Haloacetic Acids Analysis

Of the nine known species of HAAs (HAA9) found in the treated water, five (HAA5) are currently regulated at the total level of 60µg/L by the US EPA:

• Monochloroacetic acid (MCAA)
• Dichloroacetic acid (DCAA)
• Trichloroacetic acid (TCAA)
• Monobromoacetic acid (MBAA)
• Dibromoacetic acid (DBAA)

The remaining four HAAs (bromochloroacetic acid (BCAA), bromodichloroacetic acid (BDCAA), dibromochloroacetic acid (DBCAA), and tribromoacetic acid (TBAA)) are not currently regulated, but are on the Unregulated Contaminant Monitoring Rule (UCMR) 4 list for monitoring by public water systems between 2018 and 2020.

In Japan, MCAA, DCAA, and TCAA are regulated in drinking water at 0.02 ppb, 0.04 ppb, and 0.2 ppb, respectively, while China regulates DCAA and TCAA at 0.05 ppb and 0.1 ppb, respectively.

On this page, you will find:

• Gas chromatography
• IC-MS/MS
• UCMR 4

Gas chromatography is most commonly used for analyzing HAAs. EPA Methods 552.1, 552.2, 552.3, and Standard Method 6251 are approved by the U.S. EPA. These methods use: methyl tert-butyl ether (MTBE) or anion exchange resins to extract HAAs from water samples (liquid-liquid microextraction); diazomethane or acidic methanol (derivatization) to convert HAAs into methyl esters, and analysis by gas chromatography-electron capture detection (GC/ECD).

Although these methods are gold standards for regulatory compliance for analysis of HAAs, they all share the disadvantages:

• Low sensitivity detection for monochloroacetic acids (MCAA)
• Susceptible to chromatographic interference, especially for MCAA
• Identification problems due to drifting in retention time
• Long GC run time

GC-MS and SPE (solid phase extraction)-GC-MS methods for HAA analysis have therefore been developed but they have not been approved for compliance monitoring.

Here are some of the advantages of using the IC-MS/MS method:

• Direct injection
• Matrix diversion setup
• No tedious liquid-liquid extraction/sample pretreatment/derivatization
• Fully automated
• High recovery (>90%)

In addition to the US, the United Kingdom also uses EPA Method 557 for analysis of HAA5 and HAA9. Because the method is rapid and simultaneous, it is gaining more popularity for routine analysis and investigative surveys for HAAs analysis in drinking water.

In the newly developed UCMR 4  (unregulated contaminants monitoring rule 4), the EPA requires public water systems to monitor three groups of brominated HAAs (HAA5, HAA6Br, and HAA9) using EPA Methods EPA 552.3 or 557. HAA5, which is already regulated, is included in the monitoring to get better understanding of co-occurrence of HAA5 with other unregulated HAAs. As indicators, TOC (total organic carbon) and bromide samples are also collected at the same time as HAA samples are taken and analyzed using the approved EPA methods.

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