CN114200073A - Ion chromatography detection method for soluble fluoride, bromide and sulfate - Google Patents
Ion chromatography detection method for soluble fluoride, bromide and sulfate Download PDFInfo
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- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 title claims abstract description 66
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 title claims abstract description 45
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/96—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation using ion-exchange
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- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
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Abstract
The invention discloses an ion chromatography detection method of soluble fluoride, bromide and sulfate, which comprises the following steps: preparing and pretreating a soil sample to obtain a test sample; respectively preparing a fluorine ion standard solution, a bromine ion standard solution and a sulfate ion standard solution, and testing on a hydrophilic anion chromatographic column by taking sodium hydroxide as leacheate to respectively obtain standard curve spectrograms of the fluorine ions, the bromine ions and the sulfate ions in the fluorine ion standard solution, the bromine ion standard solution and the sulfate ion standard solution; and (4) taking the test sample, and obtaining the concentrations of the fluorine ions, the bromine ions and the sulfate ions in the soil sample by adopting a standard curve method. The method can quickly and accurately detect the contents of fluoride, bromide and sulfate in the soil and shorten the retention time.
Description
Technical Field
The invention belongs to the technical field of ion chromatography detection, and particularly relates to an ion chromatography detection method for soluble fluoride, bromide and sulfate.
Background
The content of fluorine in the soil is abnormal, and the health of people is often endangered through a food chain, and the data show that the content of fluorine in a human body is about 2.6g, the daily requirement is 1mg, and the daily fluorine intake of people is not more than 3mg according to the standard provided by the world health organization. The fluorine taken by human bodies in daily life is from tea, meat, fruits, vegetables and the like, the fluorine in the human bodies is mainly distributed in bones and teeth, and a proper amount of fluorine can promote the health of the teeth and the calcification of the bones, so that an acid-resistant fluorapatite protective layer is formed outside the teeth, and the hardness and the acid-resistant capability of the teeth are enhanced. While the deficiency of fluorine is easy to cause tooth decay, bone deformation, anemia and other symptoms, and the excess of fluorine is easy to cause dental fluorosis and fluorosis, and the symptoms of muscular atrophy, limb deformation and the like are caused.
The bromine in the soil enters the human body through the action of a food chain, and the content of the bromine in the soil directly influences the content of the bromine in crops, underground water and surface water. The possibility of the esophagus cancer, cervical cancer, liver cancer, nasopharyngeal cancer and other cancers is increased by drinking water containing bromine or eating crops with high bromine content for a long time.
Sulfate is often present in drinking water, and its main source is sulfate of formation minerals, which is mostly present in the form of calcium sulfate and magnesium sulfate. Dissolution of gypsum and other sulfate deposits, seawater intrusion, oxidation of sulfites and thiosulfates and the like in fully aerated ground water, and sulfate content in drinking water can be increased by domestic sewage, fertilizers, sour geothermal water, mine wastewater, tanning, industrial wastewater using sulfate or sulfuric acid in paper manufacturing, and the like.
The environment has a plurality of metal ions which can be combined with sulfate radicals into stable sulfate, and the most main physiological reflection of a human body after a large amount of sulfate is diarrhea, dehydration and gastrointestinal tract disorder; aerosol formed by sulfate in the atmosphere has the corrosion and damage effects on materials, harms the health of animals and plants, can play a catalytic role, and aggravates the toxicity of sulfuric acid mist; after the sulfate reaches the ground along with the rainfall, the sulfate can damage the soil structure, reduce the soil fertility and also have adverse effect on a water system.
The existence of fluoride, bromide and sulfate is detected under a chromatographic column, and the leacheate is sodium carbonate-sodium bicarbonate, so that the detection is long in time consumption and inconvenient to operate.
