1. The Safe Use of Peracetic Acid in the Proteins Industry
2/1/2017
Richard Warburton, Ph.D. and Lisa McCombie, MBA

2. Objectives to educate listeners on:
Advantages and uses of PAA
Best practices and recommendations on how to use PAA safely
Current and proposed exposure limits for PAA and health risks

3. PAA ADVANTAGES AND USES

4. The use of PAA spans many industries due to it’s effectiveness
Industries include: Meat and poultry production, aseptic packaging, fruits and vegetables, healthcare, water treatment, and cooling water
Use of PAA as an antimicrobial/biocide in the proteins market has surged
Advantages over competing chemistries include
Better antimicrobial properties
No harmful residues
Leaving no harmful residue allows direct application to the meat
This enables export of product to countries such as China, the EU and Russia (at least before Crimea was annexed.)

5. PAA forms an equilibrium mixture with Hydrogen Peroxide and Acetic Acid
PAA also known as peroxyacetic (CH3C(O)OOH), is an organic peroxyacid that forms an equilibrium mixture with hydrogen peroxide and acetic acid.
PAA is a strong oxidant and is very reactive, making it a great biocide
It also breakdowns quickly after contact with meats or the environment – not as fast in the air
It forms oxygen, water, and a very dilute acetic acid (the acid in vinegar)
This makes this compound very appealing to the USDA and EPA

6. Microbiocidal Activity
PAA will inactivate gram-positive and gram-negative bacteria, fungi, and yeasts in <5 minutes at <100 ppm. In the presence of organic matter, ppm is required.
Bacterial spores in suspension are inactivated in 15 seconds to 30 minutes with 500 to 10,000 ppm (0.05 to 1%).
Bacteria
Viruses
For viruses, the dosage range is wide ( ppm), with poliovirus inactivated in yeast extract in 15 minutes with 1500 to 2250 ppm.
Bacterial spores

7. EXPOSURE LIMITS AND HEALTH RISKS

8. What are the exposure limits pertaining to PAA?
AEGL’s – Acute Exposure Guidelines (US-EPA) for emergency responders
ACGIH STEL-TLV ppm (15 min TWA)
NIOSH IDLH- proposed 0.55 ppm (under review)
OSHA can use any and all of the above to cite employers under the General Duty Clause (Sec. 5 of the 1970 Occupational Health and Safety Act).

9. PAA health hazards PAA can affect you when inhaled
PAA is a HIGHLY CORROSIVE CHEMICAL and contact can severely irritate and burn the skin and eyes leading to eye damage.
Breathing PAA can irritate the nose and throat.
Breathing PAA can irritate the lungs causing coughing and/or shortness of breath.
Higher exposures can cause a build-up of fluid in the lungs (pulmonary edema), a medical emergency, with severe shortness of breath.
High or repeated exposure may affect the liver and kidneys
Source: ChemDAQ PAA Fact Sheet

10. CHEMICAL EXPOSURE

11. What causes chemical exposure in meat and poultry plants?
Chemical dosing errors
Air handling:
Unbalanced air pressure
Inadequate ventilation & extraction
Chemical storage leaks
Normal wear and tear
Equipment malfunction
Chemical pumps/ Supply line leaks
Human Error
there are a number of things that can cause chemical exposure.

12. Exposure examples
Plants using PAA sprayers tend to have higher vapor concentrations for example it is not uncommon to measure about 1 ppm near a beef carcass sprayer.
Often higher concentrations of PAA vapor are found near PAA mixing stations and so these should be outside or very well ventilated.
PAA vapor released from tote could have concentrations well above dangerous levels
Underneath conveyers tend to have higher vapor concentrations of PAA

13. Odor threshold for PAA THE PROBLEM Odor threshold for PAA is ~50 ppb
Can be smelt at concentrations well below hazardous (0.4ppm STEL)
From a safety perspective, PAA has the advantage over chemicals such as hydrogen peroxide which are almost odorless
If there are high concentrations of PAA people are usually aware
People’s noses cannot detect whether the exposure is above or below the STEL TLV.
Olfactory fatigue can occur
How do you know you’re safe?
Best method to ensure safety is to use a continuous area monitor for PAA combined with a portable monitor for daily analysis.
THE PROBLEM

14. What are the Business Risks
Lost production
Stop processing line - leaks that remain undetected until workers affected – too late
Reduced productivity
Worker distraction/complaints that aren't addressed
Productivity loss due to symptoms/Illness
Lost revenue due to reduced capacity
Damage to your brand
Regulatory citations AND monetary fines
Some of the business risks associated with chemical exposure are:
Lost Production – This can happen when leaks that remain undetected until workers are overcome and the processing line has to shut down.
Reduced Productivity – Workers distracted when concerned for their safety. Managers or supervisors are burdened by complaints that they may not be able to address.
Lost Revenues due to reduced capacity
Regulatory citations and monetary fines

