This is a good document for Amine sampling and analysis

1. A NEW METHOD FOR THE
SAMPLING AND ANALYSIS OF
AMINES
Presented by:
Sucha S. Parmar, Ph.D.
Atmospheric Analysis and Consulting, Inc.
1534 Eastman Ave., Suite A
Ventura, CA 93003

2. Purpose
Due to the ever increasing request for
analysis of Amines, both common and
unique, in addition to the need for lower
detection limits, AAC has devoted
considerable effort into developing a
universal method for the sampling and
analysis of Amines.

3. Purpose Continued
 This is largely due to the ever increasing use of
Amines throughout various industries as well
as increased emissions from many different
sources.
 This increase in usage and emissions has also
brought considerably more attention to their
associated health risks as well as their role as
an atmospheric pollutant.

4. Abstract
 In this presentation, we describe some of the
preliminary data for the measurement of
amines in air using 1-Naphthyl isothiocyanate
derivatization to produce corresponding
thioureas followed by HPLC/UV analysis. In
addition we discuss the pro’s and con’s of this
procedure and our efforts leading into phase
two of our research

5. Developmental Goals
 Some of AAC’s goals in developing this
method were:
 Cost effective
 Simplistic and adaptable sampling procedures
 Minimize interferences
 Low detection limits
 Reproducibility
 Accuracy

6. Introduction
Amines are organic compounds in which
Nitrogen serves as the key atom of this
functional group.
Structurally Amines resemble ammonia, wherein
one or more Hydrogen atoms are replaced by
organic substituents.

7. Introduction continued
The three main substituents associated
with amines are:
Alkyl Aryl Carbonyl

8. Introduction continued
Amines are typically classified in the following
manner:

9. Introduction continued
 Surfactants
 Fungicides & Biocides
 Resins & Epoxy Curing
Agents
 Corrosion inhibitors
 Lubricating Oil and Fuel
Additives
 Paints and Coatings
 Dyes
 Oil refineries (Gas
Treatment)
 Pharmaceuticals
 Pulp and Paper Industry
 Food Industry
 Agriculture
 Personal Care Products
 Auto Industry
Amines have a variety of uses throughout
many different industries

10. General Properties
 Amines act as bases just like ammonia.
 Mono, Di & Tri methylamine, as well as
ethylamine are gases at STP, while Di and
Triethylamine, as well as most other common
alkyl amines are liquids at STP.
 Higher molecular weight amines are solids.
 Gaseous amines typically give off an ammonia
smell, while liquid amines have a very distinctive
"fishy" smell.

11. General Properties Continued
 Most aliphatic amines are reasonably soluble in
water. This decreases with the increase in the
number of carbon atoms.
 Aliphatic amines are however highly soluble in
organic solvent, especially polar organic solvents.
 The aromatic amines, are typically only soluble in
organic solvents.

12. General Properties Continued
 Amines are products and precursors in many
atmospheric chemical reactions
 Amines are a nuisance and some are very toxic
 Amines react with nitrogen dioxide to form
nitrosamine, a carcinogen.
 Amines have been indicated in sick building
syndrome.

13. General Properties Continued
 Amines are also primary pollutants and are released
from various processes.
 Low molecular weight volatile amines are often used in
the manufacturing of industrial chemicals and products
such as rubber, plastics and other polymers, dyes, and
corrosion inhibitors.
 Amines are formed and emitted as byproducts in
metabolism of microorganisms, plants and animals.

14. Measurement Techniques
Existing Colorimetric Methods
 Colorimetric reaction with Nessler’s reagent
 Phenol hypochlorite reaction
 Reaction of o-phthalaldehyde (OPA) with Ammonia
followed by fluorescence detection
 The reaction of ammonia and amines with dabsyl
chloride followed by HPLC/UV analysis of amide
product.

15. Measurement Techniques
Existing GC Methods
 Amines and ammonia are sampled in 0.1 N H2SO4
followed by neutralization with NaOH in the lab to
regenerate amines. The samples are then analyzed
with GC/FID
 NIOSH 2010 (Aliphatic amines); Silica gel/GC-FID
 NIOSH 2002 (Aromatic amines); Silica gel/GC-FID
 NIOSH 2009 (Aminoethanols); Silica gel/GC-FID

16. Measurement Techniques
Other Existing Methods
 Amines are sampled in/on various solutions or sorbet
tubes containing derivatizing agents and then
analyzed by HPLC or IC.
 OSHA 60 (EDA, DETA, TETA)
 OSHA 41 (Diethylamine)
 OSHA 22 (Diphenylamine)
 OSHA PV2111 (Ethanolamine)
 NIOSH 3509 (Aminoethanols); Ion chromatography

17. Measurement Techniques
Problems with existing techniques
 Methods utilizing GC/FID suffer from poor response
factors and therefore have high detection limits.
 Methods utilizing an IC suffer from coellution
problems.
 Colorimetric methods have numerous interferences.
 Whole air sample suffer from stability and recovery
problems due to the nature of the amines.
 Existing derivatization/HPLC methods are analyte
specific and non-universal.

18. Method Development
 AAC’s initial method development is based on OSHA
method 60 which utilizes 1-NAPHTHYL
ISOTHIOCYANATE as a derivatizing agent to
produce a Thiourea Derivative.
 The proposed method is an extension of this principle
which we have adapted to the most commonly
monitored primary and secondary amines in addition
to implementing an alternative sampling method.

