Simple and sensitive determination of low‐molecular‐mass aromatic aldehydes in swimming pool water by LC‐diode array detector

Abstract

This work reports the development of a simple method for the quantitative determination of aromatic and aliphatic low-molecular-mass aldehydes (LMMAs) as disinfection by-products (DBPs) in indoor swimming pool waters after chlorination with a simplified SPE sample treatment. The method is based on the continuous in situ derivatization/preconcentration of the aldehydes with 2,4-dinitrophenylhydrazine (DNPH) on a Lichrolut EN column in the presence of β-CD. After elution, the 2,4-dinitrophenylhydrazine derivatives were separated on an RP-C(18) analytical column using gradient of ACN-water at 60-80%. The optimized sample treatment described here allowed the direct analysis of large volumes of water in order to improve the sensitivity of the method; LODs in the 60-120 ng/L range were achieved for aromatic LMMAs by using a volume of 50 mL of water, precision being 7.5% or better at a concentration level of 5 μg/L. These results indicate that the ensuing method is a useful choice for the determination of LMMAs in water samples that provides better results than reported LC alternatives in terms of the LOD (except for MS/MS detection), sample requirements for analysis and cost.

Micro solid‐phase derivatization analysis of low‐molecular mass aldehydes in treated water by micellar electrokinetic chromatography

“…This behavior can be due to the fact that aromatic LMMAs need the presence of large amounts of disinfectants and organic matter for their occurrence. These results are similar to those reported in the literature on the occurrence of LMMAs in swimming pool water (LMMA concentration range: 0.9–38 and 0.2–15.3 μg/L for aliphatic and aromatic aldehydes, respectively) , and they clearly demonstrate the robustness and good performance of the method proposed for the analysis of trace levels of aldehydes in treated water samples.…”

“…The aim of this work is to develop the first CE methodology for the determination of both aliphatic and aromatic LMMAs in treated water. Therefore, not only are the major aliphatic LMMAs (formaldehyde to butyraldehyde) detected and determined in the treated water under study, but there are also five aromatic ones (benzaldehyde, 3‐methyl, 2‐ethyl, 2,5‐dimethyl, and 3‐hydroxybenzaldehyde) based on their frequent or suspected presence in these kind of samples . However, prior to CE analysis, aldehydes should be derivatized with DNPH because the direct determination of these compounds is troublesome due to the absence of a chromophore group in their chemical structure (the benzene ring in aromatic aldehydes does not provide the sufficient chromaticity to develop sensitive methods) and high polarity and volatility.…”

“…Because of these limitations, derivatization reactions are required prior to their detection by chromatographic techniques. One of the derivatization reactions most frequently used is based on the formation of hydrazones by reaction with 2,4‐dinitrophenylhydrazine (DNPH), which are LC‐amenable . For GC analysis with MS or electron capture detection o‐ 2,3,4,5,6‐pentafluorobenzylhydroxylamine is commonly used.…”

Hollow-fiber liquid-phase microextraction coupled with miniature capillary electrophoresis for the trace analysis of four aliphatic aldehydes in water samples

“…Derivative procedure combined with chromatographic method successfully solves these problems . Among these derivative reagents for aldehydes, 2,4‐dinitrophenylhydrazine and o ‐2,3,4,5,6‐pentafluorobenzylhydroxylamine, recommended by U.S. Environmental Protection Agency , are two commonly used derivative reagents for HPLC and GC analyses, respectively. And the derivative adducts could be detected by UV or MS .…”