CN109358149A - The fast quantitative measurement method for detecting of polycyclic aromatic hydrocarbon in a kind of surface water - Google Patents
The fast quantitative measurement method for detecting of polycyclic aromatic hydrocarbon in a kind of surface water Download PDFInfo
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- CN109358149A CN109358149A CN201811304262.1A CN201811304262A CN109358149A CN 109358149 A CN109358149 A CN 109358149A CN 201811304262 A CN201811304262 A CN 201811304262A CN 109358149 A CN109358149 A CN 109358149A
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Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/062—Preparation extracting sample from raw material
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Abstract
The invention discloses a kind of fast quantitative measurement method for detecting of polycyclic aromatic hydrocarbon in surface water, it is related to a kind of detection method, its operating procedure includes PAHs extraction, high temperature thermal desorption, cold focusing enrichment and GC-MS separation, proposed adoption SBSE technology combination TD-GC-MS of the present invention, and in such a way that multiple stirring rod extract absorption simultaneously, the rapid detection method of 16 kinds of PAHs in water body is established, the content of ultra trace PAHs in surface water can be quickly measured, has the characteristics that high sensitivity, accuracy are high.
Description
Technical field
The present invention relates to a kind of detection method, in particular to the rapid quantitative detection side of polycyclic aromatic hydrocarbon in a kind of surface water
Method.
Background technique
Polycyclic aromatic hydrocarbon (polycyclic aromatic hydrocarbons, PAHs) is the organic matters imperfect combustion such as coal
When the half volatile hydrocarbon that generates, be widely present in the surrounding mediums such as water body, soil, deposit, have stronger
Environmental endocrine disrupting effect can generate harm to human health.In recent years by extensive concern both domestic and external, in China's earth's surface
Considered critical has been carried out to the content of the substance in quality standard of water environment and environmental risk assessment.
Currently, the measuring method of polycyclic aromatic hydrocarbon mainly has liquid-liquid extraction method (LLE) and solid phase extraction in surface water water body
(SPE) gas chromatography or liquid chromatography etc. are combined.These traditional pre-treating method trivial operations, extraction time are long, molten
Agent consumption is big.Therefore, more simple and convenient, the environmental-friendly water sample pretreatment technology of subsequent development, such as liquid-phase micro-extraction
(LPME), dispersion liquid extraction (DLLME), solid phase microextraction (SPME) and Stir Bar Sorptive Extraction (stir bar
Sorptiveextraction, SBSE) etc. technologies.
SBSE technology is a kind of novel solvent-free or few solvent, integrate extraction, purification, be enriched be used for trace
The water sample pretreatment technology of organic matter separation and concentration, it is the 50 of SPME maximum coating amount (0.5 μ L) that extraction coating volume is big
~250 times, theoretical adsorption capacity is much larger than SPME, has low high sensitivity, detection limit, favorable reproducibility, does not use organic solvent
The advantages that, the trace analysis of volatility and semi-volatile organic matter suitable for more clean environment water sample.Commercialization at present
Stirring and adsorbing extraction bar there is dimethyl silicone polymer (PDMS) and polyethylene-ethylene glycol improvement silanization (EG Silicon) to apply
Two kinds of layer.
Wherein, the SBSE technology of PDMS coating is many applied to the document report of PAHs in water sample, such as Le ó n (Le ó n,
2003,999 (1/2): et al.J Chromatogr A 91) applies SBSE- thermal desorption (thermal desorption, TD)-
GC-MS method is not true to 6 kinds of five rings or the detection limit of six ring polycyclic aromatic hydrocarbons, repeatability, method in surface water, underground water and tap water
Fixed degree etc. is verified, and this method has good repeatability and the rate of recovery as the result is shown, but the sorption extraction time is longer
(14h)；(Kolahgar, et al.Application of stir bar the sorptive extraction such as Kolahgar
to the determination of polycyclic aromatic hydrocarbons in aqueous samples
2002,963 (1-2): 225-230.) [J] .Journal of Chromatography A is surveyed using SBSE-TD-GC-MS method
Determine 16 kinds of PAHs in water, and residual quantity parameter after extraction time, desorption etc. is optimized, the experimental results showed that, the party
Method has good linear and detection limit, but the extraction time of 3.5h is still longer.Although SBSE technology has highly sensitive spy
Point, but limited by its adsorption mechanism, the method for existing report haves the shortcomings that extraction time is long, limits it in practice
Application.
For realize surface water in ultra trace PAHs quick measurement, proposed adoption SBSE technology combination TD-GC-MS of the present invention,
And in such a way that multiple stirring rod extract absorption simultaneously, the rapid detection method of 16 kinds of PAHs in water body is established.
Summary of the invention
In view of the deficiencies of the prior art, the present invention intends to provide a kind of the quick of polycyclic aromatic hydrocarbon in surface water
Quantitative detecting method can quickly measure the content of ultra trace PAHs in surface water.
