CN103776784A - Measuring method of concentration of anionic surface organic active substances in air - Google Patents
Measuring method of concentration of anionic surface organic active substances in air Download PDFInfo
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- CN103776784A CN103776784A CN201410058296.2A CN201410058296A CN103776784A CN 103776784 A CN103776784 A CN 103776784A CN 201410058296 A CN201410058296 A CN 201410058296A CN 103776784 A CN103776784 A CN 103776784A
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Abstract
The invention relates to a measuring method of concentration of anionic surface organic active substances in air, which comprises the following steps: treatment before sample collection; treatment before sample analysis; and calibration and measurement. The treatment before sample collection maximally lowers the influence of impurities, dust particles, ambient temperature and moisture on an experiment. The sample is treated by an ultrasonic cleaner before sample analysis, and the optimal ultrasonic frequency, water bath temperature and ultrasonic extraction time are set. By measuring the absorbance of ethyl violet active substances and using the concentration obtained on a sodium dodecyl benzene sulfonate calibration curve as the apparent concentration of the anionic surface organic active substances in air, recalculation is performed to obtain the concentration of the anionic surface organic active substances in air.
Description
Technical field
The present invention relates to a kind of measuring method of atmospheric environment index, the measuring method of anionic surface organic active substance concentration in especially a kind of atmosphere.
Background technology
In atmospheric environment overall suspended pellet, the particle that aerodynamic diameter is less than 2.5 μ m is PM
2.5, be commonly called Fine Particles.Current, Fine Particles PM
2.5focus and the forward position of atmospheric pollution research field are in the world become.Fine Particles PM
2.5be an ingredient of atmospheric aerosol, because its particle diameter is little, specific surface area is large, can provide carrier for noxious material, so it all has a great impact environmental and human health impacts.
In atmosphere, surperficial organic active substance is covered in the surface of the particle in atmospheric aerosol, namely in atmospheric aerosol such as Fine Particles PM
2.5surface coverage have surperficial organic active substance, these surperficial organic active substances can affect the light scattering of particle, change the aggregation of particle, are conducive to the nucleogenesis of water dust, can also promote the interaction that particle and human lung organize.The existence of surface organic active substance can cause the enrichment of a large amount of hydrophobicity noxious materials, such as the enrichment of fog Pesticides.
Recent research shows, the surface chemistry of the organic active substance on the particle surface in atmospheric aerosol will exceed particle core for the effect of cytosis and health effect.The heterogeneous reaction of Aerosol Surface is crossed as source or is converged and can change chemical substance circulation.It also can increase the solubleness of aerosol particle thing, also may make noxious material increase.Surface organic active substance can reduce or change the surface tension of tear film, makes eyes have dry sensation.The pellet being polluted by surperficial organic active agent can cause respiratory system mucous membrane unstable, causes allergy and asthma.
Surface organic active substance is the molecular structure with amphipathic (water wettability and lipophilicity), according to its polar head characteristic, can be divided into anionic surface organic active substance and cationic surface organic active substance.In atmosphere, in aerosol granules, negative ion is not identical with the concentration of cationic surface organic active substance, is that the impact that fine particle is caused of which kind of surperficial organic active substance is large in order to determine, must need separately to measure its concentration.
Although in the world for atmospheric aerosol fine particle (PM
2.5) feature and the environmental impact thereof of surperficial organic active substance carried out a large amount of research, but do not had unified concrete grammar for the concentration determination of yin, yang ion surface organic active substance in atmosphere.Because China's atmospheric environment has the feature of high particle concentration and hyperoxia voltinism, for systematically carrying out the research work about China's atmospheric aerosol fine particle surface organic active substance feature, be necessary first to determine the analytical approach of surperficial organic active substance in the atmosphere that is applicable to China.
Summary of the invention
The technical problem to be solved in the present invention is to provide the measuring method of anionic surface organic active substance concentration in a kind of atmosphere, to reduce or to avoid problem noted earlier.
For solving the problems of the technologies described above, the present invention proposes the measuring method of anionic surface organic active substance concentration in a kind of atmosphere, wherein, described measuring method comprises sample collection pre-treatment step; Sample analysis pre-treatment step; Calibration steps and determination step.
Wherein, described determination step is:
Get PM
2.5sample extracting solution 40mL, in 60mL extraction flask, adds acetate buffer 0.4mL, 0.1mol/L edta solution 0.1mL, the 1mol/L metabisulfite solution 0.25mL of pH=5 successively;
Continue to add 0.2mL ethyl violet solution (0.49g/L), move into 10mL toluene after shaking up again, jolting 1min fully mixes, and notes venting, leaves standstill; After layering, draw toluene in cuvette with syringe, take pure toluene as contrast, measure PM with 615nm wavelength
2.5the absorbance of sample extracting solution.
