BEHAVIOR OF VOLATILE AND EXTRACTABLE ORGANICS IN COMBINED
BIOLOGICAL/PHYSICAL-CHEMICAL TREATMENT OF MUNICIPAL WASTEWATER
by
Thomas A. Press!ey
Wastewater Research Division
Municipal Environmental Research Laboratory
Cincinnati, Ohio 45268
141982
LIBRARY
MUNICIPAL ENVIRONMENTAL RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268
-------
BEHAVIOR OF VOLATILE AND EXTRACTABLE ORGANICS IN COMBINED
BIOLOGICAL/PHYSICAL-CHEMICAL TREATMENT OF A MUNICIPAL WASTEWATER
by
Thomas A. Press!ey
Wastewater Research Division
Municipal Environmental Research Laboratory
U.S. Environmental Protection Agency
Cincinnati, Ohio 45268
ABSTRACT
The purpose of this study was to examine qualitatively and semi-
quantitatively the volatile (purgeable) organics and the semi-volatile
liquid/liquid extractable organics present after the major steps of a
reuse treatment system. Conventional GC and GC/MS methods were
employed.
The combined biological/physical-chemical treatment reuse system at
the EPA-DC Pilot Plant consisted of a screening device to remove
coarse material, lime clarification (pH 10.5), dispersed growth
nitrification, fixed film denitrification, carbon adsorption, dual
media filtration, and chlorination for disinfection. This sequence
of processes was chosen because they form a treatment system capable
of producing a high quality water from municipal raw wastewater.
Typically, effluent TOC values averaged 2 mg/1.
The final and intermediate effluents were examined for trihalomethanes
and other highly volatile organics and for organics extractable by
methylene chloride. Trihalomethanes and other purgeable organics
typically totalled 40 ug/1.
The final and intermediate effluents were examined for trihalomethanes
and other highly volatile organics and for organics extractable by
methylene chloride. Trihalomethanes and other purgeable organics
typically totalled 40 ug/1 in the raw wastewater. A sharp decrease
in concentration occurred following lime clarification and nitrifica-
tion. Chloroform levels were reduced by 70 percent and the other
trihalomethanes by 90 percent or better. Further significant reduction
in purgeable organics did not occur in the treatment train. The tri-
halomethanes, after final chlorination to a free chlorine residual
or approximately 1.0 mg/1, exhibited a sharp increase.to typical
values of 25 yg/1. Because of the low trihalomethane concentrations
after chlorination, it was concluded that removal of the humus material
by the system reduced the formation of trihalomethanes in the effluent.
The semi-volatile liquid/liquid extractable organics identified in the
raw wastewater influent were generally reduced by the reuse system to
levels not detectable by the analyses employed.
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CONTENTS
Abstract. „ i i
Introducti on 1
Experimental .. 2
Qua!ity Assurance 4
Discussion of Results §
A. Methylene Chloride Extractable Organics .... 5
B. Volatile (Purgeable) Organics 6
Conclusions • ••••• ^
References . 7
Tables:
1. Chemical Parameters Typical of the District of Columbia
Raw Wastewater and after Various Stages in the Combined
Biological/Physical-Chemical Treatment Process..... 10
2. Organic Materials Identified in the 8/3/76 Raw Waste-
water Extract .. . 11
3. Organic Materials Identified in the 11/4/76 Raw Waste-
water Extract........ 12-13
4. Organic Materials Identified in the 8/3/76 1-7 Extract... 14
5. Organic Materials Identified in the 11/4/76 1-7 Extract.. 15
6. Organic Materials Identified in the 8/3/76 K-7 Extract... 16
7. Organic Materials Identified in the 11/4/76 K-7 Extract.. 16
8. Organic Materials Identified in the 8/3/76 L-7 (Final
Effluent) Extract 17
9. Organic Materials Identified in the 11/4/76 L-7 (Final
Effluent) Extract 17
10. Halogenated Ethanes and Methanes Identified in Effluents
of the Combined Biological/Physical-Chemical Process... 18
11. Other Volatile (Purgeable) Organic Materials Identified
in Effluents of the Combined Biological/Physical-
Chemical Process 19
Figures:
1. Schematic of Combined Biological/Physical-Chemical
Treatment Process 21
2. Removal of TOC 22
3. Total Ion Chromatogram of Blank Extract 23
4. Total Ion Chromatogram of 8/3/76 H-l Neutral Extract 24-25
5. Total Ion Chromatogram of 8/3/76 H-l Neutral Extract 26-27
6. Total Ion Chromatogram of 8/3/76 H-l Base Extract 28
7. Total Ion Chromatogram of 8/3/76 1-7 Neutral Extract 29
8. Total Ion Chromatogram of 8/3/76 1-7 Acid Extract 30
9. Total Ion Chromatogram of 8/3/76 1-7 Base Extract 31
10. Total Ion Chromatogram of 11/4/76 K-7 Neutral Extract 32
11. Total Ion Chromatogram of 11/4/76 K-7 Acid Extract 33
12. Total Ion Chromatogram of 11/4/76 K-7 Base Extract 34
13. Total Ion Chromatogram of 11/4/76 L-7 Neutral Extract 35
14. Total Ion Chromatogram of 11/4/76 L-7 Acid Extract 35
15. Total Ion Chromatogram of 11/4/76 L-7 Base Extract 37
16. Removal of Volatile Organics 38
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BEHAVIOR OF VOLATILE AND EXTRACTABLE ORGANICS IN COMBINED
BIOLOGICAL/PHYSICAL-CHEMICAL TREATMENT OF MUNICIPAL WASTEWATER
Thomas A, Pressley
Research Chemist
U.S. Environmental Protection Agency
Municipal Environmental Research Laboratory
Wastewater Research Division
Cincinnati, Ohio 45268
INTRODUCTION
The increasing pollution of existing fresh water sources, as well as
the need for wastewater reuse in many parts of the world, is focusing
attention on more efficient methods of wastewater treatment. Effluents
from the more common biological treatment processes contain considerable
amounts of organic materials which are responsible for taste, odor, and
color, some of which may possess the potential for severe toxic effects
on the biota of freshwater bodies. In wastewater reuse for human
consumption, considerable attention has been given to aesthetic, as
well as physiological effects of the organic residuals thus far
identified (1).
