the oxidation or removal of NH3-N is only partial rather than

complete. The Occurrence of

Post treatment. It may be advantageous to follow breakpoint
chlorination with dechlorination by carbon adsorption or by
use a sulfur compound. Carbon adsorbs any chloroorganics
that may be produced during the breakpoint procedure. In the
Organohaiides in
case of wastewater, this may solve any problems of toxicity to
fish; in the case of water treatment, it may improve taste-and-
odor characteristics of the treated water.
Chlorinated Drinking
References
1. MAJUMDAR, S. B. ET AL. Inactivation of Poliovirus in Water by
Waters
Ozonation. Jour. WPCF, 45:12:2433 (Dec. 1973).
2. CULP, R. L.; EVANS, DAVID; & WILSON, JERRY. Advanced
Wastewater Treatment as Practiced at South Tahoe. EPA Wtr. T.A. Bellar, J.J. Lichtenberg,
Pollution Cont. Res. Ser., Pubn. 17010 ELQ, 257, (Aug. 1971).
3. MORRIS, J. CARRELL. Chlorination and Disinfection State of the and R.C. Kroner
Art. Jour. AWWA, 63:12:769 (Dec. 1971).
4. SCARPING, P. V., ET AL. A Comparative Study of the Inactivation of
Virus in Water by Chlorine. Wtr. Res., 6:959 (1972).
5. PRESSLEY, T. A.; BISHOP, D. F.; & ROAN, S. G. Ammonia-Nitrogen
Removal by Breakpoint Chlorination Envir. Set. Technol., 6:7:622 The national media have reported that the chlorination
(Jul. 1972). of water during treatment is responsible for the
6. WHITE, GEORGE C. Handbookof Chlorination. Van Nostrand formation of potentially harmful chlorinated organic
Reinhold Co., New York (1972). materials notably chloroform in the nation's water
7. MOORE, EDWARD W. Fundamentals of Chlorination of Sewage and
Waste. Wtr. Sew. Wks., 98:3:130 (Mar. 1951). supplies. The following report by three research
8. SELLECK, R. E. & COLLINS, H. F. Disinfection in Wastewater scientists from the Natl. Envir. Res. Ctr. of EPA
Reuse. Unpublished. describes that agency's research concerning these
9. AWWA Com. Rprt. Viruses in Water. Jour. AWWA, 61:10:491 organohalides. The report concludes that the number
(Oct. 1969).
10. HUDSON, H. E., JR. High-QualityWater Production and Viral Dis of organohalides formed during the chlorination
ease. Jour. AWWA, 54:10:1265 (Oct. 1962). process does not constitute any immediate threat to
11. SELLECK, R. F.; COLLINS, H. F.; & WHITE, G. C. Kinetics of the public health or welfare, but that more research
Wastewater Chlorination in Continuous Flow Processes. Proc. into possible long-term effects is warranted.
5th Intl. Conf. on Wtr. Pollution Res., 11-19, (1971).
12. ROBECK, G. G.; CLARKE, N. A.; & DOSTAL, K. A. Effectiveness of
Water Treatment Processes in Virus Removal. Jour. AWWA,
54:10:1274 (Oct. 1962). A contribution submitted to the JOURNAL on Nov. 7, 1974, by
T.A. Bellar, J.J. Lichtenberg, and R.C. Kroner (Active Member,
Bibliography AWWA), all of the Natl. Envir. Res. Ctr., EPA, Cincinnati, Ohio.

