CN109725075A - A kind of measuring method of water quality phenolic compound - Google Patents

A kind of measuring method of water quality phenolic compound Download PDF

Info

Publication number
CN109725075A
CN109725075A CN201811587446.3A CN201811587446A CN109725075A CN 109725075 A CN109725075 A CN 109725075A CN 201811587446 A CN201811587446 A CN 201811587446A CN 109725075 A CN109725075 A CN 109725075A
Authority
CN
China
Prior art keywords
water
sample
phenolic compound
measuring method
water quality
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201811587446.3A
Other languages
Chinese (zh)
Inventor
胡先云
金崇进
方爱君
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang Keda Testing Co Ltd
Original Assignee
Zhejiang Keda Testing Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhejiang Keda Testing Co Ltd filed Critical Zhejiang Keda Testing Co Ltd
Priority to CN201811587446.3A priority Critical patent/CN109725075A/en
Publication of CN109725075A publication Critical patent/CN109725075A/en
Pending legal-status Critical Current

Links

Landscapes

  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)

Abstract

The invention discloses a kind of measuring methods of water quality phenolic compound, are related to field of water quality detection, include the following steps: Step 1: acquiring the water sample of sufficient amount using vial;Step 2: reducing agent and appropriate hydrochloric acid adjusting pH < 2 is added after water sampling immediately;Step 3: the water sample of acquisition is poured into separatory funnel;Step 4: extracting to target compound, organic extractant phase liquid is obtained, and be dehydrated to organic extractant phase liquid using anhydrous sodium sulfate;Step 6: constant volume is concentrated in organic extractant phase liquid after dehydration, upper machine measurement obtains sample spectrogram;Step 7: sample spectrogram is compared with standard spectrogram, finds out each target compound and go out peak position, and calculate ρ in conjunction with calibration curveMark;Step 8: according to formula ρiMark×V1×1000/V2Calculate the concentration ρ of target compound in water samplei.Since water sample is added to reducing agent in preceding processing, thus the probability of phenolic compound oxidation is significantly reduced, to improve detection precision.

