CN102253156B - Method for determining eight kinds of odorous substances in water simultaneously - Google Patents
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Abstract
The invention belongs to the technical field of natural environment water quality monitoring and discloses a method for determining eight kinds of common odorous substances in water simultaneously through use of a method of combining purge-and-trap and gas chromatography/mass spectrometry. The method can be adopted to determine eight kinds of common odorous substances such as dimethyl sulfide (DMS), dimethyl trisulfide (DMTS), 2-isopropyl-3-methoxy pyrazine (IPMP), 2-isobutyl-3-methoxy pyrazine (IBMP), 2-methyl isobornyl (MIB), beta-cyclocitral, geosmin (GSM) and beta-ionone in water simultaneously. Any report on the method for determining the eight kinds of substances in one step is not present yet. The method disclosed by the invention fills the gap and can be used for quantitatively analyzing the eight kinds of odorous substances in water in one step, so that the detection efficiency is greatly increased.
Description
Technical field
The present invention relates to natural surroundings Water quality monitoring technical field, be specifically related to a kind of method of simultaneously measuring eight kinds of odorous substances in waters.
Background technology
Smell substance is because its foul smell has great impact to tap water and aquatic products, and causes huge economic loss.In recent years, people increase increasingly to the complaint of landscape water body, tap water and aquatic products, especially at the algal bloom burst period.Except the 2-methyl isoborneol received much concern, native olfactorin, 2-isopropyl-3-IBMP and 2-isobutyl-3-IBMP, decompose in algae dimethyl sulfide, NSC 97324, beta-cyclocitral and the beta-irisone etc. that produce in the process of rotting and also more and more receive publicity.Due to the often outburst simultaneously of these smell substances, about the removal of peculiar smell in source, bio-transformation and the plant of these smell substances, in the water environment field, be subject to gradually extensive concern.Therefore, it is considerable finding a kind of method of effective detection.
At present, a large amount of reports about odorous substances in water enrichment concentration technique is arranged.Such as, utilize solvent extraction to concentrate and can analyze 2-methyl isoborneol, native olfactorin, beta-cyclocitral and beta-irisone, and can reach and receive the detection limit (P.B.Johnsen of grams per liter, J.C.Kuan, J.Chromatogr.409 (1987) 337, M.L.Bao, K.Barbieri, D.Burrini, O.Griffini, F.Pantani, Water Res.31 (1997) 1719, H.J.Kim, K.Kim, N.S.Kim, D.S.Lee, J.Chromatogr.A 902 (2000) 389).Yet this technology is but because the boiling point of most of solvents will, higher than the boiling point (37 ℃) of dimethyl sulfide, therefore be difficult to be applicable to the enrichment to dimethyl sulfide.The closed hoop lift-off technology is widely used in the analysis of trace smell substance in water environment, the method is quite ripe for the analysis of 2-methyl isoborneol and native olfactorin in water body, and still, the method is lost time very much, complex operation, and exist again solvent to disturb for the analysis of dimethyl sulfide.The membrane extraction technology equally also can be carried out trace analysis (M.J.Yang, S.Harms, Y.Z.Luo to 2-methyl isoborneol and native olfactorin, J.Pawliszyn, Anal.Chem.66 (1994) 1339, A.K.Zander, P.Pingert, Water Res.31 (1997) 301).Although this technology, for the closed hoop lift-off technology, is greatly improved at detection limit with on analysis time, still inapplicable for lower boiling dimethyl sulfide.Solid phase extraction techniques is widely used in the extraction of smell substance equally, but same because leaching process is oversize, analysis efficiency is low, also inapplicable for lower boiling material.Along with scientific and technical development, the empty solid-phase microextraction of solid-phase microextraction and Top becomes smell substance abstraction technique at present popular water.These two kinds of technology are all easy, quick, cheap applicable, also do not need solvent.Solid-phase microextraction is also all quite outstanding when analyzing NSC 97324,2-isopropyl-3-IBMP, 2-isobutyl-3-IBMP, 2-methyl isoborneol, native olfactorin, beta-cyclocitral and beta-irisone.Yet, select a suitable sorbing material can analyze most of smell substances with regard to suitable difficulty simultaneously, also quite low for the sensitivity of lower boiling smell substance.Purge and trap, as an abstraction technique that does not need solvent, can be analyzed multiple smell substance simultaneously quickly and easily.
