CN116559140A - Raman spectrum rapid detection method for ammonia nitrogen in water body - Google Patents
Raman spectrum rapid detection method for ammonia nitrogen in water body Download PDFInfo
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- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 title claims abstract description 76
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000001514 detection method Methods 0.000 title claims abstract description 45
- 238000001237 Raman spectrum Methods 0.000 title claims abstract description 37
- 238000001069 Raman spectroscopy Methods 0.000 claims abstract description 33
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052737 gold Inorganic materials 0.000 claims abstract description 24
- 239000010931 gold Substances 0.000 claims abstract description 24
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000001212 derivatisation Methods 0.000 claims abstract description 16
- -1 ammonium ions Chemical class 0.000 claims abstract description 10
- 239000004312 hexamethylene tetramine Substances 0.000 claims abstract description 10
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims abstract description 10
- 238000005516 engineering process Methods 0.000 claims abstract description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 27
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 18
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 16
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 11
- 239000008098 formaldehyde solution Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 6
- 239000001509 sodium citrate Substances 0.000 claims description 4
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 4
- 229940038773 trisodium citrate Drugs 0.000 claims description 4
- 238000011088 calibration curve Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000004364 calculation method Methods 0.000 claims description 2
- 238000005259 measurement Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 12
- 239000003153 chemical reaction reagent Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 239000012086 standard solution Substances 0.000 description 9
- JGJLWPGRMCADHB-UHFFFAOYSA-N hypobromite Chemical compound Br[O-] JGJLWPGRMCADHB-UHFFFAOYSA-N 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
- 235000019270 ammonium chloride Nutrition 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000035945 sensitivity Effects 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- VRZJGENLTNRAIG-UHFFFAOYSA-N 4-[4-(dimethylamino)phenyl]iminonaphthalen-1-one Chemical compound C1=CC(N(C)C)=CC=C1N=C1C2=CC=CC=C2C(=O)C=C1 VRZJGENLTNRAIG-UHFFFAOYSA-N 0.000 description 3
- JVMRPSJZNHXORP-UHFFFAOYSA-N ON=O.ON=O.ON=O.N Chemical compound ON=O.ON=O.ON=O.N JVMRPSJZNHXORP-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 238000005375 photometry Methods 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 241000282376 Panthera tigris Species 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 235000019256 formaldehyde Nutrition 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 229910020756 KI—KOH Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 244000088401 Pyrus pyrifolia Species 0.000 description 1
- 235000001630 Pyrus pyrifolia var culta Nutrition 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- QKEOZZYXWAIQFO-UHFFFAOYSA-M mercury(1+);iodide Chemical compound [Hg]I QKEOZZYXWAIQFO-UHFFFAOYSA-M 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 1
- 238000012113 quantitative test Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/20—Controlling water pollution; Waste water treatment
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- Health & Medical Sciences (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention discloses a Raman spectrum rapid detection method for ammonia nitrogen in a water body, which converts ammonia nitrogen into hexamethylenetetramine by using a derivatization technology, wherein the hexamethylenetetramine has obvious Raman characteristic peak value, and a quantitative relationship exists between the characteristic peak value and the concentration of ammonium ions, so that the Raman spectrum rapid detection of ammonia nitrogen is realized, the enhancement effect of nano gold sol on the Raman spectrum is also utilized, the detection limit of low-concentration ammonia nitrogen is as low as 5mg/L, and the detection step is simple, rapid and sensitive.
Description
Technical Field
The invention belongs to the technical field of water quality detection, and particularly relates to a method for rapidly detecting ammonia nitrogen in a water body by utilizing Raman spectrum.
Background
Ammonia Nitrogen (NH) 3 -N) is an important reagent in industrial and agricultural production processes, widely existing in natural water bodies, as free ammonia (NH) 3 ) And ammonium ion (NH) 4 + ) In the form, the composition ratio of the two is mainly determined by the pH value of the solution. The ammonia nitrogen content in the water body reflects the pollution condition of nitrogen-containing organic matters to a certain extent, and plays an extremely important role in the production and health of human beings and the stabilization of an ecological system. Ammonia nitrogen is an important monitoring index in the comprehensive sewage discharge standard (GB 8078-1996) and the surface water environment quality standard (GB 3838-2002).
