CN113406221B - Method for simultaneously detecting 11 common substances in water body by utilizing ion chromatography - Google Patents
Method for simultaneously detecting 11 common substances in water body by utilizing ion chromatography Download PDFInfo
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Abstract
The invention discloses a method for simultaneously detecting 11 common substances in a water body by utilizing an ion chromatography, which comprises the following steps: 1) Drawing a standard curve and calculating a regression equation; 2) Detecting a water sample to be detected, and calculating the concentration of fluoride, chloride, nitrate, sulfate, chlorite, chlorate, bromate, nitrite, dichloroacetic acid, trichloroacetic acid and glyphosate; ion chromatography parameters: column temperature is 30 ℃; the sample injection volume is 25-250 mu L; the flow rate is 1.0mL/min, and the KOH mobile phase is eluted in a gradient way: 0 to 30.00min for 8.00mmol/L, a gradient start time of 30.00min and a gradient end time of 45.00min, wherein the elution concentration of the mobile phase is increased from 8.0mmol/L to 50mmol/L,45min to 50min for 50mmol/L,50min to 55min for 8mmol/L and a gradient period of 55min.
Description
Technical Field
The invention relates to the technical field of water quality detection, in particular to a water quality detection method by an ion chromatography, and specifically relates to a method for simultaneously detecting 11 common substances in a water body by using the ion chromatography.
Background
The recommended method for detecting dichloroacetic acid and trichloroacetic acid in urban water quality standard test method (CJ/T141-2018) is to use an IonPacAS 19 (4X 250 mm) chromatographic column, an IonPacAG 19 (4X 50 mm) protective column, an ASRS 300 anion suppressor, a column temperature of 30 ℃, a suppression current of 75mA, a sample injection volume of 1.0mL, a leaching solution of potassium hydroxide solution, a leaching solution flow rate of 1.0mL/min, and a gradient leaching of 0-35min:8mmol/L;35-43min:50mmol/L;43-48min:8mmol/L, can be separated from common anions such as fluoride, chloride, nitrate, sulfate, chlorite, chlorate, bromate, nitrite, and the like.
The method conditions of the glyphosate recommended by CJ/T141-2018 are that an IonPac AS 19 (4X 250 mm) chromatographic column, an IonPac AG 19 (4X 50 mm) protective column, an ASRS 300 anion suppressor, a column temperature of 30 ℃, a suppression current of 75mA, a sample injection volume of 25 mu L, a leaching solution flow rate of 1.0mL/min, a leaching solution concentration of 30mmol/L and isocratic leaching are used. Sample pretreatment, filtration with a needle filter with a pore size of 0.45 μm, and sample introduction.
In the conventional analysis of water quality by using a hydroxide system, anions such as fluoride, chloride, nitrate, sulfate, chlorite, chlorate and the like are detected by adopting a method of isocratic leaching and micro-volume sample injection. The method comprises the steps of detecting dichloroacetic acid and trichloroacetic acid by a gradient leaching and large-volume sample injection method, detecting glyphosate by an isocratic leaching and micro-volume sample injection method, and detecting all detection items in batches under different method conditions.
With the increase of detection items in drinking water, a plurality of items to be detected are needed, the detection method and conditions are different by adopting the existing method, and the detection of all the items is needed, so that multiple operations are needed, the operation flow is complex, the working efficiency is low, and the total detection cost is high.
