EPA CERI-89-243
States
imental Protection
Center for Environmental
Research Information
Cincinnati OH 45268
ilogy Transfer
CERI-89-243
beminars—
Wastewater Treatment
Plant Toxicity Evaluation,
Reduction and Control
Presentations - Volume I
November 16-17, 1989
Cincinnati, OH
December 7-8,1989
Chicago, IL
January 18-19, 1990
San Francisco, CA
March 1-2, 1990
Jacksonville, FL
March 15-16, 1990
Dallas, TX
May 24-25, 1990
Boston, MA
June 7-8, 1990
Charlotte, NC
June 21-22, 1990
Trenton, NJ
July 19-20, 1990
Baltimore, MD
-------
VOLUME I
U.S. ENVIRONMENTAL PROTECTION AGENCY
SEMINAR ON WASTEWATER TREATMENT
PLANT TOXICITY EVALUATION,
REDUCTION AND CONTROL
November, 1989
-------
VOLUME I
TABLE OF CONTENTS
Water Quality Based Control of Toxics in NPPES Permits 1
John Cannell, USEPA
SESSION 1 - TOXICITY REDUCTION
Toxicity Identification Evaluations
Phase I - Toxicity Characterization Procedures ....
Phase II - Toxicity Identification Procedures
Phase III - Toxicity Confirmation Procedures
Facilities, Equipment, and Laboratory Requirements
Donald Mount, USEPA
-1
-3
-15
-25
-39
TRE Industrial Protocol - Case Examples 1-48
Metal Finishing Industry 1-51
Government Arsenal 1-57
Chemical Industry Treatment Facility 1-60
Multipurpose Spcialty Chemical Plant 1-66
William Clement and G. Mick DeGraeve, Battelle
TRE Municipal Protocol - Case Examples 1-70
Patapsco Waste Water Treatment Plant 1-87
Mount Airy, North Carolina 1-105
Falling Creek Wastewater Treatment Plant 1-108
Fred Bishof, USEPA and John Botts, Engineering Science and Richard Dobbs, USEPA
Trealability Database 1-124
Glen Shaul, USEPA, Richard Osantowski and Stephanie Hansen, Radian Corp.
SESSION II - SPECIFIC TOXICANTS CONTROL
Categorical Pretreatment and Local Limits II-l
Steve Bugbee, John Cannell, and Claudia O'Brien, USEPA
Toxicily Reduction in Industrial Effluents 11-17
"Metals Distributions in Activated Sludge Systems"
from the Journal Pollution Control Federation 11-39
James W. Patterson, Patterson & Schafer
-------
WATER QUALITY BASED CONTROL OF TOXICS IN NPPES PERMITS
John Cannell, USEPA
-1-
-------
Water Quality Based Control of Toxics in NPPES Permits
John Cannell
I. Recent Developments
II. Revisions to TSD
A Surface Water Toxics Control Program
Activities Conducted Under 304(1)
B. Individual Control Strategies
III. 304(1) Changes to 40 CFR 122.44
A. Section 122.44(d)(l)(i)
B. Section 122.44(d)(l)(ii)
C. Section 122.44(d)(l)(iii)
D. Section 122.44(d)(l)(iv)
E. Section 122.44(d)(l)(v)
F. Section 122.44(d)(l)(vi)
-2-
-------
RECENT DEVELOPMENTS
WATER QUALITY ACT OP 1987
- SLUDGE
- STORMWATER
- 304(L)
COMBINED SEWER OVERFLOWS
REVISIONS TO THE TSD
DOMESTIC SEWAGE STUDY REGULATIONS
REVISIONS TO THE TSD
SCHEDULE:
• REGIONAL REVIEW (END 10/10/89)
• W1LL1AMSBURG GROUP REVIEW
-States -Interest Groups
-Industry -Environmental Groups
•FEDERAL REGISTER ANNOUNCEMENT
• BLUE RIBBON PANEL REVIEW
• FINAL DOCUMENT
FINAL DOCUMENT AVAILABLE SUMMER '9O
-3-
-------
REVISIONS TO THE TSD
MAJOR CHANGES:
CHAPTER 1: New documentation
Correlations
CHAPTER 2: Acceptable ambient concentrations
Legal basis fox AACs
CHAPTER 3: Streamlined procedures
Screening
Bioconcentration
REVISIONS TO THE TSD
MAJOR CHANGES:
CHAPTER 4: Mixing Zones
Bioconcentration
CHAPTER 5: More user-friendly!
CHAPTER 6: Permitting and Enforcement
Principles
-4-
-------
Surface Water Toxics Control Program
Activities Conducted Under §304(1)
in
I
Develop
technics!
agreements
WQA
EPA
Guktance
on §304(1)
I
Develop
h M-^.1——.—
loniiiinoP
Hstsof
(A) (I)
(A) (II)
(B)
Report instate
830S(b) Report
Submit final
lists of
sources,
andlCS's
Develop WWer
Quality Assessment
Plan (as necessary)
Develop controls under
Ming CWA authorities for
(A) 0) and (AMU) i
EPA develops
HstsorlCS's
§3040) 0)(D)
controls In
ojuaMty
^^^h^^^A^h^^A^ BMk^^
sianoBras mei
Opportunity for State
to correct
deficient submtttal
-------
Interrelationship of Waters Listed Under
Section 304(1) of the Clean Water Act
MINI LIST
(AMI):
Control actions
include use of
all existing
CWA
authorities for
toxic pollutants.
LONG LIST
Control actions
include use of
all existing
CWA
authorities for
all pollutants
and all waters.
SHORT LIST
(B):
Control actions
require
Individual
Control
Strategies.
-6-
-------
304(1)
"LONG LIST1
- 17.576 waters listed
- Range 0 to 1745, average 304
- Most east of Mississippi River
"MINI LIST'
- Few waters listed
"SHORT LIST"
- 595 waters listed
304(1)
"C LIST'
• 879 POINT SOURCES
° 625 INDUSTRIALS
- 134 METAL FINISHING
- 94 PULP ft PAPER
- 55 NATURAL GAS
- 22 ORGANIC CHEMICAL
- 21 PETROLEUM REFINING
0 24O MUNICIPALS
0 14 FEDERAL FACILITIES
• ICSs REQUIRED
Individual Control Strategies
• All known water quality problem waters impaired by
§307(a) toxics due entirery/substantjalfy to point source
discharges require an ICS (Short List)
• An ICS is a NPDES permtt plus documentatfon OB.,
TMDLs/WLAs and other rationale)
• An K:S is to produce a reduction in the dtecharge of
§307(a) tacic pollutants and achieve State WQ standards
within 3 years
• Effluent toxicants, ammonia, and chlorine must also be
controlled by permits under other CWA authorities
-7-
-------
3O4(l) Changes to 40 CFR 122.44
SUBSECTION (d) - WATER QUALITY
STANDARDS AND STATE REQUIREMENTS
- WATER QUALITY-BASED PERMIT LIMITS
FOR SPECIFIC TOXICANTS
- WHOLE EFFLUENT TOXICITY LIMITS
WHERE NECESSARY TO ACHIEVE Jk
STATE WATER QUALITY STANDARDS Jfi
Section 122.44(d)(l)(i)
ALL POLLUTANTS THAT CAUSE.
HAVE THE REASONABLE POTENTIAL
TO CAUSE OR CONTRB3UTE TO AN
EXCURSION ABOVE A WATER QUALITY
STANDARD MUST BE CONTROLLED
- Includes narrative and numerical
criteria
- Reflects EPA's approach to water
quality-based permitting
Section 122.44(d)(l)(ii)
STATES MUST USE VALID PROCEDURES
TO DETERMINE WHETHER A DISCHARGE
CAUSES. HAS THE REASONABLE
POTENTIAL TO CAUSE. OR CONTRIBUTES
TO AN EXCURSION
ACCOUNT FOR:
00
bfflt
- variability
- species sensitivity
- dilution (where allowed)
-8-
-------
Section 122.44(dKD(iii)
NPDES PERMITS MUST INCLUDE
EFFLUENT LIMITATIONS FOR EVERT
POLLUTANT THAT CAUSES, HAS THE
REASONABLE POTENTIAL TO CAUSE
OR CONTRIBUTES TO AN EXCURSION
ABOVE A NUMERIC WATER QUALITY
CRITERION
Section 122.44(d)(l)(iv)
NPDES PERMITS MUST INCLUDE WHOLE
EFFLUENT TOXICITY LIMITATIONS
WHEN A DISCHARGE CAUSES. HAS THE
REASONABLE POTENTIAL TO CAUSE,
OR CONTRIBUTES TO AN EXCURSION
ABOVE A STATE NUMERIC CRITERION
FOR WHOLE EFFLUENT TOXICITY
Section 122.44(d)(l)(v)
WHEN A DISCHARGE CAUSES. HAS THE
REASONABLE POTENTIAL TO CAUSE.
OR CONTRIBUTES TO AN EXCURSION
ABOVE A STATE NARRATIVE WATER
QUALITY CRITERION. THE PERMIT
MUST CONTAIN LIMITATIONS ON
WHOLE EFFLUENT TOXICITY
- unless chemical specific limitations
are demonstrated to be sufficient
to achieve all applicable water
quality standards
-9-
-------
Section 122.44(d)(l)(vi)
WHERE AN ACTUAL OR PROJECTED
EXCURSION ABOVE A WATER QUALITY
CRITERION 18 ATTRIBUTABLE TO A
PARTICULAR POLLUTANT FOR WHICH
THE STATE HAS NOT ADOPTED WATER
QUALITY CRITERION, THE PERMIT MUST
CONTAIN WATER QUALITY-BASED
EFFLUENT LIMITATIONS TO CONTROL
THE POLLUTANT OF CONCERN
Section 122.44(d)(l)(vi)
THREE OPTIONS:
(1) CALCULATE NUMERIC CRITERION
FOR THE POLLUTANT;
(2) USE EPA's WATER QUALITY
CRITERION FOR THE POLLUTANT; OR
(3) ESTABLISH EFFLUENT LIMITATIONS
ON AN INDICATOR PARAMETER
Section 122.44(d)(l)(vi)
IF AN INDICATOR PARAMETER IS USED,
FOUR PROVISIONS MUST BE MET:
(a) The permit must identify which
ponntants are intended to be controlled
by the indicator parameter;
(b) The net sheet must set forth the
basis for the limit;
(c) The permit must require monitoring
to show continued compliance with the
water quality standards; and
(d) The permit must contain a reopener
clause allowing for changes (as nwded) to
achieve water quality standards
-10-
-------
304(1) Changes to 4O CFR 122.44
SUBSECTION (d) - WATER QUALITY
STANDARDS AND STATE REQUIREMENTS
- WATER QUALITY-BASED PERMIT LIMITS
FOR SPECIFIC TOXICANTS
- WHOLE EFFLUENT TOXICITY LIMITS
WHERE NECESSARY TO ACHIEVE
STATE WATER QUALITY STANDARDS
-11-
-------
SESSION I
TOXICITY IDENTIFICATION EVALUATIONS
Donald Mount, USEPA
1-1
-------
TOXlCITY IDENTIFICATION EVALUATIONS
Donald Mount
I. Phase 1 - Tenacity Characterization Procedures
A Categories of Phase I Tests
B. Day 1
C. Day 2
D. Day 1 Sample Manipulations
E. ph Adjustment/Filtration Tests
F. ph Adjustment/Aeration Tests
G. ph Adjustment /CIS SPE Tests
H. Post C-18 Effluent
I. Oxidant Reduction Test
J. Chelation Test
II. Phase II - Tenacity Identification Procedures
A. Filter Sample
B. Compare Toxicity to Baseline Test
C. Condition Column
D. Elute Column Blanks
E. Additional Needs
HI. Phase III - Toxicity Confirmation Procedures
A. Q/C
B. Final Confirmation
C. Correlation
D. Expected Regression
E. Recovery of Toxicity
F. Other Species
G. Spiking Fractions
IV. Facilities, Equipment and Laboratory Requirements
A. Overview
B. Laboratory Apparatus and Reagents
C. Toxicity Testing and Chemical Analysis
D. Requirements for Key Analytical Procedures
E. Lab Equipment Needs for Phase I
F. Equipment Needs for Phase II
1-2
-------
PHASE I
TOXICITY CHARACTERIZATION PROCEDURES
The methods to generally
identify physical/chemical
nature of the contitutents
causing toxicity.
CATEGORIES OF PHASE I TESTS
• Baseline toxicity tests whole effluent
• pH adjustment (pH 3, pH | , pH 11)
• Aeration (pH 3, pH | , pH 11)
• Filtration (pH3, pH | , pH 11)
• C1S SPE (pH3, pH|, pHg)
• Sodium thiosulfate addition
• EDTA addition
• Gradual pH change (pH 6,7,8)
DAY 1
t Analyses on whole effluent
pH, TRC, hardness, alkalinity
conductivity, NH4*
• Initial toxicity test
• Sample manipulations for
Day 2 tests
1-3
-------
pH Meter
Hardness Titration
Conductivity Meter
Baseline Toxicity Tests
Log Book
Sample in Refrigerator
Baseline & Effluent Treatment Tests
are Started on Day 2.
Relevant Blanks are Sometimes
Difficult to Design.
1-4
-------
DAY 1 SAMPLE MANIPULATIONS
• pH adjustment only
pH 3, pH|5 pH 11
• pH adjustment/filtration
pHS.pH.pHU
• pH adjustment/aeration
pH 3, pH,, pH 11
• pH adjustment/solid phase
extraction
(C18SPE)pH3,pH|5pH9
pH ADJUSTMENT AFFECTS
• Solubility
• Polarity
• Volatility
• Stability & speciation
• Membrane permeability
1-5
-------
pH drifts differently
in various treatments,
Effect of pH on NH3 Toxicity to Daphnia
lO.Or
5.0
9.0
1-6
-------
10 Volumes Gas
* ** *•* J 1 Volume Effluent
Percent C02 needed depends on pH desired
and alkalinity of the sample.
DH ADJUSTMENT/FILTRATION TESTS
Determine toxicity related to
filterable materials at different
pH values.
1-7
-------
Vacuum Filtration
Pressure Filtration
Test of Filtered Sample and Baseline Toxicity
pH ADJUSTMENT/AERATION TESTS
Determine how much toxicity is
attributed to volatile or oxidizable
compounds
Aeration at pH 3, pHj, and pH 11
pH ADJUSTMENT/CIS SPE TEST
Determine the toxicity caused by
organic compounds and metal chelates
with non -polar characteristics
1-8
-------
Effluent
Reservoir
SPE
Column
Collection of Post SPE Effluent
Post C-18 Effluent
Sometimes has Artifactual Toxicity
Eluting SPE
Fraction Toxicity Test
1-9
-------
OXIDANT REDUCTION TEST
Determine the extent toxicity is
reduced by neutralizing toxicant(s) with
the addition of sodium thiosulfate
POSSIBLE NEUTRALIZABLE COMPOUNDS
• Chlorine
• Ozone
• Chlorine dioxide
• Mono & dichloroamines
• Bromine
• Iodine
• Manganese
• Copper
1-10
-------
Oxidant Reduction Test
CHELATION TEST
Determine the toxicity due to cationic
metals by the addition of EDTA as the
chelating agent.
DOSE RESPONSE CURVE
FOR EDTA ADDITIONS
O
CT)
.£
"55
03
0)
O
\.
Increasing EDTA
-------
EDTA CHELATION IS FUNCTION OF:
• Solution pH & temperature
• Type and speciation of metal
• Other ligands in solution
• Binding affinity of EDTA for the
metal
CATIONS TYPICALLY CHELATED BY EDTA
• Aluminum • Iron
• Barium • Lead
• Cadmium • Manganese (+2)
• Cobalt • Nickel
• Copper • Zinc
CATIONS WEAKLY CHELATED BY EDTA
• Arsenic • Barium
• Mercury • Strontium
• Silver • Calcium
• Magnesium • Thallium
1-12
-------
ANIONS NOT CHELATED BY EDTA
Selenides
Chromates
Hydrochromates
GRADUATED pH TEST
Determine whether toxicity is
influenced by the presence of
un-ionized ammonia.
1-13
-------
10.0
Dissociation of Ammonia vs. pH
5.or
10
I
i.Or
I
a>
0.5
O.I
6.0
7.0
8.0
PH
AH LCSO's from any Phase I tests
are compared to the Baseline Effluent
Toxicity Test.
1-14
-------
TOXICITY IDENTIFICATION
PROCEDURES
PHASE II
TOXICITY IDENTIFICATION PROCEDURES
Methods to specifically identify
suspect chemicals in the
toxic samples.
PHASE II TOXICITY IDENTIFICATION
GROUP
Non-polar organics
Cationic metals
Volatiles
Polar Organics
Ammonia
Cyanide/Sulfide
Anionic metals
APPROACH
SPE, HPLC, GC/MS, MS-MS
Atomic Absorption
?
?
Symptoms, pH adjustment
equftoxic and zeolite column
?
Atomic Absorption
1-15
-------
• Filter Sample
• Compare Toxicity
to Baseline Test
Pressure Filter
Test of Filtered Effluent Toxicity
• Condition Column
• Elute Column
Blanks
Conditioning Column
Testing Blanks
1-16
-------
Condition Column Again
STEP 1
1000 mL
Effluent
Concentration Factor
1X
6 mL high capacity
C18 SPE column
Test Post C18
1X
Figure 2-2. Step 1 for concentrating the whole effluent
chemicals on the C18 SPE column.
Collect Post Column Effluent
1-17
-------
STEP 2
6 ml high capacity
C18 SPE column
Concentration Factor
333X
Each
Conduct Toxicity Test on Each
(150/iL in 10mL water)
5X
Figure 2-3. Procedures for eluting the column with a
gradient of methanol/water solutions.
Eluting Fractions
Testing Fractions
1-18
-------
STEPS
Concentration Factor
Dilute Toxic Fractfon(s) 1:10 33X
i
Sorb on 1 ml C18 SPE Column
(discard post-CIS)
]
Dry C18 Column with Nitrogen
(optional)
Bute Column with 3-100//L volumes
of 100% Methanol
Collect Eluate Concentrate 10.000X
Conduct Toxicity Test 5X
(10/i Lin 20 ml water)
Figure 2-4 . Procedure for combining and concentrating
toxic fractions . Concentration factors
are approximate based on 2 L of effluent
and a 6 mL combined eluate for each
methanol/water gradient .
Concentrating Fractions
Concentrate Toxicity Test
1-19
-------
STEP 4
Concentration Factor
Inject 100/d. of the Concentrate 10.000X
on the HPLC C18 Column
T
Collect 25-1 ml HPLC 1.000X
Fractions
T
Conduct Toxicity Test on Each 15X
in 10mL water)
Figure 2-5. Procedure to fractionate
concentrate on the HPLC.
HPLC
HPLC Fraction Test
1-20
-------
STEPS
Concentration Facto'
Dilate Fraction(s) 1:10 100X
Extract on 1 ml_ C18 SPE Column
(dscard post-CIS;
Dry C18 SPE Column with Nitrogen (Optional)
I
Elate Column with 3-100/fL
Volumes of 100% Methanol
Collect Eluate Concentrate 5.000X
Conduct Toxicity Test 1 0X
(20/iL in 10 mL water)
Analyze Concentrate on 5 OOOX
GC/MS
Figure 2-6. Procedure to concentrate toxic HPLC
fractions (combined or individually).
Volume of eluate should be measured.
Concentrating Column
Testing Concentrate
1-21
-------
Total Ion Chromatograms of aPOTW Effluent
100 V.,
TOT
ice %r
TOT
'000 1200 ,400
60% Fraction
600
100 V.
TOT
'000 1200 WOO
80% Fraction *\\
600§00
1000
1200
1400
Compare Concentrations
with Toxicity Values
1-22
-------
Additional Needs
Synthesize Compounds
Refractionate on HPLC
More Concentration
Other Analytical Methods
Making Equitoxic Concentrations of Ammonia
PH
6.5
7.0
7.5
8.0
% Un-ionized
(NH3)
0.18
0.566
1.77
5.38
LC50 NH3
0.4
0.9
2.0
4.0
Dilution
0
71%
51%
33%
1-23
-------
Toxicity to Red Algae of Ammonia and Effluent
I20r
6 Effluent Dilution
o NH4CI
-0 12345
% EFFLUENT (or 70 mg/l ammonia)
Relationship of NH3 LC50 to Test pH.
|
8
I.
c
fc
C8
.1
c
D
7.00
7.50
8.00
8.50
9.00
Measured pH Values
1-24
-------
PHASE III
TOXICITY CONFIRMATION PROCEDURES
A series of steps that are
used to assist in confirming
the suspect toxicant(s).
Rigid Q/C Should be Employed
in Phase
The Amount of Confirmatory Data Needed
Depends on the Regulatory Decision.
FINAL CONFIRMATION
1. Toxicity vs. Concentration Correlation
2. Symptoms
3. Spiking Effluent
4. Toxicity Mass Balance
5. Other Species
6. Spiking Fractions
7. Misc.
PH
Hardness
Tissue Uptake
1-25
-------
Correlation
TOXIC UNIT = TU
EFFLUENT TU
= 100%
LC50
= 100
35
= 2.86
CHEMICAL TU
= [Concl
LC50
= 2.05 ug/J
0.70
= 2.93
r2=0.15
SLOPE=1.38*O.73
Y-INTERCEPT= 1.24*1.05
2 4 6 8 10
TOXIC UNITS OF SUSPECT TOXICANTS
1-26
-------
Expected Regression
Slope = 1
Intercept = O
"High" r2
What is "High" r2 ?
Depends on Decision
60
UJ
it40
UJ
= 20
O
X
O
R 2 =0.999
Slope«1.114
Y - lntercept= - 0.26
20 40
TOXIC UNITS OF TOXICANTS
60
1-27
-------
Positive Intercept may be caused
by unidentified toxicants.
4
6
I-
UJ
_i
u.
u.
IU
Ul
O
X
u.
O
E 2
z
O
X
o
r2=0.63
SLOPE=1.05t0.27
Y-INTERCEPT=0.19±0.57
2 4
TOXIC UNITS OF SUSPECT TOXICANTS
6
Are there Matrix Effects?
1-28
-------
RECOVERY OF TOXICITY
LC50 (Whole)
Sample Dilution Medium Effluent
Effluent Lab Water 17.2
75,80 & 85 Lab Water 16.5
Fraction
75, 80 & 85 Eft. After C-18 16.5
Fraction
CONCERNS:
1. Column doesn't remove all
2. Not all is in toxic fractions
3. Some stays on column
4. Matrix effects
Are the Toxicants Additive?
1-29
-------
Interaction of Pesticide Mixtures
08 \-
06 h
0 4 [-
02
WHOLE EFFLUENT CONCENTRATIONS OF SUSPECTED TOXICANTS (ug/l)
SAMPLE
10/6-1
10/6-11
10/6-111
10/30-1
12/3-1
12/3-11
1/12-1
1/13-1
2/3-1
2/3-11
3/3-1
3/3-11
3/23-1
3/23-11
4/28-1
4/28-11
5/17-1
5/17-11
DIAZINON
CONC.
0.06
0.22
0.23
0.17
0.25
0.60
0.43
0.43
0.24
0.19
0.30
0.28
0.17
0.36
0.57
0.21
0.14
0.59
CVP
CONC.
0.07
0.09
0.05
0.14
0.22
0.18
0.08
0.08
0.08
0.10
0.16
0.23
0.17
0.16
0.24
0.19
0.23
0.23
1-30
-------
Symptoms
Beaker of Daphnids
Spiking Effluents
Doubling concentration should
double toxicity (halve
Mass Balance
1-31
-------
LC VALUES OF TOXIC FRACTIONS
50
LC50 LC50
FRACTION ^1) (%EFF.) IU
75 12.3 61.5 1.63
80 15.2 76.0 1.32
85 28.3 142.0 0.70
PREDICTED TU 3.65 SUMTU: 3.65
MEASURED TU 2.86
Fractionation 'Mass Balance' of 2/23
SAMPLE LC50
2 ml - 75% 48% 2.1
200 \i\ • 75 (Cone) <62% >1 .6
HPLC Fraction #9 55% 1.8
HPLC Fraction #10 85% 0.29
Concentration Steps:
1. 3 ml Column 500 ml --•> 2 ml
2. 1 ml Column 2 ml - - -> 0.2 ml
3. HPLC 20 |il - - -> 16 1 ml Fractions
4. 1 ml Column 1 ml — > 0.2 ml
1-32
-------
WHOLE EFFLUENT AND SEPAK FRACTION COMBINATION
CERIODAPHNIA 48h LCsos(%)
WHOLE
EFFLUENT
ALL
FRACTIONS
TOXIC
FRACTIONS
NON TOXIC
FRACTIONS
12/3-1
12/3-11
1/12-1
1/13-1
2/3-1
2/3-11
3/3-1
3/3-11
3/23-1
3/23-11
4/28-1
4/28-11
5/17-1
5/17-11
3/23-1
3/23-H
85
36
50
52
>100
50
>100
75
27
35
44
61
44
44
81
84
61
36
34
35
87
61
94
66
33
35
58
50
49
60
60
75
70
43
32
40
•100
57
•too
88
35
41
61
61
50
63
81
100
»100
•10O
MOO
•100
•100
•100
•100
•100
71
•100
•100
•100
•100
•100
•100
•1OO
Other Species
LC50s FOR FATHEAD MINNOWS AND CERIODAPHNIA DUBIA
EXPOSED TO WHOLE EFFLUENT SAMPLES
FATHEAD MINNOW CERIODAPHNIA
SAMPLE 96h LC50(X) 48h LC50(%)
10/6-1
10/6-11
10/6-111
10/30-1
12/3-1
12/3-11
2/3-1
2/3-11
3/23-1
3/23-11
4/28-1
4/28-11
5/17-1
5/17-11
•100
•100
>100
•100
•100
>100
•100
>100
»100
>100
>100
»100
•100
>100
71
71
71
87
50
37
50
50
25
35
50
55
61
35
1-33
-------
Spiking Fractions
CERIODAPHNIA 48h LC50s(%) FOR WHOLE EFFLUENT
AND EFFLUENT SPIKED WITH TOXIC SEPAK FRACTIONS
SAMPLE
3/23/88-1
3/23/88-11
WHOLE EFFLUENT
81
84
SPIKED EFFLUENT
35
37
Is the Cause of Toxicity Consistent
from Sample to Sample?
