The Effects of Chemical Toxicity
In Wastewater Systems
Pretreatment Seminar
Hosted by: Central States Water Environment Federation
Definitions



Toxicity: An adverse effect (not necessarily lethal)
on bacterial metabolism
Toxicant: A component in the wastewater causing
an adverse effect on bacterial metabolism
Inhibition: An impairment of bacterial function

[R.E. Speece, Anaerobic Biotechnology p. 246]
Aspects Further Defining
Wastewater Toxicity

Aspects Further Defining Chemicals that are toxic
or inhibitory to wastewater bacteria.

For any material to be biologically inhibitory or
toxic, it must be in solution (soluble form as
opposed to non-soluble, particulate, form)

Toxicity is a relative term. There are many soluble
organic materials which can be either stimulatory,
toxic, or inhibitory. Examples are ammonia,
nitrogen, acetic acid, phenol, etc.
Aspects Further Defining
Wastewater Toxicity (continued)

When potential inhibitory or toxic materials are
slowly increased within the wastewater
environment, many biological organisms can
rearrange their metabolic resources.

Thus overcoming the metabolic block produced by
the normally inhibitory or toxic material. Under
shock load conditions sufficient time is not
available for this rearrangement to take place.
Aspects Further Defining
Wastewater Toxicity (continued)

Additionally other waste stream chemicals,
elements, compounds, etc. can lead to antagonism
of the toxicity or synergism of the toxicity.
 Antagonism: is defined as a reduction of the
toxic effect of one substance by the presence of
another.
 Synergism: is defined as an increase in the toxic
effect of one substance in the presence of one
or multiple other substances.
Aspects Further Defining
Wastewater Toxicity (continued)

Cumulative Inhibition refers to toxicity of a
substance as a function of both toxicant
concentration and exposure time.
Nitrification Inhibition
Mechanisms
NITRIFICATION INHIBITION
FACTORS AFFECTING
NITRIFICATION

Nitrification Inhibition/Toxicity



Nitrifying bacteria are subject to inhibition by various
organic compounds
Nitrifying bacteria will need to have a greater SRT in
wastewater systems influenced by toxicity or nitrifier
inhibition
Nitrification toxicity refers to an organic/inorganic
compound that is poisonous, and destroys the activity
of a nitrification catalyst, enzyme or that destroys the
bacteria (bleach, chlorinated solvents, phenolics, etc.)
Potential Toxic Effects-- What Do
We Mean by "Toxic?"

Toxic: 1. of, affected by, or caused by a tox.in, or
poison. 2. Acting as a poison; poisonous.

Poison: a substance that inhibits or destroys the
activity of a catalyst, enzyme, etc., or that
interferes with or checks a reaction.
 Source: Webster's New World Dictionary
FACTORS AFFECTING
NITRIFICATION

Nitrification Inhibition/Toxicity


Nitrification inhibition refers to an organic/inorganic
compound that act as a competitive or non- competitive
force to block a reaction or that cause the nitrifying
bacteria to metabolize that compound with little or no
energy yield (TCE,TCA, acetylenic compounds, pryidine
and its derivatives, etc.)
Other sources of toxicity include chelating agents &
ligands (EDTA, sodium azide, Allythiourea, DPTA),
Heavy metals (chrome, arsenic, lead etc.)
AMO & HAO Defined

AMO – Ammonia Monooxygenase

HAO – Hydroxylamine Oxioreductase
Conceptual Model for Inhibition,
Inactivation, and Recovery
 Inhibition -- There is competition for AMO.
 Inactivation -- Oxidation of the non-growth
substrate causes a toxic effect.
 Recovery -- The cells respond by making more
enzyme.
 With many compounds, as with TCE, all three
of these processes occur simultaneously.
Energy Reactions
Inhibition
 Compounds that are transformed by AMO, such as
TCE, CH4, and others cause competitive or
noncompetitive inhibition
 NH2NH2--oxidized by HAO; competitive inhibitor of HAO
 Oximes -- General Structure: R-CH=NOH;
Formaldoxime (H2C=NOH) -- formed from formaldehyde
and hydroxylamine; inhibits NH2OH oxidation; may be a
substrate for HAO; some may be noncompetitive
inhibitors of NH3 oxidation
Compounds that Interfere with
Protein Synthesis
 L-Histidine

 L-Threonine

 L-Phenylalanine
Probably by end product inhibition
Cometabolism
"The transformation of a non-growth substrate in the
obligate presence of a growth substrate or another
transformable compound.“
*Stirling, D. I., Dalton, H. 1979. FEMS Microbial. Lett. 5:315-318
Summary of Interactions Between
Toxic Compounds and Nitrifiers
 Chelators can tend to tie up the active site copper
 Metals and some other compounds can impede
protein synthesis
 The cells attempt to respond by making new
enzymes or potentially in other ways
 Large variations between species in
susceptibilities
Summary of Interactions Between
Toxic Compounds and Nitrifiers
 Broad specificity of AMO
Many compounds can cause inhibition
Competitive & noncompetitive inhibition
common
 Some compounds are oxidized; others aren't
 Some compounds cause enzyme inactivation
Where Does Toxicity
Come From?

Production Chemicals

Air Scrubber Chemicals


Boiler Treatment
Cooling Tower Treatment
Steam Line Treatment

Sanitation Chemicals

Anaerobic Treatment (to Nitrification Reactor)

Production Chemicals
 Refineries – Phenol, Phenolics, Benzene, Toluene,
Xylene, Ethyl Benzene, MEK, Diesel Range Organics, any
sulfide scavenger with an amine group
 Pulp & Paper – Terpenes, Hydrogen Sulfide, Furans,
Dioxin, Chlorinated Phenolics, “Black Liquor”, “Green
Liquor”
 Coke Plants/ Steel Mills – Cyanide, Thiocyanate, Phenol
 Food Processing Plants
Air Scrubber Chemicals
 Hydrogen Sulfide
 Mercaptans
 Chlorine Dioxide
 Chlorate
 Chlorite
 Per Acetic Acid
 Sodium Hypochlorite
 Ozone
 Peroxy Acetic Acid
Boiler Treatment



EDTA
Oxygen Scavenging
Compounds
Scale Inhibitors (CoPolymers, Acrylamides,
ATDP)
Cooling Tower Treatment






EDTA
Quats
Chlorine Dioxide
Per Oxy Acetic Acid
Carbamates
Iso-thiocyanates
Steam Line Treatment



EDTA
Alkyl Amines
Filming Amines
Sanitation Chemicals






Quaternary Ammonium
Compounds
Per Acetic Acid
Sodium Hypochlorite
Bromine Compounds
EDTA
Surfactants:
(Cationic, Anionic, Non-ionic)
Anaerobic Treatment
Can all be inhibitory to the Nitrification Process:



Hydrogen Sulfide
Reduced Sulfur Compounds
Long-Chain Fatty Acids
Sampling of Toxic Chemicals That
are High on our Radar

Inhibitory/Toxic Chemicals
Quaternary Ammonium Compounds (QAC)
 Peracetic Acid Compounds (PPA)
 Chlorine Compounds
 EDTA
 Surfactants
 Dipropyleneglycol monomethyl ether
 Bisphenol

Sampling of Toxic Chemicals That
are High on our Radar
Quaternary Ammonium Compounds
Sampling of Toxic Chemicals That
are High on our Radar

Quaternary Ammonium Compounds






Strongly cationic – attaches to organic and inorganic
surfaces
Stable and hard to break – long lasting biocidal effect
Attracts anionic constituents
Strong positive charge attaches to negatively charged
bacteria – causes membrane leakage and bacteria
death
Removal occurs through some biodegradability and
through attaching to sludge and other biosolids
Accumulation of QAC’s in undisturbed biosolids can be
source of upset conditions if solids are disturbed
Sampling of Toxic Chemicals
That are High on our Radar

Quaternary Ammonium Compounds
 Dosage rates as low as 2 mg/l/day show inhibition of nitrification
with inhibition increasing significantly as dosage rate increases to 5
mg/l/day and nitrification ceases at an accumulative dose of 15 mg/l
 Nitrification inhibition due to QAC’s increases as temperature
decreases
 Inhibition is manifested by increasing nitrite nitrogen accumulation,
increased effluent ammonia nitrogen levels, or both
 Dosage rates up to 20 mg/l/day show no toxic impact on aerobic
COD removal; COD removal efficiency declines as dosage rate
approaches 40 mg/l
Sampling of Toxic Chemicals That
are High on our Radar

Quaternary Ammonium Compounds
 Inhibition with soluble COD increases and methane gas
reduction at dosages as low as 0.5 mg/l/day with
resultant increase in volatile acids in anaerobic lagoon
effluent – increases odor potential and oxygen demand
on aerobic system
 Toxicity at cumulative level of 25 mg/l (impact same at
cumulative level as one time dose at 25 mg/l)
 Anaerobic organisms do not tend to acclimate even at
low doses
Sampling of Toxic Chemicals That
are High on our Radar
Peracetic Acid
 In anaerobic treatment Inhibition with soluble COD
increases and methane gas production decreases
at dosages as low as 0.5 mg/l/day when cumulative
level of 25 mg/l reached
 Anaerobic organisms do not tend to acclimate even
at low doses. Toxic impacts can be seen at dose
rates as low as 5 mg/l/day; toxicity occurs at
accumulative dose of 25 mg/l
Sampling of Toxic Chemicals That
are High on our Radar
Peracetic Acid
 In Aerobic environments may acclimate to dose
rate of 5 mg/l/day or less within 10 days; no
recovery seen at 10 mg/l/day or higher
dosages
 Dose rates of 5 mg/l/day toxic to nitrification
after 10 days
 Severe foaming occurs in aerobic reactors at
onset of PAA toxicity
Sampling of Toxic Chemicals That
are High on our Radar