Disclosure of Invention
The invention aims to solve the problems and provides a method for simultaneously detecting 11 common substances in a water body by utilizing ion chromatography.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for simultaneously detecting 11 common substances in a water body by utilizing ion chromatography, wherein the 11 common substances are fluoride, chloride, nitrate, sulfate, chlorite, chlorate, bromate, nitrite, dichloroacetic acid, trichloroacetic acid and glyphosate, and the detection method comprises the following steps:
1) Preparing a mixed standard solution containing fluoride, chloride, nitrate, sulfate, chlorite, chlorate, bromate, nitrite, dichloroacetic acid, trichloroacetic acid and glyphosate by using a standard substance, drawing a standard curve, and calculating a regression equation; 2) Detecting the sample injection of the water sample to be detected, and calculating the concentration of each substance in the water sample to be detected according to the peak area of each substance in the water sample to be detected and the regression equation obtained in the step 1);
ion chromatography in step 1) and step 2) employed ion Pac AS27 (4X 250 mm) column, ion Pac AG27 (4X 50 mm) guard column; the ion chromatography working parameters are as follows: the flow rate is 1.0mL/min; column temperature is 30 ℃; the sample injection volume is 25-250 mu L; the current set point is 124mA; a conductivity detector, sample measurement time is 55min; KOH mobile phase gradient elution procedure: the initial concentration is 8.00mmol/L, the final concentration is 50.00mmol/L, the final concentration is 0 to 30.00min, the gradient starting time is 30.00min, the gradient ending time is 45.00min, the mobile phase elution concentration is increased from 8.0mmol/L to 50mmol/L, the gradient is 45min to 50min, the gradient is kept at 50mmol/L, the gradient is kept at 8mmol/L for 50min to 55min, and one gradient period is 55min.
Preferably, the suppressor is an ADRS6004mm anion suppressor.
In the technical scheme, the concentration of fluoride, chloride, nitrate, sulfate, chlorite, chlorate, bromate, nitrite, dichloroacetic acid, trichloroacetic acid and glyphosate in the mixed standard solution is respectively 0.500mg/L,50.0mg/L,5.00mg/L,100.0mg/L,1.00mg/L,1.00mg/L,0.050mg/L,0.500mg/L,0.100mg/L,0.100mg/L and 0.500mg/L; the standard curves of mass concentration and peak area were obtained by mixing 25. Mu.L, 50. Mu.L, 100. Mu.L, 150. Mu.L, 200. Mu.L and 250. Mu.L of the standard liquid were sampled respectively.
In the above method, the peak time of fluoride, chlorite, bromate, chloride, dichloroacetic acid, nitrite, chlorate, nitrate, trichloroacetic acid, sulfate and glyphosate is 6.883, 10.807, 11.840, 14.773, 17.660, 19.520, 23.533, 31.460, 37.293, 42.540 and 50.420min, respectively.
In the above technical scheme, the detection limits of the fluoride, chlorite, bromate, chloride, dichloroacetic acid, nitrite, chlorate, nitrate, trichloroacetic acid, sulfate and glyphosate are respectively 0.521ppb, 0.433 ppb,0.950ppb,0.094ppb,0.900ppb,0.444ppb, 2.284 ppb,0.931ppb,10.2ppb,0.203ppb,0.199ppb, and the lower measurement limits are respectively 2.1ppb,1.7ppb,3.8ppb,0.4ppb,3.6ppb,1.8ppb,9.2ppb,3.7ppb,40.8ppb,0.8ppb and 0.8ppb.
Preferably, the second ultrafiltration device is used for filtering before the sample injection of the water sample to be detected in the step 2), the second ultrafiltration device comprises a first ultrafiltration tank (1), a second ultrafiltration tank (2), a first sample inlet pipe (3), a second sample inlet pipe (4) and a third sample inlet pipe (5), the first sample inlet pipe (3) is communicated with the lower half bin of the first ultrafiltration tank (1) through the top end, and the bottom end is used for connecting the water sample to be detected; the bottom end of the second sampling pipe (4) is communicated with the upper half bin of the primary super filter tank (1), and the top end of the second sampling pipe is communicated with the lower half bin of the secondary super filter tank (2); the bottom end of the third sampling tube (5) is communicated with the upper half bin of the secondary ultrafiltration tank (2), and the top end of the third sampling tube is connected with an ion chromatograph sample injector; the diameters of the first sampling pipe (3), the second sampling pipe (4) and the third sampling pipe (5) are sequentially reduced, and the lower half bins of the primary super filter (1) and the secondary super filter (2) are connected with a waste liquid pipe (6);
during detection, a water sample to be detected is connected with the bottom end of the first sampling tube (3), and enters the sampler of the ion chromatograph after passing through the primary ultrafiltration tank (1) and the secondary ultrafiltration tank (2).