1-34
-------
TOXIC SPE C18 METHANOL FRACTIONS
% METHANOL
SAMPLE DATE 25 SO 70 75
SO
85 90 100
10/6-1
10/6-11
10/6-111
10/30-1
12/3-1
12/3-11
1/12-1
1/13-1
2/3-1
2/3-11
3/3-1
3/3-11
3/23-1
3/23-11
4/28-1
4/28-11
5/17-1
5/17-11
X
X
X
X
X
X
X
X
X
X
X
X
X
XX
X
X
X
XX
X
X
XX
X
X
X
X
X
X
X
X
X
XX
XX
X
X
X
X
X
X
X
XX
X
X
X
COMMON LABORATORY
EQUIPMENT REQUIREMENTS
1-35
-------
COMMON LABORATORY EQUIPMENT REQUIREMENTS FOR
TIEs
• TEST ORGANISMS
• DISPOSABLE 1-OUNCE TEST CHAMBERS
• LIGHT BOX AND/OR MICROSCOPE
• pH METER AND PROBE
• 7 ml SCINTILLATION & AUTO SAMPLER WITH CAPS
• STIR PLATE
• MAGNETIC STIRRERS/BARS (PERFLOUROCARBON)
• C18 SOLID PHASE EXTRACTION COLUMNS
• AERATION DEVICE OR COMPRESSED AIR SYSTEM WITH MOLECULAR
SIEVE
• AIR STONES
• FLUID METERING PUMP WITH RESERVOIR
COMMON LABORATORY EQUIPMENT REQUIREMENTS FOR
TIEs(Continued)
• PERFLOUROCARBON
• RING STANDS
• CLAMPS
• PARAFILM
• WIRE MESH TEST CHAMBERS
• GLASS-FIBER FILTERS ( 1.0/Jm)
• IN-LINE FILTER HOUSING
• STAINLESS STEEL TWEEZERS
• GLASS WOOL
• NITROGEN
1-36
-------
COMMON LABORATORY EQUIPMENT REQUIREMENTS FOR
TIEs(Continued)
• GLASSWARE
• 10 ml AUTOMATIC PIPETTES
• 1 ml GLASS PIPETTES
• DISPOSABLE PIPETTES TIPS
• EYE DROPPER OR WIDE BORE PIPETTE
• BEAKERS-30, 50, 250, 500, & 600 ml
• TITRATION BURRETTES
• GLASS STIRRING RODS
• GRADUATED CYLINDERS-25 & 50 ml WIDE MOUTH, AND 250 & 500
ml
• ERLENMEYER FLASKS—20,40, & 80 ml
• 100ml VOLUMETRIC FLASKS
COMMON LABORATORY EQUIPMENT REQUIREMENTS FOR
TIEs(Continued)
• SOLUTJONS.CHEMICALS
• DILUTION/CONTROL WATER • CaCO3 & MgCO3
• HCL • CLEANING SOLVENTS
• NaOH SOLUTIONS • Na2S203 SOLUTIONS
• pH BUFFERS • EDTA SOLUTIONS
• HPLC GRADE METHANOL • ACS GRADE NH4CI
• HIGH PURITY WATER * HEXANE
• ZEOLITE
1-37
-------
COMPANY LABORATORY EQUIPMENT
REQUIREMENTS FOR TIEs
I HIGH PRESSURE LIQUID CHROMATOGRAPH (HPLC)
> GAS CHROMATOGRAPH/MASS
SPECTROPHOTOMETER(GC/MS)
> ATOMIC ABSORPTION SPECTROPHOTOMETER (AA)
I INDUCTIVELY COUPLED PLASMA-ATOMIC EMISSION
SPECTROMETER (ICP)
1-38
-------
FACILITIES, EQUIPMENT AND LABORATORY REQUIREMENTS
Laboratories must demonstrate competency in performing the
chemical and biological tests required as part of the TRE and
should be equipped with all the basic and complex laboratory
equipment required to conduct TREs. Laboratory personnel should
be skilled and experienced in the required methods in order to
meet quality assurance/quality control goals.
The facilities, equipment and reagents needed to perform a
TRE will be different for each element of the TRE. The general
laboratory equipment and requirements for each particular type of
analysis are briefly described in this section.
The facilities and equipment needs in the initial steps of
the TRE are generally standard. However, in the later steps of
the TRE the facility and equipment needs will be site-specific
and will depend both on the physical/chemical characteristics of
the causative toxicants and on the choice of toxicity evaluation
and control approaches. The apparatus and reagents needed to
conduct a Phase I evaluation are relatively set (not site-
specific) and are typically found in laboratories that can
perform acute toxicity tests with aquatic organisms. The
additional needed equipment (fluid metering pump, C18SPE columns,
etc.) are simple to operate and relatively inexpensive.
Laboratory apparatus and reagents needed for Phase II are a
function of the two choices of Phase II options: 1)toxicity
treatability or 2)toxicant identification/source control. The
Phase I tests must be completed before the Phase II requirements
can be determined. The requirements are very site-specific,
however, laboratories equipped to perform priority pollutant
analysis should have the more sophisticated equipment needed.
Analytical equipment that may be needed will include gas
chromatographs, mass spectrometers, high pressure liquid
chromatographs, atomic absorption spectrophotometers and/or
inductively coupled plasma atomic emission spectrometers. The
exception of equipment availability may be a HPLC which is
commercially available but not typically used in water pollution
monitoring. Other nontypical equipment (eg. zeolite,
chromatography columns, etc.) can be easily obtained and is not a
major investment. Some costs of sophisticated equipment are
GC/MS, $60-300K; AA, $35-85K (w/autosampler); and HPLC, $25-40K.
The instruments needed for treatability studies may be
available at larger POTWs or environmental engineering consulting
firms.
It is best for a laboratory to have both toxicity testing
and chemical analysis (for Phase II toxicant identification
option) and/or treatability equipment (for Phase II toxicity
treatability option) in the same location. Shipping samples
between two different labs is not recommended. This is due to:
sample toxicity degradation; the lack of communication between
chemists, biologists, engineers and others involved; and the most
crucial requirement of a TRE may be the communication between the
different disciplines.
1-39
-------
The specific requirements needed for each of the key
analytical procedures required in a TRE are summarized below.
1. Characterization Tests - Laboratories should be
equipped with pH adjustment, filtration, air stripping,
reducing agent, chelating agent and C,8 solid phase
extraction columns; fractionation capabilities to
perform characterization tests (3) (see Phase I
Laboratory Equipment Needs).
2. Toxicity Tests - Standard toxicity test equipment,
standard reference toxicants and an organism culturing
facility are required for the toxicity testing.
3. Batch Toxicity Treatability Tests - Laboratories should
be equipped with respirometer (optional), TSS, VSS, ATP
and COD analysis capabilities to conduct treatability
studies.
4. Specific Chemical Identification - More complex pieces
of equipment are required for the specific
identification of chemicals depending upon the type of
analysis needed. Equipment that may be required
includes: mass spectrometer (MS), gas chromatograph
(GC), high pressure liquid chromatograph (HPLC) with
IR, UV detectors, atonic absorption (AA)
spectrophotometer, coupled plasma atomic emission (ICP)
spectrometers, and ion chromatograph.
5. Sampling Equipment - Laboratories need to be equipped
with all the standard sampling equipment including
timed and sequential composite samplers, and flow
proportional composite samplers.
6. General Analytical Laboratory Equipment and Reagents -
General laboratory equipment such as refrigerators,
microscopes, a water purification system, and commonly
used reagents are also required. It is important to
emphasize that copper, galvanized material, lead, and
brass should not be used in collecting or storing
effluent samples or control water. Use of inert
materials such as perfluorocarbon plastics are
particulary important in the latter steps of the TRE.
1-40
-------
LAB EQUIPMENT NEEDS
FOR
PHASE I
Baseline Toxicity Test
Apparatus:
Eighteen to 20 disposable one ounce test chambers, automatic
pipette (10 ml), disposable pipette tips (10 ml), eye dropper or
wide bore pipette, light box and/or microscope (optional
depending on test species used).
Reagents:
90 to 100 test organisms of the same age and species,
dilution/control water.
Initial Toxicity Test
Apparatus:
Twelve disposable one ounce test chambers, automatic pipette
(10 ml), disposable pipette tips (10 ml), eye dropper or wide
bore pipette, light box and/or microscope (optional depending on
test species used).
Reagents:
Sixty test organisms of the same age and species,
dilution/control water.
1-41
-------
pH Adjustment Test
Apparatus:
Burettes for acid and base titrations, pH meter and probe
(solid state), 2-500 ml beakers, 2-500 ml graduated cylinders,
12-30 ml beakers, stir plate, and stir bars (perfluorocarbon).
Eight disposable one ounce test chambers, automatic pipette (10
ml), disposable pipette tips (10 ml), eye dropper or wide bore
pipette, light box and/or microscope (optional depending on test
species used).
Reagents:
1.0, 0.1 and 0.01 N NaOH, 1.2, 0.12 and 0.012 N HC1 (ACS
grade in high purity water), buffers for pH meter, 40 test
organisms of the same age and species, dilution/control water.
Aeration Test
Apparatus:
Aeration device or compressed air system with a molecular
sieve, six air stones or diffusers, six-50 ml wide mouth
graduated cylinders, burettes for acid and base titrations, pH
meter and probe, stir plate(s), and perfluorocarbon stir bars.
Fifteen disposable one ounce test chambers, automatic pipette (10
ml), disposable pipette tips (10 ml), eye dropper or wide bore
pipette, light box and/or microscope (optional depending on test
species used).
Reagents:
0.01 N NaOH, 0.012 N HC1 (ACS grade in high purity water),
buffers for pH meter calibration, 75 test organisms of the same
age and species, dilution/control water.
1-42
-------
Apparatus:
Six-250 ral graduated cylinders, eight-25 ml graduated
cylinders, burettes for acid and base titrations, pH meter and
probe (solid state), stir plate, perfluorocarbon stir bars, fluid
metering punp (stainless steel piston with carbon cylinder) with
sample reservoir, perfluorocarbon tubing, ring stands, clamps,
and 3-3 ml C,, SPE columns (200 mg sorbent) . Twenty-seven
disposable one ounce test chambers, automatic pipette (10 ml),
disposable pipette tips (10 ml), eye dropper or wide bore
pipette, light box and/or microscope (optional depending on test
species used).
Reagents:
HPLC grade methanol, high purity water, 0.01 N NaOH, 0.012 N
HC1 (ACS grade in high purity water), buffers for pH meter
calibration, 135 test organisms of the same age and species,
dilution/control water, solvents for cleaning pump and reservoir.
Oxidant Reduction Test
Apparatus:
Glass stirring rods, 1 ml glass pipette, eight to ten
disposable one ounce test chambers, automatic pipette (10 ml),
disposable pipette tips (10 ml), eye dropper or wide bore
pipette, light box and/or microscope (optional depending on test
species used).
Reagents:
Two Na2S2Oj (molarity depending on total residual chlorine
concentration as measured by the iodometric method and the
species used as test organism), 40 test organisms of the same age
and species, dilution/control water.
1-43
-------
EDTA Chelation Test
Apparatus:
Glass stirring rods, burettes for EDTA addition, 8 to 10
disposable one ounce test chambers, automatic pipette (10 ml),
disposable pipette tips (10 ml), eye dropper or wide bore
pipette, light box and/or microscope (optional depending on test
species used).
Reagents:
EDTA solutions (concentration dependent on the hardness and
salinity of the effluent and the species used as test organism),
40 test organisms of the same age and species, dilution/control
water.
Graduated pH Test
Apparatus:
Burettes for acid and base addition, magnetic stirrers, and
perfluorocarbon stir bars.
3-50 ml beakers, 3 one ounce disposable transparent test
chambers, Parafilm" or 3-600 ml beakers, wire mesh test chambers.
Reagents:
1.0 and 0.1 N NaOH or 0.1 N and 0.01 N NaOH, 1.2 N and 0.12
N HC1 or 0.12 N and 0.012 N HC1, 15 test organisms of the same
age and species, dilution/control water.
1-44
-------
Filtration Test
Apparatus:
Six-250 ml graduated cylinders, 6-250 ml beakers, fluid
metering pump (stainless steel piston with carbon cylinder) with
•ample reservoir, teflon tubing, in-line filter housing, ring
stands, clamps, [alternatively; vacuum flask (500 ml capacity),
filter stand, clamp, vacuum tubing, water aspirator or vacuum
pump], glass-fiber filters; nominal size 1.0 urn (without organic
binder), stainless steel tweezers, burettes for acid and base
titrations, pH meter and probe, stir plate, and perfluorocarbon
stir bars, fifteen disposable one ounce test chambers, automatic
pipette (10 ml), disposable pipette tips (10 ml), eye dropper or
wide bore pipette, light box and/or microscope (optional
depending on test species used).
Reagents:
Solvents and high purity water for cleaning pump reservoir
and filter, 0.1 N and 0.01 N NaOH, 0.12 N and 0.012 N HC1 (ACS
grade in high purity water), buffers for pH meter calibration, 75
test organisms of the same age and species, dilution/control
water.
EQUIPMENT NEEDS
FOR
PHASE II
Nonpolar Organic Toxicants
Apparatus:
6, 3 and/or i ml C,8 SPE columns, fluid metering pump
(stainless steel piston with carbon cylinder), with glass
reservoir, vacuum manifolds, drying manifold, adapters and luer-
lok needles to fit C,8 SPE columns, 1.0 urn glass fiber filters,
in-line filter housing, 7 ml scintillation and autosampler vials
with perfluorocarbon lined caps, 20, 40 and 80 ml Erlenmeyer
flasks, 100 ml volumetric flasks, 100 ml graduated cylinders, 250
ul syringes, GS-MS equipped with capillary column, data system
with mass spectral library, HPLC equipped with solvent delivery
system (capable of producing a solvent gradient), C,a column, UV
detector, fraction collector, one ounce disposable plastic test
chambers, automatic pipette (10 ml), disposable pipette tips (10
ml), and stirring rods, eye dropper or wide bore pipette, light
box and/or microscope (optional depending on test species used).
Reagents:
HPLC grade methanol (25, 50, 75, 80, 85, 90 and 95* methanol
in high purity water), nitrogen, high purity water, test
organisms of the appropriate age and species, dilution water.
1-45
-------
Ammonia (Eguitoxic Soln Test)
Apparatus:
Six 600 ml beakers, 6-250 ml graduated cylinders, 6 wire
mesh test chambers, 6 perfluorocarbon stir bars, magnetic
stirrers, apparatus for ammonia analysis (see EPA-600/4-79-20;
Method 350.1, 350.2 or 350.3), burettes for acid and base
titration, 6 one ounce disposable plastic test chambers,
automatic pipette (10 ml), disposable pipette tips (10 ml), eye
dropper or wide bore pipette, light box and/or microscope
(optional depending on test species used).
Reagents:
1.0 N and O.l N NaOH, 1.2 N and 0.12 N HC1, reagents for
ammonia analysis (see above reference) ACS grade NH4C1, dilution
water, test organisms of the appropriate age and species.
Ammonia (Zeolite Test)
Apparatus:
Chromatographic column with reservoir (approximately 19 mm
i.d. x 41 cm), glass wool, apparatus for ammonia analysis (see
EPA-600/4-79-020, Method 350.1, 350.2 or 350.3), 3-500 ml
beakers, 500 ml graduated cylinder, 10 one ounce disposable
plastic test chambers, automatic pipette (10 ml), disposable
pipette tips (10 ml), eye droppers or wide bore pipette, light
box and/or microscope (optional depending on test species used).
Reagents:
30g zeolite, reagents for ammonia analysis (see EPA 600/4-
79-020, Method 350.1, 350.2, or 350.3), high purity water,
dilution water, test organisms of the appropriate age and
species, ACS grade NH4C1 (optional).
1-46
-------
Cationic Metals
Apparatus:
Inductively coupled plasma-atonic emission spectrometer or
atomic absorption spectrophotometer with graphite furnace,
associated hardware and glassware specified in EPA-600/4-79-020
(selected method(s) from the 200 series), 500 ml separatory
funnel (optional), one ounce disposable plastic test chambers,
automatic pipette (10 ml), disposable pipette tips (10 ml), eye
dropper or wide bore pipette, light box and/or microscope
(optional depending on test species used).
Reagents:
Reagents as specified in EPA-600/4-79-020 for metal analysis
method(s) chosen, hexane (optional), CaC03 and MgC03 (optional),
dilution water, test organisms of the appropriate age and
species.
1-47
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TRE INDUSTRIAL PROTOCOL - CASE EXAMPLES
William Clement and G. Mick DeGraeve,
Battelle
1-48
-------
TRE INDUSTRIAL PROTOCOL - CASE EXAMPLES
William Clement and G. Mick DeGraeve
I. TRE Process
A. Overview
B. Flowchart
II. Case History - Metal Finishing Industry
A. Determination
B. Characterization
C. Toxicity Reduction Methodology Evaluation
III. Case History - Government Arsenal
A. Overview
B. Wastewater Treatment System
C. Evaluation
IV. Case History - Chemical Industry's Treatment Facility
A. Overview
B. Data
V. Case History - Multipurpose Speciality Chemical Plant
A. Overview
B. Data
1-49
-------
A TRE is a step-wise process
consisting of:
• Evaluation of existing site-specific information
• Toxicity characterization/identification/confirmation
evaluation
• Toxicity source identification
• Toxicity reduction method evaluation
• Method selection and implementation
• Follow-up monitoring
TRE Industrial Protocol Flowchart
TRE Objectives
JL
Information and
Data Acquisition
Evaluate Facility
Housekeeping
_L
Evaluate Chemical Use
Evaluate Treatment System
JL
Toxicity Identification
Evaluation
Evaluation of Treating
Final Effluent
Identification of the Source(s)
of Final Effluent Toxicity
Evaluation of Treating
Process Systems
JL
Selection and Method
Implementation
Follow-Up and Confirmation
1-50
-------
Case History of
a TRE Conducted at a
Metal Finishing Industry
Process
Municipal
Water
Water
Treatment Plant
I
0.3 MGD
Cooling Water
0.4 MGD
Processes
UJ.
001
1.2 MGD
0.8 MGD
Cooling Water
TRE Target 80% Survival of Most Sensitive
Species in 100% Effluent at 48 hr
1-51
-------
Determination of Most Sensitive
Test Species for 001 Effluent
Sample Test Date
A B
% Survival in 100% LC
50»
Species Effluent, 48 h % Effluent
D. magna 0 32.5
D. pulex 0 67.3
Fathead minnows 95 >100
EC™, % Effluent
'50>
Microtox 67 46
Toxicity of 001 Effluent Was
• Highly variable: LC50s ranged
from 14% to >100% over
one-year period
• Non-persistent
1-52
-------
Toxicity Characterization
• Toxicity was found in
— Filterables
— Organics (volatiles)
— Oxidants (reducibles)
• Individual contribution of each of these
classes displayed great variability
• Filtration followed by aeration followed
by reduction removed toxicity
Example of Variability of Sources of Toxicity
Whole Effluent Toxicity
Individual Toxicity Parameter
Filterables
Volatiles
Reducibles
Sum of Individual
Parameters
Difference Between Whole
Effluent Toxicity and Sum
of Individual Parameters
A
001
1.4
0.1
0.3
0.4
0.8
0.6
Sample
001
4.8
3.3
0.0
1.2
4.5
0.3
Data"1
B
MH17.7
3.8
0.0
3.4
7.2
>0.5
MH6(bl
6.2
2.6
0.0
>2.5
>5.2
<1.0
<•> Values In TU.s
-------
Class
Volatiles
Filterables
Identification of Causative
Agents and Sources
Agent Identification Source
Thermal products from
ABS polymer (e.g.,
styrene, acetophenome)
Reducibles a) TRC
Water traps for
extrusion process
Municipal water
b) Anionic chemical X A bath process
Toxicity Persistence
(Typical Data)
TU. (100/LCJ
Date
Sample
001
Ditch at creek
Upstream of ditch
1/2 mile downstream
of ditch in creek
A
5.0
1.4
0.0
-------
Effluent/
Receiving
Water
Mixture
Dish on
UV/Visible Lighting
Unit Enclosed in
an Environmental
Chamber
Wire Screen 2 Liter Beaker
Support Over a Magnetic Stirrer
\Stream
Substrate
Pump
Environmental Toxicity Persistence Unit
ETPU Investigation of an Industrial Effluent
4/2
4/9
. m-4/16
2 3
Time in ETPU, hr
1-55
-------
Toxicity Reduction
Methodology Evaluation
• Process changes
• Treatment (filtration, aeration,
and reduction combined)
• Treatment to mimic the ditch
1-56
-------
Case History of a
Preliminary TRE Conducted
at a Government Arsenal
Case History Overview
Arsenal production was highly variable
both in materials produced and
production scheduling
Effluent toxicity was also highly variable
Initial monitoring of toxicity failed to
disclose source or sources of causative
agent(s)
An exploratory TRE using acute toxicity
tests with D. magna was then undertaken
1-57
-------
Arsenal's Wastewater Treatment System
Effluents from Numerous Processes
Alum, Lime, pH Adjustment
rALTT
Polymer
*002
1 MGD
Summary of TIE Results
oo? Q C,harlcterization of Sixteen
002 Samples Over a Five-Month Period
38% (6) had "no toxicity"
31% (5) had "only filterable toxicity"
6% (1) had "only organic toxicity"
25% (4) had "both filterable and organic toxicity"
No "reducible" or "volatile" toxicity was found
1-58
-------
Evaluation of the Treatment System
and the TIE Data Disclosed
> Lagoon RT was in reality only
several hours
> Organic toxicity correlated well with
production of specific organic products
Toxicity Reduction Method Evaluation
For "filterable toxixity"
• Treatability studies
• Lagoon improvements
For "organic toxicity11
• Treatability studies with activated carbon
• Eventual addition of an activated carbon
treatment system to 002 planned
1-59
-------
Case History of
a TRE Conducted at a
Chemical Industry's
Treatment Facility
Case History Overview
• The chemical industry produced numerous
organic and inorganic products
• The CIWTF's effluent was consistently toxic
• A TRE was mandated by the state
regulatory agency
• The TRE target was set as
— No acute toxicity
- A NOEC > 24%
Preliminary Study of Effluent Data
Suggested the Following
"Suspect Agents"
• Organic solvents
• Organic intermediates and
by-products
• Metals
. . 1-60
• Ammonia
-------
Initial Acute Toxicity Data
(LC50 Values) From Three Species
Exposed to CIWTFs Effluent'8'
Test Date
Test Species
Fathead minnow
Daphnia magna
Daphnia pulex
Ceriodaphnia
dubia
A
20
>100
38
35
B
23
96
33
25
C
24
100
38
35
(a) 48-hour static acute toxlcfty tests initiated one day after sample
collection, with samples stored on ice in the dark
Initial Chronic Toxicity Data From Two
Species Exposed to CIWTF's Effluent
Fathead Minnow"1
Test Date
A
B
C
D
E
F
NOEC(e)
12
12
12
12
12
1.5
LOEC(d)
25
25
25
25
25
3
Ceriodaphnia™
NOEC
12("
12<"
12
12
—
—
LOEC
25">
25W
25
25
—
—
(a) Seven-day static renewal toxicrty test with newly hatched fry (based on fish wts.)