The organic materials in wastewaters affect, and are affected by, many
of the physical-chemical and biological processes in use today. A
better understanding of the composition and characteristics of the
organic materials in raw wastewater, as well as effluents after various
stages of treatment aid in better design and operation of wastewater
treatment processes. The purpose of this study was to examine
qualitatively and semi-quantitatively the behavior of the volatile
(purgeable) organic materials and the semi-volatile methylene chloride
extractable organic materials after the major steps of treatment in
a combined biological/physical-chemical treatment reuse process.
In the physical-chemical treatment of raw wastewater, lime and a
mineral salt such as MgSO*, FeCl, or alum are added to the wastewater
in the reactor to attain a pH O-T 10.5-11.6 Under these conditions,
bicarbonate ions are converted to carbonate ions and precipitated by
the excess calcium ions as calcium carbonate. Phosphorous is pre-
cipitated as calcium hydroxyapatite with soluble residuals below
0.1 mg/1 (as P). The magnesium or ferric ions, converted to their
gelatinous hydroxides, provide very efficient flocculation and sedi-
mentation of the calcium carbonate, calcium hydroxyapatite and
particulate organic matter in the clarifier following the reactor.
Following lime clarification and sedimentation, ammonia removal is
achieved by biological nitrification-denitrification or breakpoint
chlorination. The wastewater is then treated with activated carbon
(either granular or powdered) for the removal of dissolved organic
materials. In some cases, effluents from carbon adsorption are
"polished" by breakpoint chlorination for residual ammonia removal and
disinfection.
In the combined biological/physical-chemical-treatment process
examined in these studies, approximately 200 mg/1 of CaO and 15 mg/1
Fed., (as Fe) were added for lime clarification, at pH 10.5 (low pH-lime
process). Nitrification (suspended growth) and denitrification (fixed
film) were employed for ammonia removal. Methanol dosages corresponding
-------
to methanol:NO,-N ratios of 2:1 to 4:1 were used in denitrification.
Dissolved organic material was removed by passing the effluent from the
denitrification stage through granular (8 x 30 mesh) activated carbon
(Filtrasorb 300) contained in four columns in series at a 4.8 1/m s
loading rate (downflow packed bed operation). Following carbon
adsorption, the wastewater was treated with approximately 5 mg/1 of
alum as Al and passed at approximately 2 l/mzs hydraulic loading rate,
through a dual media filter, containing 0.6 meter of coal and 0.3 meter
of sand. This final flocculation and filtration step was designed to
remove particulate matter formed by, or escaping from, the carbon
adsorption stage. The wastewater was then chlorinated to achieve a
free available chlorine concentration of 1 mg/1 for removal of any
residual ammonia and for disinfection. The physical-chemical treatment
process required a total detention time of 10.6 hours at a flow rate of
35 gpm (2.2 x lO'V/s).
EXPERIMENTAL
Wastewater samples used in these studies were taken at the U.S. Environ-
mental Protection Agency-District of Columbia Pilot Plant located at
5000 Overlook Avenue, S.W., Washington, D.C. The pilot plant was
designed for research in the development and demonstration of more
efficient methods of municipal wastewater treatment. The combined
biological/physical-chemical treatment process examined in this study
is shown schematically in figure 1. Chemical parameters typical of
the District of Columbia raw wastewater and effluents after various
stages of treatment are shown in Table 1.
Wastewater grab samples were taken after the following stages within the
combined biological/physical-chemical treatment process:
Raw Wastewater (H-l)
Denitrification (1-7)
Carbon Adsorption (J-7)
Alum Coagulation and Filtration (K-7)
Chlorination and Filtration (Final Effluent) (L-7)
Samples for volatile organic analysis (VOA) were taken in 15 ml crimp-
seal bottles containing a film of Na-S^Oo sufficient to reduce the
total available chlorine in a 15 ml aliquot of water containing 30 mg/1
of total available chlorine. The bottles were completely filled to
avoid headspace losses and crimp-sealed with a teflon seal. Volatile
organic materials were determined by GC/MS on a 5 ml sample employing
the purge and trap procedures and apparatus described by Bellar and
Lichtenberg (2). The trap used in these tests was filled one third
with silica gel (Davidson 15, 35/60 mesh) and two thirds with Tenax-GC
so that the purged volatile organic materials were exposed to the
Tenax-GC first. The purged volatile organic materials adsorbed on the
trap were thermally desorbed for 3 minutes in the modified injection
port of the Finnigan 9500 gas chromatograph at 200°C and with fifteen
cc/min helium flow, on to the chromatographic column held at ambient
temperature.
Following the 3-minute thermal desorption in the injection port, the
trap was removed from the injection port of the GC. The injection port
-------
was immediately plugged with the prescribed quick-connect plug and the
trap baked out at 200°C for 20 minutes under 15 cc/min helium flow.
The trap was then plugged and allowed to cool to ambient temperature
before reuse. The gas chromatograph was equipped with a 5' glass
column of 1/4" OD (2 mm ID) and packed with Tenax-GC, 60/80 mesh
(Supelco, Inc.). The injector port was maintained at 200°C for sample
vaporization and thermal desorption of the Tenax-GC-silica gel trap.
The separator oven and transfer lines were maintained at 250°.
Temperature programming in the VGA involved maintaining the chromato-
graphic column at ambient temperature during thermal desorption of the
trap, until the water vapor eluted from the chromatographic column.
The water vapor was observed as a pressure surge in the analyzer of
the mass spectrometer—its elution required approximately two minutes.
An additional two minutes were allotted at ambient temperature before
temperature programming to 190°C at 8 deg/min. The final temperature
was maintained for 10 minutes before ending data acquisition. Data
acquisition on the Finnigan 3300 Mass Spectrometer continued following
elution of the water vapor from the chromatographic column for a total
data acquisition time of 32 minutes.
