CN109613155A - A kind of detection method of armaticity nitrogenous disinfection byproducts - Google Patents
A kind of detection method of armaticity nitrogenous disinfection byproducts Download PDFInfo
- Publication number
- CN109613155A CN109613155A CN201811445139.1A CN201811445139A CN109613155A CN 109613155 A CN109613155 A CN 109613155A CN 201811445139 A CN201811445139 A CN 201811445139A CN 109613155 A CN109613155 A CN 109613155A
- Authority
- CN
- China
- Prior art keywords
- phase extraction
- solid
- extraction column
- armaticity
- detection method
- 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
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
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
-
- 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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
-
- 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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/08—Preparation using an enricher
-
- 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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/062—Preparation extracting sample from raw material
-
- 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
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
- G01N2030/8809—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample
- G01N2030/884—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample organic compounds
Abstract
The present invention provides a kind of detection methods of armaticity nitrogenous disinfection byproducts, comprising: water sample be carried out Solid Phase Extraction pretreatment, instrument operating parameter controls and the process of operation measurement, wherein, the pretreated process of Solid Phase Extraction includes the selection of solid-phase extraction column, eluant, eluent, the pH value of water sample and eluant, eluent volume；The process of operating parameter control includes the selection of injector temperature, heating rate, retention time and sample volume；The process of operation measurement includes the determination of the determination of working curve, detection limit and the rate of recovery；Detection method of the invention is pre-processed using Solid Phase Extraction, to save the usage amount of organic solvent；The detection limit of chlorobenzene acetonitrile is below 0.5ng/L rank, obtains the higher rate of recovery, is 92-102%, provides reliable detection method for the concentration investigation and subsequent control research of the nitrogenous disinfection byproducts of low concentration in drinking water.
Description
Technical field
The invention belongs to the technical fields of municipal plumbing and environmental project, are related to water quality detection, analytical technology, specifically relate to
And a kind of detection method of the armaticity nitrogenous disinfection byproducts based on solid phase extraction concentration.
Background technique
The water quality safety of drinking water is the great livelihood issues concerning huge numbers of families.The implementation of Drinking Water Sanitization Technology is effective
It inhibits cholera, typhoid fever etc. using water as the propagation of the infectious disease of medium, makes ten hundreds of common people from the threat of these diseases.
Common disinfectant all has strong oxidizing property, while killing pathogenic microorganism, can aoxidize natural organic matter in water body, nothing
Machine object (Br-And I-) and artificial pollution to generating disinfection by-products (DBPs).Most DBPs have cytotoxicity, nerve
Toxicity, mutagenicity, genetoxic, teratogenesis and carcinogenicity.Epidemiological study as a result, it has been found that, pass through mouth and nose sucking or skin
Drinking water and some diseases disease incidence after contact sterilizing have certain association, such as bladder cancer, colon and rectum carcinoma and bad
Gestation etc..So far reported DBPs type is up to more than 600 kinds, but still has 50% or more DBPs can not due to lower concentration
It is accurately detected, belongs to unknown state.
In recent years, aromatic D BPs is widely paid close attention to due to high toxicity.2010, Qing Feng et al. existed
Chloro- Isosorbide-5-Nitrae-the benzoquinones (DCBQ) of 2,6- bis- is detected in water after disinfection, detects halogenated benzoquinones (HBQs) in drinking water for the first time simultaneously
It is confirmed as DBPs.The horizontal minimum adverse reaction concentration (LOAEL) of the observable of DCBQ is 45 μ g kg-1day-1, it is that part is received
Enter 10000 times or more of the DBPs of administrative standard.Du Haiying et al. is using T24 bladder cancer cell as culture cell, test
The cytotoxicity of four kinds of HBQs, as the result is shown haloform (THMs) and halogen second of the cytotoxicity of HBQs than being included in management regulation
Sour (HAAs) is higher by 3 orders of magnitude.HBQs can generate the active oxygen with strong oxidizing property of excessive concentrations in the cell
(ROS), the irreversible damage of intracellular DNA and protein are caused.Thereafter dihalo -4- hydroxy benzaldehyde, dihalo -4- hydroxyl
Totally 13 kinds of aromatic D BPs screen out to come in simulation water body for base-benzoic acid and sour four classes of dihalo water oxygen.Most aromatic series
The EC of DBPs50Value (concentration for causing DBPs when 50% developmental deformity) is far below THMs and HAAs class DBPs.Wherein, 2,5- dibromo
Phenol toxicity highest, EC50Value is 9.12 μm, 1584 times of chloroform (> 3.2 × 104μM), 36 times of bromofoms (7.30 × 102μ
M).For current 50% or so organic halogen still in unknown state, those in drinking water are unrecognized, and the lower DBPs of content may
With higher toxicity.
The chlorobenzene acetonitrile aromatic series nitrogenous disinfection byproducts novel for one kind, toxicity with higher, but due to lower
Concentration is always the difficult point of detection.