Chlorine Compounds
Sodium Hypochlorite
 Chlorite
 Chlorate
 Chlorine Dioxide

Sampling of Toxic Chemicals That
are High on our Radar

Bisphenol-A (BPA)
BPA has been appearing in significant
concentrations in WWTP’s and mostly
partitioned in the solid fraction of sludge
 We have been identifying BPA in 8270 SemiVolatile GC-FID Scans from rendering facilities
and beef processing plants

Sampling of Toxic Chemicals That are
High on our Radar

EDTA
Inhibits ammonium oxidation
 Inhibits anaerobic degradation
 Depletes cellular Ca2+
 Binds tightly with copper blocking enzyme action
and inhibiting nitrification
 Strongly chelates essential trace elements
necessary for anaerobic wastewater treatment

EDTA Complexed with Copper
Sampling of Toxic Chemicals That
are High on our Radar

Surfactants
Sodium Dodecyl Sulphate
 Sodium Dodecylbenzene Sulphonate
 Linear Alkylbenzene Sulphonate
 Alkyl Ethoxylates
 Can inhibit dehydrogenase activity
 Can increase toxicity of biocides via lipid
membrane disruption

Sampling of Toxic Chemicals That
are High on our Radar
Dipropyleneglycol monomethyl ether DPGME
DPGME









Dipropylene glycol monomethyl ether – DPGME
Is a solvent used to make paint thinners, paint products, fuel products
There are four isomers of Dipropylene glycol monomethyl ether
Is closely related to DiEGME (Diethyl glycol monomethyl ether) – a
solvent that would be an issue when introduced to a biological
wastewater treatment plant
DPGME - Extensively used as a fuel de-icer
Little or no biodegradation over short periods of time (days)
Can accumulate in an activated sludge system
As I researched this compound, I continually received “hits” for
nitrification inhibitors
Need to the gallons used per day
Tools to Assess Wastewater
Toxicity





Wastewater Plant Data Review
Review of MSDS, Investigation of Vendor Changes
& Inventory of Chemical Usage
Microscopic Investigation of Toxicity
Toxic Chemical Identification Methods
Laboratory Investigation of Toxicity
Tools to Assess Wastewater
Toxicity
Wastewater Plant Data Review
Report of month
Flow
Date
Jan-01
Very Good Foods
TSS
COD
MGPD
MLSS
(mg/L)
RAS
(mg/L)
01/01/01 Mon.
1.1287
4,520
11,600
01/02/01 Tue.
1.0750
4,690
13,875
01/03/01 Wed.
0.9694
4,460
01/04/01 Thu.
0.9594
01/05/01 Fri.
Anaerobic
Lagoon
pH
NH3 - N
Cl
2
Oxidation
Chamber
Ditch
Effluent
NO2
NO3
O2
Ditch
(mg/L)
Effluent
(mg/L)
Effluent
(mg/L)
20.0
21.0
0.1
8.8
11.0
12.6
0.7
8.8
9.5
0.7
9.0
Cl2
Anaerobic
Chamber
Lagoon
Effluent
TKN
(mg/L)
6.7
6.6
6.7
6.5
9,750
6.7
6.5
10.0
4,400
12,525
6.6
6.8
7.0
0.8857
4,330
9,650
6.6
6.7
9.0
01/06/01 Sat.
0.8785
4,290
14,025
6.7
6.7
01/07/01 Sun.
0.9389
4,270
10,675
6.7
6.7
01/08/01 Mon.
0.9574
4,300
10,400
6.7
6.7
01/09/01 Tue.
1.0574
4,340
11,300
6.8
6.8
01/10/01 Wed.
1.1027
4,150
9,900
6.8
01/11/01 Thu.
1.0496
4,050
10,675
01/12/01 Fri.
1.0827
3,900
01/13/01 Sat.
1.0237
01/14/01 Sun.
Final
Effluent
24hr
comp.
(mg/L)
Alkalinities
Anaerobic
Lagoon
Effluent
D.O.
Chl.
Risdual O2
Ditch
Oxidation
(mg/L)
Ditch
289.0
0.1
1.1
238.0
0.1
1.0
17.6
238.0
0.1
1.3
0.1
13.2
238.0
0.1
1.8
9.0
0.1
17.6
238.0
0.1
1.7
48.0
48.0
0.1
13.2
221.0
0.1
0.9
40.5
46.0
1.8
13.2
272.0
0.1
1.2
39.0
39.0
1.8
22.0
289.0
0.1
1.0
25.0
22.0
4.5
26.4
289.0
0.1
1.3
6.8
18.0
15.0
2.0
39.6
323.0
0.1
1.1
6.7
6.9
13.0
18.0
4.0
26.2
340.0
0.1
1.4
8,975
6.8
6.8
21.0
23.0
4.0
44.0
340.0
0.1
1.4
3,920
9,350
6.8
6.8
29.0
30.0
0.3
44.0
340.0
0.1
1.8
1.1389
3,930
10,400
6.6
6.9
24.0
19.0
9.0
13.2
408.0
0.1
1.1
01/15/01 Mon.
1.2044
3,990
10,725
6.8
6.8
25.0
22.0
18.0
74.8
374.0
0.1
1.4
01/16/01 Tue.
1.1318
4,170
10,700
6.7
6.9
30.0
27.0
20.0
176.0
323.0
0.1
1.0
01/17/01 Wed.
1.1110
4,090
10,775
6.7
6.7
27.0
20.0
21.0
180.4
357.0
0.1
1.4
01/18/01 Thu.
1.0951
4,300
10,200
6.7
6.8
24.0
21.0
12.0
132.0
357.0
0.1
1.4
01/19/01 Fri.
1.1180
4,330
10,350
6.7
6.8
28.0
21.0
8.0
66.0
357.0
0.1
1.1
01/20/01 Sat.
1.0820
4,560
11,000
6.6
6.8
20.0
21.0
17.0
44.0
306.0
0.1
1.3
01/21/01 Sun.
1.0522
4,630
12,775
6.4
6.7
18.0
15.0
22.5
70.4
289.0
0.1
1.1
01/22/01 Mon.
1.0488
4,520
10,700
6.4
6.5
17.0
15.0
184.8
176.0
272.0
0.2
1.3
01/23/01 Tue.
0.9940
4,840
13,225
6.6
6.6
19.0
22.0
228.8
25.0
204.0
0.1
1.3
01/24/01 Wed.
0.9196
4,640
12,275
6.5
6.6
34.0
30.0
40.0
40.0
221.0
0.1
1.4
01/25/01 Thu.
0.9098
4,540
9,800
6.5
6.6
18.0
22.0
40.0
308.0
238.0
0.1
1.8
01/26/01 Fri.
0.8785
9,740
8,975
6.7
6.5
27.0
23.0
40.0
396.0
221.0
0.1
0.9
01/27/01 Sat.
0.9154
4,710
9,400
6.7
6.8
19.0
25.0
60.0
352.0
221.0
0.2
0.4
01/28/01 Sun.
0.9238
4,940
10,325
6.5
6.8
23.0
26.0
80.0
264.0
187.0
0.2
0.6
01/29/01 Mon.
0.9335
5,350
10,850
7.1
6.8
39.0
45.0
90.0
303.6
136.0
0.1
0.4
01/30/01 Tue.
0.8929
5,500
11,050
7.1
7.1
30.0
24.0
100.0
475.2
272.0
0.1
0.2
01/31/01 Wed.
0.8074
5,190
10,275
7.1
7.3
30.0
22.0
90.0
396.0
323.0
0.1
0.3
1104
1704
1024
1785
1032
258.3
447.0
425.1
333.0
384.8
4.4
13.7
15.4
11.9
1120.0
1310.0
1450.0
1450.0
1600.0
Min
0.8074 3900.0
8,975
1024.0
6.4
6.5
258.3
15.0
4.4
9.0
0.1
8.8
1120.0
136.0
0.1
0.2
Average
1.0086 4631.9
10,855
1329.8
6.7
6.8
369.6
21.0
11.3
23.3
35.5
122.2
1386.0
281.3
0.1
1.1
1785.0
7.1
7.3
447.0
25.0
15.4
48.0
228.8
475.2
1600.0
408.0
0.2
1.8
Max
1.2044 9740.0 14025
American Beverage Company
Corporate Environmental Affairs
Date
Temp
(MM/DD/YY)
( oF)
pH
Feed
Rate
(ml/hr)
TOC (mg/l)
Influent
TOC Removal
Effluent
3/1/01
100.2
7.56
99
210
3/2/01
101.1
7.77
99
210
3/5/01
98.6
6.99
99
210
3/6/01
100.4
7.44
99
210
3.7
3/7/01
99.7
7.36
99
210
3.1
3/8/01
101
7.12
99
210
3/9/01
100.4
7.11
99
210
4.1
0.5
(%)
TSS
Effluent
(mg/l)
VSS
Effluent
(mg/l)
COD sol
11
0.8
9.6
6.0
0.9
0.8
98%
4.4
4.0
15
99%
5.8
3.6
under
1.6
0.9
1.8
0.7
98%
100%
27
1
Notes:
Irregularities in CODs are due to low actual concentrations - readings become less reliable as they approach 0.
High solids number on 3/1 is due to maintenance work within the reactor
Tools to Assess Wastewater
Toxicity
Review of MSDS, Investigation of Vendor Changes &
Inventory of Chemical Usage
Review of MSDS’s
Sanitizing Chemical Report
I was sent information on chemicals currently being utilized by
the processing plant in their sanitization program. Below I will
review my findings:


