CN101131381A - Method for detecting halogen acetic acid in drinking water - Google Patents
Method for detecting halogen acetic acid in drinking water Download PDFInfo
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- CN101131381A CN101131381A CNA2007100464720A CN200710046472A CN101131381A CN 101131381 A CN101131381 A CN 101131381A CN A2007100464720 A CNA2007100464720 A CN A2007100464720A CN 200710046472 A CN200710046472 A CN 200710046472A CN 101131381 A CN101131381 A CN 101131381A
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Abstract
A detection method to detect the acetic halide in drinking water of environment detection field includes the process: (1) collecting samples; (2) removing the residue chlorine; (3) saving; (4) condensation; (5) extraction: the residue water sample is added into the volumetric flask and added into the vitriol, then to add the anhydrous sodium sulfate and solve with stirring; last to add the MTBE to separate the water and organic phase; (6) derivation: the organic phase is transferred to the faucet tube with the rubber pad, which is added with the methanol sulfate firstly and covered the plug; it is heated in water bath, after cooling, the Na2SO4 is added in then to remove the water phase to add the saturation sodium bicarbonate to balance the pH; fist to release the air and remove the organic phase to tubule, last to add the Na2SO4 to absorb the water, immediately to detect by the GC-MC; (7)sample on; (8) drawing the standard curve. The invention has high sensitivity and strong to determine the sample nature.
Description
Technical field
The present invention relates to a kind of detection method, specifically is the detection method of halogen acetic acid in a kind of potable water, belongs to the environmental monitoring technology field.
Background technology
Because the drinking water source organic contamination, ubiquity haloform (THMs) and halogen acetic acid DBPs (DBPs) such as (HAAs) cause potable water to have " three cause " (teratogenesis, carcinogenic, mutagenesis) risk behind the potable water cholorination.China's " drinking water sanitary standard " GB5749-2006 HAAs (halogen acetic acid) as unconventional test item.Mainly use derivatization-vapor-phase chromatography (GC) to measure to the mensuration of halogen acetic acid at present.HAAs (halogen acetic acid) concentration rank in the chlorination potable water is generally μ g/L even lower, therefore before analyzing and testing, must carry out the enrichment pre-service to sample.In addition, strong at HAAs (halogen acetic acid) boiling point height, difficult volatilization in water, dissolubility, can cause that on chromatographic column strong absorption causes hangover, can not directly use GC (gas chromatograph) sample detection, advance generally that people GC (gas chromatograph) is preceding will to do the ester that derivatization treatment makes it to generate relatively easy gasification, utilize the different retention times of each component that carboxylate is separated then, come quantitatively corresponding HAAs (halogen acetic acid) by detecting the derivative ester that generates.
Find through literature search prior art, Beijing Disease Prevention and Control Centre builds (Wei Jianrong such as honor Wei, Jiang Lijuan, Tao Jing. halogen acetic acid in liquid-liquid extraction, the derivatization gas chromatography determination potable water, China's sanitary inspection magazine, 2005,15 (1): 43-45) adopt liquid-liquid extraction that five kinds of halogen acetic acids in the water are taken in the organic phase through methyl tertiary butyl ether (MTBE) organic solvent extracting, under acid condition, in 50 ℃ and methyl alcohol generation esterification, carried out gas chromatographic analysis as detecting device with ECD (electron capture detector).In addition, HAAs (halogen acetic acid) analyzing detecting method that USEPA (Environmental Protection Agency) recommends is: EPA (Environmental Protection Administration) 552, EPA (Environmental Protection Administration) 552.1, EPA (Environmental Protection Administration) 552.2, EPA (Environmental Protection Administration) 552.3 and StandardMethod (standard method) 6233B, they also all are to use MTBE (methyl tert-butyl ether) or anion exchange resins as extractant, with diazomethane or acidic methanol as derivatization reagent, with GC-ECD (gas chromatograph-electron capture organ) analyzing and testing.Though various impurity seldom disturb also lessly in the potable water, owing to use to concentrate, cause the concentration of various impurity also to rise and some accessory substance generation can cause interference thereupon.In addition, ECD (electron capture organ) is subject to the influence of the various phthalates that plastics and rubber brings, and causes very big peak on chromatogram, and mensuration is caused adverse effect.This method is constantly improved in a large amount of afterwards research, yet, so far still exist low for the sensitivity of chloroacetic acid, be subject to chromatogram interference, GC (vapor-phase chromatography) long operational time, to shortcomings such as the qualitative ability of unknown compound, in view of the popularity of HAAs (halogen acetic acid) existence with to human health damage, must further improve and raising existing method.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, the detection method of halogen acetic acid in a kind of potable water is provided.The sensitivity that the invention solves above-mentioned chloroacetic acid is low, be subject to the chromatogram interference, GC (vapor-phase chromatography) long operational time, to problems such as the qualitative ability of unknown compound.