Preferably, described determination step further comprises the mensuration of the absorbance of following blank test, the steps include: that the ultrapure water of getting 40mL is in 60mL extraction flask, add successively acetate buffer 0.4mL, edta solution 0.1mL, the metabisulfite solution 0.25mL of pH=5; Continue to add 0.2mL ethyl violet solution, move into 10mL toluene after shaking up again, jolting 1min fully mixes, and notes venting, leaves standstill; After layering, draw toluene in cuvette with syringe, take pure toluene as contrast, measure the absorbance of blank test with 615nm wavelength.
Preferably, described measuring method further comprises the steps: to get 11, one group of 100mL volumetric flask, move into respectively 0,3.0,6.0,9.0,12.0,15.0,18.0,21.0,24.0,27.0,30.0 μ L neopelex titers, add water to graticule, shake up, as calibration solution, adopt same step in determination step, only replace extract to do calibration test with described calibration solution, measure the absorbance of calibration test.
Preferably, described measuring method further comprises the steps: after the absorbance of absorbance deduction blank assay of the calibration test recording, and the amount of absorbance and neopelex of drawing is as the calibration curve with reference to numerical value; According to the absorbance of the sample extracting solution of measuring, the amount of the neopelex under the corresponding absorbance checking on described calibration curve, as apparent numerical value, is converted and is obtained the concentration value of anionic surface organic active substance in atmosphere by this apparent numerical value.
Wherein, described sample collection pre-treatment step is:
The quartzy sampling membrane that aluminium-foil paper is wrapped is put into muffle furnace, calcination 4h at 400 ℃ of high temperature;
Quartzy sampling membrane after calcination, in the situation that aluminium-foil paper packing is not sealed off, is placed in to balance 24h in climatic chamber, and wherein temperature is controlled within the scope of 15～30 ℃, and relative humidity is controlled in 45～55% scopes;
The quality of quartzy sampling membrane after the analytical balance that is 0.01mg by degree of accuracy weighing balance;
After weighing, seal quartzy sampling film with aluminium-foil paper, and be sealed in valve bag, put into exsiccator;
Sampling: take out the sampling film of sealing from exsiccator, open aluminium-foil paper, sampling film is placed on to PM
2.5in the film holder of sampling instrument, fix after the cutter of sampling instrument, opening power is sampled, and gathers duration 11.5h;
After having sampled, continue, with aluminium-foil paper sealing, to put into aluminium foil bag, and with valve bag sealing, be placed in balance 24h in climatic chamber (temperature is controlled within the scope of 15～30 ℃, and relative humidity is controlled in 45～55% scopes);
The analytical balance that is 0.01mg by degree of accuracy weighs the quality of the rear quartzy sampling membrane of sampling;
After weighing, continue to seal quartzy sampling film with aluminium-foil paper, and be sealed in aluminium foil bag, again with valve bag sealing, place that refrigerator-20 are ℃ freezing is saved to analysis.
Wherein, described sample analysis pre-treatment step is:
From refrigerator, take out the sampling film of freezing preservation, get 1/4 sampling film, partition, cutting becomes 1cm
2small pieces, put into beaker or PET bottle, add 50mL ultrapure water, make it sampling film small pieces described in complete submergence;
Use ultrasonic cleaner to adopt ultrasound wave to extract PM2.5 sample to the beaker immersed with described sampling film small pieces or PET bottle, wherein ultrasound wave extracts frequency and is made as 40Hz, and initial bath temperature is made as 30 ℃, and ultrasonic extraction time is made as 35min, thereby obtains PM
2.5sample solution;
With PM described in the polycarbonate membrane vacuum filtration in 0.45 μ m aperture
2.5sample solution, the filtrate obtaining is transferred in 100mL volumetric flask, and is settled to graticule with ultrapure water, obtains PM
2.5sample extracting solution 100mL;
By described PM
2.5sample extracting solution 100mL injects in 125mL polypropylene reagent bottle, and stored refrigerated is to analyzing at 4 ℃.
In the atmosphere obtaining through conversion, the concentration of anionic surface organic active substance is with the molal weight C of anionic surface organic active substance in (A) unit volume air
1be expressed as:
In formula: c---the concentration of the apparent neopelex that reads from calibration curve, μ mol/L;
V---the total amount of the air that gathers, m
3;
0.1---PM
2.5the volume of sample extracting solution.
