EPA/600/2-89/051 a
October 1989
AEROBIC AND ANAEROBIC TREATMENT
OF C.I. DISPERSE BLUE 79
Volume I.
by
David A. Gardner and Thomas J. Holdsworth
Radian Corporation
Milwaukee, Wisconsin 53214
and
Glenn M. Shaul and Kenneth A. Dostal
Water and Hazardous Waste Treatment Research Division
Risk Reduction Engineering Laboratory
Cincinnati, Ohio 45268
and
L. Don Betowski
Environmental Monitoring and Support Laboratory
Las Vegas, Nevada 89114
EPA Contract No. 68-03-3371
Project Officer
Glenn M. Shaul
Water and Hazardous Waste Treatment Research Division
Risk Reduction Engineering Laboratory
Cincinnati, Ohio 45268
RISK REDUCTION ENGINEERING LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing!
1. REPORT NO,
EPA/600/2-89/051 a
2.
3. RECIPIENT'S ACCESSION NO
pb 90 1 1 1 6 4 2 /AS
4. TITLE AND SUBTITLE
Aerobic and Anaerobic Treatment of
5. REPORT DATE
October 1989
C.I. Disperse Blue 79, Volume I
6. PERFORMING ORGANIZATION CODE
7. AUTHORSS)
D.A. Gardner & T.J. Holdsworth (I), G.M. Shaul &
K.A. Dostal (2), L.D. Betowski (3)
8. PERFORMING ORGANIZATION REPORT NO.
9, PERFORMING ORGANIZATION NAME AND AOORESS
(1) Radian Corporation, Milwaukee, Wisconsin 53214
(2) U.S. EPA, OKI), RREL, Cincinnati, Ohio 45268
(3) U.S. EPA, ORD, EMSL-LV, Las Vegas, Nevada 89114
ID. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
68-03-3371 and In—house
12. SPONSORING AGENCY NAME AND ADDRESS
Risk Reduction Engineering Laboratory
13. TYPE OF REPORT AND PERIOD COVERED
Project Report
U.S. Environmental Protection Agency
26 West Martin Luther King Drive
Cincinnati, Ohio 45268
14. SPONSORING AGENCY CODE
EPA/600/14
15. SUPPLEMENTARY notes
Project Officer: Glenn H
Shaul, FTS 684-
7408, Commercial (513) 569-7408
16. ABSTRACT
This study was conducted to determine the fate of C.I. Disperse Blue 79, one of the
largest production volume dyes, and select biodegradation products in a conventionally
operated activated sludge process and an anaerobic sludge digestion system. To achieve
this objective, a pilot study was conducted from November 1987 to February 1989. The
equipment operated included two continuous feed pilot-scale wastewater treatment
systems, consisting of one control system and one experimental system. Screened, raw
municipal wastewater fed to .the experimental treatment system was dosed with a target
concentration of 5 mg/L of active ingredient in the commercial formulation of C.I.
Disperse Blue 79. The control system was fed only the screened, raw municipal waste-
water. After acclimation and steady state conditions were reached, samples from each
system were analyzed for the dye and related compounds. A bench-scale activated sludge
system was also operated to assess the fate of dye degradation products from the
anaerobic digester in an aerobic treatment system. This system was operated to
simulate the recycle of digester supernatant to the head-end of a typical wastewater
treatment system. Volume I of the report presents the results of this extensive
research project. Findings are presented regarding; (1) the affect of the addition of
C.I. Disperse Blue 79 on the operation of an activated sludge system and an anaerobic
digester; (2) the fate of the dye in the treatment systems; and (3) the detection of
any degradation products in the systems. Volume II contains thp raw
17.
key WORDS AND DOCUMENT ANALYSIS
a. DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS
c. cosati Fkld/Group
18. DISTRIBUTION STATEMENT
Release to Public
19. SECURITY CLASS (This Report}
Unclassified
21. NO. Of PAGES
116
20. SECURITY CLASS (This page/
Unclassified
22. PRICE
EPA F orm 2220-1 4-77) previoui edition is obsolete *|
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DISCLAIMER
The information in this document has been funded wholly or in part by the
Unxted States Environments! Protect ion Agency under Contract No. 68~Q3~3371
to Radian Corporation, It has been subjected to the Agency's peer and
administrative review, and it has been approved for publication as an EPA
document. Mention of trade names or commercial products does not constitute
endorsement or recommendation for use.
ii
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FOREWORD
Today's rapidly developing and changing technologies and industrial products
and practices frequently carry with them the increased generation of
materials that, if improperly dealt with, can threaten both public health and
the environment. The U.S. Environmental Protection Agency is charged by
Congress with protecting the Nation's land, air, and water resources. Under
a mandate of national environmental laws, the agency strives to formulate
and implement actions leading to a compatible balance between human
activities and the ability of natural systems to support and nurture life.
These laws direct the EPA to perform research to define our environmental
problems, measure the impacts, and search for solutions.
The Risk Reduction Engineering Laboratory is responsible for planning,
implementing, and managing research, development, and demonstration programs
to provide an authoritative, defensible engineering basis in support of the
policies, programs, and regulations of the EPA with respect to drinking
water, wastewater, pesticides, toxic substances, solid and hazardous wastes,
and Superfund-related activities. This publication is one of the products of
that research and provides a vital communication link between the researcher
and the user community.
This report details the results of an in-depth pilot plant study to determine
the fate of C.I. Disperse Blue 79 in a conventional activated sludge
wastewater treatment system equipped with an anaerobic sludge digester.
Volume I discusses the project and analyzes, interprets, and summarizes
the results. Volume II contains the appendices which includes all of the
data and additional supporting information.
E, Timothy Oppelt, Director
Risk Reduction Engineering Laboratory
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ABSTRACT
The fate of specific azo dyes in wastewater treatment facilities is
uncertain since few detailed studies have been reported in the literature. A
better understanding of this large class of organic compounds is necessary to
assess their impact on the environment and human health. Several azo dyes
and possible biodegradation products, such as aromatic amines, have been
shown to be, or are suspected to be, carcinogenic. C.I. Disperse Blue 79,
one of the largest production volume dyes, is a water insoluble
bromodinitroaniline derived compound. In addition to C.I. Disperse Blue 79,
several analogous dyes are also used extensively.
This study was conducted to determine the fate of C.I.Disperse Blue 79,
as well as any major organic impurities identified in the commercial
formulation and select biodegradation products, in a conventionally
operated activated sludge process and an anaerobic sludge digestion system.
To achieve this objective, a pilot study was conducted from November 1987 to
February 1989 at the Milwaukee Metropolitan Sewerage District South Shore
Wastewater Treatment Plant.
The equipment operated during the study included two continuous feed
pilot-scale wastewater treatment systems, consisting of one control system
and one experimental system. Each system included a primary clarifier,
plug-flow aeration basin, secondary clarifier, and an anaerobic digester.
Screened, raw wastewater, fed to the experimental treatment system, was dosed
with a target concentration of 5 mg/L of active ingredient in the commercial
formulation of C.I. Disperse Blue 79. The control system was fed only the
screened, raw wastewater. After acclimation and steady-state conditions were
reached, the following samples from each system were analyzed for the dye and
related compounds: influent, primary effluent, activated sludge effluent,
primary sludge, waste activated sludge, digester feed, digester supernatant,
and digester effluent.
In addition to these pilot-scale systems, a bench-scale activated sludge
system was operated to assess the fate of dye degradation products from the
anaerobic digester in an aerobic treatment system. This system was operated
to simulate the recycle of digester supernatant to the head-end of a typical
wastewater treatment system.
This report presents the results of this extensive research project.
Findings are presented regarding: (1) the affect of the addition of C,I.
Disperse Blue 79 on the operation of an activated sludge system and an
anaerobic digester; (2) the fate of the dye in the treatment systems; and
(3) the detection of any degradation products in the systems.
This report was submitted in partial fulfillment of Contract No.
68-03-3371 under sponsorship of the U.S. Environmental Protection Agency.
This report covers a period from November 13, 1989 to February 16, 1989 and
work was completed June 30, 1989.
iv
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CONTENTS
Foreword iii
Abstract. iv
Figures , vi
Tables. , . viii
List of Abbreviations and Conversions xi
Acknowledgments xiii
1. Introduction 1
2. Conclusions 2
3. Recommendations . . 3
4. Description of the Project Site 4
5. Description of the Project Equipment 7
6. Project Test Plan. 14
7. Quality Assurance/Quality Control 23
8. C.I. Disperse Blue 79 Extraction Method Development 36
9. Conventional Treatment Results. 40
10. C.I. Disperse Blue 79 Analyses and Mass Balance Results 63
11. Bench-Scale Activated Sludge System.... 96
References. 102
v
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FIGURES
Number Page
X Schematic of project si. to 5
2 Aerobic wastewater treatment system . 8
3 Anaerobic digester schematic 10
4 Schematic of pilot plants with sampling locations shown ..... 11
5 Bench-scale activated sludge system 13
6 Pilot activated sludge systems feed temperatures 45
7 Pilot activated sludge systems mixed liquor temperatures. .... 45
8 Pilot activated sludge systems feed pH values 46
9 Pilot activated sludge systems mixed liquor pH values 46
10 Dissolved oxygen concentration in Unit 1 aeration tank 47
11 Dissolved oxygen concentration in Unit 2 aeration tank 47
12 Primary sludge production in pilot activated sludge systems ... 48
13 Pilot activated sludge systems primary sludge and waste mixed
liquor TSS concentrations 48
14 Pilot activated sludge systems solids retention times 49
15 Activated sludge System 1 influent and effluent TSS
concentration . ..... 49
16 Activated sludge System 2 influent and effluent TSS
concentration .............. ... 50
17 Pilot activated sludge systems influent and effluent TBOD
concentrations 50 *
18 Pilot activated sludge systems influent and effluent TCOD
concentrations 51
19 Pilot activated sludge systems influent and effluent ammonia
concentrations 51
vi
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20 Pilot activated sludge systems influent and effluent nitrate
and nitrite concentrations . 52
21 Digester 1 operating temperature. . 57
22 Digester 2 operating temperature, .......... 57
23 Digester 1 feed pH values 58
24 Digester 1 effluent pH values 58
25 Digester 2 feed pH values 59
26 Digester 2 effluent pH values 59
27 Volatile solids loading of digesters. .... ..... 60
28 Volatile solids reduction in digesters , 60
29 Gas" production from digesters 61
30 Percent methane in digester gas . 61
31 Activated sludge Unit 2 C.I. Disperse Blue 79 concentrations. . . 81
32 Activated sludge Unit 2 feed TSS and C.I. Disperse Blue 79
concentrations 81
33 Activated sludge Unit 2 primary effluent TSS and C.I. Disperse
Blue 79 concentrations. 82
34 Activated sludge Unit 2 primary sludge TSS and C.I. Disperse
Blue 79 concentrations 82
35 Activated sludge Unit 2 waste activated sludge TSS and C.I.
Disperse Blue 79 concentrations 83
36 Activated sludge Unit 2 final effluent TSS and C.I. Disperse
Blue 79 concentrations. . . 83
37 Activated sludge Unit 2 waste activated sludge TSS
concentrations vs waste activated sludge C.I. Disperse Blue 79
concentrations. 84
38 Activated sludge Unit 2 final effluent TSS concentrations vs
final effluent C.I. Disperse Blue 79 concentrations 84
vii
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TABLES
Number Page
1 Summary of South Shore Treatment Plant operational data 6
2 Activated sludge systems tank volumes ... 7
3 Target operating parameters for activated sludge pilot plants . , 17
4 Target operating parameters for anaerobic digesters . 18
5 Target operating parameters for bench~scale activated sludge
system 19
6 Sampling and analysis schedule for pilot systems. 21
7 Maximum sample holding times ...... 25
8 Data quality objectives 30
9 Statistical summary of relative difference between analytical
duplicate analyses. . 32
10 Statistical summary of relative difference between field
duplicate sample analyses .... 33
11 Statistical summary of laboratory spike recoveries 33
12 Summary of analytical completion and data deletion 34
13 Analytical duplicates from extraction procedure development
period. ... ..... 39
14 Analytical spikes from extraction procedure development period. . 39
15 Summary of activated sludge feed analytical data for the
acclimation period (Day 156-196, June 28 - August 7, 1988). . . 41
16 Summary of activated sludge pilot plant operation for the
acclimation period (Day 156-196, June 28 - August 7, 1988). . , 42
17 Summary of activated sludge feed analytical data for the dye
testing period (Day 197-268, August 8 - October 18, 1988) ... 43
18 Summary of activated sludge pilot plant operation for the dye
testing period (Day 197-268, August 8 - October 18, 1988) ... 43
viii
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19 Summary of anaerobic digester operation for the acclimation period
(Day 197-287, August 8 - November 6, 1988) 55
20 Summary of anaerobic digester operation for the dye testing period
(Day 288-330, November 7 - December 19, 1988) 56
21 Analytical duplicates performed during the dye testing period. , , 65
22 Analytical spikes performed during the dye testing period 67
23 Field duplicate samples obtained during the dye testing period . . 69
24 Field spike samples prepared during the dye testing period .... 71
25 Instrument duplicate samples obtained during the dye testing
period 74
26 Replicate instrument analyses obtained during the dye testing
period 75
27 Instrument spike samples prepared during the dye testing perxod, . 75
28 Summary of spectrophotometer and 11PL.C-UV G.I, Disperse Blue 79
analyses and total suspended solids analyses during dye testing
period 77
29 Normalized flowrates used for mass balance calculations. ..... 85
30 C.I. Disperse Blue 79 mass balance across entire treatment system. 87
31 C.I. Disperse Blue 79 mass balance across primary clarifier. ... 88
32 C.I. Disperse Blue 79 mass balance across the aeration basin and
final clarifiers ............ 89
33 Summary of spectrophotometer and HPLC-UV C.I. Disperse Blue 79
analyses and total suspended solids analyses of anaerobic
digester samples 90
34 Average anaerobic digester dye sample concentrations ....... 92
35 Mass spectrometric analysis of anaerobic digester samples 93
36 Collision activated dissociation spectra of degradation products
of C.I. Disperse Blue 79 94
37 Bromide analyses of anaerobic digester samples .... 95
38 Summary of activated sludge Unit 3 feed analytical data (Day 302-
388, November 22 - February 15, 1989) 97
39 Summary of activated sludge Unit 3 operation (Day 302-388,
November 22 - February 15, 1989) ...... 97
ix
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40 Summary of spectrophotometer and HPLC-UV C.I. Disperse Blue 79
analyses of Unit 3 samples 99
41 Flowrates used for mass balance calculations for Unit 3, .... . 100
42 C.I. Disperse Blue 79 mass balance across Unit 3 ........ . 100
43 Relative amounts of degradation products in Unit 3 . . . 101
x
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LIST OF ABBREVIATIONS AND CONVERSIONS
ABBREVIATIONS
°C
degrees
C & Tl t i g IT
cm
centimeter
D
..
difference between duplicate analyses
Dp
..
relative difference of duplicate analyses
DO
dissolved oxygen
ft
foot (feet)
EMSL-LV
--
Environmental Monitoring and Support Laboratory - Las Vegas
F/M
--
food to micro-organism ratio
g
--
gram
GC
--
gas chromatography
GC/MS
--
gas chromatography/mass spectrometry
gal
gallon
gpd
gallons per day
gph
gallons per hour
gpm
gallons per minute
HPLC
--
high performance liquid chromatography
hrs
hours
HRT
--
hydraulic retention time
in
inch
kg
kilograms
L
liter
LPD
liters per day
lb
pound
m
meter
mg
milligram
mgd
million gallons per day
mg/L
milligrams per liter
min
minute
ml
milliliter
MMSD
Milwaukee Metropolitan Sewerage District
ML
mixed liquor
MLSS
mixed liquor suspended solids
n
number of observations
NH3
ammonia
N02
nitrite
N03
nitrate
N03+N02
nitrate plus nitrite
ORD
Office of Research and Development
POI
--
point of interface
QA
quality assurance
QAPP
quality assurance project plan
QC
quality control
xi
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R
-- percent recovery of spike
RREL
-- Risk Reduction Engineering Laboratory
RS
- - return sludge
RPM
- - revolutions per minute
S
-- soluble fraction of sample
sec
- - second
SKN
-- soluble Kjeldahl nitrogen
SRT
-- solids retention time
SP
- - soluble phosphate
SSVI
-- stirred sludge volume index
TBOD
- - total biochemical oxygen demand
TCOD
- - total chemical oxygen demand
TDS
-- total dissolved solids
TKN
-- total Kjeldahl nitrogen
TP
- - total phosphate
TSS
-- total suspended solids
TWAS
-- thickened waste activated sludge
u
- - micro
US
~w microgrsins
ul
-- microliter
um
-- micrometer
vss
-- volatile suspended solids
x
-- average of replicate analyses
CONVERSIONS
°F - 1.8°C + 32
ft x 30.48 - cm
gal x 3.785 = L
-3 3
gal x 3.785 x 10 — m
gpd/ft2 x 0.0407 = m3/day m2
gpm x 3.785 = L/min
in x 2.54 = cm
lb x 0.454 = kg
3 3
lb/day 1000-ft x 16.02 = kg/day.1000m
xll
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ACKNOWLEDGMENTS
This document was prepared for EPA's Office of Research and Development
(ORD), Risk Reduction Engineering Research Laboratory (RREL) in partial
fulfillment of contract No. 68-03-3371. Mr. Glenn Shaul, Water and Hazardous
Wastes Treatment Research Division, was the Project Officer and was
responsible for technical direction throughout the study. Dr. Don Betowski,
Environmental Monitoring and Support Laboratory - Las Vegas (EMSL-LV), was
responsible for the organic analysis of samples. EPA technical assistance
was provided by Mr. Kenneth Dostal and Mr. Clyde Dempsey, RREL, and Dr. Eric
Weber, Environmental Research Laboratory, ORD.
Engineering and support services were provided by Mr. Greg Vogel and Mr.
Vince Tripi. The dye extraction procedures were developed and performed by
Mr. Karl Bombaugh and Mr. James Wojtkiewicz. Report preparation services
were provided by Mr. Clark Crosby and Ms. Sharon Yerckie. Radian-Milwaukee
laboratory personnel, with Mr. Chuck Applegate as Laboratory Manager,
performed the conventional chemical analysis.
Special thanks are also extended to the Milwaukee Metropolitan Sewerage
District South Shore Treatment Plant staff for the services and assistance
provided throughout the performance of the on-site pilot studies.
Special acknowledgment also is accorded to Abe Riefe, Ciba-Geigy Corporation,
Wayne Tiricher, Ph.D., Georgia Institute of Technology, and George Baughman,
University of Georgia, for their specific chemical and/or engineering
assistance. In addition, the authors wish to thank the European and United
States Operating Committees of the Ecology and Toxicology Association Dye
Manufacturing Industry for suppling the test compound and ongoing technical
assistance.
This project was reviewed by Professor Richard I. Dick, Cornell University,
and Professor W. Wesley Eckenfelder, Vanderbilt University, before data
collection and the report was peer reviewed by these individuals as well.
xiii
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SECTION 1
INTRODUCTION
The fate of specific azo dyes in wastewater treatment facilities is
unknown since few detailed studies have been reported in the literature, A
better understanding of this large class of organic compounds is necessary to
assess their impact on the environment and human health. Several azo dyes
and possible biodegradation products, such as aromatic amines, have been
shown to be, or are suspected to be, carcinogenic. C.I. Disperse Blue 79,
one of the largest production volume dyes, is a water insoluble bromodir.itro-
aniline derived compound. The emperical formula for the bromomethoxy form of
C.I. Disperse Blue 79 which was used in this study is C^^H^i-BrN^O^, the
molecular we ight is 625.4, and the structural formula is:
The purpose of this study was to determine the fate of C.I, Disperse
Blue 79 and select biodegradation products in a conventionally operated
activated sludge process and an anaerobic sludge digestion system. Two
continuous feed pilot-scale wastewater treatment systems, consisting of one
control system and one experimental system, were operated at the Milwaukee
Metropolitan Sewerage District (MMSD) South Shore Wastewater Treatment Plant.
Each system included a primary clarifier, plug-flow aeration basin, secondary
clarifier and an anaerobic digester. Screened, raw wastewater, fed to the
experimental treatment system, was dosed with a target concentration of 5
mg/L of active ingredient in a commercial formulation of C.I. Disperse Blue
79. The control system was fed only the screened, raw wastewater. After
acclimation and steady-state conditions were reached, the following samples
from each system were analyzed for the dye and related compounds: influent,
primary effluent, activated sludge effluent, primary sludge, waste activated
sludge, digester feed, digester supernatant, and digester effluent.
In addition to these pilot-scale systems, a bench-scale activated sludge
system was operated to assess the fate of dye degradation products from a
digester in an aerobic treatment system. This system was operated to
simulate the recycle of digester supernatant to the head-end of a typical
wastewater treatment system.
o
ii
Br HNCCH
N(CH CH CCCH I
2 2 3 2
1
Preceding page blank
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SECTION 2
CONCLUSIONS
1. The addition of C.I. Disperse Blue 79 did not adversely affect the
operation of the pilot activated sludge unit or the anaerobic digester.
Both the control and experimental activated sludge units produced
effluents typi ca 1 of rounicxpa 1 wastewater treatment systems . The
anaerobic digesters achieved volatile solids reductions within the normal
operating range for municipal digesters.
2. No evidence of C.I. Disperse Blue 79 degradation in the activated sludge
systems was found. Mass balance calculations showed that on average,
86.5% of the dye contained in the feed to the system was present in the
effluent streams.
3. The majority of the C.I. Disperse Blue 79 fed to the activated sludge
system was removed in the waste activated sludge. The average dye mass
balance obtained around the system was 86,5 percent; the dye was
partitioned in the effluent streams as follows: 3.6% in the primary
sludge, 62.3% in the waste activated sludge, and 20.4% in the final
effluent.
4. The C.I. Disperse Blue 79 was degraded in the anaerobic digester. The
dye concentration was reduced from an average feed value of 566 mg/L to
an average effluent value of 15.0 mg/L, or a 97.4% reduction.
5. Possible degradation products of the dye were detected in the digester
effluent. Some preliminary measurements were made to identify the
structure of these compounds. However, no positive identification or
quantification of the compounds was accomplished.
6. Based on limited semi-quantitative results, some of the dye degradation
products from the anaerobic digester were destroyed when treated in a
bench-scale activated sludge system.
