[advances in chemistry] aquatic humic substances volume 219 (influence on fate and treatment of...

38 Chlorinated Humic Acid Mixtures Criteria for Detection of Disinfection Byproducts in Drinking Water

Alan A. Stevens, Leown A. Moore, Clois J. Slocum, Bradford L. Smith, Dennis R. Seeger1, and John C. Ireland

Drinking Water Research Division, Water Engineering Research Laboratory, U.S. Environmental Protection Agency, Cincinnati, OH 45268

This chapter reports on the feasibility of using a chlorinated humic acid byproduct data base, developed in-house, as a drinking water quality screening tool. Specifically, a gas chromatographic-mass spectral (GC-MS) data base of more than 780 compounds identified during experiments involving the reaction of humic acids with chlorine has been compiled and systematically compared to GC-MS profiles from extracts of finished drinking water sampled from 10 preselected operating utilities. A major goal of the research was to narrow this library down to a smaller, more significant target compound list that would be representative of the chlorination byproducts most frequently encountered in the finished drinking water of utilities practicing chlorine disinfection. In addition, the study demonstrates the practicality of using the described methodology for concentrating and identifying specific compounds from water samples at low concentrations.

DRINKING WATER CHLORINATION FOR DISINFECTION PURPOSES produces numerous organic byproducts other than trihalomethanes (THMs) (1-11).

1Current address: University Hygienic Laboratory, Oakdale Campus, University of Iowa, Iowa City, IA 52242

0065-2393/89/0219-0681$06.00/0 © 1989 American Chemical Society

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In Aquatic Humic Substances; Suffet, I., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1988.

682 AQUATIC HUMIC SUBSTANCES

Naturally occurring humic substances in water serve as precursor material for reaction with chlorine to produce a variety of non-THM compound classes, a large percentage of which are halogenated (1-13). The results of most available studies on this topic suggest that the number and identity of all possible chlorination byproducts have not yet been determined. Because a need exists to estimate the true extent of the chlorination byproduct problem in full-scale drinking-water-treatment systems, we set out to develop an experimental screening approach that would reveal the maximum possible number of such byproducts.

A relatively large data base of compounds formed by the reaction of chlorine with humic acids had already been compiled in-house in previous studies. We attempted to use this data base (via computerized gas chro-matographic-mass spectral ( G C - M S ) searching techniques) to screen for water chlorination byproducts in finished drinking water sample extracts obtained from 10 representative treatment facilities. Modifications to a previously reported sample concentration technique (11) were also tested for improved separation and recovery of trace organic materials from aqueous solution.

Experimental Procedures Materials. Commercial humic acid was obtained from Fluka Chemicals (Ron-

konkoma, NY). Household bleach (Clorox) was used as the chlorinating agent. Chlorine content was determined by diluting 5 mL of Clorox to 1 L with demand-free water (Milli-Q) and titrating 50 m L of this solution to a KI-starch-iodine endpoint. Diazomethane gas was generated fresh from p-tolylsulfonylmethylnitrosamide (Diazald, Aldrich Chemical Co., Milwaukee, WI) and was stripped by nitrogen gas from the generation tube into sample vials. For the resin-granular-activated-carbon (XAD-GAC) extractions, dried, unpreserved, peroxide-free ether was prepared by treatment with acidified ferrous sulfate and sodium sulfate crystals. Buffer solutions were prepared from reagent-grade potassium dihydrogen phosphate and adjusted to the required pH with HC1 or NaOH. All glassware (except volumetric flasks) was heated for 1 h at 400 °C in a muffle furnace to remove trace organic substances.

Methods. Humic acid solutions at organic carbon concentrations representative of drinking water sources were chlorinated in the laboratory to produce chlo-rination-oxidation byproducts. Confidence in the use of the readily available commercial humic acid as a reaction-product model was based on the comparative studies reported previously by Seeger et al. (11). For typical experiments, concentrated humic acid (HA) solutions were made by mixing 800 mg of HA in 1 L of 0.02 Ν sodium hydroxide solution and stirring for 30 min. This mixture was neutralized with sulfuric acid and filtered through glass fiber filters (Whatman 934 AH).

The filtered HA concentrate was then split equally, and the 500-mL portions were each diluted to 20 L with demand-free water in separate glass containers. The solution in one container was used to produce a chlorinated sample, and the solution in the other container served as an unchlorinated control. The resulting total organic carbon (TOC) of these samples (both chlorinated and unchlorinated) was 5 to

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38. STEVENS ET AL. Disinfection Byproducts in Drinking Water 683

7 mg/L, in the range of that found in drinking water sources. Experiments were performed in duplicate, starting with a fresh concentrate of HA each time. The chlorination of HA solutions was studied at three different pH levels, 5, 7, and 11. In addition, a separate experiment with bromide was performed at pH 7. A phosphate buffer was used to control pH. The chlorine was added in sufficient quantity to produce a free chlorine residual at the end of a 3-day reaction period. After the 3-day period, the concentration of free (and total) chlorine residual was determined (14), and an excess of sodium sulfite was added to destroy that chlorine residual. The pH was then lowered to 2.0 with HC1 and the XAD-GAC extraction was initiated.

X A D - G A C Adsorption Analysis. This analysis was a variation of the procedure reported by Seeger et al. (11) to concentrate products of reactions of chlorine with natural humic materials from large volumes (10-20 L) of dilute solution. Figure 1 presents a schematic diagram of the experimental apparatus. Briefly, the XAD-GAC adsorption analysis was carried out as follows: Three 1-gal finished water samples were combined in a 20-L glass carboy. Chlorine residual was then determined by N,N-diethyl-p-phenylenediamine (DPD) titrimetric analyses (14) for free and total CI. Anhydrous Na2S03 (2 mg) was then added for each 1 mg of total CI residual and allowed to react for 30 min. An influent sample was taken for THM and total organic halogen analysis, and a check was made to be sure no chlorine remained. Phosphate buffer (100 mL) and 35 mL of 6 Ν HC1 were added to reduce the pH to the range of 2.0-2.2.