The current national standard determination method for ammonia nitrogen in water body comprises the following steps: the Naviet reagent method, the indophenol blue method and the hypobromite oxidation method. The Nashi reagent method is to generate a light reddish brown complex with ammonia nitrogen in an alkaline solution of mercury iodide and potassium iodide, and then to measure by using a photometry; therefore, the method has the problems of insufficient sensitivity, more interference factors and mercury pollution. The indophenol blue method is to react ammonium, phenol and hypochlorite under the action of a catalyst to obtain indophenol blue, and then to realize the determination of ammonium by using a photometry; although having a higher sensitivity; however, the operation is complicated, the used reagent is not stable enough, and the reproducibility is poor. The hypobromite oxidation method is that hypobromite oxidizes ammonia nitrogen into nitrite nitrogen in alkaline medium, the rest hypobromite is destroyed by acid sulfanilamide, and simultaneously, excess alkali is neutralized, then the total amount of nitrite nitrogen is measured in acid medium by diazo azo spectrophotometry, and the original nitrite nitrogen concentration is deducted, so as to obtain ammonia nitrogen concentration; the method has the advantages of complicated operation steps, high blank value and inapplicability to water bodies containing more organic matters. In a word, when the traditional photometric analysis method is used for measuring ammonia nitrogen, the problems of complex operation, time consumption, low analysis efficiency and the like exist, and the requirements of high-frequency detection of ammonia nitrogen in the water quality monitoring and wastewater treatment process are difficult to meet. Therefore, how to provide a rapid, simple and sensitive ammonia nitrogen detection method is a problem to be researched and solved in the technical field of the field.
The Raman spectrum has the characteristics of high detection speed, no need of complex sample pretreatment, easy realization of on-line continuous analysis and the like, and is particularly suitable for measuring various components in a water sample. Therefore, the quick detection of ammonia nitrogen in the water body by utilizing the Raman spectrum is an ideal way. However, free ammonia (NH) 3 ) And ammonium ion (NH) 4 + ) The raman signals of the device are very weak, and the rapid detection is difficult to realize by directly adopting the traditional raman spectroscopy.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a method for rapidly detecting ammonia nitrogen in water body, which solves the problems of free ammonia (NH) 3 ) And ammonium ion (NH) 4 + ) Is very weak in its raman signalThe problem of difficulty in realizing rapid detection by adopting a traditional Raman spectroscopy.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a Raman spectrum rapid detection method for ammonia nitrogen in a water body converts the ammonia nitrogen in the water body into hexamethylenetetramine by utilizing a derivatization technology, and utilizes the hexamethylenetetramine to have obvious Raman characteristic peak value, and a quantitative relationship exists between the characteristic peak value and the concentration of ammonium ions, so that the Raman spectrum indirect determination for rapidly detecting the ammonia nitrogen in the water body is realized, and the detection limit reaches 50mg/L.
Further, the method specifically comprises the following steps:
s1, adopting ammonium sulfate as a simulated ammonia nitrogen component, measuring by utilizing a Raman spectroscopy, and drawing a calibration curve y=2.0353x+135.9; wherein y is 1047cm -1 Peak intensity; x is the concentration of ammonia nitrogen in water, and the unit is mg/L;
s2, taking 1mL of the water body sample after precipitation and filtration, adding 0.1mL of 37% formaldehyde solution into the water body sample to obtain a mixed solution, adding nano gold sol with the same volume, uniformly mixing, and carrying out Raman spectrum measurement to obtain 1047cm -1 Peak intensity;
s3, 1047cm obtained in the step S2 -1 And (3) carrying out calculation by taking the peak intensity into the standard curve in the step S1, and obtaining the average concentration of ammonia nitrogen in water.