To realize above-mentioned first purpose, the present invention provides the following technical scheme that
The fast quantitative measurement method for detecting of polycyclic aromatic hydrocarbon in a kind of surface water, including following operating procedure:
1., PAHs extraction: correct amount water sampling is adsorbed in magnetic in conical flask, by the solid-phase extraction muddler of multiple PDMS coatings
It is placed in conical flask on power stirrer, the conical flask is then placed in ultrasonic sealing in ice-water bath and stirs 15-25min, is taken
Solid-phase extraction muddler is spare out；
2., high temperature thermal desorption: by step 1. in solid-phase extraction muddler be put into the thermal desorption pipe in thermal desorption module, high temperature
Desorption product are obtained after thermal desorption；
3., cold focusing enrichment: by step 2. obtained in desorption product be delivered in CIS cold trap, cold focusings is enriched with after being enriched with
Product；4., GC-MS separation: by step 3. obtained in enrichment product be delivered in the chromatographic column of GC-MS, obtain chromatogram, be computed
Obtain the content of PAHs in water sample.
The present invention is adsorbed the PAHs in water sample by solid-phase extraction muddler, after the completion of PAHs extraction, by solid phase
Extraction stirring rod is transferred to progress high temperature thermal desorption in thermal desorption module, subsequently enters and carries out cold focusing enrichment in CIS cold trap.By
Smaller in thermal desorption pipe volume, the adsorbed material in thermal desorption pipe is desorbed using thermal desorption device for this method, by CIS
After cold-trap carries out cold focusing merging, enters gas-chromatography separation through thermal desorption, so individually taken off relative to solid-phase extraction muddler
It is attached to effectively shorten its desorption time, while additionally aiding the PHAs for adsorbing each solid-phase extraction muddler and merging, expand
The big adsorption capacity of stirring rod, accurately measures the PHAs content in water sample convenient for GC-MS；
In addition, ice-water bath reduces the temperature of water sample, so that the PAHs solubility in water sample drops in PAHs extraction
It is low, while solid-phase extraction muddler increases the adsorption isothermequation Kp value of PHAs, and ultrasonic wave passes through water sample for energy
Pass to the PAHs in water sample so that the capacitation of PAHs molecule and become more active, solid-phase extraction muddler is stirred in magnetic force at this time
Mix son rotation and ultrasonic wave under the action of be constantly stirred in water sample, PAHs is effectively adsorbed in by Solid Phase Extraction with this
In stirring rod, the time of sorption extraction is greatly shortened, and then can quickly measure the content of ultra trace PAHs in surface water.
Further, step 1. in, the accurate 500mL water sample that measures is in 1L conical flask, by 2 10mm × 0.5mm and 1
The solid-phase extraction muddler of 20mm × 0.5mmPDMS coating is adsorbed in the magnetic stir bar after cleaning and is placed on the conical flask
In, the conical flask equipped with water sample is placed in ice-water bath, magnetic stir bar is with the revolving speed of 600r/min to water sample ultrasonic sealing
15-25min is stirred, it is spare to take out solid-phase extraction muddler.
Further, step 1. in, the accurate 500mL water sample that measures is in 1L conical flask, by 2 10mm × 0.5mm and 1
The solid-phase extraction muddler of 20mm × 0.5mm PDMS coating is adsorbed in the magnetic stir bar after cleaning and is placed on the conical flask
In, the conical flask equipped with water sample is placed in ice-water bath, magnetic stir bar is with the revolving speed of 600r/min to water sample ultrasonic sealing
20min is stirred, it is spare to take out solid-phase extraction muddler.
By using above-mentioned technical proposal, the length of stirring rod only has two kinds of models of 10mm and 20mm, by contact area
With the limitation of loading capacity, document Li Xiaomin etc. (inhale by Li Xiaomin, Zhang Qinghua, Wang Pu, Li Yingming, Jiang Guibin stirrer solid phase
Attached-thermal desorption-gas chromatography/mass spectrometry/mass spectrography quickly measures Polycyclic Aromatic Hydrocarbons In Alr [J] analytical chemistry, 2011,39 (11):
The volume for the extraction water sample recorded in 1641-1646.) is generally 10~100mL.In order to obtain higher sensitivity and analysis effect
Rate, the present invention improve volume of water sample to 500mL, correspondingly, needing to increase the quantity of stirring rod, to solve due to volume of water sample
Increase caused by adsorbing bar absorption interfacial area deficiency problem；
In addition, though have magnetic stir bar inside stirring rod, can in water sample automatic stirring, but by adsorbing bar volume mistake
Small, the not high influence of level of disruption in water sample with bulk mass, correspondingly adsorption effect is deteriorated.To solve the contradiction, this method will
The quantity of solid-phase extraction muddler increases to 3, and stirring rod is adsorbed on stirrer, and at high revolving speed (600r/min) into
Row stirring, so that the disturbance velocity of water sample is obviously accelerated, the rate of adsorption of contaminant transportation rate and stirring rod in water sample
Also it correspondingly speeds up, water sample enrichment time can be so greatly shortened in the case where not reducing sensitivity.
Further, step 1. in, the solid-phase extraction muddler using it is preceding in thermal desorption pipe with 300 DEG C of agings
30min。
By using above-mentioned technical proposal, aging process can reduce solid-phase extraction muddler and remain in the inner after desorption
The content of the PAHs in portion so that reducing PAHs remains on absorption in solid-phase extraction muddler to subsequent water sample, and then helps
In the raising present invention to the accuracy of PAHs content detection.
