Liquid chromatography/mass spectrometry (LC/MS) is an analytical technique that is widely used for the determination of various kinds of environmental contaminants. [1][2][3][4][5][6][7] Orthogonalacceleration time-of-flight mass spectrometry (oa-TOF MS) permits calculating the elemental composition of the chemical compounds for concentrations at the ppb level. 4,6,7 Generally, the use of highly selective LC/MS requires a shorter analysis time and simpler sample clean-up procedures. However, co-eluting species, such as salts, proteins, phospholipids, humic materials and sugars, have a strong effect on the ionization process, referred to as the matrix effect. As a result of the matrix effect, the reproducibility and recovery depend on the sample-preparation method. [8][9][10][11][12][13][14][15][16][17][18][19][20] The matrix effect also alters the collision-induced dissociation (CID) spectra. 2,16 In order to reliably identify and quantify compounds, special attention has to be paid to making the calibration curve 10,12,17,20 and to comparing the spectrum pattern. 21,22 The matrix effect can be eliminated by sample preparation, such as diluting the sample, liquid-liquid extraction or solid-phase extraction (SPE).
9The procedures can be time consuming, laborious and expensive, and can reduce the sensitivity.On-line SPE is one of the practical methods for shortening the clean-up operation. 3,4,13,15,[25][26][27][28] However, this approach is not suitable for simultaneously detecting compounds that have a wide variety of hydrophobicities, because at the front on the analytical column the sample zone of low hydrophobic compounds diffuse as a result of the large volume of the strong solvent that flows from the SPE cartridge.In this report, we present a new automated sample-preparation system that has both at-column-dilution (ACD) 23,24 and on-line-SPE (SPE/ACD), in order to load a large volume of strong eluent onto the analytical column.
Experimental
Apparatus and reagentsThe HPLC system was a Model 2695-chromatography manager (Waters, Milford, MA, USA) equipped with a 2 mL sample loop and a 2.5 mL syringe. The oa-TOF MS was a LCT-Premier (Waters) equipped with Z-spray electrospray (ESI) source and a Lock spray. The photodiode array (PDA) detector was a Model 2996 (Waters). Each module was controlled by MassLynx software v. 4.0 (Waters). The analytical column was an Atlantis dC18, 150 × 4.6 mm i.d., 5 μm particles (Waters). The SPE precolumn was an Oasis HLB extraction column 20 × 2.1 mm i.d., 30 μm particle size (Waters). The 10-port 2-position valve was a Model EV700-102-WA (Reodyne, Cotati, CA, USA). The 2695 pump module and the 10-port 2-position valve were electrically connected in order to control the valve. The time events of the valve were switch 1 On, sample preparation position, and switch 1 Off, analysis position. The isocratic (eluting) pump was a Reagent Manager (Waters).Carbofuran, bensulide, carbaryl, diuron, methomyl, benfuracarb, MBC (carbendazim), oxine-copper, thiophanatemethyl, thiram, daimuron, b...