United States
Environmental Protection
Agency
Municipal Environmental Research
Laboratory
Cincinnati OH 45268
EPA-600/2-79-097
August 1979
Research and Development
Treatability of
Carcinogenic and
Other Hazardous
Organic Compounds
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Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:
1. Environmental Health Effects Research
2 Environmental Protection Technology
3, Ecological Research
4 Environmental Monitoring
5 Socioeconomic Environmental Studies
6 Scientific and Technical Assessment Reports (STAR)
7 Interagency Energy-Environment Research and Development
8 "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the ENVIRONMENTAL PROTECTION TECH-
NOLOGY series This series describes research performed to develop and dem-
onstrate instrumentation, equipment, and methodology to repair or prevent en-
vironmental degradation from point and non-point sources of pollution This work
provides the new or improved technology required for the control and treatment
of pollution-sources io meet environmental quality standards.
is document Is available to the public through the National Technical Informa-
Spiingheld, Virginia 22161
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EPA-600/2-79-097
August 1979
TREATABILITY OF CARCINOGENIC AND OTHER
HAZARDOUS ORGANIC COMPOUNDS
by
Edward G. Fochtman and Walter Eisenberg
IIT Research Institute
Chicago, Illinois 60616
Contract No. CI-68-03-2559
Project Officer
Richard A. Dobbs
Wastewater Research Division
Municipal Environmental Research Laboratory
Cincinnati, Ohio 45268
MUNICIPAL ENVIRONMENTAL RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268
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DISCLAIMER
This report has been reviewed by the Municipal Environmental Research
Laboratory, U.S. Environmental Protection Agency, and approved for publica-
tion. Approval does not signify that the contents necessarily reflect the
views and policy of the Agency, nor does mention of trade names or commercial
products constitute endorsement or recommendation for use.
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FOREWORD
The Environmental Protection Agency was created because of increasing
public and government concern about the dangers of pollution to the health
and welfare of the American people. Noxious air, foul water, and spoiled
land are tragic testimony to the deterioration of our natural environment.
The complexity of that environment and the interplay between its components
require a concentrated and integrated attack on the problem.
Research and development is that necessary first step in problem solu-
tion and it involves defining the problem, measuring its impact, and search-
ing for solutions. The Municipal Environmental Research Laboratory develops
new and improved technology and systems for the prevention, treatment, and
management of wastewater and solid and hazardous waste pollutant discharges
from municipal and community sources, for the preservation and treatment of
public drinking water supplies, and to minimize the adverse economic, social,
health, and aesthetic effects of pollution. This publication is one of the
products of that research; a most vital communications link between the
researcher and the user community.
Many chemical carcinogens have been identified in effluents from munici-
pal wastewater treatment plants and in drinking water supplies. This report
presents the results of a study of the treatability of five chemical car-
cinogens found in wastewater. Three treatment systems, biodegradation,
carbon adsorption, and ozone oxidation were studied. The treatment procedures
indicate significant differences in the treatability of the compounds.
Francis T. Mayo, Director
Municipal Environmental Research
Laboratory
m
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ABSTRACT
Three methods of wastewater treatment, carbon adsorption, biodegradation,
and ozone oxidation were evaluated as potential treatment processes for
wastewater containing five different chemical carcinogens at levels of 1 mg/£
or less. The laboratory scale treatment techniques and analytical procedures
gave results that indicated that
naphthalene
can be treated by all three techniques but
reacts with ozone very slowly
1,1-diphenylhydrazine can be treated by all three processes
3-naphthylamine can be treated by all three processes
can be treated by all three processes
A.^-methylene-bis
(2-chloroaniline)
di methylni trosami ne
resists ozone oxidation, is not adsorbed
by carbon, is biodegraded in continuous
biological reactors.
This report was submitted in fulfillment of Contract No. CI-68-03-2559
by IIT Research Institute under the sponsorship of the U.S. Environmental
Protection Agency. This report covers the period June 1977 to June 1978.
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CONTENTS
Foreword iii
Abstract ' iv
Figures and Tables vi
Abbreviations and Symbols vii
Acknowledgments viii
1. Introduction 1
2. Conclusions 3
3. Recommendations 5
4. Materials and Methods 6
Selection of Compounds to be Studied 6
Biological Degradation 6
Carbon Adsorption 7
Ozone Oxidation 8
5. Experimental Procedures 10
General Procedures 10
Treatability Studies 11
Biological Degradation 11
Carbon Adsorption 11
Ozone Oxidation 13
Analytical Procedures 16
High Performance Liquid Chromatography (HPLC) - Ultra-
violet Adsorption 16
High Resolution Gas Chromatography - Flame lonization
Detection 17
Spectrophotometric Analysis 19
Quality Control 19
Reagent Control 19
Data Control 19
Accuracy and Precision 19
6. Results and Discussion 21
Biological Degradation 21
Carbon Adsorption 25
Ozone Oxidation 25
References 31
Appendices
A. Ozone Reaction Data 34
Carbon Adsorption Data 39
B. Preparation of Nutrient for Static and Continuous Biodegrada-
tion Tests 59
Preparation of Mineralized Water for Carbon Adsorption and
Ozonation Tests 60
Analysis of Benzidine plus 3,3'-Dichlorobenzidine 60
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FIGURES AND TABLES
Fi gure Page
1 Photograph of continuous biological reactor 12
2 HPLC analysis of ozonated naphthalene 28
3 HPLC analysis of ozonated B-naphthylamine 29
4 HPLC analysis of ozonated 1,1-diphenylhydrazine 30
.Table
1 Composition of Mineralized Water 10
2 Absorption Wavelength and Limits of Detection using HPLC 18
3 Absorption Wavelength and Detection Limit for UV Absorption. ... 19
4 Standard Curves for Analysis by UV Absorption 20
5 Accuracy and Precision Data 20
6 Static Biological Degradation Tests 22
7 Continuous Biological Degradation Tests 24
8 Freundlich Parameters and Capacity of GAC 26
9 Summary of Ozone Oxidation Study Results 27
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ABBREVIATIONS AND SYMBOLS
BNA 3-naphthylamine
BZ benzidine
DCB -- S.S^dichlorobenzidine
DMNA -- dimethylnitrosamine
DPH -- 1,1-diphenylhydrazine
GAC granular activated carbon
HPLC -- high performance liquid chromatography
KD Kuderna-Danish
MOCA -- A.^-methylene-bis (2-chloroaniline)
NAP -- naphthalene
vi 1
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ACKNOWLEDGMENTS
IITRI gratefully acknowledges the cooperation of the National Cancer
Institute, which provided the chemical carcinogens from the NCI repository
and the advice and assistance of R. A. Dobbs, EPA Program Officer, who pro-
vided many valuable suggestions on equipment set-up, analytical procedures,
and data presentation.
Victor Ivanuski, H. J. O'Neill, Christine Rachwalski, Peter Kroll, and
Raleigh Farlow, members of the IITRI staff, contributed to the program.
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SECTION 1
INTRODUCTION
A 1976 survey indicated that many toxic and carcinogenic chemicals were
present in treated municipal wastewater. Some of these compounds are known
to persist in the environment and could very well find their way into drinking
water supplies, Public Law 92-500 and the Toxic Substance Control Act are
aimed at regulating the amount of these toxic substances discharged to the
environment. Public Law 93-523, the Safe Drinking Water Act, placed increased
emphasis on the need to treat wastewater to insure removal of toxic chemicals
to the lowest possible level.
The Environmental Protection Agency has been directed to develop treat-
ment processes to remove toxic organic compounds from water and wastewater.
Many physical, chemical, and biological processes are already available to
reduce the concentration of these toxic chemicals in aqueous solutions to very
low levels. Hundreds of organic compounds have been identified in drinking
water supplies and treatment techniques for meeting the Interim Primary Drink-
ing Water Regulations are being proposed and developed.
The work at IITRI was directed toward the development of treatment tech-
niques to prevent the release of organic chemical carcinogens in municipal
wastewater to the environment.
The chemicals of primary concern were:
naphthalene
diphenylhydrazine
B-naphthylamine
4,4-methylene-bis (2-choroaniline)
dimethylnitrosami ne
benzidine
3,3-dichlorobenzidine
benzanthracene
acrylonitrile
chloromethyl methyl ether
ethyleneimine
The first five compounds of this list were used in three types of treat-
ment; the next two were studied in less detail, exploratory work was conducted^
on an additional two compounds. The five were subjected to three treatment
processes described in this report. Three treatment methods compatible with
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processes currently being considered for municipal wastewater were investi-
gated:
Biodegradation - the treatment method of choice for most
municipal wastewaters
Carbon Adsorption - under very active study and evaluation for
the tertiary treatment of municipal wastewater
Ozone Oxidation - /disinfection - proposed for tertiary treat-
ment of municipal wastewater and plants are
under construction.
While the ideal study technique would utilize municipal wastewater from
many sites as the source water for this study such a program would require a
very large effort to d velop definitive results and probably would not be
cost-effective. For tiiis study a mineralized distilled water contaminated
with the compound of interest was used in order to develop the first level of
information. Later studies may be conducted using wastewater from selected
municipal facilities.
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SECTION 2
CONCLUSIONS
The treatability of five chemical carcinogens in wastewater by biodegra-
dation, carbon adsorption, and ozone oxidation was determined. Biodegradation
was tested in both static and continuous reactors; two commercially available
granular activated carbons were used for determining adsorption; and ozone
oxidation was studied in a 12-liter reactor using 1 percent ozone in oxygen.
naphthalene (NAP)
- NAP was readily degraded in the static biological reactor.
- NAP was fairly easily adsorbed; 29 mg of granular activated
carbon, (GAC) per liter reduced the concentration from 1 ppm
to 0.1 ppm.
- NAP and its decomposition products reacted rapidly with ozone;
half-life of the NAP was dependent upon relative amounts of
the reactants.
- NAP was readily stripped from the aqueous solution.
1,1-diphenylhydrazine (DPH)
- DPH was readily degraded in the static biological reactors.
- DPH was easily adsorbed; 18 mg of GAC per liter reduced the
concentration from 1 ppm to 0.1 ppm.
- DPH was quickly destroyed in the ozone reactor forming
several reaction products.
3-naphthylamine (BNA)
- BNA was only partially degraded in the static biological
reactor but was completely destroyed in the continuous bio-
logical reactor.
