VISUAL, CONTINUOUS AND SIMULTANEOUS MEASUREMENT OF SOLUTION AMMONIA AND HYDROGEN ION CONCENTRATION

• US 20080076184A1
• Filed: 04/04/2007
• Published: 03/27/2008
• Est. Priority Date: 04/04/2006
• Status: Active Grant

• Current Assignee: Pacific Sentry LLC
• Original Assignee: Photonic Biosystems, Inc.
• Inventors: Putnam, David, Sharick, Janice, Putnam, Jason
• Granted Patent: US 7,790,113 B2
• Time in Patent Office: Days
• US Class Current: 436/106
• CPC Class Codes: G01N 31/221 for investigating pH value
• CPC Class Codes: G01N 33/18 Water
• CPC Class Codes: Y10T 436/17 Nitrogen containing

Abstract

Particular aspects provide novel devices and methods for accurately measuring total ammonia (NH₃ plus NH₄⁺) in a solution (e.g., freshwater and saltwater) by spatially proximate, simultaneous and continuous quantitative measurement of solution pH and ammonia. The devices overcome prior art inaccuracies relating to non-homogeneous sampling, and to spatial, temporal and thermal sampling discontinuities. Particular embodiments provide a combination pH and ammonia measuring device, comprising: a submersible member; a submersible non-bleeding ammonia-sensing portion attached to the submersible member and suitable to provide for a continuous visual indicator of solution ammonia concentration; a submersible non-bleeding pH-sensing portion attached to the submersible member and suitable to provide for a continuous visual indicator of solution pH; visual ammonia and pH indicator comparison means suitable for comparative quantitative determination of solution ammonia concentration and pH. Additional aspects provide novel ultra-sensitive devices and methods using same for measuring ammonia in air or solution.

Claims

1. A combination pH and ammonia measuring device for simultaneous, continuous measurement of solution pH and ammonia, the combination comprising:

a submersible member, or a plurality of spatially proximate, coordinately-submersible members, suitable to be at least partially submersible in a solution;

at least one submersible ammonia-sensing portion integral with or attached to the submersible member or to one or more of the proximate submersible members, the at least one ammonia-sensing portion having at least one stable detection means suitable to provide for a continuous visual indicator of solution ammonia concentration;

at least one submersible pH-sensing portion integral with or attached to the submersible member or to one or more of the proximate submersible members, the at least one pH-sensing portion having at least one stable detection means suitable to provide for a continuous visual indicator of solution pH;

a visual ammonia indicator comparison component, comparable with the at least one continuous visual indicator of the at least one ammonia-sensing portion to provide for standardized quantitative determination of solution ammonia concentration; and

a visual pH indicator comparison component, comparable with the at least one continuous visual indicator of the at least one pH-sensing portion for standardized quantitative determination of solution pH, wherein the combination is suitable to provide for simultaneous, continuous measurement of solution pH and ammonia.

2. The combination pH and ammonia measuring device of claim 1, wherein the at least one continuous visual indicator of the at least one ammonia-sensing portion comprises at least one calorimetric dye indicator.

3. The combination pH and ammonia measuring device of claim 1, wherein the at least one continuous visual indicator of the at least one pH-sensing portion comprises at least one calorimetric dye indicator.

4. The combination pH and ammonia measuring device of claim 2, wherein the at least one visual ammonia indicator comparison component comprises at least one ammonia reference color indicator comparison chart integral with or attached to the submersible member or to the proximate coordinately-submersible members.

5. The combination pH and ammonia measuring device of claim 2, wherein the visual ammonia indicator comparison component comprises at least one ammonia reference color indicator comparison chart that is physically separate from, but moveable to a position spatially proximate to the at least one ammonia-sensing portion of the submersible member or the proximate submersible members to be comparable therewith.

6. The combination pH and ammonia measuring device of claim 4, wherein the at least one ammonia reference color indicator comparison chart comprises at least one color-gradient indicator comparison chart.

7. The combination pH and ammonia measuring device of claim 6, wherein the at least one color-gradient indicator comparison chart comprises at least one linear color-gradient chart, or circular or wheel color-gradient chart.