(b) Seven-day static renewal toxfcfty test with less than 24-hour-old organisms
(based on total number of young produced)
(c) No observed effects concentration
(d) Lowest observed effects concentration
(e) Reproduction values were compared against the 1.5% concentration
values instead of the controls
1-61
-------
Toxicity Characterization
Tests - Filterable Toxicity(8)
LC™, % Effluent
'501
Untreated Effluent Filtered Effluent™
14 13
17 <13
17 15
12 <13
3.4 4.9
11 _ 13
(a) Seven samples over a nine-month time frame
(b) Effluent pressure filtered through a Gelman A/E
glass fiber filter (1.0 urn)
Toxicity Characterization
Tests — Organic Toxicity(a)
LC™, % Effluent
'SOI
Organics Removed
Untreated Effluent From the Effluent(b>
12
3.4
11
15
<13
4.9
13
15
(a) Five samples over a five-month time frame
(b) Effluent filtered and passed over XAD4 resin
1-62
-------
Toxicity Characterization
Tests — Cation Toxicity(a)
LC50, % Effluent
Untreated
14
34
35
56
Effluent With
Effluent Cations Removed'"
>100
>100
76
>100
(a) Four samples over a two-month time frame
(b) Effluent passed over a cation exchange resin
Typical Ammonia Concentrations
and Acute Toxicity Data for
the CIWTFs Final Effluent(a)
PH
7.9
8.0
7.9
7.8
7.7
Total
NH3, mg/L
51
60
80
46
52
Unionized
NH3, mg/L
1.68
2.3
2.6
1.3
1.2
LC50,
% Effluent
14
13
2.6
22
26
Toxic
Units
7.0
7.6
9.1
4.5
3.9
(a) 48-hour static acute toxlclty tests with fathead minnows
1-63
-------
Unionized Ammonia vs. Toxicity in CIWTF Effluent
15
O /
/O
/O O ' = 0.72
00 LCM - 0.4 mg/L
5p of Unionized NH,
12345
Unionized NH3, mg/L
Ammonia Concentration vs. Toxicity
of a Sample of CIWTF Effluent
o
•§
Raw Effluent
Partial
NH, Removal
More Extensive
NH, Removal
0.5 1.0
Ammonia (unionized), mg/L
1-64
-------
Acute Toxicity of
Clinoptilolite Treated Effluent"'
LC50,
Untreated Effluent
17
17
23
15
11
13
5
% Effluent
Clinoptilolite
Treated Effluent
59100
>100(c)
>100(c)
>100
>100
(a) Seven samples over a five-month period
(b) Incomplete removal of NH,
(c) 10O% survival In 100% effluent
Chronic Toxicity of Treated Effluent
NOEC, % Effluent
Untreated
Date Species Effluent Treated Effluent
Aw Fathead Minnow Acutely >50
Toxic
B Fathead Minnow 15 60 (LOEC, 100%)
Ceriodaphnia - 36 (LOEC, 60%)
Cw Fathead Minnow Acutely 100 (LOEC, >100%)
Toxic
(a) Cations removed from effluent using cation exchange resin
(b) Effluent treated with cnnoptHoNte
1-65
-------
A Case History
Implementation of a Toxicity Reduction
Evaluation at a Multipurpose Specialty
Chemical Plant
Project Objective: To develop, test, and
refine a protocol for conducting industrial
TREs to provide guidance to permit writers
and permittees
MULTI-PURPOSE SPECIALTY CHEMICAL WASH HOW DIAGRAM
1-66
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Toxicity Testing
Test Species Test System Test Duration
Daphnla magna static acute 48 hr.
Fathead minnows static acute 48 hr.
Mysidopsis bahla static acute 48 hr.
Pholobacterlum Mlcrolox 5 to 30 mln.
phosphorlum
Toxicity of Site 1 Final Effluent
(August 1985 Sample)
Species LC50 (% Effluent)
Pimephales promelas >100
- fathead minnows
Paphnia magna 0.1
Photobacterium phosphorium > 100
Fractionation Scheme
Effluent*
XAD Resin
r
Inorganic* Organic*
Method 625
J
Anions*
Resins
I
Cations*
I
Acids'
1
Base/N
Extractions
J
eutrals'Resid
* Bloassy Testing Point; Further Fractionation
and Chemical Analysis Decision Point
1-67
-------
Aquatic Toxicity Data for Dichlorvos
LC50 Test Test
Test Species (ug/L) Duration Condlllons Reference
Fathead
minnow
11,600 96 hr
17*C Toxicology Data
Bank
Daphnia
pulex
0.07 48 hr
15'C Toxicology Data
Bank, Verschueren
1983
Acute Toxicity of Amines and
Dichlorvos to Daphnia magria
Sample
Description
Dlamine
N-octylamine
Dicyclohexylamlne
Dichlorvos
48-hr EC50
5,700
> 50,000
15,700
0.08*
0.2**
* Calculated EC50 based on dlchlorvos concentration
measured In August 1985 final effluent sample.
** Final effluent sample collected at Site No. 11n February
was spiked with dichlorvos.
Fractionated Effluent - August 1985
Using Daphnia magna
Final Effluent
0.10%
Organic Fraction
0.14%
Acid Base/Neutral Residual
Subtraction Subtraction Subtraction
Inorganic Fraction
>50%
Anlonlc
Subtraction
Catlonlc
Subtraction
1.64%.
0.41%
not tested not tested
1-68
-------
Comparison of August, November, and January 6lh Samples
LC50 (% Effluent)
Sample August November January 6
Final Effluent 0.1 0.6 70.5
Comparison of Principal Peaks in
GC/MS RICs of August 1985 and
February 1986 Base/Neutral Subtractions
Scan
No. August 1985 Sample
790 Alkylamlne, MW139
BOO Ethanedlylldene Bis
832 Alkyl dlamlne, MW172
962 Alkyl amlne, possible
. MW169
1017 UID
1089 Dlchlorvos
February 1986 Sample
Possibly present, unconfirmed
Not present
(2-melhyl-2-propanamine)
Possible trace amount present
Not present
Not present
Not present
1-69
-------
TRE MUNICIPAL PROTOCOL - CASE EXAMPLES
Fred Bishop, USEPA and John Botts,
Engineering Science and Richard Dobbs, USEPA
1-70
-------
TRE MUNICIPAL PROTOCOL - CASE EXAMPLES
Fred Bishop, John Botts, and Richard Dobbs
I. Protocol
A. TRE Requirement
B. Toxicity Reduction Evaluation
C. Limitations
D. Components
E. Operations
F. Evaluations
G. Treatability Tests
H. Results
I. Sampling Decisions
J. Data
II. Case Study - Patapsco Wastewater Treatment Plant
HI. Case Study - Mount Airy, North Carolina
IV. Case Study - Falling Creek Wastewater Treatment Plant
1-71
-------
TOXICITY REDUCTION EVALUATION
PROTOCOL FOR MUNICIPAL
WASTEWATER TREATMENT PLANTS
TRE REQUIREMENT
Triggered by evidence of unacceptable
effluent toxicity
Usually a TRE plan and schedule must be
submitted
Continues until acceptable effluent toxicity
is achieved
TOXICITY REDUCTION EVALUATION
Identify the constituents causing effluent
toxicity
Locate the sources of effluent toxicants/toxicity
Evaluate the feasibility and effectiveness of
toxicity control options
1-72
-------
MUNICIPAL TRE PROTOCOL
• Development and review of a TRE plan
• Selection of appropriate steps in a TRE
• Evaluation and interpretation of the data
• Selection and implementation of control
options
LIMITATIONS OF THE PROTOCOL
Addresses Methods for Reduction in Whole
Effluent Toxicity
Limited Case Studies
1-73
-------
COMPONENTS OF THE MUNICIPAL TRE PROTOCOL
Information and Data Acquisition
POTW Performance Evaluation
Toxicity Identification Evaluation
Toxicity Source Evaluations (Tiers I and II)
POTW In-Plant Control Evaluation
Toxicity Control Selection and Implementation
POTW OPERATIONS AND PERFORMANCE DATA
NPDES Discharge Monitoring Reports
POTW Design Criteria
Process Control Data
Treatment Interferences
Process Sidestream Discharges
Wastewater Bypasses
1-74
-------
PRETREATMENT PROGRAM INFORMATION
POTW Effluent and Influent Toxicity/Toxics Data
POTW Sludge Toxics Data
Industrial Waste Survey Information
Annual Pretreatment Program Reports
Local Limits Compliance Reports
POTW PERFORMANCE EVALUATION
Evaluate major unit treatment processes
(CCP Approach)
identify deficiencies that may contribute to
effluent toxicity
Determine in-plant sources of effluent toxicants
(e.g., chlorination, bypasses)
1-75
-------
POTW PERFORMANCE EVALUATION
A limited TIE Phase I can be conducted to:
• Indicate in-plant toxicants such as chlorine
and suspended solids
• Provide information to set up treatability tests
CONVENTIONAL TREATABILITY TESTS
Recommended for Improvements in Conventional
Pollutant Treatment
Can Identify Modifications in Conventional
Treatment That Also Reduce Toxicity
CONSIDERATIONS IN TIE TESTING AT POTWS
Characterize effluent toxicant variability over time
Utilize pretreatment program data to support TIE
Can initiate treatability tests based on Phase I
results
1-76
-------
RESULTS OF TIE
Specific toxicants are identified
One fraction is consistently toxic
Variable fraction toxicity
PURPOSE OF TOXICITY SOURCE EVALUATION (TSE)
Determine Sources of Effluent Toxicants/Toxicity
Determine Feasibility of Pretreatment Control
1-77
-------
TIER I TSE - SAMPLING DECISIONS
Sewer Line Sampling:
• TIE and pretreatment program data
are limited
• POTW has a large number of lUs
Point Discharge Sampling:
• TIE and pretreatment program data
attribute toxicants to (Us
• Number of (Us is manageable
TSE TIER I APPROACHES
Chemical-Specific Tracking
Refractory Toxicity Assessment
1-78
-------
CHEMICAL-SPECIFIC TSE REQUIREMENTS
Pretreatment Program Data to Indicate Sources
Knowledge of Sewer Discharge Characteristics
Accurate Analytical And Flow Data
TSE - REFRACTORY TOXICITY ASSESSMENT
A simulation of the POTW treatment system
which utilizes toxicity tests to estimate the
amount of refractory toxicity in sewer
wastewaters.
1-79
-------
RTA SAMPLE COLLECTION, CHARACTERIZATION
AND PREPARATION
24-Hour Flow Composites
Analyze for COD, TKN, TP, IDS and pH
Adjust BOD5:N:P Ratio to 100:5:1
Adjust pH
EXAMPLE RESULTS FOR TIER I RTA
LC50(% Effluent)
Sample/ Sample/ Potential
Synthetic Primary Primary Toxicity
Source Wastewater Effluent Effluent Source
A 35 38 70 YES
B 22 77 72 NO
C 21 12 85 YES
1-80
-------
TIER II - TOXICITY SOURCE EVALUATION
Confirm Sources of Refractory Toxicity
Identified In Tier I
Determine Potential for Biological Treatment
Inhibition (optional)
Characterize Refractory Toxicity Using TIE
Phase I Tests (optional)
EXAMPLE RESULTS FOR TIER II RTA
Sample Dilution
(Times Percent Flow in POTW Influent)
10x 5x 2x
Batch Effluent LC 50 10 30 50
Batch Effluent Toxic 10 3.3 2
Units (TU)
Sum of TUs = 15.3
1-81
-------
RELATIVE TOXICITY LOADING CALCULATION
Relative Score =
Sum of TUs x Sewer Discharge Flow Rate
Where Sum of TUs = 15.3
Flow Rate = 1 mgd
Relative Score = 15.3 TU x 1 mgd = 15.3
TSE TIER II - PRETREATMENT CONTROL EVALUATION
Approaches to Local Limits Development
• Allowable headworks loading
• Industrial User management
• Case by case permitting
Equitable Cost Recovery
1-82
-------
SELECTION OF OPTIONS FOR EVALUATION
Review PPE data to determine:
• Space and equipment
• Operational control
Review TIE data to determine:
• Types of toxicants amenable to
treatment
• Treatability test design
TOXICITY TREATABILITY TESTS
Activated Sludge
Coagulation and Precipitation
Sedimentation
Granular Media Filtration
Activated Carbon
1-83
-------
EVALUATION OF TOXICITY CONTROL OPTIONS
Selection based on results of:
• PPE
• TIE
• TSE Tier I - Chemical Specific Testing
• TSE Tiers I and II - Refractory
Toxicity Assessment
• POTW Treatability Testing
POTW TECHNOLOGIES FOR CATEGORIES OF POLLUTANTS
Biodegradable
Organic Non-Biodegradable
Compounds and Organic
Ammonia Compounds
Biological Process Coagulation/
Control Precipitation
Nutrient Filtration
Addition
Activated
Carbon
1-84
-------
POTW TECHNOLOGIES FOR CATEGORIES OF POLLUTANTS
Volatile Heavy Metals
Organic and Cationic
Compounds Compounds
Biological Process pH Adjustment
Control
Aeration Coagulation/
Precipitation
Filtration
COMPARISON OF SELECTION CRITERIA FOR
TOXICITY CONTROL OPTIONS
Alternative
Selection Criteria ABC
Ability to achieve effluent toxicity limits
Ability to comply with other permits
Capital and O&M Costs
Ease of Implementation
Reliability
Environmental Impact
1-85
-------
TOXICITY CONTROL IMPLEMENTATION
Toxics Control Implementation Plan
Follow-up Monitoring
1-86
-------
CASE STUDY
TOXICITY REDUCTION EVALUATION
AT THE
PATAPSCO WASTE WATER
TREATMENT PLANT
Baltimore, Maryland
PURPOSE OF TRE CASE STUDY #1
Develop and validate procedures
for municipal TREs with emphasis on
evaluating methods for tracing
effluent toxicity to its sources.
1-87
-------
WHY PATAPSCO WAS CHOSEN FOR A CASE STUDY
• Effluent Toxicity
• Treatment Performance Problems Related
To Toxicity
• Experience in Toxicity Monitoring/Existing
Data Base
• Proximity to the Chesapeake Bay Estuary
OBJECTIVES OF THE TRE
• Evaluate Operations and Performance
• Identify Effluent Toxicants
• Trace Toxicants and/or Toxicity
• Evaluate, Select and Implement
Controls
1-88
-------
PATAPSCO TRE - CASE STUDY SCHEDULE
MONTHS
0123456789 101112131415161718
TOXICITY TESTING
PERFORMANCE REVIEW
TIE (PHASE I)
SOURCE EVALUATION
FINAL REPORT
AQUATIC TOXICITY TESTS
TEST
ENDPOINT
7-day Ceriodaphnia dubia 48-hour
7-day ChV
96-hour Mysidopsis bahia 96-hour LC 50
MICROTOX
TM
5-minute EC 59
1-89
-------
CHRONIC TOXICITY OF
PRIMARY AND SECONDARY EFFLUENT
NOEC MEAN ChV MEAN
(S.D.) (S.D.) N
Ceriodaphnia dubia
Primary Effluent 0.8 (1.1) 1.2 (1.8) 12
Secondary Effluent 2.3 (1.6) 2.8 (2.1) 45
PERCENT TOXICITY REDUCTION BY
THE PATAPSCO WWTP
MEAN (S.D.) N
MICROTOX™ 87.7 (12.2) 37
5-minute EC
50
Mysidopsis bahia 55.5 (16.8) 12
96-hour LC 59
Ceriodaphnia dubia
48-hour LC50 60.7(30.4) 13
7-day ChV 62.5 (31.1) 12
1-92
-------
SUMMARY OF TOXICITY RESULTS
Ceriodaphnia dubia was the most
sensitive species
1 Significant correlation of Ceriodaphnia
dubia and Mysidopsis bahia
Percent toxicity reduction ranged
from 50-90%
PLANT PERFORMANCE EVALUATION
Primary Treatment Did Not Reduce
Influent Toxicity
Increases in Acute Effluent Toxicity
Occurred During Reduced Plant Performance
Performance and Operations Were Not a
Major Cause of Effluent Toxicity
1-93
-------
[WA8TEWATER SAMPLE]
TIME LETHALITY TEST
ON WHOLE SAMPLE
AERATED FOR]
1 HOUR i
48-HOUR
ACUTE TEST
\
UNAERATED
48-HOUR
ACUTE TEST
FILTERED
(I.Oum) SAMPLE
UNAERATED
48-HOUR
ACUTE TEST
AERATED
TIME LETHALITY
OR 48-HOUR
TEST
RAISE pH>11
AERATE FOR 1 HR.
AND NEUTRALIZE
TIME LETHALITY
TEST
COLUMN
EXTRACTION]
I C(18) COLUMN
EXTRACTION
[EFFLUENT FROM COLUMN]
1
I TIME LETHALITY TEST]
"~
ELUTED WITH
INCREASING
CONCENTRATIONS
OF METHANOL
SEPARATION OF SAMPLE
USING ANION AND CATION
EXCHANGE RESINS
r
[48-HOUR ACUTE TEST]
48-HOUR ACUTE TEST]
1-94
-------
TIE PHASE I RESULTS
SECONDARY EFFLUENT 10 DECEMBER 1986
.0 100
90
80
70
S 60
O 50
"I 40
3 30
X 20
to 10
0
Whole Aerate Filter NH3-N C-18 Cation Anion Residual
Treatments
TIE PHASE I RESULTS
SECONDARY EFFLUENT 23 JULY 1986
O
o
100
90
80
70
60
O 50
"2 40
=» 30
£ 20
i 10
48-hour LC50
Theoretical LC50
. I
100
90
80
70
60
50
40
30
20
10
0
Whole Aerate Filter
C-18 Cation Anion Residual
Treatments
1-95
-------
CO
15
O
in
O
100
90
80
70
60
50
40
30
20
10
0
TIE PHASE I RESULTS
PRIMARY EFFLUENT 23 JULY 1986
100
90
80
70
60
50
40
30
20
10
Whole Aerate Filter
C-18 Cation Anion Residual
Treatments
TIE PHASE I RESULTS
SECONDARY EFFLUENT 23 JULY 1986
25 50 75 80 85 90 95 100
Percent Methanol Fractions From C-18 Column
1-96
-------
TIE PHASE I RESULTS
SECONDARY EFFLUENT 10 DECEMBER 1986
X
O
70
60
50
40
30
020
C 10
Z o
70
60
50
40
30
20
10
25 50 75 80 85 90 95 100
Percent Methanol Fractions From C-18 Column
REFRACTORY TOXIC I TY
ASSESSMENT (RTA)
• Collect Sewer Samples
• Batch Simulation of Activated Sludge
Treatment Process
• Measure Batch Effluent Toxicity
• Rank Sources by Relative Toxicity
Loading
1-97
-------
DESCRIPTION OF INDIRECT
INDUSTRIAL DISCHARGERS
INDUSTRY
CODE INDUSTRY PRODUCTS
A Organic Chemicals and Pesticides
B Detergent Alkylates, Hydrotropes, and
Petroleum Intermediates
C Emulsifiers, Surfactants, and Specialty
Monomers
D Organic and Inorganic Chemicals
E Washdown of Chemical Transport Trucks
RTA RESULTS - INDUSTRY B
Percent Ceriodaphnia
Industrial MICROTOX ™ (EC 50) Time Lethality (TU)
Wastewater
100
75
50
25
10
Influent
45.7
65.4
100
82.8
100
Effluent
100
100
100
—
—
Influent
76.0
88.1
100
100
—
Effluent
22.9
24.5
25.5
26.2
—
RAS 100 10.7
1-98
-------
RTA RESULTS - INDUSTRY D
Percent Ceriodaphnia
Industrial MICROTOX ™ (EC 50) Time Lethality (TU)
Wastewater
100
75
50
25
10
RAS
Influent
1.4
1.8
4.2
9.3
16.3
100
Effluent
3.2
11.5
15.7
61.6
100
Influent
16.4
21.0
24.8
51.9
90.5
16.4
Effluent
4.8
4.8
13.3
11.7
15.5
BIOMASS TOXICITY CHARACTERIZATION
Treatment
Ceriodaphnia
Time Lethality Toxic Units
#1 #2 #3
Coarse Filter 35
54
58
0.2 urn Filter 88
90
100
Centrifuge
81
1-99
87
92
-------
TIE PHASE I RESULTS
INDUSTRY A - 12 DECEMBER 1986
Theoretical LC50
Cation Anion Residual
Whole Aerate Filter NH3-N
Treatments
TIE PHASE I RESULTS
INDUSTRY A -12 MARCH 1987
o
100
90
80
70
X 80
O 50
7; 40
o 30
I 20
10
100
90
80
70
80
50
40
30
20
10
Whole Aerate Filter NH3-N C-18 Cation Anion Residual
Treatments
1-100
-------
TIE PHASE I RESULTS
INDUSTRY E - 26 MARCH 1987
IV
2
3
•o
•
O
IA
O
"i
0
i
CO
«fr
100
90
80
70
60
50
40
20
n
•
too
90
80
70
60
50
40
30
20
10
0
Whole Aerate Filter NH3-N C-18 Cation Anion Residual
Treatments
70
- 60
* 40
|S 30
"5 20
e 10
0)
S o
TIE PHASE I RESULTS
INDUSTRY A -12 MARCH 1987
25 50 75 80 85 90 95 100
Percent Methanol Fractions From C-18 Column
70
80
50
40
30
20
10
0
1-101
-------
TOXICITY IDENTIFICATION EVALUATION
OF RTA EFFLUENTS
INDUSTRY PRINCIPAL TOXIC FRACTION
A NON-POLAR ORGANICS
RESIDUAL TOXICITY
C NON-POLAR ORGANICS
RESIDUAL TOXICITY
D NON-POLAR ORGANICS
RESIDUAL TOXICITY
E ANIONS
CONCLUSIONS
The WWTP Achieved Significant
Toxicity Reduction; However,
Substantial Acute and Chronic
Toxicity Remained
Effluent Toxicity Was Not Caused
By Poor Treatment Operation Or
Performance
1-102
-------
CONCLUSIONS
(Continued)
Non-Polar Organic Compounds
Appear To Be The Principal Effluent
Toxicants
Acute Toxicity To Ceriodaphnia Was
Largely Associated With Particles
> 0.2 urn
CONCLUSIONS
(Continued)
RTA Was An Effective Tool For
Identifying Contributors To The
WWTP's Effluent Toxicity
1-103
-------
RECOMMENDATIONS
Test Enhanced Solids Removal Techniques
(e.g. Coagulation/Precipitation or Filtration)
For Sorbable Toxicity Reduction
Additional RTA Testing to Identify Sources
Contributing to the WWTP Toxicity
Pass-Through
1-104
-------
CA SE S TUD Y
MOUNT AIRY, NORTH CAROLINA
TOXICITY REDUCTION EVALUATION
MT. AIRY TOXICITY REDUCTION EVALUATION
TECHNICAL APPROACH
• CHEMICAL MEASUREMENTS
• MOCK EFFLUENTS
• TIE PHASE I TESTS
• SOURCE EVALUATION
• LOCAL PRETREATMENT LIMITATIONS
1-105
-------
MODIFIED TIE PHASE I
CATION RESIN - METALS
ORGANIC RESIN ~ ORGANICS
CHEMICAL MEASUREMENT
* FOCUSED ON ALKYL PHENOLS,
METALS, SOLVENTS
• COMPARISON OF CHEMICAL DATA
TO LITERATURE TO INDICATE TOXICANTS
1-106
-------
SOURCE EVALUATION
ALKYL PHENOLS - TEXTILE SURFACTANTS
COPPER - DYE COMPONENTS
ZINC ~ SODIUM HYDROSULFITE
SOLVENTS - TEXTILE SCOURING
PRETREATMENT CONTROL
• LINEAR ALCOHOL ETHOXYLATES IN LIEU OF
ALKYL PHENOL ETHOXYLATES
• CHEMICAL USAGE OPTIMIZATION
• REDUCED APPLICATION OF METAL-BASED DYES
• ZINC-FREE HYDROSULFITE
1-107
-------
DEVELOPMENT OF A
TOXICITY REDUCTION EVALUATION PLAN
FOR THE FALLING CREEK
WASTEWATER TREATMENT PLANT
ENGINEERING-SCIENCE
DESCRIPTION OF FACILITIES
9 MGD Advanced Secondary Treatment Plant
Treats Primarily Domestic Wastewater
No Major Industries
Discharges to Low Flow Tributary of the
James River
1-108
-------
BIOMONITORING REQUIREMENTS
Monthly:
96-Hour Pimephales promelas
Quarterly: 7-Day Ceriodaphnia dubia
TOXICITY TEST RESULTS
PERCENT EFFLUENT
DATE
1986
May
June
July
Nov
1987
June
*v^
P. Promelas
C. dubia
C. dubia
96-hr LC50 72-hr LC 50 NOEL
100
100
100
100
100
54.8
50.0
46.9
36.7
24.5
3
10
30
20
10
1-109
-------
TRE REQUIREMENT
"Upon notification . . . that a discharge is
determined to be actually or potentially
toxic . . . the permittee shall begin to
develop a toxicity reduction evaluation
plan. (Toxics Management Regulation
VR 680-14-03)"
A
ADDITIONAL REQUIREMENTS FOR
PREPARING THE TRE PLAN
Evaluation of POTW Performance
Further Toxicity Identification Evaluation
Initial Assessment of Toxicity Control
Options
1-110
-------
PERFORMANCE EVALUATION FOR
THE FALLING CREEK WWTP
Reviewed Monthly Operations and
Performance Data for the Period
January 1986 to August 1987
Conducted On-Site Review of
Treatment Facilities
COMPARISON OF EFFLUENT QUALTIY
TO PERMIT LIMITS
Parameter
BODC :
Permit Limitation (mg/l)
Monthly Weekly Actual
Average Average Average
Summer
Winter
16
29
24
44
10
9
SS:
Summer 16
Winter 29
24
44
5
8
i-in
-------
EFFLUENT QUALITY VS. EFFLUENT TOXICITY
^20
Suspended Solids
May-86 Jun-86 Jul-86 Nov-86
Sampling Period
Jun-87
INFLUENT QUALITY VS. EFFLUENT TOXICITY
May-86 Jun-86 Jul-86 Nov-86
Sampling Period
Jun-87
1-112
-------
SUMMARY OF THE POTW
PERFORMANCE EVALUATION
All Treatment Processes Operate Within
Design Specifications and Performance
Criteria
WWTP Does Not Appear to Contribute to the
Effluent Toxicity
Limited Data Suggest That the Influent is
the Source of the Toxicity
SUMMARY OF PRETREATMENT
PROGRAM REVIEW
No Categorical or Major Industries
Several Commercial Dischargers
No Likely Source of Toxicity
Additional Information Needed on
Commercial Discharges
k „
1-113
-------
TOXICITY IDENTIFICATION
EVALUATION RESULTS
Principal Toxic Component Was Non-Polar
Organic Compounds
GC/MS Indicated 15 Identified Compounds
and 30 Unidentified Compounds
Identified Peaks Included Benzothiozole,
Propanoic Acid and Cyclohexanol
SUMMARY OF TIE RESULTS
Acute Toxicity Associated With Filtrable,
Volatile and Non-Polar Organic Fractions
Type of Toxicant Varies Over Time
General Association of Toxicity With
Suspended Solids
1-114
-------
OPTIONS FOR ENHANCED
SOLIDS REMOVAL
Chemical Coagulation Followed by
Sedimentation
Chemical Coagulation Followed by
Conventional Gravity Filtration
FEASIBILITY OF ENHANCED
SOLIDS REMOVAL
Both Processes Rely on a Moderate Level
of Solids to Promote Coagulation and
Solids Separation
Expected Solids Levels After Treatment
Are 2 to 10 mg/l
Current WWTP Effluent Averages Only 7 mg/l
1-115
-------
RECOMMENDATIONS FOR THE TRE PLAN
Additional TIE Analyses to Identify the
Effluent Toxicants
Tests to Characterize the Nature and
Sources of Influent Toxicity
In-Depth Assessment of Pretreatment and
WWTP Control Options
RESULTS OF TOXICITY IDENTIFICATION
EVALUATION PHASE I
SAMPLE DATE
CLASSES OF SUSPECTED TOXICANTS
AUGUST 1988
OCTOBER 1988
FEBRUARY 1989
APRIL 1989
JUNE 1989
LC50 > 100%
AMMONIA TYPE COMPOUNDS
AND NON-POLAR ORGANICS
AMMONIA TYPE COMPOUNDS
AND NON-POLAR ORGANICS
LC50 > 100%
LC50 > 100%
1-116
-------
RESULTS OF TOXICITY IDENTIFICATION
EVALUATION PHASE II
SAMPLE DATE TOXIC METHANOL / WATER ELUATES
25 50 75 80 85 90 95 100
OCTOBER 1988 * * *
FEBRUARY 1989 * * * *
REFRACTORY TOXICITY
ASSESSMENT PROCEDURE
BATCH TESTS
Samples:
48" sewer lines
30" sewer line
20" sewer line
Combined Influent
CONDITIONS
Operational WWTP Parameters:
MLSS
Dissolved Oxygen
Food to Microorganism Ratio
ANALYSIS
Acute toxicity of batch influent
and batch effluent samples
RESULTS
Refractory wastewater toxicity:
48" sewer line
30" sewer line
20" sewer line
Combined Influent
1-117
-------
SCHEMATIC OF BATCH REACTOR
WASTEWATER SAMPLE
AND WWTP ACTIVATED SLUDGE
AIR STONE
-— MAGNETIC
STIRREr
REFRACTORY TOXICITY ASSESSMENT OF
FALLING CREEK WWTP INFLUENT WASTEWATERS
Sampling Date: February 14-15, 1989
BATCH TEST
WASTEWATERS
CERIODAPHNIA
TIMED LETHALITY
TOXIC UNITS
48" sewer influent
48" sewer influent
30" sewer influent
30" sewer effluent
20" sewer influent
20" sewer effluent
Combined influent
Combined effluent
30"+ combined effluent
20"+ combined effluent
32.2
13.1
0
0
27.0
14.7 (9.8)
27.8
18.0
11.4
9.8
1-118
-------
REFRACTORY TOXICITY ASSESSMENT OF
FALLING CREEK WWTP INFLUENT WASTEWATERS
Sampling Date: April 18-19, 1989
CERIODAPHNIA
BATCH TEST TIMED LETHALITY
WASTEWATERS TOXIC UNITS
48" sewer influent 0
48" sewer influent 0
30" sewer influent 0.8
30" sewer effluent 0 (4.9)
20" sewer influent 24.5
20" sewer effluent 0
Combined influent 4.9
Combined effluent 3.3
SUMMARY OF PHASE 2
AND 3 RESULTS
Acute effluent toxicity was attributed
primarily to non-polar organic compounds
and to a lesser extent to ammonia-type
compounds
Two of the three main sewer lines (48" and
20" lines) were found to contribute acute
refractory toxicity
1-119
-------
RECOMMENDATIONS FOR
PHASE 4 TESTING
TIE Phase II testing will be to identify
the non-polar organic compounds in the
methanol fraction found to be causing
acute effluent toxicity
Identification of the sources of the toxicity
in the sewer lines will require additional
sewer line testing and a survey of
commercial discharges
1-120
-------
PHASE 4
DEVELOPMENT OF TOXICITY CONTROL OPTIONS
TOXICITY
IDENTIFICATION
EVALUATION
PHASE II
PHASE 4A STUDY PLAN
PRETREATMENT
EVALUATION
WWTP EVALUATION
PHASE 4A REPORT/
PHASE 4B STUDY PLAN
IN-DEPTH
PRETREATMENT
EVALUATION
IN-DEPTH WWTP
EVALUATION
RECOMMEND TOXICITY CONTROL OPTION(S)
(PHASE 5)
IMPLEMENT TOXICITY CONTROL OPTION(S)
(PHASE 6)
1-121
-------
ISSUES TO CONSIDER
IN PHASE 4
The availability of pretreatment data on
commercial dischargers
The effect of the proposed nutrient control
process(es) on final effluent toxicity
The effect of WWTP sidestream discharges
on final effluent toxicity
1-122
-------
TREATABILITY DATABASE
Glen Shaul, USEPA and Richard Osantowski and
Stephanie Hansen, Radian Corp.
