CN103743843A - Method for detecting chloroacetic acid in air in workplace - Google Patents
Method for detecting chloroacetic acid in air in workplace Download PDFInfo
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- CN103743843A CN103743843A CN201410037243.2A CN201410037243A CN103743843A CN 103743843 A CN103743843 A CN 103743843A CN 201410037243 A CN201410037243 A CN 201410037243A CN 103743843 A CN103743843 A CN 103743843A
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- chloroacetic
- chloroacetic acid
- silica gel
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Abstract
The invention discloses a method for detecting chloroacetic acid in air in a workplace. The method uses a silica gel sampling tube to collect chloroacetic acid, uses deionized water as stripping liquid, and uses an anion chromatographic column for assay determination, being a rapid, sensitive, accurate and low-cost method for detecting chloroacetic acid in the workplace with an ion chromatography. Thus, a new practical way is provided for detecting chloroacetic acid in air in the workplace, and the application of the ion chromatography to occupational health surveillance is widened.
Description
Technical field
The present invention relates to chemistry in detecting technical field, particularly relate to chloroacetic detection method in a kind of workplace air.
Background technology
Chloroacetic acid (chloroaceticacid) is a kind of important organic synthesis raw material, is widely used in the fields such as agricultural chemicals, medicine, printing and dyeing.Chloroacetic acid chemical property is active, has severe corrosive, can invade human body through skin, respiratory tract or alimentary canal, and main occupational hazard is for burning.At present, in workplace, chloroacetic mensuration adopts vapor-phase chromatography conventionally, according to GBZ/T160.59-2004 < < workplace air noxious material, measure carboxylic acid compound > >, the sampling flow that chloroacetic acid detects is 1.0L/min, easily cause sampling to penetrate, and its method sensitivity is lower, and loaded down with trivial details during operating cost, operating cost is higher.Therefore, be necessary chloroacetic assay method in existing workplace air to improve.
Utilize the method for ion chromatography aqueous solution small molecular organic carboxyl acid (formic acid, acetic acid etc.) comparatively ripe, it has advantages of that selectivity is good, quick, sensitive, easy, yet, utilize at present in ion-chromatographic determination workplace the research of carboxylic acids objectionable impurities less.China starts late for the applied research in air of workplace by ion chromatography, in the < < workplace air of at present China health State Family Planning Commission issue in the mensuration > > standard of noxious material, hydrochloric acid, sulfuric acid, iodine, 4 kinds of ion chromatography methods of oxalic acid have only been listed, great majority detect and also rest in vapor-phase chromatography, and vapor-phase chromatography exists, operating cost is higher, coexisting substances disturbs, and some method also needs to use the shortcomings such as toxic reagent.
Therefore, the application of the chromatography of ions is also nowhere near, and for overcoming these shortcomings, improves the application of chromatography of ions in occupational health detects, and steps up the research of noxious material chromatography of ions detection method in workplace air to be very important.
Summary of the invention
Object of the present invention is exactly to provide chloroacetic detection method in a kind of workplace air for the defect of above-mentioned existence.The present invention gathers chloroacetic acid with silica gel sampling pipe, take deionized water as stripping liquid, select anion chromatographic column to analyze mensuration, set up a kind of chloroacetic acid method in chromatography of ions testing place quick, sensitive, accurate and with low cost, this has widened the application of the chromatography of ions in the professional monitoring of hygiene, for the detection of carboxylic acids objectionable impurities in workplace provides new feasible way.
In a kind of workplace air of the present invention, chloroacetic detection method technical scheme is, adopt the airborne chloroacetic acid in silica gel sampling pipe collecting work place, take deionized water as stripping liquid, through ion chromatography, electric conductivity detector detects, preparation standard curve, then testing sample is detected to data substitution calculate the chloroacetic acid in workplace air.
Silica gel sampling pipe is solvent desorption type, in-built 300mg/150mg silica gel.