Alkyl Polyglucoside – this material does not pose a
problem unless it was used at very high ppm’s (over 200
mg/l)
Alkyl dimethyl amine oxide/Amine alkyl diphenyloxide
disulfonate – used as foam stabilizers
Review of MSDS’s




Alkyl dimethyl amine oxide/Amine alkyl
diphenyloxide disulfonate – used as foam
stabilizers
99.8 % removal in aerobic wastewater treatment
systems
Long Alkyl chains ranging from 8-20 carbons
Main concern is metabolites formed with amine
group attached
Review of MSDS’s








Sodium Dodecylbenzene Sulfonate – Linear Alkyl Benzene
Sulfonates (LAS)
SDBS (Sodium Dodecylbenzene Sulfonate)
Anionic Surfactant
“Branched” isomer is much slower degrading than the linear form (less
toxic)
LAS (SBDS) is more toxic and yet more biodegradable
Attached paper points to nitrification toxicity starting at 11.95 mg/l
Concentrations greater than 20 mg/l is likely to impact nitrification
negatively
We need to know how many gallons per day is being utilized for
sanitization purposes
Review of MSDS’s
 Sodium Dodecylbenzene Sulfonate/Lauryl Ether Sulfonate – Lauryl
is an emulsification - wetting agent
 Lauryl ether sulfonate by itself is not a problem, but it can make
biocides more effective by interfering with the lipid membrane
wastewater bacteria use to maintain cell integrity
 Sodium dodecylbenzene sulfonate
 SDBS (Sodium Dodecylbenzene Sulfonate)
 Anionic Surfactant
Review of MSDS’s
 “Branched” isomer is much slower degrading than the linear form (less
toxic)
 LAS (SBDS) is more toxic and yet more biodegradable
 Attached paper points to nitrification toxicity starting at 11.95 mg/l
 Concentrations greater than 20 mg/l is likely to impact nitrification
negatively
 We need to know how many gallons per day is being utilized for
sanitization purposes
Review of MSDS’s









Dipropylene glycol monomethyl ether – DPGME
Is a solvent used to make paint thinners, paint products, fuel products
There are four isomers of Dipropylene glycol monomethyl ether
Is closely related to DiEGME (Diethyl glycol monomethyl ether) – a
solvent that would be an issue when introduced to a biological
wastewater treatment plant
DPGME - Extensively used as a fuel de-icer
Little or no biodegradation over short periods of time (days)
Can accumulate in an activated sludge system
As I researched this compound, I continually received “hits” for
nitrification inhibitors
Need to the gallons used per day
Microscopic Examination of
Wastewater Toxicity
Microscopic Investigation



Excess Polysaccharide production can be an
indication of waste stream toxicity
Proliferation of Flagellates often indicates a toxic
event has taken place
Many different types of micro fauna may indelicate
toxicity has Passed through the wastewater system
(flagellates, ciliates, amoebas, rotifers, etc.)
Polysaccharides
India Ink Stain
India Ink Stain MLSS
Sampled June 27, 2012
India Ink Stain Foam
Sampled June 27, 2012
Higher Life Forms
Paramecium
Flagellated Protozoan
Paramecium
Testate Amoeba
Rotifer
Toxic Chemical Identification
Methods
8270 Semi volatile Organic Scan
GC-FID Pattern Matching
8270 Semi volatile Organic Scan
GC-FID Pattern Matching
Raw Influent
1,2,4-Trichlorobenzene
2,4-Dinitrotoluene
2,6-Dimethylaniline
2,6-Dinitrotoluene
2-Chloronaphthalene
2-Chlorophenol
2-Nitrophenol
1,2-Dichlorobenzene
3,3'-Dichlorobenzidine
4,6-Dinitro-2-methylphenol
4-Bromophenylphenyl ether
4-Chloro-3-methylphenol
4-Chlorophenylphenyl ether
4-Nitrophenol
Acenaphthene
ug/L
<20.0
<20.0
<10.0
<20.0
<20.0
<20.0
<20.0
<20.0
<20.0
<20.0
<20.0
<20.0
<20.0
<20.0
<20.0
8270 Semi volatile Organic
Scan GC-FID Pattern
Raw Influent
ug/L
Matching
Acenaphthylene
Anthracene
Azobenzene
Benzidine
Benzo(a)anthracene
Benzo(a)pyrene
Benzo(b&k)fluoranthene
Benzo(b)fluoranthene
Benzo(g,h,i)perylene
1,4-Dichlorobenzene
Benzo(k)fluoranthene
Bis(2-chloroethoxy) methane
Bis(2-chloroethyl) ether
Bis(2-chloroisopropyl) ether
Bis(2-ethylhexyl) phthalate
<20.0
<20.0
<20.0
<20.0
<20.0
<20.0
<20.0
<20.0
<20.0
<20.0
<20.0
<20.0
<20.0
<20.0
<20.0
8270 Semi volatile Organic
Scan GC-FID Pattern
Matchingug/L
Raw Influent
Chrysene
2,4,5-Trichlorophenol
Dibenzo(a,h)anthracene
Diethyl phthalate
Dimethyl phthalate
Di-n-butyl phthalate
Di-n-octyl phthalate
Diphenylamine
Fluoranthene
Fluorene
Hexachlorobenzene
2,4,6-Trichlorophenol
Hexachlorobutadiene
<20.0
<20.0
<20.0
<20.0
<20.0
<20.0
<20.0
<20.0
<20.0
<20.0
<20.0
<20.0
<20.0
8270 Semi volatile Organic Scan
GC-FID Pattern Matching
Raw Influent
ug/L
Hexachlorocyclopentadiene
Hexachloroethane
Indeno(1,2,3-cd)pyrene
Isophorone
Naphthalene
Nitrobenzene
N-Nitrosodi-n-propylamine
Pentachlorophenol
2,4-Dichlorophenol
Phenanthrene
Phenol
Pyrene
2-Fluorophenol
Phenol- d5
Nitrobenzene-d5
<20.0
<20.0
<20.0
<20.0
<20.0
<20.0
<20.0
<20.0
<20.0
<20.0
71.6
<20.0
28
19
92
8270 Semi volatile Organic Scan
GC-FID Pattern Matching
Raw Influent
2-Fluorobiphenyl
2,4,6-Tribromophenol
p-Terphenyl-d14
2,4-Dimethylphenol
1,4-Dichlorobenzene-d4
Naphthalene-d8
Acenaphthene-d10
Phenanthrene-d10
Chrysene-d12
Perylene-d12
2,4-Dinitrophenol
ug/L
80
28
88
<20.0
80.0
80.0
80.0
80.0
80.0
80.0
<20.0
Quaternary Ammonium Analysis
Quaternary Ammonium
Plant S
Influent
Plant S
Effluent
Plant M
Influent
Plant P
Influent
Plant H
Influent
12.83
14.15
12.3
8.51
8.21
Didecyl dimethyl ammonium salt
0.25
0.78
0
0
0.63
Dioctyl dimethyl ammonium salt
0.42
0.94
0
0
0.37
Octyl decyl dimethyl ammonium salt
0.15
0.44
0.52
0.33
0.45
N,N-Dimethyl hexadecanammonium salt
0.67
1.13
1.25
0.36
0.42
N,N-Dimethyl dodecanammonium salt
2.12
1.95
2.94
1.25
1.46
Benzyldimethylhexadecylammonium salt
0.34
0.58
0.35
0.64
0.41
Benzyldimethyltetradecylammonium salt
1.55
2.24
1.75
1.38
0.95
Benzyldimethyldodecylammonium salt
3.95
3.82
2.4
1.93
2.58
Decyldimethyl ammonium salt
N-(3-chloro-2- hydroxypropyl) trimethylammonium
chloride (quat 188)
2,3- epoxypropyltrimethylammoniurn chloride
(epoxide)
Ammonium bromide
dicapryl dimonium chloride
I-Bromo- 3-Chloro-5,5-Dimethyhydantoin
2.63
0.79
2.83
1.24
0.94
0
0
0
0.56
0
0
0
0
0.53
0
0.75
0
1.48
0
0.26
0
0.29
0
0
0
0
0
0
0
0
Total Quaternary Ammonium Surfactants
Quaternary Ammonium Analysis
Influent
Anaerobic
Effluent
Didecyl dimethyl ammonium salt
0.59
0.17
Dioctyl dimethyl ammonium salt
0.42
0
Octyl decyl dimethyl ammonium salt
3.18
0.34
N,N-Dimethyl hexadecanammonium salt
2.04
0.53
N,N-Dimethyl dodecanammonium salt
1.82
0.29
Benzyldimethylhexadecylammonium salt
0.75
0.11
Benzyldimethyltetradecylammonium salt
1.32
0.28
Beef Plant
Quaternary Ammonium Analysis
(continued)
Influent
Anaerobic
Effluent
Benzyldimethyldodecylammonium salt
1.47
0.31
Decyldimethyl ammonium salt
N-(3-chloro-2- hydroxypropyl) trimethylammonium chloride
(quat 188)
0.97
0.22
0
0
0
0
0.29
0.69
dicapryl dimonium chloride
0
0
I-Bromo- 3-Chloro-5,5-Dimethyhydantoin
0
0
Total Quaternary Ammonium Surfactants
12.85
2.94
Beef Plant
2,3- epoxypropyltrimethyl ammoniurn chloride (epoxide)
Ammonium bromide
Sample Comparison of Quaternary
Ammonium Compounds
Concentrations
* AB: Alkyl benzyl dimethyl ammonium chloride
** Mean ± Standard deviation
(n=2)
Sample Description
Analysis Date
pH
TSS
VSS
mg/L
mg/L
Feed 10/23/09
10/28/09
10.03
360
180
Mixed Liquor 10/23/09
ML Discharge 10/23/09
DAF Eff. 11/03/09
# 1 Lagoon Front 11/03/09
# 1 Aerated Lagoon End 11/03/09
DAF Eff. 11/19/09
# 1 Lagoon Front 11/19/09
# 1 Aerated Lagoon End 11/19/09
Cargill Nebraska City 12/09/09
Vernon East Influent 12/17/09
Vernon West Influent 12/17/10
Vernon Effluent 12/17/11
10/29/09
10/29/09
11/4/09
11/4/09
11/4/09
11/24/09
11/24/09
11/24/09
12/24/09
12/24/09
12/24/09
12/24/09
6.80
6.75
11.32
7.07
7.02
4.61
6.28
6.30
4.45
5.80
6.87
6.66
1160
1420
350
1160
1160
320
960
940
2360
2640
2380
840
1060
1320
80
1000
900
220
900
660
2240
2480
420
620
TOTAL
QACs
mg AB*/L
0.20 ±
0.005**
1.54 ± 0.08
1.70 ± 0.60
0.67 ± 0.22
2.19 ± 0.03
2.12 ± 0.03
1.26 ± 0.34
2.15 ± 0.10
1.92 ±0.01
0.77 ± 0.187
7.29 ± 0.34
6.09 ±0.92
2.22 ±0.004
SOLUBLE
QACs
mg AB/L
0.07 ± 0.02
0.95 ± 0.02
0.48 ± 0.31
0.52 ± 0.06
0.89 ± 0.19
0.93 ± 0.01
0.51 ± 0.08
0.39 ± 0.08
0.71 ± 0.20
0.22 ± 0.12
1.13 ± 0.05
0.58 ± 0.001
0.86 ± 0.008
Volatile Fatty Acid
Comparative Study
Volatile Organic Acids
Formic
Acid
Acetic Propionic Butyric Valeric Isovaleric Lactic
Total VOAs
Acid
Acid
Acid
Acid
Acid
Acid
Plant I Influent
64.3
378
38.2
55.3
8.9
5.3
18.9
568.9
Plant I Effluent
11.5
68.3
13.2
21.9
5.3
3.2
8.9
132.3
Plant B Influent
Plant B Effluent
Plant G Influent
8.9
134
9.3
16.1
3.5
2.8
1.2
175.8
4.2
32.1
4.3
8.5
1.6
1.2
0.5
52.4
53.8
341
29.4
42.6
18.5
12.8
32.7
530.8
Plant G Effluent
19.3
47.3
8.2
11
4.4
5.2
1.9
97.3
Plant S Influent
21.7
227
17.6
34.2
11.8
8.9
1.6
322.8
Plant S Effluent
8.9
142
11.4
28.5
5.8
3.1
0.8
200.5
Plant M Influent
24.7
345
11.3
26.8
3.2
1.5
1.1
413.6
Plant M Effluent
Plant P Influent
Plant P Effluent
Plant H Influent
Plant H Effluent
15.1
180
22
31
13.2
9.4
0.9
271.6
38.5
407
23.7
45.6
8.4
6.6
1.2
531
18.2
89.4
11.3
19
5.3
2.8
0.7
146.7
1.2
18.9
7.5
4.7
3.7
2.8
9.4
48.2
2.3
66.8
4.1
2.7
2.2
1.8
1.3
81.2
Long Chain Fatty Acids Analysis
Beef Plant
Palmitic acid
Stearic acid
Myristic acid
Oleic acid
Palmitoleic acid
Linoleic acid
Total LCFA’s
Long Chain Fatty Acids
Influent
19.1
34
27.6
46.7
18.9
22.7
169
Anaerobic
Effluent
7.5
12.4
11.7
19.6
6.5
11.6
69.3
Essential Trace Metal Analysis
Essential Trace Metal Analysis
Anaerobic Influent mg/L
Aluminum
0.082
Calcium
18
Cobalt
< 0.0040
Copper
0.014
Iron
1.3
Magnesium
5.7
Manganese
0.027
Molybdenum
< 0.024
Nickel
0.015
Potassium
1100
Sodium
4100
Zinc
0.78
Date/ Time
12/21/11 14:16
12/21/11 14:16
12/21/11 14:16
12/21/11 14:16
12/21/11 14:16
12/21/11 14:16
12/21/11 14:16
12/21/11 14:16
12/21/11 14:16
12/21/11 13:42
12/28/11 08:53
12/21/11 14:16
Laboratory Investigation of Waste
Stream Toxicity
Bench Scale Study