1-123
-------
Treatability Database
Glen Shaul, USEPA and Richard Osantowski and Stephanie Hansen, Radian Corp.
I. Introduction
II. Discussion of the Program Format
III. Codes and Abbreviations
IV. Sample
A. Phenol
B. PCB 1254
V. Summary
VI. Questions and Answers
1-124
-------
WERL TREATABILITY
DATABASE
Introduction
The Risk Reduction Engineering Laboratory, which now includes the former
Water Engineering Research Laboratory, has developed and is continuing
to expand a database on the treatability of chemicals in various types of
waters and wastewaters. This activity is being conducted under the direction
of Mr. Kenneth A. Dostal.
The following editing rules are being used to evaluate the data prior
to entry into the database:
o Only primary references will be used.
o Bench-top and pilot-plant data from biological treatment processes
must be from acclimated systems.
o Only matched pairs of influent and effluent data will be used.
o Data will be from continous flow processes in equilibrium unless
noted by a "(B)" in the "Technology" column.
The compound name used in the database will be labled as a "Primary Name"
in the "Compound Name List". Other chemical names are synonyms for the
"Primary Name". If treatability data are not available, only information
related to chemical and physical properties, environmental data and possibly
adsorption data will be given.
If you have any questions/comments concerning this database or would like
additional information on a reference, please contact:
Mr. Kenneth A. Dostal
Risk Reduction Engineering Laboratory
Environmental Protection Agency
26 W. Martin Luther King Drive
Cincinnati, Ohio 45268
684-7503 (FTS)
(513) 569-7503 (Commercial)
Treatment Technologies Code and Abbreviation Table
Treatment Technologies
AAS - Activated Alumina Sorption
AFF - Aerobic Fixed Film
AL - Aerobic Lagoons
API - API Oil/Water Separator
AS - Activated Sludge
AirS - Air Stripping
AnFF - Anaerobic Fixed Film
AnL - Anaerobic Lagoons
BGAC - Biological Granular Activated Carbon
CAC - Chemically Assisted Clarification
ChOx - Chemical Oxidation (Parantheses shows oxidation chemical
ie. ChOx(Oz) - is ozone)
ChOx/Pt - Chemical Oxidation/Precipitation
ChPt - Chemical Precipitation
DAF - Dissolved Air Flotation
Fil - Filtration
GAG - Activated Carbon (Granular)
KPEG - Dechlorination of Toxics using an Alkoxide (Formed by the reaction
1-125
-------
of potassium hydroxide with polyethylene glycol (PEG400))
IE - Ion Exchange
PACT - Powdered Activated Carbon Addition to Activated Sludge
RBC - Rotating Biological Contactor
RO - Reverse Osmosis
SBR - Sequential Batch Reactor
SCOx - Super Critical Oxidation
SExt - Solvent Extraction
SS - Steam Stripping
Sed - Sedimentation
TF - Trickling Filter
UF - Ultrafiltration
UV - Ultraviolet Radiation
WOx - Wet Air Oxidation
NOTES:
+ is the first process unit followed in process train
by the second ie. AS -I- Fil - Activated Sludge followed
by Filtration.
w is the two units together ie. UFwPAC - Ultrafiltration
using Powdered Activated Carbon.
Scale
B - Bench Top P - Pilot plant F - Full scale
Number after letter refers to the plant number in a specific reference
(ex. F7 - plant 7 is the seventh full scale plant in the indicated report).
Matrix
C - clean water (ex. distilled)
D - domestic wastewater
GW - ground water
HL - hazardous leachate
I - industrial wastewater
I+HL - industrial waste combined with leachate from hazardous landfill
ML - municipal leachate
RCRA - RCRA listed wastewater
S - synthetic wastewater
SF - superfund wastewater
SP - spill
T - tep water
W - surface water
SIC (Standard Industrial Classification) Codes
For industrial wastewaters a 2 digit SIC code will be given following
the letter designation, i.e. I 22 is a Textile Mill Products wastewater.
If the SIC code is unknown a U will be shown, I U.
10 - Metal mining
12 - Coal mining
13 - Oil and gas extraction
20 - Food and kindered products
22 - Textile mill products
24 - Lumber and wood products
26 - Paper and allied products except computer equipment
27 - Printing and publishing
28 - Chemicals and allied products
29 - Petroleum refining and related
30 - Rubber and misc. plastic products
31 - Leather and leather products
33 - Primary metals industries
1-126
-------
34 - Fabricated metal products except machinery & transportation equip.
36 - Electronic and electric equipment
39 - Misc. manufacturing industries
47 - Transportation services
49 - Electric, gas, and sanitary
99 - Nonclassifiable establishments industries
Effluent Concentration
Effluent concentration will be given as a arithmetic mean to two
significant figures. The number of samples used to calculate the
mean is given after concentration as (n) (ex. 13 (5) - 13 is the
mean of 5 sample values).
% Removal
Percent removal wi1! be calculated on a concentration basis. If data
are available, it will also be calculated on a mass basis for
physical/chemical systems. Those vaules calculated on a mass basis
will be noted by a (m). An example would be:
% Removal: 99.95 99.95 is based on concentration
98(m) 98 is based on mass
where % Removal - Influent - Effluent
Influent
Reference Codes
A - Papers in a peer reviewed journal.
B - Government report or database.
C - Reports and/or papers other than in groups A or B not reviewed.
D - Group C papers and/or reports which have been given a. "good"
quality rating by a selected peer review.
E - Group C papers and /or reports which have been given a "poor"
quality rating by a. selected peer review. This data will only
be used when no other data are available.
Codes Identifying Additional Data Presented In The Reference
V - Volatile emissions data
S - Sludge data
$ - Costs data
Physical/Chemical Properties Data
(c) - Values presented are values that were reported calculated
in the reference as is and are only used where measured
are not available.
NA - Value for the particular property have not been found
in literature to date.
END
1-127
-------
WERL Treacabilicy Database
Ver No. 2.0
10/26/89
PHENOL
CAS NO.: 108-95-2
COMPOUND TYPE: PHENOLIC,
FORMULA: C6 H6 0
CHEMICAL AND PHYSICAL PROPERTIES
REF.
MOLECULAR WEIGHT: 94.11
MELTING POINT (C): 43
BOILING POINT (C): 181.7
VAPOR PRESSURE @ T(C), TORR: 0.35 @ 25
SOLUBILITY IN WATER @ T(C), MG/L: 8 E4 <§ 25
LOG OCTANOL/WATER PARTITION COEFFICIENT: 1.46
HENRY'S LAW CONSTANT, ATM x M3 MOLE-1:1.3 E-6 @ 25
333A
333A
333A
1006A
1006A
163A
191B
ENVIRONMENTAL DATA
REF.
CHRONIC NONCARCENOGEHIC SYSTEMIC TOXICITY
RISK ESTIMATES FOR CARCINOGENS
DRINKING WATER HEALTH ADVISORIES/STANDARDS
WATER QUALITY CRITERIA
AQUATIC TOXICITY DATABASE
4B
NA
NA
4B
5B
FREUNDLICH ISOTHERM DATA
ADSORBENT
FILTRASORB 300
FILTRASORB 300
XAD 4
FILTRASORB 400
WESTVACO WV-L
FILTRASORB 400
POLYBENZIHIDAZOLE
POLY(4- VINYL FYRIDINE)
WLTRASORB F400
FILTRASORB 400
MATRIX
C
C
C
C
C
C
C
C
C
C
K
29
21
0.91
50
13.3
0.037
0.079
0.223
78.1
77.4
1/H
0.33
0.54
0.76
0.26
0.299
0.371
0.917
0.894
0.212
0.211
Ce
UNITS
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
X/K
UNITS
mg/gm
mg/gm
mg/gm
mg/gm
mg/gm
mg/mg
mg/gm
mg/gm
mg/gm
mg/gm
REF.
138D
3B
19 3 A
72E
1083E
450D
381D
381D
1721A
489D
PHENOL
CAS NO.: 108-95-2
INFLUENT CONCENTRATION - 0-100 ug/L
EFFLUENT
TECHNOLOGY MATRIX SIC SCALE CONCENTRATION PERCENT REFERENCE
CODE ( ug/L ) REMOVAL
AS
AS
AS
AS
TF
TF
D
D
D
D
D
D
F31
F4
P
F59
F21
P
<1 (6)
<1 (3)
10 (11)
<26 (6)
1 (6)
8 (10)
>98.3
>96.4
90.0
>63
98.2
91.3
IB
IB
240A
IB
IB
240A
-S-
-S-
-S-
-S-
-S-
-S-
1-128
-------
UERL Treacability Database
Ver. No. 2.0
10/26/89
PHENOL
CAS NO.: 108-95-2
INFLUENT CONCENTRATION -
TECHNOLOGY M^IX «C SCALE CONCENTRATION PERCENT
REFERENCE
AL
AL
AS
AS
AS
AS
AS
AS
AS
AS
AS
AS
AS
CAC
TF
TF
GAC
AL
API+DAF+AS
AS
AS
AS
AS
AS
AS
AS + Fil
ChOx(Cl) (B)
ChOx(Cl) (B)
GAC
AL
AS
RBC
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
HL
I
I
I
I
I
I
I
I
I
I
I
S
SF
SF
SF
28
29
28
28
28
28
28
28
28
28
28
PI
P2
P
F28
P
F38
F19
F
PI
F30
F36
F58
F60
P
F52
P
F2
F12
F
F4
Fl
F3
F5
F31
Fll
F29
B4
Bl
B2
P
_ _ ,
84 (11)
18 (11)
<14 (8)
1 (6)
14 (11)
<1 (6)
<1 (5)
20 (31)
<8 (4)
2 (5)
25 (6)
<61 (6)
<8 (5)
99 (11)
<47 (6)
64 (11)
<10 (1)
<11 (3)
85 (4)
<20
<10 (3)
<10 (39)
<15 (7)
<10 (11)
120 (3)
<10 (15)
16
<2
10
sin
*"lfl
<10
PHENOL
-----------
33
86
>94.6
99.89
89
>99 . 44
>99.33
92.6
>97.2
98.6
94.4
>92.4
>97.2
21
>82
49
>92.6
>90.8
89.5
>87
>98.6
>96.4
>98.0
>96.3
97.9
>98.0
93.3
>98.3
99.00
>98.99
>98.99
>98.99
203A
203A
204A
IB
203A
IB
IB
201B
241B
IB
IB
IB
IB
203A
IB
203A
245B
6B
1482D
975B
6B
6B
6B
6B
6B
6B
975B
975B
1054E
192D
192D
192D
-S-
-S-
-S-
-S-
-S-
-S-
-s-
-s-
vs-
-s-
-S-
-s-
-s-
-s-
-s-
-s-
--S
--S
--$
V--
CAS NO.: 108-95-2
INFLUENT CONCENTRATION - >1-10 mg/L
EFFLUENT
MATRIX SIC SCALE CONCENTRATION PERCENT
—- ( ug/L ) REMOVAL
TECHNOLOGY
GAC
AS
AS
AS
AS
ChOx(Cl) (B)
PACT
PACT
PACT
RO
HL
I 28
I 28
I 28
I 28
I 28
I 28
I 28
I 28
SF
REFERENCE
F
F3
Fl
F28
F42
B3
B2
Bl
F40
F4
<5 (1)
6.6
160
56 (4)
<21 (10)
12
8
<2
30 (3)
120
>99.89
99.87
95.0
96.9
>99.64
99.37
99.85
>99.955
98.6
93.6
237A
975B
975B
6B
6B
975B
9758
975B
6B
250B
--$
--$
--$
--$
--$
TECHNOLOGY
SBR
AS
AS
AS + Fll
PACT
AS
INFLUENT CONCENTRATION
MATRIX SIC SCALE
CODE
HL+I U
I 28
I 28
I 28
I 28
S
P
F17
F
F26
B
B2
- >10-100 mg/L
EFFLUENT
CONCENTRATION PERCENT
( ug/L ) REMOVAL
1,000 (16)
<10 (3)
4.000
<13 (3)
<1.8
1.000
97.7
>99 . 944
95.2
>99.976
>99.991
95.0
REFERENCE
1433D ---
6B
1122E ---
6B
190E
1054E V--
1-129
-------
WERL TreatabUity Database
Ver. No. 2.0
10/26/89
PHENOL
CAS NO.: 108-95-2
INFLUENT CONCENTRATION - MOO-1000 mg/L
EFFLUENT
TECHNOLOGY MATRIX SIC SCALE CONCENTRATION PERCENT REFERENCE
CODE ( mg/L ) REMOVAL
SBR
SBR
SBRwPAC
AS
AS
RBC
SS
AS
AS
AS
AnFF
AnFF
AnFF
AnFF
WOx (B)
HL
HL
HL
I 28
I 28
I 23
I 49
S
S
S
S
S
S
S
S
P
B
B
F33
F8
P
P
B
P
B3
P
P
B
P
Bl
1 (1)
3
<1
<0.010 (13)
<0.010 (2)
1.7
160
<0.01
<0.5 (6)
0.25
0.07
0.01
<10
0.24
27
99.81
99.63
>99.88
>99.999
>99.996
99.60
24
>99.994
>99.949
99.88
99.981
99.999
>98.97
99.86
97.3
227D
64D
640
6B
6B
603E
1082E
202D
226B
1054E
231A
231A
230A
23SD
1054E
--$
--$
--$
VS-
vs-
V--
—
V--
TECHNOLOGY
WOx (B)
WOx (B)
AnFFwGAC
SExt
AnFF
AnFF
AnFF
WOx (B)
INFLUENT CONCENTRATION - >1 g/L
EFFLUENT
MATRIX SIC SCALE CONCENTRATION PERCENT
C
C
I 49
I 49
S
S
S
S
CODE
B
B
P
P
B
P
P
B2
( rng/L )
3.6
3.0 (1)
0.05
210
<1
0.03
0.7
20
REMOVAL
99.920
99.97
99.997
95.4
>99.947
99.998
99.976
99.89
REFERENCE
1101D
236A
249D
1082E
230A
231A
231A
1054E
...
V--
WERL TreatahiUty Database
Reference Number: 231A
Wang, Y.T., M.T. Suidan, and B.E. Rlttman. "Anaerobic Treatment of Phenol
by an Expanded-bed Reactor", Journal WPCF, Vol. 58, No. 3, pp 227-233
(March 1986).
Used an upflow, completely-mixed, expanded-bed anaerobic piloc plant for
588 days.
Reactor:
Dia. - 10.2 cm ID
Length - 134.6 cm
Flow rate - 4.5 al/mln
Recycle - 5.1 L/min
EBCT - 1 day
Media - 2.4 kg of GAC
Expansion - (approx.) 25%
Temp. - 35 C
*END OF DATA*
1-130
-------
WERL Treatabilicy Database
Ver No. 2.0
10/26/89
PCB 1254
CAS NO.: 11097-69-1
COMPOUND TYPE: PCB,
FORMULA: C12 H5 CL5 (48%)
CHEMICAL AND PHYSICAL PROPERTIES REF.
MOLECULAR WEIGHT: 328.4 378B
MELTING POINT (C) : N#.
BOILING POINT (C): 365 TO 390 378B
VAPOR PRESSURE @ T(C), TORR: 7.71 E-5 @ 25 378B
SOLUBILITY IN WATER @ T(C), MG/L: 0.057 @ 24 463A
LOG OCTANOL/WATER PARTITION COEFFICIENT: 6.03 (EST) 378B
HENRY'S LAW CONSTANT, ATM x M3 MOLE-1:8.37 E-3 @ 25 191B
ENVIRONMENTAL DATA REF.
CHRONIC NONCARCENOGENIC SYSTEMIC TOXICITY NA
RISK ESTIMATES FOR CARCINOGENS NA
DRINKING WATER HEALTH ADVISORIES/STANDARDS NA
WATER QUALITY CRITERIA 345B
AQUATIC TOXICITY DATABASE 5B
_ FREUNDLICH ISOTHERM DATA
Ce X/M
ADSORBENT MATRIX K 1/N UNITS UNITS REF.
FILTRASORB 400 C 0.73 1.14 ug/L mg/gra 764B
PCB 1254
CAS NO.: 11097-69-1
INFLUENT CONCENTRATION - 0-100 ug/L
EFFLUENT
TECHNOLOGY MATRIX SIC SCALE CONCENTRATION PERCENT REFERENCE
CODE ( ug/L ) REMOVAL
AFF S B2 0.36 (17) 64 70A -S-
INFLUENT CONCENTRATION - MOO-1000 ug/L
EFFLUENT
TECHNOLOGY MATRIX SIC SCALE CONCENTRATION PERCENT REFERENCE
CODE ( ug/L ) REMOVAL
AFF S Bl 11 (19) 98.9 70A -S-
1-131
-------
WERL Treatability Database Reference Number: 70A
Vitkus, T., P.E. Gaffney, and E.P. Lewis, "Bioassay System for Industrial
Chemical Effects on the Waste Treatment Process: PCS Interaction", Journal
WPCF, Vol. 57, No. 9. pp 935-941 (September 1985).
This study presents the results of using a lab-scale, fixed-film biomass to
evaluate long-term effects of continuous exposure to Aroclor 1254. The
system consisted of a set of four, 6 x 24 in. corrugated glass plates
supported on a tray arranged to incline the plates at a 10 degree downward
angle. The biomass attaches and grows on the glass.
