Occurrence of Fluorescent Whitening Agents in Sewage and River Water Determined by Solid-Phase Extraction and High-Performance Liquid Chromatography

Abstract

Fluorescent whitening agents (FWAs) used in laundry detergents were determined in aqueous samples from sewage treatment plants and rivers using solid-phase extraction (SPE) and high-performance liquid chromatography (HPLC) with post-column UV irradiation and fluorescence detection. FWAs were extracted from 10−200-mL water samples with C18 bonded- phase silica extraction disks and eluted with methanol-containing tetrabutylammonium ion-pairing reagent. No further sample cleanup steps were necessary due to the sensitive and selective fluorescence detection. Recovery of FWAs from raw sewage, primary effluent, secondary effluent, and river water ranged from 76 to 96%. The overall precision of the method, indicated by the relative standard deviation, ranged from 1 to 11%. The limit of quantification was less than 30 ng/L. The concentrations of the two most frequently used FWAs ranged from 7 to 21 μg/L in primary effluent, from 2.6 to 8.9 μg/L in secondary effluent, and from 0.04 to 0.57 μg/L in river water. FWA mass flows calculated from river water concentrations ranged from 0.45 to 1.2 mg day-1 person-1. If calculated on the basis of the consumed amount of FWAs, 1.4−5.6% was found in surface water. Light-induced isomerization and liquid−solid partitioning of FWA isomers were studied in samples of raw sewage and primary and secondary effluent. Isomers formed during the exposure to sunlight were found to have lower affinity for the suspended solids in sewage than the parent FWAs.

A review of current applications of mass spectrometry for biomarker/molecular tracer elucidations

“…Many of those compounds are of environmental concern due to their production quantities, toxicity, persistence, and tendency to bioaccumulate (Schwarzenbach, Gschwend, & Imboden, 1993DeCaprio, 1997;Eganhouse, 1997;Takada et al, 1997;Aboul-Kassim & Simoneit, 2001). They can enter the hydrosphere (Hites, 1973(Hites, , 1977Lopez-Avila & Hites, 1980;Poiger et al, 1996;Leeming et al, 1997;Suter et al, 1997Suter et al, , 1999Simonich et al, 2000), atmosphere (Atlas et al, 1993;Baker & Hites, 1997;Hillery, Basu, & Hites, 1997;Strandberg et al, 2001;Whiteaker & Prather, 2003), geosphere into soils and sediments (Hom et al, 1974;Eglinton, Simoneit, & Zoro, 1975;Beller & Simoneit, 1986, 1988Kumata, Takada, & Ogura, 1997;Reiser, Toljander, & Giger, 1997;Stoll et al, 1997;Rogge, Medeiros, & Simoneit, 2004a-c), and up the food chain in biota (Risebrough et al, 1967;Bowes et al, 1973;Goldberg et al, 1978;Spitzer et al, 1978;Jarman et al, 1992Jarman et al, , 1993Simonich & Hites, 1995a). These applications of MS will keep increasing as more problems become evident, and as the sensitivities of the instrumental methods increase to ever-improved detection limits.…”

“…HPLC-MS is used for polar trace compounds (Poiger et al, 1996;Suter, Riediker, & Giger, 1999;McArdell et al, 2003). The application of the chemical ionization (CIMS) technique is of utility for compounds with low-intensity molecular ions or low abundances of initial fragments from M Áþ .…”

LC‐PDA and LC‐ESI‐MS separation and determination of process‐related substances arising from stilbene‐type fluorescent whitening agents. Application to monitoring of their photodegradation products in industrial effluents and aqueous environmental systems

“…The aqueous solutions of these stilbenesulfonic acids undergo rapid conversion by absorbing UV radiation from sunlight, yielding the corresponding Z isomers, aldehydes, acids, etc. Poiger et al have identified some of the aromatic sulphonate derivatives coming from the degradation of FWAs after treatment of drinking water in bank filtrates and rivers [3,4]. The presence of stilbenesulfonic acids and their degraded products in ground and surface waters causes environmental problems, which, in turn, call for efficient analytical methods for separation and determination of these compounds in aqueous media.…”

Online identification of the fluorescent whitening agent 4,4-bis(2-sulfostyrol)biphenyl using a sweeping technique combined with capillary electrophoresis/77 K fluorescence spectroscopy

“…It is water-soluble (because of the sulfonate group) and has a high affinity for cellulose (because of its large structure), which makes it a suitable product for whitening applications [9][10][11][12][13][14][15][16][17][18], and is commonly used in cleaning detergents for laundry washing. The worldwide production of this compound was 3000 tons in 1992 [9].…”