Waste Stream
Investigation
Organics Analysis
(GC-MS, HPLC, etc.)
Element Analysis
(Cations, Anions,
Essential Trace
Elements)





Bench Scale Models of
Wastewater systems
Respiromic Studies
Anaerobic Gas Production
Studies
Nitrification Testing
(Toxicity & Growth)
System Design Studies
Bench Scale Study




Bench Scale Emulation Studies of Activated
Sludge, Aerated Stabilization Basins & Fixed Film
Process
Respiromic Studies (To precisely monitor oxygen
consumption in test reactors with identical mass
transfer rates)
Anaerobic Gas Production Studies (To monitor
methane, sulfide, CO2 & hydrogen gas production
during trace element addition assays
Nitrification Testing (Toxicity & Growth)
Bench Scale Reactor Investigation
of Waste Stream Toxicity
Pilot Scale Reactors
Pilot Scale Reactors
Pilot Scale Reactors
aeration pumps
insulation
Influent
metered pump
heated baths
Effluent
aeration stones
Respirometry Investigation of
Waste Stream Toxicity
Respirometry
RSA - 8000 RESPIROMETER
RSA’s PF-8000 Pulse-Flow
Respirometer
Respirometry
Respirometry
Methane Gas Produced (mL)
Anaerobic Gas Production Study
(BMP)
7000
6750
6500
6250
6000
5750
5500
5250
5000
4750
4500
4250
4000
3750
3500
3250
3000
2750
2500
2250
2000
1750
1500
1250
1000
750
500
250
0
Plant E
Plant E w/20 ppm TESS
Plant F
Plant F w/ 20 ppm TESS
0
25
50
75
100
Time (hrs)
125
150
175
Respirometry Test – Aerobic
Biodgredation
Anoxic Denitrification Test
Biological Methane Production
Biological Methane Production
Tensiometer Investigation of
Waste Stream Toxicity
Tensiometer
Theta Lite Optical Tensiometer
 Surface Tension Analysis
 Contact Angle

Tensiometer
Pre-Treatment Pond – 58 dynes/cm
 Mixed Liquor – 62 – dynes/cm

For comparison: Tap Water – 72 dynes/cm
 Aerobic Food Processing Wastewater EQ –
65-68 dynes/cm

Nitrification Toxicity Testing
Nitrification Toxicity Test
Setup
Test Procedure
•
•
•
•
Four 1000mL reactors
Run 500mL tests of Control consisting of DI H2O versus 10%, 25%,
and 50% concentration of waste water matrix being tested
Add ammonium chloride to 100 ppm and your buffer system to
control pH between 7.6-7.8
Add nitrifiers and turn air on to begin the test, run the test until
the control reaches near 0 ppm NH3-N
Nitrification Toxicity Test

Description: The Nitrification Inhibition/Toxicity
Test is a twenty-four-hour nitrification inhibition
screening that analyzes the nitrification activity of a
standardized quantity of concentrated nitrifying
bacterial cultures.


The nitrifying bacteria utilized in the Nitrification
Inhibition/Toxicity test are used to evaluate the
toxicity to nitrifying bacteria of specific waste
streams versus a “control”. The control consists of
distilled water, pH buffers, and a source of
alkalinity and 10 ml of concentrated nitrifying
bacteria.
Nitrification Toxicity Test

