ION MOLECULE REACTOR AND SETUP FOR ANALYZING COMPLEX MIXTURES

Abstract

An ion molecule reactor for generating analyte ions from analytes comprises: a) a reaction volume in which reagent ions can interact with the analytes in order to form analyte ions; b) at least one analyte inlet for introducing the analytes along an inlet path into the reaction volume whereby, preferably, the inlet path runs essentially along at least a first section of the predefined transit path in the reaction volume; c) at least one reagent ion source and/or at least one reagent ion inlet for providing reagent ions into the reaction volume; d) optionally, at least one ion guide comprising an electrode arrangement which is configured for producing an alternating electrical, magnetic and/or electromagnetic field, that allows for guiding the reagent ions and/or the analyte ions at least along a section of the predefined transit path, preferably along the whole transit path, through the reaction volume.

Claims

1. Ion molecule reactor for generating analyte ions from analytes, the ion molecule reactor comprising: a) a reaction volume in which reagent ions can interact with the analytes in order to form analyte ions: b) at least one analyte inlet for introducing the analytes along an inlet path into the reaction volume: c) at least one reagent ion source and/or at least one reagent ion inlet for providing reagent ions into the reaction volume: d) at least one ion guide comprising an electrode arrangement which is configured for producing an alternating electrical, magnetic and/or electromagnetic field, that allows for guiding the reagent ions and/or the analyte ions at least along a section of the predefined transit path through the reaction volume: e) the at least one reagent ion source and/or the at least one reagent ion inlet comprising at least one guiding element for guiding reagent ions before entering the reaction volume.

2. Ion molecule reactor for generating analyte ions from analytes, the ion molecule reactor comprising: a) a reaction volume in which reagent ions can interact with the analytes in order to form analyte ions: b) at least one analyte inlet for introducing the analytes along an inlet path into the reaction volume: c) at least one reagent ion source and/or at least one reagent ion inlet for providing reagent ions into the reaction volume; d) at least one ion guide comprising an electrode arrangement which is configured for producing an alternating electrical, magnetic and/or electromagnetic field, that allows for guiding the reagent ions and/or the analyte ions at least along a section of the predefined transit path through the reaction volume: e) the ion molecule reactor further comprises a tubular element at least partially, preferably fully, surrounding the reaction volume and/or the transit path, the tubular element comprising at least one porous and/or gas permeable section in particular for introducing a fluid into the reaction volume and/or for removing neutrals and ions having left the predefined transit path out of the reaction volume and/or the ion molecule reactor.

3. Ion molecule reactor according to any of claim 1 or 2, whereby the at least one reagent ion source and/or the at least one reagent ion inlet is configured to produce an overall beam of reagent ions with rotational symmetry or with circular symmetry with regard to an axis defined by a direction of the first section of the transit path, the inlet path and/or the analyte inlet.

4. Ion molecule reactor according to any of claim 1 or 2, whereby the ion guide comprises an electrode arrangement with at least two electrodes, whereby the electrodes are individually addressable.

5. Ion molecule reactor according to any of claim 1 or 2, whereby the ion guide comprises a multipole electrode arrangement, an ion funnel and/or an ion carpet.

6. Ion molecule reactor according to any of claim 1 or 2, whereby reagent ions can be introduced into the reaction volume along at least two distinct directions and/or from at least two distinct positions.

7. Ion molecule reactor according to claim 1, whereby the ion molecule reactor comprises at least one porous and/or gas permeable section.

8. Ion molecule reactor according to claim 2, whereby the at least one reagent ion source and/or the at least one reagent ion inlet comprises at least one guiding element for guiding reagent ions before entering the reaction volume.

9. Ion molecule reactor according to any of claim 1 or 8, whereby the at least one guiding element produces an electrical, magnetic and/or electromagnetic field that allows for guiding the reagent ions before entering the reaction volume.

10. Ion molecule reactor according to any of claim 1 or 8, whereby the at least one guiding element comprises an electrode arrangement.

11. Ion molecule reactor according to claim 5, whereby the ion funnel comprises a stack of at least two ring electrodes whose inner diameter gradually decreases.

12. Ion molecule reactor according to any of claim 1 or 2, whereby the inlet path runs essentially along at least a first section of the predefined transit path in the reaction volume.

13. Method for generating analyte ions with an ion molecule reactor comprising the steps of: a) Introducing analytes into a reaction volume of a chamber of the ion molecule reactor through an analyte inlet: b) Providing reagent ions and introducing the reagent ions into the reaction volume: c) Letting the reagent ions interact with the analytes in order to form analyte ions: d) Guiding the reagent ions and/or the analyte ions with an ion guide along a predefined transit path through the reaction volume;

14. Method according to claim 13, whereby the analytes are introduced into the reaction volume along an inlet path into the reaction volume whereby a direction of the inlet path runs essentially along at least a first section of the predefined transit path in the reaction volume.

15. Method according to claim 13, whereby the analytes are introduced into the reaction volume in the form of a mixture together with a plurality of further chemical species.

16. Method according to claim 15, whereby the mixture comprises or consists of vapour containing substances evaporated from cork.

17. Method according to claim 13, whereby the analytes comprise or consist of at least one compound selected from the group of 2,4,6-trichloroanisole (TCA), 2,3,4,6-tetrachloroanisole (TeCA), 2,3,4,5,6-pentachloroanisole (PCA) and 2,4,6-tribromoanisole (TBA).

18. Method according to claim 15, whereby the mixture furthermore comprises a carrier gas.

19. Method according to claim 13, whereby a pressure in the ion molecule reactor is below 500 mbar.

20. Method according to claim 13, whereby the analyte ions are generated from the analytes and the reagent ions by chemical ionisation.

21. Method according to claim 20, whereby the reagent ions are chosen such that a population of unprotonated analyte ions (M.sup.+) formed is greater than a population of protonated analyte ions (MH.sup.+) formed.