- BNA was fairly easily adsorbed; 37 mg of GAC per liter
reduced the concentration from 1.0 ppm to 0.1 ppm.
- BNA did not readily strip from the ozone reactor but did
react with the ozone to give a ha If-life of 1.6 min.
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4,4-methylene-bis (2-chloroaniline) (MOCA}
- MOCA was not degraded in the static biological reactor but
was degraded in the continuous biological reactor.
- MOCA was fairly easily adsorbed; 33 mg of GAC per liter
reduced the concentration from 1.0 ppm to 0.1 ppm.
- MOCA was not stripped from the ozone reactor; its half-life
with ozone was 3 min.
dimethylnitrosamine (DMNA)
- DMNA was partially degraded in the static biological reactors;
concentration was reduced from 50-70 percent. It was destroyed
in the continuous biological reactors; 2 ppm concentrations
were reduced to <0.1 ppm.
- DMNA was not effectively adsorbed by GAC.
- DMNA did not react with ozone nor was it effectively stripped
from the solution.
One objective of the program was to develop treatability tests which
could be used for study of additional compounds. The results for these five
compounds have covered a range of results and indicate broad applicability.
The compounds studied have included:
(1) Compounds treatable in static biological reactors (NAP, DPH)
(2) Compounds not treatable in static biological reactors but treatable
in continuous biological reactors (DMNA, BNA, MOCA)
(3) Compounds that can be adsorbed by GAC (NAP, DPH, BNA, MOCA)
(4) Compounds that not effectively be,adsorbed by GAC, (DMNA)
(5) Compounds that are stripped from a gas-liquid reactor (NAP)
(6) Compounds that cannot be stripped from an ozone reactor but
readily react with ozone (BNA, MOCA)
(7) Compounds that are neither stripped nor reacted in the ozone
reactor.
It was determined that no one treatment process removed all compounds and that
all compounds studied could be treated by at least one of the processes.
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SECTION 3
RECOMMENDATIONS
It is recommended that these treatability studies be continued and ex-
panded. Additional chemical carcinogens found in municipal wastewater should
be studied. The carbon adsorption and ozone oxidation studies should be ex-
panded to include either an actual municipal wastewater or a simulated
municipal wastewater.
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SECTION 4
MATERIALS AND METHODS
SELECTION OF COMPOUNDS TO BE STUDIED
AH of the compounds studied, except for naphthalene, were selected from
the list of 14 chemical carcinogens published by NIOSH. The compounds selec-
ted were chosen on the basis of their stability in water, water solubility,
and the availability of analytical techniques. Solubility data for concen-
trations of interest were very limited.
The investigation of a number of compounds was halted during the program.
These compounds included benz(a)anthracene, 2,7-dichlorodibenzo-p-dioxin,
1,2-diphenylhydrazine, benzidine and 3,3-dichlorobenzidine. Benz(a)anthracene
and 2,7-dichlorodibenzo-p-dioxin were eliminated from consideration because
their solubilities were below the concentration range selected in the experi-
mental protocol (less than 0.3 ppm).
During the carbon adsorption studies it was discovered that 1,2-dipheynl-
hydrazine was unstable and readily converted to azobenzene with time.
1,1-diphenylhydrazine of acceptable purity was substituted for this compound.
The analysis of benzidine proved difficult at the ppm level and below.
The analytical procedure consisted of the following steps: solvent extrac-
tion with methylene chloride, drying and concentration with a K-D evaporation,
and analysis by high performance liquid chromatography with ultraviolet
absorption detection. The recovery of benzidine from mineralized water spiked
at the one ppm level could not be reproduced and varied from 33.0 to 79.9 per-
cent. The method was scrutinized to determine the source of variability in
the analysis. In the drying and concentration steps of the procedure, benzi-
dine recovery was quantitative. In a single experiment it was further shown
that only 55 percent of the benzidine in a sample was recovered by extraction.
Attempts to find the remaining benzidine failed. It was shown that there was
no benzidine remaining in the water sample after the original extraction, and
further there was not benzidine adsorbed onto the surface of the glass separa-
tory funnel. It can only be concluded that the missing benzidine was lost in
some way. The procedure was abandoned at this point since it did not appear
that these difficulties could be easily overcome.
BIOLOGICAL DEGRADATION
A simple static screening test for the assessment of the biodegradability
of organic compounds, reported by Bunch and Chambers,1 formed the basis of the
static tests performed during this study. Bunch and Chambers conducted the
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the test at room temperature using a 200 ml nutrient solution based on yeast
extract in a flask without a shaker. We increased the scale of the test and
used 2,000 ml of solution in 1 gal glass containers in order to obtain a sam-
ple large enough to give reliable analysis.
Bunch and Chambers seeded the nutrient/organic solution with sewage and
allowed the bacteria to act on the nutrient and organic for 7 days. After
analyzing the organic they used a 10 percent aliquot of the 7-day mixture to
seed a fresh nutrient/organic mixture. This procedure was repeated until
28 test-days had been completed.
Baird, Carmonan, and Jenkins2 used conventional Warburg techniques to
assess the toxic effect of selected aromatic amines on organisms found in
typical activated sludges. Their dosage levels exceeded manyfold the solu-
bility levels of some compounds. Gas chromatographic or colormetric analysis
was used. They were able to measure depletion of the organic as well as its
toxic effect on the sewage organisms.
While the Warburg technique permits rapid screening of the toxicity of
compounds it does not confirm the degradation. The limited sample size does
not permit analysis of very low concentrations by current HPLC techniques.
Static reactors are convenient to use and require little equipment, how-
ever, continuous biological reactors better simulate the treatment that
municipal wastewater normally receives. Laboratory reactors can be made to
simulate this continuous biological system. Such units can be operated steady
state and give reliable results if they are carefully designed and operated.
We used a continuous reactor with an aeration chamber of about 300 ml. Sludge
separated in the side arm while treated water overflowed at the top of the
sidearm. Sterilized nutrient solution containing the organic was pumped to
the reactor. The flow through the reactor generally exceeded 1 liter per day,
providing a sample which was adequate for most analyses.
In a study of the biodegradation of benzidine, Tabak and Earth3 used 5.7
liter aerobic suspended growth reactors and the supernatant from settled
domestic wastewater for a 7-week test period. The feed was doped with as high
as 32 ppm of benzidine, which was degraded to 10-12 ppm.
Carbon Adsorption
The adsorption of organics from aqueous solutions has been used in a wide
variety of applications and is currently being evaluated for the purification
of municipal wastewater. Early results have been promising and, if the final
evaluation of carbon adsorption is favorable, there is a real possibility that
the process will be utilized by many municipalities.
V. L. Snoeyink1* studied the adsorption of humic substances in combination
with trace amounts of chlorophenols and polynuclear hydrocarbons at various pH
levels and developed corresponding mathematical descriptions.
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The Freundlich adsorption isotherm is generally used to describe the ad-
sorption equilibrium and can be expressed as:
X
M
1/n
where X is C -C^
C is Amount of organic in the untreated solution
Cf is Amount of organic in the treated solution
M is Weight of adsorbent (carbon)
K is Empirical constant
n is Empirical constant
K is the X intercept of the plot of the isotherm at Cf = 1 and 1/n is the
slope of the line on logarithmic paper.
The equation can be rearranged to permit easy calculation of the carbon
dosage required to reduce an initial concentration to a specified residual
concentration. If (C - Cf) is substituted for X the equation becomes:
Co " Cf . .
This equation is linear when M, the carbon dose, is plotted against C , the
initial concentration, on ordinary coordinate paper.
The isotherm data can be used to calculate countercurrent dosages of
carbon. This technique treats a solution with fresh carbon, and removes the
carbon by filtration. The solution is then treated with a second batch of
fresh carbon, which is also recovered by filtration and used to treat a batch
of the more concentrated feed material.
Although the extensive carbon adsorption literature has reports on the
adsorption of pesticides,5'6 fatty acids,7 amines,8'9 aromatics,8 and chlori-
nated hydrocarbons, there is very limited published data on the adsorption of
carcinogenic compounds at low, 1 mg/£, and lower concentrations
reported here dealt with chemicals identified as carcinogens
Ozone Oxidation
The work
Ozone has long been used to treat drinking water in Europe. Only two
U.S. cities, Philadelphia, Pennsylvania and Whiting, Indiana were treating
drinking water with ozone at the time of the International Conference on Ozone
in Chicago, Illinois in 1959. A Second International Conference in Washington,
D.C. in 19739 appears to have generated more widespread interest in ozone for
drinking water and wastewater treatment. Since 1973 several additional sym-
posia have been held much research and pilot plant data has been generated,
additional treatment plants have been activated, many new plants are being de-
signed, and nine plants are under construction. The current largest U.S.
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plant at Springfield, Missouri, uses 3600 Ibs ozone per day to treat 30 MGD
of municipal wastewater.
In chemical kinetics studies it is usually found that the rate of reac
tion is proportional to the concentrations of the two substances reacting:
§ = -kC[03]
where C is concentration of pollutant, mg/£
[03J is concentration of ozone, mg/H
t is time, min
k is rate constant, £/mg-min
If ozone is present in large excess, then [0.,] will not vary with [C].
Then Equation 1 integrates to
C1
In pi = -k[0,]At (2)
wo »3
where subscripts 1 and 2 refer to times t,
and
At = t2 -
Equation 2 implies that for each interval of time, At, the concentration de-
creases by a constant ratio. If the ratio is 1/2, then At is the half-life.
Thus either half-life or rate constant k is a suitable measure of treatability
by ozone. In these studies we have used half-life of the compound under a
specific set of reactor conditions as a measure of ozone oxidation treat-
ability.
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SECTION 5
EXPERIMENTAL PROCEDURES
GENERAL PROCEDURES
The laboratory procedures used during these studies were based upon pub-
lished reports of the treatment of water containing low concentrations of
organic chemicals and upon in-house experience. The use of carcinogenic
chemicals imposed a number of restrictions and precautions concerning the
amounts of materials, concentrations, laboratory manipulations, protective
clothing, ventilation, and waste disposal.
All standard solutions of carcinogens were prepared and handled by staff
who are under medical surveillance in a facility especially designed for
chemical carcinogens. These staff members also doped the aqueous solutions to
be treated. Analytical staff and the principal laboratory investigator were
also under medical surveillance.
Wastes from the laboratory work were incinerated in equipment which ser-
vices the laboratories using chemical carcinogens.
