Chemical suppressors and method of use

This application is a divisional application of U.S. application Ser. No. 10/356,345, filed on Jan. 30, 2003.

The present application relates to a chemical suppression device and method for reducing the concentration of matrix ions of opposite charge to ions to be analyzed, and specifically for use of an ion chromatography suppressor or to a pretreatment device.

Ion chromatography is a known technique for the analysis of ions which typically includes a chromatographic separation stage using an eluent containing an electrolyte, and an eluent suppression stage, followed by detection, typically by an electrical conductivity detector. In the chromatographic separation stage, ions of an injected sample are eluted through a separation column using an electrolyte as the eluent. In the suppression stage, electrical conductivity of the electrolyte is suppressed but not that of the separated ions so that the latter may be determined by a conductivity cell. This technique is described in detail in U.S. Pat. Nos. 3,897,213; 3,920,397; 3,925,019; and 3,926,559.

Suppression or stripping of the electrolyte is described in the above prior art references by an ion exchange resin bed. A different form of suppressor column is described and published in U.S. Pat. No. 4,474,664, in which a charged ion exchange membrane in the form of a fiber or sheet is used in place of the resin bed.

The sample and eluent are passed on one side of the membrane with a flowing regenerant on the other side, the membrane partitioning the regenerant from the effluent of chromatographic separation. The membrane passes ions of the same charge as the exchangeable ions of the membrane to convert the electrolyte of the eluent to weakly ionized form, followed by detection of the ions.

Another membrane suppressor device is disclosed in U.S. Pat. No. 4,751,004. There, a hollow fiber suppressor is packed with polymer beads to reduce band spreading. There is a suggestion that such packing may be used with other membrane forms. Furthermore, there is a suggestion that the function of the fiber suppressor is improved by using ion exchange packing beads. No theory is set forth as to why such particles would function in an improved manner.

Another suppression system is disclosed in U.S. Pat. No. 4,459,357. There, the effluent from a chromatographic column is passed through an open flow channel defined by flat membranes on both sides of the channel. On the opposite sides of both membranes are open channels through which regenerant solution is passed. As with the fiber suppressor, the flat membranes pass ions of the same charge as the exchangeable ions of the membrane. An electric field is passed between electrodes on opposite sides of the effluent channel to increase the mobility of the ion exchange. One problem with this electrodialytic membrane suppressor system is that very high voltages (50-500 volts DC) are required. As the liquid stream becomes deionized, electrical resistance increases, resulting in substantial heat production. Such heat is detrimental to effective detection because it greatly increases noise and decreases sensitivity.

In U.S. Pat. No. 4,403,039, another form of electrodialytic suppressor is disclosed in which the ion exchange membranes are in the form of concentric tubes. One of the electrodes is at the center of the innermost tube. One problem with this form of suppressor is limited exchange capacity. Although the electrical field enhances ion mobility, the device is still dependent on diffusion of ions in the bulk solution to the membrane.

Another form of suppressor is described in U.S. Pat. No. 4,999,098. In this apparatus, the suppressor includes at least one regenerant compartment and one chromatographic effluent compartment separated by an ion exchange membrane sheet. The sheet allows transmembrane passage of ions of the same charge as its exchangeable ions. Ion exchange screens are used in the regenerant and effluent compartments. Flow from the effluent compartment is directed to a detector, such as an electrical conductivity detector, for detecting the resolved ionic species. The screens provide ion exchange sites and serve to provide site-to-site transfer paths across the effluent flow channel so that suppression capacity is no longer limited by diffusion of ions in the bulk solution to the membrane. A sandwich suppressor is also disclosed including a second membrane sheet opposite to the first membrane sheet and defining a second regenerant compartment. Spaced electrodes are disclosed in communication with both regenerant chambers along the length of the suppressor. By applying an electrical potential across the electrodes, there is an increase in the suppression capacity of the device. The patent discloses a typical regenerant solution (acid or base) flowing in the regenerant flow channels and supplied from a regenerant delivery source. In a typical anion analysis system, sodium hydroxide is the electrolyte developing reagent and sulfuric acid is the regenerant. The patent also discloses the possibility of using water to replace the regenerant solution in the electrodialytic mode.

In one form of sandwich suppressor of the foregoing type sold by Dionex Corporation for more than one year, for cation analysis, sulfonated and aminated screens of capacity similar to that of the eluent channel were disposed in the regenerant channel. The purpose of the sulfonated screen was to allow improved lifetime under solvent conditions.

U.S. Pat. No. 5,045,204 discloses an electrodialytic device using an ion exchange membrane separating two flowing solutions in flow-through channels for generating a high purity chromatography eluent (e.g., NaOH). Water is electrolyzed in a product channel to provide the source of hydroxide ion for sodium which diffuses across the membrane. The patent discloses a mode of eliminating hydrogen gas generated in the product channel.

