CN112147244A - Method for identifying high-risk disinfection byproducts in water, device and application thereof - Google Patents
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Abstract
The invention belongs to the technical field of environmental health and water quality analysis, and particularly relates to a method for identifying high-risk disinfection byproducts in water, and a device and application thereof. The invention discloses a method for identifying high-risk disinfection byproducts in water, which comprises the following steps: s1, collecting and pretreating a water sample to be treated, and quantifying the concentration, the type and the level of a disinfection by-product; s2, calculating and obtaining the comprehensive toxicity of the disinfection by-products based on the cytotoxicity, genetic toxicity and developmental toxicity databases; and S3, coupling the comprehensive toxicity and the generation potential of the disinfection byproducts, and judging the toxicity risk. The method adopts a method for measuring the generation potential of a simulated water distribution system, objectively and comprehensively evaluates the concentration level of DBPs, and has more reference and guidance values through biological and chemical evaluation coupling. The method of the invention has clear steps and easy operation and implementation, and can be applied to various water supply quality monitoring departments, water plants and detection units.
Description
Technical Field
The invention belongs to the technical field of environmental health and water quality analysis, and particularly relates to a method and a device for identifying and sequencing risks of test disinfection byproducts.
Background
The disinfection is a necessary measure for ensuring the safety of drinking water in order to kill pathogenic microorganisms in the water. At present, the drinking water disinfection technology mainly comprises chlorine disinfection, chloramine disinfection, chlorine dioxide disinfection, ozone disinfection and ultraviolet disinfection. But drinking water disinfection is two-sided, and when killing pathogenic microorganisms in water, the drinking water disinfection often also generates a plurality of disinfection by-products (DBPs). More than 700 DBPs have been discovered globally, many DBPs have mutagenicity and carcinogenicity, and people research also shows that the DBPs exposure has correlation with diseases such as poor reproductive fate, tumors and the like. The balance between the risk of spreading water-mediated epidemics caused by aquatic microorganisms and the risk of chemical toxicity caused by exposure of DBPs, especially the identification of high-risk DBPs, has become one of the hot spots of the research on the safety guarantee of drinking water.
Regarding identification of high-risk DBPs, many previous studies have determined the order of priority control of several DBPs at individual toxicity levels or concentration levels. Excess disinfectant is mostly added for measuring the generation potential of the DBPs concentration level of an actual water sample, which may cause the detection concentration to be higher than the actual concentration level. At present, three evaluation indexes of chronic cytotoxicity, acute genetic toxicity and developmental toxicity are used for identifying toxicity. Among them, cytotoxicity is the mere cell death, cell lysis and cell growth inhibition caused by certain chemicals or products. Genotoxicity refers to the toxic effect of environmental factors acting on an organism to cause various damages to its genetic material at the chromosome level, molecular level and base level. Developmental toxicity refers to the effects of certain substances on induction or display, including in embryonic and fetal stages, as well as postnatal induction or display, i.e., on the structure and function of prenatal embryos, fetuses, and postnatal juveniles.
It has been found that the variety of DBPs is continuously abundant, and it is difficult to quantitatively judge which DBPs have higher risk effect only by chemical analysis or the toxicity of a certain substance. A more accurate method of generating potential analysis combined with a more comprehensive toxicity assessment is needed to identify high risk disinfection by-products in clear drinking water. Further develop follow-up DBPs cooperative control, promote drinking water quality.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the technical problem to be solved by the invention is to provide a DBPs risk identification method, which is used for rapidly and accurately evaluating DBPs based on generation potential, cytotoxicity, genotoxicity and developmental toxicity.
In one aspect, the invention provides a method for identifying high-risk disinfection byproducts in water, comprising the following steps:
s1, collecting and pretreating a water sample to be treated, and quantifying the concentration type and level of the disinfection by-products;
s2, calculating and obtaining the comprehensive toxicity of the disinfection by-products based on the cytotoxicity, genetic toxicity and developmental toxicity databases;
and S3, coupling the comprehensive toxicity and the generation potential of the disinfection byproducts, and judging the toxicity risk.
The water can be tap water, sewage and other water bodies which are subjected to disinfection treatment. For example, domestic drinking water should be disinfected (GB 5749-2006). Preferably, the contact time of the free chlorine and the water is not less than 30min, and the residual chlorine of the effluent is not less than 0.3mg/L and not more than 4 mg/L; if monochloramine is adopted for disinfection, the contact time of the monochloramine and water is not less than 120min, and the residual chlorine of the effluent is not less than 0.5 mg/L and not more than 3 mg/L.