Since many of the materials studied had limited solubility, in the range
of 2 mg/£, water with very low organic chemical content was prepared by
reverse osmosis, deionization, and filtration through a membrane filter. With
less than 0.01 mg/£ organic carbon, this water caused negligible analytical
background.
The composition of water likely to be encountered in field situations was
simulated with mineralized water. Table 1 describes the composition of the
mineralized water. (Preparation procedures appear in Appendix A).
TABLE 1. COMPOSITION OF MINERALIZED WATER
Ion Cone., mg/£ Ion Cone., mg/£
Na+
K+
Ca++
Mg++
92 PC.*"
12.6 S0,,=
100 Cl~
25.3 alkalinity"*"
10
100
177
200
10
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TREATABILITY STUDIES
Treatability is the removal or decomposition of a compound in water.
Treatability experiments measure the amount of the compaund remaining in the
water after various durations of treatment. Important variables are the
initial concentration of the compound, the duration of treatment, and perhaps
other conditions such as temperature and pH. During this program the experi-
mental procedures for the three basic methods of treatment were established.
Use of these procedures will permit the comparison of the ease of treatment
of various compounds by each treatment procedure.
Biological Degradation
Two types of biological degradation tests, a static test and a continuous
test, were conducted. Those compounds which were not degraded in the static
test were tested in the continuous mode.
The static test, patterned after the procedure o'f Bunch and Chambers,
seeded a 2-liter carcinogen-doped nutrient solution with supernatant liquid
from the mixed liquor return line of the activated sludge wastewater treatment
plant (southwest) of the Metropolitan Sanitary District of Greater Chicago.
The seeded nutrient solution was placed in 1-gallon clear glass bottles
and the desired concentration of carcinogen, usually 2.0 mg/£, was added as an
alcohol solution. The bottles were placed on the bench top and occasionally
agitated during the next 7 days. A 1-liter sample was then taken for analysis,
and another 200 ml was withdrawn to seed a fresh nutrient solution. The mix-
ture was again doped with the desired amount of carcinogen and the test con-
tinued for another 7 days. Visible differences in the apparent viscosity,
color, and turbidity of the solutions were observed.
The continuous tests simulated the activated sludge process on a very
small laboratory scale. Glass reactors (See Figure 1) with a capacity of
approximately 300 ml in the aerated chamber were used. This gave a hold-up
time of 6 hours at a flow of 1.2 liters per day.
The continuous reactors were seeded at start-up with the same material as
used for the static tests. Feed consisted of the same nutrient-carcinogen
doped solution as used with the static test, except that the nutrient solution,
which had to be prepared daily, was heat-sterilized before adding the carcino-
gen. A composite 24-hour sample was taken each seventh day for analysis.
The preparation procedure for the nutrient solution used in both the
static and continuous tests is given in the appendix.
Carbon Adsorption
A series of eight 1-liter glass-stoppered reagent bottles were used for
each carbon adsorption isotherm determination. Automatic pipettes were used
to charge clean and well-rinsed bottles with a known amount of an aqueous
suspension of activated carbon of known concentration. The bottles were
filled with the doped water to the bottom of the stopper to avoid ullage over
11
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WATER
OVERFLOW
SLUDGE
CHAMBER
RECIRCULATING
ARM
Figure 1. Drawing of continuous biological reactor.
12
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the solution. The suspensions were agitated with magnetic stirrers for at
least 2 hours before removing a sample for analysis.
Six carbon-adsorption samples were obtained from the eight bottles. One
bottle served as a control and did not receive any carbon nor was it filtered.
A second bottle did not receive carbon but was filtered. These two samples
served as an analytical control for assessing' the role of filtration in re-
moving the organic from the water. Initial studies indicated that glass fiber
filters adsorbed only very small amounts of the organic. The filtered sample
also indicated whether or not the organic was completely dissolved or re-
mained as finely, divided undissolved particles.
Two granular activated carbons, Filtrasorb 400 and Darco KB, were used to
assess adsorption characteristics of the organic. The granular carbons were
ball-milled for 24 hours, then sieved. The process was repeated until 90-95
percent of the material passed the 200 mesh screen. The minus 200 mesh
material was composited and used for the entire program.
Samples were analyzed by u.v. absorption or by extraction, concentration,
and HPLC, with a u.v. detector or capillary gas chromatograph with a nitrogen
detector.
Ozone Oxidation
The ozone treatability studies assessed the technical feasibility of re-
ducing organic carcinogens to acceptable concentration by oxidation with
ozone.
The laboratory equipment and procedures selected for the ozone treat-
ability studies were derived from many technical and mechanical/physical
considerations as listed below.
Technical Factors--
1. The reactor must provide for good mass transfer of the ozone from
the gas to the liquid.
2. It must be possible to measure or make a reasonable estimate of the
ozone concentration in the water.
3. Concentrations must permit measurement of reaction times.
4. Stripping of the contaminant must be determined.
5. Compensation for ozone autodecomposition may be necessary.
6. Detection of any by-products remaining in the water is desirable.
Operational Factors--
1. The reactor must be sufficiently large to permit withdrawal of
approximately five samples, as large as 1 liter each, during a
run and continue to function effectively.
13
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2. The reactor must be as small as practical to minimize the amount
of carcinogen that must be handled.
3. The reactor must be capable of easy decontamination.
4. Ozone concentration in the gas must be representative of that either
currently used or proposed by engineers designing plant installations.
Initially, ozone concentration was measured in the gas and in the water
by the standard methods. Later, ozone concentration in the gas was measured
with a Dasibi Environmental Corp. ozone monitor and in the water with a Delta
Scientific Co. ozone monitor. The equilibrium ozone concentration in water
was found to be close to that reported in the literature. The Welsbach liter-
ature gives:
mg/£ 03 in water = n 20 fat 30°C)
mg/£ 03 in 02 '
The concentration of ozone in the water under treatment is a function of
the concentration in the gas, the supply rate, temperature, autodecomposition,
and the reaction with dissolved organics. The autodecomposition rate is
highly dependent upon pH.
Since the organic, especially volatile, compounds, may be stripped from
the solution by the gas, it is important that the gas flow rate be represen-
tative of the flow rate that may be encountered in the field.
Gloyna and Eckenfelder11 give an example of diffused aeration where
3,400 cfm is used in an 81,000 cu ft tank, or 0.042 liters of air per liter of
water. This value is based upon a biological aeration system and is lower
than the gas flow rate used by investigators studying the effect of ozone.
Lambert12 relates that five different research teams investigating the
effect of temperature on the ozonation of simulated mobile hospital wastewater
reported widely varying results. He attributes part of the variance to the
widely different ozone reactors, which ranged from round-bottom flasks, to
commercially available fermentors, to pilot-scale, multi-stage continuously-
stirred tank reactors.
See13 used a flow rate of 23.6 liters per minute in a 14-liter stirred
reactor or 1.7 liters of gas per minute per liter of water in his study of the
treatment of a mobile hospital wastewater.
Pileg11* used a small, 1-liter reactor, and a gas flow of 40 liters per
hour or 0.67 liters per minute of gas per liter of reactor volume in a study
of two different types of municipal wastewater.
Shambaugh and Melnyk15 used a 1-liter stirred reactor equipped with a
sparger and a gas flow of 0.6 liters per minute. At 1 wt% ozone in the gas,
the water reached a concentration of about 0.5 mg 03/liter after 90 seconds.
This is approximately the equilibrium concentration at pH = 9. A study ef the
relative rates of mass transfer and ozone decomposition at various pH levels
14
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showed that a pH change from 8.0 to 9.0 decreased the steady state ozone con-
centration in their reactor by a factor of three.
Rosen16 cites operating and planned ozone dosages as:
Location Ozone Dose
Woodlands, TX 8 mg/£
Indiantown, FL 10
Estes Park, CO 6
Mahoning Co. , OH 6
Springfield, MO 10
Pensacola, FL 6
Armstrong17 states that an ozone dose of 3.25 mg/£ was required for dis-
infection of secondary treatment plant effluent.
Naimie18 noted the relationship between ozone demand and suspended
solids for a pure oxygen activated sludge system as:
Water Analysis, Ozone Demand
TSS COD
Filtered Effluent 0 30 1.0-2.5
Gravity Filtered 6 30 1.5-4
Unfiltered 15-30 30 3.5 - 8.5
Since most municipal secondary treatment effluents contain 20 mg/£ Total
Suspended Solids, an ozone demand of 8 mg/£ may be realistic.
Selection of the gas flow rate for the laboratory studies is important
since the flow rate affects the rate of stripping of the organic from the
water. Dilling19 gives the evaporation as:
H = C air = 16.04 PM
C water TS
where H is Henry's law constant
C
air is equilibrium concentration in air
r
water is equilibrium concentration in water
P is vapor pressure of pure solute in mmHg
M is gram molecular wt of solute
T is temperature, °K
S is solubility of solute in water mg/£.
15
-------
This equation gives an indication of the stripping of the organic; how-
eve'r, the limited solubility and vapor pressure data restricts the use.
On the basis of this brief review and our in-house experience it was de
cided to set up the ozone treatability reactor as follows:
Reactor volume:
Reactor diameter:
Reactor height:
Agitator:
Sparger:
Gas flow:
Ozone concentration:
Ozone dose rate:
12 liters
8% in.
14 in.
4-blade turbine
coarse glass frit
2.4 £pm
1 wt%
" » fcfe? *
pH: 7.5
Temperature: ambient, 25°C.
ANALYTICAL PROCEDURES
Wherever possible, analytical procedures used in the program were based
upon published EPA procedures. Analytical techniques involved HPLC, u.v.
absorption, and capillary gas chromatography.
High Performance Liquid Chromatography (HPLC) - Ultraviolet Adsorption
The volume of the sample was measured in a graduated cylinder, and the
sample was transferred to a 2-liter separatory funnel. The graduated cylin-
der was washed with the extracting solvent (distilled-in-glass methylene
chloride) which was then transferred to the separatory funnel.
Neutral Extraction--
The sample was serially extracted with three portions of methylene
chloride. In the case of a liter sample, 400 X 150 X 150 ml portions were
used. Each sample was extracted for 1 minute by the clock. In cases where
the concentration was known to be high (>2 ppm) a proportionally small amount
of sample was used.