After approximately 10 L had been passed through the columns in the adsorption mode (Figure 1A)—the XAD resin above the GAC—the columns, inverted so the GAC was above the XAD, were drained of water. Special fittings were then connected to the top and bottom of the connected columns so that ether could be distilled through a side arm leading to a condenser at the top. The condensed ether drained directly onto the GAC and eventually flooded the entire column length. In this way, ether was continuously refluxed (Figure IB) through the connected GAC and XAD columns, backwashing the previously adsorbed organic compounds. The extracted organic compounds were concentrated in the receiving flask at the bottom.

After 3 h of continuous extraction, the ether was cooled; 1 mL of 1 Ν HC1 was added (to ensure a pH <1), and the aqueous layer (about 10 mL) was separated from the ether layer. The ether layer was dried over Na2S04. The aqueous layer was re-extracted with an additional 25 mL of ether and was dried with the same Na2S04. The ether extracts were combined and concentrated to approximately 3 mL in a concentrating apparatus (Kuderna-Danish) followed by the addition of 0.25 mL of methanol. The concentrate was then washed into a 7-mL vial (marked at 5 mL) and was diluted to 5 mL with additional previously dried ether. Finally, samples were derivatized with diazomethane (21).

An internal standard, 1-chloro-n-dodecane, was added to a 0.1-mL aliquot of the 5-mL sample just prior to analysis by splitless injection onto a 50-m by 0.20-mm i.d. (SP-2100, Hewlett Packard) or a 60-m by 0.256-mm i.d. (DB-5 + , J & W Scientific) fused silica capillary column. A gas chromatograph (Finnigan, model 9500) was used with the column exiting directly into the ion source of a quadrupole mass spectrometer (Finnigan, model 3300) operated at 70 eV in the electron-impact mode. The data were collected and processed with the data system (Finnigan, INCOS, model 3200) previously described (11).

All peaks were normalized on the area of the internal standard. A library was developed containing all compounds detected in the extracts of the chlorinated HA samples. This library contained 782 total entries. Ten finished drinking water samples

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Condenser

A Adsorption mode Β Extraction mode

Figure 1. Schematic diagram of apparatus used to concentrate trace organic compounds from aqueous solution. A , apparatus configured in adsorption

mode; and B, apparatus configured in desorption-extraction mode.

were analyzed with the same techniques as for the H A studies. The compounds found in these finished water samples were then compared to those previously entered into the library from the H A studies.

Selection of Drinking Water Utilities. The 10 utilities intentionally selected for this study represent a wide geographic area and several source types. Represented are ground and surface water, large and small populations served, and low and high

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38. STEVENS ET AL. Disinfection Byproducts in Dunking Water 685

organic carbon contents. Utilities A-C were selected because of known disinfection byproduct problems. All of the utilities use free chlorine as a disinfectant at some point in their treatment schemes. Sampling was performed between July and December 1985.

Results and Discussion Before we could perform a cross comparison between G C - M S data derived from the 10 utilities with the chlorinated H A data base, it was necessary to establish a meaningful criterion that would define which of the 782 compounds in our library could be attributed solely to the chlorination process. After extensive evaluation of the data, we defined a chlorination byproduct as any single compound entry whose total ion current area count was at least 3 times the area count of the control for both of two duplicate runs and at each of three p H values investigated (pH 5, 7, and 11). Approximately 500 of the 782 compounds in our chlorinated humic substances G C - M S library fit our criterion for a chlorination byproduct. This 3 X criterion served as the basis for screening the G C - M S extract data from the 10 utilities; the same 3 X criterion was applied to each sample extract and associated blanks.

Computerized reverse searching was applied (II) to compare the chlorinated humic substances subset library of approximately 500 chlorination byproduct compounds to all data collected at the 10 locations. Table I displays the search results and lists 196 compounds found (cumulatively) that may be attributed to the chlorination process.

Eight compounds were manually excluded from the automated search procedure because their ubiquitous presence at multiple sites was anticipated from earlier studies (15-19): chloroform, bromodichloromethane, dibromochloromethane, bromoform, dichloroacetonitrile, bromochloro-acetonitrile, dibromoacetonitrile, and chloropicrin were all detected in significant quantities. As expected, locations A - C had the highest T H M concentrations because a conscious effort had been made to locate and sample utilities with acknowledged byproduct problems. These three utilities also exhibited some of the higher dichloroacetonitrile and chloropicrin concentrations relative to the others in the group. The presence of these compounds is by no means surprising, and their formation during water chlorination is well known (15-19).

In contrast to the eight compounds mentioned, much less is known about the 196 remaining compounds listed in Table I and found at one or more of the 10 utilities. For example, 128 of the 196 compounds have unknown structures. That is, the mass spectra of these compounds have no available reference spectrum match in a full U.S. Environmental Protection Agency-National Bureau of Standards data base search (20) and are awaiting manual interpretation. Of these 128 entries, 63 are known to contain at least chlorine. Tentative structures or functional groups other than chlorine have

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Tab

le I

. Met

hyla

ted

Byp

rodu

cts

of C

hlor

inat

ion

of H

umic

Aci

d Fo

und

at 1

0 Lo

catio

ns

Util

ity/L

og A

rea

Cou

nf

Com

pou

nd'

R

RT

b A

Β

C

D

Ε F

G

H

/ /

Cou

nt?

1 1-

Eth

oxy-

l-met

hoxy

met

hane

0.