Summary of the invention
The present invention is aiming at the shortcomings in the prior art, it is therefore an objective to provide a kind of detection side of armaticity nitrogenous disinfection byproducts
Method.
In order to achieve the above objectives, solution of the invention is:
A kind of detection method of armaticity nitrogenous disinfection byproducts comprising: water sample is subjected to Solid Phase Extraction pretreatment, and
Analysis detection.
Wherein, armaticity nitrogenous disinfection byproducts are chlorobenzene acetonitrile；Chlorobenzene acetonitrile is selected from 2- chlorobenzene acetonitrile, 3- chlorobenzene second
Nitrile, 4- chlorobenzene acetonitrile, 2,3- dichloro benzyl cyanide, 2,4 dichloro benzene acetonitrile, 2,5- dichloro benzyl cyanide, 2,6- dichloro benzyl cyanide, 3,
One or more of 4- dichloro benzyl cyanide and 3,5- dichloro benzyl cyanide.
The pretreated process of Solid Phase Extraction includes the pH value of solid-phase extraction column, eluant, eluent, water sample as a preferred method,
With the selection of eluant, eluent volume.
The pretreated detailed process of Solid Phase Extraction as a preferred method, are as follows:
(1) pH value of water sample is adjusted with phosphate, hydrochloric acid and lye to 1-12, with methanol activated solid extraction column, with super
Pure water cleans solid-phase extraction column, then makes water sample by solid-phase extraction column, then with the dry solid-phase extraction column of nitrogen；
(2) target substance on solid-phase extraction column is eluted with the eluant, eluent of 3-10mL, will be finally eluted with nitrogen
Agent is concentrated to get concentrate, then detects the sample injection bottle that concentrate is transferred to 1.5mL.
As a preferred method, in step (1), the volume of water sample is 1 ± 0.5L.
As a preferred method, in step (1), phosphatic concentration be 0.01mol/L, lye be selected from sodium hydroxide or
One or more of potassium hydroxide.
As a preferred method, in step (1), the volume of methanol is 6 ± 1mL, and flow velocity when activation is 1 ± 0.5mL/
min。
As a preferred method, in step (1), solid-phase extraction column is selected from HLB solid-phase extraction column, ENVI-18 solid phase extracts
Take one or more of column, WAX solid-phase extraction column and Elut-PH solid-phase extraction column.
As a preferred method, in step (1), the volume of ultrapure water is 6 ± 2mL, flow velocity when cleaning is 1 ±
0.5mL/min。
As a preferred method, in step (1), the flow velocity that water sample passes through solid-phase extraction column is 4 ± 2mL/min.
As a preferred method, in step (1), the nitrogen dry time is 30 ± 2min.
As a preferred method, in step (2), eluant, eluent is selected from methylene chloride, n-hexane, hexamethylene and ethyl acetate
One or more of.
As a preferred method, in step (2), flow velocity when elution is 1 ± 0.5mL/min.
As a preferred method, in step (2), the volume of concentrate is 1 ± 0.5mL.
Analysis detection includes the process of operating parameter control and operation measurement as a preferred method,.
As a preferred method, operating parameter control process include injector temperature, heating rate, the retention time and
The selection of sample volume.
Injector temperature is 220-240 DEG C as a preferred method,.
Heating rate is 20-35 DEG C/min as a preferred method,.
The retention time is 3-5min as a preferred method,.
Sample volume is 3-10 μ L as a preferred method,.
The process for running measurement as a preferred method, includes the determination of working curve, detects limit and the rate of recovery really
It is fixed.
By adopting the above scheme, the beneficial effects of the present invention are:
The first, detection method of the invention is pre-processed using Solid Phase Extraction, to save the usage amount of organic solvent；Chlorine
The detection limit of benzene acetonitrile is below 0.5ng/L rank, obtains the higher rate of recovery, is 92-102%, is low in drinking water
The concentration of the nitrogenous disinfection byproducts of concentration is investigated and subsequent control research provides reliable detection method.
The second, detection method of the invention uses GC-MS detecting instrument, and Optimum Temperature Raising program, determines detailed instrument
Device parameter avoids isomer and is difficult to the problem of separating in GC-MS detection, ensure that its good separating degree.
Detailed description of the invention
Fig. 1 is that the process of the detection method of the armaticity nitrogenous disinfection byproducts of the invention based on solid phase extraction concentration is shown
It is intended to.
Fig. 2 is that the operation of the detection method of the armaticity nitrogenous disinfection byproducts of the invention based on solid phase extraction concentration is shown
It is intended to.
Fig. 3 is the standard of 2- chlorobenzene acetonitrile in the armaticity nitrogenous disinfection byproducts of the invention based on solid phase extraction concentration
Curve synoptic diagram.
Fig. 4 is the standard of 3- chlorobenzene acetonitrile in the armaticity nitrogenous disinfection byproducts of the invention based on solid phase extraction concentration
Curve synoptic diagram.
