AU671727B2 - Atomic absorption spectrometer - Google Patents
Atomic absorption spectrometer Download PDFInfo
- Publication number
- AU671727B2 AU671727B2 AU63085/94A AU6308594A AU671727B2 AU 671727 B2 AU671727 B2 AU 671727B2 AU 63085/94 A AU63085/94 A AU 63085/94A AU 6308594 A AU6308594 A AU 6308594A AU 671727 B2 AU671727 B2 AU 671727B2
- Authority
- AU
- Australia
- Prior art keywords
- atomic absorption
- sample
- absorption spectrometer
- radiation
- mercury
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/3103—Atomic absorption analysis
Description
r *4 *4 4 .444 44 4.
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AUSTRALIA
Patents Act 1990
ORIGINAL
COMPLETE SPECIFICATION STANDARD PATENT Application Number: Lodged: Invention Title: ATOMIC ABSORPTION SPECTROMETER The following statement is a full description of this invention, including the best method of performing it known to us
-A
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I
e I i Atomic Absorption Spectrometer The present invention relates to an atomic absorption spectrometer for measuring the mercury concentrations in a sample, with the spectrometer comprising a means for producing predetermined emission lines of the mercury, a sample accommodating chamber that can be irradiated with light of the emission lines, and means for measuring the extinction of the radiation passing through the sample accommodating chamber.
It is known that atomic absorption spectrometry is employed for mercury analysis. The Hg atom has two suitable lines which end at the ground state of the atom, but greatly differ in their detection sensitivity. Robinson, P.J.
Slevin, G. D. Hindman, D. K. Wolcott, Anal. Chem. Acta 61, 431, 1972).
Furthermore, mercury spectrometers for each of the suitable wavelengths are already known, with a grating, prism or a selective photocell being used for narrowing the spectrum of the Hg low-pressure discharge lamp which is employed as a background radiator. Hoffmann, Ch. Ludke, Fresenius Z. Anal. Chem. 298, 9-11, 1979).
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r s 1 r 12 a. a aaaa a r;rr*rs~rrl,-itr
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2 A disadvantage of the known assemblies is that only a limited concentration range with a high detection sensitivity can be covered because of deviation from the proportionality between measurement signal and mercury concentration. An extension of the concentration range has so far only been possible by way of relatively cumbersome enrichment or dilution methods or by the use of two devices with different concentration measuring ranges.
Furthermore, it is known that fluorescence radiation on line 253.7 nm is also used for the determination of mercury. It is marked by a high detection strength and a great concentration determination range. Thompson, R.
G. Godden Analyst 100, 544-548, 1975). The disadvantage of this arrangement is, however, that the determination of the concentration of mercury may be disturbed by fluorescenceextinguishing processes. Another disadvantage is that the fluorescence intensity is small in relation with the primary radiation. This requires a high sensitivity of the receiver and additional assemblies for keeping superimposition of the fluorescent light by scattered primary radiation small.
It is also known that the arrangement for the flowinjection method is coupled with an arrangement for the determination of mercury according to the atomic absorption method on line 253.7 nm. A disadvantage of this assembly is, however, that the detection sensitivity and the determinable concentration range do not satisfy many requirements. Another disadvantage is that special means .4 4 *4 4 4 *444 4 4r 4 *4* 4 4 44 4 4.
44
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3 which serve wavelength selection have to be used in this assembly.
It is now the object of the present invention to determine mercury with a high detection sensitivity within a large concentration range in a reliable manner and with a simple inexpensive assembly.
Starting from an atomic absorption spectrometer of the above-mentioned type, this object is attained according to the invention by the measures that a means is provided for simultaneously producing the emission lines 184.9 and 253.7 nm, and that two means are provided for measuring the extinction, the means having electro-optical transducers which are each responsive with different sensitivity to radiation of the emission line 184.9 and 253.7 nm, i. respectively, and are arranged such that radiation passing through the sample accommodating chamber simultaneously impinges on the two electro-optical transducers, and that only the extinction measurement values that fall within the extinction value ranges respectively assigned to the two extinction measuring means serve to determine the mercury concentration.
This leads to the considerable advantage that the measurement range is considerably enlarged in a measuring device. This is especially of great importance if only one Z sample is available for measurement, which sample would be forfeited if a measurement was performed in a device with S an inappropriate measurement range.
{lJ
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4 A CsTe photocathode which is substantially responsive to radiation of the emission line 253.7 and a CsI photocathode which is substantially responsive to radiation of the emission line 184.9 are preferably provided as eletrooptical transducers.