Further, step 2. in, the condition of high temperature thermal desorption are as follows: 50 DEG C of initial temperature, with the speed liter of 250 DEG C/min
Temperature keeps 3min, not shunt mode to 280 DEG C.
By using above-mentioned technical proposal, in general, the desorption time of solid-phase extraction muddler is longer, is desorbed more thorough
Bottom.Elevated temperature desorption in the prior art usually requires to be warming up to 280 DEG C from 50 DEG C of rates with 60 DEG C/min, then keeps again
5min, such PAHs can occur corresponding substitution reaction because being under hot environment for a long time and form derivative, and then lead
The type and content for detecting resulting PAHs and reality are caused biggish deviation occur.The present invention investigated thermal desorption speed (100,
150,200,250 and 300 DEG C/min) and the retention time (1.0,3.0,5.0 and 7.0min) to desorption rate influence (respectively referring to
Fig. 1 and Fig. 2), the results show that increase of 16 kinds of PAHs with thermal desorption speed and retention time, the peak area of the two is in first
Reduce after increase, comprehensively considers the curve distribution variation of two attached drawings, the thermal desorption time is finally set as 3.0min.
Further, step 3. in, it is cold focus enrichment condition are as follows: -20 DEG C of initial temperature, be warming up to 280 with 20 DEG C/s
DEG C, keep 1min, solvent vent mode.
By using above-mentioned technical proposal, cold focus temperature is that impact analysis object is transferred to gas-chromatography from stirring rod
Important experiment parameter, the present invention investigated respectively cold focus temperature be 20,0, -20, -40, -80 DEG C when, the peak of PAHs chromatographic peak
Area (referring to Fig. 3), the results show that the peak area of most PAHs is relatively high when cold focus temperature is -20 DEG C, because
Cold focus temperature is finally set as -20 DEG C by this；
In addition, the present invention investigated heating rate (10,12,15,20 and 25 DEG C/s) to 16 kinds of PAHs peak areas influence (referring to
Fig. 4), the results showed that, when heating rate is between 10-25 DEG C/s, the peak area of PAHs is in downward trend after first rising, therefore
The heating rate of cold focusing is finally set as 20 DEG C/s；
The present invention has also investigated cold-trap desorption time (1.0,2.0,4.0,6.0 and 8.0min) to the shadow of target analytes peak area
It rings (referring to Fig. 5), the results showed that, desorption time is between 1.0~8.0min, and the peak area variation of PAHs is little, therefore, finally
Cold-trap desorption time is set as 1.0min.
Further, step 4. in, the Elevated Temperature Conditions of GC-MS are as follows: 50 DEG C of initial temperature, keep 1min, with 20 DEG C/min
320 DEG C are warming up to, 5min is kept the temperature.
By using above-mentioned technical proposal, GC-MS has good linear pass when measuring PAHs under above-mentioned Elevated Temperature Conditions
System, can preferably measure the PAHs content in water sample, to improve the present invention to the accuracy of PHAs assay.
Further, step 4. in, the ion source of GC-MS is the source EI, and ion source temperature is 280 DEG C, interface temperature 280
℃。
By using above-mentioned technical proposal, 280 DEG C are set by ion source temperature and enables to the quick capacitation of PAHs and sends out
Raw ionization forms the positively charged ion of different charge-mass ratios, and then improves the efficiency of chromatography；Interface temperature is disposed as
280 DEG C can reduce PHAs a possibility that interface is detained, so as to effectively improve the accurate of PHAs content detection
Degree.
Further, step 4. in, the chromatographic column of GC-MS is DB-5MS capillary column.
By using above-mentioned technical proposal, DB-5MS capillary column has good inertia to reactive compound, so that color
Spectrogram is more complete, can preferably be separated to PHAs；In addition, DB-5MS capillary column is chromatography common in gas-chromatography
Column, chromatographic column buying is convenient, if break down to be replaced in time.
Further, step 4. in, the carrier gas of GC-MS is helium, flow velocity 1mL/min.
By using above-mentioned technical proposal, helium is inert gas, will not be chemically reacted with PHAs, can be fast
Speed bombardment chromatographic column in PHAs molecule and obtain water sample ion, then in the long period obtain stabilizing ion stream, passed through after
The effect of accelerating field is successively effectively eluted, to contribute to form complete chromatogram in order to which operator contains PHAs
The statistics of amount.
In conclusion the invention has the following advantages:
1, the present invention is by being placed in progress ultrasonic sealing stirring in ice-water bath for water sample, so that the PHAs in water sample is quickly inhaled
It invests in solid-phase extraction muddler, then PHAs content is surveyed through the absorption of high warm, cold focusing enrichment and GC-MS separation again
It is fixed, have the characteristics that extraction time is short, detection accuracy is high；
2, the present invention is by the magnetic stir bar of different magnetic force sizes in the adsorption rate and effect for increasing solid-phase extraction muddler；
3, the present invention is limited by high temperature thermal desorption, the cold condition for focusing enrichment and GC-MS, is effectively increased in water sample
The accuracy of PHAs content detection.