Preferably, the filter membrane of the primary ultrafiltration tank (1) is a 0.45 μm filter membrane, and the filter membrane of the secondary ultrafiltration tank (2) is a 0.22 μm filter membrane.
The beneficial effects of the invention are as follows: the method can be used for simultaneously detecting 11 common anions and compounds in a water sample, and each detection item can be separated and detected by using one method condition without switching the method. From experimental patterns and experimental data, fluoride, chlorite, bromate, chloride, dichloroacetic acid, nitrite, chlorate, nitrate, trichloroacetic acid, sulfate and glyphosate are detected by the method, the peak is good, each item to be detected can be well separated, and the precision and the accuracy meet the standard requirements. The batch detection is facilitated, the working time is saved, and the detection cost is reduced.
Drawings
FIG. 1 is a schematic diagram of the structure of a secondary ultrafiltration device in example 1.
FIG. 2 is a peak-to-peak diagram of 11 test substances in example 2.
FIG. 3 is a peak-to-peak diagram of 11 test substances in example 3.
Detailed Description
The invention is further illustrated, but is not limited, by the following examples.
The experimental methods in the following examples are conventional methods unless otherwise specified; the chemical reagents used, unless otherwise specified, are all conventional and commercially available.
Example 1 British blue two-stage Ultrafiltration device
At present, the blue ultrafiltration for the ion chromatograph has only one stage of ultrafiltration, but when the impurities in the sample to be detected are more, coarse particle impurities can be removed firstly, then fine filtration is carried out, and the filtration is carried out step by step in a grading way, so that the filtration is more thorough.
Therefore, the invention prepares the British blue secondary ultrafiltration device shown in figure 1, which is used for filtering the water sample to be detected step by step, and reducing impurities. The blue secondary ultrafiltration device shown in figure 1 mainly comprises a primary ultrafiltration tank 1, a secondary ultrafiltration tank 2, a first sample inlet pipe 3, a second sample inlet pipe 4 and a third sample inlet pipe 5. The first sampling tube 3 is communicated with the lower half bin of the primary ultrafiltration tank 1 through the top end, and the bottom end is used for connecting a water sample to be detected; the bottom end of the second sampling tube 4 is communicated with the upper half bin of the primary super filter 1, and the top end is communicated with the lower half bin of the secondary super filter 2; the bottom end of the third sampling tube 5 is communicated with the upper half bin of the secondary ultrafiltration tank 2, and the top end is used for being connected with an ion chromatograph sample injector; the diameters of the first sampling pipe 3, the second sampling pipe 4 and the third sampling pipe 5 are sequentially reduced, and the lower half bins of the primary ultrafiltration tank 1 and the secondary ultrafiltration tank 2 are connected with a waste liquid pipe 6; the filter membrane of the primary ultrafiltration tank 1 is a filter membrane of 0.45 mu m, and the filter membrane of the secondary ultrafiltration tank 2 is a filter membrane of 0.22 mu m. During detection, a water sample to be detected is connected with the bottom end of the first sampling tube 3, and enters the sample injector of the ion chromatograph after passing through the primary ultrafiltration tank 1 and the secondary ultrafiltration tank 2.
By adopting the British blue secondary ultrafiltration device, a water sample is filtered by a 0.45 mu m filter membrane of the primary ultrafiltration tank 1 to obtain coarse particles, and then is filtered by a 0.22 mu m filter membrane of the secondary ultrafiltration tank 2 to obtain fine particles. The diameters of the first sampling pipe 3, the second sampling pipe 4 and the third sampling pipe 5 are sequentially reduced, and the flow difference of the pipe diameters makes the filtration easier. The lower half bin of the primary super filter 1 and the secondary super filter 2 is also connected with a waste liquid pipe 6, so as to ensure enough sample injection quantity and discharge redundant water samples.