22. Method according to claim 13, whereby the reagent ions are chosen from NO.sup.+ and/or O.sub.2.sup.+.

23. Method according to claim 13, whereby the analyte ions produced in the ion molecule reactor are introduced into a mass analyzer selected from a time-of-flight mass analyzer, a quadrupole mass analyzer, an ion trap analyzer, a sector field mass analyzer, and/or a Fourier transform ion cyclotron resonance analyzer.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0283] The drawings used to explain the embodiments show:

[0284] FIG. 1A cross-section of a first ion molecule reactor with an annular reagent ion inlet around the analyte inlet and an ion guide composed of a multipole electrode arrangement:

[0285] FIG. 2A cross-section of a second ion molecule reactor with two separate reagent ion inlets mounted diametrically opposite in the cylindrical peripheral surface of a housing of the chamber and an ion guide composed of a multipole electrode arrangement:

[0286] FIG. 3A cross-section of a third ion molecule reactor with a housing comprising a gas permeable section and an out tubular element enclosing the housing in order to remove and/or introduce fluids from or into the reaction volume, respectively. Additionally, the third ion molecule reactor a multipole electrode arrangement within the ring-shaped free volume between the tubular element and the housing which in operation can generate a rotating multipole field. As well an ion funnel is arranged outside the housing where the analyte ions leave the housing of the ion molecule reactor:

[0287] FIG. 4A cross-section of a fourth ion molecule reactor with an ion guide composed of a multipole electrode arrangement and furthermore comprising an integrated ion-source which allows for introducing reagent ions through a gas permeable section of the housing:

[0288] FIG. 5A mass spectrometer setup comprising the second ion molecule reactor of FIG. 2 as well as a differential pumping stage and a mass analyzer:

[0289] FIG. 6A cross-section of a fifth ion molecule reactor comprising a gas permeable section along the whole length of the reaction volume:

[0290] FIG. 7A cross-section of a sixth ion molecule reactor comprising an ion guide consisting of a multipole electrode arrangement in combination with an ion funnel;

[0291] FIG. 8A cross-section of a seventh ion molecule reactor comprising an ion guide consisting of an ion carpet:

[0292] FIG. 9A cross-section of an eighth ion molecule reactor comprising reagent ion inlets with additional guiding elements and an ion funnel as an ion guide which are connected to separate voltage generators;

[0293] FIG. 10A top view along the longitudinal axis of the ion funnel of the ion molecule reactor shown in FIG. 3;

[0294] FIG. 11A top view along the longitudinal axis of the ion carpet used in the ion molecule reactor shown in FIG. 8:

[0295] FIG. 12A cross sectional view along a longitudinal axis of a headspace sampler for cork stoppers:

[0296] FIG. 13A schematic view of the headspace sampler of FIG. 12 connected to the setup shown in FIG. 5:

[0297] FIG. 14A schematic view of an automated sampling unit for analysing cork stoppers. With the unit, cork stoppers can stepwise be moved on a conveyor belt whereby a sampler is sequentially placed over a cork stopper to be analysed with a linear manipulator;

[0298] FIG. 15A setup with four of the samplers shown in FIG. 12 connected to a multiport valve for switching between the individual samplers;

[0299] FIG. 16a A sample holder comprising several chambers for receiving a plurality of samples in a top view;

[0300] FIG. 16b A cross section along line A-A of the sample holder of FIG. 16a;

[0301] FIG. 17a An arrangement comprising a removal station for removing analytes from a specific chamber and the sample holder of FIG. 16a whereby, a part of the chambers are covered with an inlet closing member and an outlet closing member (not visible in FIG. 17a) in a top view:

[0302] FIG. 17b A detail of the arrangement of FIG. 17a in a cross-sectional view along the dashed line in FIG. 17a, whereby through openings in the inlet closing member and the outlet closing member are placed centrally over the chambers such that they are open at both ends:

[0303] FIG. 17c The arrangement of FIG. 17b whereby the sample holder has been rotated to a position wherein the chambers are closed:

[0304] FIG. 17d The arrangement of FIG. 17b whereby the sample holder has been rotated to a position wherein the through openings of the inlet closing member and the through openings of the outlet closing member are in fluid communication with the grooves in the sample holder:

[0305] FIG. 18A schematic view of a setup for measuring analytes from solid samples, such as cork stoppers, comprising the arrangement of FIG. 17a, preheating station, a loading unit and an ion molecular reactor:

[0306] FIG. 19A perspective view of a preheating station wherein the samples are kept in open receptacles which are part of a movable chain:

[0307] FIG. 20A section of the moveable chain used in the preheating station of FIG. 19.

[0308] In the figures, the same components are given the same reference symbols.

PREFERRED EMBODIMENTS

[0309] FIG. 1 shows a cross section of a first ion molecule reactor 100. The ion molecule reactor 100 comprises a hollow cylindrical housing 110 having a longitudinal axis 111 and a reaction volume 140 inside the housing 110. Thereby, the housing 110 forms a tubular element surrounding the reaction volume. The housing is e.g. made from a doped lead silicate glass with a resistive layer on the inside. A length of the housing in longitudinal direction is for example 100 mm, an inner diameter is 10 mm and an outer diameter is 13 mm. The electrical resistance between the right axial end 113 and the left axial end 114 of the housing 110 is e.g. 1 G?.

[0310] At the right side in FIG. 1 the housing 110 has a circular opening 112 at the right axial end 113 being concentric with the longitudinal axis 111. The circular opening is an exit orifice, e.g. with an aperture diameter of 1 mm. In FIG. 1 at the left axial end 114, a hollow cylindrical analyte inlet 120 runs along the longitudinal axis 111 of the ion molecule reactor 100. Through the analyte inlet 120, analytes 121, e.g. volatile organic compounds, can be introduced into the reaction volume 140 along an inlet path 122. The inlet path 122 of the analytes runs along a predefined transit path 141 in the reaction volume 140 whereby the transit path 141 runs along the longitudinal axis 111 of the housing 110.

[0311] Also at the left side in FIG. 1, an annular or ring-shaped reagent ion inlet 130 is arranged concentrically around the analyte inlet 120. Thus, the reagent ion inlet 130 is located radially outwards with respect to the predefined transit path 141 and the inlet path 122. Due to the ring-shaped or annular form, reagent ions 131 can be introduced into the reaction volume 140 from essentially all of the positions on the ring-shaped opening. The reagent ions are produced in a reagent ion source, e.g. a conventional plasma discharge reagent ion source, which is not shown in FIG. 1.

[0312] In operation, analytes 121 will undergo chemical ionisation upon collisions with reagent ions 131. Thereby, charged analyte ions 123 are formed.

[0313] In order to guide the analyte ions and the reagent ions through the reaction volume 140 along the transit path 141, the first ion molecule reactor 100 comprises an ion guide which is composed of several electrodes. Specifically, the housing 110 is surrounded by a set of four cylindrical rod electrodes 150, 151 (only two electrodes are visible in FIG. 1). All of the rod electrodes 150, 151 are regularly arranged around the housing 110 in equal angular distances and run in a direction parallel to the longitudinal axis 111 of the housing 110. In operation, the four rod electrodes 150, 151 are connected to an RF generating device (not shown), where two opposite rod electrodes 150, 151 each are connected in parallel. Between neighbouring electrodes an RF-only voltage is applied, for example with a frequency of 1-10 MHz. Thereby, a multipole guiding field is generated which allows for guiding and focussing analyte ions 123 and reagent ions 131 along the transit path 141.

