Intelligent analysis method for trace detection of phosphate based on icp-ms

Abstract

The application relates to the technical field of analytical chemistry, and discloses an intelligent phosphate trace detection analysis method based on ICP-MS, which comprises the following steps: ionizing an aerosol of a phosphate solution to be detected to obtain a phosphorus characteristic ion beam; setting a mass filter window to perform mass-to-charge ratio screening on the phosphorus characteristic ion beam to obtain a candidate ion stream; recording the instantaneous response intensity ratio of an internal standard element and the phosphorus element in real time to construct a dynamic correction coefficient sequence, and determining the median value of continuous sampling points in the dynamic correction coefficient sequence as a dynamic internal standard correction factor; based on the dynamic internal standard correction factor, performing real-time weighted compensation on the original signal intensity of the phosphorus element in the candidate ion stream to obtain a phosphorus signal intensity sequence; performing mapping inversion on the phosphorus signal intensity sequence to obtain a phosphate ion concentration value, and performing robust statistical processing on the phosphate ion concentration value to obtain a final trace detection result; and the application can improve the efficiency of phosphate trace detection.

Description

Technical Field

[0001] This invention relates to the field of analytical chemistry, and in particular to an intelligent analytical method for the detection of trace phosphates based on ICP-MS. Background Technology

[0002] Traditional ICP-MS-based trace phosphate detection techniques are susceptible to matrix interference and instrument noise during sample ionization and signal acquisition. The extraction of phosphorus characteristic ion beam signals is prone to deviation, and the mass-to-charge ratio screening process lacks an adaptive control mechanism, making it easy for non-target ion interference signals to be mixed in. This results in insufficient stability and purity of the original detection signal, making it difficult to accurately capture the characteristic response of trace phosphate.

[0003] Existing detection systems mostly use static calibration modes for internal standard correction, which cannot match instrument response drift and instantaneous signal fluctuations in real time, resulting in limited correction compensation effects. At the same time, the detection data lacks a robust statistical processing mechanism, outliers cannot be effectively removed, and concentration inversion results are easily interfered with. Ultimately, this leads to low sensitivity and accuracy in phosphate trace detection, and the detection efficiency and data reliability cannot meet the requirements of high-precision analysis. Therefore, how to improve the efficiency of phosphate trace detection has become an urgent problem to be solved. Summary of the Invention

[0004] This invention provides an intelligent analytical method for the detection of trace amounts of phosphate based on ICP-MS, in order to solve the problems mentioned in the background art.

[0005] To achieve the above objectives, the present invention provides an intelligent analytical method for trace phosphate detection based on ICP-MS, comprising:

[0006] A. The phosphate solution to be tested is converted into an aerosol, and the aerosol is ionized to obtain the phosphorus characteristic ion beam of the phosphate solution to be tested;

[0007] B. Set a mass filter window according to the standard mass-to-charge ratio of phosphorus, and screen the phosphorus characteristic ion beams by mass-to-charge ratio based on the mass filter window to obtain the candidate ion stream of the phosphate solution to be tested;

[0008] C. Introduce an internal standard element of known concentration into the candidate ion stream, record the instantaneous response intensity ratio of the internal standard element to phosphorus element in real time, construct a dynamic correction coefficient sequence based on the instantaneous response intensity ratio, and determine the median value of continuous sampling points in the dynamic correction coefficient sequence as the dynamic internal standard correction factor of the phosphate solution to be tested.

[0009] D. Based on the dynamic internal standard correction factor, the original signal intensity of phosphorus in the candidate ion flow is weighted and compensated in real time to obtain the phosphorus signal intensity sequence of the phosphate solution to be tested;

[0010] E. Map and invert the phosphorus signal intensity sequence to obtain the phosphate ion concentration value of the phosphate solution to be tested, and perform robust statistical processing on the phosphate ion concentration value to obtain the final trace detection result of the phosphate solution to be tested.

[0011] In a preferred embodiment, the step of converting the phosphate solution to be tested into an aerosol and ionizing the aerosol to obtain the phosphorus characteristic ion beam of the phosphate solution to be tested includes:

[0012] The phosphate solution to be tested is converted into an aerosol by an atomizer, and the aerosol is ionized to obtain discrete signal segments of the phosphate solution to be tested.

[0013] Background noise is evaluated on the discrete signal segment, and continuous data intervals with signal strength higher than the background noise threshold are extracted to obtain the effective signal interval of the discrete signal segment;

[0014] Within the effective signal range, the characteristic signal peak of phosphorus is identified, and the ratio of the peak area to the peak height of the characteristic signal peak is used as the phosphorus ion beam intensity characterization value of the discrete signal segment.

[0015] Based on the phosphorus ion beam intensity characterization value, the effective signal range is calibrated by mass axis to obtain the phosphorus characteristic ion beam of the phosphate solution to be tested.

[0016] In a preferred embodiment, the step of setting a mass filter window based on the standard mass-to-charge ratio of phosphorus, and screening the phosphorus characteristic ion beams by mass-to-charge ratio based on the mass filter window to obtain candidate ion currents for the phosphate solution to be tested, includes:

[0017] The measured mass-to-charge ratio of the sampling points in the phosphorus characteristic ion beam is obtained, and the deviation of the measured mass-to-charge ratio is analyzed with the standard mass-to-charge ratio of phosphorus to obtain the deviation sequence of the phosphorus characteristic ion beam.

