Ion-Chromatographic Determination of Three Short-Chain Carboxylic

Chapter 19

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Ion-Chromatographic Determination of Three Short-Chain Carboxylic Acids in Ozonated Drinking Water Ching-Yuan Kuo, Hsiao-Chiu Wang, Stuart W. Krasner, and Marshall Κ Davis Water Quality Division, Metropolitan Water District of Southern California, 700 Moreno Avenue, La Verne, CA 91750-3399

A direct ion chromatography method was applied to the determination of short-chain carboxylic acids (acetic, formic, and oxalic) in drinking water treated with ozone. These organic acids were separated on an anion exchange column (Ionpac AS11; Dionex Corp., Sunnyvale, CA), using a 50-μL sample loop. Samples were collectedfromthe ozone pilot plant of the Metropolitan Water District of Southern California to study the formation of carboxylic acids and their removal by two differ ent types of biologically activefilters.Preliminary results indicate that the carboxylic acid concentrations out of the ozone contactor were the greatest for oxalic acid (-380 μg/L), followed by formic (-130 μ/L) and acetic (-60 μg/L) acid, and that the sum of the three acids on a carbon basis was -160 μg/L. Approximately 80 percent of these car boxylic acids were removed during biofiltration. Aldehydes and assim ilable organic carbon (AOC) were also measuredfromthe same batch of samples, and the removal percentages were similar to those obtained in the carboxylic acid analyses. The percentfractionsof AOC at the ozone effluent for combined carboxylic acids and combined aldehydes were 36.9 and 3.7 percent, respectively. Because of concerns about health effects and regulations governing chlorination by products, the Metropolitan Water District of Southern California (MWDSC) and many other water agencies and utilities are actively investigating alternative disinfectants, such as ozone, to replace chlorine. The various by-products produced by the applica tion of ozone are being extensively studied (7). Furthermore, the ozonation of natural organic matter in the source water can produce smaller and more biodegradable or ganic compounds, collectively referred to as assimilable organic carbon (AOC), which can be used as nutrients for bacteria and may cause microbial regrowth problems in a water distribution system (2-4). 0097-6156/96/0649-0350$15.00/0 © 1996 American Chemical Society In Water Disinfection and Natural Organic Matter; Minear, R., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1996.


19. KUO ET AL.

IC Determination ofThree Short-Chain Carboxylic Acids

351

AOC is measured by the maximum bacterial growth in the water sample and is compared with the previously established growth curves in an acetate or oxalate sub strate (2,4). Although AOC is a good indicator for the biological regrowth potential of the water, nine days are required to determine biofiltration process removal efficien cies, and a more rapid test is needed. Schechter and Singer (5) indicated that there was a strong correlation between the AOC and aldehydes produced by ozone and that aldehydes could be utilized as potential surrogates for AOC. However, the total amount of aldehydes accounts for only a small percentage of the AOC. Other frac tions identified were oxoacids and carboxylic acids (tf), but the oxalic acid was not analyzed in the study. Thus, the development of a low-level analytical method for lowmolecular-weight carboxylic acids, including oxalate, should provide additional infor mation for the study of the formation and removal of ozonation DBPs and the biostability of the treated water. Gas chromatography (GC), ion-exclusion chromatography (EEC), and ion chromatography (IC) have been used to determine organic acids. The GC method, however, involves time-consuming procedures such as extraction and derivatization (99 percent pure) carboxylic acids in the form of their sodium salts. Formate and acetate were obtainedfromAldrich Chemical Co. (Milwaukee, WI). Oxalate was obtainedfromSpectrum Chemical Corp. (Gardena, CA). An anti-biodegradation agent was prepared by dissolving 1,000 mg of reagent-grade mercuric chloride (HgCb) in 100 mL of ultrapure water. Stock and Working Calibration Solutions. Individual stock carboxylic acid (acetate, formate, oxalate) solutions at 10,000 mg/L were prepared in ultrapure water and stored in amber glass bottles at 4°C. An intermediate stock standard solution of mixed acids (at concentrations of 10 mg/L each) was prepared weeklyfromthe

In Water Disinfection and Natural Organic Matter; Minear, R., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1996.