Preferably, the pretreatment method in step S1 is to filter the water sample to be treated to remove impurities while adjusting the pH to neutral, for example, 7.0 to 8.0.
In a preferred embodiment of the invention, the water sample is passed through a 0.45 μm microfiltration membrane, and the pH of the water sample is adjusted to about 7.0 using sulfuric acid and sodium hydroxide.
Preferably, 1-4mg/L chlorine is added into the water sample to be treated in step S1, so that the residual chlorine amount is 0.5-1.5mg/L after 24 hours, and a quenching agent is added to quench the residual chlorine and is used for measuring the generation potential.
The quenching agent can adopt any one or more of commercially available conventional quenching agents, such as ascorbic acid, sodium thiosulfate, sodium sulfite or ammonium chloride.
Preferably, the generating potential is determined using a simulated water distribution system (SDS). The calculation of the potential energy by the SDS method refers to the simulation of a water distribution system disinfection experiment, namely, the disinfection experiment is carried out by adding a certain amount of disinfectant, so that the residual chlorine of the water sample after 24 days is about 1.0 mg/L.
The toxicity data is derived from conventional toxicity reports of water body pollutants, and comprises various related databases, books and magazines, website published data, scientific reports and the like. For example, selected from the following literature:
zebraphis embryo biology of 15 chlorinated, brominated, and iodinated discovery by-products (PMID: 28774621. J Environ Sci (China)2017 Aug; 58 DOI: 10.1016/J. jes.2017.05.008. Handian D, Truong L, Simonich M, Tanguay R, Westerhoff P, etc.);
"haloacetitriles vs. regulated haloacetic acids? In a formula (PMID: 17310735 journal Vol: environ. Sci. Technol.2007 Jan 15; 41(2) DOI: 10.1021/es0617441 Muellner MG, Wagner ED, McCalla K, Richardson SD, Woo YT, Plewa MJ, etc.);
halonitromethane driving water degeneration bypass products chemical characteristics and macrologic cell cytotoxicity and geneticity (PMID: 14740718 journal volume: environ. Sci. technol. 2004 Jan 01; 38(1) DOI: 10.1021/es030477l. list of authors: Plewa MJ, Wagner ED, Jazwierska P, Richardson SD, ChenPH, McKague AB, etc.);
mammalian cell cytoxicity and genoxicity of the haloacetic acids, a major class of driving water disinfection by-products, PMID (journal of 20839218, Environ. mol. Mutagen. 2010 Oct-Dec; 51 DOI: 10.1002/em.20585. list of authors: Plewa MJ, Simmons JE, Richardson, Wagner, et al);
occurence and Comparative approach of Haloacetaldehyde Disinfactant Byproductsin drining Water (PMID: journal of 25942416: environ. Sci. Technol.2015 Dec 01; 49 (23)) DOI: 10.1021/es506358x. list of authors: Jeong CH, Postio C, Richardson SD, Simmons JE, Kimura SY,
BJ, Barcelo D, Liang P, etc.)
Occurence and mammarian cell sensitivity of orthogonal disfigurement bypass in driving water (PMID: journal of 19068814, environ. Sci. Technol. 2008. Nov 15; 42(22) DOI: 10.1021/es8011699 k. Author List: Richardson SD, Fasano F, Ellington JJ, Crumley FG, Buettner KM, Evans JJ, Blount BC, Silva LK, etc.);
occurence, synthesis, and mammalia cell cytotoxicity and geneticity of haloacetamides an observing class of nitrogenes driving water inactivation byproducts, (PMID: 18323128, journal of Environ. Sci. Techniol. 2008 Feb 01; 42(3) DOI 10.1021/es071754 h. author list Plewa MJ, Muellner MG, Richardson SD, Fasano F, Buetner tKM, Woo YT, McKague AB, etc.);
development of haloacetonitrile formation and toxicity research in drinking water (journal of environmental and health, 2014,31(008): 741. 745. in oceans, campsis, Zhang Ying, etc.).
Preferably, in step S2, the cytotoxicity is based on cells including Chinese mouse ovarian cells, human bladder cancer cells, and the like.