[0018] A deviation acceptance threshold is set, and sampling points that do not exceed the deviation acceptance threshold are selected from the deviation sequence to obtain the initial set of sampling points for the phosphorus characteristic ion beam;

[0019] The measured mass-to-charge ratio values ​​in the initial sampling point set are subjected to local median smoothing to obtain the mass-to-charge ratio distribution curve of the phosphorus characteristic ion beam, and the endpoint values ​​of the continuous stable interval in the mass-to-charge ratio distribution curve are extracted.

[0020] Using the endpoint values ​​as the boundaries of the mass filtering window, the mass-to-charge ratio of the signal points in the phosphorus characteristic ion beam is determined to obtain the candidate ion current of the phosphate solution to be tested.

[0021] In a preferred embodiment, the step of introducing an internal standard element of known concentration into the candidate ion stream and recording the instantaneous response intensity ratio of the internal standard element to phosphorus element in real time includes:

[0022] Obtain the first intensity data of the internal standard element and the second intensity data of the phosphorus element simultaneously collected at the sampling time in the candidate ion flow;

[0023] The first intensity data of the internal standard element and the second intensity data of the phosphorus element are time-stamped to obtain the synchronous data pair of the candidate ion current;

[0024] The background noise of the synchronous data pair is subtracted to obtain the net internal standard intensity and net phosphorus intensity of the candidate ion current, and the ratio between the net internal standard intensity and the net phosphorus intensity is used as the instantaneous response intensity ratio of the candidate ion current.

[0025] In a preferred embodiment, the step of constructing a dynamic correction coefficient sequence based on the instantaneous response intensity ratio, and determining the median value of consecutive sampling points in the dynamic correction coefficient sequence as the dynamic internal standard correction factor for the phosphate solution to be tested, includes:

[0026] The instantaneous response intensity ratios are arranged and combined according to the sampling order to obtain the original ratio sequence of the phosphate solution to be tested;

[0027] The original ratio sequence is cleaned of outliers to obtain the cleaned ratio sequence of the phosphate solution to be tested.

[0028] The concentration normalization factor is set according to the ratio between the known concentration of the internal standard element and the standard reference concentration;

[0029] Based on the concentration normalization coefficient, the ratio sequence after washing is weighted to obtain the weighted ratio sequence of the phosphate solution to be tested;

[0030] Arrange the weighted ratio sequence in chronological order to obtain the dynamic correction coefficient sequence of the phosphate solution to be tested;

[0031] The median value of consecutive sampling points in the dynamic correction coefficient sequence is determined as the dynamic internal standard correction factor of the phosphate solution to be tested.

[0032] In a preferred embodiment, the step of performing real-time weighted compensation on the original signal intensity of phosphorus in the candidate ion current based on the dynamic internal standard correction factor to obtain the phosphorus signal intensity sequence of the phosphate solution to be tested includes:

[0033] The original signal intensity value of phosphorus in the candidate ion flow is read point by point;

[0034] The original signal intensity value is compensated and corrected according to the dynamic internal standard correction factor to obtain the compensated signal intensity value of the candidate ion current;

[0035] The compensated signal intensity values ​​are reconstructed in time sequence to obtain the phosphorus signal intensity sequence of the phosphate solution to be tested.

[0036] In a preferred embodiment, the formula for calculating the compensated signal strength value is:

[0037] ;

[0038] in, This represents the compensated signal strength value. This represents the original signal strength value. This represents the dynamic internal standard correction factor. This represents the preset instrument response drift compensation coefficient.

[0039] In a preferred embodiment, the step of mapping and inverting the phosphorus signal intensity sequence to obtain the phosphate ion concentration value of the phosphate solution to be tested includes:

[0040] Concentration inversion is performed on the signal intensity values ​​in the phosphorus signal intensity sequence to obtain a preliminary concentration sequence of the phosphate solution to be tested;

[0041] Linear interpolation is performed on the preliminary concentration sequence to obtain the concentration data sequence of the phosphate solution to be tested;

[0042] The concentration values ​​corresponding to the sampling points in the concentration data sequence are determined as the phosphate ion concentration values ​​of the phosphate solution to be tested.

[0043] In a preferred embodiment, the step of performing robust statistical processing on the phosphate ion concentration value to obtain the final trace detection result of the phosphate solution to be tested includes:

[0044] Arrange the phosphate ion concentration values ​​to obtain the phosphate ion concentration sequence of the phosphate solution to be tested, and use the median of the phosphate ion concentration sequence as the first robust estimator of the phosphate solution to be tested.

[0045] The absolute deviation between the concentration values ​​in the phosphate ion concentration sequence and the first robust estimator is statistically analyzed to obtain the absolute deviation sequence of the phosphate solution to be tested, and the median of the absolute deviation sequence is used as the scale estimator of the phosphate solution to be tested.

[0046] Dividing the absolute deviation by the scale estimate yields the standardized residual of the phosphate solution to be tested.

[0047] Based on the standardized residuals, outlier removal is performed on the phosphate ion concentration sequence to obtain the effective concentration subset of the phosphate solution to be tested.

[0048] The arithmetic mean of the effective concentration subset is used as the final trace detection result of the phosphate solution to be tested.