[0314] Additionally, between the right axial end 113 and the left axial end 114 of the housing, a voltage generating device (not shown) can be connected which allows for applying a voltage and generating a transport field (DC field) which runs in parallel to the longitudinal axis 111 of the housing 110. Thus, the housing as such acts as a further electrode. The transport field allows for accelerating and/or decelerating the ions towards the opening 112 at the right axial end.

[0315] The four cylindrical rod electrodes 150, 151 and the housing 110 together constitute an effective ion guide which allows for selectively guiding ions in the reaction volume 140 without affecting neutrals.

[0316] FIG. 2 shows a cross section of a second ion molecule reactor 200. Apart from the reagent ion inlet, ion molecule reactor 200 is essentially identical with the first ion molecule reactor 100. Thus, all of the elements and parts 210, 211, 212, 213, 214, 220, 221, 222, 223, 231, 240, 241, 250 and 251 of the second reactor 200 correspond to elements and parts 110, 111, 112, 113, 114, 120, 121, 122, 123, 131, 140, 141, 150 and 151 of the first reactor 100. For example, analyte inlet 220 of the second ion molecule reactor 200 is essentially identical to analyte inlet 120 of the first ion molecule reactor 100, et cetera.

[0317] However, the second ion molecule reactor 200 does not comprise a ring-shaped reagent ion inlet which is arranged concentrically around the analyte inlet as with the first ion molecule reactor 100. Instead, the second ion molecule reactor 200 comprises two separate analyte inlets 230a, 230b which are mounted diametrically opposite in the cylindrical peripheral surface of the housing 210 at positions near the left axial end 214. Both of the two analyte inlets 230a, 230b are hollow cylindrical tubes which run in a direction orthogonal to the longitudinal axis 211 of the ion molecule reactor 200. Thus, reagent ions 231 can be introduced into the reaction volume 240 from essentially two different positions and in opposing directions, each of them essentially perpendicular to the longitudinal axis 211. Also in this case, the reagent ions 231 are produced in a reagent ion source, e.g. a conventional plasma discharge reagent ion source, which is not shown in FIG. 2.

[0318] Without being bound by theory it is believed that due to the introduction of the reagent ions from two opposing directions, the reagent ions are decelerated in front of the analyte inlet 220 by electrostatic repulsion and captured by the ion guide elements, i.e. the four cylindrical rod electrodes 250, 251 (only two of the four electrodes are shown in FIG. 2) and the housing 210.

[0319] FIG. 3 shows a cross section of a third ion molecule reactor 300 which is partly similar to the second ion molecule reactor 200. Specifically, all of the elements and parts 310, 311, 312, 313, 314, 320, 321, 322, 323, 330a, 330b, 331, 340, 341, 350 and 351 of the third reactor 300 correspond to elements and parts 210, 211, 212, 213, 214, 220, 221, 222, 223, 230a, 230b, 231, 240, 241, 250 and 251 of the second reactor 200. For example, analyte inlet 320 of the third ion molecule reactor 300 is essentially identical to analyte inlet 220 of the second ion molecule reactor 200, et cetera.

[0320] However, in addition to the second ion molecule reactor 200, the third ion molecule reactor 300 furthermore comprises an outer tubular element 370 of hollow cylindrical shape, which is e.g. made from stainless steel and which encloses the housing 310 concentrically over most of its length. The inner diameter of the outer tubular element 370 is larger than the outer diameter of the housing 310, such that the four rod electrodes 350, 351 are located within the ring-shaped free volume 372 between the housing 310 and the outer tubular element 370. At the outer surface of the outer tubular element 370, an opening 371 for introducing fluids and/or for evacuating the free volume 372 between the two tubular elements is mounted.

[0321] Also, the housing 310, in a section that is enclosed by the outer tubular element 370, comprises a ring-shaped and gas permeable section 360, e.g. made of a frit material. Apart from the opening 371 and the gas permeable section 360, the outer tubular element is mounted in a gas tight manner on the housing 310. Thus, the tubular housing 310 comprises a first section which is non-porous or gas tight and a second section which is porous or gas-permeable.

[0322] In operation, when evacuating the free volume 372 between the two tubular elements 310, 370, neutrals (e.g. non-ionized analytes 321) or ions having left the transit path 341, path can be removed from the reaction volume 340 and the ion molecule reactor 300 via the opening 371. Therefore, conventional vacuum pumps can be used (not shown in FIG. 3).

[0323] Additionally, the ion molecule reactor 300 comprises an ion funnel 380 which is arranged behind the opening 312 at the right axial end 313 outside the housing 310. The ion funnel 380 consists of a stack of four metallic ring electrodes 381 whose inner diameter gradually decreases. This allows for specifically extract analyte ions in a defined direction and with a high yield out of the reaction volume 340. FIG. 10 shows a top view of the ion funnel 380.

[0324] Moreover, if in operation an appropriate rotating multipole field is generated with the four cylindrical rod electrodes 350, 351, analyte ions 323 can orbit around the mean flight path in a spiral like trajectory (dashed spiral line in FIG. 3) while being transported towards the opening 312.

[0325] FIG. 4 shows a cross section of a fourth ion molecule reactor 400 which is partly similar to the third ion molecule reactor 300. Specifically, all of the elements and parts 410, 411, 412, 413, 414, 420, 421, 422, 423, 431, 440, 441, 450, 451, 470, 471 and 472 of the fourth reactor 400 correspond to elements and parts 310, 311, 312, 313, 314, 320, 321, 322, 323, 331, 340, 341, 350, 351, 370, 371 and 372 of the third reactor 300. For example, analyte inlet 420 of the fourth ion molecule reactor 400 is essentially identical to analyte inlet 320 of the third ion molecule reactor 300, et cetera.

[0326] However, with the fourth reactor 400, there are no separate analyte inlets which are mounted diametrically opposite in the cylindrical peripheral surface of the housing. Instead, the housing 410, in a section that is enclosed by the outer tubular element 470, comprises a ring-shaped and gas permeable section 460, which is arranged close to the left axial end 414. Radially outwards, a ring-shaped x-ray source 490 is mounted on the outside surface of the outer tubular element 470.

[0327] In operation, neutral reagents 431a can be introduced into the ring-shaped free volume 472 between the housing 410 and the outer tubular element 470. Thereby, the pressure in the ring-shaped free volume 472 is chosen higher than in the reaction volume 440, such that the reagents are forced to enter the reaction volume 440 through the gas permeable section 460. In the region of the x-ray source, neutral reagents are ionized by the x-rays such that the gas permeable section 460 functions as an annular reagent ion inlet providing reagent ions from all radial directions perpendicular with respect to the longitudinal axis 411.