The adoption of the quartz blue secondary ultrafiltration device can omit an independent water sample pretreatment process, and the adoption of secondary filtration ensures that the filtration effect is better, the detection result is not easily affected by impurities, the detection result is more accurate, the batch detection is more facilitated, and the working time is saved.
The following examples 2 and 3 were performed by connecting the blue-in secondary ultrafiltration device of fig. 1 to an autosampler of an ion chromatograph.
EXAMPLE 2 Pre-experiment
Ion chromatography was performed using an ion PacAS27 (4X 250 mm) column, an ion PacAG27 (4X 50 mm) guard column; the ion chromatography working parameters are as follows: the flow rate is 1.0mL/min; column temperature is 30 ℃; the sample injection volume is 50 mu L; the current set point is 50mA; a conductivity detector; ADRS6004mm inhibitor; sample measurement time: for 40min; KOH flow equality 20mmol/L elution, peak times for fluoride, chlorite, bromate, chloride, dichloroacetic acid, nitrite, chlorate, nitrate, glyphosate, sulfate and trichloroacetic acid were 4.377, 6.243, 6.780, 8.250, 9.620, 10.660, 12.783, 16.823, 20.363, 21.500 and 32.577min, respectively (as shown in FIG. 2). The peak-out time of the chlorite and the bromate is about 0.54min, when the nitrite concentration in the water sample to be detected is high, the peak-out time of the chlorite and the bromate can be partially overlapped with the peak-out time of the bromate, and when the sulfate content is high, the peak-out time of the glyphosate is covered, so that the accuracy of the concentration of the chlorite, the bromate, the glyphosate and the sulfate waiting for the substance to be detected in the sample is affected.
The experiment uses gradient elution instead of isocratic elution, keeps low concentration of 8.00mmol/L elution in 0 to 30.00min, and uses a mobile phase with lower concentration to elute easily eluted fluoride, chlorite, bromate, chloride, dichloroacetic acid, nitrite and chlorate first, and the peak-off time difference between the fluoride, the chlorite, the bromate, the chloride, the dichloroacetic acid, the nitrite and the chlorate is larger than 1min, so that the fluoride, the nitrite, the chlorate can be completely separated and the fluoride, the chlorite, the chloride, the dichloroacetic acid and the nitrite can not affect each other. The elution concentration of the mobile phase is increased from 8.0mmol/L to 50mmol/L after 30.00min to 45.00min, nitrate, trichloroacetic acid and sulfate are eluted in the time period, 8mmol/L is kept for 50min to 55min, glyphosate is eluted, and the peak-out time of nitrate, trichloroacetic acid, sulfate and glyphosate is far apart, so that accurate quantification can be realized.
Example 3
1 reagents, instruments and working conditions
The required reagents: nitrogen, purity greater than or equal to 99.999%, potassium hydroxide leacheate (brand: thermo).
Instrument: semer femto Dionex Aquion-Rfic ion chromatograph, dionex AS-AP autosampler, ionPac AS27 (4×250 mm) column (Dionex, dynam America), ionPac AG27 (4×50 mm) guard column (Dionex, dynam America), ADRS6004mm suppressor (Dionex, dynam America), flow rate 1.0mL/min, column temperature 30 ℃, sample volume 25-250 μL, current set point 124mA, conductivity detector, sample measurement time 55min. The instrument test condition parameters are listed in table 1.
KOH mobile phase gradient elution procedure: the initial concentration is 8.00mmol/L, the final concentration is 50.00mmol/L, the final concentration is 0 to 30.00min, the gradient starting time is 30.00min, the gradient ending time is 45.00min, the mobile phase elution concentration is increased from 8.0mmol/L to 50mmol/L, the gradient is 45min to 50min, the gradient is kept at 50mmol/L, the gradient is kept at 8mmol/L for 50min to 55min, and one gradient period is 55min.
Experimental water: ultrapure water produced by a Millipore ultrapure water machine has a resistivity of 18.2 M.OMEGA.cm.
