CN115144502A - Method for investigating toxicity characteristics of wastewater discharged from chemical industrial park - Google Patents
Method for investigating toxicity characteristics of wastewater discharged from chemical industrial park Download PDFInfo
- Publication number
- CN115144502A CN115144502A CN202210793025.6A CN202210793025A CN115144502A CN 115144502 A CN115144502 A CN 115144502A CN 202210793025 A CN202210793025 A CN 202210793025A CN 115144502 A CN115144502 A CN 115144502A
- Authority
- CN
- China
- Prior art keywords
- wastewater
- park
- typical
- discharged
- pollutants
- 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
Links
- 239000002351 wastewater Substances 0.000 title claims abstract description 62
- 239000000126 substance Substances 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 27
- 231100000419 toxicity Toxicity 0.000 title claims abstract description 22
- 230000001988 toxicity Effects 0.000 title claims abstract description 22
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 46
- 231100000719 pollutant Toxicity 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000004458 analytical method Methods 0.000 claims abstract description 25
- 238000001514 detection method Methods 0.000 claims abstract description 24
- 238000001819 mass spectrum Methods 0.000 claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 claims abstract description 21
- 238000012216 screening Methods 0.000 claims abstract description 18
- 239000010865 sewage Substances 0.000 claims abstract description 15
- 230000003595 spectral effect Effects 0.000 claims abstract description 12
- 238000011835 investigation Methods 0.000 claims abstract description 11
- 238000005070 sampling Methods 0.000 claims abstract description 11
- 238000001228 spectrum Methods 0.000 claims abstract description 9
- 231100001234 toxic pollutant Toxicity 0.000 claims abstract description 9
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 29
- 239000012071 phase Substances 0.000 claims description 27
- 150000002500 ions Chemical class 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 238000012544 monitoring process Methods 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000004949 mass spectrometry Methods 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 claims description 5
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 5
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 claims description 5
- 238000002189 fluorescence spectrum Methods 0.000 claims description 4
- 229910001385 heavy metal Inorganic materials 0.000 claims description 4
- 238000002347 injection Methods 0.000 claims description 4
- 239000007924 injection Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000012855 volatile organic compound Substances 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 230000005540 biological transmission Effects 0.000 claims description 3
- 239000012159 carrier gas Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 230000003247 decreasing effect Effects 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000010828 elution Methods 0.000 claims description 3
- 238000004945 emulsification Methods 0.000 claims description 3
- HQVFCQRVQFYGRJ-UHFFFAOYSA-N formic acid;hydrate Chemical compound O.OC=O HQVFCQRVQFYGRJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 230000002209 hydrophobic effect Effects 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 3
- 150000002894 organic compounds Chemical class 0.000 claims description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Substances OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 3
- -1 perchloric acid ions Chemical class 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- 238000012502 risk assessment Methods 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 3
- 239000012498 ultrapure water Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 239000012074 organic phase Substances 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims 1
- 230000009931 harmful effect Effects 0.000 description 6
- 231100000331 toxic Toxicity 0.000 description 6
- 230000002588 toxic effect Effects 0.000 description 6
- 239000002957 persistent organic pollutant Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000012847 fine chemical Substances 0.000 description 4
- 239000010842 industrial wastewater Substances 0.000 description 4
- 238000004255 ion exchange chromatography Methods 0.000 description 4
- 230000005284 excitation Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000000132 electrospray ionisation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 210000000056 organ Anatomy 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000003440 toxic substance Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002124 endocrine Effects 0.000 description 1
- 238000003891 environmental analysis Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000007726 management method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000005181 nitrobenzenes Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 231100000915 pathological change Toxicity 0.000 description 1
- 230000036285 pathological change Effects 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 230000035790 physiological processes and functions Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000007619 statistical method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 231100000048 toxicity data Toxicity 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- G01N30/02—Column chromatography
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
-
- 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
- G01N21/64—Fluorescence; Phosphorescence
-
- 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
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
- G01N30/7233—Mass spectrometers interfaced to liquid or supercritical fluid chromatograph
- G01N30/724—Nebulising, aerosol formation or ionisation
- G01N30/7266—Nebulising, aerosol formation or ionisation by electric field, e.g. electrospray
-
- 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
- G01N21/64—Fluorescence; Phosphorescence
- G01N2021/6417—Spectrofluorimetric devices
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Dispersion Chemistry (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention discloses a method for investigating toxicity characteristics of wastewater discharged from a chemical industrial park, which comprises the following steps: (1) Surveying and sampling, collecting data of the park and enterprises, generalizing a logical relation graph of the park enterprise production and discharge wastewater based on data sorting and on-site investigation and analysis, and identifying key nodes; (2) Primarily screening toxic pollutants discharged from the wastewater of the park; (3) The method comprises the following steps of summarizing key nodes for wastewater generation, treatment and discharge by combining an enterprise wastewater treatment mode in a park and the operation condition of a park sewage plant, and collecting a typical water sample; (4) Water sample detection, wherein firstly, the water sample is subjected to spectrum detection, and then mass spectrum detection and analysis are carried out, so that typical pollutants are identified; (5) Establishing a typical enterprise pollutant mass spectrum library in an industrial area based on typical pollutants; and annotating the spectral fingerprint of the typical pollutant of the wastewater produced and discharged by the enterprise based on the mass spectrum characteristics of the typical pollutant, and determining the spectral fingerprint of the typical pollutant.