352

WATER DISINFECTION AND NATURAL ORGANIC MATTER

individual stock solutions. Because of their unstable nature, working calibration stan dards were prepared daily at concentration levels of 20, 50, 100, 250, and 500 μg/L from the 10-mg/L intermediate stock solution. IC and Data System. Analyses were performed on an ion chromatograph (model 2020; Dionex) equipped with an autosampler, an advanced gradient pump, a pulsed electrochemical detector operated in the conductivity mode, and an anion selfregeneration suppressor (ASRS). The separation of the carboxylic acids was achieved by using an Ionpac AGI 1 guard column and an Ionpac ASH analytical column (both from Dionex). Α 50-μΙ, injection loop was installed on the injection port. A software package (AI-450, Dionex) was used to control all operations of the IC system modules and to integrate the data signal acquired by the interface module. Eluent A certified sodium hydroxide (NaOH) solution at 50 percent (on a weight basis), with low carbonate content, was obtainedfromFisher Scientific (Tustin, CA). The working eluents were prepared as follows: Thefirsteluent bottle contained a low concentration of NaOH (approximately 1.0 mM) prepared by pipetting and mix ing 0.105 mL of the 50-percent NaOH solution into 2,000 mL of ultrapure water that had previously been purged with ultrapure helium gas at a head pressure of 8 psi for 10 min to remove dissolved carbon dioxide. A second NaOH eluent at approximately 100 mM was prepared by pipetting and mixing 10.5 mL of 50-percent stock NaOH solution into 1,984 mL (by removing 16 mLfrom2,000 mL) of ultrapure water that had been purged with ultrapure helium gas for 10 min. A third eluent bottle was filled with ultrapure water to be mixed in-line with the above two NaOH solutions to create a more diluted NaOH eluent during the isocratic and gradient analysis modes. An anion trap column (ATC-1; Dionex) was installed in-line to the gradient pump outlet and prior to the injection valve to remove anion impuritiesfromthe eluent before it entered the injection port and columns. Anion Self-Regenerating Suppressor (ASRS). Baseline suppression was achieved by using an ASRS to yield a stable baseline with a low-conductivity output. The ASRS ran in the external water mode with the controller set at unit #1, which is equivalent to an electric current of 50 mA. The 4-L water reservoir wasfilledto ca pacity with ultrapure water and purged with helium gas before starting the overnight analysis to ensure retention of sufficient water to prevent damage to the ASRS. Sample Preparation. Ozone Quenching Agents. Residual ozone had to be removedfrom(or quenched out of) the samplefromthe ozone contactor to prevent further oxidation and formation of additional DBPs during storage. Preliminary testing results for diethylamine (9) and potassium iodide (considered as ozone-quenching agents) showed inconsistent recoveries on the spiked values of the three carboxylic acids, and the use of diethylamine or potassium iodide as a quenching agent was not pursued further. Instead, an alternative procedure—very gentle and slow aeration of the sample bottle—was used in this study to remove residual ozone. This was done by leaving some headspace in the sample bottle and air-stripping the entire bottle with a capillarytip glass pipette for only 1-2 min. The gentle aeration did not produce any apparent interference, nor did it strip out the carboxylic acid analytes of interest.



