Fate and Effect of Quaternary Ammonium Compounds and

1

Fate and Effect of Quaternary Ammonium Compounds and Peracetic Acid Solutions on Protein Industry Wastewater

Biological Treatment Processes

Spyros G. Pavlostathis, PhD, BCEEMSchool of Civil and Environmental Engineering

Georgia Institute of TechnologyAtlanta, GA 30332, USA

[email protected]

Environmental Conference for the Meat and Poultry IndustryInternational Production & Processing Expo

Georgia World Congress CenterAtlanta, GA

February 11, 2019

2

DisinfectantsDistribution of Disinfectants in US EPA-Registered Formulations

Household Use Industrial & Institutional Use

Fu et al., Handbook for Cleaning/Decontamination of Surfaces (2007)

3

Quaternary Ammonium Compounds (QACs)Outline

Quaternary Ammonium Compounds (QACs)Outline

Quaternary Ammonium Compounds (QACs) Structures, properties, toxicity Biodegradability/toxicity

Aerobic/nitrifying conditions Nitrate-reducing conditions Fermentative/methanogenic conditions Biological nitrogen removal (BNR) system

4

Quaternary Ammonium Compounds – Structures

N+Cl-

N+Cl-

N+Cl-

N+Cl-

N+Cl-

N+Cl-

Monoalkonium Chlorides Dialkonium Chlorides

Benzalkonium Chlorides

C12

C14

C16

Dioctyldimethyl ammonium chloride (DC8DMA-Cl)

Octyldecyldimethyl ammonium chloride (DC8-10DMA-Cl)

Didecyldimethyl ammonium chloride (DC10DMA-Cl)

C8 C

8

C8

C10

C10 C10

Dodecylbenzyldimethyl ammonium chloride (C12BDMA-Cl)

Tetradecylbenzyldimethyl ammonium chloride (C14BDMA-Cl)

Hexadecylbenzyldimethyl ammonium chloride (C16BDMA-Cl)

N+C12H25Cl-

N+C14H29

Cl-

N+C16H33Cl-

Dodecyltrimethyl ammonium chloride (C12TMA-Cl)

Tetradecyltrimethyl ammonium chloride (C14TMA-Cl)

Hexadecyltrimethyl ammonium chloride (C16TMA-Cl)

5

EC50 (mg/L)

0.0 0.4 0.8 1.2 1.6

DODAC

BAC

ODDAC

DDAC

HDTAC N+Cl-

N+Cl-

N+Cl-

N+

RCl-

N+Cl-

5-minute Acute Toxicity

Hexadecyltrimethyl ammonium chloride

Didecyldimethyl ammonium chloride

Octyldecyldimethyl ammonium chloride

Benzalkonium chloride

Dioctyldimethyl ammonium chloride

15-minute Acute Toxicity

EC50 (mg/L)

0.0 0.4 0.8 1.2 1.6

DODAC

BAC

ODDAC

DDAC

HDTAC

QAC toxicity increases with increased exposure time

Toxicity increases with increased CMC valueCMC: Critical Micelle Concentration

CMC (mM)0.1 1 10 100

EC50

( M

)

0.01

0.1

1

10

QACs – Toxicity (Microtox® Test)

Tezel, PhD Thesis 2009

6

QACs – Biodegradation under Aerobic Conditions Biotransformation Pathway of Benzalkonium Chloride (BAC)

Tezel et al., Environ. Sci. Technol., 2012

TOXICITY

EC50

- 15

min

(M

)

0

100

200

300

400

C14BAC0.72 μM

BDMA BMABA

350-fold less toxic

N+

C14H29

H+N

C14H27O2

NH2+

O O-

NH4+CO2+

CO2

CO2

-oxidation

-oxidation

Benzoyl CoAand

pathways

Tetradecylbenzyldimethyl ammonium

Tetradecanoate

Benzyldimethyl amine

Dimethyl amine

Benzoate

Dealkylation

Debenzylation

BDMA

+H2N+H3N

Benzylmethyl amineBMA

Benzyl amineBA

7

QACs – Biodegradation under Aerobic Conditions BAC to Biomass (VSS) Ratio

Zhang et al., Water Res., 2011

ParametersCeq Equilibrium liquid-phase BAC

concentration (mg/L)kI2 Observed solid-phase BAC utilization

rate constant (mg BAC/mg VSS-h)KI Observed inhibition coefficient (mg

BAC/L)