Description
Technical Field
The invention relates to the technical field of wastewater detection, in particular to a method for investigating toxicity characteristics of wastewater discharged from a chemical industrial park.
Background
At present, the wastewater discharged by sewage treatment plants in chemical industrial parks executes the first grade A discharge standard of pollutant discharge Standard of urban Sewage treatment plants (GB 18918-2002), and mainly monitors 12 basic control items and 7 pollutants, and does not monitor other toxic and harmful substances. Except conventional pollutants such as COD (chemical oxygen demand), ammonia nitrogen and the like, the wastewater discharged from a chemical industrial park often generates toxic and harmful characteristic pollutants such as benzene series, aniline and nitrobenzene, and once the toxic and harmful substances are discharged to a surface water body along with the wastewater, toxic and harmful effects can be generated in a larger range for a longer time. Once entering the body of aquatic organisms, after accumulating to a certain concentration, the aquatic organisms can generate biochemical or biophysical actions with body fluids and organ tissues, disturb or destroy the normal physiological functions of the organisms, cause temporary or permanent pathological changes of certain organs and systems, and even endanger life.
In order to comprehensively and accurately investigate and evaluate the toxicity condition of the wastewater in the chemical industry park, comprehensively improve the wastewater pollution prevention level and promote the continuous and stable improvement of the water environment in the drainage basin, the investigation of the toxicity characteristic of the wastewater discharge in the chemical industry park is necessary to be carried out, so that organic pollutants which are high in toxicity, easy to accumulate, high in potential environmental risk and strong in pertinence are screened out, priority monitoring and key control are carried out, the water quality safety is guaranteed, and the ecological health is protected.
Disclosure of Invention
Aiming at the technical defects, the invention aims to provide a method for investigating the toxicity characteristics of wastewater discharged from a chemical industrial park, so as to solve the problems in the background art.
In order to solve the technical problem, the invention adopts the following technical scheme:
the basic conditions of production scale, production process, raw materials, products and the like of an enterprise are examined in detail;
combining pollutant toxicity data related to the water environment and background data of a chemical industry park, and primarily screening a list of priority control toxic pollutants;
the method comprises the following steps of summarizing key nodes for wastewater generation, treatment and discharge by combining an enterprise wastewater treatment mode in a park and the operation condition of a park sewage plant, and collecting a typical water sample;
the method comprises the steps of respectively connecting a Gas Chromatograph (GC), a Liquid Chromatograph (LC) and an Ion Chromatograph (IC) with a Mass Spectrum (MS) in series in two stages, analyzing the structural characteristics of the wastewater generated by each enterprise production line, comparing the structural characteristics with a screening list, analyzing the feasibility of pollutant monitoring management, and finally determining the toxic substances discharged by the wastewater in the chemical industry park.
Specifically, the invention provides a method for investigating toxicity characteristics of wastewater discharged from a chemical industrial park, which comprises the following steps:
(1) Surveying and sampling, collecting data of the park and enterprises, generalizing a park enterprise production and discharge wastewater logical relation graph based on data sorting and field investigation analysis, and identifying key nodes;
(2) Primarily screening toxic pollutants discharged from the wastewater of the park;
(3) The method comprises the following steps of summarizing key nodes for wastewater generation, treatment and discharge by combining an enterprise wastewater treatment mode in a park and the operation condition of a park sewage plant, and collecting a typical water sample;
(4) Water sample detection, wherein firstly, the water sample is subjected to spectrum detection, and then mass spectrum detection and analysis are carried out, so that typical pollutants are identified;
(5) Establishing a typical enterprise pollutant mass spectrum library in an industrial area based on typical pollutants; and annotating the spectral fingerprint of the typical pollutant of the wastewater produced and discharged by the enterprise based on the mass spectrum characteristics of the typical pollutant, and determining the spectral fingerprint of the typical pollutant.
