CN108709944B - Method for simultaneously detecting 6 chlorobenzene acetonitrile serving as nitrogenous aromatic disinfection by-product in drinking water - Google Patents
Method for simultaneously detecting 6 chlorobenzene acetonitrile serving as nitrogenous aromatic disinfection by-product in drinking water Download PDFInfo
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Abstract
The invention provides a method for simultaneously detecting 6 chlorobenzene acetonitrile serving as a nitrogenous aromatic disinfection byproduct in drinking water, which comprises the following steps: sample pretreatment, analysis condition optimization and operation determination, wherein the sample pretreatment comprises determination of the pH value of a water sample and a chlorination terminator; the optimization of analysis conditions comprises the determination of a column incubator temperature program, column head pressure, sample injection quantity, sample injection port temperature and chromatographic identification time zone; the operation measurement comprises the determination of a standard curve, a method detection limit and a recovery rate; the invention provides a new idea for simultaneously detecting 6 kinds of chloroacrylonitrile as the nitrogenous aromatic disinfection byproducts, which is different from the method for detecting a single disinfection byproduct in the prior art, and greatly improves the analysis efficiency, thereby laying a foundation for simultaneously detecting a plurality of aromatic disinfection byproducts; in addition, the GC/MS combined instrument is adopted to avoid the phenomena of peak tailing and the like, ensure normal peak emergence and shorten the analysis time, thereby obtaining higher method detection limit and smaller relative standard deviation.
Description
Technical Field
The invention belongs to the technical field of municipal water supply and drainage and environmental engineering, relates to a water quality detection and analysis technology, and particularly relates to a method for simultaneously detecting 6 chlorobenzene acetonitrile serving as a nitrogenous aromatic disinfection byproduct in drinking water.
Background
The drinking water disinfection process achieves the aim of ensuring the safety of drinking water by inactivating pathogenic bacteria, but simultaneously, a series of disinfection byproducts are generated, thus posing a threat to the health of people [1 ]. Epidemiological studies have shown that long-term consumption of chlorinated and disinfected water may lead to an increase in the prevalence of bladder cancer [2 ]. However, researchers have not screened for disinfection byproducts that cause bladder cancer to be pathogenic [3 ]. In addition, epidemiological studies indicate that disinfection by-products may also be detrimental to human reproductive health [4 ]. To date, more than 700 of disinfection byproducts have been reported [5], but more than 50% of the total organic halogen has not been identified [1], and these unidentified disinfection byproducts are likely to be potential carcinogens. Therefore, detection and discrimination of the disinfection byproducts is particularly important. In recent years, nitrogen-containing disinfection by-products (nitrosamines, cyanogen halides, haloacetonitrile, haloacetamides, nitromethane, etc.) have been attracting attention because of their high toxicity [6 ]. With the progress of detection technology and the improvement of detection precision, aromatic disinfection byproducts are continuously detected in drinking water. In 2010, researchers first detected halogenated benzoquinone disinfection byproducts (HBQs) in experimental water samples [7 ]. The data show that HBQs are widely present in drinking water systems in Canada and the United states at concentration levels of 3.3 to 274ng/L [8], and that the presence of aromatic disinfection byproducts such as halobenzoic acid, halophenol and halonitrophenol are subsequently detected in drinking water [1 ]. Toxicology results show that aromatic disinfection byproducts are orders of magnitude more cytotoxic than aliphatic disinfection byproducts [2 ].
Nitrogen-containing organic matters and aromatic organic matters widely exist in water [9], and in the disinfection process, the nitrogen-containing aromatic disinfection byproducts are generated by chemical reaction with chlorine/chloroammonia. Hitherto, few systematic detection technologies aiming at a plurality of nitrogen-containing aromatic disinfection byproducts in drinking water exist in China, the chloroacrylonitrile is a novel nitrogen-containing aromatic disinfection byproduct, and researches and detection methods of the chloroacrylonitrile are not reported, so that the establishment of a convenient, effective and quick detection method is crucial to the detection and control researches of 6 chloroacrylonitrile. In addition, most of the detection of the disinfection byproducts uses a gas chromatography-electron capture detector, and the detection is qualitative by means of comparison of retention time of standard substances, although qualitative and quantitative analysis can be well completed, the intermediate products generated in the chlorination reaction have no distinguishing capability, and the research on the generation mechanism of the disinfection byproducts is inconvenient to develop.
Reference documents:
1.Krasner,S.W.；Weinberg,H.S.；Richardson,S.D.；Pastor,S.J.；Chinn,R.；Sclimenti,M.J.；
Onstad,G.D.；Thruston,A.D.,Occurrence of a New Generation of Disinfection Byproducts.Environ.Sci.Technol.2006,40,(23),7175-7185.
2.Villanueva,C.M.；Cantor,K.P.；Grimalt,J.O.；Malats,N.；Silverman,D.；Tardon,A.；
Garcia-Closas,R.；Serra,C.；Carrato,A.；
-Vinyals,G.,Bladder cancer and exposure to water disinfectionby-products through ingestion,bathing,showering,and swimming in pools.AM.J.
EPIDEMIOL.2007,165,(2),148.
3.Li,X.F.；Mitch,W.A.,Drinking Water Disinfection Byproducts(DBPs)and Human Health Effects:Multidisciplinary Challenges and Opportunities.Environ.Sci.269Technol.2017.
4.Grellier,J.；Bennett,J.；Patelarou,E.；Smith,R.B.；Toledano,M.B.；Rushton,L.；Briggs,D.J.；
Nieuwenhuijsen,M.J.,Exposure to disinfection by-products,fetal growth,and prematurity:a systematicreview and meta-analysis.Epidemiology 2010,21,(3),300-13.
