CN102297913A - Method for measuring harmful substance-hexanolactam in air of workplace - Google Patents
Method for measuring harmful substance-hexanolactam in air of workplace Download PDFInfo
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- CN102297913A CN102297913A CN2011102074203A CN201110207420A CN102297913A CN 102297913 A CN102297913 A CN 102297913A CN 2011102074203 A CN2011102074203 A CN 2011102074203A CN 201110207420 A CN201110207420 A CN 201110207420A CN 102297913 A CN102297913 A CN 102297913A
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Abstract
The invention relates to a method for measuring harmful substance-hexanolactam in the air of a workplace. In the method for measuring the harmful substance-hexanolactam in the air of the workplace, a liquid chromatography-tandem mass spectrometer is utilized to carry out detection. The method for detecting the harmful substance-hexanolactam in the air of the workplace by utilizing the liquid chromatography-tandem mass spectrometer is convenient, rapid, accurate and reliable, has small interference and a low detection limit and is capable of meeting the requirements of people on detection work and research. According to the invention in the aspect, the blank of the method for measuring the harmful substance-hexanolactam in the air of the workplace by utilizing the liquid chromatography-tandem mass spectrometer (LC-MS/MS) is filled.
Description
Technical field
The present invention relates to the assay method of objectionable impurities caprolactam content in a kind of workplace air, particularly relate to a kind of method of measuring objectionable impurities caprolactam content in the workplace air by the liquid chromatography-tandem mass spectrometry combined instrument.
Background technology
Caprolactam is a kind of amides compound, be the hydroscopicity flaky crystal at normal temperatures, main application is to generate polyamide section (crying nylon-6 section or polyamide fibre-6 section usually) by polymerization, can further be processed into nylon fibre, engineering plastics, plastic sheeting etc.Along with China's development of economic construction, the market demand of caprolactam increases fast.Discover, caprolactam is in the extensive application of Polymer Synthesizing industry, not only can pollute environment, eyes and nervous centralis to human body also have spread effect, particularly to brain stem, can cause the infringement of parenchymal viscera, the human body skin contact also can cause dermatitis, and taking in the body then can influence liver.In production environment, caprolactam can be present in the air with dust, steam and smoke condition, and GBZ 2-2007 workplace adverse factor occupation exposure limit: the average allowable concentration PC-TWA of caprolactam time weight is 5 mg/m
3Therefore, for scientific basis more accurately is provided to labour protection, be necessary caprolactam is carried out qualitative and detection by quantitative.But present national occupational health standard does not have the assay method of caprolactam in the workplace air.
GB/T 23296-2009 " the mensuration vapor-phase chromatography of caprolactam and caprolactam salt in the food contact material macromolecular material food analogies " adopts vapor-phase chromatography, but because caprolactam is solid-state at normal temperatures, not volatile, may cause the injection port gasification not exclusively, have residually, and detection limit is also than higher; GB/T 5009.125-2003 " mensuration of caprolactam in nylon 6 resin and the moulding product " adopts high performance liquid chromatography, is qualitative inaccurate when having chaff interference but use the weak point of objectionable impurities caprolactam in this method testing place air.
The present invention propose a kind of can be qualitative exactly and the detection method of quantitative caprolactam by the liquid chromatography-tandem mass spectrometry combined instrument, this method has characteristics such as analytical approach is accurate, quick, interference is little, detection limit is low, can satisfy people's testing and research needs.The method blank that the liquid chromatography-tandem mass spectrometry combined instrument is measured objectionable impurities caprolactam in the workplace air has been filled up in the invention of this method.
Summary of the invention
Technical matters to be solved by this invention is, overcomes the defective of above-mentioned prior art and the assay method of objectionable impurities caprolactam content in a kind of workplace air is provided.
The assay method of objectionable impurities caprolactam in the workplace air of the present invention is to utilize liquid chromatography-tandem mass spectrometry combined instrument (LC-MS/MS) to detect.