Detailed description of the invention
Fig. 1 is the line chart of the peak area of desorption rate and 16 kinds of PAHs absorption peaks；
Fig. 2 is the line chart of the retention time of thermal desorption and the peak area of 16 kinds of PAHs absorption peaks；
Fig. 3 is the line chart of the peak area of cold focus temperature and 16 kinds of PAHs absorption peaks；
Fig. 4 is the line chart of the peak area of the cold heating rate for focusing enrichment and 16 kinds of PAHs absorption peaks；
Fig. 5 is the line chart of the peak area of cold-trap desorption time and 16 kinds of PAHs absorption peaks.
Specific embodiment
Below in conjunction with attached drawing, invention is further described in detail.
1, instrument and reagent
1.1, GC-MS is purchased from Waters, US, 6890 gas chromatograph-mass spectrometer (GC-MS) of model Agilent, equipped with heat
Be desorbed module (thermal desorption unit, TDU) and cold sampling system (cooled injection system,
CIS), chromatographic column is 30m × 0.25mm, 0.25 μm of DB-5MS capillary column；
1.2, solid-phase extraction muddler: being purchased from Gerstel company of Germany, and specification is 10mm × 0.5mm and 20mm × 0.5mm two
Kind, coating is PDMS absorbent coating；
1.3, HJ-6A bull magnetic stirring apparatus is purchased from Jiangsu Ke Xi instrument company；
1.4, ultrasonic wave vibration head is purchased from Nanjing Han Zhou Science and Technology Ltd., model YTH-50-40；
1.5, Milli-Q ultrapure water system is purchased from U.S. Millipore company；
1.6,16 kinds of PAHs standard solution: including naphthalene (naphthalene, Nap), acenaphthylene (acenaphthylene, Acy), acenaphthene
(acenaphthene, Ace), fluorenes (fluorene, Fle), luxuriant and rich with fragrance (phenanthrene, Phe), anthracene (anthracene, An), glimmering
Anthracene (fluoranthene, Flu), pyrene (pyrene, Pyr), 1,2- benzanthracene (1,2-benzanthracene, BaA),
(chrysene, Chr), benzo [b] fluoranthene (benzo [b] fluoranthene, BbF), benzo [k] fluoranthene (benzo [k]
Fluoranthene, BkF), benzo [a] pyrene (benzo [a] pyrene, BaP), indeno [1,2,3-cd] pyrene (indeno [1,2,
3-cd] pyrene, Ind), dibenzo [a, h] anthracene (dibenz [a, h] anthracene, DahA), benzo [g, h, i]
(benzo [g, h, i] perylene, BghiP), mass concentration is 0.2mg/mL, is purchased from Shanghai Bellingwell company.It takes above-mentioned
PAHs standard solution with methanol dilution and prepares the PAHs standard working solution that mass concentration is 10 μ g/L, matching while using.
2, embodiment
2.1, embodiment 1
The fast quantitative measurement method for detecting of polycyclic aromatic hydrocarbon in a kind of surface water, including following operating procedure:
1., PAHs extraction
A, 500mL water sample is accurately measured, is placed in 1L conical flask；
B, the solid-phase extraction muddler of 2 10mm × 0.5mm and 1 20mm × 0.5mmPDMS coatings is placed in thermal desorption module
Thermal desorption pipe in, with 300 DEG C of aging 30min；
C, in the polytetrafluoroethylene (PTFE) magnetic stir bar after the solid-phase extraction muddler in step b by aging being adsorbed in cleaning,
The conical flask is sealed with rubber stopper after in the conical flask being subsequently placed in step a；
D, the conical flask in step c is placed in the beaker for filling ice water, while puts into ultrasonic wave vibration head into beaker, then should
Beaker is placed in HJ-6A bull magnetic stirring apparatus；
E, the ultrasonic wave vibration head and HJ-6A bull magnetic stirring apparatus in starting step d, magnetic stir bar is with the revolving speed of 600r/min
After stirring 15min to water sample ultrasonic sealing, it is spare to take out solid-phase extraction muddler；
2., high temperature thermal desorption
1. solid-phase extraction muddler that step is obtained in e is put into the thermal desorption pipe of thermal desorption module, and it is de- that high warm is arranged
Attached condition are as follows: 50 DEG C of initial temperature, be warming up to 280 DEG C with the speed of 250 DEG C/min, keep 3min, shunt mode, does not obtain
Desorption product；
3., cold focusing enrichment
By step 2. obtained in desorption product be delivered in CIS cold trap, be arranged it is cold focus enrichment condition are as follows: initial temperature -20
DEG C, 280 DEG C are warming up to 20 DEG C/s, keeps 1min, solvent vent mode obtains enrichment product；
4., GC-MS separation
By step 3. obtained in enrichment product be delivered in the chromatographic column of GC-MS, the Elevated Temperature Conditions of GC-MS are set are as follows: initial temperature
50 DEG C of degree keeps 1min, is warming up to 320 DEG C with 20 DEG C/min, keeps the temperature 5min, and wherein ion source is the source EI, and ion source temperature is
280 DEG C, interface temperature is 280 DEG C, ionizing energy 70eV, and scanning mode is full scan, scanning range m/z45-550, with
The flow velocity of 1mL/min is loaded into helium, obtains chromatogram, is computed the content for obtaining PAHs in water sample.