U.S. Pat. No. 5,248,426 discloses a suppressor of the general type described in U.S. Pat. No. 4,999,098 in an ion chromatography system in which the effluent from the detector is recycled to the flow channel(s) in the suppressor adjacent the sample stream flow channel.

U.S. Pat. No. 5,597,481 disclosed a suppressor-type device of the foregoing type used in sample pretreatment to reduce or suppress matrix ions in the eluent of opposite charge to the analyte ions and then to analyze the analytes in their conductive forms. Using existing suppressor devices, ion exchange interactions and hydrophobic interaction of the analytic, particularly in the eluent flow channel, affects recovery of certain analytes such as oligonucleotides and oligosaccharides. In order to improve recovery, high concentrations of eluents coupled with solvents are generally used. Similarly, in order to elute certain highly charged multifunctional analytes from the chromatographic column, high concentrations of eluents are normally used. High concentrations of eluents, however, are not easily suppressed.

U.S. Pat. No. 6,077,434 discloses, methods and apparatus are provided of improved current efficiency. In one embodiment, an aqueous sample stream including analyte ions of one charge and matrix ions of opposite charge flows through a sample stream flow channel, while flowing an aqueous stream through an ion receiving flow channel separated therefrom by a first ion exchange membrane, and passing a current between the channels to reduce the concentration of the matrix ions. The sample stream flow channel has an upstream sample stream portion containing the matrix ions and an adjacent downstream portion in which the matrix ions have been suppressed. The upstream portion has an electrical resistance no greater than about 0.9 times that of the downstream portion. The ion receiving flow channel includes stationary flow-through first packing of ion exchange material. Neutral or low capacity packing may be disposed in the sample stream flow channel. In another embodiment, a second ion exchange membrane adjacent to the sample stream flow channel is used defining an ion source flow channel through which another aqueous stream flows. The first membrane has a net charge of no greater than about 0.9 times the net charge of the second membrane. In another embodiment, the downstream portion has a net charge of no greater than about 0.9 times the net charge of the upstream portion. In a further embodiment, current is passed at a first amperage between the upstream sample stream portion and an adjacent upstream ion receiving stream portion using first and second electrodes, and a second current is passed at a second lower amperage between the downstream sample stream portion and an adjacent downstream ion receiving stream portion using third and fourth electrodes.

There is a need to provide other ways to increase the capacity of suppressors and suppressor-like pretreatment devices to permit suppression of a high concentration of eluent. Similarly, in sample preparation applications it would be useful to have a suppressor with improved recovery of analytes and suppress high concentrations of eluent or mobile phase.

In one embodiment of the invention, a non-electrolytic apparatus is provided for treating an aqueous sample stream including analyte ions and matrix ions of opposite charge. The apparatus comprises a first ion exchange membrane capable of passing only ions of opposite charge to the analyte ions, a sample stream flow channel, a first aqueous stream ion receiving flow channel adjacent one side of the sample stream flow channel and separated therefrom by the first ion exchange membrane, and stationary flow-through first packing of ion exchange material disposed in the sample stream flow channel of the same charge as the first membrane and having a first ion exchange capacity for the matrix ions. The first ion receiving channel has an ion exchange capacity for the matrix ions less than about 25% of the first ion exchange capacity for the matrix ions. The application does not include electrodes disposed to apply an electric field between the sample stream flow channel and the first ion receiving flow channel.

In another embodiment, a chromatography apparatus including apparatus is provided for treating an aqueous sample stream including analyte ions and matrix ions of opposite charge, the apparatus comprising a chromatography separator having an inlet and an outlet, the inlet being in fluid communication with the sample stream. The treating apparatus is disposed upstream or downstream from the chromatography separator and comprises a first ion exchange membrane capable of passing only ions of opposite charge to the analyte ions, a sample stream flow channel, a first aqueous stream ion receiving flow channel adjacent one side of the sample stream flow channel and separated therefrom by the first ion exchange membrane. Stationary flow-through first packing of ion exchange material is disposed in the sample stream flow channel of the same charge as the first membrane and having a first ion exchange capacity for the matrix ions. The first ion receiving channel has an ion exchange capacity for the matrix ions less than about 25% of the first ion exchange capacity for the matrix ions.

In another embodiment, a non-electrolytic method is provided for treating an aqueous sample stream including analyte ions of one charge and matrix ions of opposite charge to the analyte ions. The method comprises flowing the sample stream through a sample stream flow channel, simultaneously flowing an aqueous stream through an ion receiving flow channel separated therefrom by a first ion exchange membrane capable of passing only ions of opposite charge to the analyte ions and of blocking bulk liquid flow to reduce the concentration of the matrix ions in an effluent from the sample stream flow channel, the sample stream flow channel having stationary flow-through first packing of ion exchange material disposed in the sample stream flow channel of the same charge as the first membrane and having a first ion exchange capacity for the matrix ions. The ion receiving channel has an ion exchange capacity for the matrix ions less than about 25% of the first ion exchange capacity for the matrix ion. No electric field is applied between the sample stream flow channel and the first ion receiving flow channel.