Data reported is from the unit with 1 ppm feed of Aroclor 1254 and the unit
with 1 ppb feed of Aroclor 1254. For data on the hexane fe
-------
SESSION II
CATEGORICAL PRETREATMENT AND LOCAL LIMITS
Steve Bugbee, John Cannell, Claudia O'Brien, USEPA
ri-i
-------
Categorical Pretreatment and Local Limits
Steve Bugbee, John Canned, Claudia O'Brien, USEPA
I. Overview
II. Pretreatment Problems
III. Goals and Objectives
IV. National Pretreatment Program Strategy
A. Standards
B. Local Pretreatment Programs
V. Local Limits
A. Evolution of Local Limits
B. General Characteristics
C. Purposes of Local Limits
D. Who Develops Local Limits
E. Approaches
VI. Overview of Methodology for Developing Local Limits
A. Collecting Data
B. Develop Maximum Allowable Headworks Loadings
C. Determine Maximum Allowable Industrial Loading
D. Allocate Allowable Industrial Loading
II-2
-------
SCOPE OF THE PRETREATMENT PROGRAM
Municipal Sewage
Sludge
Indirect Industrial
Users
[160,000 Industrial/Commercial
30,000 Significant lUs]
[7.7 Million Metric Tons/Year
15,000 Permits]
Domestic Sources
Stormwater
(Industrial)
[25,000 Permits]
Direct
Industrial
Sources
[46,000 Permits]
Separate
Stormwater
(Municipal)
[169 Cities and
39 Counties]
bmbined
Sewer
Overflows
(CSOs)
[20,000 Overflows]
Municipal
Treatment
Plants
vo\[ 15,000 Permits]
STATISTICS:
* I Us contribute > 1.4 billion Ibs/yr. of metals and 83 million Ibs/yr of toxic organics to
POTWs
* 1500 POTWs receive > 80% of the 40 billion gallon total daily flow and > 90% of
the 8 billion gallon industrial daily flow
II-3
-------
PRETREATMENT PROBLEMS
Industrial discharges to sewer systems may have serious impacts on
POTW operations, receiving water quality, sludge quality, and compliance with
the NPDES permit.
3 cxoosure o' Workers to
To*iC SuOMan
nazaiQO(ji Fumes
Limiieo or More
Exoensive Sludge
Disposal Ootions
n ol Collection
S.siem or of me
Sijwaae Treatmeni Plant
Interference
Plant Treatment
System
6. Pass-Througb of
Toxic Pollutants
into Surface Waters
II-4
-------
GOALS AND OBJECTIVES
A. Goals of the CWA
1. Protect human health and the environment
2. Allow public recreation
B. Objectives of pretreatment
1. Prevent pass
2. Prevent interference, including sludge use and/or
disposal
3. Improve/encourage recycling and reclamation
MECHANISMS TO ACHIEVE OBJECTIVES
• National categorical standards
• National general and specific prohibited discharges
• Local limits developed by each control authority for site-
specific reasons.
II-5
-------
NATIONAL PRETREATMENT PROGRAM STRATEGY
STANDARDS
National Prohibited Discharge Standards
* Apply to ail non-domestic users of POTWs
* General prohibition against any pollutant causing:
-passthrough
-interference
* Specific prohibitions against discharges which:
-create fire or explosion hazard
-cause corrosion (pH < 5.0)
-cause obstruction (eg. solid or viscous pollutants)
-cause interference because of discharge volume or pollutant
concentration
-excessive heat
National Categorical Pretreatment Standards (see attached list)
* Technology based
* 25 categories promulgated with pretreatment standards which focus on
toxic pollutants
* locally enforced
Local Limits
* Developed by POTWs, as a requirement of the approved local pretreatment
program
* Implement general prohibition against passthrough and interference
* Implement specific prohibitions
* Designed to specifically consider local conditions in addressing environmental
impacts. Based upon consideration of:
-nature of industrial contributions
-ability of POTW to accept and treat wastes
-receiving stream
-sludge management
-NPDES permit requirements
II-6
-------
StMMABV STATUS Of NATIONAL CATEGORICAL PKKTREATMEHT STANDARDS: MILESTONE DATES
FINAL REGULATIONS
5/19/88
Industry Category
Aluminum Forming
Battery Manufacturing
Coll Coating (Phase I)
Coll Coating (Canmaklng)
Copper ForaIng
Electrical and Electronic
Components (Phase I)
Electrical and Electronic
Components (Phase II)
Electroplating
Inorganic Chemicals
(Interim, Phase I, and
Phase II)
Iron and Steel
Leather Tanning and
Finishing
Metal Finishing
Metal Molding and Casting
(Foundries) ,
Nonferrous Metals Forming
and Metal Powders
Nonferrous Metals Manufacturing
(Phase I)
Nonferrous Metals Manufacturing
(Phase 11)
Organic Chemicals, Plastics
and Synthetic Fibers
40 CFR
Part
467
461
465
465
468
469
469
413
415
420
425
433
464
471
421
421
Proposed
New Source
Rule Date
11-22-82
U-10-82
01-12-81
02-10-83
11-12-82
08-24-82
03-09-83
07-03-803
07-24-80
10-25-83
01-07-81
07-02-79
01-21-87
08-31-823
H-15-82
03-05-84
02-17-83
01-22-87
06-27-84
Promulgation
Date
10-24-83
03-09-84
12-01-82
11-17-83
08-15-83
04-08-83
12-14-83
01-28-81
07-15-83
07-20-77
06-29-82
08-22-84
05-27-82
11-23-82
04 M)f
07-15-83
10-30-85
08-23-85
03-08-84
Ol -21 -88
09-20-85
Effective
Date
12-07-83
04-23-84
01-17-83
01-02-84
09-26-83
05-19-83
01-27-84
03-30-81
08-29-83
07-20-77
08-12-82
10-05-84
07-10-82
01-06-83
05-04-88
08-29-83
12-13-85
10-07-85
04-23-84
03-07-88
1 1 -04-85
BMR Due Date
06-04-84
10-20-84
07-16-83
06-30-84
03-25-84
H-15-83
07-25-84
09-26-81 (Non-lnteg.)
06-25-83 (Integrated)
02-25-84 (TTO)
01-16-78
05-09-83
04-03-85
04-06-83
07-05-83
10-31-88
02-25-84
06-11-86
04-05-86
10-20-84
O6-06-88
05-03-86
PSES 90-Day
Conpllance Compliance Hep
Date Out Dale
10-24-86
03-09-87
12-01-85
11-17-86
08-15-86
07-01-84 (TTO)2
11 -08-85 (As)
07-14-86
04-27-84 (Non-lnteg.)
06-30-84 (Integrated)
07-15-86 (TTO)
07-20-80*
06-29-85
08-22-87
07-10-85
11-25-85
03-31-89 (Subpjri C)
06-30-84 (Part 413, TT")b
07-10-85 (Part 420. TTO)
02-15-86 (Final)
10-31-88
08-23-88
03-09-87
02-22-88 (Subiuri .»
09-20-88
OI-22-tt/
06-O7-8/
03-01-86
02-15-87
11-13-86
09-i9-H4
O2 -06-86
10-12-B6
(17-26-84
O9-28-8't
10-13-86
10-18-811
09-27-H'i
U-20-8/
10-OB-b')
02-23-Hl,
06-29-89
09-2B-H4
IO-08-H5
05-16-86
01 -29-B'J
11-21 HB
06-07 -«'
OV02 H»
I2-I9-HH
414,416 03-21-83
11-05-87
12-21-87
06-20-88
O2 -114 'M
-------
0/H-i.
Rev I
/19/88
SUHtAKV STATUS Ot NATIONAL CATEGORICAL FBETRKATMENT STANDARDS: MILESTONE DATES (Continued)
FINAL REGULATIONS
Industry Category
Pesticide Chemical*
Petroleum Refining
Pharmaceutical*
Manufacturing
Porcelain Enameling
Pulp, Paper, Paper board
Steam Electric Power
Ceneratlon
Timber Produces Processing
Footnotes:
TKo d*t<» af t h» nrnmneil nil* f
40 CFR
Part
455
419
439
466
430,431
423
429
ar parh mtf»onr\
Proposed
New Source
Rule Date
11-30-82
12-21-79
11-26-82
02-27-81
01-06-81
10-14-80
10-31-79
i IB iiflpd to A,
Promulgation
Date
I 0-04 -8 58
10-18-82
10-27-83
11-24-82
11-18-82
11-19-82
01-26-81
et eral n*» t h*» n**u
Effective
Date BMR Due Date
—
12-01-82 05-30-83
12-12-83 06-09-84
01-07-83 07-06-83
01-03-83 07-02-83
01-02-83 07-01-83
03-30-81 09-26-81
i source fltatus of an Industrial I
PSES
Compliance
Dale
12-01-85
10-27-86
11-25-85
o;-oi-84
07-01-84
01-26-84
faclllrv. Industrial f»*<-llll
90-Day
Compl lance Report
Due Date
03-01-85
01-25-87
02-23-86
09-29-84
09-29-84
04-25-H4
existence or that began construction of the regulated processes prior to that date are considered existing sources. New sources are facilities that
began construction of the regulated processes after the date of the proposed rule.
The compliance date for total toxic organlcs (TTO) for facilities subject to existing source Electrical and Electronic Components, Phase I regulations Is
July 1, 1984. The compliance date for arsenic under this category is November 8, 1985.
The Electroplating proposed rule date Is not used to determine ti -:w H»UI e/exlsting source status of a facility. The Metal Klnlshing proposed rule
date Is used to make this determination for all electroplating and ueial Mulshing facilities.
4
The compliance date for Subparts A, B. L, AL, AR, BA, and BC of the Inorganic Chemicals category la July 20, 1980. The compliance dale for Subparts Al,
AU, 8L, BM, UN, and BO (except discharges from copper sulfate or nickel aulfate processes) Is August 22, 1987. The compliance date tor copper suit alt- or
nickel sulfate processes and for all Subparts of Part 415 not listed above Is June 29, 1985.
These dates' apply only to Subpart C.
Existing sources that are subject to the Hetal Finishing standards in 40 CFR Part 433 must comply only with the Interim llalt for Total Toxl. organ its
(TTO) by June 30, 1984. Plants also subject to the Iron and Steel Manufacturing standards In 40 CFR Part 420 must comply with the Interim rro linli l>y
July 10, 1985. The compliance date for metals, cyanide, and final TTO Is February 15, 1986 for all sources.
These dates are for subpart J, tungsten category
On July 25, 1986, the Eleventh Circuit Court of Appeals remanded to the EPA the final regulation originally promulgated on O. • tuber 4. I9H'> lor i he
Pesticide Chemical* category. EPA removed the regulation from the Code of Federal Regulations on4December 15, 1986 (40 KR 44911).
Note: The compliance date for any dlacharge that is subject to pretrtatment standards for new source facilities (HSNS) Is ilie s.ime il.iii- .is i h.-
'commencement of the discharge.
-------
LOCAL PRETREATMPNT PROGRAMS
Requirement for Local Program
* greater than or equal to 5 million gallons per day (mgd) design flow = local
pretreatment program required
* less than 5 mgd = program may be required where necessary to prevent
passthroughand interference
Local Program Components
* Legal authority * POTW sampling of industrial users
* Industrial user survey * Enforcement
and pollutant characterization * Reporting to the State or EPA
* Local limits * POTW inspections of industrial users
* Industrial user control * Industrial user ^onitoring and reporting
mechanisms (eg. industrial user permits)
II-9
-------
Number of Local Approved Pretreatmenl Programs
Required Local Programs - 1481
Total Approved Prograw - 1429
Region 1 75
2 79
Region 3 137
Reckn 4 39*
Region S
Region 6
Recta 7
Region 8
Region 9
Region 10
325
124
77
52
121
43
1977
1978
1981
1985
1987
EVOLUTION OF LOCAL LIMITS
Use of local limits initially proposed
Local limits adopted
40 CFR § 403.5 (c), (d), (e) promulgated by
EPA
Local limits policy memorandum
Guidance Manual on the Development and
Implementation of Local Limitations Under I IK
Pretreatment Program
11-10
-------
NEED FOR LOCAL LIMITS
Categorical standards do not address all contributed
pollutants
Categorical standards do not regulate other significant
industries
Categorical standards may not adequately protect a
particular POTW, its collection system, sludge quality, or
personnel
GENERAL CHARACTERISTICS OF
CATEGORICAL PRETREATMENT
STANDARDS AND LOCAL LIMITS
CHARACTERISTICS
Basis
Type of Limitations
Objective
Units
Point of Application
CATEGORICAL
PRETREATMENT STANDARDS
Technology (BAT)
Production/Concentration
Baseline Requirements
Daily Maximum/Maximum
Monthly Average
End of Regulated Process
LOCAL
LIMITS
Technical Evaluation
Concentration
Local Environmental
Objectives
Instantaneous/Da i ly
Maximum
End of Pipe
11-11
-------
PURPOSES OF LOCAL LIMITS
• Protect receiving stream
• Correct existing problems
• Prevent potential problems
• Protect POTW/personnel
• Increase efficiency and cut
O & M costs
• Increase sludge disposal options
WHO DEVELOPS LOCAL LIMITS?
[40 CFR § 403.5]
All POTWs required to have a pretreatment program must
develop and enforce local limits to implement the
general and specific prohibited discharges
All other POTWs with existing pass through or
interference problems must also develop and enforce local
limits.
11-12
-------
POLLUTANTS OF CONCERN
Types of Pollutants Sources Origin
Conventionals • Industrial • Pipe
Toxic pollutants • Commercial • Truck
Nonconventionals • Residential • Rail
Whole effluent toxicity
APPROACHES FOR ESTABLISHING
LOCAL LIMITS
Allowable headwords loading
Collection system
Industrial user ma^^ment practice plans
Case-by-case permitting
OVERVIEW OF METHODOLOGY
FOR DEVELOPING LOCAL LIMITS
Step 1 Collect data for local limits development
Step 2 Develop maximum allowable headwords loadings
Step 3 Determine maximum allowable industrial loading
Step 4 Allocate allowable industrial loading
11-13
-------
STEP 1. COLLECTING DATA FOR LOCAL
LIMITS DEVELOPMENT
Identify pollutants of concern
Determine applicable environmental criteria
Collect site specific data from:
- POTW treatment plant
Industrial users
Domestic/background sources
Conduct headworks analysis
STEP 2. DEVELOP MAXIMUM ALLOWABLE
HEADWORKS LOADINGS
May be Based on:
• Water quality criteria/standards
• NPDES limits
• Operational problems/inhibition
• Sludge disposal options
11-14
-------
STEP 3. DETERMINE MAXIMUM ALLOWABLE
INDUSTRIAL LOADING
• Subtract domestic/background contributions
• Subtract safety/growth factors
STEP 4. ALLOCATE ALLOWABLE
INDUSTRIAL LOADING
• Conservative pollutants
- Uniform allocation to all Ills
- Uniform allocation to selected lUs
- Varying allocations to lUs
• Nonconservative pollutants
11-15
-------
INDUSTRIAL FLOW
DOMESTIC FLOW
Inhibition threshold values
Activated sludge (C
Anaerobic digestion
LAND APPLICATION
TREATMENT PLANT
RECEIVING STREAM
background concentration (CjJ
stream water quafity standard (C^J
-------
TOXICITY REDUCTION IN INDUSTRIAL EFFLUENTS
James Patterson, Patterson & Schafer
11-17
-------
TOXICITY REDUCTION IN
INDUSTRIAL EFFLUENTS
James W. Patterson, Ph.D.
Patterson Schafer, Inc.
Suite 917
39 S. LaSalle Street
Chicago, IL 60603
I. Introduction
A. In-plant control options
1. Source elimination
2. Source segregation
a) Recycle/recovery/reuse
b) Off-site management
c) Segregated treatment and discharge
B. End-of-pipe control options
1. Equalization
2. Pretreatment
3. Combined Waste Treatment
II. Sources and Control of Anionic Pollutants
A. Aresenite and Arsenate
1. Industry sources and concentrations (Table 1)
2. Treatment processes (Tables 2 and 3)
a) Precipitation
b) Coprecipitation
c) Other processes
B. Hexavalent Chromium
1. Industry sources and concentrations (Table 4)
2. Treatment processes
a) Chemical reduction (Table 5)
b) Ion exchange (Table 6)
c) Evaporative recovery
d) Full-scale performance
11-18
-------
C. Cyanide
1. Industry sources and concentrations (Tables 7 and 8)
2. Treatment methods
a) Electrolytic decomposition (Table 9)
b) Alkaline chlorination (Tables 10 and 11)
c) Ozonation (Table 10)
3. Performance of Cyanide treatment processes
D. Fluoride
1. Industry sources and concentrations (Table 12)
2. Treatment processes (Table 13)
a) Lime precipitation
b) Alum coprecipitation
c) Adsorption
d) Efficiencies of fluoride treatment technologies
E. Selenite and Selenate
1. Industry sources and concentrations (Table 14)
2. Treatment processes (Tables 15 and 16)
III. Sources and Control of Cationic Metallic Pollutants
A. Cadmium
1. Industry sources and concentrations (Table 17)
2. Treatment processes
a) Hydroxide precipitation (Table 18)
b) Sulfide precipitation (Table 19)
c) Ion exchange
3. Trivalent Chromium
1. Industry sources and concentrations (Table 20)
2. Precipitation treatment (Table 21)
C. Copper
1. Industry sources and concentrations (Table 22)
II-19
-------
2. Treatment processes
a) Hydroxide precipitation (Table 23)
b) Sulfide precipitation (Table 24)
c) Ion exchange
d) Electrolytic recovery (Table 25)
D. Ferrous and Ferric Iron
1. Industry sources and concentrations (Table 26)
2. Oxidation-precipitation treatment (Table 27)
E. Lead
1. Industry sources and concentrations (Table 28)
2. Precipitation treatment (Table 29)
F. Mercury
1. Industry sources and concentrations (Table 30)
2. Treatment processes (Table 31)
a) Sulfide precipitation
b) Ion exchange
c) Coagulation
d) Adsorption
G. Nickel
1. Industry sources and concentrations (Table 32)
2. Treatment processes
a) Precipitation (Table 33)
b) Ion exchange
c) Evaporative recovery
d» Reverse osmosis
H. Zinc
1. Industry sources and concentrations (Table 34)
2. Treatment processes
a) Hydroxide precipitation (Table 35)
b) Sulfide precipitation (Table 36)
c) Reverse osmosis (Tables 37 and 38)
d) Electrolytic recovery (Table 39)
e) Evaporative recovery (Table 40)
ri-20
-------
REFERENCES
Note; All information not otherwise referenced is taken from -
Patterson, J.W., Industrial Wastewater Treatment Technology,
Butterworth Publishers, Inc., Stoneham, Massachusetts, 1985.
Eller, J. et al, "Water Reuse and Recycling in Industry," Journal
American Water Works Association, 62:3, 1970.
Kosarek, L. J., "Water Reclamation and Reuse in the Power,
Petrochemical Processing, and Mining Industries," in Proceedings,
Water Reuse Symposium, AWWA Research Foundation, Denver,
Colorado, 1979.
Matthews, J.E., Industrial Reuse and Recycle of Wastewaters,
U.S. Environmental Protection Agency Report EPA-600/2-80-183,
Kerr Laboratory, Ada, Oklahoma 74820, 1980.
National Academy of Sciences - National Academy of Engineering,
Water Quality Criteria, Washington, D.C., 1972.
National Association of Manufcturers, "Water Reuse in Industry,"
Washington, D.C., 1965.
Patterson, J. W., Industrial Wastewater Treatment Technology,
Butterworth Publishers, Inc., Stoneham, Massachusetts, 1985.
Schmidt, C.J. et al, "Wastewater Reclamation and Reuse at
Military Installations," in Water Reuse, E. J. Middlebrooks,
editor, Ann Arbor Science Publishers, Ann Arbor, Michigan, 1982.
Treweek, G.B., "Industrial Reuse of Wastewater: Quantity, Quality
and Cost," in Water Reuse, E.J. Middlebrooks, editor, Ann Arbor „_
Science Publishers, Ann Arbor, Michigan, 1982. *•
11-21
-------
Table 1. Arsenic Concentrations Reported for Industrial Wastewaters
Source
Insecticide Manufacture
Gold Ore Extraction
Gold Ore Extraction
Acid Mine Drainage
Acid Mine Drainage
Sulfuric Acid Manufacture
Zinc Ore Extraction
Copper Ore-Slag Granulation
Copper Ore-Acid Leaching
Copper Ore-Acid Leaching
Arsenic Trioxide Plant
Electrolytic Copper Refining
Boric Acid Production
Ammonia Manufacture
Wood Products Preserving
Timber Products Processing
Geothermal Water 0
Geothermal Power Plant Condensate
Coal-Fired Power Plant Ash
Pond Water 0.
Steam Electric Plant Cleaning
Coal Cleaning Leachate
Reference numbers from Patterson,
Treatment Technology, Butterworth
Arsenic (met/1)
Total Soluble Reference
362
910 10.1
1012 132
6.0-22.0
2.3
200-500
0.1-0.68
0.05-5.70
0.15-19.0
230
310
0.001-51
0.04-0.92
430
13-50
0-14
.03-3.0
11
001-1.0
0.0-310
0.76
1985, Industrial Wastewater
Pub 1 i shers , lncT7 Stoneham,
14
11
11
12
15
13
9
10
10
15
10
10
16
17
18
19
6
21
6
20
22
MA.
Table 2, Pilot Treatment Systems for Arsenic Removal
System
Iron
Low Lime
High Lime
Coagulant
Ferric
Lime 8
Ferric
Lime @
sulfate 3 45 mg/1 Fe
260 mg/1
sulfate 6 20 mg/1 Fe
600 mg/1
PH
6.0
10.0
11.5
Table 3. Pilot Plant Arsenic Removal
System
Iron
Low Lime
High Lime
Cumulat
Settling
90
79
73
ive Percent
+ Filtration
89
79
75
Removal
+ Carbon
96-98
82-84
84-88
Effluent
Concentration
(m
0.06
0.92
0.77
11-22
-------
Table 4. H*xavalent Chromium Waatewater Sources and Concentrations
c
Industrial Source Av
Leather Tanning 40
Sodium Dichromate Production
Sodiam Dichromate-Chromic
Acid Manufacture 1300
Chromic Oxide Production 101
(Particulate
Chrome Pigments Production
Multiproduct Pigments
Manufacturing
Paint Manufacturing
Dye Bouse Haste 300
Ink Formulating Waste 150
Municipal Refuse Incinerator
Scrubber Water 0.5
Ferroalloy Manufacturing
Aluminum Manufacturing 136
Production of:
Automobile Grills 700
Automobile Parts 30
Automobile Parts 11.5
Carburetors
Carburetors 91
Missile Parts 1
Typewriters and Office Machines 16
Silverware 5
Metal Fasteners 52
Ornamental Metal Parts 9
Specific Metal Treatment Operations:
Bright Dip Rinse
Bright Dip Bath
Etching Bath
Anodizing Bath 173
Anodizing Bath
Anodizing Rinse 49
Anodizing Rinse
Anodizing Rinse
Anodizing and Plating Rinse 10.4
Plating 1300
Plating 600
Plating
Plating
Plating 688'
Plating Bath Rinae 450
Plating Bath Rinsa 2310
Platinct Bath Rinse 73
Chromium (VI)
Saneje
560-1490
-
-
CrO,)
J 17-957
2-2000
0.4-7.5
-
-
-
0.06-121
-
-
-
-
46-81
-
_
-
-
-
-
1-6
10,000-50,000
200-58,000
-
15,000-52,000
-
30-100
0.2-30
-
-
-
100,000-270,000
60-80
-
-
-
-
Reference
2
3
4
5
6
7
a
9
3
10
11
12
13
13
14
15
16
13
13
13
13
14
7
2
18
19
20
19
20
21
16
22
2
20
23
24
24
25
26
Ra£«r«nca number* from Patterson, 1985
Table S. Summary of Treatment Levels Reported for Hexavalent
Chromium Wastes-Chemical Reduction
Chromium(VI) Concentration (mg/1)
Treatment Chemical
Sulfur Dioxide
Sulfur Dioxide
Sulfur Dioxide
Sulfur Dioxide
Sulfur Dioxide
Sulfur Dioxide
Bisulfite
Bisulfite
Bisullfite
Bisulfite
Bisulfite plus
Hydrazine
Metabisulf ite
Metabisulfite
Metabisulf ite
Metabisulfite
Ferrous Sulfate
Ferrous Sulfate
(Waste Pickle Liquor)
Initial
100
-
-
-
-
0.23-1.5
140
-
450-688
10.4
8-20. S
70
-
-
-
-
1300
Final
<0.05
0.3-1.3
1.0
0.01
0.05
0.1
0.7-1.0
0.05-0.1
<0.10
<0.005
0.1
0.5
0.025-0.05
0.1
0.001-0.4
1.0
0.01
Reference
5
39
41
42
43
44
27
49
24
16
29
32
100
S3
54
57
4
^leference numbers from Patterson, 1985
Table 6. Ion Exchange Performance in Hexavalent Chromium
Removal
Waatewater Source
Cooling Tower
Slowdown
Plating Rinsewater
Pigment Manufacture
* Ibs chromate/ ft
ChromiumL
Influent
17.9
10.0
7.4-10.3
9.0
44.8
41.6
1,210
resin
mq/1 Resin
Effluent Caoacitva
1.8 5-6
1.0 2.5-4.5
1.0
0.2 2.5
0.025 1.7-2.0
0.01 5.2-6.3
<0.5
Reference
71
73
74
75
76
77
78
Reference numbers from Patterson, 1985
11-23
-------
Table 7. Concentrations of Cyanide in Plating Wastewaters
Average
Process (mq/l>
Plating Rinse 2
Plating Rinse 700
Plating Rinse
Plating Rinse 32.5
Plating Rinse 25
Plating Rinse
Plating Rinse
Plating Rinse 3
Plating Rinse 55.6
Bright Dip
Alkaline Cleaning Bath
Plating Bath 30,000
Plating Bath
Plating Bath
Brass
Bronze
Cadmium
Copper
Silver
Tin-Zinc
Zinc
Range
(mq/1)
0.3-4
10-25
60-80
30-50
1.4-256
15-20
4,000-8,000
45,000-100,000
16,000-48,000
40,000-50,000
20,000-67,000
15,000-67,000
12,000-60,000
40,000-50,000
4,000-64,000
Reference numbers from Patterson, 1985
Table 8. Cyanide Levels in Wastewatern Other Than
Plating Industry
Industrial Source
Blast Furnace Scrubber Water
Blast Furnace Scrubber Water
Blast Furnace Scrubber Water
Ferroalloy Scrubber Waters
Coke Plant Waste Streams
Coke Oven Liquor
Decantation Tank
Final Cooler Condensate
Benzole Separator
Oil Generation Plant Separator
Spent Limed Liquor
Coke Plant Ammonia Liquor
Coke Plant Ammonia Liquor
Coke Plant Ammonia Liquor
Coke Plant Waste
Coke Plant Waste
Coke Plant Waste
Color Film Bleaching Process
Hydrogen Cyanide Manufacturing
Coal Conversion Wastes
Coal Conversion (Synthane)
Gold Ore Extraction
Explosives Manufacture
Petroleum Refining
Paint and Ink Formulation
Cyanide
Concentration
(mq/1)
0.2-1.4
2.4
48.5
0.7-5.4
0-8
8
196
2736
104
4
2-44.5
20-60
7.5-39.6
10.0-38.1
100
91-110
71
14-42
(28 avg)
2-30
1-6
18.2-22.3
0.0-2.6
0.0-1.5
0.0-2.0
Reference
2
3
4
5
6
7
8
9
2
8
8
10
11
8,12-14
From the
Reference
15
15
16
17
18
19
20
21
22
23
15
24
25
26
23
27
28
28
28
Reference numbers from Patterson, 1985
11-24
-------
Table 9. Electrolytic Decomposition of Cyanide Waste
Initial Cyanide Tim« to
Run Concentration Decompose
No. (mg/1) (Days)
1 95,000 16
2 75,000 17
3 50,000 10
4 75,000 18
5 65,000 12
6 100,000 17
7 55,000 14
8 45,000 7
9 50,000 14
10 55,000 8
11 48,000 12
Final
Cyanide
Concentration
(mg/1)
0.1
0.2
0.4
0.2
0.2
0.3
0.4
0.1
0.1
0.2
0.4
Table 10. Treatment Levels for Cyanide Wastewaters
Cyanide Concentration
(mq/1)
Treatment Process Initial Final
Alkaline Chlorination3 28(avg) 2.0
Alkaline Chlorination3 - 1.7
Alkaline Chlorination3 _ 0 x
Alkaline Chlorinationb - 0.4
Alkaline Chlorinationb 700 0.0
Alkaline Chlorinationb 32.5 0.0
Alkaline Chlorinationb 1.3 0.25
Alkaline Chlorinationb - 0.6
Alkaline Chlorinationc 5.1 0.1
Electrolytic
Decomposition 45,000-100,000 0.1-0.5
Electrolytic Decompositon 20 0.5
Ozonation 25 0.0
fca Single-stage chlorination.