2.2, embodiment 2
Difference from example 1 is that the step of the present embodiment, 1. the ultrasonic sealing mixing time in e was 20min.
2.3, embodiment 3
Difference from example 1 is that the step of the present embodiment, 1. the ultrasonic sealing mixing time in e was 25min.
2.4, embodiment 4
Difference from example 1 is that 1. the step of the present embodiment, uses 3 10mm × 0.5mmPDMS coatings in b
Solid-phase extraction muddler.
2.5, embodiment 5
The fast quantitative measurement method for detecting of polycyclic aromatic hydrocarbon in a kind of surface water, including following operating procedure:
1., PAHs extraction
A, 500mL water sample is accurately measured, is placed in 1L conical flask；
B, the solid-phase extraction muddler of 2 10mm × 0.5mm and 1 20mm × 0.5mmPDMS coatings is placed in thermal desorption module
Thermal desorption pipe in, with 280 DEG C of aging 60min；
C, in the polytetrafluoroethylene (PTFE) magnetic stir bar after the solid-phase extraction muddler in step b by aging being adsorbed in cleaning,
The conical flask is sealed with rubber stopper after in the conical flask being subsequently placed in step a；
D, the conical flask in step c is placed in the beaker for filling ice water, while puts into ultrasonic wave vibration head into beaker, then should
Beaker is placed in HJ-6A bull magnetic stirring apparatus；
E, the ultrasonic wave vibration head and HJ-6A bull magnetic stirring apparatus in starting step d, magnetic stir bar is with the revolving speed of 600r/min
After stirring 15min to water sample ultrasonic sealing, it is spare to take out solid-phase extraction muddler；
2., high temperature thermal desorption
1. solid-phase extraction muddler that step is obtained in e is put into the thermal desorption pipe of thermal desorption module, and it is de- that high warm is arranged
Attached condition are as follows: 50 DEG C of initial temperature, be warming up to 290 DEG C with the speed of 200 DEG C/min, keep 5min, shunt mode, does not obtain
Desorption product；
3., cold focusing enrichment
By step 2. obtained in desorption product be delivered in CIS cold trap, be arranged it is cold focus enrichment condition are as follows: initial temperature -20
DEG C, 300 DEG C are warming up to 12 DEG C/s, keeps 1min, solvent vent mode obtains enrichment product；
4., GC-MS separation
By step 3. obtained in enrichment product be delivered in the chromatographic column of GC-MS, the Elevated Temperature Conditions of GC-MS are set are as follows: initial temperature
50 DEG C of degree keeps 1min, is warming up to 260 DEG C with 10 DEG C/min, then be warming up to 310 DEG C with 15 DEG C/min, keeps the temperature 3min, wherein from
Component is the source EI, and ion source temperature is 200 DEG C, and interface temperature is 250 DEG C, and ionizing energy 70eV, scanning mode is full scan,
Scanning range is m/z45-550, is loaded into helium with the flow velocity of 1mL/min, obtains chromatogram, is computed and obtains PAHs in water sample
Content.
3, comparative example 1
Difference from example 1 is that the step of this comparative example, 1. the conical flask in d was placed directly in HJ-6A bull magnetic
In power blender, 60min is extracted with 600r/min stirring at normal temperature.
4, linear relationship
The PAHs standard working solution for measuring the 10 μ g/L of 10,25,50,250,500 μ L respectively, preparing 500mL mass concentration is
0.2, the mark-on blank water sample of 0.5,1,5,10ng/L, and respectively by embodiment 1 to the method for embodiment 5 and comparative example 1 into
Row measurement, is ordinate (y), corresponding mass concentration for horizontal seat using chromatographic peak area in the range of linearity of 0.2~10ng/L
It marks (x, ng/L), draws standard curve, obtain linear equation and related coefficient (r) (referring to table 1-6).
The result shows that be followed successively by embodiment 1 to the related coefficient of embodiment 5 and comparative example 1 r > 0.99905, r >
0.99991, r > 0.99912, r > 0.99727, r > 0.99718 and r > 0.95860 (referring to table 1-6), thus it is of the invention linear
Relationship is substantially better than comparative example 1, in addition, the related coefficient of embodiment 2 is more excellent, therefore in embodiment 1 into embodiment 5
Selecting embodiment 2 is preferred embodiment.