Disclosure of Invention
The invention aims to provide an ion chromatography detection method for soluble fluoride, bromide and sulfate, which can quickly and accurately detect the content of the fluoride, the bromide and the sulfate in soil and shorten the retention time.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the ion chromatography detection method of soluble fluoride, bromide and sulfate is characterized by comprising the following steps:
preparing and pretreating a soil sample to obtain a test sample;
respectively preparing a fluorine ion standard solution, a bromine ion standard solution and a sulfate ion standard solution, and testing on a hydrophilic anion chromatographic column by taking sodium hydroxide as leacheate to respectively obtain standard curve spectrograms of the fluorine ions, the bromine ions and the sulfate ions in the fluorine ion standard solution, the bromine ion standard solution and the sulfate ion standard solution;
and (4) taking the test sample, and obtaining the concentrations of the fluorine ions, the bromine ions and the sulfate ions in the soil sample by adopting a standard curve method.
And further, testing the test sample on a hydrophilic anion chromatographic column by using sodium hydroxide as an eluent to obtain a standard curve spectrogram of the fluoride ions, the bromide ions and the sulfate ions in the test sample, and further obtaining the concentrations of the fluoride ions, the bromide ions and the sulfate ions in the soil sample.
Further, chromatographic conditions: a chromatographic column: SH-AC-3 anion 4.0 x 250mm, eluent concentration: sodium hydroxide 15mmol/L, flow rate: 1.0mL/min, column oven: 35 ℃, sample introduction: 30 μ L.
Further, the concentration calculation formula of the fluoride ions, bromide ions and sulfate ions in the soil sample is as follows:
wherein M is the content of anions in the sample, H is the peak height of the anions in the sample, and H0The anion peak height of a blank sample is shown, a is the intercept of a linear regression equation, b is the slope of the linear regression equation, f is the dilution multiple of the sample, and V is the sample weighing capacity.
Further, the method also comprises the steps of precision and repeatability detection.
The invention has the technical effects that:
the method can quickly and accurately detect the contents of fluoride, bromide and sulfate in the soil, is a practical and reliable detection method with strong operability, and can meet the detection requirements of mass production and scientific research.
(1) The invention adopts a simple and convenient pretreatment method, and uses a leacheate for the first time: sodium hydroxide, in SH-AC-3 (anion) 4.0 x 250mm chromatographic column under rapid accurate separation.
(2) The method greatly shortens retention time, saves time cost, has reasonable degree of separation, accurate test result, good linearity, reasonable and effective sample recovery rate, RSD less than 2%, relative error less than 8% and low detection limit of ion chromatography.
The invention has the advantages of shortening the detection time, reducing the cost, quickly, effectively and accurately measuring the concentration by detecting the soluble anions in the soil and the solid wastes, and meeting the requirements of quick detection and scientific research in mass production.
Drawings
FIG. 1 is a graph of a standard curve of fluoride ion in the present invention;
FIG. 2 is a spectrum of a standard curve of bromide ions in the present invention;
FIG. 3 is a standard curve spectrum of sulfate ions in the present invention;
FIG. 4 is a standard spectrum of the present invention with the concentration of 0.5mg/L of fluoride ion, 0.5mg/L of bromide ion, and 20.0mg/L of sulfate ion.
Detailed Description
The following description sufficiently illustrates specific embodiments of the invention to enable those skilled in the art to practice and reproduce it.
The instruments and reagents used in the invention:
Milli-Q Advantage A10 model ultrapure water unit (Millipore, USA); JC-TP electronic balance (minimum weight of 0.01mg, Qingdao Jinghong Licheng); ion chromatograph CIC-D100 (Ohiowa, Inc., Qingdao); an anion suppressor type SHY-a-6 (young island hehan ltd); a conductance detector; SH-AC-3 hydrophilic anion chromatographic column; HW-2000 chromatographic workstation.
The standard substance for analyzing the components of fluoride ions, bromide ions and sulfate ions in water is 60mg/L (national defense science and technology industry applies a first-level chemical metering station); sodium hydroxide (guaranteed reagent, Tianjin, Daloco chemical reagent works).
The ion chromatography detection method of soluble fluoride, bromide and sulfate specifically comprises the following steps:
step 1: preparing and pretreating a soil sample to obtain a test sample;
and (3) putting the soil sample into a muffle furnace for drying, cooling for 20 minutes, crushing to 20 meshes by using a sample crusher, and filtering. Weighing 2 g of crushed sample powder, putting the crushed sample powder into a 100mL centrifuge tube, adding 60mL of ultrapure water for centrifugation, setting the centrifuge for 15 minutes at a rotating speed of 3000 rpm, and taking supernatant to obtain a test sample after centrifugation.
