CN113109459A - Method for testing generation potential of nitrogen-containing disinfection by-product by adopting chlorine disinfectant - Google Patents

Method for testing generation potential of nitrogen-containing disinfection by-product by adopting chlorine disinfectant Download PDF

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CN113109459A
CN113109459A CN202011037807.4A CN202011037807A CN113109459A CN 113109459 A CN113109459 A CN 113109459A CN 202011037807 A CN202011037807 A CN 202011037807A CN 113109459 A CN113109459 A CN 113109459A
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CN113109459B (en
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黄璜
李忠禹
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Sun Yat Sen University
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Abstract

The invention belongs to the field of water body detection, and discloses a method for testing the generation potential of a nitrogen-containing disinfection by-product by using a chlorine disinfectant, which comprises the following steps: (1) determination of TOC and NH of Water samples3-a concentration value of N; (2) according to the mass concentration meter, adding chlorine into a water sample with the addition of TOC +8 XNH3-N of chlorine disinfectant, reaction for 24 ± 1 h; (3) after the reaction is finished, the generation amounts of the dihalo acetonitrile and the dihalo acetamide are measured, and the generation potentials of the two nitrogen-containing disinfection byproducts are measured. Compared with the existing Krasner method, the method for measuring the generation potential of the nitrogen-containing disinfection by-products has the advantages that the method for measuring the generation potential of the nitrogen-containing disinfection by-products has higher accuracy.