19. KUO ET AL.

IC Determination of Three Short-Chain Carboxylic Acids

Anti-Biodegradation Agents. Based on early observations in this study, the carboxylic acids were not stable and degraded rapidly if not preserved. The spike recoveries of the samples without an anti-biodegradation agent were typically at low percentage levels (sometimes even 0) as a result of biological degradation. The IC manufacturer (Dionex Corp.) recommended using chromate at 10 mg/L to stabilize the sample and calibration standardsfrombacterial degradation at room temperature (10). However, the use of chromate at 10 mg/L severely interfered with the measurement of oxalate at low concentrations. The chromate peak overshadowed the tiny oxalate peak, which completely disappearedfromthe chromatogram. Chloroform, chloramine, and HgCl were also tested as anti-biodegradation agents during this study. HgCl had been used successfully as an anti-biodegradation agent in the aldehydes method outlined by Sclimenti and colleagues (8). The HgCl solution was added at 10 \xL per 10 mL of sample. The chloramine was added to the sample at a final concentration of 1 mg/L. The chloroform (adding 50 μL at 0.1 percent to 50 mL of sample) was used by the University of Waterloo (Peldszus, S., Department of Civil Engineering; personal communication, 1995) in the analysis of organic acids by IC. The HgCl and chloramines, but not the chloroform, showed satisfactory results based on spike recoveries and the sample stability test. Information recently receivedfromthe University of Waterloo (Peldszus, S., personal communica tion, July 3, 1996) indicates that chloroform should be added at 50 μΣ, per 50 mL of sample. HgCl was chosen for the IC method because of concern about possible reactions of chloramine with the organic matter in water. Because HgCl is a very toxic compound, care must be taken in its handling and disposal. 2

2

2

2

2

2

Solid-Phase Sample Pretreatment A hydrogen cartridge (OnGuard-H*, P/N 39596; Dionex) was attached in-line between the autosampler outlet and the sample injection loop. The purpose of using the hydrogen cartridge was to lower the sample pH (without adding acids) and to remove cations (primarily the mercury used as a preservative)fromthe sample matrix. The cartridge has male and female Luer connectors on each end. Two adap ters were needed tofitthe Luer connectors to the pipe threads so that the hydrogen cartridge could be installed in-line to the autosampler outlet. Afreshcartridge was attached in-line for each daily analysis. Analysis and Maintenance. Analysis Conditions. All samples for regular analysis were collected in 60-mL brown glass bottles, with mercuric chloride preservative added before sample collection. The bottles were partiallyfilled,but with some headspace left so the sample could be aerated with compressed laboratory air to remove residual ozone. The IC system setup and analytical conditions are summarized in Table I. Acid-Washing of ASRS. Approximately 5 mL of 0.5 Ν sulfuric acid was in jected through the eluent outlet of the ASRS and soaked for a few minutes to clean the ASRS. Both the eluent inlet and outlet lines were then connected back to the ASRS. Next, the system was stabilized by pumping the regular-strength eluent (0.1 mM NaOH) through the ASRS. This ASRS acid-washing step was performed before each daily analytical run.


353

354



Table L IC System Conditions IC system: Dionex 2020 IC Autosampler: ASM-2 Analytical column: Ionpac ASH Guard column: Ionpac AGI 1 Detector output range: 0.01 Anion trap column:Ionpac ATC-1 Gradient pump: GPM-2 at 1 mL/min Stock eluent: Eluent 1-1 mMNaOH Eluent 2-100 mA/NaOH Eluent 3—ultrapure water Working eluents: Isocratic mode—5 min, 0.1 mM NaOH Eluent 1 10% Eluent 3 90% Gradient mode—30 min, linear increase from 0.1 mMto 10 mMNaOH Initial stage Final stage Eluent 1 10% 0% Eluent 2 0% 10% Eluent 3 90% 90% Stabilizing mode—15 min, 0.1 mM Eluent 1 10% Eluent 3 90% Suppression: ASRS in external water mode @ 7 psi Controller current at setting #1; 50 mA Detection: Conductivity detector Sample size: 50 |iL Sample pretreatment: On-line H+ cartridge Suppressor cleaning: 0.5#H SO 2