The present invention is achieved by the following technical solutions, the present invention includes following steps:
(1) sampling: when water tap was taken a sample, the tap of fetching boiling water earlier discharged water, sampling again after the water temperature of emitting is constant.
Described sampling, sampling container uses the screw socket plug sampling bottle of brown band teflon gasket, and repeatedly washes through tap water and ultrapure water.
(2) remove chlorine residue: add granular ammonium chloride,, prevent to generate more halogen acetic acid and biodegradation the residual combined chloride that changes into of free chlorine in the water sample.
(3) preserve: the sealing of water sample lucifuge is preserved, but can not be freezing.
Described preservation, its temperature are below 6 ℃, and the time is below 14 days.
(4) concentrate: the water sample of preserving is taken out, make it return to room temperature, get the part water sample and vacuumize evaporation and obtain remaining water sample.
The described part water sample of getting vacuumizes evaporation and obtains remaining water sample, is meant: get the 200mL water sample, use Rotary Evaporators to vacuumize evaporation 5 hours to about 20mL remnants water sample under 65 ℃.
(5) extraction: in volumetric flask, add all remaining water samples, dropwise add sulfuric acid again, next take advantage of waste heat and add anhydrous sodium sulfate immediately and shake dissolving immediately.Add MTBE (methyl tert-butyl ether), manually acutely shake after the sealing, allow water and organic phase layering.
Described all remaining water samples that add in volumetric flask are meant: the remaining water sample of step (4) gained is poured in the volumetric flask, after pouring out, the container water of adorning remaining water sample is cleaned twice, the washing lotion after the cleaning also will add volumetric flask.
Described adding sulfuric acid is meant: add sulfuric acid adjusting pH and be lower than 0.5, mix back pH detection paper.
Described adding MTBE (methyl tert-butyl ether) is meant: add 2mL MTBE (methyl tert-butyl ether), mark 1 in wherein containing, 2-dibromopropane 1000 μ g/L.
(6) derivatization: pipette upper organic phase to the cock test tube with rubber packing, this pipe adds the sulfuric acid methanol solution in advance, covers stopper, insertion water-bath heating, cool off after the water-bath, add metabisulfite solution, inhale and remove and discard lower floor's water, add in the saturated sodium bicarbonate solution and pH, of short duration shaking unscrewed the bottleneck venting for the first time, pipettes upper organic phase to tubule, add the anhydrous sodium sulfate suction at last, go up sample immediately and enter the combined gas chromatography mass spectrometry detection.
The described upper organic phase that pipettes is meant: pipette the 1.5mL upper organic phase to the cock test tube of 10mL band rubber packing, this pipe adds 2mL10% sulfuric acid methanol solution in advance, and excessive acidifying methyl alcohol makes reaction more thorough.
Described insertion water-bath heating is meant: insert 2 hours ± 10min of 50 ± 2 ℃ of water-bath heating of temperature, seal the film sealing, same batch sample is carried out water-bath simultaneously.
Cool off after the described water-bath, be meant: after the water-bath at but 10min of 4 ℃ of refrigerator and cooled.