The current report about smell substance in employing Puffing and trapping extraction water body also seldom, is not more reported the NSC 97324, beta-cyclocitral and the beta-irisone that produce while with purge and trap, detecting algal bloom simultaneously.K.Awaji for example, in R.Briggs (Eds), Instrumentation, Control and Automation of Water and Wastewater Treatment and Transport Systems, Pergamon Press Ltd, Oxford, 1990, pp.639; M.W.Buettner, G.A.Schelk, Water Quality Technology Conference, Proceedings-PTS1 AND 2-Advances in Water Analysis And Treatment, Amer.Water Works Assoc., Denver, 1992, pp.1083; S.W.Lloyd, J.M.Lea, P.V.Zimba, C.C.Grimm, Water Res.32 (1998) 2140; A.Salemi, S.Lacorte, H.Bagheri, D.Barcelo, J.Chromatogr.A 1136 (2006) 170. reports, with 2-methyl isoborneol and the native olfactorin in the purge and trap condensed water.W.Wardencki, J.Microcolumn Sep.7 (1995) 51. and X.H.Cheng, E.Peterkin, the concentrated dimethyl sulfide of Water Environ.Res.79 (2007) 571. application purge and trap, A.Salemi, S.Lacorte, H.Bagheri, D.Barcelo, J.Chromatogr.A 1136 (2006) 170) reported with the concentrated 2-of analysis of purge and trap isopropyl-3-IBMP and 2-isobutyl-3-IBMP.At A.Salemi, S.Lacorte, H.Bagheri, D.Barcelo, J.Chromatogr.A 1136 (2006) 170) report in, will add 5 gram sodium chloride in 20 ml waters, then purge 20 minutes under the helium gas flow of 35 ml/min, under this condition, the detection limit of 2-isopropyl-3-IBMP, 2-isobutyl-3-IBMP, 2-methyl isoborneol, native olfactorin is at 2ng/L.But shortcoming is clearly, sodium chloride can be taken by sweep gas to the top of scavenging duct, is then rushed in pipeline and valve, often can cause obstruction and the spool wearing and tearing of pipeline.Equally, sample temperature is consideration not, and different sample temperatures is remarkable for the effectiveness affects purged.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, provide a kind of method of purge and trap-gas chromatography mass spectrometry of utilizing to measure eight kinds of common odorous substances in waters simultaneously.The method energy Simultaneous Determination dimethyl sulfide (DMS), NSC 97324 (DMTS), 2-isopropyl-3-IBMP (IPMP), 2-isobutyl-3-IBMP (IBMP), 2-methyl isoborneol (MIB), beta-cyclocitral (β-Cyclocitral), native olfactorin (GSM) and these eight kinds of common odorous substances in waters of beta-irisone (β-Ionone).Prior art adopts diverse ways to divide several times above-mentioned eight kinds of material demands according to different separately character (polarity, boiling point) and measures, not yet have above-mentioned eight kinds of reports that material adopts a kind of method once to measure at present, the inventive method has been filled up this blank, disposable quantitative test above-mentioned eight kinds of odorous substances in waters, greatly improved detection efficiency.
Therefore, based on this goal of the invention, a kind of method step that utilizes full-automatic purging trapping-gas chromatography combined with mass spectrometry simultaneously to measure eight kinds of odorous substances in waters is as follows:
(1) connection of instrument and setting thereof
A, connection: the full-automatic trapping sample concentration instrument that purges is connected with the communication of gas phase, referring to the operation manual (version 2 .0) of Eclipse purge and trap sample concentration instrument, the 22nd page to the 24th page.Purge and trap sample concentration instrument is connected with the gas circuit of gas phase, referring to Eclipse purge and trap sample concentration instrument operation manual (version 2 .0), and the 48th page to the 50th page.