5.Richardson,S.D.；Ternes,T.A.,Water Analysis:Emerging Contaminants and Current Issues.Anal.Chem.2018,90,(1),398-428.
6.Krasner,S.W.；Mitch,W.A.；Westerhoff,P.；Dotson,A.,Formation and control of emerging C-andN-DBPs in drinking water.J.Am.Water Works Assn.2012,104,(11),E582-E595.
7.Zhao,Y.L.；Qin,F.；Boyd,J.M.；Anichina,J.；Li,X.F.,Characterization and Determination of
Chloro-and Bromo-Benzoquinones as New Chlorination Disinfection Byproducts in Drinking Water.Anal.Chem.2010,82,(11),4599-605.
8.Zhao,Y.L.；Anichina,J.；Lu,X.F.；Bull,R.J.；Krasner,S.W.；Hrudey,S.E.；Li,X.F.,
Occurrenceand formation of chloro-and bromo-benzoquinones during drinking water disinfection.Water Res.2012,46,(14),4351-4360.
9.Saunders,J.F.；Yu,Y.；McCutchan Jr,J.H.；Rosario-Ortiz,F.L.,Characterizing Limits of
Precisionfor Dissolved Organic Nitrogen Calculations.2017.
disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a method for simultaneously detecting 6 chlorobenzene acetonitrile serving as a nitrogenous aromatic disinfection byproduct in drinking water.
In order to achieve the above purpose, the solution of the invention is as follows:
a method for simultaneously detecting 6 chlorobenzene acetonitrile serving as a nitrogenous aromatic disinfection byproduct in drinking water comprises the following steps: sample pretreatment, analysis condition optimization and running measurement.
In fact, the nitrogenous aromatic disinfection by-product chloroacrylonitrile in the water sample of drinking water consists of 4-chloroacrylonitrile, 2, 3-dichlorophenylacetonitrile, 2, 4-dichlorophenylacetonitrile, 2, 5-dichlorophenylacetonitrile, 2, 6-dichlorophenylacetonitrile and 3, 4-dichlorophenylacetonitrile.
The chlorobenzene acetonitrile is divided into 6 kinds in total due to the difference of the number of chlorine atoms and the substitution position of chlorine; wherein, 2, 3-dichlorobenzyl cyanide, 2, 4-dichlorobenzyl cyanide, 2, 5-dichlorobenzyl cyanide, 2, 6-dichlorobenzyl cyanide and 3, 4-dichlorobenzyl cyanide are isomers.
Further, the method for simultaneously detecting 6 chlorobenzene acetonitrile serving as the nitrogenous aromatic disinfection by-product in the drinking water specifically comprises the following steps:
(1) enriching a water sample of the drinking water in a liquid-liquid extraction pretreatment mode;
(2) determining operation parameters of a gas chromatography/mass spectrometry (GC/MS) combined instrument, wherein the operation parameters comprise a column temperature box temperature rise program, column head pressure, sample injection quantity, sample injection port temperature and a chromatographic identification time zone;
(3) establishing a standard curve of 6 kinds of chlorobenzene acetonitrile;
(4) analyzing the water sample by using a gas chromatography/mass spectrometer, performing qualitative analysis according to the obtained chromatogram and mass spectrum, and determining the peak emergence time of 6 kinds of chloroacrylonitrile in the water sample by using a standard curve of 6 kinds of chloroacrylonitrile established by an external standard method.
In the step (1), the process of enriching the water sample of the drinking water comprises the following steps: putting a 10mL water sample of drinking water into a 25mL glass vial, adding 200 mu mol/L terminator for dechlorination, adjusting the pH value of the water sample, adding 2.0g of anhydrous sodium sulfate, and manually shaking to fully dissolve the water sample; then, 2.0mL of an extractant was added, and the mixture was shaken at 2500r/min with an IKA shaker for 5.0min and allowed to stand for 10.0 min.
Specifically, the process of sample pretreatment specifically comprises the determination of the pH value of the water sample and the chlorination terminator.
Further, the pH value of the water sample is 5-9, and the pH value of the water sample is preferably 7.
Further, the terminating agent (i.e., chlorinated terminating agent) is selected from one or more of ascorbic acid, sodium thiosulfate, ammonium chloride, sodium arsenite, and sodium sulfite.
Further, the extractant is methyl tert-butyl ether.
Specifically, in the step (2), a gas chromatography-mass spectrometry (GC/MS) instrument is used for analysis and detection, that is, analysis condition optimization includes determination of a column oven temperature rise program, column head pressure, sample injection amount, sample injection port temperature and a chromatography identification time zone.
Further, the column head pressure is 134.2 ± 0.3KPa, preferably 134.2 KPa.
Further, the amount of the sample is 1.0 to 10. mu.L, preferably 1.0. mu.L.
Further, the injection port temperature is 100 to 250.0 ℃, preferably 230.0 ℃.
Further, the chromatographic identification time zone is 0.1-1.0min, preferably 0.2 min.
In fact, in a gas chromatography/mass spectrometry (GC/MS) spectrometer, each substance corresponds to a retention time on the Gas Chromatography (GC) and an ion fragment with characteristics on the Mass Spectrometry (MS), and therefore, the qualitative principle of the GC/MS spectrometer is to combine the two substances for dual-qualitative determination. The selection of the analysis parameters (namely, the column incubator temperature program, column head pressure, sample introduction amount, sample introduction port temperature and chromatographic identification time zone) determines the retention time of various chlorobenzonitrile on the GC, and the aim of optimizing the analysis parameters is to better separate the various chlorobenzonitrile on the GC; various chlorobenzonitriles produced ion fragments under bombardment by an EI ionization source (70eV electrons) in MS.