Preferably, in step S2, the genetic toxicity includes DNA damage or chromosome damage.
Preferably, in step S2, the developmental toxicity is against an organism selected from the group consisting of nereis, artemia, mice and rats.
Preferably, the database of cytotoxicity, genotoxicity and developmental toxicity is updated periodically and continuously adjusted according to the collected information.
Preferably, in step S3, the step of coupling the comprehensive toxicity and the generation potential of the disinfection byproducts includes calculating a toxicity value x the generation potential of each disinfection byproduct to obtain a coupling value, and then comprehensively sorting the coupling values of all the disinfection byproducts to obtain a list of high-risk disinfection byproducts.
On the other hand, the invention provides a set of device for identifying high-risk disinfection byproducts in water, which comprises water quality pretreatment equipment, a disinfection byproduct quantitative instrument, a comprehensive toxicity calculation instrument for the disinfection byproducts and a toxicity risk judgment instrument for the disinfection byproducts;
the water quality pretreatment equipment filters a water sample to be treated, removes impurities and adjusts the pH value to 7.0-8.0;
the disinfection by-product quantitative instrument is connected with the water quality pretreatment equipment, collects the pretreated water sample and quantifies the disinfection by-products in the water sample;
the comprehensive toxicity calculating instrument of the disinfection byproducts calculates and obtains the comprehensive toxicity of the disinfection byproducts based on a cytotoxicity, genetic toxicity and developmental toxicity database;
the toxicity risk judgment instrument of the disinfection by-products is respectively connected with the comprehensive toxicity calculator of the disinfection by-products, and the comprehensive toxicity of the disinfection by-products is coupled with the generation potential to judge the toxicity risk of the disinfection by-products.
Preferably, the water quality filtration in the invention can be carried out by using a sand core filtration device or a filter head.
Preferably, the disinfection by-product quantification apparatus may employ a gas chromatography instrument. And generating potential, namely a detection result of the gas chromatograph.
Preferably, the sterilization by-products in the water sample after the quantitative pretreatment are determined, and the type and the concentration of the sterilization by-products are determined by using a gas chromatograph with an electron capture detector or a gas chromatograph mass spectrometer.
The invention discloses a DBPs risk identification technical method combining potential analysis and toxicity effect evaluation and a corresponding device, which take potential generation, cytotoxicity, genetic toxicity and developmental toxicity as cores. In a preferred embodiment of the present invention, the technical method comprises the following steps: s1, collecting water samples by different treatment processes of a water plant and preprocessing the water samples, and quantifying the concentration, the type and the level of DBPs by means of chemical analysis means such as a gas chromatograph and the like; s2, calculating and obtaining biological toxicity data of DBPs based on a toxicity database; and S3, coupling the toxicity level and the generation potential of the DBPs, namely judging the risk of the DBPs in the drinking water by using the toxicity value multiplied by the generation potential.
For example, the DBPs detection method described in S1 includes the steps of taking 10-15mL of water sample, sequentially adding 3-5g of anhydrous sodium sulfate and 2mL of methyl tert-butyl ether, then oscillating for 5min in an oscillator at an oscillation speed of 2000-2800r/min, standing for 3-10min, taking the upper layer of extractant solution, and determining the concentration of the disinfection by-products by using a gas chromatograph-electron capture detector (GC-ECD).
For example, the GC-ECD instrument condition control includes: adopting GC-ECD as a main instrument for detecting carbon-containing and nitrogen-containing disinfection byproducts; controlling the sample injection amount to be 1-3 mu L; the temperature of the injection port is controlled at 200 ℃, the temperature of the column box is kept at 32 ℃ for 10 minutes, the temperature is increased to 110 ℃ at the speed of 5 ℃/min, and then the temperature is increased to 200 ℃ and 250 ℃ at the speed of 10 ℃/min and kept for 5 minutes. Nitrogen was used as a carrier gas at a constant flow rate of 1-3 mL/min. The temperature of the detector was 280 ℃ and the current was set at 1.0-2.0 nA.
Or, the DBPs detection method of S1 includes the steps of taking 10-15mL of water sample, sequentially adding 3-5g of anhydrous sodium sulfate, 1mL of concentrated sulfuric acid and 3-5mL of methyl tert-butyl ether, then oscillating for 5min in an oscillator, standing for 3-10min, taking 2mL of upper-layer extractant solution, adding 10-15mL of acidified methanol, reacting in a water bath at 50 ℃ for 2h, adding 1-3mL of saturated sodium bicarbonate, and taking the upper-layer extractant solution for gas chromatography mass spectrometry (GC-MS) determination.