The test samples, are either spiked with various
concentration of the chemical being tested or is a
percentage of a waste stream being evaluated for
toxicity. The “test” samples are then evaluated
against the control. Each test utilizes the same
volume of material and is equal in volume to the
distilled water utilized in the control test. AmmoniaNitrogen (NH3-N) and pH are monitored before and
after the test.
Nitrification Toxicity/Inhibition
Study (Test Setup Example)
 The Control Test was run with 100% distilled water versus four
Screening Tests.
 The first Influent Test was run at 25% Influent (25% Influent to 75%
DI water). The second Influent Test, was run with 50% Influent
 (50% Influent to 50% DI water).
 The first Mixed Liquor Test was run at 25% Mixed Liquor (25%
Mixed Liquor to 75% DI water). The second Mixed Liquor Test, was
run with 50% Mixed Liquor (50% Mixed Liquor to 50% DI water).
 The Control Reactor and each Test Reactor had their pH adjusted
to 7.5. 10 ml of a nitrifying bacteria concentrate was added to each
500 ml test reactor. Each reactor was then aerated with identical
air stones with controlled air pressure to each stone. The
ammonia-nitrogen was tested at the start of the study and at the
conclusion of the 24-hour study.
Beef Processing Facility
in Colorado
Chicken Processing Plant
in Arkansas
Rendering Plant in Iowa
Nitrification Toxicity Can Be Used
To Evaluate Specific Chemical
Toxicity
Nitrification Toxicity Testing
Individual Product Testing
REACT-OX TM 151
REACT-OX® 151 Nitrification
Toxicity Test
REACT-OX® 151 is a product which is used in air scrubber
systems as a cleaning agent. The following study was
conducted to see if REACT-OX® 151 showed any type of toxic
or inhibitory effect of nitrifying microorganisms. We used
concentrations of 210ppm, 420ppm, 1050ppm, and 2100ppm
of 151 to see if there was any inhibitory or toxic effect. The
study was conducted over the course of a 5 hour period of
time using a Trizma Buffering system to maintain a stable pH
between 7.6 and 7.9 over the course of the study.
REACT-OX® 151 Nitrification
Toxicity Test
151 Toxicity Study
130
120
110
100
90
NH3 (mg/L)
80
control
70
210 ppm
60
420 ppm
1050 ppm
50
2100 ppm
40
30
20
10
0
0
0.5
1
1.5
2
2.5
3
Time (Hours)
3.5
4
4.5
5
5.5
REACT-OX® 151 Nitrification
Toxicity Test
Over the course of the study there was a steady drop
in ammonia levels in the control as well as all of the
tests showing that REACT-OX® 151 did not show any
signs of toxicity or inhibition in the nitrification
process.
Bench Scale Treatability Studies
NeutraQuatTM Case Study
ANAEROBIC METHANE PRODUCTION STUDY
TO EVALUATE THE FULL-SCALE EFICACY OF
TWO BIOCHEMICALS USED TO NEUTRALIZE
THE IMPACT OF QUATERNARY
AMMONIUM COMPOUNDS IN A PORK
PROCESSING WASTE STREAM
RSA - 8000 RESPIROMETER
RSA’s PF-8000 Pulse-Flow
Respirometer
Scope of the Study
Quaternary ammonium compounds can negatively
affect the performance of anaerobic wastewater
treatment. This study was conducted to evaluate
two quaternary ammonium neutralizing biochemicals in a bench-scale setting utilizing a
Respirometer Systems and Applications (RSA) PF8000 Pulse-Flow Respirometer to measure gas
production in test reactors that were impacted by
known amounts of a quaternary ammonium
compound.
Case Study Overview
Anaerobic biomass from the processor’s wastewater
treatment system and a quaternary ammonium
compound utilized for disinfection at the pork
processing plant were shipped to Respirometer
Systems and Applications (RSA) in Fayetteville, AR.
Overview (continued)
Under the direction of Dr. James Young the benchscale gas production study was performed utilizing a
Respirometer Systems and Applications (RSA) PF8000 Pulse-Flow Respirometer.
Overview (continued)
Eight discrete anaerobic reactors were utilized in the
study. Each reactor received identical amounts of
anaerobic biomass and was periodically fed 2400 mg of
acetate. Two “Control” reactors were ran to better assess
the final test results.
Overview (continued)
Six “Test” Reactors were used in the study and were
amended with either 7.5 or 15 mg/l of the provided
quaternary ammonium compound. Of the six Test
Reactors two were amended with Quat Lock™ and
two were amended with NeutraQuat™. A two stage
study was performed. The 1st Stage ran for 72 hours
and the 2nd stage ran for 84 hours.
RSA – 8000 RESPIROMETER
RSA’s PF-8000 Pulse-Flow respirometers are designed specifically
to measure oxygen uptake for aerobic biological reactions and gas
production from anaerobic and anoxic biological reactions.
METHODS:
REACTORS 1-3
Test Setup
The anaerobic sludge was mixed and the following reactors
were set up for the Methane Production Study:
REACTOR 1 - 500ml Anaerobic Sludge – Control
(w/ 2400 mg acetate added @ Time 0 & Time 24 hr.)
REACTOR 2 - 500ml Anaerobic Sludge – 7.5 mg/l Quat
(7.5 mg/l Quat and 2400 mg acetate added @ Time 0 & Time
24 hr.)
REACTOR 3 - 500ml Anaerobic Sludge – 15 mg/l Quat
(15 mg/l Quat and 2400 mg acetate added @ Time 0 & Time 24
hr.)
METHODS:
REACTORS 4-7
Test Setup
REACTOR 4 - 500ml Anaerobic Sludge – 7.5 mg/l Quat & 7.5 mg/l Quat Lock
(7.5 mg/l Quat – 7.5 mg/l Quat Lock and 2400 mg acetate added @ Time 0 & Time
24 hr.)
REACTOR 5 - 500ml Anaerobic Sludge – 7.5 mg/l Quat & 7.5 mg/l
NEUTRAQUAT (7.5 mg/l Quat – 7.5 mg/l NEUTRAQUAT and 2400 mg acetate
added @ Time 0 & Time 24 hr.)
REACTOR 6 - 500ml Anaerobic Sludge – 15 mg/l Quat & 15 mg/l Quat Lock
(15 mg/l Quat – 15 mg/l Quat Lock and 2400 mg acetate added @ Time 0 & Time
24 hr.)
REACTOR 7 - 500ml Anaerobic Sludge – 15 mg/l Quat & 15 mg/l NEUTRAQUAT
(15 mg/l Quat – 15 mg/l NEUTRAQUAT and 2400 mg acetate added @ Time 0 &
Time 24 hr.)
METHODS (continued)
Test Setup (continued)
STAGE 1 – Ran for 72 hours. The Test Reactors were
amended with the components listed above at Time 0 and
Time = 24 hrs.
STAGE 2 - Ran for 84 hours. The Test Reactors were
amended with the components listed above at Time 0.
2400 mg of acetate was reintroduced at Time = 18 hours
& Time = 36 hours.
1A) TOTAL COMBINED
METHANE PRODUCTION TESTS
STAGE 2
STAGE 1
(Total Methane Production)
1B) TOTAL COMBINED
METHANE PRODUCTION TESTS
STAGE 2
STAGE 1
(Methane Production Rate)
2A) NEUTRAQUAT METHANE
PRODUCTION TESTS
STAGE 2
STAGE 1
2B) NEUTRAQUAT METHANE
PRODUCTION TESTS
STAGE 2
STAGE 1
3A) QUAT LOCK METHANE
PRODUCTION TESTS
STAGE 2
STAGE 1
3B) QUAT LOCK METHANE
PRODUCTION TESTS
STAGE 1
STAGE 2
CONCLUSION
NeutraQuat™ amended Test Reactors showed
significantly greater methane production than Quat
Lock™ amended Test Reactors for all levels of
quaternary ammonium or acetate additions. Quat
Lock™ amended Test Reactors showed less methane
production than the test reactors receiving only the
quaternary ammonia compound as an additive
(realized a greater toxicity effect).
Bench Scale Treatability Studies
Bench Scale Treatability Study –
Pickling Waste Stream
Bench Scale Treatability Study –
Pickling Waste Stream
An anaerobic lagoon followed by an activated sludge
wastewater treatment process was emulated in a
pilot-scale wastewater plant consisting of a 4-liter
anaerobic reactor followed by a 6-liter aerated
continuously stirred biological reactor (test volume of
both the anaerobic reactor and aerobic reactor was
4-liters) that was operated as a sequencing batch
reactor (SBR).
Description of Work
An influent reservoir containing wastewater containing React
Tank effluent process wastewater provided the influent waste
stream for the wastewater treatment system microcosm.
During the first phase of the treatability study a competent
biological biomass (seed development) was established in
both the anaerobic reactor and aerobic SBR. The biomass in
each reactor was developed from the anaerobic biomass and
from mixed liquor secured from the wastewater treatment
system. The mixed liquor was maintained at 4000 mg/l MLSS
(+ or – 250 mg/l) in the SBR reactor throughout the course of
the study.)
BENCH-SCALE STUDY WWT
MICROCOSM SET UP CHART
WEEK NUMBER
May 1- May 6
May 7- June 1
June 2- June 15
June 16- July 10
DESCRIPTION OF WASTEWATER
TEST NAME
Amendments
MICROCOSM
To Anaerobic Reactor: React Tank
Control
Effluent 1L
To Anaerobic Reactor: React Tank 75 ml PW + 5 ml May 14 – Osmo-Cure Started
Effluent 1L/day + 75 ml Pickle
Sodium di@ 10 ml initial then 1 ml/day
water
acetate/potassiu Hydrocarrier-TR Introduced
To Aerobic Reactor: 5 ml Sodium
m lactate
@ 500 mg/l, then 100
di-acetate/potassium lactate
mg/day
To Anaerobic Reactor: React Tank
75 ml PW + 10
Effluent 1L/day + 75 ml Pickle
ml Sodium diwater
acetate/potassiu
To Aerobic Reactor: 10 ml Sodium
m lactate
di-acetate/potassium lactate
75 ml PW + 20
To Anaerobic Reactor: React Tank
ml Sodium diEffluent 1L/day + 75 ml Pickle acetate/potassiu
water
m lactate
To Aerobic Reactor: 20 ml Sodium
di-acetate/potassium lactate
June 20 Osmo-Cure
increased to 3 ml/day
HydroCarrier-TR Introduced
@ 500 mg/l, then 200
mg/day
Description of Work: (Continued)