Fig. 5 is the standard of 4- chlorobenzene acetonitrile in the armaticity nitrogenous disinfection byproducts of the invention based on solid phase extraction concentration
Curve synoptic diagram.
Fig. 6 is 2,4 dichloro benzene acetonitrile in the armaticity nitrogenous disinfection byproducts of the invention based on solid phase extraction concentration
Standard curve schematic diagram.
Fig. 7 is 2,5- dichloro benzyl cyanide in the armaticity nitrogenous disinfection byproducts of the invention based on solid phase extraction concentration
Standard curve schematic diagram.
Fig. 8 is 2,6- dichloro benzyl cyanide in the armaticity nitrogenous disinfection byproducts of the invention based on solid phase extraction concentration
Standard curve schematic diagram.
Fig. 9 is 2,3- dichloro benzyl cyanide in the armaticity nitrogenous disinfection byproducts of the invention based on solid phase extraction concentration
Standard curve schematic diagram.
Figure 10 is 3,5- dichloro benzyl cyanide in the armaticity nitrogenous disinfection byproducts of the invention based on solid phase extraction concentration
Standard curve schematic diagram.
Figure 11 is 3,4- dichloro benzyl cyanide in the armaticity nitrogenous disinfection byproducts of the invention based on solid phase extraction concentration
Standard curve schematic diagram.
Figure 12 is that nine kinds of chlorobenzene acetonitriles exist in the armaticity nitrogenous disinfection byproducts of the invention based on solid phase extraction concentration
The chromatogram under mode is swept entirely.
Specific embodiment
The detection method of the present invention provides a kind of armaticity nitrogenous disinfection byproducts based on solid phase extraction concentration.
<detection methods of the armaticity nitrogenous disinfection byproducts based on solid phase extraction concentration>
A kind of detection method of the armaticity nitrogenous disinfection byproducts based on solid phase extraction concentration includes: as shown in Figure 1, will
Water sample carries out the process of Solid Phase Extraction pretreatment, operating parameter control and operation measurement；Armaticity nitrogenous disinfection byproducts are chlorine
Benzene acetonitrile.
In fact, in water sample in armaticity nitrogenous disinfection byproducts chlorobenzene acetonitrile include 2- chlorobenzene acetonitrile, 3- chlorobenzene acetonitrile,
4- chlorobenzene acetonitrile, 2,3- dichloro benzyl cyanide, 2,4 dichloro benzene acetonitrile, 2,5- dichloro benzyl cyanide, 2,6- dichloro benzyl cyanide, 3,4- bis-
Chlorobenzene acetonitrile and 3,5- dichloro benzyl cyanide.
For chlorobenzene acetonitrile because of the difference of chlorine atom number and chlorine the position of substitution, one is divided into 9 kinds；Wherein, 2- chlorobenzene acetonitrile, 3-
Chlorobenzene acetonitrile and 4- chlorobenzene acetonitrile are isomer；2,3- dichloro benzyl cyanide, 2,4 dichloro benzene acetonitrile, 2,5- dichloro-benzenes second
Nitrile, 2,6- dichloro benzyl cyanide, 3,4- dichloro benzyl cyanide and 3,5- dichloro benzyl cyanide are isomer.Molecular structural formula is specifically such as
Under:
The molecular structural formula of 2- chlorobenzene acetonitrile are as follows:
The molecular structural formula of 3- chlorobenzene acetonitrile are as follows:
The molecular structural formula of 4- chlorobenzene acetonitrile are as follows:
The molecular structural formula of 2,3- dichloro benzyl cyanide are as follows:
The molecular structural formula of 2,4 dichloro benzene acetonitrile are as follows:
The molecular structural formula of 2,5- dichloro benzyl cyanide are as follows:
The molecular structural formula of 2,6- dichloro benzyl cyanide are as follows:
The molecular structural formula of 3,4- dichloro benzyl cyanide are as follows:
The molecular structural formula of 3,5- dichloro benzyl cyanide are as follows:
[determinations of 1. Solid Phase Extraction pretreatment parameters]
Specifically, the pretreated process of Solid Phase Extraction include solid-phase extraction column type, eluant, eluent type, the pH value of water sample and
The selection of eluant, eluent volume.
Nine kinds of chlorobenzene acetonitrile standard items are utilized in the optimization experiment of Solid Phase Extraction parameter, measure target under different experimental conditions
The rate of recovery of analyte.Water sample used in parameter optimization is laboratory preparation, takes appropriate standard items to be dissolved in organic solvent and prepares standard
Product mixed solution prepares working solution after being diluted with buffer solution.The buffer preparation of different pH: the phosphoric acid of 0.01mol/L
Salt (disodium hydrogen phosphate and sodium dihydrogen phosphate or dipotassium hydrogen phosphate and potassium dihydrogen phosphate) is dissolved in ultrapure water, with hydrochloric acid and hydrogen
Sodium oxide molybdena is adjusted to specified pH value.Using organic solvent diluting target analytes to various concentration, standard curve is established.Configuration
The concentration of nine kinds of chlorobenzene acetonitriles of 1L is the sample of 100ng/L, and the concentration of object is measured after Solid Phase Extraction pretreatment, is returned
Yield is determined according to formula (1).Solid phase extraction manipulations flow diagram is as shown in Figure 2.