Adopt the airborne chloroacetic acid in silica gel sampling pipe collecting work place and resolving to be specially: silica gel sampling pipe two ends are opened in sampling in sampling location, 150mg end is connected with air sampler, flow 0.2-0.5L/min, gather 10-25min, 2 sections of the front and back silica gel of adopting sample is added respectively to deionized water, sealing jolting 1-3min, resolves 25-40min, and stripping liquid is after filtering for measuring.
Stripping liquid is through 0.45 μ m water-based filtering with microporous membrane.
Stratographic analysis adopts anion chromatographic column.
Chromatographiccondition is: mobile phase: 4.0mMNaHCO
3+ 10% acetone, flow velocity: 1.0ml/min, sampling volume: 20 μ l, regenerated liquid: 0.1mol/L sulfuric acid solution.
Preparation standard curve is specially: get 10ml volumetric flask, add about 5ml deionized water, after accurately weighing, add a certain amount of chloroacetic acid, accurately weigh again, with deionized water, be settled to scale, mix, for standard reserving solution, with deionized water, be diluted to 100 μ g/ml chloroacetic acid standard solution before use, configuration 1,3,5,7,10 μ g/ml chloroacetic acid standard series, for measuring.
The computing formula that data are calculated chloroacetic acid concentration in air is: C=10 (c
1+ c
2)/(Vo D), wherein C is chloroacetic concentration in air, mg/m
3; c
1,c
2for chloroacetic concentration in section silica gel stripping liquid before and after recording, μ g/ml; 10 is the cumulative volume of stripping liquid, ml; V
0for standard sample volume, L; D is desorption efficiency, %.
Beneficial effect of the present invention is: set up and utilized anion chromatographic column to measure chloroacetic Ion Chromatographic Method in workplace air.Adopt the airborne chloroacetic acid in silica gel sampling pipe collecting work place, sample introduction after deionized water desorb, separated through anion chromatographic column, electric conductivity detector detects.Chloroacetic acid presents good linear relationship when concentration range is 1.0 μ g/ml ~ 10.0 μ g/ml, and related coefficient is 0.9992, and the signal to noise ratio (S/N ratio) (S/N) of take is limited to 0.04 μ g/ml as 3 definite methods detect, and concentration limit is 0.09mg/m
3(to gather 4.5L air sample).Relative standard deviation is 1.13% ~ 1.45%, and in silica gel sampling pipe, chloroacetic acid desorption efficiency is 95.3% ~ 103.1%, and sample can at least be stablized and preserve 7 days at 4 ℃.
The method is highly sensitive, and precision is good, with low cost, simple to operate, and selected stripping liquid is pollution-free, is applicable to batch samples and detects, and the method can be used for the mensuration of chloroacetic short time concentration and time weighted average concentration in workplace air.This method, by selecting rational conditional combination, for accurate evaluation chloroacetic acid provides effective mensuration means to the harm of health, provides reference frame for further studying carboxylic-acid substance in ion chromatography workplace air.
accompanying drawing explanation:
Figure 1 shows that Common Anions and chloroacetic acid separate colors spectrogram;
Figure 2 shows that the chromatogram of on-the-spot sample in embodiment.
In Fig. 1,1-F
-, 2-chloroacetic acid, 3-Cl
-, 4-Br
-, 5-NO
3 - .
embodiment:
In order to understand better the present invention, with instantiation, describe technical scheme of the present invention in detail below.
1 materials and methods
The 1.1 logical 883 type ion chromatographs of instrument Switzerland ten thousand, 863 type automatic samplers, electric conductivity detector, the conventional anion analysis post (4.0mm * 250.0mm) of MetrosepASUPP4-250/4.0 type.GilAir-5 air sampler (being equipped with low discharge adjustment module), silica gel sampling pipe (solvent desorption type, in-built 300mg/150mg silica gel), 0.45 μ m water-based miillpore filter.