5 mg BAC/L

10 mg BAC/L

20 mg BAC/L

Benzalkonium Chloride (BAC): 5, 10, 20 mg/LBiomass: 500 mg VSS/L

8

Effect of QAC on NitrificationBenzalkonium chloride (BAC) mixture 2 mg/L 5 mg/L

10 mg/L 15 mg/L

20 mg/L

AB CONCENTRATION (mg /L)

0 2 4 6 8 10

1/v

0.0

0.4

0.8

1.2

1.6

2.0

2.4 - Sorptive affinity of BAC for the cell membrane significantly affects membrane-bound enzymes involved in nitrification

- Inhibition coefficient Ki estimated graphically assuming non-competitive inhibition at relatively high NH4

+

concentration

Ki = 1.5 ± 0.9 mg/L BAC (R2 = 0.985)

imaxmax KVI

Vv

11

Yang et al., Biores. Technol., 2015

BAC (mg/L)

9

Effect of QAC & Temperature on NitrificationBAC-free

5 mg BAC/L

Temperature transition: 10 to 19oC(5 mg BAC/L)Temperature

(oC)

Relative Specific Ammonia Removal Rate

BAC-free reactors

BAC-amendedreactorsa

24 1.00 0.2919 0.55 0.29

15 0.30 0.19

10 0.09 0.08a 5 mg/L

Yang et al., Biores. Technol., 2015

10

QACs – Fate & Effect under Nitrate-Reducing Conditions Batch Serum Bottle Assay

Culture: Mixed methanogenic cultureElectron Donor: Glucose (750 mg COD/L)Electron Acceptor: Nitrate (70 mg N/L)QAC: 0-100 mg/L (Benzalkonium chloride; BAC)

N+

RCl-

Benzalkonium chloridePredominantly C14 BDMA-Cl

DENITRIFICATION

Q cyt cd

NO3-

NO2-

NO

N2O

N2

NARNIR

NOR

NOS

Fp Fe-S cyt b cyt bc1

Denitrification is partially inhibited, i.e. at the level of N2O

to N2 transformation at andabove 50 mg BAC/L

Q cyt cdFp cyt b cyt bc1

NIR

NO3-

NO2-

NH2OHNH3

DNRA

NARHAR

Fe-S

Dissimilatory nitrate reduction to ammonia (DNRA) is inhibited at

and above 50 mg BAC/L

Periplasmic enzyme

BAC CONCENTRATION (mg l-1)

0 10 25 50 75 100PRO

CES

SED

NIT

RO

GEN

(m

mol

l-1 )

0

2

4

6NH3N2

N2OExpected Total N

Nitrogen Balance

Tezel & Pavlostathis, Environ. Sci. Technol., 2009

11

Batch Serum Bottle AssayCulture: Mixed methanogenic cultureElectron Donor: Dextrin/Peptone mixture

(1200 mg COD/L)QACs: 0-100 mg/L

N+Cl-

Didecyl

N+Cl-

Octyl Decyl

N+

RCl-

Alkyl BenzylDioctyl

N+Cl-

ComplexOrganics Fatty Acids

Acetate

H2

CH4

Fermentation Methanogenesis

QACs – Fate & Effect under Fermentative/Methanogenic Conditions

EXPECTED CONC. (mg/L)0 20 40 60 80 100 120

MEA

SUR

ED C

ON

C. (

mg/

L)

0

20

40

60

80

100

120

Alkyl BenzylDidecylDioctylOctyl Decyl

VQ100% Recovery

No Biotransformation

Hollow: Total QAC conc.Filled: Aqueous phase QAC conc.