180

5.8

4.6

4.6

5.0

5.4

5.0

5.3

4.2

4.2

5.8

10

2 A

cetic

aci

d, d

ichl

oro-

, met

hyl e

ster

0.

363

6.0

5.8

5.6

5.2

5.2

4.7

5.3

5.9

5.0

4.1

10

3

Oxi

rane

, tri

chlo

rom

ethy

l-0.

432

4.6

4.0

4.2

4.0

4.3

3.7

4.2

4.4

3.3

2.7

10

4 B

utan

edio

ic a

cid,

2,2

-dim

ethy

l-, d

imet

hyl e

ster

0.

632

4.4

4.3

4.0

3.6

4.1

3.3

3.2

3.7

3.4

3.1

10

5 B

enzo

ic a

cid,

met

hyl e

ster

0.

640

4.4

4.3

4.2

4.2

4.1

4.1

3.8

4.6

3.9

2.8

10

6 D

odec

anoi

c ac

id, m

ethy

l est

er

1.04

0 3.

2 3.

5 3.

4 3.

7 3.

9 3.

5 3.

5 3.

7 3.

8 2.

9 10

7

Prop

anoi

c ac

id, 2

,2-d

ichl

oro-

, m

ethy

l est

er

0.38

1 4.

7 4.

6 4.

6 3.

8 4.

0 3.

0 3.

9 4.

5 3.

5 —

9

8 (X

)C1

com

poun

d? (G

AC

#31

) 0.

582

4.1

3.8

3.8

3.6

3.7

3.2

3.3

4.4

3.2

—

9 9

Pent

aned

ioic

aci

d, d

imet

hyl e

ster

isom

er

0.58

8 4.

4 4.

7 4.

4 3.

9 4.

5 3.

4 3.

6 3.

9 3.

6 —

9

10 M

ethy

lfura

ncar

boxy

lic a

cid,

met

hyl e

ster

? 0.

613

4.7

3.4

3.6

3.7

3.6

3.2

3.4

3.8

3.4

—

9 11

Chl

orob

utan

edio

ic a

cid,

dim

ethy

l est

er is

omer

0.

681

4.4

4.5

4.0

4.0

4.2

3.6

3.8

4.4

3.4

—

9 12

Hex

aned

ioic

aci

d, d

imet

hyl e

ster

isom

er (

GA

C #

39)

0.71

7 3.

2 3.

7 3.

0 2.

5 3.

1 1.

9

2.3

2.8

2.5

—

9 13

Chl

orin

e co

mpo

und?

(LM

#71

) 0.

723

4.8

4.4

3.6

3.9

3.5

3.2

3.4

4.7

3.1

—

9 14

Unk

now

n di

oic

acid

, dim

ethy

l est

er (G

AC

#43

) 0.

943

3.5

3.6

3.5

2.9

3.1

2.5

2.9

2.9

3.1

—

9 15

Ben

zene

dica

rbox

ylic

aci

d, d

imet

hyl e

ster

isom

er

0.99

3 3.

9 4.

1

3.9

3.9

4.0

3.9

4.2

4.3

4.0

—

9 9 16

Ben

zene

trica

rbox

ylic

aci

d, tr

imet

hyl e

ster

isom

er

1.27

3 3.

6 3.

7 3.

3 2.

8 —

2.

8 2.

7 3.

4 3.

4 2.

9 9 9

17 E

then

e, tr

ichl

oro-

0.20

5 3.

5 3.

3 3.

2 3.

0 3.

2 3.

0 3.

2 —

—

3.

9 8

18 P

ropa

noic

aci

d, 2

-chl

oro-

, m

ethy

l est

er

0.29

2 3.

8 4.

0 3.

7 3.

6 3.

6 3.

3 3.

3 —

—

3.

1 8

19 U

nkno

wn

(#13

9)

0.40

6 —

3.

7 —

3.

7 4.

0 3.

4 3.

4 3.

0 3.

5 3.

3 8

20 H

exan

oic

acid

, met

hyl e

ster

0.

453

3.7

3.9

—

3.5

3.8

3.4

3.6

3.7

3.4

—

8 21

(X)C

1 co

mpo

und?

(LM

#21

0)

0.65

4 4.

0 —

4.

5 4.

1

4.3

3.8

4.4

5.1

3.5

—

8 22

(X)C

1 co

mpo

und?

(ML

#10

) 0.

735

4.2

3.5

3.5

3.6

3.7

2.8

4.1

4.3

—

—

8 8 23

Non

anoi

c ac

id, m

ethy

l est

er

0.77

3 3.

0 3.

6 3.

0 3.

4 3.

6 3.

3 3.

4 —

3.

3 —

8 8

24 M

ethy

lfura

ndica

rbox

ylic

aci

d, d

imet

hyl e

ster

isom

er

0.95

9 4.

4 —

4.

0 3.

4 3.

3 3.

2 4.

0 4.

4 3.

3 —

8 8

25 U

nkno

wn

(#58

5)

1.05

9 3.

7 3.

4 —

3.

2 3.

7 3.

0 3.

1 3.

9 3.

1 —

8 8

26 U

nkno

wn

(#57

6)

0.22

7 3.

6 3.

5 4.

2 4.

7 4.

6 4.

3 —

—

—

3.

9 7

27 P

enta

noic

aci

d, m

ethy

l est

er

0.33

4 3.

4 3.

6 3.

3 3.

1 3.

5 3.

1 3.

4 —

—

—

7

28 2

-Hex

ene,

l-m

etho

xy-3

-met

hyl-

0.38

1 —

—

3.

9 4.

0 —

3.

9 2.

9 2.

9 4.

0 4.

0 7

29 P

ropa

nedi

ol a

cid,

dim

ethy

l est

er

0.45

9 —

—

3.