The assay method of objectionable impurities caprolactam in the above-mentioned workplace air, its concrete steps are as follows:
(1) sample collecting, transportation and preservation part
Two impinger of adorning 10.0 mL water in each of connecting, sealing absorption tube port is put into sales kit (SK) with absorption tube and is brought to sampled point; Take out absorption tube and be connected,, write down temperature, air pressure and the humidity of sampled point simultaneously with 15 minutes air samples of 3 L/min traffic samplings with atmosphere sampling instrument;
After the sampling, seal the air inlet/outlet of absorption tube immediately, uprightly place transportation and preservation in the cleaning container.Should analyze as early as possible behind the sample collecting,, should under 4 ℃ of conditions, keep in Dark Place, be no more than 7 days as can not in time analyzing;
(2) analysis part of sample
The absorption of adopting sample is washed the draft tube inwall 3 times of absorption tube night, after shaking up, to absorb and pour into night in the tool plug test tube, adopt disposable sample introduction needle to suck about 1 mL sample, organic phase pin type filter through 0.2 μ m filters directly injection liquid phase sample introduction bottle of back, detects with the liquid chromatography-tandem mass spectrometry combined instrument.If the concentration of determinand surpasses measurement range in the sample liquid, available absorption dilution at night back is measured, and multiply by extension rate during calculating;
In the step (2), the Ultra Performance Liquid Chromatography instrument be Acquity UPLC (waters company, USA), tandem mass spectrometer be the triple level Four bar of Quattro Premier XE mass spectrum (waters company, USA);
Liquid phase chromatogram condition is:
ACQUITY UPLC BEHC18 reverse-phase chromatographic column (2.1 mm * 50 mm * 1.7 μ m);
Column temperature: 40-60 ℃;
Sample size: 3-10 μ L;
Flow rate of mobile phase: 0.3-0.6 mL/min;
Moving phase is made up of organic phase and inorganic phase solvent, and organic phase can be methyl alcohol, formic acid, acetone, second eyeball etc., also can be that wherein two or more mixed solution is formed, and inorganic is water mutually;
The moving phase type of elution can adopt isocratic elution or linear gradient elution;
The tandem mass spectrum condition:
Adopt the ionization of electron spray positively ionized pattern;
Multipole ionic reaction detection mode;
Source temperature: 100 ℃-300 ℃;
Taper hole voltage: 20-80 V;
Collision energy: 10-50 V;
Mass spectrum is optimized: Q1 full scan scope is 90-130, and unit resolution rate sweep time is 0.2 s.The collision energy that adopts in the MRM pattern is 17 ev, and the quantitative reaction passage is m/z 113.5-69, and the qualitative reaction passage is 113.5-79, and single reaction channel sweep time is 0.2 s;
Concrete mass spectrum condition is as follows:
| Parameter | Optimised value |
| Capillary voltage? (V) | 3.0 |
| Cone voltage? (V) | 38 |
| Source temperature? (℃ ) | 100 |
| Desolvation temperature? (℃) | 400 |
| Desolvation gas flow? (L/h ) | 700 |
| Cone gas flow? (L/h ) | 50 |
| Collision energy? (ev) | 17 |
| Collision Gas flow（ml/min） | 0.8 |
(3) drafting of typical curve
Accurately take by weighing a certain amount of caprolactam solid standard specimen, be dissolved in the water, quantitatively be transferred in the volumetric flask, and be diluted to scale, this solution is 1000 μ g/mL caprolactam standard stock solutions.Face with before, become the standard series of 5 concentration gradients with 1:9 methanol solvent dilution, the liquid chromatography-tandem mass spectrometry combined instrument is adjusted to the optimum determining state, measure each standard series; Each concentration replication 3 times, with peak area to caprolactam concentration (μ g/L) drawing standard curve; Coefficient R〉0.9990;
(4) calculating section
With the operating conditions working sample and the blank solution of bioassay standard series, the sample peak area of measuring deducted the peak area of blank after, get the concentration of caprolactam by typical curve, computation process is:
By formula (1) sampling volume is converted into the standard sample volume
In the formula:
Vo-standard sample volume, L;
V-sampling volume, L;
The temperature of t-sampled point, ℃;
The atmospheric pressure of P-sampled point, kPa;
Calculate the concentration of caprolactam in the air by formula (2):
In the formula:
The concentration of caprolactam in C-air, mg/ m
3
The volume of v-sample solution, ml;
The concentration of the caprolactam of c-record, μ g/ml;
Vo-standard sample volume, L.