CO

D P

RO

CES

SED

(%)

0

20

40

60

80

100

QAC CONC. (mg/L)0 20 40 60 80 100

0

20

40

60

80

100

0 20 40 60 80 100

(A) (B)

(C) (D)

as CH4as VFAsTotal

(A) Alkyl Benzyl (B) Didecyl (C) Dioctyl (D) Octyl Decyl

QACs are more inhibitory to methanogenesis than fermentation

QACs XTezel et al., Water Res., 2006

12

1 2 3

Biological Nitrogen Removal (BNR) System

1) Ammonia release (R1)

2) Nitrification (R3)

3) Denitrification (R2)

32422 NONONH OO

2223 NONNONONO CarbonCarbonCarbonCarbon

4NHNOrganic Hydrolysis

R1 R2R3

Settler

13


• BAC was degraded in R3 (aerobic conditions)• Initial exposure to BAC negatively affected the system nitrogen

removal efficiency• Nitrification inhibition• Ammonia oxidizers recovered first, followed by nitrite oxidizers• Nitrate reduction in the anoxic reactor was not affected • Full recovery in 27 days

TIME (Days)30 35 40 45 50 55 60 65 70

BA

C (m

g/L)

0

1

2

3

4

5

6

7

Feed R1 R2 R3

Effluent

NIT

RO

GEN

(mgN

/L)

0

20

40

60

80

100

12345678910

NIT

RO

GEN

(mgN

/L)

0

20

40

60

80

100

12345678910

TIME (Days)

30 32 34 36 38 40 42 44 46 48 50 52 54 56 58 60 62 64 66 68 70 72

NIT

RO

GEN

(mgN

/L)

0

20

40

60

80

100

12345678910

NO2- NO3

- pHNH3Anoxic

Aerobic

Effluent

pH

BAC–bearing Poultry Wastewater (5 mg/L since day 30)

Hajaya & Pavlostathis, Biores. Technol., 2012

14


TIME (Days)

70 105 140 175 210 245 280 315 350 385

BAC

(mg/

L)

0

10

20

30

40

50

60

Feed R1 R2 R3

Effluent

525 532 539 546 553 560 5670

20

40

60

80

100

120

140

BAC–bearing Poultry Wastewater (10 - 120 mg/L; 530 days)

TIME (Days)

70 105 140 175 210 245 280 315 350 385 420 455 490 525 560

NIT

RO

GEN

(mgN

/L)

0

20

40

60

80

100

pH

1

2

3

4

5

6

7

8

9Effluent NO2- NO3

- pHNH3

The system was acclimated to BAC-bearing poultry wastewater at gradually increasing BAC levels

The acclimated system• Withstood high BAC spikes,

completely removing BAC• Sustained its original, pre-BAC

exposure, high nitrogen removal efficiency

• Nitrifying bacteria became gradually resistant to BAC

Hajaya & Pavlostathis, Biores. Technol., 2012

15

Biological Nitrogen Removal (BNR) SystemDenitrification During BAC Exposure (Day 400)

BAC was not transformed under denitrifying conditions

Hajaya, PhD Thesis, 2011

C

NIT

RO

GEN

(mg

N)

0

2

4

6

0

2

4

6 BAC-free

D

E F

TIME (Days)

NO2-

NO3-

N2

10 mg BAC/L 15 mg BAC/L

0

2

4

6 20 mg BAC/L 25 mg BAC/L

TIME (Days)0.0 0.4 0.8 1.2 1.6 2.0

0

2

4

6 30 mg BAC/L

0.0 0.4 0.8 1.2 1.6 2.00

2

4

6 45 mg BAC/L

5 mg BAC/L

INITIAL 0 5 10 15 20 25 30 45

NIT

RO

GEN

(mg

N)

0

4

8

12

16 NH4+

N2 NO3

-

A

B

BAC INTIAL CONCENTRATION (mg/L)0 5 10 15 20 25 30 45

RSN

RR

(%)

0

20

40

60

80

100

EXPECTED BAC (mg/L)

0 5 10 15 20 25 30 35 40 45 50

MEA

SUR

ED B

AC

(mg/

L)