[0049] Compared with the prior art, the present invention has the following beneficial effects:

[0050] 1. This invention completes phosphorus signal calibration through dynamic internal standard correction and real-time weighted compensation, optimizes the detection data processing logic, significantly improves the intelligent analysis efficiency of phosphate trace detection based on ICP-MS, and ensures stable output of detection signals.

[0051] 2. This invention achieves accurate measurement of phosphate ion concentration through precise mass-to-charge ratio screening, robust statistical processing, and signal mapping inversion, effectively eliminating abnormal data interference, improving the accuracy and consistency of trace detection results, and providing reliable intelligent analysis support for trace phosphate detection. Attached Figure Description

[0052] Figure 1 This is a flowchart illustrating an intelligent analysis method for trace phosphate detection based on ICP-MS provided in an embodiment of the present invention.

[0053] The realization of the objective, functional features and advantages of the present invention will be further explained in conjunction with the embodiments and with reference to the accompanying drawings. Detailed Implementation

[0054] It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

[0055] This application provides an intelligent analysis method for trace phosphate detection based on ICP-MS. The executing entity of the intelligent analysis method for trace phosphate detection based on ICP-MS includes, but is not limited to, at least one of the following electronic devices that can be configured to execute the method provided in this application: a server, a terminal, etc. In other words, the intelligent analysis method for trace phosphate detection based on ICP-MS can be executed by software or hardware installed on a terminal device or a server device. The server includes, but is not limited to, a single server, a server cluster, a cloud server, or a cloud server cluster. The server can be an independent server or a cloud server that provides basic cloud computing services such as cloud services, cloud databases, cloud computing, cloud functions, cloud storage, network services, cloud communication, middleware services, domain name services, security services, content delivery networks (CDN), and big data and artificial intelligence platforms.

[0056] Reference Figure 1 The diagram shown is a flowchart of an intelligent analysis method for trace phosphate detection based on ICP-MS provided in an embodiment of the present invention. In this embodiment, the intelligent analysis method for trace phosphate detection based on ICP-MS includes:

[0057] A. The phosphate solution to be tested is converted into an aerosol, and the aerosol is ionized to obtain the phosphorus characteristic ion beam of the phosphate solution to be tested;

[0058] In this embodiment of the invention, the step of converting the phosphate solution to be tested into an aerosol and ionizing the aerosol to obtain the phosphorus characteristic ion beam of the phosphate solution to be tested includes:

[0059] The phosphate solution to be tested is converted into an aerosol by an atomizer, and the aerosol is ionized to obtain discrete signal segments of the phosphate solution to be tested.

[0060] Background noise is evaluated on the discrete signal segment, and continuous data intervals with signal strength higher than the background noise threshold are extracted to obtain the effective signal interval of the discrete signal segment;

[0061] Within the effective signal range, the characteristic signal peak of phosphorus is identified, and the ratio of the peak area to the peak height of the characteristic signal peak is used as the phosphorus ion beam intensity characterization value of the discrete signal segment.

[0062] Based on the phosphorus ion beam intensity characterization value, the effective signal range is calibrated by mass axis to obtain the phosphorus characteristic ion beam of the phosphate solution to be tested.

[0063] The phosphate solution to be tested is decomposed into tiny droplets by the atomization of the nebulizer. These tiny droplets form a uniform aerosol in the transmission channel. The aerosol is then ionized by the ionization device, which converts the phosphate components in the aerosol into charged ions. The charged ions are transmitted in the detection channel and form segmented electrical signal outputs, ultimately yielding discrete signal segments of the phosphate solution to be tested.

[0064] The basic signal data of discrete signal segments are collected under no-sample input conditions. The signal intensity of each data point in the discrete signal segment is compared with the basic signal data one by one to determine the background noise threshold that distinguishes effective signals from noise. The background noise threshold is determined by the 3σ method, that is, the standard deviation σ of 10 blank signals is collected, and the background noise threshold is 3σ. All data points of the discrete signal segment are traversed sequentially, and data points with signal intensity higher than the background noise threshold are selected. These data points are combined into a continuous data interval according to the order of collection. This continuous data interval is the effective signal interval of the discrete signal segment.

[0065] Within the effective signal range, the location of the signal peak is determined based on the fluctuation trajectory of the signal intensity. The characteristic signal peak belonging to phosphorus is accurately identified. The signal intensity of all data points within the characteristic signal peak range is accumulated to obtain the peak area. The signal intensity value corresponding to the highest point of the characteristic signal peak is read as the peak height. The peak area value is divided by the peak height value to obtain the corresponding ratio, which is used as the phosphorus ion beam intensity characterization value of the discrete signal segment.

[0066] Using the intensity of the phosphorus ion beam as a calibration reference, the mass-to-charge ratio position of all ion signals within the effective signal range is corrected one by one to eliminate the mass-to-charge ratio deviation generated during signal transmission and detection, so that the ion signals within the effective signal range completely match the mass-to-charge ratio characteristics of phosphorus. The ion signals after correction are the characteristic phosphorus ion beam of the phosphate solution to be tested.

[0067] The beneficial effects are that by generating standardized discrete signal segments through atomization and ionization, effective signal intervals are accurately selected and specific phosphorus ion beam intensity characterization values ​​are determined. After completing mass axis calibration, a pure and well-defined phosphorus characteristic ion beam is obtained, completely eliminating the interference of background noise on the signal, accurately locking the characteristic signal of phosphorus, providing a stable and accurate basic ion signal for subsequent trace phosphate detection, and ensuring the purity and reliability of the detection signal.