Two-stage chlorination.
High-pH, high-temperature process.
Reference numbers from Patterson, 1985
Table 11. Summary of Plating Industry Cyanide
Range of
No. of Flows
Treatment Process Plants (1,000 qpd)
Batch Chlorination 9 1-624
Continuous Chlorination 16 23-1,000
Integrated Process 5 18-192
Electrolytic Decomposition 2 60-630
Evaporation 5 8-100
Percent
Removal Reference
92.9 25
67
40
10
100 3
100 5
80.7 68
68
98 44
99.99+ 11
97.5 50
100 7
Treatment
Effluent Cyanide
(mg/1)
Range Avg
•CO.01-0.2 <0.04
0.0-<1.0 <0.10
0.02-<0.10 <0.05
0.35-1.0 0.68
<0. 3-1.1 <0.55
11-25
-------
Table 12. Reported Fluoride Levels in Industrial wastewaters
Source
Computer Circuits
Printed Cir".- i •' -.•-£ ;
Aluminum ore SPS? : v. '.no
Coke Plant Aima»ni.-<
Recovery Still
Steel Manufacture
Sintering Plants
Blast Furnaci
Basic Oxygen Furnace
Open Hearth f irnare
Electric Arc Farnacc
Fluoride Concentration
(ma/1 •
Banqe Avg Reference
57.8 7
'7.5 !5
10,2-1,500 147.7 9
10--100 - 10
^
8.5
Q, 49-23. C 14.0
3.75-! '. 9.1
4>-3~Ur 106.5
1-V - 8.2
Aluminum Production
(Gas Scrubber Wast'?)
Phosphate Ore
Furnace Slag Quench
73-270
'1,000
11
12
Phosphoric Acid Production
Phosphoric Acid Production
Phosphoric Acid Production
Phosphoric Acid Production
Phosphate Fertilizer Plant Waste
Phosphate Fertilizer Plant Waste
Hydrogen Fluoride Manufacture
Hydrogen Fluoride Manufacture
Glass Manufacture
TV Picture Tube
Incandescant Bulb Frost
Pressed and Blown Glass
Fluobocate Plating Bath
Titanium Descaling Bath
Aluminum Deoxidizer Bath
Steel Alloy O-ssca'.ing B'sth
Acidic Coal Cleaning Haste
30-150
4,000-1:;, ooo
11,100
1, ,460
308
1,050
13.0
193
143
•>.,30C
194-1, ?8C
.1 .: 4
6o,ooo-" • . :• •..'
2,250
16,000 ' !-; ,'" '
.-.. . __ 81
13
14
14
14
15
16
17
18
5
S
19
19
19
20
Reference nunibar* froa-. Patterson, 1985
Table 13. Su/ratecv
-------
Table 14. Industrial Sources and Haatswater Concentrations of
Selenium
Industry
Coal Mining
Coal File Drainage
Power Plant Scrubber Waste
Power Plant Ash Pond
Incinerator Ash Quench Hater
Petroleum Refining
Iron and Steel
Continuous Casting
Basic Oxygen Furnace
Iron Ore Milling
Copper Production
Ore Milling
Milling and Smelting
Milling, Smelting and Refining
Smelting and Refining
Lead/Zinc Ore Milling
Molybdenum Ore Milling
Titanium Ore Milling
Zinc Smelting
Hydrofluoric Acid Production
Copper Sulfate Production
Seleniun
Concentration
(uq/1)
2-50
1-30
1-2,200
<20-2,500
1-170
3-42
5-23
25-62
220
37
20
200
320
220
700
20-140
40
15
7,000
63
200
Reference
1
2
3
4
2
1
5
1
1
1
1
1
1
6
1
1
1
7
1
8
Reference numbers from Patterson, 1985
Table 15. Pilot Treatability Results for Selenium
Treatment
Cumulative Percent Removal
Initial Se Activated
(ug/1) Sedimentation + Filtration +• Carbon
Lime at 415 mg/1
to pH 11.5
Ferric chloride at
40 mg/1 as Fe and
500
36
35
96
pH 6.2
Alum at 220 mg/1 and
pH 6.4
50
500
68
53
80
48
77
82
Table 16. Removal of Selenium by Bench-Scale Advanced
Wastewater Treatment Processes
Process
Percent
Removal
Lime Precipitation-Settling (pH 7.6)
Cation Exchange
Cation Plus Anion Exchange
Process Sequence*
1st sand Filtration
2nd Activated Carbon
3rd Cation Exchange
4th Anion Exchange
16.2
0.9
99.7
9.5
43.2
44.7
99.9
a Cumulative removal after lime precipitation plus indicated
process sequence.
11-27
-------
Table 17. Cadmium Concentrations Reported for Industrial
Hastewaters
Process
Plating Rinse Haters
Automobile Heating
Control Manufacturing
Automatic Barrel Zn and Cd Plant
Mixed Plating, Manual Cd
Mixed Manual Barrel and Rack
Large Installations
Rinse Dragout
Rinse Dragout
Rinse Dragout
Rinse Dragout
Rinse Dragout
Large Job Shop
Recirculating Rinse
Metal Finishing Plant
Bright Dip and Passivation
Plating Baths
Nonferrous Metals Manufacture
Copper Smelting
Lead Smelting and Refining
Zinc Smelting and Refining
Copper and Zinc Smelting
Zinc Smelting and Refining
Iron and Steel Manufacturing
Iron Foundry Wastewater
Paint and Ink Formulation
Rubber Processing
Porcelain Enameling
Acid Lead Mine Drainage
Acid Mine Drainage
Coal Cleaning Acid Leachate
Cadmium
Concentration
(rnq/l)
14-22
10-15
0.9
7-12
15 avg, 50 max
48
158
0.1-6.0
0.4
58
3.1
1,000-3,330
2-8
2,000-5,000
0.09-1.08
0.08-1.20
0.02-33.0
15
0.02-33.0
0.00-80
0.16-0.95
0.00-0.81
0.00-0.72
0.00-9.60
1,000
400-1,000
0.21
Reference
4
5
6
5
7
8
9
10
11
11
12
10
13
5
14
15
15
11
16
17
18
17
17
17
1
19
20
Reference numbers from Patterson, 1985
Table 18. Hydroxide Precipitation Treatment for Cadmium
Method
Hydroxide Precipitation
Hydroxide Precipitation
plus Filtration
Hydroxide Precipitation
plus Filtration
Initial
Treatment Cd
pH (mq/1)
8.0
10.0
9.0
9.3-10.6
-
9.4-10.2
10.0
10.0
11.0
11.0
_
-
-
4.0
5.2
1.2
0.34
0.34
-
-
Final
Cd Percent
(ma/D Removal Reference
1.0
0.10
0.54
0.2
0.4
0.7
0.054
0.033
0.00075
0.00070
„
-
-
95
92
45
84.1
90.3
-
-
23
23
24
6
6
6
18
18
25
25
Hydroxide Precipitation
plus Filtration 11.5
Hydroxide Precipitation
plus Filtration
Coprecipitation with
Ferrous Hydroxide 6.0
Coprecipitation with
0.014
0.08
0.050
26
27
26
Ferrous Hydroxide
Coprecipitation with Alum
10.0
6.4
0.044
0.7 0.39 45
26
28
Reference numbers from Patterson, 1985
Table 19. Comparison of Lime and Lime plus Sulfide Precipitation
of Cadmium
Initial
Concentration
0.40
15.00
58.00
1.40
1.40
Treatment
DH
9.0
8.5
10.0
8.5
10.0
Lime -
Settled
0.098
0.080
1.130
0.432
0.073
Lime -
Filtered
0.011
0.007
0.923
0.360
0.066
Lime +
Sulfide-
Settled
0.055
0.050
0.026
-
-
Lime +
Sulfide-
Filtered
0.029
0.002
<0.010
-
-
11-28
-------
Table 20. Trivalent and Total Chromium Content of Industrial
Nastewaters•
Source
Ornamental Metal Facility
Total Waste
Cooling Tower Slowdown
Sheepskin Tannery
Tannery
Tannery
Steel Mill Effluent
Stainless Steel Acid Rinse
Metal Plating
Circuit Board Chrome Rinse
Aluminum Anodizing
Aluminum Anodizing
Dye House Wastes
Spent Etchants
Piston Ring Coating
Coal Cleaning Leachate
Titanium Dioxide Production
Sodium Dichromate Production
Sodium Dichromate Production
Trivalent Total
(mq/1) (mq/1)
7.25 16
60 250
15-60 15-60
42 42
47-52 47-52
5-10 5-10
3.5 3.6
10.2 11.8
32 105
28 164
1-400 1-430
300 600
7,000- 22,200-
45,000 87,000
0.14-4.7 0.16-4.7
0.42 0.42
50 50
240 800
10 1,500
Reference
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
24
24
Reference numbers from Patterson, 1985
Table 21. Summary of Trivalent
Method PH
Precipitation
Precipitation 8.8
Precipitation 12.2
Precipitation 7-8
Precipitation
Precipitation 8.5
with Sand Filtration 8.5
Precipitation
Precipitation 7.8-8.2
Precipitation 8.5-10.5
Precipitation
Precipitation 8.8-10.1
Precipitation 8.5
Precipitation
Precipitation 9.8-10.0
with Filtration 9.8-10.0
Chromium Treatment
Chromium (mq/lj
Initial Final
0.75
650 18
650 0.3
140 1.0
1300 0.06
7400 1.3-4.
7400 0.3-1.
2.2 0.02
16.0 0.06-0.
26.0 0.44-0.
11.75 2.50
0.6-30
47-52 0.3-1.
164 1
49.4 0.17
49.4 0.05
Reference
5
28
28
33
34
6 37
3 37
40
15 10
86 49
16
50
5 13
18
24
24
Reference numbers from Patterson,
H-29
-------
Table 22. Concentrations of Copper in Industrial Process Wastewaters
Process
Plating Rinse
Plating Rinse
Plating Rinse
Plating Rinse
Plating Rinse
Plating Rinse
Plating Rinse
Plating Rinse
Plating Rinse
Plating Rinse
Plating Rinse
Copper Plating Bath Rinse
First Rinse
Second Rinse
Welding wire Copper Plating
Plating Bath
Spent Acid
Rinsewater
Appliance Manufacturing
Spent Acids
Alkaline Hastes
Integrated Circuit Manufacture
Circuit Board Manufacture
Circuit Board Manufacture
Automobile Heater Production
Metal Finishing
Reference numbers from Patterson,
Table 22. (Continued)
Process
Silver Plating
silver Bearing
Acid Hastes
Alkaline wastes
Brass Plating
Pickling Bath Wastes
Bright Dip Wastes
Aluminum Anodizing
Anodizing and Plating
Anodizing and Plating
Brass Mill Rinse
Brass Mill Rinse
Brass Mill Bichromate picJcle
Brass and Copper wire Mill
Brass and Copper Pickle
Brass and Copper Bright Dip
Copper Mill Rinse
Copper Tube Mill
Copper Wire Mill
Copper Ore Extraction
Gold Ore Extraction
Gold Ore Extraction
Acid Mine Drainage
Acid Mine Drainage
Acid Mine Drainage
Paint Formulation
Ink Formulation
Copper Concentration
(ma/1)
20-120
0-7.9
20 !avg)
5.2-41
6.2-88
2.0-36.0
3-30
11.4
2.8-7.8 (4.5 avg)
21
24
183
2.2
3,640
34
2-10
0.06-11.0
0-1.0
0.23
16.5-77
2.3
24-33 (28 avg)
0.5-5
1985
Copper Concentration
(mq/1)
3-900 (12 avg)
30-590 (135 avg)
3.2-19 15.1 avg)
4.0-23
7.0-44
0.2-2.0
1.3
4.7
4.4-8.5
74-888
4.5-74
75-124
60-90
20-35
19-74
10 (avg)
800 (avg)
0.28-0.33
20
3.2
0.12-3.9
51.6-128.0
3.6-76
0.04-0.40
0.01-6.4
Reference
7
8
9
10
11
12
13
14
15
16
16
17
18
14
19
20
16
21
22
Reference
15
15
23
16
16
24
25
25
13
13
13
24
26
26
27
28
29
30
31
32
33
33 „
11-30
-------
Table 23. Suaraary of Effluent Copper Concentrations After
Hydroxide Precipitation Treatment
Copper Concentration (mq/i;
Source (Treatment)
Metal Processing (Lime!
Nonferrous Metal
Processing (Lime)
Metal Processing (Lime)
Initial
204-385
-
-
Final
0.5
0.2-2.3
1.4-7.8 (prior
1
Reference
52
53,54
55
Electroplating
(Caustic, Soda
Ash + Hydrazine)
Machine Plating
(Lime + Coagulant)
to sand filtration)
6.0-15.5 0.09-0.24 (sol.)
0.30-0.45 (tot.) 56
2.2 57
Metal Finishing (Lime)
Brass Mill (Lime)
Plating
Plating (CN oxidation,
Cr reduction,
neutralization)
Wood Preserving (Lime)
Brass Mill
(Hydrazine + Caustic)
Silver Plating (CN
oxidation, Lime +
FeCl3)
Copper Sulfate
Manufacture (Lime)
Integrated Circuit
Manufacture (Lime)
-
10-20
-
11.4
0.25-1.1
75-124
30 (avg)
433
0.23
0-1.2 (0.19 avg)
1-2
0.02-0.2
2.0
0.1-0.35
0.25-0.85
0.16-0.3 (with
sand filtration)
0.14-1.25 (0.48
avg)
0.05
58
26
59
60
61
62
15
36
19
Reference numbers from Patterson, 1985
Table 24. Comparison of Lime versus Lime plus Sulfide Precipitation
Treatment for Copper
Treatment
PH
8.5a
8 .5b
8.5 =
8.5d
9.3=
10. fla
Initial
Concentration
21
7
4
2
1
2
.0
.0
.7
.3
.3
.0
Lime Treatment
Clarified
1
0
0
1
0
0
.30
.04
.14
.80
.24
.91
Filtered
0.
<0.
<0.
0.
0.
0.
37
01
01
20
24
94
Lime plus
Sulfide Treatment
Clarified Filtered
2
0
0
1
0
0
.25
.04
.08
.90
.21
.06
0
<0
0
<0
0
0
.17
.01
.02
.01
.17
.16
Wastewater Source: a = electroplating c • electroplating plus
b ** smelter scrubbing anodizing
d « printed circuit board
Table 25. Reduction of Copper and Cyanide by Batch
Electrolysis [93]
Days of Treatment
Start
1
4
6
a
11
18
Copper
(g/1)
26
23
11
6
2
0
-
Cyanide
(mg/1)
75
50
12
5
2
,000
,000
,500
,980
,200
750
0.2
PH
12.2
11.7
10.4
10.0
9.8
9.7
9.5
11-31
-------
Table 26. Iron Concentrations Reported for Industrial
Source
Steel Manufacture
Waste Pickle Liquor
Waste Pickle Liquor
Pickle Bath Rinse
Pickle Bath Rinse
Pickle Bath Rinse
Steel Cold Finishing Mills
Steel Mill Plant Wastes
Metal Processing and Plating
Appliance Manufacture
Automobile Heating Controls
Appliances
Mixed Hastes
Spent Acids
Chrome Plating
Chrome Plating
Zinc Plating
Copper Plating
Plating Hastes
Plating Wastes
Plating Hastes
Hydrochloric Pickle Acid
Copper Plating Bath
Printed Circuit Board Manufacture
Titanium Dioxide Manufacture
Titanium Dioxide Manufacture
Aluminum Hot Rolling
Paint Manufacture
Ink Formulation
Dye House wastes
Power Plant Operations
Boiler Tube cleaning
Air Preheater Cleaning
Acidic Coal Cleaning Haste
Iron
Concentration
(ma/1) Reference
96,800
70,000
200-5,000
60-1,300
175
60-150
25-75
0.09-1.9
1.5-31
0.2-20
25-60
40
64
3.4
11.6-120
2-4
1.9-7.8
6-25
98,000
23,000
12.5
0.02-31,000
136
3,210
3.8-37.3
134
31.5
1,125
1,860
1,680 (ferrous)
1,630 (ferric)
15
16
17
18
19
20
21
22
23
24
16
25
25
26
27
28
29
26
26
30
31
32
33
34
34
35
36
37
Reference numbers from Patterson, 1985
Table 27. Precipitation Treatment Results for Iron Wastewaters
Iron Concentration
(ma/1) Treatment
Source
Base Metal Acid
Mine Drainage3
Initial
713
1202
1138
93
Final
0.54
0.58
0.25
0.42
0.16
0.53
0.22
pH Comments Reference
without filtration
With filtration
Without filtration
with filtration
without filtration
With filtration
46
Boiler and Air
Preheater
Cleaning Wastes 1125-1860
Titanium Dioxide
Manufacture
Titanium Dioxide
Manufacture 159
Steel Hill Wastes
(Rinsa I Spent
Pickle) 25-75
Graphite Mine
Drainage
Plating Rinse 7.8
Chrome Plating
Rinse 64
Zinc Plating Rinse 3.4
Iron Blue Pigment
Manufacture
Heavy Farm Equipment
Manufacture 56
0.20
0.48
0.19
1.0
0.10
0.11
<0.05
<0.05
1.0
1.6-3.1
Range 0.1-3.0
10.0 Without filtration
10.0 With filtration
Microflotation for
6.9 solids separation
11.0 with filtration
11.6 With filtration
Range 0.2-2.0
8.5-10.5
31
32
21
55
23
25
25
6
11
1 Pilot plant results
Reference numbers from Patterson,
1985
11-32
-------
Table 28. Reported Lead Levels in Industrial Mastevaters
Industry
Battery Manufacture,
Particulate Lead
Soluble Lead
Battery Manufacture,
Particulate Lead
Soluble Lead
Battery Manufacture
Battery Recovery
Plating
Plating
Plating
Plating Pickle Liquor
Television Tube Manufacture
Printed Circuit Board Manufacture
Glass Manufacture
Porcelain Enameling
Chlor-Alkali Plant
Mining Process Water
Ammunition Plant
Tetraethyl Lead Manufacture
Organic Lead
Inorganic Lead
Tetraethyl Lead Manufacture
Spent Ink
Paint Manufacture
Paint and Ink Formulation
Pigment Manufacture
Pigment Manufacture
Lead (ma/1)
5-48
0.5-25
0.4-66.5
2.6-5.1
40.3-319.4
11.7
2-140
0-30
0.2-2.0
10
380-400
1.65
0.43-100
2.9
1,160
0.013-0.098
6.5
126.7-144.8
66.1-84.9
45
94
1.1-10.0
86
1-200
0.2-843
Reference
2
3
23
4
8
6
24
25
26
27
28
29
30
31
32
33
34
35
36
29
37
9
Reference numbers from Patterson, 1985
Table 28. (Continued)
Lead (mcr/1) Reference
Industry
Textile Dyeing
Steel Manufacture,
Vacuum Degassing Process
Rubber Hose Manufacture,
Lead Sheath Process
Foundry
Foundry
Piston Ring Manufacture
3.4 38,39
0.47-1.39 20
63
7.7
29-170
94.6
22
29
40
41
Table 29. Effect of pH on Lead Removal
Settled Suoernatant [50]
DH
5.2
-
-
7.1
-
-
8.0
9.2
10.5
10. a
11. 0
11.6
n
Lead ( mg/1 )
107
-
-
37
-
-
11.9
10.7
2.9
1.5
4.2
8.9
6
6
7
7
7
8
9
10
10
Soluble Concentration [51]
pH
-
.3
.6
.1
.4
.6
.5
.4
.5
.8
Lead* (aw/1) Leadb
-
24.6 1.
1.10
0.
0.131 0.
0.
0.055 0.
0.215 4.
0.150
8.
-
-
(ma/1)
30
035
025
040
075
10
36
" Inorganic carbon less than 2 mg/1.
Inorganic carbon is 3-5 mg/1.