In the atmosphere obtaining through conversion, the concentration of anionic surface organic active substance is with the quality C of anionic surface organic active substance in (B) unit volume air
2be expressed as:
In formula: c---the concentration of the apparent neopelex that reads from calibration curve, μ mol;
V---the total amount of the air that gathers, m3;
0.1---PM
2.5the volume of sample extracting solution, L;
344.4---the mean molecular weight of neopelex.
In the atmosphere obtaining through conversion, the concentration of anionic surface organic active substance is with (C) unit mass PM
2.5the molal weight C of middle anionic surface organic active substance
3be expressed as:
In formula: c---the concentration of the apparent neopelex that reads from calibration curve, μ mol;
M---the gross mass of the aerosol granules that gathers, g;
0.1---PM
2.5the volume of sample extracting solution, L.
In the atmosphere obtaining through conversion, the concentration of anionic surface organic active substance is with (D) unit mass PM
2.5the quality C of middle anionic surface organic active substance
4be expressed as:
In formula: c---the concentration of the apparent neopelex that reads from calibration curve, μ mol;
M---the gross mass of the aerosol granules that gathers, g;
0.1---PM
2.5the volume of sample extracting solution, L;
344.4---the mean molecular weight of neopelex.
The present invention processes before having taked rigorous measure to sample collection, makes every effort to reduce as far as possible impurity, dust granules, environment temperature, the impact of moisture on experiment.Before taking ultrasonic cleaner to sample analysis before sample analysis, process, be subject to the impact of temperature and volatilize for fear of organic principle, set optimum ultrasonic frequency, bath temperature and ultrasonic extraction time simultaneously.The measuring method of anionic surface organic active substance concentration in atmosphere of the present invention, can be by measuring the absorbance of ethyl violet active substance, the apparent concentration of anionic surface organic active substance in using the concentration of the corresponding neopelex that checks on the calibration curve of neopelex as atmosphere, thus the concentration of anionic surface organic active substance in atmosphere can be obtained through converting.Measuring method of the present invention can, for the practical technique of reappearing, be a kind of refinement and the improvement to existing theory after a kind of optimization is provided, make it can be really for the measurement of atmosphere anionic surface organic active substance concentration.
Embodiment
Understand for technical characterictic of the present invention, object and effect being had more clearly, below by the specific embodiment of the present invention, the present invention is described in detail.
In atmosphere of the present invention, the ultimate principle of the measuring method of anionic surface organic active substance concentration is, utilize dye of positive ion ethyl violet and anionic surface organic active substance generation associated reaction, raw empurpled organic associated matter, is referred to as ethyl violet active substance EVAS.This organic associated matter can be extracted by toluene, its colourity is directly proportional to concentration, the absorbance of measuring toluene layer with spectrophotometer at wavelength 615nm place, obtains the concentration of this organic associated matter with this, thereby calculates the concentration that obtains anionic surface organic active substance in atmosphere.
Above-mentioned principle of the present invention is only the description of probability, but when reality is used, need to consider repeatability and the accuracy of measurement result.Wherein need to consider about accuracy aspect the problem how as far as possible to avoid interference, be exactly the precision problem that how to improve measurement in addition.
The existing technical concerns about utilizing ethyl violet and anionic surface organic active substance generation associated reaction to measure be all often the measurement problem in solvent stage, for the organic active substance how obtaining in atmosphere, how to preserve, how to be dissolved in solvent and to go not all to be described later in detail, cause those skilled in the art how cannot to know this application of principle in actual measuring process, therefore, in atmosphere provided by the present invention, the measuring method of anionic surface organic active substance concentration can be for the practical technique of reappearing after being actually a kind of optimization, a kind of refinement and the improvement to existing theory, make it can be really for the measurement of atmosphere anionic surface organic active substance concentration.
Specifically, in atmosphere of the present invention, the measuring method of anionic surface organic active substance concentration is divided and is comprised generally sample collection pre-treatment step from step; Sample analysis pre-treatment step; Calibration steps and determination step be totally five parts, below these steps is elaborated respectively.
The pre-treatment of step 1 sample collection
1.1, the quartzy sampling membrane of aluminium-foil paper being wrapped is put into muffle furnace, calcination 4h at 400 ℃ of high temperature.
The object of high temperature sintering is the impurity of removing in quartzy sampling membrane, in order to avoid affect sample analysis result.Adopt the object of aluminium foil paper bag sampling membrane to have two: one, remove the impurity on aluminium-foil paper; Its two, prevent that the residue on muffle furnace inwall from dropping on filter membrane.