The rate of recovery=measurement result/theoretical concentration × 100% (1)
(1.1) selection of solid-phase extraction column type
Selecting suitable solid-phase extraction column includes: 1) to have stronger selectivity to target analytes；2) in wider pH
There is preferable adsorption capacity to target analytes in the range of value；3) there is biggish capacity.Wherein, HLB solid-phase extraction column and
ENVI-18 solid-phase extraction column all has good adsorption effect to polarity and middle polar substances, and Elut-PH solid-phase extraction column is to non-
Polar substances have stronger selectivity, and due to the influence of phenyl ring cloud density, Elut-PH solid-phase extraction column is to chain
Structural material and aromatic substance have different selectivity.Reverse phase absorption can occur when sample passes through WAX solid-phase extraction column
It is acted on two kinds of ion exchange, therefore it all has good reserve capability to long-chain and short chain.Preliminary screening goes out four kinds of possibility
Suitable solid-phase extraction column, the pH value for adjusting water sample is 7, uses the methylene chloride of 5mL as eluant, eluent, investigates HLB, ENVI-
18, influence of the tetra- kinds of solid-phase extraction columns of WAX and Elut-PH to nine kinds of chlorobenzene acetonitrile rate of recovery.The rate of recovery is closer to 100%, then
The accuracy of method is higher, and it is most suitable to obtain ENVI-18 solid-phase extraction column as the result is shown, specification 30mg, 3mL.
(1.2) selection of eluant, eluent type
Object adsorbed through solid-phase extraction column after with suitable eluent, the principle of eluent is similar
It is compatible, eluant, eluent commonly with opposed polarity, i.e. methylene chloride, n-hexane, hexamethylene and ethyl acetate are chosen, investigates four
Influence of the kind eluant, eluent to nine kinds of chlorobenzene acetonitrile rate of recovery.In this experiment, ENVI-18 solid-phase extraction column, water sample pH value are selected
7 are adjusted to, the rate of recovery after four kinds of eluents of 5mL is compared, obtains the rate of recovery of methylene chloride closer to 100%, most
It is suitable as eluant, eluent.
(1.3) selection of water sample pH value
The pH value of solution will affect the degree of target analytes ionization, to influence its rate of recovery, therefore investigate nine
Kind chlorobenzene acetonitrile is in the rate of recovery that pH value is 1-12.In this experiment, solid-phase extraction column selects ENVI-18 solid-phase extraction column, washes
The methylene chloride of 5mL is chosen in de- agent, and comparison pH value is the rate of recovery of the sample of 1-12 after Solid Phase Extraction.It obtains being shown in pH
Value is that the rate of recovery in 2-7 is all larger than 80%, with the rate of recovery closest to 100% when pH value is 5.
(1.4) selection of eluant, eluent volume
Eluant, eluent volume is too small to may cause target analytes elution not exclusively, eluant, eluent volume is excessive will cause it is organic molten
The waste of agent and concentration link need the long period.Therefore investigated three kinds of common eluant, eluent volumes (3mL, 5mL and
10mL) to the influence of nine kinds of chlorobenzene acetonitrile rate of recovery.In this experiment, solid-phase extraction column selects ENVI-18 solid-phase extraction column, sample
The pH value of product is 5, the rate of recovery of the contrast sample after different volumes eluent.The rate of recovery of the eluant, eluent of 3mL is relatively low,
The basic indistinction of the eluant, eluent rate of recovery of 5mL and 10mL, as the principle for saving organic solvent, the methylene chloride for choosing 5mL is made
For eluant, eluent.
The pretreated detailed process of further Solid Phase Extraction are as follows:
(1) pH value of water sample is adjusted with phosphate, hydrochloric acid and lye to 1-12, with methanol activated solid extraction column, with super
Pure water cleans solid-phase extraction column, then makes water sample by solid-phase extraction column, then with the dry solid-phase extraction column of nitrogen；
(2) target substance on solid-phase extraction column is eluted with the eluant, eluent of 3-10mL, will be finally eluted with nitrogen
Agent is concentrated to get concentrate, then detects the sample injection bottle that concentrate is transferred to 1.5mL.
Wherein, in step (1), the volume of water sample can be 1 ± 0.5L, preferably 1L.
In step (1), phosphatic concentration can be 0.01mol/L, and lye is in sodium hydroxide or potassium hydroxide
More than one.
In step (1), the volume of methanol can be 6 ± 1mL, preferably 6mL；Flow velocity when activation can for 1 ±
0.5mL/min, preferably 1mL/min.