Reference numbers from Patterson, 1985
11-33
-------
Table 30. Levels of Mercury in Industrial Wastewaters
Waste
Paper Mill
Fertilizer Mill
Smelting Plant
Chlor-Alkali Plant
Chlor-Alkali Plant 4
Chlor-Alkali Plant
Chlor-Alkali plant 3
Chlor-Alkali Plant
Chlor-Alkali Plant
Water Based Paint
Paint and Ink Formulation
Acetaldehyde Production
Fluorescent Lamp Production
Coal Fly Ash Pond Effluent
Textile Dyeing Waste
Textile Mill Waste
Secondary Lead Battery Recovery
Rubber Processing
Mercury
20-34
0.26-40
20-40
80-2,000
,600-5,100
1,400-2,800
,000-8,000
300-6,000
21,500
300
0-120,000
20,000
2
2-3
15,000
11
0.66 (Total)
<0.20 (Soluble)
0-720
Reference
9
9
9
9
10
5
11
12
13
7
14
8
15
16
17
18
9
14
Reference numbers from Patterson, 1985
Table 31. Summary of Treatment Technology for Mercury
Technology
Sulfide Precipitation
Ion Exchange
Alum Coagulation
Iron Coagulation
Activated Carbon
High Initial Hg
Moderate Initial Hg
Low Initial Hg
Lower Limit
of
Treatment Capability
(Ha, ua/1)
10-20
1-5
1-10
0.5-5
20
2.0
0.25
11-34
-------
Table it. Summary of Nickel concentrations Reported in
Wastewaters
Nickel Concentration
Source
Plating Plants
Four plants
Five plants
Rinse waters
Large plating plant
segregated flow
combined flow
Large job shop
Plating of zinc castings
Plating of plastics
Manual Barrel and Rack
Nickel Plate Rinse
Nickel Plate Rinse
Nickel Plating Rinse
Nickel Plating Rinse
Nickel Plating Rinse
Plating and Anodizing Rinse
Mixed Plating Rinse
Mixed Plating Rinse
Electroless copper plating
Tableware Plating
Silver bearing waste
Acid waste
Alkaline waste
Metal Finishing
Mixed wastes
Acid wastes
Alkaline wastes
Small parts fabrication
Brass pickling
Metal forging rinse
Steel pickling
Stainless steel pickling
Stainless steel pickling
Business Machine Manufacture
Plating wastes
Pickling wastes
Range
2-205
5-58
2-900
-
-
-
45-55
30-40
15-25
-
-
-
-
-
-
-
0.93-2.2
0-150
0-30
10-130
0.4-3.2
17-51
12-48
2-21
179-184
-
0.77-1.06
5-10
0.2-400
-
5-35
6-32
AVO
-
24
-
88
46
5.7
-
-
-
132
134
110
119
99
3.2
35
-
-
5
33
1.9
-
-
_
181
3
-
-
-
250
11
17
Reference
3
4
5
7
a
8
8
9
10
11
12
12
12
12
13
14
15
15
15
16
16
16
17
18
19
20
21
22
15
15
Reference numbers from Patterson, 1985
Table 32. ( Continued)
Nickel Concentration
(HKJ/I)
Source
Other
Mine drainage
Acid mine drainage
Acid mine drainage
Alkaline mine drainage
Coal storage pile drainage
Fly ash ponds
Acidic coal cleaning waste
Gold ore extraction
Gold ore extraction
Boiler tube cleaning
Boiler cleaning
acid waste
alkaline waste
Dye house effluent
Paint and ink formulation
Porcelain enameling
Nickel sulfate manufacture
Copper sulfate manufacture
Titanium dioxide manufacture
Sodium dichromate manufacture
Range
0.19-0.51
0.46-3.4
0.01-5.6
0.01-0.18
1-10
0.06-0.15
-
—
-
0.5-15.8
80-400
1-10
67.5
0-40
0.25-67
470-890
-
-
0.6-7.8
Avg
-
-
0.72
0.02
-
-
7.5
1.4
6.5
-
-
0.5
14
-
22
1.3
—
Reference
23
24
25
25
26
26
27
28
29
30
31
32
32
22
22
22
22
Table 33. Comparison of Lime Versus Lime Plus Sulfide
Precipitation of Nickel in Electroplating Wastewaters
Wastewater
Parameter
Treatment pH
Initial Nickel, mg/1
Lime Treatment
Clarifier Effluent
Filter Effluent
Lime plus Sulfide
Clarifier Effluent
Filter Effluent
A B
8.5 8.75
119.0 99.0
12.0 16.0
9.4 12.0
11.0 7.0
3.5 4.2
C
9.0
3.2
0.47
0.07
0.35
0.20
11-35
-------
Table 34. Concentrations at Zinc- in Process Wastewaters
Industrial Process
Metal Processing
Bright dip wastes
Brass mill wastes
Brass mill wastes
Pickle bath
Pickle bath
PicJcle bath
Wire mill pickle
Electrogalvanizing rinse
Bonderizing baths
Bonderizing rinse
Conversion coating rinse
Plating
General
General
General
General
General
General
Chrome
Nickel
Zinc
Zinc
Zinc
Zinc
Zinc
Zinc
Brass
Brass
Plating on zinc castings
Galvanizing of cold rolled steal
Anodizing plus plating
Zinc Concentration
(ma/11
0.2-37.0
40-1, 4S3
3-10
4.3-4].. I
0.5-37
20-35
36-374
500
1,000-1,000
?'.)
30.7
2.4-13.8
55-120
15-20
5-10
7.0-215
440-;PO
245-1,050
30
480
20-30
70-150
42
70-350
23. 2
11-55
10-60
3-6
2-88
0.3-33
Reference
2
3
3
2
3
4
5
S
7
7
8
9
10
11
4
2
12
13
13
13
4
2
14
15
16
2
13
4
17
12
Reference numbers from Patterson, 1985
Table 34. (Continued)
1\\-
Industrial Process
Ravon Wastes
General
Sar.eral
Other
Latex rubber products
Vulcanized fiber
Cooling tower blowdown
Cooling tower blowdown
Cooling tower blowdown
power plant boiler cleaning waste
Municipal refuse incinerator
scrubber water
Paint manufacturing wastes
Ink formulating (tub washwater)
Dye house waste
Textile Dyeing waste
Chrome pigment manufacturing
Chrome pigment manufacturing
Hydrofluoric acid production
Sodium bisulfite production
Petroleum refining
Ferroalloy smelting scrubber wa.i-,e*3
Nonferrous smelting'
scrubber water
Lead smelting
Lead battery manufacture
Gold ore milling
Ferrous foundry
Steel making - open hearth
Steel making - degassing
Primary copper smelting anrt refining
Acid plant blowdown
Arsenic plant washdown
Secondary copper manufacturing
Zinc smelting
Combined
Acid plant effluent
Auxiliary metal reclamation L
Scrap steel cupola scrubber wata "
Coal mine drainage
Acidic coal cleaning leachatge
Base metal mine drainage
c. Conc?nr:ra
-------
Table 35. Summary of Hydroxide Precipitation Treatment Results for
Zinc Hastevaters
Zinc Concentration
Industrial (ma/1)
Source Initial
Zinc Plating
General Plating 18.4
General Plating -
General Plating 55-120
General Plating 4.1
General Plating 46
Vulcanized Fiber 100-300
Brass Wire Mill 36-374
Tableware Plant 16.1
Viscose Rayon 20-120
Viscose Rayon 70
Viscose Rayon 20
Metal Fabrication
Radiator Manufacture-
Blast Furnace Gas
Scrubber Water 50
Zinc Smelter 744
1,5-00
Ferroalloy
Wastes 11.2-34
3-89
Ferrous Foundry 72
Deep Coal Mine -
Acid Waters 33-7.2
Final
o.:-o.s
2
0-6
1.0
0.39
2.9
1.9
2.8
2.9
1.0
0.08-1.60
0.02-0.23
0.88-1.5
3-5
1.0
0.5-1.2
0.1-0.5
0.33-2.37
0.03-0.38
0.2
50
2.6
0.29-2.5
4.2-7.9
1.26
0.41
0.01-10
Comments3
pB 8.7-9.3
pH 9.0
sand filtration
pH 7.5
pH 8.5
pH 9.2
pH 9.8
pH 10.5
pH 8.5-9.5
integrated treatment
copper recovery
sand filtration
pH 5
sedimentation
sand filtration
sedimentation
sand filtration
pH 8.8
sedimentation
sand filtration
Reference
46
47
48
10
49
14
23
for 5
2
20
50
19
51
52
53
42
42
26
26
38
1
All treatment involved
Special or additional a
"Comments."
Reference numbers from
precipitation plus sedimentation.
apact3 of treatment are indicated under
Patterson, 1985
Table 36. Comparison of Lime Precipitation versus Two-Stage Lime
Precipitation-Sulfide Precipitation Treatment for Zinc
Treatment
Wastewater Source pH
Printed Circuit Board
Plating Rinsewater
Plating Rinsewater
Plating Rinsewater
Plating Rinsewater
Plating Rinsewater
Plating Rinsewater
Plating Rinsewater
Plating Rinsewater
Nonferrous Smelter
3.5
8.75
9.0
8.5
8.75
10.0
8.5
8.5
9.0
8.5
10.0
8.5
Initial
Zinc
(mq/1)
0.770
90.0
11.0
13.0
253.0
290
2.8
440
440
930
930
114
Lime Precipitation
Clarified Filtered
0.430
1.00
2.15
0.625
0.400
1.20
0.044
75.0
37.0
9.6
3.3
0.511
0.053
0.210
0.167
0.010
0.295
0.510
0.010
71.0
29.0
1.4
1.0
0.030
Two Stage
Treatment
0.011
0.010
0.331
0.005
0.008
0.012
0.011
4.7
2.0
0.340
0.036
Table 37. Average Performance of Reverse Osmosis System
Parameter
pH
Zinc (mg/1)
Iron (mg/1)
Phosphate (mg/1 as P)
TDS (mg/1)
RO Feed
5.1
7.3
0.5
414
750
RO Permeate
4.9
2.2
<0.2
109
238
11-37
-------
Table 38. Pilot Scale Results for Reverse Osmosis Treatment of
Zinc Hastewater
Industry Source
Zinc Concentration
(ug/U
Percent
Feed
Permeate Removal
Zinc Cyanide Plating Rinse
Steam Electric Power Plant
Steam Electric Power Plant
Textile Mill
Textile Mill
Textile Mill
Textile Mill
Textile Mill
Textile Mill
Textile Mill
Textile Mill
Textile Mill
Textile Mill
Cooling Tower Slowdown
1,700
30
98
300
780
7,200
5,400
460
520
7,200
1,400
4,100
1,200
24,000
9,700
10,000
53
3
140
6,600
250
360
360
30
180
22
430
37
300
82
99
98
(-20)
46
31
95
98
96
98
98
>99
97
Table 39. Electrolytic Treatment of Zinc Cyanide Wastes
Concentration
(mo/1)
Waste
A
B
Parameter
Zinc
Cyanide
Zinc
Copper
Cyanide
Initial
352
258
117
842
1,230
Final
0.7
12.0
0.3
0.5
<0.1
Table 40. Reported Effluent Zinc Concentrations in the Plating
Industry
Tvoe of Treatment
Evaporation
Continuous Chemical Precipitation
Effluent Zinc
Concentration
(mq/1)
0.15
18.4
0.12
0.4
0.6
0.25
0.08
0.87
0.35
0.8
0.5
0.5
0.32
Batch Chemical Precipitation
Integrated Process
Electrolytic Recovery
0.03
5.0
0.14
0.20
0,45
0.32
7.9
0-05
0.05
11-38
-------
V\fater Pollution Gontid federation
Metals distributions in activated
sEudge systems
James W. Patterson, Prasad S. Kodukula
11-39
-------
» Copyright as pan of the May 1984, JOURNAL WATER POLLUTION CONTROL
FEDERATION, Washington, D. C. 20037
Printed in U- S. A.
Metals distributions in activated
sludge systems
James W. Patterson, Prasad S. Kodukula
11-40
-------
Metals distributions in activated
sludge systems
James W. Patterson, Prasad S. Kodukula
In recent years, there has been widespread interest in the
chemistry, biological effects, environmental fate, and control of
metals. This interest developed as a result of the recognition of
potential adverse health effects and environmental impacts as-
sociated with wastewater discharge and the disposal of metal-
laden industrial and municipal wastewater treatment sludges.
Metals discharging directly from industrial facilities have been
managed under effluent limitations guidelines and National
Pollutant Discharge Elimination System (NPDES) permits.
However, control of industrial and non-industrial metals con-
taminating combined municipal-industrial, publicly owned
treatment works (POTW) effluents is much more complex.
Industrial pretreatment programs, such as those successfully
implemented by numerous local authorities,'-2 are intended to
reduce the industrial contribution, and thereby the overall
POTW influent metals concentrations, to levels which protect
POTW operation and yield acceptable POTW effluent and sludge
metals concentrations. However, inability to relate influent metal
concentration to POTW intermediate process stage or effluent
and sludge metal concentrations has made the design of such
pretreatment programs difficult, and their predicted effects un-
certain. Indeed, this lack of an accurate method of predicting
metals distribution has been a key weakness in the development
of effective pretreatment regulations.3
Metals in municipal wastewater originate from a variety of
industrial, commercial, and domestic activities,4'7 as well as
storm runoff.8'* Numerous field monitoring studies demonstrated
that the influent metals concentration, and the efficiency with
which metals are removed, varies widely between plants.l0-"
This is demonstrated in the field results summarized in Tables
1 and 2. Further, there is convincing evidence that at individual
plants, metal influent concentrations can vary widely with time,
falling in diurnal,9-12 weekly" and apparently random'3 patterns.
Depending on the individual metal, the influent, or operational
characteristics of the treatment system, a given metal may cause
POTW operational or environmental problems by: producing
toxic effects which interfere with the operation of biological
treatment .A: ems, accumulating on sludge solids to a hazardous
extent during sludge processing or disposal, or appearing in the
POTW effluent in sufficiently high concentration to result in
adverse receiving water effects. Typically, POTW influent metals
concentrations are not high enough to affect the treatment ef-
ficiency of biological systems.14
Numerous researchers reported the results of studies designed
to define, characterize, and describe the partitioning behavior
of metals in combined wastewater treatment systems.9'l3-13-"
Although metals removal efficiencies vary among full-scale
treatment plants, and with time within individual plants3'"-13-21-26
(see Table 2), some empirical relationships were reported. Kon-
rad and Kleinert27 found fair to good correlation between influent
and effluent concentrations for seven metals in a study of 35
Wisconsin POTWs. Similar results were obtained in another
study of 20 full-scale plants," and in an extensive pilot plant
study.28 Brown et a/.21 observed a linear increase in percentage
total metals removal with increasing total influent metals con-
centrations, for six midwestern POTWs. They also reported a
strong correlation between percentage metals removal and per-
centage suspended solids removal. A similar observation was
made by Haas2' from performance data on six Chicago plants.
Haas noted that total effluent metals increased as effluent sus-
pended solids increased. Such empirical correlations do not
occur uniformly however, and there currently is no reliable
method for predicting the behavior of metals in POTW systems.
Development of a prediction method will be useful in several
ways. Given the influent and operational characteristics of a
wastewater treatment plant, the metal concentrations in the
sludge and the final effluent could be predicted as a function
of influent metal concentration. Pretreatment standards for
metals from industrial operations could be developed on the
basis of rational POTW performance criteria, and operational
modifications within a POTW could be evaluated with regard
to their impacts on metals distribution and removal.
Empirical models based on controlled pilot plant
studies can confidently predict the removal of
metals by the activated sludge process.
There seems to be a relative lack of understanding of the
principal mechanisms affecting the distribution of metals be-
tween the soluble and solid phases of activated sludge systems.
Numerous bench- and pilot-scale studies were performed on
metals partitioning in raw wastewater and activated sludge mixed
liquor,17"20'28'30-31 and these studies provided valuable insights
into aspects such as apparent or pseudo-isothermal metals-solids
association, and the influence of soluble phase ligands. It has
been well established that the kinetics of metals uptake by the
solids are rapid (within the time frame of normal POTW hy-
draulic residence times), that metals-solids associations are
readily reversible,52'" and that pH has a strong influence on the
extent of metal uptake and metal solubility."l718 However, the
effects of other wastewater and process variables are less well
defined.
It has been postulated that association and dissociation be-
tween activated sludge unit influent metals and mixed liquor
432
11-41
Journal WPCF, Volume 56, Number 5
-------
Process Research
Table 1 — Influent metals concentrations for 239 publicly
owned treatment plants.10
Influent concentration, MQ/L
Metal
Aluminum
Cadmium
Chromium
Copper
Iron
Lead
Nickel
Zinc
Range
1.7-186000
0.2-2 140
0.8-83 300
01-36500
6.0-999 000
1.0-11 600
2.0-111 400
01-28700
Median
(all
data)
3390
24
400
420
3180
120
230
520
Mean,
<4%
industry
1 796
320
75
151
2581
74
85
417
Mean,
>4%
industry
3457
303
476
489
5339
161
319
640
random concentration mixtures, to pilot activated sludge units.
Concentrations of all metals were set at levels low enough to
avoid inorganic metal salt precipitation and toxic effects.
The pilot plant experimental system incorporated eight parallel
treatment trains. Each train included a dosing tank for adding
a metals mixture to the influent raw wastewater, a primary
clarifier, activated sludge aeration tank, and secondary clarifier.
During each run, a treatment train was dosed with a unique
metals mixture and operated for 3 to 5 weeks under steady-
state dosing conditions. No process stream samples were collected
during the first week following a change in metal dosing mixture.
and 8-hour composite samples were collected 2 to 3 times per
week thereafter for the duration of the run. A total of 39 ex-
perimental runs was performed.
Table 3 presents the average measured concentrations (raw
suspended solids (MLSS) act to buffer the variability of the
secondary effluent metals content.2:U4 At high influent metals
levels the MLSS take up a large fraction of the metals, but could
release metals back into solution during episodes of low influent
metals concentrations. A significant portion of most metals in
POTW effluents are in soluble form. The system residence time
of MLSS is long compared to hydraulic residence time (HRT)
and the associated soluble components, and this "buffering"
effect could yield a reduced variation in POTW effluent metals
as compared to that in the influent.
This paper describes models developed to predict the distri-
bution of metals in activated sludge system process streams.
The data used to develop the models were obtained through
extended pilot studies.28 The objectives of the study were to
evaluate the effects of wastewater and plant operational variables
on the distribution of selected metals between the soluble and
solid phases of the process streams of a conventional activated
sludge system, and to develop an empirical model which de-
scribes the metals distribution in the individual treatment system
process streams.
MATERIALS AND METHODS
This study focused on eight metals: aluminum (Al), cadmium
(Cd), trivalent chromium (Cr), copper (Cu), iron (Fe), lead (Pb),
nickel (Ni), and zinc (Zn). The trivalent form of chromium was
selected because very little hexavalent chromium is present in
the influent wastewater to most treatment plants, as a result of
reducing conditions.34 The test metals were dosed, as various
Table 2—Metals removals measured in 17 activated
sludge POTWs."
Metal
Aluminum
Cadmium
Chromium
Copper
Iron
Lead
Nickel
Zinc
Influent
concentration
range, itg/L
140-4910
1-1 800
8-2380
34-1 190
215-12028
16-935
11-1 930
23-7680
Percent
Range
63-97
(-)50-94
(-)100-96
17-95
67-98
(-)57-94
(-)775-67
55-90
removal
Median
86
50
78
81
88
74
33
81
Table 3—Summary of average raw wastewater total met-
als concentrations, ng/L (Runs 1-39).
Run
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
32
33
34
35
36
37
38
39
Al
783
433
1003
1310
678
298
375
372
851
932
383
495
500
295
710
678
678
295
677
520
661
983
655
385
785
240
834
890
669
278
567
216
740
778
1574
1193
678
337
693
Cd
25
42
140
80
12
124
63
143
94
60
28
77
105
154
93
55
12
137
88
138
146
54
24
157
135
128
77
37
11
63
69
98
15
222
87
102
11
87
81
Cr
135
143
174
630
113
84
150
128
838
600
155
159
153
122
1062
460
113
97
183
144
500
420
106
137
109
124
513
530
113
62
90
128
114
253
140
100
113
84
124
Cu
393
359
274
280
90
161
177
530
463
150
429
479
271
625
338
240
90
173
453
625
425
270
308
460
367
180
363
350
90
162
213
210
302
756
1071
510
98
170
269
Fe
1265
1542
1750
1460
1399
1247
1292
1610
4000
2675
1439
1641
1521
2220
3360
1534
1399
1576
636
1510
3225
2510
1378
2243
2492
1488
3200
2350
1399
1527
936
650
1384
2322
2117
1510
1344
1483
671
Pb
81
93
293
140
35
37
75
320
186
150
57
88
158
170
150
90
35
154
267
475
150
140
41
75
221
190
175
180
35
100
143
120
66
200
260
160
50
97
100
Ni
672
756
1629
2740
334
369
1780
1220
2788
838
795
1002
869
986
1220
1615
245
352
2983
3263
1678
1263
699
653
4008
6075
2050
2132
330
366
490
438
603
1522
708
319
216
373
619
Zn
482
413
1114
826
409
383
481
830
733
1583
510
617
643
553
1002
1575
409
450
1114
694
1025
1860
550
477
514
766
1462
2160
409
440
429
644
520
536
540
463
464
413
450
May 1984
11-42
433
-------
Patterson & Kodukula
wastewater background plus dosed increment) of metals in the
raw wastewater for the 39 runs. The dosed incremental metals
concentrations and combinations were selected on a random
basis to simulate low, high, and mixed concentrations of metals
in raw wastewater.
Domestic wastewater was continuously pumped from a City
of Chicago sewer line serving the campus residence area to a
laboratory grit chamber. Settled grit was discharged. Raw waste-
water overflowed from the grit chamber into a 300-gallon stirred
holding tank with an average detention time of 6 hours. The
holding tank was equipped with a low-level alarm to cut off
all downstream pumps and valves (except for return activated
sludge pumps), in the event that the raw wastewater flow was
interrupted. The raw wastewater was pumped on a continuous
basis into a small recirculating header tank, and then to eight
parallel dosing tanks, each with a two-hour detention time.
Prepared concentrated metals mixtures were metered into each
chemical dosing tank, according to the experimental protocol
for that particular run.
Each dosing tank overflowed at 230 mL/min to that system's
primary clarifier. The primary clarifier overflowed through a
flow splitter, to control hydraulic loading to the activated sludge
unit. Settled primary sludge (PS) was withdrawn manually each
day. Each activated sludge unit was constructed as a 5-chamber,
100-L total capacity unit. Criteria for the activated sludge and
clarifier units were based on the design of Mulbarger and Cas-
telli."
Activated sludge mixed liquor overflowed by gravity to the
secondary clarifier, where settled sludge was returned by a peri-
staltic pump to the aeration tank. The recycle ratio used for all
Table 4—Average* and ranges of parameters values— all data.
Parameter
PH
Median
range
Total suspended
solids
Ave
range
Volatile suspended
solids
Ave
range
Soluble organic
carbon
Ave.
range
Aluminum
Total
Ave.
range
Soluble
Ave
range
% Soluble
Ave
Cadmium
Toial
Ave
range
Soluble
Ave.
range
% Solub:,.
Avt.
Chromium
Total
Ave
range
Soluble
Ave,
range
% Soluble
Ave.
RW
7.3
6.7-7.8
83
22-551
62
2-460
36
3-294
652
63-5100
81
11-425
12.4
85
3-650
11
1-305
12.9
241
1-8-1 700
4
2-17
1.7
PE
76
7.3-7.8
52
16-231
36
1-196
19
1-106
478
24-3032
79
8-375
16.5
68
2-514
14
1-295
20.6
170
5-650
5
2-9
29
ML
7.8
76-8.0
1906
610-10116
1 246
150-8106
12
1-200
7 179
526-21 000
61
0-325
0.8
411
4-810
15
1-98
3.6
1292
10-3 150
4
2-9
0.3
SE
8.3
7.9-8.4
23
12-273
13
1-220
11
1-38
455
67-2 732
86
5-350
18.9
44
2-382
13
1-67
29.5
162
31-1600
4
2-5
24
PT^ter
Copper
Total
Ave.
Range
Soluble
Ave.
range
% Soluble
Ave
Iron
Total
Ave
range
Soluble
Ave.
range
% Soluble
Ave
Lead
Total
Ave.
range
Soluble
Ave.
range
% Soluble
Ave.
Nickel
Total
Ave.
range
Soluble
Ave
range
% Soluble
Ave.
Zinc
Total
Ave.
range
Soluble
Ave.
range
% Soluble
Ave.
RW
338
11-2900
17
1-157
5.0
1 778
200-7000
134
5-783
75
142
0-1069
24
2-197
169
1 126
22-8500
319
8-1 168
283
741
100-5000
90
2-1000
12.1
PE
272
3-913
12
1-100
4.3
1228
200-3500
97
5-842
78
100
0-600
33
2-248
33.0
605
5-15000
278
9-1 479
46.0
609
80-3400
80
1-430
13.1
ML
3615
4-8500
14
1-96
04
28184
1 048-8 400
67
3-865
0.2
1 971
11-9000
24
2-474
12
6602
77-23 000
290
5-975
44
11589
1000-36000
79
2-900
0.7
SE
171
11-1 866
14
1-50
82
1025
100-5800
47
3-580
4.7
64
0-1 200
18
2-211
283
715
10-5000
250
3-849
350
514
100-4 100
65
1-900
126
Note—Suspended solids, and soluble organic carbon expressed as mg/L. metals concentrations as M9/L.
434
11-43
Journal WPCF, Volume 56, Number 5
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Process Research
activated sludge units in this study was 0.5. Excess sludge was
either wasted directly from the secondary clarifier or by inter-
mittent interval wasting of activated sludge unit overflow, as
was best for controlling sludge age. The HRT and the target
solids retention time (SRT) for all activated sludge units in this
study were, respectively, 6 hours and 10 days. Sampling from
each process stream except primary and secondary sludge (SS)
was by timer activated solenoid switch flow diverters, to yield
8-hour composite samples.