Described adding metabisulfite solution, lower floor's water is removed and discards in suction, be meant: the metabisulfite solution that adds 4mL concentration 150g/L suppresses esterification and helps two to be separated, vibration back stacking is less than 2min, remove and discard lower floor's water with the suction of 5mL transfer pipet, make the no more than 0.3mL of residual water, can be complete to guarantee ensuing neutralization reaction.
Described of short duration shaking, its number of times are 4 times.
The described upper organic phase that pipettes is meant to tubule: use 250 μ L liquid-transfering guns to pipette upper organic phase 0.5mL to 1.5mL tubule.
(7) sample introduction: sample size 1 μ L, temperature programme is: keep 10min for 40 ℃, programming rate is 2 ℃/min, keeps 5min for 140 ℃, keeps 3min for 240 ℃, no split sampling.
(8) drawing standard curve: preparation standard reserving solution and hybrid standard storing solution are that the 200mL standard of 6 concentration is used liquid again with its dilution, are respectively: 5 μ g/L, 10 μ g/L, 20 μ g/L, 40 μ g/L, 80 μ g/L, 400 μ g/L.After concentrating pre-service, go up the sample analysis.Liken to halogen acetic acid concentration and interior mark concentration (1000 μ g/L) and to be X-axis, halogen acetic acid peak area and interior mark peak area ratio are made typical curve as Y-axis with above data.Typical curve is used to calculate halogen acetic acid concentration behind the water determination.
The present invention is directed to GC (vapor-phase chromatography) to the qualitative ability of unknown compound, replace electron capture detector (ECD) with mass detector (MS), though MS (mass spectrum) analysis cost and method detection limit are all than GC-ECD (gas chromatograph-electron capture organ) height, but MS (mass spectrum) has unique identification capacity to unknown compound, qualitative energy force rate ECD (electron capture organ) is strong, though it requires tested component is the compound of pure compound or 2-3 component, but GC/MS (gas chromatography/mass spectrometry) coupling, maximize favourable factors and minimize unfavourable ones each other, both can be qualitative to unknown compound, again can be quantitative to trace components.
Adopt the inventive method, the typical curve linear fit related coefficient of resulting 4 kinds of halogen acetic acids is better than building Wei related coefficient among the Rong Wenxian (r) between 0.99 ~ 0.999 all greater than 0.999; The relative standard deviation RSD that halogen acetic acid is measured under the 40 μ g/L between 6.15%～12.16%, can be controlled at that Unite States Standard (USS) method EPA552.3 requires 20% within; Recovery of standard addition is 81.7%～107%, can be controlled at that Unite States Standard (USS) method EPA552.3 requires ± 30% within, be better than building Wei among the Rong Wenxian 74.4% ~ 120% recovery of standard addition.
Description of drawings
Fig. 1 is a halogen acetic acid content synoptic diagram in the pipe network
Embodiment
Below in conjunction with accompanying drawing embodiments of the invention are elaborated: present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment transfers the pumping plant water outlet with output water, centre in the actual water system in somewhere and somewhere tap water outlet water sample is that detected object detects.Concrete implementation condition:
1. detecting instrument and main agents
Application of gas chromatorgraphy/mass adopts the AutoSystem XL GC/TurboMass MS of U.S. Perkin Elmer company.Halogen acetic acid reference material: chloroacetic acid (MCAA), dichloroacetic acid (DCAA), trichloroacetic acid (TCAA), a bromoacetic acid (MBAA), dibromoacetic acid (DBAA), U.S.'s import chromatographically pure (GC); Methyl tert-butyl ether (MTBE): import chromatographically pure (HPLC); Interior mark 1,2-dibromopropane: import chromatographically pure (GC), relative density 1.937; Methyl alcohol: chromatographically pure; The concentrated sulphuric acid: homemade high-quality pure; Anhydrous sodium sulfate: homemade analysis is pure, before using in muffle furnace 400 ℃ of baking 4h phthalates and other organic compounds to eliminate wherein to be mixed with; Sodium bicarbonate: homemade analysis is pure.