Preferably, the screening method in step (2) is: comprehensively screening to obtain an optimal control pollutant primary selection list according to the appearance frequency analysis, the hazard analysis, the water environment toxicity analysis and the environment risk analysis based on the chemical stock of the park by combining the characteristics of the park; and analyzing the feasibility of monitoring and managing the screened pollutants, and primarily screening toxic pollutants discharged by wastewater.
Preferably, the spectrum detection in step (4) is: the method comprises the steps of (1) passing a water sample through a membrane to obtain a DOM solution, detecting TOC of the DOM solution, and diluting the concentration of the DOM solution to 10-40mg/L; measuring a three-dimensional fluorescence spectrum by adopting an F-7000 type fluorescence spectrophotometer, and processing data by using FL solutions2.1 software; the DOM solution was placed in a 1cm quartz cuvette using Milli-Q ultrapure water as a blank.
Preferably, the mass spectrometric detection and analysis in step (4) comprises: sample pretreatment, GC-MS volatile organic compounds, LC-MS semi-volatile hydrophobic organic compounds, IC-MS heavy metal ions and perchloric acid ions.
Preferably, the sample pretreatment is as follows: transferring the wastewater sample into a separating funnel, washing the conical flask twice by using deionized water, merging the washing liquid into the separating funnel, washing the conical flask twice by using petroleum ether and diethyl ether, merging the conical flask into the separating funnel, slightly shaking for 2min, standing and layering; transferring the lower water phase to another separating funnel, extracting once with petroleum ether and diethyl ether, and combining the organic phases; washing the extractive solution with deionized water to neutral, shaking to prevent emulsification, dewatering the extractive solution with glass funnel filled with anhydrous sodium sulfate, transferring to a concentration bottle, concentrating to dry, and adding n-hexane for redissolution to purify.
Preferably, the GC-MS volatile organic compound is
Chromatographic conditions are as follows: sample inlet temperature: 280 ℃; no shunt sampling; carrier gas: high purity helium, 4.16; sample introduction amount: 1.0 μ L; column flow rate: 1ml/min; initial temperature: keeping the temperature at 40 ℃ for 4min, raising the temperature to 300 ℃ at the speed of 8 ℃/min, and keeping the temperature until the last target compound;
mass spectrum conditions: an electron impact source (EI); ion source temperature: 180 ℃; transmission line temperature: 280 ℃; ionization energy: 70eV; mass spectrum scanning range: 35amu to 500amu; the data acquisition mode is as follows: full scan mode or selective ion scan.
Preferably, the LC-MS semi-volatile-hydrophobic organic compound
The specification of the selected chromatographic column is WpHC18; mobile phase: the phase A is methanol, the phase B is 1% acetic acid, and the volume ratio of the mobile phase is 60; the wavelength of the ultraviolet detector is 271nm; the flow rate was set at 1.0mLmin-1; the injection volume is 20 mu L;
a chemical intermediate is connected with a quadrupole flight time mass spectrometer through a high performance liquid chromatography in series;
separating the mixture in liquid phase by using Shim-pack XR-ODSS chromatographic column, and controlling the temperature of the chromatographic column at 35 ℃;
the mobile phase A is methanol, the mobile phase B is 0.1% formic acid water, and the gradient elution time is 23min;
the gradient is set according to the proportion of the mobile phase A: 0 to 2min,5 percent; linearly increasing to 95 percent within 2-16 min; 16-20 min, and maintaining at 95%; linearly decreasing to 5% in 20-21 min; 21-23 min, keeping at 5%;
the mobile phase speed is 0.3mL min-1;
the mass spectrometry adopts a positive ion mode and an electrospray ion source;
the ion spraying voltage is 5500V, the drying air is 25PSI, and the atomizing air is 6PSI;
typical mass spectral parameters are: m/z ranges from 100 to 500; accumulating the time for 100ms; the declustering voltage is 80V; the collision energy was 15V.
The invention has the beneficial effects that:
organic pollutants with high toxicity, easy accumulation, high potential environmental risk and strong pertinence can be effectively screened out to implement preferential monitoring and key control.
Strengthens the control of the toxicity of the wastewater in chemical industry parks and chemical industry concentration areas and ensures the water quality safety and ecological health.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic diagram of a technical route for investigating toxicity characteristics of wastewater discharged by an embodiment of the present invention;
fig. 2 is a schematic diagram of a wastewater discharge map and sampling points of a part of enterprises in a park according to an embodiment of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it is to be understood that the terms "upper", "lower", "front", "rear", "left", "right", "top", "bottom", "inner", "outer", and the like, are used in the orientations and positional relationships indicated in the drawings, which are based on the orientations and positional relationships indicated in the drawings, and are used for convenience of description and simplicity of description, but do not indicate or imply that the devices or elements referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, are not to be construed as limiting the present invention.
