United States
                   Environmental Protection
                   Agency
Environmental Research
Laboratory
Athens G A 30613
                   Research and Development
EPA-600/S4-82-072  Mar. 1983
&ERA         Project  Summary
                   Analysis of Chlorinated  Organic
                   Compounds  Formed  During
                   Chlorination  of Wastewater
                     Products
                   W. H. Glaze, J. L Burleson, J. E. Henderson IV, P. C. Jones, W. Kinstley, G. R.
                   Peyton, R. Rawley, F. Y. Saleh and G. Smith
                     Chemical by-products produced dur-
                   ing the Chlorination of municipal waste-
                   water were examined in a study that
                   employed several specially modified
                   analytical methodologies. Volatile by-
                   products were examined with the use of
                   gas chromatography with selective de-
                   tectors and gas chromatography/mass
                   spectrometry (GC/MS). With the use of
                   XAD resins for concentrating trace
                   organics hi the wastewater samples
                   before and after Chlorination, a number
                   of chlorinated aromatic and aliphatic
                   compounds were found after Chlorin-
                   ation and superchlorination.
                     A rapid and convenient microextrac-
                   tion method was developed that is
                   suitable for analyzing trihalomethanes
                   and other volatile halogenated organics
                   at the microgram-per-liter level in
                   water. Also, a computer program was
                   developed that may be used in con-
                   junction with a GC/MS computerized
                   data system to identify polyhalogenated
                   compounds present as minor compo-
                   nents of a complex chemical mixture. A
                   procedure was also developed to de-
                   termine  the concentrations of amino
                   acids in wastewaters, sludges,  and
                   septage  before and after Chlorination.
                   Two chlorinated derivatives of tyrosine
                   were found in a superchlorinated sep-
                   tage sample.
                     Non-volatile compounds in natural
                   waters and municipal wastewaters,
                   before and after Chlorination. were
                   studied with the use  of high perform-
                   ance liquid chromatography. Fractions
 collected before Chlorination of the
 sample showed  that trihalomethane
 formation  potential was  spread
 throughout the natural polymer. After
 Chlorination, total organic halides of
 a non-volatile nature were determined
 by adsorption of the organics on either
 XAD  resins or  powdered activated
 carbon (PAC) followed by elution of the
 resin and combustion of the eluate or by
 direct combustion of the PAC. In both
 cases,  it was  found that  organic
 halogen  was spread  throughout the
 natural polymer, although Chlorination
 at the levels used (20-30 mg/L) did not
 much affect the  average  molecular
 weight of the polymer.
  This Pro/act Summary was developed
 by EPA's Environmental Research Lab-
 oratory, Athens. GA, to announce key
 findings of the research project that is
 fully documented in a separate report of
 the same title (see Project Report order-
 ing information at back).

 Objectives
  This report describes a series of studies
 that examined the chemical by-products
 formed during the Chlorination of mu-
 nicipal wastewater effluents. When the
 research began in 1974, little was known
 about this subject; since then, the ques-
tion  of by-products formed during  the
Chlorination of all types of waters  has
been investigated extensively. It is now
well established that by-products  are
produced whenever chlorine is used as a
disinfectant or a biocide. Among these

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arethetrihalomethanes, now the subject
of regulations  that limit their concen-
tration in drinking water.
  The objectives of the research reported
here were:
 1.  to develop methods for separating
    and identifying the types and quan-
    tities of volatile by-products produced
    during the chlorination  of water,
    particularly municipal  wastewater
    after secondary treatment. Central to
    this effort was the evaluation of XAD
    resins for concentrating trace organ-
    ics in water and the  use of  gas
    chromatography with selective detec-
    tors and  gas chromatography/mass
    spectrometry (GC/MS) for elucidat-
    ing the  structures of  these  sub-
    stances.
2.  to develop separation methods based
    on hig'h performance liquid chroma-
    tography (HPLC)  for  the  study of
    wastewater effluents  and  natural
    waters before and after chlorination.
    The purpose of these studies was to
    extend our knowledge  about non-
    volatile compounds in water and, in
    particular,  to  determine   whether
    halogenated non-volatile compounds
    are produced during chlorination of
    water and wastewater.
3.  to investigate  the  chlorinated  by-
    products produced when  very large
    doses of chlorine (1000-3000 mg/L)
    are used  to treat wastewaters,
    sludges,  and septage. The  use of
    such high doses has been  proposed
    as a  method  for disinfecting  and
    stabilizing septage and sludge and as
    a possible alternative wastewater
    treatment scheme for small systems.