[0328] FIG. 5 shows a schematic view of a mass spectrometer 500 comprising the second ion molecule reactor 200 as described with FIG. 2. Thereby, analyte ions emerging from the circular opening 212 of the ion molecule reactor are fed into an optional differential pumping interface 501 in order to further reduce the pressure and then into a mass analyzer 502, e.g. a time-of-flight mass analyzer.

[0329] FIG. 6 shows a cross section of a fifth ion molecule reactor 600. The ion molecule reactor 600 comprises a hollow cylindrical housing 610 having a longitudinal axis 611 and a reaction volume 640 inside the housing 610. Thereby, the housing 610 forms a tubular element surrounding the reaction volume 640. At the circular left and right end sides 613, 614, the housing is e.g. made from stainless steel while the whole curved surface area of the housing 610 is made of a ring-shaped and gas permeable section 660, e.g. a frit.

[0330] In addition, an outer tubular element 670 of hollow cylindrical shape, which is e.g. made from stainless steel, encloses the housing 610 concentrically over the complete length of the housing 610. The inner diameter of the outer tubular element 670 is larger than the out diameter of the housing 610 such that a ring-shaped free volume 672 between the housing 610 and the outer tubular element 670 is formed. At the outer surface of the outer tubular element 670, an opening 671 for introducing fluids, e.g. neutral reagent gas 631a, is mounted. Radially outwards, a ring-shaped x-ray source 690 is mounted on the outside surface of the outer tubular element 670.

[0331] At the right side in FIG. 6, the housing 610 has a circular opening 612 at the right axial end 613 being concentric with the longitudinal axis 611. In FIG. 6 at the left axial end 614, a hollow cylindrical analyte inlet 620 runs along the longitudinal axis 611 of the ion molecule reactor 600. Through the analyte inlet 620, analytes 621, e.g. volatile organic compounds, can be introduced into the reaction volume 640 along an inlet path 622. The inlet path 622 of the analytes runs along a predefined transit path 641 in the reaction volume 640 whereby the transit path 641 runs along the longitudinal axis 611 of the housing 110.

[0332] In operation, neutral reagent gas 631a is ionized by the x-ray source 690 in order to form reagent ions 631 which are introduced radially through the gas permeable section 660 into the reaction volume 640. Thereby, analytes 621 in the reaction volume 640 will undergo chemical ionisation upon collision with reagent ions 631. Thereby, charged analyte ions 123 are formed.

[0333] Due to the radial flow of reagent ions 631 the flow of analytes 621 and analyte ions 641 towards the wall or the gas permeable section 660, respectively, is reduced or inhibited.

[0334] FIG. 7 shows a cross section of a sixth ion molecule reactor 700 which is similar to the first ion molecule reactor 100 shown in FIG. 1. Specifically, all of the elements and parts 710, 711, 712, 713, 714, 720, 721, 722, 723, 730, 731, 740, 741, 750 and 751 of the sixth chamber 700 correspond to elements and parts 110, 111, 112, 113, 114, 120, 121, 122, 123, 130, 131, 140, 141, 150 and 151 of the first reactor 100. For example, analyte inlet 720 of the sixth ion molecule reactor 700 is identical to analyte inlet 120 of the first ion molecule reactor 100, et cetera.

[0335] Additionally, the sixth reactor comprises an ion funnel 780 which is located inside the housing 710 in front of the right axial end 713. The ion funnel 780 comprises a stack of four metallic ring electrodes 781 and is essentially identical with the ion funnel 380 shown in FIGS. 3 and 10. The electrodes 781 of the ion funnel 780 are coaxial with respect to the transit path 741 or the longitudinal axis 711, respectively. In operation, the four ring electrodes 781 are connected to an RF generating device (not shown), whereby out-of-phase alternating RF potentials, typically with a frequency of 0.1-10 MHz, are applied to adjacent electrodes, such that charged analyte ions 723 are radially confined as they pass through the ion funnel 780.

[0336] FIG. 8 shows a cross section of a seventh ion molecule reactor 800 which is partly similar to the second ion molecule reactor 200 shown in FIG. 2. Specifically, all of the elements and parts 810, 811, 812, 813, 814, 820, 821, 822, 823, 830a, 830b, 831, 840 and 841 of the seventh reactor 800 correspond to elements and parts 210, 211, 212, 213, 214, 220, 221, 222, 223, 230a, 230b, 231, 240 and 241 of the second reactor 200. For example, analyte inlet 820 of the seventh ion molecule reactor 800 is identical to analyte inlet 220 of the second ion molecule reactor 200, et cetera.

[0337] However, the ion molecule reactor 800 does not comprise any rod electrodes. Instead, the seventh reactor 800 comprises an ion carpet 880 which is located in the reaction volume 840 close to the analyte inlet 820 and the reagent ion inlets 830a, 830b. The ion carpet 880 consists of an essentially planar arrangement of five metallic ring electrodes 881 which are mounted concentrically on an isolating support with a central orifice. The electrodes 881 as well as the central orifice of the ion carpet 880 are coaxial with respect to the transit path 841 or the longitudinal axis 811, respectively. FIG. 11 shows a top view of the ion carpet 800 along the longitudinal axis 811.

[0338] In operation, the five ring electrodes 881 are connected to an RF generating device (not shown) and a voltage is applied to the electrodes 881, such that an alternating electric field, typically with a frequency of 0.1-10 MHz, is generated which funnels reagent ions and/or analyte ions through the central orifice. Thereby, a guiding field is generated which allows for guiding and focussing analyte ions 823 and reagent ions 831 along the transit path 841. A similar device and its operation is described for example in US 2013/0120897 A1 (Amerom et al.).

[0339] FIG. 9 shows a cross section of an eighth ion molecule reactor 900 which is partly similar to the second ion molecule reactor 200 shown in FIG. 2. Specifically, all of the elements and parts 910, 911, 912, 913, 914, 920, 921, 922, 923, 930a, 930b, 931, 940 and 941 of the eighth reactor 900 correspond to elements and parts 210, 211, 212, 213, 214, 220, 221, 222, 223, 230a, 230b, 231, 240 and 241 of the second reactor 200. For example, analyte inlet 920 of the eighth ion molecule reactor 800 is identical to analyte inlet 220 of the second ion molecule reactor 200, et cetera.

[0340] However, the ion molecule reactor 900 does not comprise any rod electrodes inside the housing 910. Instead, the eighth reactor 900 comprises an ion funnel 980 which is located in the reaction volume 940 close to the analyte inlet 920 and the reagent ion inlets 930a, 930b and which is arranged coaxially with respect to the longitudinal axis 911. The ion funnel 940 consists of four ring electrodes and is essentially identical to ion funnels 380, 780 shown in FIGS. 3, 7 and 10 and is also operated in a similar manner.