Basic Extraction--
The pH of the sample was adjusted to 11 or greater with 6N NaOH using
multi-range pH paper. The sample was extracted as described in the neutral
extraction.
16
-------
Acid Extraction--
The pH of the sample was adjusted to 2 or less with 6N HC£ using multi-
range pH paper. It was extracted as described in the neutral extraction.
Extract Drying
The combined solvent extracts were dried and filtered by passing these
through a short column of anhydrous sodium sulfate which had been prewashed
in the column with methylene chloride. After drying the extract, the sodium
sulfate was rinsed with the extracting solvent which was added to the extract.
Extract Concentration--
The solvent extract was concentrated to ^20 ml in a Kuderna-Danish (KD)
apparatus fitted with a 3-ball macro-Snyder column and a 10-ml calibrated
receiver tube. Then 5 ml of distilled-in-glass methanol were added and the
extracts were evaporated to 5 ml. When the KD apparatus had cooled to room
temperature, the receiver was removed and a micro-Snyder column was attached.
The extract was carefully evaporated to a volume suitable for analysis usually
3 ml, and the internal standard, phenanthrene, was added.
Samples not analyzed immediately were stored in amber vials with Teflon
inserts at refrigerator temperatures. No loss of methylene chloride was
observed during storage if the vials were tightly sealed.
High Performance Liquid Chromatographic Analysis--
The samples were analyzed on a Waters Model 244 ALC/GPC liquid chromato-
graph equipped with a Model 660 Solvent Programmer for gradient elution and a
Schoeffel HS870 ultraviolet absorption detector. Elution of the samples on a
30 cm x 4 mm Bondapak Ci8 column was achieved using a methanol water gradient
going from 60 percent to 100 percent methanol in 20 minutes.
These elution conditions were used for 3-naphthylamine, 1,1-diphenyl-
hydrazine, and 4,4'-methylene-b.is(2-chloroaniline). In the case of naphtha-
lene, the samples were eluted isocratically at a solvent composition of 80
percent methanol:20 percent water. The solvent flow rate was 2 ml per minute
in all cases. Table 2 provides the absorption wavelength used for each com-
pound, and the limit of detection for each.
High Resolution Gas Chromatography - Flame lonization Detection
This procedure was used for the analysis of benzidine and 3,3-dichloro-
benzidine and is a modification of one reported by M. Bowman and C. Nony.18
The volume of the sample was measured in a graduated cylinder and the
sample was transferred to a 500 ml liter separatory funnel. The graduated
cylinder was washed with the extracting solvent (distilled-in-glass benzene)
and this was transferred to the separatory funnel.
Basic Extraction--
The pH of the solution was adjusted to 11 or greater with 6N NaOH using
multi-range pH paper. The sample, usually 250 ml, was extracted with three
portions of benzene 40 x 20 x 20 ml.
17
-------
TABLE 2. ABSORPTION WAVELENGTH AND LIMITS OF DETECTION USING HPLC
Compound
Absorption
Wavelength (nm)
Detection Limit
Naphthalene
3-Naphthalene
4,4'-Methylene-bis(2-chloroaniline)
1 , 1-Di phenyl hydrazi ne
Benzidine
280
280
280
280
265
100 ng
80 ng
60 ng
100 ng
60 ng
Extract Drying
The combined solvent extracts were dried and filtered by passing these
through a short column of anhydrous sodium sulfate. The sodium sulfate was
prewashed in the column with benzene. After drying the sodium sulfate was
rinsed with the extracting solvent and this was added to the extract.
Extract Concentration--
The solvent extract was concentrated to 2 ml in a Kuderna-Danish appara-
tus fitted with a 3-ball macro-Snyder column, and a 4 ml calibrated receiver
tube. The concentration was performed under a slight vacuum, obtained using
a water aspirator.
Derivatization--
A pentafluoropropronic anhydride (PFP) derivative was prepared for the
aromatic amines, benzidine and 3,3-dichlorobenzidine. In this procedure, one
drop of triethyl amine was added to the sample (^2 ml) in a 20 ml vial,
followed by the addition of .5 ml of PFP reagent. The tube was immediately
sealed, shaken, and heated in a 50°C water bath for 20 minutes. The reaction
was terminated by adding 5 ml of phosphate buffer, pH - 6.0. The tube was
shaken for 1 minute, and after the phases were separated, the aqueous layer
was discarded. The extraction was repeated with an additional 5 ml of buffer.
The benzene layer was separated and the internal standard, 2,6-dimethylnaph-
thalene, was added. The sample was then analyzed by high resolution gas
chromatography.
A Hewlett Packard Model 5840A gas chromatograph was used for the analy-
ses. The samples were chromatographed on a 25 meter OV-17 glass capillary
column. The chromatographic conditions are given below.
initial temperature - 150°C held for 6 min after injection
program - 150°C to 225°C at a rate of 4° per minute
flow - 7 cm3/sec
split - 19/1
attenuation - 16 x 10°12 amps/mv
18
-------
The limit of detection was 50 nanograms for each compound.
Spectrophotometric Analysis
Concentration of aromatic compounds were measured in the carbon absorp-
tion experiments through Spectrophotometric analysis. Ultraviolet absorption
was measured by Gary 14 spectrophotometer with 1 and 10-cm cells. All dilu-
tions of the compounds were freshly prepared in mineralized water. (The
absorption wavelengths utilized are given in Table 3). Readings were correc-
ted for solvent blanks, and absorptions were plotted vs. concentrations for
the compounds to produce a standard curve. (Data for the calibration curves
are given in Table 4).
QUALITY CONTROL
Reagent Control
Each time a sample or group of samples was to be analyzed, a standard
solution containing the internal standard and the compound under analysis were
analyzed to maintain instrument control. Duplicate analyses were found to
agree to within +_ 2%. The records of these analyses were kept with the sample
and blank records. A blank is an experiment that undergoes all analytical
procedures, except that no compound other than the internal standard is
present.
Data Control
All experimental data was recorded on laboratory data sheets and trans-
cribed into bound IITRI logbooks.
Accuracy and Precision
The accuracy and precision of the high performance liquid chromatography
is given in Table 5. Duplicate analyses were performed on water samples
spiked with individual compounds at the level of 0.5 ppm.
TABLE 3. ABSORPTION WAVELENGTH AND DETECTION LIMIT FOR UV ABSORPTION
Compound Wavelength (nm) Detection Limit (ppm)
Benzidine
3-Naphthylamine
4,4'-Methylene-bis(2-chloroaniline)
Naphthalene
1 , 1-Di phenyl hydrazi ne
281
285
240
276
230
0.17
0.08
0.30
0.20
0.05
19
-------
TABLE 4. STANDARD CURVES FOR ANALYSIS BY UV ABSORPTION
Compound m b
Benzidine 7.306 -0.0887
Naphthalene 3.9330 -0.0820
4,4-Methylene 2.0606 -0.0225
b1s(2-chloro-
aniline)
1,1-Dlphenyl- 16.487 +0.067
hydrazine
$-Naphthylam1ne 28.075 +0.091
r
0.99999 1.0 cm cell
X = 281.5 nm
0.9998 10 cm cell
X = 276 nm
0.999 10 cm cell
X = 240 nm
0.998 1.0 cm cell
X = 230 nm
0.999 1.0 cm cell
X = 285 nm
X
Y
Y
m
b
r
X
= optical density (O.D.).
= mX + b (equation of the line obtained
of the calibration)
= compound concentration (mg/£).
= slope of the line.
= intercept.
= correlation coefficient.
= wavelength.
TABLE 5. ACCURACY AND
by linear regression analysis
PRECISION DATA
Compound
1 , 1-Di phenyl hydrazi ne
4,4'-Methylene-bis(2-chloroaniline)
3-Naphythylamine
Naphthalene
Percent Recovery
83.3 + 4.4
84.0 + 3.2
99.7 +2.4
95.4 + 1.2
20
-------
SECTION 6
RESULTS AND DISCUSSION
The three procedures used to treat dilute aqueous solutions of these
carcinogens resulted in a range of removal. Some compounds were almost com-
pletely removed by one treatment procedure, whereas other treatment procedures
were ineffective. The range of treatability of each compound for each process
is discussed in the following sections.
BIOLOGICAL DEGRADATION
Two types of biological degradation were used: a static and a continuous
system. Those compounds which were not degraded during static tests were
treated in a continuous biological reactor.
Static Biological Degradation Tests
All of the compounds under study were screened by the static biological
test. In these test biological seed from an activated sludge plant were
supplied with the nutrient solution which had been doped with approximately
2 ppm of the carcinogen. The growth was allowed to continue for 7 days, a
sample removed, and a fresh doped nutrient solution seeded with 10 percent
of the solution from the previous week. Results of these tests are presented
in Table 6.
Naphthalene was readily degraded during the static biological test.
After a weeks acclimatization, the naphthalene was reduced from 2 ppm to non-
detectable during the 7-day test.
1,1-Diphenylhydrazine was also reduced from 2 ppm to nondetectable levels
during the 7-day biological test.
g-Naphthylamine was reduced by about 40 percent (2.15 to 1.26 mg/£) after
a 10-week acclimatization period.
4,4'-Methylene-bis(2-ch1oroam'1ine) was not effectively biologically de-
composed during the static tests.
Dimethylnitrosamine was partially decomposed in the static biological
tests.
21
-------
TABLE 6. STATIC BIOLOGICAL DEGRADATION TESTS (All values in mg/£)
ro
IN)
Original Culture
Doped
7- Day
1st Sub-Culture
Doped
7- Day
2nd Sub-Culture
Doped
7 -Day
3rd Sub-Culture
Doped
7- Day
4th Sub-Culture
Doped
7- Day
5th Sub-Culture
Doped
7- Day
6th Sub-Culture
Doped
7- Day
Naphthalene
1.97
0.12
1.76
N.D.
2.02
N.D.
2.12
0.06
1.98
N.D.
1.95
N.D.
1.96
N.D.
Di methyl -
nitrosamine
1.82
0.52
1.88
0.52
1.88
1.0
2.33
1.0
1.98
0.9
2.30
1.40
1,1-Diphenyl-
hydrazine
2.02
Lost
2.24
1.20
2.15
1.03
2.48
N.D.
2.05
N.D.
2.32
N.D.
2.17
N.D.