A Finnigan 3300 mass spectrometer was utilized in these studies to
provide mass spectra of the components separated by the gas chromato-
graph. The Finnigan 3300 GC/MS system was interfaced to a Systems
150 GC/MS Data System (PDP-S) for rapid processing of mass spectral
data.
The GC/MS system was operated in the control mode over a mass range of
30-200, 201-400 amu, using integration times of 8 ms/amu,yfor a 3.8
second scan time for the VGA. Sensitivity was set at 10" amps/volt
and electron energy was 70 ev. Real time attenuation was set so that
750 ng of chloroform produced a full scale response in order to have a
working range of 1 to 150 ppb chloroform.
Grab samples taken for the analysis of methylene chloride extractable
acidic, neutral, and basic organic materials were contained in 1 gallon
wide-mouth glass jars under an aluminum foil seal. The jars were
filled in order to avoid head space losses. The samples were not
dechlorinated. The samples were packed in ice and shipped by air
express to the Cincinnati laboratory for extraction. The time interval
between sample selection and sample extraction was 24-48 hours. The
samples, usually 4-liter aliquots, were extracted in 6-liter separatory
funnels with methylene chloride for acidic, neutral, and basic
materials. The methylene chloride extracts were dried, concentrated,
and the solvent changed to acetone according to the procedure described
in the EPA GC/MS Procedural Manual (3). The final acidic, neutral, and
basic methylene chloride extractable organic materials (now in acetone),
were concentrated, under a gentle flow of dry nitrogen, to 1.0 ml and
held at 4°C for GC/MS analysis.
The Finnigan 9500 gas chromatograph used in the analysis of the acidic,
neutral, and basic extracts was equipped with a 30-meter glass capil-
lary column coated with SE-30 and possessing 86,000 effective
theoretical plates.
The gas chromatograph was modified to allow the flow rate of the helium
carrier gas to be controlled by adjusting the pressure regulator at the
main cylinder rather than at the controls of the gas chromatograph.
The Finnigan GC/MS system was further modified for these studies by
installing a glass-lined transfer line to deliver the column effluent
-------
directly to the analysis of the mass spectrometer, by-passing the
separator.
The helium pressure was adjusted to approximately 7 psi and the Grob
injector adjusted to yield a linear velocity of 30 cm/sec through the
column at 100°C with pentane, and a split ratio of approximately 30:1.
The injector and transfer lines were maintained at 270°C. The Grob
injector was closed for at least 30 seconds prior to sample injection,
and opened 30 seconds after injection of the sample.
Temperature programming selected for the analysis of the acidic,
neutral, and basic extracts started at approximately 30°C (ambient
temperature) and was programmed to 250°C at 4 degrees per minute. The
final temperature was maintained for 15 minutes for a total data
acquisition run time of 70 minutes. Temperature programming and data
acquisition were begun 3 minutes after sample injection in order to
avoid data acquisition during elution of the solvent.
Additional mass spectrometric conditions employed in the analysis of
the acidic, neutral, and basic extracts included operation in the
control-mode over the mass range of 20-200, and 201-500, with
integration times of 2 and 4 ms/amu respectively. The electron
energy was set at 70 ev. and the emission current was 0.5 amp.
Amplifier sensitivity was set at 10"7 amps/volt. The ion energy,
extractor, and lens voltages were adjusted for optimum peak, shape and
sensitivity.
QUALITY ASSURANCE
Quality assurance measures during the VOA involved achieving ion
abundance data from perfluorotributyl amine, which matched that taken
when the mass spectrometer was properly tuned and verified from ion
abundance data from decafluorotriphenylphosphine. Additional sensi-
tivity and chromatographic performance checks were made by running
fresh standard solutions.
Quality assurance measures throughout the analysis of the acidic,
neutral, and basic extracts involved strict compliance with the GC/MS
tuning and sensitivity recommendations prescribed by Eichelberger and
Budde (4) with decafluorotriphenylphosphine under identical sample
analysis conditions. Additional column performance and sensitivity
checks were made by running a C-,0, C-.Q, and C2Q hydrocarbon mixture.
Sensitivity was achieved so that 10 ng of the Hydrocarbons produced a
4:1 signal to noise ratio.
Compound identifications were made by computerized spectral matching
techniques and by running and matching against known standards when
available. Blanks were carried through each extraction process and
compensations were made during data analysis. All glassware exposed
to the sample prior to GC/MS analysis was previously cleaned by being
washed with hot detergent solution, rinsed with tap water, rinsed with
distilled water, air dried and heated in a muffle furnace at 400°C for
30 minutes.
The methylene chloride and acetone solvents used in these tests were
"distilled in glass" quality obtained from Burdick and Jackson and
were used as received. The anhydrous sodium sulfate for_drying the
extracts was analytical reagent quality, obtained from Fisher
Scientific Co., and was used as received.
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DISCUSSION OF RESULTS
A. Methylene Chloride Extractable Organics
The complexity of the total ion chromatograms of the extracts of
methylene chloride extractable materials from wastewater after varying
stages of physical-chemical treatment seemed to parallel the TOC and
COD values (Table 2). The total ion chromatograms of the various
extracts are presented to demonstrate effluent quality and are typical
(Fig. 3-15). The methylene chloride extractable materials in the raw
wastewaters (H-l) showed considerable variation in content as well
as in complexity of the total ion chromatograms. No single organic
compound was found in the 8/3/76 raw wastewater extracts above 10 ppb
(Table 3). In the 11/4/76 raw wastewater extracts, only stearic and
palmitic acids were found at concentrations above 10 ppb. These acids,
as well as 1 auric and oleic were found in the neutral fraction and were
not found at concentrations above 1 ppb in the acidic fraction.
Caffein was also found in the neutral fraction and not detected in the
basic fraction (Table 4). The large number of saturated and unsaturated
aliphatic hydrocarbons detected in the raw wastewater extracts indicate
motor oil and other internal combustion engine by-products. No organic
bases were detected in the raw wastewater extracts except caffein and
a trace of a compound tentatively identified as N,N-diphenylhydrazine
(Table 4).