The linear equation of 16 kinds of PAHs, related coefficient (r), relative standard deviation (RSD) (RSD) and side in 1 embodiment 1 of table
Method detection limit (MDL)
| Linear equation | r | RSD (n=5)/% | MDLs/(ng/L) | |
| Nap | Y=(58.66x+296.14) × 103 | 0.99910 | 5.65 | 0.055 |
| Acy | Y=(31.25x+5.22) × 103 | 0.99945 | 6.25 | 0.010 |
| Ace | Y=(22.38x+8.26) × 103 | 0.99973 | 5.22 | 0.035 |
| Fle | Y=(47.03x+14.21) × 103 | 0.99947 | 6.86 | 0.011 |
| Phe | Y=(350.24x+47.52) × 103 | 0.99905 | 7.13 | 0.035 |
| An | Y=(41.25x+8.23) × 103 | 0.99927 | 5.78 | 0.010 |
| Flu | Y=(189.52x+8.27) × 103 | 0.99905 | 5.74 | 0.025 |
| Pyr | Y=(140.23x+4.22) × 103 | 0.99922 | 6.58 | 0.036 |
| BaA | Y=(18.62x+7.05) × 103 | 0.99956 | 5.68 | 0.040 |
| Chr | Y=(32.05x+15.60) × 103 | 0.99918 | 7.15 | 0.038 |
| BbF | Y=(5.16x+7.50) × 103 | 0.99966 | 6.76 | 0.045 |
| BkF | Y=(6.56x+8.12) × 103 | 0.99915 | 5.22 | 0.019 |
| BaP | Y=(4.12x+7.96) × 103 | 0.99937 | 6.92 | 0.053 |
| Ind | Y=(1.82x+4.68) × 103 | 0.99958 | 7.15 | 0.040 |
| DahA | Y=(2.01x+2.15) × 103 | 0.99972 | 7.41 | 0.020 |
| BghiP | Y=(2.40x+4.50) × 103 | 0.99909 | 6.80 | 0.010 |
The linear equation of 16 kinds of PAHs, related coefficient (r), relative standard deviation (RSD) and method detection limit in 2 embodiment 2 of table
(MDL)
| Linear equation | r | RSD (n=5)/% | MDLs/(ng/L) | |
| Nap | Y=(58.26x+296.50) × 103 | 0.99991 | 1.65 | 0.020 |
| Acy | Y=(31.28x+5.32) × 103 | 0.99998 | 2.25 | 0.006 |
| Ace | Y=(22.10x+8.22) × 103 | 0.99993 | 1.89 | 0.012 |
| Fle | Y=(47.21x+14.21) × 103 | 0.99997 | 1.67 | 0.005 |
| Phe | Y=(350.20x+47.22) × 103 | 0.99991 | 2.13 | 0.011 |
| An | Y=(41.28x+8.36) × 103 | 0.99998 | 1.58 | 0.006 |
| Flu | Y=(188.23x+9.19) × 103 | 0.99996 | 2.04 | 0.010 |
| Pyr | Y=(140.56x+4.28) × 103 | 0.99993 | 2.20 | 0.005 |
| BaA | Y=(18.59x+7.15) × 103 | 0.99998 | 2.11 | 0.009 |
| Chr | Y=(32.15x+15.49) × 103 | 0.99993 | 1.85 | 0.008 |
| BbF | Y=(5.20x+7.14) × 103 | 0.99996 | 1.76 | 0.010 |
| BkF | Y=(6.61x+8.01) × 103 | 0.99997 | 2.03 | 0.015 |
| BaP | Y=(4.30x+7.88) × 103 | 0.99991 | 1.92 | 0.006 |
| Ind | Y=(1.79x+4.24) × 103 | 0.99992 | 2.15 | 0.009 |
| DahA | Y=(2.23x+2.21) × 103 | 0.99995 | 2.31 | 0.010 |
| BghiP | Y=(2.45x+4.13) × 103 | 0.99994 | 1.80 | 0.008 |
The linear equation of 16 kinds of PAHs, related coefficient (r), relative standard deviation (RSD) and method detection limit in 3 embodiment 3 of table
(MDL)
| Linear equation | r | RSD (n=5)/% | MDLs/(ng/L) | |
| Nap | Y=(58.22x+297.14) × 103 | 0.99912 | 6.15 | 0.050 |
| Acy | Y=(31.20x+5.50) × 103 | 0.99976 | 7.03 | 0.015 |
| Ace | Y=(22.18x+8.75) × 103 | 0.99953 | 6.89 | 0.022 |
| Fle | Y=(47.13x+14.15) × 103 | 0.99941 | 7.15 | 0.035 |
| Phe | Y=(350.31x+47.35) × 103 | 0.99925 | 7.10 | 0.027 |
| An | Y=(41.22x+8.32) × 103 | 0.99953 | 6.56 | 0.018 |
| Flu | Y=(189.29x+8.32) × 103 | 0.99937 | 6.84 | 0.026 |
| Pyr | Y=(140.21x+4.15) × 103 | 0.99936 | 6.58 | 0.005 |
| BaA | Y=(18.59x+7.05) × 103 | 0.99969 | 7.08 | 0.043 |
| Chr | Y=(32.16x+15.46) × 103 | 0.99978 | 7.19 | 0.035 |
| BbF | Y=(5.19x+7.46) × 103 | 0.99953 | 6.76 | 0.025 |
| BkF | Y=(6.40x+8.52) × 103 | 0.99981 | 6.03 | 0.019 |
| BaP | Y=(4.32x+7.85) × 103 | 0.99943 | 6.95 | 0.023 |
| Ind | Y=(1.92x+4.52) × 103 | 0.99927 | 7.09 | 0.045 |
| DahA | Y=(2.11x+2.35) × 103 | 0.99943 | 7.32 | 0.025 |
| BghiP | Y=(2.43x+4.23) × 103 | 0.99919 | 6.93 | 0.038 |
The linear equation of 16 kinds of PAHs, related coefficient (r), relative standard deviation (RSD) and method detection limit in 4 embodiment 4 of table
(MDL)
The linear equation of 16 kinds of PAHs, related coefficient (r), relative standard deviation (RSD) and method detection limit in 5 embodiment 5 of table
(MDL)
| Linear equation | r | RSD (n=5)/% | MDLs/(ng/L) | |
| Nap | Y=(59.20x+298.14) × 103 | 0.99769 | 10.65 | 0.120 |
| Acy | Y=(32.01x+5.35) × 103 | 0.99752 | 9.25 | 0.053 |
| Ace | Y=(22.20x+9.03) × 103 | 0.99873 | 9.62 | 0.022 |
| Fle | Y=(48.23x+10.21) × 103 | 0.99845 | 9.76 | 0.012 |