[0068] B. Set a mass filter window according to the standard mass-to-charge ratio of phosphorus, and screen the phosphorus characteristic ion beams by mass-to-charge ratio based on the mass filter window to obtain the candidate ion stream of the phosphate solution to be tested;

[0069] In this embodiment of the invention, the step of setting a mass filter window based on the standard mass-to-charge ratio of phosphorus, and screening the phosphorus characteristic ion beam by mass-to-charge ratio based on the mass filter window to obtain the candidate ion current of the phosphate solution to be tested, includes:

[0070] The measured mass-to-charge ratio of the sampling points in the phosphorus characteristic ion beam is obtained, and the deviation of the measured mass-to-charge ratio is analyzed with the standard mass-to-charge ratio of phosphorus to obtain the deviation sequence of the phosphorus characteristic ion beam.

[0071] A deviation acceptance threshold is set, and sampling points that do not exceed the deviation acceptance threshold are selected from the deviation sequence to obtain the initial set of sampling points for the phosphorus characteristic ion beam;

[0072] The measured mass-to-charge ratio values ​​in the initial sampling point set are subjected to local median smoothing to obtain the mass-to-charge ratio distribution curve of the phosphorus characteristic ion beam, and the endpoint values ​​of the continuous stable interval in the mass-to-charge ratio distribution curve are extracted.

[0073] Using the endpoint values ​​as the boundaries of the mass filtering window, the mass-to-charge ratio of the signal points in the phosphorus characteristic ion beam is determined to obtain the candidate ion current of the phosphate solution to be tested.

[0074] The measured mass-to-charge ratio values ​​of each sampling point in the phosphorus characteristic ion beam are collected sequentially. The numerical difference between the measured mass-to-charge ratio value of each sampling point and the standard mass-to-charge ratio of phosphorus is calculated. The differences calculated from all sampling points are arranged in the order of sampling. After the arrangement is completed, the deviation sequence of the phosphorus characteristic ion beam is obtained.

[0075] The deviation acceptance threshold is set to the standard mass-to-charge ratio of phosphorus ( ). 31 For P, m / z=30.97), ±0.05, all difference data in the deviation sequence are traversed one by one, and all sampling points whose difference values ​​do not exceed the deviation acceptance threshold are screened out. These screened sampling points are combined into a whole to obtain the initial sampling point set of phosphorus characteristic ion beam.

[0076] Using multiple adjacent measured mass-to-charge ratio values ​​in the initial sampling point set as a local processing unit, all measured mass-to-charge ratio values ​​within each local processing unit are extracted sequentially. The mass-to-charge ratio value at the middle position within each local processing unit is found, and this middle value replaces the original measured mass-to-charge ratio value of the corresponding local processing unit. After replacing all local processing units, the processed values ​​are connected in the sampling order to form a continuously changing curve, which is the mass-to-charge ratio distribution curve of the phosphorus characteristic ion beam. The continuous interval where the signal value remains stable is found along the mass-to-charge ratio distribution curve, and the values ​​corresponding to the start and end positions of the continuous interval are determined to obtain the endpoint values ​​of the continuous stable interval in the mass-to-charge ratio distribution curve.

[0077] The endpoint values ​​of the extracted continuous stable intervals are used as the two sides of the mass filter window. The measured mass-to-charge ratio of each signal point in the phosphorus characteristic ion beam is checked one by one to determine whether the measured mass-to-charge ratio falls within the boundary range of the mass filter window. All signal points that meet the boundary range requirements are integrated together to obtain the candidate ion current of the phosphate solution to be tested.

[0078] The beneficial effects are that the initial screening is completed by analyzing the deviation between the measured mass-to-charge ratio and the standard mass-to-charge ratio, and then the distribution of mass-to-charge ratio data is optimized by local median smoothing, the boundary of the mass filtering window is accurately determined and the signal point is assigned, effectively eliminating interference signals with excessive mass-to-charge ratio deviation, and obtaining candidate ion currents with higher purity and stability, providing a reliable data carrier for subsequent internal standard correction and signal intensity compensation.

[0079] C. Introduce an internal standard element of known concentration into the candidate ion stream, record the instantaneous response intensity ratio of the internal standard element to phosphorus element in real time, construct a dynamic correction coefficient sequence based on the instantaneous response intensity ratio, and determine the median value of continuous sampling points in the dynamic correction coefficient sequence as the dynamic internal standard correction factor of the phosphate solution to be tested.

[0080] In this embodiment of the invention, the step of introducing an internal standard element of known concentration into the candidate ion stream and recording the instantaneous response intensity ratio of the internal standard element to phosphorus element in real time includes:

[0081] Obtain the first intensity data of the internal standard element and the second intensity data of the phosphorus element simultaneously collected at the sampling time in the candidate ion flow;

[0082] The first intensity data of the internal standard element and the second intensity data of the phosphorus element are time-stamped to obtain the synchronous data pair of the candidate ion current;

[0083] The background noise of the synchronous data pair is subtracted to obtain the net internal standard intensity and net phosphorus intensity of the candidate ion current, and the ratio between the net internal standard intensity and the net phosphorus intensity is used as the instantaneous response intensity ratio of the candidate ion current.