Description

A kind of measuring method of water quality phenolic compound
Technical field
The present invention relates to field of water quality detection, in particular to a kind of measuring method of water quality phenolic compound.
Background technique
As Chinese society macroeconomic is horizontally constantly promoted, country and various circles of society are for asking in terms of environmental protection Topic is also increasingly to pay close attention to.And water resource is as our bases for the survival of mankind, along with China is exactly originally a water The big country of shortage of resources so the protection for water resource, and becomes compatriots and the responsibility shirked is not allowed by various circles of society.
During this period, for the detection of water quality, become us to the weight adopted an effective measure during fwaater resources protection Reference index is wanted, such as passes through amount of nitrogen oxides, microbial pathogens content, the content of beary metal etc. in detection water.
And phenolic compound is to common are machine pollutant in water body, sum has as many as several hundred kinds.Meanwhile phenolic compound It is from a wealth of sources, during the industrial and agricultural production for generally resulting from the mankind, such as the industry such as coking, papermaking, medicine, printing and dyeing, chemical industry Discharge, degradation of pesticide and environment itself biogeochemical cycle all there may be.And these phenolic compounds have cause Cancer, teratogenesis and mutagenic genotoxic potential, long-term drinking by the drinking water of phenolic compounds pollution, can cause dizzy, eruption and The symptom of the nervous systems such as itch, part phenolic substances have been put into Environment Priority detection organic pollutant.Such as world health Organize (WHO) that 2,4,6- trichlorophenol, 2,4,6,-Ts and pentachlorophenol are classified as 2B pollutant, it is possible to there is carcinogenic effect to the mankind.Institute With the monitoring for phenols compound in water quality is that we cannot be neglected important link.
For this purpose, China has promulgated HJ676-2013 " measurement liquid-liquid extraction/gas-chromatography of water quality phenolic compound for 2013 Method " standard, primarily directed to the measurement of main 13 kinds of seriously polluted phenols compounds in water quality.
But due to the wherein phenolic compound in 6 in phenolic compound in 13, phenol, 2-chlorophenol, 3- cresols, 2,4- Xylenol, 4- chlorophenol and 6 kinds of substances of the chloro- 3- cresols of 4- are more unstable with respect to remaining 7 kinds of phenolic compound, are easily oxidized, institute When doing blank water sample detection, often can not all obtain accurate peak value, thus, the mistake of water sample detection easy to increase Difference.
Summary of the invention
It is easy to operate the object of the present invention is to provide a kind of measuring method of water quality phenolic compound, it can be effectively Improve the accuracy of water quality detection.
Above-mentioned technical purpose of the invention has the technical scheme that a kind of water quality phenolic compound Measuring method includes the following steps:
Step 1: utilizing the water sample of vial acquisition sufficient amount;
Step 2: reducing agent and appropriate hydrochloric acid adjusting pH < 2 is added after water sampling immediately;
Step 3: the water sample of acquisition is poured into separatory funnel;
Step 4: extracting to target compound, organic extractant phase liquid is obtained, and using anhydrous sodium sulfate to organic extractant phase Liquid is dehydrated;
Step 6: constant volume is concentrated in organic extractant phase liquid after dehydration, upper machine measurement obtains sample spectrogram;
Step 7: sample spectrogram is compared with standard spectrogram, finds out each target compound and go out peak position, and combine calibration curve Calculate ρMark
Step 8: according to formula ρiMark×V1×1000/V2Calculate the concentration ρ of target compound in water samplei, in formula: ρiWater The concentration of target compound in sample, μ g/L;ρMarkResulting target compound concentration, mg/L are calculated by calibration curve;V1Extraction Constant volume after liquid concentration, mL;V2The sample volume of water sample, mL.
By using above-mentioned technical proposal, reducing agent is added in water sample, can consume the dissolved oxygen in water in this way, thus The probability that the phenolic compound in water sample is aoxidized by water oxygen is reduced, and then is also advantageous for improving returning phenolic compound Yield.
Preferably, the reducing agent is ascorbic acid.
By using above-mentioned technical proposal, since ascorbic acid is strong reductant, and this reducing agent is soluble easily in water, and It will not be chemically reacted with phenolic compound to be measured, meanwhile, it is also not easy by solvent extraction.Thus, in the mistake of upper machine testing It is smaller to the test result interference of phenolic compound to be measured in journey, meanwhile, reduction also can be fully played, phenol is avoided The probability that class compound is oxidized.