B, instrument setting:
A, purge and trap sample concentration instrument: (U.S. OI analytical instrument company, filler is TENAX (2,6-diphenylene oxide polymer, specific surface area: 35m to select No. 7 collecting traps
2/ g, nonpolar, the maximum temperature that can bear is 350 ℃, 24cm), and 25 milliliters of scavenging ducts, 40 ml/min high-purity nitrogens (purity 99.999%) purge 12 minutes, high-purity helium (purity 99.999%) desorption 4 minutes; Sample is heated to 55 ℃; 80 ℃ of scavenging duct stationary installations; 250 ℃ of six-way valves; Water supervisor when purging 110 ℃, during desorption 0 ℃, while curing 240 ℃; When the trapping well purges 30 ℃, during pre-desorption 170 ℃, during desorption 180 ℃, while curing 200 ℃; 270 ℃ of transfer lines.After purging end, instrument cleans three times automatically.
B, gas chromatograph-mass spectrometer: Shimadzu GCMS-QP2010Plus (Japanese Shimadzu company), HP-5MS UI capillary column (30m * 0.25mm * 0.25 μ m, U.S. Agilent company) carrier gas is helium.Gas phase condition arranges as follows: 270 ℃ of injection ports, total flow 14 ml/min, post flow 1 ml/min, split ratio 10: 1; The furnace temperature program is as follows: 50 ℃ keep 2 minutes, and 10 ℃/minute are warming up to 150 ℃, and then 5 ℃/minute are warming up to 220 ℃.The mass spectrum condition is as follows: 200 ℃ of ion source temperatures, 250 ℃ of interface temperature, 1.69 minutes volume mute times, electron bombardment ionization source (70eV).All the other conditions generate by instrument hands-off tuning.
Instrument connects after having arranged the mixed standard solution that at first uses eight kinds of odorous substances in waters (hereinafter described standard reserving solution two is diluted to 500 and receives grams per liter) to be measured retention time (seeing accompanying drawing 1) and determines selection ion (seeing attached list 1) under the full scan pattern, then selection ion and retention time are set in the mass spectrum condition.
(2) making of typical curve
A, standard items:
Dimethyl sulfide (purity>99.0%, Japanese TCI company, Tokyo);
NSC 97324 (purity>98.0%, Japanese TCI company, Tokyo);
Beta-cyclocitral (purity>90.0%, SIGMA, Shanghai);
2-isopropyl-3-IBMP (purity>98.0%, J& K, Beijing);
2-isobutyl-3-IBMP (purity>99.0%, Acros Organics, the U.S.);
Beta-irisone (purity>96.0%, Acros Organics, the U.S.).
Take respectively each 0.01 gram of above six kinds of materials and be dissolved in 100 ml methanol, the mixed standard solution A that to be prepared into concentration be 100 ug/ml.
2-methyl isoborneol (purity>99.8%, SIGMA, Shanghai);
Soil olfactorin (purity>99.9%, SIGMA, Shanghai);
Be mixed with above-mentioned two kinds of materials the mixed standard solution B (solvent is methyl alcohol) that 2-methyl isoborneol and native olfactorin concentration are 100 ug/ml.
Mixed standard solution A, B all seal 4 ℃ of preservations.
B, get each 50 microlitres of hybrid standard A and B respectively, with ultrapure water, be settled to 10 milliliters, get again 1 milliliter after mixing and be settled to 50 milliliters with ultrapure water, obtain the standard reserving solution two that eight kinds of material concentrations are 10 micrograms per litre.Standard reserving solution two is prepared before use.
C, with ultrapure water, standard reserving solution two is diluted to concentration and is respectively 1,5,10,50,100,200,300, the 500 series standard solution production standard curves of receiving grams per liter.
After d, instrument detect, take concentration as horizontal ordinate, take peak area as ordinate, draw respectively the typical curve of eight kinds of smell substances.
The typical curve that accompanying drawing 2 is 2-methyl isoborneol (MIB).
