CN112730590A - Method for detecting sulfur stable isotope in water sample of landscape river - Google Patents
Method for detecting sulfur stable isotope in water sample of landscape river Download PDFInfo
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Abstract
本发明公开了一种以SO+模式检测景观河道水样品中硫稳定同位素的方法，具体步骤为景观河道水样品经过滤、酸化、沉淀、蒸干后，装入锡杯并包裹，采用元素分析仪‑稳定同位素质谱联用仪检测待测样品。本发明优化离子源参数，通过调谐灯丝电压实现高能电子流对SO2 +的二次电离作用生成SO+，再通过调谐四级杆电压使产生的SO+进行有效分离，从而提升了景观河道水样品硫同位素比值的准确性和效率，结果精密度高，重现性好，易于操作及设备维护。The invention discloses a method for detecting sulfur stable isotopes in landscape river water samples in SO + mode. The specific steps are that after the landscape river water samples are filtered, acidified, precipitated and evaporated to dryness, they are put into tin cups and wrapped, and elemental analysis is adopted. The instrument-stable isotope mass spectrometer detects the sample to be tested. The invention optimizes the parameters of the ion source, realizes the secondary ionization of SO 2 + by the high-energy electron flow by tuning the filament voltage to generate SO + , and then effectively separates the generated SO + by tuning the voltage of the quadrupole, thereby improving the water quality of the landscape river. Accuracy and efficiency of sample sulfur isotope ratio, high precision, good reproducibility, easy operation and equipment maintenance.
Description
The invention obtains the subsidies of Tianjin large-scale education fund (043-.
Technical Field
The invention belongs to the technical field of stable isotope analysis, and particularly relates to a method for detecting a sulfur stable isotope in a water sample of a landscape river.
Background
The current sulfur stable isotope analysis technology is developed rapidly and is widely applied to relevant fields such as environmental protection, agricultural production and the like. Research reports show that the sulfur stable isotope technology plays an important role in the aspects of sulfur element migration and conversion mechanism, pollutant source tracing and the like in water.
At present, the common sulfur stable isotope analysis method is that an element analyzer is used in combination with a mass spectrometer, namely, sulfur in a sample is oxidized into sulfur dioxide by the element analyzer, and then the sulfur dioxide (SO) is oxidized by an ion source of the isotope mass spectrometer2) Conversion to sulfur dioxide ion (SO)2 +) Sulfur isotope ratio analysis was performed. But SO involved in the process2 +(and its δ S34 isotope) have a high mass-to-charge ratio of 64, 66 m/e. The stable isotope mass spectrometer generally simultaneously undertakes the carbon-nitrogen isotope detection task, and the mass-to-charge ratios of the carbon dioxide (and the delta C13 isotope thereof) and the nitrogen ion (and the delta N15 isotope thereof) involved in the stable isotope mass spectrometer are respectively CO2 +(m/e 44, 45) and N2 +(m/e 28, 29). Due to SO in conventional sulfur dioxide analysis2 +The mass-to-charge ratio is obviously higher than that of CO2 +And N2 +Mass to charge ratio. When the carbon-nitrogen isotope detection is converted into the sulfur isotope detection, the SO with higher mass-to-charge ratio is influenced by the instrument memory effect2 +It is difficult to focus on the receiver effectively, affecting the detection result. To eliminate the memory effect of the instrument, long-time debugging work is often required to improve the accuracy and reproducibility of sulfur isotope detection, and vice versa.
The invention realizes the high-energy electron current to SO by tuning the filament voltage of the ion source2 +The ions are ionized for the second time to generate sulfur monoxide ions (SO)+) And by optimizing the quadrupole voltage pair SO+Effective separation is carried out. And SO+And δ S34 isotope mass-to-charge ratio of 48, 50, and CO2 +And N2 +The mass-to-charge ratio is closer, which is beneficial to improving the accuracy and the reproducibility of the detection of the sulfur stable isotope, reducing the influence of the memory effect and improving the detection efficiency.