Table 1 instrument detection condition parameters
Standard substance: fluoride, bromate, chloride and chlorate concentrations are 1000mg/L, chlorite and nitrite standard concentrations are 100mg/L, nitrate concentrations are 500mg/L, and sulfate is 5000mg/L, all purchased from the institute of environmental protection agency standard samples; the concentration of trichloroacetic acid is 1000mg/L, and the concentration of glyphosate is 100mg/L, which are all purchased from Beijing altar ink quality inspection technology Co., ltd; the concentration of dichloroacetic acid was 1000mg/L, purchased from Beijing coast HongMong standards materials technology Co., ltd. The matrix of each standard is pure water except that the matrix of dichloroacetic acid and trichloroacetic acid is methanol.
The working condition of the invention is as follows: ion Pac AS27 (4X 250 mm) column; ion Pac AG27 (4X 50 mm) guard column; the flow rate is 1.0mL/min; column temperature is 30 ℃; the sample injection volume is 25-250 mu L; the current is 124mA; ADRS6004mm inhibitor; gradient leaching; the measurement time is 55min; and (3) sampling each detection item once, separating and detecting, and switching the method conditions. Wherein the fluoride (F) - ) Chlorite (ClO) 2 - ) Bromates (BrO) 3 - ) Chloride (Cl) - ) Dichloroacetic acid (DCA), nitrite (NO) 2 - ) Chlorate (ClO) 3 - ) Nitrate (NO) 3 - ) Trichloroacetic acid (TCA), sulfate (SO) 4 2- ) And the peak-to-peak time of the glyphosate (CGL) is 6.883, 10.807, 11.840, 14.773, 17.660, 19.520, 23.533, 31.460, 37.293, 42.540 and 50.420min respectively, and the peak-to-peak of each component is shown in figure 3, so that the peak-to-peak shapes are good, the peak-to-peak shapes can be well separated, and the peak-to-peak interference is avoided.
2 detection method
2.1 drawing of Standard Curve and determination of sample injection volume
Standard curves were prepared and sample volumes were determined according to "sanitary Standard for Drinking Water" (GB 5749-2006) with a limit of 0.05mg/L for dichloroacetic acid, a limit of 0.1mg/L for trichloroacetic acid, a limit of 0.7mg/L for glyphosate, a limit of 0.01mg/L for bromate (when ozone is used), a limit of 0.7mg/L for chlorite (when chlorine dioxide is used), a limit of 0.7mg/L for chlorate (when composite chlorine dioxide is used), and the approximate concentrations of each substance in a body of water.
And respectively sucking 1.00mL of standard fluoride, bromate, dichloroacetic acid, chlorate and trichloroacetic acid, respectively diluting 2.00mL of glyphosate with ultrapure water to 100mL volumetric flasks, and preparing into medium stock solutions with fluoride, bromate, dichloroacetic acid, chlorate and trichloroacetic acid concentration of 10.0mg/L and glyphosate concentration of 2.00 mg/L. The fluoride, bromate, dichloroacetic acid, chlorate, trichloroacetic acid and glyphosate are respectively absorbed in 2.5mL, 0.25mL, 0.5mL, 5.0mL, 0.5mL and 12.5mL, and the standard substances of chloride, nitrate, sulfate, chlorite and nitrite are respectively absorbed in 2.5mL, 0.50mL, 1.0mL, 0.5mL and 0.25mL, and are added into a volumetric flask and diluted to constant volume to 50.0mL, so as to prepare mixed standard solutions of fluoride, chloride, nitrate, sulfate, chlorite, chlorate, bromate, nitrite, dichloroacetic acid, trichloroacetic acid and glyphosate with the concentration of 0.500mg/L,50.0mg/L,5.00mg/L,100.0mg/L,1.00mg/L, 0.050mg/L, 0.100mg/L and 0.500mg/L respectively. The trace amount of matrix methanol in the standard substances of dichloroacetic acid and trichloroacetic acid does not interfere with the detection of the sample. The standard curves of mass concentration and peak area were obtained by injecting 25. Mu.L, 50. Mu.L, 100. Mu.L, 150. Mu.L, 200. Mu.L and 250. Mu.L of the mixed standard solution, respectively, and the curve equation and correlation coefficient are shown in Table 2.
