CN110763776A - LC-HG-AFS detection method of thioarsenate - Google Patents

LC-HG-AFS detection method of thioarsenate Download PDF

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CN110763776A
CN110763776A CN201910994874.6A CN201910994874A CN110763776A CN 110763776 A CN110763776 A CN 110763776A CN 201910994874 A CN201910994874 A CN 201910994874A CN 110763776 A CN110763776 A CN 110763776A
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单慧媚
彭三曦
廖丹雪
潘敖然
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Guilin University of Technology
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Abstract

The invention discloses an LC-HG-AFS detection method of mono-thioarsenate, which comprises the following steps: preparing a test solution containing a sample to be tested; testing the test solution by adopting an LC-HG-AFS combined technology; calculating the mass concentration of the thioarsenate according to the working curve of the thioarsenate, wherein the working curve of the thioarsenate is established by the following method: preparing a thioarsenate sample, measuring the total arsenic mass concentration of the thioarsenate sample, and respectively measuring the mass concentration of arsenite and the mass concentration of arsenate in the thioarsenate sample by adopting an external standard method to establish a working curve of the thioarsenate. The method has the beneficial effect of providing detection technical support for researching the behavior characteristics of the monothioarsenate in the underground water.

Description

LC-HG-AFS detection method of thioarsenate
Technical Field
The invention relates to the technical field of environment detection. More specifically, the invention relates to an LC-HG-AFS detection method of mono-thioarsenate.
Background
Arsenic pollution in groundwater is one of the current environmental hot problems, and chronic arsenic poisoning can be caused by long-term intake of human bodies. In the iron-rich and sulfur-rich environment, the presence of thioarsenate is often detected in addition to the common arsenate, arsenite, and morphological separation is therefore required. Morphological separation mainly includes Ion Chromatography (IC), Liquid Chromatography (LC), Anion Exchange Chromatography (AEC), Capillary Electrophoresis (CE), and the like. In most of the applications, the ICP-MS detection is performed after morphological separation is performed by using IC, but the test cost is high. As a newly discovered arsenic form, thioarsenate needs a more convenient and economical detection method for directly determining the concentration of thioarsenate in a water environment.
Disclosure of Invention
An object of the present invention is to solve at least the above problems and to provide at least the advantages described later.
The invention also aims to provide an LC-HG-AFS detection method of the mono-thioarsenate, which provides a detection technical support for researching the behavior characteristics of the mono-thioarsenate in underground water.
To achieve these objects and other advantages in accordance with the present invention, there is provided a method for LC-HG-AFS detection of mono-thioarsenate, comprising the steps of:
step 1, preparing a test solution containing a sample to be tested;
step 2, testing the test solution by adopting an LC-HG-AFS combined technology;
step 3, calculating the mass concentration of the monothioarsenate according to the working curve of the monothioarsenate, wherein the establishing method of the working curve of the monothioarsenate comprises the following steps: preparing a thioarsenate sample, measuring the total arsenic mass concentration and recording as rhoTotal arsenicRespectively measuring the mass concentration of arsenite and the mass concentration of arsenate in a thioarsenate sample by adopting an external standard method, and respectively recording as rhoArsenite salt、ρArsenate saltThe calculation method of the mass concentration of the monothioarsenate in the monothioarsenate sample is recorded as rhoMonothioarsenate=ρTotal arsenicArsenite saltArsenate saltAnd establishing a working curve of the thioarsenate according to the sample volume and the mass concentration of the thioarsenate corresponding to the sample volume.
Preferably, the mass concentration of arsenite is calculated according to a standard curve of arsenite, and the mass concentration of arsenate is calculated according to a standard curve of arsenate.
Preferably, the method further comprises the following steps: step 4, verifying a working curve of the monothioarsenate, which specifically comprises the following steps: and (3) configuring monothioarsenate samples with different concentrations in the step (3) for testing, calculating the mass concentration of monothioarsenate by using the working curve of monothioarsenate in the step (3), and calculating the standard deviation of the monothioarsenate samples with different concentrations.
Preferably, the mobile phase of the LC-HG-AFS coupling technology is phosphate buffer solution, and the phosphate buffer solution is diammonium hydrogen phosphate solution.
Preferably, the flow rate of a high-pressure liquid phase pump of the LC-HG-AFS combined technology is 1.0-1.2 mL/min, and a chromatographic column is a PRP-X100 anion exchange chromatographic column.
Preferably, in the LC-HG-AFS combined technology, the negative high voltage of the atomic fluorescence spectrum is 270-280V, the carrier gas flow is 400-450 mL/min, the shielding gas flow is 600-650 mL/min, the rotation speed of a peristaltic pump is 65-80 r/min, the total current of the arsenic lamp is 80-85 mA, and the auxiliary current is 35-40 mA.