| Phe | Y=(352.26x+47.03) × 103 | 0.99752 | 10.13 | 0.025 |
| An | Y=(41.79x+10.23) × 103 | 0.99827 | 9.75 | 0.027 |
| Flu | Y=(188.12x+8.89) × 103 | 0.99815 | 10.74 | 0.012 |
| Pyr | Y=(140.76x+5.21) × 103 | 0.99718 | 9.59 | 0.025 |
| BaA | Y=(18.02x+7.23) × 103 | 0.99756 | 10.68 | 0.096 |
| Chr | Y=(32.22x+15.19) × 103 | 0.99818 | 10.15 | 0.081 |
| BbF | Y=(5.16x+7.50) × 103 | 0.99860 | 9.78 | 0.102 |
| BkF | Y=(6.63x+8.47) × 103 | 0.99875 | 10.22 | 0.085 |
| BaP | Y=(4.57x+7.16) × 103 | 0.99737 | 9.92 | 0.052 |
| Ind | Y=(1.69x+6.68) × 103 | 0.99858 | 10.16 | 0.108 |
| DahA | Y=(2.71x+3.15) × 103 | 0.99772 | 10.41 | 0.065 |
| BghiP | Y=(2.15x+5.23) × 103 | 0.99909 | 10.22 | 0.095 |
The linear equation of 16 kinds of PAHs, related coefficient (r), relative standard deviation (RSD) method detection limit in 6 comparative example 1 of table
(MDL)
5, method detection limit and accuracy
Embodiment 1 is successively pressed to embodiment 5 and comparison to the 500mL blank mark-on water sample containing 16 kinds of PAHs (1.0ng/L)
The relative standard deviation (RSD) of the method METHOD FOR CONTINUOUS DETERMINATION of example 15 times, measurement result is followed successively by 5.22%-7.41%, 1.58%-
2.31%, 6.03%-7.32%, 9.13%-10.22%, 9.25%-10.68%, 4.69%-17.92% (referring to table 1-6),
Therefore, the present invention is more stable relative to comparative example 1, can the stable PHAs content in water sample measured.
It is determined method detection limit (MDL) with 3 times of standard deviations, embodiment 1 to the MDL of embodiment 5 and comparative example 1 is successively
For 0.010ng/L-0.055ng/L, 0.005ng/L-0.020ng/L, 0.005ng/L-0.050ng/L, 0.025ng/L-
0.105ng/L, 0.012ng/L-0.120ng/L and 0.036ng/L-0.500ng/L (referring to table 1-6, n=7), wherein the present invention
The MDL of acquisition is obviously due to the MDL that comparative example 1 obtains, and detection time is shorter, therefore is detected using detection method of the invention
PHAs content in water sample has the characteristics that high sensitivity, accuracy are high, detection time is short.Wherein, in embodiment 1 to embodiment
In 5, the RSD and MDL of embodiment 2 are minimum, therefore selecting embodiment 2 is to have preferred embodiment.
In addition, method detection limit of the invention fully meets GB3838-2002 water environment quality standard (BaP limit
Value 2.8ng/L), GB5749-2006 standards for drinking water quality (determining polycyclic aromatic hydrocarbon total amount limit value 2000ng/L) and the U.S.
The code requirement of Environmental Protection Agency (16 kinds of PAHs total amounts, 0.2 μ g/L).
6, recovery of standard addition
For the reliability of the further method of inspection, the 500mL blank mark-on water sample containing 16 kinds of PAHs (10ng/L) is successively pressed
Embodiment 1 to the method for embodiment 5 and comparative example 1 carries out recovery test, and every group of sample is averaged after being measured in parallel 3 times
Value, as a result referring to table 7.It should be noted that blank mark-on water sample and 0.2ng/L, 0.5ng/L that mass concentration is 10ng/L,
The difference of 1ng/L and 5ng/L is little, is detected by taking the blank mark-on water sample of 10ng/L as an example herein.
Content and recovery of standard addition (n=3) of the 7 16 kinds of PAHs of table in water sample
Referring to table 7, the recovery of standard addition of embodiment 1 to embodiment 5 and comparative example 1 be followed successively by 94.8%-105.6%,
98.6%-101.0%, 94.6%-105.2%, 85.6%-110.3%, 80.5%-118.6%, 56.9%-135.3%,
Middle recovery of standard addition range of the invention is significantly less than the recovery of standard addition range of comparative example 1, it can thus be concluded that using of the invention
Method detects the PHAs accuracy in water sample, and the recovery of standard addition range of embodiment 2 is minimum, therefore it is preferred for selecting embodiment 2
Embodiment.