Phase II of the Bench Scale treatability study to determine the
effect of Pickling Water on wastewater nitrification was performed
to identify waste stream amendments that would allow for
competent nitrification during periods of high waste stream
conductivity and during introductions of the disinfectant
potassium lactate/sodium di-acetate.
During the one week acclimation period (May 1 – May 6) no
amendments were introduced into the waste water microcosm. On
May 14 the mineral aggregate microcarrier – Hydrocarrier-TR was
introduced into the Aeration Reactor at a dosage amount of 500
mg/l (and at a continuing rate of 100 mg per day). In addition, the
osmoprotecterant, OSMOCURE, was introduced at a rate of 1 ml
per day.
Description of Work: (Continued)
OSMO-CURE (a biochemical with osmoprotecterant
qualities), was introduced at an increased rate of 3
ml per day starting on June 20. HydroCarrier-TR was
increased on June 20th with an additional 500 mg/l
one time introduction and then maintained at 200 mg
daily introduction rate. OSMO-CURE and
HydroCarrier-TR were fed at these rates to the end
of the study (July 10).
Results
The “Bench-Scale Treatability To Determine the Effect of Pickling
Water on Wastewater Nitrification” Phase I study examined the
impact on wastewater nitrification when increasing amounts of
pickle water was fed into the influent and was tracked by comparing
the wastewater conductivity (in umhos/cm) to the ammonia-nitrogen
concentration in the pilot-scale effluent. This second study or
addendum study was performed to assess the feasibility in utilizing
a micro-carrier, with toxicity reducing capabilities and as a vehicle
for providing large amounts of surface area for sessile bacteria to
attach to and thus utilize exopolysaccharides for bacterial colony
protection in combination with a osmoprotecterant, Osmo-Cure that
provides necessary cosolvents to assist with the osmolality gradient
when the wastewater conductivity is rapidly increased.
Results
The previous study revealed that the pickle water does
exert a negative impact on wastewater nitrification as
the conductivity exceeds 13,00 umhos/cm. However,
in this study wastewater nitrification continued up to
17,000 umhos/cm. The wastewater amendments
Osmo-Cure and HydroCarrier-TR can be beneficial in
maintaining waste stream nitrification in an high
wastewater conductivity environment (up to 17,00
umhos/cm) and when simultaneously experiencing the
effect of the “water activity” depressant potassium
lactate/sodium di-acetate.
Pickling Study Treatability Data
Nitification Data

30
NH3-N (mg/L)
25
20
15
10
5
0
NH3-N (mg/L)
Pickling Study Treatability
Data
Date
NH3-N (mg/L)
Date2
NH3-N (mg/L)2
7-May
23.8
8-Jun
8.4
8-May
3.04
12-Jun
3.35
9-May
19.5
13-Jun
2.8
10-May
27.6
14-Jun
2.68
11-May
24.4
15-Jun
3.85
14-May
26.4
18-Jun
13.75
15-May
6.44
19-Jun
12.5
17-May
4.17
20-Jun
26.75
18-May
3.15
21-Jun
6.55
21-May
3
22-Jun
5.85
22-May
5.53
25-Jun
5.85
23-May
8.8
26-Jun
5.4
24-May
1.88
27-Jun
7.85
25-May
1.77
28-Jun
3.9
29-May
2.16
2-Jul
7.85
30-May
2.06
3-Jul
6.45
31-May
3.2
5-Jul
7.05
1-Jun
2.2
9-Jul
3.65
6-Jun
5.37
10-Jul
5.02
7-Jun
7.5
Bench Scale Treatability Study –
Poultry Plant – Quat Toxicity
Bench Scale Treatability Study
Poultry Plant – Quat Toxicity
Bench-Scale Treatability Study
Bench Scale treatability study to determine the
effect of Missouri Plant’s pre-treatment effluent
on wastewater nitrification, utilizing the mixed
liquor from an actively nitrifying wastewater
treatment at a poultry processing plant process.
Bench-Scale Treatability Study
WWT MICROCOSM SET UP CHART
TEST
NUMBER
DESCRIPTION OF WASTEWATER MIROCOSM
TEST
NAME
TEST 1
Tennessee Anaerobic Effluent
CONTROL
TEST 2
Influent – Missouri Effluent
Missouri A
TEST 3
Influent – Missouri Effluent (w/5 ml NeutraQuat)
Missouri B
Bench Scale Treatability Study –
Poultry Processing Plant
Bench Scale Treatability Study
Reactors
Bench Scale Treatability Study
Reactors
Bench-Scale Treatability Study
Date
Sample ID
Test 1
12/5/2011 Test 2
Test 3
Test 1
12/6/2011 Test 2
Test 3
Test 1
12/7/2011 Test 2
Test 3
Test 1
12/8/2011 Test 2
Test 3
Test 1
12/9/2011 Test 2
Test 3
Test 1
12/12/2011 Test 2
Test 3
pH level
7.42
7.46
7.43
7.40
7.52
7.39
7.45
7.50
7.37
n/a
n/a
n/a
7.42
7.59
7.32
7.47
7.59
7.42
Ammonia Nitrogen Level
(NH3-N)
0.58 mg\l
0.59 mg\l
0.64 mg\l
0.64 mg\l
0.71 mg\l
0.55 mg\l
0.61 mg\l
0.93 mg\l
0.49 mg\l
0.63 mg\l
1.12 mg\l
0.47 mg\l
0.59 mg\l
1.72 mg\l
0.42 mg\l
0.59 mg\l
1.08 mg\l
0.31 mg\l
Bench-Scale Treatability Study
Date
12/13/2011
12/14/2011
12/15/2011
12/16/2011
12/20/2011
12/21/2011
Sample ID
Test 1
Test 2
Test 3
Test 1
Test 2
Test 3
Test 1
Test 2
Test 3
Test 1
Test 2
Test 3
Test 1
Test 2
Test 3
Test 1
Test 2
Test 3
pH level
7.49
7.57
7.39
7.47
7.61
7.41
7.45
7.53
7.41
7.39
7.51
7.43
7.43
7.56
7.37
7.42
7.52
7.41
Ammonia Nitrogen Level
(NH3-N)
0.61 mg\l
1.37 mg\l
0.35 mg\l
0.77 mg\l
1.98 mg\l
0.39 mg\l
0.72 mg\l
3.69 mg\l
0.41 mg\l
0.72 mg\l
3.96 mg\l
0.39 mg\l
0.62 mg\l
4.36 mg\l
0.44 mg\l
0.64 mg\l
4.61 mg\l
0.47 mg\l
Bench-Scale Treatability Study
Date
12/22/2011
12/27/2011
12/28/2011
12/29/2011
12/30/2011
Sample ID
Test 1
Test 2
Test 3
Test 1
Test 2
Test 3
Test 1
Test 2
Test 3
Test 1
Test 2
Test 3
Test 1
Test 2
Test 3
pH level
7.43
7.58
7.38
7.43
7.51
7.47
7.48
7.47
7.34
7.47
7.52
7.32
7.42
7.53
7.45
Ammonia Nitrogen Level
(NH3-N)
0.69 mg\l
2.28 mg\l
0.45 mg\l
0.73 mg\l
2.12 mg\l
0.47 mg\l
0.71 mg\l
1.96 mg\l
0.49 mg\l
0.73 mg\l
1.29 mg\l
0.51 mg\l
0.71 mg\l
1.17 mg\l
0.52 mg\l
Ammonia Nitrogen NH3-N
0.00 mg\l
12/28/…
Test 2
12/30/…
12/29/…
1.00 mg\l
12/27/…
12/26/…
12/25/…
12/24/…
12/23/…
3.50 mg\l
12/22/…
4.00 mg\l
12/21/…
12/20/…
12/19/…
12/18/…
12/17/…
12/16/…
12/15/…
12/14/…
12/13/…
12/12/…
12/11/…
12/10/…
12/09/…
12/08/…
12/07/…
12/06/…
12/05/…
Bench-Scale Treatability Study
Nitrification Study
5.00 mg\l
4.50 mg\l
Test 3
3.00 mg\l
2.50 mg\l
2.00 mg\l
1.50 mg\l
Test 1
0.50 mg\l
Wastewater Plant Case Studies
Carbon Black Plant
 Rendering Plant
 Beef Processing Plant
 Poultry Processing Plant

Wastewater Plant Case Studies
Carbon Black Plant
Carbon Black Plant
(Case Study)


Wastewater Toxicity Reduction to Re-Establish
Competent Nitrification
Overview –



The facility is located in Bay Town, TX and utilizes
carbon bottoms to manufacture Carbon Black
New wastewater discharge criteria pertaining to the
Chocolate Bayou brought effluent discharge limits down
to 10 ppm of ammonia-nitrogen
Currently the wastewater plant was discharging
ammonia-nitrogen at a concentration greater than 50
ppm
Wastewater Facility Layout
Pond#1
1.8 MG
Influent
Pond#2
1.4 MG
Borrow Pit
w/ Aeration
4.8 MG
Effluent
Chocolate
Bayou
Problems To Overcome