4

Cleaning of ATC-1. The ATC-1 column was cleaned with 100 mM NaOH when the system started to show high-conductivity output at the time of stabilization of the system baseline. The ATC-1 was disconnectedfromthe system before cleaning to prevent this high-concentration NaOH eluentfrombeing introduced into the columns and the suppressor. Anion Interference. Fluoride is a potential interference in acetate analyses. During the initial period of method development, it was discovered that the fluoride and acetate peaks were located very close to each other, and both appeared at the early stage of the chromatogram (Figure 8). To ensure good separation of fluoride and acetate, the eluent concentration was lowered so thatfluoridecould be present



19. KUO ET AL.

IC Determination ofThree Short-Chain Carboxylic Acids

in the water at up to 0.5 mg/L without interfering with acetate recovery under the current system configuration and analytical procedures. As Figure 8 also indicates, the chloride peak appeared farther awayfromthe acetate and formate, minimizing the interference of chloride. The sulfate peak was too well separatedfromthe oxalate peak to be considered a possible interference. MWDSC's source waters contain fluoride in the range of 0.1 to 0.4 mg/L, chloride at 40 to 110 mg/L, and sulfate at 30 to 290 mg/L. Stability Tests. Stability tests were conducted over a period of up to 3 weeks (testing was stopped when a component showed a significant decrease in concentra tion). Three types of sample matrices (ultrapure water, raw water, and ozonated water) were prepared for the stability tests. Each sample matrix was treated with and without HgCl . Samples were stored in a refrigerator at 4°C when not being analyzed and were brought to room temperature before being prepared for analysis. The carboxylic acids, at concentrations of 50 μg/L each, were prepared in ultrapure water. The raw-water sample for the stability test was spiked with 50 or 100 μg/L of the carboxylic acids to increase the background amounts of the three car boxylic acids. In addition, an ozonated water (with ambient levels of the carboxylic acids) was evaluated with and without HgCb preservation. Pilot-Plant Studies. MWDSC has evaluated ozone for primary disinfection, followed by conventional treatment and biologically activefiltersto remove the AOC (II). At the pilot plant, the ozonated water was diverted into two types offiltercol umns that utilized either granular activated carbon (GAC) or anthracite coal as the primaryfiltermedium. Bothfiltercolumns used 6-in. diameter glass pipe with 20 in. offiltermedia, 6 in. of sand, and 4 in. of gravel. Theflowwas 1 gal/min per filter. The ozone dose was approximately 2 mg/L. The total organic carbon concen tration of the incoming raw water was approximately 3 mg/L. The pH of the raw water was slightly below 8, and the water temperature was approximately 24°C. The turbidity variedfrom1.5 to 17.0 NTU during the testing period. Some limited and preliminary sampling of the pilot plant was performed for the carboxylic acids. In addition, samples were collected for the determination of AOC and aldehydes. The AOC was determined by a modification of the van der Kooij procedure (4), and the aldehydes were determined by a GC method (8). 2

Results and Discussion Analytical Parameters. Stability Tests. In ultrapure water, the carboxylic acids were stable through out the 17-day testing period (either with or without HgCk) except for acetate in the unpreserved sample, which decreased some time after the fourth day of testing (Figures 1 and 2). In the unpreserved raw water (without HgCb), the oxalate was not degraded throughout the 3-day test period (Figure 3), whereas the acetate and formate exhibited a significant decrease even on thefirstday of testing (Day 0). The total ana lytical run time for a 10-sample analysis is typically 18 hours; obviously, the carboxylic acid reductions during this 18-hour period can be very significant. This indicates that a preservative is a must for carboxylic acid analysis, even if the samples are analyzed


355

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Figure 2. Stability of Carboxylic Acids in Ultrapure Water Preserved with HgCI 2


