[Advances in Chemistry] Aquatic Humic Substances Volume 219 (Influence on Fate and Treatment of Pollutants) || Chlorinated Humic Acid Mixtures

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  • 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 chlo-rine has been compiled and systematically compared to GC-MS pro-files from extracts of finished drinking water sampled from 10 pre-selected operating utilities. A major goal of the research was to narrow this library down to a smaller, more significant target com-pound 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 con-centrations.

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

  • 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 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 GACthe 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 HC1 was added (to ensure a pH

  • 684 AQUATIC HUMIC SUBSTANCES

    Condenser

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

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

  • 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

    C

    D

    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

    <

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