Still further, the nano gold sol is prepared by the following method: 100mL of 0.01% chloroauric acid solution is heated and boiled, 3mL of 1% trisodium citrate solution is added dropwise, stirring is continued until the solution turns into wine red, and the solution is cooled and stored in a refrigerator at 4 ℃ for standby.
The pH value of the water body sample is 6-8.
The Raman spectrometer light source is 578nm, and the power is 100mW.
Compared with the prior art, the invention has the following beneficial effects:
1. the Raman spectrum of ammonia nitrogen is very weak and is difficult to directly analyze and measure, so the invention converts ammonia nitrogen into hexamethylenetetramine by utilizing a derivatization technology, the hexamethylenetetramine has obvious Raman characteristic peak value, and quantitative relation exists between the characteristic peak value and the concentration of ammonium ions, thereby realizing the rapid determination of the Raman spectrum of ammonia nitrogen.
2. The invention utilizes the enhancement effect of the nano gold sol on the Raman spectrum, improves the sensitivity of ammonia nitrogen detection, realizes the determination of low-concentration ammonia nitrogen, and has the detection limit of 5mg/L at the minimum.
3. The detection method is simple and convenient to operate, has high detection speed, can be completed within 1 minute, and can meet the requirements of ammonia nitrogen high-frequency detection in the water quality monitoring and wastewater treatment processes. The invention adopts the derivatization technology, avoids the interference of other components, ensures more accurate ammonia nitrogen content detection and avoids the problem of environmental pollution.
Drawings
FIG. 1 is a Raman spectrum of ammonium chloride, ammonium sulfate and formaldehyde;
FIG. 2 is a Raman spectrum of the product after derivatization with formaldehyde;
FIG. 3 is a Raman spectrum of formaldehyde before and after enhancement of the nano gold sol;
FIG. 4 shows Raman spectra of the derivatized product before and after gold sol addition;
FIG. 5 is a Raman spectrum after derivatization with different concentrations of ammonium sulfate;
FIG. 6 is a graph of ammonia nitrogen content (mg/L) versus 1047cm for example 1 -1 Calibration graph of peak intensity.
Detailed Description
The following describes the embodiments of the present invention in further detail with reference to specific examples.
Numerical ranges in this disclosure are understood to also specifically disclose each intermediate value between the upper and lower limits of the ranges. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control. As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The experimental methods used in the present invention are conventional methods unless otherwise specified.
The materials, reagents and the like used in the present invention can be synthesized by a method of purchase or known method unless otherwise specified.
In the quantitative test of the invention, three repeated experiments are set, and the results are averaged.
The invention aims at the fact that the Raman spectrum of ammonia nitrogen is very weak, and is difficult to directly analyze and measure; and the traditional detection method is difficult to realize the rapid detection of ammonia nitrogen, hexamethylenetetramine is generated by utilizing the reaction of formaldehyde and ammonium ions, the hexamethylenetetramine has obvious Raman characteristic peak value, and the characteristic peak value and the ammonia nitrogen concentration have quantitative relation, so that the rapid detection of ammonia nitrogen is realized, and the selectivity of the detection method is greatly improved. Meanwhile, in order to improve the sensitivity of the detection method, the Raman enhancement effect of the nano gold sol is utilized, so that the rapid detection of the Raman spectrum of the low-concentration ammonia nitrogen is realized, and a technical support is provided for the rapid detection of the ammonia nitrogen in the wastewater.
The related materials include: 37% formaldehyde is used as a derivatization reagent, ammonium chloride and ammonium sulfate are used as simulated ammonia nitrogen components, and chloroauric acid and trisodium citrate are used for preparing the nano gold sol material.
The instrument involved: raman spectrometer (578 nm,100 mw) for example: IPS, product of american ocean.
1. Determination of characteristic peaks of formaldehyde-derived ammonia nitrogen formation
1. The Raman spectra of 100mg/L ammonium chloride, 10mg/L ammonium sulfate solution and 37% formaldehyde solution were measured by Raman spectrometer to confirm the respective Raman characteristic peaks, and the results are shown in FIG. 1.