Specifically, running the assay includes determination of a standard curve, a process limit of detection, and a recovery rate.
In the step (3), the specific process of establishing the standard curve of 6 kinds of chlorobenzene acetonitrile is as follows:
(a) preparing a mixed standard solution: respectively weighing 20mg of 4-chlorophenylacetonitrile, 20mg of 2, 3-chlorophenylacetonitrile, 20mg of 2, 4-dichlorophenylacetonitrile, 20mg of 2, 5-dichlorophenylacetonitrile, 20mg of 2, 6-dichlorophenylacetonitrile and 20mg of 3, 4-dichlorophenylacetonitrile, dissolving in 20mL of methyl tert-butyl ether, mixing to prepare a mixed standard solution with the same concentration of each chlorophenylacetonitrile (the initial concentration is 1mg/mL), and placing in a brown bottle;
(b) preparing the mixed standard solution in the step (a) into a gradient standard correction solution by using ultrapure water (Millipore, the resistivity is 18M omega cm), wherein the gradient mass concentration is respectively 1 mu g/L, 5 mu g/L, 10 mu g/L, 20 mu g/L, 50 mu g/L, 100 mu g/L and 200 mu g/L;
(c) and carrying out batch processing analysis on the gradient standard correction fluid by adopting a gas chromatography/mass spectrometer, and respectively generating standard curves of 6 kinds of chlorobenzene acetonitrile by utilizing a lab solution workstation, wherein the abscissa is the mass concentration of the chlorobenzene acetonitrile, and the ordinate is the peak area of the chlorobenzene acetonitrile.
By adopting the detection method, the 6 chlorobenzonitrile can be well separated in the analysis process, the linearity is good (r ^2 is more than 0.99) within the range of 1-200 mu g/L, and the recovery rate of the 6 chlorobenzonitrile is between 87-95 percent; the Detection Limit (Limit of Method Detection, MDL) of the Method is below 100 ng/L; the Relative Standard Deviation (RSD) is less than 10.0%.
Further, in the step (4), the peak time of 4-dichlorophenylacetonitrile is 11.110 + -0.005 min, the peak time of 2, 4-dichlorophenylacetonitrile is 11.680 + -0.005 min, the peak time of 2, 5-dichlorophenylacetonitrile is 13.150 + -0.005 min, the peak time of 2, 6-dichlorophenylacetonitrile is 13.375 + -0.005 min, the peak time of 2, 3-dichlorophenylacetonitrile is 13.600 + -0.005 min, and the peak time of 3, 4-dichlorophenylacetonitrile is 14.385 + -0.005 min.
Due to the adoption of the scheme, the invention has the beneficial effects that:
firstly, the invention provides a new idea for simultaneously detecting 6 chlorobenzene acetonitrile which is a nitrogenous aromatic disinfection byproduct in drinking water, which is different from the method for detecting a single disinfection byproduct in the prior art, and the analysis efficiency is greatly improved, thereby laying a foundation for simultaneously detecting a plurality of aromatic disinfection byproducts.
Secondly, the invention provides the method for simultaneously detecting the novel nitrogenous aromatic disinfection by-product-chloro-phenylacetonitrile in the drinking water for the first time, and the GC/MS combined instrument is adopted, so that the qualitative capability is strong and the accuracy is high through dual qualitative of retention time and ion fragment information, and the analysis parameters of the GC/MS combined instrument are further determined, therefore, the good separation of 6 kinds of chloro-phenylacetonitriles can be simultaneously realized, the phenomena of peak trailing and the like are avoided, the normal peak emergence is ensured, the analysis time is shortened, and the higher method detection limit and the smaller relative standard deviation are obtained.
Thirdly, the GC/MS combined instrument adopts automatic sample introduction, determines the operation parameters of the automatic sample introduction, is convenient and quick, and improves the efficiency; in addition, the GC/MS combination instrument can utilize the ion fragment information (namely mass-to-charge ratio) of substances in a sample to be compared with the ion fragment information in an NIST standard spectrum library, so that the molecular structure of an intermediate product is identified and analyzed, and a foundation is provided for the research of a generation mechanism of the chlorobenzene acetonitrile.
Fourthly, the invention adopts a pretreatment method of small-volume liquid-liquid extraction, namely 6 chlorobenzene acetonitrile in the water sample is extracted and enriched, and compared with the traditional extraction mode (the water sample volume is 200mL) while the enrichment times are ensured, the consumption of the water sample, the chlorination terminator and the extractant is saved, and the cost is also reduced.
Drawings
FIG. 1 is a schematic flow chart of the method for simultaneously detecting 6 chlorophenylacetonitrile as a nitrogenous aromatic disinfection byproduct in drinking water.
FIG. 2 is a schematic diagram of a standard curve for simultaneously detecting 4-chlorobenzonitrile in nitrogenous aromatic disinfection byproducts in drinking water according to the invention.
FIG. 3 is a schematic diagram of a standard curve for simultaneously detecting 2, 4-dichlorophenylacetonitrile in nitrogenous aromatic disinfection byproducts in drinking water according to the invention.
FIG. 4 is a schematic diagram of a standard curve for simultaneously detecting 2, 5-dichlorophenylacetonitrile in nitrogenous aromatic disinfection byproducts in drinking water according to the invention.
FIG. 5 is a schematic diagram of a standard curve for simultaneously detecting 2, 6-dichlorophenylacetonitrile in nitrogenous aromatic disinfection byproducts in drinking water according to the invention.
FIG. 6 is a schematic diagram of a standard curve for simultaneously detecting 2, 3-dichlorophenylacetonitrile in nitrogenous aromatic disinfection byproducts in drinking water according to the invention.
