X-ray fluorescence analysis device and method

Abstract

To provide an XRF analysis apparatus capable of providing economical, convenient and reliable analysis.SOLUTION: There is provided an X-ray fluorescence analysis apparatus for analyzing a sample. The X-ray fluorescence analysis apparatus comprises an X-ray source, a measurement chamber for holding the sample in air, and an X-ray detector. The X-ray source is arranged to irradiate the sample with a primary X-ray beam so as to cause the sample to fluoresce. The X-ray detector is arranged to detect characteristic X-rays emitted by the sample and to determine an X-ray intensity measurement associated with the characteristic X-rays. An X-ray filter, which transmits the primary X-ray beam, is arranged between the X-ray source and the sample. The X-ray source comprises an anode of material having an atomic number that is less than 25. The X-ray fluorescence analysis apparatus further comprises a sensor mechanism configured to sense air pressure and air temperature. A processor receives the X-ray intensity measurement. The processor also receives air pressure data and air temperature data from the sensor mechanism. The processor is configured to carry out a compensation calculation for adjusting the X-ray intensity measurement using the air pressure data and the air temperature data.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to an X-ray fluorescence analyzer and a method for performing X-ray fluorescence analysis. In particular, the present invention relates to an X-ray fluorescence analyzer and a method for characterizing samples containing trace amounts (e.g., less than 50 mg / kg) of light elements. [Background technology]

[0002] X-ray fluorescence (XRF) analysis is an elemental analysis technique used to obtain information about the composition of a sample. During XRF analysis, X-rays are irradiated onto a sample, causing the sample to fluoresce (i.e., emit characteristic X-rays). The X-rays emitted by the sample are detected by an X-ray detector. Energy dispersive X-ray fluorescence (ED-XRF) allows for the near-simultaneous detection of different characteristic X-rays (i.e., emitted X-rays with different energies), which can help facilitate convenient and time-efficient analysis.

[0003] In general, XRF analytical measurements should be precise and accurate. Measurements should be repeatable (as measured by tests performed by the same operator using the same equipment in the same testing environment) and reproducible (as measured by each independent test). To achieve this, XRF analyzers must have a high level of analytical performance. This can be particularly important when XRF measurements are required to comply with national or international standards. There is a need for cost-effective XRF analysis that can be performed conveniently. It is desirable to measure accurately without requiring long measurement times (e.g., to maximize throughput). It is also desirable for XRF analyzers to be able to reach the lower limits of detection and quantification even with short measurement times.

[0004] In some fields, achieving reliable, convenient, and cost-effective XRF analysis can be particularly challenging. For example, some industries may be required to analyze samples (e.g., petroleum and petroleum products or biofuels) to identify and quantify trace amounts of some light elements (i.e., "light" elements are those with atomic number Z of 18 or less). As mentioned previously, these measurements may be required to comply with national / international standards (e.g., International Standard ISO 13032:2012 "Petroleum products -- Determination of low levels of sulfur in motor fuels -- Energy dispersive X-ray fluorescence spectroscopy").

[0005] Some existing XRF analyzers can identify and quantify trace amounts of light elements, but to do so, they typically require helium. As helium becomes more expensive and less readily available, the requirement for helium can become less cost-effective and convenient. Furthermore, helium may be considered an unnecessary auxiliary (e.g., it may be difficult or expensive to store helium safely on an oil rig). Summary of the Invention [Problem to be solved by the invention]

[0006] It would be desirable to provide an XRF analyzer that is economical, convenient, and provides reliable analysis. In particular, it would be desirable to provide a cost-effective X-ray analyzer that is compliant with the international standard ISO 13032:2012, "Petroleum products -- Determination of low levels of sulfur in motor fuels -- Energy dispersive X-ray fluorescence spectroscopy." [Means for solving the problem]

[0007] According to one aspect of the present invention, there is provided an X-ray fluorescence spectrometer for analyzing a sample, comprising: a measurement chamber for holding the sample in an air atmosphere; an x-ray source positioned to irradiate a sample with a primary x-ray beam, the x-ray source having an anode comprising a material having an atomic number less than 25; an X-ray filter disposed between the X-ray source and the sample, the X-ray filter configured to transmit the primary X-ray beam and to attenuate at least a portion of X-rays having energies between 2 keV and 3 keV; an x-ray detector positioned to detect x-rays emitted by the sample and configured to determine an x-ray intensity measurement and an x-ray energy measurement; a sensor mechanism configured to measure air pressure and air temperature; 1. A processor, comprising: receiving an x-ray intensity measurement; and receiving air pressure measurements and air temperature measurements from the sensor mechanism; and Performs correction calculations to adjust the X-ray intensity measurements using air pressure and air temperature measurements and a processor configured as An X-ray fluorescence analysis apparatus comprising:

[0008] The sample contains an analyte that may have an atomic number of 17. This combination of features allows highly reliable results to be obtained using an X-ray fluorescence analyzer, even when the analyte is present in only small amounts in the sample. At the same time, the use of helium is avoided because the sample is measured in an air atmosphere. In this way, the X-ray analyzer becomes more convenient and cost-effective to use.

