Polish Journal of Environmental Studies Vol. 11, No.

2 (2002), 185-187

Letter to Editor

Some Remarks on Gas Chromatographic

Challenges in the Context of Green Analytical
Chemistry

W. Wardencki, J. Namieśnik
Department of Analytical Chemistry, Chemical Faculty, Technical University of Gdansk,
80-952 Gdansk, 11/12 Narutowicza, Poland

Received: November 20, 2001

Accepted: January 4, 2002

Abstract
As researchers involved in chromatography for 30 years we would like to present three approaches of implementation
of principles of green chemistry into gas chromatography.

Introduction environment. Green chemistry standards have become

alternatives to the traditional pollute-and-clean-up prac-
There is no doubt that our lives have been improved tice.
by chemistry. However, activities of chemists and chemi- The activity of analytical chemists in laboratories, i.e.
cal engineers, both in industry and in laboratories, can through uncontrolled disposal of chemical waste, used
also adversely affect the quality of the natural environ- reagents, etc., may also exert (however to a lesser extent)
ment. It is easy to find several environmental problems as a negative influence on the environment. Therefore, fur-
familiar examples of chemistry gone wrong. The growing ther development of green chemistry should also com-
public concern over protecting our environment has led prise the development of green analytical chemistry.
us to introduce regulations to limit pollution and expo- The specific principles of chemical practise related to
sure to hazardous chemicals and materials. Such a situ- sustainable development are summarized as the Twelve
ation obligates the chemists to change the attitude to Principles of Green chemistry [2], proposed in 1998.
their activities. Generally, their work should link the de- They can be found elsewhere, for example at the
sign of chemical products and processes with their im- home-page of the American Chemical Society
pacts on human health and the environment. In this re-
(www.acs.org/education/greenchem/principles.html) or in
spect the essential duties of the chemical community can
be considered in two main directions: the Journal of Chemical Education [3].
- improving the level of pro-environmental awareness Considering these principles it is easy to indicate the
at all levels of training (schools, universities and indus directions which will decide about the "green" character
try), which should result in preparation of specialists ca of analytical chemistry [4]. The following should be
pable of handling and solving common environmental treated as the top priorities:
problems, - eliminating or minimizing the use of chemical re
- changing chemical activity into a such way that it will agents, particularly organic solvents, from analytical
be conducted in an enviromently friendly manner. methods,
Recently, a significant increase of such actions has - eliminating from analytical procedures chemicals
been observed and the term Green Chemistry has been with high toxicity and ecotoxicity,
introduced to describe them [1]. Green chemisty en- - reducing steps demanding much labor and energy,
compasses all aspects and types of chemical processes in particular analytical methods (per single analyte).
that reduce negative impacts on human health and the - reducing the impact of chemicals on human health.
186 Wardenecki W., Nemieśnik J.