(3) detection of water sample
A, water sample Making and banking: water sample is through filter membrane (the glass fiber filter paper GF/C that Britain whatman company produces, aperture 1.2 μ m, thickness 260 μ m) filter to remove particle, filtrate proceeds to (40 milliliters, 40 ml sample bottle, spiral cover, PTFE face pellosil pad (being all that U.S. OI analytical instrument company produces), U.S. OI analytical instrument company produces).Receive grams per liter to mark-on 20 and 300 in filtrate respectively with standard reserving solution two, 4 ℃ of preservations of filtrate and mark-on liquid;
B, detection: the filtrate after filtrate and mark-on is directly analyzed this eight kinds of odorous substances in waters with purge and trap-Gc/ms Analyser:
The selection ion of eight kinds of smell substances of table 1
The a-quota ion
(4) utilize typical curve to calculate the concentration of these eight kinds of odorous substances in waters.
Advantage and the beneficial effect of the inventive method are as follows:
1. the automaticity of the inventive method is high, between the gas chromatograph-mass spectrometer (GCMS) (GC-MS) that is used for the purge and trap of example enrichment and detects for odorous substances in water, synchronization mechanism is arranged, smell substance in sample is resent to GC-MS and is detected all and synchronously carry out continuously through purging absorption, thermal desorption, and in other method except full automatic solid-phase microextraction, sample preparation and upper GC-MS detect and separately carry out, and detection efficiency is very low.
2. the inventive method is highly sensitive, and the detection limit of eight kinds of odorous substances in waters is all below the odor threshold of this smell substance, and therefore, the inventive method can be measured the smell substance that sense organ is difficult to aware.
3. the method for the inventive method based on purge and trap-gas chromatography mass spectrometry measured eight kinds of smell substances in water body simultaneously, neither needs solvent, easy to be quick again, all has very high sensitivity for these eight kinds of materials simultaneously.The most important thing is eight kinds of smell substances with different volatility and polarity that this method produces in the time of can measuring algal bloom simultaneously.The inventive method is to being widely used in detecting the dynamic change of eight kinds of smell substances in the natural water body that breaks out wawter bloom.
The accompanying drawing explanation
Fig. 1 utilizes the total ion current figure of smell substance standard items under the full scan pattern.The retention time of dimethyl sulfide (DMS), NSC 97324 (DMTS), 2-isopropyl-3-IBMP (IPMP), 2-isobutyl-3-IBMP (IBMP), 2-methyl isoborneol (MIB), beta-cyclocitral (β-Cyclocitral), native olfactorin (GSM) and beta-irisone (β-Ionone) is followed successively by 1.897min, 6.957min, 8.997min, 10.354min, 10.471min, 11.017min, 13.835min, 15.039min.
The typical curve that Fig. 2 is 2-methyl isoborneol (MIB).
Fig. 3 is that eight kinds of smell substance dimethyl sulfides (DMS) in the water body of East Lake, NSC 97324 (DMTS), 2-isopropyl-3-IBMP (IPMP), 2-isobutyl-3-IBMP (IBMP), 2-methyl isoborneol (MIB), beta-cyclocitral (β-Cyclocitral), native olfactorin (GSM) and beta-irisone (β-Ionone) are at the total ion current figure selected under ion scan.
Embodiment
Below in conjunction with specific embodiment, the inventive method is described in further detail:
A kind of method of simultaneously measuring eight kinds of odorous substances in waters, its step is as follows:
(1) connection of instrument and setting thereof
A, connection: the full-automatic trapping sample concentration instrument that purges is connected with the communication of gas phase, referring to Eclipse purge and trap sample concentration instrument operation manual (version 2 .0), and the 22nd page to the 24th page.Purge and trap sample concentration instrument is connected with the gas circuit of gas phase, referring to Eclipse purge and trap sample concentration instrument operation manual (version 2 .0), and the 48th page to the 50th page.
