CN112362722B - Quantitative analysis method for laser ablation inductively coupled plasma mass spectrum - Google Patents
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Abstract
The invention aims to provide a quantitative analysis method of laser ablation inductively coupled plasma mass spectrometry, which overcomes the matrix effect and realizes the quantitative analysis of a sample to be detected without matrix matching so as to improve the analysis accuracy and efficiency. The invention comprises the following steps: (1) preparing a standard solution containing an element to be detected, dripping the standard solution on the surface of a sample to be detected, and drying to obtain a dry liquid drop area; (2) and (4) carrying out laser ablation inductively coupled plasma mass spectrometry detection on the dry liquid drop area, drawing a quantitative calibration curve, and analyzing to obtain the content of the element to be detected in the sample to be detected.
Description
Technical Field
The invention belongs to the field of analytical chemistry, and relates to a method for analyzing element content in a solid sample by using laser ablation inductively coupled plasma mass spectrometry.
Background
The laser ablation inductively coupled plasma mass spectrometry is used as a direct analysis means of a solid sample, and particles generated by the laser ablation sample are directly introduced into the inductively coupled plasma mass spectrometry for detection by means of purging of carrier gas, so that the complicated pretreatment process of the sample is avoided, and the detection sensitivity is good. The laser ablation is used as a sample introduction system, the interference generated by oxide ions in the detection system is effectively reduced by adopting a solid direct sample introduction mode, the sample consumption is low by adopting the laser ablation mode, and the micro-damage analysis of the sample can be realized. Therefore, the laser ablation inductively coupled plasma mass spectrometry is considered to be a technology with application prospect in the direct solid sample analysis method.
However, the matrix effect is a main factor influencing the analysis accuracy when the laser ablation inductively coupled plasma mass spectrometry is used for establishing a quantitative analysis method. The matrix refers to the main components of the sample to be detected except the elements to be detected. The matrix effect refers to the influence of matrix elements on response signals of the elements to be detected. Therefore, if accurate quantitative analysis data is to be obtained, it is necessary to achieve complete matching between the matrix of the solid standard substance and the matrix of the sample to be measured.
Disclosure of Invention
In view of this, the present invention aims to provide a method for quantitatively analyzing a laser ablation inductively coupled plasma mass spectrum, which overcomes a matrix effect, and realizes quantitative analysis of a sample to be detected without matrix matching, so as to improve analysis accuracy and efficiency.
Therefore, the invention adopts the following technical scheme: a quantitative analysis method of laser ablation inductively coupled plasma mass spectrometry is characterized by comprising the following steps:
(1) preparing a standard solution containing an element to be detected, dripping the standard solution on the surface of a sample to be detected, and drying to obtain a dry liquid drop area;
(2) and (4) carrying out laser ablation inductively coupled plasma mass spectrometry detection on the dry liquid drop area, drawing a quantitative calibration curve, and analyzing to obtain the content of the element to be detected in the sample to be detected.
According to the invention, standard solution is directly dripped on the surface of a sample to be detected, a dry liquid drop area after liquid drop drying is taken as an ablation area, matrix matching is realized, and quantitative analysis of laser ablation inductively coupled plasma mass spectrometry is established.
Preferably, a standard solution containing the element to be detected is prepared and dripped on the surface of the sample to be detected, and the standard solution is dried until the solvent on the surface is completely volatilized to form a dried liquid drop.
Preferably, the dry liquid drop area after the liquid drop is dried is used as an ablation area to ablate the sample to be tested.
Preferably, the laser ablates areas of different concentrations of dry droplets in a line and/or area scan fashion. For a certain dry drop region, linear scanning along the diameter direction (short time consumption and poor stability) or an internally tangent square surface scanning mode (long time consumption and good stability) can be adopted.
Preferably, the laser ablation adopts a laser wavelength of 213nm, the laser energy is 60% -80%, the laser ablation aperture is set to 100-200 μm, and the scanning speed is set to 30-50 μm/s. Within the range, the response signal sensitivity is high, the stability is good, and the existence of the dry liquid drop can not influence the denudation condition of the sample.
Preferably, the calculated mass of the element to be measured in the dry liquid drop ablated by one pulse is used as an abscissa, the response signal of the element to be measured is used as an ordinate, and the mass of the element to be measured ablated by one pulse is extrapolated by a standard addition method. And solving the total mass of the sample to be detected after pulse ablation, wherein the ratio of the total mass to the total mass is the concentration of the corresponding element to be detected in the sample.
