Solution cathode glow discharge elemental analysis

1. A solution cathode glow discharge (SCGD) apparatus comprising:

an anode adapted to connect to a dc power source, the anode having an anode tip;

a grounding electrode adapted to connect to the dc power source, the grounding electrode having a grounding electrode tip proximate the anode, the region proximate the grounding electrode tip and the anode tip forming a plasma emission region;

a capillary tube adapted to receive a solution sample, the capillary tube having an outlet tip proximate the grounding electrode tip; and

a solution-catching collar between the outlet tip of the capillary tube and a base of the grounding electrode tip, adapted to maintain a solution level proximate the plasma emission region.

2. The SCGD apparatus of claim 1 , the solution-catching collar comprising a circular weir.

3. The SCGD apparatus of claim 2 , further comprising a circular bubble blocker, proximate the outlet tip of the capillary tube to prevent bubbles from directly entering the plasma emission region.

4. The SCGD apparatus of claim 2 , the solution-catching collar situated between about 0.3 and 3.0 mm below the outlet tip of the capillary tube.

5. The SCGD apparatus of claim 1 , the solution-catching collar comprising a wicking element.

6. The SCGD apparatus of claim 5 , the wicking element comprising a glass frit wick or a porous ceramic wick.

7. The SCGD apparatus of claim 6 , wherein the wick is disk shaped.

8. The SCGD apparatus of claim 6 , wherein the wick is tapered, having a wick tip proximate the grounding electrode tip.

9. The SCGD apparatus of claim 5 , further comprising an annular flow restrictor around the grounding electrode such that, in operation, a region of the grounding electrode is substantially covered by waste sample solution.

10. The SCGD apparatus of claim 9 , the annular flow restrictor comprising an O-ring or a secondary wicking element.

11. The SCGD apparatus of claim 1 , wherein the anode and the grounding electrode are fixed, the distance between the anode tip and the grounding electrode tip set in advance of operation.

12. The SCGD apparatus of claim 1 , further comprising a thermally conductive copper heat sink thermally connected with the anode to dissipate heat from the anode.

13. A method of analyzing a solution sample comprising:

providing the solution cathode glow discharge (SCGD) apparatus of claim 1 ;

providing the solution sample to the capillary tube of the SCGD apparatus at a sampling flow rate less than 2.0 mL/min;

initiating or maintaining a stable plasma glow discharge by applying an electrical current; and

analyzing the glow discharge emission.

14. The method of claim 13 , wherein the solution catching collar is a circular weir.

15. The method of claim 13 , wherein the solution catching collar is a wicking element.

16. The method of claim 15 , the SCGD apparatus further comprising an annular flow restrictor around the grounding electrode such that, in operation, a region of the grounding electrode is substantially covered by waste sample solution.

17. The method of claim 13 , wherein the sampling flow rate is about 1.5 mL/min.

18. The method of claim 13 , wherein the step of initiating the stable plasma glow discharge comprises pulsing the solution sample at an initiation flow rate, the initiation flow rate greater than the sampling flow rate.

19. The method of claim 18 , further comprising contacting an anode of the SCGD apparatus with the solution sample during the initiating.

20. The method of claim 13 , conducted online or continuous or in a real-time environment.

21. The method of claim 13 , wherein the step of analyzing the glow discharge emission comprises applying a low pass filter to remove high frequency noise.

22. The method of claim 13 , wherein the step of analyzing the glow discharge emission comprises detecting one or more molecular species.

23. The method of claim 22 , further comprising differentiating isotopes of the one or more molecular species.

24. The method of claim 23 , wherein the one or more molecular species are dissolved silica or colloidal silica.

25. A method of measuring colloidal counterions in an acidified solution sample containing clay, the method comprising:

providing a solution cathode glow discharge (SCGD) apparatus;

providing an unfiltered solution sample to a capillary tube of the SCGD;

initiating or maintaining a plasma glow discharge by applying an electrical current; and

detecting at least the sodium glow discharge emission from the unfiltered solution sample;

providing a filtered solution sample to the capillary tube, the filtered solution sample being substantially free from clay;

initiating or maintaining a plasma glow discharge by applying an electrical current; and

detecting at least the sodium glow discharge emission from the filtered solution sample;

subtracting the sodium glow discharge emission of the filtered solution sample from the sodium glow discharge emission of the unfiltered solution sample to indicate a measure of clay counterions released by acidification.

26. The method of claim 25 , wherein the net sodium glow discharge emission indicates a relative clay content of the solution sample.

27. The method of claim 25 , wherein the SCGD apparatus comprises the SCGD apparatus of claim 1 .