting Purdue intermediate criteria removed from panelist pool Prime time manually increased by “iterative searching” the olfactometer Uniform starting scale step where most sensitive panelist responds with GDR

5 June 2000 Remedial training session for panelists noncompliant with Purdue intermediate criterion to determine re instatement qualifications

12 June 2000 Starting scale step determined with “whittling” procedure Uniform starting scale step where most sensitive panelist does GGDR

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Date

n-bu

tano

l OD

Cb,

ppb

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

H2S

OD

Cb,

ppb

n-butanol

H2S

n-butanol vs. Hydrogen Sulfide

Odor Intensity Relative perceived psychological strength of odor Suprathreshold levels only (>ODT) Static Odor Intensity Referencing Scale (n-b in water)

Five concentrations of n-butanol with 3X progression Often used by field odor inspectors Objectively match intensities

Scale # N-butanol in water, ppm Strength

0 0 No odor

1 250 Very faint

2 750 Faint

3 2,250 Moderate

4 6,750 Strong

5 20,250 Very strong

Persistence of Odor

Odor concentration, OU/m3

Intensity

(log scale)

Fullstrength

Odor detection concentration

Detection Threshold

Persistence = slope = A/B

A

B

1 10 100 1,000 10,000

Persistence of Nursery Pig Odor

Hedonic Tone Degree to which an odor is subjectively perceived as pleasant

or unpleasant Perceptions vary widely among people

An emotional reaction Personal odor preference Individual odor experience

Purdue: -10 (extremely unpleasant) to 0 (neither) to +10 (extremely pleasant)

VDI 3882 proposed a –4 to +4 scale.

VDI 3882Determination of Hedonic Tone

Conclusive assessment about odor nuisance not possible with DT alone.

Determine intensity and HT separately. Polarity profiles of panelists, e.g. strong vs. weak, soft vs. hard, mild

vs severe, etc. for words and chemicals. Six suprathreshold concentrations starting with panel threshold, or to

only undiluted test sample. Random presentations Calculate Hc and Hs to represent sample. Behavior curve of hedonic odor tone:

Assume acceptable hedonic odor tone. Determine reduction % needed if inlet odor ht behavior is known. If cleaning process changes composition, then tests must be done on outlet

air. HT behavior curves allow prediction of ht in the immission zone. Changed hedonic tone must be taken into account with abatement

technologies. Vanillin in dipropylene glycol should result in +2.9 to +1.9. Guaiacol in water should result in –0.8 to –2.0.

Behavior Curve of H.T. (VDI 3882)

“HT Behavior Curve” of Nursery Odor

Odor Character DescriptorsEarthy Floral Foods Spicy Offensive M edicinal ChemicalAnimal Carnation Almond Anise Blood Alcohol AlcoholAshes Eucalyptus Apple Basil Burnt Anesthetic AromaticBark Flowery Burnt Black Pepper Cadaverous Camphor Car Exhaust

Chalk Fragrant Cantalope Caraway Decayed Cater Oil Cleaning FluidCork Geranium Caramel Caraway Fecal Chorine Creosote

Decay Iris Celery Chili Powder Foul Disinfectant GasolineGrass Lavender Cherry Cilantro Garbage Ether KeroseneHay Perfumy Coconut Cinnamon Pungent Mineral Oil Metallic

Herbal Rose Coffee Cloves Putrid Phenolic MothballLeaves Violet Cucumber Coriander Rancid Soapy OilyMildew Fish Curry Raw Meat Paint

Molassas Fresh bread Dill Rotten Paint ThinnerMold Fruity Mint Septic Petroleum

Mushroom Garlic Nutmeg Sewer Pine OilMusky Grape Peppermint Sour PlasticMusty Grapefruit Sassafras Sulfur SolventPeat Green Pepper Spearmint Swampy Tar

Pine Tree Honeydew Tea Leaves Urine TurpentineStale Lemon Vinegar Varnish

Wet Leaves Maple Vomit VinylNuts Woody

OnionOrange

Adjectives of Odor Descriptors

Burnt, chopped, cooked, decayed, dry, fermented, foul, fresh, new, old

Rancid, raw, rotten, scorched, shredded, stale, wet

Odor Evaluations of Corn Wet Mill

Corn Plant, Summer, 2000Albert J. Heber, Ph.D., P.E.

ODCb Hedonic tone IntensityDT ppb DT' R1 R2 R1 R2

Scrub inlet, T1 12879 60 14635 -1.81 -3.19 2.09 3.94Scrub outlet, T1 7837 60 8906 -1.44 -2.94 2.19 3.69Scrub outlet, T2 7869 60 8941 -1.44 -3.06 1.75 3.75Scrub inlet no H2O 7174 60 8152 -1.13 -3.13 1.63 3.75Scrub outlet no H2O 5817 60 6611 -0.81 -2.38 1.56 3.38Control 15681 52 15258 -1.19 -1.56 1.69 2.63Ess. Oil at 50:1 28746 42 22855 -0.38 -0.31 1.63 2.31Ess. Oil at 100:1 32118 42 25537 0.69 0.25 1.88 2.50

Scrub inlet, T1 burnt sugar creosote f ried soybeans pungent, burnt antiseptic

Scrub outlet, T1 burnt syrup tar f ried soybeans autoclaved grass decayed

Scrub outlet, T2 corn syrup chemical f ried soybeans steamed grass pungent, acidic

Scrub inlet no H2O burnt carbon sour f ried soybeans steamed grass decayed

Scrub outlet no H2O corn syrup turpentine f ried soybeans steamed grass vinegar

Control organic burnt corn f resh bread uncooked bread autoclaved grass

Ess. Oil at 50:1 burned potato chips burnt malt maple syrup rubbery burnt bread

Ess. Oil at 100:1 baked potato burnt malt baked bread paint over baked bread

Character descriptors (sample)