2. test method
It is concentrated to use liquid-liquid micro-extraction method (LLE) that sample is separated, and utilizes HAAs (halogen acetic acid) partition factor different in methyl tert-butyl ether and water, realizes the extract and separate enrichment.Extractant is selected methyl tert-butyl ether (MTBE), and esterifying agent is selected acidifying methyl alcohol.Adopt internal standard method, internal standard compound selects 1, the 2-dibromopropane.
3. the enforcement implementation procedure of whole embodiment is as follows:
(1) sampling: when water tap was taken a sample, the tap of fetching boiling water earlier discharged water, and took a sample up to the constant back of the water temperature of emitting (needing 3-5 minute usually) again.Sampling container uses the screw socket plug sampling bottle of brown band teflon gasket, be repeatedly with tap water and ultrapure water flushing.
(2) remove chlorine residue: the ratio with the 100mg/L water sample adds granular ammonium chloride, the residual combined chloride that changes into of free chlorine in the water sample, prevents to generate more halogen acetic acid and biodegradation.
(3) preserve: 6 ℃ of following lucifuge sealings of water sample are preserved, but can not be freezing, preserve at most 14 days
(4) concentrate: the water sample of preserving is taken out, make it return to room temperature.Get the 200mL water sample, use Rotary Evaporators under 65 ℃, to vacuumize evaporation and arrived the remaining water sample of about 20mL in 5 hours.
(5) extraction: in the 25mL volumetric flask, add all remaining water samples (water cleans the container secondary of adorning remaining water sample, and this washing lotion of twice also will add in the volumetric flask), dropwise add 1mL sulfuric acid adjusting pH again and be lower than 0.5 (mixing back pH detection paper).Next taking advantage of waste heat adds the 9g anhydrous sodium sulfate immediately and shakes dissolving immediately.Accurately add 2mL MTBE (mark 1 in containing, 2-dibromopropane 1000 μ g/L), manually acutely shake 5min after the sealing, wait for that layering 5min allows water and organic phase layering.
(6) derivatization: pipette the 1.5mL upper organic phase to the cock test tube of 10mL band rubber packing, this pipe adds 2mL10% sulfuric acid methanol solution in advance, covers stopper, and excessive acidifying methyl alcohol makes reaction more thorough.Insert 2 hours ± 10min of 50 ± 2 ℃ of water-bath heating of temperature, require to seal the film sealing.Same batch sample is preferably carried out water-bath simultaneously.After the water-bath at but 10min of 4 ℃ of refrigerator and cooled.The metabisulfite solution that adds 4mL concentration 150g/L suppresses esterification and helps two to be separated, stacking does not surpass 2min behind the vibration 1min, remove and discard lower floor's water with the suction of 5mL transfer pipet, make the no more than 0.3mL of residual water, can be complete to guarantee ensuing neutralization reaction.Add in the 1mL saturated sodium bicarbonate solution and pH, of short duration shaking 4 times unscrewed the bottleneck venting for the first time, uses 250 μ L liquid-transfering guns to pipette upper organic phase 0.5mL to 1.5mL tubule.Add the suction of 0.1g anhydrous sodium sulfate at last, go up sample immediately.
(7) sample introduction: 1 μ L, 40 ℃ of 10min (middle 2 ℃/min), 140 ℃ of 5min, 240 ℃ of 3min, no split sampling.
(8) typical curve is drawn: preparation standard reserving solution and hybrid standard storing solution are that the 200mL standard of 6 concentration is used liquid again with its dilution, are respectively: 5 μ g/L, 10 μ g/L, 20 μ g/L, 40 μ g/L, 80 μ g/L, 400 μ g/L.After concentrating pre-service, go up the sample analysis.Liken to halogen acetic acid concentration and interior mark concentration (1000 μ g/L) and to be X-axis, halogen acetic acid peak area and interior mark peak area ratio are as Y-axis, make typical curve with above data, obtaining dichloroacetic acid typical curve fit equation is Y=0.71681+13.22364X, and related coefficient (R) is 0.99945; The trichloroacetic acid fit equation is Y=0.06094+11.86763X, and related coefficient (R) is 0.99959; One bromoacetic acid fit equation is Y=0.11158+0.47119X, and related coefficient (R) is 0.99902; The dibromoacetic acid fit equation is Y=-0.16698+21.22446X, and related coefficient (R) is 0.99902.The standard working curve linearly dependent coefficient that simulates has good straight linear all greater than 0.999.