For example, the GC-MS instrument condition control includes: the sample inlet temperature is 200 ℃, the detector temperature is 260 ℃, and the RTX-5MS chromatographic column adopts the following temperature programming mode, the temperature is kept at 35 ℃ for 10 minutes, is increased to 75 ℃ at the speed of 5 ℃/min and is kept for 15 minutes, is increased to 100 ℃ at the speed of 5 ℃/min and is kept for 5 minutes, and is increased to 135 ℃ at the speed of 5 ℃/min and is kept for 2 minutes.
In another aspect, the invention provides the use of the method or the apparatus for determining the risk of toxicity of disinfection byproducts in a water sample to be tested.
The method or the device can be used for determining the type and the concentration (level) of the disinfection byproducts in the water sample to be treated, judging the toxicity risk of the disinfection byproducts according to the analysis of the disinfection byproducts, obtaining a toxicity risk ranking list of the disinfection byproducts and providing a water sample treatment basis for relevant units.
In a preferred embodiment of the invention, the water sample to be tested originates from a municipal water supply plant.
Preferably, the comprehensive toxicity of DBPs is obtained by calculation based on cell toxicity, genetic toxicity and developmental toxicity databases reported at home and abroad.
Preferably, the chemical analysis is combined with the biological test, i.e., the toxicity level of DBPs is coupled with the generation potential, the toxicity value x the generation potential is used to judge the toxicity risk, and the components of high-risk DBPs in the water plant are identified.
The invention discloses a method for identifying high-risk disinfection byproducts in water, which comprises the following steps: firstly, collecting effluent of different treatment processes of a water plant, performing a potential test, and quantifying the type and concentration level of DBPs by means of chemical analysis means such as a gas chromatograph; then, based on a cytotoxicity, genotoxicity and developmental toxicity database, obtaining compound biological toxicity data of DBPs; and finally, coupling the toxicity level of the DBPs with the generation potential to carry out chemical and biological synchronous evaluation, namely integrating the toxicity value and the generation potential to judge the risk of the DBPs in the drinking water, and screening out high-risk DBPs. The method is a comprehensive and effective DBPs risk identification and sequencing method, and the method has clear steps and is easy to operate and implement; the method can be applied to various water supply quality monitoring departments, water plants and detection units.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following advantages and positive effects:
1. the invention provides a DBPs risk identification technical method, which adopts a simulated water distribution system (SDS) generation potential determination method and objectively evaluates the concentration level of DBPs.
2. The method for evaluating the toxicity of the DBPs uses cytotoxicity, genetic toxicity, developmental toxicity and carcinogenic toxicity, and comprehensively evaluates the toxicity characteristics of the DBPs.
3. The DBPs risk identification technical method provided by the invention has more reference and guidance values through biological and chemical evaluation coupling.
Drawings
FIG. 1 is a schematic diagram of the DBPs evaluation process according to the present invention.
As shown in fig. 1, the present invention provides a method for generating DBPs by combining potential analysis with toxic effect evaluation, comprising the steps of:
and S1, collecting water samples in different treatment processes of a water works and preprocessing the water samples, and quantifying the concentration types and levels of DBPs by means of chemical analysis means such as a gas chromatograph and the like.
S2, as shown in attached table 1, the comprehensive toxicity of DBPs is obtained by calculation according to toxicity data reported at home and abroad.
And S3, coupling the toxicity level and the generation potential of the DBPs, and judging the toxicity risk by using the toxicity value multiplied by the generation potential.
Detailed Description
The invention will be described in more detail hereinafter with reference to the accompanying drawings, in which embodiments of the invention are shown. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. In the drawings, the size and relative sizes of layers and regions may be exaggerated for clarity.
It should be noted that the reagent dosage, the instrument condition, and the reagent type mentioned in the present application can be adjusted according to the actual water body condition, and are not limited to the above description.
As those skilled in the art will appreciate, the present invention may be embodied in many other specific forms without departing from the spirit or scope thereof. Although embodiments of the present invention have been described, it is to be understood that the present invention should not be limited to those precise embodiments, and that various changes and modifications can be effected therein by one skilled in the art without departing from the scope or spirit of the invention as defined by the appended claims. This is explained in more detail below with reference to an exemplary embodiment.