05

101520253035404550

Liquid Phase100% Recovery

Total

16

Quaternary Ammonium Compounds (QACs) – Summary Susceptibility of BNR microbial processes to BAC differ:

nitrification > denitrification > organics utilization > fermentation QAC levels in aerobic/activated sludge systems above a specific threshold value (15 mg/L

in our BNR study) result in nitrification inhibition leading to low ammonia removal rate and incomplete nitrification (i.e., accumulation of nitrite)

QACs biotransformation takes place under aerobic conditions (also under specific nitrate reduction conditions)

QACs are recalcitrant under fermentative/anaerobic conditions Continuous treatment of QAC-bearing wastewater in a BNR system resulted in the

development of QAC biodegradation capacity by the heterotrophs and QAC resistance by the nitrifiers

Overall, the rational design and operation of BNR systems supports the continuous use of QACs as antimicrobial agents in food processing facilities, while avoiding any negative impacts on biological treatment systems

17

Peracetic Acid (PAA) – OutlinePeracetic Acid (PAA) – Outline Peracetic Acid (PAA)

Structure, properties, reactions PAA in poultry processing/waste streams PAA decomposition PAA Bioassays

18

Peracetic Acid (a.k.a. Peroxyacetic Acid; PAA) PAA Structure

CH3COOOH

PAA PropertiesProperty ValueCAS 79-21-0Molecular Weight 76.051 g/molViscosity 3.28 cP at 25oCpKa 8.2Boiling Point 110oC at 1 atmMelting Point -0.2oC at 1 atmWater Solubility 1000 g/L at 25oCDensity 1.226 g/cm3 at 15oCVapor Pressure 2.6 kPa at 20oClog Kow -1.07Henry's Constant 660 mol/kg-barEnthalpy of Vaporization 44.2 kJ/mol at 15oCEnthalpy of Dissociation 428.0 kJ/mol at 25oC

19

PAA Reactions & Products

PAA in aqueous solution at a pH range of 5.5 to 9 may be degraded according to the following three reactions (Yuan et al., 1997):1. Spontaneous decomposition to form acetic acid and oxygen (pH < 8.2):

2 CH3COOOH → 2 CH3COOH + O2

2. Hydrolysis to form acetic acid and hydrogen peroxide (pH 8.2 – 9.0):CH3COOOH + H2O → CH3COOH + H2O2

3. Transition metal catalyzed decomposition:CH3COOOH + M → O2 + decomposition products

20

Commercial PAA Solutions Composition

Commercially available PAA solutions are quaternary equilibrium mixtures of acetic acid (CH3COOH), hydrogen peroxide (H2O2), peracetic acid (CH3COOOH), and water:

CH3COOH + H2O2 ↔ CH3COOOH + H2OTypical concentrations (%, w/w):PAA 20-23 14.7-15.7Acetic acid 33-39 40-50H2O2 8.5-10.5 5-6

Stabilizers/ChelatorsStabilize PAA during storage, preventing the reaction of PAA and H2O2 with free metal ions in Fenton-type reactionsCommon stabilizer:1-hydroxyethylidene-1,1-diphosphonic acid (HEDP; etidronic acid)Concentration specified by FDA in Food Contact Substance Notifications (FCN)Example FCN 001419 for PAA use in poultry processing (max. dose, ppm):

2,000 ppm as PAA, 770 ppm as H2O2, 100 ppm as HEDP

HEDP

21

PAA Use in Poultry Processing

PAA UsesScalderChillersDip tanksBelt washersSprays, etc.