1.2, by the quartzy sampling membrane after calcination in the situation that aluminium-foil paper packing is not sealed off, be placed in balance 24h in climatic chamber, wherein temperature is controlled within the scope of 15～30 ℃, relative humidity is controlled in 45～55% scopes.
The effect of this step is to guarantee that stand-by quartzy sampling membrane is placed under constant temperature and humidity condition, in order to avoid the change of temperature or humidity exerts an influence to the weight of quartz filter.Still there is the existence of air climatic chamber inside, and therefore not sealing off is in order to avoid as much as possible airborne dust to drop on filter membrane, avoids the analysis of sample to produce error.
1.3, the quality of quartzy sampling membrane after the analytical balance that is 0.01mg by degree of accuracy weighing balance.
Sampling film weighing before and after sampling is in order to obtain PM on sampling membrane
2.5the quality of sample, the acquisition of these data is for unit of account quality PM
2.5in mass concentration or the amount of substance concentration of contained anionic surface organic active substance, and study PM
2.5pM in the mass concentration of middle anionic surface organic active substance and atmosphere
2.5the relation of mass concentration.
1.4, after weighing, seal quartzy sampling film with aluminium-foil paper, and be sealed in valve bag, put into exsiccator.
The sealing of sampling film is in order to avoid the particle in atmosphere to drop on film surface as far as possible.Put into exsiccator can guarantee sampling film before sampling in drier environment, avoid atmosphere moisture to have impact to sampling film.
1.5, sampling, gathers duration 11.5h.
Concrete sampling step is: from exsiccator, take out the sampling film of sealing, open aluminium-foil paper, one whole sampling film is placed on to PM
2.5in the film holder of sampling instrument, fix after the cutter of sampling instrument, opening power is sampled.The sampling instrument used of sampling in this programme is large flow PM
2.5sampling instrument, flow is more than or equal to 1m
3/ min, the sampling film that this instrument is corresponding is of a size of 203mm × 254mm, does not need to reduce sampling film when sampling.It is in order to gather PM round the clock that sampling duration is set as 11.5h
2.5sample.That sampling duration affects is collected PM
2.5quality.
According to the collection flow of adopted sampling instrument and collection duration, be easy to calculate the total amount that obtains the air gathering, for example, in this programme, if flow is 1m
3/ min, gathers duration 11.5 hours, the total amount V=1m of the air of collection
3/ min*11.5h*60min/h=690m
3.
1.6, after having sampled, continue, with aluminium-foil paper sealing, to put into aluminium foil bag, and with valve bag sealing, be placed in balance 24h in climatic chamber (temperature is controlled within the scope of 15～30 ℃, and relative humidity is controlled in 45～55% scopes).
The object of above-mentioned steps is to avoid the particle in atmosphere to drop on film surface as far as possible, affects PM
2.5quality.
1.7, the analytical balance that is 0.01mg by degree of accuracy weighs the quality of the rear quartzy sampling membrane of sampling;
Same, in this step, sampling film weighing before and after sampling is in order to obtain PM on filter membrane
2.5the quality of sample, the acquisition of these data is for unit of account quality PM
2.5in mass concentration or the amount of substance concentration of contained anionic surface organic active substance, and study PM
2.5pM in the mass concentration of middle anionic surface organic active substance and atmosphere
2.5the relation of mass concentration.
That is according to the load-bearing quality after the sampling of the load-bearing quality before sampling in step 1.3 and this step, the difference of the two can obtain the gross mass of gathered aerosol granules.
1.8, after weighing, continue to seal quartzy sampling film with aluminium-foil paper, and be sealed in aluminium foil bag, again with valve bag sealing, place that refrigerator-20 are ℃ freezing is saved to analysis.
In this step, because the organic principle in sample is volatile in the time that temperature is higher, in order to guarantee the complete of composition, sample must be saved to analysis under low-temperature condition.But easily damp in refrigerator, in order to prevent the sample moisture absorption, must sealing place.
From finding out for the detailed description of step 1 above, measuring method of the present invention is in order to realize better measurement result, take a set of very rigorous measure to carry out the treatment step before sample collection, make every effort to reduce as far as possible impurity, dust granules, environment temperature, the impact of moisture on experiment, avoid subsequent sample analysis to produce error.Meanwhile, be subject to the impact of temperature and volatilize for fear of the organic principle of sample afterwards of sampling, after adopting, having carried out low temperature preservation, and carried out sealing placement, to avoid the interference of low temperature moisture.
