AU762611B2 - Method for solid-phase microextraction and analysis, and a collector for this method - Google Patents

Method for solid-phase microextraction and analysis, and a collector for this method Download PDF

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Publication number
AU762611B2
AU762611B2 AU20623/00A AU2062300A AU762611B2 AU 762611 B2 AU762611 B2 AU 762611B2 AU 20623/00 A AU20623/00 A AU 20623/00A AU 2062300 A AU2062300 A AU 2062300A AU 762611 B2 AU762611 B2 AU 762611B2
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AU
Australia
Prior art keywords
substances
collector
solid
analysis
carrier
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Expired
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AU20623/00A
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AU2062300A (en
Inventor
Erik Baltussen
Frank David
Patrick Sandra
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Gerstel Systemtechnik GmbH and Co KG
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Gerstel Systemtechnik GmbH and Co KG
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Priority claimed from DE1999113809 external-priority patent/DE19913809C2/en
Application filed by Gerstel Systemtechnik GmbH and Co KG filed Critical Gerstel Systemtechnik GmbH and Co KG
Publication of AU2062300A publication Critical patent/AU2062300A/en
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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G01N30/12—Preparation by evaporation
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/34—Purifying; Cleaning
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/40—Concentrating samples
    • G01N1/405—Concentrating samples by adsorption or absorption
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N2030/009—Extraction
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G01N30/12—Preparation by evaporation
    • G01N2030/121—Preparation by evaporation cooling; cold traps
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G01N30/12—Preparation by evaporation
    • G01N2030/126—Preparation by evaporation evaporating sample
    • G01N2030/128—Thermal desorption analysis

Abstract

Collector comprises a rod-like support having a coating made from a tube-like absorbing and/or adsorbing material depending on the substances being investigated.