The concentration of the element to be detected in the sample obtained by calculation through the method is consistent with the result obtained by the inductively coupled plasma emission spectrum after the sample is digested, and the method is high in accuracy.
Preferably, a surfactant and/or a high boiling point solvent having a low surface tension is added to the standard solution. The low surface tension is, for example, less than 60mN/m (20 ℃), and the high boiling point is greater than 150 ℃.
Preferably, in order to make the area of the formed dry liquid drop relatively small, eliminate the influence of the dry liquid drop on the sample degradation and ensure that the dry liquid drop can be completely degraded without secondary deposition, the volume of the liquid drop dripped on the surface of the sample is as small as possible. The droplet volume is preferably 0.2-1.0. mu.L.
Preferably, the drying temperature of the droplets can be controlled during the drying process until the droplets are completely dried.
Preferably, the response signal of the element to be detected is used as a vertical coordinate, and the distribution of the element in the dry liquid drop is uniform under the condition that the existence of the dry liquid drop does not influence the degradation of the sample to be detected. In the drying process of the liquid drop, the drying speed of the edge of the liquid drop is higher than that of the inside of the liquid drop, so that a complementary flow from the inside of the liquid drop to the edge of the liquid drop is generated, and therefore elements in a dry liquid drop area after the liquid drop is dried are not uniformly distributed, namely a 'coffee ring' phenomenon exists. The addition amount of the surfactant and/or the high-boiling-point solvent with low surface tension, the drying temperature and the like in the standard solution are controlled, so that Marangoni convection driven by surface tension difference or temperature difference and flowing from the edge of the liquid drop to the inside of the liquid drop is generated in the liquid drop during the drying process, the coffee ring phenomenon in the drying process of the liquid drop is inhibited, and the element distribution in the dry liquid drop is uniform.
Preferably, the mass of the element to be measured in the dry droplet ablated by one pulse is taken as the abscissa in the quantitative analysis method. The mass of the element to be detected in the dry liquid drop ablated by one pulse is calculated by the ratio of the mass of the element to be detected in the dry liquid drop ablated by the laser to the total number of pulses required by the ablation:
the ablation mass ng of the element to be measured in the dry droplet is the concentration μ g/mL of the standard solution × volume mL × 10 of the droplet-3The area of the denuded zone in the x dry drop accounts for the total percent
Wherein the ablation area as a percentage of the total area of the dry droplet is the size of the laser ablation spot μm × length of the ablated line μm × number of line scans/[ π × (radius of the dry droplet μm)2]。
The total number of pulses is the time s required to ablate an ablation line of a corresponding length × the set frequency Hz of the laser × the number of line scans.
Preferably, the total mass of the sample to be tested, which has been ablated by one pulse, is obtained by weighing: the method comprises the steps of weighing the mass difference of a sample before and after denudation by a balance, and dividing the mass difference by the total number of pulses corresponding to denudation to obtain the mass of the sample to be detected, wherein the mass of the sample to be detected is obtained by pulse denudation.
Preferably, in order to make the weighing result of the balance more accurate, the mass difference between the sample before and after the sample is degraded should be as large as possible, so that the number of pulses required by the sample to be measured should be as large as possible. The number of pulses required can be determined by how easily the sample is to be degraded.
In order to solve the problem of matrix effect of the laser ablation inductively coupled plasma mass spectrometry, the invention directly drops a series of standard solutions of elements to be measured on the surface of a sample to be measured, optimizes the drying process of liquid drops, takes a dried dry liquid drop area as an ablation area, realizes matrix matching and accurately quantifies the content of the elements to be measured in the sample.
Drawings
FIG. 1 is a diagram showing the distribution of Nd in 0.3. mu.L of a 20. mu.g/mL standard Nd solution containing 2 wt.% F-127 in dried droplets obtained after drying at 80-105 ℃;
FIG. 2 is a diagram showing the distribution of Nd in 0.3. mu.L of a 20. mu.g/mL standard Nd solution containing 4 wt% formamide in dried droplets obtained after drying at 25-45 ℃;
FIG. 3 is a calibration curve of the neodymium element in NIST612 obtained by optimizing the amount of surfactant F-127 added and the drying temperature;
fig. 4 is a calibration curve of the neodymium element in NIST612 obtained by optimizing the amount of formamide added and the drying temperature.