The invention utilizes ion source high-energy electron current to SO2 +Secondary ionization of ions to produce SO+The method is used for detecting the sulfur isotope, realizes the rapid and accurate detection of the sulfur isotope ratio of the water sample of the scenic river channel, and carries out the original sulfur stable isotope detection technologyThe supplementation is done.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for detecting sulfur stable isotopes in a landscape river water sample, which is characterized by comprising the following steps:
(1) filtering, acidifying, precipitating and evaporating a landscape river water sample, accurately weighing 1-10 mg of the sample, filling the sample into a tin cup and wrapping the sample;
(2) detecting a sample to be detected by adopting an element analyzer-stable isotope mass spectrometer; the elemental analyzer parameters were: the oxidation tube is 1020 ℃, the column temperature box is 80 ℃, and the catalysts in the quartz tube in the oxidation furnace are 25 g of tungsten oxide and 50 g of granular pure copper;
(3) ionizing sample by high-energy ion source to generate SO+(ii) a Ion source parameters of the stable isotope mass spectrometer are as follows: the core voltage of the ion source is 6.2KV, and the filament voltage of the ion source is-114V;
(4) mass analyzer pair SO+Separating isotope signals; the stable isotope mass spectrometer mass analyzer parameters were: the voltage of the first-level quadrupole is minus 128V, and the voltage of the second-level quadrupole is 147V;
(5) and analyzing the isotope value of the sample under the conditions to obtain the sulfur isotope value of the sample, repeatedly detecting for 5 times, and counting the experimental result.
The invention further discloses a method for detecting the sulfur stable isotope in the water sample of the landscape river, and the method is applied to the aspect of improving the accuracy of detecting the sulfur stable isotope in the water sample of the landscape river. The experimental results show that: the method has the advantages of good reproducibility, high analysis efficiency, high accuracy and the like, can meet the requirement of sulfur stable isotope detection of water samples of landscape riverways, and can achieve the sulfur stable isotope analysis accuracy SD (thousandths) of 0.05 and the sulfur stable isotope analysis stability SD (thousandths) of 0.08, which cannot be achieved by the conventional sulfur dioxide mode analysis method.
The invention mainly solves the problem of poor detection accuracy of the stable isotope of sulfur in the water sample of the landscape river, and overcomes the influence of sulfur dioxide ions with high mass-to-charge ratio on the detection of the isotope of sulfur caused by the memory effect of an instrument. The method mainly considers that sulfur dioxide ions are replaced by sulfur monoxide ions with lower mass-to-charge ratio by controlling the parameters of the ion source and the mass analyzer so as to improve the accuracy and the reproducibility of detecting sulfur isotopes in the landscape river water sample.
Compared with the prior art, the method for detecting the stable isotope in the sulfur in the water sample of the landscape river disclosed by the invention has the positive effects that:
(1) the method has the advantages of easy operation, no influence of instrument memory effect on the detection of the sulfur stable isotope ratio, high accuracy, good reproducibility and the like.
(2) Compared with the prior art, the method solves the problem that sulfur dioxide ions with high mass-to-charge ratio have influence on the detection of the sulfur isotope due to the instrument memory effect when the stable isotope in the water sample of the landscape river is detected, and improves the accuracy and the reproducibility of the detection of the sulfur isotope.
Detailed Description
The invention is described below by means of specific embodiments. Unless otherwise specified, the technical means used in the present invention are well known to those skilled in the art. In addition, the embodiments should be considered illustrative, and not restrictive, of the scope of the invention, which is defined solely by the claims. It will be apparent to those skilled in the art that various changes or modifications in the components and amounts of the materials used in these embodiments can be made without departing from the spirit and scope of the invention. The raw materials and reagents used in the present invention are commercially available.
Example 1
The method for detecting the sulfur stable isotope in the water sample of the landscape river comprises the following steps:
a. filtering and acidifying a landscape river water sample to remove carbonate, adding barium chloride to generate barium sulfate precipitate to fix sulfate radical, filtering again to collect barium sulfate precipitate, evaporating the precipitate at 50 ℃ to dryness, accurately weighing 5.0mg of precipitate, filling the precipitate into a tin cup and wrapping.
b. In the detection of the sulfur stable isotope (δ S34), IAEA-S-1 (silver sulfide, δ S34 ═ 0.30 ‰), IAEA-S-3 (silver sulfide, δ S34 ═ 32.3 ‰), and NBS-127 (barium sulfate, δ S34 ═ 20.3 ‰) were used as standards.
c. Detecting a sample to be detected by adopting an element analyzer-stable isotope mass spectrometer; the elemental analyzer parameters were: the oxidation tube is 1020 ℃, the column temperature box is 80 ℃, and the catalyst in the quartz tube in the oxidation furnace is 25 g of tungsten oxide and 50 g of granular pure copper.