Following lime precipitation (clarification), biological nitrification
and denitrification, (1-7), the methylene-chloride extractable organic
materials in the wastewater were dramatically reduced from that of the
raw wastewater (Tables 5 and 6) (Fig. 7-9). Only acetic acid was
identified in the neutral fraction of 1-7 at a concentration greater
than one ppb (Table 6). This probably was sample contamination
since acetic acid is sufficiently volatile to have been lost during
Kuderna-Danish concentration and should not have been extracted into
the neutral fraction.
Following carbon adsorption, GC/MS analysis of the K-7 extracts
revealed further reduction of complexity in the total ion chromatograms
(Fig. 10-12). The TOC and COD analyses revealed a parallel reduction
of total organic matter- No compounds were identified in any of the
K-7 extracts at concentrations greater than 1 ppb (Tables 7 and 8).
Likewise, no peaks were observed in the total ion chromatograms of the
K-7 extracts that could have represented concentrations greater than
1 ppb.
Following chlorination for residual ammonia removal and disinfection
and alum addition and filtration for residual turbidity removal, the
total ion chromatograms of the final effluent (L-7) extracts revealed
no significant difference from those of the K-7 extracts (Tables 9 and
10) (Fig. 13-15). All of the compounds identified in the L-7 extracts
were at the low ppb levels (1-5 ppb) or at the lower limits of
detection by GC/MS under the conditions employed in these tests. These
low concentrations encountered in the methylene chloride extracts of
the final effluents from the wastewater treatment system made spectral
identification difficult and was responsible for most of the tentative
identifications made.
Considerable quantities of chlorinated and brominated cyclohexanes,
cyclohexenes, and cyclohexanols were detected in the neutral and acidic
extracts of the final effluent (L-7) (Fig. 13 and 14). The presence of
-------
these compounds was attributed to the extraction of wastewater
containing free chlorine residuals with methylene chloride preserved
with cyclohexene (5}.
B. Volatile (Purgeable) Organics
Halogenated ethanes and methanes were compiled into a separate table
here for special discussion due to the recent emphasis placed on these
materials as possible carcinogens.
In the Washington, D.C. raw wastewater, chloroform concentrations
averaged a rather steady 10 ug/1 in the summertime grab samples
Other halogenated methanes and ethanes identified in the raw
wastewater were at concentrations below 10 ug/1 (Table 11). The
concentration of chloroform in the wastewater was reduced 50 to 100
percent following biological nitrification and denitrification (1-7).
The concentrations of other halogenated methanes and ethanes
identified in the wastewater following biological nitrification and
denitrification were reduced to levels not detectable by the conditions
employed in these tasks. This reduction in the concentration of
volatile halogenated methanes and ethanes was attributed to the purging
action of the aeration step incorporated in the nitrification step
previously described (Fig. 1). No further reductions in the volatile
halogenated methanes and ethanes were observed following the carbon
adsorption (J-7). Indeed, chloroform concentrations may have increased
slightly following carbon adsorption as shown in the 7/1/76 to 7/8/76
tests.
After chlorination to a free chlorine residual of approximately 1 mg/1,
the final effluent (L-7) contained concentrations of chloroform
ranging from 5 to 10 ug/1. Other halogenated methane and ethane'
concentrations increased from undetectable levels to levels ranging
from 3 to 5 ug/1 (Fig. 16). More data is necessary to substantiate
this apparent formation of halogenated methanes and ethanes by
chlorination of treated wastewaters, because in these studies, no
attempt was made to ascertain that the chlorine used in the chlorination
step was not contaminated with chloroform and other volatile halogenated
materials.
Other volatile (purgeable)/organic materials identified in the waste-
waters are tabulated in Table 12. Organic compounds other than the
halogenated methanes and ethanes were not consistently detected in the
final effluent (L-7) above 1 ug/1-
CONCLUSIONS
The dramatic reduction in the total organic material in the wastewater
following lime clarification and biological nitrification and denitri-
fication, as monitored by COD and TOC paralleled the reduction
in the complexity and number of peaks in the respective gas chromatograms
(Fig. 2). The efficient removal of the specific organic matter by lime
precipitation and biological nitrification and denitrification
(ammonia removal step) suggested effective:
a. Adsorption and absorption by the gelatinous hydroxides
formed during the lime clarification step, with subsequent
removal by sedimentation (occlusion).
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b. Purging of the more volatile organic materials
from the water during the aeration step of
biological nitrification.
c. Biological degradation of the organic materials
and/or adsorption into the bio-mass during
the nitrification and denitrification processes.
The activated carbon process reduced the'wastewater TOC from approxi-
mately 6 mg/1 to 2 mg/1. The absence of peaks in the gas chromatograms
of the acidic, neutral, and basic fractions of the extracts from
treated wastewater samples taken after the activated carbon treatment
step indicated that the residual organic materials GV 2 mg/1 of TOC)
may be of amphoteric nature and thus not extractable by organic
solvents used in analytical methods, or that any specific extractable
organic may be at concentration levels below the level of detection
employed in these tests. Further work is needed to characterize the
2 mg/1 of residual TOC in the renovated water.
The results of these studies of the behavior of volatile and extract-
able organics in a combined biological/physical-chemical treatment of a
municipal raw wastewater revealed final effluent concentrations of
halogenated methanes and ethanes, other volatile organic materials,
and the extractable materials to be similar to those found in
finished drinking waters during the EPA National Reconnaissance
Survey of 1975. The specific organic compounds identified in the
final effluent have also been identified in finished drinking
waters (6).
A portion of the VOA data generated in this study has been presented in
a previous report (6). It is suggested that this reference be con-
sulted for a detailed comparison of the reuse effluent with finished
drinking waters.
REFERENCES
1. DUNHAM, L. J.; O'HARA, R. W.; & TAYLOR, F. B. Studies on Pollu-
tants from Processed Water. Amer. J. Public Health, 57:12:2178
(June 1967).