[0009] The x-ray filter is for attenuating x-rays within an energy range corresponding to the characteristic radiation of the analyte. The sensor mechanism may include a single sensor capable of detecting both air pressure and air temperature. Alternatively, the sensor mechanism may include an air pressure sensor and a separate air temperature sensor. In some embodiments, the sensor mechanism may include multiple air pressure sensors, multiple air temperature sensors, or both.

[0010] The correction calculation may include calculating a correction factor to account for the effect of the air pressure and air temperature at the time of measurement on the measured X-ray intensity.

[0011] The X-ray detector may be configured to measure a plurality of X-ray intensities, each corresponding to a different X-ray energy, and the processor may be configured to calculate a corresponding plurality of correction factors, each corresponding to a different XRF emitter, and in particular, a different elemental XRF emitter.

[0012] The x-ray source may include an x-ray tube configured to operate at an x-ray tube power of 20 W or less.

[0013] By utilizing this combination of features, the inventors have realized that high analytical performance can be achieved even for low atomic number elements while still utilizing a relatively low-power (and cost-effective) X-ray tube. X-ray tube power is the product of the X-ray tube current and the X-ray tube voltage (i.e., the voltage applied across the cathode and anode). As those skilled in the art will appreciate, X-ray tubes typically operate within a maximum voltage and power range. The X-ray tube voltage at which the X-ray tube is operated determines the maximum current at which the X-ray tube must operate. In other words, every operating voltage (up to the maximum voltage) has a maximum current associated with it. The maximum power of an X-ray tube is limited by design parameters such as the cathode design and material, the anode material and construction, and the design of the high-voltage generator. The maximum power of an X-ray tube may be 20 W.

[0014] The X-ray filter may provide greater than 95% attenuation for X-ray energies greater than 2 keV and less than 3 keV. The X-ray filter may provide greater than 95% attenuation for an energy range between 2.0 keV and 2.9 keV.

[0015] The X-ray filter may comprise a filter element for attenuating X-rays, the filter element may comprise aluminum and have a thickness between 10 μm and 25 μm.

[0016] The thickness of the X-ray filter may be changed by replacing the filter element.

[0017] The anode may comprise any of vanadium, chromium, titanium, and scandium.

[0018] The anode may be a solid anode, preferably vanadium or chromium, and most preferably the anode may be a vanadium anode, i.e. the X-ray source may have a vanadium anode.

[0019] The X-ray detector may be an energy dispersive X-ray detector.

[0020] The energy dispersive X-ray detector can detect X-rays of different energies (i.e., corresponding to different characteristic XRF emissions) substantially simultaneously. The X-ray detector may include a pulse processor configured to process voltage pulses. The X-ray detector may be a solid-state processor and may have a resolution of greater than 50 eV to less than 300 eV (e.g., 150 eV).

[0021] The X-ray fluorescence analyzer may further include a housing, in which an X-ray source, a measurement chamber, an X-ray detector, and an X-ray filter are provided.

[0022] By providing a sensor mechanism within the housing, the sensor mechanism can measure ambient air pressure and ambient air temperature, thus providing measurements of the air pressure and air temperature within the measurement chamber.

[0023] According to another aspect of the present invention, there is provided a method for performing X-ray fluorescence analysis on a sample, comprising the steps of: Holding the sample in an air atmosphere in a measurement chamber; generating a primary X-ray beam from an anode comprising a material having an atomic number less than 25 and irradiating the sample with the primary X-ray beam; using an x-ray filter to attenuate at least some x-rays from the anode, the x-rays having energies between 2 keV and 3 keV; sensing ambient air pressure and ambient air temperature; detecting X-rays emitted by the sample; performing a correction calculation using the air pressure and air temperature measurements to adjust the x-ray intensity measurements; A method is provided that includes:

[0024] The measurement chamber holds the sample in an air atmosphere, and therefore the X-ray fluorescence analyzer may be configured so that the amount of helium in the measurement chamber is less than 1% by volume during X-ray fluorescence measurement.