Volatile  By-Products  of Super-
chlorination of Wastewater Prod-
ucts
  Samples investigated  in this study
included  raw  municipal  sewage,  sec-
ondary municipal  effluent,  anaerobic
digestor supernatant, combined sludges,
and septage. In most  cases, by-products
examined were from  the chlorination of
these  samples using 1000-3000 mg/L
chlorine,  but  chlorinated  by-products
were also found in samples chlorinated
with  lower doses.  Volatile by-products
identified included  a  series of polychlo-
rinated phenols, chloroform, chlorinated
benzenes and  alkyl benzenes, polyhalo-
genated  acetones, and  other aliphatic
halides (Table 1). In a separate study, the
chlorination  of amino acids in  municipal
wastes   was   also  examined  with
emphasis on determining chlorinated by-
Table 1.   Summary of Chlorinated Organics Found in Superchlorinated Municipal Wastewate,
Compound
Number
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
Compound Name*
Chloroform
Dibromochloromethane
Dichlorobutane
3-chloro-2-methylbut-1 -ene
Chlorocyclohexane (1 18)
Chloroalkyl acetate
o -Dichlorobemene
p-Dichlorobemene
Chloroethylbenzene
Tetrachloroacetone
Pentachloroacetone
Hexachloroacetone
Trichlorobenzene
Dichloroethylbenzene
Chlorocumene (154)
N-methy/-trichloroaniline (209)
Dichlorotoluene
Trichlorophenol
Chloro-a-methyl benzyl alcohol
Dichloromethoxytoluene
Trichloromethylstyrene (220)
Trichloroethylbenzene (208)
Dichloro-a-methyl benzyl alcohol (190)
Dichloro - b i sfethoxyjbenzene (220)
Dichloro-a-methyl benzyl alcohol (190)
Trichloro-N-methylanisole
Trichloro-a-methyl benzyl alcohol
Trichloro-a-methyl benzyl alcohol
Tetrachlorophenol
Trichloro-a-methyl benzyl alcohol
Trichlorocumene (222)
Tetrachloroethylstyrene (268)
Trichlorodimethoxybenzene (240)
Tetrachloromethoxytoluene (258)
Dichloroaniline derivative (205)
Dichloroaromatic derivative (249)
Dichloroacetate derivative (203)
Trichlorophthalate derivative (296)
Tetrachlorophthalate derivative (340)
Identifi-
cation
Status
1.9
1.9
d.g
1
d,g
d
f
f
e
e
f
f
f
f
d.g
d.g
e.g
e
e.g
e.g
d.9
d.g
d
d.g
d
e.g
e
e
f
e
d
d
d
d
c
c
c.g
c
c
Concen-
tration''
//g/L

-
27
285
20
-
10
10
21
11
30
30
-
20
-
10
-
-
-
32
10
12
10
30
-
-
25
25
30
50
-
-
-
4
13
15
20
-
~
   "Compounds may be listed more than once if GC retention times indicate distinct positional
    isomers.
   ^Quantitative vahies should only be considered as estimates, because response factors and
    recovery data were not available for our extraction system.
   "Mass spectra I information is too incomplete to propose a structure; probable molecular weight
    is indicated in parentheses.
   ''Fragmentation pattern tentatively suggests proposed compound; probable molecular weight
    is indicated in parentheses.
   'Probable identification is based on mass spectral interpretation.
    'Completed identification is based on MS interpretation and confirmed by comparison with a
    reference spectrum.
   'Compounds.were identified in runs other than November 12, 1974.

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 products. Chloro- and dichlorotyrosine
 were found in a superchlorinated septage
 sample, and other neutral products were
 also characterized.
            432/0
          Retention Volume (mL)

Figure  1.    Size exclusion chromatograms
           of Cross Lake sample,  freeze
           dried water soluble fraction. A.
           unchlorinated; B, chlorinated at
           20 mg/L for five days.
  With  the exception of the  studies
searching for amino acid by-products, the
separation procedure used in these inves-
tigations was XAD resin  adsorption,
followed by ether elution, evaporative
concentration, and GC analysis. Selective
detectors(halogen-sensitive Coulson elec-
trolytic conductivity and electron capture)
and  GC/MS were used for identifying
halogenated by-products.
  Amino acids were concentrated by
sequential adsorption/elution from
DOWEX 50W-X8 and Chelex-100 resins,
followed by derivatization to the N(0)-
heptafluorobutyryl n-propyl (or /so-amyl)
esters. Identification and quantification
was  with GC/MS. Amino acids in raw
and  chlorinated  municipal  wastewater
determined by this method, were com-
pared with  levels determined by a Beck-
mann amino acid analyzer with generally
good agreement.