8. The combination pH and ammonia measuring device of claim 3, wherein the at least one visual pH indicator comparison component comprises at least one pH reference color indicator comparison chart integral with or attached to the submersible member or to the proximate submersible members.

9. The combination pH and ammonia measuring device of claim 3, wherein the visual pH indicator comparison means comprises at least one pH reference color indicator comparison chart that is physically separate from, but movable to a position spatially proximate to the at least one pH-sensing portion of the submersible member or to the proximate submersible members to be comparable therewith.

10. The combination pH and ammonia measuring device of claim 8, wherein the at least one pH reference color indicator comparison chart comprises at least one color-gradient indicator comparison chart.

11. The combination pH and ammonia measuring device of claim 10, wherein the at least one color-gradient indicator comparison chart comprises at least one linear color-gradient chart, or circular or wheel color-gradient chart.

12. The combination pH and ammonia measuring device of claim 1, wherein the at least one ammonia-sensing portion is suitable to detect ammonia in the range of about 0.05 to about 0.5 ppm, about 0.05 to about 1.0 ppm, or about 0.005 to about 0.1 ppm.

13. The combination pH and ammonia measuring device of claim 12, wherein the at least one ammonia-sensing portion is suitable to detect ammonia in the range of about 0.005 to about 0.1 ppm.

14. The combination pH and ammonia measuring device of claim 2, wherein the at least one ammonia-sensing portion comprises a bromophenol blue dye in a porous PTFE support.

15. The combination pH and ammonia measuring device of claim 1, further comprising relational means for quantitatively determining total ammonia (NH₃ plus NH₄⁺), based on the at least one visual indicator of solution ammonia concentration and the at least one visual indicator of solution pH, in combination with the respective at least one quantitative ammonia and pH comparison components.

32. The combination pH and ammonia measuring device of any one of claims 1 and 16, wherein at least one of the at least one submersible ammonia-sensing portion or the at least one submersible pH-sensing portion further comprises an antimicrobial agent.

33. The combination pH and ammonia measuring device of claim 32, wherein the antimicrobial agent comprises at least one agent selected from the group consisting of silver, colloidal silver, silver dioxide, titanium dioxide, Triclosan, or Thiabendazole-based antimicrobials, silane quaternary ammonium salts;

namely, 3-(trimethoxysilyl) propyldimethyl octadecyl ammonium.

34. The combination pH and ammonia measuring device of claim 32, wherein the antimicrobial agent comprises a barrier material having pores small enough to preclude contact of the sensor by microbes, but large enough to allow for passage of water and ions therethrough.

35. The combination pH and ammonia measuring device of claim 32, wherein the barrier material comprises at least one porous membrane material selected from the group consisting of polyether sulfone, nylon, and polycarbonate.

37. The method of claim 36, wherein the combination pH and ammonia measuring device for simultaneous, continuous measurement of solution pH and ammonia is as described in claim 1.

48. The combination pH and ammonia measuring device of any one of claims 1 and 16, comprising a plurality of submersible ammonia-sensing portions, wherein at least two of the ammonia sensing portions have different ammonia sensitivities.

49. The combination pH and ammonia measuring device of claim 48, wherein the at least two ammonia sensing portions having different ammonia sensitivities each have a different sensitivity range selected from the ammonia sensitivity range group consisting of about 0.05 to about 0.5 ppm, about 0.05 to about 1.0 ppm, about 0.005 to about 0.1 ppm, about 0.005 ppm to about 0.05 ppm, and about 0.005 ppm to 0.05 ppm.

50. The combination pH and ammonia measuring device of claim 48, comprising at least three submersible ammonia-sensing portions each having a different ammonia sensitivity.

51. The combination pH and ammonia measuring device of claim 50, wherein the at least three ammonia sensing portions having different ammonia sensitivities each have a different sensitivity range selected from the ammonia sensitivity range group consisting of about 0.05 to about 0.5 ppm, about 0.05 to about 1.0 ppm, about 0.005 to about 0.1 ppm, about 0.005 ppm to about 0.05 ppm, and about 0.005 ppm to 0.05 ppm.