The pre-treatment of step 2 sample analysis
2.1, from refrigerator, take out the sampling film of freezing preservation, get 1/4 sampling film, partition, cutting becomes 1cm
2small pieces, put into beaker (150mL) or PET bottle (50mL), add about 50mL ultrapure water (25 ℃, 18.18M Ω * cm), make it complete submergence sampling film small pieces.
In abovementioned steps, the sampling film that low temperature seal is preserved is one whole (203mm × 254mm), in this step, getting 1/4 sampling film is that under the sampling film cutting that sealing is preserved, 1/4(is of a size of 101.5mm × 127mm), like this can be at the minimum sampling film consumption that guarantees to get on the basis that anionic surface organic active substance can determine.
2.2, use ultrasonic cleaner to adopt ultrasound wave to extract PM to the beaker immersed with described sampling film small pieces or PET bottle
2.5sample, wherein ultrasound wave extracts frequency and is made as 40Hz, and initial bath temperature is made as 30 ℃, and ultrasonic extraction time is made as 35min, thereby obtains PM
2.5sample solution.
Specifically, this step is sample extraction process, is in order to make PM
2.5water-soluble component in sample is soluble in water, thereby obtains PM
2.5sample extracting solution.Sonic oscillation is conducive to course of dissolution, can guarantee that water-soluble component is as much as possible to enter in water, reduces loss.
Ultrasonic extraction frequency, ultrasonic water bath temperature and ultrasonic extraction time, these three parameters directly affect PM
2.5the concentration of anionic surface organic active substance in sample extracting solution is the key factor that affects sample extracting solution absorbance measurement.Confirm 1. PM through experiment
2.5in sample extracting solution, the concentration of anionic surface organic active substance increases with the increase of ultrasonic extraction frequency.Therefore, selecting the maximum operation frequency 40Hz of this experiment institute use ultrasonic cleaner is the ultrasonic extraction frequency of the best.2. in ultrasonic leaching process, have the generation of energy, cause water temperature to change, therefore, ultrasonic leaching process can be set an initial bath temperature.Bath temperature is too low, and the solubleness of anionic surface organic active substance is lower, is unfavorable for leaching process.Too high bath temperature can promote volatilization or the decomposition of anionic surface organic active substance in leaching process, reduces the extraction efficiency of anionic surface organic active substance; In addition, in ultrasonic leaching process, ultrasonic vibration also can bring certain heat energy, and therefore, too high ultrasonic water bath temperature can have a negative impact to the extraction of anionic surface organic active substance.According to experimental result, choose 30 ℃ for best initial bath temperature.3., when ultrasonic extraction time is too short, anionic surface organic active substance can not enter in water completely; And ultrasonic extraction time when long, ultrasonic vibration produces heat energy, causes bath temperature to raise, and has promoted volatilization or the decomposition of anionic surface organic active substance, therefore, selects the ultrasonic extraction time of 35min comparatively suitable.
2.3, with the polycarbonate membrane vacuum filtration PM in 0.45 μ m aperture
2.5sample solution, the filtrate obtaining is transferred in 100mL volumetric flask (clean nutsch filter receiving flask 2-3 time with distilled water, cleaning fluid is also transferred in volumetric flask), and is settled to graticule with ultrapure water, obtains PM
2.5sample extracting solution 100mL.
2.4, PM
2.5sample extracting solution 100mL injects in 125mL polypropylene reagent bottle, and stored refrigerated is to analyzing at 4 ℃.
In this step, due to PM
2.5organic principle in sample extracting solution is volatile in the time that temperature is higher, and in order to guarantee the complete of composition, sample must be saved to analysis at low-temperature condition lower seal.
From finding out for the detailed description of step 2 above, measuring method of the present invention is in order to be dissolved into the organic principle of sample collection as far as possible in ultrapure water, before having taked ultrasonic cleaner to sample analysis, process, be subject to the impact of temperature and volatilize for fear of organic principle simultaneously, optimum ultrasonic frequency, bath temperature and ultrasonic extraction time are set, this is the result that inventor optimizes through creative work, and those skilled in the art cannot obtain any technology enlightenment according to prior art.
Step 3 is calibrated
3.1, get 11, one group of 100mL volumetric flask, move into respectively 0,3.0,6.0,9.0,12.0,15.0,18.0,21.0,24.0,27.0,30.0 μ L neopelex titers, add water to graticule, shake up, as calibration solution.Press the same determination step of subsequent step 4, only replace extract to do calibration test with described calibration solution, measure the absorbance of calibration test.
3.2, then deduct after the blank value (absorbance of zero standard solution) of blank test with the absorbance recording, the amount (μ mol) of absorbance and corresponding neopelex (LAS) of drawing is as the calibration curve with reference to numerical value.