Example (b):
taking a fine chemical industry industrial area of an industrial park as an example, FIG. 1 is a technical route chart for investigating and evaluating the toxicity characteristics of wastewater discharged from the park,
by collecting the data of environmental evaluation, production scale, production process, production period, marketing and the like of the fine chemical industry area of the industrial park, the current situations of wastewater generation and treatment condition, park sewage treatment plants, wastewater discharge ports, water receiving bodies and the like of the production line of an enterprise are investigated on site, the wastewater discharge logic diagram of the park enterprise is generalized, and key nodes are identified.
Collecting wastewater samples of each key node in different periods, and monitoring the pH, EC, temperature, DO and the like of the wastewater on site; and the GC, the LC and the IC are respectively connected with the MS in series in two stages, the structural characteristics of the wastewater generated by each enterprise production line are analyzed, and the typical pollutants are finally identified by combining a primary screening priority control toxic pollutant list.
Specific embodiments are as follows:
investigation sampling, collecting the data of the garden and the enterprises, generalizing the logical relationship diagram of the industrial wastewater of the garden enterprises based on data sorting and on-site investigation analysis, and identifying key nodes:
collecting DEM (digital elevation model) of a chemical industry park (chemical industry centralized area), high-resolution remote sensing images, administrative districts and land utilization space distribution maps, and surveying the current situation characteristics of hydrological water systems, water quality and water quantity, water ecology and the like of the industrial area; collecting reports of the park planning environmental assessment, the assessment ability, the clean production and the like of enterprises in the park, and knowing relevant conditions of production scale, production process, chemical use, storage and the like; investigating related conditions such as enterprise wastewater discharge amount, wastewater characteristics, sewage treatment facility scale, process, effluent execution standard and the like; the operation condition of the sewage plant in the park, the treatment scale and process of the sewage plant, the effluent execution standard, the water quality reaching the standard and the like; based on data arrangement and field investigation and analysis, generalizing a logical relation graph of the industrial wastewater of the park;
as shown in fig. 2, taking an industrial park fine chemical industry area as an example, a key node is identified.
(II) preliminarily screening toxic pollutants discharged from the park wastewater:
chemical industry park enterprises are various, and a large amount of volatile or semi-volatile organic substances and other toxic substances are generated in the production process. According to the principle of screening priority control pollutants, combining the characteristics of a park and analyzing the occurrence frequency of a list, wherein the list used comprises a domestic or foreign developed countries such as the United states, europe, japan and the like, a key list of related priority control pollutants, a list of toxic and harmful substances, a list of endocrine substances and the like; hazard analysis, water environment toxicity analysis and environment risk analysis based on the chemical stock in the garden, and obtaining an optimal pollutant primary selection list by using a comprehensive screening method; and analyzing the feasibility of monitoring and managing the pollutants obtained by screening, and primarily screening the pollutants into toxic pollutants discharged by wastewater.
(III) combine enterprise's waste water treatment mode and the operation conditions of garden sewage factory in the garden, the key node of generalized waste water production, processing, emission gathers typical water sample:
fig. 2 shows the arrangement of sampling points for wastewater produced and discharged by some enterprises in a park, taking a certain fine chemical industry area as an example.
The waste water that the garden enterprise produced generally adopts the processing mode of "enterprise preliminary treatment + sewage treatment plant processing", handles the back through the inside sewage treatment facility of enterprise earlier, according to the regional planning distribution in garden, gets into corresponding sewage treatment plant, and the external environment is gone into to sewage treatment plant after handling.
And (3) preliminarily planning each sampling point to collect samples for 2 times in an investigation period by combining the production period, production raw materials, product yield, wastewater discharge characteristics and water quantity characteristics of an enterprise under field investigation, wherein the sampling point position needs to cover all production lines.
Detecting pH, EC and temperature in situ, and detecting CODCr, TN and NH in laboratory 3 And (4) carrying out detection and analysis on toxic and harmful characteristic pollutants and the like simultaneously by basic items such as-N and TP.
(IV) water sample detection, wherein the water sample is subjected to spectrum detection firstly, and then mass spectrum detection and analysis are carried out, so that typical pollutants are identified:
wherein the spectrum detection is as follows:
and (3) coating a water sample by 0.45 mu m to obtain a DOM solution, detecting the TOC of the DOM solution, and diluting the DOM solution to the concentration of 10-40mg/L, preferably 40, 30, 20 and 10mg/L.
The measurement of the three-dimensional fluorescence spectrum is completed by adopting an F-7000 type fluorescence spectrophotometer, and data processing is carried out by using FL solutions2.1 software. The DOM solution was placed in a 1cm quartz cuvette, using Milli-Q ultrapure water as a blank.