BERG, G. How's Your Virus I.Q? Wtr. Waste Engrg., 10:35 (Oct. 1971).
BERGER, BERNARD B. Current Perspectives in Disinfection. Proc. Natl.
Specialty Conf. on Disinfection, (Jul. 1970).
COLLINS, H. F.; SELLECK, R. E,; & WHITE, G. C. Problems in Obtaining
Adequate Sewage Disinfection. Proc. Natl. Specialty Conf. on
Disinfection, ASCE, (1971).
CULP, G. L. & CULP, R. L. New Concepts in Water Purification. Van
Nostrand Reinhold Co., New York (1974).
KABLER, P. W., ET AL. Viricidal Efficiency of Disinfectants in Water.
Public Health Rprt., 76:565 (1961).
KELLEY, S. & SANDERSON, W. W. The Effect of Chlorine in Water on
Enteric Viruses. Amer. Jour. Public Health, 48:1233 (1958).
KELLEY, S. & SANDERSON, W. W. The Effect of Chlorine in Water on
Enteric Viruses 2. The Effect of Combined Chlorine on
Poliomyelitis and Coxsackie Viruses. Amer. Jour. Public Health,
50:14 (1960).
KRUSE, C. S., ET AL. Halogen Action on Bacterial, Viruses and Protozoa.
Proc. Natl. Specialty Conf. on Disinfection, ASCE, (Jul. 1970).
KRUSE, C. W.; OLIVIERI, V. P.; & KAWATA, K. The Enhancement of
Viral Inactivation by Halogens. Wtr. Sew. Wks., 6:187 (Jun.
1971).
LOTHROP, T. L. & SPROUL, O. J. High-Level Inactivation of Viruses in
Wastewater by Chlorination. Jour. WPCF, 41:567 (1969).
PALIN, A. T. Chemical Aspects of Chlorination. Jour. Inst. Wtr. Engrs.,
4:565 (1950).
PALIN, A. T. A Study of the Chloro Derivatives of Ammonia and Re
lated Compounds with Special Reference to Their Formation in
the Chlorination of Natural and Polluted Waters. Wtr. Waste
Engrg., 151 (1950).
SORBER, C. A.; MALINA, J. F., JR.; & SAGIC, B. P. Quantitative Pro
cedure for Evaluating the Performance Level of Water and
Waste Water Treatment Processes at Naturally Occuring Virus
Levels. Envir. Sci. Technol., 6:5:438 (May 1972).
DECEMBER 1974
In recent years there has been great speculation and con
cern about the effect of chlorination upon organic materials
contained in natural waters and wastewaters. Considering the
widespread use of chlorine in water- and sewage-treatment
processes, household and commercial laundering, paper-pulp
bleaching, and related processes, it is easy to postulate the
possible inadvertent, widespread production of chlorinated
organic materials. There are an infinite number of organic
materials commonly contained in natural waters and waste-
waters that may react with free chlorine. For the most part
mechanisms for these reactions have not been studied
because rapid and precise analytical methods capable of
monitoring the reaction products have not been available.
Kleopfer and Fairless,1 Novak et at,2 Friloux,3'4 Grob,5 and
others6 have reported the presence of organohalides in
finished waters, but because of the nature of the studies made
and the analytical methods used, no conclusions could be
drawn as to the source of these compounds.
Recently the Methods Dev. and Qual. Assurance Lab. of
the Natl. Envir. Res. Ctr. in Cincinnati has developed and re
ported on a procedure for isolating and measuring nanogram
quantities of volatile and semi-volatile organic materials in
wastewaters (see "Determining Volatile Organics at
Microgram-Per- Litre Levels by Gas Chromatography" on
T.A. BELLAR ET AL 703