As can be seen from FIG. 1 (Raman spectrum including ammonium chloride, ammonium sulfate and formaldehyde), 100mg/L of ammonium chloride has no obvious Raman characteristic peak, and 10mg/L of ammonium sulfate has a concentration of 980cm -1 Is characterized by SO 4 2- Raman characteristic peaks of (a) are obtained. From this, it is difficult to directly obtain NH in solution by conventional Raman spectroscopy 4 + Raman characteristic peaks of (a) are obtained. Formaldehyde at 540, 910, 1047, 1319 and 1494cm -1 Has obvious characteristic peak.
2. Respectively transferring 50mg/L and 150mg/L (NH) 4 ) 2 SO 4 1mL of each solution was added with 0.1mL of 37% formaldehyde solution, and the mixture was mixed uniformly at room temperature to induce derivatization of ammonium ions with formaldehyde, and the Raman spectrum of the product after derivatization was measured, as shown in FIG. 2.
As can be seen from FIG. 2, the formaldehyde derivatizes the ammonium ions at 501, 711, 916 and 1047cm -1 Has obvious characteristic peak and has quantitative relation with the concentration of ammonium ions, thereby realizing the rapid determination of the Raman spectrum of ammonia nitrogen. Wherein 501, 711, 916cm -1 To generate new raman characteristic peaks after derivatization, the peaks increase with increasing ammonium ion concentration. And 1047cm -1 Although the peak of the derivative is overlapped with the Raman characteristic peak of formaldehyde, under the condition of derivatization of formaldehyde with the same concentration, the peak value is increased along with the increase of the concentration of ammonium ions, and the increasing trend is more obvious, thereby confirming 1047cm -1 The peak is also a characteristic peak of the derivative product.
2. Research shows that nano Jin Rong has enhancement effect on Raman spectrum of ammonia nitrogen derivatization product
1. To confirm whether the nanogold sol has an effect on the raman spectrum of the derivatizing agent formaldehyde, a 37% formaldehyde solution was mixed with the nanogold sol in a volume ratio of 1:1, and the raman spectrum was measured, as shown in fig. 3.
As can be seen from fig. 3, no raman spectrum enhancement of formaldehyde was observed after the addition of the gold sol, but instead, the addition solution of the gold sol was diluted, and the tendency of the corresponding raman peak to decrease was observed, so that it was confirmed that the nano gold sol had no raman enhancement effect on formaldehyde.
The preparation method of the nano gold sol comprises the following steps: taking 100mL of 0.01% chloroauric acid solution, heating and boiling, adding 3mL of 1% trisodium citrate solution, continuously stirring until the solution turns into wine red, namely the nano gold sol, cooling and storing in a refrigerator at 4 ℃ for later use.
2. Transferring 1mL of 10mg/L ammonium sulfate, adding 0.1mL of 37% formaldehyde solution, mixing with nano gold sol in a volume ratio of 1:1, and measuring Raman signals of the product after derivatization before and after gold sol addition, wherein the Raman signals are shown in FIG. 4.
As can be seen from FIG. 4, the Raman signal was weak after the 10mg/L ammonium sulfate derivatization reaction, but when gold sol was added, it was found at 442, 711, 761, 916, 1047 and 1093cm -1 There is a distinct Raman signal present, 711, 916 and 1047cm -1 With 50, 150mg/L (NH) 4 ) 2 SO 4 The peak value of the product after derivatization is consistent and 1047cm -1 The peak is the strongest. Therefore, the nano gold sol has obvious enhancement effect on the Raman spectrum of the derivatized product, can greatly reduce the detection limit and improve the sensitivity of the detection method.
3. And transferring 1mL of 5, 50 and 100mg/L ammonium sulfate, respectively adding 0.1mL of 37% formaldehyde solution for mixing, mixing with nano gold sol according to the volume ratio of 1:1 during detection, and measuring the Raman signal of the nano gold sol, wherein the Raman signal is shown in FIG. 5.
