System and method for rapid analysis of polycyclic aromatic hydrocarbons

Patent metadata

Field	Value
Publication number	US-9518960-B2
Application number	US-201414503998-A
Country	US
Kind code	B2
Filing date	Oct 1, 2014
Priority date	Oct 2, 2013
Publication date	Dec 13, 2016
Grant date	Dec 13, 2016

Abstract

The subject technology is directed to a CO 2 -based system and method for rapid determination of the levels and/or the presence or absence of polycyclic aromatic hydrocarbons (PAHs).

First claim

What is claimed is:

1. A method for detecting one or more polycyclic aromatic hydrocarbons (PAHs) in a sample by means of a CO 2 -based chromatography analysis comprising:
providing a sample comprising one or more PAHs for analysis; wherein the sample is prepared with, extracted or dissolved in a diluent comprising at least 60% organic solvent, with the proviso that the sample is analyzed without a solvent exchange step;
applying the sample to a chromatography column with a solid stationary phase comprising inorganic or hybrid particles having a mean particle size of about 0.5 to about 3.5 microns, wherein said particles have a non-polar or polar/non-polar surface functionality, and wherein the particles retain said one or more PAHs;
eluting the one or more PAHs from the chromatography column by a mobile phase comprising a mixture of liquid CO 2 and a modifier to form one or more eluted PAHs; wherein the mobile phase has a pre-column dwell volume of about 75 μL to about 500 μL; and
detecting said one or more eluted PAHs.

2. The method of claim 1 , wherein the sample is not subject to a derivatization step.

3. The method of claim 2 , wherein the organic portion of the hybrid particles comprises substituted or unsubstituted C 1 -C 18 alkylene, alkenylene, alkynylene or arylene moiety bridging two or more atoms of the inorganic portion.

4. The method of claim 1 , wherein the particles having a non-polar surface functionality comprise capped particles with non-polar surface modifiers comprising an alkyl group, alkenyl group, alkynyl group, aryl group, an alkyl or aryl group containing one or more embedded non-polar functionalities, or a mixture thereof.

5. The method of claim 1 , wherein the particles having a polar/non-polar surface functionality comprise uncapped particles with free surface hydroxyl groups and non-polar surface modifiers comprising an alkyl group, alkenyl group, alkynyl group, aryl group, an alkyl or aryl group containing one or more embedded non-polar functionalities, or a mixture thereof.

6. The method of claim 1 , wherein the particles have a mean particle size of about 0.5 to about 2 microns.

7. The method of claim 1 , wherein the particles have a mean pore volume in the range of about 0.1 to about 2.5 cm/g.

8. The method of claim 1 , wherein the particles have a mean pore diameter in the range of about 100 to about 1000 Angstroms.

9. The method of claim 1 , wherein the inorganic particles comprise aluminum, titanium, cerium, zirconium, barium, cobalt, copper, europium, gadolinium, iron, nickel, samarium, silver, titanium, diamond, zinc, boron or oxides thereof, silicon carbide, carbon black, carbon nanotubes, ceramic, glass, metallic materials or mixtures thereof.

10. The method of claim 1 , wherein the hybrid particles comprise an inorganic portion and an organic portion.

11. The method of claim 10 , wherein the inorganic portion of the hybrid particles comprises silicone, aluminum, titanium, cerium, zirconium, barium, cobalt, copper, europium, gadolinium, iron, nickel, samarium, silver, titanium, diamond, zinc, boron or oxides thereof, silicon carbide, carbon black, carbon nanotubes, ceramic, glass, metallic materials or mixtures thereof.

12. The method of claim 10 , wherein the organic portion of the hybrid particles comprises substituted or unsubstituted C 1 -C 18 alkane, alkylene, alkenylene, alkynylene or arylene moiety bonded to one or more atoms of the inorganic portion.

13. The method of claim 1 , wherein the chromatography column is kept in a temperature range of about 5° C. to about 85° C.