The excitation light source is a 150W xenon arc lamp, the photomultiplier voltage is 700V, the scanning range of the excitation wavelength (Ex) is 200-450 nm, the scanning range of the emission wavelength (Em) is 260-550 nm, the width of the excitation and emission slits is 5nm, the response time is 0.5s, the scanning speed is 2400nm/min, and the scanning interval is 10nm.
Wherein, the mass spectrometric detection and analysis comprises:
(1) Sample pretreatment
Pretreatment of samples reference:
extracting conditions of GB/T22220-2008, GB/T9695.24-2008, GB/T5009.128-2003 and AOAC official method 933.08 according to the extracting conditions in GB/T22220-2008: transferring the wastewater sample to a 250mL separating funnel, washing the conical flask with 30mL deionized water twice, merging the washing liquid into the separating funnel, washing the conical flask with 40mL petroleum ether + ether (volume ratio, 1); the lower aqueous phase was then transferred to another 250mL separatory funnel and extracted once more with 30mL of petroleum ether + diethyl ether (volume ratio, 1). Washing the extract with deionized water 100mL each time to neutrality, shaking gently during the first washing to prevent emulsification, dehydrating the extract with glass funnel containing 10g anhydrous sodium sulfate, transferring to a concentration bottle, concentrating to dryness, and adding 5mL n-hexane for redissolving to purify.
(2) GC-MS volatile organics:
the gas chromatography is applied to the determination of organic pollutants in industrial wastewater, the volatile organic pollutants in the industrial wastewater comprise volatile halogenated organic compounds, aromatic hydrocarbons, acrolein, nitrobenzene compounds and the like, and the gas chromatography has the characteristics of high resolution, strong flexibility, strong selectivity, high analysis speed and the like. In the detection process, substances such as hydrocarbon isomers or isotopes with similar properties and characteristics can be accurately analyzed.
Chromatographic conditions are as follows: sample inlet temperature: 280 ℃; no shunt sampling; carrier gas: high purity helium (4.16); sample injection amount: 1.0 μ L; column flow rate: 1ml/min; initial temperature: 40 ℃ for 4min, and increasing the temperature to 300 ℃ at a rate of 8 ℃/min until the last target compound is obtained.
Mass spectrum conditions: an electron impact source (EI); ion source temperature: 180 ℃; transmission line temperature: 280 ℃; ionization energy: 70eV; mass spectrum scanning range: 35amu to 500amu; the data acquisition mode comprises the following steps: full Scan (Scan) mode or selective ion Scan (SIM).
(3) LC-MS semi-volatile-hydrophobic organic:
MS is a common analytical technique for the identification and analysis of components to be detected by the preparation, separation and detection of gas phase ions. The analysis and detection by mass spectrometry has become an essential means for routine environmental analysis and research. High performance liquid chromatography was used to determine the concentration of typical (hydrophobic) organic contaminants in the solution. The specification of the selected chromatographic column is WpH C18 (4.6 mm multiplied by 250mm,5 mu m); mobile phase: the phase A is methanol, the phase B is 1% acetic acid, and the volume ratio of the mobile phase is 60; the wavelength of the ultraviolet detector is 271nm; the flow rate was set at 1.0mLmin-1; the injection volume was 20. Mu.L.
The chemical intermediate is connected with a quadrupole time-of-flight mass spectrometer detector in series through a high performance liquid chromatography. The mixture was separated in a liquid phase using a Shim-packXR-ODS column (2.0 mm. Times.75 mm. Times.3.5 μm, shimadzu, kyoto, japan) whose column temperature was controlled at 35 ℃. The mobile phase A was methanol, the mobile phase B was 0.1% formic acid water, and the gradient elution time was 23min. The gradient is set according to the proportion of the mobile phase A: 0 to 2min,5 percent; linearly increasing to 95 percent within 2-16 min; 16-20 min, and maintaining at 95%; linearly decreasing to 5% in 20-21 min; 21-23 min, and maintaining at 5%. The mobile phase velocity was 0.3mLmin-1. Mass spectrometry was performed using positive ion mode, electrospray ionization (ESI). The ion spraying voltage is 5500V, the drying air is 25PSI, and the atomizing air is 6PSI;
typical mass spectral parameters are as follows: m/z ranges from 100 to 500; accumulating the time for 100ms; the declustering voltage is 80V; the collision energy was 15V. Data analysis used MarkerView software, and material qualitative and semi-quantitative PeakView software.