2. BELLAR, T. A. & LICHTENBERG, J. J. The Determination of Volatile
Organic Compounds at the ug/1 level in Water by Gas Chromatography.
EPA-670/4-75-009, Nov. 1974, Municipal Environmental Research
Laboratory, U.S. Environmental Protection Agency, Cincinnati,
Ohio 45268.
3. An EPA-GC/MS Procedural Manual (William L. Budde & James W.
Eichelberger, editors). Environmental Monitoring and Support
Laboratory, Office of Research and Development, U.S. Environ-
mental Protection Agency, Cincinnati, Ohio 45268.
4. EICHELBERGER, J. W.; HARRIS, L. E.; & BUDDE, W. L. Reference
Compound to Calibrate Ion Abundance Measurements in Gas
Chromatography-Mass Spectrometry Systems. Anal. Chem., 47:7:
(June 1975).
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Private Communication: Dr. Theodore 0. Meiggs, Chief, Chemistry
Branch3 U.S. EPA, Office of Enforcement, National Enforcement
Investigations Center, Building 53, Box 25227, Denver Federal
Center, Denver, Colorado 80225.
H. P. & ENGLISH, J. N. Water Treatment for Reuse and
Its Contribution to Water Supplies. EPA-600/2-78-027, March 1978,
Municipal Environmental Research Laboratory, U.S. Environmental
Protection Agency, Cincinnati, Ohio 45268.
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TABLES
1. Chemical Parameters Typical of the District of Columbia
Raw Wastewater and after Various Stages in the Combined
Biological/Physical-Chemical Treatment Process.. 10
2. Organic Materials Identified in the 8/3/76 Raw Waste-
water Extract ,. 11
3.- Organic Materials Identified in the 11/4/76 Raw Waste-
water Extract 12-13
4. Organic Materials Identified in the 8/3/76 1-7
Extract 14
5. Organic Materials Identified in the 11/4/76 1-7
Extract. 15
6. Organic Materials Identified in the 8/3/76 K-7
Extract. 16
7. Organic Materials Identified in the 11/4/76 K-7
Extract 16
8. Organic Materials Identified in the 8/3/76 L-7
(Final Effluent) Extract 17
9. Organic Materials Identified in the 11/4/76 L-7
(Final Effluent) Extract 17
10. Halogenated Ethanes and Methanes Identified in Effluents
of the Combined Biological/Physical-Chemical Process... 18
11. Other Volatile (Purgeable) Organic Materials Identified
in Effluents of the Combined Biological/Physical-
Chemical Process 19
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TABLE 1
Chemical Parameters Typical of the District of Columbia
Raw Wastewater and After Various Stages in the
Combined Biological/Physical-Chemical Treatment Process
Chemical Parameters
Alkalinity, P
Alkalinity, MO
pH
Conductivity (MHOS)
TOC
BOD
COD
Total P (P04)
TKN
NH3-N
NOj + NO^-N
Suspended Solids
VSS
TS
Ca++
T-Fe
Mg+H"
Cl"
so4:
Na+
K+
F"
MBAS
A!***
H-l
—
126
7.2
-
72
104
237
15.0
19.0
16.0
0.89
107
83.0
-
32
1.3
6.5
-
-
-
-
0.7
8.9
-
1-7
—
.
-.
-
7.0
4.5
18.5
0.3
0.76
0.20
4.7
3.9
2.7
-
-
-
-
.
-
-
-
-
.28
-
K-7
».
.
7.5
-
2.5
1.3
6.6
0.17
0.25
0.95
4.8
0.97
-
-
-
-
-
-
-
-
-
-
-
.25
L-7
-
96
7.5
710,000
2.7
2,8
6.5
0.16
0.22
0.65
4.8
0.86
-
368
56
0.6
5.4
68.7
50.7
34.1
8.2
0.7
.14
-
10
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TABLE 2
Organic Materials Identified in the 8/3/76
Raw Wastewater Extract
Compound Concentration (ug/D
H-l Neutrals
Tetrachloroethylene 3
Methylethylbenzene 1
Trimethylbenzene 1
Trimethylbenzene 1
Saturated Aliphatic Hydrocarbon 1
Aromatic Hydrocarbon 1
Saturated Aliphatic Hydrocarbon 1
Saturated Aliphatic Hydrocarbon 1
Saturated Aliphatic Hydrocarbon 1
H-l Acids
Caprylic Acid 1
Octanoic Acid 1
Nonanoic Acid 1
Decanoic Acid (Tentative) 1
Palmitic Acid 1
Oleic Acid 2
Stearic Acid 2
H-l Bases
Caffein 1
11
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TABLE 3
Organic Materials Identified in the 11/4/76
Raw Wastewater Extract
Compound Concentration (yg/1)
H-l Neutrals
Tetrachloroethylene 2
1,3-Xylene 1
2-Butaxyethane 2
Dioctylether (Tentative) 1
l=Methylethylbenzene 1
? 1
Trimethylbenzene 1
Saturated Aliphatic Hydrocarbon 1
Saturated Aliphatic Hydrocarbon 1
Trimethylbenzene 2
Methyl-isopropylcyclohexane 1
? 2
Saturated Aliphatic Hydrocarbon 1
? 3
? 3
? 1
Alpha Terpinol - 1
Alpha Terpinol 2
? 3
? 3
Saturated Aliphatic Hydrocarbon 1
Saturated Aliphatic Hydrocarbon 2
Saturated Aliphatic Hydrocarbon 1
Saturated Aliphatic Hydrocarbon 2
Saturated Aliphatic Hydrocarbon 4