FIG. 7 is a schematic diagram of a standard curve for simultaneously detecting 3, 4-dichlorophenylacetonitrile in nitrogenous aromatic disinfection byproducts in drinking water according to the invention.
FIG. 8 is a chromatogram of the total scan mode for simultaneously detecting 6 chlorobenzonitrile in the nitrogenous aromatic disinfection byproducts in the drinking water.
Detailed Description
The invention provides a method for simultaneously detecting 6 chlorobenzene acetonitrile serving as a nitrogenous aromatic disinfection byproduct in drinking water.
< method for simultaneously detecting 6 chlorobenzene acetonitrile as a nitrogenous aromatic disinfection by-product in drinking water >
The method for simultaneously detecting 6 chlorobenzene acetonitrile serving as a nitrogenous aromatic disinfection byproduct in drinking water comprises the following steps: sample pretreatment, analysis condition optimization and running measurement.
In fact, the nitrogenous aromatic disinfection by-product chloroacrylonitrile in the water sample of drinking water consists of 4-chloroacrylonitrile, 2, 3-dichlorophenylacetonitrile, 2, 4-dichlorophenylacetonitrile, 2, 5-dichlorophenylacetonitrile, 2, 6-dichlorophenylacetonitrile and 3, 4-dichlorophenylacetonitrile.
The chlorobenzene acetonitrile is divided into 6 kinds in total due to the difference of the number of chlorine atoms and the substitution position of chlorine; wherein, 2, 3-dichlorobenzyl cyanide, 2, 4-dichlorobenzyl cyanide, 2, 5-dichlorobenzyl cyanide, 2, 6-dichlorobenzyl cyanide and 3, 4-dichlorobenzyl cyanide are isomers. The molecular structural formula is specifically as follows:
the molecular structural formula of the 4-chlorobenzonitrile is as follows:
the molecular structural formula of the 2, 3-dichlorobenzyl cyanide is as follows:
the molecular structural formula of the 2, 4-dichlorobenzyl cyanide is as follows:
the molecular structural formula of the 2, 5-dichlorobenzyl cyanide is as follows:
the molecular structural formula of the 2, 6-dichlorobenzyl cyanide is as follows:
the molecular structural formula of the 3, 4-dichlorobenzyl cyanide is as follows:
further, the method for simultaneously detecting 6 chlorobenzene acetonitrile serving as the nitrogenous aromatic disinfection by-product in the drinking water specifically comprises the following steps:
(1) enriching a water sample of the drinking water in a liquid-liquid extraction pretreatment mode;
(2) determining operation parameters of a gas chromatography/mass spectrometry (GC/MS) combined instrument, wherein the operation parameters comprise a column temperature box temperature rise program, column head pressure, sample injection quantity, sample injection port temperature and a chromatographic identification time zone;
(3) establishing a standard curve of 6 kinds of chlorobenzene acetonitrile;
(4) and analyzing the water sample by using a gas chromatography/mass spectrometer, performing qualitative analysis according to the obtained chromatogram and mass spectrogram, and determining the peak emergence time of 6 kinds of chloroacrylonitrile in the water sample by using a standard curve of 6 kinds of chloroacrylonitrile established by an external standard method.
[ pretreatment of sample ]
In the step (1), the specific process of the enrichment pretreatment of the water sample of the drinking water is as follows:
putting a water sample of 10mL drinking water into a 25mL glass vial, adding 200 mu mol/L chlorination terminator for dechlorination, adjusting the pH value of the water sample, adding 2.0g anhydrous sodium sulfate, and manually shaking to fully dissolve the water sample; then, 2.0mL of an extractant was added, and the mixture was shaken at 2500r/min with an IKA shaker for 5.0min and allowed to stand for 10.0 min.
Wherein, the purpose of adding the anhydrous sodium sulfate is as follows: the generation of emulsion in the extraction process is reduced, thereby improving the extraction efficiency.
In practice, sample pretreatment involves determination of the pH of the aqueous sample and the optimal chlorination stop agent.
(determination of pH value of Water sample)
Further, the pH of a water sample of drinking water needs to be adjusted before the extraction process.
The determination process of the optimal pH value comprises the following steps: the stability of 6 chlorobenzonitriles in buffer solutions of pH 5, pH 6, pH 7, pH 8 and pH 9 was measured to compare the hydrolysis rates. Wherein the buffer solution is prepared from 10mmol/L sodium dihydrogen phosphate or disodium hydrogen phosphate, and is adjusted to the above specified pH value with sodium hydroxide and hydrochloric acid. The solution obtained by adding the buffer solution into 6 kinds of chloro-phenylacetonitriles respectively is stored for 120 hours at 23.0 +/-0.5 ℃ in a dark place, and the residual contents of the 6 kinds of chloro-phenylacetonitriles are measured and compared at 0 hour, 12 hour, 24 hour, 36 hour, 48 hour, 72 hour, 96 hour and 120 hour. The results show that 6 chlorophenylacetonitriles are most stable at pH 7.
(determination of Chlorination terminator)
In practice, the chlorination terminator is selected from one or more of ascorbic acid, sodium thiosulfate, ammonium chloride, sodium arsenite and sodium sulfite.
The determination process of the optimal chlorination terminator comprises the following steps: preparing 6 chlorobenzene acetonitrile mixed standard sample aqueous solutions with the same concentration (0.6 mu mol/L), wherein one water sample is not added with a chlorination terminator, 200 mu mol/L of ascorbic acid, sodium thiosulfate, ammonium chloride, sodium arsenite (namely sodium meta-arsenite) and sodium sulfite are respectively added into the other solutions, adjusting the pH value of all the solutions to be 7, carrying out a light-shielding reaction at 23.0 +/-0.5 ℃ for 24 hours, then carrying out liquid-liquid extraction, and then carrying out GC/MS analysis. The chlorination terminator used when the peak area is the largest can be obtained is sodium sulfite.