Furthermore, the provision of a beam splitter between the sample accommodating chamber and the electro-optical transducers has turned out to be expedient.
The beam splitter preferably consists of a quartz plate. It has surprisingly been found that a quartz plate can be used as a beam splitter for said application and that, when a beam splitter is used, adequate light intensities are nevertheless available for achieving a sufficient measuring accuracy.
The quartz plate has a suitable thickness 1 mm).
9.
Other preferred embodiments will become apparent from the subclaims.
The invention shall now be explained in the following with reference to preferred embodiments shown in the drawing, in which: FIG. 1 is a diagrammatic illustration of a preferred 4. embodiment of an atomic absorption spectrometer designed in accordance with the invention with a supply device for introducing the sample into the .sample accommodating chamber; j
I'
Mt- r- FIG.2 is an illustration of two different functional positions of the FIA valve shown in FIG. 1; FIG. 3 shows the course of the measurement curves of the measured extinction in response to the time for a first electro-optical transducer which is preferably responsive to radiation of the wavelength 185 nm and for a second phototransducer which is preferably responsive to radiation of the wavelength 254 nm; and FIG. 4 shows two mercury calibration curves by which a respectively measured extinction is assigned to a specific mercury concentration in ng for the first optical transducer that is preferably responsive to radiation of the wavelength 185 nm, and a second electro-optical transducer that is preferably responsive to radiation of the wavelength 254 nm.
In FIG. 1, numeral 1 designates the atomic absorption spectrometer in a general way. Numeral 2 designates a radiation source which produces radiation of the emission lines 184.9 and 253.7 of mercury. Such a radiation source may, for instance, be comprised by a mercury low-pressure discharge lamp. The radiation produced thereby is radiated y, via a window (not shown in more detail) through a sample accommodating chamber 3. In the present embodiment the sample accommodating chamber is formed by a cylindrical S cell which is closed by quartz plates 4 and 5 at its I -0 opposite ends. The quartz plates may for instance have a phot thickness of 1 mm The cell can be closed after the sample turr: has been filled in, and heating devices may for instance be provided for converting the mercury contained in the sample The into its atomic state. The mercury sample is preferably desi 31 1-introduced already in its atomic state in a carrier gas IBsamr fh low into the cell or even passed via an inlet 6 and an IIcomm Soutlet 7 on the cell through the latter during measurement. val~ pros .01 CPi In the direction of the longitudinal axis of the cell, a firs beam splitter 8 is arranged at the end of cell 3 which is I:Rcont opposite to the radiation source 2. The beam splitter 8 consists of a quartz disk which has a thickness of about 1 Furl 0mm The quartz disk is positioned at an angle of 450 iqi relative to the longitudinal axis of the cell. Part of the comi radiation leaving the cell can thus pass through the beam r of I splitter while another part is deflected by the beam cn splitter by 90° from said direction by way of reflection. A PrOE J (1r i ~first electro-optical transducer 9 is arranged along the dv longitudinal axis of the cell behind the beam splitter while a second electro-optical transducer 10 is arranged in A r~ a direction turned by 90" in comparison therewith in such a 22 1 manner that it absorbs radiation reflected by beam splitter jsece 8. whic 090 com By contrast, only the radiation passing through the Jbeam ]argo d I splitter impinges on the first electro-optical tran.>ucer dev.
J Y 9. The electro-optical transducers may be of the type which 99.: dev itis preferably responsive to one of the two emission lines i 1 moc 184.9 and 253.7, respectively. A CsI photocathode for dev: measuring the intensity of the line 184.9 nm and a CsTe haflo S S ~j~ii 4 0 7 photocathode for measuring the emission line 253.7 have turned out to be especially advantageous.
The sample introducing device, which is generally designated by 11, comprises a sample storing means and a sample removing device 12. The sample removing device communicates via a line 13 with a sample proportioning valve 14, which may be a so-called FIA valve. The sample proportioning valve 14 communicates via a line 15 with a first pump 16. Waste liquid can be discharged into a container (not shown) at end 17 of line Furthermore, there is provided a line 18 via which carrier liquid can be supplied at end 19 thereof. Line 18 communicates via a second pump 20 with another connection of the sample proportioning valve 14. Line 18 can be connected in a corresponding position of the sample proportioning valve 14 with a line 21 that ends in a mixing device 22.