Detailed Description
The present invention is described in detail below with reference to the drawings and embodiments in the examples of the present invention, and it should be understood that the following embodiments are only illustrative and not restrictive of the present invention.
In one embodiment of the invention, a series of standard solutions of elements to be detected with different concentrations are directly dripped on the surface of a sample to be detected, a dry liquid droplet area after liquid droplet drying is taken as an ablation area, the dry liquid droplet is ablated in a line and/or surface scanning mode, and a standard curve is established to quantify the content of the elements to be detected in the sample. The drying process of the liquid drops is optimized by adding a surfactant or a high boiling point solvent to the standard solution and controlling the drying temperature. The method of the present invention is exemplified below.
Preparation of standard solution. In some embodiments, the surfactant and/or the high boiling point solvent are weighed in a reagent bottle, a standard solution of the element to be detected is added into the reagent bottle, and deionized water is used as the solvent to dilute the solution to obtain a solution with a corresponding concentration for standby. The standard solution contains the surfactant and/or the high-boiling point solvent, so that the phenomenon of uneven distribution of elements to be detected in the droplet drying process can be effectively improved. The surfactant is not particularly limited, and any substance that can significantly reduce the surface energy of water when dissolved in water may be used, and may be selected from, for example, F-127 (polyoxyethylene polyoxypropylene ether block copolymer), P-123 (polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer), and SDS (sodium dodecyl sulfate). The high boiling point solvent is a solvent having a boiling point of 150 ℃ or higher and a surface tension of less than 60mN/m (20 ℃). The solvent may be selected from one of formamide, ethylene glycol, diethylene glycol, for example. In addition, the standard solution can also contain colored substances such as methylene blue, methyl blue, Congo red and the like, so that the residual area of the dry liquid drop can be positioned better.
The presence of the surfactant can make the droplet generate a supplementary flow from the inside of the droplet to the edge of the droplet due to the fact that the drying speed of the edge of the droplet is higher than that of the inside of the droplet in the drying process of the droplet, so that the concentration of the surfactant at the edge of the droplet is higher than that of the surfactant at the inside of the droplet, and the Marangoni convection from the edge of the droplet to the inside of the droplet is generated under the induction of the surface tension difference so as to inhibit the coffee ring phenomenon in the drying process of the droplet. The high boiling point solvent has smaller surface tension and the water as the low boiling point solvent has larger surface tension, and because the drying speed of the edge of the liquid drop is larger than the drying speed of the inner part in the drying process, a supplementary flow from the inner part of the liquid drop to the outer part of the liquid drop exists, the concentration of the high boiling point solvent at the edge of the liquid drop is larger than that of the high boiling point solvent in the inner part of the liquid drop, the surface tension of the edge of the liquid drop is smaller than that of the inner part of the liquid drop, and Marangoni convection from the edge of the liquid drop to the inner part of the liquid drop is generated to inhibit the coffee ring phenomenon in the drying process of the liquid drop.
In the standard solution, the mass concentration of the surfactant may be 2 to 3.5 wt%. If the concentration of the surfactant is too low, the Marangoni convection is difficult to generate or is small, and the phenomenon of 'coffee ring' formed after the droplets are dried cannot be improved; if the concentration of the surfactant is too high, the detection of the inductively coupled plasma mass spectrometry is affected by excessive introduction of the organic substances.
The mass concentration of the high boiling point solvent in the standard solution may be 3.5 to 4.5 wt%. If the concentration of the high-boiling point solvent is too low, marangoni convection is difficult to generate or small, and the coffee ring phenomenon formed after the liquid drops are dried cannot be improved; if the concentration of the high boiling point solvent is too large, the detection of the inductively coupled plasma mass spectrometry is affected by excessive introduction of the organic substance.
And selecting a series of standard solutions of elements to be detected with different concentrations so as to prepare a series of standard solutions with different concentrations. For example, more than 4 standard solutions of different concentrations may be prepared. According to the method, more accurate results can be obtained by preparing less standard solutions with different concentrations. For example, the number of standard solutions with different concentrations can be 4-5.