The purpose of adding the chlorination terminator is as follows: generally, the disinfected drinking water contains 0.05-4.0mg/L of residual chlorine, the residual chlorine has strong oxidizability and can react with the chlorobenzene acetonitrile to influence the accuracy of a detection result, therefore, a proper chlorination terminator is selected to terminate the progress of the chlorination reaction, and the loss of the chlorobenzene acetonitrile concentration in the process of sample transportation or storage is reduced as much as possible.
(extracting agent)
The extractant is methyl tert-butyl ether.
[ optimization of analysis conditions ]
In fact, in step (2), the analysis condition optimization includes determination of column oven temperature program, column head pressure, sample volume, sample inlet temperature and chromatographic identification time band.
(determination of temperature program of column oven)
The determination process of the column oven temperature rise program in the gas chromatograph comprises the following steps: comparing the peak-out time, peak height and peak area of 6 chlorobenzene acetonitrile, under the condition of ensuring short total time, increasing the peak-out time interval of adjacent peaks, and increasing the peak height and peak area as much as possible, thereby determining the optimal initial temperature, end point temperature, temperature-rising speed and the retention time at the end of each temperature-rising stage. Wherein the initial temperature is usually 20-50 ℃ to ensure that all low-boiling components in the sample are well separated; the end point temperature is required to ensure that the peak shape of the final peak component in the sample is sharp and completely separated, and the maximum use temperature of the gas chromatograph is not exceeded; the temperature rising speed is required to enable the peaks of all components in the analysis to be well separated, and because the boiling points, the polarities and other properties of the 6 chlorobenzene acetonitrile are different and some properties are relatively close, the separation is difficult, so that the aim of setting a plurality of different temperature rising speeds is to better separate the 6 chlorobenzene acetonitrile.
Therefore, the method for determining the temperature-raising program of the column incubator can overcome the phenomenon of peak tailing of 6 kinds of phenylacetonitrile, so that each piece of phenylacetonitrile is completely separated, and the 6 kinds of phenylacetonitriles are ensured to respectively and normally produce peaks.
(determination of column head pressure)
The column pressure of the gas chromatograph is 134.2 +/-0.3 KPa, and preferably 134.2 KPa.
Specifically, the method comprises the following steps: the process of determining the column head pressure is as follows: under the condition that other parameters of the gas chromatograph are not changed, the column head pressure in the parameters of the gas chromatograph is changed, and the column head pressure which ensures that 6 chlorobenzene acetonitrile normally appears is the optimal column head pressure.
(determination of sample amount)
The amount of sample to be introduced into the gas chromatograph is 1.0 to 10. mu.L, preferably 1.0 to 5.0. mu.L, and more preferably 1.0. mu.L.
Specifically, the method comprises the following steps: the determination process of the optimal sampling amount comprises the following steps: under the condition that other parameters of the gas chromatograph are not changed, the gas chromatograph is set to be in a full-scan mode, the sample volumes are respectively set to be 1 mu L, 2 mu L, 3 mu L, 4 mu L and 5 mu L, and the sample volume when the peak area of the total ion peak of the 6 types of the chlorobenzonitrile corresponding to the unit sample volume is maximum is the optimal sample volume.
(determination of sample inlet temperature)
The gas chromatograph has a sample inlet temperature of 100 to 250.0 ℃, preferably 110 to 250.0 ℃, and more preferably 230.0 ℃.
Specifically, the method comprises the following steps: the determination process of the injection port temperature is as follows: the sample inlet temperature is to rapidly vaporize the sample injected into the sample inlet, under the condition that other parameters of the gas chromatograph are not changed, the sample inlet temperature is respectively set to be 100 ℃, 130 ℃, 150 ℃, 170 ℃, 200 ℃, 230 ℃, 240 ℃ and the like, and when the peak emergence of 6 chlorobenzene acetonitrile reaches good separation, the sample inlet temperature with the highest peak area is the optimal sample inlet temperature.
(determination of chromatographic identification time band)
The chromatographic identification time band of the gas chromatograph is 0.1-1.0min, preferably 0.2 min.
Specifically, the method comprises the following steps: the determination process of the chromatographic identification time band comprises the following steps: in the process of measuring a water sample, the peak time of a target substance and the peak time of a standard substance are different from each other due to the influence of a sample matrix, and the peak time of the target substance and the peak time of the standard substance are shifted before and after the peak time of the standard substance. Because isomers exist in the 6 chlorophenylacetonitrile, the peak-appearance time is relatively close, if the time band is set to be too wide, good separation of chromatographic peaks of all components cannot be realized, and if the time band is set to be too narrow, the sensitivity to a sample matrix is too high, so that the 6 chlorophenylacetonitrile in a water sample cannot be normally measured. Therefore, under the condition that other parameters of the gas chromatograph are not changed, the time bands are respectively set to be 0.1min, 0.2min, 0.4min, 0.6min, 0.8min and 1.0min, and the time band of normal peak emergence when the peak emergence of the 6 chlorobenzonitrile reaches good separation is the optimal chromatographic identification time band.