Step 2: respectively preparing a fluorine ion standard solution, a bromine ion standard solution and a sulfate ion standard solution; sodium hydroxide is used as leacheate to test on a hydrophilic anion chromatographic column, and standard curve spectrograms of fluorine ions, bromine ions and sulfate ions in a fluorine ion standard solution, a bromine ion standard solution and a sulfate ion standard solution are respectively obtained;
the preparation concentrations are respectively as follows: 0.1mg/L, 0.2mg/L, 0.5mg/L, 1.0mg/L, 2.0mg/L, 3.0mg/L of a fluoride ion standard solution;
the preparation concentrations are respectively as follows: 0.1mg/L, 0.2mg/L, 0.5mg/L, 1.0mg/L, 2.0mg/L, 3.0mg/L of bromide ion standard solution;
the preparation concentrations are respectively as follows: 2.0mg/L, 4.0mg/L, 10.0mg/L, 20.0mg/L, 40.0mg/L, 60.0mg/L of sulfate ion standard solution.
The chromatographic conditions are optimized for testing, and are as follows:
a. a chromatographic column: SH-AC-3 (anionic) 4.0 x 250mm
b. Concentration of the leacheate: sodium hydroxide 15mmol/L
c. Flow rate: 1.0mL/min
d. Column oven: 35 deg.C
e. Sample introduction amount: 30 μ L.
The anion retention time can be shortened by using sodium hydroxide (15mmol/L) as the eluent, wherein the retention time of fluorine ions is 3.693 minutes, the retention time of bromine ions is 6.943 minutes, and the retention time of sulfate ions is 12.080 minutes.
A common eluent in the art is sodium carbonate + sodium bicarbonate on an SH-AC-3 (anionic) 4.0 x 250mm column. The SH-AC-3 anion chromatographic column is a hydrophilic anion chromatographic column, and a high molecular polymeric structure, an alkyl quaternary amine matrix and a carbonate separation system are grafted on the surface of the hydrophilic anion chromatographic column, so that the chromatographic column cannot be damaged by using a sodium carbonate + sodium bicarbonate system. 1 mmol/L: in 2.4mmol/L sodium bicarbonate and sodium carbonate leacheate, the retention time of fluoride ions is 4.490 minutes, the retention time of bromide ions is 11.647 minutes, and the retention time of sulfate ions is 35.250 minutes.
The invention uses an eluent: sodium hydroxide, in SH-AC-3 (anion) 4.0 x 250mm chromatographic column under rapid accurate separation. The ion exchange resin with low exchange capacity is used to separate ions and is widely applied in ion chromatography, the main filler type is organic ion exchange resin, styrene-divinylbenzene copolymer is used as a framework, sulfonic groups are introduced to benzene rings to form strong acid type cation exchange resin, tertiary amine groups are introduced to form quaternary amine type strong base anion exchange resin, the exchange resin has a physical structure of a macroporous or thin shell type or porous surface layer type so as to rapidly reach exchange balance, the ion exchange resin can be used in any pH range due to acid and alkali resistance, is easy to regenerate and treat, has long service life, and does not pollute the use of sodium hydroxide as eluent and does not reduce column efficiency. Sodium hydroxide is used as the leacheate, and the product for inhibiting the reaction is water, so that the background conductivity value of the leacheate is low, the negative peak of water can be reduced, and the retention time can be shortened. The fluoride retention time was 3.693 minutes, the bromide retention time was 6.943 minutes, and the sulfate retention time was 12.080 minutes.
The standard curve equation of the measured fluorine ions is as follows: y is 3.04e +006x, and the correlation coefficient is: 0.9991, detection limit is: 0.0004 mg/L.
FIG. 1 shows a standard curve spectrum of fluorine ions in the present invention.