Gas Chromatographic Challenges and can be automated by connection with gas chromatog-
raphy. Static and dynamic headspace techniques have
The main demands for analysts using chromato- frequently been used in practice during last ten years.
graphic methods wishing to implement the principles of One dynamic version, i.e. purge and trap (PT) is broadly
green analytical chemistry are as follows: recommended by the U.S. EPA and is widely accepted as
- utilization - as much as possible - of so-called direct the method of choice for routine analysis of volatile or-
chromatographic analysis, which permits us to determine ganic compounds in water. Static headspace microextrac-
analytes in a sample without any pretreatment or sample tion is also becoming very popular mainly because it does
preparation not need such sophisticated instrumental construction as
- reduction of labor and energy consumption, e.g. re the PT technique. Recently, different membrane-based
ducing sample preparation time when direct chromato techniques, like membrane inlet mass spectrometry
graphic analysis is not possible (MIMS) and purge-and membrane mass spectrometry
- elimination or reduction of the amount of solvent (PAM MS) have also been proposed.
from sample preparation steps applied before final Supercritical fluid extraction (SFE) has many advan-
chromatographic analysis tages over conventional extraction methods:
- conducting all operations with solvents in a hermetic - it requires far less time to achieve extraction
systems - the solvent used, usually carbon dioxide, is
- reducing matrix interferences non-toxic, available in high purity at low cost
- reducing chromatographic run time - solvation characteristic of typical supercritical media
- reducing the need for reanalysis can be altered by changing either the pressure or tem
- integration of steps of analytical procedures, ie. by perature of the fluid.
using hyphenated techniques. SFE, unlike conventional extraction techniques, does
Implementation of principles of green chemistry into not require preconcentration steps and offers the possi-
gas chromatography can be performed in many ways. bility of eliminating clean-up steps often required in
First of all, eliminating or minimizing the amount of sol- other extraction methods before detection. Supercritical
vent in sample preparation techniques before final fluids have become popular extraction media for differ-
chromatographic analysis is highly recommended. There- ent types of analytes from matrices like human and ani-
fore, techniques using gas and supercritical fluids for ex- mal tissues, sediments, fly ash, sewage. As application
traction of many pollutants are very popular. Also, the ranges are being extended, interest in SFE is increasing.
importance of fast chromatography, especially with field-
portable instrumentation, is quickly gaining attention.
Coupling of gas chromatography with techniques having
high identification ability, e.g. with mass spectrometry, Preconcentration of Pollutants Followed
(GC/MS) has gained prominence because confirmation by Thermal Desorption
can be achieved in the same step as analysis with second
dimension of information. This provides increased A standard method for the measurement of volatile
confidence in the result in conjuction with increased organic compounds in workplace or environmental air
effectiveness. involves sampling polluted air on a suitable sorbing
agent, followed by recovery of the sample by solvent or
thermal desorption [6].
Solventless Sample Preparation Advantages of thermal desorption versus conven-
tional solvent extraction include 1000-fold improvement
Techniques in detection limits, no chromatographic interference
from solvent or solvent impurities, enhanced sample
Typical methods for sample preparation of different throughput and lower cost per analysis. Another benefit
environmental samples usually involve liquid-liquid or is that thermal desorption is a very straightforward gas
liquid-solid extraction with an organic solvent often fol- extraction process. Considering these advantages it can
lowed by clean up and preconcentration steps. These be stated that thermal desorption fullfils all requirements
methods are time consuming and costly in the amount of of introducing principles of green chemistry into
solvent required. Greater concern over the disposal of chromatographic analysis. Its use in practice still be-
usually toxic solvents and their impact on the environ- comes more popular also due to the fact that commercial
ment has led towards cleaner extraction methods. Such systems are now available which meet all basic criteria
methods are commonly described as solventless sample and offer numerous features for simplifying and enhanc-
preparation techniques [5]. Three approaches are strongly ing the operator's work.
recommended among these techniques, i.e. gas extraction
and membrane-based techniques and supercritical fluid
extraction.
Gas extraction techniques are the most widely used High-Speed (fast) Gas Chromatography
for isolation of volatile pollutants from different ma-
trices, mainly due to the fact that they can be considered Since the introduction of gas chromatography in 1952,
as proecological (solvent-free ) methods of isolation and there have been unceasing efforts in improve separation
enrichment. Furthermore, most versions of these tech- speed [7]. Reduction of overall analysis time provides
niques provide the required sensitivity (up to ppt level)
Some Remarks ... 187

significant savings in time and money. The use of fast and an exceptionally high range of velocities of the car-
chromatography can be especially attractive for labora- rier gas at which the column retains its high efficiency.
tories where many routine samples are analyzed on
a daily base. It can also be beneficial in situations where
a short time-to-result is needed. References
The main routes toward faster separation include,
amongst others: 1. ANASTAS P.T. Green Chemistry and the Role of Analytical
- decreasing the inner diameter of the capillary col Methodology Development. Crit. Rev. Anal. Chem. 29, 167,
umns 1999.
- fast temperature programming 2. ANASTAS P.T. Green Chemistry. Theory and Practice. Ox
- application of shorter columns ford University Press, New York, 1998, p. 30.
- working at turbulent flow 3. HJERESEN D.L, SCHUTT D.L, BOESE J.M. Green
- vacuum outlet operation Chemisty and Education. J. Chem. Educ, 77, 1543, 2001.
4. NAMIESNIK J. Green analytical chemistry - some remarks.
- working above optimal carrier gas velocities.
J. Sep. Sci. 24,10, 2001.
Recently, high speed separation is performed on col-
5. NAMIESNIK J., WARDENCKI W. Solventless Sample
umns that consist of a bundle of 900-2000 microcapilla- Preparation Techniques in Environmental Analysis. J. High
ries of small (20-40 µm) internal diameter, referred to as Resol. Chromatogr. , 23, 297, 2000.
polycapillary or microcapillary columns (MC). Such 6. HARPER M. Sorbent trapping of volatile organic com
a bundle allows one to eliminate the deficiences asso- pounds from air. J. Chromatogr. A, 885, 129, 2000.
ciated with the use of capillary and packed columns while 7. CRAMERS C.A., JANNSSEN H-G., VAN DEURSE M.M,
the advantages of both are preserved. The use of these LECLER P.A. High-speed chromatography: an overview of
columns enables fast separation of large samples injected various concepts. J. Chromatogr. A, 856, 315, 1999.