A reducing agent can be introduced into the mixing device 22 past valve 14 via end 23 of another line 24 and the second pump 20. Downstream of the connection point 25, at which the carrier liquid and the reducing agent are combined, the supply of a neutral gas or noble gas, such as argon, into line 27 is controlled via a pressure control device 26. Line 27 terminates in a gas/liquid separation S device 28. Gas can directly be introduced into the cell via line 29 which is cos,.cted to the gas/liquid separation device on the one hand and inlet 6 at cell 3 on the other hand. Waste liquid can be discharged from the gas/liquid
WON
-Y-
8 separation device via a line 30 and the second pump 20 at the end 31 of line 30 into a container (not shown).
FIG. 2 illustrates the two possible positions A and B of the sample proportioning valve 14. Line 13 is connected to line 15 via metering loop 35 in position A. Line 18 is connected to line 21 via metering loop 35 in position B.
The sample supply device 11 operates as follows: In position A of the sample proportioning valve 14, which is shown in FIG. 2, a sample liquid flow is transported from the sampling device 12 via line 13, sample proportioning loop 35 of the sample proportioning valve 14, line 15 and the first pump 16 towards end 17 of line 15. As soon as the sample proportioning loop 35 has entirely been filled with the sample, the sample proportioning valve is moved into position B, which is illustrated in FIG. 2. A predetermined amount of sample is first sealed in the sample proportioning loop 35. The amount of sample desired for the assay can be determined by selecting different sample proportioning loops 35 with which sample amounts of e.g. 0.5 or 1 ml or less or more can be proportioned.
As soon as sample proportioning valve 14 has been moved into position B, carrier liquid is pumped through the sample proportioning loop 35 from line 18 with the aid of the second pump 20, and the sample is thus supplied into the sample mixing device 22. Reducing agent is continuously supplied via line 24 at the mixing point 25 into said sample mixing device 22. The mercury in the sample is i II~ a a...r reduced by the reducing agent into its atomic state. A carrier gas flow with a specific flow rate is produced by supplying, argon gas at a predetermined pressure with the aid of the pressure control device 26. If this carrier gas flow still includes liquid, the liquid is separated in the gas/liquid separation device. While the liquid amount is transported via line 30 and the second pump to the outlet end 31 as waste liquid, the carrier gas flow which contains the mercury sample in the atomic state flows via line 29 and inlet 6 into cell 3 and at the end thereof through outlet 7 out of the cell.
In one embodiment the cell had an inner diameter i 0.6 cm and a length L 20 cm. This gives a volume V 3 23 cm The flow of argon gas was F 100 ml/60 s. Hence, the flow rate was so great that within a time of F x V 13.8 s the whole volume of the cell was replaced once. The measurement time was preferably chosen such that it was at least five times the period of change for the replacement of the volume of the cell.
The atomic absorption spectrometer is calibrated such that the light intensity 10 is measured both on the first and second photocathodes 9 and 10, respectively, while cell 3 is irradiated with radiation from radiation source 2 when only carrier gas first flows through the cell at a predetermined rate of e.g. 100 ml/min without addition of a sample by valve 14. The measurement values of the light intensity 10 that are normally different for the two cathodes represent the unattenuated radiation of the background radiator Hg lamp 2. Then a predetermined amount .X Fr~; i..