3-Naphthyl-
amine
2.07
1.04
1.77
1.67
1.73
1.78
1.92
1.91
2.25
2.00
1.96
1.30
2.04
1.66
4,4'-Methylene-
bis(2-chloro-
aniline)
2.12
1.90
2.16
2.42
2.08
2.31
1.81
1.76
2.11
2.09
2.10
1.95
2.01
1.89
(continued)
-------
TABLE 6 (continued)
4,4'-Methylene-
Dimethyl- 1,1-Diphenyl- 3-Naphthyl- bis(2-chloro-
Naphthalene nitrosamine hydrazine amine aniline)
7th Sub-Culture
Doped -- 1.74
7-Day -- - 1.07
8th Sub-Culture
Doped -- -- -- 2.42
7-Day -- 1.77
9th Sub-Culture
Doped -- -- -- 1.93
^ 7-Day 1.53
CO
10th Sub-Culture
Doped -- -- 2.15
7-Day -- 1.21
llth Sub-Culture
Doped -- -- -- 2.15
7-Day 1.26
stop
N.D. = nondetectable.
-------
Continuous Biological Reactor Tests
Three compounds were tested using the continuous biological reactors:
4,4-methylene-bis (2-chloroaniline)
dimethylnitrosamine
g-naphthylamine
Fresh nutrient solution was prepared and doped every day. Table 7 records the
level of contaminant in the nutrient solution given on the day before the ef-
fluent sample was collected. Thus, the nutrient solution containing 1.78 mg/&
dimethylnitrosamine was started through the system on the 6th day of the test
and the effluent was collected for the next 24 hours and analyzed (0.42 mg/£).
TABLE 7. CONTINUOUS BIOLOGICAL DEGRADATION TESTS (All values
Day of Test
6 Doped
7 Effluent
13 Doped
14 Effluent
20 Doped
21 Effluent
27 Doped
28 Effluent
34 Doped
35 Effluent
41 Doped
42 Effluent
Di methyl -
nitrosamine
1.78
0.42
1.86
0.27
2.29
0.08
2.29
0.1
1.93
<0.01
2.24
6-Naphthyl-
amine
2.11
0.28
2.03
0.25
1.79
.32
1.80
1.93
.09
2.20
N.D.
4,4'-Methylene-bis
(2-chloroaniline)
2.02
0.09
2.00
0.09
2.19
N.D.
2.33
0.13
1.95
0.05
1.79
N.D.
Dimethylnitrosamine was readily decomposed in the continuous biological
reactor. Concentrations of 2.29 mg/£ were reduced to between 0.09 and 0.01
mg/£. The side arm and recirculation leg of the reactor clogged with large
floes and some floe remained in the aerated chamber.
4.4'-Methy1ene-bis (2-chloroaniline) was degraded from 2.02 to 0.09 mg/£
in the biological reactor. Small white floes formed and circulated freely
throughout the system.
24
-------
3-Naphthylanrine was readily decomposed in the continuous biological re-
actor; it was reduced from 2.11 to 0.22 mg/& at the end of the first week and
during extended operation the biomass appeared to adapt to the BNA until at
6 weeks it was reduced from 2.20 mg/£ to non-detectable (<0.1 ppm).
CARBON ADSORPTION
All carbon adsorption studies were conducted to determine the isotherms
using two commercially available granulated activated carbons, Darco KB and
Filtrasorb 400. Table 8 presents the results for each compound studied, giv-
ing the Freundlich parameters, correlation coefficients, and adsorption
capacity of each carbon for each compound. Isotherms and actual data are
given in the appendix.
The adsorption capacity of the carbons varied about twofold for those
compounds that were adsorbed. The compounds absorbed had very limited solu-
bility, while the DMNA was readily soluble and was not adsorbed.
OZONE OXIDATION
Most of the compounds studied were oxidized by ozone; for some, products
of the oxidation were observed during the analysis.
For these treatability studies the half-life of the compound was used to
characterize the reactivity or treatability. Correction was made for the
stripping of the compound from solution by the oxygen. Some compounds reacted
with the oxygen-saturated water without application of ozone. The compounds
studied and the method of test indicated a wide spread in the stripping and
ozone reactivity of the compounds. Compounds such as MOCA and DMNA were very
stable to oxygen stripping. DMNA was stable to ozone oxidation while MOCA was
readily degraded. Data for each of these compounds are presented in the
appendix and summarized in Table 9.
Ozone solubility in water in equilibrium with 1 percent ozone in oxygen
was about 3 to 4 mg/£ at the conditions of the test. This is not a large
excess of ozone and at times the rate of disappearance of the compound of in-
terest may have been limited by ozone concentration. Naphthalene can illus-
trate this point. One would expect that several different reactions are
involved in the oxidation of naphthalene to carbon dioxide and water. First
the primary reaction involving naphthalene and the formation of a secondary
compound. This secondary compound (and subsequent degradation products) com-
pete for the available ozone. If the secondary products have a reaction rate
with ozone much greater than the NAP/ozone rate the ozone in the system is de-
pleted until the secondary product is consumed.
The above considerations make it necessary to compare the ozone oxidation
characteristics of compounds under identical experimental conditions.
25
-------
TABLE 8. FREUNDLICH PARAMETERS AND CAPACITY OF GAC
Mol.
Compounds wt
Naphthalene 128
Darco
Filtrasorb
1,1-Diphenyl-
hydrazine 184
Darco
Filtrasorb
3-Naphthylamine 143
Darco
Filtrasorb
4,4'-Methylene-bis
(2-chloroaniline) 264
Darco
Filtrasorb
Dimethyl nitrosamine 74
Darco
Filtrasorb
Freundlich
Parameters
PH
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
K
58
176
92
135
67
150
93
188
1.4xlO"6
6.8xlO~5
I7n
0.276
0.524
0.257
0.158
0.395
0.302
0.554
0.637
8.15
6.57
Correl .
Coef.
0.982
0.993
0.918
0.751
0.819
0.939
0.957
0.895
0.715
0.617
Adsorption mg Carbon per
Capacity Liter to Reduce
at 1 ppm from 1.0 mg/£
mg/gm Carbon to 0.1 mg/£
58
176
92
135
67
150
93
188
1.4xlO"6
6.8xlO"5
28
17
19
10
36
12
35
21
--
-------
TABLE 9. SUMMARY OF OZONE OXIDATION STUDY RESULTS
Compound
Naphthalene
1 , 1-Di phenyl hydrazi ne
3-Naphthylamine
4,4'-Methylene-bis
(2-chloroaniline)
Di methyl nitrosamine
Stripping
half-life, min.
(1)
0.5
<45
(3)
(4)
Ozone reaction
half-life, min.
(2)
0.4
1.6
(5)
(5)
(1) Readily stripped; half-life time dependent upon gas flow and initial
concentration.
(2) Fast reaction; half-life time dependent upon initial concentration
and ozone feed rate.
(3) Not stripped; <1% in 40 min.
(4) Not stripped; <1% in 130 min.
(5) No reaction; <1% in 130 min.
The HPLC results for naphthalene are given in Figure 2. The compound
plus an internal standard is indicated. Two minutes after the start of the
reaction a second compound appeared and increased in concentration through the
70-minute reaction period. No attempt was made to identify this compound.
During this time the ozone concentration in the solution was less than the
saturation value, thus indicating the reaction was mass-transfer limited.
When B-naphthylamine was reacted with ozone it was very rapidly degraded.
The analysis of the samples taken during the first 4.5 minutes of the reaction
are shown in Figure 3.
The ozonation of 1,1-diphenylhydrazine resulted in several by-products as
indicated in Figure 4.
27
-------
NAPHTHALENE/Oj SAMPLE (M2778-1A
INJECTION VOLUME 20 P*
TIME: IMMEDIATELY FOLLOWING
ADDITION OF NAPHTHALENE]
TO THE REACTOR
NAPHTHALENE/Oj SAMPLE CW2778-2A
INJECTION VOLUME 20 U*
TIME: 2 MINUTES
NAPHTHALENE/0? SAMPLE
042778-3A
INJECTION VOLUME 20 V1
TIME: 5 MINUTES
NAPHTHALENE/0- SAMPL
INJECTION VOLUME 20
TIME: 10 MINUTES
NAPHTHALENE/0^
INJECTION VOLUME 12 ft
TIME: 20 MINUTES
SAMPLE 042773-5A
NAPHTHALENE/0-j SAMPLE 042778-6A
INJECTION VOLUME 12 Ml
TIME: 40 MINUTES
1
NAPHTHALENE/Oj SAMPLE 012778-7A
INJECTION VOLUME
TIME: 70 MINUTES
15
FIGURE 2. HPLC ANALYSIS OF OZONATED NAPHTHALENE 5 MICRON ZORBOX ODS IN A 4,6 MM x 25.0 CM
COLUMN; SOLVENT: METHANOL: WATER (80:20, v;v); ISOCRATIC ELUTION FLOW RATE:
1 M*/MIN; 25°c; 1500 PSI; DETECTION: uu AT 280 MM; SENSITIVITY 1,0 AUFS
28
-------
B-NAPHTHYLAMINE/Oj SAMPLE
041878-lA
INJECTION VOLUME 20 V»-
TIME: IMMEDIATELY FOLLOWING THE
ADDITION OF 3-NAPHTHYLAMINE
TO THE REACTOR
B-NAPHTHYLAMINE/Oj SAMPLE 041878-2A
INJECTION VOLUME - 20 U*
TIME: 1,5 MINUTES
B-NAPHTHYLAMINE/Oj SAMPLE 041878-3A
INJECTION VOLUME - 20 Vs-
TIME: 4,5 MINUTES
FIGURE 3, HPLC ANALYSIS OF OZONATED B-NAPHTHYLAMINE 10 MICRON v BONDPAK CIS COLUMN IN
A 4,0 MM x 30,0 CM COLUMN; SOLVENT: METHANOL: WATER (60:40, v;v) PLUS 1%
ACETIC ACID; LINEAR GRADIENT ELUTION, 60% METHANOL TO 100% METHANOL IN 20
MINUTES; FLOW RATE 2 M'/MIN; 25 c; 1500 PSI; DETECTION: uv AT 280 NM;
SENSITIVITY 1,0 AUFS
29
-------
Ijl-DIPHENYLHYDRAZINE/Uj SAMPLE
041378-lA
INJECTION VOLUME 15 ,,£
SENSITIVITY 1,0 AUFS
TIME: IMMEDIATELY FOLLOWING THE
ADDITION OF 1,1
DIPHENYLHYDRAZINE TO THE
REACTOR
1,1-DIPHENYLHYDRAZINE/Oj
INJECTION VOLUME 15 u?