19. KUO ETAL.

IC Determination of Three Short-Chain Carboxylic Adds

immediately after collection. The raw-water sample preserved with HgCl was stable for the full 17-day test period (Figure 4). The ozonated sample without preservation showed a decrease in acetate concentration on the third day of testing, whereas the other two carboxylic acids were not degraded during the 3-day test period (Figure 5). Again, the preserved ozonated sample showed excellent stability throughout the 17-day test period (Figure 6). Solid-Phase Sample Pretreatment. Sample pretreatment with a hydrogen cartridge sharpened the peaks of the three carboxylic acids and allowed the separation of fluoride from acetate. Figures 7 and 8 show two chromatograms of the same sample before and after hydrogen cartridge pretreatment. Positive Analyte Area Value Drift. A positive analyte area value driftdefined as a scenario in which the area values of the analytes gradually and positively increase over time (Figure 9)—was observed in the early methods development. The drift rate of the area values for acetate and formate was approximately twice as high as that for oxalate. This phenomenon was overcome by introducing the acid-washing step for the ASRS before an analytical run. Neither pre-stabilization of the IC system with the high-concentration NaOH eluent nor purging with high-concentration eluent after the oxalate peak was beneficial in dimimshing the area value drift. In fact, the in troduction of the high-concentration eluent to the ASRS might have been the primary cause of the positive analyte area value drift.


2

Quality Assurance. Calibration Curves. Small amounts of acetic and oxalic acids were often ob served in the reagent water; therefore, a blank was included in the daily run so that blank-adjusted area values of the standards could be used to construct the calibration curve. The calibration curves of the three carboxylic acids were linear over the range studied (i.e., 20 to 500 μg/L). The regression coefficient of the calibration curve was usually 0.999 or better. Method Detection Limits (MDLs) and Minimum Reporting Limits (MRLs). MDLs were determined by measuring the 20^g/L standard seven times under the same analytical conditions. The mean and the standard deviation (S.D.) of the seven replicates for acetate, formate, and oxalate were 20.9±1.1, 23.3 ±1.1, and 20.1 ±0.7 μg/L, respectively. The MDLs were calculated at a 95-percent confidence level based on tripling the S.D. value. The calculated MDLs were 2-3 μg/L for the three carboxylic acids. Currently, the MRL is 15 μg/L for all three acids as a result of detection of the analytes in the blank. The MRL of 15 μg/L for formate is probably overconservative. Accuracy and Precision. The study determined the accuracy and precision of seven ozonated samples spiked with 50 or 100 μg/L acetate, formate, and oxalate. The average accuracy for the three carboxylic acids rangedfrom103 to 112 percent, and the S.D. of the accuracy rangedfrom5.6 to 11.4 percent. The average precision of the replicate samples for the three analytes rangedfrom2.0 to 5.8 μg/L; the S.D. of the precision rangedfrom1.7 to 3.6 μg/L.


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Figure 3. Stability of Carboxylic Acids in Fortified Raw Water without Preservation


19. K U O E T A L


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19. KUO ET AL.

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Pilot-Plant Studies. Preliminary Carboxylic Acid Results. Preliminary results of the carboxylic acid measurementsfromthe pilot-plant ozone contactor,filterinfluent, andfilteref fluents are presented in Table Π. This testing was conducted after operating condi tions in the pilot plant had stabilized and thefilterbeds were believed to be biologically active. In addition, the results of the analyses for AOC and aldehydes are presented in Tables III and IV, respectively.

Table Π. Carboxylic Acids from OzonatedVBiofiltered State Project Water* 0

Concentration Sample Location

Filter Influent Reduction from

Acetate Formate Oxalate Acetate Formate Oxalate ( g/L) (Mg/L) (Mg/L) (%) (%) (%) M

60.8 Ozone effluent 37.5 Filter influent 7.2 GACfiltereffluent Anthracitefiltereffluent 9.2

130.5 103.8 20.8 23.1

382.4 283.1 57.8 59.6

80.4 75.2

80.0 77.7

79.5 78.8

Ozone dose = 2.1 - 2.2 mg/L, pH = 7.7, turbidity = 17.0 NTU. Sample preserved with HgCfc. Average of three samples collected on consecutive days.

b c

Table m. AOC from OzonatedVBiofiltered State Project Water % Reduction from Filter Concentration " Influent: Total Total PI7 NOX AOC (MgCL) (MgC/L) frgC/L) 1