22

PAA in Poultry Processing

Concerns relative to PAA in biological treatment processes PAA solutions are acidic (acetic acid); potential for lower influent pH depends on

the alkalinity of the wastewater and/or biological mixed liquor Increased influent soluble COD due to PAA and acetic acid, leaching of meat

components (e.g., protein, fat) Impact on the treatment efficiency of biological treatment processes such as:

COD removal Nitrification (i.e., NH4

+ NO2- NO3

-) Denitrification (i.e., NO3

- NO2- NO N2O N2)

Phosphorus removal Anaerobic degradation (e.g., anaerobic lagoons)

Whole Effluent Toxicity (WET) test failure

23

PAA in Poultry Processing

Industry “perceived causes” relative to the effect of PAA on biological treatment processes Potential adverse effect of PAA and/or its transformation products reacting with

wastewater organic components and/or biomass Deficiency of (micro)nutrients (e.g., Fe, Cu, Mg, other transition metals)

attributed to the sequestering effect of stabilizers and chelating agents (e.g., HEDP) Nutrient deficiency could be a significant problem for poultry processing

plants which use low hardness water (e.g., surface water) as process water PAA and/or H2O2 reaction with chloraminated process water

24

PAA in Poultry Processing Typical chiller operation

Final MainChiller Pre Birds + NaOHWater

PAA Solution

Typical PAA: 600-1000 40-60 40-60(ppm)

80-250

pH

02468

1012

TIME (hour)0 1 2 3 4 5 6

PAA

(mg/

L)

0

200

400

600

800

1000

Pre-chillerMain chiller Final chiller

Main chillerPre-chiller

25

Characteristics of Poultry Wastewater

Pre-Chille

r (C1)

Main Chille

r (C2)

Finishing Chille

r (C3)

Chiller O

verflo

w (WW1)

DAF Influ

ent (W

W1)DAF Efflu

ent (W

W3)

CO

NC

ENTR

ATIO

N (m

g/L)

500

1000

1500

2000

2500

3000

3500

4000

4500

5000

Total COD Crude Protein Lipids Carbohydrates

26

PAA in Poultry Waste Streams Plant PAA concentration and pH over

timeStart of empting chillers at 16:30 pH

4.04.55.05.56.06.5

PAA

(mg/

L)

05

1015202530

TIME

12:00:00 13:00:00 14:00:00 15:00:00 16:00:00 17:00:00 18:00:00

PAA

(mg/

L)

05

1015202530

DAF Influent/Effluent

DAF Effluent

DAF Influent

pH

345678

TIME

12:00:00 13:00:00 14:00:00 15:00:00 16:00:00 17:00:00 18:00:00

PAA

(mg/

L)

075

150225300375

Chiller Floor Drain

27

PAA Decomposition Fast PAA transformation

at pH = 11 (Irreversible) Effect of pH (DI water)

pH

0

2

4

6

8

10

TIME (hour)

0 24 48 72 96 120 144 168 192

PAA

(mg/

L)

0

2

4

6

8

PAA SpeciationCH3COOOH vs. CH3COOO-pKa = 8.2 (I = 0 M, 25oC)

pH0

2

4

6

8

10

12

14

TIME (hour)

0.0 0.5 1.0 1.5 2.0 2.5

PAA

(mg/

L)

0

2

4

6

8

10

H2SO4

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

5 6 7 8 9 10 11

Frac

tion

pH

28

PAA Decomposition DAF Effluent

Effluent total COD: 650 mg/L Effluent pH: 5.7 pH upon PAA addition: 4.7 Final pH: 4.5 to 4.6 Initial PAA: 100 mg/L

TIME (Hours)

0 2 4 6 8 10

PAA

(mg/

L)

0

20

40

60

80

1004oC 10oC

15oC 22oC 30oC

Temp. (oC) 4 10 15 22 30

Rate (k, h-1) 0.54 0.66 0.73 0.89 1.28

t0.5 (Hours) 1.28 1.05 0.95 0.78 0.54

1/T (K-1)

0.0032 0.0033 0.0034 0.0035 0.0036 0.0037

ln k

-0.8

-0.6

-0.4

-0.2

0.0

0.2

0.4ln k = 9.32 - 2,772(1/T)R2 = 0.972

Activation energy = 23 kJ/mol Q10 = 1.4

29

PAA Decomposition Uncontrolled vs. Controlled pH DAF Effluent

Effluent total COD: 650 mg/L Effluent pH: 5.7 Initial PAA: 800 mg/L

PAA

(mg/

L)0

100200300400500600700800900

pH 4/3.4pH 4 constant

TIME (Hours)