(4) IC-MS heavy metal ion and perchlorate ion:
the ion chromatography is one of high performance liquid chromatography technologies, and is suitable for detecting organic pollutants such as heavy metal ions or perchloric acid ions in water. When the ion chromatography is used for detecting a mixture formed by a plurality of components in a water body, the ion chromatography can be used for high-efficiency separation and qualitative and quantitative analysis. The ion chromatography detector is divided into an electrochemical detector and an optical detector, and can greatly improve the accuracy and the sensitivity of qualitative and quantitative detection after being combined with mass spectrometry.
Establishing a typical enterprise pollutant mass spectrum library in an industrial area based on typical pollutants; annotate its spectrum fingerprint based on enterprise produces and arranges waste water typical pollutant mass spectrum characteristic, confirm the spectrum fingerprint of typical pollutant:
processing three-dimensional fluorescence spectrum data of industrial area enterprise production and discharge wastewater by using technologies such as data cleaning, conversion, fusion and the like, and establishing a spectrum fingerprint database according to industrial area enterprise industry; identifying typical pollutants by using a mathematical statistical method based on mass spectrometry analysis of GC, IC and LC of the enterprise wastewater, and establishing a typical enterprise pollutant mass spectrum library in an industrial area; and annotating the spectral fingerprint of the typical pollutant of the enterprise production wastewater based on the mass spectrum characteristics of the typical pollutant, and determining the spectral fingerprint of the typical pollutant.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (7)
1. A method for investigating toxicity characteristics of wastewater discharged from chemical industrial parks is characterized by comprising the following steps:
(1) Surveying and sampling, collecting data of the park and enterprises, generalizing a park enterprise production and discharge wastewater logical relation graph based on data sorting and field investigation analysis, and identifying key nodes;
(6) Preliminarily screening toxic pollutants discharged by the wastewater of the park;
(7) The method comprises the following steps of summarizing key nodes for wastewater generation, treatment and discharge by combining an enterprise wastewater treatment mode in a park and the operation condition of a park sewage plant, and collecting a typical water sample;
(8) Water sample detection, wherein firstly, the water sample is subjected to spectrum detection, and then mass spectrum detection and analysis are carried out, so that typical pollutants are identified;
(9) Establishing a typical enterprise pollutant mass spectrum library in an industrial area based on typical pollutants; and annotating the spectral fingerprint of the typical pollutant of the wastewater produced and discharged by the enterprise based on the mass spectrum characteristics of the typical pollutant, and determining the spectral fingerprint of the typical pollutant.
2. The method for investigating toxicity characteristics of wastewater discharged from a chemical industrial park according to claim 1, wherein the screening method in the step (2) comprises: according to the characteristics of the park, comprehensively screening to obtain an optimal pollutant primary selection list according to the occurrence frequency analysis, the hazard analysis, the water environment toxicity analysis and the environment risk analysis based on the chemical stock of the park; and analyzing the feasibility of monitoring and managing the pollutants obtained by screening, and primarily screening the pollutants into toxic pollutants discharged by wastewater.
3. The method for investigating the toxicity characteristics of wastewater discharged from a chemical industrial park as claimed in claim 1, wherein the spectral detection in step (4) is: the method comprises the steps of (1) coating a water sample to obtain a DOM solution, detecting TOC of the DOM solution, and diluting the DOM solution to 10-40mg/L; measuring the three-dimensional fluorescence spectrum by adopting an F-7000 type fluorescence spectrophotometer, and processing data by using FL solutions2.1 software; the DOM solution was placed in a 1cm quartz cuvette using Milli-Q ultrapure water as a blank.
4. The method for investigating toxicity characteristics of wastewater discharged from a chemical industrial park as claimed in claim 1, wherein the mass spectrometric detection and analysis in step (4) comprises: sample pretreatment, GC-MS volatile organic compounds, LC-MS semi-volatile hydrophobic organic compounds, IC-MS heavy metal ions and perchloric acid ions.
5. The method for investigating the toxicity characteristics of wastewater discharged from a chemical industrial park according to claim 4, wherein the sample pretreatment comprises the following steps: transferring the wastewater sample into a separating funnel, washing the conical flask twice by using deionized water, merging the washing liquid into the separating funnel, washing the conical flask twice by using petroleum ether and diethyl ether, merging the conical flask into the separating funnel, slightly shaking for 2min, standing and layering; transferring the lower water phase to another separating funnel, extracting once with petroleum ether and diethyl ether, and combining the organic phases; washing the extractive solution with deionized water to neutral, shaking to prevent emulsification, dewatering the extractive solution with glass funnel filled with anhydrous sodium sulfate, transferring to a concentration bottle, concentrating to dry, and adding n-hexane for redissolution to purify.