page 739 of this issue of JOURNAL AWWA). Preliminary ob
servations made during the development of this technique
showed the presence of organochlorine compounds in
laboratory-distilled and tap water. Further observations also
indicated the presence of some brominated hydrocarbons in
the tap waters. Raw river water, the source of the tap water,
contained none or much lower concentrations of the
organohalides. Since their presence in water may represent a
possible health hazard and reflect a background level for in
dustrial effluents, it was decided to quantitate and to attempt
to identify the source of these compounds.
Experimental
Apparatus. A gas chromatograph* was equipped with a dual-
flame ionization detector and a microcoulometric detector
(halide mode). Dual, stainless-steel columns, 180-cm (6-ft)
long x 2.67 mm (0.105 in.) ID were packed with
Chromosorb-101 (60-80 mesh). The oven temperature was
isothermal at 190C or programmed from 150C to 270C at
6.5C/min. Nitrogen, at 50 ml/min, was employed as the car
rier gas.
Another gas chromatographt with a mass spectrometer*
controlled by a data acquisition system§ was employed. The
glass column, 240-cm (8-ft) long x 2-mm (0.078-in.) ID, was
packed with Chromosorb-101 (50-60 mesh). Helium, at 30
ml/min, was employed as the carrier gas. The initial oven tem
perature of 125C was held for 3 min and then programmed to
220C at 4C/min.
The purging device, trap, and desorption system used for
this work have been described previously (see "Determining
Volatile Organics at Microgram-Per-Litre Levels by Gas
chromatography" on page 739 of this issue of JOURNAL
AWWA).
Reagents. Water free of interfering organics was prepared by
passing distilled water through a Millipore Super-Q water-
treatment system.
Standard, stock solutions were prepared by injecting 1-5 pi
of the compound to be determined into a 1-1 volumetric flask
partially filled with organic-free water. The mixture was then
diluted to volume with organic-free water to give concentra
tions between 1 and 7 mg/1. Dilutions were then made from
the stock solution by pipetting a known quantity of stock solu
tion into a partially filled volumetric flask and diluting to
volume with organic-free water. For low-level work (1-10 jig/
1), a 1:10 dilution of the stock solution was prepared, and sec-'
ondary dilutions were prepared from this solution as required.
Procedure. Water samples were collected in 125- or 500-ml,
ground-glass, stoppered bottles. The bottles were carefully
filled; no bubbles were allowed to pass through the samples as
the bottles filled. Care was taken to eliminate the air space
above the samples by overfilling the bottles and then displac
ing part of each sample with the glass stopper. Analyses were
performed as soon as possible after the sample collection.
Time lapsed between collection and analyses was noted.
The water samples were analyzed for volatile components
by the following procedure. Nitrogen (200 ml at 10-15 ml/
min) was bubbled through 5.0 ml of sample to transfer the
volatiles from the aqueous phase to the gaseous phase. The
organic materials contained in the gaseous phase were con
centrated by using a noncryogenic, trapping technique7'8
Perkin-Elmer 900 model
tVarian Aerograph 1400 model
tFinnigan 1015 C Quadrupole model
§Systems Industries 150 Data Acquisition system
704 MANAGEMENT
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followed by a gas-chromatographic analysis. This procedure
(see "Determining Volatile Organics at Microgram-Per-Litre
Levels by Gas Chromatography" on page of this issue of
Journal AWWA) provides a method capable of analyzing for
organic materials that are < 2 per cent soluble in water and
that boil below 150C. An average detection limit of 1 jug/1 was
achieved.
Tentative qualitative identifications were made by
microcoulometric-gas chromatography (MCT) and then
confirmed by gas-chromatography mass-spectrographic
(GC-MS) techniques. Structure determinations were verified
with the use of a conversational-mass-spectral retrieval
system.9 Quantitative data were generated with the use of the
flame-ionization (FID) and MCT detectors.
Standard solutions of chloroform were prepared in
"organic-free" distilled water at concentrations similar to
those found in the unknowns. The standards and unknowns
were analyzed in an identical manner, and peak areas were
measured and compared for quantitative determination. At
the time of analysis, reagent-grade bromodichloromethane
and dibromochloromethane were not available in the
laboratory. Since the FID and the MCT should respond quan
titatively in an identical manner to all of these trihaloge-
nated-methane compounds, 10' 11 quantitative values were
generated using the peak-area response of chloroform.
Samples were collected from several sources for this study.
These sources included a major surface stream., a municipal
water-treatment plant, finished tap water from widespread
locations, and a sewage-treatment plant.
Results and Discussion
Initial gas-chromatographic analyses were conducted on
the laboratory tap water with the use of the FID and MCT.
Subsequently the samples were analyzed by GC-MS to verify
the identity of the compounds detected in the finished waters.
The GC-MS-reconstructed chromatogram and the identified
components are shown in Fig. 1. Unequivocal qualitative
identifications of ethyl alcohol, chloroform, bromodichloro
methane, and dibromochloromethane were made with the
use of this instrumentation. The FID-GC was calibrated for
the trihalogenated-methane compounds. Although the pres
ence of ethyl alcohol was verified by the mass spectrometer,
no quantitative data were obtained.
As a matter of interest, analyses were conducted on other
finished waters. The organohalide content found in these
waters and their raw-water sources are listed in Table 1.
Where the water source was low in total organics, such as well
water, the resulting concentrations of haiogenated products
were low. Where the water source was high in total organics,
such as surface waters, the resulting concentrations of haioge
nated products were high.
Several samples were collected from various parts of a
water-treatment plant in a progressive manner identical to the
path of the water as it was processed through the plant (see
Fig. 2). Table 2 shows the quantitative data obtained from
these samples.
Large amounts of chloroform are stored and used in the
EPA laboratory. To determine whether or not accidental con
tamination of the samples was occurring in the laboratory,
several analyses were performed upon the raw river water.
These analyses were made alternately with the analyses of the
samples from the water-treatment plant (Table 2) throughout
the day. The raw river-water concentrations found were con
stant at 0.9 0.2 fj.g/1. Based on these resul.ts, it was deter-
JOURNAL AWWA
 15518833, 1974, 12, Downloaded from https://awwa.onlinelibrary.wiley.com/doi/10.1002/j.1551-8833.1974.tb02129.x by Tsinghua University Library, Wiley Online Library on [10/09/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
TABLE 1 TABLE 2
Trihalogenated-Methane Content of Various Municipal Water Supplies Trihalogenated-Methane Content of Water From Water-Treatment Plant