Whether wherein, zero standard solution is in order to obtain blank absorbency, contaminated with the stable of blank absorbency determining apparatus and reagent.That is to say, replacing extract with 100mL ultrapure water is at PM
2.5in sample extracting solution analysis, measuring the sample of blank absorbency, is same implication with zero standard solution, after will describe in detail this.
In this step, measure by neopelex (LAS) titer the absorbance calibration curve contrasting under variable concentrations, for avoiding interference, need to deduct the blank value of blank test.Same, in follow-up determination step, PM
2.5after the absorbance measurement of sample extracting solution, can on calibration curve, check in the concentration value of corresponding neopelex (LAS), using this as apparent value, in order to replace the concentration of anionic surface organic active substance in atmosphere.
Wherein, neopelex (LAS) claim again sodium n-alkylbenzenesulfonate, and its alkyl carbon chain is at C
10～C
13between, average is 12, and mean molecular weight is 344.4, is most popular anionic surfactant, and in State Standard of the People's Republic of China GB7494-37 " mensuration of water quality anionic surfactant ", LAS is selected as reference material.With reference to Chinese scholars to PM
2.5the mensuration of middle anionic surface organic active substance, LAS can also be served as PM
2.5the representative of middle anionic surface organic active substance.
Step 4 is measured
4.1, get PM
2.5sample extracting solution 40mL, in 60mL extraction flask, adds acetate buffer 0.4mL, 0.1mol/L edta solution (EDTA solution) 0.1mL, the 1mol/L metabisulfite solution 0.25mL of pH=5 successively.
In this programme, edta solution (EDTA solution) is screening agent, can avoid PM
2.5the impact of middle heavy metal on absorbance.
4.2, continue to add 0.2mL ethyl violet solution (concentration is 0.49g/L), after shaking up, moving into 10mL toluene (is PM again
2.5the volume ratio of sample extracting solution and toluene extractant is 4:1), jolting 1min fully mixes solution, notes venting, leaves standstill.After layering, draw toluene in cuvette with syringe, take pure toluene as contrast, measure PM with 615nm wavelength
2.5the absorbance of sample extracting solution, calibration solution and blank test.Should use the cuvette of identical light path.After each mensuration, clean cuvette with toluene.
According to the absorbance of the sample extracting solution of measuring, the amount of the neopelex under the corresponding absorbance checking on such alignment curve, as apparent numerical value, is converted and is obtained the concentration value of anionic surface organic active substance in atmosphere by this apparent numerical value.
In this step, during due to extraction vibration, the volatile generation gas of extractant, the pressure in bottle can increase, and therefore notes exitting.
Should be noted that: 1. each batch sample will be done primary blank test and a kind of extraction completely of calibrating solution.2. before measuring at every turn, the toluene extract in oscillation extraction bottle, and wash cuvette with this liquid, then cuvette is full of.At 615nm place, take toluene as reference liquid, the absorbance of working sample extract, calibration solution and blank test.Should use the cuvette of identical light path.After each mensuration, clean cuvette with toluene.3. deduct after the absorbance of blank test with the absorbance of extract, check in the concentration of (neopelex) LAS from calibration curve.
4.3, blank test
Regulation by 4.1,4.2 is carried out blank test, only replaces extract with 40mL ultrapure water.For avoiding error, it should be noted that under test condition, the absorbance of every 10mm optical length blank test should not exceed 0.02, otherwise carefully whether checkout facility and reagent have pollution.
Concrete steps are that (1) gets the ultrapure water of 40mL in 60mL extraction flask, adds successively acetate buffer 0.4mL, 0.1mol/L edta solution 0.1mL, the 1mol/L metabisulfite solution 0.25mL of pH=5; (2) continue to add 0.2mL ethyl violet solution (0.49g/L), move into 10mL toluene (volume ratio that is ultrapure water and toluene extractant is 10:1) after shaking up again, jolting 1min fully mixes, and notes venting, leaves standstill; After layering, draw toluene in cuvette with syringe, take pure toluene as contrast, measure the absorbance of blank test with 615nm wavelength.
The expression of result
Visible according to the detailed description of abovementioned steps 1～4, in atmosphere of the present invention, the measuring method of anionic surface organic active substance concentration is based on above-mentioned steps, can be by measuring the absorbance of ethyl violet active substance (EVAS), the apparent concentration of anionic surface organic active substance in using the concentration of the corresponding neopelex (LAS) that checks on the calibration curve of neopelex (LAS) as atmosphere, thus can obtain respectively following four kinds of concentration results through converting:
(A) molal weight of anionic surface organic active substance in unit volume air;
(B) quality of anionic surface organic active substance in unit volume air;
(C) unit mass PM
2.5the molal weight of middle anionic surface organic active substance;
(D) unit mass PM
2.5the quality of middle anionic surface organic active substance.