[0084] The step of constructing a dynamic correction coefficient sequence based on the instantaneous response intensity ratio, and determining the median value of consecutive sampling points in the dynamic correction coefficient sequence as the dynamic internal standard correction factor for the phosphate solution to be tested, includes:

[0085] The instantaneous response intensity ratios are arranged and combined according to the sampling order to obtain the original ratio sequence of the phosphate solution to be tested;

[0086] The original ratio sequence is cleaned of outliers to obtain the cleaned ratio sequence of the phosphate solution to be tested.

[0087] The concentration normalization factor is set according to the ratio between the known concentration of the internal standard element and the standard reference concentration;

[0088] Based on the concentration normalization coefficient, the ratio sequence after washing is weighted to obtain the weighted ratio sequence of the phosphate solution to be tested;

[0089] Arrange the weighted ratio sequence in chronological order to obtain the dynamic correction coefficient sequence of the phosphate solution to be tested;

[0090] The median value of consecutive sampling points in the dynamic correction coefficient sequence is determined as the dynamic internal standard correction factor of the phosphate solution to be tested.

[0091] During the detection of candidate ion currents, signal data are collected synchronously at a unified sampling time. The signal intensity data corresponding to the internal standard element collected at the same sampling time is recorded as the first intensity data of the internal standard element, and the signal intensity data corresponding to the phosphorus element collected at the same sampling time is recorded as the second intensity data of the phosphorus element. Among them, germanium or indium is selected as the internal standard element, and the concentration of the internal standard element working solution is 10 μg / L.

[0092] The time stamp information corresponding to the first intensity data of the internal standard element and the second intensity data of the phosphorus element are extracted. The first intensity data of the internal standard element with completely consistent time stamp information is paired and combined with the second intensity data of the phosphorus element. After all pairings are completed, the synchronous data pairs of candidate ion currents are obtained.

[0093] The background noise intensity data of the candidate ion current under ion-free input conditions are collected. The net intensity of the internal standard of the candidate ion current is obtained by subtracting the corresponding background noise intensity data from the first intensity data of the internal standard element in the synchronous data pair. The net intensity of the phosphorus of the candidate ion current is obtained by subtracting the corresponding background noise intensity data from the second intensity data of the phosphorus element in the synchronous data pair. The value obtained by dividing the net intensity of the internal standard by the net intensity of the phosphorus is used as the instantaneous response intensity ratio of the candidate ion current.

[0094] Arrange all the calculated instantaneous response intensity ratios in the order of actual sampling. After arranging all the instantaneous response intensity ratios, the original ratio sequence of the phosphate solution to be tested is obtained.

[0095] Each value in the original ratio sequence is iterated one by one. The size relationship of multiple adjacent values ​​is compared. Values ​​that are significantly different from the surrounding values ​​are removed, and values ​​that conform to the overall trend are retained. After the removal is completed, the ratio sequence of the phosphate solution to be tested after washing is obtained.

[0096] Calculate the ratio between the known concentration of the internal standard element and the standard reference concentration, and determine a fixed value as the concentration normalization coefficient based on this ratio.

[0097] Each value in the cleaned ratio sequence is multiplied by the concentration normalization coefficient. After multiplying all values, a weighted ratio sequence of the phosphate solution to be tested is obtained.

[0098] All values ​​in the weighted ratio sequence are rearranged according to the sampling time sequence to obtain the dynamic correction coefficient sequence of the phosphate solution to be tested.

[0099] Extract all values ​​corresponding to consecutive sampling points in the dynamic correction coefficient sequence, arrange these values ​​in order of magnitude, and find the value in the middle position. This value is the dynamic internal standard correction factor of the phosphate solution to be tested.

[0100] The beneficial effects are that by synchronously acquiring and aligning with timestamps, the temporal matching of the intensity data of the internal standard element and phosphorus element is ensured. After removing the background noise, pure net intensity data is obtained and an accurate instantaneous response intensity ratio is obtained. Then, a stable dynamic correction coefficient sequence is constructed by outlier cleaning, concentration normalization weighting, and temporal sorting. The dynamic internal standard correction factor is determined by the median value of continuous sampling points, making the internal standard correction process more stable and accurate, and providing a reliable correction basis for subsequent signal intensity compensation.

[0101] D. Based on the dynamic internal standard correction factor, the original signal intensity of phosphorus in the candidate ion flow is weighted and compensated in real time to obtain the phosphorus signal intensity sequence of the phosphate solution to be tested;

[0102] In this embodiment of the invention, the step of performing real-time weighted compensation on the original signal intensity of phosphorus in the candidate ion current based on the dynamic internal standard correction factor to obtain the phosphorus signal intensity sequence of the phosphate solution to be tested includes:

[0103] The original signal intensity value of phosphorus in the candidate ion flow is read point by point;

[0104] The original signal intensity value is compensated and corrected according to the dynamic internal standard correction factor to obtain the compensated signal intensity value of the candidate ion current;

[0105] The compensated signal intensity values ​​are reconstructed in time sequence to obtain the phosphorus signal intensity sequence of the phosphate solution to be tested.

[0106] The formula for calculating the compensated signal strength value is as follows:

[0107] ;

[0108] in, This represents the compensated signal strength value. This represents the original signal strength value. This represents the dynamic internal standard correction factor. This represents the preset instrument response drift compensation coefficient.