Description

AUSTRALIA
Patents Act 1990 COMPLETE SPECIFICATION FOR A STANDARD PATENT
ORIGINAL
Applicant(s): GERSTEL SYSTEMTECHNIK GMBH CO. KG Actual Inventor(s): Patrick Sandra; Erik Baltussen and Frank David Address for Service: PATENT ATTORNEY SERVICES 26 Ellingworth Parade Box Hill Victoria 3128 Australia Title: -METHOD FOR SOLID-PHASE MICROEXTRACTION AND ANALYSIS, AND A COLLECTOR FOR THIS METHOD The following statement is a full description of this invention, including the best method of performing it known to me/us:- 1 r* Method for solid-phase microextraction and analysis, and a collector for this method Field of the Invention The invention relates to a method for solid-phase microextraction and analysis of substances originating for example from a carrier fluid and to a collector for use within this method. The invention also relates to a collector, which serves as a passive collector in a gaseous, for example loaded environment containing substances to be analyzed and a method for solid-phase microextration and analysis of this substances.
Description of the Related Art 15 A method of this type is known from Boyd-Boland et al., Environ. Sci. Technol. Vol. 28, No. 13, 1994, 569A-574A and from EP 0,523,092 B1, in which a special syringe is used, which has a fiber which can be telescoped through the syringe needle. The fiber, which is o expediently coated, is brought into contact with the carrier fluid which 20 contains the substances to be examined and at the same time is being stirred, after which the fiber is retracted and the syringe needle is introduced into a feeding device of an analyzer, followed by desorption of adhering substances using a carrier gas. The fiber has only a very limited absorption capacity for substances which are to be examined and, .0 25 moreover, is only dipped into the stirred carrier fluid, so that consequently the sensitivity of the analysis itself leaves something to be desired if the coated fiber is vibrated. In addition, it is known from DE 196 19 790 C2 to have the microfiber functioning as a collector rotate about its own axis by means of an electric motor with a rotational speed of one's choice.
Summary of the Invention An object of the invention is to provide a method for solidphase microextraction and analysis of substances to be analyzed and originating for example from a carrier fluid, which provides a significantly improved sensitivity.
Another object of the invention is to provide a collector for solid-phase microextraction and analysis of substances to be analyzed and originating for example from a carrier fluid.
A further object of invention is to provide a collector which may be used within the method for solid-phase microextraction and analysis of substances.
A still other object of the invention is to provide a collector as a passive collector for solid-phase microextraction and analysis of substances for example pollutants to be analyzed and originating, for example from an environment.
A still other object of the invention is to provide a method for solid-phase microextraction and analysis of substances to be analyzed and originate from an environment, for example pollutants.
A subject of the invention is a method for solid-phase microextraction and analysis of substances in a carrier fluid, in which a collector is brought into contact with the stirred fluid containing the substances for a sufficient time and is then subjected to a solid-phase 15 extraction directed at at least one substance adhering to the collector, and desorbed substances are transported for analysis by means of a carrier gas, wherein the carrier fluid containing the substances is stirred in a receptacle of a magnetic stirrer by means of a coated magnetic stirring element as collector, and/or the carrier fluid is made to move intimately relative to the collector by means of ultrasound, and afterwards the stirring element is arranged in a solid-phase extraction device.
Another subject of the invention is a collector for the solidphase microextraction and analysis of substances to be examined, in particular for use in a thermal desorption apparatus of a gas 25 chromatograph, comprising a carrier made from magnetic material, which is suitable as a stirring element for a magnetic stirrer and is provided with a sorbent and/or adsorbent coating for the substances to be examined.
A still other subject of the invention is a coated magnetic collector, which serves as a passive collector in a gaseous, for example loaded environment containing substances to be analyzed.
A still other subject of the invention is a method for the solidphase microextraction and analysis of substances in an environment, in which a collector is exposed to the environment for a sufficient time as a passive collector and then the collector is positioned in a solid-phase extraction device, desorbed substances being transported for analysis by means of a carrier gas.
The use of a stirring element which is actuated by a magnetic stirrer and/or an ultrasonic agitator increases the accuracy of analysis very considerably, and moreover it is possible to use large-volume receptacles, for example liter receptacles, for the fluid containing the substances to be examined.