7 3.

8 3.

6 3.

4 3.

4 3.

5 3.

4 —

7

30 (X

)C1

com

poun

d? (L

M #

209)

0.

506

3.1

2.7

—

3.7

4.1

3.3

4.1

4.6

—

—

7 31

Unk

now

n (G

AC

#30

) 0.

518

—

3.9

—

3.4

3.9

2.8

2.7

—

2.2

2.4

7

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32 C

3-B

enze

ne is

omer

(#47

3)

33 (X

)C1

com

poun

d? (L

M #

53)

34 (X

)C1

com

poun

d? (M

L #1

3)

35 D

ecan

oic

acid

, met

hyl e

ster

36

Oct

aned

ioic

aci

d, d

imet

hyl e

ster

37

Ben

zene

dica

rbox

ylic

aci

d, d

imet

hyl e

ster

isom

er

38 M

ethy

lben

zene

dica

rbox

ylie

aci

d, d

imet

hyl e

ster

isom

er

39 U

nkno

wn

(LM

#17

8)

40 1

,4-D

ioxa

ne

41 A

cetic

aci

d, c

hlor

o-, m

ethy

l est

er

42 M

ethy

lbut

anoi

c ac

id, m

ethy

l est

er

43 U

nkno

wn

(#13

8)

44 C

hlor

inat

ed m

ethy

l est

er (G

AC #

29)

45 A

cetic

aci

d, tr

ichl

oro-

, met

hyl e

ster

46

Hep

tano

ic a

cid,

met

hyl e

ster

47

Unk

now

n (#

175)

48

Unk

now

n (#

412)

49

Ben

zene

dica

rbox

ylic

aci

d, d

imet

hyl e

ster

isom

er

50 N

onan

edio

ic a

cid,

dim

ethy

l es

ter

51 A

lipha

tic a

cid,

met

hyl e

ster

(FL

#14)

52

2-M

ethy

l-3-p

enta

none

53

Chl

orin

ated

met

hyl e

ster

(GAC

#27

) 54

Alip

hatic

cpd

(#43

5)

55 3

,3- D

ichl

orop

rope

noic

aci

d, m

ethy

l est

er

56 B

enza

ldeh

yde

57 B

enzo

nitr

ile

58 U

nkno

wn

(#59

6)

59 (X

)C1

com

poun

d (M

L #8

) 60

(X)C

1 co

mpo

und

(#51

2)

61 B

enze

neac

eton

itrile

62

(X)C

1 co

mpo

und?

(#16

8)

0.53

4 3.

2 3.

2 3.

2 3.

1 3.

2 3.

5 3.

5 —

7

8 0.

597

4.1

3.0

3.4

—

2.3

—

2.5

3.3

3.0

—

7 8

0.76

7 4.

3 4.

2 4.

2 —

3.

6 —

3.

4 4.

4 3.

2 —

7

0.86

7 3.

1 2.

9 3.

3 —

3.

3 3.

1 3.

3 3.

2 —

7

0.96

6 —

2.

1

2.5

2.6

2.1

2.3

3.0

2.5

—

7 < m

1.

027

3.4

3.1

—

3.3

2.9

3.2

—

3.1

3.5

—

7 ζ V

) 1.

073

—

3.2

2.7

3.1

2.7

2.5

3.4

3.0

—

7 PI

1.31

5 —

3.

2 3.

1 2.

9 2.

9 3.

0 3.

0 3.

0 7

Η

0.20

7 —

3.

8 4.

7 4.

6 4.

4 4.

3 —

—

3.

0 6

ί> Γ

0.26

8 4.

2 —

3.

8 3.

7 3.

5 3.

6 —

—

3.

3 6

0.28

2 4.

4 4.

1

3.9

—

3.4

3.7

3.4

—

—

—

6 0.

367

—

—

3.5

3.4

2.9

—

3.1

3.6

2.9

6 0.

414

3.8

3.7

3.6

—

—

—

2.4

2.8

2.4

—

6 δ:

0.

448

5.3

4.9

4.6

—

—

—

3.8

5.2

3.6

—

6

nfect

0.56

6 —

. —

2.

8 3.

2 2.

9 3.

1 3.

1 2.

8 —

6

nfect

0.75

4 3.

1 3.

3 2.

7 2.

0 2.

5 —

—

2.

3 —

—

6

ο*

0.87

6 —

—

2.

9 3.

0 2.

6 3.

2 4.

0 2.

6 —

6

1.01

7 3.

5 3.

1 2.

9 3.

3 —

3.

2 —

3.

0 —

—

6

1.04

9 —

—

2.

5 2.

9 2.

4 2.

9 3.

4 2.

8 —

6

2 1.

395

3.3

3.1

2.8

2.8

3.2

3.0

—

6 Ό

§"

0.24

8 —

—

. —

3.

3 3.

4 3.

2 3.

3 —

—

3.

2 5

ο 0.

318

—.

—

3.2

3.1

2.9

3.2

—

4.0

—

5 00

0.40

0 —

—

3.

3 3.

5 3.

3 3.

3 —

—

3.

0 5

55*

0.46

7 4.

7 4.

0 —

2.

9 2.

9 —

—

—

—

2.

6 5

0.49

0 .—

—

—

3.

0 —

3.

0 3.

8 3.

5 3.

5 —

5

2.

0.50

2 4.

6 —

4.

4 4.

2 3.

4 3.

9 —

—

—

—

5

27

0.60

1 —

3.

3 —

2.

3 2.

6 1.

8

—

3.1

—

—

5 0.

603

3.0

—

—

2.8

2.9

—

2.9

3.7

—

—

5 0.

690

—

—

3.6

3.6

2.5

2.7

3.5

—

—

5 g*

0.

