The determination of trace ions contained in seawater is one of the most difficult tasks in ion chromatography owing to the effect of a high concentration of matrix ions. Various stationary phases have been reported for ion chromatographic determination of trace ions in seawater samples, involving lowcapacity anion-exchange columns as well as C18 reversedphase columns coated with cetyltrimethylammonium ion, 1 a semi-microcolumn (35 × 1 mm i.d.) packed with styrenedivinylbenzene copolymer, 2 conventional-size monolithic ODS columns coated with cetyltrimethylammonium ion, 3 a reversedphase C18 packed column modified with Zwittergent-3-14 micelles, 4 and reversed-phase C30 stationary phase coated with poly(ethylene glycol). 5 We have found that monolithic silica capillary columns dynamically modified with cetyltrimethylammonium ion also allowed the determination of bromide in seawater without tedious pretreatments. 6 The stability of the retention time of analyte anions could be improved by adding 0.1 mM cetyltrimethylammonium chloride (CTAC) into the eluent. Monolithic silica capillary columns achieved rapid separation at lower inlet pressures owing to the unique pore structures. However, when the eluent contained no cetyltrimethylammonium ion in the eluent, the retention time of anions gradually deceased. More hydrophobic modifiers are preferred to obtain more stable stationary phases.Using a dilauryldimethylammonium bromide (DDAB) coated short (30 × 4.6 mm) ODS analytical column (3-μm particle size) and a 5 mM phthalate eluent (pH 7.5), the isocratic separation of nine common anions in 160 s was possible. 7 A reversedphase monolithic ODS column was permanently coated with DDAB to perform ultrafast separations of iodate, chloride, nitrite, bromide, nitrate, phosphate, and sulfate in as little as 30 s. 8 Separations were performed using 6 mM o-cyanophenol (pH 7.0) at flow rates of up to 10 mL/min and suppressed conductivity detection. It is reported that columns coated with DDAB were stable for up to 12 h of continuous use at 5 mL/min when a DDAB-coated guard column was placed upstream from the injector. 8 Very short silica-based monolithic columns (0.5 -1 cm) coated with DDAB were also used for achieving rapid low-pressure ion chromatographic separations of inorganic anions. 9 The present work tried to obtain stable stationary phases for ion chromatography. DDAB was examined for the modification of monolithic silica gel to obtain an anionexchange stationary phase. The prepared columns were applied to the rapid determination of bromide in seawater samples.
Experimental
ApparatusAn eluent was supplied by applying pressure from a nitrogen gas cylinder, or by using a Model MF2 Microfeeder (Azumadenki Kogyo, Tokyo, Japan) equipped with a 0.5-mL MS-GAN050 gas-tight syringe (Ito, Fuji, Japan). In the former case the eluent was filled in a 0.8-mL loop attached to a Model 7000 6-way switching valve (Rheodyne, Cotati, CA, USA). A sample was loaded by using a CN4-4344-.02 nanovolume sample injector with an injection volume ...