In the figure, Y is 3.04e +006x and r is 0.9991, which is a linear equation and a correlation coefficient, and shows that the standard curve of the configuration of the sodium hydroxide as the leacheate is good in linearity and the measurement result is accurate and reliable.
The standard curve equation of the measured bromide ions is as follows: y3.999 e +005x, the correlation coefficient is: 0.9999, detection limit: 0.0059 mg/L.
FIG. 2 shows a standard curve spectrum of bromide ions in the present invention.
In the figure, Y is 3.999e +005x is a linear equation, r is 0.9999 is a correlation coefficient, which shows that the standard curve prepared by using sodium hydroxide as the leacheate has good linearity and the measurement result is accurate and reliable.
The standard curve equation of the sulfate ions is as follows: y is 2.73e +005x, and the correlation coefficient is: 0.9995, detection limit: 0.0096 mg/L.
FIG. 3 shows the standard curve spectrum of sulfate ion in the present invention.
In the figure, Y is 2.73e +005x and r is 0.9995 is a correlation coefficient, which shows that the standard curve prepared by using sodium hydroxide as the leacheate has good linearity and the measurement result is accurate and reliable.
And step 3: and (4) taking the test sample, and obtaining the concentrations of the fluorine ions, the bromine ions and the sulfate ions in the soil sample by adopting a standard curve method.
And (3) testing the test sample on a hydrophilic anion chromatographic column by using sodium hydroxide as leacheate to obtain a standard curve spectrogram of the fluoride ions, bromide ions and sulfate ions in the test sample, and obtaining the concentrations of the fluoride ions, the bromide ions and the sulfate ions in the soil sample.
Sodium carbonate and sodium bicarbonate are used as leacheate in an SH-AC-3 chromatographic column, so that negative peak interference of water occurs, and accurate determination of fluorine ions is influenced. Sodium hydroxide is used as leacheate, a product after inhibition is water, background conductivity is much lower than that of a carbonate system, and relative noise is low. The leacheate is used for diluting the sample at one time, so that the influence of the negative peak of water can be reduced, and the accuracy and reliability of data can be ensured. Under the condition of optimal leaching, technical indexes such as standard curves, detection limits, precision, accuracy and the like of anions all meet the relevant requirements of the method, and obviously, the SH-AC-3 can select sodium hydroxide as the leaching solution.
(1) And testing a sample: taking 30 mu L of supernatant liquor, and testing on a machine;
(2) and spectrogram processing: the concentration of each soluble anion (fluoride, bromide, sulfate) was calculated using a standard curve method.
When the component content in the sample is determined, a chromatogram is drawn under the same chromatographic conditions as the standard curve is drawn, the chromatographic peak area or peak height is measured, and then the concentration of the component in the sample injected into the chromatographic column is directly checked out on the standard curve according to the peak area and the peak height.
As shown in FIG. 4, the standard spectrum of the present invention is 0.5mg/L fluoride ion, 0.5mg/L bromide ion, and 20.0mg/L sulfate ion.
(3) And calculating formula: the content of fluoride, bromide and sulfate in the soil is calculated by the formula (1):
in the formula:
m-content of anions in the sample, mg/kg;
h-peak height of anion in sample;
H0-the anion peak height of the blank;
a-intercept of the linear regression equation;
b-the slope of the linear regression equation;
f-dilution factor of the sample;
v-sample weighing, g.
And 4, step 4: and (5) detecting the precision and repeatability.
a. Precision experiment
The fluorine ion concentration is 1.00mg/L, the bromine ion concentration is 1.00mg/L, the sulfate ion concentration is 20.0mg/L, and continuous sample introduction is carried out for six times through an ion chromatograph, and the result shows that the instrument precision is good, the repeatability is stable, the calculated concentration RSD is 1.21-2.81%, and the peak height RSD is 1.15-2.12%.
Under chromatographic conditions, test samples were prepared at different concentrations with experimental ultrapure water, and the measurements were repeated for the test samples at different concentrations.
b. And (4) pretreatment of a test sample.