694

—

2.8

2.7

2.2

—

3.2

3.1

—

5 ST

1

0.69

8 —

—

2.

2 1.

7

1.7

—

2.9

2.0

—

5

Con

tinue

d on

nex

t pa

ge.

Dow

nloa

ded

by U

CSF

LIB

CK

M R

SCS

MG

MT

on

Sept

embe

r 4,

201

4 | h

ttp://

pubs

.acs

.org

P

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n D

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Dec

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r 15

, 198

8 | d

oi: 1

0.10

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a-19

88-0

219.

ch03

8


Tabl

e I.

Met

hyla

ted

Byp

rodu

cts

of C

hlor

inat

ion

of H

umic

Aci

d Fo

und

at 1

0 Lo

catio

ns (

Con

tinue

d)

Uti

lity

/Lo

g A

rea

Cou

nt

Com

pou

nd"

R

RT

b A

Β C

D Ε

F G

H

I

Com

63

Dich

loro

acet

amid

e iso

mer

(#5

13)

0.70

5 5.

1

4.9

4.5

4.0

2.3

5 64

(X)C

1 co

mpo

und?

(LM

#31

5)

0.73

1 —

—

—

2.

8 2.

5 2.

0 2.

8 3.

7 —

—

5

65 U

nkno

wn

(LM

#26

0)

0.73

9 3.

5 —

—

3.

1 2.

7 2.

3 2.

6 —

—

—

5

66 2

,2-D

imet

hylp

enta

nedi

oie

acid

, dim

ethy

l est

er

0.75

7 —

3.

3 2.

7 2.

7 3.

1 —

—

—

—

3.

3 5

67 (X

)C1

com

poun

d? (#

176)

0.

763

3.8

3.5

3.4

3.0

—

—

—

3.9

—

—

5 68

Hex

aned

ioic

aci

d, d

imet

hyl e

ster

0.

783

—

—

—

2.9

3.2

—

2.6

3.0

2.5

—

5 69

(X)C

1 co

mpo

und?

(#19

5)

0.88

9 3.

5 2.

7 2.

7 2.

6 —

—

—

3.

2 —

—

5

70 U

nkno

wn

(#20

9)

1.03

4 —

—

—

2.

4 —

2.

0 2.

3 2.

6 2.

4 —

5

71 U

nkno

wn

(#39

0)

1.20

8 —

2.

5 —

2.

9 —

1.

7 2.

8 3.

0 —

—

5

72 U

nkno

wn

#646

0.

383

—

—

—

3.4

—

—

—

—

—

—

4

73 U

nkno

wn

#651

0.

416

—

—

—

3.6

—

4

74 U

nkno

wn

#656

0.

444

4.1

4

75 B

rom

ochl

oroa

cetic

aci

d, m

ethy

l est

er (M

L #7

) 0.

453

—

5.2

4.

5 —

—

—

—

4.

0 4.

4 —

4

76

Cyc

loal

kane

or

olef

inic

cpd

(GAC

#20

) 0.

541

—

—

—

2.1

3.6

2.0

—

—

2.4

—

4

77 U

nkno

wn

#669

0.

559

—

—

—

3.4

—

—

—

—

—

—

4

78 H

exan

edio

ic a

cid,

dim

ethy

l est

er (

#329

) 0.

694

—

3.2

2.8

—

2.8

2.1

—

—

—

—

4

79 (X

)C1

com

poun

d? (M

L #1

1)

0.73

9 —

—

—

3.

4 3.

3 —

3.

2 3.

9 —

—

4

80

Unk

now

n (#

331)

0.

744

—

—

—

2.3

—

2.2

3.4

3.4

—

—

4

81 U

nkno

wn

(#18

1)

0.78

5 —

3.

2 3.

5 —

—

—

—

3.

6 2.

8 —

4

82

Unk

now

n (#

186)

0.

800

—

—

—

3.2

3.6

—

3.1

2.9

—

—

4

83 U

nkno

wn

(#L

M #

263)

0.

907

—

—

—

3.3

3.0

—

—

3.7

2.9

—

4

84 A

lipha

tic a

cid,

met

hyl e

ster

(#2

02)

0.95

6 —

—

—

2.

6 2.

6 —

2.

4 2.

5 —

—

4

85

Alip

hatic

aci

d, m

ethy

l est

er (#

450)

1.

218

3.5

3.9

4.5

—

4.3

—

—

—

—

—

4

86 A

lipha

tic cp

d (#

488)

1.

235

—

—

—

—

2.9

2.4

—

2.8

2.7

—

4

87 M

etha

ne,

tetr

achl

oro-

0.17

8 2.

9 3.

4 2.

7 3

88 U

nkno

wn

(#59

4)

0.25

9 —

3.

7 —

4.

0 —

3.

9 —

—

—

—

3

89 U

nkno

wn

(#31

4)

0.29

4 —

—

—

4.

0 —

—

3.

8 —

—

4.

1 3

90 T

etra

chlo

roet

hene

0.

319

—

—

2.6

—

3.0

—

—

—

—

3.4

3 91

CgH

ig is

omer

0.

322

—

1.0

—

2.

5 —

—

—

—

3.

7 2.

5 3

92 U

nkno

wn

#635

0.

326

3 93

Hex

amet

hylcy

clotr

isilo

xane

0.

353

—

3.8

3.9

4.0

—

3

> ο c s ο Χ c g ο c m

C/5 H >

ζ η m

Dow

nloa

ded

by U

CSF

LIB

CK

M R

SCS

MG

MT

on

Sept

embe

r 4,

201

4 | h

ttp://

pubs

.acs

.org

P

ublic

atio

n D

ate:

Dec

embe

r 15

, 198

8 | d

oi: 1

0.10

21/b

a-19

88-0

219.

ch03

8


94 C

3-be

nzen

e iso

mer

(#46

3)

0.50

6 —

—

—

3.