In step (1), solid-phase extraction column is selected from HLB solid-phase extraction column, ENVI-18 solid-phase extraction column, WAX Solid Phase Extraction
One or more of column and Elut-PH solid-phase extraction column.
In step (1), the volume of ultrapure water can be 6 ± 2mL, preferably 6mL；Flow velocity when cleaning can for 1 ±
0.5mL/min, preferably 1mL/min.
In step (1), the flow velocity that water sample passes through solid-phase extraction column can be 4 ± 2mL/min, preferably 4mL/min.
In step (1), the nitrogen dry time can be 30 ± 2min, preferably 30min.
In step (2), eluant, eluent is selected from one or more of methylene chloride, n-hexane, hexamethylene and ethyl acetate.
In step (2), flow velocity when elution can be 1 ± 0.5mL/min, preferably 1mL/min.
In step (2), the volume of concentrate can be 1 ± 0.5mL, preferably 1.5mL.
[optimizations of 2. instrument operating parameters]
The process of operating parameter control includes the selection of injector temperature, heating rate, retention time and sample volume.
(2.1) selection of injector temperature
The boiling point of nine kinds of chlorobenzene acetonitriles is above 200 DEG C, thus needs to improve the temperature of injection port.Keep other conditions ginseng
Number is constant, injector temperature is set as 180 DEG C, 190 DEG C, 200 DEG C, 210 DEG C, 220 DEG C, 230 DEG C and 240 DEG C, comparison is different
At a temperature of peak area variation, finally determine best injector temperature range be 220-240 DEG C.
(2.2) determination of heating rate and retention time
By adjusting the initial temperature of temperature program, retention time and heating rate, the appearance of nine kinds of chlorobenzene acetonitriles is compared
Time, chromatographic peak separating degree, peak height and peak area, finally obtain following temperature program: initial temperature is 50 DEG C, keeps 5min；
110 DEG C are risen to the speed of 25 DEG C/min again, keeps 2min；155 DEG C are risen to the speed of 35 DEG C/min, keeps 3min.Finally
220 DEG C are risen to the speed of 20 DEG C/min, keeps 3min.Isomer can be overcome to be difficult to the case where separating, guarantee nine kinds of chlorine
Benzene acetonitrile all can normal appearance.
(2.3) determination of best sample volume
Control other instruments condition it is constant, detection pattern be full scan detect, by sample volume be respectively set as 3 μ L, 5 μ L and
10 μ L, for sample volume, instrument can only carry out the peak area that tie substance is investigated in integer setting.Comparison has obtained best sample volume
For 10 μ L, when less than 10 μ L, gained peak area is too small.
[3. operation measurement]
Operation measurement includes the determination of standard curve, method detection limit and the rate of recovery.
(3.1) determination of standard curve
Before the appearance time for measuring nine kinds of chlorobenzene acetonitriles, the standard curve of nine kinds of chlorobenzene acetonitriles is first established, it is specific
Process are as follows:
(a), configure mixed standard solution: weigh respectively appropriate (guaranteeing accurately to weigh) 2- chlorobenzene acetonitrile,
3- chlorobenzene acetonitrile, 4- chlorobenzene acetonitrile, 2,3- dichloro benzyl cyanide, 2,4 dichloro benzene acetonitrile, 2,5- dichloro benzyl cyanide, 2,6- dichloro-benzenes
Acetonitrile, 3,4- dichloro benzyl cyanide and 3,5- dichloro benzyl cyanide are dissolved in organic solvent (one in methylene chloride and methyl tertiary butyl ether(MTBE)
Kind) in, it is mixedly configured into the mixed standard solution of each chlorobenzene acetonitrile concentration identical (initial concentration is 1mg/mL), is placed in
In brown bottle；
(b), using above-mentioned identical organic solvent diluting mixed standard solution and gradient standard correction liquid, gradient are configured to
Mass concentration is respectively 1 μ g/L, 5 μ g/L, 10 μ g/L, 20 μ g/L, 50 μ g/L, 100 μ g/L and 200 μ g/L；
(c), batch processing analysis is carried out to above-mentioned gradient standard correction liquid using Gc/ms Analyser, utilizes lab
Solution work station generates the standard curve of nine kinds of chlorobenzene acetonitriles respectively, and the canonical plotting of nine kinds of chlorobenzene acetonitriles such as Fig. 3 is extremely
Shown in Figure 11.