[0341] Moreover, with the eighth ion molecule reactor 900, each of the regent ion inlets 930a, 930b comprises a guiding element 990a, 990b for guiding the reagent ions 931 before entering the reaction volume 940. The guiding elements 990a, 990b consist for example of four rod electrodes which are regularly arranged around the reagent ion inlets 930a, 930b. Thereby, opposing electrodes are connected in parallel whereas between neighbouring electrodes an RF-only voltage, typically with a frequency of 0.1-10 MHZ, is applied. Thereby, a multipole guiding field is generated which allows for guiding and focussing reagent ions 931 before entering the inner volume of the housing 910 or the reaction volume 940, respectively.

[0342] For applying appropriate voltages to the ion funnel 980, a first voltage generating device 901 with an RF voltage and a DC voltage output is connected to the electrodes of the ion funnel 980. A further voltage generating device 902 is connected to the guiding elements 990a, 990b which allows for supplying appropriate voltages to the guiding elements 990a, 990b.

[0343] FIG. 12 shows a cross sectional view along a longitudinal axis of a headspace sampler 1200. The sampler 1200 comprises a hollow cylindrical container 1210 with a circular base area. Apart from an outlet opening in the form of a short connecting piece 1215 with a central bore, the upper end face side 1212 of the container 1210 is closed while the opposite lower end face of the container 1210 has a central and circular opening 1213. Close to the lower end face 1213, a frit ring 1214 is embedded within the lateral cylinder wall of the container 1210. Thereby, the frit ring 1214 is arranged concentrically with respect to a longitudinal axis of the container 1210.

[0344] The frit ring 1214 is made of an air permeable frit material which allows for a fluid communication through the wall of the container 1210.

[0345] Apart from the frit ring 1214, the sampler 1200 is for example made of stainless steel.

[0346] The container 1210 is comprised within a spaced apart tubular cylindrical encasing 1220, such that there is an enclosed, ring-shaped free volume 1224 around the lateral surface 1216 of the container 1210. The short connecting piece 1215 of the container 1210 extends through the upper end face 1222 of the encasing 1220. The lower end face 1223 of the encasing has a central and circular opening which is of the same size as the circular opening 1213 of the container 1210. In a lateral wall of the encasing 1220, an inlet in the form of a short connection piece 1221 is provided which allows for introducing a fluid into the free volume 1224 between container 1210 and encasing 1220. Inside the free volume 1224, a fluid can be heated up by the lateral surface 1216 of the container 1210 which in turn can be heated by the lateral surface 1216 of the container 1210. Thus, the arrangement represents a heat-exchanger element.

[0347] As also shown in FIG. 12, a cork stopper 1250 of circular cylindrical shape with a diameter smaller than the inner diameter of the container 1210 can be partly placed inside the container 1210 through the opening 1213. The cork stopper 1250 does not contact any elements of the sampler 1200 and between cork stopper 1205 and container 1210 there is a free passage such that the inside of container freely communicates with an outside of the sampler 1200. Hence, with this non-hermetically closed arrangement, an overpressure drain is realized.

[0348] In operation, the container can be heated with a heating element (not shown), which is for example embedded inside the wall of the container 1210, to an elevated temperature of e.g. 150? C. Thereby, analytes 1251, such as TCA, and possibly at least some further species 1253 comprised in the cork stopper 1250 are evaporated (indicated by dashed arrows) and concentrated in the form of gaseous analytes 1252 and further gaseous species 1254 around the outer surface of the cork stopper 1250.

[0349] Simultaneously a carrier gas 1260, e.g. N.sub.2, is delivered through the connection piece 1221 inside the free volume 1224 where, the carrier gas 1260 is heated up by the lateral surface 1216 of the container 1210. The heated carrier gas 1261 then enters the inside of the container 1210 through the frit ring 1214, moves along the surface of the cork stopper 1250 inside the container 1250 whereby the gaseous analytes 1252 and further gaseous species 1254 are mixed with the heated carrier gas 1261 and transferred towards the outlet or the short connection piece 1215. Any overpressure of the carrier gas 1261 or any overpressure inside the container 1210, respectively, will automatically be released thanks to the free passage in the region of the lower end face side 1211 of the container 1210.

[0350] Thus, a gaseous mixture 1263 consisting of heated carrier gas 1263, analytes 1252 and further species 1254 exits the short connection piece 1215 of the sampler 1250.

[0351] FIG. 13 shows a schematic view of the sampler 1200 of FIG. 12 connected to the setup shown in FIG. 5. Specifically, the gaseous mixture 1263 exiting the outlet 1215 of the sampler 1200 is introduced into the second ion molecule reactor 200 shown in FIG. 2 via analyte inlet 220. Thereby, the gaseous mixture 1263 represents the analytes 221 shown in FIG. 2.

[0352] Upon chemical ionisation in ion molecule reactor 200, analyte ions and ions of further species are then produced in the second ion molecule reactor 200 whereby for analysing haloanisols (e.g. TCA) in cork stoppers, it is preferred to use NO.sup.+ as reagent ions 231. Preferably, a pressure in the ion molecule reactor 200 is 1-5 mbar.

[0353] Analyte ions and ions of further species emerging from the circular opening 212 of the ion molecule reactor are fed into an optional differential pumping interface 501 in order to further reduce the pressure and then into a mass analyzer 502, e.g. a time-of-flight mass analyzer.

[0354] In FIG. 14, a schematic view of an automated sampling unit 1400 is shown. The sampling unit comprises a conveyor belt 1410 which can be loaded with cork stoppers 1450, 1451, 1452, 1452 and which can be moved stepwise towards the right side in FIG. 14. A sampler 1200 is mounted on a linear manipulator 1420 that is capable of moving the sampler 1200 up and down in order to place the sampler 1200 over a cork stopper and subsequently remove the sample from the cork stopper.

[0355] In FIG. 14, the sampler 1200 is show in a position over a specific cork stopper 1452 which is to be analysed. Thereby, a gaseous mixture 1263 comprising inter alia the analytes of interest are for example delivered to an ion molecule reactor as explained in FIG. 13.

[0356] Once the analysis of this specific cork stopper 1452 is finished, the manipulator 1420 will move the sampler 1200 up into a hold position (indicated by dashed lines). When the sampler 1200 is in hold position, the conveyor belt 1410 will move to the right, such that the next cork stopper 1451 to be analysed is placed below the sampler 1200. Thereby, the cork stopper 1452 will be moved to the right side in FIG. 14 where further cork stoppers 1453 already analysed are located.

[0357] Then, the manipulator 1420 moves the sampler 1200 down, so that the next cork stopper 1451 can be analysed. Subsequently, the remaining cork stoppers 1450 can be treated in the same manner.