Sample Location

Ozone effluent Filter influent GACfiltereffluent Anthracitefiltereffluent

116.3 106.5 33.4 36.9

327.6 320.3 84.1 84.2

443.9 426.9 117.5 121.1

72.5 71.7

Ozonated on same days as carboxylic acid samples in Table Π. Average of three samples collected on consecutive days. b


19. K U O E T A L


Table IV. Aldehydes from OzonatedTBiofiltered State Project Water Concentration

ReductionfromFilter Influent


Formal- Methyl Formal- Methyl dehyde Glyoxal Glyoxal dehyde Glyoxal Glyoxal Sample Location (Mg/L) (Mg/L) (Mg/L) (%) (%) (%)

Ozone effluent 19.1 19.4 Filter influent 3.7 GACfiltereffluent Anthracite filter effluent 0.3

10.7 8.7 2.4 2.6

8.3 5.9 0.8 0.6

80.9 98.5

72.4 70.1

86.4 89.8

Ozonated on same days as carboxylic acid samples in Table II. Average of three samples collected on consecutive days. b

The carboxylic acid that was produced in the largest amounts after the ozone contactor was oxalate (at approximately 380 pg/L), followed by formate (at approxi mately 130 μg/L) and acetate (at approximately 60 μg/L). The sum of the three car boxylic acids on a carbon basis was approximately 160 pg/L. The average percent removal of the three carboxylic acidsfromeither type of biologically activefilterwas approximately 80 percent. Comparison of Carboxylic Acid, Aldehyde, and AOC Results. Table V compares the levels of the sum of acetate, formate, and oxalate; the sum of formal dehyde, glyoxal, and methyl glyoxal; and the total AOC. All concentrations are pre sented on a carbon basis for easy comparison. Although only limited data are available at this time, some interesting observations can be made.

Table V. AOC and Proposed AOC Surrogates from Ozonated/Biofiltered California State Project Water

Sample Type

Ozone effluent Filter influent GACfiltereffluent Anthracitefiltereffluent

Sum ofAcetate, Sum ofFormaldehyde, Total Formate, and Glyoxal, and Methyl AOC Oxalate (MgC/L) Glyoxal (MgC/L) (MgC/L)

163.7 120.1 24.2 26.2

16.2 14.3 2.9 1.5

443.7 427.0 117.7 121.3


363


364


Based on the values after the ozone contactor, the sum of acetate, formate, and oxalate accounted for a greater percentage of the AOC values (36.9 percent on a carbon basis) than did the sum of the formaldehyde, glyoxal, and methyl glyoxal (3.7 percent on a carbon basis). The removal percentages for the sum of the carboxylic acids, the sum of the aldehydes, and the total AOC through the biologically activefiltersare presented in Table VI. These removals are based on comparison of thefiltereffluents with the filter influent. In general, the removals were between 70 and 80 percent for all three analytical method groups and for bothfiltermedia. These preliminary data suggest that it may be possible to use the carboxylic acid IC method as a surrogate procedure for the measurement of AOC. Table VI. Removal of AOC and Proposed AOC Surrogates Through Biologically Active Filters

Filter

GAC Anthracite

Sum ofAcetate, Sum ofFormaldehyde, Total AOC Formate, & Oxalate Glyoxal, & Methyl Glyoxal Removal Removal (%) Removal (%) (%)