Preferably, the quality of the ascorbic acid of addition and the volume ratio of water sample are 18.45~22.33mg/L.
By using above-mentioned technical proposal, since under room temperature, the dissolved oxygen concentration in water is 8.38mg/L, and according to anti-bad The quality of hematic acid and the volume ratio of water sample are that 18.45~22.33mg/L adds ascorbic acid, can be greatly lowered in water and dissolve The content of oxygen, to also just further reduced the probability that phenolic compound is oxidized.
Preferably, the quality of the ascorbic acid of addition and the volume ratio of water sample are 20.39mg/L.
It is molten in water when the amount of the ascorbic acid of addition is 20.39mg/ water L by using above-mentioned technical proposal The concentration of oxygen is solved already close to zero, to guarantee to test in effective situation again, can also reduce the usage amount of ascorbic acid.
Preferably, step 1 is before sampling, the water sample of first mild agitation sample point.
By using above-mentioned technical proposal, the accuracy during water sampling is helped to improve in this way.
Preferably, during the water sampling of step 1, Brown Glass Brown glass bottles and jars only must be filled gas of not leaving a blank.
By using above-mentioned technical proposal, oxygen content whole in Brown Glass Brown glass bottles and jars only can be reduced in this way, and then also Advantageously reduce the probability that phenolic compound is oxidized.
Preferably, it needs to deflate in time in extraction process again in step 4.
By using above-mentioned technical proposal, it on the one hand can be improved safety in this way, on the other hand also help to avoid Bubble is mixed into machine test process, and influences the accuracy of test result.
In conclusion the invention has the following advantages:
1, by adding reducing agent into water sample, it can be effectively reduced the probability that phenolic compound is oxidized in this way;
2, select ascorbic acid as reducing agent, this is because ascorbic acid is soluble easily in water, and is not easy to be come out by solvent extraction, because And the test of target compound is interfered smaller;
3, Brown Glass Brown glass bottles and jars only is selected during water sampling, and guarantees that vial expires bottle and do not leave a blank gas, can then reduce water in this way Oxygen affects target compound test in sample.
Detailed description of the invention
Fig. 1 is that mixed be marked in after dichloromethane/ethyl acetate in the mixed solvent dilutes 500 times of 13 kinds of phenolic compounds is marked Quasi- spectrogram;
Fig. 2 is the relational graph for adding the content of ascorbic acid quality and volume of water sample ratio and dissolved oxygen;
Fig. 3 is the gas phase spectrogram for controlling sample 1;
Fig. 4 is the gas phase spectrogram of comparative example.
Specific embodiment
Embodiment:
A kind of measuring method of water quality phenolic compound, comprising the following steps:
S1: standard production and test,
Step a: the mixed mark of 13 kinds of phenolic compounds is diluted into 500 times, 200 respectively at dichloromethane/ethyl acetate in the mixed solvent Again, 100 times, 40 times, 20 times and 10 times, obtain six groups of standard specimens;
Step b: by six groups of standard specimens and one group of blank sample examination with computer, obtaining standard spectrogram, as shown in Fig. 1 and each phenol generalization The calibration curve of object is closed, as shown in table 1.
The standard curve of 1 13 kinds of phenolic compounds of table
Serial number Target compound Standard curve function Correlation r2
1 Phenol Y=10.67265x+2.46508 0.99974
2 2-chlorophenol Y=8.05010x+1.70854 0.99976
3 3- cresols Y=11.03797x+2.84950 0.99972
4 2- nitrophenols Y=6.51895x+3.06530e-1 0.99972
5 2,4- xylenols Y=11.72419x+2.57409 0.99975
6 2,4- Dichlorophenols Y=6.37532x+1.89746 0.99971
7 4- chlorophenol Y=7.79943x+2.25983 0.99970
8 The chloro- 3- cresols of 4- Y=8.49327x+2.25522 0.99970
9 2,4,6- trichlorophenols Y=5.33086x+5.30619e-1 0.99965
10 2,4- dinitrophenol dinitrophenolates Y=2.84312x-6.84649 0.99519
11 4- nitrophenols Y=6.24704x-1.45286 0.99963
12 2- methyl -4,6- dinitrophenol dinitrophenolate Y=4.71370x-5.77555 0.99857
13 Pentachlorophenol Y=3.83034x-1.00824 0.99964
Here, measuring gas phase spectrogram after 200 times, 100 times, 40 times, 20 times and 10 times of mark dilution mixed for 13 kinds of phenolic compounds Similar to 500 times of gas phase spectrogram of dilution, only there is difference in the size of peak area, so no longer record herein.Gas phase test It is the prior art, it is identical as standard HJ 676-2013.
In addition, 13 kinds of phenolic compounds herein mix each concentration in mark, as shown in following table two:
The concentration of each phenolic compound in the mixed mark of 2 13 kinds of phenolic compounds of table
S2, sample test:
The test of river water sample:
Step 1: by the river water mild agitation of sample point, water sample is acquired using the Brown Glass Brown glass bottles and jars only that volume is 1L, and guarantee brown Vial fills gas of not leaving a blank;
Step 2: 20.39mg ascorbic acid being added into water sample, makes it completely dissolved, while it is 38% that mass fraction, which is added, Water sample is adjusted pH < 2 by hydrochloric acid;