Composite samples of the dosed raw sewage, primary effluent,
activated sludge mixed liquor, and secondary effluent were col-
lected between 4 and 12 times during each run. Total and soluble
metal analyses were performed on all process liquid samples.
Primary and secondary sludge samples were analyzed for total
metals. In addition, pH, total suspended solids (TSS), and volatile
suspended solids (VSS) were also measured on all samples. Sam-
ples of the process liquids were routinely analyzed for soluble
organic carbon (SOC), phosphate, sulfate, chloride and am-
monia-nitrogen (NHrN).
Analytical procedures. Methods of chemical analysis were in
accordance with EPA methods.36 Metal analyses were performed
by atomic absorption spectrometry with standard additions or,
for low metals concentrations, the flameless technique was used.
Total metals were determined using standard digestion proce-
dures.36 Soluble metal was determined on sample nitrate, using
a 0.45 jtm membrane acid-washed filter. Soluble organic and
inorganic carbon concentrations were determined by a carbon
analyzer. Ammonia, orthophosphate, chloride, and sulfate were
measured according to EPA procedures.36 TSS is reported as
the weight of the dry solids per liter of sample retained by a
0.45 pm membrane filter. VSS is reported as the weight of TSS
volatilized after ignition at 600°C.
RESULTS AND DISCUSSION
System performance characteristics. The range and average
values of various parameters for raw wastewater (RW), primary
effluent (PE), mixed liquor (ML), and secondary effluent (SE)
for the 39 runs are summarized in Table 4. Table 5 summarizes
primary and secondary sludge results. Ranges are for all data
collected, and the averages ?.;e calculated from the averaged
results of each run. As is evident in Table 4. a wide range of
values for each parameter was observed in the raw wastewater
feed. As would be expected, the range of values for other process
liquids is also wide.
The influent wastewater to the pilot treatment systems was
relatively weak, averaging 83 mg/L TSS and 38 mg/L SOC.
Influent NH3-N averaged 3.5 mg/L and effluent NH3-N averaged
0.4 mg/L. The primary clarifier effluent TSS averaged 52
mg/L, representing a primary clarifier TSS removal efficiency
of 37%. Overall TSS removal efficiency, from RW to SE, was
72%. There was a strong correlation between VSS and TSS.
The ratio of VSS to TSS in all process streams was approxi-
mately 0.7.
The primary clarifiers sometimes performed erratically, with
occasional negative TSS removal efficiencies. Settled sludge
bridging was a problem in the secondary clarifiers, and sometimes
resulted in the interruption of sludge return to the aeration tank.
Mechanical rakes were eventually installed in the secondary
clarifiers, and effectively solved this problem. There was very
little primary or excess secondary sludge produced because of
the weak influent.
Table 5—Averages and ranges of primary and secondary
sludge values—all data.
Parameter
Primary
aludg*
pH
Median
range
Total suspended solids
Ave.
range
Volatile suspended solids
Ave.
range
6.9
6.5-7.3
7297
173-21 894
5054
12-15430
Secondary
•ludg*
7.8
7.6-8.0
6300
1899-12225
4388
1 224-7 896
Total aluminum
Ave.
range
Total cadmium
Ave.
range
Total chromium
Ave.
range
Total copper
Ave.
range
Total iron
Ave.
range
Total lead
Ave.
range
Total nickel
Ave.
range
Total zinc
Ave.
range
19.67
5.38-52.82
0.63
0.16-1.81
1.74
0.29-3.43
4.91
1.94-7.52
59.32
30.83-105.60
3.47
0.71-7.52
12.16
0.88-23.94
31.45
9.88-67.24
19.03
1.32-46.13
0.65
0.29-1.60
1.73
0.82-3.81
5.04
1 .64-8.26
52.47
4.75-114.00
3.38
0.64-7.74
8.94
0.55-21 .80
21.03
2.14-63.74
All units except pH in mg/L
As indicated by the reduction in SOC across the primary
clarifier, there seemed to be biological activity in that unit process.
Overall SOC reduction across the treatment systems averaged
71%, representing an average secondary effluent SOC value of
11 mg/L. There was no significant correlation between VSS and
SOC in any process liquid. This indicates that influent VSS and
SOC varied independently in strength.
System metals behavior. The patterns of metals transport
across the treatment systems were extremely interesting. The
range of RW concentrations for each metal was quite broad,
reflecting the combination of natural fluctuations in the influent
RW metals levels, and the dosing of the RW with mixtures of
metals in the laboratory. As can be seen in Table 4, there was
a reduction in the average total metal concentration across the
primary clarifier. The difference between the total and soluble
metals concentration is the concentration of solids-bound metal.
May 1984
435
11-44
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Patterson & Kodukula
Table 6 summarizes the average removal efficiencies of total
metal and of solids-bound metal across the primary clarifier.
For comparison, results from 6-day, flow-composited monitoring
at two full-scale POTWs are included.
The total concentrations of metals in the ML are much higher
than in the RW, typically by 5- to 10-fold. For iron, lead, and
zinc the concentration factor is closer to 15-fold. Comparing
the ML with PE total metals concentrations, ML is 15- to 25-
fold higher for all metals, except cadmium and chromium where
ML is 6- to 8-fold higher. The metals in the ML are predom-
inantly bound to the MLSS. Table 4 shows that the soluble
metals in the ML represent less than 1% of the total metal,
except for cadmium, lead, and nickel which are somewhat higher.
Solids-bound metal also represents the dominant fraction in the
other process streams.
Table 5 shows that the total metals concentrations in the
primary and secondary sludges are extremely close except for
nickel and zinc, which are more concentrated in the PS. The
secondary sludge total metal concentration for all metals except
aluminum is between 1.4- and 1.8-fold higher than the ML
total metal concentrations. The ratio for aluminum is 2.6.
A cursory examination of the averaged soluble metals con-
centrations presented in Table 4 suggests that they remained
constant for each metal, across each unit process of the treatment
train and within the bounds of experimental error. However,
there may in fact have been subtle changes in soluble metal
concentration across each unit process. Such changes were dif-
ficult to detect for cadmium, chromium, copper or lead, where
the soluble concentrations were low and often near the detection
limit in each process stream.
The soluble metals levels for aluminum, iron, nickel and zinc
were higher however, and statistical analysis of the influent and
effluent soluble metals levels across each of the three unit pro-
cesses (primary clarifier, aeration tank, and secondary clarifier)
indicates shifts in soluble metals concentration across each
treatment unit. With two exceptions the shift was toward a
reduction in soluble metals in the unit process effluent and with
correlation coefficients of determination (r2) between 0.90 and
0.98. Soluble iron was reduced across the primary clarifier, but
r2 was only 0.84. The second exception was increased aluminum
across the secondary clarifier, with r2 of 0.97. Changes in soluble
concentrations of the four metals evaluated across individual
unit processes ranged between 10 and 30%.
Solids-bound metals. Intriguing results were obtained when
the data of Table 4 were evaluated in terms of solids-bound
metals concentrations per unit weight of process liquid solids
(/ig bound metal per mg TSS). Averaged values for these results
are presented in Table 7. Metals concentrations in raw waste-
water solids ranged from 0.89 (cadmium) to 19.81 (iron) Mg/
mg TSS. Nickel, which is difficult to remove, is in fact highly
enriched in the raw wastewater and all subsequent process stage
solids.
Table 7 also demonstrates that the primary clarifier effluent
solids were enriched with all metals except for lead and nickel,
when compared to the clarifier influent (RW) solids. As dem-
onstrated in Table 7 by the calculated ratios of adjacent process
liquids around the clarifiers, the solids-bound metals in the pri-
mary effluent which were enriched over the raw wastewater had
10% (iron) to 30% (zinc) more metal per unit weight of TSS
than the RW solids.
Solids-bound metals concentrations on the MLSS were de-
pleted, compared to the primary clarifier effluent. This depletion
could reflect solids dilution of the reactor influent metal through
sludge yield. However, the ML:PE ratios ranged from 0.20 (cad-
mium) to 0.79 (lead), and if sludge yield were the sole factor
involved in solids-bound metals concentration reduction, the
ML:PE ratios among metals would have been fairly constant.
The solids in the secondary effluent were highly enriched in
all metals, when compared to the mixed liquor levels. Enrich-
ment factors (Table 7) ranged from 1.96 (lead) to 10.1 (chro-
mium). The results were not comparable to those seen across
the primary clarifier, except that in both instances iron and lead
enrichment were low. This suggests that the association of metals
with the primary clarifier process solids is governed differently
than the association with secondary clarifier solids.
More significantly, the data of Table 7 indicate that in both
RW and ML, the degree of association of any metal with the
settleable solids is different than the degree of metal association
with non-settleable (clarifier effluent) solids. For example, taking
the average conditions around the primary clarifier from Table
Table 6-—Average removal efficiencies across primary clarifier.
Tfsla study, % removal
P»n. - 'i,->
Alurnii i
C.»dmi'j,M
Chromicm
Copper
Iron
Lead
Nickel
Zinc
TSS
VSS
Total
concentration
27
20
29
20
31
42
46
18
—
—
Solids-bound
fraction
30
27
30
19
31
43
59
19
37
42
Pia
RW/PE
366/324
174/251
414/440
922/688
2888/1705
58/185
164/272
1615/1100
178/90
90/61
EPA study11
nt 12
% Removal
10
-
-
25
41
-
-
32
49
32
Pla
RW/PE
3554/2988
9/8
107/83
98/84
2035/2257
47/10
54/58
224/249
187/132
34/28
nt 19
% Removal
16
11
22
14
-
79
-
-
29
18
Note—Concentration units for Plants 12 and 19 are ng/L total metal.
436
11-45
Journal WPCF, Volume 56, Number 5
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Process Research
Table 7—Average and compared metals concentrations
per unit weight of process stream solids.
Mttftl concentration,
TSS
Ratios across
clarifiw for
process
liquids
RW
PE
ML
SE PE:RW SE:ML
Aluminum
Cadmium
Chromium
Copper
Iron
Lead
Nickel
Zinc
688
0.89
286
387
19.81
142
972
7.84
7.67
1.04
3.17
5.00
21.75
1.29
6.29
10.17
3.73
0.21
0.68
1.89
14.75
1.02
3.31
6.04
16.04
1.35
6.87
6.83
42.52
2.00
20.22
1952
1.11
1.17
1.11
1.29
1.10
0.91
0.65
1.30
4.30
6.43
10.10
3.61
2.88
1.96
6.11
3.23
4, the aluminum concentration per unit of total RW TSS was
6.88 pg/mg; the concentration for the settleable TSS fraction
was calculated to be 5.45 Mg/mg; and the concentration in the
RW non-settleable TSS (PE TSS) was 7.67 /ig/mg. Except for
lead and nickel in RW, where the settleable solids seemed to
be more enriched than the non-settleable solids, all metals in
both RW and ML were depleted in the settleable solids, com-
pared to the non-settleable solids.
DEVELOPMENT OF METALS
DISTRIBUTION MODELS
Researchers have reported isothermal metals sorption onto
MLSS, and a consequent correlation between bound metal con-
centration per unit weight of TSS and residual soluble metal
concentration." However, most such experiments have been
performed at atypically high metals dosages, yielding several
mg/L of residual soluble metal. Both Langmuir and Freundlich
results have been reported. The fit of the data of this study to
either sorption isotherm model was extremely poor. Bench-
scale batch sorption experiments are performed under carefully
controlled conditions, including constant pH and VSS concen-
tration, and addition of a single metal in soluble form. These
conditions do not reflect the situation of continuous-flow ac-
tivated sludge units receiving time-varying primary clarified
wastewater.
In addition to residual soluble metal concentration, a number
of other parameters, including pH, SOC, VSS, and total metal
concentration (A/r), were evaluated with regard to their cor-
relation with the weight of solids-bound metal (Ms) per unit
weight of VSS. As for the parameter soluble metal, no correlation
of Ms/VSS was found with either pH or SOC. An attempt to
correlate Afy/VSS with MT suggested a log-log relationship, al-
though for most metals there was significant scatter in the
graphed data. A regression analysis of this relationship, taking
the form of Equation 1, yielded r2 values of 0.75 or less for
most metals and process streams.
(1)
However, the correlations were better than for other variables
tested and a further evaluation of the influence of A/r, plus VSS
-^ =alogA/r +
i.o
Figure 1A—Adsorption distribution relationships for copper-raw waste-
water. (Note: The numerical value adjacent to each data point is the
measured VSS concentration.)
concentration, led to the development of metals distribution
Model 1.
Model I. The averaged data of each process stream of the 39
runs was culled for approximately equal levels of VSS, and these
run results were plotted as Afs/VSS versus Mr- Example results
for copper in RW, PE, ML, and SE are presented in Figure 1.
The graphs reveal that at constant VSS, there is a linear cor-
relation between A/s/VSS and MT in all process streams. The
relationship takes the form of Equation 2, where S is the slope
at constant VSS.
Ms/VSS = S(MT) (2)
The relationships described in Figure 1 and by Equation 2 reveal
the following distribution trends. At constant VSS, the amount
of solid-bound copper increases as total copper concentration
increases. Also, at constant total copper concentration, the solid-
bound copper per unit weight of VSS decreases with increasing
VSS. Although these trends might seem intuitively apparent,
they have not previously been confirmed by experimental data
on continuous-flow activated sludge systems. An evaluation of
i.o
Figure IB—Adsorption distribution relationships for copper-primary
effluent. (Note: The numerical value adjacent to each data point is the
measured VSS concentration.)
May 1984
437
11-46
-------
Patterson & Kodukula
Table 8-
modell.
•Regression constants for th* metals distribution
Figure 1C—Adsorption distribution relationships for copper-activated
sludge mixed liquor. (Note: The numerical value adjacent to each data
point is the measured VSS concentration.)
each of the eight metals for each process stream revealed that
the data in all instances fit Equation 2.
Furthermore, as seen in Figure 1 and found for all eight
metals, the value of S decreases with increasing process stream
VSS concentration. Analysis of this trend revealed that 5 is an
inverse function of VSS, of the form of Equation 3.
5 = \/(AxVSS + B)
(3)
Substituting Equation 3 into Equation 2 yields metal distribution
Model I
Ms MT
VSS ^(VSS) + B
(4)
where
A/j/VSS =
MT =
VSS = mg/L
A = constant, no units, and
B = constant, units of mg/L.
1.0
Figure 1C -Adsorption distribution relationships for copper-secondary
effluent. (Note: The numerical value adjacent to each data point is the
measured VSS concentration.)
ProcM* liquid
Con-
stant
RW
SE
Aluminum
Cadmium
Chromium
Copper
Iron
Lead
Nickel
Zinc
A
B
A
B
A
B
A
B
A
B
A
B
A
B
A
B
1.23
-0.58
1.34
-1.37
1.05
-0.70
1.06
0.67
1.17
-2.59
1.34
2.93
1.52
-2.15
1.09
7.34
0.96
11.23
1.24
2.50
1.03
0.01
108
-0.71
1.11
-0.28
1.50
-6.13
1.94
-1.37
1.16
1.42
1.00
11.19
1.05
-17.02
1.00
0.01
1.00
4,88
0.99
24.07
1.00
21.19
1.00
92.69
1.00
1662
1.09
326
1.08
6.45
1.02
0.15
1.02
1.02
102
0.84
1.70
-1.18
2.69
-13.77
0.90
5.06
Equation 4 is rearranged to yield Equation 4a which expresses
the ratio of MT to Ms as a function of ,4, B, and reciprocal VSS
concentration.
A/r/A/5 = A + B/VSS
(4a)
Regression analysis of the results of the 39 experimental runs,
using Equation 4. yielded the values of A and B listed in Table
8, and revealed excellent correlation (except for nickel in PE)
of Model I with the experimental results (Table 9). Most values
of A in Table 8 are 1.0 or greater, although three values are less
than 1.0. Values of A below 1.0 seem to be an artifact of ex-
perimental variability. From Equation 4a as VSS increases, the
final term of the equation approaches zero and A must therefore
have a value of 1.0 or greater.
In fact, it is probable that the value of A must be exactly 1.0.
Kodukula and Patterson33 have recently reported bench-scale
data for cadmium and nickel, in terms of soluble metal as a
Table 9—Correlation coefficients (r2) for the metals dis-
tribution model I.
ProcM* liquid
Metal
Aluminum
Cadmium
Chromium
Copper
Iron
Lead
Nickel
Zinc
RW
0.959
0.970
0.999
0.996
0.989
0.877
0.803
0.953
PE
0.749
0.837
0.999
0.989
0.984
0.840
0.560
0.914
ML
0.999
0.997
0.999
0.999
0.998
0.997
0.986
0.999
SE
0.852
0.720
0.999
0.992
0.949
0.826
0.909
0.814
438
11-47
Journal WPCF, Volume 56, Number 5
-------
Process Research
function of MT and VSS, which fit the pattern presented in
Figure 2. At zero VSS there is obviously a 1:1 relationship
between soluble metal and A/r, up to the metal precipitation
limit. For a given A/r, soluble metal decreases with increasing
VSS. Each line of Figure 2 takes the form that soluble metal,
the difference between Mr and Ms is
Table 10—Regression constant B1 and estimated con-
stant fl* for model 1 when A = 1.0.
MT - Ms = S(MT). (5)
'is 1.0 and is also an inverse function of VSS of
C
At zero VSS,
the form,
Substitution of Equation 6 into 5 and rearrangement yields,
I + ^ (7)
Comparison of Equation 7 with 4a then indicates that A = 1.0.
Equation 7 is easily transformed into a linear isotherm of the
form:
A/s/VSS = (\IB\MT - Ms) = (1/flXsoluble metal) (7a)
Model I was again tested against the experimental data to
determine the values of B where A is 1.0, and the correlation.
Values for r2 were slightly lower than for the original form of
Model I, but not significantly so. Regression constants for B
(indicated as B1) are given in Table 10, where A is 1.0. B*
values, also presented in Table 10, are discussed below.
Adjustment of model constants. The regression constants for
Model 1 are obtained from a data base which incorporates a
wide range of values for process stream variables. However, it
is probable that these constants are somewhat specific to the
raw wastewater and operational mode in this study. For example,
pH has been demonstrated to have a strong influence on the
equilibrium distribution of metals.1733 Thus, the Model 1 con-
stants may vary with waste nature and specific POTW config-
uration, although the general form of Model 1 is believed to be
widely applicable, and site-specific constants can be easily de-
termined.
Figure 2—Concentration of soluble metal as a function of total metal
and suspended solids concentrations.
May 1984
Metal
Aluminum
Cadmium
Chromium
Copper
Iron
Lead
Nickel
Zinc
Con-
stant
B'
8*
e1
B*
e1
B'
B1
B'
B'
B'
B1
fl'
fl1
B*
fl1
fl*
Process liquid
RW
8.80
72.56
9.22
84.50
1.05
61.03
3.28
118.07
5.05
64.11
12.61
46.39
24.51
34.99
8.57
131.92
PE
7.13
9.33
1.09
1.66
3.09
17.73
30.61
5.44
ML
10.68
78.56
47.20
155.39
3.87
176.77
4.84
61.22
2.97
47.48
15.36
45.40
57.25
159.21
8.55
58.86
SE
3.03
5.45
0.33
1.16
0.62
5.09
6.99
1.88
There is one adjustment of constants which seems necessary
to accurately predict mass balances around the unit processes
of a treatment train. The data of Table 7 indicate that in both
RW and ML, each metal is distributed disproportionately be-
tween the settleable and non-settleable solids within the process
stream. Presumably, the clarifier effluent solids (and their as-
sociated constants) represent the non-settleable component en-
tering the clarifier. Then, adjusted constants can be estimated
for the settleable component as follows:
*r.ml+ r
AVSS
(8)
where:
= change in solids-bound metal across clarifier,
AVSS = change in VSS across clarifier, mg/L,
MT = clarifier influent total metal, Mg/L, and
B* is estimated for the settleable portion of the influent
VSS.
B* has been calculated from Equation 8 based on the average
operating conditions of Table 4, and its values are summarized
in Table 10.
The following example demonstrates the application of B*.
Determine the total primary clarifier effluent copper concen-
tration for an influent total copper concentration (Mr) of 500
Mg/L, influent VSS of 150 mg/L, and clarifier VSS removal
efficiency of 40% (AVSS = 60 mg/L). Equation 8 is used to
calculate AA/5 to be 168 ng/L. The total effluent copper
concentration is the difference between M^ and AA/S, or
332 Mg/L.
Model II. This model was obtained through a simplification
of Model I, and gives the following results. Using Model I
439
11-48
-------
Patterson & Kodukula
(Equation 4a) in process streams such as ML, with high VSS
concentration, the Model I term fi/VSS becomes negligible.
Under this condition, the term for VSS is lost from Model I,
and a new Model II relationship as presented in Equation 9 is
suggested.
MT = pMs + q (9)
It was initially believed that Model II might only achieve good
correlation for the ML data. However, as demonstrated in Table
1 1, excellent correlation was found for Model II for all process
streams and metals. Indeed, the correlation of Model II with
the experimental data of the 39 runs was equal to or somewhat
better than that with Model I.
Table 12 presents the regression constants for Model II. A
literal interpretation of Model II indicates that q must represent
the soluble metal concentration (when Ms is zero). A comparison
of q with the average soluble metals levels of Table 4 reveals
that these concentrations are indeed quite close in value to q
for each metal and process stream.
Model II is attractive in view of its simplicity, but is perhaps
overly simplistic and certainly should not be applied beyond
the range of the experimental conditions from which it was
developed. Further, Model I seems to be more powerful in
predicting mass balances around treatment systems because it
incorporates VSS, one of the principal process variables of the
activated sludge system. Nevertheless, within individual process
streams. Model II is at least as accurate as Model I in predicting
metals distributions.
Table 12 — Regression constants for
button model II.
the metals distri-
Process liquid
Metal
Aluminum
Cadmium
Chromium
Copper
Iron
Lead
Nickel
Zinc
Units of q
Con-
stant
P
q
P
q
p
q
P
q
P
Q
P
q
P
q
P
Q
are M9/L
Raw
waste-
water
0.953
107
1.045
11
1.002
4
1.016
12
0.997
173
1.036
15
1.033
276
0.928
137
Primary
effluent
0.890
122
1.089
9
1.004
3
1.018
7
0.992
107
1.024
13
1.090
2456
0.961
96
Mlxed
liquor
1.003
38
1.035
1
1.001
2
1.001
9
0.999
106
1.007
10
1.019
172
0.997
108
StCOfflQ*
•ry
effluent
0.955
100
1.022
12
1.007
3
1.001
12
0.945
108
1 137
11
1300
106
0.943
90
CONCLUSIONS
Despite extensive laboratory and field studies over the past
25 years, little advance has been made in the ability to predict
metals distributions and removal in POTWs. Carefully controlled
bench-scale experiments indicated that a number of wastewater
and process variables can affect metals distribution between the
soluble and solids phases, but these results have not been easily
extrapolated to continuous-flow systems receiving time-varying
inputs of real wastewater.
Based on extensive pilot plant data, empirical metals distri-
bution models have been developed which are believed to be
generally applicable. The models accurately predict the distri-
bution of process stream metals between the soluble and solids
phases. Further, there is convincing evidence that solids-bound
Table 11- Correlation coefficients (r1) for the metals dis-
tribution model II.
Process liquid
Meta!
Aluminum
Cadmium
Chromium
Copper
Iron
Lead
Nickel
Zinc
Raw
waste-
water
Primary
affluent
Mixed
liquor
Second-
ary
•fllutnt
0.975
0.963
0.999
0.998
0.993
0976
0964
0.981
0.961
0.944
0.999
0.998
0.985
0.981
0.909
0.992
0.999
0.994
0999
0.999
0.999
0.999
0.999
0.999
0.961
0.947
0.999
0.998
0.983
0.953
0.913
0.988
metals are disproportionately distributed between settleable and
non-settleable solids in both raw wastewater and activated sludge
mixed liquor, and Model I allows for that disproportionate dis-
tribution and accurately predicts metals removal across treatment
train unit processes.
Credits. This work was supported by U. S. Environmental
Protection Agency Cooperative Agreement No. R806582. The
project officer was Dr. Thomas E. Short, Robert S. Kerr En-
vironmental Research Laboratory, Ada. Okla. The data base
used to develop the predictive models for metals distribution
was generated under U. S. Environmental Protection Agency
Grant No. R804538. Note that although the research described
in this article has been funded wholly or in part by the U. S.
Environmental Protection Agency (EPA), it has not been sub-
jected to EPA review and therefore does not necessarily reflect
the views of EPA and no official endorsement should be inferred.
ACKNOWLEDGMENTS
Authors. James W. Patterson is professor and chairman,
and Prasad S. Kodukula is instructor and doctoral can-
didate, at the Pritzker Department of Environmental En-
gineering, (llinois Institute of Technology, Chicago. Cor-
respondence should be addressed to James W. Patterson,
Illinois Institute of Technology, Armour College of En-
gineering, IIT Center, Chicago, IL 60616.
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