With prior art relatively, advantage of the present invention is:
(1) adopt liquid chromatography-tandem mass spectrometry combined instrument of the present invention to carry out the detection of objectionable impurities caprolactam in the workplace air, compare existing gas chromatographic technique and high-efficient liquid phase chromatogram technology, this analytical approach fast, accurate and effective, interference be little, precision and accuracy are all less than 10%, detect and be limited to 0.08 μ g/L, concentration limit is 1.8 * 10
-5Mg/m
3(to gather the 45L air sample);
(2) by selecting suitable moving phase, control suitable flow velocity, can make caprolactam in the sample carry out optimization from;
(3) by selecting multipole ionic reaction detection mode, method selectivity height, qualitative accurately, detection limit is low.
This shows that the method among the present invention is the mensuration of objectionable impurities caprolactam content in the workplace air, provide a kind of not only reliable but also accurate feasible method, the needs that can satisfy research and produce.
Description of drawings
The caprolactam total ions chromatogram that Fig. 1 is detected for the embodiment of the invention 1, the ordinate in this chromatogram is represented peak intensity, and horizontal ordinate is represented retention time, and unit is minute;
The canonical plotting of the caprolactam that Fig. 2 is detected for the embodiment of the invention 1, the ordinate in this canonical plotting is represented the response of liquid chromatography peak area, and horizontal ordinate is represented the concentration of caprolactam, and unit is μ g/L.
Embodiment
The polymerization plant sampled point (temperature: 20 ℃, air pressure: 100.3 kPa), take out absorption tube and be connected, with 15 minutes air samples of 3 L/min traffic samplings with atmosphere sampling instrument.After the sampling, seal the air inlet/outlet of absorption tube immediately, uprightly place in the cleaning container.The absorption of adopting sample is washed the draft tube inwall 3 times of absorption tube night, after shaking up, to absorb and pour into night in the tool plug test tube, adopt disposable sample introduction needle to suck about 1 mL sample, organic phase pin type filter through 0.2 μ m filters directly injection liquid phase sample introduction bottle of back, detects with the liquid chromatography-tandem mass spectrometry combined instrument.Do blank determination with 1:9 methanol solvent simultaneously.If the concentration of determinand surpasses measurement range in the sample liquid, available absorption dilution at night back is measured, and multiply by extension rate during calculating.
(3) drafting of typical curve
Accurately take by weighing 0.1000g caprolactam solid standard specimen, be dissolved in the water, quantitatively be transferred in the 100 mL volumetric flasks, and be diluted to scale, this solution is 1000 μ g/mL standard stock solutions.Before facing usefulness, become the standard working curve of 5 concentration gradients (10,20,40,80,160 μ g/L) stand-by with 1:9 methanol solvent dilution.The liquid chromatography-tandem mass spectrometry combined instrument is adjusted to the optimum determining state, measures each standard series; Each concentration replication 3 times, with peak area to caprolactam concentration (μ g/L) drawing standard curve; Coefficient R〉0.9990.
Detecting instrument is the liquid chromatography-tandem mass spectrometry combined instrument, wherein the Ultra Performance Liquid Chromatography instrument be Acquity UPLC (waters company, USA), tandem mass spectrometer is the triple level Four bar of a Quattro Premier XE mass spectrum (waters company, USA), testing conditions is:
Chromatographic column: ACQUITY UPLC BEH C18 (2.1 mm * 50 mm * 1.7 μ m);
Column temperature: 40 ℃;
Sample size: 5 μ L;
Flow rate of mobile phase: 0.3 mL/min;
Moving phase is formed: gradient elution, and concrete eluent gradient is as shown in table 1, and wherein, A is methyl alcohol mutually, and B is 0.1% formic acid/aqueous solution mutually;
| Time(min) | A | | CURVE | |
| 0 | 10 | 90 | INITIAL | |
| 3 | 30 | 70 | 6 | |
| 5 | 100 | 0 | 1 | |
| 8 | 10 | 90 | 1 |
The tandem mass spectrum condition:
Ion gun: electron spray ESI, positive ion;
Scan mode: multiple-reaction monitoring MRM;
Source temperature: 100 ℃-300 ℃;
Taper hole voltage: 20-80 V;
Collision energy: 10-50 V;
Mass spectrum is optimized: Q1 full scan scope is 90-130, and unit resolution rate sweep time is 0.2 s.The collision energy that adopts in the MRM pattern is 17 ev, and the quantitative reaction passage is m/z 113.5-69, and the qualitative reaction passage is 113.5-79, and single reaction channel sweep time is 0.2 s;
Concrete mass spectrum condition:
| Parameter | Optimized value |
| Capillary voltage? (V) | 3.0 |
| Cone voltage? (V) | 38 |
| Source temperature? (℃ ) | 100 |
| Desolvation temperature? (℃) | 400 |
| Desolvation gas flow? (L/h ) | 700 |
| Cone gas flow? (L/h ) | 50 |
| Collision energy? (ev) | 17 |
| Collision Gas flow (ml/min) | 0.8 |
Qualitative according to retention time, the peak area external standard method is quantitative.