Non-Volatile By-Products of Chlo-
rination  of Natural Waters and
Wastewaters
  Two methods were used to investigate
non-volatile by-products: an adsorption-
combustion-microcoulometric procedure,
which sought to  measure total organic
halides (TOX), and a series of HPLC-based
procedures with various detectors, includ-
ing  manual  collection of fractions for
TOX, dissolved organic carbon (DOC), and
trihalomethane  formation potential
(THMFP) measurements. (THMFP meas-
ures the potential of naturally occurring
organics to form  trihalomethanes upon
chlorination. The ratio of THMFP to DOC
is a measure of this potential normalized
to the organic content of the sample.)
  Samples included a secondary munic-
ipal wastewater effluent and water from
a reservoir in western Louisiana (Cross
Lake).  The non-volatile organic com-
pounds were isolated by freeze drying
and redissolved to obtain fractions soluble
in neutral, acid, or base solutions. Further
fractionation of the neutral fraction  by
size exclusion HPLC showed  that chlo-
rination changes the molecular weight
profile of the natural polymer only slightly
(Figure 1). Moreover, before chlorination,
trihalomethane  formation potential is
spread through the molecular  size range
of the polymer (Table 2). Fractionation of
the polymer after  chlorination  showed
that the non-volatile organic-bound halo-
gen (NVTOX) is also spread throughout
the polymer (Table 3). These results show
that the potential for forming  THMs and
 other halogenated  by-products is most
 likely a characteristic of the organics in
natural waters, and moreover, that floe-
culation techniques are  not likely  to
remove THMFP entirely.
  Fractionation of  the freeze-dried acid
soluble fraction of the natural polymer
with a weak anion exchange  resin with
pH gradient elution produced fractions in
three separate pH regions (Figure  2).
Model compound  studies suggest that
one of these fractions has a  pK« value
similar  to that of phenols, and another,
the pK. value of hydroxybenzoic acids.
The nature of the third fraction,  which
occurs to various extents in waters from
different sources, is unknown.
Tibia 2.   Characteristics of the Water Soluble Fractions of Cross Lake Water Collected by Site Exclusion HPLC (Unchlorinated)
Fraction
Number
1
2
3
4
S
Average
Sum
Molecular Weight flange
31.6x10*-
22.3 x JO3 -
19.1 x 10*-
15.9 x 10s -
6.3 x 103 -
10.5 x

15.9 x 10*
7.9x10*
7.1 x 10*
5. 1 x 103
0.2 x 10*
10*

Molecular Weight
at Pk Maximum
22.4 x 10*
14.2 x 10*
10.3 x 10*
7.9 x 10*
3.9 x 10*


DOC'
X
0.63
0.93
1.28
1.22
0.91

4.97
(mg/L)
S*
O.O4
0.00
0.04
0.20
0.20


THMFP' (ug/L)
X S*
31
73
7
2
95 1O
43
62

304 (252 as
5
2

CD
THMFP*
DOC
X Sb
.049
.078
.074
.035
.068
.061

.011
.002
.008
.004
.002
.005

 'DOC - Dissolved Organic Carbon.
 "S = Standard Deviation.
 "THMFP = trihalomethane formation potential using a chlorine dose of 20 mg/L, 3 days, pH 6 5
 "Units of THMFP/DOC in mg THMFP/mg C.

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Tibli 3.     Characteristics of the Water Soluble Fractions of Cross Lake Water Collected by Size Exclusion HPLC (Chlorinated*)
Fraction
Number
1
2
3
4
5
Average
Sum
Molecular Weight Range
31.6 x103-
19.1 x103-
15.9 x 103-
1 2.6x1 03-
7.1 xW3-
8.2 x

14.2 x
6.9 x
6.3 x
2.2 x
0.1 5 x
103

JO3
103
103
W3
103


Molecular Weight
at Pk Maximum
19.1 x
12.6 x
7.1 x
3.9 x
2.5 x


JO3
W3
W3
W3
W3


DOC
X
1.04
0.98
1.00
0.64
0.52

4.18
(mg/L)
S"
0.48
0.16
0.36
0.08
0.04


NVTOX°
X
65
47
86
20
42

260

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W. H. Glaze, J. L Burleson, J. E. Henderson IV. P. C. Jones, W. Kinstley. G. R.
  Peyton,  ft. Rawley, F. Y.  Saleh, and G. Smith are with North Texas State
  University, Demon, TX 76203.
A. W. Garrison is the EPA Project Officer (see below).
The  complete  report, entitled  "Analysis of Chlorinated Organic Compounds
  Formed During Chlorination of Wastewater Products," (Order No. PB 83-144
  444; Cost: $17.50, subject to change) will be available only from:
        National Technical Information Service
        5285 Port Royal Road
        Springfield, VA 22161
        Telephone: 703-487-4650
The EPA Project Officer can be contacted at:
        Environmental Research Laboratory
        U.S. Environmental Protection Agency
        College Station Road
        Athens,  GA 30613
                                                                                          *USGPO: 1983-659-095-593

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Environmental Protection
Agency
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Information
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