B, instrument setting:
A, purge and trap sample concentration instrument: (U.S. OI analytical instrument company, filler is TENAX (2,6-diphenylene oxide polymer), specific surface area: 35m to select No. 7 collecting traps
2/ g, nonpolar, the maximum temperature that can bear is 350 ℃, length 24cm), 25 milliliters of scavenging ducts, 40 ml/min high-purity nitrogens (purity 99.999%) purge 12 minutes, high-purity helium (purity 99.999%) desorption 4 minutes; Sample is heated to 55 ℃; 80 ℃ of scavenging duct stationary installations; 250 ℃ of six-way valves; Water supervisor when purging 110 ℃, during desorption 0 ℃, while curing 240 ℃; When the trapping well purges 30 ℃, during pre-desorption 170 ℃, during desorption 180 ℃, while curing 200 ℃; 270 ℃ of transfer lines.After purging end, instrument cleans three times automatically.
B, gas chromatograph-mass spectrometer: Shimadzu GCMS-QP2010Plus (Japanese Shimadzu company), HP-5MS UI capillary column (30m * 0.25mm * 0.25 μ m, U.S. Agilent company) carrier gas is helium.Gas phase condition arranges as follows: 270 ℃ of injection ports, total flow 14 ml/min, post flow 1 ml/min, split ratio 10: 1; The furnace temperature program is as follows: 50 ℃ keep 2 minutes, and 10 ℃/minute are warming up to 150 ℃, and then 5 ℃/minute are warming up to 220 ℃.The mass spectrum condition is as follows: 200 ℃ of ion source temperatures, 250 ℃ of interface temperature, 1.69 minutes volume mute times, electron bombardment ionization source (70eV).All the other conditions generate by instrument hands-off tuning.
At first the Application standard product are measured retention time (seeing accompanying drawing 1) and are determined and select ion to see attached list 1 under the full scan pattern, then selection ion and retention time are set in the mass spectrum condition.
(2) making of typical curve
A, standard items:
Dimethyl sulfide (purity>99.0%, Japanese TCI company, Tokyo);
NSC 97324 (purity>98.0%, Japanese TCI company, Tokyo);
Beta-cyclocitral (purity>90.0%, SIGMA, Shanghai);
2-isopropyl-3-IBMP (purity>98.0%, J& K, Beijing);
2-isobutyl-3-IBMP (purity>99.0%, Acros Organics, the U.S.);
Beta-irisone (purity>96.0%, Acros Organics, the U.S.).
Take respectively each 0.01 gram of above six kinds of materials and be dissolved in 100 ml methanol, the mixed standard solution A that to be prepared into concentration be 100 ug/ml.
2-methyl isoborneol (purity>99.8%) and native olfactorin (purity>99.9%) concentration are the methyl alcohol mixed standard solution B (SIGMA, Shanghai) of 100 ug/ml.
Mixed standard solution A, B all seal 4 ℃ of preservations.
B, get each 50 microlitres of mixed standard solution A and B respectively, with ultrapure water, be settled to 10 milliliters, get again 1 milliliter after mixing and be settled to 50 milliliters with ultrapure water, the standard reserving solution two that to obtain concentration be 10 micrograms per litre.Standard reserving solution two is prepared before use.
C, with ultrapure water, standard reserving solution two is diluted to concentration and is respectively 1,5,10,50,100,200,300, the 500 series standard solution production standard curves of receiving grams per liter.
After d, instrument detect, take concentration as horizontal ordinate, take peak area as ordinate, draw the typical curve of eight kinds of smell substances.
The linear relationship of the typical curve of eight kinds of smell substances is all good:
Dimethyl sulfide R=0.99967
NSC 97324 R=0.99971
2-isopropyl-3-IBMP R=0.99989
2-isobutyl-3-IBMP R=0.99937
2-methyl isoborneol R=0.99999
Beta-cyclocitral R=0.99993
Soil olfactorin R=0.99993
Beta-irisone R=0.99986
The typical curve that accompanying drawing 2 is 2-methyl isoborneol (MIB).