19. Method Development Continued
 The proposed sampling method incorporates a typical method
5 Train which utilizes a heated probe and filter followed by
two impingers containing an organic solvent (IPA or DMF)
and NITC followed by a fourth impinger filled with silica gel.
 Heated
Probe
 Heated
Filter Box
 Ice
Bath
 Silica Gel
impinger
 Open
impinger
 NITC/IPA
impingers
 To
Pump/Meter

20. Derivatization Technique

21. Derivatization Technique

22. Derivatization Technique
 Unfortunately one major problem exists with this derivatization
technique. NITC is incapable of derivatizing tertiary amines.
• Primary amines have one alkyl group while secondary amines have
two alkyl groups. Both of these types of amines have a hydrogen
that is available in the derivatization with NITC. The accessible
hydrogen atoms are the key to stabilizing the thiourea derivative.
Tertiary amines are not derivatized by NITC because they have three
alkyl groups present therefore there is no hydrogen available.
 Alternative derivatization techniques will be discussed in phase two
of our research and development

23. Experimental Tasks Performed
 Preparation of amine-naphthylisothiocyanate urea
derivatives in suitable solvents.
 Determination of UV spectra of amine derivatives,
absorption maxima, extinction coefficients, etc., using
Jasco V-550 UV/Visible spectrophotometer.
 HPLC analysis of individual amine derivatives to
determine retention times.

24. Experimental Tasks Performed
Continued
 HPLC analysis of a mixture of various primary
and secondary amines to find right conditions
for complete separation.
 Calibration of HPLC for a mixture of amines to
determine response factors, method detection
limits, etc.
 Spike recovery study and evaluation.

25. Experimental Tasks Performed
Continued
The following is the list of Amines investigated in
Phase One of method development:
 Methylamine
 Ethylamine
 Dimethylamine
 Diethylamine
 Ethylenediamine
 Diethylenetriamine
 Triethylenetriamine
 Monoethanolamine
 Diethanolamine
 Isobutylamine
 Cyclohexylamine

26. Spectral Analysis
Maximum Absorbance
-0.2
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
2
200 250 300 350 400 450
Wavelength (nm)
Abs
Methylamine Dimethylamine

27. Spectral Analysis Continued
Amine
Absorption
Maximum
(nm)
Extinction
Coefficient
(cm/mol)
Methylamine 297 75215
Dimethylamine 297 71585
Ethylamine 296 43688
Diethylamine 309 33631
Ethylenediamine 297 32216
Isobutylamine 297 37983

28. Example Chromatogram
under optimized analytical conditions

29. Initial Calibration
Amines Calibration Curve
0
2000000
4000000
6000000
8000000
10000000
12000000
14000000
16000000
18000000
0 10 20 30 40 50 60
Concentration (ug/mL)
Response
Methylamine Isobutylamine Ethylamine
Linear (Methylamine) Linear (Ethylamine) Linear (Isobutylamine)

30. Spike Recovery Study
Analyte
Recovery
Concentration
(ug/ml)
Practical
Concentration
(ug/mL)
Percent
Recovery
(%)
Initial
Calibration
Factor
Daily
Calibration
Factor
%RPD**
Methylamine 10.000 10.021 100 306531 307174 0.2
Dimethylamine 10.000 9.904 99 272289 269666 1.0
Ethylamine 10.000 9.840 98 267485 263211 1.6
Diethylamine 10.000 9.574 96 160530 153691 4.4
Ethylenediamine 10.000 9.530 95 269898 257215 4.8
Isobutylamine 10.000 9.874 99 158135 156143 1.3

31. Conclusion
 AAC has successfully developed a new method
for measurement of primary and secondary
amines.
 Using this method, amines can be easily sampled
in a solution of 1-Naphthylisothiocyanate in a
suitable solvent.
 Linearity, reproducibility, and adaptability has
been achieved.

32. Conclusion continued
 This derivatization reaction is fast, quantitative and works at
room temperature.
 All samples can be analyzed directly on HPLC/UV system
without further treatment.
 This technique is far more sensitive and selective compared
to any other GC or HPLC Method available.

33. Conclusion continued
 Based on an instrument detection limit of 0.05 ug/ml, an
impinger volume of 10 ml, and a sampling volume of 50
Liters, the overall theoretical detection limit for this method is
estimated to be between 1.0 and 10.0 ppbv.
 A corresponding reliable Practical Quantitation limit is
therefore estimated to be between 5.0 and 25.0 ppbv.

34. Future Research Work
 Extend this study to ammonia and other primary
and secondary amines.
 Expand the method to be able to utilize optional
sampling media such as NITC coated filters and
Silica Gel tubes.
 Perform actual field sampling.
 Perform Holding time studies.
 Comparison with other techniques.

35. Research and
Development Phase Two
AAC is in the process of investigating two additional
derivatizing reagents including:
Phenacyl Bromide
2-Bromo-3’-nitroacetophenone
Experiments have shown that these agents will allow for
the derivatization of tertiary amines as well as primary
and secondary.

36. Derivatization Technique

37. Phase Two Continued
The following list is a summary of some of the amines which
AAC proposes to incorporate into Phase Two:
 Ammonia
 Methylamine
 Ethylamine
 Dimethylamine
 Diethylamine
 Trimethylamine
 Triethylamine
 Ethylenediamine
 Diethylenetriamine
 Triethylenetriamine
 Monoethanolamine
 Diethanolamine
 Triethanolamine
 Isopropylamine
 N-propylamine
 Isobutylamine
 Ethylhexylamine
 Cyclohexylamine
 Diphenylamine
 N,N-Dimethylethylamine

38. Acknowledgements
Marcus Hueppe - Laboratory Manager, AAC
Kristia Parker – Chemist, AAC
Connie Fuller – Chemist, AAC