Triethanolamine-based esterquat in sediments: New analytical method, environmental occurrence, and homologue composition.

The cationic surfactant triethanolamine-based esterquat (TEAQ) is a main ingredient in commercial fabric softeners and is produced and used in large quantities. However, little information is available for its occurrence in the environment, particularly in sediments. Here, we developed an analytical method for quantifying TEAQ in sediment and investigated TEAQ contamination in Japanese river and lake sediments. In our analytical method, TEAQ concentrations were measured by liquid chromatography-tandem mass spectrometry using a polymer-based size-exclusion column, which resulted in excellent peak shapes. TEAQ was detected at significant levels in procedural blanks, resulting in a method limit of detection in the sediment of 8.9-97 µg/kg-dry for TEAQ monoesters and 0.6-24 µg/kg-dry for TEAQ diesters. TEAQ was detected in 22 out of 26 sediment samples, with the sum of all homologue concentrations being up to 1340 µg/kg-dry. The concentration of TEAQ in sediments was high at locations where the concentrations of benzalkoniums and the organic carbon content were also high. TEAQ was detected in 8 out of 14 commercial fabric softeners at concentrations of 1.7-7.4 wt%. TEAQ homologues containing only saturated fatty acids accounted for 83 ± 5% of the total TEAQ in the sediments, whereas those with unsaturated fatty acids accounted for 71 ± 14% of the total TEAQ in a commercial technical mixture and the softener products. The results of this study will be useful for the environmental risk assessment of esterquats.

Freely dissolved concentration profile and Hyalella azteca toxicity of cationic surfactant C12-benzalkonium in spiked-sediment toxicity test.

The freely dissolved concentrations (Cfree) have been considered a useful metric for exposure of aquatic organisms to organic contaminants. However, Cfree for cationic surfactants has rarely been measured, and its use in sediment toxicity tests has not been evaluated. In this study, Cfree of the cationic surfactant benzyldodecyldimethylammonium (C12-benzalkonium; C12-BAC) in water-only and spiked-sediment toxicity tests with the amphipod Hyalella azteca was analyzed using a passive sampling method. Polyacrylate-coated glass fibers were adopted as the passive sampler. Sorption isotherms of C12-BAC to the polyacrylate fibers were measured in chemical conditions comparable to those of the toxicity tests and used for Cfree calculation in both tests. Detailed concentration analysis in the sediment toxicity test demonstrated a high concentration gradient of C12-BAC between sediment and overlying water; Cfree in pore water was 17-78 times higher than Cfree in overlying water and was 7.2-13 times higher than Cfree at the sediment-water interface. The 50 % lethal concentration and bioconcentration factor of H. azteca obtained in the water-only test (23 µg/L and 140 ± 70 L/kg-wet, respectively) agreed with those calculated based on Cfree in pore water in the sediment test (49 µg/L and 140 ± 90 L/kg-wet, respectively), indicating that H. azteca is exposed mainly to the freely dissolved fraction in pore water. We concluded that Cfree in pore water is a useful exposure metric for H. azteca to cationic surfactants.

Utilization of Anion-exchange Guard Column as an Ion Chromatographic Column of Anions Including Application to Simultaneous Separation of Anions and Cations.

This study demonstrated that a guard column containing anion-exchange resin has the potential for use as a separation column for acid eluent. Specifically, a 1-cm long anion-exchange guard column with a 4.6-mm internal diameter provided good separation of monovalent inorganic anions, by elution of 8 mM tartaric acid or 4 mM malic acid. Using the guard column with acid eluent could be applied to evaluation of nitrite and nitrate ions in mountain and urban river water samples. When the guard column was connected in front of a cation-exchange separation column (15 cm long × 4.6 mm internal diameter) in a series, the system provided simultaneous separation of anions and cations in eluent of 8 mM tartaric acid and 0.5 mM 18-crown-6 ether by a single injection.