Saturated Aliphatic Hydrocarbon 2
1,3-dimethylnaphthalene 4
Saturated Aliphatic Hydrocarbon 2
Saturated Aliphatic Hydrocarbon 2
Trimethylnaphthalene 4
Saturated Aliphatic Hydrocarbon. 1
Aliphatic Ketone 1
Saturated Aliphatic Hydrocarbon 2
Saturated Aliphatic Hydrocarbon 3
Laurie Acid 2
Saturated Aliphatic Hydrocarbon 1
Saturated Aliphatic Hydrocarbon 1
Saturated Aliphatic Hydrocarbon 1
Saturated Aliphatic Hydrocarbon 2
Saturated Aliphatic Hydrocarbon 1
Oleic Acid 3
Caffein 1
Saturated Hydrocarbon 1
Palmitic Acid > 20
Saturated Hydrocarbon -
Stearic Acid > 20
? 2
Saturated Hydrocarbon 1
Saturated Hydrocarbon 1
Steroid 1
Steroid 1
12
-------
TABLE 3 (Cont'd)
Organic Materials Identified in the 11/4/76
Raw Wastewater Extract
Compound Concentration (ug/D
H-l Acids
3-methyl pentanal 1
Nitroethylpropionate (Tentative) 1
2-N-butoxyethanol 1
Hexanoic Acid (Tentative) 1
Saturated Aliphatic Hydrocarbon 1
Saturated Aliphatic Hydrocarbon 1
Saturated Aliphatic Hydrocarbon 1
Saturated Aliphatic Hydrocarbon 2
Saturated Aliphatic Hydrocarbon 3
Saturated Aliphatic Hydrocarbon 1
Saturated Aliphatic Hydrocarbon 1
Saturated Aliphatic Hydrocarbon 1
Unsaturated Hydrocarbon 1
Saturated Aliphatic Hydrocarbon 3
2-Undecenal (Tentative) 1
Saturated Aliphatic Hydrocarbon . 1
Saturated Aliphatic Hydrocarbon C^-Ci? 3
Saturated Aliphatic Hydrocarbon Ci2 U 2
Saturated Aliphatic Hydrocarbon 3
Saturated Aliphatic Hydrocarbon cg~C]_3 2
Saturated Aliphatic Hydrocarbon 1
Saturated Aliphatic Hydrocarbon 1
Saturated Aliphatic Hydrocarbon 1
Saturated Aliphatic Hydrocarbon C12~G22 1
Unsaturated Hydrocarbon 1
Saturated Aliphatic Hydrocarbon 1
Palmitic Acid 1
Di(2-ethylhexyl) phthalate 1
H-l Bases
N,N-Diphenyl hydrazine (trace)
? 1
7 1
13
-------
TABLE 4
Organic Materials Identified in the 8/3/76
1-7 Extract
Compound Concentration (ug/D
1-7 Neutrals
5 methyl-1-hexene 1
1-octene 1
3-Nonone (Tentative) 1
3-hexanol 1
Tetraethyl lead 1
Tetramethylsilane 1
Butyl phthalate 1
1-7 Acids
Saturated Aliphatic Hydrocarbon 1
Unsaturated Aliphatic Hydrocarbon 1
Benzothiazole 1
Butyl phthalate 1
1-7 Bases
No peaks above 1 ppb
14
-------
TABLE 5
Organic Materials Identified in the 11/4/76
1-7 Extract
Compound Concentration (yg/1)
1-7 Neutrals
Acetic Acid 3
Saturated Aliphatic Hydrocarbon 1
Saturated Aliphatic Hydrocarbon 1
1,2-ethane diacetate 1
Aliphatic Alcohol 1
Cyclohexenone 1
Saturated Aliphatic Hydrocarbon 1
? 1
4-heptanone 1
4-chlorocyclohexanol 1
? 1
? 1
Aliphatic Hydrocarbon 1
? 1
Saturated Aliphatic Hydrocarbon 1
Saturated Aliphatic Hydrocarbon 1
4-methyl-2,6-ditert-butylphenol 1
Saturated Aliphatic Hydrocarbon 1
4-ethyl-2,6-ditert-butylphenol 1
Diethylphthalate 1
Aromatic Hydrocarbon 1
? 2
l,2-dimethyl-4-benzylbenzene 1
Saturated Aliphatic Hydrocarbon 1
Saturated Aliphatic Hydrocarbon 1
Saturated Aliphatic Hydrocarbon 1
? 1
1-7 Acids
No peaks above 1 ppb
1-7 Bases
No peaks above 1 ppb
15
-------
TABLE 6
Organic Materials Identified in the
8/3/76 K-7 Extract
Compound Concentration (ug/D
K-7 Acids
Acetic Acid . 1
Unsaturated Hydrocarbon 1
Unsaturated Hydrocarbon 1
3-heptanol 1
3-heptanone 1
K-7 Bases
No peaks above 1 ppb
TABLE 7
Organic Materials Identified in the
11/4/76 K-7 Extract
Compound Concentration (ug/1)
K-7 Neutrals
Unsaturated Aliphatic Hydrocarbon 1
Unsaturated Aliphatic Hydrocarbon 1
K-7 Acids
Unsaturated Hydrocarbon 1
Unsaturated Hydrocarbon 1
Di-(2-ethylhexyl) phthalate 1
"a-phthalate" 1
K-7 Bases
Unsaturated Hydrocarbon 1
Unsaturated Hydrocarbon 1
N,N-diphenylhydrazine (Tentative) 1
16
-------
TABLE 8
Organic Materials Identified in the 8/3/76
L-7 (Final Effluent) Extract
Compound Concentration (ug/D
L-7 Neutrals
Dnsaturated Hydrocarbon (C, .-C..-) 2
Isobutyl phthalate 9 3
L-7 Acids
No peaks above 1 ppb
L-7 Bases
5-methyl-l-hexene 1
Trans-2-octenal (Tentative) 3
TABLE 9
Organic Materials Identified in the 11/4/76
L-7 (Final Effluent) Extract
Compound Concentration (ug/1)
L-7 Neutrals
Unsaturated Aliphatic Hydrocarbon 2
Unsaturated Aliphatic Hydrocarbon 2
3-methyl-2-pentanone 1
Saturated Aliphatic Hydrocarbon 1
C-n-C-2 Carboxylic Acid 2
Dusobutyl phthalate 1
2-fautoxy-2-oxoethyl-butyl phthalate 4
Diisooctylphthalate 2
L-7 Acids
Hydroxy-2-propanone 1
Acetic Acid !