15. BEST PRACTICES

16. Peracetic Acid Vapor Monitoring Recommendations
It is highly recommended to use a combination of continuous fixed area monitoring and periodic spot checking throughout any facility that uses PAA
Continuous fixed area monitoring is recommended in the following areas
Near concentrated PAA totes/tanks, dilution lines, and pump stations
Any area where employees have experienced symptoms or known risks are present for exposure
Portable monitoring is recommended as a daily routine combined with any additional spot checks needed throughout the day
PAA sprayers and dip tanks may put off different levels of vapors each day
It is important to incorporate vapor monitoring into your QC and safety program
Can be used to assess real-time personal exposure
Facilities can use these monitors to improve work practices, optimize engineering controls, and/or add PPE as needed to ensure the safe use of PAA

17. PAA Historical Measurement Challenges
Historically, sensors that measure PAA were unavailable, so people measured Hydrogen Peroxide and Acetic Acid since they have OSHA PELs (Gas detection tubes, H2O2 sensors, impingers)
If these levels read OK, then they assumed that PAA levels were OK as well
This is a problem – PAA is the most hazardous component and needs to be measured specifically
Other methods are extremely cumbersome and do not provide real-time results
ChemDAQ’s PAA sensor does not respond to Acetic Acid and employs patent pending filter technology that prevents interference from Hydrogen Peroxide.
This sensor has been independently validated by many of our customers
Validation by the University of Florence has been submitted for publication in an international peer reviewed Occupational Safety and Health journal
Enviro Tech has also independently validated and has posted their validation on their website

18. PPE Recommendations when handling PAA
At a minimum, chemical-resistant gloves (Neoprene) and splash-proof eye protection should be worn.
Adding a face shield is appropriate if working with larger quantities. 
Concentrated PAA should only be handled in a well-ventilated area.
Prolonged exposure, or exposure above OELs may require the use of a suitable respirator.
Can use the ChemDAQ monitor to determine what PPE is appropriate
If a respirator is used, it should be full face to protect eyes
Filter cartridges validated for PAA are available
Source:

19. Storage considerations
PAA decomposes slowly during storage, giving off oxygen, and should be stored in appropriately vented containers. 
Use in well ventilated area, or preferably outside
It is also important to use appropriate materials when sourcing dosing or transferring equipment for concentrated PAA. 
Glass, polyethylene (HDPE/LLDPE) and Teflon (PTFE) are all suitable for handling concentrated solutions.
Stainless steel and other polymers should only be used where exposure is short term. 
Once diluted to the “at use” concentration (usually 100 ppm – 200ppm), most materials except Tygon and rubber are suitable.
See SDS for specific info for PAA blend used
Source:

20. PAA spill recommendations
In ALL hazardous material spills, the primary concern is the protection of personnel. The secondary concern is to confine the contamination, but ONLY if you are specifically trained under 29 CFR to do so.
Your facility should have its own specific cleanup procedure and all personnel handling such material, should have received instruction on that procedure.
Appropriate PPE should be worn
You can use the ChemDAQ portable monitor to assess the risk
Small Spill:
Dilute with water and mop up, or absorb with an inert dry material
Place in an appropriate waste disposal container.
If necessary: Neutralize the residue with a dilute solution of sodium
carbonate or other appropriate neutralizer.
Source:

21. PAA spill recommendations con’t
Large Spill:
PAA is a flammable liquid, oxidizing material and organic peroxide.
Most PAA solutions used in poultry/meat processing are <15% and are not flammable
Keep away from heat and sources of ignition.
Stop leak ONLY if without risk.
Absorb with DRY earth, sand or other non-combustible material.
Avoid contact with a combustible material (wood, paper, oil, clothing...). Keep substance damp using water spray.
Do not use metal tools or equipment. Do not touch spilled material. Use water spray to reduce vapors.
Prevent entry into sewers, basements or confined areas; dike if needed.
Call for assistance on disposal.
Neutralize the residue with a dilute solution of sodium carbonate.
Be careful that the product is not present at a concentration level above TLV
It is recommended to design an area where totes are used/stored to control a spill
Source:

22. Common chemicals used in meat and poultry processing
Peracetic Acid (PAA)
Chlorine
Chlorine Dioxide
Ozone
Positives
 Highly effective as a biocide, high reactivity causes quick degradation to harmless byproducts, leaving behind no residue
Effective against a wide range of bacteria
More effective than Chlorine, leaves behind little to no residue
Very effective, leaves behind little to no residue
Negatives
Health effects
Health effects, leaves behind harmful residue, banned in some areas of the world
Health effects, must generate onsite
Exposure Limits
ACGIH STEL-TLV 0.4ppm
NIOSH IDLH 0.55ppm (proposed)
ACGIH TLV 0.5ppm
OSHA PEL 1ppm
NIOSH IDLH 10ppm
ACGIH TWA 0.1ppm
OSHA PEL 0.1ppm NIOSH IDLH 5ppm
ACGIH TLV ppm
It is important to note that all these chemicals are used to kill microorganisms, and all can cause health effects. We must focus on improving the safe use of effective biocides.

23. Team up with ChemDAQ and other safety conscious companies for a voice in the industry!
Aseptic and Antimicrobial Processing and Packaging Association (AAPPA)
AAPPA was created to fill a need in the food & beverage industry to develop standards and best practices for the safe handling and use of aseptic and intervention chemicals. The organization also responds to proposed regulatory changes that may negatively affect the industry and advocates for sound science in the development of such regulations.

24. Thank you for your attention!
Please stop by our booth #1214 for more information regarding Peracetic Acid, monitoring solutions, and AAPPA.