(4) calculating section
With the operating conditions working sample and the blank solution of bioassay standard series, the sample peak area of measuring deducted the peak area of blank after, get the concentration of caprolactam by typical curve, the computing formula of caprolactam content is in the sample:
By formula (1) sampling volume is converted into the standard sample volume
In the formula:
Vo-standard sample volume, L;
V-sampling volume, L;
The temperature of t-sampled point, ℃;
The atmospheric pressure of P-sampled point, kPa;
Calculate the concentration of caprolactam in the air by formula (2):
In the formula:
The concentration of caprolactam in C-air, mg/ m
3
The volume of v-sample solution, ml;
The concentration of the caprolactam of c-record, μ g/ml;
Vo-standard sample volume, L.
After this plastic sheeting workshop air sample repeated test 6 times, calculate by above-mentioned formula, by testing result relative standard deviation＜10% as can be known.
| ? | 1 | 2 | 3 | 4 | 5 | 6 | Mean value | RSD |
| The result (10 -4 mg/m 3) | 9.48 | 9.45 | 9.46 | 9.46 | 9.45 | 9.46 | 9.46 | 0.12% |
Embodiment 2, the mensuration of caprolactam in certain chemical fibre factory's blowing workshop air.
Blowing workshop sampled point (temperature: 22 ℃, air pressure: 99.3 kPa), take out absorption tube and be connected, with 15 minutes air samples of 3 L/min traffic samplings with atmosphere sampling instrument.After the sampling, seal the air inlet/outlet of absorption tube immediately, uprightly place in the cleaning container.The absorption of adopting sample is washed the draft tube inwall 3 times of absorption tube night, after shaking up, to absorb and pour into night in the tool plug test tube, adopt disposable sample introduction needle to suck about 1 mL sample, organic phase pin type filter through 0.2 μ m filters directly injection liquid phase sample introduction bottle of back, detects with the liquid chromatography-tandem mass spectrometry combined instrument.Do blank determination with 1:9 methanol solvent simultaneously.If the concentration of determinand surpasses measurement range in the sample liquid, available absorption dilution at night back is measured, and multiply by extension rate during calculating.
(3) drafting of typical curve
Accurately take by weighing 0.1000 g caprolactam solid standard specimen, be dissolved in the water, quantitatively be transferred in the 100 mL volumetric flasks, and be diluted to scale, this solution is 1000 μ g/mL standard stock solutions.Before facing usefulness, become the standard working curve of 5 concentration gradients (1,2,5,10,20 μ g/L) stand-by with 1:9 methanol solvent dilution.The liquid chromatography-tandem mass spectrometry combined instrument is adjusted to the optimum determining state, measures each standard series; Each concentration replication 3 times, with peak area to caprolactam concentration (μ g/L) drawing standard curve, coefficient R 0.9990.
Detecting instrument is the liquid chromatography-tandem mass spectrometry combined instrument, wherein the Ultra Performance Liquid Chromatography instrument be Acquity UPLC (waters company, USA), tandem mass spectrometer is the triple level Four bar of a Quattro Premier XE mass spectrum (waters company, USA), testing conditions is:
Chromatographic column: ACQUITY UPLC BEH C18 (2.1 mm * 50 mm * 1.7 μ m);
Column temperature: 40 ℃;
Sample size: 5 μ L;
Flow rate of mobile phase: 0.3 mL/min;
Moving phase is formed: gradient elution, and concrete eluent gradient is as shown in table 1, and wherein, A is methyl alcohol mutually, and B is 0.1% formic acid/aqueous solution mutually;
| Time(min) | A | | CURVE | |
| 0 | 10 | 90 | INITIAL | |
| 3 | 30 | 70 | 6 | |
| 5 | 100 | 0 | 1 | |
| 8 | 10 | 90 | 1 |
The tandem mass spectrum condition:
Ion gun: electron spray ESI, positive ion;
Scan mode: multiple-reaction monitoring MRM;
Source temperature: 100 ℃-300 ℃;
Taper hole voltage: 20-80 V;
Collision energy: 10-50 V;
Mass spectrum is optimized: Q1 full scan scope is 90-130, and unit resolution rate sweep time is 0.2 s.The collision energy that adopts in the MRM pattern is 17 ev, and the quantitative reaction passage is m/z 113.5-69, and the qualitative reaction passage is 113.5-79, and single reaction channel sweep time is 0.2 s;
Concrete mass spectrum condition:
| Parameter | Optimized value |
| Capillary voltage? (V) | 3.0 |
| Cone voltage? (V) | 38 |
| Source temperature? (℃ ) | 100 |
| Desolvation temperature? (℃) | 400 |
| Desolvation gas flow? (L/h ) | 700 |
| Cone gas flow? (L/h ) | 50 |
| Collision energy? (ev) | 17 |
| Collision Gas flow (ml/min) | 0.8 |
Qualitative according to retention time, the external standard peak area method is quantitative.