Step 3: amount shakes up water sample, measures 500mL and pours into 1000mL separatory funnel, and 30g sodium chloride, oscillation dissolution is added;
Step 4: being added 60mL dichloromethane/ethyl acetate mixed solvent, shakes, releasing gas, then shaking out 5~ 10min stands 10min or more, until organic phase is sufficiently separated with water phase, collects organic phase;
Step 5: repeating extraction 1~2 time, merges organic phase.Organic phase is dehydrated through anhydrous sodium sulfate, and with q. s. methylene chloride/ Ethyl acetate mixed solvent washs anhydrous sodium sulfate, collects organic extractant phase liquid;
Step 6: being transferred to concentrate bottle for the extract liquor after dehydration and drying, is concentrated into 1.0mL at 45 DEG C or less with enrichment facility, Dichloromethane/ethyl acetate mixed solvent 3.0mL is added, then is concentrated and is settled to 1.0mL, upper gas chromatograph for determination obtains sample Product spectrogram;
Step 7: sample spectrogram is compared with standard spectrogram, and that finds out corresponding phenolic compound goes out peak position, and according to Know that standard curve obtains ρMark
Step 8: according to formula ρiMark×V1×1000/V2Calculate the concentration ρ of target compound in water samplei, in formula: ρiWater The concentration of target compound in sample, μ g/L;ρMarkResulting target compound concentration, mg/L are calculated by calibration curve;V1Extraction Constant volume after liquid concentration, mL;V2The sample volume of water sample, mL.Wherein, the sample point of river water is located at Taizhou Jiangjiang Jiang Bin Park section.As a result as shown in Table 3:
The content of 13 kinds of phenolic compounds in three water sample of table
Serial number Target compound ρMark/mg/L ρi/mg/L
1 Phenol 0 0
2 2-chlorophenol 0 0
3 3- cresols 0 0
4 2- nitrophenols 0 0
5 2,4- xylenols 0 0
6 2,4- Dichlorophenols 0 0
7 4- chlorophenol 0 0
8 The chloro- 3- cresols of 4- 0 0
9 2,4,6- trichlorophenols 0 0
10 2,4- dinitrophenol dinitrophenolates 0 0
11 4- nitrophenols 0 0
12 2- methyl -4,6- dinitrophenol dinitrophenolate 0 0
13 Pentachlorophenol 0 0
13 kinds of phenolic compounds are not detected from the water sample in upper table two as can be seen that river.
Furthermore from attached drawing 2 as can be seen that the additive amount and volume of water sample ratio of ascorbic acid are in 18.45~20.33mg/L Between when, oxygen content significantly decreases, and when ascorbic acid additive amount and volume of water sample ratio reach 20.39mg/L's When, the content fall of dissolved oxygen very little.Comprehensive whole consideration, additive amount and the volume of water sample ratio of ascorbic acid It is best that value reaches 20.39mg/L.
S3, quality control test:
Step I: it is separately added into the mixed mark of 13 kinds of phenolic compounds of various concentration in the separatory funnel of step 3 again in S2, obtains Control sample 1, control sample 2 and control sample 3;
Step II: will control sample 1, and control sample 2 and control sample 3 are handled according to the processing mode of water sample in S2, then upper gas Chromatography measurement, obtains each control sample gas phase spectrogram, as shown in Fig. 3, and is calculated according to standard curve, controls 13 in sample The concentration of kind phenolic compound, as shown in Table 4;
Step III: it is poor that the content of calculated 13 kinds of phenolic compounds is made with 13 kinds of content of phenolic compounds in S2 water sample, it It is compared again with the concentration of phenolic compound in practical each control sample of table five afterwards, obtains the rate of recovery, as a result as shown in Table 6.
The concentration of the calculated each control sample of table four
The concentration of the practical each control sample of table five
The rate of recovery of each phenolic compound of table six
The test method that can be seen that the application by the result of table six is higher for the recycling of the phenolic compound in water.
In addition, the gas phase spectrogram of control sample 2 and the gas phase spectrogram and control sample 1 that control sample 3 approaches, only deposited on peak area In difference, because without showing.
Comparative example:
A kind of measuring method of water quality phenolic compound is with the difference for controlling sample 1 in embodiment one, surveys doing quality control During examination and it is not added with ascorbic acid, obtains the gas phase spectrogram such as attached drawing 4.From spectrogram it is clear that there are many Phenolic compound does not go out cutting edge of a knife or a sword, and then has proved amply in actual mechanical process, and the addition of ascorbic acid is for improving test Precision plays a significant role.
This specific embodiment is only explanation of the invention, is not limitation of the present invention, those skilled in the art Member can according to need the modification that not creative contribution is made to the present embodiment after reading this specification, but as long as at this All by the protection of Patent Law in the scope of the claims of invention.