SENSITIVITY 1.0 AUFS
TIME: 2 MINUTES
SAMPLE 041378-2A
1,1-DIPHENYLriDRAZIN^
INJECTION VOLUME 25 pJ<.J
SENSITIVITY 0.1 AUFS
TIME: 6 MINUTES
SAMPLE 041378-3A
FIGURE 4, HPLC ANALYSIS OF OZONATED 1,1 DIPHENYLHYDRAZINE in MICRON p BONDAPAK c!8 IN
A 4,0 MM X 30,0 CM COLUMNJ SOLVENT: METHANOL: WATER (60:40, v; v) PLUS 17.
ACETIC ACIDJ LINEAR GRADIENT ELUTION, 60% TO 100% METHANOL IN 20 MINUTES; FLOW
RATE, 2 M*/MINj 25°Cj 1500 PSIj DETECTION: Uv AT 280 NM
30
-------
REFERENCES
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31
-------
REFERENCES (continued)
13. See, G. G., K. K. Kachalia, and T. S. Stenson. Research & Development
of an Ozone Contractor for the Oxidation of Refractory Organics. Forum
on Ozone Disinfection. International Ozone Institute, Syracuse, New York,
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14. Pileg, M., D. Mador, R. Kalbo, E. Katzenelson, and H. Shuval. Chemical
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New York, 1977.
15. Shambough, R. L., and P. B. Melnyk. The Influence of Spontaneous Decom-
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Ozone Disinfection. International Ozone Institute, Syracuse, New York,
1977.
16. Rosen, H. M. Ozone Wastewater Disinfection State-of-the-Art. Forum on
Ozone Disinfection. International Ozone Institute, Syracuse, New York,
1977.
17. Armstrong, E. T. Ozone Disinfection of Wastewater Optimum System Design.
Forum on Ozone Disinfection. International Ozone Institute, Syracuse,
New York, 1977.
18. Naimie, H. Ozone, An Alternative to Chlorine Disinfection, A Comparative
Cost Estimate. Forum on Ozone Disinfection. International Ozone Insti-
tute, Syracuse, New York, 1977.
19. Dilling, W. L. Evaporation Rates of Chloromethanes, Ethanes, Ethylenes,
Propanes, and Propylenes from Dilute Aqueous Solution. E.S.T., 2(4):
405, 1977.
20. Bowman, M. C., J. R. King, and C. L. Holer. Benzidine and Congeners:
Analytical Chemical Properties and Trace Analysis in Fine Substrates.
International J. Environmental Anal. Chem., 4: 205, 1976.
21. Bowman, M. C., and L. G. Rushing. Trace Analysis of 3,3-Dichlorobenzi-
dine in Animal Chow, Wastewater, and Human Urine by Three Gas Chromato-
graphic Procedures. Arch. Environ. Contam. andToxicol., 6: 471-482,
1977.
22. Rinde, E., and W. Troll. Colormetric Assay for Aromatic Amine. Anal.
Chem., 48(3): 544, 1976.
32
-------
REFERENCES (continued)
23. Schulze, J., C. Ganz, and D. Parkes. Determination of Trace Quantities
of Aromatic Amines in Dye Stuff. Anal. Chem., 50(1): 171, 1978.
24. Wood, G., and J. W. Nickols. Sampling and Analysis of Organic Bases in
Air. Presented at the American Industrial Hygiene Conference, May 7-12,
1978, Los Angeles, California.
25. Nony, C. R., and M. C. Bowman. Carcinogens and Analogs: Trace Analysis
of Thirteen Compounds in Admixture in Wastewater and Human Urine.
Intern. J. Environ. Anal. Chem. Submitted for publication.
26. Private Communication, F. K. Kawahara, EPA, Environmental Monitoring and
Support Laboratory, Cincinnati, Ohio, March 1978
33
-------
APPENDIX A
OZONE REACTION DATA
TABLE A-l. STRIPPING AND OZONATION OF NAPHTHALENE (25°C)
Oxygen
Time
(min)
Flow
Wt. %
03
Ozone in Water
pH
Naphthalene
mg/£
STRIPPING
0
2
5
10
20
40
2.4
2.4
2.4
2.4
2.4
2.4
0
0
0
0
0
0
0
0
0
0
0
0
___
6.48
5.91
5.93
2.54
3.49
OZONATION
0
2
5
10
20
40
70
2.4
2.4
2.4
2.4
2.4
2.4
2.4
0.8
0.8
0.90
.98
.97
.97
.98
0.0
0.7
.85
.30
.15
.12
.05
8.2
8.0
7.9
8.2
___
8.2
w » _
7.36
6.54
5.97
5.24
3.48
1.46
1.16
34
-------
TABLE A-2. STRIPPING AND OZONATION OF 1.1 DIPHENYLHYDRAZINE
(25°C)
Time
(min)
Gas Flow Wt. % 1,1-Diphenyl-
£/min Ozone hydrazine, mg/&
STRIPPING
0
1
7
12
22
2.4
2.4
2.4
2.4
2.4
0
0
0
0
0
9.98
2.88
0.86
N.D.1
N.D.2
OZONATION
0
2
6
12
30
2.4
2.4
2.4
2.4
2.4
1.00
1.01
1.01
1.00
1.01
9.9
0.35
N.D.3
N.D.3
N.D.
N.D. = Nondetectable.
Secondary products, 13 peaks on hplc.
215 peaks on hplc.
320 peaks on hplc.
35
-------
TABLE A-3. STRIPPING AND OZONATION OF g-NAPHTHYLAMINE
(24°C)
Time
(min)
Gas Flow
5,/min
Wt. %
Ozone pH
3-Naphthylamine
mg/£
STRIPPING
0
5
15
25
45
2.4
2.4
2.4
2.4
2.4
0
0
0
0
0
11.6
11.6
11.2
12.2
11.3
OZONATION
0
1.5
4.5
10
20
40
2.4
2.4
2.4
2.4
2.4
2.4
1.00 -
1.02 8.0
1.03 8.1
1.03 6.8
1.01 6.4
1.01 6.6
11.0
5.94
.Ol1
.082
.062
.042
U peaks on hplc.
Decomposition products caused some interference.
36
-------
TABLE A-4. STRIPPING AND OZQNATION OF 4,4'-METHYLENE-BIS(2-CHLOROANILINE)
Time
(min)
Gas Flow
£/min
Ozone
Wt. %
pH
MOCA
mg/Z
STRIPPING
0
2
5
10
20
40
2.4
2.4
2.4
2.4
2.4
2.4
0
0
0
0
0
0
1.59
1.82
1.81
1.75
1.69
1.77
OZONATION
0
2
5
10
20
40
70
100
2.4
2.4
2.4
2.4
2.4
2.4
2.4
2.4
1.10
1.08
1.07
1.07
1.06
1.00
1.00
0.99
7.0
7.5
8.2
7.0
7
7
7
7
1.52
1.01
N.D.*
N.D.
N.D.
N.D.
N.D.
N.D.
*N.D. = Nondetectable.
37
-------
TABLE A-5. STRIPPING AND OZONATION OF N-DIMETHYLNITROSAMINE
Time
(mln)
0
2
4
8
15
30
60
90
120
0
2
5
11
20
40
70
100
130
Ozone
Wt. X, Gas
0
1.06
1.05
1.07
1.00
1.00
1.00
1.00
1.00
0
1.00
1.02
1.02
1.01
1.00
1.01
1.01
1.00
pH
8.8
9.0
8.9
8.3
8.2
8.2
7.3
6.3
4.5
0
0
0
0
4.7
4.5
Ozone
ppm in H20
0.05
3.9
4.3
4.3
3.3
2.5
2.0
2.0
2.1
,05
.05
.5
4.6
3.8
3.4
4.1
4.2
3.7
N-DMNA
(rag/A)
10
7
6
6
6
5
5
5
5
35*
29
39
39
33
30
31
29
30
*Run made with distilled water in place of mineralized water.
38
-------
CARBON ADSORPTION DATA
COMPOUND: Naphthalene/Darco
STRUCTURE:
FORMULA:
MOL. WT.
128.19
FREUNDLICH
PARAMETERS
K
1/n
Corr. Coef. r
INITIAL CONC. mg/l
10
1.0
0.1
PH
7.5
58.3
0.276
0.982
ADSORPTION CAPACITY, mg/gm
110
58
30.. 9
CARBON DOSES REQUIRED TO ACHIEVE INDICATED CHANGE
IN CONCENTRATION^
Cf, mg/l
Co, mg/l
10
1.0
0.1
0.01
1.0
154
--
--
0.1
312
28
--
--
0.01
611
61
6
--
0.001
1154
12
1
--
(a) Carbon doses in mg/l at neutral pH.
REMARKS:
39
-------
Naphthalene/Darco
:
8
6
4
Z
o 3
CO
(X 2
o
p 1
^> 8
X 6
Q
UJ 4
S
8 3
D
O> i
E 8
3
2
1
W"
100
10
i
.*-*
^
. -
<*
**
^
^
^
«
^--^«^^
^--^
k
*»
^*
^
>
.^^
A
. '
***
*
+»
*-
2 3456789 2 34567891 2 3456789
o.ooi o.oi 0:1 i
,--
^^
A
^
*"
2 3 456789
.0 10. (
RESIDUAL CONC. (Cf) mg/l
CARBON
DOSE mg/l
0
4.04
10.23
20.46
40.12
80.26
PH= 7.5
Cf C0-Cf-X X/M
9.30
9.30
8.30
7.30
5.56
3.47
--
1.00
2.00
3.74
5.83
--
97
97
93
73
pH*
Cf C0-Cf'X X/M
Carbon
mq
Dose
/I
0
9.9
49.6
[01.9
pH= 7.5
Cf C0-CfX X/M
0.96
0.33
0.02
0.002
--
0.63
0.94
0.958
63.6
19.0
9.4
40
-------
COMPOUND- NaPhtha1ene/Fi1trasorb-400
STRUCTURE:
FORMULA:
MOL. WT.