Description

Method for testing generation potential of nitrogen-containing disinfection by-product by adopting chlorine disinfectant
Technical Field
The invention belongs to the field of water body detection, and particularly relates to a method for testing the generation potential of a nitrogen-containing disinfection by-product by using a chlorine disinfectant.
Background
The disinfection can effectively guarantee the biological safety of drinking water, but common chlorine or chloramine disinfectants can generate disinfection byproducts (DBPs, a series of byproducts generated by reaction of drinking water disinfectants and organic matters in water in the drinking water disinfection process) with organic matters in water, wherein carbon-containing disinfection byproducts such as trichloromethane, chloral and the like are listed in drinking water quality standards or specifications of many countries and regions. In recent years, nitrogen-containing disinfection by-products such as haloacetonitrile and haloacetamide have been attracting much attention because of their higher toxicity, and in particular, nitrogen-containing disinfection by-products such as Dihaloacetonitrile (DHANs) and dihaloacetamide (DHAcAms) which are dihaloacetonitrile and dihaloacetamide are generally detected in drinking water.
In the disinfection process, organic substances which react with chlorine or chloramine to generate DBPs are called precursors, and in order to better evaluate the water quality and improve the disinfection mode, the content of the precursors in the water body needs to be acquired. However, because the precursor content cannot be directly measured, the precursor content of DBPs in water is usually characterized by using a DBPs Formation Potential (FP) test.
For FP test of carbon-containing disinfection byproducts such as trichloromethane, the generation amount of DBPs is maximized by controlling certain pH and temperature and enabling organic matters in water to completely react with a disinfectant to generate DBPs under the conditions of high disinfectant dosage and long-time contact. In recent years, the FP test method proposed by Krasner et al (i.e., Krasner method) is widely used, and the chlorine addition amount in the chlorine disinfection FP test is (in terms of effective chlorine mass concentration): cl2(total organic carbon, the total amount of organic matter in water is expressed as carbon content, and the result is expressed as mass concentration (mg/L) of carbon (C)) +8 xnh3N (Ammonia Nitrogen, meaning free Ammonia (NH) in Water3) And ammonium ion (NH)4 +) Nitrogen in the form, expressed as mass concentration of nitrogen (N) (mg/L) +10, with a reaction time of 24 h.
However, the nitrogen-containing disinfection byproducts generated, such as DHANs and DHAcAms, are easily hydrolyzed, and the excessive free chlorine further promotes the decomposition of the nitrogen-containing disinfection byproducts, so that the generated concentration is reduced, and the measured generation potential of the nitrogen-containing disinfection byproducts is lower than the actual value, so that the accuracy of the measurement by the Krasner method is insufficient, and the accurate measurement cannot be realized.
In response to the deficiencies of the Krasner method, it is desirable to provide a more accurate test for the potential for the formation of nitrogen-containing disinfection byproducts using chlorine disinfectants.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, compared with the existing Krasner method, the method for testing the generation potential of the nitrogen-containing disinfection by-product by adopting the chlorine disinfectant can test higher generation potential of the nitrogen-containing disinfection by-product and has better accuracy.
A method for testing the potential for the formation of nitrogen-containing disinfection byproducts using chlorine disinfectant comprising the steps of:
(1) determination of TOC and NH of Water samples3-a concentration value of N;
(2) according to the mass concentration meter, adding chlorine into a water sample with the addition of TOC +8 XNH3-N of chlorine disinfectant, reaction for 24 ± 1 h;
(3) after the reaction is finished, the generation amounts of the dihalo acetonitrile and the dihalo acetamide are measured, and the generation potentials of the two nitrogen-containing disinfection byproducts are measured.
By adopting the test method, the tested dihalo-acetonitrile and dihalo-acetamide have the highest generation amount, and the generation potentials of the two nitrogen-containing disinfection byproducts in the chlorine disinfection process can be fully measured.
Wherein the dosage unit of the chlorine dosage in the step (2) is mg/L (taking available chlorine Cl)2Meter).
Preferably, in the step (2), a neutral buffer solution is added into a water sample, and then a chlorine disinfectant is added for reaction. Because the pH can influence the generation of dihalogen acetonitrile and dihalogen acetamide, the generation concentration is reduced, and the pH value of a water sample can be kept stable by adding a neutral buffer solution, so that the measured result is more accurate.
More preferably, the neutral buffer is a phosphate buffer.
Most preferably, a phosphate buffer is added in the step (2) to adjust the phosphate content in the water sample to 10-20 mM.
Preferably, the temperature of the reaction in step (2) is controlled to be 23-27 ℃.
Preferably, after the reaction in step (2) is completed, a dechlorinating agent is added to remove residual chlorine. Residual chlorine may remain in the water after the reaction is completed, and an excessive amount of dechlorinating agent is added to stop further chlorination reaction and prevent decomposition of nitrogen-containing disinfection byproducts by the residual chlorine.
More preferably, the dechlorinating agent is ascorbic acid. The ascorbic acid can effectively dechlorinate and ensure the stability of the haloacetamide, but other common dechlorinating agents such as sodium thiosulfate and sodium sulfite have certain decomposition effect on the haloacetamide, so the ascorbic acid is the better dechlorinating agent.
Preferably, in the step (3), the generation amounts of dihaloacetonitrile and dihaloacetamide are determined by gas chromatography-electron capture detector detection (GC/ECD method).
Compared with the prior art, the invention has the following beneficial effects:
compared with the widely used Krasner method, the method for testing the nitrogen-containing disinfection by-product generation potential can test the nitrogen-containing disinfection by-product generation potential and has better accuracy. Provides a technical basis for the development of a drinking water plant adopting chlorine disinfectant for disinfection to control the source of the nitrogenous disinfection by-products, thereby improving the safety of drinking water and effectively ensuring the drinking water health of people.
Drawings
FIG. 1 shows the potential of generating nitrogen-containing disinfection byproducts in a Beijiang water sample under different chlorine dosage and reaction time conditions by using a chlorine disinfectant;