52. The combination pH and ammonia measuring device of any one of claims 1 and 16, further comprising a temperature sensing portion to provide for readout of temperature.

53. The combination pH and ammonia measuring device of any one of claims 1 and 16, wherein at least one of the ammonia sensing and pH sensing portions is suitably configured and disposed to extend sufficiently horizontally around one or more sides of the main body member so that a side view of at least one of the ammonia sensing and pH sensing portions by a user is operatively sufficient to provide for sensor input to the user.

57. The combination pH and ammonia measuring device of any one of claims 1 and 16, comprising at least one light blocking element to reduce or preclude degrading or bleaching of the sensor dyes, or of the inks used to create the at least one comparative standard indicator component.

58. The combination pH and ammonia measuring device of claim 57, wherein the light blocking aspect comprises a light-absorbing or reflective shield or shroud operatively positionable to cover at least a portion of the sensor device.

16. A combination pH and ammonia measuring device for simultaneous, continuous measurement of solution pH and ammonia, the combination comprising:

an attachment base member;

a submersible member, or a plurality of spatially proximate, coordinately-submersible members, reversibly attachable to the attachment base member, and suitable to be at least partially submersible in a solution;

at least one submersible ammonia-sensing portion integral with or attached to the submersible member or to one or more of the proximate submersible members, the at least one ammonia-sensing portion having at least one stable detection means suitable to provide for a continuous visual indicator of solution ammonia concentration;

at least one submersible pH-sensing portion integral with or attached to the submersible member or to one or more of the proximate submersible members, the at least one pH-sensing portion having at least one stable detection means suitable to provide for a continuous visual indicator of solution pH;

a visual ammonia indicator comparison component, comparable with the at least one continuous visual indicator of the at least one ammonia-sensing portion to provide for standardized quantitative determination of solution ammonia concentration; and

a visual pH indicator comparison component, comparable with the at least one continuous visual indicator of the at least one pH-sensing portion to provide for standardized quantitative determination of solution pH, wherein the combination is suitable to provide for simultaneous, continuous measurement of solution pH and ammonia.

17. The combination pH and ammonia measuring device of claim 16, wherein the at least one continuous visual indicator of the at least one ammonia-sensing portion comprises at least one calorimetric dye indicator.

18. The combination pH and ammonia measuring device of claim 16, wherein the at least one continuous visual indicator of the pH-sensing portion comprises at least one calorimetric dye indicator.

19. The combination pH and ammonia measuring device of claim 17, wherein the visual ammonia indicator comparison component comprises at least one ammonia reference color indicator comparison chart integral with or attached to the attachment base member.

20. The combination pH and ammonia measuring device of claim 17, wherein the visual ammonia indicator comparison component comprises at least one ammonia reference color indicator comparison chart that is physically separate from the attachment base member, but movable to a position spatially proximate to the at least one ammonia-sensing portion of the submersible member or the proximate submersible members to be comparable therewith.

21. The combination pH and ammonia measuring device of claim 19, wherein the at least one ammonia reference color indicator comparison chart comprises at least one color-gradient indicator comparison chart.

22. The combination pH and ammonia measuring device of claim 21, wherein the at least one color-gradient indicator comparison chart comprises at least one linear color-gradient chart, or circular or wheel color-gradient chart.

23. The combination pH and ammonia measuring device of claim 18, wherein the visual pH indicator comparison component comprises at least one pH reference color indicator comparison chart integral with or attached to the attachment base member.

24. The combination pH and ammonia measuring device of claim 18, wherein the visual pH indicator comparison component comprises at least one pH reference color indicator comparison chart that is physically separate from the attachment base member, but movable to a position spatially proximate to the at least one ammonia-sensing portion of the submersible member or the proximate submersible members, to be comparable therewith.

25. The combination pH and ammonia measuring device of claim 23, wherein the at least one pH reference color indicator comparison chart comprises at least one color-gradient indicator comparison chart.

26. The combination pH and ammonia measuring device of claim 25, wherein the at least one color-gradient indicator comparison chart comprises at least one linear color-gradient chart, or circular or wheel color-gradient chart.