Using the canonical plotting for nine kinds of chlorobenzene acetonitriles that external standard method is established, water sample is detected by GC/MS, is such as schemed
Shown in 12, the appearance time of 2- chlorobenzene acetonitrile can be 11.250 ± 0.005min, preferably 11.250min；3- chlorobenzene acetonitrile
Appearance time can be 11.770 ± 0.005min, preferably 11.770min；The appearance time of 4- chlorobenzene acetonitrile can be
11.805 ± 0.005min, preferably 11.805min；The appearance time of 2,4 dichloro benzene acetonitrile can for 13.355 ±
0.005min, preferably 13.355min；The appearance time of 2,5- dichloro benzyl cyanides can be 13.535 ± 0.005min, preferably
For 13.535min；The appearance time of 2,6- dichloro benzyl cyanides can be 13.685 ± 0.005min, preferably 13.685min；2,
The appearance time of 3- dichloro benzyl cyanide can be 13.875 ± 0.005min, preferably 13.875min；3,5- dichloro benzyl cyanide
Appearance time can be 14.065 ± 0.005min, preferably 14.065min；The appearance time of 3,4- dichloro benzyl cyanide can be
14.590 ± 0.005min, preferably 14.590min.
(3.2) determination of method detection limit and the rate of recovery
Using detection method of the invention, so that nine kinds of chlorobenzene acetonitriles can realize good separation in the analysis process, in 1-
Linear good (R within the scope of 200 μ g/L2> 0.99), the rate of recovery of nine kinds of chlorobenzene acetonitriles is between 92-102%；Method detection limit
(Limit of Method Detection, MDL) is in 0.5ng/L or less.
To sum up, the detection method of the armaticity nitrogenous disinfection byproducts of the invention based on solid phase extraction concentration specifically:
(1) it takes 1L water sample in vial, adjusts water using the sodium dihydrogen phosphate, hydrochloric acid and sodium hydroxide of 0.01mol/L
The pH value of sample activates ENVI-I8 solid-phase extraction column to 5, with 6mL methanol with the speed of 1mL/min, with the ultrapure water of 6mL with 1mL/
The speed of min cleans ENVI-I8 solid-phase extraction column, then so that water sample is passed through ENVI-I8 Solid Phase Extraction with the speed of 4mL/min
Column, later with the dry ENVI-I8 solid-phase extraction column of stable nitrogen, the dry time is 30min；
(2) target substance on ENVI-I8 solid-phase extraction column is carried out with the speed of 1mL/min with the methylene chloride of 5mL
Elution, is finally concentrated into 1mL for the methylene chloride of 5mL with nitrogen, methylene chloride is then transferred to the sample injection bottle of 1.5mL, is sent
Enter GC-MS autosampler to be detected.
When measurement, the design parameter of GC-MS are as follows:
Carrier gas is high-purity helium, and carrier gas flux control mode is pressure control, and input mode is Splitless injecting-Sample, injection port
Temperature is 220 DEG C, and mass detector temperature is 260 DEG C, ion source electron impact ion source, and electron energy 70eV detects mould
Formula is selection ion detection, and initial temperature is 50 DEG C, keeps 5min；110 DEG C are risen to the speed of 25 DEG C/min again, is kept
2min；155 DEG C are risen to the speed of 35 DEG C/min, keeps 3min；220 DEG C finally are risen to the speed of 20 DEG C/min, is kept
3min。
The appearance time of 2- chlorobenzene acetonitrile can be 11.250min, and the appearance time of 3- chlorobenzene acetonitrile is 11.770min,
The appearance time of 4- chlorobenzene acetonitrile is 11.805min, and the appearance time of 2,4- dichloro benzyl cyanides is 13.355min, 2,5- dichloros
The appearance time of benzene acetonitrile is 13.535min, and the appearance time of 2,6- dichloro benzyl cyanides is 13.685min, 2,3- dichloro-benzenes second
The appearance time of nitrile is 13.875min, and the appearance time of 3,5- dichloro benzyl cyanides is 14.065min, 3,4- dichloro benzyl cyanides
Appearance time is 14.590min.The detection limit range of above-mentioned nine kinds of chlorobenzene acetonitriles is 0.15-0.37ng/L, is lower than 0.5ng/L,
The rate of recovery is between 92-102%.
The above-mentioned description to embodiment is that this hair can be understood and used for the ease of those skilled in the art
It is bright.Those skilled in the art obviously readily can make various modifications to these embodiments, and described herein one
As principle be applied in other embodiments, without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments.
Those skilled in the art's principle according to the present invention, not departing from improvement that scope of the invention is made and modification all should be at this
Within the protection scope of invention.
Claims (8)
1. a kind of detection method of armaticity nitrogenous disinfection byproducts, it is characterised in that: comprising: which water sample is carried out Solid Phase Extraction
Pretreatment, and analysis detection；
The armaticity nitrogenous disinfection byproducts are chlorobenzene acetonitrile；
The chlorobenzene acetonitrile is selected from 2- chlorobenzene acetonitrile, 3- chlorobenzene acetonitrile, 4- chlorobenzene acetonitrile, 2,3- dichloro benzyl cyanide, 2,4- dichloro
One of benzene acetonitrile, 2,5- dichloro benzyl cyanide, 2,6- dichloro benzyl cyanide, 3,4- dichloro benzyl cyanide and 3,5- dichloro benzyl cyanide with
On.