FIG. 2 shows the potential of generating nitrogen-containing disinfection byproducts from Xijiang water samples using chlorine disinfectant at different chlorine dosages and reaction times.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples are given for illustration. It should be noted that the following examples are not intended to limit the scope of the claimed invention.
The starting materials, reagents or apparatuses used in the following examples are conventionally commercially available or can be obtained by conventionally known methods, unless otherwise specified.
Example 1
In this embodiment, the intake water of two drinking water plants in the mountain of Buddha, Guangdong province is used as the water sample to be tested. The water sources are north river and west river respectively, are important water sources of numerous water plants in the mountain of Buddha, and have outstanding representativeness.
In the embodiment, sodium hypochlorite is used as a chlorine disinfectant, and the influence of different chlorine dosage and reaction time on the potential generation of nitrogen-containing disinfection byproducts DHANs and DHAcAms is tested, wherein the test method specifically comprises the following steps:
(1) filtering water sample with 0.45 μm water system filter membrane, determining TOC concentration with TOC analyzer of Shimadzu corporation, and determining NH with ammonia nitrogen concentration determinator (HI96700) of HANNA corporation3-N concentration.
(2) Buffer pH 7 containing 122mM Na was prepared2HPO4·12H2O and 78mM NaH2PO4·2H2And O, storing in a refrigerator at 4 ℃ for later use. The mixture was mixed with a magnetic heating stirrer and returned to room temperature before each use. And adding the phosphoric acid buffer solution into a water sample to ensure that the content of phosphate in the water sample reaches 20mM so as to keep the pH value of the water sample stable, and carrying out a chlorine disinfection test at room temperature and 25 ℃ in a dark place.
Because liquid chlorine and chlorine easily cause laboratory potential safety hazard, for the safety consideration and make things convenient for the laboratory to the actual determination of quality of water, adopt sodium hypochlorite to represent the chlorine of throwing when disinfecting in this embodiment. 0.6mL of sodium hypochlorite (containing 4% -4.99% of available chlorine) is measured and added into 19.4mL of ultrapure water, and the mixture is uniformly mixed for later use. The chlorine disinfectant was diluted 800 times (39.95 mL of ultrapure water was added to 0.05mL of the disinfectant) and the concentration of free chlorine was measured with a DPD residual chlorine tester manufactured by HANNA, whereby the concentration of the prepared chlorine disinfectant (Cl) was determined2mg/L) × 800 measured free chlorine concentration (mg/L).
Selecting TOC +8 XNH according to the chlorine adding amount in the water sample by a mass concentration meter3-N(I)、2×TOC+8×NH3-N(II)、3×TOC+8×NH3-N(III)、3×TOC+8×NH3-N+5(IV)、3×TOC+8×NH3And (N + 10) calculating the required adding amount of the chlorine disinfectant in the water sample, adding the corresponding amount of the chlorine disinfectant for reaction, and respectively selecting the reaction time for 4, 6, 10 and 24 hours.
After the reaction is finished, adding excessive ascorbic acid into a water sample to remove residual chlorine in the water body.
(3) And (3) performing liquid-liquid extraction on the water sample subjected to dechlorination by using ascorbic acid in the step (2) by using methyl tert-butyl ether, and determining the concentrations of dihalo acetonitrile and dihalo acetamide by using a gas chromatography-electron capture detector detection method (GC/ECD method) to determine the generation potential of the nitrogen-containing disinfection byproducts.
The method comprises the following specific steps: a60 mL bottle was charged with 3mL of a methyl t-butyl ether extractant containing 100. mu.g/L of 1, 2-dibromopropane as an internal standard, and 6g of anhydrous sodium sulfate was added, and the anhydrous sodium sulfate was dissolved by rapid shaking and shaken for 2min with a shaker, followed by standing for 10 min. After standing, the upper extract was taken for DBPs determination.
The dihalo acetonitrile is measured by a GC/ECD method, a DB-5 chromatographic column is adopted, and the measuring program is as follows: maintaining at 35 deg.C for 9 min; heating to 40 deg.C at a speed of 2 deg.C/min, and maintaining for 1 min; the temperature is raised to 160 ℃ at a speed of 20 ℃/min and kept for 5 min. The detector ECD temperature is 290 ℃, and the average flow velocity of purging is 18.7 cm/s;
dihaloacetamide was also determined by GC/ECD using a DB-1701 column, procedure for its determination: maintaining at 35 deg.C for 3 min; raising the temperature to 220 ℃ at the speed of 20 ℃/min and keeping the temperature for 1.5 min. The detector ECD temperature was 290 ℃ and the average flow rate of the purge was 18.7 cm/s.
Method effect test
The test results of example 1 are shown in fig. 1 and fig. 2, wherein fig. 1 shows the potential for generating nitrogen-containing disinfection byproducts of a water sample from north river at different chlorine input amounts and reaction times, fig. 2 shows the potential for generating nitrogen-containing disinfection byproducts of a water sample from west river at different chlorine input amounts and reaction times, and the test results are as follows:
under the condition of lower chlorine dosage (I, II), the generation amount of DHANs and DHAcAms is gradually increased along with the increase of reaction time; at higher chlorine loadings (III-V), however, the amounts of DHANs and DHAcAms formed increased and then decreased or gradually decreased as the reaction time increased. The production amounts of DHANs and DHAcAms of two water samples of Xijiang and Beijiang are both low in chlorine input (I, TOC +8 XNH)3-N), maximum long reaction time (24 h).
The method for measuring the highest potential of the generation of the nitrogen-containing disinfection byproducts (the adding amount of chlorine is TOC +8 XNH)3-N (mg/L), transResponse time 24h) as a test method of the present invention, compared to the nitrogen-containing disinfection by-product generation potential as measured by the Krasner method, the results are shown in table 1:
TABLE 1 potential results of the formation of nitrogenous disinfection byproducts DHANs and DHAcAms as determined by the test methods of the present invention and by the Krasner test method
Figure BDA0002705654110000051
As can be seen from Table 1, compared with the conventional Krasner method, the nitrogen-containing disinfection byproducts DHANs and DHAcAms obtained by the method have significantly higher generation potential and better accuracy. Therefore, when the water body is disinfected by chlorine, the test conditions for accurately measuring the generation potential of the nitrogen-containing disinfection byproducts of the water body are as follows: chlorine dosage TOC +8 XNH3-N (mg/L), reaction time 24 h.