6. The chemical industrial park wastewater discharge toxicity characteristic investigation method according to claim 4, characterized in that, the GC-MS volatile organic compounds
Chromatographic conditions are as follows: sample inlet temperature: 280 ℃; no shunt sampling; carrier gas: high purity helium, 4.16; sample introduction amount: 1.0 mu L; column flow rate: 1ml/min; initial temperature: keeping the temperature at 40 ℃ for 4min, raising the temperature to 300 ℃ at the speed of 8 ℃/min, and keeping the temperature until the last target compound;
mass spectrum conditions: an electron bombardment source; ion source temperature: 180 ℃; transmission line temperature: 280 ℃; ionization energy: 70eV; mass spectrum scanning range: 35amu to 500amu; the data acquisition mode is as follows: full scan mode or selective ion scan.
7. The chemical industrial park wastewater discharge toxicity characteristic investigation method of claim 4, wherein the LC-MS semi-volatile-hydrophobic organic matter
The specification of the selected chromatographic column is WpH C18; mobile phase: the phase A is methanol, the phase B is 1% acetic acid, and the volume ratio of the mobile phase is 60; the wavelength of the ultraviolet detector is 271nm; the flow rate was set to 1.0mL min-1; the injection volume is 20 mu L;
a chemical intermediate is connected with a quadrupole flight time mass spectrometer through a high performance liquid chromatography in series;
separating the mixture in liquid phase by using Shim-packXR-ODSS chromatographic column, and controlling the temperature of the chromatographic column at 35 ℃;
the mobile phase A is methanol, the mobile phase B is 0.1% formic acid water, and the gradient elution time is 23min;
the gradient is set according to the proportion of the mobile phase A: 0 to 2min,5 percent; linearly increasing to 95 percent within 2-16 min; 16-20 min, and keeping the temperature at 95%; linearly decreasing to 5 percent in 20-21 min; 21-23 min, keeping at 5%;
the mobile phase speed is 0.3mL min-1;
the mass spectrometry adopts a positive ion mode and an electrospray ion source;
the ion spraying voltage is 5500V, the drying air is 25PSI, and the atomizing air is 6PSI;
typical mass spectral parameters are: m/z ranges from 100 to 500; accumulating the time for 100ms; the declustering voltage is 80V; the collision energy was 15V.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210793025.6A CN115144502A (en) | 2022-07-05 | 2022-07-05 | Method for investigating toxicity characteristics of wastewater discharged from chemical industrial park |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210793025.6A CN115144502A (en) | 2022-07-05 | 2022-07-05 | Method for investigating toxicity characteristics of wastewater discharged from chemical industrial park |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115144502A true CN115144502A (en) | 2022-10-04 |
Family
ID=83411786
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210793025.6A Pending CN115144502A (en) | 2022-07-05 | 2022-07-05 | Method for investigating toxicity characteristics of wastewater discharged from chemical industrial park |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115144502A (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104483298A (en) * | 2014-12-10 | 2015-04-01 | 陕西科技大学 | Water quality detecting method for tannery wastewater treatment process |
| CN105784650A (en) * | 2016-03-04 | 2016-07-20 | 长江大学 | Online monitoring method for organic matter contamination of surface water |
| CN106018359A (en) * | 2016-05-12 | 2016-10-12 | 常州市排水管理处 | Sewage plant water-quality monitoring early-warning method and system |
| CN108287140A (en) * | 2018-01-29 | 2018-07-17 | 陕西科技大学 | A kind of method and device for sewage treatment plant's real time on-line monitoring |
| CN110083585A (en) * | 2019-03-15 | 2019-08-02 | 清华大学 | A kind of water pollution discharge source database and its method for building up |
| CN110609021A (en) * | 2019-08-15 | 2019-12-24 | 成都市环境保护科学研究院 | River basin pollutant characteristic analysis method based on three-dimensional fluorescence spectrum |
| CN111562327A (en) * | 2020-05-25 | 2020-08-21 | 南京大学 | Molecular network-based non-target screening and analyzing method for toxic organic pollutants in wastewater |
| WO2021217745A1 (en) * | 2020-04-26 | 2021-11-04 | 南京大学 | High-throughput screening method for non-target biomarker employing pollutant metabolic turbulence |
| CN113603166A (en) * | 2021-08-09 | 2021-11-05 | 中节能环保投资发展(江西)有限公司 | Industrial park district water pollutant management and control system that traces to source |
-
2022
- 2022-07-05 CN CN202210793025.6A patent/CN115144502A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104483298A (en) * | 2014-12-10 | 2015-04-01 | 陕西科技大学 | Water quality detecting method for tannery wastewater treatment process |