2
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SECTION 3
RECOMMENDATIONS
Sufficient data were obtained in this study to determine the fate of
C.I. Disperse Blue 79 in a conventional treatment plant. Results showed that
the dye had little to no impact on the operation of the wastewater treatment
system unit operations, but it concentrated in the waste activated sludge and
was degraded to a significant extent in an anaerobic digester. Preliminary
work was performed to identify the degradation products formed in the
anaerobic digester. However, further work was not conducted to verify the
identity and quantify the degradation products or to fully assess their
treatability in biological systems. Based on the findings of this study,
there are two key areas in which further evaluation is recommended. These
areas are described below:
1. Because of the apparent concentration of the dye in activated sludge
solids, the effect of improved solids removal in the secondary clarifier
and its impact on the effluent dye concentration warrants further
investigation. This should include evaluating coagulant aids and longer
settling times to improve removal.
2. Additional work should be performed to positively identify the breakdown
products of the C.I. Disperse Blue 79 material formed in the anaerobic
digester. The identity of these compounds might help to assess the
effect of C.I. Disperse Blue 79 on the effluent quality from a
conventional activated sludge treatment system.
3
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SECTION 4
DESCRIPTION OF THE PROJECT SITE
The pilot plant work was performed at the MMSD South Shore Wastewater
Treatment Plant, The South Shore plant serves the southern and western
portion of the Milwaukee Metropolitan area. The average wastewater flow to
the plant in 1986 was 101 million gallons per day (MGD), Approximately
eighty percent of this flow was municipal sewage and the remaining twenty
percent was comprised of various industrial wastewaters.
A schematic diagram of the South Shore plant is presented in Figure 1.
The primary treatment at the plant consists of coarse screening, grit
removal, and primary sedimentation. In addition, pickle liquor is added
just prior to primary sedimentation for phosphorous removal. A
conventional activated sludge system is used for secondary treatment.
The treated water is chlorinated and discharged to Lake Michigan.
The waste activated sludge from the secondary clarifiers is thickened
using dissolved air flotation units. A portion of the thickened waste
activated sludge (TWAS) is combined with the primary sludge and stabilized
in anaerobic digesters. The remaining TWAS is transferred to the MMSD Jones
Island sewage treatment plant for processing to produce fertilizer. The
digested sludge is thickened in lagoons and then either applied to land as a
soil conditioner or transferred to Jones Island for fertilizer production.
Important operational data from the South Shore plant are summarized in
Table 1. The data in Table 1 are average values for the eight year period
from 1979 to 1986.
The pilot equipment used for this study was contained in a mobile
trailer. For the winter months, the trailer was parked inside the
incinerator building, which is located near the head end of the plant.
Discharge from the biological treatment system was directed to a floor
drain in the incinerator building. The trailer was moved outside in the
spring when construction started inside the incinerator building. The
discharge from the trailer was then directed to a sanitary sewer manhole.
A large centrifugal pump located in the coarse screening building
adjacent to the incinerator building was used to supply raw wastewater
to the pilot trailer. The centrifugal pump was used for sampling incoming
raw wastewater. Piping was installed to divert a portion of the flow from
the sampling pump to the trailer for use in the pilot systems.
4
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Johns Island WWTP
Debris
1 CY/D
Wastewater Intake
98 MOD
2 CY/D
Incine
rator
Ash
Landfill
,5 a/o
Debris
Grit
Return
Activated
Sludge
36, KGD
Coarse Screen
Chamber
Grit
Chamber
Primary Settling
Tanks
Aeration
Tanks
Secondary Settling
Tanks
Chlorine Contact
Chamber
97 KGD
1
LAKE MICHIGAN
Figure 1,
SOUTH SHORE WASTEWATER TREATMENT PLANT
1985 DAILY AfERAGES
Sample Stream
for Pilot Study
Recycled to Plant
Pickle Liquor
Addition
Sludge 250.000 C/D (70 Dry Tong 6.« Solids)
Scum
Digester#
95 DT/B
300-600 G/D
Sludge
Thickening
Tanks
100,000 G/D
15 DT/D 3% Solids
Haste Activated Sludge
1.1 MGD (33 DT/D
IX Solids)
WAS 130,000 G/D
18 DT/D 31 Solids
350,000 G/D
. 40-60 Kt/D 31 Solids
Devotering and
Storage Lagoons
Digester Cos
1 Mil. CF/D
Jones Island WWTP
for Hilorganite Prod.
Land
Application
AGRI-LIFE
47 DT/D
10X Solids
Schematic of project site.
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TABLE 1. SUMMARY OF SOUTH SHORE TREATMENT PLANT OPERATIONAL DATA
(Average, 1979-1986)
Parameter Value
Flow (MGD) 84
Influent BOD (mg/L) 168
Primary Effluent BOD (mg/L) 96
Final Effluent BOD (mg/L) 11
HRT (hr) 5.5
SRT (day) 7
MLSS (mg/L) 1700
Percent Volatile Suspended Solids 71
Waste Activated Sludge Production
(Dry Tons/day) 32
(MGD) 1.1
(Percent Solids) 0.71
Anaerobic Digester Loading
(lbs VSS/ft • day) 0.077
6
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SECTION 5
DESCRIPTION OF THE PROJECT EQUIPMENT
INTRODUCTION
Two pilot-scale treatment systems were operated for the duration of this
study. Each pilot system included both an activated sludge unit and an
anaerobic digester. One of the systems was operated as a control (Unit 1),
while the second was used as the experimental treatment system (Unit 2). In
addition, a bench-scale activated sludge system (Unit 3) was operated during
the later part of the study. On-site analyses were performed in the bench
area of the trailer and in a lab located in the treatment plant
administration building.
PILOT PLANT EQUIPMENT DESCRIPTION
The pilot study was performed using the U.S. EPA Mobile Biological Pilot
Plant. The trailer included a raw waste mix tank, a dye mix tank, two
activated sludge pilot units, two anaerobic digesters, two centrifuges, a
sample refrigerator, two sinks and counter space for bench testing.
Each pilot activated sludge unit consisted of a contact tank, a conical
shaped primary clarifier, an aeration tank and a conical shaped secondary
clarifier. The contact tanks were installed to ensure the dye was uniformly
mixed with the feed and to obtain a 30 minute contact time between the raw
wastewater and the dye. A diagram of a unit is displayed in Figure 2. The
actual volumes of the tanks are listed in Table 2.
TABLE 2. ACTIVATED SLUDGE SYSTEMS TANK VOLUMES
Unit 1
Unit 2
Tank
(Control)
(Experimental)
Contact Tank
(gal)
4.49
4.70
(L)
17.0
17.8
Primary Clarifier
(gal)
13.2
13.2
-------
ADJUSTABLE
HEIR
BAFFLE
VEHT
EFFLUENT
0,14? fiPH
ess* ml/min)
206 ML
SAMPLE
CUP
OVERFLOW
TO DRAIN
ISCO
WH
IF
TANK
ISCO
50 GAL Cta* LITER >•
AERATION TANK
SAMPLE
POINT
0.14? 9PM
CS56 ML/MNJ
TM
0.153 «W
-------
Each aeration tank was made of acrylic plastic and was separated into
three cells in order to operate as a plug flow system. Air flow to each cell
of the aeration basin was controlled with rotameters and metering valves.
The clarifiers were also constructed from acrylic plastic and contained
an adjustable overflow weir. The secondary clarifiers were equipped with a
mechanical scraping device operated by a variable speed electric motor and
controller. For this study the scrapers were set at approximately 1 rpm.
Each anaerobic sludge digester was a cylindrical shaped vessel
constructed of clear PVC (Figure 3). The total volume of the digester was
70 L (18.5 gal) with an operating volume of 39.0 L (10.3 gal). The operating
volume could be adjusted if needed. Each digester was equipped with a heater
to maintain the design operating temperature. Mixers were also included to
keep the contents homogenous in both temperature and solids content.
Digested sludge was manually wasted twice per day. Thickened sludge was fed
twice per day following digested sludge wastage. The feed sludge was fed
from the top through a funnel.
Gas meters equipped with foam traps were used to measure the gas
produced from the anaerobic digesters. A two-liter gas bag was installed
in-line to each gas meter to avoid back flow of gas when digester wasting was
performed. Also, in each gas line was a tee with a septum for syringe
removal of gas samples. Manometers were connected to the gas line to measure
the operating pressure of the digesters.
The feed to the two activated sludge pilot units consisted of the raw,
unscreened sewage which entered the South Shore plant. As described in
Section 4, part of the flow from a sampling pump was diverted to the pilot
trailer. The raw wastewater was pumped to a mixed tank equipped with an
overflow pipe to the drain. A plastic strainer was partially submerged in
the mix tank to screen out coarse solids from the feed. The feed for each
unit was drawn from within the strainer by individual peristaltic pumps. A
schematic flow diagram of both units is shown on Figure 4.
The feed flowed from the mix tank to a contact tank with "gentle mixing"
provided by 1/4 hp Lightning mixers. The "gentle mixing" was required to
maintain a uniform feed quality without breaking up the solids in the feed.
The contact tanks were bottom fed with a stand-pipe used for overflow feed to
the primary clarifiers. The primary clarifier effluent flowed by gravity to
the aeration basin through a 200-mL sample cup. A valve on the bottom of the
conical shaped clarifier allowed for manual wasting of the primary sludge.
The mixed liquor was gravity fed to the final clarifier. Effluent from the
final clarifier flowed by gravity through a 200-mL sample cup to the drain.
Return sludge from the final clarifier was pumped to the front end of the
aeration basin by a peristaltic pump, A portion of the mixed liquor was
transferred with a peristaltic pump operating under timer control to a waste
sludge holding tank.
The pilot systems were equipped with a ventilation system to vent offgas
from the aeration basins. A header assembly connected the covers of these
units to an exhaust fan which was vented out of the trailer.
9
-------
1/25 HP
VARIABLE
SPEED
MIXER
STORAGE
OAS
SAMPLE
POINT
I IUMW
POLYETHYLENE
BEARING
PLACES
THICKENED SLUDGE
FOAM
TRAP
FROM ACTIVATED
SLUDGE UNIT
2" SS PIPE
SILICONE
I Jf—
)ggssg|g|
IB.5 GAL
C 70 L 3
TOTAL
VOLUME
15* 10
CLEAR
PVC SHELL
10.3 GAL
C39 L)
OPERATING
VOLUME
15 DAY 3RT
HEATER
WITH 95
OPERATIVE
TEMP
500 W
I to V
DIGESTED
SLUDGE
TO DRAIN
0.69 GPP
(2.6 LPD )
SAMPLE LOCATION FOR
ORGANIC ANALYSIS
SUPPORT
STAND
Figure 3. Anaerobic digester schematic
10
-------
Sample
i Locations
F -
Raw Waste
D -
Dye
PS -
Primary Sludge
PE -
Primary Effluent
All -
Aeration Tank 1, Cell 1
A21 -
Aeration Tank 2» Cell I
W -
Waste Sludge
SP -
Supernatant
DF -
Digester Feed
FE -
Final Effluent
DE -
Digester Effluent
G -
Gss
CS -
Centrifuge Bolide
0,F.
- OVERFLOW
0
- PUMP
O
- SAMPLE POINT
CONTROL SYSTEM
(SYSTEM 1)
EXPERIMENTAL SYSTEM
(SYSTEM 2)
WASTEWATER
MIX
TANK
SCREEN
CONTACT
rm
CONTACT
TANK
PRIMARY
CLARIFIER
PRIMARY
CLARIFIER
AERATION
TAUK
AERATION
TANK
CELL 1
CELL I
CELL 2
A12
liKliL 2
A22
CELL 3
A13
CELL 3
SP1
LIQUID
SOLID
THICKENER
SOLID
THICKENER.
SECONDARY
CLARIFIER
SECONDARY
CLARIFIER
EXCESS TO
EXCESS 10
EXCESS TO
DRAIN
EXCESS TO
DRAIN
DRAIN
DRAIK
ANAEROBIC
DIGESTER
ANAEROBIC
DIGESTER
FINAL
EFFLUENT
FINAL
EFFLUENT
Figure k. Schematic of pilot plants with sampling locations shown.
11
-------
The pilot systems sampling locations are shown on Figure 4. Automatic
composite samplers were installed at sample locations Fl, F2, PE1, PE2, FE1,
and FE2,
The bench-scale activated sludge system used was a Horizon Ecology
Company Bio-Oxidation System and is depicted on Figure 5, The system
consists of a 6-liter outer cone, a 2-liter inner cone, and a 125-ml
clarifier tube. The area between the inner and outer cone serves as the
aeration basin. The area between the inner cone and clarifier tube is for
sludge recycle, and the clarifier tube is a settling zone for effluent
clarification. The inner and outer cones are constructed of Vitax while the
clarifier tube is constructed of acrylic.
12
-------
EFFLUENT
6.7 GPD
C 25 LPD)
WASTE
ACTIVATED
SLUDGE
0.23 GPD
CO,86 LPD)
T~r
FEED
6.9 GPD
C 26 LPD 3
AIR
DIFFUSERS
AIR
PUMP
RESERVOIR
RESERVOIR
»
• SAMPLE LOCATION FOR ORGANIC ANALYSIS
Figure 5. Bench-scale activated sludge system schematic (Unit. 3),
-------
SECTION 6
PROJECT TEST PLAN
INTRODUCTION
The test plan for this project was developed over several months. The
first draft was written in October 1987. The original draft was modified as
necessary to address comments from EPA and incorporate changes in the program
as they occurred. The final test plan for this study was completed in March
1988.
This study was originally planned to consist of two distinct phases.
Different forms of Disperse Blue 79 were to be fed to the experimental pilot
system during the two phases. The objective of each phase was to study the
fate of the target dye compound and any degradation products which could be
identified in a conventional activated sludge system. However, near the end
of tests with the first dye form, testing of the second dye was cancelled
because it was decided that differences in dye form was not an important
parameter for this study.
For the last four months of the study, a bench-scale activated sludge
system (Unit 3) was operated. The purpose of operating Unit 3 was to study
the fate of dye degradation products produced in the anaerobic digester. The
feed mixture to Unit 3 contained centrifuged digester effluent from the
experimental system (Unit 2).
The original plan was for Radian to operate the pilot systems, perform
conventional analyses, and ship samples to EMSL-LV for organic compounds
analyses. The task of performing the dye extraction procedure in preparation
for organic analyses was given to Radian during the course of the project.
The development of the extraction procedure is detailed in Section 8. The
test plan for operation and sampling of the pilot systems is outlined below.
ACCLIMATION AND STARTUP
To begin operation of the activated sludge systems, the raw waste flow
was started to the mix tank, the feed pumps to the contact tanks were turned
on, and the primary clarifiers were allowed to fill. The two aeration basins
and two final clarifiers were filled with mixed liquor from the full-scale
plant. Aeration was started immediately. The sludge recycle pumps were
started after the sludge in the clarifier had settled. The sludge wastage
rates were set for a targeted 7-day SRT after the primary clarifier was
filled and primary effluent flow to the aeration basin had begun. The dye
feed to Unit 2 was started after five days of operation.
14
-------
The digesters were filled with sludge from the full-scale digester. The
gas space above the sludge was purged with nitrogen. The mixers were set at
approximately 20 rpm. The heater was then started and set to maintain
a 35 C operating temperature.
EQUIPMENT OPERATION
The pilot plants were operated 24 hours per day, seven days per week
throughout the study. Generally one person was on-site 4 to 5 hours each day
to maintain the systems and obtain samples.
Raw municipal wastewater was pumped from the main plant sampling pump to
the mix tank (Figure 4). Waste from the mix tank was pumped to the contact
tank of each system while dye was pumped only to the contact tank of Unit 2.
The flows to each unit were individually measured, using the volume/stopwatch
method, and controlled using variable speed pumps.
The primary clarifier effluents flowed by gravity through 200-mL
sampling cups and into the aeration basins. The primary sludges were
manually wasted once per day. The mixed liquors flowed by gravity from the
aeration tanks to the secondary clarifiers. The mixed liquors entered the
secondary clarifiers on the side near the bottom of the cone. The sludges
were thickened in the secondary clarifier and the return sludges were pumped
to the front end of the aeration basin at a constant rate. The clarified
effluents then flowed out to the sampling cups and to the drain.
Airflow to each aeration tank was controlled to maintain a minimum
target dissolved oxygen (DO) concentration of 2.0 mg/L. DO measurements were
performed once per day in each cell of the aeration basins to determine what
adjustments, if any, were needed to maintain the minimum targeted DO.
Mixed liquor was wasted from each unit four times per hour via a
peristaltic pump controlled by a timer. The waste sludges were stored in
calibrated 38 L (10 gal) containers. The volume of sludge to be wasted
was calculated based on the most recent effluent TSS and waste sludge TSS
values. The sludge in the container was mixed and sampled, measured, and
processed to prepare digester feed.
The entire volume of waste activated and primary sludge was mixed and
then thickened by centrifugation to form sludge cakes which were used to
prepare the digester feeds. The digester feed was a combination of the
sludge cake diluted by the centrate to a targeted total volatile solids (TVS)
concentration of 1.8 percent. The amount of cake required to achieve the 1.8
percent TVS feed concentration varied with the TVS of the sludge cake.
Ideally, TVS analysis of the sludge cake would be required daily to insure
correct preparation of the feed. However, a consistent ratio of TVS to TS
was found to exist and was verified by periodic analysis of the digester
feed. Therefore, daily analysis for TVS was not required to maintain a
constant volatile solids loading and solids retention time (SRT) in the
digester.
Due to the time required for total solids analysis, the centrifuge cake
prepared on a given day was sampled and stored for use in feed preparation
15
-------
the following day. The procedure used for the digester feed preparation was
as follows;
1. Collect the desired volume of waste activated sludge from the
aeration basins over a 24-hour period, with the collection container
iced during collection,
2. Waste sludge from the primary clarifiers at the end of the waste
activated sludge collection period.
3. Sample the two sludges as necessary according to the sampling schedule
(shown later in this Test Plan).
4. Allow waste activated sludge to settle and decant off supernatant, saving
the supernatant.
5. Mix the primary sludge with the gravity thickened waste activated sludge.
6. Centrifuge the sludges and pour off the centrate. Mix the centrate with
the supernatant from the gravity thickening step.
7. Continue centrifugation of sludge mixture until all the sludge is reduced
to a cake. Sample the centrifuge cake and store centrifuge cake at 4 C,
Measure volume of supernatant and sample as per the sampling schedule.
Store one gallon of supernatant in refrigerator,
8. Analyze the centrifuge cake for total solids.
9. Calculate the mass of centrifuge cake solids required from the previous
day, based on the total solids analysis, to prepare the digester feed
with the target TVS concentration. Weigh out the calculated mass of
centrifuge solids and add supernatant to bring up to 2.7 L,
10. Blend the mixture, obtain a 100 ml sample of the prepared feed sludge,
and store remaining volume in a refrigerator.
After the feed was prepared, the thickened sludge was fed to the
digester. A 1.3 liter volume of digested sludge was withdrawn from the
digester and an equal volume of feed was added. The remaining 1.3 liters of
prepared feed sludge was added in a similar manner the following morning.
Feed for Unit 3 (bench-scale activated sludge system) was prepared daily
using primary effluent from the experimental pilot unit (PE2), supernatant
and centrate from the preparation of digester feed (SF2), and centrate from
the digester effluent (DE2). The feed mixture was chosen to simulate
operation of the South Shore plant with recycle from the waste activated
sludge and digester thickening operations. The feed volumes used were as
follows; 26 L of PE2, 200 ml of SP2, and 800 ml of DE2 centrate. The
fraction of digester supernatant was slightly higher than actual operation of
the South Shore plant to increase the dye degradation products concentration
in the Unit 3 feed.
16
-------
Feed to Unit 3 was continuously pumped into the system from the feed
tank (see Figure 5); the feed tank was continuously mixed to prevent settling
of solids. Effluent was pumped to a calibrated holding tank from the
clarification tube. Mixed liquor was wasted from the system four times per
hour using a pump and timer arrangement.
Airflow to Unit 3 was controlled via a rotometer to maintain a minimum
DO concentration of 2 mg/L and maintain adequate mixing. Generally it was
necessary to maintain a DO higher than 2 mg/L to obtain adequate mixing in
the unit.
OPERATING PARAMETERS
Target operating parameters of the pilot activated sludge units and the
anaerobic digesters were selected based on long term operational data from
the South Shore plant. The operational parameters for the activated sludge
units and the anaerobic digesters are summarized in Tables 3 and 4,
respectively.
TABLE 3. TARGET OPERATING PARAMETERS FOR ACTIVATED SLUDGE PILOT PLANTS
Pilot Plant
Parameter
Control
Experimental
Treatment Unit
Aeration Tank Volume (gal)
(L)
50
189
50
189
Raw Feed Flow (gpm)
(L/min)
HRT (hr)
3
Aerator Loading (lb BOD/1QOO ft * day)
(kg BOD/m » day)
MLSS (mg/L)
(Percent volatile solids of total)
SRT (day)
F/M (lb BOD/lb MLVSS-day)
(g BOD/g MLVSS.day)
Dye Flow Rate 144 mg/L active dye (gpm)
(L/min)
0.152
0.575
5.5
26
0.42
1700
71
0.35
0.35
0.152
0.575
5.5
26
0.42
1700
71
0.35
0.35
0.0053
0.02
17
-------
TABLE 4, TARGET OPERATING PARAMETERS FOR ANAEROBIC DIGESTERS
Pilot Plant
Parameter
Control Experimental
Treatment Unit
1
2
Digester Operating Vol (gal)
(L)
10.3
39
10.3
39
Feed Sludge Flow (gal/day)
(L/day)
0.69
2.6
0.69
2.6
Feed Sludge Solids (total, percent)
(volatile, percent)
2,4
1.8
2.4
1.8
Solids Retention Time (days)
15
15
3
Digester Loading (lb TVS/ft « day)
(kg TVS/m • day)
0.077
1.2
0,077
1.2
The digester operating conditions were chosen so that, when possible,
the values were in the range of typical operating parameters of anaerobic
digesters. Although a 15 day SRT is within the recommended range of high
rate ^igestion (10-20 dajp, (1)), the volatile solids loading of 1.2 kg
TVS/m * day (0.077 lbs/ft * day) ^hat was used in the s|udy is below the
recommended range (2,4-6,4 kg/ra *day, 0,15-0.4 lbs/ft »day). However, the
South Shore plant, as well as many other full-scale plants, often operate
below the recommended range. For this reason, the pilot-scale digesters were,
operated to simulate the full-scale plant.
Table 5 shows the target operating parameters for the bench-scale
activated sludge unit. The HRT and SRT are based on the total volume (6L) of
the unit.