Concentration- M£" Concentration pg/t

Raw- Bromo- Dibromo- Free Bromo- Dibromo-
Sampling Water Date Chloro dichloro- chloro- Samp. Cl Chloro dichloro-
Sites chloro-
Source Coll. form methane methane Sample Source Point am form methane methane
100* surface 8-73 94.0
100' 20.8 2.0 Raw river water 1 0.0 0.9 «
surface 2-74 37.3 9.1 1.3 River water treated with
lOlt surface 2-74 70.3 10.2 0.4* chlorine and alum-chlorine
102t surface 2-74 152.0 6.2 0.9* contact time 80 min. 2 6 22.1
2-74 6.3 0.7
103t surface 84.0 2.9 <0.1 Three- day-old
104' well 8-73 2.9
104* § § settled water 3 2 60.8 18.0 1.1
well 2-74 4.4 1.9 0.9* Water flowing from settled
105* well 2-74 1.7 1.1 0.8* area to filterst 4 2.2 127 21.9 2.4
106t well 12-73 3.5 § § Filter effluent 5 * 83.9 18.0 1.7
Finished water 6 1.75 94.0 20.8 2.0
'Sample age < 4 hr
tSampIe age unknown; >24 hr 'None detected. If present, the concentration is <0.1
^Approximate value, 20 per cent tCarbon slurry added at this point
§No data ^Unknown

TABLE 3
Organochlorine Compounds in Water From Sewage-Treatment Plant

Concentration ng/l

Influent Effluent Effluent

Before Before After
Compound* Treatment Chlorination Chlorination
Methylene chloride 8.2 2.9 3.4
Chloroform 9.3 7.1 12.1
1 ,1 ,1-Trichloroethane 16.5 9.0 8.5
1 ,1 ,2-Trichloroethylene 40.4 8.6 9.8
1 ,1 ,2,2-Tetrachloroethylene 6.2 3.9 4.2
2 Dichlorobenzen.es 10.6 5.6 6.3
60 80 100 S Trichlorobenzenes 66.9 56.7 56.9
Spectrum Number
All confirmed by GC-MS
Fig. 1. Reconstructed GC-MS Chromatogram of Finished Water