(3) detection of water sample
A, water sample Making and banking: (Britain whatman company produces the GF/C film to get Wuhan East Lake (in August, 2010 sampling) water sample filtering membrane, aperture 1.2 μ m, thickness 260 μ m) filter to remove particle, filtrate proceeds to (40 milliliters, 40 ml sample bottle, spiral cover, PTFE face pellosil pad, U.S. OI analytical instrument company).From the water sample filtrate in East Lake, receive grams per liter to mark-on 20 and 300 in filtrate respectively with standard reserving solution two, 4 ℃ of preservations of filtrate and mark-on liquid;
B, detection: the filtrate after filtrate and mark-on is directly analyzed this eight kinds of odorous substances in waters with purge and trap-Gc/ms Analyser:
The total ion current figure that accompanying drawing 3 is eight kinds of smell substance dimethyl sulfides (DMS) in the water sample of East Lake, NSC 97324 (DMTS), 2-isopropyl-3-IBMP (IPMP), 2-isobutyl-3-IBMP (IBMP), 2-methyl isoborneol (MIB), beta-cyclocitral (β-Cyclocitral), native olfactorin (GSM) and beta-irisone (β-Ionone).
(4) utilize typical curve to calculate the concentration of these eight kinds of odorous substances in waters.
The concentration of methyl ether in the water sample of East Lake (DMS) is: 13ng/L;
The concentration of NSC 97324 (DMTS) is: 1ng/L;
The concentration of 2-isopropyl-3-IBMP (IPMP) is: do not detect;
The concentration of 2-isobutyl-3-IBMP (IBMP) is: do not detect;
The concentration of 2-methyl isoborneol (MIB) is: 3ng/L;
The concentration of β-cyclocitral (β-Cyclocitral) is: 4ng/L;
The concentration of soil olfactorin (GSM) is: 1ng/L;
The concentration of alpha, beta-lonone (β-Ionone) is: 16ng/L.
(5) checking of method
Linearity, degree of accuracy, repeatability and detection limit to purge and trap gaseous mass spectrum combined instrument detection method of the present invention are verified.Be applied to the analysis of lake water sample simultaneously, comprise matrix effect, robustness and the recovery.
A, typical curve, repeatability and detection limit: the range of linearity from 1 to 500 is received grams per liter, is provided with eight concentration gradients.The typical curve of eight kinds of materials calculates and shows, linearly dependent coefficient (R) all is greater than 0.999, and the residual error scope is 83% to 124%.Repeatability is less than 7.72% (6 repetitions) when 100 receive grams per liter, is less than 8.59% (6 repetitions) when 2 receive grams per liter, meets accuracy requirement.Equal at 3 o'clock in signal to noise ratio (S/N ratio), detection limit is received grams per liter (mark liquid concentration be 10 receive grams per liter) 0.08～1.5, in Table 2.
The analytical applications of b, lake water sample: be the practicality of check the method, matrix effect is to consider.Process lake water and lake water add standard specimen and compare (East Lake water sample), significantly do not disturb.Thereby there do not is a matrix effect.The recovery needs checking equally.After East Lake lake water water sample is filtered respectively mark-on 20 and 300 receive grams per liter, calculate respectively its recovery of standard addition after detection, result shows that recovery of standard addition is between 80.54%～114.91%, when 20 receive grams per liter, RSD is less than 10.5%, 300 RSD while receiving grams per liter and is less than 5.5%, in Table 3.From the analysis result in 10 lakes of deifferent regions.China in Table 4.
Table 2: detection limit (signal to noise ratio (S/N ratio) equals 3), relative standard deviation all (repeats for six times)
Table 3: the relative standard deviation of East Lake water sample mark-on (repeating for 5 times), the recovery and uncertainty
Table 4: smell substance concentration in ten eutrophic lakes
" a " means to be above standard the curve upper limit, the sample concentration then calculated after dilution detects again,
"-" means not detect.
C, result show that the method is applicable to the analysis of trace smell substance in lake water.
The calculating of uncertainty: the preparation that maximum potential uncertainty is standard specimen and the processing of sample, because other uncertainty is very little, can ignore, only need to consider repeated u (F), the uncertainty of recovery u (R) and relative residual error u (E).According to the statistical method of Urachem/Citac Guide, result sees table 3, and computing formula is as follows:
U＝[u(F)
2+u(R)
2+u(E)
2]
1/2×100％
Wherein, u (E)=(X-X
i)/X, x is the standard specimen concentration of preparation; X
istandard specimen concentration by curve calculation.
