Disinfection
byproducts (DBPs) are a ubiquitous source of chemical
exposure in drinking water and have been associated with serious health
impacts in human epidemiologic studies. While toxicology studies have
pinpointed DBPs with the greatest toxic potency, analytical methods
have been lacking for quantifying complete classes of most toxic DBPs
at sufficiently low quantification limits (ng/L). This new method
reports the parts-per-trillion quantification for 61 toxicologically
significant DBPs from 7 different chemical classes, including unregulated
iodinated haloacetic acids (HAAs) and trihalomethanes (THMs), haloacetaldehydes,
haloketones, haloacetonitriles, halonitromethanes, and haloacetamides,
in addition to regulated HAAs and THMs. The final optimized method
uses salt-assisted liquid–liquid extraction in a single extraction
method for a wide range of DBPs, producing the lowest method detection
limits to-date for many compounds, including highly toxic iodinated,
brominated, and nitrogen-containing DBPs. Extracts were divided for
the analysis of the HAAs (including iodinated HAAs) by diazomethane
derivatization and analysis using a GC-triple quadrupole mass spectrometer
with multiple reaction monitoring, resulting in higher signal-to-noise
ratios, greater selectivity, and improved detection of these compounds.
The remaining DBPs were analyzed using a GC-single quadrupole mass
spectrometer with selected ion monitoring, utilizing a multimode inlet
allowed for lower injection temperatures to allow the analysis of
thermally labile DBPs. Finally, the use of a specialty-phase GC column
(Restek Rtx-200) significantly improved peak shapes, which improved
separations and lowered detection limits. Method detection limits
for most DBPs were between 15 and 100 ng/L, and relative standard
deviations in tap water samples were mostly between 0.2 and 30%. DBP
concentrations in real samples ranged from 40 to 17 760 ng/L for this
study.