Example 1
A certain water works in south China is selected, and the treatment processes adopted by the water works comprise pre-ozone, coagulating sedimentation, pre-sand filtration, ozone-biological activated carbon, post-sand filtration and chlorination disinfection. Samples were collected from each sampling point and stored in 5L glass bottles, and the samples were transported to the laboratory after adjusting the pH to around 7 with sulfuric acid and sodium hydroxide. Immediately after collection, SDS generation potential was tested in the laboratory. 1-4mg/L of chlorine is added into a 500ml brown glass bottle without a headspace, so that the residual chlorine amount is 1.0 +/-0.2 mg/L after 24 hours; then adding ascorbic acid with 1.5 times of residual chlorine to terminate chlorination reaction; the analysis of N-DBPs such as halogenated nitromethane, trihalomethane, haloacetonitrile, halogenated acetamide and the like with small boiling point and good thermal stability is carried out by using GC-ECD. In this case, the potential concentrations of DCAN (dichloroacetonitrile), DBAN (dibromoacetonitrile) and TCAN (trichloroacetonitrile) SDS generated in the post-sand-filtered water were 8.4. mu.g/L, 0.5. mu.g/L and 4.9. mu.g/L, respectively.
Based on the published toxicity database, the following toxicity data of DCAN (dichloroacetonitrile) and DBAN (dibromoacetonitrile) are found, and the comprehensive toxicity of DCAN can be obtained by the following formulas in sequence, as shown in table 1:
the compound toxicity potential calculation formula is as follows:
ITIX＝(CTVX×CX) (4)
ITIx-the composite toxicity potential index of DBP,
CTVx-complex toxicity value of DBP (M-1),
Cxthe SDS-generating potential of DBP.
Calculating a composite toxicity value by the following formula:
％C1/2 x-the cytotoxicity value (M) of DBP,
SCGEGen.potencyx-the genotoxicity value (M) of the DBP,
LOEL-developmental toxicity value (M) of DBP.
Table 1: toxicity data for haloacetonitrile species
From the above, ITIDCAN＝(CTVDCAN×CDCAN)＝107.89×10-3×8.4/109.94＝0.82×10-2
ITIDBAN＝(CTVDBAN×CDBAN)＝251.42×10-3×0.5/198.84＝0.63×10-3
ITITCAN＝(CTVTCAN×CTCAN)＝11.94×10-3×4.9/144.39＝0.41×10-3
Therefore, the risk of haloacetonitrile substances in the water sample is DCAN > DBAN > TCAN; therefore, DCAN should be of major concern during the subsequent disinfection process in water plants.
Example 2
A certain water works in south China is selected, and the treatment processes adopted by the water works comprise pre-ozone, coagulating sedimentation, pre-sand filtration, ozone-biological activated carbon, post-sand filtration and chlorination disinfection. Samples were collected from each sampling point and stored in 5L glass bottles, and the samples were transported to the laboratory after adjusting the pH to around 7 with sulfuric acid and sodium hydroxide. Immediately after collection, SDS generation potential was tested in the laboratory. 1-4mg/L of chlorine is added into a 500ml brown glass bottle without a headspace, so that the residual chlorine amount is 1.0 +/-0.2 mg/L after 24 hours; then adding ascorbic acid with 1.5 times of residual chlorine to terminate chlorination reaction; analyzing N-DBPs (N-DBPs) such as halogenated nitromethane, trihalomethane, haloacetonitrile, halogenated acetamide and the like with small boiling point and good thermal stability by using GC-ECD (gas chromatography-electron capture device); HAAs of polar and strong-acid organic matters are subjected to derivatization by methanol and then are detected and analyzed by GC-MS. In this case, the concentrations of potential for formation of SDS of CAM (chloroacetamide), BAM (bromoacetamide) and IAM (iodoacetamide) in the post-sand-leach water were 0.5. mu.g/L, 1.0. mu.g/L and 0.1. mu.g/L, respectively.