Preferably, the current carrying under the hydride generation condition in the LC-HG-AFS coupling technology is 6-8% hydrochloric acid solution, and the reducing agent is 2-3% potassium borohydride and 0.3-0.4% potassium hydroxide solution.
The invention at least comprises the following beneficial effects: the method adopts LC-HG-AFS combined technology to detect the concentration of the mono-thio-arsenate in the water environment, has the advantages of less sample consumption, simple solution preparation, lower requirement on an anion exchange column and no need of using alkaline solution for gradient elution; the arsenic form in the test solution can be basically and completely eluted and separated, and the loss of the total arsenic content is small; a detection method of thioarsenate LC-HG-AFS provides a detection technical support for researching the behavior characteristics of the thioarsenate LC-HG-AFS in underground water.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Drawings
FIG. 1 is a schematic structural diagram of an LC-HG-AFS in an embodiment of the present invention;
FIG. 2 is a schematic view of an arsenic form elution apparatus according to an embodiment of the present invention;
FIG. 3 is a graph showing a standard curve for arsenite and a standard curve for arsenate in an embodiment of the present invention;
FIG. 4 is a LC-HG-AFS spectrum of sample No. 1 in example of the present invention;
FIG. 5 is a schematic representation of the working curve of the monothioarsenate salt of sample No. 1 in example 1 of the present invention;
FIG. 6 is a graph showing the working curve of the monothioarsenate salt of sample No. 2 in the example of the present invention;
FIG. 7 is a graph showing a comparison of the working curves of Monothioarsenate Nos. 1 and 2 in accordance with examples of the present invention.
Detailed Description
The present invention is further described in detail below with reference to examples so that those skilled in the art can practice the invention with reference to the description.
It is to be noted that the experimental methods described in the following embodiments are all conventional methods unless otherwise specified, and the reagents and materials are commercially available unless otherwise specified.
An LC-HG-AFS detection method of thioarsenate comprises the following steps:
the LC-HG-AFS condition parameter settings are shown in Table 1;
TABLE 1
(1) Establishing an arsenite standard curve and an arsenate standard curve by using an LC-HG-AFS combined technology;
are respectively prepared with the concentration of 20,40. 60, 80 and 100 mu g/L arsenite As (III) standard solution and arsenate As (V) standard solution, the injection volumes are respectively 10, 20, 30, 40 and 50 mu L, and the measured results are shown in Table 2. A standard curve is prepared by using external standard calibration, the standard curve is shown in figure 3, and the standard curve of arsenite is as follows: 7133.6C-9770.2, R20.9995; the standard curve for arsenate was: 5301.7C-2128.6, R2=0.9998。
TABLE 2 gradient values of the standard curve
Figure BDA0002239433590000032
Figure BDA0002239433590000041
(2) Establishing a working curve of the mono-thioarsenate by using an LC-HG-AFS combined technology;
the method specifically comprises the following steps: configuring a sample No. 1, constructing a working curve of the mono-thioarsenate by using the sample No. 1, diluting the sample No. 1 by 10 times with the sample No. 1 containing the sodium mono-thioarsenate as 355 mu g/L, and measuring the total arsenic concentration to be 40.5865 mu g/L by utilizing atomic fluorescence. And (3) performing LC-HG-AFS detection, setting the injection volume to be 10, 30, 40, 50 and 100 mu L, setting the arsenite peak emergence time to be about 2-3 min, setting the monothioarsenate peak emergence time to be about 18-22 min, and showing the test results in table 3 as shown in figure 4. The arsenite concentration is 3.7541 mu g/L when the injection volume is 10 mu L by using the arsenite standard curve calibration. The peak area of the monothioarsenate measured by different sample injection volumes has good correlation and linear correlation coefficient R2The value is greater than 99.9%. Assuming that the concentration of the monothioarsenate is a when the sample injection volume is 10 muL, the concentrations of the monothioarsenate are 3a, 4a, 5a and 10a when the sample injection volume is 30, 40, 50 and 100 muL, respectively, wherein a represents the total arsenic concentration measured by atomic fluorescence minus the arsenite and arsenate concentrations measured by LC-HG-AFS.
TABLE 3 external standard method for testing sample No. 1
Figure BDA0002239433590000042
Note: when 100. mu.L of sample was injected, the peak value of As (V) was observed, and the quantitative concentration was 13.0435. mu.g/L.
The arsenate content in the sample is low, and no obvious peak value is detected when samples are injected with 10, 30, 40 and 50 mu L. When the sample injection amount is 100 mu L, the arsenate concentration is 13.0435 mu g/L measured by an external standard method, and when the sample injection volume is 10 mu L, the concentration is 1.3044 mu g/L.
Using the formula rhoMonothioarsenate=ρTotal arsenicArsenite saltArsenate saltWhen the injection volume is 10 mu L, the concentration of the monothioarsenate is calculated to be 35.528 mu g/L. Since the injection volumes were proportional to the measured concentration of mono-thioarsenate, the corresponding concentration of thioarsenate was 35.528, 106.584, 142.112, 177.640 and 355.280 μ g/L for injection volumes of 10, 30, 40, 50 and 100 μ L, respectively.