[0025] The x-ray source may include an x-ray tube, and may generate x-rays by operating the x-ray tube at an x-ray tube power of less than 20 watts.

[0026] The correction calculation may include calculating a correction factor to account for the effect of the air pressure and air temperature at the time of measurement on the measured X-ray intensity.

[0027] The X-ray detector may be configured to measure a plurality of X-ray intensities, each corresponding to a different energy range, and the processor may be configured to calculate a corresponding plurality of correction factors, each corresponding to a different XRF emitter, and in particular, a different elemental XRF emitter.

[0028] The anode may include vanadium, chromium, titanium, or scandium. The method may further include using an x-ray filter to filter x-rays from the x-ray source by attenuating at least some x-rays having energies between 2 keV and 3 keV.

[0029] The anode is a solid anode, preferably vanadium or chromium. Most preferably, the anode is a vanadium anode. The X-ray filter comprises a filter element for attenuating X-rays. The filter element may comprise aluminum and may have a thickness between 10 μm and 25 μm. The X-ray filter may attenuate at least 95% of X-rays having an energy between 2 keV and 3 keV. Alternatively, the X-ray filter may attenuate at least 95% of X-rays having an energy between 2.0 keV and 2.9 keV.

[0030] The sample may contain petroleum, petroleum products, biofuel, or the sample may contain an analyte with an atomic number of 17, or both.

[0031] The sample may further include at least one of sulfur, chlorine, and phosphorus. The amount of at least one of sulfur, chlorine, and phosphorus in the sample may be less than 50 mg / kg, preferably less than 10 mg / kg.

[0032] Embodiments of the present invention will now be described, by way of example only, with reference to the accompanying drawings, in which: [Brief explanation of the drawings]

[0033] [Figure 1] 1 shows a schematic perspective view of an X-ray fluorescence analyzer in accordance with an embodiment. [Figure 2] 2 shows a schematic view of the interior of the embodiment of FIG. 1. [Figure 3] 1 shows a highly schematic diagram of an X-ray fluorescence analyzer according to an embodiment; [Figure 4] 1 illustrates an X-ray fluorescence analysis method in accordance with an embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0034] It should be noted that these figures are schematic and are not drawn to scale: the relative dimensions and proportions of some of the figures have been shown exaggerated or reduced in size for clarity and convenience in the drawings.

[0035] FIG. 1 illustrates an X-ray fluorescence analysis device 1 in one embodiment of the present invention. The XRF device is a "benchtop" XRF analyzer. It includes a housing 3 having a measurement chamber 5 for holding a sample (not shown). The measurement chamber 5 has a cavity 4 inside the housing 3 and a cover 9. In FIG. 1, the cover 9 is shown in an open configuration to allow a user to insert a sample into the cavity 4 of the measurement chamber 5. Once the sample is inserted into the measurement chamber 5, the cover 9 can be moved to a closed configuration to close the cavity 4. An XRF analysis may then be performed on the sample.

[0036] During XRF analysis, the sample is held in the measurement chamber 5. The X-ray analysis device can achieve high analytical performance without the need for vacuum sealing or helium in the measurement chamber 5. Therefore, in each embodiment, the atmosphere in the measurement chamber 5 is not controlled. That is, the measurement chamber 5 is not vacuum sealed, and helium purging of the measurement chamber is not required. Therefore, the X-ray fluorescence analysis device can be used more cost-effectively and conveniently.

[0037] The XRF analyzer 1 also has an X-ray source (not shown in FIG. 1 ) positioned within the housing 3 and arranged to irradiate a sample in the measurement chamber 5. The XRF analyzer is configured to operate the X-ray tube at an X-ray tube power of less than 20 W. As such, the XRF analyzer can achieve high analytical performance with a low-power X-ray source.

[0038] A sensor mechanism 11 is mounted inside the housing 3 near the measurement chamber. In FIG. 1, the sensor mechanism 11 has two sensor elements 12. One of the sensor elements 12 is configured to measure air pressure, and the other sensor element 12 is configured to measure air temperature. The sensor elements are shown with dashed lines to indicate that they are located inside the housing but outside the measurement chamber. By measuring the ambient air pressure and ambient air temperature using the sensor elements 12, the air pressure and air temperature inside the measurement chamber 5 can be estimated. The sensor mechanism is configured to transmit the air pressure and air temperature measurements to a processor (not shown in FIG. 1). The processor uses the measurements to perform environmental correction. The environmental correction is performed by adjusting the X-ray intensity data acquired by the X-ray detector.