[0109] Phosphorus signal values ​​corresponding to each sampling point in the candidate ion stream are extracted sequentially according to the sampling order. These values ​​are the original signal intensity values ​​of phosphorus in the candidate ion stream, ensuring that the original signal intensity values ​​of all sampling points are completely read.

[0110] The determined dynamic internal standard correction factor is combined with each original signal strength value for correction. The deviation and fluctuation in the original signal are offset by the dynamic internal standard correction factor. After the correction is completed, the compensated signal strength value of the corresponding sampling point is obtained.

[0111] The original signal intensity values ​​were obtained by sampling point by point from the candidate ion stream. The dynamic internal standard correction factor was determined by the median value of consecutive sampling points in the dynamic correction coefficient sequence. The dynamic correction coefficient sequence was obtained by arranging the weighted ratio sequence in chronological order. The weighted ratio sequence was obtained by weighting the cleaned ratio sequence with the concentration normalization coefficient. The cleaned ratio sequence was obtained by cleaning outliers from the original ratio sequence. The original ratio sequence was obtained by arranging and combining the instantaneous response intensity ratios in the sampling order. The instantaneous response intensity ratios were obtained by subtracting background noise from the synchronous data. The ratio between the net intensity of the internal standard and the net intensity of phosphorus is determined. The synchronous data is obtained by aligning the timestamps of the first intensity data of the internal standard element and the second intensity data of the phosphorus element, which are collected simultaneously at the sampling time in the candidate ion flow. The preset instrument response drift compensation coefficient is preset after the instrument is calibrated at the factory and adjusted in the actual detection scenario. The value range is 0.95~1.05. In this embodiment, K=1.00. The compensated signal intensity value is obtained by multiplying the original signal intensity value by the dynamic internal standard correction factor and the preset instrument response drift compensation coefficient in sequence.

[0112] This calculation process achieves real-time weighted compensation for the original phosphorus signal intensity in the candidate ion stream. Real-time weighted compensation can eliminate signal deviations caused by internal standard response fluctuations and instrument response drift. After eliminating the signal deviations, a precise and stable phosphorus signal intensity sequence of the phosphate solution to be tested can be obtained. When the original signal intensity value increases, the compensated signal intensity value increases synchronously. When the dynamic internal standard correction factor increases, the compensated signal intensity value increases synchronously. When the preset instrument response drift compensation coefficient increases, the compensated signal intensity value increases synchronously. When the original signal intensity value, dynamic internal standard correction factor, and preset instrument response drift compensation coefficient remain constant, the compensated signal intensity value remains constant.

[0113] The compensated signal intensity values ​​corresponding to all sampling points are arranged sequentially according to the original sampling time order. The independent compensated signal intensity values ​​are integrated into a continuous time series data. After the arrangement is completed, the phosphorus signal intensity sequence of the phosphate solution to be tested is obtained.

[0114] The beneficial effects are that by reading the original signal intensity values ​​point by point, the comprehensiveness of data acquisition is ensured; by using the dynamic internal standard correction factor, accurate signal compensation and correction are completed, effectively eliminating the deviation and fluctuation of the original signal; and by time-series reconstruction, a continuous and regular phosphorus signal intensity sequence is formed, providing stable and reliable signal data support for the subsequent mapping and inversion of phosphate ion concentration.

[0115] E. Map and invert the phosphorus signal intensity sequence to obtain the phosphate ion concentration value of the phosphate solution to be tested, and perform robust statistical processing on the phosphate ion concentration value to obtain the final trace detection result of the phosphate solution to be tested.

[0116] In this embodiment of the invention, the step of mapping and inverting the phosphorus signal intensity sequence to obtain the phosphate ion concentration value of the phosphate solution to be tested includes:

[0117] Concentration inversion is performed on the signal intensity values ​​in the phosphorus signal intensity sequence to obtain a preliminary concentration sequence of the phosphate solution to be tested;

[0118] Linear interpolation is performed on the preliminary concentration sequence to obtain the concentration data sequence of the phosphate solution to be tested;

[0119] The concentration values ​​corresponding to the sampling points in the concentration data sequence are determined as the phosphate ion concentration values ​​of the phosphate solution to be tested.

[0120] The robust statistical processing of the phosphate ion concentration value to obtain the final trace detection result of the phosphate solution to be tested includes:

[0121] Arrange the phosphate ion concentration values ​​to obtain the phosphate ion concentration sequence of the phosphate solution to be tested, and use the median of the phosphate ion concentration sequence as the first robust estimator of the phosphate solution to be tested.

[0122] The absolute deviation between the concentration values ​​in the phosphate ion concentration sequence and the first robust estimator is statistically analyzed to obtain the absolute deviation sequence of the phosphate solution to be tested, and the median of the absolute deviation sequence is used as the scale estimator of the phosphate solution to be tested.

[0123] Dividing the absolute deviation by the scale estimate yields the standardized residual of the phosphate solution to be tested.

[0124] Based on the standardized residuals, outlier removal is performed on the phosphate ion concentration sequence to obtain the effective concentration subset of the phosphate solution to be tested.

[0125] The arithmetic mean of the effective concentration subset is used as the final trace detection result of the phosphate solution to be tested.

[0126] Each signal intensity value in the phosphorus signal intensity sequence is converted into a concentration value according to the corresponding conversion relationship between phosphorus element signal intensity and phosphate ion concentration. All the converted concentration values ​​are combined in the original order to obtain the preliminary concentration sequence of the phosphate solution to be tested.