,,----0-00-

Bromodichloro Methane

Settled Water Average Age-

Three Days

30 40 50
Chlorine Contact Time-hr

Carbon Slurry
Fig. 3. Chlorinated Ohio River Water
Filter

mined that little or no contamination of the samples occurred

in the laboratory.
The data reported in Table 2 show that the trihalogenated
Chlorine
methanes originate at the water-treatment plant. It is interest
ing to note that each time additional chlorine is added to
• Finished Water maintain or increase the free-chlorine concentration of the
f J-* Indicates Sampling Point
water, a significant increase in the chloroform level results
(see Fig. 2). The decrease in the concentration of trihaloge
Fig. 2. Water-Treatment-Plant Sampling Points nated methanes after sampling-point four evidently results
DECEMBER 1974 T.A. BELLAR ET AL 705

from the introduction of an activated-carbon slurry.
A second series of analyses was performed on raw river
water that had been treated with alum and chlorine. The sam
ple was collected at the water-treatment plant and held in the
laboratory for 71 hr. It was analyzed five times within the first
6 hr. After standing overnight it was analyzed at 26, 28, 29,
and 71. hr. The concentrations of halogenated methanes
found can be seen in Fig. 3.
These data show that in this static system, after a single ad
dition of free chlorine, trihalogenated-methane compounds
are formed. The concentration of these compounds increased
with respect to chlorine contact time up to approximately 15
hr. Little or no increase was noted after that time. This obser
vation and the previous observation that each addition of free
chlorine produces an increase in the concentration of
trihaiogenated methanes show that these compounds are not
introduced as impurities contained in the alum or the chlorine
used for treatment of the water. It is apparent that a chemical
reaction is taking place between free chlorine and organic
compounds present in the water. One possible mechanism for
the formation of chloroform is suggested by the compounds
detected in the tap water ethanol and trihaiogenated
methanes (no mono- or dihalogenated compounds were
found in the tap water). The ethanol oxidizes to acetaldehyde.
The acetaldehyde reacts with free chlorine to form chloral.
The chloral reacts with water to form chloral hydrate, and the
chloral hydrate then decomposes to form chloroform.
O O H
CH3-CH 2OH — CH3-C-H - C13-C-C-H - C13-C-C-(OH) 2
CHC13
At this time, the authors have no experimental evidence to
show that this is in fact the mechanism by which the
chloroform is produced.
The presence of the two brominated compounds listed in
Table 1 probably results from bromine impurities contained
in the chlorine. The bromine would react in the same manner
as chlorine to form the brominated homologs. The concentra
tion of the tribrominated homolog, bromoform, if present,
was below the detection limit of the method. Other
researchers1 have reported the presence of these trihaiogen
ated compounds, including bromoform, in finished waters,
but the possibility that they may have resulted from the
chlorination process was not suggested.
Table 3 lists results of the analyses of grab samples col
lected at several stages of treatment in a local sewage-treat
ment plant. Since this treatment plant serves a large industrial
as well as a municipal area, a multitude of diverse organic
compounds should be present at all times. Because of the con
stantly changing composition of the water entering the plant,
drawing any comparisons between the quantitative data for
the influent water and the effluent water is difficult. The in
crease of the chloroform concentration in the chlorinated
effluent, however, appears to be due to chlorination. The
variation in the concentrations of the chlorinated compounds
before and after chlorination ranged from 0.2 to 1.2 /u.g/1, ex
cept for chloroform which increased by 5 /Ag/1. This increase,