Claims (8)

1. A method for testing the potential for the formation of nitrogen-containing disinfection byproducts using chlorine disinfectant comprising the steps of:
(1) determination of TOC and NH of Water samples3-a concentration value of N;
(2) according to the mass concentration meter, adding chlorine into a water sample with the addition of TOC +8 XNH3-N of chlorine disinfectant, reaction for 24 ± 1 h;
(3) after the reaction is finished, the generation amounts of the dihalo acetonitrile and the dihalo acetamide are measured, and the generation potentials of the two nitrogen-containing disinfection byproducts are measured.
2. The method according to claim 1, wherein in the step (2), the neutral buffer solution is added to the water sample, and then the chlorine disinfectant is added to the water sample to perform the reaction.
3. The method according to claim 2, wherein the neutral buffer is a phosphate buffer.
4. The method according to claim 3, wherein the phosphate buffer is added in the step (2) to adjust the phosphate content in the water sample to 10 to 20 mM.
5. The method according to claim 1, wherein the temperature of the reaction in the step (2) is controlled to 23 to 27 ℃.
6. The process according to claim 1, wherein a dechlorinating agent is added to remove residual chlorine after the completion of the reaction in the step (2).
7. The process according to claim 6, wherein the dechlorinating agent is ascorbic acid.
8. The process according to claim 1, wherein the amounts of dihaloacetonitrile and dihaloacetamide produced are measured in step (3) by gas chromatography-electron capture detector detection.
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Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
ZHANG HUA ET AL.: "Characterization of dissolved organic matter fractions and its relationship with the disinfection by-product formation", 《JOURNAL OF ENVIRONMENTAL SCIENCES》 *
王雨: "污水深度处理次氯酸钠消毒副产物生成潜能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 *
程冬馨 等: "供水管网生物膜有机物的二氯乙腈与二氯乙酰胺生成特性", 《环境科学学报》 *

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