And transferring a series of standard solutions with different concentrations to different positions on the surface of the sample through a liquid transfer gun, and drying the standard solutions under the drying modes of an infrared lamp or room temperature and the like. The dropping amount of the standard solution can be 0.2-1.0 mu L, so that the area of the formed dry liquid drop can be relatively small, the influence of the dry liquid drop on the sample degradation is eliminated, and the dry liquid drop can be completely degraded without secondary deposition. The drying temperature of the liquid drops can be controlled in the liquid drop drying process until the liquid drops are completely dried. In some embodiments, the standard solution contains a surfactant and the drying temperature is 80-105 ℃. In some examples, the standard solution contains a high boiling point solvent and the drying temperature is 25-45 ℃. The droplets dry to form a region of dry droplets. The radius of the dry droplet region may be 1400-1900 μm.
The dry droplet area is ablated (not only the dry droplet but also the sample covered by the dry droplet). The dry drop areas with different concentrations can be denudated by adopting a line and/or surface scanning mode, and specifically, a line scanning mode (short time consumption and poor stability) along the diameter direction or an internally tangent square surface scanning mode (long time consumption and good stability) is adopted for a certain dry drop area. And calculating to obtain the mass of the element to be detected in the dry liquid drop ablated by one pulse. And weighing to obtain the total mass of the sample to be tested, which is degraded by one pulse.
And (3) taking the mass of the element to be detected in the dry liquid drop subjected to pulse ablation as a horizontal coordinate, taking the response signal of the corresponding element to be detected as a vertical coordinate to obtain a standard curve of the element to be detected, and extrapolating by adopting a standard addition method to obtain the mass of the element to be detected in the sample subjected to pulse ablation. The ratio of the numerical value to the total mass of the sample to be detected obtained by calculating one pulse ablation is the concentration of the element to be detected in the sample.
The present invention will be described in further detail with reference to examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that insubstantial modifications and adaptations of the invention by those skilled in the art based on the foregoing description are intended to be included within the scope of the invention. The following examples of specific concentrations, temperatures, reagents, etc. are also merely illustrative of suitable ranges, i.e., one skilled in the art can select from suitable ranges through the description herein, and are not intended to be limited to the specific values exemplified below.
Parameters of the instrument: the laser ablation adopts a Nd-YAG laser ablation sample injection system of Cetac213nm, the laser wavelength is 213nm, the laser energy is 70 percent, the laser frequency is 20Hz, the ablation aperture is 200 mu m, the scanning speed is 30 mu m/s, and the helium flow is 0.7L/min; ICP-MS is a Thermo X series II CCT type four-stage rod, argon is used as carrier gas, and the flow of the argon is 0.7L/min.
Example 1
The surfactants F-1270 g, 0.05g, 0.10g and 0.15g are respectively weighed into a reagent bottle, and 20 mug/mL neodymium element standard solution is used for weighing to 5 g. The prepared solution is transferred by 0.3 mu L of a pipetting gun with the specification of 0.1-2.5 mu L to the surface of a sample to be measured. When the surfactant F-127 was added in an amount of 2 to 3% by weight and dried under an infrared lamp (80 to 105 ℃ C.), the distribution of the elements in the resulting dry droplets was relatively uniform (see FIG. 1).
A series of standard solutions of neodymium element at different concentrations, for example, 0. mu.g/mL, 2.5. mu.g/mL, 5. mu.g/mL, 10. mu.g/mL, were prepared, and the amount of surfactant F-127 added to the standard solution was controlled to be 2% by weight. Accurately transferring 0.3 mu L of each standard solution of the series to the surface of a NIST612 sample by using a pipette gun, and placing the sample under an infrared lamp for drying, wherein the drying temperature is controlled to be 80-105 ℃. After drying, the radius of the dry droplet is 1400-1900 μm. The areas where the dry droplets remained were ablated by multi-line scanning and a standard curve was established (see fig. 3). The standard curve was extrapolated to the mass of neodymium in NIST612, which had been ablated by one pulse. One pulse was ablated by weighing to a mass of 4.2ng/pulse for NIST 612. The calculated content of neodymium element in NIST612 is basically consistent with the standard value, and the reliability of the scheme is proved (see Table 1). 4.2ng/pluse is the total mass of the sample (NIST612) ablated by one pulse; the mass of the element to be measured in a pulse ablated sample (NIST612) was obtained by establishing a calibration curve, as shown in fig. 3, where the absolute value of the intersection of the curve with the x-axis, i.e., 0.0001649ng/pluse, is the mass of the element to be measured in a pulse ablated sample (NIST 612); the ratio of the denudation mass of the element to be detected in the sample to the total mass of the sample to be detected obtained by denudation is the concentration of the element to be detected in the sample (see table 1), and 39.81 +/-2.94 mg/kg in table 1 is the result obtained by three times of repeated tests.