Thus, the operating parameters of the gas chromatograph are: capillary column: the model is as follows: rtx-5MS, column length: 30m, inner diameter: 0.25mm, film thickness: 0.25 μm; the column head pressure is: 134.2 +/-0.3 KPa; the sample injection amount is as follows: 1.0-10 μ L; the sample introduction mode is as follows: no shunt sampling; the sample inlet temperature is: 100-250.0 ℃; the sample introduction time is as follows: 1.0 min; the carrier gas is: high purity helium gas; the flow control method of the carrier gas is as follows: controlling the pressure; the total flow rate was: 31.5 mL/min; the column flow rate was: 2.31 mL/min; the linear velocity is: 3312 cm/min; the purging flow is 6.0 mL/min; data acquisition and analysis: a GC/MS solution software workstation; column oven temperature program: the initial temperature was: keeping the temperature at 20-50 ℃ for 5.0min, then heating to 110 ℃ at the speed of 25.00 ℃/min, and keeping the temperature for 2.0 min; then raising the temperature to 155 ℃ at the speed of 35.00 ℃/min, and keeping the temperature for 3.0 min; heating to 220 deg.C at a speed of 20.00 deg.C/min, and maintaining for 3.0 min; the chromatographic identification time bands are: 0.1-1.0 min.
Mass spectrometer operating parameters: the ion source temperature is: at 200 ℃, the interface temperature is: 260 ℃; the solvent delay time was: 3.0 min; the ion source is an electron impact ion source (EI); the electron energy is: 70 eV; the detection mode is as follows: selective ion detection (SIM); the scanning parameters are: the start time is: 5.00min, end time: 19.00min, channel 1:116.00m/z, channel 2:151.00m/z, channel 3:89.00 m/z; the start time is: 12.12min, end time: 19.00min, channel 1:150.00m/z, channel 2:185.00m/z, channel 3:152.00m/z, channel 4:114.00m/z, channel 5:73.00m/z, and channel 6:147.00 m/z.
[ running measurement ]
The running measurements included determination of the standard curve, the process detection limit, and the recovery.
(determination of Standard Curve)
Before the peak time of 6 kinds of chlorobenzene acetonitrile is measured, a standard curve of 6 kinds of chlorobenzene acetonitrile is established, and the specific process is as follows:
(a) preparing a mixed standard solution: respectively weighing 20mg of 4-chlorophenylacetonitrile, 20mg of 2, 3-dichlorophenylacetonitrile, 20mg of 2, 4-dichlorophenylacetonitrile, 20mg of 2, 5-dichlorophenylacetonitrile, 20mg of 2, 6-dichlorophenylacetonitrile and 20mg of 3, 4-dichlorophenylacetonitrile, dissolving in 20mL of methyl tert-butyl ether, mixing to prepare a mixed standard solution with the same concentration of each chlorophenylacetonitrile (the initial concentration is 1mg/mL), and placing in a brown bottle;
(b) preparing the mixed standard solution in the step (a) into a gradient standard correction solution by using ultrapure water (Millipore, the resistivity is 18M omega cm), wherein the gradient mass concentration is respectively 1 mu g/L, 5 mu g/L, 10 mu g/L, 20 mu g/L, 50 mu g/L, 100 mu g/L and 200 mu g/L;
(c) and carrying out batch analysis on the gradient standard correction fluid by using a gas chromatography/mass spectrometer, and respectively generating standard curves of 6 kinds of chloroacrylonitrile by using a lab solution workstation, wherein the standard curve graphs of the 6 kinds of chloroacrylonitrile are shown in fig. 2 to 7, the abscissa is the mass concentration (mu g/L) of the chloroacrylonitrile, and the ordinate is the peak area of the chloroacrylonitrile. The integral of the signal intensity in the retention time is a peak area, the peak area is in direct proportion to the mass concentration of the chlorobenzene acetonitrile, and the relation between the standard peak area and the mass concentration can be obtained by a standard curve, namely the mass concentration of the chlorobenzene acetonitrile in an unknown sample can be obtained by using the known peak area when the unknown sample is measured.
The method comprises the steps of adopting a standard curve diagram of 6 kinds of chlorobenzene acetonitrile established by an external standard method, detecting a water sample by GC/MS (gas chromatography/mass spectrometry), wherein as shown in figure 8, the abscissa is time (min), the ordinate is ion fragment strength, and is unit-free, and the peak-off time of 4-chlorobenzene acetonitrile can be 11.110 +/-0.005 min, preferably 11.110 min; the peak time of the 2, 4-dichlorophenylacetonitrile can be 11.680 +/-0.005 min, and is preferably 11.680 min; the peak time of the 2, 5-dichlorophenylacetonitrile can be 13.150 +/-0.005 min, and is preferably 13.150 min; the peak time of the 2, 6-dichlorophenylacetonitrile can be 13.375 +/-0.005 min, and is preferably 13.375 min; the peak time of the 2, 3-dichlorophenylacetonitrile can be 13.600 +/-0.005 min, and is preferably 13.600 min; the peak time of 3, 4-dichlorophenylacetonitrile may be 14.385. + -. 0.005min, preferably 14.385 min.
After 6 kinds of chlorobenzene acetonitrile are separated in GC, MS detects the time of corresponding ion fragments of various chlorobenzene acetonitrile, so that the peak time is related to the properties of instrument parameters, material boiling points, polarity and the like.
(determination of method detection Limit and recovery)
By adopting the detection method, the 6 chlorobenzonitrile can be well separated in the analysis process, the linearity is good (r ^2 is more than 0.99) within the range of 1-200 mu g/L, and the recovery rate of the 6 chlorobenzonitrile is between 87-95 percent; the Detection Limit (Limit of Method Detection, MDL) of the Method is below 100 ng/L; the Relative Standard Deviation (RSD) is less than 10.0%.