Further objects, advantages and embodiments of the invention are evident from the following description.
The invention is explained in more detail below with reference to exemplary embodiments of the invention, which are illustrated in the attached drawings, of a device for carrying out the method and of passive collectors.
Brief Description of the Drawings Fig. 1 is a diagrammatic view of a device for carrying out the method for solid-phase microextraction and analysis of substances which are in a carrier fluid.
o :Figs. 2 to 4 show various embodiments of passive collectors, 15 in section.
loll Fig. 5 shows a comparison of two equilibrium curves relating to the prior art and the invention.
Fig. 6 is a diagrammatic view of a further device for carrying out the method for solid-phase microextraction and analysis of substances 20 which are in a carrier fluid.
Fig. 7 is a diagrammatic view of a headspace receptacle.
Description of Preferred Embodiments In accordance with Fig. 1, a magnetic stirrer 1 is provided, which 25 comprises a receptacle 3 which is positioned on a base 2, is in the form of a beaker and may expediently be closed at its top side by a septum 4.
Before it is closed by the septum 4, the receptacle 3 receives a carrier fluid containing substances which are to be analyzed. The receptacle 3 may have been filled and closed in advance at a sampling point. The carrier fluid may be water and/or an organic solvent or a mixture thereof or liquefied gas.
The base 2 comprises an electric motor 5, the shaft of which bears an magnet 6 eccentrically. In the receptacle 3, there is a stirring ball 7 made from ferromagnetic material, such as iron or steel, which is advantageously glass- or plastic-sheathed and has a diameter in the range of a few millimeters. The plastic sheating 7a used may, for example, be polytetrafluoroethylene or another fluorinated hydrocarbon polymer. The stirring ball 7 is preferably covered with an active phase 7b for sorption/adsorption of substances contained in the carrier fluid. This may be a coating selected from the group comprising polyethylene glycol, silicone, polyimide, octadecyltrichlorosilane, polymethylvinylchlorosilane, liquid-crystal polyacrylates, grafted self-organized monomolecular layers and inorganic coating materials.
The stirring ball 7 can be stirred for a sufficient time during which it comes into intensive contact with the carrier fluid and therefore with the substances contained therein and sorbs and/or adsorbs the latter, so that it serves as a collector. After the end of stirring, the stirring ball 7 is picked up and introduced in a solid-phase extraction device, preferably a desorption device 8. The latter advantageously comprises a desorption tube 9 with a diameter section whose diameter is slightly greater than that of the stirring ball 7, followed, via a frustoconical section, by a diameter section whose diameter is smaller than that of the stirring ball 7. The desorption device 8 is part of an analyzer 10, for example of a gas 15 chromatograph, connected to a carrier gas port 11, so that carrier gas flows S-through the desorption tube 9 passing the stirring ball 7, desorbing substances adhering thereto, and can supply these substances for analysis. The desorption device 8 preferably comprises a heating device 12, in order to carry out a thermal desorption.
20 The stirring ball 7 can be removed from the receptacle 3 automatically by means of a discharging device 13 which penetrates the septum 4 and may be designed- in the form- of a-gripping device, suction device or also as a magnet, and can be positioned in the desorption tube 9, which can then be placed automatically in the desorption device 8, so that 25 the entire solid-phase microextraction and analysis can be performed automatically. For this purpose, appropriate receptacle 3 for a plurality of samples can be arranged on a turntable which can rotate in steps and beneath which, in one position, the base 2 of the magnetic stirrer 1 is arranged.
In order to achieve reproducible measurements, stirring times of approx. 45 to 60 min are generally required.
As an alternative to a stirring element in the form of a stirring ball, it is also possible to use an element in the form of a stirring rod 14.
This may have a coated rod-like carrier 15 made from ferromagnetic or paramagnetic material; in the latter case, it should have a minimum length of approximately 2cm, while shorter lengths are also possible if ferromagnetic material is used. For example, it may be a rod-like carrier which is rounded at the ends and is entirely coated with the active phase (Fig. 3) or also a carrier comprising a section of wire which is surrounded by a cylindrical sheath 16 made from material of the active phase which is in the form of a flexible tube (Fig. By way of example, the rod-like carrier 15 may have a diameter of approx. 3 to 6 mm.