[0127] Between adjacent concentration values ​​in the initial concentration sequence, the concentration values ​​in each sampling interval are supplemented according to the linear change law, so that the concentration data completely covers all sampling nodes. After supplementation, a continuous and complete set of values ​​is formed, and the concentration data sequence of the phosphate solution to be tested is obtained.

[0128] Extract the concentration value corresponding to each actual sampling point in the concentration data sequence, and directly determine these values ​​as the phosphate ion concentration value of the phosphate solution to be tested.

[0129] All phosphate ion concentration values ​​are arranged in ascending order of value. After the arrangement is completed, a sequence of phosphate ion concentrations of the phosphate solution to be tested is formed. The value in the middle position of the sequence is selected as the first robust estimator of the phosphate solution to be tested.

[0130] The absolute value of the difference between each concentration value in the phosphate ion concentration sequence and the first robust estimator is calculated. All absolute values ​​are combined in their original order to obtain the absolute deviation sequence of the phosphate solution to be tested. The value in the middle position of the absolute deviation sequence is selected as the scale estimator of the phosphate solution to be tested.

[0131] Divide each absolute deviation value in the absolute deviation sequence by the scale estimate to obtain the corresponding value. Combine all the calculation results to form the standardized residual of the phosphate solution to be tested.

[0132] Phosphate ion concentration sequences are screened based on the numerical range of the standardized residuals. Concentration values ​​whose standardized residuals exceed the reasonable range are removed, and the remaining numerical combinations form the effective concentration subset of the phosphate solution to be tested.

[0133] The final trace detection result of the phosphate solution to be tested is obtained by summing all the concentration values ​​in the effective concentration subset and dividing the sum by the number of values ​​in the effective concentration subset.

[0134] The beneficial effects are that complete and accurate phosphate ion concentration values ​​are obtained through concentration inversion and linear interpolation, robust estimators and scaling estimators are constructed based on the median, outliers are accurately removed through standardized residuals, and the results are finally output as the arithmetic mean of the effective concentration subset. The entire process avoids data anomalies and fluctuations, and significantly improves the accuracy, stability and reliability of phosphate trace detection results.

[0135] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the present invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the present invention.

[0136] This application embodiment can acquire and process relevant data based on artificial intelligence technology. Artificial intelligence is the theory, method, technology, and application system that uses digital computers or machines controlled by digital computers to simulate, extend, and expand human intelligence, perceive the environment, acquire knowledge, and use that knowledge to obtain optimal results.

[0137] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims

1. An intelligent analytical method for trace phosphate detection based on ICP-MS, characterized in that, The method includes: A. The phosphate solution to be tested is converted into an aerosol, and the aerosol is ionized to obtain the phosphorus characteristic ion beam of the phosphate solution to be tested; B. Set a mass filter window according to the standard mass-to-charge ratio of phosphorus, and screen the phosphorus characteristic ion beams by mass-to-charge ratio based on the mass filter window to obtain the candidate ion stream of the phosphate solution to be tested; C. Introduce an internal standard element of known concentration into the candidate ion stream, record the instantaneous response intensity ratio of the internal standard element to phosphorus element in real time, construct a dynamic correction coefficient sequence based on the instantaneous response intensity ratio, and determine the median value of continuous sampling points in the dynamic correction coefficient sequence as the dynamic internal standard correction factor of the phosphate solution to be tested. D. Based on the dynamic internal standard correction factor, the original signal intensity of phosphorus in the candidate ion flow is weighted and compensated in real time to obtain the phosphorus signal intensity sequence of the phosphate solution to be tested; E. Map and invert the phosphorus signal intensity sequence to obtain the phosphate ion concentration value of the phosphate solution to be tested, and perform robust statistical processing on the phosphate ion concentration value to obtain the final trace detection result of the phosphate solution to be tested.

2. The intelligent analytical method for trace phosphate detection based on ICP-MS as described in claim 1, characterized in that, The step of converting the phosphate solution to be tested into an aerosol and ionizing the aerosol to obtain the phosphorus characteristic ion beam of the phosphate solution to be tested includes: The phosphate solution to be tested is converted into an aerosol by an atomizer, and the aerosol is ionized to obtain discrete signal segments of the phosphate solution to be tested. Background noise is evaluated on the discrete signal segment, and continuous data intervals with signal strength higher than the background noise threshold are extracted to obtain the effective signal interval of the discrete signal segment; Within the effective signal range, the characteristic signal peak of phosphorus is identified, and the ratio of the peak area to the peak height of the characteristic signal peak is used as the phosphorus ion beam intensity characterization value of the discrete signal segment. Based on the phosphorus ion beam intensity characterization value, the effective signal range is calibrated by mass axis to obtain the phosphorus characteristic ion beam of the phosphate solution to be tested.