• FIELD MONITORING ACTIVITY
The Radian field engineer(s) were responsible for the operation of the
pilot and bench units and sample collection from the units. The specific
activities performed included:
1, Measuring and recording feed, return sludge, and dye flows daily and
adjusting the flow rates if necessary. The measured volume/stopwatch
method was used to measure flow rates. Also the volume of the main dye
tank was monitored to verify proper operation of the dye feed system.
2. Measuring and recording dissolved oxygen concentrations in each cell of
the aeration basins. Also measuring, recording, and adjusting the
air flow rate to each cell.
18
-------
TABLE 5, TARGET OPERATING PARAMETERS FOR BENCH-SCALE ACTIVATED
SLUDGE SYSTEM
Parameter Unit 3
Reactor Volume (gal) 1.6
(L) 6.0
Feed Flow (gpd) 6.9
(L/day) 26
HRT (hr) 5.5
SRT (day) 7
3. Measuring and recording pH of the feeds, first cell of the aeration
basins, anaerobic digester sludges and digester effluents. Measurement
of pH was performed on samples immediately following withdrawal from the
units.
4. Measuring the temperature of the aeration basin and of samples
immediately upon withdrawal from the digesters.
5. Manually wasting primary sludges and measuring volumes wasted.
6. Three times per week, determining the amount of solids wasted from the
two activated sludge units by measuring the volume and TSS of the waste
mixed liquor in the waste solids holding tanks and the secondary
effluent TSS. The volume of sludge wasted from both units was
recorded daily.
7. Measuring and recording gas volume produced from the anaerobic
digesters.
8. Preparing feed for digesters according to procedure outlined
previously. Measuring the volume of thickened sludge and supernatant
daily. Measuring and recording the volume of sludge fed to and wasted
from each digester daily.
9. Performing standard bench tests, as needed, to aid in monitoring and
controlling each system. Mixed liquor settling tests were performed
routinely to aid in selecting the proper sludge return rate. Mixed
liquor oxygen uptake rate, and stirred sludge volume index (SSVI) were
determined periodically during steady-state operation.
10. Performing necessary maintenance and repair of treatment equipment.
11. Recording all observations and activities not on data sheets in a daily
log.
19
-------
SAMPLING AND ANALYTICAL ACTIVITY
The Radian field engineer(s) were responsible for obtaining samples and
submitting tbem to the appropriate laboratories. The sampling locations were
shown in Figure 5. Automatic composite samplers were installed at sample
locations Fl, F2, PE1, PE2, FE1 and FE2. Composite samples were collected at
sample points Wl and W2 using peristaltic pumps. Grab samples were obtained
from sample points PS1, PS2, SP1, SP2, DFl, DF2, DEI and DE2 (for volatile
acids, alkalinity, pH, and temperature measurements) Gl, G2, All, A21, D, CS1
and CS2. Grab-composite samples of the two portions per day of digested
sludge (DEI ad DE2) were obtained for solids and dye analyses. The specific
sampling duties included
1. Obtaining and labeling periodic composite and grab samples according to
the sampling schedule in Table 6. Samples for on-site testing were
analyzed immediately.
2. Preparing and packaging samples for shipment for analyses not performed
on-site. Initiating chain-of-custody procedures, filling out analytical
request sheets and maintaining sample shipping containers. This
included samples for analysis at the Radian Milwaukee laboratory and
organic analysis at the EMSL-LV laboratory.
3. Preparing field replicates, blanks and spiked samples in accordance
with the quality assurance program.
The Radian chemist(s) were responsible for storage and analysis of samples to
be analyzed at the Milwaukee Laboratory. The chemist(s) performed the
following activities:
1. Log in and storage of all samples submitted by the field engineer. This
included preserving samples for reanalysis, if necessary.
2. Performing requested analysis within specified holding times.
The sampling schedule shown in Table 6 was used as a guide; sampling
frequency was increased or decreased as deemed necessary throughout the
course of the study.
The acclimation period for Phase I was approximately 38 weeks because of
analytical methods development required to properly analyze the dye and
related products (See Section 9). During the time period when the dye
extraction procedure was being developed, sampling quality assurance (QA)
activities were reduced to a minimum maintenance schedule. The sampling and
QA schedules were increased to the frequencies indicated when dye sampling of
the pilot systems was initiated.
TEST SCHEDULE
As indicated previously, operation of the pilot biological treatment
systems was to be performed in two phases. However, only Phase I, testing of
the bromomethoxy form of C.I. Disperse Blue 79 was performed. Phase II, the
testing of the bromoethoxy form of C.I. Disperse Blue 79 was cancelled.
20
-------
TABLE 6. SAMPLING AND ANALYSIS SCHEDULE FOR PILOT SYSTEMS
Parameter Minimum Frequency
Sample
Type
Sample Points*
pH
1/Day
2/Day
Grab
Grab
Fl, F2, Allj A21,
DF1, DF2
DEI, DE2
Temperature
1/Day
2/Day
In-situ •
Grab
Fl, F2, All, A21
DEI, DE2
Dissolved Oxygen
1/Day
In-situ
All, A12, A13, A21,
A22, A23
Suspended Solids
3/Week
3/Week
Corap
Grab
Fl, F2, PE1, PE2,
FE1, FE2, DEI, DE2,
Wl, W2
SP1, SP2, PS1, PS2
DF1, DF2
Total Solids
3/Week
3/Week
Grab-Comp
Grab
DEI, DE2
DF1, DF2, CS1, CS2
Total Volatile Solids
3/Week
3/Week
Grab-Comp
Grab
DEI, DE2
DF1, DF2
TBOD
1/Week
Comp
Fl, F2, FE1, FE2
TCOD
2/Week
Comp
Fl, F2, FE1, FE2
NK3, N03+N02, TKN
1/Week
Comp
Fl, F2, PE1, PE2, FE1,
FE2
Alkalinity
3/Week
Grab
DEI, DE2
Volatile Acids
1/Week
Grab
DEI, DE2
Dye and Related Compounds
-Activated Sludge Systems
2/Week
2/Week
Comp
Grab
Fl, F2, PE1, PE2,
FE1, FE2, Wl, W2
D, PS1, PS2
-Anaerobic Digesters
2/Week
2/Week
Grab-Comp
Grab
DEI, DE2
DF1, DF2, SP1, SP2
Gas Content (C02 + CH4)
1/Week
Grab
Gl, G2
Gas Volume
7/Week
Gl, G2
* Codes refer to Figure 4, page 11.
21
-------
The activated sludge units were operated at the setpoint conditions
until steady-state was reached and the analytical method for the dye and
related compounds was verified. Steady-state was determined based on
achieving constant operational conditions such as mixed liquor suspended
solids (MLSS) concentrations and maintaining a satisfactory final effluent
(30 fflg/L or less suspended solids and 30 mg/L or less total BOD). When
steady-state operation of the activated sludge units was achieved and a
method for dye analysis was developed, sampling of the activated sludge units
for dye analysis was initiated. This sampling was continued until enough
data was gathered for material balance calculations.
The activated sludge units and anaerobic digesters were not sampled for
dye analysis concurrently due to limitations on the number of sample
extractions and analyses that could be carried out at one time. The
anaerobic digesters were operated over the period when the activated sludge
units were being sampled for dye analysis. By the time the activated sludge
sampling was complete, the anaerobic digesters had reached steady-state based
on gas production and volatile solids reduction. When the dye analysis of
the activated sludge units was complete, sampling of the anaerobic systems
was started. The operation of the pilot systems was continued until
sufficient data had been obtained from both the activated sludge units and
the anaerob ic cLigcss teirs t The totcil cLyo sciinp 1 pcxnod wsts £ippicoxi.nist©]Ly^ 21
weeks,
-------
SECTION 7
QUALITY ASSURANCE/QUALITY CONTROL
INTRODUCTION
Composite and grab samples were obtained during the pilot plant
operation to monitor equipment operation and to evaluate pilot plant
performance. Some of the analyses were performed on-site; however, most
samples were transferred from the test site to the Radian Corporation
laboratory in Milwaukee, Wisconsin for analyses and tests. This section
describes the quality assurance (QA) procedures utilized for sampling,
shipping, and storing samples, the quality control (QC) measures used for
analysis, and analytical QC results. The analytical QC results of the dye
extraction, field spikes, and field duplicates are contained in Section 10.
The pilot plant operators obtained samples, added appropriate preserva-
tives , transferred samples to the appropriate containers for shipment and
storage, and initiated the sample identification records by use of a sample
log, container labels, chain-of-custody sheets, and sample analysis request
sheets. The operators also performed routine measurements of temperature,
dissolved oxygen, pH, and selected solids analyses.
Analyses for TCOD, TBOD, TSS, VSS, TS, TVS, nitrate+nitrite (N03+N02),
ammonia (NH3), volatile acids, and methane were performed at the Radian-
Milwaukee laboratory. Samples were extracted at Radian and shipped to
EMSL-LV for dye and related organic analyses.
The quality assurance practices utilized are described in a Quality
Assurance Project Plan (QAPP) dated September 15, 1988 (2).
SAMPLING PROCEDURES
Sample Collection
ISCO automatic samplers were used to take one sample every 30 minutes
over the daily compositing period of the feed, primary effluents, and final
effluents. The entire volume of mixed liquor wasted from each aeration basin
was collected in separate compositing containers. At the end of the
compositing period, the entire contents of each container was thoroughly
mixed and representative samples were obtained and placed in the appropriate
sample bottles for analysis. All compositing containers were iced during
sample collection. Sufficient ice was used so that unmelted ice was present
during the entire compositing period. The compositing bottles were emptied,
rinsed with service water, drained, and returned to the composite sampler.
23
-------
The operation of the samplers was checked periodically during the day to
reduce chance of sample loss and/or contamination because of sampler
malfunction. Plastic compositing containers of two gallon capacity were used
in the ISCO samplers for sample collection. Plastic containers were also
used to collect and store the waste mixed liquor, primary waste sludge,
digested waste sludge, and digester feed sludge.
The anaerobic digesters were fed and wasted twice per day. The two
portions of waste sludge were combined, mixed and sampled for TSS, TS, TVS,
and dye analysis. A grab sample of the morning waste sludge was obtained for
volatile acids, alkalinity, pH, and temperature measurements. Grab samples
were also taken of the dye slurry, the primary clarifier sludge, the aeration
basin, the anaerobic digester gas, and the liquid and sludge phases from the
thickening of the combined primary sludge and waste activated sludge.
Sample Containers
Liquid samples were stored in new polyethylene sample bottles with
polyethylene foam-lined plastic caps for all analyses except specific
organics analysis. Prior to use, the bottles were washed with detergent,
rinsed with tap water and demineralized water, and dried. Cleaned bottles
were capped until used.
Amber-glass bottles with Teflon^ lined caps were used for liquid and
sludge samples that were analyzed for dye content and/or dye degradation
products. The bottles were purchased pre-cleaned and ready to use.- The
cleaning procedure used by the bottle supplier for the sample bottles and the
caps was as follows:
1. Hot water wash
2. Tap water rinse
3. Rinse with 1:1 nitric acid
4. Rinse with deionized water
5. Rinse with methylene chloride
6. Oven dry
7. Cap until ready for use
Gas tight syringes equipped with valves for sample storage were used to
collect digester samples. The samples were injected directly into the gas
chromatograph (GC) from the sample syringes.
Sample Identification
Each composite sample and each grab sample that was analyzed for
parameters other than pH, dissolved oxygen or temperature, was assigned a
unique identification number. Each sample bottle was affixed with a label
with space available for the unique ID number and other pertinent sampling
information such as date, description, preservation, project number, and
initials of sampler. This information was also entered into the field
sampling log. Sample chain-of-custody sheets were completed for samples
analyzed at a location other than the pilot plant test site.
24
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Measurements performed in situ (dissolved oxygen and temperature) and
samples taken only for instantaneous pH measurement were not numbered. The
information from these measurements was entered directly on the appropriate
operation data sheets along with time and date of measurement, sample
description, location, and identity of the person taking the measurement.
Sample Preparation and Preservation
Samples for the analysis of TBOD, TSS, TVS, TS, alkalinity, volatile
acids, and specific organic compounds (dye) were placed in sample bottles and
refrigerated. Samples for the analysis of ammonia and nitrate+nitrite were
filtered through 0.45 micron membrane filters immediately after collection.
Acidification to pH less than 2 with sulfuric acid was performed on samples
for TCOD, TKN, ammonia, and nitrate+nitrite analysis. No preservation was
necessary for digester gas samples.
Sample Holding Time
The maximum sample holding times
Table 7. These are the maximum times
TABLE 7. MAXIMUM
used for various analyses are listed in
allowed between sample collection (or
SAMPLE HOLDING TIME
Parameter
Maximum Holding Time
TBOD
TSS, VSS, TS, TVS. TDS
pH
TCOD, SCOD
TKN
Ammonia
Nitrate & nitrite
Nitrite
Alkalinity
Volatile Acids
Digester gas
Dye (organics)
48 hours
7 days
do immediately
28 days
28 days
28 days
28 days
48 hours
24 hours
Acidify and centrifuge sample
immediately. Inject within 48 hours.
48 hours
no specified time
25
-------
end of compositing period) and the start of analysis for properly preserved
sampled kept at 4 C or less. Although no specific holding time for dye
analysis was determined, the samples were generally extracted within 48
hours.
ANALYTICAL PROCEDURES
The analytical procedures listed below as EPA Methods (eg. EPA Method
325.3) are procedures described in Methods for Chemical Analyses of Water and
Wastes. EPA-600/4-79-020, revised March, 1983 (3).
Procedures Used bv Pilot Plant Operators
Analytical procedures used by the pilot plant operators are listed
below:
pH--
pH measurements were performed using EPA Method 150.1 with a Corning pH
meter. The pH meter was standardized daily using buffers of pH 4, 7 and 10.
Temperature--
Temperature measurements were made according to EPA Method 170.1 with a
laboratory thermometer which had been checked for accuracy against a standard
National Bureau of Standards traceable thermometer.
DO - -
DO measurements were made in situ using EPA Method 360.1 with a YSI
Model 54A dissolved oxygen meter with a Model 5739 dissolved oxygen probe.
This probe had a built-in stirring mechanism to ensure adequate liquid
velocity across the membrane. The DO meter was standardized at least once a
day using air-saturated tap water. The dissolved oxygen concentration of the
tap water was determined chemically using the azide modification titration
method (Method 42IB, Standard Methods for the Examination of Water and
Wastewater. 15th Ed.) (4),
Oxygen Uptake Rates - -
Oxygen uptake rate measurements were performed on grab samples of mixed
liquor obtained immediately before analysis. Mixed liquor samples were
aerated for a short period before testing. Uptake rates were performed on
mixed liquor samples in 300-ml BOD bottles using a YSI Model 5720A BOD probe
and a YSI 54A DO meter. A recorder was used to plot the change in dissolved
oxygen with time. The straight-line portion of the depletion curve, a linear
plot of DO concentration vs. time, was used to determine the oxygen uptake
rate. The probe and meter were standardized immediately prior to performing
the oxygen uptake tests with air-saturated tap water. The DO concentration
of the tap water was determined by Method 421B described above.
TS--
EPA Method 160.4 was used. Samples were evaporated to dryness in an
oven at 103-105 C. Each sample was analyzed in duplicate.
26
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Radian Corporation-Milwaukee Laboratory Analytical Procedures
Analytical procedures and quality control checks used by the Radian
laboratory in Milwaukee are listed below:
TCOD--
The Hach colorimetric procedure described in Hach Water Analysis
Handbook (5) was used. This is an EPA approved procedure utilizing
prepackaged reagent in reaction tubes to which a known volume (2 ml) of
sample is added. The reaction tubes are then used for digestion and color
measurement. A Bausch & Lomb Spectronic 100 spectrophotometer was calibrated
and used for color measurements. All measurements were made with the low
level (0 to 150 mg/L) reaction tubes using appropriate dilution for high
strength samples. At least one reference standard was analyzed each day TCOD
or SCOD analyses were performed to check the calibration curve. At least two
reagent blanks were also analyzed. At least one duplicate was performed for
every fifth sample and one spike was made for every tenth sample as specified
by the QAPP.
TSS and VSS--
EPA Methods 160.2 (TSS) and 160.4 (VSS) were utilized. These methods
consist of filtration of a known volume through a glass fiber filter pad and
drying at 100-105 C for TSS and subsequent ignition at 550 C for VSS. Each
sample was analyzed in duplicate. A reagent blank was analyzed with each
analytical batch.
TS and TVS - -
EPA Methods 160.3 (TS) and 160.4 (TVS) were utilized. Samples were
evagorated to dryness in an oven at 103-105 C for TS followed by ignition at
550 C for TVS. Duplicate analys es were performed on each sample.
TB0D--
Method 507 described in Standard Methods for the Examination of Water
and Wastewater. (15th Ed.) (4) was used. Samples were seeded with screened
raw wastewater (sample point Fl). Each batch of samples analyzed for T80D
included a dilution water blank, a seed blank and at least two bottles of a
glucose-glutamic acid reference standard. At least one sample from each set
was analyzed in duplicate.
TKN and Ammonia--
EPA Method 351.3 was used for TKN and Method 350.2 was used for ammonia.
Duplicates were analyzed every fifth sample and spikes every tenth sample.
Samples for TKN analysis were digested and the resultant ammonia separated by
distillation. For ammonia measurements, the ammonia in the sample was
measured by the Technicon Autoanalyzer using the Automated Phenate Method
(EPA Method 350.1). Calibration standards were run before each sample set
and at least one standard was reanalyzed every tenth sample. The baseline
was checked between each sample using wash solution.
Nitrate+Nitrite Nitrogen--
The automated cadmium reduction method (EPA Method 353,2) was used.
Every fifth sample was duplicated and every tenth sample was spiked, with at
least one duplicate and spike analyzed per sample set. The Technicon
27
-------
Autoanalyzer was standardized before each sample set arid the calibration
checked after every tenth sample. The baseline was checked between each
sample using wash solution.
Alkalinity--
EPA Method 310,1 was used. The sample is titrated to an
electrometrically determined end point of pH 4.5. Certified standard
solutions were used for all analysis. At least one sample was duplicated
each day samples were analyzed.
Volatile Acids--
The method described in Andrews, J.F., J.F. Thomas and E.A. Pearson,
"Determination of Volatile Acids by Gas Chromatography" (6) was used. This
analysis was performed on a gas chromatograph equipped with a flame
ionization detector and appropriate column to give separation of the
individual acids C^-C,.. Results were reported as total volatile acids
(acetic acid). Every fifth sample was duplicated and every tenth sample was
spiked.
Digester Gas--
Method 511B described in Standard Methods for the Examination of Water
and Wastewater. (15th Edition;) was used. The digester gas sample was
analyzed on a gas chromatograph equipped with a thermal conductivity
detector. All samples were analyzed in duplicate. A calibration curve was
prepared using certified gas mixtures for each gas analyzed. Results were
verified each analysis day by injecting a standard gas mixture.
Dye Extraction--
The extraction procedure was developed at Radian and is outlined in
Section 8 of this report.
Organic (Dye) Analyses--
The analyses for dye content and dye degradation products were performed
by EPA, EMSL-LV. The samples were received from Radian-Milwaukee by
overnight delivery. The samples were kept cold in shipment. On arrival in
Las Vegas aliquots of the samples were placed in 2 mL sampling vials with
Teflon-lined segta and screw caps. The remainder of the sample was kept
refrigerated (4 C). The samples were analyzed as soon as possible. If the
samples were not analyzed immediately, the sample vials were placed in the
refrigerator until ready for analysis. Approximately ninety percent of the
samples were analyzed for dye content within six days.
The samples were analyzed for Disperse Blue 79 by a Spectra-Physics
SP8100XR High Performance Liquid Chromatography (HPLC) with autosampler and a
Hewlett-Packard diode array UV-visible detector. A wavelength of 575 nm
with a bandwidth of 40 nm was selected to monitor C.I, Disperse Blue 79. A
secondary wavelength of 450 nm with a bandwidth of 300 nm was also used for
these samples. A 10-cm (4.6 mm I.D.) reversed phase column with a octadecyl
silica solid phase was initially used to separate C.I, Disperse Blue 79
before detection. The initial gradient program for the mobile phase was 70
percent methanol, 30 percent water with a 2 minute hold; ramp to 100 percent
methanol in 10 minutes and hold for 5 minutes. Later analyses utilized a
28
-------
5-cm column with a faster program (70:30, methanol:water with a 2 minute
hold; ramp to 100 percent methanol in 5 minutes and hold for 5 minutes).
A blank analysis and a 4-point calibration curve were performed for each
set of samples. Linearity of this curve and consistency in the slope from
day to day were required before the sample concentration values were
accepted. A correlation coefficient of greater than 0,997 was required.
Daily deviations of >20 percent in the slope were examined. The limit of
detection of the instrument for C.I. Disperse Blue 79 was 0.25 mg/L. Values
within a factor of 3 of this number were subject to more variation than other
concentrations. Initially field blanks and field spikes were used to check
the precision and accuracy of the system. Later instrument duplicates and
instrument spikes were added at one each per sample set to further access
these parameters.
Samples were analyzed for C.I. Disperse Blue 79 degradation products by
therntospray ionization mass spectrometry and tandem mass spectrometry (MS/MS)
using direction injection or via column chromatography. This part of the
project was research oriented so the QA/QC parameters were not well defined.
Briefly the thermospray ionization is a "soft" technique for generating ions
from nonvolatile or thermally labile compounds. It is "soft" in the sense
that little energy goes into the ionization process and the resultant spectra
have one or two ions per compound. To derive structural data from these
spectra tandem mass spectrometry techniques must be used. Collision
activated dissociation spectra are then generated which show better
specificity and contain information about the structure of the unknown
compound. In this study, samples representing both the control and the
experimental system were injected into the thermospray ionization mass
spectrometer. Searches were made for ions that were present in the
experimental system and not in the control. These ions were then subject to
the tandem mass spectrometric techniques to acquire the collision activated
dissociation spectra.
QUALITY ASSURANCE RESULTS
Data Quality Objectives
Data quality objectives for the Radian Laboratory are listed in Table 8,
In cases where precision and accuracy objectives were not met, all samples
analyzed since the last acceptable QC sample were reanalyzed if the samples
were still available and sample storage conditions and holding times were not
exceeded.