(4) calculating section
With the operating conditions working sample and the blank solution of bioassay standard series, the sample peak area of measuring deducted the peak area of blank after, get the concentration of caprolactam by typical curve, the computing formula of caprolactam content is in the sample:
By formula (1) sampling volume is converted into the standard sample volume
In the formula:
Vo-standard sample volume, L;
V-sampling volume, L;
The temperature of t-sampled point, ℃;
The atmospheric pressure of P-sampled point, kPa;
Calculate the concentration of caprolactam in the air by formula (2):
In the formula:
The concentration of caprolactam in C-air, mg/ m
3
The volume of v-sample solution, ml;
The concentration of the caprolactam of c-record, μ g/ml;
Vo-standard sample volume, L.
After this chemical fibre factory's blowing workshop air sample repeated test 6 times, calculate by above-mentioned formula, by testing result relative standard deviation＜10% as can be known.
| ? | 1 | 2 | 3 | 4 | 5 | 6 | Mean value | RSD |
| The result (10 -4 mg/m 3) | 1.42 | 1.43 | 1.41 | 1.40 | 1.44 | 1.41 | 1.42 | 1.04% |
Obviously, those skilled in the art, can constitute assay method with of the present invention a kind of by the mensuration of liquid chromatography-tandem mass spectrometry combined instrument to objectionable impurities caprolactam content in the workplace air to objectionable impurities caprolactam content in all kinds workplace air.
The foregoing description is only for the usefulness that the present invention is described; and be not to be limitation of the present invention; the those of ordinary skill in relevant technologies field; without departing from the present invention; can also make various variations and modification; therefore all technical schemes that are equal to also should belong to category of the present invention, and scope of patent protection of the present invention should be limited by each claim.
Claims (7)
1. the assay method of objectionable impurities caprolactam in the workplace air is characterized in that: utilize the liquid chromatography-tandem mass spectrometry combined instrument to detect.
2. the assay method of objectionable impurities caprolactam in the workplace air as claimed in claim 1, it is characterized in that: the testing conditions of the liquid chromatography-tandem mass spectrometry combined instrument of use is: liquid phase chromatogram condition is: the C18 reverse-phase chromatographic column, column temperature 40-60 ℃, sample size 3-10 μ L, flow rate of mobile phase 0.3-0.6 mL/min, moving phase is made up of organic phase and inorganic phase solvent, organic phase can be methyl alcohol, formic acid, acetone, second eyeball etc., also can be that wherein two or more mixed solution is formed, inorganic be water mutually; The moving phase type of elution can adopt isocratic elution or linear gradient elution; Tandem mass spectrum condition: adopt the ionization of electron spray positively ionized pattern, multipole ionic reaction detection mode, 100 ℃-300 ℃ of source temperatures, taper hole voltage 20-80 V, collision energy 10-50 V.
3. the assay method of objectionable impurities caprolactam in the workplace air as claimed in claim 1, it is characterized in that: concrete operation steps is as follows:
(1) sample collecting, transportation and preservation part: gather air sample with two series connection impinger of adorning 10.0 mL water in each;
(2) analysis part of sample: will transfer to after the absorption liquid filtration in the liquid phase sample introduction bottle for measuring, if caprolactam concentration is measured behind the diluted absorption solution with same concentration above measurement range in the sample liquid;
(3) drafting of typical curve: accurately take by weighing a certain amount of caprolactam solid standard specimen, be dissolved in the water, quantitatively be transferred in the volumetric flask, and be diluted to scale, this solution is caprolactam standard stock solution; Face with before, become the standard series of 5 concentration gradients with 1:9 methanol solvent dilution, measure each standard series with the liquid chromatography-tandem mass spectrometry combined instrument then, with peak area to caprolactam concentration drawing standard curve;
(4) calculating section: with the operating conditions working sample and the blank solution of bioassay standard series, the sample peak area of measuring deducted the peak area of blank after, get the concentration of caprolactam by typical curve.