Specifically, the molal weight C of anionic surface organic active substance in (A) unit volume air obtaining through conversion
1for:
In formula: c---the concentration of apparent (neopelex) LAS of reading from calibration curve, μ mol/L;
V---the total amount of the air that gathers, m
3; Referring to step 1.5;
0.1---PM
2.5the volume of sample extracting solution.
Through the quality C of anionic surface organic active substance in (B) unit volume air obtaining that converts
2for:
In formula: c---the concentration of apparent (neopelex) LAS of reading from calibration curve, μ mol;
V---the total amount of the air that gathers, m
3; Referring to step 1.5;
0.1---PM
2.5the volume of sample extracting solution, L;
344.4---the mean molecular weight of neopelex (LAS).
Through (C) the unit mass PM that converts and obtain
2.5the molal weight C of middle anionic surface organic active substance
3for:
In formula: c---the concentration of apparent (neopelex) LAS of reading from calibration curve, μ mol/L;
M---the gross mass of the aerosol granules that gathers, g; Referring to step 1.7;
0.1---PM
2.5the volume of sample extracting solution, L.
Through (D) the unit mass PM that converts and obtain
2.5the quality C of middle anionic surface organic active substance
4for:
In formula: c---the concentration of apparent (neopelex) LAS of reading from calibration curve, μ mol;
M---the gross mass of the aerosol granules that gathers, g; Referring to step 1.7;
0.1---the volume of PM2.5 sample extracting solution, L;
344.4---the mean molecular weight of neopelex (LAS).
The foregoing is only the schematic embodiment of the present invention, not in order to limit scope of the present invention.Any those skilled in the art, not departing from equivalent variations, modification and the combination done under the prerequisite of design of the present invention and principle, all should belong to the scope of protection of the invention.
Claims (10)
1. a measuring method for anionic surface organic active substance concentration in atmosphere, is characterized in that, described measuring method comprises sample collection pre-treatment step; Sample analysis pre-treatment step; Calibration steps and determination step;
Wherein, obtain PM by described sample analysis pre-treatment step
2.5sample extracting solution;
Described determination step is:
Get PM
2.5sample extracting solution 40mL, in 60mL extraction flask, adds acetate buffer 0.4mL, 0.1mol/L edta solution 0.1mL, the 1mol/L metabisulfite solution 0.25mL of pH=5 successively;
Continue to add 0.2mL ethyl violet solution (0.49g/L), move into 10mL toluene after shaking up again, jolting 1min fully mixes, and notes venting, leaves standstill; After layering, draw toluene in cuvette with syringe, take pure toluene as contrast, measure PM with 615nm wavelength
2.5the absorbance of sample extracting solution.
2. measuring method as claimed in claim 1, is characterized in that, described determination step further comprises the mensuration of the absorbance of following blank test, the steps include:
Get the ultrapure water of 40mL in 60mL extraction flask, add successively acetate buffer 0.4mL, 0.1mol/L edta solution 0.1mL, the 1mol/L metabisulfite solution 0.25mL of pH=5;
Continue to add 0.2mL ethyl violet solution (0.49g/L), move into 10mL toluene after shaking up again, jolting 1min fully mixes, and notes venting, leaves standstill; After layering, draw toluene in cuvette with syringe, take pure toluene as contrast, measure the absorbance of blank test with 615nm wavelength.
3. measuring method as claimed in claim 2, is characterized in that, described calibration steps is:
Get 11, one group of 100mL volumetric flask, move into respectively 0,3.0,6.0,9.0,12.0,15.0,18.0,21.0,24.0,27.0,30.0 μ L neopelex titers, add water to graticule, shake up, as calibration solution, adopt same step in claim 1, only replace extract to do calibration test with described calibration solution, measure the absorbance of calibration test.
4. measuring method as claimed in claim 3, is characterized in that, further comprises the steps:
After the absorbance of the blank assay recording in the absorbance deduction claim 2 with the calibration test that records, the amount of absorbance and neopelex of drawing is as the calibration curve with reference to numerical value;
According to the absorbance of the sample extracting solution of measuring in claim 1, the amount of the neopelex under the corresponding absorbance checking on described calibration curve, as apparent numerical value, is converted and is obtained the concentration value of anionic surface organic active substance in atmosphere by this apparent numerical value.