Example 2
0.2g of formamide solution is weighed into a reagent bottle, 0.002g of methylene blue is added, and the solution is weighed to 5g by using a 20 mu g/mL neodymium element standard solution. The prepared solution is transferred to the surface of a sample to be tested by 0.3 mu L of 0-2.5 mu L of a pipetting gun and is placed under an infrared lamp (25-45 ℃) for drying, and the distribution of elements in the dry liquid drop obtained by the scheme is relatively uniform (see figure 2).
A series of neodymium element standard solutions with different concentrations, such as 0 mu g/mL,2.5 mu g/mL,5 mu g/mL and 10 mu g/mL, are prepared, and the addition amount of formamide in the standard solution is controlled to be 4 wt% and the addition amount of methylene blue is controlled to be 0.04 wt%. Accurately transferring 0.3. mu.L of each standard solution to the surface of NIST612 sample by using a 0.1-2.5. mu.L pipetting gun, and drying under an infrared lamp at 25-45 deg.C. After drying, the radius of the dry droplet was 1400-1900 μm. The areas where the dry droplets remained were ablated by multi-line scanning and a standard curve was established (see fig. 4). The standard curve was extrapolated to the mass of neodymium in NIST612 after a pulse ablation. A pulse ablation to a mass of 4.1ng/pulse for NIST612 was obtained by weighing. The calculated content of neodymium element in NIST612 is basically consistent with the standard value, and the reliability of the scheme is proved (see Table 1). 4.1ng/plus is the total mass of one pulse ablated sample (NIST612) obtained by weighing; the mass of the element to be measured in a pulse-ablated sample (NIST612) was obtained by establishing a calibration curve, as shown in fig. 4, whose absolute value of the intersection with the x-axis, i.e., 0.0001502ng/pluse, is the mass of the element to be measured in a pulse-ablated sample (NIST 612); the ratio of the denudation mass of the element to be detected in the sample to the total mass of the sample to be detected obtained by denudation is the concentration of the element to be detected in the sample, and 35.58 +/-3.51 mg/kg in the table 1 is the result obtained by three times of repeated tests.
TABLE 1 analysis of the Neodymium element in NIST612 by the method of quantitative analysis of dry drops
Claims (3)
1. A quantitative analysis method of laser ablation inductively coupled plasma mass spectrometry is characterized by comprising the following steps:
(1) preparing a standard solution containing an element to be detected, dripping the standard solution on the surface of a sample to be detected, and drying to obtain a dry liquid drop area;
(2) performing laser ablation inductively coupled plasma mass spectrometry detection on the dry drop region, drawing a quantitative calibration curve, and analyzing to obtain the content of an element to be detected in a sample to be detected;
the standard solution also contains a high boiling point solvent, the boiling point of the high boiling point solvent is more than 150 ℃, the surface tension of the high boiling point solvent at 20 ℃ is less than 60mN/m, the high boiling point solvent is selected from one of formamide, ethylene glycol and diethylene glycol, and the mass concentration of the high boiling point solvent is 3.5-4.5 wt%;
the drying temperature is 25-45 ℃;
the standard solution also contains a colored substance capable of positioning the dry droplet region, wherein the colored substance comprises methylene blue, methyl blue and Congo red;
the dropping amount of the standard solution is 0.2-1.0 mu L, and the radius of the dry liquid drop area is 1400-1900 mu m;
the step (2) comprises the following steps:
using the mass of the element to be detected in the dry liquid drop obtained by pulse ablation as a horizontal coordinate, using the response signal of the element to be detected as a vertical coordinate, extrapolating by adopting a standard addition method to obtain the mass of the element to be detected in the sample ablated by pulse,
and (3) solving the total mass of the sample to be detected after the sample is degraded under one pulse, wherein the ratio of the mass of the element to be detected to the total mass is the concentration of the corresponding element to be detected in the sample.
2. The quantitative analysis method for laser ablation inductively coupled plasma mass spectrometry of claim 1, wherein the standard solution containing the element to be detected on the surface of the sample to be detected is dripped and dried until the solvent is completely volatilized.
3. The quantitative analysis method for laser ablation inductively coupled plasma mass spectrometry of claim 1, wherein the laser ablates areas of dry droplets of different concentrations by line scanning and/or area scanning.
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