Claims (8)

1. a kind of measuring method of water quality phenolic compound, includes the following steps:
Step 1: utilizing the water sample of vial acquisition sufficient amount;
Step 2: reducing agent and appropriate hydrochloric acid adjusting pH < 2 is added after water sampling immediately;
Step 3: the water sample of acquisition is poured into separatory funnel;
Step 4: extracting to target compound, organic extractant phase liquid is obtained, and using anhydrous sodium sulfate to organic extractant phase Liquid is dehydrated;
Step 6: constant volume is concentrated in organic extractant phase liquid after dehydration, upper machine measurement obtains sample spectrogram;
Step 7: sample spectrogram is compared with standard spectrogram, finds out each target compound and go out peak position, and combine calibration curve Calculate ρMark
Step 8: according to formula ρiMark×V1×1000/V2Calculate the concentration ρ of target compound in water samplei, in formula: ρiWater sample The concentration of middle target compound, μ g/L;ρMarkResulting target compound concentration, mg/L are calculated by calibration curve;V1Extract liquor Constant volume after concentration, mL;V2The sample volume of water sample, mL.
2. a kind of measuring method of water quality phenolic compound according to claim 1, it is characterised in that: the reducing agent is Ascorbic acid.
3. a kind of measuring method of water quality phenolic compound according to claim 2, it is characterised in that: the Vitamin C of addition The quality of acid and the volume ratio of water sample are 18.45~92.23mg/L.
4. a kind of measuring method of water quality phenolic compound according to claim 3, it is characterised in that: the Vitamin C of addition The quality of acid and the volume ratio of water sample are 55.39mg/L.
5. a kind of measuring method of water quality phenolic compound according to claim 1, it is characterised in that: step 1 is sampling Before, the water sample of first mild agitation sample point.
6. a kind of measuring method of water quality phenolic compound according to claim 1, it is characterised in that: the water intaking of step 1 During sample, Brown Glass Brown glass bottles and jars only must be filled gas of not leaving a blank.
7. a kind of measuring method of water quality phenolic compound according to claim 1, it is characterised in that: the glass of step 1 Bottle is Brown Glass Brown glass bottles and jars only.
8. a kind of measuring method of water quality phenolic compound according to claim 1, it is characterised in that: extract again in step 4 It needs to deflate in time during taking.
CN201811587446.3A 2018-12-25 2018-12-25 A kind of measuring method of water quality phenolic compound Pending CN109725075A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811587446.3A CN109725075A (en) 2018-12-25 2018-12-25 A kind of measuring method of water quality phenolic compound

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811587446.3A CN109725075A (en) 2018-12-25 2018-12-25 A kind of measuring method of water quality phenolic compound

Publications (1)

Publication Number Publication Date
CN109725075A true CN109725075A (en) 2019-05-07

Family

ID=66296347

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811587446.3A Pending CN109725075A (en) 2018-12-25 2018-12-25 A kind of measuring method of water quality phenolic compound

Country Status (1)

Country Link
CN (1) CN109725075A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110514774A (en) * 2019-08-30 2019-11-29 哈尔滨工业大学 A kind of method of phenolic compound in analysis water