I -r 1 f 41 ff7 1:' i r: I l of sample is successively added to the gas flow in accordance with the capacity of the sample proportioning loop 35 with respectively different concentrations of mercury. During passage of the sample through the cell there is an increased absorption of the radiation of both emission lines 184.9 and 253.7, respectively. If the ratio of the previously measured reference intensity Io and of the intensity I measured with the sample is arithmetically formed for the light intensities I measured during passage of each sample past the two cathodes 9 and 10, and if the logarithm is formed therefrom, one obtains the mathematical value of the extinction E log I0/I. The curve of the i extinction values determined thereby during passage of a sample through the cell has about the appearance shown in FIG. 3. The time during measurement is plotted in seconds on the abscissa while the extinction values formed thereby are plotted on the ordinate. Signals 'ith about the same extinction first appear on the two photocathodes 9 and during passage of the pure carrier gas within the period of about 2 to 17 seconds. The carrier flow which transports the sample flows through the cell from this time onwards and produces a curve with a considerably rising extinction on the photocathode which is substantially adjusted to the .emission line 185 nm whereas at the same time the other photocathode adjusted to the emission line 254 nm shows an only negligibly increased signal with increased extinction values. As becomes apparent from the curve, the sample passes through the cell approximately during a period of from 13 to 14 seconds. To determine the extinction values to be used for calibrating the spectrometer, either the method for determining the extinction value in the peak of I4 i i
I
q each absorption curve may be used or a method in which the extinction value is determined by integration of the area positioned below the peak curve. If one chooses the determination of the extinction value according to the peak of the respective curve, this will yield, for instance, an extinction value of about 0.03 on the photocathode which is substantially responsive to the emission line 185 nm while the extinction value for the photocathode substantially responsive to the emission wavelength 254 nm is at about 0.003. Hence, both extinction values virtually differ by a factor The extinction values determined with the standard samples are shown in FIG. 4 in two respective curves (185 nm and 254 nm) in a diagram in which the concentration of mercury is indicated on the abscissa in ng and the extinction on the ordinate. As becomes apparent, the calibration curve for 185 nm has a straight steep rise in the range of very low mercury concentrations, namely from 0.01 to 1 ng. In comparison therewith, the sensitivity of the photocathode which is responsive to the emission line 254 nm is smaller by virtually one power of ten. This curve, however, has a straight steep rise in the range of about 0.5 to more than 100 ng. These different properties of the respective photocathodes are advantageously used by the invention such that the mercury concentration, i.e. the amount of mercury contained in the predetermined sample volume, is determined such that the measurement values of the photocathode (185 nm) are used for the determination of the mercury amount when the extinction values measured on said photocathode are within an extinction range of from 0.001 to 0.1 in the 14 d calibration diagram shown in FIG. 4, while the amount of mercury is determined by way of the extinction values measured by the photocathode (254 nm) when the extinction values measured there are approximately in the range between 0.01 and i. Such an automatic switching between the respective measurement ranges can easily be implemented electronically, with the aid of comparators. A considerably enlarged dynamic measuring range can be implemented in this way, the concentration measuring range which can be achieved in this way covers a total range of about four orders of magnitude, namely, for instance, 0.01 to 100 ng mercury.
The enhanced measuring capacity shall once again be explained with reference to the two following examples, of which example 1 relates to the analysis of rain water with added mercury and the second example to an analysis of mercury in urine.
r r r rr r r o ri r r rr r rrr *r 0"
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F
-JS r 'y Example 1 r r r r r o r Sample Extinction Volume: 0.5 ml Reducing Agent 0.2% NaBH 4 in 1% SnC12 in 0.05% NaOH 0.3% HCl Carrier Liquid 3% HCl, superpure 3% HCL, superpure Standard: ng/l 0.00148 0.0019 50 ng/l 0.00523 0.0041 100 ng/l 0.01076 rain water 0.00552 0.0037 Hg Content/pg 28 23 A sample volume of 0.5 ml was respectively used in Example 1. 0.2% NaBH 4 in 0.05% NaOH was used as a reducing agent and 3% HCl superpure was used as carrier liquid whereas in a second different run 1% SnC1 2 in 0.3% HCl was used as a reducing agent and 3% HCl superpure as carrier liquid. The extinctions for three different standards, namely 30 ng/l, ng/l and 100 ng/l were then determined. Thereupon a rain water sample was determined according to both methods with an extinction value of 0.0052 in one case and 0.0037 in another case. A Hg content of 28 picograms followed in the first case from the two measurements and of 23 picograms in
I
i i 'j j *0 :0 #0 4 14 the other case. 25 picograms were measured in corresponding assays with the same sample in the Lake Constance Water Supply Works of Ueberlingen.
Example 2 .1 Analysis nf Hg in urine Reducing Agent: Carrier Liquid: Sample Volume: 0.2% NaBH 4 0.05% NaOH 3% HCl superpure 1 ml *4*4
P
0J PP P
P
P.
P
Hg ContentC /.g/l Samples Measured Nominal Lanonorm 1 10.0 0.5 11.8 2 Bio-RAD1 8.1 0.5 5.2 2 Humanurin 0.3 0.03
Claims (10)
1. An atomic absorption spectrometer fro measuring the mercury concentration in a sample comprising means for producing predetermined emission lines of the mercury, a sample accommodating chamber which can be irradiated with radiation of the emission lines, as well as means for measuring the extinction of the radiation passing through the sample accommodating chamber, characterized in that there is provided a means which produces the emission lines 184.9 and 253.7 nm at the same time, and that two means are i provided for measuring the extinction, said means having electro-optical transducers which are each responsive with a different sensitivity to radiation of the emission line 184.9 and 253.7 nm, respectively, and are arranged such that i* diation passing through the sample accommodating chamber simultaneously impinges on said two electro-optical transducers and that only the extinction values falling within extinction value ranges respectively assigned to said two j extinction measuring means serve to determine the mercury concentration.