3. The intelligent analytical method for trace phosphate detection based on ICP-MS as described in claim 1, characterized in that, The step of setting a mass filter window based on the standard mass-to-charge ratio of phosphorus, and then screening the phosphorus characteristic ion beams by mass-to-charge ratio based on the mass filter window to obtain candidate ion currents for the phosphate solution to be tested, includes: The measured mass-to-charge ratio of the sampling points in the phosphorus characteristic ion beam is obtained, and the deviation of the measured mass-to-charge ratio is analyzed with the standard mass-to-charge ratio of phosphorus to obtain the deviation sequence of the phosphorus characteristic ion beam. A deviation acceptance threshold is set, and sampling points that do not exceed the deviation acceptance threshold are selected from the deviation sequence to obtain the initial set of sampling points for the phosphorus characteristic ion beam; The measured mass-to-charge ratio values ​​in the initial sampling point set are subjected to local median smoothing to obtain the mass-to-charge ratio distribution curve of the phosphorus characteristic ion beam, and the endpoint values ​​of the continuous stable interval in the mass-to-charge ratio distribution curve are extracted. Using the endpoint values ​​as the boundaries of the mass filtering window, the mass-to-charge ratio of the signal points in the phosphorus characteristic ion beam is determined to obtain the candidate ion current of the phosphate solution to be tested.

4. The intelligent analytical method for trace phosphate detection based on ICP-MS as described in claim 1, characterized in that, The step of introducing an internal standard element of known concentration into the candidate ion stream and recording the instantaneous response intensity ratio of the internal standard element to phosphorus element in real time includes: Obtain the first intensity data of the internal standard element and the second intensity data of the phosphorus element simultaneously collected at the sampling time in the candidate ion flow; The first intensity data of the internal standard element and the second intensity data of the phosphorus element are time-stamped to obtain the synchronous data pair of the candidate ion current; The background noise of the synchronous data pair is subtracted to obtain the net internal standard intensity and net phosphorus intensity of the candidate ion current, and the ratio between the net internal standard intensity and the net phosphorus intensity is used as the instantaneous response intensity ratio of the candidate ion current.

5. The intelligent analytical method for trace phosphate detection based on ICP-MS as described in claim 4, characterized in that, The step of constructing a dynamic correction coefficient sequence based on the instantaneous response intensity ratio, and determining the median value of consecutive sampling points in the dynamic correction coefficient sequence as the dynamic internal standard correction factor for the phosphate solution to be tested, includes: The instantaneous response intensity ratios are arranged and combined according to the sampling order to obtain the original ratio sequence of the phosphate solution to be tested; The original ratio sequence is cleaned of outliers to obtain the cleaned ratio sequence of the phosphate solution to be tested. The concentration normalization factor is set according to the ratio between the known concentration of the internal standard element and the standard reference concentration; Based on the concentration normalization coefficient, the ratio sequence after washing is weighted to obtain the weighted ratio sequence of the phosphate solution to be tested; Arrange the weighted ratio sequence in chronological order to obtain the dynamic correction coefficient sequence of the phosphate solution to be tested; The median value of consecutive sampling points in the dynamic correction coefficient sequence is determined as the dynamic internal standard correction factor of the phosphate solution to be tested.

6. The intelligent analytical method for trace phosphate detection based on ICP-MS as described in claim 1, characterized in that, The step of performing real-time weighted compensation on the original signal intensity of phosphorus in the candidate ion current based on the dynamic internal standard correction factor to obtain the phosphorus signal intensity sequence of the phosphate solution to be tested includes: The original signal intensity value of phosphorus in the candidate ion flow is read point by point; The original signal intensity value is compensated and corrected according to the dynamic internal standard correction factor to obtain the compensated signal intensity value of the candidate ion current; The compensated signal intensity values ​​are reconstructed in time sequence to obtain the phosphorus signal intensity sequence of the phosphate solution to be tested.

7. The intelligent analytical method for trace phosphate detection based on ICP-MS as described in claim 6, characterized in that, The formula for calculating the compensated signal strength value is as follows: ; in, This represents the compensated signal strength value. This represents the original signal strength value. This represents the dynamic internal standard correction factor. This represents the preset instrument response drift compensation coefficient.

8. The intelligent analytical method for trace phosphate detection based on ICP-MS as described in claim 1, characterized in that, The process of mapping and inverting the phosphorus signal intensity sequence to obtain the phosphate ion concentration value of the phosphate solution to be tested includes: Concentration inversion is performed on the signal intensity values ​​in the phosphorus signal intensity sequence to obtain a preliminary concentration sequence of the phosphate solution to be tested; Linear interpolation is performed on the preliminary concentration sequence to obtain the concentration data sequence of the phosphate solution to be tested; The concentration values ​​corresponding to the sampling points in the concentration data sequence are determined as the phosphate ion concentration values ​​of the phosphate solution to be tested.

9. The intelligent analytical method for trace phosphate detection based on ICP-MS as described in claim 8, characterized in that, The robust statistical processing of the phosphate ion concentration value to obtain the final trace detection result of the phosphate solution to be tested includes: Arrange the phosphate ion concentration values ​​to obtain the phosphate ion concentration sequence of the phosphate solution to be tested, and use the median of the phosphate ion concentration sequence as the first robust estimator of the phosphate solution to be tested. The absolute deviation between the concentration values ​​in the phosphate ion concentration sequence and the first robust estimator is statistically analyzed to obtain the absolute deviation sequence of the phosphate solution to be tested, and the median of the absolute deviation sequence is used as the scale estimator of the phosphate solution to be tested. Dividing the absolute deviation by the scale estimate yields the standardized residual of the phosphate solution to be tested. Based on the standardized residuals, outlier removal is performed on the phosphate ion concentration sequence to obtain the effective concentration subset of the phosphate solution to be tested. The arithmetic mean of the effective concentration subset is used as the final trace detection result of the phosphate solution to be tested.

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