(9) relative standard deviation (RSD): 7 ultrapure water mark-ons (40 μ g/L) sample of taking standard reserving solution preparation carries out replicate determination after the pre-service, the relative standard deviation (RSD) of four kinds of halogen acetic acids of statistics, and the result is as shown in table 1:
The relative standard deviation (RSD) of table 1 four kinds of halogen acetic acids under 40 μ g/L concentration
| DCAA | TCAA | MBAA | DBAA | |
| Standard deviation (SD, μ g/L) mean value (μ g/L) relative standard deviation (RSD, %) | 3.4512 38.3408 9.0013 | 2.4122 39.2402 6.1471 | 5.4783 45.0349 12.1647 | 2.4472 32.4091 7.5510 |
As can be seen from Table 1, the RSD that halogen acetic acid is measured under the 40 μ g/L between 6.15%～12.16%, can be controlled at that Unite States Standard (USS) method EPA552.3 requires 20% within.
(10) recovery
Be about at 5 kinds of halogen acetic acid content and add an amount of hybrid standard storing solution in the substrate water sample of 20 μ g/L and be formulated as and add the water sample that scalar is respectively 10 μ g/L, 20 μ g/L, 40 μ g/L, measure its recovery.The computing formula of the recovery is:
R＝(A-B)/C×100％ (1)
Wherein, the R=recovery, sample determination value behind the A=mark-on, the B=background values, C=adds scalar.
The embodiment gained recovery 81.7%～107%, can be controlled at that Unite States Standard (USS) method EPA552.3 requires ± 30% within.
The foregoing description result such as Fig. 1 show, only detect dichloroacetic acid and trichloroacetic acid among the embodiment, and a bromoacetic acid and dibromoacetic acid do not detect.Halogen acetic acid (total amount)＜0.06mg/L that detected halogen acetic acid concentration requires far below " urban water supply water quality standard ", main dichloroacetic acid and trichloroacetic acid concentration are lower than the dichloroacetic acid 0.05 (mg/L) that " unconventional Interventions Requested of Drinking Water water quality and limit value " requires, trichloroacetic acid 0.1 (mg/L).Dichloroacetic acid and trichloroacetic acid concentration reduce gradually along the pipe network course of conveying.
Claims (10)
1. the detection method of halogen acetic acid in the potable water is characterized in that, comprises the steps:
(1) sampling: when water tap was taken a sample, the tap of fetching boiling water earlier discharged water, sampling again after the water temperature of emitting is constant;
(2) remove chlorine residue: add granular ammonium chloride, the residual combined chloride that changes into of free chlorine in the water sample;
(3) preserve: the sealing of water sample lucifuge is preserved;
(4) concentrate: the water sample of preserving is taken out, make it return to room temperature, get the part water sample and vacuumize evaporation and obtain remaining water sample;
(5) extraction: in volumetric flask, add all remaining water samples, dropwise add sulfuric acid again, next add anhydrous sodium sulfate and shake dissolving immediately, add methyl tert-butyl ether, manually acutely shake after the sealing, allow water and organic phase layering;
(6) derivatization: pipette upper organic phase to the cock test tube with rubber packing, this pipe adds the sulfuric acid methanol solution in advance, covers stopper, insertion water-bath heating, cool off after the water-bath, add metabisulfite solution, inhale and remove and discard lower floor's water, add in the saturated sodium bicarbonate solution and pH, of short duration shaking unscrewed the bottleneck venting for the first time, pipettes upper organic phase to tubule, add the anhydrous sodium sulfate suction at last, go up sample immediately and enter the combined gas chromatography mass spectrometry detection;
(7) sample introduction: no split sampling;
(8) drawing standard curve is used to calculate halogen acetic acid concentration behind the water determination.