As can be seen from FIG. 5, at 1047cm -1 The peak is most pronounced and 1047cm with increasing ammonium sulfate concentration -1 The peak value is increased, namely, a quantitative relation exists between the peak value and the concentration of ammonium ions, so that a rapid detection method of ammonia nitrogen in the water body can be established.
3. Examples
Example 1
Accurately weighing 0.010g of ammonium sulfate, dissolving and fixing the ammonium sulfate in a 100mL volumetric flask to obtain 100mg/L ammonium sulfate standard stock solution. And respectively transferring 0.5mL, 2.0mL, 5.0mL, 10.0mL and 15.0mL of ammonium sulfate standard stock solution into a 10mL colorimetric tube, and obtaining 5mg/L, 20mg/L, 50mg/L, 100mg/L and 150mg/L of ammonium sulfate series standard solutions after constant volume. Removing ammonium sulfate series standard solution1mL of each solution is added with 0.1mL of 37% formaldehyde solution for mixing, and the solution is mixed with nano gold sol according to the volume ratio of 1:1 before detection, the Raman signal of the solution is measured, and a calibration curve is drawn, as shown in FIG. 6, so that the preparation method comprises the following steps of: y=2.0353x+135.9, r2= 0.9992. Wherein y is 1047cm -1 The peak intensity, x is the concentration of ammonia nitrogen in water, and the unit is mg/L. The detection limit reaches 5mg/L.
In the same manner as above, a repeatability test was performed. The results are shown in Table 1, and the relative standard deviation is equivalent to that of the national standard Navier reagent method.
TABLE 1 results of the repeatability test of the invention
Example 2
Taking 100mL of a school lake water sample, filtering the water sample by a 0.45 mu m microporous filter membrane, and determining the pH value to be 6.8. Taking 3 parts of filtered lake water with 1mL as analysis samples, adding 0.1mL of 37% formaldehyde solution for mixing, mixing with nano gold sol according to the volume ratio of 1:1, measuring Raman signals of 3 parts of samples, and obtaining 1047cm -1 And calculating the ammonia nitrogen concentration in the water sample by using the standard curve according to the peak intensity, and measuring that the average concentration of the ammonia nitrogen in the water sample is 65.6mg/L. The detection takes about 1 minute or so.
Example 3
Taking 100mL of tiger river water sample, adding zinc sulfate (100 g/L) for flocculating precipitation for 10 minutes, taking 50mL of supernatant for measuring pH value to be 6.4, taking 3 parts of pretreated water sample as analysis samples, adding 0.1mL of 37% formaldehyde solution for mixing, mixing with nano gold sol according to the volume ratio of 1:1, measuring Raman signals of 3 parts of samples, and obtaining 1047cm -1 And calculating the ammonia nitrogen concentration in the water sample according to the peak intensity and the standard curve, and measuring that the average concentration of the ammonia nitrogen in the water sample is 125.3mg/L. The detection takes about 1 minute or so.
Example 4
The method and the national standard Navier reagent method are adopted to measure the standard recovery rate of the water sample. The Nahner reagent method comprises the following specific steps: respectively transferring 25mL of ammonium chloride standard solution of 10mg/L, 20mg/L, 50mg/L, 100mg/L and 150mg/L to a colorimetric tube,adding 0.5mL of 500g/L potassium sodium tartrate solution, and uniformly mixing; add 0.5mL of Nardostat (HgI) 2 -KI-KOH), and allowed to stand for 20 minutes. Measuring absorbance of the sample at 420nm with water as reference, and drawing standard curve of y=0.0253 x+0.0062, R 2 =0.9993. Wherein y is an absorbance value; x is the concentration of ammonia nitrogen, and the unit is mg/L. And calculating the ammonia nitrogen concentration in the water sample according to the standard curve. The method takes about 30 minutes for detection.