2. An atomic absorption spectrometer according to claim 1, characterized in that a CsTe photocathode which is predominantly responsive to radiation of the emission line 253.7 and a CsI photocathode which is substantially responsive to radiation of the emission line 184.9 are provided as electro-optical transducers.
3. An atomic absorption spectrometer according to claim 1 or 2, characterized in that a beam splitter is provided between the sample accommodating chamber and the electro-optical transducers.
4. An atomic absorption spectrometer according to claim 3, characterized in that said beam splitter consists of a quartz plate.
5. An atomic absorption spectrometer according to claim 4, characterized in that said quartz plate has a thickness of 1 nm. 16
6. An atomic absorption spectrometer according to any one of claims 3 to characterized in that said beam splitter is arranged under 450 relative to the axis of the light beam exiting from said sample chamber, that one of said electro- optical transducers is arranged along said axis, and that the other electro-optical transducer is arranged at an angle of 90° relative to the axis.
7. An atomic absorption spectrometer according to any one of claims 1 to 6, characterized in that said sample accommodating chamber is connected to a means for transferring mercury from a solution into a carrier gas.
8. An atomic absorption spectrometer according to claim 7, characterized in that said means for transferring mercury comprises a flow-injection system.
9. An atomic absorption spectrometer according to any one of claims 1 to 8, characterized in that said means for producing predetermined emission lines of the mercury comprises a Hg low-pressure discharge lamp. DATED this 5th day of July 1996. BODENSEEWERK PERKIN-ELMER GMBH WATERMARK PATENT TRADEMARK ATTORNEYS S.290 BURWOOD ROAD HAWTHORN VICTORIA 3122 AUSTRALIA VAX doc 07 AU6308594.WP IAS:SI:JL VAX doc 07 AU6308594.WPC j L-s^O |1 i1Jr -I w i i I- IN I Abstract Atomic Absorption Spectrometer 9 r 9 In an atomic absorption spectrometer the dynamic measurement range is considerably increased by the measures that there is provided a radiation source which produces the emission linus 253.7 and 184.9 at the same time, that said radiation simultaneously impinges through the test sample on two electro-optical transducers of which the one transducer is substantially sensitive to the emission line
253.7 and the other one to the emission line 184.9 nm. A total measurement range covering about four orders of magnitude can be implemented thereby. i r I Pt.. 9,*4t #444 *4 4 94 4 49 p
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4316513 | 1993-05-17 | ||
DE4316513A DE4316513B4 (en) | 1993-05-17 | 1993-05-17 | Atomic Absorption Spectrometer |
Publications (2)
Publication Number | Publication Date |
---|---|
AU6308594A AU6308594A (en) | 1994-11-24 |
AU671727B2 true AU671727B2 (en) | 1996-09-05 |
Family
ID=6488314
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
AU63085/94A Ceased AU671727B2 (en) | 1993-05-17 | 1994-05-13 | Atomic absorption spectrometer |
Country Status (6)
Country | Link |
---|---|
JP (1) | JPH07140068A (en) |
AU (1) | AU671727B2 (en) |
DE (1) | DE4316513B4 (en) |
FR (1) | FR2705459B1 (en) |
GB (1) | GB2278438B (en) |
IT (1) | IT1269778B (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19602801A1 (en) * | 1996-01-26 | 1997-07-31 | Bodenseewerk Perkin Elmer Co | Method and device for atomic absorption spectroscopy |
WO2010113682A1 (en) * | 2009-04-01 | 2010-10-07 | 株式会社トクヤマ | Radiographic image detector |
EP2482057B1 (en) * | 2011-01-27 | 2013-03-20 | Sick Ag | Gas analyser for measuring the mercury content of a gas and calibration method |
WO2019043858A1 (en) * | 2017-08-31 | 2019-03-07 | 株式会社島津製作所 | Atomic absorption spectrophotometer and atomic absorption measurement method |