79.8 78.2

79.7 89.5

72.4 71.6

Summary and Conclusions The quality assurance data indicate that IC is an excellent tool for the quantitative de termination of low-molecular-weight carboxylic acids such as acetate, formate, and oxalate in water treated with ozone. In the results for the samples collectedfromthe ozone pilot-plant studies, the Ionpac ASH column (Dionex), in conjunction with a conductivity detector, showed acceptable accuracy and precision. All three analytes in the samples pretreated with an in-line H* cartridge (Dionex) showed reasonable peak shapes and sensitivities when a 50-μ1^ injection loop was used. The stability tests indicated that acetate is the least stable analyte among the three carboxylic acids, whereas oxalate is the most stable. The preservation of samples with HgCl elimi nated biodégradation, allowing the samples to be stored for analysis at least as long as 17 days. Sulfuric acid cleaning of the ASRS before analysis was required to diminish positive analyte area drift. In addition, cleaning of the ATC-1 was a necessary step to reach a status of low baseline conductivity output during analysis. The sample turnaround time is approximately 24 hours for a batch of 10 to 15 samples (overnight analysis), and the results can be reported the next morning. The pilot-plant data, though very preliminary, showed some interesting results. At an ozone dose of 2 mg/L, the ozone effluent samples of California state project water produced acetate, formate, and oxalate at approximately 160 μg C/L. The oxa late was the major product of the three carboxylic acids, accounting for approximately 2



19. KUO ET AL.


365

60 to 65 percent of the sum of three carboxylic acids, followed by formate at 25 to 30 percent of the sum and acetate at 10 percent of the sum. There was approx-imately an 80-percent reduction of the three carboxylic acids through the biologically active filter. These carboxylic acids accounted for approximately 28 percent of the AOC (on a carbon basis) at thefilterinfluent (37 percent at the ozone effluent) and may be useful surrogatesforAOC in ozonation/biofiltration studies. Currently, an alternative anti-biodegradation agent, additional carboxylic acids and ketoacids, and interference by other anions are being investigated. MWDSC is conducting biofiltration studies at its ozone demonstration plant. The method reported in this chapter is being used to collect information on carboxylic acids after ozonation and to evaluate their potential as surrogates for AOC. Acknowledgments The authors wish to thank the pilot-plant staff for the preparation of the ozonated samples; Patrick Hacker and Michael Sclimenti for the analyses of AOC and alde hydes, respectively; and Peggy Kimball and Robert La Londe for technical editing of the manuscript and preparation of the graphics, respectively. References 1. Disinfection By-Products in Water Treatment: The Chemistry of Their Forma tion andControl;Minear, R.A.; Amy G.L., Eds.; CRC Press, Inc.: Boca Raton, FL, 1995. 2. van der Kooij, D.; Visser, Α.; Hijnen, W.A.M. J. AWWA 1982, 74, 540-545. 3. Huck, P.M.; Fedorak, P.M.; Anderson, W.B. J. AWWA 1991, 83, 69-80. 4. Hacker, P.A.; Paszko-Kolva, C.; Stewart, M.H. Ozone Sci. & Engrg. 1994, 16, 197-212. 5. Schechter, D.S.; Singer, P.C. Ozone Sci. & Engrg. 1995, 17, 53-69. 6. Andrews, S.A.; Huck, P.M. Ozone Sci. & Engrg. 1994, 16, 1-12. 7. Le Lacheur, R.; Glaze, W. Environ Sci. & Technol. 1996, 30, 1072-1080. 8. Sclimenti, M.J.; Krasner, S.W.; Weinberg, H.S.; Glaze, W.H. In American Water Works Association Proceedings: 1990 Water Quality Technology Conference; AWWA: Denver, CO, 1991; pp 477-501. 9. Kuo, C-Y; Stalker, G; Weinberg, H.S. In American Water Works Association Proceedings: 1990 Water Quality Technology Conference; AWWA: Denver, CO, 1991; pp 503-525. 10. Installation Instructions and Troubleshooting Guide for IONPACAS11Analyti cal Column, Dionex Document #034791; Dionex Corp.: Sunnyvale, CA, 1993. 11. Coffey, B.M.; Krasner, S.W.; Sclimenti, M.J.; Hacker, P.Α.; Gramith, J.T. In American Water Works Association Proceedings: 1995 Water Quality Tech nology Conference; AWWA: Denver, CO, 1996; pp 503-525.


Ion-Chromatographic Determination of Three Short-Chain Carboxylic

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