14. The method of claim 1 , wherein the mobile phase further comprises a modifier added to the liquid CO 2 in a constant or gradient mode or both over an elution period or a fraction thereof.

15. The method of claim 14 , wherein the modifier is a polar water-miscible organic solvent selected from the group consisting of methanol, ethanol or isopropanol, acetonitrile, acetone, tetrahydrofuran, mixtures thereof, and mixtures of water and any of these solvents.

16. The method of claim 14 , wherein the gradient mode comprises increasing or decreasing flow volume of the modifier.

17. The method of claim 14 , wherein the elution period is about 5 minutes.

18. The method of claim 14 , wherein the gradient mode comprises increasing the flow volume of the modifier from about 0% to about 50% (v/v CO 2 ) or any intervals therebetween.

19. The method of claim 14 , wherein the gradient mode comprises increasing the flow volume of the modifier from about 0% to about 25% (v/v CO 2 ).

20. The method of claim 1 , wherein the liquid CO 2 is in a supercritical state or a subcritical state or both.

21. The method of claim 1 , wherein the detection comprises determining the levels or the presence or absence of the one or more PAHs.

22. The method of claim 1 , wherein the detection is by way of a mass spectrometer; Evaporative Light Scattering (ELS) detector, Circular Dichroism (CD) detector, Flame Ionization Detector (FID) or a photodiode array detector (PDA).

23. The method of claim 1 , wherein the sample comprises an environmental sample, chemical sample, food sample, biological sample, or an extract thereof.

24. The method of claim 1 , wherein the chromatography column is part of a chromatography system comprising a pre-column mobile phase dwell volume of about 100 to about 500 μL; wherein said pre-column mobile phase dwell volume is the volume of the mobile phase present in a fluidic connection between a junction at which the CO 2 and the modifier are mixed and the head of the chromatography column.

25. The method of claim 1 , wherein the one or more PAHs are eluted from the chromatography column by the mobile phase with a flow rate of about 1 to 4 mL/min.

26. The method of claim 1 , wherein the chromatography column has a length of about 50 to 150 mm and an internal diameter about 2 to 4 mm.

27. A chromatography method for detecting one or more polycyclic aromatic hydrocarbons (PAHs) in a sample comprising the steps of:
providing a sample comprising one or more PAHs for analysis; wherein the sample is prepared with, extracted or dissolved in a diluent comprising at least 60% organic solvent, with the proviso that the sample is analyzed without a solvent exchange step;
applying the sample to a chromatography column with a solid stationary phase comprising inorganic or hybrid particles having a mean particle size of about 0.5 to about 3.5 microns, wherein said particles have a polar surface functionality, and wherein the particles retain said one or more PAHs;
eluting the one or more PAHs from the chromatography column by a mobile phase comprising a liquid CO 2 to form one or more eluted PAHs, wherein the mobile phase has a pre-column dwell volume of about 75 μL to about 500 μL; and
detecting said one or more eluted PAHs by a mass spectrometer.

28. A method for detecting one or more PAHs comprising:
(1) providing a sample comprising one or more PAHs for analysis; wherein the sample is prepared with, extracted or dissolved in a diluent comprising at least 60% organic solvent, with the proviso that the sample is not subject to a solvent exchange step;
(2) applying the sample to a chromatography system comprising:
(a) a column with a solid stationary phase comprising an inorganic or hybrid particle having a mean particle size of about 0.5 to about 3.5 micro

Assignees

• Waters Technologies Corp

Inventors

• Nema Tarang
• Gay Melvin
• Ritchie Mark

Classifications

• G01N30/52

  Physical parameters · CPC title

• G01N2030/8854

  involving hydrocarbons · CPC title

• G01N30/68

  Flame ionisation detectors · CPC title

• G01N30/88

  Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 · CPC title

• G01N2030/525

  surface properties, e.g. porosity · CPC title