The higher the recovery rate is, the closer the detection result value is to the theoretical value is, the more reliable the detection method is; the higher detection limit of the method means that the chlorobenzene acetonitrile with lower concentration can be detected; and the smaller relative standard deviation means that the difference of a plurality of detection results is not large, so that the authenticity of the detection result is ensured.
The present invention will be further described with reference to the following examples.
Example (b):
the method for simultaneously detecting 6 chlorobenzene acetonitrile serving as a nitrogenous aromatic disinfection byproduct in drinking water comprises the following steps:
(1) and enriching the water sample of the drinking water in a liquid-liquid extraction pretreatment mode.
Specifically, a 10mL water sample of drinking water was placed in a 25mL glass vial, 200 μmol/L sodium sulfite (as a chlorination terminator) was added for dechlorination, the pH of the water sample was adjusted to 7, 2.0g anhydrous sodium sulfate was added, and the mixture was sufficiently dissolved by manual shaking; 2.0mL of methyl tert-butyl ether (as an extractant) was added, the mixture was shaken at 2500r/min for 5.0min using an IKA shaker, allowed to stand for 10.0min, and 1mL of the upper methyl tert-butyl ether solution was taken out and placed in a sample vial for GC/MS measurement.
(2) And determining the operation parameters of the GC/MS.
Specifically, the operating parameters of the gas chromatograph are: capillary column: the model is as follows: rtx-5MS, column length: 30m, inner diameter: 0.25mm, the film thickness is: 0.25 μm; the column head pressure is: 134.2 KPa; the sample injection amount is as follows: 1.0 μ L; the sample introduction mode is as follows: no shunt sampling; the sample inlet temperature is: 230.0 ℃ of; the sample introduction time is as follows: 1.0 min; the carrier gas is: high purity helium gas; the flow control method of the carrier gas is as follows: controlling the pressure; the total flow rate was: 31.5 mL/min; the column flow rate was: 2.31 mL/min; the linear velocity is: 3312 cm/min; the purging flow is 6.0 mL/min; data acquisition and analysis: a GC/MS solution software workstation; column oven temperature program: the initial temperature was: keeping the temperature at 50 ℃ for 5.0min, then heating to 110 ℃ at the speed of 25.00 ℃/min, and keeping the temperature for 2.0 min; then raising the temperature to 155 ℃ at the speed of 35.00 ℃/min, and keeping the temperature for 3.0 min; heating to 220 deg.C at a speed of 20.00 deg.C/min, and maintaining for 3.0 min; the chromatographic identification time bands are: 0.2 min.
Mass spectrometer operating parameters: the ion source temperature is: at 200 ℃, the interface temperature is: 260 ℃; the solvent delay time was: 3.0 min; the ion source is an electron impact ion source (EI); the electron energy is: 70 eV; the detection mode is as follows: selective ion detection (SIM); the scanning parameters are: the start time is: 5.00min, end time: 19.00min, channel 1:116.00m/z, channel 2:151.00m/z, channel 3:89.00 m/z; the start time is: 12.12min, end time: 19.00min, channel 1:150.00m/z, channel 2:185.00m/z, channel 3:152.00m/z, channel 4:114.00m/z, channel 5:73.00m/z, and channel 6:147.00 m/z.
(3) And establishing standard curves of 6 kinds of chlorobenzene acetonitrile.
Specifically, (a) preparing a mixed standard solution: respectively weighing 20mg of 4-chlorophenylacetonitrile, 20mg of 2, 3-dichlorophenylacetonitrile, 20mg of 2, 4-dichlorophenylacetonitrile, 20mg of 2, 5-dichlorophenylacetonitrile, 20mg of 2, 6-dichlorophenylacetonitrile and 20mg of 3, 4-dichlorophenylacetonitrile, dissolving in 20mL of methyl tert-butyl ether, mixing to prepare a mixed standard solution with the same concentration of each chlorophenylacetonitrile (the initial concentration is 1mg/mL), and placing in a brown bottle;
(b) preparing the mixed standard solution in the step (a) into a gradient standard correction solution by using ultrapure water (Millipore, the resistivity is 18M omega cm), wherein the gradient mass concentration is respectively 1 mu g/L, 5 mu g/L, 10 mu g/L, 20 mu g/L, 50 mu g/L, 100 mu g/L and 200 mu g/L;
(c) and carrying out batch processing analysis on the gradient standard correction fluid by adopting a gas chromatography/mass spectrometer, and respectively generating standard curves of 6 kinds of chlorobenzene acetonitrile by utilizing a lab solution workstation, wherein the abscissa is the mass concentration of the chlorobenzene acetonitrile, and the ordinate is the peak area of the chlorobenzene acetonitrile.
(4) And analyzing the water sample by using a gas chromatography/mass spectrometer, performing qualitative analysis according to the obtained chromatogram and mass spectrogram, and determining the peak emergence time of 6 kinds of chloroacrylonitrile in the water sample by using a standard curve of 6 kinds of chloroacrylonitrile established by an external standard method.
Specifically, the peak time of 4-dichlorophenylacetonitrile is 11.110min, the peak time of 2, 4-dichlorophenylacetonitrile is 11.680min, the peak time of 2, 5-dichlorophenylacetonitrile is 13.150min, the peak time of 2, 6-dichlorophenylacetonitrile is 13.375min, the peak time of 2, 3-dichlorophenylacetonitrile is 13.600min, and the peak time of 3, 4-dichlorophenylacetonitrile is 14.385 min.
By adopting the detection method, the 6 chlorobenzonitrile can be well separated in the analysis process, the linearity is good (r ^2 is more than 0.99) within the range of 1-200 mu g/L, and the recovery rate of the 6 chlorobenzonitrile is 90 percent; the Detection Limit (Limit of Method Detection, MDL) of the Method is below 100 ng/L; the Relative Standard Deviation (RSD) is less than 10.0%.