4. the assay method of objectionable impurities caprolactam in the workplace air as claimed in claim 3, it is characterized in that: the impinger of 10.0 mL water is adorned in two of step (1) series connection in each, sealing absorption tube port is put into sales kit (SK) with absorption tube and is brought to sampled point; Take out absorption tube and be connected,, write down temperature, air pressure and the humidity of sampled point simultaneously with 15 minutes air samples of 3 L/min traffic samplings with atmosphere sampling instrument; After the sampling, seal the air inlet/outlet of absorption tube immediately, uprightly place transportation and preservation in the cleaning container; Should analyze as early as possible behind the sample collecting,, should under 4 ℃ of conditions, keep in Dark Place, be no more than 7 days as can not in time analyzing.
5. the assay method of objectionable impurities caprolactam in the workplace air as claimed in claim 3, it is characterized in that: the draft tube inwall 3 times of absorption tube is washed in the absorption that step (2) will be adopted sample night, after shaking up, to absorb and pour into night in the tool plug test tube, adopt disposable sample introduction needle to suck about 1 mL sample, organic phase pin type filter through 0.2 μ m filters directly injection liquid phase sample introduction bottle of back, detects with the liquid chromatography-tandem mass spectrometry combined instrument; If the concentration of determinand surpasses measurement range in the sample liquid, available absorption dilution at night back is measured, and multiply by extension rate during calculating.
6. the assay method of objectionable impurities caprolactam in the workplace air as claimed in claim 3, it is characterized in that: the concrete method for drafting of step (3) typical curve is: accurately take by weighing 0.1000 g caprolactam solid standard specimen, be dissolved in the water, quantitatively be transferred in the 100 mL volumetric flasks, and being diluted to scale, this solution is 1000 μ g/mL standard stock solutions; Before facing usefulness, become the standard series of 5 concentration gradients with 1:9 methanol solvent dilution; The liquid chromatography-tandem mass spectrometry combined instrument is adjusted to the optimum determining state, measures each standard series; Each concentration replication 3 times, with peak area to caprolactam concentration (μ g/L) drawing standard curve; Coefficient R〉0.9990.
7. the assay method of objectionable impurities caprolactam in the workplace air as claimed in claim 3, it is characterized in that: the caprolactam concentration computing formula is as follows in the workplace:
By formula (1) sampling volume is converted into the standard sample volume
In the formula:
Vo-standard sample volume, L;
V-sampling volume, L;
The temperature of t-sampled point, ℃;
The atmospheric pressure of P-sampled point, kPa;
Calculate the concentration of caprolactam in the air by formula (2):
In the formula:
The concentration of caprolactam in C-air, mg/ m
3
The volume of v-sample solution, ml;
The concentration of the caprolactam of c-record, μ g/ml;
Vo-standard sample volume, L.
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| CN103499654A (en) * | 2013-09-29 | 2014-01-08 | 浙江省医学科学院 | Collection method and measurement method for alkali metals and compounds thereof in air in working place |
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| CN107870167A (en) * | 2016-09-27 | 2018-04-03 | 上海宝钢工业技术服务有限公司 | The assay method of beryllium and its compound concentration in workplace air |
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| CN103499654A (en) * | 2013-09-29 | 2014-01-08 | 浙江省医学科学院 | Collection method and measurement method for alkali metals and compounds thereof in air in working place |
| CN103499654B (en) * | 2013-09-29 | 2015-04-29 | 浙江省医学科学院 | Collection method and measurement method for alkali metals and compounds thereof in air in working place |
| CN105092741A (en) * | 2015-09-25 | 2015-11-25 | 四川科伦药业股份有限公司 | Method for detecting 3-amino-2-azepanone through high performance liquid chromatography |
| CN107870167A (en) * | 2016-09-27 | 2018-04-03 | 上海宝钢工业技术服务有限公司 | The assay method of beryllium and its compound concentration in workplace air |
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