0 1 2 3 4 5 6

PAA

(mg/

L)

0100200300400500600700800900


PAA

(mg/

L)

0100200300400500600700800900


TIME (Hours)

0 1 2 3 4 5 6

PAA

(mg/

L)

0100200300400500600700800900


30

PAA Decomposition – Possible Products

PAA1 PAA2 A1 A2 B1 B2 C1 C2

CO

NC

ENTR

ATIO

N (m

M)

0

1

2

3

4

5

6

7

8

PAA AcH

Possible PAA Reactions1) Spontaneous decomposition (pH < 8.2)

2 CH3COOOH → 2 CH3COOH + O22) Hydrolysis (pH 8.2 – 9.0)

CH3COOOH + H2O → CH3COOH + H2O23) Transition metal catalyzed decomposition

CH3COOOH + M → O2 + decomp. products

Acetate production DAF Effluent (pH = 6.0) PAA stock solution: PAA/Acetate 160/310 mg/L Solutions (PAA/Acetate, mM):

A: 0.53/1.28; B: 1.05/2.56; C: 2.10/5.12(1) Initial; (2) Final (PAA completely decomposed)

PAA to acetate conversion: 101.3±1.0%

31

PAA Bioassays – Stock Culture Mixed aerobic/facultative culture

SRT = 21 days; HRT = 2.3 days Feed: DAF effluent; 850 – 1,000 mg/L total COD Alkalinity: 4.2 g NaHCO3/Lfeed TSS: 0.8 – 1.0 g/L VSS: 0.7 – 0.9 g/L pH: 6.0 – 8.0 Effluent soluble COD: 60 – 100 mg/L

SOLU

BLE

CO

D (m

g/L)

0

100

200

300

400

500

600

700

TIME (Days)0 1 2 3 4 5 6 7 8

NIT

RO

GEN

(mg/

L)0

25

50

75

100

125

150

175

200

Aerobic Anoxic Aerobic

NH4+-N

NO2--N

NO3--N

32

Bioassay 1 – Effect of PAA on Nitrification Mixed aerobic culture: COD removal/Nitrification (22oC)

Five series (control, 5, 10, 20, 40 mg PAA/L; direct addition) TSS/VSS: 2.11/1.64 g/L; glucose: 100 mg COD/L 4.2 g NaHCO3/L; 100 mg NH4

+-N/L; Initial pH: 7.0 – 8.8

TIME (Days)

0 1 2 3 4 5 6 7

DO

(mg/

L)

0

2

4

6

8

10

12

14

16

18

TIME (Days)

0 1 2 3 4 5 6 7

SOLU

BLE

CO

D (m

g/L)

0

200

400

600

800

1000

1200

0 (Control)510

2040

Initial PAA (mg/L):

33

Bioassay 1 – Effect of PAA on Nitrification Mixed aerobic culture: Nitrification Ammonia removal rates (ARR)

PAA (mg/L)ARR

(mg NH4+-N/L-h)

NormalizedARR

0 (Control) 7.2 1.00

5 7.2 1.00

10 6.6 0.92

20 4.7 0.6540 1.6 0.22

PAA (mg/L)0 10 20 30 40 50

NO

RM

ALIZ

ED A

RR

0.0

0.2

0.4

0.6

0.8

1.0

IC50 = 27 mg PAA/L

NH

4+ -N (m

g/L)

0

20

40

60

80

100

120

TIME (Days)0 1 2 3 4 5 6 7

NO

2- -N (m

g/L)

0

10

20

30

40

50N

O3- -N

(mg/

L)0

50

100

150

200

TIME (Days)0 1 2 3 4 5 6 7

TOTA

L IN

OR

GAN

IC N

(mg/

L)

0

50

100

150

200

0 (Control) 5 10 20 40Initial PAA (mg/L):

34

Bioassay 2 – Direct vs. Indirect PAA Addition Mixed aerobic/facultative culture (22oC)