[0358] Thus, the sampling unit 1400 is configured to collect at least one analyte from each sample and to sequentially introduce the at least analyte from each sample into the reaction volume of ion molecule reactor.

[0359] FIG. 15 shows a setup 1500 with four samplers 1200a, 1200b, 1200c, 1200d and a multiport valve 1520 comprising four valve inlets 1521, 1522, 1523, 1524 and two valve outlets 1525, 1526. All of the samplers 1200a, 1200b, 1200c, 1200d are identical in construction with the sampler 1200 shown in FIG. 12. Each one of the four samplers 1200a, 1200b, 1200c, 1200d is connected with its outlet 1215a, 1215b, 1215c, 1215d to one of the four valve inlets 1521, 1522, 1523, 1524 via a gas conduit.

[0360] With the multiport valve 1520 it is possible to sequentially analyse samples previously placed in the samplers 1200a, 1200b, 1200c, 1200d by internally connecting each of the valve inlets 1521, 1522, 1523, 1524 to the valve outlet 1526, which in turn can be connected to an ion molecule reactor. A second outlet 1526 of the multiport valve 1526 can e.g. be used for flushing the multiport valve and the samplers.

[0361] Thus, with the multiport valve 1520 it is possible to load several samples in parallel into the plurality of samplers 1200a, 1200b, 1200c, 1200d and to sequentially or simultaneously introduce the analytes collected in each of the plurality of samplers into an ion molecule reactor.

[0362] FIG. 16a shows a sample holder 1600 which is can be used in a sampling unit in a top view whereas FIG. 16b show a cross section through the sample holder 1600 along the line A-A in FIG. 16a.

[0363] The sample holder 1600 consists of a hollow circular cylinder 1601 with 10 regularly spaced chambers 1611, 1612, 1613, 1614, 1615, 1616, 1617, 1618, 1619, 1620 which are designed as cylindrical bores with longitudinal axes running in a direction parallel to the longitudinal axis of the hollow circular cylinder 1601 from the lower end face 1602 to the upper end face 1603 of the hollow circular cylinder 1601. Each of the chambers 1611-1620 has an inlet 1611.2, 1612.2, 1613.2, 1614.2, 1615.2, 1616.2, 1617.2, 1618.2, 1619.2, 1620.2 in the upper end face 1603 and an outlet 1611.1, 1612.1, 1613.1, 1614.1, 1615.1 (the outlets of chambers 1616, 1617, 1618, 1619 and 1620 are not shown in FIGS. 16a and 16b) in the lower end face 1602. The hollow circular cylinder 1601 is e.g. made of aluminum.

[0364] Between the inlets 1611.2-1620.2 of the chambers 1611-1620, there are 10 regularly spaced stopped grooves 1630a, 1630b, 1630c, 1630d, 1630e, 1630f, 1630g, 1630h, 1630i, 1630j present in the upper end face 1603 which begin in a radially outward region of the upper end face 1603 and runs in radial direction towards the inner edge of the upper end face 1603. Similarly, between the outlets 1611.1-1620.1 of the chambers 1611-1620, there are 10 regularly spaced stopped grooves 1620a, 1620b, 1620c, 1620d, 1620e, 1630f (groves between chambers 1616/1617, 1617/1618, 1618/1619, and 1619/1620 are not shown in FIGS. 16a and 16b) present in the lower end face 1602 which begin in a radially outward region of the upper end face and runs in radial direction towards the inner edge of the upper end face 1602.

[0365] As shown in FIGS. 16a and 16b, there is a circular groove 1603a surrounding the inlets 1611.2-1620.2 of the chambers 1611-1620 in the upper end face 1603. The circular grove 1603a interconnects all of the stopped grooves 1630a-1630j at their radially outward ends such that a gaseous fluid can be fed from the circular groove 1603a into the stopped grooves 1630a-1630j. Similarly, there is a circular groove 1602a surrounding the outlets 1611.1-1620.1 of the chambers 1611-1620 in the lower end face 1602. The circular grove 1602a interconnects all of the stopped grooves 1620a-1620j such that a gaseous fluid can be fed from the circular groove 1602a into the stopped grooves 1620a-1620j.

[0366] FIG. 17a shows an arrangement comprising the sample holder 1600 of FIG. 16a in a top view, whereas FIG. 17b shows a detail of the arrangement 1700 in a cross section sectional view along the dashed line in FIG. 17a. Thereby, on top of the upper end face 1603, an inlet closing member 1702 which covers chambers 1611-1618 is arranged (chambers 1619 and 1620 are not covered). The inlet closing member 1702 consists of a solid ring segment shaped disc, e.g. made of polytetrafluoroethylene (PTFE) with a similar width as the upper end face 1603. For each of the chambers 1611-1618 which are covered by the inlet closing member 1702, the inlet closing member 1702 comprises a through opening 1702.1, 1702.2, 1702.3, 1702.4, 1702.5, 1702.6, 1702.7, 1702.8. In the configuration shown in FIG. 17a, 17b the through openings 1702.1-1702.8 are placed centrally above the chambers 1611-1618 so that the chambers 1611-1618 are open at the inlet side. Additionally, the inlet closing member 1702 comprises at least one opening 1740 which is located over the circular groove 1603a for feeding a gaseous fluid into the circular groove 1603a.

[0367] Likewise, below the lower end face 1602, an outlet closing member 1701 is arranged. The outlet closing member 1701 consists as well of a solid ring shaped disc, e.g. made of polytetrafluoroethylene (PTFE) with a similar shape as the inlet closing member 1702. For each of the chambers 1611-1618 which are covered by the outlet closing member (chambers 1619 and 1620 are not covered), the outlet closing member 1701 comprises a through opening 1701.1, 1701.2 . . . . , 1701.8. In the configuration shown in FIG. 17a, the through openings 1701.1-1701.8 are placed centrally below the chambers 1611-1618 so that the chambers 1611-1618 are open at the outlet side. Additionally, the outlet closing member 1701 comprises an opening (not shown) which is located over the circular groove 1602a for feeding a gaseous fluid into the circular groove 1602a.

[0368] Additionally, the arrangement shown in FIGS. 17a and 17b comprises a removal station 1710 for retrieving analytes evaporated from a sample SI (schematically indicated by dashed lines) in chamber 1611 and removing them from the sampling unit. The removal station 1710 comprises a gas inlet 1711 which is placed on top of inlet closing member 1702 over chamber 1611 and which is in fluid communication with through opening 1702.1. Since through opening 1702.1 is as well in fluid communication with chamber 1611, a carrier gas can be introduced into chamber 1611. Placed below the outlet closing member 1701, in the region of chamber 1611, there is a sampler outlet 1712 which is in fluid communication with through opening 1701.1.