The sample injection volumes of 10, 30, 40, 50 and 100 μ L are used as gradients, an external standard method is used for establishing a monothioarsenate working curve, the external standard calibration result is shown in Table 4, and monothioarsenate is abbreviated as monothio in Table 4. The minimum concentration of monothioarsenate detected was 35.53. mu.g/L, and the monothioarsenate working curve is shown in FIG. 5. Arsenite working curve: sNumber 1=6962.0C-5764.2,R20.9993; one thioarsenate working curve: sNumber 1=3264.0C-18940,R2=0.9996。
TABLE 4 external standard calibration Table No. 1 sample
Figure BDA0002239433590000051
And (3) configuring a No. 2 sample, constructing a working curve of the sodium sulfoarsenate by using the No. 2 sample, wherein the content of the sodium sulfoarsenate in the No. 2 sample is 360 mu g/L, the No. 2 sample is diluted by 10 times, and the total arsenic concentration is 41.4749 mu g/L by utilizing atomic fluorescence measurement. LC-HG-AFS detection, the injection volume is 30, 40, 50 and 100 μ L, and the test results are shown in Table 5. The arsenite concentration is calibrated by an external standard method, and when the reduced injection volume is 10 mu L, the average concentration is 3.5072 mu g/L. Differential sample volume and measurementThe peak area of the obtained monothioarsenate has good correlation and linear correlation coefficient R2The value is greater than 99.9%. Assuming that the concentration of the monothioarsenate is b in a sample volume of 10. mu.L, the concentration of the monothioarsenate is 3b, 4b, 5b and 10b in sample volumes of 30, 40, 50 and 100. mu.L, respectively.
TABLE 5 external standard method for testing sample No. 2
Figure BDA0002239433590000052
Figure BDA0002239433590000061
Note: when 100. mu.L of sample was injected, the peak value of As (V) was observed, and the quantitative concentration was 15.3277. mu.g/L.
The working curve of sample No. 2 was constructed in the same manner, and the external standard calibration results are shown in table 6, wherein monothioarsenate is abbreviated as monothio in table 6, and the standard curve is shown in fig. 6. Arsenite working curve: sNumber 2=6874.5C-4043.0,R20.9992; one thioarsenate working curve: sNumber 2=3166.5C-2773.4,R2=0.9999。
TABLE 6 external standard calibration Table No. 2 sample
(3) Verification of working curves for sample No. 1 and sample No. 2
The arsenite working curve established for sample No. 1 is: sNumber 1=6962.0C-5764.2,R20.9993; the arsenite working curve established for sample No. 2 is: sNumber 2=6874.5C-4043.0,R20.9992; the arsenite standard curve of the standard substance is as follows: 7133.6C-9770.2, R20.9995. The monothioarsenate working curve established for sample No. 1 is: sNumber 1=3264.0C-18940,R20.9996; the monothioarsenate working curve established for sample No. 2 is: sNumber 2=3166.5C-2773.4,R20.9999. 1 sampleThe monothioarsenate working curves established for sample nos. 2 and 2 are relatively close, as shown in figure 7.
The working curves established for sample No. 1 were used to measure sample No. 2, sample No. 3 and sample No. 4, wherein the sample No. 3 contained sodium monothioarsenate at 455. mu.g/L, the sample No. 4 contained sodium monothioarsenate at 360. mu.g/L, and the sample injection volume was 100. mu.L, and the results are shown in Table 7, in which monothioarsenate is abbreviated as monothio in Table 7. The measurement results of the arsenite concentration and the standard curve of arsenite measured with the working curve of sample No. 1 are very close, with relative standard deviations of 0.44%, 1.82%, and 1.17%, respectively. The measured concentration of monothioarsenate was also relatively close to the theoretical value, with relative standard deviations of 1.20%, 2.33% and 4.41%, respectively.
Samples No. 1, No. 3 and No. 4 were also measured using the working curve established for sample No. 2, with a sample injection volume of 100. mu.L, and the results are shown in Table 7. The relative standard deviations obtained from the measurement results of the arsenite concentration measured with the working curve of sample No. 2 and the standard curve of arsenite were 0.79%, 2.44% and 1.80%, respectively; the relative standard deviations of the measured monothioarsenate concentration and the theoretical value were 1.71%, 3.71% and 5.58%, respectively.
The measurement results of the curve 1 and the curve 2 can be obtained, the measurement values of the two working curves are close to the theoretical value, and the calibration result of the working curve 1 is superior to that of the working curve 2.
TABLE 7 LC-HG-AFS test results sample Nos. 3 and 4
Figure BDA0002239433590000071
(4) Detection limit determination
The noise mean was calculated by selecting 5 curves that were not tested on the same day. The detection limit was determined to be 33.03. mu.g/L by diluting the sample with 3-fold signal-to-noise ratio as the detection limit.
While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable to various fields of endeavor for which the invention may be embodied with additional modifications as would be readily apparent to those skilled in the art, and the invention is therefore not limited to the details given herein and to the embodiments shown and described without departing from the generic concept as defined by the claims and their equivalents.