FR3132770B1 (en) * | 2022-02-11 | 2024-02-02 | Ifp Energies Now | Method for monitoring the concentration of a chemical compound in a fluid over time, using an optical measuring system |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB979850A (en) * | 1960-06-03 | 1965-01-06 | Onera (Off Nat Aerospatiale) | Improvements in methods and apparatus for measuring the relative amount of a given component of a mixture of substances by selective absorption of infrared radiation |
US3734620A (en) * | 1971-04-01 | 1973-05-22 | Ibm | Multiple band atomic absorption apparatus for simultaneously measuring different physical parameters of a material |
DE3324606A1 (en) * | 1983-07-08 | 1985-01-17 | Dr. Bruno Lange Gmbh, 1000 Berlin | Apparatus for measuring and determining the nitrate content of liquids |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1105413A (en) * | 1964-10-16 | 1968-03-06 | Barringer Research Ltd | Method and apparatus for detecting traces of substances |
US3586441A (en) * | 1967-07-12 | 1971-06-22 | Instrumentation Labor Inc | Atomic absorption spectroanalysis system |
US3590255A (en) * | 1969-02-28 | 1971-06-29 | Instrumentation Labor Inc | Analysis system |
SU734511A1 (en) * | 1976-01-13 | 1980-05-15 | Всесоюзный Научно-Исследовательский И Конструкторский Институт Научного Приборостроения | Mercury vapour analyzer |
DE2707090A1 (en) * | 1977-02-18 | 1978-08-24 | Siemens Ag | GAS ANALYZER |
DE7809818U1 (en) * | 1977-05-12 | 1978-09-28 | Jenoptik Jena Gmbh, Ddr 6900 Jena | Device for the determination of mercury |
DD130965A1 (en) * | 1977-05-12 | 1978-05-17 | Erwin Hoffmann | ARRANGEMENT FOR DETERMINING MERCURY |
US4195932A (en) * | 1978-07-03 | 1980-04-01 | Abbott Laboratories | Absorption spectrophotometer |
JPS5563744A (en) * | 1978-11-06 | 1980-05-14 | Keiichiro Fuwa | Non-dispersion type vacuum ultraviolet ray mercury analyzer |
DE3723178C2 (en) * | 1987-07-14 | 1996-01-25 | Bodenseewerk Perkin Elmer Co | Method and device for flow injection analysis in combination with atomic absorption spectroscopy |
DE3917955A1 (en) * | 1989-06-02 | 1990-12-06 | Bodenseewerk Perkin Elmer Co | DEVICE FOR ANALYZING MERCURY OR HYDRIDE IMAGES BY ATOMIC ABSORPTION MEASUREMENT |
-
1993
- 1993-05-17 DE DE4316513A patent/DE4316513B4/en not_active Expired - Lifetime
-
1994
- 1994-05-11 GB GB9409423A patent/GB2278438B/en not_active Expired - Lifetime
- 1994-05-13 AU AU63085/94A patent/AU671727B2/en not_active Ceased
- 1994-05-16 IT ITMI940977A patent/IT1269778B/en active IP Right Grant
- 1994-05-17 FR FR9406155A patent/FR2705459B1/en not_active Expired - Lifetime
- 1994-05-17 JP JP6102727A patent/JPH07140068A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB979850A (en) * | 1960-06-03 | 1965-01-06 | Onera (Off Nat Aerospatiale) | Improvements in methods and apparatus for measuring the relative amount of a given component of a mixture of substances by selective absorption of infrared radiation |
US3734620A (en) * | 1971-04-01 | 1973-05-22 | Ibm | Multiple band atomic absorption apparatus for simultaneously measuring different physical parameters of a material |
DE3324606A1 (en) * | 1983-07-08 | 1985-01-17 | Dr. Bruno Lange Gmbh, 1000 Berlin | Apparatus for measuring and determining the nitrate content of liquids |
Also Published As
Publication number | Publication date |
---|---|
IT1269778B (en) | 1997-04-15 |
GB9409423D0 (en) | 1994-06-29 |
AU6308594A (en) | 1994-11-24 |
DE4316513B4 (en) | 2006-06-29 |
FR2705459A1 (en) | 1994-11-25 |
FR2705459B1 (en) | 1996-08-23 |
ITMI940977A1 (en) | 1995-11-16 |
GB2278438B (en) | 1996-11-27 |
GB2278438A (en) | 1994-11-30 |
DE4316513A1 (en) | 1994-11-24 |
JPH07140068A (en) | 1995-06-02 |
ITMI940977A0 (en) | 1994-05-16 |
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Owner name: PERKIN ELMER BODENSEEWERK ZWEIGNIEDERLASSUNG DER B Free format text: FORMER OWNER WAS: BODENSEEWERK PERKIN-ELMER GMBH |
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MK14 | Patent ceased section 143(a) (annual fees not paid) or expired |