2 2.

9 —

—

—

—

2.

8 3

95 A

lipha

tic c

pd (#

403)

0.

625

—

—

—

—

2.8

2.4

—

2.3

—

—

3 96

Unk

now

n (#

158)

0.

626

—

—

—

2.5

2.9

—

—

3.2

—

—

3 97

Alip

hatic

com

poun

d (#

404)

0.

628

—

—

—

2.7

2.9

2.4

—

—

—

—

3 98

Unk

now

n (#

162)

0.

650

—

—

—

2.8

2.3

—

1.8

—

—

—

3 99

(X)C

1 co

mpo

und?

(LM

#65

) 0.

695

3.0

—

—

—

—

—

1.8

3.2

—

—

3 10

0 U

nkno

wn

(#59

0)

0.73

0 —

3.

6 3.

5 2.

0 —

—

—

—

—

—

3

101

Unk

now

n (#

431)

0.

840

—

—

—

2.5

—

2.2

2.0

—

—

—

3 10

2 U

nkno

wn

(#19

4)

0.87

1 —

—

—

2.

9 —

2.

4 —

3.

2 —

—

3

103

(X)C

1 co

mpo

und

(#56

7)

0.87

1 —

—

—

—

2.

4 —

2.

6 4.

1 —

—

3

104

(X)C

1 co

mpo

und?

(#19

6)

0.90

1 —

—

—

—

2.

6 —

2.

2 3.

1 —

—

3

105

Dio

ic a

cid,

dim

ethy

l est

er is

omer

(FL

#20

) 0.

993

_ _

—

2.3

—

—

—

2.6

2.3

—

3 10

6 (X

)C1

com

poun

d? (M

L #1

8)

0.99

3 3.

3 —

—

—

—

—

2.

4 3.

4 —

—

3

107

Unk

now

n (#

212)

1.

064

—

—

—

3.0

3.4

—

—

3.5

—

—

3 10

8 U

nkno

wn

(#21

4)

1.08

6 —

—

—

—

2.

5 —

2.

3 —

2.

5 —

3

109

Alip

hatic

aci

d, m

ethy

l est

er

1.11

8 —

—

—

2.

9 —

2.

6 —

—

2.

7 —

3

110

(X)C

1 co

mpo

und?

(LM

#14

3)

1.23

0 —

—

—

2.

6 —

—

2.

9 —

2.

7 —

3

111

Dib

rom

omet

hane

0.

198

3.9

—

—

—

3.2

—

—

—

—

—

2 11

2 A

ceta

ldeh

yde,

tri

chlo

ro-

0.22

1 3.

5 3.

4 —

—

—

—

—

—

—

—

2

113

2,2-

Dic

hlor

obut

anoi

c ac

id, m

ethy

l est

er

0.50

0 3.

3 —

3.

0 —

—

—

—

—

—

—

2

114

(X)C

1 co

mpo

und?

(#15

4)

0.55

3 3.

3 2.

7 —

—

—

—

—

—

—

—

2

115

Unk

now

n (#

325)

0.

563

—

—

—

—

2.8

—

—

3.1

—

—

2 11

6 (X

)C1

com

poun

d? (L

M #

314)

0.

595

—

—

—

—

—

—

2.0

2.8

—

—

2 11

7 (X

)C1

com

poun

d? (#

156)

0.

596

3.2

—

—

—

—

—

—

2.6

—

—

2 11

8 (X

)C1

com

poun

d? (#

161)

0.

643

—

—

—

—

—

—

2.2

3.6

—

—

2 11

9 (X

)C1

com

poun

d? (M

L #9

) 0.

677

3.5

—

3.2

—

—

—

—

—

—

—

2 12

0 Pe

ntan

edio

ic a

cid,

dim

ethy

l est

er is

omer

(GA

C #

34)

0.67

9 —

—

—

—

—

2.

6 —

—

2.

6 —

2

121

(X)C

1 co

mpo

und?

(LM

#30

7)

0.70

1 —

—

—

—

—

—

2.

4 3.

2 —

—

2

122

Alip

hatic

cpd

(#51

4)

0.73

5 —

—

—

2.

6 3.

0 —

—

—

—

—

2

123

(X)C

1 co

mpo

und?

(#17

3)

0.74

1 —

—

2.

5 —

—

—

—

3.

3 —

—

2

124

Ben

zoic

aci

d, 3

-met

hyl-,

met

hyl e

ster

0.

752

—

—

2.7

—

2.5

—

—

—

—

—

2

Con

tinue

d on

nex

t pa

ge.

Dow

nloa

ded

by U

CSF

LIB

CK

M R

SCS

MG

MT

on

Sept

embe

r 4,

201

4 | h

ttp://

pubs

.acs

.org

P

ublic

atio

n D

ate:

Dec

embe

r 15

, 198

8 | d

oi: 1

0.10

21/b

a-19

88-0

219.

ch03

8


Tabl

e I.

Met

hyla

ted

Byp

rodu

cts

of C

hlor

inat

ion

of H

umic

Aci

d Fo

und

at 1

0 Lo

catio

ns (

Con

tinue

d)

Com

pou

nd"

R

RT

b A

BC

DE

FG

HI

J C

oun

t1

125

Ben

zoic

aci

d, 4

-met

hyl-,

met

hyl e

ster

0.

760

—

—

—

—

2.5

—

—

2.3

—

—

2 12

6 CI

com

poun

d? (L

M #

77)

0.76

8 3.

7 —

—

2.

6 —

—

—

—

—

—

2

127

(X)C

1 co

mpo

und?

(#18

4)

0.79

3 3.

8 —

—

—

—

—

—

3.