2. the detection method of armaticity nitrogenous disinfection byproducts according to claim 1, it is characterised in that: the solid phase extraction
Taking pretreated process includes the selection of solid-phase extraction column, eluant, eluent, the pH value of water sample and eluant, eluent volume.
3. the detection method of armaticity nitrogenous disinfection byproducts according to claim 2, it is characterised in that: the solid phase extraction
Take pretreated process are as follows:
(1) ultrapure water is used with methanol activated solid extraction column to 1-12 with the pH value that phosphate, hydrochloric acid and lye adjust water sample
Solid-phase extraction column is cleaned, then makes water sample by solid-phase extraction column, then with the dry solid-phase extraction column of nitrogen；
(2) target substance on solid-phase extraction column is eluted with the eluant, eluent of 3-10mL, it is finally with nitrogen that eluant, eluent is dense
Contracting obtains concentrate, then detects the sample injection bottle that concentrate is transferred to 1.5mL.
4. the detection method of armaticity nitrogenous disinfection byproducts according to claim 3, it is characterised in that: in step (1),
The volume of the water sample is 1 ± 0.5L；
Preferably, in step (1), the phosphatic concentration is 0.01mol/L；The lye is selected from sodium hydroxide or hydroxide
One or more of potassium；
Preferably, in step (1), the volume of the methanol is 6 ± 1mL, and flow velocity when activation is 1 ± 0.5mL/min；
Preferably, in step (1), it is solid that the solid-phase extraction column is selected from HLB solid-phase extraction column, ENVI-18 solid-phase extraction column, WAX
One or more of phase extraction column and Elut-PH solid-phase extraction column；
Preferably, in step (1), the volume of the ultrapure water is 6 ± 2mL, and flow velocity when cleaning is 1 ± 0.5mL/min；
Preferably, in step (1), the flow velocity that the water sample passes through solid-phase extraction column is 4 ± 2mL/min；
Preferably, in step (1), the nitrogen dry time is 30 ± 2min；
Preferably, in step (2), the eluant, eluent be selected from one of methylene chloride, n-hexane, hexamethylene and ethyl acetate with
On；
Preferably, in step (2), the flow velocity when elution is 1 ± 0.5mL/min；
Preferably, in step (2), the volume of the concentrate is 1 ± 0.5mL.
5. the detection method of armaticity nitrogenous disinfection byproducts according to claim 1, it is characterised in that: the analysis inspection
Survey includes that operating parameter controls and run the process measured.
6. the detection method of armaticity nitrogenous disinfection byproducts according to claim 5, it is characterised in that: the operation ginseng
The process of number control includes the selection of injector temperature, heating rate, retention time and sample volume.
7. the detection method of armaticity nitrogenous disinfection byproducts according to claim 6, it is characterised in that: the injection port
Temperature is 220-240 DEG C；
Preferably, the heating rate is 20-35 DEG C/min；
Preferably, the retention time is 3-5min；
Preferably, the sample volume is 3-10 μ L.
8. the detection method of armaticity nitrogenous disinfection byproducts according to claim 5, it is characterised in that: the operation is surveyed
Fixed process includes the determination of the determination of working curve, detection limit and the rate of recovery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811445139.1A CN109613155A (en) | 2018-11-29 | 2018-11-29 | A kind of detection method of armaticity nitrogenous disinfection byproducts |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811445139.1A CN109613155A (en) | 2018-11-29 | 2018-11-29 | A kind of detection method of armaticity nitrogenous disinfection byproducts |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109613155A true CN109613155A (en) | 2019-04-12 |
Family
ID=66006518
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811445139.1A Pending CN109613155A (en) | 2018-11-29 | 2018-11-29 | A kind of detection method of armaticity nitrogenous disinfection byproducts |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109613155A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114113370A (en) * | 2021-10-29 | 2022-03-01 | 东南大学 | Analysis method of aromatic halogenated disinfection byproducts in water |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102495156A (en) * | 2011-12-14 | 2012-06-13 | 广西壮族自治区环境监测中心站 | Pre-treatment and analysis method of semi-volatile organic materials and organophosphorus pesticides in water |
| CN102520084A (en) * | 2011-12-12 | 2012-06-27 | 同济大学 | Method for determining trace nitrogen-containing disinfection by-product dimethyl nitrosamine in water |
| CN108241027A (en) * | 2016-12-26 | 2018-07-03 | 昆明学院 | The assay method of chlorobenzene compound in environmental water sample |
| CN108709944A (en) * | 2018-04-27 | 2018-10-26 | 同济大学 | The method for detecting nitrogenous -6 kinds of chlorobenzene acetonitriles of armaticity disinfection by-products in drinking water simultaneously |
-
2018