Table 2: toxicity data for haloacetamides
The following data are obtained by calculation:
ITICAM＝(CTVCAM×CCAM)＝14.87×0.5×10-3/78.50＝9.48×10-5
ITIBAM＝(CTVBAM×CBAM)＝29.99×1.0×10-3/137.96＝0.21×10-3
ITIIAM＝(CTVIAM×CIAM)＝15.00×0.1×10-3/184.96＝8.11×10-6
therefore, the risk of haloacetonitrile substances in the water sample is BAM > CAM > IAM; BAMs should therefore be of major concern during subsequent disinfection processes in waterworks.
Claims (9)
1. A method of identifying high risk disinfection byproducts in water, comprising the steps of:
s1, collecting and pretreating a water sample to be treated, and quantifying the type and content of disinfection byproducts;
s2, calculating and obtaining the comprehensive toxicity of the disinfection by-products based on the cytotoxicity, genetic toxicity and developmental toxicity databases;
and S3, coupling the comprehensive toxicity and the generation potential of the disinfection by-products, and judging the toxicity risk of the disinfection by-products.
2. The identification method according to claim 1,
in step S1, the pretreatment is to filter the water sample to be treated to remove impurities, and simultaneously adjust the pH of the water sample to be treated to 7.0-8.0.
3. The identification method according to claim 1,
in step S1, 1-4mg/L chlorine is added into the water sample to be processed, the residual chlorine amount after 24 hours is 0.5-1.5mg/L, and a quenching agent is added to quench the residual chlorine for measuring the generating potential.
4. The identification method according to claim 3,
the quenching agent is selected from any one or more of ascorbic acid, sodium thiosulfate, sodium sulfite or ammonium chloride.
5. The identification method according to claim 1, wherein, in step S2,
the genetic toxicity comprises DNA damage or chromosome damage;
the cytotoxicity is based on Chinese mouse ovarian cells or human bladder cancer cells;
the developmental toxicity targeted organisms include nereis, artemia, mice or rats.
6. The identification method according to claim 1,
in step S3, the coupling of the combined toxicity and potential generation of the disinfection byproducts includes:
calculating the toxicity value multiplied by the generation potential of each disinfection by-product to obtain a coupling value; and/or
And comprehensively sequencing the coupling values of all disinfection byproducts to obtain a list of high-risk disinfection byproducts.
7. A device for identifying high-risk disinfection byproducts in liquid is characterized by comprising water quality pretreatment equipment, a disinfection byproduct quantitative instrument, a comprehensive toxicity calculation instrument for the disinfection byproducts and a toxicity risk judgment instrument for the disinfection byproducts;
the water quality pretreatment equipment filters a water sample to be treated, removes impurities, and adjusts the pH value of the water sample to be treated to 7.0-8.0;
the disinfection by-product quantitative instrument is connected with the water quality pretreatment equipment, collects the pretreated water sample and quantifies the disinfection by-products in the water sample;
the comprehensive toxicity calculating instrument of the disinfection by-products obtains the comprehensive toxicity of the disinfection by-products based on cytotoxicity, genetic toxicity and developmental toxicity data, and presents the result to a toxicity risk judging instrument of the disinfection by-products;
the toxicity risk judgment instrument of the disinfection byproducts is respectively connected with the comprehensive toxicity calculator of the disinfection byproducts, the comprehensive toxicity of the disinfection byproducts is coupled with the generation potential, the composite toxicity potentials of the disinfection byproducts are sequenced, and the toxicity risk of the disinfection byproducts is judged.
8. The apparatus of claim 7, wherein the quantitative amount of disinfection byproducts in the pretreated liquid comprises: determining the type and concentration of the disinfection by-product by using a gas chromatography instrument;
the gas chromatography apparatus comprises a gas chromatograph with an electron capture detector or a gas chromatography mass spectrometer.
9. Use of a device according to claim 7 or 8 for determining the risk of toxicity of by-products in water samples to be treated.
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| CN113030303A (en) * | 2021-02-26 | 2021-06-25 | 浙江工业大学 | Prediction method for high-risk area of disinfection by-products of long-distance water supply pipe network |
| CN113049707A (en) * | 2021-03-22 | 2021-06-29 | 山东省城市供排水水质监测中心 | On-line liquid-liquid extraction gas chromatography-mass spectrometry method for determining monobromo-dichloroacetonitrile in water |
| CN118191258A (en) * | 2024-05-17 | 2024-06-14 | 同济大学 | Method for identifying key high-toxicity disinfection byproducts in drinking water by taking genotoxicity as guide |
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