1 —

—

2

128

(X)C

1 co

mpo

und?

(LM

#85

) 0.

818

2.8

—

—

—

—

—

—

2.8

—

—

2 12

9 (X

)C1

com

poun

d (#

517)

0.

819

—

—

—

2.3

—

—

—

3.0

—

—

2 13

0 U

nkno

wn

(LM

#26

2)

0.82

2 —

—

—

3.

5 —

2.

6 —

—

—

—

2

131

(X)C

1 co

mpo

und

(#51

9)

0.83

0 3.

8 —

—

—

—

—

—

2.

7 —

—

2

132

Unk

now

n (#

338)

0.

839

—

—

—

—

—

—

—

2.4

2.4

—

2 13

3 H

epta

nedi

oic

acid

, dim

ethy

l est

er

0.87

6 —

—

—

—

3.

4 —

1.

9 —

—

—

2

134

2-M

ethy

lpro

pano

ic a

cid,

2,2

-dim

ethy

l-l-(2

-hyd

roxy

)-

0.90

3 —

—

—

2.

3 —

2.

4 —

—

—

—

2

135

Ben

zoic

aci

d, 3

-met

hoxy

-, m

ethy

l est

er

0.91

1 —

—

—

—

3.

0 —

2.

3 —

—

—

2

136

Unk

now

n (#

343)

0.

938

__

__

__

__

2.9

3.1

—

—

2 13

7 (X

)C1

com

poun

d (G

AC #

42)

0.93

9 —

—

—

2.

1 —

—

2.

4 —

—

—

2

138

(X)C

1 co

mpo

und

(#41

8)

0.95

2 —

—

—

2.

8 3.

2 —

—

—

—

—

2

139

3,4-

Dim

etho

xybe

nzoi

c ac

id, m

ethy

l est

er

0.08

2 —

—

—

—

—

—

—

3.

1 3.

0 —

2

140

Acid

met

hyl e

ster

?

1.12

7 —

—

—

2.

2 2.

5 —

—

—

—

—

2

141

Unk

now

n (L

M #

129)

1.

144

—

—

—

—

—

—

2.8

3.1

—

—

2 14

2 B

enze

netr

icar

boxy

lic a

cid,

trim

ethy

l est

er is

omer

1.

260

—

—

—

2.8

—

2.3

—

—

—

—

2 14

3 A

lipha

tic a

cid,

met

hyl e

ster

(L

M #

204)

1.

264

—

—

—

—

3.7

2.4

—

—

—

—

2 14

4 B

enze

netr

icar

boxy

lic a

cid,

trim

ethy

l est

er is

omer

1.

316

—

—

—

2.7

—

2.2

—

—

—

—

2 14

5 U

nkno

wn

(#36

2)

1.36

6 —

—

—

—

2.

5 —

—

2.

5 —

—

2

146

Unk

now

n (#

477)

0.

230

—

—

—

—

3.7

—

—

—

—

—

147

Unk

now

n (#

398)

0.

298

3.7

—

—

—

—

—

—

—

—

—

148

2-Pr

opan

one,

1,1

,1-tr

ichl

oro-

0.

350

__

__

_ 4.

0 —

—

—

—

—

14

9 (X

)C1

com

poun

d (#

326)

0.

621

—

—

—

—

—

—

—

3.0

—

—

150

(X)C

1 co

mpo

und?

(#43

6)

0.62

3 4.

0 —

—

—

—

—

—

—

—

—

15

1 B

uten

edio

ic a

cid

isom

er (#

437)

0.

638

—

3.7

—

—

—

—

—

—

—

—

152

Unk

now

n (#

328)

0.

659

—

—

—

—

—

2.4

—

—

—

—

153

Unk

now

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38. STEVENS ET AL. Disinfection Byproducts in Drinking Water 693

been assigned to 68 byproducts. Of these 68 byproducts, 44 are aliphatic or aromatic acids, some of which are halogenated. Five of the remaining 22 compounds are non-THM volatiles, four are ethers, two are aldehydes, two are ketones, two are nonhalogenated aromatic substances, four are orga-nonitrogen compounds, and four do not represent any single class. Work is currently in progress to confirm the identities of these compounds by comparison of retention time and full-scan mass spectra with authentic standards.

The logarithm of the individual MS area counts for each location are listed under the respective utility code headings across the top of the table. These values represent relative order-of-magnitude concentrations for a given compound across the utilities in the study. The transformed area counts are not relative to each other across compounds. A minus sign in the log area count column indicates that the compound was not detected. Of the 196 entries, 122 (62%) have average areas of 1000 or more. The area counts were reproducible from one run to the next within a factor of 2 approximately 85% of the time during analysis of the duplicate data for each of the three varied-pH studies.

Table II lists the frequency of occurrence of the entries with counts by number of locations with that entry and cumulative totals of locations. This format provides easy reference to the number of locations with counts above or below a given level. For example, 110 entries can be found at three or more locations and at three or fewer locations. Half the locations sampled (5) had 71 of the entries present.

Conclusions

A substantial amount of work remains to be done in identifying the unknowns in Table I. We do, however, consider the reduction of the chlorination byproduct candidate list from over 700 entries down to around 500 (via the

Table II. Frequency of Occurrence of the 196 Chlorination Byproduct Data Base Entries Found at 10 Locations

Parameter 10 9 8 7 6 5 4 3 2 2 Number of entries

occurring at this number of locations 6 10 9 14 12 20 15 24 35 51

Cumulative number of entries at this (or greater) number of locations 6 16 25 39 51 71 86 110 145 196

Cumulative number of entries at this (or fewer) number of locations 196 190 180 171 157 145 125 110 86 51

NOTE: The numbers at the top of the column are locations 1-10.