27. The combination pH and ammonia measuring device of claim 16, wherein the at least one ammonia-sensing portion is suitable to detect ammonia in the range of about 0.05 to about 0.5 ppm, about 0.05 to about 1.0 ppm, or about 0.005 to about 0.1 ppm.

28. The combination pH and ammonia measuring device of claim 27, wherein the at least one ammonia-sensing portion is suitable to detect ammonia in the range of about 0.005 to about 0.1 ppm.

29. The combination pH and ammonia measuring device of claim 17, wherein the at least one ammonia-sensing portion comprises a bromophenol blue dye in a porous PTFE support.

30. The combination pH and ammonia measuring device of claim 16, wherein the attachment base member is at least partially submersible in a solution, and wherein the visual ammonia indicator comparison component and the visual pH indicator comparison component are integral with or attached to the attachment base member or to the submersible member or to at least one of the proximate submersible members.

31. The combination pH and ammonia measuring device of claim 16, further comprising relational means to quantitatively determine total ammonia (NH₃ plus NH₄⁺), based on the at least one visual indicator of solution ammonia concentration and the at least one visual indicator of solution pH, in combination with the respective at least one quantitative ammonia and pH comparison components.

38. The method of claim 36, wherein the combination pH and ammonia measuring device for simultaneous, continuous measurement of solution pH and ammonia is as described in claim 16.

36. A method for determining the total ammonia concentration in a solution, comprising:

submersing, in a solution, a combination pH and ammonia measuring device for simultaneous, continuous quantitative measurement of solution pH and ammonia; and

quantitatively determining total ammonia (NH₃ plus NH₄⁺), based on at least one visual indicator of solution ammonia concentration and at least one visual indicator of solution pH.

39. An ammonia detection device, comprising porous matrix polytetrafluoroethylene (PTFE) having an ammonia-sensitive immobilized dye, the immobilized dye suitable to provide for a calorimetric determination of ammonia level, and wherein the detectible range of ammonia comprises a range of about 0.005 to about 0.1 ppm.

40. The ammonia detection device of claim 39, wherein the ammonia-sensitive immobilized dye is BPB dye.

41. The ammonia detection device of claim 39, wherein the porous matrix polytetrafluoroethylene (PTFE) comprises a composite supported microporous PTFE medium, comprising a PTFE microporous membrane having secured directly to at least one face thereof a PTFE web of microfibres.

42. The device of claim 39, wherein calorimetric determination of ammonia level is continuous and reversible within the detectible range.

43. A method for detecting ammonia in air, comprising exposing the ammonia detection device of claim 39 to air, wherein a calorimetric determination of air ammonia level is, at least in part, afforded.

44. The method of claim 43, comprising optical sensing to interrogate the color of the ammonia-sensitive immobilized dye.

45. A method for detecting ammonia in solution, comprising exposing the ammonia detection device of claim 39 to a test solution, wherein a calorimetric determination of solution ammonia level is, at least in part, afforded.

46. The method of claim 45, comprising optical sensing to interrogate the color of the ammonia-sensitive immobilized dye.

47. The method of claim 43, wherein calorimetric determination of ammonia level is continuous and reversible within the detectible range.

54. A pH or ammonia measuring device, or a combination pH and ammonia measuring device, comprising at least one main body member having face and side surfaces, the member comprising at least one ammonia sensing portion and at least one pH sensing portion, wherein at least one of the ammonia sensing and pH sensing portions is suitably configured and disposed to extend sufficiently horizontally around at least one of the side surfaces, or a portion thereof, of the main body member sensor so that a side view of at least one of the ammonia sensing and pH sensing portions by a user is operatively sufficient to provide for at least one of ammonia and pH sensor input to the user.

55. The pH and ammonia measuring device of claim 54, wherein the main body member comprises a plate having front and rear plate face surfaces defining a plate depth, and having side surfaces.

56. A pH or ammonia measuring device, or a combination pH and ammonia measuring device, comprising at least one of a light-sensitive sensor dye and ink;

and at least one light blocking element to reduce or preclude degrading or bleaching of the sensor dye or ink.