[0039] 1, the X-ray analysis instrument 1 also includes a display, such as a touchscreen display 7, which is supported by the housing 3. The display 7 may provide access to control inputs to allow a user to control the X-ray fluorescence analysis instrument. The display 7 may be configured to display measurement data, such as X-ray intensity data and data acquired by a sensor mechanism.

[0040] When a sample contains small amounts of elements with low atomic numbers, such as sulfur, it is difficult to obtain repeatable and reproducible measurements without controlling the atmosphere in the measurement chamber 5 (i.e., without using a vacuum-sealed measurement chamber or purging). However, the inventors have surprisingly discovered that by providing an XRF analyzer with a combination of incident X-ray components and environmental compensation, high analytical performance can be achieved. In particular, when evaluating sulfur-containing samples, it is possible to meet the repeatability and reproducibility required by International Standard ISO 13032:2012, "Petroleum products—Determination of low levels of sulfur in automotive fuels—Energy dispersive X-ray fluorescence spectroscopy."

[0041] FIG. 2 shows a portion of the interior of the housing of the X-ray fluorescence analyzer 1 of FIG. 1 when a sample 15 is present in the measurement chamber. The sample 15 may be, for example, a fuel sample containing a small amount of an analyte with a low atomic number, such as sulfur. The X-ray source 13 is an X-ray tube configured to operate at an X-ray tube power of less than 20 W and is positioned to irradiate the sample 15 with X-rays 14. During operation, the X-ray tube emits X-rays for exciting the sample along with other X-rays (which contribute to background radiation). An X-ray filter 17 is positioned between the sample and the X-ray source and is configured to significantly attenuate X-rays within an energy range corresponding to the characteristic X-rays emitted by the analyte, e.g., X-rays greater than 2 keV and less than 3 keV. The X-ray filter 17 transmits the X-rays for exciting the sample with little or no attenuation. An energy-dispersive X-ray detector 19 is positioned to receive the characteristic X-rays 18 emitted by the sample 15.

[0042] The inventors have surprisingly discovered that samples containing low atomic number elements (i.e., elements with atomic numbers ≦18) can be analyzed at low cost and without the need for helium or vacuum sealing, while achieving high analytical performance. In particular, by combining an X-ray source having an anode that is a material with an atomic number less than 25, an X-ray filter configured to attenuate X-rays in the range of 2 keV to less than 3 keV, and environmental compensation, the X-ray fluorescence analyzer in some embodiments can achieve high repeatability and reproducibility in a convenient and cost-effective manner.

[0043] In one embodiment, the X-ray source is an X-ray tube including a chrome anode, and the X-ray filter is an aluminum filter. The filter has a thickness between 10 μm and 25 μm. For example, the filter may include a filter element and a frame for holding the filter element. The filter element has a thickness between 10 μm and 25 μm, and the frame can hold a filter of any thickness within that range. The filter element can be removed from the frame and replaced with another filter element of a different thickness. Thus, the filter elements are interchangeable. This combination of incident X-ray components and environmental compensation allows high analytical performance to be achieved for samples containing small amounts (e.g., less than 50 mg / kg) of light elements (such as chlorine, sulfur, phosphorus, or a combination thereof) without the use of helium or vacuum sealing, and while operating at low X-ray tube power (e.g., less than 20 W).

[0044] In another embodiment, the X-ray source is an X-ray tube containing a vanadium anode. The X-ray filter is an aluminum filter at least 10 μm thick. The thickness of the X-ray filter can be changed by replacing the filter element. When primary X-rays from the vanadium anode strike a sample, they emit fluorescent secondary X-rays. These X-rays are detected by an energy dispersive X-ray detector 19. This combination of incident X-ray components and environmental correction allows high analytical performance to be achieved for samples containing small amounts of low atomic number elements (such as chlorine, sulfur, phosphorus, or combinations thereof) without the use of helium or vacuum sealing, and while operating at low X-ray tube power (e.g., less than 20 W). Furthermore, this embodiment can achieve high analytical performance even for samples containing trace amounts of sulfur (e.g., less than 10 mg / kg).