The low, medium and high three test samples with different concentrations are used for the labeling test, and each test sample is continuously measured for 6 times, and the low-concentration anion F-、Br-、SO4 2-Ions are 0.2mg/L, 0.1mg/L and 2.0mg/L respectively, and the anion F has medium concentration-、Br-、SO4 2-Ions of 0.5mg/L, 0.5mg/L and 10.0mg/L, respectively, and a high concentration of anion F-、Br-、SO4 2-The ions are respectively 3.0mg/L, 3.0mg/L and 60.0mg/L, and the average content, relative error and relative standard deviation are as follows:
c. and (5) detecting the test sample.
The sample is subjected to the pretreatment and the machine test, the result is measured for six times, the average value is obtained, and the calculation is as follows:
d. the recovery of the sample was tested on a standard addition.
The normalized recovery was calculated from the test samples by adding the normalized amount and the actual measured content as follows:
according to HW-2000 chromatographic workstation software, the fluorine ion separation degree is 5.62, the bromine ion separation degree is 2.05, the peak separation degree represents the separation degree of two adjacent peaks, the larger R is, the better the two adjacent components are separated, no other peak appears behind sulfate ions, and the peak separation degree is not calculated. Wherein the concentration RSD is 1.21-2.81%, the peak height RSD is 1.15-2.12%, the relative standard deviation of fluorine ions is 0.88-1.39%, the relative standard deviation of bromine ions is 1.06-1.69%, the relative standard deviation of sulfate ions is 0.10-1.54%, the recovery rate of fluorine ions is 101.5-104.25%, the recovery rate of bromine ions is 95.5-106.5%, and the recovery rate of sulfate ions is 97.5-101.5%.
The above examples are intended to be illustrative of the present invention and not to be limiting thereof, and various changes and modifications may be made by those skilled in the relevant art without departing from the scope of the invention. The terminology used herein is for the purpose of description and illustration, rather than of limitation. As the present invention may be embodied in several forms without departing from the spirit or essential characteristics thereof, it should also be understood that the above-described embodiments are not limited by any of the details of the foregoing description, but rather should be construed broadly within its spirit and scope as defined in the appended claims.
Claims (5)
1. An ion chromatography detection method for soluble fluoride, bromide and sulfate is characterized by comprising the following steps:
preparing and pretreating a soil sample to obtain a test sample;
respectively preparing a fluorine ion standard solution, a bromine ion standard solution and a sulfate ion standard solution, and testing on a hydrophilic anion chromatographic column by taking sodium hydroxide as leacheate to respectively obtain standard curve spectrograms of the fluorine ions, the bromine ions and the sulfate ions in the fluorine ion standard solution, the bromine ion standard solution and the sulfate ion standard solution;
and (4) taking the test sample, and obtaining the concentrations of the fluorine ions, the bromine ions and the sulfate ions in the soil sample by adopting a standard curve method.
2. The method for ion chromatographic detection of soluble fluoride, bromide and sulfate according to claim 1, wherein sodium hydroxide is used as eluent to test a test sample on a hydrophilic anion chromatographic column to obtain a standard curve spectrogram of fluoride ions, bromide ions and sulfate ions in the test sample, and further obtain the concentrations of the fluoride ions, the bromide ions and the sulfate ions in the soil sample.
3. The method for ion chromatographic detection of soluble fluoride, bromide, sulfate according to claim 1, wherein the chromatographic conditions are: a chromatographic column: SH-AC-3 anion 4.0 x 250mm, eluent concentration: sodium hydroxide 15mmol/L, flow rate: 1.0mL/min, column oven: 35 ℃, sample introduction: 30 μ L.
4. The method for ion chromatographic detection of soluble fluoride, bromide and sulfate according to claim 1, wherein the concentration of fluoride, bromide and sulfate in the soil sample is calculated by the formula:
wherein M is the content of anions in the sample, H is the peak height of the anions in the sample, and H0The anion peak height of a blank sample is shown, a is the intercept of a linear regression equation, b is the slope of the linear regression equation, f is the dilution multiple of the sample, and V is the sample weighing capacity.
5. The method for ion chromatographic detection of soluble fluoride, bromide and sulfate according to claim 1, further comprising the step of precision and reproducibility measurement.
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