128.19
FREUNDLICH
PARAMETERS
K
1/n
Corr. Coef. r
INITIAL CONC mg/l
10
1.0
0.1
pH
7.5
176
0.524
0.993
ADSORPTION CAPACITY, mg/gm
588
176
53
CARBON DOSES REQUIRED TO ACHIEVE INDICATED CHANGE
IN CONCENTRATION^
Cf, mg/l
Co, mg/l
10
1.0
0. 1
0.01
1.0
51
--
--
--
0.1
188
17
--
--
0.01
634
63
5.7
--
0.001
2121
212
21
2
(a) Carbon doses in mg/l at neutral pH.
REMARKS:
41
-------
COMPOUND'- Naphtha lene/Filtrasorb-400
1
8
6
o 3
m
o: 2
<
o
E1
o
LJ *
CD ,
a: 3
0
in 2
Q
<
O> i
E.
"
2
\ 4
x 4
0
i
1000
100
10
1
+>
f
Y
^'
^
^
_?*
s-
s
s*
r*
*
l-
^
I
^
s*
*
s
£. ^
I 2 3456789!
.001 .01
3 4 5 67891
34567891
RESIDUAL C$NC. (Cf) mg/l
2 "3 4567891
1.0 10.0
CARBON
DOSE mg/l
0
11.2
22.3
56.1
168.3
224.4
PH= 7.5
Cf C0-Cf*X X/M
9.94
5.3
3.0
0.71
0.17
0.06
--
4.64
6.94
9.23
9.77
9.88
--
414
311
165
58
44
pH =
cf CO-G^X X/M
pH =
Cf C0-Cf-X X/M
42
-------
COMPOUND: 1 ,1-Diphenyl hydrazine/Darco
STRUCTURE:
N-N
FORMULA:
C12H12N2
184.2
FREUNDLICH
PARAMETERS
K
1/n
Corr. Coef. r
INITIAL CONC. rtig/l
10
1.0
0.1
pH
7.5
92
0.257
0.918
ADSORPTION CAPACITY, mg/gm
166
92
51
CARBON DOSES REQUIRED TO ACHIEVE INDICATED CHANGE
IN CONCENTRATION^
Cf, mg/l
Co, mg/l
10
1.0
0.1
0.01
1.0
98
-
0.1
194
19
0.01
355
35
3
-
0.001
641
64
6
1
(a) Carbon doses in mg/l at neutral pH.
REMARKS:
43
-------
f DM POUND! I,l-Dipheny1 hydra zine/Darco
1
X/M, mg ADSORBED/ gm CARBON
O
J , f\> W Jk OD f\> UJ A 0* CD
1000
100
10
*
.
*
»
^
, ^ -"""
- ^
A
A
--
. '
I
\
2 34567891 2 34567891 2 34567891 2 3456789
01 o.oi o.i i.o
RESIDUAL CONC. (Cf) mg/l
CARBON
DOSE mg/l
0
4.04
10.22
20.44
40.13
80.26
160.5
10.22
PH= 7.5
Cf C0-Cf«X X/M
10.03
10.19
8.31
7.51
3.35
2.30
0.21
8.51
--
--
1.72
2.88
6.6S
7.73
9.C2
1.52
--
--
168
141
166
96
61
148
pH*
cf CO-G^X X/M
pH =
Cf C0-CfX X/M
44
-------
COMPOUND:
STRUCTURE:
,l-Diphenylhydrazine/Filtrasorb-400
N -
FORMULA:
C12H12N
12n2
MOL WT.
184.24
FREUNDLICH
PARAMETERS
K
1/n
Corr. Coef. r
INITIAL CONC. mg/l
10
1.0
0.1
pH
7.5
135
0.158
0 .751
ADSORPTION CAPACITY, mg/gm
194
135
94
CARBON DOSES REQUIRED TO ACHIEVE INDICATED CHANGE
IN CONCENTRATION^
C, mg/l
Co, mg/l
10
1.0
0.1
0.01
1.0
66
--
--
0.1
104
10
--
0.01
153
15
1.5
--
0.001
221
22
2
0.2
(a) Carbon doses in mg/l at neutral pH.
RtMAKKS:
45
-------
COMPOUND:.
1,1-Diphenylhydrazine/Filtrasorb-400
CQ
1000
UJ «
$ *
8 2
Q
6
100
10
.001
34567691
3 4567 891
34567891
.01 0.1 1.0
RESIDUAL CONC. (Cf) mg/l
3 4567891
10
CARBON
DOSE mg/l
0
4.6
11.16
56.08
112.0
4.6
PH= 7.5
Cf C0-Cf«X X/M
9.95
9.07
7.83
0.46
0.39
9.09
0.88
2.12
9.49
9.56
0.86
191
190
167
85
187
pH =
cf CO-CY-X X/M
pH =
Cf CQ-CI-X X/M
46
-------
COMPOUND:
STRUCTURE:
B-Naphthylamine/Darco
010
FORMULA:
MOL. WT.
143.19
FREUNDLICH
PARAMETERS
K
1/n
Corr. Coef. r
INITIAL CONC. mg/l
10
1.0
0.1
pH
7.5
67
0.395
0.819
ADSORPTION CAPACITY, mg/gm
171
67
28
CARBON DOSES REQUIRED TO ACHIEVE INDICATED CHANGE
IN CONCENTRATION*0)
Cf, mg/l
Co, mg/l
10
1.0
0.1
0.01
1.0
13
--
_-
--
0.1
356
36
--
--
0.01
892
88
8
--
0.001
2219
222
20
2
(a) Carbon doses in mg/l at neutral pH.
REMARKS:
47
-------
rnMPDIINin: c.-Naphthylamine/Darco
X/M, mg ADSORBED/ gm CARBON
ro oj j» 01 01 r\j CM .* O .OD pow^cnoD
1000
100
10
^
^
A
**
^
>
.1
\f
^*
_^^~
jr
A
**
I 2345 67891
0.001 0.01
2 34567891 2 34567891
RESIDUAL CONC. (Cf) mg/l
2 3 4 5 6 7891
10
CARBON
DOSE mg/l
0
1.13
2.26
4.04
10.23
20.46
40.13
80.26
PH= 7.5
Cf C0-Cf*X X/M
1 .40
1.34
1.20
1.10
0.75
0.34
0.20
0.00
--
0.06
0.20
0.30
0.65
1.06
1.20
--
--
53
88
74
64
52
30
--
pH-
Cf C0-Cf'X X/M
pH =
Cf Co-Cf-X X/M
48
-------
COMPOUND' B-Naphthylamine/Filtrasorb-400
STRUCTURE:
FORMULA:
MOL. WT.
143.19
FREUNDLICH
PARAMETERS
K
1/n
Corr. Coef. r
INITIAL CONC. mg/l
10
1.0
0.1
pH
7.5
150
0.302
0.939
ADSORPTION CAPACITY, mg/gm
301
150
75
CARBON DOSES REQUIRED TO ACHIEVE INDICATED CHANGE
IN CONCENTRATION^
Cj, mg/l
Co, mg/l
10
1.0
0.1
0.01
1.0
120
_
_
-
0.1
132
12
__
-
0.01
268
27
2.4
-
0.001
536
54
5.4
0.5
(a) Carbon doses in mg/l at neutral pH.
REMARKS:
49
-------
1
z
o 3
m
cc 2
<
o
E '
O> 8
\ 6
Q
UJ 4
00 ,
tr 3
o
in 2
Q
<
0> i
E 6
\
X
3
2
100
100
10
«
^
1 *
4
»
>,.*
*-*
**
»
^
H
r'
2 3456789 2 34567891 2 3456789
0.001 0.01 0.1
.-*
^*
«-
^
2 3 456789
1.0 1
RESIDUAL CONC. (Cf) mg/l
CARBON
DOSE mg/l
0
1.06
2.12
4.09
10.84
21.68
41.22
PH=7.5
Cf C0-Cf«X X/M
1 .4
1.24
1.10
0.78
0.20
0.08
0.00
0.16
0.30
.62
1.20
1.32
_
151
142
152
111
61
_
pH«
Cf C0-Cf*X X/M
pH =
Cf C0-Cf-X X/M
50
-------
COMPOUND:
STRUCTURE:
4,4'-Methylene-Bis(2-chloroani1ine)/Darco
FORMULA:
Ci2H]2Cl2N;
MOL. WT. 264.28
FREUNDLICH
PARAMETERS
K
1/n
Corr. Coef. r
INITIAL CONC. mg/l
pH
7.5
93
.554
.957
ADSORPTION CAPACITY, cng/gm
333
93
26
CARBON DOSES REQUIRED TO ACHIEVE INDICATED CHANGE
IN CONCENTRATION^
Cj, mg/l
Co, mg/l
10
1.0
0.1
0.01
1.0
96
-
-
0.1
381
35
-
-
0.01
1377
137
14
0.001
4937
443
44
4.4
(a) Carbon doses in mg/l of neutral pH.
REMARKS:
51
-------
1
8
6
4
z
0 3
GQ
GC 2
0
/- 1
A/M, mg ADSORBED/ gn
- PO w .& » ro GJ * Oi CD
1000
100
10
yXl
j
'
k
'L X^
X
4
X
L^X
'
,
I*"1
^
i
>
^
A
I 2 3456769!
'°01 '01
2 34567891
34567891
2 34567891
RESIDUAL CONC. (Cf) mg/l
CARBON
DOSE mg/l
0
1.13
2.26
4.04
10.23
20.46
40.13
80.26
PH= 7.5
Cf C0-Cf«X X/M
1.46
1.33
1.24
1.04
0.77
0.30
0.10
0.08
0.13
.22
.42
.69
1.16
1.36
1.38
115
97
104
67
57
34
17
pH«
Cf C0-Cf-X X/M
pH =
Cf C0-Ci'X X/M
52
-------
COMPOUND- 4,4l-Methylene-Bis(2-chloroaniline)/Filtrasorb-400
STRUCTURE:
CH;
Cl
NH;
NH2
FORMULA:
C13H]?C12N2
MOL. WT.
264.28
FREUNDLICH
PARAMETERS
K
1/n
Corr. Coef. r
INITIAL CONC. mg/l
10
1.0
0.1
pH
7.5
188
.637
.895
ADSORPTION CAPACITY, mg/gm
815
188
43
CARBON DOSES REQUIRED TO ACHIEVE INDICATED CHANGE
IN CONCENTRATION^
Cf, mg/l
Co, mg/l
10
1.0
0.1
0.01
1.0
48
0.1
228
21
.