d. Ionizing sample by high-energy ion source to generate SO+(ii) a Ion source parameters of the stable isotope mass spectrometer are as follows: the core voltage of the ion source is 6.2KV, and the filament voltage of the ion source is-114V.
e. Mass analyzer pair SO+Separating isotope signals; the stable isotope mass spectrometer mass analyzer parameters were: the voltage of the first-level quadrupole is minus 128V, and the voltage of the second-level quadrupole is 147V.
f. And analyzing the isotope values of the standard substance and the sample under the conditions, establishing a standard curve by taking the signal value of the standard substance as a horizontal coordinate and the standard isotope value of the standard substance as a vertical coordinate, and bringing the signal value of the sample into the standard curve to obtain the sulfur isotope value of the sample. And repeating the detection for 5 times, and counting the experimental results.
g. The invention mainly uses the following instruments: nu Horizon type stable isotope mass spectrometer, EuroVector EA3000 type element analyzer.
Landscape river water samples were treated by the above procedure and tested 5 times repeatedly, the results are shown in table 1.
TABLE 1. results of the accuracy test of. delta. S34
Example 2
The method for detecting the sulfur stable isotope in the water sample of the landscape river comprises the following steps:
a. filtering and acidifying a landscape river water sample to remove carbonate, adding barium chloride to generate a barium sulfate precipitate to fix sulfate radicals, filtering again to collect the barium sulfate precipitate, evaporating the precipitate to dryness at 50 ℃, accurately weighing 1.0, 2.5, 4.0, 5.5, 7.0, 8.5 and 10.0mg of precipitate, respectively, filling into a tin cup and wrapping.
b. In the detection of the sulfur stable isotope (δ S34), IAEA-S-1 (silver sulfide, δ S34 ═ 0.30 ‰), IAEA-S-3 (silver sulfide, δ S34 ═ 32.3 ‰), and NBS-127 (barium sulfate, δ S34 ═ 20.3 ‰) were used as standards.
c. Detecting a sample to be detected by adopting an element analyzer-stable isotope mass spectrometer; the elemental analyzer parameters were: the oxidation tube is 1020 ℃, the column temperature box is 80 ℃, and the catalyst in the quartz tube in the oxidation furnace is 25 g of tungsten oxide and 50 g of granular pure copper.
d. Ionizing sample by high-energy ion source to generate SO+(ii) a Ion source parameters of the stable isotope mass spectrometer are as follows: the core voltage of the ion source is 6.2KV, and the filament voltage of the ion source is-114V.
e. Mass analyzer pair SO+Separating isotope signals; the stable isotope mass spectrometer mass analyzer parameters were: the voltage of the first-level quadrupole is minus 128V, and the voltage of the second-level quadrupole is 147V.
f. And analyzing the isotope values of the standard substance and the sample under the conditions, establishing a standard curve by taking the signal value of the standard substance as a horizontal coordinate and the standard isotope value of the standard substance as a vertical coordinate, and bringing the signal value of the sample into the standard curve to obtain the sulfur isotope value of the sample. And repeating the detection for 5 times, and counting the experimental results.
g. The invention mainly uses the following instruments: nu Horizon type stable isotope mass spectrometer, EuroVector EA3000 type element analyzer.
Landscape river water samples were treated by the above procedure and the stability of the process was examined and the results are shown in table 2.
TABLE 2. results of stability test of δ S34(‰)
Example 3
Comparative test
In conclusion, the method has the advantages of reproducibility, high efficiency, high accuracy, easiness in operation, high equipment maintenance and the like, and can effectively overcome the defects of the current landscape river water sample sulfur isotope detection technology.
Claims (2)
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| JP2007333528A (en) * | 2006-06-14 | 2007-12-27 | Jeol Ltd | Product ion spectrum creating method and apparatus |
| CN103134851A (en) * | 2011-11-23 | 2013-06-05 | 中国石油化工股份有限公司 | Direct measuring apparatus and measuring method for hydrogen sulfide content and sulfur isotope in natural gas |
| GB201902350D0 (en) * | 2017-02-23 | 2019-04-10 | Thermo Fisher Scient Bremen Gmbh | Methods in mass spectrometry using collision gas as ion source |
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