Quality Assurance Review of Analytical Data
Analytical data reported by the Radian laboratories are listed in
Appendix A, Tables A-l to A-10. Letter codes were added to the list of data
in these tables to indicate data that did not meet all quality control
requirements. All requested analyses are indicated by a datum value or a QC
review code letter indicating the reason for a missing value. Blank spaces
indicate that analyses were not requested for these samples. A QC review
code letter adjacent to a number value indicates that the QC associated with
29
-------
TABLE 8. DATA QUALITY OBJECTIVES
*+ s #
Parameter Precision Accuracy Completeness
Volatile Acids
dr
-
15%
100±15%
>95%
Methane
dr
_
15%
Not
Measured
>95%
Total Dissolved Solids (IDS)
dr
-
151
Rot
Measured
>95*
Total Suspended Solids (TSS)
dr
dr
D
mm
15% for X >50 mg/L
20% for X - 20 to 50 rag/L
4 mg/L for X <20 mg/L
Not
Measured
>95%
Volatile Suspended Solids (VSS)
dr
£
-
20% for X >50 mg/L
301 for X - 20 to 50 mg/L
6 mg/L for X <20 mg/L
Not
Measured
>95%
Total Solids (TS)
de
-
151
Sot
Measured
>95%
Total Volatile Solids (TVS)
dr
-
201
Not
Measured
>95%
BOD Parameters
(T30D, SBOD)
de
-
201
R -
100+20%
>90%
Total COD (TCOD)
Soluble COD (SCOD)
dr
-
154
R -
100+15%
>951
Alkalinity
dr
-
15%
Not
Measured
>951
Kjeldahl Nitrogen (TKK)
Anur.or.ia Nitrogen (NH3)
dr
-
151
R -
100+15%
>95%
Nitrate Nitrogen (N03)
Nitrite Nitrogen (N02)
dr
-
15%
R -
100+15%
>90%
Dye Extraction and
Analysis Procedures
dr
-
201
R -
100+20%
>95%
200 (replicate I - replicate 2^
* Dg - relative difference - replicate 1 + replicate 2 Note; replicate 1 >replicate 2
+ D - difference between duplicate analysis
100 (St)ike sample - unsoiked sampled
$ R - percent recovery — spike concentration
100 (number of acceptable data valuesi
# Completeness »= number of submitted samples
** Recovery for BOD parameters based on glucose-glutamic acid reference standard.
30
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that value was deficient in the area related to the code letter. The codes
used are listed below:
Code A - The value was part of an analytical group where the spike recoveries
were outside the acceptable range.
Code B - The value was part of an analytical group where the reported
duplicate relative difference was outside the acceptable range.
Code C - The value was part of a group where spike recoveries were not
reported. This included cases where spiked samples were lost during
analysis as well as where spiking was not performed.
Code D - The value was part of an analytical group where duplicates were not
reported. In some cases, the duplicate was lost during analysis or
insufficient sample volume was available to run a duplicate.
Code E - The sample was analyzed after the maximum holding time was exceeded.
Code F - The dilution water oxygen depletion was greater than the allowable
value.
Only the data generated during the period when dye analyses were
performed (starting Day 197, August 8, 1988) are included in the QA report.
The data generated during the period when the analytical procedure for dye
analysis was being developed are not included in the QA Summary.
Statistical Evaluation of Laboratory Precision
The results of duplicate analytical measurements are included in Tables
A-l through A-10. The mean values and standard deviation for the relative
difference between duplicates are listed in Table 9. Of the 1,506 duplicate
analyses performed, 1,498 (99.5 percent) were within the precision data
quality objectives listed in Table 8. Six TSS measurements and two ammonia
measurements were outside the precision criteria. For samples with values
below the detection limit, including all volatile acid measurements, no
relative difference was calculated and these samples are not included in the
summary table.
For approximately ten percent of the samples submitted, field duplicate
samples were included along with the regular samples. The field duplicate
samples consisted of two bottles filled from the same compositing container
and submitted as separate samples with unique identification numbers. The
results of field duplicate analyses are presented in Table A-11 and
summarized in Table 10. Of the 309 field duplicate samples submitted 292
(94.5%) were within the data quality objectives listed in Table 8. One TSS,
three COD, one ammonia, three nitrate+nitrite, one TKN and eight methane
values exceeded the acceptance criteria. The nutrient values which exceeded
the criteria were generally low values, around 1 mg/L. The methane analyses
which exceeded the precision criteria showed evidence of one of the two
samples contaminated by air, thus interfering with the analyses (see Table
A-9) .
31
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TABLE 9. STATISTICAL SUMMARY OF RELATIVE DIFFERENCE BETWEEN
* ANALYTICAL DUPLICATE ANALYSES
Parameter
Observations
Mean Relative
Difference
(%)
Standard
Deviation
<%)
TSS
932
4.5
4.5
TS
192
0.6
0.7
TVS
191
0.8
0.5
TCOD
29
4.3
3.2
TBOD
18
5.0
4.8
Ammonia
53
3.0
5.7
N03+N02
54
1.8
2.4
TKN
11
2.2
2.0
Alkalinity
25
1.1
0.6
Statistical Evaluation of Laboratory Accuracy
The results of analyses of spiked samples are listed in Table A-12. The
mean and standard deviation values for recovery are listed in Table 11. All
of the 48 spiked samples analyzed had recoveries within the accuracy data
quality objectives listed in Table 8. Samples with the unspiked values less
than the detection limit were not included in the summary table.
Analytical Completeness and Data Acceptance
A summary of the number of analyses requested, the number which met all
QA specifications and percent within QA specifications are summarized in
Table 12. All analyses requested were completed. However, some analyses did
not meet all QA specifications as outlined in the QA Project Plan. Of all
analyses requested, 93.2 percent were within the QA specifications. Analyses
that did not meet QA specifications are discussed in the following
paragraphs. All data were used in graphs and tables within the report,
regardless of acceptance status, unless otherwise noted in the text.
32
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TABLE 10. STATISTICAL SUMMARY OF RELATIVE DIFFERENCE BETWEEN
FIELD DUPLICATE SAMPLE ANALYSES
Mean Relative Standard
Difference* Deviation
Parameter Observations (%) (%)
TSS
99
4.4
6.8
TS
38
0.7
1.3
TVS
38
1.1
2.3
TCOD
20
8.4
10.5
TBOD
19
4.1
4.2
Ammonia
8
10.0
19.9
N03+N02
8
13.7
20.6
TKN
10
4.8
5.2
Alkalinity
28
1.8
1.9
Methane
41
10,7
13.6
* Relative difference = 200 (re-plicate 1 - replicate 2)
replicate 1 + replicate 2
where replicate 1 > replicate 2
TABLE 11. STATISTICAL SUMMARY OF LABORATORY SPIKE RECOVERIES
Mean Standard
Recovery* Deviation
Parameter Observations (%) (%)
TCOD 18 98.6 6.2
Ammonia 9 99.4 6.6
N03+N02 10 103.4 7.0
TKN 11 96.1 2.1
* Recovery = 100 (Spiked sample - unspiked sample)
spike concentration
33
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TABLE 12. SUMMARY OF ANALYTICAL COMPLETION DATA
Parameter
Analyses
Requested
Data
Within QA
Specifications
Percent
Within QA
Specifications
A
QC Review Codes
B C D E
F
TSS
932
925
99.2
0
5
0
0
2
0
TS
192
192
100,0
0
0
0
0
0
0
TVS
191
191
100.0
0
0
0
0
0
0
TCOD
148
148
100.0
0
0
0
0
0
0
TBOD
107
80
74.8
0
0
0
5
0
27
NH3
75
75
100.0
0
0
0
0
0
0
NO3~NO2
78
71
91.0
7
0
0
0
0
0
TKN
76
69
90.8
0
0
0
7
0
0
Alkalinity
99
76
76,8
0
0
0
23
0
0
Methane
83
67
80.7
0
16
0
0
0
0
Volatile Acids 51
0
0.0
0
0
51
51
0
0
Total
2032
1894
93.2
7
21
51
86
2
27
TSS, TS, TVS, TCOD, and ammonia analyses met QA specifications greater
than 95 percent of the time. The percent of BOD analyses within QA
specifications was only 74.8 percent because the dilution water was not
within the maximum dissolved oxygen depletion. This resulted because of
variable laboratory water quality but was actually corrected for in the TBOD
calculation; therefore, it is relatively insignificant. The relative TBOD
values are still valid and the data acceptable to meet the objectives of the
project. The fraction of N03+N02 and TKN analyses with QA specifications
were 91.0 and 90.8 percent, respectively. These percentages are slightly
below the objective level of 95% because one set of data for each parameter
did not meet the QA specification. The low number of analyses conducted for
these parameters cause a single set of data to have a large effect on the
percentage of data that meets QA specifications.
The alkalinity, percent methane, and volatile acid measurements were
used to assess the operation of the anaerobic digesters. These parameters
were operational in nature as opposed to a measurement of performance.
Therefore, QA requirements were relaxed somewhat to reduce analytical costs.
The semi-quantitative data collected was deemed acceptable to meet the
34
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requirements of the project. Some duplicates for alkalinity analyses were
omitted. In addition, no spikes or duplicate analyses were performed for
volatile acids because all but one of the values were below the detection
limit of 50 mg/L. The low volatile acid concentrations indicate successful
anaerobic digester operation; therefore, exact quantitative values were not
necessary. Some of the gas samples from the digesters were grossly
contaminated with air from outside of the digester as evidenced by the
analytical results (see Table A-9). This sampling problem resulted in a
completion percentage lower than specified.
Overall the analytical procedures were acceptable to meet all the
objectives of the project. The omission of some QA on selected analyses in
no way affected the satisfactory completion of the project.
35
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SECTION 8
C.I. DISPERSE BLUE 79 EXTRACTION METHOD DEVELOPMENT
A viable method for the determination of the concentration of C.I.
Disperse Blue 79 in the various sample matrices was essential for the
completion of the project. In this study, an extraction procedure was
developed for use in conjunction with a high performance liquid chromato-
graphy (HPLC) analytical method. The development of the extraction procedure
is described in the following section. HPLC analysis of the extracts was
performed at EMSL-LV. The HPLC analytical method is described in Section 7.
PROJECT BACKGROUND
The dye extraction work was first performed by another laboratory under
contract from EMSL-LV. The first set of samples for dye extraction and
analysis were sent to the outside laboratory on December 28, 1987,
Additional sample sets were sent during January, February and early March
1988 for dye extraction method development and verification.
The initial extraction work performed consisted of spiking samples from
the control unit and determining the spike recoveries. Several extraction
methods on the various samples were utilized. The samples containing large
amounts of solids were spiked and extracted as total samples as well as
separated into liquid and solid fractions, spiked, extracted and the extracts
combined for analysis. In addition, some samples were spiked, the solids
were then separated, the liquid and solid phases were extracted, and the
extracts were combined. Methylene chloride was used for all sample
extractions.
The data from this initial extraction work was submitted directly to
RREL by EMSL-LV and is not included in this report. None of the extraction
methods yielded dye spike recoveries which were adequate to meet the needs of
the project.
As a result, in April it was decided to perform the sample extraction
work at the Radian-Milwaukee office. The dye extraction work performed at
Radian is described in the following sections.
DYE EXTRACTION METHOD DEVELOPMENT
To proceed with the dye extraction method development, Radian personnel
consulted with Dr. Don Betowski of EMSL-LV and Dr. Eric Weber of EPA-Athens,
Georgia. The preliminary development work was based on information obtained
from consultations with EPA personnel and is described in Appendix C.
36
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Initial experiments with methylene chloride showed that C.I. Disperse Blue 79
could be quantitatively extracted from distilled water "but not from the pilot
plant samples. Previous work by Dr. Weber indicated that an extraction
procedure using acetonitrile could be used for C.I. Disperse Blue 79.
Initial acetonitrile extraction experiments conducted at Radian yielded
promising results. An extraction procedure was developed and is contained in
Appendix C, as well as a proposed test plan for evaluating the method.
The test plan described in Appendix C consisted of performing various
spike recovery tests on samples from the control unit. The control unit
samples do not contain dye prior to spike addition. The test plan was
completed as well as numerous other experiments to evaluate the method.
Extraction of samples from the experimental unit, which contained dye, were
also performed at Radian and the extracts were sent to EMSL-LV for analysis.
Some problems with the extraction procedure at Radian as well as the
analytical procedure at EMSL-LV were encountered during the initial
experiments. However, the problems at both facilities were resolved. The
final C.I. Disperse Blue 79 extraction procedure is as follows:
APPARATUS: Spectrophotometer (UV-Vis)
Vortex Geni
10, 25, 50, 100 ml Volumetric Flasks
Graduated Transfer Pipet (1 ml)
Volumetric Delivery Pipets 1, 2, 5, 10, 15 ml (Class A)
Centrifuge 2300-2400 RPM 17 cm Radius Producing 1000 RCF (xg)
50-ml Conical Polypropylene Centrifuge Tubes with caps
10-ml HPLC Sample Filtration Syringe with 0.4 um Filter
Matched Round Cuvetts, 1 cm path length
REAGENTS: Acetonitrile 99+% Spectrograde
Acetone Spectrograde
Purified C.I. Disperse Blue 79
PROCEDURE:
1. Measure 10 ml of sample in a 10 ml volumetric flask and pour into a
50-ml centrifuge tube. Rinse the volumetric flask several times
with a total volume of 15-ml of acetonitrile and quantitatively
transfer all washings to the centrifuge tube. Cap the centrifuge
tube and place on the Vortex Geni for approximately 30 sec.
2. Centrifuge for 10 minutes and pour the supernatant into a 10 ml
HPLC sample filtration syringe and filter through a 0.4 um filter.
37
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3. After appropriate dilution with 60% V/V acetoriitrile/DI water, if
necessary, read the percent transmittance or absorbance on the
spectrophotometer after zeroing with D.I. water.
4. Calculate the dye concentration from a calibration curve which was
constructed using a range of 0.1 mg/1 to 3.0 mg/1 dye concentrations
prepared by water dilutions of a stock solution of 0.5 mg/ml purified
dye in acetone,
5. Duplicate every 5th sample, and spike every 10th sample using an
appropriate amount of the 0.5 mg/ml purified dye in acetone. The
spike should be added to a 25-ml volumetric flask along with 10-ml
of selected sample measured from a 10-ml volumetric flask. The 10-ml
volumetric should then be rinsed with acetonitrile several times
into the 25-ml volumetric and, finally, the 25-ml volumetric should
be diluted to the mark with acetonitrile.
CALCULATIONS:
Disperse Blue 79 (mg/L) - Dilution Factor x
f(Measured Absorbance)-(Intercept of Calibration Curve)!
{Slope of Calibration Curve)
Relative % Difference between Duplicates =
200 x fist Result - 2nd Result!
[1st Result + 2nd Result]
% Spike Recovery =
(Concentration of Spiked Sample - Concentration of TJnspiked Sample) x 100
Concentration Added by Spiking
PRECISION AND ACCURACY:
% Spike Recovery = +/- 20%
Relative difference between duplicates = +/- 20%
The spectrophotometer was used for monitoring the extraction procedure
and the values obtained were not used for Disperse Blue 79 mass balances.
Rather, the dye concentration of samples were determined using on HFLC-UV
technique performed at EMSL-LV.
Analytical duplicate and spike recovery results for sample extractions
performed after the procedure was developed are summarized in Table 13 and
Table 14, respectively.
For analytical duplicate measurements, the entire extraction procedure
was performed on duplicate aliquots. The data in Table 13 indicate the
acetonitrile extraction method is reproducible within twenty percent or less.
Samples listed in Table 14 were spiked with the acetone dye solution,
extracted and analyzed. Recoveries in the range of 80 to 120 percent were
obtained.
38
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TABLE 13. ANALYTICAL DUPLICATES FROM EXTRACTION PROCEDURE DEVELOPMENT PERIOD
Sample
Date
Sample
Location
Replicate 1
(mg/L)
Replicate 2
(mg/L)
Percent
Difference
7/28/88
F2
4.49
5.18
14
8/8/88
W2
120
123
2
8/1/88
F2
5.93
5.77
3
8/1/88
PS 2
43.9
40.0
9
8/3/88
F2
4.68
4.52
3
8/3/88
PE2
6.27
6.36
1
TABLE 14. ANALYTICAL SPIKES FROM EXTRACTION PROCEDURE DEVELOPMENT PERIOD
Sample
Date
Sample
Location
Unspiked
Sample
(mg/L)
Spike
Added
(mg/L)
Spiked
Sample
(mg/L)
Percent
Recovery-
7/28/88
F2
5.18
5.0
10.8
US
7/28/88
PS2
23.4
25.0
49.2
103
7/28/88
W2
114
50.0
165
102
7/28/88
PE2
5.0 8
5.00
11.1
120
7/28/88
FE2
1.10
5.00
5.95
97
7/28/88
BLANK
<0.22
25.0
25.9
104
8/1/88
F2
5.87
5.00
11.0
103
8/1/88
W2
119
50,0
167
96
8/1/88
PS 2
42.3
50.0
89.2
94
8/1/88
PE2
5.50
5.00
11.4
118
8/1/88
FE2
0.68
5.00
5,90
104
8/3/88
BLANK
<0.23
5.00
5.00
100
8/3/88
PE2
6.36
5.00
11.6
105
39
-------
SECTION 9
CONVENTIONAL TREATMENT RESULTS
INTRODUCTION
Two pilot activated sludge systems, two pilot anaerobic digesters, and
one bench-scale activated sludge system were operated during this study. The
systems were operated for longer than initially planned because of the time
required to develop methods for analysis of C.I. Disperse Blue 79 in the
various sample matrices. A large amount of data was generated during the
extended acclimation period of the treatment systems, Only the data from the
portion of the acclimation period just preceding the dye sampling period are
included in this report.
The conventional treatment test results (e.g., TSS, TBOD, SRT) of the
activated sludge systems and anaerobic digesters are presented in this
section. The results of dye analyses are presented in Section 10.
ACTIVATED SLUDGE PILOT PLANTS
The activated sludge units were monitored daily and sampled periodically
to assure proper operation. Operational data are contained in Appendix B,
Tables B-l through B-6, while the analytical data from the units are
presented in Tables B-5 through B-10.
Acclimation Period
The two activated sludge pilot units were started up on November 13,
1987. The aeration basins and final clarifiers were filled with mixed liquor
from the full-scale plant. The air flow to each aeration basins was started
as the basin was filled; the sludge recycle pumps, feed pumps, and waste
sludge pumps were then started. On November 18, 1987 the dye feed to the
experimental unit (Unit 2) was started.
The activated sludge units were operated and sampled according to the
project test plan (outlined In Section 6), from November 13, 1987 through
March 24, 1988. During this time period, work on developing a sample
extraction and analytical procedure was in progress (see Section 8). Because
of the unexpectedly long period of time required for the development of an
extraction procedure, the sample schedule was reduced to a minimum
maintenance schedule. A minimum number of analyses and the operational
measurements necessary to insure satisfactory operation of the systems were
performed during this time.
40
-------
The large amount of raw data collected during the extended acclimation
period of the activated sludge systems are not included in this report.
However, the data for the period from June 8 to August 7, 1988 (Day 156-196),
the period just prior to initiation of dye testing, are summarized in Tables
15 and 16. These data show that there were no significant differences in the
operation of the two activated sludge units before the dye testing period.
The feed to both units was similar with respect to pH, temperature, TSS,
and TBOD. The DO was slightly lower in the Unit 1 aeration basin than in the
Unit 2 aeration basin but otherwise the systems operation were very similar.
The Unit 1 average SRT was 6.16 days while Unit 2 average SRT was 6.19 days.
The SRT for both systems was slightly below the target value (7 days) because
of the need to control the mixed liquor suspended solids (MLSS) concentra-
tion. More sludge was wasted than necessary to maintain a 7-day SRT to keep
the MLSS at about 3,000 mg/L.
It was necessary to keep the MLSS around 3,000 mg/L, because settling
problems were experienced in the secondary clarifiers when the mixed liquor
was significantly above this level.
Dve Testing Period
On August 8, 1988, sampling of the activated sludge units for dye
analysis was initiated. Development of the sample extraction procedure was
complete and the Radian and EMSL-LV laboratories were ready to receive
samples. The sample schedule presented in Table 6 for the activated sludge
systems, including all QA samples and field measurements, was resumed. The
activated sludge units were sampled for dye analysis from August 8 to October
18, 1988. The operational and analytical data for this period are presented
in Tables 17 and 18 and Figures 6 through 20.
TABLE 15. SUMMARY OF ACTIVATED SLUDGE FEED ANALYTICAL DATA FOR THE
ACCLIMATION PERIOD (DAY 156-196, JUNE 28 - AUGUST 7, 1988)
Unit
1
Unit 2
Parameter
Average (n)
Range
Averag
e (n)
Range
pH
* (39)
6.8-7.5
*
(40)
6.9-7.7
Temperature (°C)
19.5 (39)
17.0-22.0
19.5
(40)
17.5-23.0
TSS (mg/L)
305 (6)
222-412
291
(5)
237-365
TBOD (mg/L)
213 (1)
200
(1)
* Average pH values not calculated.
41
-------
TABLE 16, SUMMARY OF ACTIVATED SLUDGE PILOT PLANT OPERATION FOR THE
ACCLIMATION PERIOD (DAY 156-196, JUNE 28 - AUGUST 7, 1988)
Unit 1
Unit 2
Parameter
Average (n)
Range
Average (n) Range
Operation Data
Feed Flow (ml/min)
579
(40)
542-650
572
(40)
378-612
Primary Sludge Flow (L/day)
4,4
(40)
2.0-11.2
4.4
(40)
3,0-6.8
RS Flow (ml/min)
613
(40)
548-750
587
(40)
565-621
RS Flow (% of Feed)
106
(40)
92.8-131
103
(40)
93.7-153
Waste ML Flow (L/day)
22.9
(40)
18.9-28.9
23.4
(40)
18.0-28.0
HRT (hrs)
5.24
(40)
4.67-5.60
5.42
(40)
5.04-8,16
SRT (days)
6.16
(6)
5.50-7.85
6.19
(6)
5.96-6.61
Mixed Liouor Data
Temperature ( C)
21.0
(40)
17.5-28.0
21.0
(40)
18.0-27.5
pH
*
(40)
6.8-7.6
*
(40)
6.7-7.6
DO, Cell 1 (mg/L)
1.5
(39)
0.5-3.8
2.2
(39)
0.4-4.7
DO, Cell 2 (mg/L)
3.2
(39)
0.5-6.0
3.9
(39)
0.5-5.6
DO, Cell 3 (mg/L)
3.3
(39)
1.2-5.4
4.4
(35)
0.4-6.0
TSS (mg/L)
3010
(6)
2320-3620
3220
(6)
2780-3460
Primary Sludee Data
TSS (mg/L)
19500
(6)
14300-26800
16600
(6)
12500-20800
Primary Effluent Data
TSS (mg/L)
167
(6)
120-209
138
(6)
118-171
Final Effluent Data
TBOD (mg/L)
20
(1)
14
(1)
TSS (mg/L)
25
(6)
14-39
25
(6)
17-32
* Average pH values not calculated,
42
-------
TABLE 17. SUMMARY OF ACTIVATED SLUDGE FEED ANALYTICAL DATA FOR THE DYE
TESTING PERIOD (DAY 197-268, AUGUST 8 - OCTOBER 18, 1988)
Unit 1
Unit 2
Parameter
Average (it)
Range
Average (n)
Range
pH
*
(72)
6.8-8.0
*
(72)
6.7-7.6
Temperature (°C)
20.0
(72)
18,5-22.0
20.0
(72)
19.0-22.0
TSS (mg/L)
238
(31)
168-348
211
(32)
116-304
TCOD (mg/L)
364
(20)
246-478
375
(20)
252-480
TBOD (mg/L)
182
(10)
156-217
177
(10)
150-219
TKN (mg/L)
32.5
(11)
27.2-39.8
31.0
(11)
26.7-36.1
NH3-N (mg/L)
22.5
(10)
17.2-32.3
20.7
(ID
16.0-28.4
N03+N02-N (mg/L)
0.34
(11)
<0.02-0.96
0.24
(11)
<0.02-1.12
* Average pH values not calculated.