Swine House Odors and Emissions

Nursery Odor

Variable Average

Number of pigs 164

Mean pig weight, lb 30

Ventilation rate, cfm/AU 495

Inside temperature, °F 71

Outside temperature, °F 53

Incoming ambient air Odor concentration, OU/m3 18

Pit exhaust air Odor concentration, OU/m3 199

Intensity, ppm BIW 813

Hedonic tone -5.9

Swine Lagoon Odor

Variable Mean

Ammonia, mg/m³ 3.8

Hydrogen sulfide, µg/m³ 143

Sulfur dioxide, µg/m³ 39

Carbon dioxide, mg/m³ 875

Odor concentration, OU/m³ 67

Hedonic tone -1.7

Odor intensity, ppm BIW 1404

Daily Ammonia Emission Rates, g/d-AU

Hydrogen Sulfide Concentrations

1 to 1,527 ppb

H2S odor detection concentration = 1 ppb

Hydrogen Sulfide Concentrations

Site 2

H2S odor threshold concentration = 1 ppb

Ambient Hydrogen SulfideNear 12,000-Pig Nursery-Finishing Site

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Co

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on

, p

pb

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Wind Direction, degrees

April 6 - September 24

NW SE1st 2nd

Bldg

1st Bldg 1st

2nd 2ndH2S odor threshold

concentration = 1 ppb

Hydrogen Sulfide vs. OdorSwine Buildings

H2S odor threshold concentration = 1 ppb

Hydrogen Sulfide vs. Odor(Swine Lagoon)

DT = 1.21x0.92

R2 = 0.49

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800

0 100 200 300 400 500H2S Concentration, ppb

Odo

r C

once

ntra

tion,

OU

/m3

Ammonia

Hydrogen Sulfide

Peak of H2S when flushingwith lagoon effluent!!

25-pig room, Purdue swine farm

Daily Mean Pit Exhaust Concentration

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NH

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mg

/m3

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/m3

■=NH3

●=H2S

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2/27 3/13 3/27 4/10 4/24 5/8 5/22 6/5Day of Test

Ven

tila

tio

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ate,

m3

s-1

Inlet T

Ventilation Rate

Exhaust T

Emission Rate

-10

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on

, O

UE s

-1 A

U-1

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per

atu

re, o

C

mc=36.4%pH=8.4

mc=26.0%pH=8.3

mc=25.0%pH=8.3

Mean = 50,400 OUE/s = 65.6 OUE/s-AU = 7.53 OUE/s-m2

National Livestock Consent Agreement and Air Emissions Study

The purpose of this research project is to provide quality-assured air emission data from representative swine farms in the U.S., to U.S. EPA, in the effort to determine which farms might fall under regulatory authority. Following sound scientific principles, this project will collect new data and aggregate existing emissions data from previous studies. These data will serve as the beginning of a database to which new data can be added as emissions and against which control technologies can be compared.

Objectives:

Determine whether individual swine farms are likely to emit particulate matter (both total suspended particulate [TSP], particles smaller than 10 and 2.5 microns [PM10 & PM2.5]), and volatile organic compounds (VOC) in excess of applicable Clean Air Act (CAA) thresholds.

Determine whether individual swine farms are likely to emit ammonia (NH3) and hydrogen sulfide (H2S) in excess of applicable Comprehensive Environmental Response, Compensation and Liability Act (CERCLA) reporting requirements.

Vulnerability for Past Emissions

Odor complaints are driving air enforcement Emissions enforcement is new to agriculture Lawsuits often result in

heavy penalties expensive legal & consultant fees emissions monitoring control requirements management interruption – expensive even if you win

Here’s the rub: vulnerability for past violations

Real-Time Emission Data to be Collected by PELFCA

Ammonia – chemiluminescence NOx - chemiluminescence Hydrogen sulfide – Pulsed-Fluorescence Carbon dioxide – Photoacoustic Infrared FTIR for ammonia and some VOC UV for ammonia and hydrogen sulfide PM10 – (TEOM) PM2.5 – Partisol dichomotous sampler VOC: GC-MS (32 samples per site) TSP: integrated samples with Illinois method. Building airflow (fan status, pressure, vane anemometer,

FANS) Include ambient measurements of PM, gases

Operational Data to be Collected by PELFCA

Heating, flushing, feeder, and fan operation Temperature and humidity Building static pressure Animal activity Lighting Wind speed and direction Solar radiation Animal inventory and mass Manure production Manure removals Manure, feed and water analysis Milk production Egg production

P2

M: manifold

P: pumpS: solenoid

H2SF

CH4/NMHC

FTIR

P3

FNH3

Analyzers

6.4 mm OD3.2 mm ID vinyl

Cal gases

CO2

Zero air

NH3

H2S

NO

SO2

S12

S1

M2

9.5 mm OD,6.4 mm ID Teflon

6-port manifold

F: filter

C6H14/CH4

Cal gas circuit

Exhaust

Vinyl

M3

Flow restrictors

P1

M1

Bypass pumping system

Vinyl

9.5 mm OD, 6.4 mm ID Teflon

1

JarP4

Rotameter

Leak test circuit

1

P Pressure gage

Air valve

C

S13Calibration line

11-14-03

pFlow

dP (+/-)

Sampling probes,

10-115 mlong

6-port diluter

(5 L/min)

Bag fillport

p

Pressuresensor

M4Exhaust

A

Mass flow meter

fB

f

Mass flow meter

f

PCDAQ