2. the detection method of halogen acetic acid is characterized in that in the potable water according to claim 1, in the step (1), and described sampling, sampling container uses the screw socket plug sampling bottle of brown band teflon gasket, and repeatedly washes through tap water and ultrapure water.
3. the detection method of halogen acetic acid is characterized in that in the potable water according to claim 1, in the step (3), and described preservation, its temperature is below 6 ℃, the time is below 14 days.
4. the detection method of halogen acetic acid in the potable water according to claim 1, it is characterized in that in the step (4), the described part water sample of getting vacuumizes evaporation and obtains remaining water sample, be meant: get the 200mL water sample, use Rotary Evaporators under 65 ℃, to vacuumize evaporation and arrived the remaining water sample of about 20mL in 5 hours.
5. the detection method of halogen acetic acid is characterized in that in the potable water according to claim 1, and in the step (5), described adding sulfuric acid is meant: add sulfuric acid adjusting pH and be lower than 0.5, mix back pH detection paper.
6. the detection method of halogen acetic acid is characterized in that in the potable water according to claim 1, and described adding methyl tert-butyl ether is meant: add the 2mL methyl tert-butyl ether, mark 1 in wherein containing, 2-dibromopropane 1000 μ g/L.
7. the detection method of halogen acetic acid in the potable water according to claim 1, it is characterized in that, in the step (6), the described upper organic phase that pipettes, be meant: pipette the 1.5mL upper organic phase to the cock test tube of 10mL band rubber packing, this pipe adds 2mL10% sulfuric acid methanol solution in advance, and excessive acidifying methyl alcohol makes reaction more thorough;
Described insertion water-bath heating is meant: insert 2 hours ± 10min of 50 ± 2 ℃ of water-bath heating of temperature, seal the film sealing, same batch sample is carried out water-bath simultaneously;
Cool off after the described water-bath, be meant: after the water-bath at but 10min of 4 ℃ of refrigerator and cooled.
8. according to the detection method of halogen acetic acid in claim 1 or the 7 described potable water, it is characterized in that, in the step (6), described adding metabisulfite solution, lower floor's water is removed and discards in suction, is meant: add the metabisulfite solution of 4mL concentration 150g/L, vibration back stacking is less than 2min, remove and discard lower floor's water with the suction of 5mL transfer pipet, make the no more than 0.3mL of residual water;
Described of short duration shaking, its number of times are 4 times;
The described upper organic phase that pipettes is meant to tubule: use 250 μ L liquid-transfering guns to pipette upper organic phase 0.5mL to 1.5mL tubule.
9. the detection method of halogen acetic acid is characterized in that in the potable water according to claim 1, in the step (7), described sample introduction, concrete parameter is: sample size 1 μ L, temperature programme is: keep 10min for 40 ℃, programming rate is 2 ℃/min, keeps 5min for 140 ℃, keeps 3min for 240 ℃.
10. the detection method of halogen acetic acid in the potable water according to claim 1, it is characterized in that, in the step (8), described drawing standard curve, be specially: preparation standard reserving solution and hybrid standard storing solution are that the 200mL standard of 6 concentration is used liquid again with its dilution, are respectively: 5 μ g/L, 10 μ g/L, 20 μ g/L, 40 μ g/L, 80 μ g/L, 400 μ g/L, go up the sample analysis after concentrating pre-service, likening to halogen acetic acid concentration and interior mark concentration 1000 μ g/L is X-axis, and halogen acetic acid peak area and interior mark peak area ratio are as Y-axis, make typical curve with above data, typical curve is used to calculate halogen acetic acid concentration behind the water determination.