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3 X criterion) to be a significant first step toward the overall goal of identifying major disinfection byproducts in drinking water. Almost 200 compounds out of the reduced collection of500 were found in one or more field test locations. This fact indicates that the chlorinated H A library matching scheme we have devised offers a meaningful approach to organic contaminant screening of drinking water. Further, the approach seems to focus on those humic acid chlorination products that may be most important in drinking water-treatment work, health studies, and possibly drinking water regulatory considerations.

In spite of previous criticism (22), it has recently been demonstrated that chlorination of both commercially available humic acids and humic material derived from various natural soil sources produces essentially the same major chlorination byproducts (23). This equivalence is true in particular for the known mutagenic chlorination byproducts, including the highly potent Ames mutagen M X (24-25), which was not included in our 782-compound data base at the time of the study.

This study augments (and greatly expands) previous investigations (1-10) into the characterization of aqueous chlorination products of humic substances. In particular, the combination X A D - G A C technique employed for isolation and concentration of sample components has revealed nearly an order of magnitude more compounds than previously reported. Future work wil l focus on identification of unknowns and on treatment techniques for effective removal of the major contaminants found with the greatest frequency at multiple sites.

References 1. Miller, J. W.; Uden, P. C. Environ. Sci. Technol. 1983, 17, 150-156. 2. Glaze, W. H.; Peyton, G. R.; Saleh, F. Y.; Huang, F. Y. Int. J. Environ. Anal.

Chem. 1979, 7, 143-160. 3. Rook, J. J. Water Chlorination: Environ. Impact Health Eff. 1980, 3, 85-98. 4. Peters, C. J.; Young, R. J.; Perry, R. Environ. Sci. Technol. 1980, 14, 1391-1395. 5. Quimby, B. D.; Delaney, M . F.; Uden, P. C.; Barnes, R. M . Anal. Chem. 1980,

52, 259-263. 6. Christman, R. F.; Johnson, J. D.; Norwood, D. L. ; Liao, W. T.; Haas, J. R.;

Pfaender, F. K.; Webb, M . R.; Bobenrieth, M . J. Chlorination of Aquatic Humic Substances; U.S. Environmental Protection Agency Project Summary, EPA-600/2-81-016; U.S. Environmental Protection Agency: Cincinnati, OH, 1981; 178 pp.

7. McCreary, J. J.; Snoeyink, V. L. Environ. Sci. Technol. 1981, 15, 193-197. 8. McCreary, J. J.; Snoeyink, V. L. Water. Res. 1980, 14, 151. 9. Christman, R. F.; Johnson, J. D.; Pfaender, F. K.; Norwood, D.; Webb, M.;

Hass, J. R.; Bobenrieth, M . J. Water Chlorination: Environ. Impact Health Eff. 1980 3, 75-82.

10. Norwood, D. L.; Thompson, G. P.; St. Aubin, J. J.; Millington, D. S.; Christman, R. F.; Johnson, J. D. In Safe Drinking Water: The Impact of Chemicals on a Limited Resource; Rice, R. G., Ed.; Lewis: Chelsea, MI, 1985; pp 109-121.

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38. STEVENS ET AL. Disinfection Byproducts in Drinking Water 6 9 5

11. Seeger, D. R.; Moore, L. Α.; Stevens, A. A. Water Chlorination: Chem. Environ. Impact Health Eff. 1985, 5, 859-873.

12. Christman, R. F.; Norwood, D. L. ; Millington, D. S.; Johnson, J. D.; Stevens, A. A. Environ. Sci. Technol. 1983, 17, 625-628.

13. Norwood, D. L. ; Johnson, J. D.; Christman, R. F. Water Chlorination: Environ. Impact Health Eff. 1983, 4, 191-200.

14. Standard Methods for the Examination of Water and Wastewater, 16th ed.; Greenberg, A. E. ; Trussell, R. R.; Clesceri, L. S., Eds.; American Pharmaceutical Association, American Water Works Association, and Water Pollution Control Federation: Washington, DC, 1985; pp 306-309.

15. Bellar, Τ. Α.; Lichtenberg, J. J.; Kroner, R. C. J. Am. Water Works Assoc. 1974, 66, 703-706.

16. Rook, J. J. Water Treat. Exam. 1974, 23, 234-243. 17. Oliver, B. G. Environ. Sci. Technol. 1983, 17, 80-83. 18. Duguet, J. P.; Tsutsumi, Y.; Mallevialle, J.; Fiessinger, F. Water Chlorination:

Chem. Environ. Impact Health Eff. 1985, 5, 1201-1213. 19. Trehy, M . L. ; Yost, R. Α.; Miles, C. J. Environ. Sci. Technol. 1986, 20,

1117-1122. 20. EPA/NBS Mass Spectral Database Magnetic Tape; Office of Standard Reference

Data, National Bureau of Standards: Gaithersburg, MD. 21. Schlenk, H.; Gellerman, J. L. Anal. Chem. 1960, 32, 1412-1414. 22. Malcolm, R. L. ; MacCarthy, P. Environ. Sci. Technol. 1986, 20, 904-911. 23. Kopfler, F. C.; Ringhand, H . P.; Meier, J.; Kaylor, W. Water Chlorination:

Environ. Impact Health Eff. 1988, 6, in press. 24. Holmbom, B.; Kronberg, L. ; Hemming, J.; Reunanen, M . ; Backlund, P.;

Tikkanen, L. Water Chlorination: Environ. Impact Health Eff. 1988, 6, in press. 25. Meier, J. R.; Knohl, R. B.; Merrick, B. A.; Smallwood, C. L. Water Chlorination:

Environ. Impact Health Eff. 1988, 6, in press.

RECEIVED for review July 24, 1987. ACCEPTED for publication February 8, 1988.

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