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102175790A (en) * 2011-01-07 2011-09-07 山东省农业科学院中心实验室 HPLC (high performance liquid chromatography) method for synchronously detecting five polyphenols in apples and distinguishing varieties
CN103336069A (en) * 2013-06-13 2013-10-02 江苏省农业科学院 HPLC (High Performance Liquid Chromatography) determination method of phenolic compounds in peach fruit
CN106124646A (en) * 2016-06-12 2016-11-16 南京大学 A kind of detect the method for polarity phenol chloro/bromo disinfection byproduct (DBP) in water
CN109030664A (en) * 2018-09-27 2018-12-18 湖北科技学院 The method for measuring the content of 7 kinds of polyphenol active ingredients in different cultivars sweet osmanthus simultaneously by HPLC-MS-MS method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102175790A (en) * 2011-01-07 2011-09-07 山东省农业科学院中心实验室 HPLC (high performance liquid chromatography) method for synchronously detecting five polyphenols in apples and distinguishing varieties
CN103336069A (en) * 2013-06-13 2013-10-02 江苏省农业科学院 HPLC (High Performance Liquid Chromatography) determination method of phenolic compounds in peach fruit
CN106124646A (en) * 2016-06-12 2016-11-16 南京大学 A kind of detect the method for polarity phenol chloro/bromo disinfection byproduct (DBP) in water
CN109030664A (en) * 2018-09-27 2018-12-18 湖北科技学院 The method for measuring the content of 7 kinds of polyphenol active ingredients in different cultivars sweet osmanthus simultaneously by HPLC-MS-MS method

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
A. PENALVER 等: "Solid-phase microextraction coupled to high-performance liquid chromatography to determine phenolic compounds in water samples", 《JOURNAL OF CHROMATOGRAPHY A》 *
刘娟: "气相色谱法测定废水中酚的方法探究", 《淮海工学院学报(自然科学版)》 *
环境保护部: "《中华人民共和国国家环境保护标准 HJ 676-2013》", 21 November 2013 *
黄云 等: "用快速分离柱高效液相色谱法测定烟草中的几种酚", 《分析试验室》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110514774A (en) * 2019-08-30 2019-11-29 哈尔滨工业大学 A kind of method of phenolic compound in analysis water
CN110514774B (en) * 2019-08-30 2021-07-20 哈尔滨工业大学 Method for analyzing phenolic compounds in water

Similar Documents

Publication Publication Date Title
CN105203665B (en) Method for detecting content of lactic acid in feed acidifier
CN102928528B (en) High performance liquid chromatography-mass spectrometry detecting method of 16 fat soluble saxitoxins in shellfish meet
CN101701914A (en) Analysis detection method for calcium element in ore
CN106018312A (en) Detection method for total petroleum hydrocarbon in contaminated soil
CN109725075A (en) A kind of measuring method of water quality phenolic compound
CN104359901A (en) Rapid detecting method for hydroxymethyl furfural in honey
CN106841457B (en) The measuring method of methaqualone and diazepam residual quantity in a kind of animal derived food
CN108152425B (en) Method for detecting lignanoids in sesame oil by high performance liquid chromatography
CN112326847B (en) Method for detecting impurities in isophthalonitrile
CN105223179A (en) A kind of method of arsenic, antimony and the mercury that can extract in AFS DETERMINATION leather
CN109633021B (en) Method for detecting additive in sufentanil medicine
CN112946136B (en) Method for determining content of mesylate in ozesamicin
CN108008033A (en) A kind of method for measuring water nitrite and nitrous acid content
CN108169388A (en) The assay method of 18 kinds of polycyclic aromatic hydrocarbon PAHs in filling tires oil
CN108061730A (en) A kind of organics removal is to on-line determination ammonia nitrogen device and interference method
CN101051027A (en) Method for water phase detecting micro mercury in water or waste water by spectrophotometry
CN104407085B (en) Application liquid matter-matter combined instrument measures the method for chloromycetin in freshwater bed mud
KR101340767B1 (en) the detecting method for low concentration of phosphate
CN111337611A (en) Method for detecting malachite green, leucomalachite green, crystal violet and leucocyte crystal violet in aquatic products
CN109613174B (en) Method for detecting content of total alkaloids in quassia
CN108267520B (en) Method for detecting residual solvent dichloroethane in tert-butanone production process by using FID detector
CN108061713A (en) The method for measuring jam nitrite
CN106324241B (en) The assay method of Determination of Polyphenols in a kind of Litter-fall
CN108776110A (en) A method of utilizing the COD in the Microwave Digestion detection sewage of silver-free catalyst
CN108195829A (en) A kind of method of ammonia nitrogen in measurement water body

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20190507

RJ01 Rejection of invention patent application after publication