| CN105784650A (en) * | 2016-03-04 | 2016-07-20 | 长江大学 | Online monitoring method for organic matter contamination of surface water |
| CN106018359A (en) * | 2016-05-12 | 2016-10-12 | 常州市排水管理处 | Sewage plant water-quality monitoring early-warning method and system |
| CN108287140A (en) * | 2018-01-29 | 2018-07-17 | 陕西科技大学 | A kind of method and device for sewage treatment plant's real time on-line monitoring |
| CN110083585A (en) * | 2019-03-15 | 2019-08-02 | 清华大学 | A kind of water pollution discharge source database and its method for building up |
| CN110609021A (en) * | 2019-08-15 | 2019-12-24 | 成都市环境保护科学研究院 | River basin pollutant characteristic analysis method based on three-dimensional fluorescence spectrum |
| WO2021217745A1 (en) * | 2020-04-26 | 2021-11-04 | 南京大学 | High-throughput screening method for non-target biomarker employing pollutant metabolic turbulence |
| CN111562327A (en) * | 2020-05-25 | 2020-08-21 | 南京大学 | Molecular network-based non-target screening and analyzing method for toxic organic pollutants in wastewater |
| CN113603166A (en) * | 2021-08-09 | 2021-11-05 | 中节能环保投资发展(江西)有限公司 | Industrial park district water pollutant management and control system that traces to source |
Non-Patent Citations (1)
| Title |
|---|
| 张涛;胡冠九;邓爱萍;王荟;穆肃;: "江苏沿江某化工园区有机污染调查与研究", 中国环境监测, no. 01, pages 60 - 61 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Bahlmann et al. | Immunoassays as high-throughput tools: monitoring spatial and temporal variations of carbamazepine, caffeine and cetirizine in surface and wastewaters | |
| Horton et al. | Semi-automated analysis of microplastics in complex wastewater samples | |
| Bijlsma et al. | Investigation of drugs of abuse and relevant metabolites in Dutch sewage water by liquid chromatography coupled to high resolution mass spectrometry | |
| US20240027419A1 (en) | Method and system for intelligent source tracing of organic pollution of water body | |
| Wilkinson et al. | Markers of anthropogenic contamination: A validated method for quantification of pharmaceuticals, illicit drug metabolites, perfluorinated compounds, and plasticisers in sewage treatment effluent and rain runoff | |
| Matthijs et al. | Environmental monitoring for linear alkylbenzene sulfonate, alcohol ethoxylate, alcohol ethoxy sulfate, alcohol sulfate, and soap | |
| Comoretto et al. | Comparing pharmaceutical and pesticide loads into a small Mediterranean river | |
| Wang et al. | Suspect, non-target and target screening of pharmaceuticals and personal care products (PPCPs) in a drinking water system | |
| Calisto et al. | Application of an ELISA to the quantification of carbamazepine in ground, surface and wastewaters and validation with LC–MS/MS | |
| Zhao et al. | Characterization of CDOM from urban waters in Northern-Northeastern China using excitation-emission matrix fluorescence and parallel factor analysis | |
| Becouze-Lareure et al. | Source characterisation and loads of metals and pesticides in urban wet weather discharges | |
| Liu et al. | Non-target and target screening of per-and polyfluoroalkyl substances in landfill leachate and impact on groundwater in Guangzhou, China | |
| CN110083585B (en) | Water pollution discharge source database and establishing method thereof | |
| Deffontis et al. | Impact of dry weather discharges on annual pollution from a separate storm sewer in Toulouse, France | |
| Borrull et al. | A simple, fast method for the analysis of 20 contaminants of emerging concern in river water using large-volume direct injection liquid chromatography-tandem mass spectrometry | |
| CN111562242A (en) | Method for quickly identifying source of overflowing sewage in rainy days of urban drainage system | |
| CN105784881A (en) | Determination method of perfluorinated compound isomer in soil and/or plants | |
| Zhu et al. | Online recognition of drainage type based on UV-vis spectra and derivative neural network algorithm | |
| Zhang et al. | Sources of nitrate‑nitrogen in urban runoff over and during rainfall events with different grades | |
| Lee et al. | Chemicals of emerging concern in water and bottom sediment in Great Lakes areas of concern, 2010 to 2011-Collection methods, analyses methods, quality assurance, and data | |
| CN103234925A (en) | Method for rapidly determining trace quantity of thallium in drinking water | |
| Liu et al. | Profile and removal of endocrine disrupting chemicals by using an ER/AR competitive ligand binding assay and chemical analyses | |
| Huang et al. | Occurrence of per-and polyfluoroalkyl substances (PFAS) in municipal solid waste landfill leachates from western China | |
| Gruber et al. | Quantification of pollution loads from CSOs into surface water bodies by means of online techniques | |
| CN114563381A (en) | Water body pollution tracing method |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20221004 |