Wherein the peak time of 4-dichlorophenylacetonitrile is 11.110 +/-0.005 min, the peak time of 2, 4-dichlorophenylacetonitrile is 11.680 +/-0.005 min, the peak time of 2, 5-dichlorophenylacetonitrile is 13.150 +/-0.005 min, the peak time of 2, 6-dichlorophenylacetonitrile is 13.375 +/-0.005 min, the peak time of 2, 3-dichlorophenylacetonitrile is 13.600 +/-0.005 min, and the peak time of 3, 4-dichlorophenylacetonitrile is 14.385 +/-0.005 min.
In the gas chromatograph, the column head pressure is within 134.2 + -0.3 KPa, the sample injection amount is within 1.0-10 μ L, the sample injection port temperature is within 100-250.0 ℃, and the chromatographic identification time zone is within 0.1-1.0 min.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments and the generic principles defined herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments. Those skilled in the art should appreciate that many modifications and variations are possible in light of the above teaching without departing from the scope of the invention.
Claims (11)
1. A method for simultaneously detecting 6 chlorobenzene acetonitrile which is a nitrogenous aromatic disinfection by-product in drinking water is characterized in that: which comprises the following steps:
enriching a water sample of the drinking water in a pretreatment mode, and then detecting the enriched water sample;
the nitrogenous aromatic disinfection by-product chlorobenzonitrile in the water sample of the drinking water consists of 4-chlorobenzonitrile, 2, 3-dichlorophenylacetonitrile, 2, 4-dichlorophenylacetonitrile, 2, 5-dichlorophenylacetonitrile, 2, 6-dichlorophenylacetonitrile and 3, 4-dichlorophenylacetonitrile;
the process of enriching the water sample of the drinking water comprises the following steps:
adding a terminator into a water sample of the drinking water, adjusting the pH value of the water sample, and adding an extracting agent to perform liquid-liquid extraction;
the terminator is sodium sulfite; the pH value of the water sample is 7;
the detection process is to adopt a gas chromatography-mass spectrometer for analysis and detection, and comprises the determination of a column incubator temperature-rising program, column head pressure, sample injection quantity, sample injection port temperature and a chromatographic identification time zone;
the capillary column model is Rtx-5 MS;
column oven temperature program: the initial temperature was: keeping the temperature at 20-50 ℃ for 5.0min, then heating to 110 ℃ at the speed of 25.00 ℃/min, and keeping the temperature for 2.0 min; then raising the temperature to 155 ℃ at the speed of 35.00 ℃/min, and keeping the temperature for 3.0 min; then the temperature is raised to 220 ℃ at the speed of 20.00 ℃/min and is kept for 3.0 min.
2. The method for simultaneously detecting 6 chlorophenylacetonitrile as a nitrogenous aromatic disinfection by-product in drinking water according to claim 1, wherein the method comprises the following steps: the peak time of the 4-dichlorophenylacetonitrile is 11.110 +/-0.005 min, the peak time of the 2, 4-dichlorophenylacetonitrile is 11.680 +/-0.005 min, the peak time of the 2, 5-dichlorophenylacetonitrile is 13.150 +/-0.005 min, the peak time of the 2, 6-dichlorophenylacetonitrile is 13.375 +/-0.005 min, the peak time of the 2, 3-dichlorophenylacetonitrile is 13.600 +/-0.005 min, and the peak time of the 3, 4-dichlorophenylacetonitrile is 14.385 +/-0.005 min.
3. The method for simultaneously detecting 6 chlorophenylacetonitrile as a nitrogenous aromatic disinfection by-product in drinking water according to claim 1, wherein the method comprises the following steps: the extractant is methyl tert-butyl ether.
4. The method for simultaneously detecting 6 chlorophenylacetonitrile as a nitrogenous aromatic disinfection by-product in drinking water according to claim 1, wherein the method comprises the following steps: the column head pressure is 134.2 +/-0.3 KPa.
5. The method for simultaneously detecting 6 chlorophenylacetonitrile as a nitrogenous aromatic disinfection by-product in drinking water according to claim 1, wherein the method comprises the following steps: the column head pressure is 134.2 KPa.
6. The method for simultaneously detecting 6 chlorophenylacetonitrile as a nitrogenous aromatic disinfection by-product in drinking water according to claim 1, wherein the method comprises the following steps: the sample injection amount is 1.0-10 mu L.
7. The method for simultaneously detecting 6 chlorophenylacetonitrile as a nitrogenous aromatic disinfection by-product in drinking water according to claim 1, wherein the method comprises the following steps: the sample injection amount is 1.0 muL.
8. The method for simultaneously detecting 6 chlorophenylacetonitrile as a nitrogenous aromatic disinfection by-product in drinking water according to claim 1, wherein the method comprises the following steps: the temperature of the sample inlet is 100-250.0 ℃.
9. The method for simultaneously detecting 6 chlorophenylacetonitrile as a nitrogenous aromatic disinfection by-product in drinking water according to claim 1, wherein the method comprises the following steps: the injection port temperature is 230.0 ℃.
10. The method for simultaneously detecting 6 chlorophenylacetonitrile as a nitrogenous aromatic disinfection by-product in drinking water according to claim 1, wherein the method comprises the following steps: the chromatographic identification time band is 0.1-1.0 min.
11. The method for simultaneously detecting 6 chlorophenylacetonitrile as a nitrogenous aromatic disinfection by-product in drinking water according to claim 1, wherein the method comprises the following steps: the chromatographic identification time band is 0.2 min.
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