Three series: control, 20 mg PAA/L direct/indirect addition Nitrification (7 d), Denitrification (1.4 d), Nitrification (8 d) TSS/VSS: 1.88/1.56 g/L; DAF effluent: 790 mg COD/L 4.2 g NaHCO3/L; initial ammonia: 45 mg N/L (from feed) Initial pH: 7.7 – 8.0

PAA in poultry mixed culture & feed Feed: 990 mg COD/L; pH = 5.9 Mixed Liquor: 1.88 g TSS/L; 1.56 g VSS/L; pH = 8.5 Supernatant: 50 mg COD/L; pH = 5.4

TIME (Min)

0 10 20 30 40 50 60 70 80 90

PAA

(mg/

L)

0

5

10

15

20

25

30

Feed PAA Mixed Liquor PAA Supernatant PAA

DO & COD removal

DO

(mg/

L)

0

2

4

6

8

10

12

14

TIME (Days)0 2 4 6 8 10 12 14 16 18

sCO

D (m

g/L)

0

200

400

600

800

1000

1200

Aerobic Anoxic Aerobic

0 (Control)20 (Direct)20 (Indirect)

PAA (mg/L):

35

Bioassay 2 – Direct vs. Indirect PAA Addition Mixed aerobic/facultative culture

Nitrification Denitrification Nitrification

NH

4+ -N (m

g/L)

0

10

20

30

40

50

60

70

80

TIME (Days)0 2 4 6 8 10 12 14 16 18

NO

2- -N (m

g/L)

0

10

20

30

40

50

60

70

80TIME (Days)

0 2 4 6 8 10 12 14 16 18

NO

3- -N (m

g/L)

0

20

40

60

80

100

120

140

0 (Control)20 (Direct)20 (Indirect)

PAA (mg/L):

Aerobic Anoxic Aerobic Aerobic Anoxic Aerobic

36

Peracetic Acid (PAA) – Summary PAA in poultry chiller drain wastewater may be in excess of 250 ppm High PAA demand of poultry processing wastewater; fast decay (t0.5 < 2 h) Pre DAF wastewater PAA levels are expected to be below 100 ppm as a result of

Dilution of chiller drain wastewater with other plant wastewater streams High PAA decay in the wastewater stream

Low residual PAA removal by the DAF process (<20%) PAA carryover to biological treatment systems is possible

At the end of the plant processing shift/sanitation cycle In case of accidental spills (?)

PAA decay is significantly affected by pH, especially above pH 6 Temperature (Q10 = 1.4)

Complete transformation of 150 mg PAA/L to acetate in DAF effluent at pH 5 to 6; transient PAA transformation products and their possible effect are unknown

Effect of PAA on biological treatment processes Negligible effect on soluble COD removal Excessive cell lysis at 40 mg/L PAA (loss of biomass; increased oxygen demand) Nitrification inhibition at 20 mg PAA/L and higher (IC50 = 27 mg PAA/L); nitrite

accumulation and slow conversion to nitrate

37

Acknowledgments Quaternary Ammonium Compounds Funding

State of Georgia/FoodPAC US Poultry & Egg Association

People Dr. Ulas Tezel (PhD student) - Bogazici University, Turkey Dr. Malek Hajaya (PhD student) - Dr. Zainab Ismail (Visiting Scholar) - University of Baghdad, Iraq Dr. Kexun Li (Visiting Scholar) – Nankai University, China Mr. Jeongwoo Yang (MS Student) – Import/Export Bank, S. Korea

Peracetic Acid Funding

US Poultry & Egg Association People

Jinchen Chen (PhD Student)

38

Fate and Effect of Quaternary Ammonium Compounds and Peracetic Acid Solutions on Protein Industry Wastewater

Biological Treatment Processes

Spyros G. Pavlostathis, PhD, BCEEMSchool of Civil and Environmental Engineering

Georgia Institute of TechnologyAtlanta, GA 30332, USA

[email protected]

Environmental Conference for the Meat and Poultry IndustryInternational Production & Processing Expo

Georgia World Congress CenterAtlanta, GA

February 11, 2019

Documents

Fate and Effect of Quaternary Ammonium Compounds and