TABLE 2 working curves of 11 test substances
2.2 detection Limit of the method
The concentrations of fluoride, chlorite, bromate, chloride, dichloroacetic acid, nitrite, chlorate, nitrate, trichloroacetic acid, sulfate and glyphosate were 0.010mg/L,0.020mg/L,0.010mg/L,0.010mg/L, 0.020mg/L,0.020mg/L, 0.020mg/L,0.010mg/L,0.010mg/L,0.100mg/L,0.050mg/L, and the detection limits of the respective detection items were 0.521ppb, 0.438 ppb,0.094ppb,0.900ppb,0.444ppb, 2.284 ppb, 10.203ppb, 0.199ppb ppb, and the lower limit was 2.1ppb,1.7, 3.4, 3.8, 0.8ppb, and the lower limit was 2.1, 3.8ppb, and the lower limit was calculated from the signal-to-noise ratio (S/N) of the instrument.
TABLE 3 detection limits and measurement lower limits of 11 detection substances
| Detecting items | F - | ClO 2 - | B r O 3 - | Cl - | DCA | NO 2 - | ClO 3 - | NO 3 - | TCA | SO 4 2- | CGL |
| Concentration (mg/L) | 0.010 | 0.020 | 0.010 | 0.010 | 0.010 | 0.020 | 0.020 | 0.010 | 0.010 | 0.100 | 0.050 |
| S/N (mean value) | 57.6 | 137.7 | 31.6 | 320.3 | 33.3 | 135.1 | 26.2 | 32.2 | 2.9 | 1478.6 | 753.7 |
| Detection limit (ppb) | 0.521 | 0.436 | 0.950 | 0.094 | 0.900 | 0.444 | 2.294 | 0.931 | 10.2 | 0.203 | 0.199 |
| Lower limit of measurement (ppb) | 2.1 | 1.7 | 3.8 | 0.4 | 3.6 | 1.8 | 9.2 | 3.7 | 40.8 | 0.8 | 0.8 |
2.3 precision and accuracy
The concentrations of fluoride, chlorite, bromate, chloride, dichloroacetic acid, nitrite, chlorate, nitrate, trichloroacetic acid, sulfate and glyphosate were 0.010mg/L,0.020mg/L,0.010mg/L,0.010mg/L, 0.020mg/L,0.020mg/L, 0.020mg/L,0.010mg/L,0.010mg/L,0.010mg/L, 0.100mg/L,0.050mg/L, respectively, were prepared using the standard substance, and the measurement was repeated 7 times, and the precision of the measurement results was calculated, and the results are shown in Table 4.
The ultrapure water and the factory water were recovered by labeling and measured in parallel for 5 times, and the labeling recovery rate was calculated, and the results are shown in Table 5.
TABLE 4 precision of low concentration of 11 detection substances
TABLE 5 accuracy of measurement results of 11 detection substances
In summary, as can be seen from the experimental data in fig. 3 and tables 2-5, the method for detecting fluoride, chlorite, bromate, chloride, dichloroacetic acid, nitrite, chlorate, nitrate, trichloroacetic acid, sulfate and glyphosate has good peak-to-peak shape, each item to be detected can be well separated, and the precision and accuracy can meet the requirements.