[0045] 3 shows a schematic diagram of an X-ray fluorescence analyzer 20 according to an embodiment of the present invention. The X-ray fluorescence analyzer 20 includes a housing 23, an X-ray source 33, an X-ray detector 39, and a measurement chamber 25 for holding a sample. An X-ray filter 37 is disposed between the X-ray source and the sample. The X-ray filter is configured to attenuate X-rays with energies between 2 keV and 3 keV. The X-ray fluorescence analyzer 20 also includes a sensor mechanism 31 disposed to sense the ambient air pressure and temperature inside the housing 23 (and outside the measurement chamber).

[0046] In the embodiment shown in FIG. 3 , the processor 40 is located outside the housing, remote from the housing. However, in some other embodiments, the processor 40 can be located inside the housing. The sensor mechanism 31 and the X-ray detector 39 are in communication with the processor 40 (as shown by the dashed lines). The X-ray detector outputs X-ray intensity data to the processor. The sensor mechanism 31 outputs an air temperature measurement indicating the air temperature and air pressure measurement indicating the air pressure inside the measurement chamber at the time the X-ray intensity data was measured. The sensor mechanism 31 transmits the air temperature and air pressure measurements to the processor 40. Communication between the sensor mechanism 31 and the processor 40 may be via a wired connection or a wireless connection (e.g., wireless internet, Bluetooth™, etc.). The processor 40 uses the X-ray intensity data and the air temperature and air pressure data to calculate a corrected X-ray intensity value, as will be described in more detail with reference to FIG. 4 .

[0047] 4 illustrates an X-ray fluorescence analysis method according to an embodiment of the present invention. First, in an irradiation step, a sample is placed in the measurement chamber of a benchtop XRF analyzer (for example, the XRF analyzer described in conjunction with FIG. 1). An X-ray beam is generated from an X-ray tube including an anode with an atomic number less than 25. The X-ray tube operates at an X-ray tube power of less than 20 W. Then, the sample is irradiated with X-rays while held in an air atmosphere (where the amount of helium in the measurement chamber may be less than 1% by volume).

[0048] While the sample is being irradiated, ambient air pressure and temperature are measured by a sensor mechanism mounted on the outside of the housing of the XRF analyzer, and the air pressure and temperature measurements are transmitted to a processor.

[0049] In the X-ray detection step, each X-ray emitted by the sample is detected as a voltage pulse by the X-ray detector, which transmits the voltage pulse to a processor, which processes the detected voltage pulse to obtain X-ray intensity data (X-ray intensity vs. energy).

[0050] Next, in the correction calculation step, the processor performs a correction calculation to adjust the X-ray intensity measurement using the air pressure measurement and the air temperature measurement. The correction calculation determines how the X-ray intensity corresponding to a particular characteristic X-ray attenuates. The correction calculation may include modifying the X-ray intensity of the characteristic X-ray taking into account the air pressure measurement and the air temperature measurement. For example, the correction calculation may include calculating a correction factor that represents the attenuation of the intensity of the characteristic X-ray emitted by the sample in the measurement atmosphere relative to a reference X-ray intensity at the same energy (and under the reference air pressure and air temperature).

[0051] In some embodiments, the correction calculation may include determining how the X-ray intensities corresponding to each of a plurality of characteristic X-rays emitted from the sample attenuate. For example, a correction factor may be calculated for each of the plurality of characteristic X-rays. Further, the correction calculation may include determining how the X-ray intensities of the incident X-ray spectrum, or the X-ray intensities of the background scatter, or both, attenuate.

[0052] It should be understood that various modifications can be made to the illustrated embodiment without departing from the scope of the claims.

[0053] Although the embodiment of FIG. 1 includes two sensor elements, the X-ray fluorescence analyzer can be equipped with any number of sensor elements.

[0054] Preferably, the sensor mechanism is located within the housing but external to the measurement chamber. However, in some embodiments, the sensor mechanism may be located within the measurement chamber. In other embodiments, the sensor mechanism is located external to the housing of the XRF device.

[0055] The X-ray filter is preferably an aluminum filter. However, the X-ray filter may alternatively be a silicon-based filter. In some embodiments, the X-ray filter comprises a layer of selenium on a polymer support.

[0056] The anode of the X-ray tube does not have to be vanadium. Instead, the anode of the X-ray tube may be a chromium, titanium, or scandium anode. The anode may be vanadium, chromium, titanium, or scandium, or a combination thereof.

[0057] The X-ray analysis device may or may not include a display. If the X-ray fluorescence analysis device includes a display, the display may be any type of electronic display capable of displaying measurement data. For example, the display may be an LCD display or an LED-based display. The display may or may not be a touchscreen display.