TABLE 18. SUMMARY OF ACTIVATED SLUDGE PILOT PLANT OPERATION FOR THE DYE
TESTING PERIOD (DAY 197-268, AUGUST 8 - OCTOBER 18, 1988)
Unit 1
Unit 2
Parameter
Average (n)
Range
Average (n)
Range
Operation Data
Feed Flow (ml/min)
577
(72)
542-670
580
(72)
517-626
Primary Sludge Flow (L/day)
4.2
(72)
2.0-6,7
4.1
(72)
2.0-6.5
RS Flow (ml/min)
716
(72)
580-802
708
(72)
544-816
RS Flow (% of Feed)
124
(72)
100-144
122
(72)
94.9-141
Waste ML Flow (L/day)
23.8
(72)
18.2-30.4
23.9
(72)
19.8-31.6
HRT (hrs)
5,28
(72)
4.56-5.52
5.28
(72)
4.80-5.76
SRT (days)
5.94
(31)
4.02-7,37
5.87
(31)
4.43-7.06
(continued)
43
-------
TABLE 18 (continued)
Unit 1 Unit 2
Parameter
Average (n)
Range
Average (n)
Range
Mixed Liauor Data
Temp, (°C)
20.0
CM
r-
v/
16.0-25.0
20.0 (72)
15.0-25.0
pH
*
(72)
6.8-8.0
* (72)
6.8-7.6
DO, Cell 1 (mg/L)
2.4
(72)
0.7-7.0
2.8 (72)
0.6-8.3
DO, Cell 2 (mg/L)
3.6
(72)
0.4-7.9
3.5 (72)
0.3-8.4
DO, Cell 3 (mg/L)
3.6
(72)
0.3-8.0
3.9 (72)
0.2-8.5
TSS (mg/L)
3030
(31)
1200-3640
3060 (31)
2110-3860
0£ Uptake Rate (mg/L hr)
34.8
: (7)
16.3-77.1
36.9 (7)
22.5-82.3
SSVI (ml/g)
73.1
• (5)
59.4-80.8
58.0 (5)
51.2-66.9
Primary Sludpe Data
TSS (mg/L)
17400
(31)
11000-28100
15300 (31)
8490-27200
Primary Effluent Data
TSS (mg/L)
134
(31)
83-260
139 (31)
94-199
NH3-N (mg/L)
CM
CM
(11)
18.2-31.5
21.7 (11)
15.4-30.6
N03+N02-N (mg/L)
0.33
(11)
<0,02-1.21
0.27 (11)
<0.02-1.10
TKN (mg/L)
32.6
(11)
25.4-40.6
32.2 (11)
26.6-38.0
Final Effluent Data
TCOD (mg/L)
59.2
(20)
19.7-121
73.5 (20)
20.6 -115
TBOD (mg/L)
16
(10)
5-30
21 (10)
7-37
TSS (mg/L)
27
(31)
9-73
31 (31)
9-72
NH3-N (mg/L)
0.26
(11)
<0.02-0.62
0.18 (11)
<0.02-0.32
N03+N02-N (mg/L)
19.7
(11)
15.8-25.0
20.0 (11)
15,5-24.5
TKN (mg/L)
3.15
(ID
0.84-5.60
3.35 (11)
0.80-5.60
* Average pH values not calculated,
44
-------
3
"S
Q-
E
o>
+ - unrtl
x - tmitz
16,0 t
15.0
L
195
J 1_
210
J I I L
225 240 255
Day Number
Figure 6, Pilot activated sludge systems feed temperatures,
o>
:5
"6
£
a>
+ - unit 1
x - unit 2
195
Figure 7,
210
225
240
270
Day Number
Pilot activated sludge systems mixed liquor temperatures.
45
-------
9.0
8.0 r
7.0
+ - trit 1
x - unit 2
6.0
15 210 225 240 255 270
Day Number
Figure 8. Pilot activated sludge systems feed pH values.
zn
9.0
8J3
7.0
6.0
+ - unit 1
* - unit 2
B5
2f
225
240
255
270
Day Number
Figure 9# Pilot activated sludge systems mixed liquor pH values.
46
-------
C7>
s?
o
•x?
C!!5
i 3.0 f-
fca
+ -dwrnber1
x-chamber2
~ -chamber 3
195
210
255
225 240
Day Number
Figure 10. Dissolved oxygen concentration in Unit 1 aeration tank.
».0
9.0
8.0
7.0
6.0
5.0
4.0
3.0
2A
10
240
255
270
195
210
225
Day Number
Figure 11. Dissolved oxygen concentration in Unit- 2 aeration tank.
47
-------
so
$
i
§
ll
tfc
135
tzo
«5
90
75
SO
«
30
5
0
t
>1
+ -p«1
j-ps2
t *
$V'' x\
' k
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\ f\
x >r"
i
'¦¦ +/
' ¦•• ' (
v it '
\+i
\ X
Xfa
*
*
*
X a \
! \
-------
9
8
7
6
5
4
3
195 210 225 240 255 270
Day Number
Figure 14. Pilot activated sludge systems solids retention time.
400
SO
. t
300 j- !\
' '¦ \
r s
250 h ! *—t
1
i
t
A
f \
X
\ *
r.
rr 200
i
£ 60
-J.
\ ¦ V \ ,
! \ j *\ •' ^
* \ ft \ 4 y/ \
t
'%
K
X; \ 7 VN
\f!
i \
m
m r
o
m
Jv X, , v '
*-x
I X-X-.
* LA ^ ^ ^
* \!X-J
X X
t%H3*' 11\ ~~^x"
e
! ,.„l
I
I-,- I 1
v J3 tj-
210
225 240
fty taber
J
270
Figure 15. Activated Sludge System 1 influent and effluent TSS
concentrations.
49
-------
$
400
350
300
l 1:
t
+ -fl
x-pe2
o-M
250 r
h
200 r!
%
h '
so
100
so r
0
* \
X
/
i;
i 1
k -i/Sf- ~x ^ •> ' v*
^4 * -*
;\\. hi
^ \\fi aj]H
* \ ' n \\ 7 \ '• \
t
4-
\* \ *\, N '
\I
X
s I
X
^ ,\ A . A
LtvP-B-^-ri kEr-%-Er-'® S^P ^ qj
195
210
255
225 240
!ty Number
Figure 16, Activated Sludge System 2 influent, and effluent TSS
concentrations,
m
250
[
225
r
i
r
i
i
200
j
L
175
F"
150
r
r
125
r
h
100
l_
i
r
75
i
50
\-
l
25
L
L ,
0
L:
n-fel
¦ - f«2
J L
¦ e
- a
*Ti
m
210
225 240
Day Number
255
270
Figure 17. Pilot activated sludge systems influent, and effluent TBOD
concentrations.
50
-------
o>
o
500
450 i-
I
400 j-
h
350
300 f
I
f"
250 j-
200
150 -
100 -
A/
V
\ /
Y
+ -fi
X-f2
I
if \
yn-n K ^ i
^ \ A / /
v*
\
V
' /'
'4
o
\
tf
i j
'a'
\"D-< a b - i
D - fe1
a - fe2
P
\"0-r e
\ '
¦
_X
-V
\ ~
*/
e — -It ¦
85
210
225
240
255
270
Day Number
Figure 18. Pilot activated sludge systems influent and effluent TCOD
concentrations.
85 210 225 240 255 270
Day Number
Figure 19. Pilot activated sludge systems influent and effluent ammonia
concentrations.
51
-------
300
25 S)
200
1BJ0
tt.0
5J)
OJ
o-fel
«-f«2
+ -«
x-f2
210
m
240
255
m
Day Number
Figure 20. Pilot activated sludge systems influent and effluent nitrate
and nitrite concentrations.
The data in Figure 6 shows that the temperature of the feed to both
reactors was similar; Figure 7 shows that mixed liquor temperatures were also
similar for the two reactors. The average temperature of both Unit 1 and
Unit 2 mixed liquors was 20.0 C. The fluctuation in temperature of the mixed
liquors was caused by changes in ambient temperature. The relatively low
volume of 182 L exposed to the atmosphere for 5.5 hours was greatly
influenced by the temperature in the trailer. The pH of both the feed and
mixed liquors were also comparable (Figures 8 and 9). The DO in the aeration
basins varied significantly (Figures 10 and 11) but the average values of all
cells were above 2 mg/L. The variation in DO was probably due to changes in
waste strength from rain events, industrial discharges, etc. The DO was only
measured once per day and the air flow rate adjusted once per day, if
necessary, following the DO measurement. Other operating parameters, such as
feed flow, return sludge flow, and primary sludge production (Figure 12) also
experienced daily variations but the average values were very similar for the
two units.
Return sludge flow and mixed liquor waste volumes were adjusted to
control minor settling problems, such as floating sludge, as the problems
occurred. The waste mixed liquor TSS concentrations were generally very
similar for both units (Figure 13). Again the SRT for both units was below
the 7 day target value. However, the average values for the two units were
almost identical at 5.94 days for Unit 1 and 5.87 days for Unit 2.
The primary effluent data from Unit 1 and Unit 2 (Table 18) indicate
that the two primary clarifiers operated similarly. The effluent values were
52
-------
similar with respect to TSS, NH3, N03+N02, and TKN. The TSS removal across
the clarifiers, however, were 44 percent and 34 percent for Unit 1 and Unit
2, respectively. The difference in removal is due to a higher feed TSS value
in Unit 1 (238 mg/L) than Unit 2 (211 mg/L). The other parameters for the
feeds, such as TCOD, TBOD, arid nutrients, did not indicate any difference
between the feeds. The cause of the higher TSS values in the Unit 1 feed was
not determined.
The difference in the feed TSS value resulted in a difference in the TSS
concentrations of the primary sludges, although the volumes were similar.
The primary sludge from Unit 1 averaged 17,400 mg/L TSS while the Unit 2
primary sludge averaged 15,300 mg/L. Mass balances across the primary
clarifiers indicated 93% of the feed solids were accounted for in the primary
effluent plus primary sludge from Unit 1 and 101% from Unit 2.
The average TSS concentrations in effluents from the Unit 1 and Unit 2
activated sludge systems were 27 mg/L and 31 mg/L, respectively (Figures 15
and 16). The effluent TCOD was higher in the Unit 2 effluent (73,5 mg/L)
than Unit 1 effluent (59.2 mg/L) (Figure 18). The effluent TBOD values from
Unit 2 was 21 mg/L while the Unit 1 value was 16 mg/L (Figure 17). The
higher TCOD and TBOD levels in Unit 2 effluents may have resulted from
addition of the dye compound and inert ingredients in the dye formulation.
The average ammonia concentration in the Unit 1 and Unit 2 feeds were
22.5 and 20.7 mg/L, respectively, while the effluent values were 0.26 and
0.18 mg/L, respectively (Figure 19). The Unit 1 and Unit 2 average feed
N03+N02 concentrations were 0.34 and 0.24 mg/L, respectively, and the
effluent values were 19.7 and 20.0 mg/L (Figure 20). These data indicate
that nitrification was virtually complete in both units. The TKN plus
N03+N02 was about 32 mg/L in both feeds and 20 mg/L in the effluents; the
lower total nitrogen level in the effluents indicate some denitrification may
also have occurred. Denitrification in the secondary clarifiers may have
contributed to the formation of floating sludge in the clarifiers. However,
because the waste activated sludge samples were not analyzed for nutrients, a
complete nitrogen balance was not possible.
Overall, the data collected during the study show that addition of the
dye material did not noticeably affect the operation of the activated sludge
process. Both the control and experimental units achieved normal TBOD
reduction for municipal wastewater. The effluent TSS values were on the high
side of the usual range required for discharge. However, efficient solids
separation is often difficult to obtain in pilot-scale systems.
ANAEROBIC DIGESTERS
The anaerobic digesters were also monitored daily and sampled
periodically. In addition, feed for the anaerobic digesters was prepared
daily as outlined in Section 6. Appendix B, Tables B-ll and B-12 contain the
operational data from the digesters while the analytical data are presented
in Tables B-13 and B-14.
53
-------
Acclimation Period
Both anaerobic digesters were in operation by January 25, 1988. The
digesters were initially filled with digested sludge from the full-scale
plant. The head space above the liquid was purged with nitrogen immediately
after the units were filled and sealed. The stirrers and heaters were turned
on and set at the proper operating conditions. Feeding of the digesters was
started the day after the units were filled.
The digesters were operated in accordance with the project plan outlined
in Section 6 until March 24, 1988. As with the activated sludge systems, the
digesters were put on a minimum sampling and maintenance schedule until dye
testing was initiated. The operational and analytical data from the
digesters for the period from August 8 to November 8, 1988 are summarized in
Table 19.
The average feed TVS was slightly lower for Unit 1 (1.72%) than Unit 2
(1.82%), but both units were close to the target value of 1.8% TVS, The
total gas production from Unit 1 was slightly less than from Unit 2 but the
gas production per kg TVS destroyed was equal (Table 19). Both units
achieved slightly more than 46% volatile solids reduction. The volatile
acids concentrations for all samples was below 50 mg/L. The low volatile
acids concentration is probably a result of the low loading rate used for the
study.
The data in Table 19 show that both anaerobic digesters performed well.
The dye present in the feed to Unit 2 had no apparent effect on the operation
of the system.
Dye Testing Period
The anaerobic digesters were sampled for dye content from November 7 to
December 19, 1988. During this time period the sample schedule in Table 6
was followed. The operational data for this time period are presented in
Table 20 and Figures 21 through 30.
The average operating temperature of both units was 35.0°C. The
Digester 1 operating temperature, however, was more variable than the Unit 2
temperature (Figures 21 and 22). The difference in operating temperature
control occurred because Unit 2 was equipped with a slightly higher quality
immersion heater than Digester 1. The pH values for the digester feeds
ranged from 6.6 to 7.2 while the effluent values ranged from 6.6 to 7.0
(Figures 23 through 26).
The volatile solids loading to both^units was consistent (Figure 27) and
the average values of 1.21 and 1.22 kg/m day for Digester 1 and Digester 2,
respectively, were very close to the target value of 1.2 kg TVS/m day. The
TVS reductions were variable (Figure 28) but the average reductions of 47.8
percent for Unit 1 and 46.4 percent for Unit 2 were within the normal range
for anaerobic digesters (1).
The total gas production from the Unit 1 (16.26 L/day) was lower than
from Unit 2 (18.68 L/day) (see Figure 29). The gas production per TVS
54
-------
TABLE 19. SUMMARY OF ANAEROBIC DIGESTER OPERATION FOR THE ACCLIMATION
PERIOD (DAY 197-287, AUGUST 8 - NOVEMBER 6, 1988)
Unit
1
Unit
2
Parameter
Average (n)
Range
Average (n)
Range
Feed Data
pH
* (89)
6.4-7.2
* (88)
6.4-7.4
TSS (mg/L)
20800 (13)
16000-23500
21700 (13)
18600-23600
TS (%)
2.32 (13)
1.84-2.48
2.42 (13)
2.26-2.54
TVS (%)
1.72 (13)
1.42-1.92
1.82 (13)
1.70-1.98
Flow (L/day)
2.6 (91)
2.6-2.6
1.6 (91)
2.6-2,6
Effluent Data
pH
* (179)
6.3-7.3
* (179)
6.4-7.2
0
Temperature ( C)
35.5 (188)
31.5-38.5
35.5 (189)
33.5-38.0
TSS (mg/L)
12400 (13)
11700-13400
12400 (13)
11800-13400
TS (%)
1.46 (13)
1.38-1.61
1.53-(13)
1.45-1,59
TVS (1)
0.92 (13)
0.86-1.04
0,97 (13)
0,89-1.04
Flow (L/day)
2.6 (91)
2.6-2.6
2.6 (91)
2.6-2.6
Operational Data
Alkalinity (mg/L)
2880 (14)
2610-3210
2690 (14)
2440-2960
Volatile Acids (mg/L)
<50 (13)
<50-<50
<50 (13)
<50-<50
3
Loading (kg TVS/m 'day)
1.15 (13)
1.28-0,95
1.21 (13)
1.13-1.32
TVS Reduction (%)
46.4 (13)
26.8-52.2
46,5 (13)
42.9-50.9
Gas Flow (STP) (L/day)
17.14 (91)
8.47-22.64
18.31 (89)
10.00-26.16
Gas Production
(m /kg TVS destroyed)
0.84 (13)
0.37-1.87
0.84 (12)
0.48-1.04
Percent CH4 in Gas
60.0 (13)
57.2-63.4
58.9 (12)
55.2-65.4
Percent C02 in Gas
36.3 (13)
29.3-38.4
36.4 (12)
33.4-38.7
* Average pH values not calculated.
Note: Temperature arid pH ranges listed in table are for Individual
measurements while the figures show average values for the day.
55
-------
TABLE 20. SUMMARY OF ANAEROBIC DIGESTER OPERATION FOR THE DYE TESTING
PERIOD (DAY 288-330, NOVEMBER 7 - DECEMBER 19, 1988)
Unit 1
Unit 2
Parameter
Average (n)
Range
Average (n)
Range
Feed Data
pH
*
(42)
6.6-7.2
A
(43)
6.7-7.2
TSS (mg/L)
21300
(16)
18800-23600
21400
(17)
19400-23400
TS (%)
2.42
(16)
2.14-2.60
2.42
(17)
2.21-2.72
TVS (%)
1.81
(16)
1.58-2.05
1.82
(17)
1.67-2.16
Flow (L/day)
2.6
(43)
2.6-2.6
2.6
(43)
2.6-2.6
Effluent Data
pH
"k
(85)
6.6-7.0
•k
(86)
6.6-7.0
o
Temperature ( C)
35,0
(90)
31.5-39.5
35.0
(93)
33.0-36.0
TSS (mg/L)
12700
(17)
11600-15400
12200
(17)
11400-13200
TS (%)
1.46
(17)
1.38-1.54
1.48
(17)
1.44-1.52
TVS (%)
0.94
(17)
0.89-0.99
0.97
(17)
0,90-1.04
Flow (L/day)
2.6
(43)
2.6-2.6
2.6
(43)
2.6-2.6
Operational Data
Alkalinity (mg/L)
2930
(16)
2440-3090
2820
<16)
2710-3080
Volatile Acids (mg/L)
<51
(4)
<50-54
<5C
' (4)
<50-<50
Loading (kg TVS/m^* day)
1.21
(16)
1.05-1.37
1.22
(17)
1.11-1.44
TVS Reduction (%)
47.8
(16)
42.8-55.1
46.4
(17)
39.2-54.6
Gas Flow (STP) (L/day)
16.26
(42)
10.82-23.05
18.68
(42)
8.82-23 .02
Gas Production
(m /kg TVS destroyed)
0.76
(16)
0.59-0.96
0.87
(17)
0.54-1.09
Percent CH4 in Gas
58.9
(5)
53.5-64.3
57.9
(5)
54.1-60.7
Percent C02 in Gas
35.6
(5)
«
33.4-37.8
35.1
(5)
29.8-38.7
* Average pH values not calculated.
Note: Temperature and pH ranges listed in table are for individual
measurements while the figures show average values for the day.
56
-------
50 jD
45.0
425
35.0 1
f—
1
r
1
30,0
27,5
265 290 295 300 305 310 315 320 325 330 335
Day Number
Figure 21. Digester 1 operating temperature.
t=
o
o.
E
50,0
m r
L
45.0
42.5
40.0
37.5
35.0
32i |-
m
m
25-0
++
V
4-++
/"VS-A, j
i i i i i i i i i
j i i i i i
290
300
305 310 315
Day Number
Figure 22. Digester 2 operating temperature.
32D
325
330
57
-------
m
85
Si)
75
7J0
6-5
6jQ
55
-++++ /, * % *
*{ * V n. \ 4 \
¥
t 1 I f 1 I 1 1
I ! i ! t i i f s I p
235 290 295 3C0 305 313 315 330 325 i50 335
Dcy Number
Figure 23. Digester 1 feed pH values.
9u0
85
&0
75
7j0
65
60
55
5JD
x - momng reodngt
+ - aftwroo! readngs
In dram ttnwji tha awrage
X
J I I 1 1 L 1 l_J 1 1 1 1 1 1 1 1 1—
285 290 295 30C 305 310 315 320 325 330 335
Day Number
Figure 24. Digester 1 effluent pH values.
58
-------
ao p
85 I-
U
W r~
i
75 f-
I
t-
7j0 *
65
M
I-
55 L
< i ¦ i ¦ ..i * i_
H'
V
5J
S_l 1 I _1 I L L
_L_J L
J I I
285 290 245 300 305 310 315
Dcy Number
Figure 25. Digester 2 feed pH values.
320 325 330 335
+ -ironing rtofiig
sc-tftenwonrwxiig
foe draw through aiwoge
90
85
BjO b
I
J-
f
15
CO «
St=£
:§
rrr
65
6£
55
5J3 i i i I i I i 1 i I l I i 1 i 1 j l i
285 290 295 300 305 310 36 320 325 330 335
Daytaler
Figure 26. Digester 2 effluent pH values.
59
-------
_a*t
¥
*D
2J)
18
16
14
12
10
08
0.6
0.4
02
0.0
+ -irit 1
x - unit 2
_1 J 1 l J I ! i I : L
-I J_
L_J I -J--L
285 290 295 300 305 310 355 320 325 330 335
Day Number
Figure 27. Total volatile solids loading of digesters.
60.0
j
45.0 -
!
t—
U.
I
J l I
i
285 290 295 300 305 310 3$ 320 325 330 335
Day Number
Figure 28. Total volatile solids reduction in digesters.