- 2018-11-29 CN CN201811445139.1A patent/CN109613155A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102520084A (en) * | 2011-12-12 | 2012-06-27 | 同济大学 | Method for determining trace nitrogen-containing disinfection by-product dimethyl nitrosamine in water |
| CN102495156A (en) * | 2011-12-14 | 2012-06-13 | 广西壮族自治区环境监测中心站 | Pre-treatment and analysis method of semi-volatile organic materials and organophosphorus pesticides in water |
| CN108241027A (en) * | 2016-12-26 | 2018-07-03 | 昆明学院 | The assay method of chlorobenzene compound in environmental water sample |
| CN108709944A (en) * | 2018-04-27 | 2018-10-26 | 同济大学 | The method for detecting nitrogenous -6 kinds of chlorobenzene acetonitriles of armaticity disinfection by-products in drinking water simultaneously |
Non-Patent Citations (3)
| Title |
|---|
| 王英等: "GC/MS法测定水中氯苯类有机污染物的固相萃取研究", 《现代科学仪器》 * |
| 陈军等: "固相萃取-气质联用法测定水中有机氯农药和氯苯类化合物", 《环境监测管理与技术》 * |
| 陈红云等: "固相萃取-GC-MS法测定近海水域中非挥发性有机污染物", 《浙江化工》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114113370A (en) * | 2021-10-29 | 2022-03-01 | 东南大学 | Analysis method of aromatic halogenated disinfection byproducts in water |
| CN114113370B (en) * | 2021-10-29 | 2024-03-26 | 东南大学 | Analysis method of aromatic halogenated disinfection byproducts in water |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106124653B (en) | 5 kinds of Nitrofuran metatolites and the how remaining detection method of chloramphenicol in shrimp | |
| Pimenta et al. | Simultaneous potentiometric and fluorimetric determination of diclofenac in a sequential injection analysis system | |
| Mei et al. | Determination of trace bisphenol A in complex samples using selective molecularly imprinted solid-phase extraction coupled with capillary electrophoresis | |
| Liu | Determination of mercury and methylmercury in seafood by ion chromatography using photo-induced chemical vapor generation atomic fluorescence spectrometric detection | |
| Zhang et al. | Trace determination and occurrence of eight chlorophenylacetonitriles: An emerging class of aromatic nitrogenous disinfection byproducts in drinking water | |
| Asiabi et al. | Development of electrochemically controlled packed-in-tube solid phase microextraction method for sensitive analysis of acidic drugs in biological samples | |
| Wen et al. | A simple and rapid method for simultaneous determination of benzoic and sorbic acids in food using in-tube solid-phase microextraction coupled with high-performance liquid chromatography | |
| CN109142572A (en) | A variety of drugs are synchronous in a kind of environment multimedium extracts and determination method | |
| Rahman et al. | Application of speciated isotope dilution mass spectrometry to evaluate extraction methods for determining mercury speciation in soils and sediments | |
| Zhou et al. | Development of integrated chemiluminescence flow sensor for the determination of adrenaline and isoprenaline | |
| CN107655991B (en) | Method for measuring 6 kinds of phthalate in soil | |
| Huang et al. | A single pump cycling-column-switching technique coupled with homemade high exchange capacity columns for the determination of iodate in iodized edible salt by ion chromatography with UV detection | |
| CN107037149A (en) | Ethiprole and its metabolite residue amount method for measuring in a kind of egg | |
| Liu et al. | Trace analysis of sulfonylurea herbicides in water by on-line continuous flow liquid membrane extraction–C18 precolumn liquid chromatography with ultraviolet absorbance detection | |
| CN105651922A (en) | Method for measuring PPCPs (pharmaceuticals and personal care products) in environmental water sample | |
| Miravet et al. | New considerations about the separation and quantification of antimony species by ion chromatography–hydride generation atomic fluorescence spectrometry | |
| Schwarzer et al. | Rapid quantification of the nitrification inhibitor dicyandiamide in soil samples, nutrient media and bacterial cell-free extracts | |
| CN109613155A (en) | A kind of detection method of armaticity nitrogenous disinfection byproducts | |
| CN115236229A (en) | Gas chromatography-mass spectrometry analysis method for haloacetic acid in drinking water | |
| Wong et al. | On-line monitoring of the photolysis of benzyl acetate and 3, 5-dimethoxybenzyl acetate by membrane introduction mass spectrometry | |
| Liang et al. | Flow injection analysis of nanomolar level orthophosphate in seawater with solid phase enrichment and colorimetric detection | |
| Kubáň et al. | Determination of five priority haloacetic acids by capillary electrophoresis with contactless conductivity detection and solid phase extraction preconcentration | |
| Medina et al. | A very simple resolution of the mixture paracetamol and salicylamide by flow injection–solid phase spectrophotometry | |
| Yan et al. | Determination of nateglinide in animal plasma by micellar electrokinetic chromatography and on-line sweeping technique | |
| CN104713954B (en) | Method for detecting content of haloacetonitrile substances in water sample through dispersive liquid-liquid microextraction programmed temperature gas chromatography-mass spectrometry |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190412 |