[0058] In some embodiments, the processor is separate from the housing. In other embodiments, the processor may be located within the housing. The processor may be integrated with or separate from the X-ray detector.

Claims

1. An X-ray fluorescence analyzer for analyzing a sample, comprising: a measurement chamber for holding the sample in an air atmosphere; an x-ray source positioned to irradiate the sample with a primary x-ray beam, the x-ray source having an anode comprising a material with an atomic number less than 25; An X-ray filter comprising: disposed between the X-ray source and the sample, an X-ray filter configured to transmit the primary X-ray beam and to attenuate at least a portion of X-rays having an energy between 2 keV and 3 keV; 1. An X-ray detector comprising: arranged to detect X-rays emitted by the sample; an x-ray detector configured to determine x-ray intensity measurements and x-ray energy measurements; a sensor mechanism configured to measure air pressure and air temperature; 1. A processor, comprising: receiving the x-ray intensity measurements; and receiving air pressure and air temperature measurements from the sensor mechanism; and Performing a correction calculation using the air pressure measurement and the air temperature measurement to adjust the x-ray intensity measurement. and a processor configured as An X-ray fluorescence analyzer comprising:

2. 2. The X-ray fluorescence analyzer according to claim 1, the correction calculation includes calculating a correction coefficient representing an influence of air pressure and air temperature at the time of measurement on the X-ray intensity measurement value; X-ray fluorescence analyzer.

3. 3. The X-ray fluorescence analyzer according to claim 1, the x-ray detector is configured to determine a plurality of x-ray intensities; the plurality of X-ray intensities correspond to different X-ray energies, the processor being configured to calculate a corresponding plurality of correction factors; X-ray fluorescence analyzer.

4. An X-ray fluorescence analysis apparatus according to claim 1 or 2, the x-ray source comprises an x-ray tube configured to operate at an x-ray tube power of 20 W or less; X-ray fluorescence analyzer.

5. An X-ray fluorescence analysis apparatus according to claim 1 or 2, The X-ray filter is Attenuation of greater than 95% at X-ray energies greater than 2 keV and less than 3 keV, or the filter has an attenuation of greater than 95% in the energy range between 2.0 keV and 2.9 keV; X-ray fluorescence analyzer.

6. An X-ray fluorescence analysis apparatus according to claim 1 or 2, the X-ray filter having a filter element for attenuating X-rays; The filter element comprises aluminum and has a thickness between 10 μm and 25 μm. X-ray fluorescence analyzer.

7. An X-ray fluorescence analyzer according to claim 1 or 2, The anode contains any one of vanadium, chromium, titanium, and scandium. X-ray fluorescence analyzer.

8. 7. The X-ray fluorescence analyzer according to claim 6, the X-ray source has a vanadium anode; X-ray fluorescence analyzer.

9. An X-ray fluorescence analyzer according to claim 1 or 2, the X-ray detector is an energy dispersive X-ray detector; X-ray fluorescence analyzer.

10. The X-ray fluorescence analyzer according to claim 1, Further comprising a housing, The housing contains the X-ray source, the measurement chamber, the X-ray detector, and the X-ray filter. X-ray fluorescence analyzer.

11. 1. A method for performing X-ray fluorescence analysis on a sample, comprising: Holding the sample in an air atmosphere in a measurement chamber; generating a primary X-ray beam from an anode comprising a material with an atomic number less than 25 and irradiating the sample with the primary X-ray beam; using an x-ray filter to attenuate at least some x-rays from the anode, the x-rays having an energy between 2 keV and 3 keV; sensing ambient air pressure and ambient air temperature; detecting X-rays emitted by the sample; performing a correction calculation using the air pressure measurement and the air temperature measurement to adjust the x-ray intensity measurement; A method comprising:

12. 12. The method of claim 11, the X-ray source comprises an X-ray tube; The X-rays are generated by operating the X-ray tube at an X-ray tube output of less than 20 W. method.

13. 13. The method of claim 11 or 12, the correction calculation includes calculating a correction coefficient representing an influence of air pressure and air temperature at the time of measurement on the X-ray intensity measurement value; method.

14. The method according to claim 11 or 12, the anode contains any one of vanadium, chromium, titanium, and scandium; the method further includes using an X-ray filter to filter X-rays from the X-ray source by attenuating at least some X-rays having energies between 2 keV and 3 keV; method.

15. The method according to claim 11 or 12, the sample comprises petroleum, petroleum products, or biofuels; or the sample contains an analyte having an atomic number of 17; or It's both. method.

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