Sample 1: taking two parts of 100mL water sample 1 (school lake water, ammonia nitrogen content of 65.6 mg/L), pretreating the water sample, adding 1.0mL ammonia nitrogen standard solution with concentration of 1000mg/L, and determining the concentration of ammonia nitrogen in the solution after the addition of the standard solution under the same condition by using the method disclosed by the invention, wherein n=3.
Sample 2: taking two parts of 100mL self-made simulated water sample, adding 1.0mL ammonia nitrogen standard solution with the concentration of 1000mg/L into the self-made simulated water sample, and determining the concentration of ammonia nitrogen in the solution after the addition of the standard solution under the same conditions by using the method disclosed by the invention, wherein n=3.
Sample 3: taking two parts of 100mL water sample 2 (tiger river water sample with ammonia nitrogen content of 125.3 mg/L), pretreating the water sample, adding 1.0mL ammonia nitrogen standard solution with concentration of 5000mg/L, and determining the concentration of ammonia nitrogen in the solution after the standard addition by using the method under the same conditions, wherein n=3.
Sample 4: taking two parts of 100mL simulated water sample, adding 1.0mL ammonia nitrogen standard solution with the concentration of 5000mg/L into the simulated water sample, and determining the concentration of ammonia nitrogen in the solution after the addition of the standard solution under the same conditions by using the method disclosed by the invention, wherein n=3.
n=3 are repeated 3 times.
The results of the addition of the standard recovery are shown in Table 2.
Table 2 labeled recovery test
As shown in Table 2, the invention can meet the requirement of ammonia nitrogen detection of water quality, and has the advantages of reliable method, high detection speed, small error, and more than 20 minutes consumed by the Nami reagent method.
The experimental water is ammonia-free water.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the technical solution, and those skilled in the art should understand that modifications and equivalents may be made to the technical solution of the present invention without departing from the spirit and scope of the present invention, and all such modifications and equivalents are included in the scope of the claims.
Claims (5)
1. A Raman spectrum rapid detection method for ammonia nitrogen in a water body is characterized in that a derivatization technology is utilized to convert the ammonia nitrogen in the water body into hexamethylenetetramine, the hexamethylenetetramine has obvious Raman characteristic peak value, and a quantitative relationship exists between the characteristic peak value and the concentration of ammonium ions, so that the Raman spectrum rapid indirect determination of the ammonia nitrogen in the water body is realized, and the detection limit reaches 50mg/L.
2. The rapid detection method of raman spectrum of ammonia nitrogen in a water body according to claim 1, comprising the following steps:
s1, adopting ammonium sulfate as a simulated ammonia nitrogen component, and drawing a calibration curve y= 2.0353x+135.9; wherein y is 1047 and 1047cm -1 Peak intensity; x is the concentration of ammonia nitrogen in water, and the unit is mg/L;
s2, taking 1mL of the water body sample after precipitation and filtration, adding 0.1mL of 37% formaldehyde solution into the water body sample to obtain a mixed solution, adding nano gold sol with the same volume, uniformly mixing, and carrying out Raman spectrum measurement to obtain 1047cm -1 Peak intensity;
s3, 1047cm obtained in the step S2 -1 And (3) carrying out calculation by taking the peak intensity into the standard curve in the step S1, and obtaining the average concentration of ammonia nitrogen in water.
3. The rapid detection method of raman spectrum of ammonia nitrogen in water according to claim 1, wherein the nano gold sol is prepared by the following method: 100mL of 0.01% chloroauric acid solution is heated and boiled, 3mL of 1% trisodium citrate solution is added dropwise, stirring is continued until the solution turns into wine red, and the solution is cooled and stored in a refrigerator at 4 ℃ for standby.
4. The rapid detection method of raman spectra of ammonia nitrogen in a water body according to claim 1, wherein the pH value of the water body sample is 6-8.
5. The rapid detection method of raman spectrum of ammonia nitrogen in water according to claim 1, wherein the light source of the raman spectrometer is 578nm, and the power is 100mW.
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