Workshop Topics  Odour Emission Measurement  Swine Odour and Emissions  Poultry Odour and Emissions  Nationwide Emissions Project

Odor/Odorous Gases  Typical livestock odorants  Sulfides (H 2 S)  Volatile fatty acids (VFAs)  Mercaptans  Ammonia (NH 3 ) & amines  Alcohols  Aldehydes  Esters  Carbonyls Source: J. Sweeten, et al. 2/14/02

Tedlar bag Odor Sample Collection Overnight express to odor lab

Bag Sampling  New 10-L Tedlar bags  flushed with N 2  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

Odor Measurements  Field olfactometer  For evaluating ambient air  Determines odor concentrations with human nose  Six dilution ratios  Dynamic, forced-choice olfactometer  For evaluating source samples  Utilizes human olfactometric senses (4-8 people)  Odor threshold where 50% of panel is correct  Gas chromatography, mass spectrometry (GC-MS)  Separates gases  Measures presence and concentration  Hydrogen sulfide (popular surrogate gas for odor)  Sensor arrays (electronic nose)

Odor Emission Descriptors 1. Concentration = mass/vol.,  g/m 3  OU/m 3 2. Emission rate = concentration x airflow rate = mass/unit time (kg/day) = OU/sec 3. Flux = mass/unit time/unit area (kg/sec/m 2 ); OU/sec/m 2 Example (Smith & Watts, 1994 cited by Sweeten et al., 2002 Dry pad/manure surface: 5 OU/s-m 2 Wet pad/manure surface: 100 OU/s-m 2 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  ODC b = 1000 C b /ODT b  prEN standard (CEN, 2001)  Panelist performance criteria (n=10):  20 < mean ODC b < 80 ppb  Standard deviation of log ODC b < 2.3  Panel performance criteria (n=10):  31 < mean ODC b < 51 ppb  A <  R <  Purdue interim criteria for panelists (n=5)  10 < mean ODC b < 160 ppb  Needed only about two months

Results for 57.5 ppm n-butanol reference odor Assessor Step Log D A A B B C C D D E E Final Results: Response Key: D 1 = Incorrect GuessAvg. Log Value = Correct Guess 5 = Incorrect Detection Dilutions to threshold1,544 6 = Correct Detection 8 = Correct Recognition Odor detection concentration = 57,500 ppb / 1,544 = 37 ppb compared to CEN requirements of 20 to 80 ppb

Study Ratings (Watts,1999)  5: prEN olfactometry  4: NVN2820 olfactometry, report ODC b  3: Nonstandard olfactometry, no ODC b  2: Scentometer  1: Casual sniffing

Repeatability

Accuracy

Date Method changes 1 Oct 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 reinstatement qualifications 12 June 2000 Starting scale step determined with “whittling” procedure Uniform starting scale step where most sensitive panelist does GGDR

n-butanol vs. Hydrogen Sulfide

Conclusions  prEN for accuracy and repeatability with n-butanol have been achieved and maintained  Hydrogen sulfide correlated with n- butanol

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, ppmStrength 00No odor 1250Very faint 2750Faint 32,250Moderate 46,750Strong 520,250Very strong

Persistence of Odor Odor concentration, OU/m 3 Intensity (log scale) Full strength Odor detection concentration Detection Threshold Persistence = slope = A/B A B ,00010,000

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 3882 Determination 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 H c and H s 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  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 Descriptors

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 Character descriptors (sample)

Swine House Odors and Emissions

Nursery Odor VariableAverage Number of pigs164 Mean pig weight, lb30 Ventilation rate, cfm/AU495 Inside temperature, °F71 Outside temperature, °F53 Incoming ambient air Odor concentration, OU/m 3 18 Pit exhaust air Odor concentration, OU/m Intensity, ppm BIW813 Hedonic tone-5.9

Swine Lagoon Odor VariableMean Ammonia, mg/m³3.8 Hydrogen sulfide, µg/m³143 Sulfur dioxide, µg/m³39 Carbon dioxide, mg/m³875 Odor concentration, OU/m³67 Hedonic tone-1.7 Odor intensity, ppm BIW1404

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

Diurnal H 2 S Concentration Hour of day Pit concentration, ppb 3B, n = 24

Ambient Hydrogen Sulfide Near 12,000-Pig Nursery-Finishing Site 1st 2nd Bldg 1st Bldg 1st 2nd H2S odor threshold concentration = 1 ppb

Hydrogen Sulfide vs. Odor Swine Buildings H2S odor threshold concentration = 1 ppb

Hydrogen Sulfide vs. Odor (Swine Lagoon)

Ammonia Hydrogen Sulfide Peak of H 2 S when flushing with lagoon effluent!! 25-pig room, Purdue swine farm

Daily Mean Pit Exhaust Concentration ■=NH 3 ●=H 2 S

/273/133/274/104/245/85/226/5 Day of Test Ventilation Rate, m 3 s Inlet T Ventilation Rate Exhaust T Emission Rate Emission, OU E s AU Temperature, o C mc=36.4% pH=8.4 mc=26.0% pH=8.3 mc=25.0% pH=8.3 Mean = 50,400 OU E /s = 65.6 OU E /s-AU = 7.53 OU E /s-m 2

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  PM 10 – (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: pump S: solenoid H2SH2S F CH 4 /NMHC FTIR P3 F NH 3 Analyzers 6.4 mm OD 3.2 mm ID vinyl Cal gases CO 2 Zero air NH 3 H2SH2S NO SO 2 S12 S1 M2 9.5 mm OD, 6.4 mm ID Teflon 6-port manifold F: filter C 6 H 14 /CH 4 Cal gas circuit Exhaust Vinyl M3 Flow restrictors P1 M1 Bypass pumping system Vinyl 9.5 mm OD, 6.4 mm ID Teflon 1 Jar P4 Rotameter Leak test circuit 1 P Pressure gage Air valve C S13 Calibration line p Flow dP (+/-) Sampling probes, m long 6-port diluter (5 L/min) Bag fill port p Pressure sensor M4 Exhaust A Mass flow meter f B f Mass flow meter f PC DAQ