To sum up, by means of the present invention detect surface water in polycyclic aromatic hydrocarbon (PHAs) content, have detection time it is short,
The high feature of high sensitivity, accuracy.
This specific embodiment is only explanation of the invention, is not limitation of the present invention, those skilled in the art
Member can according to need the modification that not creative contribution is made to the present embodiment after reading this specification, but as long as at this
All by the protection of Patent Law in the scope of the claims of invention.
Claims (10)
1. the fast quantitative measurement method for detecting of polycyclic aromatic hydrocarbon in a kind of surface water, which is characterized in that including following operating procedure:
1., PAHs extraction: correct amount water sampling is adsorbed in magnetic in conical flask, by the solid-phase extraction muddler of multiple PDMS coatings
It is placed in conical flask on power stirrer, the conical flask is then placed in ultrasonic sealing in ice-water bath and stirs 15-25min, is taken
Solid-phase extraction muddler is spare out；
2., high temperature thermal desorption: by step 1. in solid-phase extraction muddler be put into the thermal desorption pipe in thermal desorption module, high temperature
Desorption product are obtained after thermal desorption；
3., cold focusing enrichment: by step 2. obtained in desorption product be delivered in CIS cold trap, cold focusings is enriched with after being enriched with
Product；
4., GC-MS separation: by step 3. obtained in enrichment product be delivered in the chromatographic column of GC-MS, chromatogram is obtained, through counting
Calculate the content for obtaining PAHs in water sample.
2. the fast quantitative measurement method for detecting of polycyclic aromatic hydrocarbon in a kind of surface water according to claim 1, which is characterized in that step
Suddenly 1. in, the accurate 500mL water sample that measures is in 1L conical flask, by 2 10mm × 0.5mm and 1 20mm × 0.5mmPDMS coatings
Solid-phase extraction muddler be adsorbed in cleaning after magnetic stir bar on be placed in the conical flask, will be equipped with water sample conical flask
It is placed in ice-water bath, magnetic stir bar stirs 15-25min to water sample ultrasonic sealing with the revolving speed of 600r/min, takes out solid phase
It is spare to extract stirring rod.
3. the fast quantitative measurement method for detecting of polycyclic aromatic hydrocarbon in a kind of surface water according to claim 1, which is characterized in that step
Suddenly 1. in, the accurate 500mL water sample that measures is in 1L conical flask, by 2 10mm × 0.5mm and 1 20mm × 0.5mmPDMS coatings
Solid-phase extraction muddler be adsorbed in cleaning after magnetic stir bar on be placed in the conical flask, will be equipped with water sample conical flask
It is placed in ice-water bath, magnetic stir bar stirs 20min to water sample ultrasonic sealing with the revolving speed of 600r/min, takes out Solid Phase Extraction
Stirring rod is spare.
4. the fast quantitative measurement method for detecting of polycyclic aromatic hydrocarbon in a kind of surface water as claimed in any of claims 1 to 3,
It is characterized in that, step 1. in, the solid-phase extraction muddler using it is preceding in thermal desorption pipe with 300 DEG C of aging 30min.
5. the fast quantitative measurement method for detecting of polycyclic aromatic hydrocarbon in a kind of surface water according to claim 1, which is characterized in that step
Suddenly 2. in, the condition of high temperature thermal desorption are as follows: 50 DEG C of initial temperature, be warming up to 280 DEG C with the speed of 250 DEG C/min, keep 3min,
Not shunt mode.
6. the fast quantitative measurement method for detecting of polycyclic aromatic hydrocarbon in a kind of surface water according to claim 1, which is characterized in that step
Suddenly 3. in, the cold condition for focusing enrichment are as follows: -20 DEG C of initial temperature, be warming up to 280 DEG C with 20 DEG C/s, keep 1min, solvent vent
Mode.
7. the fast quantitative measurement method for detecting of polycyclic aromatic hydrocarbon in a kind of surface water according to claim 1, which is characterized in that step
Suddenly 4. in, the Elevated Temperature Conditions of GC-MS are as follows: 50 DEG C of initial temperature, keep 1min, be warming up to 320 DEG C with 20 DEG C/min, heat preservation
5min。
8. the fast quantitative measurement method for detecting of polycyclic aromatic hydrocarbon in a kind of surface water according to claim 7, which is characterized in that step
Suddenly 4. in, the ion source of GC-MS is the source EI, and ion source temperature is 280 DEG C, and interface temperature is 280 DEG C.
9. the fast quantitative measurement method for detecting of polycyclic aromatic hydrocarbon in a kind of surface water according to claim 1, which is characterized in that step
Suddenly 4. in, the chromatographic column of GC-MS is DB-5MS capillary column.
10. the fast quantitative measurement method for detecting of polycyclic aromatic hydrocarbon in a kind of surface water according to claim 1, which is characterized in that
Step 4. in, the carrier gas of GC-MS is helium, flow velocity 1mL/min.
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