Claims (1)
1. a method of simultaneously measuring eight kinds of water body in lake smell substances is characterized in that step is as follows:
(1) connection of instrument and setting thereof
A, connection: the full-automatic trapping sample concentration instrument that purges is connected with the gas circuit of the gas chromatography of gas chromatograph-mass spectrometer (GCMS);
B, instrument setting:
A, purge and trap sample concentration instrument: select No. 7 collecting traps of U.S. OI analytical instrument company, filler is TENAX, 25 milliliters of scavenging ducts, 40 ml/min high purity nitrogen purge 12 minutes, attached 4 minutes of high-pure helium qi exhaustion; Sample is heated to 55 ℃; 80 ℃ of scavenging duct stationary installations; 250 ℃ of six-way valves; Water supervisor when purging 110 ℃, during desorption 0 ℃, while curing 240 ℃; When the trapping well purges 30 ℃, during pre-desorption 170 ℃, during desorption 180 ℃, while curing 200 ℃; 270 ℃ of transfer lines, after purging end, instrument cleans three times automatically;
B, gas chromatograph-mass spectrometer (GCMS): HP-5MS UI capillary column: 30m * 0.25mm * 0.25 μ m, carrier gas is helium; Gas phase condition arranges as follows: 270 ℃ of injection ports, total flow 14 ml/min, post flow 1 ml/min, split ratio 10:1; The furnace temperature program is as follows: 50 ℃ keep 2 minutes, and 10 ℃/minute are warming up to 150 ℃, and then 5 ℃/minute are warming up to 220 ℃; The mass spectrum condition is as follows: 200 ℃ of ion source temperatures, and 250 ℃ of interface temperature, 1.69 minutes volume mute times, electron bombardment ionization source 70eV, all the other conditions generate by instrument hands-off tuning;
After the instrument connection has arranged, at first use the mixed standard solution of eight kinds of odorous substances in waters measure retention time and determine and select ion under the full scan pattern, then selection ion and retention time are set in the mass spectrum condition;
Described eight kinds of odorous substances in waters are dimethyl sulfide, NSC 97324,2-isopropyl-3-IBMP, 2-isobutyl-3-IBMP, 2-methyl isoborneol, beta-cyclocitral, native olfactorin and beta-irisone;
(2) making of typical curve
A, each 0.01 gram of standard items that takes respectively dimethyl sulfide, NSC 97324, beta-cyclocitral, 2-isopropyl-3-IBMP, 2-isobutyl-3-IBMP and six kinds of materials of beta-irisone are dissolved in 100 ml methanol, the mixed standard solution A that to be prepared into concentration be 100 ug/ml;
Preparation 2-methyl isoborneol and each concentration of native olfactorin are the mixed standard solution B of 100 ug/ml, and solvent is methyl alcohol;
Mixed standard solution A, B all seal 4 ℃ of preservations;
B, quantitatively dilute with ultrapure water after mixed standard solution A and B equal-volume are mixed, obtain the standard reserving solution two that eight kinds of material concentrations are 10 micrograms per litre;
C, with ultrapure water, standard reserving solution two is diluted to concentration and is respectively 1,5,10,50,100,200,300, the 500 series standard solution production standard curves of receiving grams per liter;
After d, instrument detect, take concentration as horizontal ordinate, peak area is ordinate, draws respectively the typical curve of eight kinds of smell substances;
(3) detection of water sample
A, water sample Making and banking: membrane filtration is to remove particle after filtration for water sample, and filtrate proceeds to 40 ml sample bottles;
Described filter membrane is the glass fiber filter paper GF/C that Britain whatman company produces, aperture 1.2 μ m, thickness 260 μ m;
B, detection: filtrate is directly analyzed this eight kinds of odorous substances in waters with purge and trap-Gc/ms Analyser;
(4) utilize typical curve to calculate the concentration of these eight kinds of odorous substances in waters.
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| CN102721640B (en) * | 2012-05-28 | 2014-05-14 | 浙江大学 | Method for rapidly measuring number of microcystis cells in water sample |
| CN103063775B (en) * | 2012-12-28 | 2014-06-18 | 青岛啤酒股份有限公司 | Method for detecting dimethyl trisulfide in beer |
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