It is also possible to achieve improved analysis if the carrier fluid which contains the substances and is situated in a receptacle containing a collector, which is preferably a stirring ball 7, is alternatively or additionally set in motion by means of ultrasound. Fig. 6 shows one embodiment of such an ultrasonic stirring device as a resonator unit 17 in which one or more ultrasonic generators (vibrators) 19, which are shielded by means of insulating plate 18, are incorporated at the bottom and/or on the sides of a housing 20. A metal wall 21 which is mounted in front of the ultrasonic generator 19 and has a wall thickness of d n*/2 (X:acoustic wavelength) transmits the vibrations to a coupling liquid 22 in the resonator .i unit 17, preferably water, which is set in motion. The receptacle containing 15 the substances to be analyzed is introduced into the resonator unitl7.
In this case, the receptacle 3 is also advantageously one of a magnetic stirrer, in which case stirring is carried out by means of the coated magnetic stirring ball 7 as collector, so that the ultrasound is applied in o addition to the magnetic stirring.
20 In general, thermal, liquid or desorption by means of supercritical gases is possible.
As an alternative to being introduced into a thermal desorption device 8, the stirring element can be arranged in a headspace receptacle 23 (Fig. the diameter of which is only slightly greater than the diameter 25 of the stirring ball 7, by means of the discharging device 13. The headspace receptacle 23 is then closed by means of a septum 24 and a sealing ring 25, using a closure instrument, and is introduced into a headspace head 26. In the latter, the headspace receptacle 23 is preheated by means of a heating device 27 and there is a build-up of pressure, during which an equilibrium for the volatile substances to be examined with the gas phase 28 above the stirring ball 7 is established.
These substances can be removed by means of a syringe which penetrates the septum 24 and can be fed to the separation column of, for example, a gas chromatograph.
As an alternative to being desorbed in a thermal desorption device 8, the stirring element may also be introduced into an extraction device containing an organic liquid, the organic liquid used exhibiting a high level of interaction with the substances to be examined and absorbing the latter if necessary during a stirring movement of the stirring element with respect to this liquid, after which the liquid which is enriched with the substances to be examined is taken up by means of a syringe and taken to a feeding device of, for example, a gas chromatograph, in order to be fed for analysis, for example using a gas-chromatography separation column, by means of a carrier gas.
Due to the use of a stirring element in a magnetic stirrer or, alternatively or additionally, in an ultrasonic agitator and its intensive contact with the carrier fluid containing the substances to be examined, it is possible to achieve a sensitivity of analysis which is orders of magnitude, for example about 1000 times, better than the use of the known fiber. Fig. shows a diagram comparing the yield (plotted on the ordinate) of absorbed substances for a known fiber coated with active phase (curve A) and a stirring rod which is sheathed by active phase and has been stirred by 1 means of the magnetic stirrer according to the invention (curve B) at mass equilibrium, the concentration quotient of a substance in octanol and water being plotted on the abscissa. This coefficient (for normal temperature) can be found in the literature for a wide range of substances.
For example, if this concentration quotient is 100, it can be seen from the diagram shown in Fig. 5 that in this case the coated fiber provides a yield of approximately 1% and the invention provides a yield of approximately At a concentration quotient of below 100, the coated fiber cannot generally carry out any reliable measurement, while the sheathed stirring element generally still allows absolute reliable measurements. Generally, the covered stirring element improves the measurement accuracy considerably, i.e. by powers of 10, and widens the measurement range considerably, in that the sensitivity of analysis is improved approximately by a factor of 1000. With the sheathed stirring element, there is generally no need for the sensitivity of analysis to be improved by heating the liquid containing the substances to be examined, as is necessary in many cases for a coated fiber, and cause moreover measurement errors.
Moreover, a stirring element of this type may be arranged as a passive collector in a gaseous, for example loaded environment containing substances to be examined or may be carried by a person working in the environment, in which case the passive collector is exposed to the environment for a sufficient time and afterwards the substances which it has sorbed and/or adsorbed are subjected to extraction, after which desorbed substances are transported for analysis by means of a carrier gas via a feeding device, for example in order to monitor personal exposure to pollutants.
Although the foregoing has been a description of preferred embodiments of the invention, it will be apparent to those skilled in the art that numerous variations and modifications may be made in the invention without departing from the scope as described herein.
o• 8