5. measuring method as claimed in claim 3, is characterized in that, described sample collection pre-treatment step is:
The quartzy sampling membrane that aluminium-foil paper is wrapped is put into muffle furnace, calcination 4h at 400 ℃ of high temperature;
Quartzy sampling membrane after calcination, in the situation that aluminium-foil paper packing is not sealed off, is placed in to balance 24h in climatic chamber, and wherein temperature is controlled within the scope of 15～30 ℃, and relative humidity is controlled in 45～55% scopes;
The quality of quartzy sampling membrane after the analytical balance that is 0.01mg by degree of accuracy weighing balance;
After weighing, seal quartzy sampling film with aluminium-foil paper, and be sealed in valve bag, put into exsiccator;
Sampling: take out the sampling film of sealing from exsiccator, open aluminium-foil paper, sampling film is placed on to PM
2.5in the film holder of sampling instrument, fix after the cutter of sampling instrument, opening power is sampled, and gathers duration 11.5h;
After having sampled, continue, with aluminium-foil paper sealing, to put into aluminium foil bag, and with valve bag sealing, be placed in balance 24h in climatic chamber (temperature is controlled within the scope of 15～30 ℃, and relative humidity is controlled in 45～55% scopes);
The analytical balance that is 0.01mg by degree of accuracy weighs the quality of the rear quartzy sampling membrane of sampling;
After weighing, continue to seal quartzy sampling film with aluminium-foil paper, and be sealed in aluminium foil bag, again with valve bag sealing, place that refrigerator-20 are ℃ freezing is saved to analysis.
6. measuring method as claimed in claim 1, is characterized in that, described sample analysis pre-treatment step is:
From refrigerator, take out the sampling film of freezing preservation, get 1/4 sampling film, partition, cutting becomes 1cm
2small pieces, put into beaker or PET bottle, add about 50mL ultrapure water, make it sampling film small pieces described in complete submergence;
Use ultrasonic cleaner to adopt ultrasound wave to extract PM to the beaker immersed with described sampling film small pieces or PET bottle
2.5sample, wherein ultrasound wave extracts frequency and is made as 40Hz, and initial bath temperature is made as 30 ℃, and ultrasonic extraction time is made as 35min, thereby obtains PM
2.5sample solution;
With PM described in the polycarbonate membrane vacuum filtration in 0.45 μ m aperture
2.5sample solution, the filtrate obtaining is transferred in 100mL volumetric flask, and is settled to graticule with ultrapure water, obtains described PM
2.5sample extracting solution 100mL;
By described PM
2.5sample extracting solution 100mL injects in 125mL polypropylene reagent bottle, and stored refrigerated is to analyzing at 4 ℃.
7. measuring method as claimed in claim 4, is characterized in that, in the atmosphere obtaining that converts, the concentration of anionic surface organic active substance is with the molal weight C of anionic surface organic active substance in (A) unit volume air
1be expressed as:
In formula: c---the concentration of the apparent neopelex that reads from calibration curve, μ mol/L;
V---the total amount of the air that gathers, m
3;
0.1---PM
2.5the volume of sample extracting solution.
8. measuring method as claimed in claim 6, is characterized in that, in the atmosphere obtaining that converts, the concentration of anionic surface organic active substance is with the quality C of anionic surface organic active substance in (B) unit volume air
2be expressed as:
In formula: c---the concentration of the apparent neopelex that reads from calibration curve, μ mol;
V---the total amount of the air that gathers, m
3;
0.1---PM
2.5the volume of sample extracting solution, L;
344.4---the mean molecular weight of neopelex.
9. measuring method as claimed in claim 4, is characterized in that, in the atmosphere obtaining that converts, the concentration of anionic surface organic active substance is with (C) unit mass PM
2.5the molal weight C of middle anionic surface organic active substance
3be expressed as:
In formula: c---the concentration of the apparent neopelex that reads from calibration curve, μ mol;
M---the gross mass of the aerosol granules that gathers, g;
0.1---PM
2.5the volume of sample extracting solution, L.
10. measuring method as claimed in claim 4, is characterized in that, in the atmosphere obtaining that converts, the concentration of anionic surface organic active substance is with (D) unit mass PM
2.5the quality C of middle anionic surface organic active substance
4be expressed as:
In formula: c---the concentration of the apparent neopelex that reads from calibration curve, μ mol;
M---the gross mass of the aerosol granules that gathers, g;
0.1---PM
2.5the volume of sample extracting solution, L;
344.4---the mean molecular weight of neopelex.
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