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| CN101915814A (en) * | 2010-07-27 | 2010-12-15 | 中国蓝星（集团）股份有限公司 | Method for detecting azoisobutyronitrile residue in acrylonitrile polymerization solution |
| CN103149286A (en) * | 2013-02-04 | 2013-06-12 | 国家海洋局天津海水淡化与综合利用研究所 | Method for detecting chloroacetic acid in seawater desalting strong brine |
| CN103837631A (en) * | 2014-01-26 | 2014-06-04 | 浙江工业大学 | Method of detecting content of 1,1-dichloroacetone in drinking water by GC/MS combination |
| CN103901121A (en) * | 2012-12-28 | 2014-07-02 | 上海宝钢工业技术服务有限公司 | Method for analyzing chloroacetic acid in drinking water by gas chromatograph-mass spectrometer |
| CN105717208A (en) * | 2016-01-28 | 2016-06-29 | 哈尔滨工业大学 | Method for synchronously determining content of trihalomethane and haloacetic acid in drinking water |
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| CN103901121A (en) * | 2012-12-28 | 2014-07-02 | 上海宝钢工业技术服务有限公司 | Method for analyzing chloroacetic acid in drinking water by gas chromatograph-mass spectrometer |
| CN103901121B (en) * | 2012-12-28 | 2016-12-07 | 上海宝钢工业技术服务有限公司 | Gas chromatograph-mass spectrometer analyzes the method for chloracetic acid in drinking water |
| CN103149286A (en) * | 2013-02-04 | 2013-06-12 | 国家海洋局天津海水淡化与综合利用研究所 | Method for detecting chloroacetic acid in seawater desalting strong brine |
| CN103837631A (en) * | 2014-01-26 | 2014-06-04 | 浙江工业大学 | Method of detecting content of 1,1-dichloroacetone in drinking water by GC/MS combination |
| CN105717208A (en) * | 2016-01-28 | 2016-06-29 | 哈尔滨工业大学 | Method for synchronously determining content of trihalomethane and haloacetic acid in drinking water |
| CN106404506A (en) * | 2016-08-25 | 2017-02-15 | 深圳市有为环境科技有限公司 | Residual chlorine treating unit, and water quality biotoxicity detector |
| CN106525670A (en) * | 2017-01-24 | 2017-03-22 | 淄博市环境监测站 | Method for simultaneously detecting nine haloacetic acids in PM2.5 fine particulate matters in air |
| CN106645499A (en) * | 2017-01-24 | 2017-05-10 | 淄博市环境监测站 | Method capable of determining nine haloacetic acids in air or waste gas at the same time in one time |
| CN107064378A (en) * | 2017-01-24 | 2017-08-18 | 淄博市环境监测站 | The detection method of a variety of halogen acetic acids in air or waste gas |
| CN107064378B (en) * | 2017-01-24 | 2019-03-12 | 肖洋 | The detection method of a variety of halogen acetic acids in air or exhaust gas |
| CN106645499B (en) * | 2017-01-24 | 2019-03-08 | 肖洋 | The disposable method for measuring nine kinds of halogen acetic acids in air or exhaust gas simultaneously |
| CN106525670B (en) * | 2017-01-24 | 2019-03-12 | 肖洋 | The method for measuring nine kinds of halogen acetic acids in air PM2.5 fine particle simultaneously |
| CN109212050A (en) * | 2018-07-07 | 2019-01-15 | 丁立平 | The gas chromatography of nine kinds of trace halogen acetic acids in a kind of measurement barreled drinking water |
| CN109212050B (en) * | 2018-07-07 | 2021-05-14 | 丁立平 | Gas chromatography for determining nine trace haloacetic acids in barreled drinking water |
| CN109799298A (en) * | 2019-02-20 | 2019-05-24 | 南京海纳医药科技股份有限公司 | Detection method in relation to substance in a kind of pyrrole Lun Panai bulk pharmaceutical chemicals |
| CN109799298B (en) * | 2019-02-20 | 2022-01-07 | 南京海纳医药科技股份有限公司 | Detection method of related substances in Perampanel bulk drug |
| CN111272927A (en) * | 2020-03-20 | 2020-06-12 | 同济大学 | Method for improving accuracy of haloacetic acid gas chromatography detection |
| CN114441675A (en) * | 2022-01-18 | 2022-05-06 | 哈尔滨工业大学（深圳） | Pretreatment method and automatic pretreatment device for haloacetic acid detection |
| WO2024016761A1 (en) * | 2022-07-20 | 2024-01-25 | 苏州大学 | Gas chromatography-mass spectrometry analysis method for haloacetic acid in drinking water |
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