1.2 reagent chloroacetic acids (chromatographically pure, Chengdu Ai Ke chemical reagent company limited), deionized water (resistivity >18M Ω cm), NaHCO
3(top grade is pure, Tianjin Kermel Chemical Reagent Co., Ltd.), acetone (top grade is pure, economic and technological development zone, Laiyang Fine Chemical Works).
1.3 method
1.3.1 sample and in sampling location, open silica gel sampling pipe two ends, 150mg end is connected with air sampler, flow 0.3L/min, gathers 15min.2 sections of the front and back silica gel of adopting sample is poured into respectively in 20ml tool plug test tube, respectively added 10ml deionized water, sealing jolting 1min, resolves 30min, and stripping liquid supplies to measure after 0.45 μ m water-based filtering with microporous membrane.
1.3.2 chromatographic condition mobile phase: 4.0mMNaHCO
3+ 10% acetone, flow velocity: 1.0ml/min, sampling volume: 20 μ l, regenerated liquid: 0.1mol/L sulfuric acid solution.
1.3.3 10ml volumetric flask is got in typical curve configuration, adds about 5ml deionized water.After accurately weighing, add a certain amount of chloroacetic acid, more accurately weigh, with deionized water, be settled to scale, mixing, is standard reserving solution, is diluted to 100 μ g/ml chloroacetic acid standard solution before use with deionized water, configuration 1,3,5,7,10 μ g/ml chloroacetic acid standard series, for measuring.
1.3.4 in data calculating air, the computing formula of chloroacetic acid concentration is: C=10 (c
1+ c
2)/(Vo D), wherein C is chloroacetic concentration in air, mg/m
3; c
1,c
2for chloroacetic concentration in section silica gel stripping liquid before and after recording, μ g/ml; 10 is the cumulative volume of stripping liquid, ml; V
0for standard sample volume, L; D is desorption efficiency, %.
2 results
The selection of 2.1 chromatography condition chromatographic columns, mobile phase and concentration directly affect separation efficiency and the detection sensitivity of chromatographic peak.For the scope of application of raising method and for cost-saving consideration, the present invention selects anion chromatographic column (MetrosepASUPP4-250/4.0 type) to carry out Separation Research.Because chloroacetic acid is similar to chlorion chromatographic behavior, both retention times are very approaching, if adopt standard flow phase (1.8mMNa
2cO
3+ 1.7mMNaHCO
3) analyze, chloroacetic acid and chlorion chromatographic peak can be overlapping, cannot carry out qualitative and quantitative analysis, therefore need to select suitable chromatographic condition to measure, and through Optimal Experimental, find to adopt 4.0mMNaHCO
3when+10% acetone mobile phase, flow velocity 1.0ml/min, chloroacetic acid and chlorion good separation, chloroacetic acid retention time is 10.2min, as shown in Figure 1.
2.2 methods linearities and detection limit are according to above-mentioned experiment condition, standard series sample (1,3,5,7,10 μ g/ml) is analyzed, sample introduction 20 μ l, repeat 6 times, to record the corresponding corresponding chloroacetic acid concentration drawing standard curve of peak height average, gained typical curve linear equation is y=0.0332x-0.0005, correlation coefficient r=0.9992, according to 3 times of signal to noise ratio (S/N ratio)s (
s/N=3) calculate it and detect and be limited to 0.04 μ g/ml, under sampling volume 4.5L condition, the concentration limit of method is 0.09mg/m
3.The vapor-phase chromatography adopting in the assay method > > (GBZ/T160.59-2004) of carboxylic acid compound in China < < workplace air at present detects and is limited to 3.2 μ g/ml.Can relatively draw thus, the sensivity indexes such as its detection limit of this chromatography of ions are obviously better than vapor-phase chromatography.
2.3 method precision experiments are under selected chromatographic condition, getting concentration and be the chloroacetic acid sample of 3.0,5.0,7.0 μ g/ml analyzes, every kind of concentration replication 6 times, and so repeat METHOD FOR CONTINUOUS DETERMINATION 3 days, result is as table 1, chloroacetic acid RSD is 1.13 ~ 1.45%, meets chemical substance assay method > > requirement in < < workplace air.