[0369] Since through opening 1701.1 additionally is in fluid communication with chamber 1611, gaseous fluids can be retrieved from chamber 1611.

[0370] Thus, in the configuration shown in FIG. 17a, 17b, by introducing a carrier gas flow into chamber 1611 through gas inlet 1711, the analytes evaporated from sample SI can be removed via the sampler outlet 1712. If the sampler outlet 1712 is connected to an analyte inlet of an ion molecule reactor, the analytes can directly be fed into an ion molecule reactor, e.g. an ion molecule reactor 100, 200, 300, 400, 700, 800, or 900 as described above.

[0371] At the same time, chambers 1612-1618 can be flushed with a low flow of the gaseous fluid through openings 1702.2, 1702.3, 1702.4, 1702.5, 1702.6, 1702.7, 1702.8 of the inlet closing member 1702 and through openings 1701.2, 1701.3, 1701.4, 1701.5, 1701.6, 1701.7, 1701.8 of the outlet closing member 1701.

[0372] Chambers 1619 and 1620 which are not covered by the inlet closing member 1702 and the outlet closing member 1701 in the configuration of FIG. 17a, 17b are freely accessible, e.g. for loading or unloading samples.

[0373] Additionally, the arrangement shown in FIG. 17a, 17b comprises a heating unit with a controller, a heating element and a temperature sensor temperature (not shown in FIG. 17a, 17b) for setting a predefined constant of the sample holder 1600, for example a temperature of about 130? C.

[0374] In operation, a gaseous fluid, e.g. hot air is introduced into the grooves 1620a-1620j and 1630a-1630j in order to produce an air curtain between neighbouring chambers in order to reduce cross-contaminations between samples. Thereby, the air is delivered via channels 1620a. 1,1620f.1, 1630a. 1, 1630f.1 in to grooves 1630a and 1630f and likewise into the other grooves.

[0375] In the arrangement of FIGS. 17a and 17b, the sample holder 1600 is rotatably mounted between the inlet closing member 1702 and the outlet closing member 1701 which are fix in position. Thus, by rotation the sample holder 1600, it is possible to bring the through openings of the inlet closing member 1702 and the through openings of the outlet closing member 1701 over a section of the sample holder 1600 next to the inlet openings or next to the outlet openings, respectively, of the chambers. This situation is shown in FIG. 17c. Thus all of the chambers (e.g. chambers 1611, 1612, 1613) which are covered by the inlet closing member 1702 and the outlet closing member 1701 are closed in this situation. Thus, the sides of the inlet closing member 1702 and the outlet closing member 1701 facing the chambers (inward facing sides) can be cleaned with the air flowing through and escaping form grooves 1620a-1620f and 1630a-1630f covered by the inlet closing member 1702 and the outlet closing member 1701.

[0376] Specifically, the inward facing sides of the inlet closing member 1702 and outlet closing member 1701 are always being cleaned by the air flowing through the grooves 1630a-1630j when the sample holder 1600 is moving. The cleaning air sweeps the whole surface exposed to the sample between different samples.

[0377] When further rotating the sample holder 1600, a position can be reached in which the through openings of the inlet closing member 1702 are in fluid communication with the grooves (e.g. 1620a-d and 1630a-d) covered by the inlet closing member 1702 or the outlet closing member 1701, respectively. This situation is shown in FIG. 17d. Thereby, the through openings (e.g. 1701.1, 1701.2, 1701.3) of the outlet closing member 1701 as well as the sampler outlet 1712 can be flushed and cleaned with gas. Additionally, this position allows for a reference measurement or zero measurement, respectively.

[0378] FIG. 18 shows a schematic view of a setup 1800 for measuring analytes from solid samples such as cork stoppers. In the setup 1800, an arrangement as shown in FIG. 17a, 17b is mounted. Thereby, the inlet closing member 1702 and the outlet closing member 1701 are enclosed in a ring segment shaped housing 1810 which allows for delivering a gaseous fluid to the inlet closing member and for discharging a gaseous fluid from the outlet closing member. The sampler outlet 1712 is connected to an ion molecular reactor 1830 which is for example identical in construction with the ion molecule reactors 100, 200, 300, 400, 700, 800 or 900 as described above.

[0379] Additionally, the setup 1800 comprises a preheating station 1820 in which a plurality of samples S can be preheated to a constant temperature. The preheating station comprises a controller, a heating element and a temperature sensor (not shown) for setting the predefined constant temperature. Heating is for example effected with a hot air generating device (not shown).

[0380] The setup 1800 also comprises a loading unit 1821 for placing an individual sample S in a chamber of the sample holder and/or for removing samples from the chambers. The loading unit 1821 is placed next to a region of sample holder 1600 which is not enclosed by the housing 1810. Thus, in this region, samples can directly be introduced into the freely accessible chambers (e.g. chambers 1611 and 1612 in this configuration). By rotation of the sample holder 1600, different chambers can be loaded or unloaded sequentially.

[0381] FIG. 19 shows a perspective view of a preheating station 1900 which can for example be used in the setup of FIG. 18. The preheating station 1900 comprises a snake-shaped pathway 1920 on a flat table on which a chain 1921 of interlinked and open receptacles for individual samples (see FIG. 20 for details) is movably mounted. The chain 1921 is driven by a motorized gearwheel and redirected several times with free-running gears. A feeding station 1923 allows for introducing cork samples into the receptacles. The preheating station 1900 furthermore comprises a covering 1925 which comprises two hot air generating devices 1924. If the covering 1925 is closed, hot air is flowed around the samples in the receptacles.

[0382] Additionally, a loading unit 1922 is integrated in the preheating station 1900 (see upper left-hand side in FIG. 19). In operation, the chain 1921 of interlinked and open receptacles is moved over the loading unit where at a defined position, an opening is present in the pathway 1920 of the preheating station, such that an individual sample from the receptacle located over the opening can move downwards out of the receptacle, driven by gravity. If the preheating station is properly placed over a sample holder such as e.g. shown in FIG. 18, the sample can directly be introduced into a chamber of the sample holder.

[0383] In between loading unit 1922 and feeding station 1923, the receptacles are cleaned e.g. with hot air before new cork samples are introduced. Additionally or alternatively, the receptacles can be cleaned with another gas, a liquid and/or mechanically.

[0384] FIG. 20 shows a section of the moveable chain 1921 of FIG. 19 in detail. The moveable chain 1921 comprises a series of cylindrical pipe pieces 1921.1a, 1921.1b which are held together by a pair of outer links 1921.2a which alternate with a pair of inner links 1921.2b. Outer links 1921.2a and inner links are pivotable with respect to each other. Additionally, the chain 1921 comprises a lateral flange 1921.3 for better guiding the chain. The cylindrical pipe pieces 1921.1a, 1921.1b in which the samples, e.g. cork stoppers, are received, are open at both ends.