Claims (2)
1. A method for simultaneously detecting 11 common substances in a water body by utilizing ion chromatography is characterized by comprising the following steps of: the 11 common substances are fluoride, chloride, nitrate, sulfate, chlorite, chlorate, bromate, nitrite, dichloroacetic acid, trichloroacetic acid and glyphosate, and the detection method comprises the following steps:
1) Preparing a mixed standard solution containing fluoride, chloride, nitrate, sulfate, chlorite, chlorate, bromate, nitrite, dichloroacetic acid, trichloroacetic acid and glyphosate by using a standard substance; the concentration of fluoride, chloride, nitrate, sulfate, chlorite, chlorate, bromate, nitrite, dichloroacetic acid, trichloroacetic acid and glyphosate in the mixed standard solution is respectively 0.500mg/L,50.0mg/L,5.00mg/L,100.0mg/L,1.00mg/L,1.00mg/L,0.050mg/L,0.500mg/L,0.100mg/L,0.100mg/L and 0.500mg/L; mixing standard liquids of 25 mu L,50 mu L,100 mu L, 150 mu L, 200 mu L and 250 mu L to obtain standard curves of mass concentration and peak area, and calculating a regression equation;
2) Detecting the sample injection of the water sample to be detected, and calculating the concentration of each substance in the water sample to be detected according to the peak area of each substance in the water sample to be detected and the regression equation obtained in the step 1);
the method comprises the steps that in the step 2), a secondary ultrafiltration device is used for filtering before sample injection of a water sample to be detected, the secondary ultrafiltration device comprises a primary ultrafiltration tank (1), a secondary ultrafiltration tank (2), a first sample inlet pipe (3), a second sample inlet pipe (4) and a third sample inlet pipe (5), the first sample inlet pipe (3) is communicated with the lower half bin of the primary ultrafiltration tank (1) through the top end, and the bottom end is used for connecting the water sample to be detected; the bottom end of the second sampling pipe (4) is communicated with the upper half bin of the primary super filter tank (1), and the top end of the second sampling pipe is communicated with the lower half bin of the secondary super filter tank (2); the bottom end of the third sampling tube (5) is communicated with the upper half bin of the secondary ultrafiltration tank (2), and the top end of the third sampling tube is connected with an ion chromatograph sample injector; the diameters of the first sampling pipe (3), the second sampling pipe (4) and the third sampling pipe (5) are sequentially reduced, and the lower half bins of the primary super filter (1) and the secondary super filter (2) are connected with a waste liquid pipe (6); during detection, a water sample to be detected is connected with the bottom end of a first sampling tube (3), and enters a sample injector of an ion chromatograph after passing through a primary ultrafiltration tank (1) and a secondary ultrafiltration tank (2);
the ion chromatography in the step 1) and the step 2) adopts an IonPacAS27 chromatographic column and an IonPacAG27 protective column; the ion chromatography working parameters are as follows: the flow rate is 1.0mL/min; column temperature is 30 ℃; the sample injection volume is 25-250 mu L; the current set point is 124mA; conductivity detector, sample measurement time: 55min; KOH mobile phase gradient elution procedure: initial concentration 8.00mmol/L, final concentration 50.00mmol/L, holding 8.00mmol/L for 0 to 30.00min, gradient start time 30.00min, end time 45.00min, mobile phase elution concentration rising from 8.0mmol/L to 50mmol/L for 45 to 50min, holding 50mmol/L, holding 8mmol/L for 50 to 55min, one gradient period being 55min;
the suppressor is an ADRS6004mm anion suppressor;
in the method, peak-off times of fluoride, chlorite, bromate, chloride, dichloroacetic acid, nitrite, chlorate, nitrate, trichloroacetic acid, sulfate and glyphosate are 6.883, 10.807, 11.840, 14.773, 17.660, 19.520, 23.533, 31.460, 37.293, 42.540 and 50.420min respectively; the detection limits of the fluoride, chlorite, bromate, chloride, dichloroacetic acid, nitrite, chlorate, nitrate, trichloroacetic acid, sulfate and glyphosate are respectively 0.521ppb, 0.433 ppb,0.950ppb,0.094ppb,0.900ppb,0.444ppb,2.294ppb,0.931ppb,10.2ppb,0.203ppb and 0.199ppb, and the lower measurement limits are respectively 2.1ppb,1.7ppb,3.8ppb,0.4ppb,3.6ppb,1.8ppb,9.2ppb,3.7ppb,40.8ppb,0.8ppb and 0.8ppb.
2. The method of claim 1, wherein: the filter membrane of the primary ultrafiltration tank (1) is a filter membrane with the diameter of 0.45 mu m, and the filter membrane of the secondary ultrafiltration tank (2) is a filter membrane with the diameter of 0.22 mu m.
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