N-Nitrosamines make up a nonhalogenated group
of disinfection byproducts that form during chloramination, particularly
in drinking waters impacted by wastewater treatment plant (WWTP) effluents.
Here, we reveal a size-resolved fluorescence-based precursor surrogate
for tracking total N-nitrosamine formation potential
(TONOFP) through oxidative treatment. Samples were collected at seven
WWTPs, at the finished effluent and prior to final disinfection (i.e.,
secondary effluent). Asymmetric flow field-flow fractionation (AF4)
with inline fluorescence detection at excitation and emission wavelengths
of 280 and 340 nm, respectively (i.e., I
280/340), showed protein-rich natural organic matter peaks between 10–445
and 445–1500 kDa. TONOFP was measured by chemiluminescence
on samples dosed with 250 mg L–1 Cl2 monochloramine
at pH 7 for 7 days. Metrics from AF4 I
280/340 (i.e., area under the curve and peak height) and I
257/277 from whole water excitation–emission matrices
were leveraged in multivariate models to develop correlations with
TONOFP. The TONOFP of the finished effluent divided by that of the
secondary effluent (i.e., the TONOFP Ratio) was strongly correlated
(R
2 = 0.996; p = 0.000)
to a model of AUC for the 10–445 kDa peak, maximal peak height,
and I
257/277. This TONOFP precursor surrogate
requires 2 mL of sample and is transformational with respect to assessing
the impact of oxidative treatments on N-nitrosamine
precursor concentrations.
Modified carbon nanotubes (CNTs) and CNT micropillars are shown to adsorb organic precursors of disinfection byproducts, most notably those of totalN-nitrosamines.
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