[0385] The preheating station 1900 can be operated in a manner synchronized to a sampling unit, e.g. the sampling unit 1700, with the help of an appropriate controller unit.

[0386] While the ion molecule reactors, mass spectrometers, samplers, arrangements, setups and methods described herein constitute preferred embodiments of this invention, it is to be understood that the invention is not limited to these embodiments, and that changes may be made therein without departing from the scope of the invention.

[0387] For example, in all of the ion molecule reactors 100, 200, 300, 400, 700, 800, 900 different and/or additional ion guides and/or electrode arrangements can be used to guide and/or focus the ions along the predefined transit paths.

[0388] For example, instead of a quadrupole setup as used in reactors 100, 200, 300 400, an octapole setup or a setup with any another number of rod electrodes can be used. Also a combined quadrupol/octapol setup can be suitable. Also, in all ion molecule reactors, e.g. additional ring electrodes can be attached inside and/or outside the housing.

[0389] In all ion molecule reactors 100, 200, 300, 400, 700 the cylindrical rod electrodes can for example be arranged within the housings. Also it is possible to use housings with electrodes integrated in the walls of the housing instead of external cylindrical rod electrodes. With ion molecule reactors 800, 900 additional ion guides in the form of multipole electrodes can e.g. be added in order to further guide the ions inside or outside the reaction volumes.

[0390] Also, the size, shapes and numbers of the electrodes described in the exemplary embodiments can be different. For example, the rod electrodes described with FIGS. 1, 2, 3, 4 and 7 can have a non-circular cross section. Moreover, the number and shape of the electrodes of the ion funnels or ion carpets described in FIGS. 3, 7, 8, 10 and 11 can be adapted if desired.

[0391] Although in the present ion molecule reactors, the predefined transit path is defined along a straight line along the longitudinal axis, transit paths which run along a non-longitudinal axis and/or transit paths with curved sections are possible.

[0392] Moreover, it is possible to foresee reagent ion inlets and/or reagent ion sources with other geometries. For example, in the embodiment of FIG. 2, a reagent ion inlet with ring-shaped nozzle could be used instead of the two separate inlets 230a, 230b. Also more than two separate inlets could be foreseen, e.g. 3, 4, 5, 7 or even more inlets which are preferably arranged symmetrically around the reaction volume.

[0393] Concerning the shape of the housings, non-cylindrical shapes, e.g. cuboidal shaped housing or even more complex shapes are possible as well. Specific sizes and proportions of the housings of the ion molecule reactors are not limited at all and can be adapted to specific needs if desired.

[0394] Also, the housing can be made of at least partially or fully flexible or bendable material, e.g. from plastics material. In a special embodiment, the ion molecule reactors or their housings, respectively, can be made of a bendable tube. Such a setup allows for example to effectively transfer ions over quite long distances, e.g. several meters. An embodiment with a bendable tube makes it for example possible to use the ion molecule reactor as a probe or a probe head, respectively, for taking analyte samples at random positions, e.g. similar to a vacuum cleaner.

[0395] If desired, means for heating and/or cooling can be included in the ion molecule reactors, which e.g. allow for heating and/or cooling the housings.

[0396] Also the gas permeable sections in the embodiments shown in FIGS. 3 and 4 can be used to introduce a sheath gas in order to further reduce wall effects.

[0397] Especially, in the embodiment of FIG. 3, the gas permeable section 360 can be used to introduce a sheath gas instead of removing neutrals from the reaction volume. This is an alternative approach for reducing wall effects in the ion molecule reactor. Thereby, the gas permeable section 360 can cover the whole cylindrical surface area of the housing 310 within the outer tubular element 370. In contrast to prior art systems which use a laminar flow of sheath gas with rather high pressures, the present setup results in a much lower pressure in the reaction volume.

[0398] Also, in the embodiment of FIG. 6, reagent inlets such as e.g. shown in FIG. 1 or 3 can be foreseen. In this case, instead of introducing regent ions through the gas permeable section 660, a sheath gas can be introduced into the housing 610 for reducing wall effects in the ion molecule reactor.

[0399] Moreover, the sampler 1200 shown in FIG. 12 can have a different geometry, for example it can have a cuboid container. Also it is possible to omit the encasing 1220 and to directly introduce a carrier gas 1260 via the frit ring 1214. Thereby, the carrier gas 1260 may for example be heated before with an external heater.

[0400] The container 1210 can also designed such that the complete sample, such as a cork stopper, can be taken up inside the container. Thereby, a closure might be provided in order to close the container hermetically or non-hermetically. For a non-hermetic closure, a cap with an air permeable membrane or section might be used.

[0401] Regarding the automated sampling unit 1400 of FIG. 14, it is for example possible to provide several samplers 1200 on a manipulator 1420. In this case, it is possible to pre-heat and/or analyse several samples in parallel. Thereby, it can be advantageous to use a multiport valve 1520 as shown in FIG. 15 for connecting the individual samplers with an ion molecule reactor.

[0402] Instead of the linear manipulator 1420 shown in FIG. 14, a two- or three-axis manipulator or a robotic arm can be used. Also, a circular manipulator can be used. Thereby, the conveyor belt can be omitted if desired.

[0403] Also it is possible to attach a second ion molecule reactor at the second valve outlet 1525 of the multiport valve 1520 in order to be able to measure several samples in parallel. This kind of parallel processing can help to increase the throughput further. Also, if the multiport valve has further outlets, additional ion molecule reactors can be attached.

[0404] Instead of the sample holder 1600 shown in FIG. 16a, 16b, a sample holder with more or less than 10 chambers, e.g. with 50, 75 or 100 chambers, can be used. Also, the sample holder 1600 not necessarily is of round shape. It is in principle possible to provide a straight sample holder.

[0405] The preheating station 1900 shown in FIG. 19 can be different in design as well. For example, instead or in addition to a hot air generating device, one or more heating rods can be used. Also it is possible to replace the chain 1921 by another conveying device, e.g. a conveyor band. Moreover, a manipulator can be used to take the samples out of the receptacles and/or to place them into the chambers of the sample holder. In this case, the samples can also be placed in receptacles with a closed end and/or stationary receptacles which are fixed in the preheating station.

[0406] In summary, it is to be noted that highly beneficial setups for ion molecule reactors and samplers are provided which allow for greatly increasing the efficiency of chemical ionisation and providing ionized analytes with a surprisingly high yield. In particular, due to the inventive ion molecule reactors, mass spectrometers, samplers, arrangements, setups and methods, it becomes possible to detect and analyse analytes with high sensitivity and allowing for a high sample throughput such as required in the detection of cork taint and/or haloanisols in cork stoppers.