60
-------
&•
~cs
25J3 j-
22JS -
20J3 -
L
175 r
!_
to t-
V
125 U
tLO
r
75 j-
L.
&0 j~
25 j-
L
u
t
xH ft +x
x i 'a t
i \ ! X i
A*
t\
* \ *; \ # 1 1
\ i ?<£ i i
V\$H
/\ V * f
* ' \K V* /M.
* &A *rt t.
: , f* t ^ ^ i \ :
+.. * ' ; 1 X
V' i • /
ti
jf-
+
L
K
+
X x
\ r
i
\ :
\ i
\l
i
A-
J I L_
J i L.
+ -
x-dgestor2
1 i 1
J I i i I L
290
295
300
305 310 36
Day Number
Figure 29. Gas production from digesters.
320 325
mo i
i
m I + -<%ester1
t"
30D p
r
mo H
L
no j-
Q_0 [ ! I 1 1 1 I I I i ! 1 I L I 1 I I I !
285 290 295 300 305 310 315 320 15 330 335
Day Number
Figure 30. Percent, methane in digester gas.
61
-------
destroyed was also lower for Unit 1 at 0.76 m /kg TVS than for Unit 2 at 0.87
m /kg TVS. The reason for the lower gas production from Digester 1 was not
determined. All other parameters, including percent methane of the gas
produced (Figure 30) were comparable.
The operation of both digesters was typical for low-loaded municipal
digesters. Based on the digester data collected, addition of C.I. Disperse
Blue 79 to the feed did not affect digester operation.
62
-------
SECTION 10
C.I. DISPERSE BLUE 79 ANALYSES AND MASS BALANCE RESULTS
INTRODUCTION
The objective of this study was to determine the fate of C.I. Disperse
Blue 79 in a conventional wastewater treatment plant. For this study, the
dye was obtained in its commercial form, which contains approximately 26%
active ingredient. The dye material was prepared as a slurry which was then
mixed with screened municipal wastewater from the MMSD South Shore Plant and
fed to the experimental activated sludge unit. A mixture of primary sludge
and waste activated sludge from the activated sludge system was fed to the
experimental digester. The results of the sample analyses of "both the
control unit (Unit 1) and the experimental unit (Unit 2) are discussed in
this section. In addition, mass balance calculations across the systems are
presented.
The sample extracts were analyzed via a spectrophotometer at the Radian
laboratory and by HPLC-UV at EMSL-LV. As discussed in Section 8, the
spectrophotometer analyses were used as relative values to monitor the sample
extraction procedure. The HPLC-UV analyses were performed to obtain the
actual concentration of C.I. Disperse Blue 79 in the samples. There is no
separation of interferences in the spectrophotometry procedure. Other
compounds which adsorb at 580 ran will also be detected by the spectrophoto-
meter, whereas, the HPLC-UV procedure may separate interferences present In
the samples. When interferences are present in a sample, the concentration
determined by HPLC-UV analysis may be less than the concentration as
determined by the spectrophotometer.
QUALITY ASSURANCE
Quality assurance data are included to assess the procedures used for
sampling, sample extractions, and HPLC-UV sample analyses. It should be
emphasized that the primary purpose of performing sample analyses for dye by
spectrophotometry was to verify the extraction procedure and not to obtain
absolute concentrations.
Extraction Procedure Precision and Accuracy
To measure the accuracy and precision of the extraction procedure,
analytical duplicates and analytical spikes were performed. An analytical
duplicate consisted of measuring two aliquots of a single sample and
performing the extraction procedure on both aliquots. The relative
difference of the two extractions was then calculated. For an analytical
spike, a known quantity of purified dye material in an acetone solution was
63
-------
added to a sample aliquot and the sample extracted. The percent recovery of
the spike was calculated (see Section 8 for the equations used).
In general, one out of every five samples was duplicated. At a minimum,
one sample was duplicated every day that dye extractions were performed. The
analytical duplicate analyses performed are summarized in Table 21. The
average relative difference was 4.3% with a standard deviation of 6.7% for
the 54 analyses performed (not including samples below the detection limit).
Only two out of 59 duplicate analyses resulted in greater than a 20% relative
difference. These data indicate that the dye extraction procedure was
readily reproducible within the specified QA parameters.
At least one analytical spike was performed each day that dye
extractions were made. Table 22 presents the results of the analytical
spikes performed. The average recovery of 34 spikes (not including samples
below the detection limit) was 105% with a standard deviation of 12.9%. Four
of the 34 spike recoveries exceeded the specified + 20% precision. The
results indicate that there was no problem with recovery of the pure dye
material from the various sample matrices.
Sampling Precision and Accuracy
Field duplicate samples were obtained and field spike samples were
prepared to ensure that proper sample collection procedures were used. Field
duplicate samples were prepared by filling two separate sample containers
from a single compositing container. Field spike samples were prepared by
splitting a sample into two containers with one of the splits containing a
measured volume of sample. A known amount of spike solution was added to the
measured sample volume. The spike solution was prepared with commercial dye
material in water.
The field duplicate sample analyses are presented in Table 23. Both the
spectrophotometer measurements conducted at Radian and the HPLC-UV measure-
ments performed at EMSL-LV are included in Table 23. The average relative
difference for the spectrophotometer analyses was 9.4% with a standard
deviation of 15.3%, while the HPLC-UV analyses average was 13.4% with a
standard deviation of 18.6%. Five of the 38 spectrophotometer values and 8
out of 34 HPLC-UV values were above 20% relative difference. The majority of
the field duplicates with the high percent relative difference were low
concentration samples where a small difference in absolute value resulted in
a large relative difference.
The results from field spike analyses are summarized in Table 24. The
average recovery was 114% with a standard deviation of 36.9% for the
spectrophotometer analyses and 96.7% with a standard deviation of 52.6% for
the HPLC-UV analyses. While the average spike recoveries were acceptable
there was considerable scatter in the data for both the spectrophotometer and
HPLC-UV analyses.
Considering that the average spike recoveries were very close to 100%,
it is not likely that degradation or some other mechanism for loss of the dye
during sample storage took place. The scatter in the spike recoveries could
be due to the use of the impure commercial product for preparation of spike
64
-------
TABLE 21. ANALYTICAL DUPLICATES PERFORMED DURING THE DYE TESTING PERIOD
Sample
Date
Sample
Location
Replicate 1
(mg/L)
Replicate 2
(mg/L)
Relative
Difference
(%)
8/8/88
F2-D
5.37
5.26
2.1
8/8/88
D
165
168
1.8
8/9/88
W2-D
105
108
2.8
8/9/88
D
170
170
0.0
8/15/88
¥2
100
99.9
0.1
8/15/88
PS1
<0.25
<0.25
8/16/88
FEl
<0.25
<0.25
*
8/16/88
F2
5.27
5.86
10.6
8/16/88
F2-S
11.5
' 11.7
1.7
8/22/88
PS2-D
36.1
34.8
3.7
8/22/88
PS2-S
51.3
52.3
1.9
8/23/88
Wl
<0.25
<0.25
*
8/23/88
PE2
5.23
5.23
0.0
8/29/88
PE1
<0.25
<0.25
•k
8/29/88
W2
99.5
90.6
9.4
8/29/88
F2-S
10.8
10.8
0.0
8/30/88
FE2-S
6.26
6.24
0.3
9/6/88
DF1
1.08
0.93
14.9
9/6/88
DF2
675
654
3.2
9/6/88
F2
5.27
5.27
0.0
9/6/88
PE2-D
9.01
9.01
0.0
9/12/88
W2
77.5
78.3
1.0
(continued)
65
-------
TABLE 21 (continued)
Sample
Date
Sample
Location
Replicate 1
(mg/L)
Replicate 2
(mg/L)
Relative
Difference
(%)
9/13/88
F2
4.80
4.82
0.4
9/13/88
FE2-D
0,82
0.72
13.0
9/20/88
F2
4.64
4.56
1.7
9/20/88
PE2
6.10
6.16
1.0
9/26/88
F2
5.28
5.23
1.0
9/26/88
FE2-D
1.63
1.72
5.4
9/27/88
DE2
7.30
7.32
0.3
9/27/88
F2
4.64
4.74
2.1
10/3/88
F2
5.44
5.38
1.1
10/3/88
W2
137
139
1.4
10/4/88
F2
k . 95
4.91
0.8
10/4/88
FE2
1.83
1.79
2.2
10/7/88
F2
4.86
5.12
5.2
10/10/88
PE2
5.06
5.23
3.3
10/10/88
W2-D
140
135
3.6
10/11/88
FE2-D
0.79
0.79
0.0
10/17/88
F2
5.00
5.06
1.2
10/17/88
PE2
4.87
4.97
2.0
10/18/88
PE2
4.08
4.31
5.5
11/7/88
DF2
346
349
0.9
11/8/88
DE2-D
4.28
4.29
0.2
11/14/88
SF2
13.8
14.0
1.4
(continued)
66
-------
TABLE 21 (continued)
Relative
Sample
Sample
Replicate 1
Replicate 2
Difference
Date
Location
(mg/L)
(mg/L)
(%)
11/14/88
DE2-S
23,5
23.5
0.0
11/15/88
DEI
0.86
0.58
38.9
11/28/88
SP1
<0,25
<0.25
*
11/28/88
DEI
0.82
0.63
26.2
11/29/88
DE2
15.8
15.5
1.9
12/12/88
DE2 - D
15.0
15.8
5.2
12/13/88
DE2
17.8
19.8
10.6
12/19/88
DE2
18.2
18.8
3.2
1/11/89
FE3-D
1.66
1.60
3.7
1/16/89
W3
23.5
24.1
2.5
1/17/89
FE3-5
6.45
6.04
6.6
1/24/89
W3-D
36.2
32.3
11.4
1/30/89
DE2-S
15.0
15.7
4.6
1/31/89
DE2-D
7.10
6.89
3.0
2/7/89
FE3
3.21
3.31
3.1
* Percent difference calculation not applicable.
TABLE 22, ANALYTICAL SPIKES PERFORMED DURING THE DYE TESTING PERIOD
Sample
Date
Sample
Location
Unspiked
Sample
(mg/L)
Spike
Added
(mg/L)
Spiked
Sample
(mg/L)
Recovery
(%>
8/8/88
8/9/88
F2-S
W2-S
6.30
134
5.00
50,0
11.5
191
104
114
(continued)
67
-------
TABLE 22 (continued)
Sample
Date
Sample
Location
Unspiked
S amp1e
(mg/L)
Spike
Added
(mg/L)
Spiked
Sample
(mg/L)
Recovery
<%)
8/15/88
PS1
<0.25
5.00
4.87
*
8/16/88
F2-S
11.6
5.00
16.1
90.0
8/22/88
PS2
35.4
25.0
58 ,4
92.0
8/22/88
PS2-S
51.8
50.0
105
106
8/23/88
PE2
5.23
5.00
10.9
113
8/29/88
W2
95.0
50.0
135
80
8/30/88
S p i Ice
Solution
504
100
613
109
9/6/88
F2
5.27
5.00
10.8
111
9/12/88
FE2
0.40
5.00
6.00
112
9/13/88
FE2-D
0.77
5.00
5.25
89.6
9/20/88
PE2
6.13
5.00
11.3
103
9/26/88
FE2-D
1.68
5.00
7.03
107
9/27/88
F2
4.69
5.00
10.9
124
10/3/88
m
138
50.0
194
112
10/4/88
FE2
1,81
5.00
6.90
102
10/7/88
F2
4.99
5.00
10.4
108
10/10/88
FE2
5.14
5.00
11.3
123
10/11/88
F2
5.00
5.00
10.5
110
10/17/88
PE2
4.92
5.00
10.0
102
11/7/88
DE2
10.9
5.00
15.8
98.0
11/8/88
DE2-D
4.28
5.00
9.97
114
11/12/88
SP2
13.9
10.0
25.2
113
(continued)
68
-------
TABLE 22 (continued)
S HEtp X B
Date
S snip X e
Location
Unspiked
SampXe
(mg/L)
Spike
Added
(mg/L)
Spiked
SampXe
(mg/L)
Recovery
(%)
11/15/88
11/29/88
12/12/88
12/13/88
1/11/89
1/16/89
1/17/89
1/24/89
1/30/89
1/31/89
2/7/89
DE2
DE2
DE2-D
DE2
FE3-D
m
FE3-S
W3-D
DE2-S
DE2-D
FE3
18.6
15.6
15.4
18.8
1.63
23.8
6.24
34.2
15.4
7.10
3.26
10.0
5.00
5.00
5.00
10.0
50.0
5.0
50.0
10.0
10.0
5.00
24.8
19.9
20.8
25.2
12.4
73.1
11.9
86.0
25.4
18.4
8.80
62.0
86.0
108
128
108
98.6
113
104
100
113
111
* Percent recovery calculation not applicable.
TABLE 23, FIELD DUPLICATE SAMPLES OBTAINED DURING THE DYE TESTING PERIOD
Spectrophotometer Analyses
HPLC-UV Analyses
Sample
Date
Sample
Location
Measured Value, (mg/L)
Sample 1 Sample 2
Relative
Difference
<%)
Measured Value, (mg/L)
Sample 1* Sample 2*
Relative
Difference
(%)
8/8/88
F2
5.32
5.32
0.0
4.05
4.73
15.5
8/9/88
W2
96.5
106
9.4
78.0
87.9
11.9
8/15/88
PE2
5.10
5.23
2.5
4.53
4.60
1.5
8/16/88
FE2
1.21
0.89
30.5
1.00
1.00
0.0
8/22/88
PS 2
36.2
35.4
2.2
40.3
41,3
2.4
8/23/88
FE2
0.86
0.95
9.9
0.26
0.46
55.6
8/29/88
F2
5.19
5.00
3.7
4.50
5.25
15.4
(continued)
69
-------
TABLE 23 (continued)
Spectrophotometer Analyses HFLC-UV Analyses
Sample
Date
Sample
Location
Measured Value, (usg/L)
Sample 1 Sample 2
Relative
Difference
<%)
Measured Value
Sample 1*
, (mg/L)
Sample 2*
Relative
Difference
{%)
8/30/89
W2
105
110
4.6
90.0
89.8
0.2
9/6/88
F2
5.27
5.35
1,5
5.25
5.90
11.6
9/6/88
FE2
8.66
9.01
4.0
9.03
8.30
8.4
9/12/88
PS 2
33.8
33.8
0.0
28.8
29.5
2.4
9/13/88
FE2
1.10
0.77
35.3
0.54
0.43
22.7
9/20/88
V2
96.1
94.8
1.4
79.3
79.5
0.2
9/26/88
FE2
1.65
1.68
1.8
1.23
1.19
3.3
9/27/88
PS2
41.5
45.0
8.1
34.8
35.8
2.8
10/3/88
F2
5.41
5.44
0.6
5.73
6.63
14.6
10/4/88
PE2
5.00
5.29
5.6
4.38
4.35
0.7
10/4/88
D
174
171
1.7
139
172
21.2
10/10/8
m
136
138
1.5
109
113
3.6
10/11/8
FE2
0.65
0.71
8.8
1.65
1.45
12.9
10/17/8
PS2
19.8
23.0
15.0
16.2
17.3
6.6
10/18/8
F2
4.15
4.31
3.8
5.68
5,68
0.0
11/8/88
DE2
4.26
4.28
0.5
0.69
1.67
83.0
11/13/8
SP2
2.47
2.38
3.7
0.70
0.88
22.8
11/15/88
DF2
546
612
11.4
410
415
1.2
11/28/88
DF1
0.62
0.91
37.9
ND
ND
+
11/29/88
DEI
0.66
0.65
1.5
ND
ND
+
12/12/88
DE2
15.2
15.4
1.3
8.35
8.83
5.6
12/13/88
DF1
1.27
1.26
0.8
0.75
0.55
30.8
12/19/88
DF2
541
537
0.7
340
338
0.6
1/11/89
FE3
3.59
1.63
75.1
1.17
1.08
8.00
1/16/89
FE3
0.49
0.75
41.9
0.29
0.52
56.8
(continued)
70
-------
TABLE 23 (continued)
Spectrophotometer Analyses HPLC-UV Analyses
Relative Relative
Sample Sample Measured Value, (mg/L) Difference Measured Value, (mg/L) Difference
Date Location Sample 1 Sample 2 (%) Sample 1* Sample 2* (%)
1/17/89
F3
4.69
4.45
5.25
3.55
3.65
2.8
1/24/89
W3
38.7
34.2
12.3
27.0
29.0
7.1
1/30/89
DF2
257
249
3.2
212
218
2.8
1/31/89
DE2
7.24
7.00
3.4
3.55
2.85
21.9
2/7/89
DE2
9.46
9.68
2.3
$
2/14/89
DEI
0.89
0.85
4.6
ND
ND
+
* ND Not detected, HPLC-UV detection limit ¦= 0.25 mg/L.
+ Percent difference calculation not applicable.
$ Duplicate sample analysis not completed.
TABLE 24. FIELD SPIKE SAMPLES PREPARED DURING THE DYE TESTING PERIOD
Spectrophotometer Analyses HPLC-UV Analyses
Sample
Date
Sample
Location
Sp ike
Added
(mg/L)
Unspiked
Sample
(mg/L)*
Spiked
Sample
(mg/L)
Percent
Recovery
Unspiked
Sample
(mg/L)*
Spiked
Sample
(mg/L)
Percent
Recovery
8/8/88
F2
0.49
5.31
6.30
202
4.58
6.38
367
8/9/88
m
44.5
91.8
134
94.8
75.4
135
134
8/15/88
PE2
4.84
5.11
10.0
101
4.51
8.90
90.7
8/16/88
F2
4.84
5.50
11.6
126
3.94
8.70
98.3
8/22/88
PS 2
14.2
34.8
51.8
120
39.6
52.5
90.8
8/23/88
FE2
4.84
0.89
6.39
114
0.36
3.48
64.5
8/29/88
F2
4.84
5.05
10.8
119
4.83
7.25
50.0
8/29/88
D
44.5
155
194
87.6
118
160
94.4
8/30/88
FE2
4.84
0.82
6.25
112
ND
5.15
+
9/6/88
F2
4.84
5.22
12.3
146
5.52
11.4
121
(continued)
71
-------
TABLE 24 (continued)
Spectrophotometer Analyses HPLC-UV Analyses
Sample
Date
Sample
Location
Spike
Added
(mg/L)
Unspiked
S amp le
(mg/L)*
Spiked
Sample
(mg/L)
Percent
Recovery
Unspiked
Sample
(mg/L)*
Spiked
S snip X ©
(mg/L)
Percent
Recovery
9/6/88
PE2
4.84
8.57
15.3
139
8.57
15.4
141
9/12/88
W2
44,5
70.8
124
120
63.0
105
94.4
9/13/88
PS2
14.2
32.3
50.2
126
26.2
40.8
103
9/20/88
D
44.5
163
216
119
124
164
89.9
9/26/88
F2
4.84
5.21
5.86
13.4
3.76
9.60
121
9/27/88
FE2
4.84
1.08
4.53
71,3
6.09
4.98
+
10/3/88
D
44.5
158
230
162
134
172
85,4
10/4/88
¥2
44.5
124
165
92.1
104
141
83.1
10/10/88
PS2
14.2
43.1
52.1
63.4
31.4
38.3
48.6
10/11/88
D
44.5
161
230
155
128
172
98.9
10/17/88
F2
4.84
4.98
11.1
126
5.38
11.1
118
10/18/88
FE2
4.84
ND
4,44
+
ND
4.73
+
11/14/88
DE2
4.84
18.5
23.5
103
12.4
14.6
45.4
11/15/88
DF2
109
443
561
108
320
445
115
11/27/88
SP2
2.26
1.17
3.62
108
0.50
1.68
52.2
11/29/88
DE2
2.26
12.6
15.7
137
6.61
8.35
77.0
12/4/88
SP2
4.53
0.55
5.38
107
0.17
3.25
68.0
12/6/88
DF2
210
616
823
98.6
357
788
205
12/6/88
DE2
4.53
11.3
16,9
124
5.59
9.73
91.4
12/12/88
DF2
210
562
751
90.0
409
550
67.1
12/13/88
DE2
4.53
18.6
21.6
66.2
$
12/19/88
DE2
4.53
18.3
21.6
72.8
3.99
7.43
75.9
1/11/89
F3
22.0
4.82
30.0
114
2.80
18.8
72.7
(continued)
72
-------
TABLE 24 (continued)
Spectrophotometer Analyses HFLC-UV Analyses
Sample
Date
Sample
Location
Spike
Added
(mg/L)
Unspiked
Sample
(mg/L)*
Spiked
Sample
(mg/L)
Percent
Recovery
Uns piked
Sample
(mg/L)*
Spiked
Sample
(mg/L)
Percent
Recovery
1/16/89
W3
41.6
21.6
72.3
222
18.4
50.3
76.7
1/17/89
FES
4.53
0.74
6.24
121
0.64
4.65
88.5
1/24/89
W3
41.6
33.1
101
163
25.4
67.0
100
1/30/89
F3
4.53
4.82
10.7
130
3.50
7.75
93.8
1/30/89
DF2
210
230
498
128
210
445
112
1/30/89
DE2
4.53
10.2
15.4
115
4.80
7.48
59.2
1/31/89
FE3
4.53
1.17
6.64
121
0.82
5.14
95.4
1/31/89
DF2
210
257
493
112
218
408
90.5
1/31/89
DE2
4.53
7.03
11.9
108
3.17
6.78
79.7
2/7/89
DE2
4.53
9.48
14.7
115
6.43
9.45
66.7
2/14/89
DE2
4.53
12.1
17.9
128
8.54
13.0
98.4
2/14/89
DF2
210
524
577
25.2
414
495
38.6
* ND - Not detected, HPLC-UV arid spectrophotometer detection limit = 0.25 mg/L.
+ = Percent recovery calculation not applicable.
$ = Analyses not completed.
material. C.I. Disperse Blue 79 is almost insoluble in water. The pure
material does not disperse in water but forms clumps of dye solid. As a
result, the purified dye material in water could not be used for spike
solution preparation. The commercial product contains dispersants which
form more of a slurry when mixed with water. However, it is possible that
the commercial product slurry is not consistent and thus a representative
spike was not always added to the sample.
The analytical spike recoveries for the dye extraction were much more
consistent than the field spikes. A solution of pure material in acetone
was used for the analytical spikes. An acetone solution was not used for
the field spikes to avoid the introduction of a solvent into the samples.
However, based on the results of the field spikes any future work should
include a study of field spike samples with the use of various solvents for
preparation of the spike solution.