Table 1 Precision Experiment result (n=6)
。
18 silica gel sampling pipes are got in 2.4 analyzing efficiency experiments, are divided into 3 groups, with micro syringe, respectively add and contain 30,50,70 μ g chloroacetic acid storing solutions, seal immediately silica gel sampling pipe two ends.After placement is spent the night, 2 sections of front and back silica gel is poured into respectively in 20ml tool plug test tube, added the desorb of 10ml deionized water, jam-pack pipe close, jolting 1min, resolves after 30min, respectively gets 5ml stripping liquid, and sample introduction 20 μ l analyze.Make one group of silica gel sampling pipe blank simultaneously, during calculating, deduct blank value.Result is as shown in table 2, under this method condition, chloroacetic acid desorption efficiency is 95.3% ~ 103.1%, meets chemical substance assay method > > requirement in < < workplace air.
Table 2 desorption efficiency measurement result
12 silica gel sampling pipes are got in 2.5 sample stability experiments, be divided into 4 groups, every group 3, add respectively a certain amount of chloroacetic acid standard reserving solution, seal immediately silica gel sampling pipe, analyzed one group the same day, all the other are placed in 4 ℃ of preservations of refrigerator, then respectively at the 3rd, 5,7 days, respectively take out one group and analyze mensuration, the loss percentage of different time sample is deposited in calculating, experimental result shows, it is 96.0% that sample is deposited its average recovery rate after 7 days, therefore silica gel sampling pipe can at least can be preserved 7 days after gathering chloroacetic acid under 4 ℃ of environment.
In the workplace air of the anti-Fa Duimoucong pesticide producing of 2.6 on-the-spot sample determinations employing the present invention enterprise, chloroacetic acid is measured, and obtains the satisfied effect that detects, and for evaluating this pesticide producing enterprise work place air quality, provides reliable Data support.From on-the-spot sample chromatogram figure (asking for an interview Figure of description Fig. 2), in scene or silica gel sampling pipe, there are other materials simultaneously, but noiseless to Analysis of Chloroacetic Acid.
3 conclusions
The present invention has set up chloroacetic ion chromatography method in workplace, and method adopts silica gel sampling pipe collected specimens, adopts deionized water desorb, selects anion chromatographic column analysis, electric conductivity detector to detect.Experimental result shows, the good separation that this method is measured, and have highly sensitively, and precision is good, with low cost, and simple operation and other advantages is applicable to chloroacetic mensuration in workplace air.This method, for accurate evaluation chloroacetic acid provides effective mensuration means to the harm of health, provides reference frame for further studying carboxylic-acid substance in ion chromatography workplace air.
Claims (8)
1. chloroacetic detection method in a workplace air, it is characterized in that, adopt the airborne chloroacetic acid in silica gel sampling pipe collecting work place, take deionized water as stripping liquid, through ion chromatography, electric conductivity detector detects, preparation standard curve, then testing sample is detected to data substitution calculate the chloroacetic acid in workplace air.
2. chloroacetic detection method in a kind of workplace air according to claim 1, is characterized in that, silica gel sampling pipe is solvent desorption type, in-built 300mg/150mg silica gel.
3. chloroacetic detection method in a kind of workplace air according to claim 2, it is characterized in that, adopt the airborne chloroacetic acid in silica gel sampling pipe collecting work place and resolving to be specially: silica gel sampling pipe two ends are opened in sampling in sampling location, 150mg end is connected with air sampler, flow 0.2-0.5L/min, gather 10-25min, 2 sections of the front and back silica gel of adopting sample is added respectively to deionized water, sealing jolting 1-3min, resolve 25-40min, stripping liquid is after filtering for measuring.
4. chloroacetic detection method in a kind of workplace air according to claim 3, is characterized in that, stripping liquid is through 0.45 μ m water-based filtering with microporous membrane.