Unsaturated Hydrocarbon 1
Di-(2-ethylhexyl) phthalate 1
L-7 Bases
No peaks from sample above 1 ppb
17
-------
TABLE 10
Halogenated Ethanes and Methanes Identified in
Effluents of the Combined Biological/Physical-Chemical Process
Compound
H-l
Extract No.
1-7 J-7
L-7
6/18/76
Chloroform
Bromodichloromethane
Dibromochloromethane
Bromofonn
Carbon tetrachloride
Tetrachloroethylene
1,1,1-Trichloroethane
7/1/76
Chloroform
Bromodichloromethane
Dibromochloromethane
Bromoform
Carbon tetrachloride
Tetrachloroethylene
1,1,1-Trichloroethane
7/3/76
Chloroform
Bromodichloromethane
Dibromochloromethane
Bromoform
Carbon tetrachloride
Te trachloroethylene
1,1,1-Trichloroethane
10
5
2
4
10
1
4
3
2
5
2
7
3
1
10
5
5
10
1
5
4
3
2
1
Trace
—
_
-
-
6
-
Trace
_
-
—
5
3
—
_
—
—
18
-------
TABLE 11
Other Volatile (Purgeable) Organic Materials
Identified in Effluents of the Combined
Biological/Physical-Chemical Process
Compound H-l 1-7 J-7 K-7
6/18/76;
Acetaldehyde -* /* /
Methanol - - - -
Acetone / / / /
Dichloromethane 10 - 1 1
Acrolein - / - /
Carbon disulfide - /
Dimethyl disulfide 6 -
Toluene 2 -
Xylene 1 /
Alkyl benzene 1 -
Benzaldehyde - /
7/1/76;
Acetaldehyde / - - -
Methanol - - -
Acetone / / / /
Dichloromethane 1 - 1 -
Acrolein / -
Carbon disulfide / -
Dimethyl disulfide - -
Toluene 2 - / -
Xylene - / / /
Alkyl benzene / _ _ _
Benzaldehyde - / - 5
7/8/76;
Acetaldehyde - ~
Methanol / ~
Acetone J / / /
Dichloromethane ~ / 2 /
Acrolein ~ ~ ~ ~
Carbon disulfide - - / -
Dimethyl disulfide - "/"/"/
Toluene 2 , , \.
Xylene - / / ~
Alkyl benzene ~ ~
Benzaldehyde ~ - - v
Compounds represented by a dash (-) =» not detected.
Compounds represented by a check (/) = trace amounts (less than
1 Ug/1.
19
-------
FIGURES
1. Schematic of Combined Biological/Phystcal-Chemical
Treatment Process , 21
2. Removal of TOO 1... 22
3. Total Ion Chromatogram of 81 ank Extract. 23
4. Total Ion Chromatogram of 8/3/76 H-l Neutral Extract... 24-25
5. Total Ion Chromatogram of 8/3/76 H-l Neutral Extract... 26-27
6. Total Ion Chromatogram of 8/3/76 H-l Base Extract...... 28
7. Total Ion Chromatogram of 8/3/76 1-7 Neutral Extract... 29
8. Total Ion Chromatogram of 8/3/76 1-7 Acid Extract .. 30
9. Total Ion Chromatogram of 8/3/76 1-7 Base Extract 31
10. Total Ion Chromatogram of 11/4/76 K-7 Neutral Extract.. 32
11. Total Ion Chromatogram of 11/4/76 K-7 Acid Extract 33
12. Total Ion Chromatogram of 11/4/76 K-7 Base Extract 34
13. Total Ion Chromatogram of 11/4/76 L-7 Neutral Extract.. 35
14. Total Ion Chromatogram of 11/4/76 L-7 Acid Extract 36
15. Total Ion Chromatogram of 11/4/76 L-7 Base Extract 37
16. Removal of Volatile Organics 38
20
-------
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DENITRIFICATION COLUMNS,
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12
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13
i
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I
J
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J2
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POLYMER KQ
J4
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£
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T • • • »- *•" •J a • * • - ^j^ i &
DENITRIFICATION CARBON ABSORPTION | HOLDING TANK~]
K7
CHLORINE
LO
CONTACT
TANK
CHLORINATION
L
L7
Fig. 1. Schematic Flow Diagram
FINAL EFFLUENT
-------
70
60
50
^ 40
0>
E
u
O
30
20
10
TREATMENT PROCESS
.Fig. 2. Removal of TOG
22
-------
10J
ea -
CO
%
rrrrr
' ''•' '-J - *-
mrrrn-rrn i rrrri i i i » rrrT]
2UD
333
rrrr I
1313
S03
£01)
7fl3
"I1
609
r-rrrTTTTrri i 11 I 11 i
1039
1100
rrr frr ITT rrrr r rr rnri i rrr f rrr •
J2UU lj.')J HJU
Fig. 3, Total Ion Chromatogram of Blank Extract
-------
eo-
10
20-
ni mill ii ii
1203 130(3
111 ii 111111 ii 111 n i irn i ii 111 ii i ii 11111 ii i n 111 ii iii 11111 ii i ii
SBO GOO ^(O B03 800 1000 1100
11 rrrif ITM rri i rri i r 111