0.01
999
99
9
-
0.001
4329
433
43
4
(a) Carbon doses in mg/l at neutral pH.
REMARKS:
53
-------
1
e
o 3
m
QL. 2
<
O
E1
\ 6
Q
LJ 4
OD
cr 3
o ,
(f) 2
Q
<
Oi i
E.
8
5 6
\
x *
1
1000
100
10
/
\
/
s
/
t
11
/
/>
^
^
-^
/
s
\^
/
{
/
k
^"
^
^x
^x
1*
I 2 3^567691
0.001 0.01
2 34567891 2 34567891
RESIDUAL CONC. (Cf) mg/l
2 3 4567891
10
CARBON
DOSE mg/l
0
1.13
2.26
4.04
20.46
40.13
80.26
PH= 7.5
Cf C0-Cf = X X/M
1.38
1.18
1.00
0.60
0.08
0.05
0.07
0.20
.38
.78
1.30
1.33
1.31
177
168
193
64
33
16
pH-
Cf C0-Cf-X X/M
PH =
Cf C0-Cf-X X/M
54
-------
COMPOUND: N-Dimethyl/nitrosamine/Darco
STRUCTURE:
CH_
CH,
N-N=0
FORMULA:
MOL WT. 74-08
FREUNDLICH
PARAMETERS
K
1/n
Corr. Coef. r
INITIAL CONC. mg/l
10
1.0
0.1
PH
7.5
1 .45 x 10~6
8.15
.715
ADSORPTION CAPACITY, mg/gm
197
1.45 x icf 6
_
CARBON DOSES REQUIRED TO ACHIEVE INDICATED CHANGE
IN CONCENTRATION^
Cf, mg/l
Co, mg/l
10
1.0
0.1
0.01
1.0
>io6
_
_
-
0.1
-
_
_
-
0.01
-
_
_
-
0.001
_
_
-
(o) Carbon doses in mg/l at neutral pH.
REMARKS:
55
-------
COMPOUND' N'-Dimethylnitrosamine/Darco
O
00
cr
u
E
o
LU
CD
o:
O
(/)
Q
6 i
_ 6
100
10
l.C
I 2 34567891
0.01 0.1
2 34567891 2 34567891 2 34567891
RESIDUAL CONC. (Cf) mg/l 10'°
CARBON
DOSE mg/l
0
A.O
8.1
15.3
46.0
100.6
181.5
251
pH =
Cf C0-Cf-X X/M
8.5
9.5
8.0
8.5
7.5
7.5
6.5
7.0
-
0.5
1.0
1.0
2.0
1.5
-
62
22
10
11
6
pH-
Cf C0-Cf*X X/M
pH *
cf CO-CY-X X/M
56
-------
COMPOUND- N-Dimethylnitrosamine/Filtrasorb 400
STRUCTURE-.
CH3
CH:
N N = 0
FORMULA:
;CH3).,NNO
MOL. WT.
74.08
FREUNDLICH
PARAMETERS
K
1/n
Corr. Coef. r
INITIAL CONC. mg/l
10
1.0
0.1
pH
7. 5
6.79 x 10"5
6.57
0.617
ADSORPTION CAPACITY, mg/gm
252
6.79 x 10""
CARBON DOSES REQUIRED TO ACHIEVE INDICATED CHANGE
IN CONCENTRATION^
C, mg/l
Co, mg/l
10
1.0
0.1
0.01
1.0
10~s
0.1
-
0.01
-
0.001
(a) Carbon doses in mg/l ot neutral pH.
ktMAKKS:
57
-------
N-Dimethylnitrosamine/FII trasorb 400
1
B
6
4
0 3
CD
cr 2
o
E '
Q) 8
"V 6
Q
UJ 4
£ >
8 «
O
O> I
E 6
2E 6
x 4
3
2
1
0
I
100
10
1.0
1
1
r
i
f
i
;
4
1
/I
I
L
f*
I
/
/
2 34567891 2 34567691 2 3456769
.01 0.1 1.0 1
2 3 456789
0 10(
RESIDUAL CONC. (Cf) mg/l
CARBON
DOSE mg/l
0
4.6
9.2
18.4
41.2
96.0
146.4
288.0
PH= 7.5
Cf C0-Cf«X X/M
9.0
9.0
7.5
8.0
8.0
7.0
fi.5
6.5
--
--
1.5
1.0
1.0
2.0
2.5
2.5
--
--
163
54
24
21
17
9
pH«
cf CO-CY-X X/M'
pH-
Cf C0-CfX X/M
^
58
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APPENDIX B
PREPARATION OF NUTRIENT FOR STATIC AND
CONTINUOUS BIODEGRADATION TESTS
NUTRIENT
Reagents
1. Distilled water.
2. Calcium chloride solution:
Dissolve 27.5 g anhydrous CaCl2 in distilled water and dilute to
1 Z.
3. Magnesium sulfate solution:
Dissolve 22.5 g MgSO^HaO in distilled water and dilute to 1 £.
4. Ferric chloride solution:
Dissolve 0.25 g FeCl3'6H20 in distilled water and dilute to 1 H.
These solutions should be stored in the dark, preferably in a
refrigerator, and discarded at the first sign of turbidity.
5. Phosphate buffer solution:
Dissolve 8.5 g potassium dihydrogen phosphate, KH2POi*, 21.75 g
dipotassium hydrogen phosphate, K2HPOi,, 33.4 g disodium hydrogen
phosphate heptahydrate, Na2HP0^7H20, and 1.7 g ammonium chloride
NhUCl, in about 500 ml distilled water and dilute to 1 I.
Preparation of Medium
For each liter of distilled water add 1 ml of each of the following solu-
tions in the order indicated, mixing after each addition:
1. Calcium chloride solution
2. Magnesium sulfate solution
3. Ferric chloride solution
4. Phosphate buffer solution.
Weight 0.055 g of yeast extract (Difco or equivalent), add 1 to 1 £ of the
above solution and dissolve. Dispense 90 ml of medium into 250-ml Erlenmeyer
59
-------
flasks. The medium should be used within 3 hours after preparation unless
sterilized. If an autoclave is available, larger batches of medium may be
prepared, dispensed in flasks, and sterilized at 121°C for 15 min. When this
is done, sufficient additional distilled water must be added to the medium to
offset the sterilization loss. The flasks should be stoppered with cotton
and capped with aluminum foil before sterilization. Foil caps and cotton
stoppers are used to retard evaporation and maintain sterility until the med-
ium is used. They are removed during the test.
PREPARATION OF MINERALIZED WATER FOR
CARBON ADSORPTION AND OZONATION TESTS
MINERALIZED WATER
Stock Solutions
1. Dissolve 21.96 g potassium dihydrogen phosphate, K^POtt, in
1 £ H20.
2. Dissolve 128.38 g magnesium sulfate heptahydrate MgS01+-7H20,
in 1 £ H20.
3. Dissolve 273.7 g calcium chloride hexahydrate CaC£2-6H20, in
1 £ H20.
Preparation
Use 95 m£ of each stock solution in 45 £ of water. Adjust the pH from
the 6.8 of the stock solution to 7.5 by adding 16.8 g of sodium bicarbonate,
NaHC03.
ANALYSIS OF BENZIDINE PLUS 3,3'-DICHLOROBENZIDINE
A survey of the literature revealed that a number of methods have been
reported for the analysis of benzidine in different matrices.20~~25 The pro-
cedure of Nony and Bowman25 was chosen. It involves solvent extraction of
the sample with benzene, drying and concentration using a K-D evaporator, de-
rivatization and analysis by gas chromatography-flame ionization detection.
The method is described below. The EPA Chloramine T complexation method26
was not considered because of the possible formation of interferences in the
treatment experiments. The procedure of Nony and Bowman was found to be sat-
isfactory. A benzidine recovery of 86.5 percent +_ 6.4 percent, was obtained
in the analysis of duplicate samples spiked at the ppm level. In several
cases, however, the samples were not completely derivatized for some reason.
Similar problems were encountered by F. K. Kawahara26 of EPA's Environmental
Monitoring and Support Laboratory, Cincinnati, Ohio, who is also using the
Nony and Bowman procedure for the analysis of benzidine in wastewater. Some
additional development work will be required before this procedure can be
used for routine analysis.
60
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
REPORT NO.
EPA-600/2-79-097
3. RECIPIENT'S ACCESSI ON- NO.
!~LE AND SUBTITLE
5. REPORT DATE
TREATABILITY OF CARCINOGENIC AND OTHER HAZARDOUS
ORGANIC COMPOUNDS
August 1979 (Issuing Date)
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
Edward G. Fochtman and Walter Eisenberg
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
IIT Research Institute
10 West 35th Street
Chicago, Illinois 60616
10. PROGRAM ELEMENT NO.
1BC611. SOS #5.Task AE/02
11. CONTRACT/GRANT NO.
Contract No. CI-68-03-2559
12. SPONSORING AGENCY NAME AND ADDRESS
Municipal Environmental Research Laboratory-Cinti,OH
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati.Ohio 45268
13. TYPE OF RE PORT AND PERIOD COVERED
Final (6/17/77- 6/17/78)
14. SPONSORING AGENCY CODE
EPA/600/14
15. SUPPLEMENTARY NOTES
Project Officer: Richard A. Dobbs (513/684-7649)
16. ABSTRACT
This research program was conducted to determine the capability of
bielogical and physical-chemical treatment processes to remove chemical
carcinogens and other hazardous organic compounds from water and wastewater.
Treatment processes investigated included biological degradation, activated
carbon adsorption and oxidation with ozone. Compounds studied were naphtha-
lene, 1,1-diphenylhydrazine, 3-naphthylamine, 4,4'-methylene-bis (2-chloroaniline),
and dimethylnitrosamine. All compounds were amenable to biological treatment
in continuous flow reactors. Ozone and activated carbon provided effective
treatment for all except dimethylnitrosamine.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
jb.IDENTIFIERS/OPEN ENDED TERMS C. COSATI Field/Group
Sewage Treatment*, Chemical Removal
(Sewage Treatment)*, Activated Carbon
Treatment
Physical-Chemical
Treatment
Biological Treatment
13B
13. DISTRIBUTION STATEMENT
Release to Public
19. SECURITY CLASS (This Report)
Unclassified
21 . NO. OF PAGES
69
20. SECURITY CLASS (This page)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
61
« U S GOVERNMENT PRINTING OFFICE 1979 -657-146/5469
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