5. chloroacetic detection method in a kind of workplace air according to claim 4, is characterized in that, stratographic analysis adopts anion chromatographic column.
6. chloroacetic detection method in a kind of workplace air according to claim 5, is characterized in that, chromatographiccondition is: mobile phase: 4.0mMNaHCO
3+ 10% acetone, flow velocity: 1.0ml/min, sampling volume: 20 μ l, regenerated liquid: 0.1mol/L sulfuric acid solution.
7. chloroacetic detection method in a kind of workplace air according to claim 6, it is characterized in that, preparation standard curve is specially: get 10ml volumetric flask, add about 5ml deionized water, after accurately weighing, add a certain amount of chloroacetic acid, accurately weigh again, with deionized water, be settled to scale, mix, for standard reserving solution, with deionized water, be diluted to 100 μ g/ml chloroacetic acid standard solution before use, configuration 1,3,5,7,10 μ g/ml chloroacetic acid standard series, for measuring.
8. chloroacetic detection method in a kind of workplace air according to claim 7, is characterized in that, the computing formula that data are calculated chloroacetic acid concentration in air is: C=10 (c
1+ c
2)/(Vo D), wherein C is chloroacetic concentration in air, mg/m
3; c
1,c
2for chloroacetic concentration in section silica gel stripping liquid before and after recording, μ g/ml; 10 is the cumulative volume of stripping liquid, ml; V
0for standard sample volume, L; D is desorption efficiency, %.
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Cited By (6)
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| CN105043953A (en) * | 2015-08-17 | 2015-11-11 | 国网山东省电力公司电力科学研究院 | Method for estimating dust exposure concentration for operating personnel of thermal power enterprise |
| CN106908548A (en) * | 2017-03-30 | 2017-06-30 | 浙江中检测研究院股份有限公司 | The detection method of carboxylic acid content in a kind of air |
| CN109991358A (en) * | 2019-04-09 | 2019-07-09 | 上海实朴检测技术服务有限公司 | Measure chloroacetic method in soil |
| CN110441464A (en) * | 2019-08-09 | 2019-11-12 | 南通化学环境监测站有限公司 | Monoxone method for measurement of concentration in a kind of workplace carboxylic acids |
| CN112129855A (en) * | 2020-09-23 | 2020-12-25 | 浙江省疾病预防控制中心 | Method for measuring chloroacetic acid concentration in air by gas chromatography and application thereof |
| CN113109462A (en) * | 2021-03-10 | 2021-07-13 | 南京海纳医药科技股份有限公司 | Method for detecting chloroacetic acid in lidocaine |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105043953A (en) * | 2015-08-17 | 2015-11-11 | 国网山东省电力公司电力科学研究院 | Method for estimating dust exposure concentration for operating personnel of thermal power enterprise |
| CN106908548A (en) * | 2017-03-30 | 2017-06-30 | 浙江中检测研究院股份有限公司 | The detection method of carboxylic acid content in a kind of air |
| CN106908548B (en) * | 2017-03-30 | 2019-07-12 | 浙江中一检测研究院股份有限公司 | The detection method of carboxylic acid content in a kind of air |
| CN109991358A (en) * | 2019-04-09 | 2019-07-09 | 上海实朴检测技术服务有限公司 | Measure chloroacetic method in soil |
| CN110441464A (en) * | 2019-08-09 | 2019-11-12 | 南通化学环境监测站有限公司 | Monoxone method for measurement of concentration in a kind of workplace carboxylic acids |
| CN112129855A (en) * | 2020-09-23 | 2020-12-25 | 浙江省疾病预防控制中心 | Method for measuring chloroacetic acid concentration in air by gas chromatography and application thereof |
| CN113109462A (en) * | 2021-03-10 | 2021-07-13 | 南京海纳医药科技股份有限公司 | Method for detecting chloroacetic acid in lidocaine |
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Application publication date: 20140423 |