Fig. 4, Total Ion Chromatogram of 8/3/76 H-l Neutral Extract
-------
100-i
ea-
GO-
ro
en
20-
11 11111111111111 ii 11111111 ii 111111111 [ 11111 r 11 ii 111
ion i7oa ieoo
ri 1111 ii 111 ii 1111111111111111 n 11111
2000 2100 ??fa 23OO
2100 2SOO
royrr
2COO
I 11 I 1 I I I I I l I I
2fltVJ
Fig. 4 (Cont'd). Total Ion ChromatogrAm Pf 8/3/76 H-l Neutral Extract
-------
ro
cr\
IfltJ-l
ea-
ee-
2fl~
1 n ri ii n 111111 iri i rn 11 fit 11111 n 1111
noa. e
-------
100-1
80-
68-
10-
20-
rrni 111 »i i n 1111111111111111111 n 1111 nn 111111111111111111 mi i n 1111111111| i n 111111111111 n 11 j n 11111 ri| 11 rrrni i| i n 111111| 1111 m 11 j
lead nao IBM isdfl zaoa 2100 2200 23oo 2100 2sao 2£tM r/oo
Fig, 5 (Cont'd). Total Ion Chromatogram of 8/3/76 H-l Neutral Extract
-------
60-
cx>
20 H
1111111 ?lTi il{VYi u i ufTii rm ii i^ i irrn i iri 111 ri ri i > i> i irrii in 11 »i i n fi in 1111111 n 11^ 111111111*1111 Ai it 11111»»i i ^ 11111
ioa SM gaa 100 soo eoa 700 ooa sou 1000 neo \2&3 iscn neu
Fig. 6. Total Iqn ChromAtogrsni of 8/3/76 H-] Base Extract
-------
eo-
60-
to
10-
20-
n i 11111 ii 11 iTTrTn M'I i f. j I n i I'lTTfj iVi 11 iTrfp'ryriTTTTprrFr
100 200 300 1OO &00 £00
I|...,.M,,|,,, ......,,...,,,,,,,,
1100
703
eca
sso
loaa
I Mil. .11. 1)1
1200
Fig. 7, Total Ion Chromatogram of 8/3/76 J-7 Neutral Extract
-------
CO
CD
loa—i
ea-
10-
20-
-J
i
-X
rri ri 11 n 11 imfi'l i f ft il I*TI i iniTriif i 1111'l i i]t rii i u 111 h 111 u 11111111111 ip'i 111»1111111111 n i'i i lifi i n 11 iTi
loa goo aea -wo soa eeo 700 eoo aaa itaa iioa
1 1 ill 1 111 1 1 1 1 1 rrrrriTTri
12tt3 1330
Fig. 8. Total Ion Chromatogram of 8/3/76 1-7 Acid Extract
-------
60 H
60 H
20 -1
A
Jl.
'l 1 i'l 1 1 ri 1 1 111 I'm II n 11 Till 1 I'l II Mil I 1 1 1 I 1 1 i II 1 1 1 1 I i-iiTTiii-nnnTiiTTi n-ii|iiiiiiiii|iiiiiiiii|iiiiiiiiT|iiii-ii-ii-iiiiii ITTTII i i ii i ii i ii IB
100 203 3flfl 103 503 6£» 700 600 9£H JOM HOfl 120J 43M JWO
Fig. 9. Total Ion Chromatogratn of 8/3/76 J-7 Base Extract
-------
icw
60-
ro
10
20-
.,, f.... V, rf | V
?ao eaa
'
L.J
,ir,Mrrrrrrrpri
TrnrrryTTrrrrrT-rpTrrn
10J 20d
3U3 103
itwa uoo J2uj
Fig. 10. Total Ion Chromatogram of 11/4/76 K-7 Neutral Extract
-------
10) -i
OJ
CO
63 -
20-
J
Trn
>
"
K
i
,,,,
U
Vj__ fv
2«J 3aa itu soj eoa ?oo eoj aaj »onj ntw i2dj
riyrrr
IJ.W
HiM
Fig. 11. Total Ion Chromatogram of 11/4/76 K-7 Add Extract
-------
loo
eo-
60-
20-
i ii 1 1 1 ii i Ti'yriYi
100 500
i ti i i' n 11 ir 1111 i-i 11 rn 11 n 1111
eoa 7oa eoo aao 1000 nod
i1 mi ir 11 rmurnniTi u mil iinl'ifurirriTmi iTm iHTrrmTn i n nrrnrrT
i in 1 in 1
10d 203
MI 1 1
300
I I I I I I
Fig. 12. Total Ion Chromatogram of 11/4/76 K-7 Base Extract
-------
iaa-i
60
to-
20
OWL
IflO
1111 i ii 11 r 11111'l i
300 100
11 i 11 II II i I 'TfT'l 11 11 I 11 11
SOO 600 700
rrpn
600
ri 11111111111 i'i 111 i 1111 n i»11»1111111111
1000 1100 1200 1300 StOfl
Fig. 13. Total Ion Chromatogram of 11/4/76 L-7 Neutral Extract
-------
ea-
eo-
OJ
cr>
20-
1 1 1 1 1 1 1 » i r 1 1 1 1 » 1 1
iaa zaa
1 1 1 1 1 1 1 1 1 1 1 ii 1 1 1 1 1 1 1 1 1 1 1 1 1 1 ! i n i IT i
3oa lea sea eoa
'i i i
1 1 1 i
700
1 1 M'I rmt*!*rpTn
eoa sso
1 1 i'i 1 1 1 1 1 1 1 » n 1
1000 1100
1 n 1 1 ii i 1
1203
1 1 1 r 1 1
Fig. 14. Total Ion Chromatogram of 11/4/76 L-7 Acid Extract
-------
60-
60-
10-
20-
_^_
lAkJJLjL^/^Mr^ | |
1 1 I 1 1 I 1 I'l IT • ii|iii~iiiiii|ii«iiiiiiiiiiiBi«ii|«*0iii«'>|««'«i«>>»| |««i*>«<<«|i>iiiiiii|*ii«iiiii|iiigeiRii I R |-f i e 1 8 1 f"| 1 I'll 'I 1 1 1 I I 11
103 200 300 100 SOO GOO 700 fltH 8O3 1000 1100 1200 1300 1100
Fig. 15. Total Ion Chromatogrein) of 11/4/76 L-7 Base Extract
-------
TO
i
l/>
a
z
D
o
a.
2
O
u
u
Z
<
O
on
O
O
>
O CHLOROFORM
• BROMODICHLOROMETHANE
X DIBROMOCHLOROMETHANE
A BROMOFORM
O CARBON TETRACHLORIDE
• 1,2 DICHLOROETHANE
TREATMENT PROCESS
Fig. 16. Removal of Volatile Organics
38
------- |