while small, is well above the observed variation ( 20 per
cent) of the method at its lower limit of detection. The close
ness of the results for the other chlorinated compounds and
the close proximity of the sampling points before and after
chlorination indicate that the increase in the concentration of
chloroform results from the chlorination process. Since the
amount of chlorine added at the sewage-treatment plant was
706 MANAGEMENT
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low (0.25 ppm total chlorine) when compared with that added
at the water-treatment plant, and since the contact time be
tween collection and analysis was < 2 hr, the low concentra
tion of chloroform is not surprising.
Conclusions
Chloroform and other trihaiogenated methanes have been
detected in several municipal water supplies. The highest con
centrations (37-150 jig/I) of these compounds were found in
finished waters having surface waters as their source. These
compounds form as a result of chlorination processes during
water treatment. Since a primary limiting factor is the pres
ence of free chlorine in the water, the repeated addition of
chlorine at various stages of the treatment process plays an
important role in determining the ultimate concentrations of
organohalogens that occur.
Although the trihaiogenated compounds resulting from
chlorination are not an acute hazard to man at the levels
detected (oral, lethal dose of chloroform to mice is 120 mg/
kg,12 their presence suggests the need to monitor finished
waters for these and other organohalogens and to determine
whether there may be chronic effects. There is a need to de
velop analytical methodology so that the chemistry of the
chlorination process can be fully studied and understood.
In addition to chloroform, several othe;r halogenated
aliphatic and aromatic compounds were detected in a sewage-
treatment-plant's influent and effluent waters.
Acknowledgment
The authors wish to thank James W. Eichelberger and Dr.
Lawrence E. Harris for providing the GC-MS analyses; and
Dr. Fred K. Kawahara for consultation regarding possible
reaction mechanisms for the formation of the trihaiogenated
methanes.
References
1. KLEOPFER, R.D. & FAIRLESS, B.J. Characterization of Organic
Components in a Municipal Water Supply. Envir. Sci. Technol.,
6:12:1036 (Nov. 1972).
2. NOVAK, J. ET AL. Analysis of Organic Constituents Present in
Drinking Water. Jour. Chromatog., 76:1:45 (Feb. 1973).
3. FRILOUX, J. Identification of Hazardous Materials Lower
Mississippi River. Prog. Rprt. USPHS (Oct. 1970).
4. FRILOUX, J. Petrochemical Wastes as a Pollution Problem in the
Lower Mississippi River. EPA Rprt. Lower Mississippi Basin
Ofce., Wtr. Qual. Ofce. Baton Rouge, La. (Oct. 1971).
5. GROB, K. & GROB, G. Organic Substances in Potable Water and its
Precursor, Part II. Applications in the Area of Zurich. Jour. Chro
matog., 90:2:303 (Apr. 1974).
6. Industrial Pollution of the Lower Mississippi River in Louisiana.
EPA, Region VI, Dallas, Tex. (Apr. 1972).
7. BELLA*, T.A. & SIGSBY, J.E. Analysis of Light Aromatic Car-
bonyls, Phenols, and Methyl Naphthylenes in Automotive Emis
sions by Gas Chromatography. EPA, Res. Triangle Pk., N.C.
(1970).
8. BELLAR, T.A. & SIGSBY, J.E. Non-Cryogenic Trapping Techniques
for Gas Chromatography. Internal Rprt. EPA, Res. Triangle Pk.,
N.C. (1970).
9. HELLER, S.R. Conservational Mass Spectral Retrieval System and
its Uss as an Aid in Structure Determination. Anal. Chem.,
44:12::1951 (Oct. 1972).
10. DEWAK, R.A. The Flame lonization Detector; A Theoretical Ap
proach. Jour. Chromatog., 6:312 (1961).
11. GALLWAY, W.S.; STERNBERG, J.C.; & JONES, T.L. A Theoretical In
terpretation of Hydrogen Flame lonization Detector Response.
12th Pittsburgh Conf. on Anal. Chem. and Appl. Spectro., Pit
tsburgh, Pa. (Feb. 1961).
12. Toxic Substances List 1972 (H.E. Christensen, editor). HEW,
Health Svces. and Mental Health Admin., NIOSH, Rockville,
Md. (1972).
JOURNAL AWWA