High Waste Stream Cyanide (>30 mg/l)

pH was too low in Ponds #1 & #2 resulting in toxic
cyanide conditions

There was no clarifier to maintain mixed liquor at a
high enough biomass level to maintain competent
nitrification
How Was This Wastewater
System Fixed?
1)
The pH was brought in Ponds #1 & #2 utilizing
calcium hydroxide and sodium hydroxide (pH
brought up to 8.1)
2)
Ferric Chloride was utilized to convert the cyanide
to thiocyanate.
3)
A blend of yeast extract, dry corn steep, sucrose
and biotin were fed into Ponds #1 & #2 to provide
the indigenous bacteria population with additional
vitamins, biological co-factors, growth factors and
co-substrates
How Was This Wastewater
System Fixed?
4)
A batch fed enriched reactor was employed to
grow significant quantities or nitrifying bacteria
that were then fed continuously into the Borrow
Pit
5)
Additional aeration & mixing was added to the
Borrow Pit to allow for adequate oxygen levels to
maintain competent nitrification.
Wastewater Plant Case Studies
Rendering Facility Wastewater Plant
Rendering Facility
Periodic Loss Of Nitrification
Sample: A Rendering Facility with periodic loss of nitrification
due to waste stream toxicity.
Overview:
 A poultry rendering plant was experiencing periodic
losses of nitrification in its wastewater treatment system.
 Rendering Plant often produce high loading of ammonianitrogen to their nitrification treatment system
 During the summer months ammonia-nitrogen can
exceed 1000 mg/l in the influent of the oxidation ditch
Rendering Facility (Continued)
 Periodic break-throughs of effluent NH3-N were taking
place
 A review of wastewater plant operating data revealed
that the loss of nitrification took place during periods
when the oxidation ditch's free chlorine tested out higher
than normal (Normal 0.0 mg/l to 0.2 mg/l)
 MSDS were reviewed from the boiler treatment, cooling
towers, air scrubbers and truck-wash
 During the review process a new chemical being used in
the truck washing area was identified as “Aluma-Bright”
and it contained hydro-flouric acid. This chemical is very
toxic to nitrifying bacteria and needed to be investigated.
Wastewater Treatment Plant
Diagram
Anaerobic
Lagoon
5.8 MG
Oxidation Ditch
2.4 MG
Internal Clarifier
Problems to Overcome
 Ammonia-nitrogen flirting with exceeding the effluent
permit values
 Unknown toxicant coming to the wastewater treatment
plant that is only partially explained by the discovery of
the hydro-flouric acid found in “Aluma-Brite” and the
concurrence of high effluent NH3-N when the
measurement of free chlorine was above 0.2 mg/l.
 After exhausting other leads and focusing on oxidizing
compounds, the chlorine dioxide generator system
focused on that may be the culprit
Problems to Overcome (continued)
 It was determined that the process was using significant
amounts of sodium hypochlorite and that the pH control
of the Chlorine Dioxide fluctuated to excess. This
needed to be examined.
 [During Chlorine Dioxide generation variation in the
targeted pH of 7.2 results in the formation of chlorite &
chlorate instead of the harmless compound chloride]
 Additional wastewater testing revealed that indeed
chlorite & chlorate were “breaking through” all the way to
O2 ditch.
How Was This Situation Rectified
1) Closer examination revealed that the “Aluma-Brite” was
utilized off-site at a truck wash and it was unlikely that
hydro-flouric acid was reaching the wastewater plant at
any significant concentration. A HPLC test performed on
several composite samples verified this information
2) During the generation of chlorine dioxide, the fluctuations
in waste stream pH resulted in chlorite & chlorate
generation that somehow passed through the anaerobic
lagoon.
How Was This Situation Rectified
(continued)
3) A Standard Operating Procedure was developed that both
addressed periodic losses of Sodium Hypochlorite and
the generation of chlorite/ chlorate. Utilizing an ORP
(Oxidation/ Reduction probe) a blend of Sodium Meta Bisulfite/thiosulfate and a proprietary reducing compound
complexed with a biochemical with an affinity for chlorite/
chlorate.
4) In addition to the reduced sulfur chlorite/chlorate
mitigating formulation, a mineral micro-carrier with a
strong cation exchange for ammonia-nitrogen was fed to
the oxidation ditch to enhance wastewater nitrification.
Introduce
Reducing
Chem
HydroCarrier-EN
@ 400 lbs/day
Capture of
Hydrocarrier/Biomass
Oxidation Ditch
Clarifier
Hydrocarrier @
10% MLVSS
Return of Hydrocarrier/Biomass
Standard Operating Procedure –
Poultry Rendering Plant
Wastewater Biomass Protection
Following A Chlorine Release
Standard Operating Procedure –
Poultry Rendering Plant
Immediate Response Actions
 Notify the wastewater operator on duty of the
chlorine spill or release. Inform the
wastewater operator of the approximate
volume lost, the waste stream the chlorine
was introduced into and the form of chlorine
spilled or released (10% sodium hypochlorite or chlorine dioxide generated
oxidant).
Standard Operating Procedure –
Poultry Rendering Plant
The wastewater operator will then shut off the
appropriate pump to isolate the chlorine
Standard Operating Procedure –
Poultry Rendering Plant


Corrective Response
In situations where chlorine is spilled or released,
1.38 pounds of reducing chemical should be
introduced for each gallon of 10% sodium hypochlorite solution spilled or released and 1.5 pounds
of Reducing chemical should be introduced for
each gallon of chlorine dioxide generated oxidant
released.
Standard Operating Procedure –
Poultry Rendering Plant
Monitoring Corrective Response

A) Oxidation Reduction Potential (ORP) of each
sewer will be utilized to monitor the oxidation state
of each waste stream as a means of tracking the
potential chlorine content.
Standard Operating Procedure –
Poultry Rendering Plant

B) ORP measurements should be taken from the
wastewater holding tank(s). ORP readings of + 50
mv or greater will need to be treated with an
additional amount of Reducing chemical
(introduced in 50 pound increments) until the ORP
is reduced below –100 mv.
Standard Operating Procedure –
Poultry Rendering Plant

C) In the Condensate Stream, ORP testing should
be performed in the EQ Pond after a spill of 10%
sodium hypochlorite solution or a release of
chlorine dioxide generated oxidant. After a
benchmark ORP reading, the surface aerators
should be turned on in the EQ Pond. Surface
aerators can be turned off when air borne chlorine
starts to diminish.
Wastewater Plant Case Studies
Beef Processing Wastewater Plant
Beef Processing Plant
Beef Processing Plant: Catastrophic Loss Of Nitrification Due To
Anaerobic Waste Stream Toxicity
Overview:
 A beef processing plant/rendering facility experienced a
near complete loss of nitrification
 Ammonia-Nitrogen rose in the final effluent to a point just
below loading coming into the nitrification portion of the
wastewater plant.
 A review of MSDS’s changes in the sanitation vendors and
wastewater plant operation data did not reveal any
abnormalities
Beef Processing Plant (Continued)
 Hydro Solutions was brought on-site to investigate the
causative factors behind this significant loss of nitrification
 Bench-Scale Nitrification Toxicity Tests revealed significant
nitrification toxicity/inhibition emanating from the
anaerobic effluent
 Wastewater samples from the anaerobic lagoon’s revealed
high volatile fatty acids, elevated long chain fatty acids,
significant concentrations of quaternary ammonium
compounds (>30 mg/l) and low BOD removal efficiency
(less than 60% removal as compound to the anaerobic
influent BOD)
Wastewater Treatment
Plant Diagram
Influent
1.0 MG
1.0 MG
Anaerobic Lagoon
1.0 MG
Anoxic
Treatment
0.8 MG
Clarifier
1.0 MG
Aeration
Basins
1.0 MG
1.0 MG
Clarifier
Effluent
Problems to Overcome
 High effluent NH3-N due to toxicity/inhibition
emanating from anaerobic treatment instability.
 High concentrations of Long Chain Fatty Acids in
Anaerobic Effluent
 Significant concentration of Quaternary Ammonium
Compounds coming to anaerobic treatment and then
passed through to the nitrification process (>30 mg/l)
 Deficient concentrations of essential trace elements
Co, Ni, Mo & Mn.
How Was This Wastewater
System Fixed?
1) A Quaternary Ammonium Compound
detoxification agent, NeutraQuatTM was fed to
the anaerobic treatment system which led to a
20 mg/l drop in quat concentrations in both the
anaerobic influent and effluent.
2) A specific essential trace metal formula (for this
particular waste stream) was introduced on a
continuous basis (trace metal concentrations of
Co, Ni, Mo and Mn were all brought up to
adequate levels.)
Listing of Chemical Toxicity
Concentration Levels
Anaerobic Digester Toxicity Concentration
 Levels Toxicity of Different Compounds to
Nitrification

Wastewater Plant Case Studies
Poultry Processing Wastewater Plant
Overview
Poultry
Processing
Plant
Over
View
of Waste
Water Tools.
 Total loss of nitrification ultimately leading to break
point chlorination
 Flow – 1.3 MGD NH3-N Loading – 160-200 mg/l
 SBR – Aeration Basin - Clarifier
 Effluent NH3-N eventually rose well above 100 mg/l
 D.O. above 3.0 mg/l – pH 7.1 to 7.4 MLSS 3800
mg/l in SBR and 3200 mg/l in Aeration Basin