Claims (13)

1. Method for solid-phase microextraction and analysis of substances in a carrier fluid, in which a collector is brought into contact with the stirred fluid containing the substances for a sufficient time and is then subjected to a solid-phase extraction directed at at least one substance adhering to the collector, and desorbed substances are transported for analysis by means of a carrier gas, characterized in that the carrier fluid containing the substances is stirred in a receptacle of a magnetic stirrer by means of a coated magnetic stirring element as collector, and/or the carrier fluid is made to move intimately relative to the collector by means of ultrasound, and afterwards the stirring element is arranged in a solid-phase extraction device
2. Method according to Claim 1, characterized in that a stirring element which has a glass or plastic coating is used.
3. Method according to one of Claims 1 or 2, characterized in that the stirring element used has a coating selected from the group consisting of polyethylene glycol, silicone, polyimide, octadecyltrichlorosilane, polymethylvinylchlorosilane, liquid-crystal poly- 20 acrylates, grafted self-organized monomolecular layers and inorganic coating materials.
4. Method according to one of Claims 1 to 3, characterized in that the stirring element is removed through a septum which closes the receptacle of the magnetic stirrer by means of an automatic discharging device and is placed in a desorption tube Method according to one of Claims 1 to 4, characterized in that the stirring element used is a stirring ball.
6. Method according to one of Claims 1 to 4, characterized in that the stirring element used is a stirring rod.
7. Method according to Claim 6, characterized in that the stirring element used is a sheathed section of wire.
8. Method according to one of Claims 1 to 7, characterized in that the solid-phase extraction is carried out thermally.
9. Method according to Claim 8, characterized in that the solid- phase extraction is carried out dynamically (Fig. 1) or statically (Fig. 7). Method according to one of Claims 1 to 7, characterized in that the solid-phase extraction is carried out using an organic fluid with a high level of interaction with regard to the substances to be examined, and then a sample which is absorbed with a syringe is placed in a feeding device through which a carrier-gas stream flows.
11. Method according to one of Claims 1 to 10, characterized in that a gas-chromatographic analysis is carried out.
12. Collector for the solid-phase microextraction and analysis of substances to be examined, in particular for use in a thermal desorption apparatus of a gas chromatograph, comprising a carrier made from magnetic material, which is suitable as a stirring element for a magnetic stirrer and is provided with a sorbent and/or adsorbent coating for the substances to be examined.
13. Collector according to Claim 12, characterized in that the carrier has a coating selected from the group consisting of polyethylene glycol, silicone, polyimide, octadecyltrichlorosilane, polymethylvinylchloro- silane, liquid-crystal polyacrylates, grafted self-organized monomolecular layers and inorganic coating materials.
14. Collector according to Claim 12 or 13, characterized in that 15 the carrier is rod-shaped, in particular is a section of wire.
15. Method for the solid-phase microextraction and analysis of substances in an environment, in which a collector according to one of Claims 12 to 14 is exposed to the environment for a sufficient time as a passive collector and then the collector is positioned in a solid-phase 20 extraction device, desorbed substances being transported for analysis by means of a carrier gas. Dated this 2nd day of March 2000 PATENT ATTORNEY SERVICES Attorneys for GERSTEL SYSTEMTECHNIK GMBH CO. KG
AU20623/00A 1999-03-26 2000-03-02 Method for solid-phase microextraction and analysis, and a collector for this method Expired AU762611B2 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE19913809 1999-03-26
DE1999113809 DE19913809C2 (en) 1999-03-26 1999-03-26 Solid phase micro extraction and analysis method
DE19933017A DE19933017A1 (en) 1999-03-26 1999-07-14 Solid phase micro-extrusion and analysis procedures
DE19933017 1999-07-14

Publications (2)

Publication Number Publication Date
AU2062300A AU2062300A (en) 2000-09-28
AU762611B2 true AU762611B2 (en) 2003-07-03

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AU20623/00A Expired AU762611B2 (en) 1999-03-26 2000-03-02 Method for solid-phase microextraction and analysis, and a collector for this method

Country Status (9)

Country Link
EP (2) EP1039288B1 (en)
JP (1) JP3462443B2 (en)
KR (1) KR100479595B1 (en)
CN (1) CN1189730C (en)
AT (2) ATE274691T1 (en)
AU (1) AU762611B2 (en)
CA (1) CA2300411C (en)
DE (3) DE19933017A1 (en)
ES (2) ES2318206T5 (en)

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US10139317B2 (en) * 2015-10-30 2018-11-27 South Dakota Board Of Regents Methods and apparatuses for trace and ultratrace analysis
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KR20180105231A (en) 2016-02-03 2018-09-27 게스테루 가부시키가이샤 Organic component extraction device
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CN112742063A (en) * 2020-12-22 2021-05-04 中华人民共和国乌鲁木齐海关 Method for optimizing ultrasonic extraction conditions of o-dichlorobenzene in textile solid waste
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WO1997011763A1 (en) * 1995-09-28 1997-04-03 Varian Associates, Inc. Solid phase microextraction with vibration
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