Claims (7)

1. An LC-HG-AFS detection method of thioarsenate is characterized by comprising the following steps:
step 1, preparing a test solution containing a sample to be tested;
step 2, testing the test solution by adopting an LC-HG-AFS combined technology;
step 3, calculating the mass concentration of the monothioarsenate according to the working curve of the monothioarsenate, wherein the establishing method of the working curve of the monothioarsenate comprises the following steps: preparing a thioarsenate sample, measuring the total arsenic mass concentration and recording as rhoTotal arsenicRespectively measuring the mass concentration of arsenite and the mass concentration of arsenate in a thioarsenate sample by adopting an external standard method, and respectively recording as rhoArsenite salt、ρArsenate saltThe calculation method of the mass concentration of the monothioarsenate in the monothioarsenate sample is recorded as rhoMonothioarsenate=ρTotal arsenicArsenite saltArsenate saltAnd establishing a working curve of the thioarsenate according to the sample volume and the mass concentration of the thioarsenate corresponding to the sample volume.
2. The LC-HG-AFS method of claim 1, wherein the concentration of arsenite is calculated from a standard curve of arsenite, and the concentration of arsenate is calculated from a standard curve of arsenate.
3. The LC-HG-AFS assay of monothioarsenate according to claim 1, further comprising: step 4, verifying a working curve of the monothioarsenate, which specifically comprises the following steps: and (3) configuring monothioarsenate samples with different concentrations in the step (3) for testing, calculating the mass concentration of monothioarsenate by using the working curve of monothioarsenate in the step (3), and calculating the standard deviation of the monothioarsenate samples with different concentrations.
4. The method for LC-HG-AFS detection of mono-thio-arsenate according to claim 1, wherein the mobile phase of the LC-HG-AFS combined technology is phosphate buffer solution, and the phosphate buffer solution is diammonium phosphate solution.
5. The LC-HG-AFS detection method of mono-thio-arsenate according to claim 1, wherein the high-pressure liquid pump flow rate of the LC-HG-AFS combined technology is 1.0-1.2 mL/min, and the chromatographic column is a PRP-X100 anion exchange chromatographic column.
6. The LC-HG-AFS detection method of mono-thio-arsenate according to claim 1, wherein in the LC-HG-AFS combined technology, the negative high voltage of the atomic fluorescence spectrum is 270-280V, the carrier gas flow is 400-450 mL/min, the shielding gas flow is 600-650 mL/min, the rotation speed of a peristaltic pump is 65-80 r/min, the total current of the arsenic lamp is 80-85 mA, and the auxiliary current is 35-40 mA.
7. The LC-HG-AFS detection method of mono-thio arsenate according to claim 1, wherein the carrier current of the hydride generation condition in the LC-HG-AFS combined technology is 6-8% hydrochloric acid solution, and the reducing agent is 2-3% potassium borohydride and 0.3-0.4% potassium hydroxide solution.
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