73
-------
HPLC-UV Instrument Precision and Accuracy
Instrument duplicates and instrument spikes were performed to assess
the precision and accuracy of the HPLC with UV-visible detection. The
instrument duplicate consisted of measuring two aliquots of the dye extract
sample into two sample vials and performing the HPLC-UV analysis on both.
The relative difference of the two measurements was calculated. Replicate
sample analyses were also performed. In this case, three identical samples
were analyzed and the relative standard deviation of the three measurements
was reported. The instrument spike was formulated by adding a known amount
of an acetonitrile/water solution of purified dye material to a sample
aliquot. The spiked water was analyzed and the percent recovery of the
spike was calculated.
The instrument duplicate results are summarized in Table 25 and the
instrument replicate results are summarized in Table 26. One instrument
duplicate was out of control (65.3%) and another duplicate was analyzed on
the same data set with favorable results (0,5%). The only other duplicate
greater than 20% relative difference involved measurements close to the
detection limit. The average relative difference of all the duplicate
measurements except the first duplicate was 6.8% with a standard deviation
of 9.1%. The replicate analyses average relative difference was 4.8% with a
standard deviation of 3.1%.
TABLE 25. INSTRUMENT DUPLICATE SAMPLES OBTAINED DURING THE DYE
TESTING PERIOD
HPLC-UV Analyses
Relative
Sample Sample Measured Value, fmg/L) Difference
Date Location Sample 1 Sample 2 (%)
12/13/88
DE2
5.18
2.63
65.3
12/13/88
DE2
5.78
5.75
0.5
1/11/89
DE2
8.95
7.73
14.6
1/16/89
ML3
29.3
29.5
0.7
1/26/89
FE3
0.56
0.44
24.0
1/31/89
FE3S
5.25
5.03
4.3
2/7/89
F3
2.90
2.85
1.7
2/14/89
¥3
44.0
43.3
1.6
74
-------
TABLE 26. REPLICATE INSTRUMENT ANALYSES OBTAINED DURING THE DYE
TESTING PERIOD
HPLC-UV Analyses
Relative
Standard
Sample Sample Measured Value. fmg/L) Deviation
Date Location Sample 1 Sample 2 Sample 3 (%)
1/17/89 F3 3.80 3.28 3.33 8.4
1/17/89 W3 20.9 19.8 19.7 3.3
1/30/89 DE2S 9.25 8.75 9.03 2.8
The instrument spike results are summarized in Table 27. The average
recovery of the spikes was 103% with a standard deviation of 10.5%. The five
spike recoveries are all within + 20%.
ACTIVATED SLUDGE PILOT SYSTEMS
The activated sludge pilot systems were sampled for dye analyses from
August 8, 1988 through October 18, 1988. The data are contained in Appendix
D, Table D-l, Initially, both the control unit and the experimental unit
were sampled for dye analyses. Only the feed (Fl) and waste activated
sludge (Wl) from the control unit were analyzed by HPLC-UV while the feed
-------
The feed and waste mixed liquor samples from Unit 1 contained detectable
quantities of a material adsorbable at 580 nut when analyzed by the
spectrophotometer. However, C.I, Disperse Blue 79 was not detected by
HPLC-UV in any of the F1 or W1 samples analyzed. Because the first nine sets
of samples contained no detectable dye concentration, the analysis of control
unit samples was discontinued. The data obtained was sufficient to show no
detectable background concentration of dye was present in the raw municipal
wastewater feed.
The results of the spectrophotometer analyses, HPLC-UV analyses, and the
corresponding TSS concentrations from the experimental unit are summarized in
Table 28. The C.I. Disperse Blue 79 concentrations from Unit 2 are
presented in Figure 31. Figures 32 through 36 present the dye and TSS
concentrations for each sample point. The data presented in Figures 31-36
and the following discussion are based on the dye analyses conducted by
HPLC-UV and shown in Table 28.
The average dye concentration in the feed to the primary clarifier was
4.40 mg/L and the average final effluent concentration was <0.93 mg/L. These
values yielded an average dye removal of >79%. However, although five out of
19 effluent samples were below the 0.25 mg/L detection limit, the effluent
dye concentration varied from <0.25 mg/L to 3.70 mg/L. The variation in
effluent dye concentration may have been caused by the variation in effluent
TSS concentration.
The data in Figures 32, 33, and 34 do not indicate a significant
correlation between TSS and dye concentration for the feed, primary effluent,
and primary sludge. However, the data in Figures 35 and 36 suggest some
correlation between the TSS concentration and the dye concentration in the
waste activated sludge and the final effluent. The TSS concentration vs the
dye concentration for waste activated sludge and final effluent are graphed
in Figures 37 and 38, respectively. The correlation coefficient between the
TSS and dye concentrations is 0.76 for the waste activated sludge and 0.78
for the final effluent. In addition, calculations performed on the data in
Table 28 show that for each gram of suspended solids contained in the waste
activated sludge, 30 mg of dye solids were present while the effluent
contained 33 mg of dye solids for each gram of suspended solids. The
correlation between TSS and dye concentrations indicates that the dye has a
high affinity for the activated sludge solids. The dye in the effluent was
probably not dissolved, suspended, or colloidal dye material pasing through
the treatment system, but was dye associated with the activated sludge
solids. The relationship between solids concentrations and dye
concentrations may be significant in terms of controlling removal of dye from
a wastewater stream. Approximately 21% of the dye fed to the unit was
contained in the final effluent; however, most of this dye concentration was
probably associated with the suspended solids in the final effluent. The
average effluent TSS concentration of the samples analyzed for dye was 28
mg/L. Improved solids removal in the final clarifier might result in a lower
dye concentration in the effluent.
Mass balance calculations for the dye were made on all days when dye
analyses were performed. The flowrates used for mass balance calculations
are presented in Table 29. These flowrates were normalized based on flow
76
-------
TABLE 28. SUMMARY OF SPECTROPHOTOMETER AND HPLC-UV C.I. DISPERSE BLUE 79
ANALYSES AND TOTAL SUSPENDED SOLIDS ANALYSES DURING DYE
TESTING PERIOD
Dye Concentration fmg/L) Dve Concentration fmg/L)
S<3 triples
Location
Spectro-
photometer
HPLC-UV
TSS
(mg/L)
Spectro-
photometer HPLC-UV
TSS
(mg/L)
8/8/88
8/9/88
F2
5.32
4.39
189
4.49
4.43
284
PE2
5.40
4.00
131
4.34
4.08
155
PS 2
24.2
25.1
15,000
38.6
33.7
26,300
W2
in
94.9
2,910
101
83.0
2,990
FE2
0.78
1.01
22
1.42
1.04
36
D
166
139
*
170
148
•k
8/16/88
F2
5,02
4.43
184
5.56
3.98
220
PE2
5.16
4.56
105
5.04
4.03
134
PS2
27.2
22.2
11,300
27.3
20.4
13,900
W2
100
86.0
3,000
103
89.5
3,070
FE2
0.42
<0.25
20
1.05
1,00
22
D
155
136
*
172
145
*
8/22/8
8
8/23/88
F2
5.44
3,08
166
5.26
3.13
260
PE2
6.16
3.63
127
5,23
2.88
140
PS2
35.8
40.8
15,000
37.2
30.8
20,100
W2
115
110
3,200
115
91.8
3,160
FE2
4.45
3,70
65
0.90
0.36
24
D
167
150
*
161
138
"k
(continued)
77
-------
TABLE 28 (continued)
Sample
Location
Spectro-
photometer HPLC-UV
TSS
(mg/L)
Spectro-
photometer HPLC-UV
TSS
(mg/L)
8/29/88
8/30/88
F2
5.10
4.88
191
4.82
5.20
304
PE2
5.58
4.50
132
5.08
4.33
174
PS2
37.9
29.5
13,700
35.2
30.8
17,900
W2
95.0
80.3
2,860
108
89.9
3,100
FE2
1.03
0.60
30
0.83
<0.25
26
D
171
130
"k
177
*
*
9/6/88
9/12/88
F2
5.31
5.58
168
4.71
4.28
208
PE2
8.84
8.66
116
4.97
4.15
124
PS2
156
106
13,400
33.8
29.2
12,800
W2
108
88.5
2,340
77.9
69.3
2,120
FE2
1.97
3.08
36
0.40
0.76
23
D
172
158
*
173
135
*
9/13/88
9/20/88
F2
4.81
3.88
202
4.60
4.93
206
PE2
5.35
4.43
144
6.13
5.98
193
PS 2
33.3
27.0
13,600
35.9
30.5
18,600
W2
70.3
60,0
2,110
95.4
79.4
3,080
FE2
0.94
0.48
31
1.02
2.15
39
D
167
127
*
179
137
*
(continued)
78
-------
TABLE 28 (continued)
Dve Concentration (me/L') Dve Concentration (mg/L)
Sample
Location
Spectro-
photometer HPLC-UV
TSS
(mg/L)
Spectro-
photometer
HPLC-UV
TSS
(mg/L)
F2
5.26
3.80
146
4.69
3.15
178
PE2
5.42
4.20
104
5.08
6.15
126
PS2
64.9
51.3
11,700
43.2
35.2
13,000
W2
136
88.8
2,800
128
92.5
3,000
FE2
1.66
1.21
32
1.09
<0.25
26
D
186
141
•k
181
137
*
10/3/88
10/4/88
F2
5.42
6.18
140
4.93
4.08
244
PE2
5.60
6.95
95
5.14
4.36
145
PS 2
60.3
50.8
9,890
42.8
34.5
16,200
W2
138
120
3,260
137
' 115
3,240
FE2
0.72
<0.25
33
1.81
1.75
51
D
174
147
*
172
139
¦k
10/10/88
10/11/88
F2
4.89
3.90
174
5.00
4.85
286
PE2
5.14
3.90
100
4.82
5.28
160
PS2
44.4
32.3
11,100
55.4
43.0
18,000
W2
137
111
3,380
141
111
3,570
FE2
0.50
0.50
11
0.68
1.55
24
D
174
137
•k
177
141
*
(continued)
-------
TABLE 28 (continued)
Dye Concentration (rag/L)
Sample Spectro- TSS
Location photometer HPLC-UV (mg/L)
Dye Concentration (mg/L)
Spectro- TSS
photometer HPLC-UV (mg/L)
10/17/88
10/18/88
F2
5.03
5.43
186
4.23
5.68
251
PE2
4.92
6.38
94
4.20
5.63
142
PS2
21.4
16.8
9,540
24.0
19.9
8,490
¥2
127
108
3,680
122
97.0
3,700
FE2
<0.25
0.39
14
<0.25
<0.25
9
D
174
138
¦k
161
132
*
Average Values
Spectrophotometer
HPLC
TSS
Average (n)
Range
Average (n) Range
Average (n) Range
F2 4.98 (19) 4.49-5.56
PE2 5.20 (19) 4.20-6.16
PS2 38.0 (19) 21.4-64.9
W2 114 (19) 70.3-141
FE2 <1.06 (19) <0.25-4.45
D 171 (19) 155-186
4.40 (19) 3.08-6.18
4.71 (19) 2.88-6.95
31,8 (19) 16.8-51.3 14,500 (19)
212 (19) 140-304
133 (19) 94-193
8,450-
26,300
93.5 (19)
60-120
3,060 (19) 2,110-
3,700
<0.93 (19) <0.25-3.70
139 (18) 127-150
28 (19)
* Analysis not performed.
+ 9/6/88 data not included.
9-65
80
-------
mo
Mi)
25X
m
u
*U)
5JOO
(LOO
l-J
•-V /\
+ -f2
x - pe2
o-f«2
\ '
-
Jt V" /
%•
•**-' IIL^
/ \
/ m*~——
. jifc-
¦-¦2
»-ps2
¦d
-K.
- *¦+•-
..-S-
,* *
' i y !
i / I
* k
% ¦"
-JM
i-rP I Pi Brt~ - — -1 ~93 *" "* I n< I "* 'fi 1
W
too
m
sw
m
m
255
m
C~4
cn
O-
oT
.
o>
P-.
a
Fig
22S 2tt
1% Humber
ure 31. Activated sludge Unit 2 C.I. Disperse Blue 79 concentrations,
crs
u~>
15.0
£L0
MO
3.00
3,00
m
2V
225 240
Dny Number
255
270
a-
Figure 32. Activated sludge Unit 2 feed TSS and'C.I. Disperse Blue 79
concentrations.
81
-------
195 213 225 240 255 270
Day Number
Figure 33. Activated sludge Unit 2 primary effluent TSS and C.I.
Disperse Blue 79 concentrations.
27000
24300
21600
WOO
16200
CT
13500
CT!
_E
crt
10800
in
8100
5400
2700
0
210
240
255
270
Day Number
Figure 34. Activated sludge Unit 2 primary sludge TSS and C.I.
Disperse Blue 79 concentrations.
82
-------
to
u~i
I—
250
225
200
175
150
125
cr
cr>
100
&
75j0
500
2&0
OAS
Day Number
Figure 35. Activated sludge Unit 2 waste activated sludge TSS and
C.I. Disperse Blue 79 concentrations .
70
60
50
40
\
JeL x h \
GO I I
t rt (- |
Jc
20
¥
%h
/!
/ I
' I
I
*/
/ I
I
x-tss
f - (fye
>/
/X
~—^k
A
/ s
-I* I
¦¦V
I L
!
i \
vx
*ir
! s ' s
i \ i \
' ' -f \
i 4 , ' 1
-31 Hi i
10.0
ioo
8M
7.00
6.00
5.00
4.00
100
zoo
too
0.00
2D
225 240
Day Number
255
270
Figure 36, Activated sludge Unit 2 final effluent TSS and C.I. Disperse
Blue 79 concentrations.
83
-------
=i
E
i-f
-------
TABLE 29. NORMALIZED FLOWRATES USED FOR MASS BALANCE CALCULATIONS
Date
Influent
¦ p2
(L/day)
Effluents
PE2
(L/day)
PS2
(L/day)
W2
(L/day)
FE2
(L/day)
8/8/88
8/9/88
8/15/88
8/16/88
8/22/88
8/23/88
8/29/88
8/30/88
9/12/88
9/13/88
9/20/88
9/26/88
9/27/88
10/3/88
10/4/88
10/10/88
10/11/88
10/17/88
10/18/88
807
866
807
778
818
821
817
821
831
848
864
861
894
785
832
827
830
808
795
798
856
798
769
809
812
807
812
822
839
854
852
884
776
823
818
820
798
783
3.5
4.3
4.0
4.2
3.8
4.0
4.5
4.3
4.0
4.0
4.4
3.3
4.4
3.8
4.2
4.0
4.6
5.1
6.5
25.9
23.3
23.5
22.
23
23
20
21
21
20
23
23.0
23.0
24.0
25.0
24.0
23.7
28.8
28.7
772
833
774
746
786
789
786
790
800
819
830
829
861
752
798
794
796
769
754
85
-------
readings taken before, during, and after the sample period. The flowrates
were also corrected for the samples obtained during the sampling period.
Because of the sample volume correction, the primary effluent volume plus
primary sludge volume do not add up to the influent volume.
The mass balance calculations for each sample day are listed in Tables
30-32. The data for September 6 were not included because of operating
problems. Mass balances across the entire system showed that an average of
86.5% of the dye contained in the feed stream was accounted for in the
effluent streams. The primary sludge, waste activated sludge, and final
effluent contained an average of 3.6%, 62.3%, and 20.4%, respectively, of
the dye fed to the system (the percentages of the three streams do not add
up to the total due to rounding off the individual values). The majority of
the dye fed to the system was contained in the waste activated sludge.
The mass balance calculations across the primary clarifier indicated
109% of the dye in the feed was contained in the primary sludge plus primary
effluent. The average primary effluent concentration was 4.71 mg/L while the
average feed concentration was 4.40 mg/L. The primary sludge contained only
3.6% of the dye mass fed to the system. Thus, the feed and primary effluent
dye concentrations should have been similar. The fact that the primary
effluent samples were slightly higher than the feed concentration was
probably the result of experimental error. The TSS concentration of the feed
samples averaged 212 mg/L while the primary effluent TSS average was 133
mg/L; these data give an average suspended solids removal of 37%.
The aeration basin plus final clarifier mass balance calculations
results showed 78.1% of the dye contained in the primary effluent was
accounted for in the final effluent plus waste activated sludge. This
recovery was slightly less than the recovery across the entire treatment
system because the primary effluent concentration was slightly larger than
the feed concentration,
ANAEROBIC DIGESTERS
Preliminary samples from the anaerobic digesters were analyzed for dye
concentration while the activated sludge systems sampling was conducted.
The preliminary data showed the extraction method was applicable to the
digester feed and effluent samples. The full digester sample schedule was
performed from November 7 through December 19, 1988. All the dye analytical
data is contained in Appendix D, Table D-l. The spectrophotometer, HPLC-UV,
and TSS concentrations of the digester samples are presented in Table 33
while the average concentrations are summarized in Table 34.
Samples of the control unit feed (DF1), effluent (DEI), and supernatant
from the digester feed preparation (SPl) were analyzed for dye content. In
general, the spectrophotometer analyses detected dye in the control feed and
effluent samples while the HPLC-UV analyses indicated lower or nondetectable
concentrations. Neither analytical method detected dye in any of the
supernatant samples collected from Unit 1.
Detectable concentrations of dye were identified by HPLC-UV in five out
of ten DF1 samples and four out of ten DEI samples. The average
86
-------
TABLE 30, C.I. DISPERSE BLUE 79 MASS BALANCE ACROSS
ENTIRE TREATMENT SYSTEM*
Dye In Dye Out
Sample F2 PS2 W2 FE2 Total Percent
Date {mg/day) (mg/day) (mg/day) (mg/day) (mg/day) Recovered
8/8/88
3,540
88
2,460
780
3,330
94.1
8/9/88
3,840
140
1,930
866
2,940
76.6
8/15/88
3,580
89
2,020
194+
2,300
64.2
8/16/88
3,100
86
2,040
746
2,870
92.6
8/22/88
2,520
160
2,580
2,910
5,650
224
8/23/88
2,570
120
2,120
284
2,520
98.0
8/29/88
3,990
130
1,670
472
2,270
56.9
8/30/88
4,270
130
1,940
198+
2,270
53.2
9/12/88
3,560
120
1,520
608
2,250
63,2
9/13/88
3,290
110
1,210
393
1,710
52.0
9/20/88
4,260
130
1,900
1,780
3,810
89.4
9/26/88
3,270
170
2,040
1,000
3,210
98.2
9/27/88
2,820
150
2,130
215+
2,500
88.6
10/3/88
4,850
190
3,310
188+
3,690
76.1
10/4/88
3,390
140
2,880
1,400
4,420
130
10/10/88
3,220
130
2,660
397
3,190
99.1
10/11/88
4,020
200
2,630
1,230
4,060
101
10/17/88
4,390
86
3,110
298
3,490
79.5
10/18/88
4,520
130
2,780
188
3,100
68.6
Average
3,630
130
2,260
740
3,140
86.5
Percent
of Dye
Feed in
Effluent
Stream
3.6
62.3
20.4
86.5
* Calculations based on HFLC-UV analyses.
+ Dye not detected in sample. Detection limit of 0.25 mg/L used in
calculation.
87
-------
TABLE 31. C.I. DISPERSE BLUE 79 MASS BALANCE ACROSS PRIMARY CLARIFIER*
Dye In Dye Out
Sample F2 PE2 PS2 Total Percent
Date (mg/day) (rag/day) (rap,/day) (mg/day) Recovered
8/8/88
3,540
3,190
88
3,280
92.6
8/9/88
3,840
3,490
140
3,630
94.5
8/15/88
3,580
3,640
89
3,730
104
8/16/88
3,100
3,100
86
3,190
103
8/22/88
2,520
2,940
160
3,100
123
8/23/88
2,570
2,340
120
2,460
95.7
8/29/88
3,990
3,630
130
3,760
94.2
8/30/88
4,270
3,520
130
3,650
85.5
9/12/88
3,560
3,410
120
3,530
99.2
9/13/88
3,290
3,720
110
3,830
116
9/20/88
4,260
5,110
130
5,240
123
9/26/88
3,270
3,580
170
3,750
115
9/27/88
2,820
5,250
150
5,400
191
10/3/88
4,850
5,390
190
5,580
115
10/4/88
3,390
3,590
140
3,740
110
10/10/88
3,220
3,190
130
3,320
103
10/11/88
4,020
4,330
200
4,530
113
10/17/88
4,390
5,090
86
5,180
118
10/18/88
4,520
4,410
130
4,540
100
Average
3,630
3,840
130
3,970
109
Percent
106
3.6
109
of Dye Feed
In Effluent
Stream
* Calculations based on HPLC-UV analyses.
88
-------
TABLE 32. C.I. DISPERSE BLUE 79 MASS BALANCE ACROSS THE AERATION BASIN
AND FINAL CLARIFIER*
Dye In Dye Out
Sample PE2 W2 FE2 Total Percent
Date (mg/day) (mg/day) (mg/day) (mg/day) Recovered
8/8/88
3,190
2,460
780
3,240
99.0
8/9/88
3,490
1,930
866
2,800
82.8
8/15/88
3,640
2,020
194+
2,210
61.5
8/16/88
3,100
2,040
746
2,790
90.0
8/22/88
2,940
2,580
2,910
5,490
185
8/23/88
2,340
2,120
284
2,400
00
•"•J
8/29/88
3,630
1,670
472
2,140
59.0
8/30/88
3,520
1,940
198+
2,140
60.8
9/12/88
3,410
1,520
608
2,130
62.5
9/13/88
3,720
1,210
393
1,600
43.0
9/20/88
5,110
1,900
1,780
3,680
72.0
9/26/88
3,580
2,040
1,000
3,040
84.9
9/27/88
5,250
2,130
215+
2,340
44.6
10/3/88
5,390
3,310
188+
3,500
64.9
10/4/88
3,590
2,880
1,400
4,280
119
10/10/88
3,190
2,660
397
3,060
95.9
10/11/88
4,330
2,630
1,230
3,860
89.1
10/17/88
5,090
3,110
298
3,410
67.0
10/18/88
4,410
2,780
194
2,970
67.3
Average
3,840
2,260
740
3,000
78.1
Percent of
Dye Feed
Effluent
Stream
58.8
19.3
78.1
* Calculations based on HPLC-UV analyses.
+ Dye not detected in sample. Detection limit of 0.25 mg/L used in
calculation.