Overview



Reviewed MSDS from Sanitation, Boilers, Air
Scrubbers and Production – checked out O.K.
Finally found that EDTA was being utilized at a
rate of 50 gallon per day
Formalized a plan of action to reduce the impact
of the EDTA already in the wastewater system,
discontinue EDTA usage, utilize a mineral based
micro-carrier with a high cation exchange
capacity for ammonium and haul in RAS form a
local rendering plant
Waste Water Case Study
Poultry Processing Wastewater Plant
EDTA INHIBITION
SBR
CMAS
Clarifier
How Was This Wastewater
System Fixed?
1) Calcium Hydroxide and copper sulfide were fed into
the wastewater system to blind out the EDTA and
supply bioavailable copper for nitrification
2) A specific mineral based micro-carrier with a high
cation exchange capacity for ammonium was fed
into the wastewater system at 15% of the total solids
in the wastewater system until the system was
achieving full nitrification for two months.
3) RAS from a local rendering facility was fed to the
WWTP.
4) Nitrification recovered within 10 days after the above
changes were began.
NH3-N Trend Poultry Plant
SBR vs. Aeration Basin Ammonia
SBR NH3-N mg/L
A.B. NH3-N
150
140
130
120
110
100
90
80
70
60
50
40
30
20
10
0
29- 1- 2- 3- 4- 5- 6- 7- 8- 9- 10- 11- 12- 13- 14- 15- 16- 17- 18- 19- 20- 21- 22- 23- 24- 25- 26- 27- 28- 29- 30- 31- 1- 2- 3- 4- 5- 6- 7- 8- 9- 10- 11- 12- 13- 14- 15Feb Mar Mar Mar Mar Mar Mar Mar Mar Mar Mar Mar Mar Mar Mar Mar Mar Mar Mar Mar Mar Mar Mar Mar Mar Mar Mar Mar Mar Mar Mar Mar Apr Apr Apr Apr Apr Apr Apr Apr Apr Apr Apr Apr Apr Apr Apr
SBR NH3-N mg/L 22 41 49 67 57 57 61 85 136 106 107 102 92 95 75 58 44 44 45 42 46 53 45 55 53 56 57 39 35 24 9 15 19 39 52 50 65 58 61 45 32 25 20 2 2 12 5
A.B. NH3-N
33 30 31 35 40 45 46 50 63 78 89 86 90 91 86 81 70 61 54 46 46 47 41 45 45 44 46 43 36 20 11 7 13 20 25 35 40 32 23 13 13 7.5 5 1.5 0.4 1.1 9.7
Anaerobic Toxicity
Concentration Levels
TABLE 9
PUBLISHED CONCENTRATION LEVELS OF SELECTED ORGANIC CHEMICALS
IMPACTING ANAEROBIC SLUDGE DIGESTION PERFORMANCE
Concentration of Organic Chemical In digester – milligrams per liter
Unacclimated System
Organic Chemical
Acetaldehyde
Acetic acid
Acetone
Adipic acid
Acrolein
Acrylic acid
Acrylontrile
Allyl alcohol
NOTE: Inhibition level
decreases with increasing
volatile acid concentration
1-amino, 2 propanol
4-Amminobutynic acid
Aniline
First Notice
Reduction In Activity
0 – 2 (29)
4,000+ (29)
4,000+ (29)
1,000+ (30)
4,000+ (29)
5 – 10 (29)
5 – 10 (30)
5 – 10 (29)
5 – 10 (29)
<10 (30)
<100 (30)
125 – 150 (29)
4,000+ (29)
40 – 50 (29)
Fifty Percent
Reduction In Activity
350 -400 (29)
10 – 15 (29)
20 – 50 (29)
800 – 900 (29)
150 – 200 (29)
90 – 100 (30)
1,000+ (30)
2,400 – 2,500 (29)
Mignone, Nicholas A., Biological Inhibition / Toxicity Control In Municipal Anaerobic Digestion Facilities
Acclimated System
First Notice
Reduction In Activity
Anaerobic Toxicity
Concentration Levels
PUBLISHED CONCENTRATION LEVELS OF SELECTED ORGANIC CHEMICALS
IMPACTING ANAEROBIC SLUDGE DIGESTION PERFORMANCE
Concentration of Organic Chemical In digester – milligrams per liter
Unacclimated System
Organic Chemical
Benzoic acid
1-Butanol
sec-Butanol
tert-Butanol
sec-Butylamine
Butyraldehyde
Butyric acid
First Notice
Reduction In Activity
225 -250 (29)
4,000+ (29)
1,000+ (30)
4,000+ (29)
<100 (30)
4,000+ (29)
<100 (30)
4,000+ (29)
100 – 200 (29)
4,000+ (29)
Crotonic acid
1,000 – 1,200 (29)
15 – 25 (29)
Trace (30)
30 – 40 (29)
Trace (29)
200 – 300 (29)
5 – 10 (29)
<5 (30)
4,000+ (29)
Dextrpse
Diethylamine
Diethylene glycol
N,N-dimethylaniline
Dodecane
1,000+ (30)
40 -50 (30)
<10 (30)
1,000+ (30)
1,000+ (30)
Catechol
3-Chairo-1,2-propandiol
Chloroform
1-Chloropropane
1-Chloropropene
2-Chloropropionic acid
Crotonaldehyde
Fifty Percent
Reduction In Activity
Acclimated System
First Notice
Reduction In Activity
1,000+ (30)
1,000+ (30)
2,800 – 3,000 (29)
2,500 – 2,600 (29)
600 – 660 (29)
125 – 150 (29)
5 – 10 (29)
700 – 800 (29)
400 – 450 (29)
50 – 100 (30)
300 – 500 (30)
1,000+ (30)
Mignone, Nicholas A., Biological Inhibition / Toxicity Control In Municipal Anaerobic Digestion Facilities
180 – 200 (30)
Anaerobic Toxicity (continued)
Concentration Levels
PUBLISHED CONCENTRATION LEVELS OF SELECTED ORGANIC CHEMICALS
IMPACTING ANAEROBIC SLUDGE DIGESTION PERFORMANCE
Concentration of Organic Chemical In digester – milligrams per liter
Unacclimated System
Organic Chemical
Ethyl
acetate
Ethyl acrylate
Ethyl benzene
2-Ethyl-1-hexanol
Ethylene diamine
Ethylene dichloride
Ethylene glycol
First Notice
Reduction In Activity
4,000+ (29)
1,000+ (30)
300 – 350 (29)
<10 (30)
40 – 50 (29)
1,000+ (30)
1,000+ (30)
15 -20 (30)
150 200 (30)
900+ (30)
Formic acid
Fumaric acid
5 – 10 (29)
<10 (30)
2,000 – 2,300 (29)
1,000 – 1,200 (29)
Glutaric acid
Glycerol
80 – 100 (29)
4,000+ (29)
Hexanoic acid
Hydroquinone
550 – 600 (29)
400 – 500 (20)
Formaldehyde
Fifty Percent
Reduction In Activity
1,200 – 1,300 (29)
300 – 500 (30)
300 -325 (29)
100 -200 (30)
50 – 60 (29)
50 – 100 (30)
Mignone, Nicholas A., Biological Inhibition / Toxicity Control In Municipal Anaerobic Digestion Facilities
Acclimated System
First Notice
Reduction In Activity
15 -20 (30)
Anaerobic Toxicity (continued)
Concentration Levels
PUBLISHED CONCENTRATION LEVELS OF SELECTED ORGANIC CHEMICALS
IMPACTING ANAEROBIC SLUDGE DIGESTION PERFORMANCE
Concentration of Organic Chemical In digester – milligrams per liter
Unacclimated System
Organic Chemical
First Notice
Reduction In Activity
Fifty Percent
Reduction In Activity
Kerosene
<50 (30)
500+ (30)
Lauric acid
40 – 50 (20)
200 – 225 (29)
Maleic acid
Methanol
Methyl acetate
Methyl ethyl ketone
Methyl isobutyl keytone
2-Methyl-5-ethyl pyridine
200 – 300 (29)
900 – 1,000 (29)
4,000 (29)
4,000+ (29)
<10 (30)
<50 (30)
Nitrobenzene
Trace (29)
Phenol
40 – 50 (29)
<50 (30)
4,000 (29)
500 – 600 (29)
100 – 150 (29)
4,000+ (29)
700 – 800 (29)
4,000+ (29)
Phthalic acid
Propanal
Propanol
2-Propanol
Propionic acid
Propylene glycol
Acclimated System
First Notice
Reduction In Activity
4,000 (29)
100 – 150 (30)
90 – 100 (30)
2,400 – 2,500 (29)
Mignone, Nicholas A., Biological Inhibition / Toxicity Control In Municipal Anaerobic Digestion Facilities
<50 (30)
Anaerobic Toxicity (continued)
Concentration Levels
PUBLISHED CONCENTRATION LEVELS OF SELECTED ORGANIC CHEMICALS
IMPACTING ANAEROBIC SLUDGE DIGESTION PERFORMANCE
Concentration Of Organic Chemical In Digester – milligrams per liter
Nonacclimated System
Organic Chemical
First Notice
Reduction In Activity
Fifty Percent
Reduction In Activity
Resorcinol
500 – 600 (29)
3,000 – 3,200 (29)
Sodium acrylate
Sodium benzoate
Sorbic acid
Succinic acid
<50 (30)
260 -300 (30)
4,000+ (29)
4,000+ (29)
500+ (30)
Tetralin
1,000+ (30)
Valeric acid
Vinyl acetate
4,000+ (29)
300 – 350 (30)
Acclimated System
First Notice
Reduction In Activity
50 (30)
900 – 1,000 (30)
Source: USEPA, Identification and Control of Petrochemical Pollutants Inhibitory to Anaerobic Processes, USEPA Washington D.C.
20460, EPA-R2-73-194 (1973).
Mignone, Nicholas A., Biological Inhibition / Toxicity Control In Municipal Anaerobic Digestion Facilities
Toxicity of Different Compounds
to Nitrification
Toxicity of Different Compounds
to Nitrification
Toxicity of Different Compounds
to Nitrification
Toxicity of Different Compounds
to Nitrification
Toxicity of Different Compounds
to Nitrification
Toxicity of Different Compounds
to Nitrification
Toxicity of Different Compounds
to Nitrification
Toxicity of Different Compounds
to Nitrification
Toxicity of Different Compounds
to Nitrification
Toxicity of Different Compounds
to Nitrification
Toxicity of Different Compounds
to Nitrification
Toxicity of Different Compounds
to Nitrification
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