89
-------
TABLE 33. SUMMARY OF SPECTROPHOTOMETER AND HPLC-UV G.I. DISPERSE BLUE 79
ANALYSES AND TOTAL SUSPENDED SOLIDS ANALYSES OF ANAEROBIC
DIGESTER SAMPLES
Dve Concentration (mg/L)
Sample Spectro- TSS
Location photometer HPLC-UV (mg/L)
Dve Concentration (mg/L)
Spectro- TSS
photometer HPLC-UV (mg/L)
SP1
DF1
DEI
SP2
DF2
DE2
11/7/88
<0.25
6.90
1.53
1.85
348
10.9
<0.25
7,78
2.78
4.20
323
7.73
260
23,400
12,400
115
21,200
12,400
11/8/88
<0.25
3.44
9.34
1.16
541
4.28
<0.25
1.69
5.95
3.30
483
1.18
66
22,400
13,500
53
23,400
13,200
11/14/88
SP1
DF1
DEI
SP2
DF2
DE2
<0.25
1.10
0.67
13,9
635
18.7
<0.25
<0.25
<0.25
11.8
553
12.5
96
21,200
12,400
326
20,200
11,400
11/15/88
<0.25 <0.25
1,20
0.72
2.47
570
18.6
0.50
<0.25
0.79
412
13.3
298
19,800
11,800
88
19,800
12,200
11/28/88
11/29/8
SP1
DF1
DEI
SP2
DF2
DE2
<0.25
0.76
0,72
0.95
607
20.8
<0.25
<0.25
<0.25
1.22
558
15.0
51
20,200
12,600
52
20,200
12,400
<0.25
0.82
•0.66
1.18
609
12.7
<0.25
<0.25
<0.25
0.51
580
6.68
34
18,800
11,900
52
20,600
12,200
(continued)
90
-------
TABLE 33 (continued)
Dve Concentration (me/L*)
Dve Concentra
tion fme/L)
Sample
Location
Spectro-
photometer
HPLC-UV
TSS
(mg/L)
Spectro-
photometer
HPLC-UV
TSS
(mg/L)
12/5/88
12/6/88
SP1
*
*
284
*
*
78
DF1
0.90
<0.25
21,200
1.03
2.65
21,700
DEI
0.98
0.38
12,400
0.31
<0.25
14,000
SP2
1.76
1.27
74
0.61
0.54
46
DF2
*
*
21,600
678
393
22,000
DE2
*
*
11,800
11.8
5.65
12,400
12/12/88
12/13/88
SP1
'k
*
33
*
*
54
DF1
*
*
*
1.26
0.65
22,500
DEI
0.65
1.62
11,600
2.83
*
11,700
SP2
1.44
0.92
48
1.35
0.96
50
DF2
618
450
23,100
517
343
21,600
DE2
15.3
12/19/.
8.59
88
12,800
18.8
3.90
12,900
SP1
*
*
39
DF1
2.37
<0.25
23,600
DEI
1.48
<0.25
12,600
SP2
1.63
<0.25
69
DF2
539
339
23,300
DE2
18.5
4.03
12,700
* Analysis not performed.
91
-------
TABLE 34. AVERAGE ANAEROBIC DIGESTER DYE SAMPLE CONCENTRATIONS
Dye Concentration (mg/L)
Sample Spectrophotometer HPLC-UV TSS (mg/L)
Location Average (n) Range Average (n) Range Average (n) Range
SP1
<0.25
' (5)
<0.25-<0.25
<0.25 (6)
<0.25-<0.25
118
(11)
33-298
DF1
1.98
(10)
0.76-6.90
<1.45 (10)
<0.25-7.78
21,500
(10)
18,800-23,600
DEI
1.81
(11)
0.31-9.34
<1.22 (10)
<0.25-5.95
12,400
(11)
11,600-14,000
SP2
2.57
(11)
0.61-13.9
<2.34 (10)
<0.25-11.8
88
(11)
46-326
DF2
566
(10)
348-678
443 (10)
323-580
21,500
(11)
19,800-23,400
DE2
15.0
(10)
4.28-20.8
7.86 (10)
1.18-15.0
12,400
(11)
11,400-13,200
concentration of dye in the DF1 and DEI samples was <1,45 mg/L and <1.22
mg/L, respectively. While small concentrations were detected in select
samples from the control digesters, it is not likely that the dye was present
in a significant concentration in the raw wastewater. The low level of dye
in the control digester samples would have had little impact on the much
larger concentrations of dye detected in the experimental unit samples. The
source of the dye in the control digester samples could have been sample
contamination, pilot unit contamination, or a very low concentration of dye
present in the raw wastewater.
The average Unit 2 feed dye concentration was 443 mg/L while the average
effluent concentration was 7.86 mg/L. On the average, 98,2% of the dye
contained in the sludge fed to the anaerobic digester was degraded. There
was no obvious correlation between TSS concentration and dye concentration in
the feed or effluent samples from the digesters.
Thermospray ionization mass spectrometery was used to identify
degradation products of C.I. Disperse Blue 79 in the anaerobic digester
effluent. The parent dye was observable under this ionization technique, but
because of the electronegativity of many of the functional groups on the
molecule (e.g., NO^, Br) the sensitivity of the technique for this compound
was poor. Four major degradation compounds that have been tentatively
identified were found in significant amounts in the digester effluent. Their
exact identity and amounts have not been verified because authentic standards
were not available. These compounds are expected to show a better response
than the parent dye because of either removal or reduction of the
electronegative moieties that were suppressing the sensitivity of C.I.
Disperse Blue 79. Table 35 summarizes the relative amounts of these
compounds (A, B, C, D) which have molecular weights of 283, 358, 400, and 478
daltons, respectively, for the February 14, 1989 samples. The relative
amounts of these compounds were greater in the digester effluent than in the
digester feed. Information about the structure of these compounds is
discussed below.
92
-------
TABLE 35. MASS SPECTROMETRY ANALYSIS OF ANAEROBIC DIGESTER SAMPLES
Sample Relative Amounts (Arbitrary Units)
Location A(MW 283) B(MW 358) C(Mw 400) D(MW 478)
DF1 26000 7300 7400 1700
DF2 24000 6400 6300 43000
DE2 568000 264000 365000 225000
The thermospray technique is both a liquid chromatograph/mass
spectrometric (LC/MS) interface and ionization technique. The interface is
used for nonvolatile or thermally labiile compounds that are not amenable for
gas chromatographic (GC) introduction. Thermospray ionization deposits a
small amount of energy into the ionization process and generally little
fragmentation of compounds results. If a compound has a relatively high
proton affinity (above ammonia on the proton affinity scale [>207 kcal/mol]),
usually only the protonated molecule appears as the (M+H) ion (at one mass
unit or dalton greater than the molecular weight). The thermospray
ionization mass spectrum of C.I. Disperse Blue 79 shows the (M+H) ion at m/z
625 and 627 (since the dye has one bromine atom, and bromine has two
naturally occurring isotopes that are approximately equal in abundance and
two mass units apart, two peaks occur for this specific ion). But the
spectrum also shows considerable fragmentation. In addition, the sensitivity
of thermospray ionization for this dye is poor. Since C.I. Disperse Blue 79
has two nitro groups and a bromine which are strong electron withdrawing
substituents on one of the benzene rings in its structure, the protonated
molecule or (M+H) is destabilized. A loss of sensitivity and fragmentation
from the breakdown of the protonated molecule result.
Four major ions were identified in the thermospary ionization mass
spectrum of the sample from the spiked reactor; these ions were not present
in the sample from the control system. These four ions appeared at
mass-to-charge ratios of 284, 359, 401, and 479 which indicated molecular
weights of 283, 358, 400, and 478, respectively. Since these ions were
present as intense peaks, it was suspected that the compounds from which
these ions came have high proton affinities, and if they were truly
degradation products of C.I. Disperse Blue 79, the electronegative groups had
either been removed or reduced. The biological or chemical reduction of a
nitro group to an amino functionality is common to anaerobic conditions.
The next procedure in identifying these compounds was the generation of
collision activated dissociation spectra on a tandem mass spectrometer (a
triple quadrupole mass spectrometer). The ion of interest is made to collide
energetically with an inert gas and the fragments of that collision
monitored. These spectra are summarized in Table 36. The compound
represented by myz 479 contains one bromxne sxnce the thermospray ionization
mass spectrum also contains m/z 481 of equal intensity. It is possible that
93
-------
TABLE 36. COLLISION ACTIVATED DISSOCIATION SPECTRA OF DEGRADATION
PRODUCTS OF C.I. DIPERSE BLUE 79
Parent Ion, m/z Daughter Ions, m/z (% Relative Abundance)
284 284(100), 239(75), 208(20)
401 401(100), 383(5), 356(25) , 87(5)
359 359(100), 314(50), 299(20)
479 479(100), 461(20), 437(20), 434(25), 419(30),
403(60), 392(60), 361(20), 87(5)
the structures of the compounds represented by the m/z 479 ion and the m/z
401 ion are related, differing by the replacement of a bromine by a hydrogen.
Both also show the m/z 87 ion in their collision spectra. This same ion is
present in the collision spectrum of C.I. Disperse Blue 79 and is the
C„H^0C(0)CH^ ion. These degradation products have retained at least one of
tnese ester groups. Hydrolysis of both ester groups is likely to have taken
place in the other two compounds. A major fragment ion in all the compounds
is the ion formed by the loss of 45 daltons from the parent ion. This is
probably due to loss of the C„H^0H moiety. There is a further loss of 31
daltons in the collision spectrum of the parent ion, m/z 284. This is either
CH^OH or CH^. Therefore, the most likely choice for the compound that gives
the (M+H) ion m/z 284 is C.I. Disperse Blue 79 with its ester groups
hydrolyzed and which has been reduced at the azo linkage to give the
corresponding amine.
High resolution mass measurements were performed on two of the
compounds. The ion at m/z 401 was attributed to a compound that has an
empirical formula, C^H^N^O^. The ion at m/z 479 was due to a compound with
the empirical formula, C^QH^^NgO^Br. Again these compounds differ by a
bromine and a hydrogen. These data are consistent with both structures
having one of the ester groups hydrolyzed and one intact. Additionally, the
two nitro groups have been reduced to the amino (NH„) functionality. The
replacement of the methoxy group by a hydrogen and the methyl group on the
amide by another hydrogen are harder to explain, but are consistent with mass
spectral data.
The compound associated with the m/z 359 ion is 42 daltons from the
compound associated with the ion at m/z 401. Consequently, they may have the
same structure, but the compound of molecular weight 358 has both ester
groups hydrolyzed.
Many of the preceding arguments are speculative. They are consistent
with the data, but final proof rests with obtaining authentic standards and
generating mass spectra from these compounds.
94
-------
Some of the potential degradation pathways of C.I. Disperse Blue 79
could result in liberation of bromide from the dye compound. Bromide
analyses were also performed on the anaerobic digester feeds and effluents to
determine if bromide was liberated in the digester. Various analytical
methods were tested before an appropriate procedure was identified.
Initially, an ion selective electrode method was performed. However, this
method yielded unacceptable spike recoveries, probably due to matrix
interferences. EPA Method 320.1(3) was also attempted, but it proved to be
unacceptable for the digester samples. However, a modified Method 320.1 was
found to be acceptable and the results of the sample analyses performed using
this procedure are presented in Table 37.
The one set of data from the control unit sample analyses did not show
any significant difference in the bromide concentration between the feed and
effluent. However, in both sets of data from the experimental unit, the
bromide concentration was much lower in the feed than the effluent. The
average of the two feed samples was 2.50 mg/L while the effluent was 39.0
mg/L. For the one set of samples for which dye analyses are also available,
the dye concentration was reduced from 250 mg/L to 9.46 mg/L. These data
indicate that bromide was being liberated during dye degradation in the
anaerobic digester. However, the limited data available is not sufficient to
perform conclusive bromide mass balance calculations.
TABLE 37. BROMIDE ANALYSES OF ANAEROBIC DIGESTER SAMPLES
Sample
Location
S amp1e
Date
Bromide
Concentration
(ng/D
C.I. Disperse Blue 79
Concentration
(mg/L)
DF2
1/5/89
1.75
ie
DE2
1/5/89
40.8
it
DF1
2/7/89
0.85
¦k
DEI
2/7/89
0.66
-k
DF2
2/7/89
3.24
250
DE2
2/7/89
37.1
9.46
* Analysis not performed.
95
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SECTION 11
BENCH-SCALE ACTIVATED SLUDGE SYSTEM
INTRODUCTION
During normal operation of a wastewater treatment system, the
supernatant from sludge lagoons or other digested sludge thickening
operations is returned to the head-end of the plant for treatment. The
bench-scale activated sludge system (Unit 3) was operated to study the fate
of dye degradation products from the anaerobic digester in an activated
sludge system. The supernatant (SP2) from the sludge thickening operation
used for preparation of the digester feed was mixed with centrate from
centrifuging digester effluent (DE2) and primary effluent (PE2) to prepare
feed for Unit 3. The SP2 was added to simulate the effluents produced from
the thickening of waste activated sludge in a typical plant.
The centrate from DE2 represented about 3% of the total feed volume
(F3). This fraction of digester centrate is about four times as much as
would be added based on data from the South Shore Treatment Plant. The
higher proportion of digester centrate was added to enhance the detection of
dye degradation products in the Unit 3 samples.
CONVENTIONAL TREATMENT RESULTS
Unit 3 operation was started on November 11, 1988. The unit was seeded
with mixed liquor from Unit 2. Aeration was started immediately followed by
preparation of the feed mixture and start up of the feed and waste sludge
pumps. Sample collection was initiated on November 11, 1989.
The feed characteristics are summarized in Table 38. The average feed
TSS concentration was 130 mg/L, which was very close to the average primary
effluent concentration (feed to the aeration basin) of 139 mg/L from Unit 2.
The feed TCOD and TBOD concentrations were slightly less than the respective
concentrations in the feed to Unit 2, but are not directly comparable. No
measurements of the primary effluent TCOD and TBOD, which were the feed to
the pilot system aeration basins, were performed.
The operational and analytical data from Unit 3 are presented in Table
39. The average HRT was 6.04 hours, which was slightly higher than the Unit
2 value of 5.28 hours, while the average SRT for Unit 3 was 4.83 days which
was lower than the Unit 2 average value of 5.94 days. The Unit 3 average SRT
was lower than the target value of 7 days due to a relatively high average
effluent TSS value of 40 mg/L. The bench-scale unit settling performance was
more variable than that in the pilot units.
96
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TABLE 38. SUMMARY OF ACTIVATED SLUDGE UNIT 3 FEED ANALYTICAL DATA
(DAY 302-388, NOVEMBER 22 - FEBRUARY 15, 1989)
Parameter
Unit 3
Average (ri)
Range
pll * (73) 6.9-7.5
TSS (uig/L) 130 (17) 84-216
TCOD (mg/L) 336 (6) 229-399
TBOD (mg/L) 158 (6) 98-194
* Average pH value not calculated.
TABLE 39. SUMMARY OF ACTIVATED SLUDGE UNIT 3 OPERATION
(DAY 302-388, NOVEMBER 22 - FEBRUARY 15, 1989)
Unit 3
Parameter
Average (n)
Range
Operation Data
Feed Flow (L/day)
24.2 (84)
28.8-16.4
Waste ML Flow (L/day)
0.76 (83)
0.0-1.3
HRT (hrs)
6.04 (84)
5.00-8.80
SRT (days)
4.83 (16)
2.52-14.5
Mixed Liquor Data
Temp. (°C)
21.5 (86)
12.0-31.0
pH
* (83)
6.8-8.1
DO, Cell 1 (mg/L)
5.6 (82)
0.1-10.0
TSS (mg/L)
1650 (19)
564-3000
Final Effluent Data
TSS (mg/L)
40 (17)
10-102
TCOD (mg/L)
116 (6)
55.3-160
TBOD (mg/L)
31 (6)
10-46
97
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The average effluent TCOD and TBOD values were also higher than the
pilot unit values. The higher effluent values were probably due to the
higher TSS levels in the final effluent. The performance of Unit 3 with
respect to TSS, TBOD, and TCOD removal was not as good as the pilot units,
but was typical of a bench-scale unit.
C.I. DISPERSE BLUE 79 RESULTS
Samples from Unit 3 were obtained from January 11 to February 14, 1989
for the dye and related compound analyses. Table 40 contains the analytical
data from the feed ( P* 3), waste activated sludge (W3), and fxnal effluent
(FE3). The average feed dye concentration was 3.43 mg/L while the average
effluent concentration was 1.32 mg/L for a removal efficiency of 62%. The
effluent concentration was probably high due to the relatively high TSS
concentration in the final effluent.
Mass balance calculations of the dye across Unit 3 were performed. The
flowrates used for the calculations are presented in Table 41, while the
calculation results are contained in Table 42. On the average, 75.3% of the
dye fed to the unit was accounted for in the effluents from the unit. The
mass balance for Unit 2 showed 86.5% of the dye was recovered. While the
recovery from Unit 3 was slightly lower, it does not appear that significant
degradation of the dye was occurring in the bench-scale activated sludge
system,
The degradation products of C.I. Disperse Blue 79 were monitored in the
influent, effluent, and waste activated sludge from Unit 3, Because no
positive identification was made of the by-products, quantification was not
possible. However, some general observations can be made concerning the
degradation products based on relative amounts which are summarized in Table
43. The trend is for the concentration of these compounds to decrease across
Unit 3. These numbers roughly reflect the 3% amount of DE2 that make up the
feed (e.g., the relative amount of degradation product A in F3 is 3% of the
amount of A in DE2 for the February 14 samples).. The final effluent samples
always show the lowest concentrations of the degradation products. The
concentrations of the degradation products for F3 on January 24 appear to be
low; but, the values for the W3 and FE3 samples for that date are consistent
with the general trend. However, the data are not complete enough to further
comment. Further evaluation of the degradation products and their fate in
biological treatment systems may be subject for further project work.
98
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TABLE 40. SUMMARY OF SPECTROPHOTOMETER AND HPLC-UV C.I. DISPERSE BLUE 79
ANALYSES AND TOTAL SUSPENDED SOLIDS ANALYSES OF UNIT 3 SAMPLES
Sample
Spectro
TSS
Spectro-
TSS
Location photometer HPLC-UV
(mg/L)
photometer HPLC-UV
(mg/L)
1/11/89
1/16/89
F3
5.06
2.83
114
5.04
4.28
107
¥3
47.7
45.5
1,140
23.8
20.2
1,980
FE3
2.61
1.12
39
0.62
0.40
20
1/17/89
1/24/89
F3
4.57
3.55
145
4.30
3.60
216
m
27.1
21.4
2,050
36.4
28.0
3,000
FE3
0.75
0.65
25
0.70
0.35
40
1/30/89
1/31/89
F3
4.87
3.53
93
4.45
3.50
176
m
73.5
64.3
2,680
63.3
46.3
2,500
FE3
1.23
2.30
86
1.18
0.83
22
2/7/89
2/14/89
F3
3.72
2,88
171
4.42
3.28
137
¥3
37.1
31.5
1,630
50.9
43.6
2,190
FE3
3.26
2.25
90
3.28
2.63
102
AVERAGE VALUES
Spectrophotometer
HPLC
TSS
Average (n)
Range
Average (n)
Range
Average (n)
Range
F3
4.55 (8)
3.
72-5.06
3.43 (8)
2.
83
-4.28
1.45
93-216
W3
45.0 (8)
23.8-73.5
37.6 (8)
20
.2
-64.3
2,150 1,140-3,000
FE3
1.70 (8)
0.
62-3.28
1.32 (8)
0.
35
-2.63
53
20-102
99
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TABLE 41. FLOWRATES USED FOR MASS BALANCE CALCULATIONS FOR UNIT 3
Influent Effluent
__ _ F£3
Date (L/day) (L/day) (L/day)
1/11/89
28.0
1.04
27.0
1/16/89
26.2
0.97
25.2
1/17/89
26.2
1.02
25.2
1/24/89
25.5
0.77
24.7
1/30/89
25.8
1.01
24.8
1/31/89
25.6
0.98
24.6
2/7/89
26.0
1.00
25.0
2/14/89
26.0
0.50
25.5
TABLE 42. C.I. DISPERSE BLUE 79 MASS BALANCE ACROSS UNIT 3*
Dye In Dye Out
Sample F3 W3 FE3 Total Percent
Date (mg/day) (mg/day) (mg/day) (mg/day) Recovery
1/11/89
79.2
47.3
30,2
77.5
97.8
1/16/89
112
19.6
10.1
29.7
26.5
1/17/89
93.0
21.8
16.4
38.2
41.1
1/24/89
91.8
21.6
8.6
30.2
32.9
1/30/89
91.1
64.9
57.0
121.9
134
1/31/89
89.6
45.4
20.4
65.8
73.4
2/7/89
74.9
31.5
56.2
87.7
117
2/14/89
85.3
21.8
67.1
88.9
104
Average
89.6
34.2
33.2
67.5
75.3
Percent of
38.2
37.0
75.3
Dye Feed
in Effluent
Stream
* Calculations based on HPLC-UV analyses.
100
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TABLE 43. RELATIVE AMOUNTS OF DEGRADATION PRODUCTS IN UNIT 3
Sample
Location
Sample
Date
Relative Amounts ^Arbitrary Units')
A(MW 283) B(MW 358) C(MW 400) D(MW 478)
DE2
F3
m
W3D
FE3
DE2
DF2
F3
W3
FE3
1/24/89
1/24/89
1/24/89
1/24/89
1/24/89
2/14/89
2/14/89
2/14/89
2/14/89
2/14/89
157000
2300
5500
5400
2400
568000
24000
18000
6800
2800
140000
600
1100
1300
500
264000
6400
3000
1100
1000
151000
700
2100
2000
900
365000
6300
3800
3400
1700
10000
ND
600
1000
40
225000
43000
1700
4100
700
101
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REFERENCES
1. Process Design Manual for Sludge Treatment and Disposal. U.S. EPA Report
No. 625/1-79-011, September, 1979.
2. Quality Assurance Project Plan for Aerobic and Anaerobic Treatment of
C.I. Disperse Blue 79, EPA Contract No. 68-03-3371, Radian Corporation,
Milwaukee, Wisconsin, September 15, 1988.
3. Methods for Chemical Analysis of Water and Wastes. EPA 600/4-79-020,
U.S. Environmental Protection Agency, Environmental Monitoring and
Support Laboratory, Cincinnati, Ohio, 1979 (revised 1983).
4. Standard Methods for the Examination of Water and Wastewater. 15th Ed.,
APHA, AWWA, WPCF, 1980.
5. Hach Water Analysis Handbook. No. 11-01-84-SED, Hach Chemical Company,
Loveland, Colorado, 1984.
6 » Andrews, J. F., Thomas, J,F., and Pearson, E.A, Determmation of Volatile
Acids by Gas Chromatography, "Water and Sewage Works, 111:206-210, 1964.
102
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