CN105842329A - Device and method for representing organic nitrogen in deposit on basis of high resolution mass spectrum - Google Patents
Device and method for representing organic nitrogen in deposit on basis of high resolution mass spectrum Download PDFInfo
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Abstract
The invention provides an experiment device and an experiment method for representing organic nitrogen in deposit on the basis of a high resolution mass spectrum. The experiment device comprises an oscillation device, an ultrasonic device, a centrifuging device, a filtering device, a solid phase extraction column and a high-resolution mass spectrometer which are arranged in sequence. As the deposit has relatively complex components, a response effect which meets the tests is hard to achieve and the detection standard cannot be met when soluble organic nitrogen in the deposit is tested by using the high resolution mass spectrum. According to the experiment device, the oscillation device, the ultrasonic device and the centrifuging device are arranged in sequence for pretreatment on the deposit, so that the response intensity can be effectively improved, a detection baseline can be lowered, high resolution mass spectrum representation of the organic nitrogen in the deposit can be achieved, and high-precision and high-reliability detection on the soluble organic nitrogen in the deposit can be achieved. Basis is provided for deep study on characteristics and release mechanisms of the soluble organic nitrogen in the deposit of the field.
Description
Technical field
The invention belongs to lake organic nitrogen analysis field, be specifically related to a kind of experimental provision and method being characterized settlement soluble organic nitrogen by high resolution mass spectrum.
Background technology
Soluble organic nitrogen (DON) in lake sediment refers to the organic nitrogen that can be extracted by water or saline solution in deposit.The constituent of soluble organic nitrogen is extremely complex, including protein matter, little molecule acid, macromolecular polymer class and lignin, tannic acid etc..The release of soluble organic nitrogen has important impact to lake water quality, is an important nitrogen source of water body in lake, is also to promote microorganism and one of aquatic plants growth, the factor causing lake eutrophication.Therefore, research soluble organic nitrogen content in deposit and distribution character, the nitrogen cycle mechanism understood in water body in lake and process, raising are had for the control of water body in lake with improvement and is of great significance.
In recent years, although the attention rate of settlement soluble organic nitrogen is increased by this area, but actually rare currently for the research of soluble organic nitrogen assay method in deposit.Prior art is when carrying out experimentation to the soluble organic nitrogen in deposit, its content is measured typically by Indirect Determination, concretely comprise the following steps: first pass through persulfuric acid oxidizing process or the content of high-temperature S removal method mensuration solubility total nitrogen (TDN), and measure the total amount of ammoniacal nitrogen and nitrate nitrogen, obtain the content of soluble inorganic nitrogen (TIN), deduct the value of soluble inorganic nitrogen by solubility total nitrogen, thus be calculated the content of soluble organic nitrogen.This Indirect Determination can detect that the content of soluble organic nitrogen, but the constituent of soluble organic nitrogen cannot carry out qualitative detection, thus is difficult to meet the needs of research work.And for lake sediment, it is achieved the difficulty of qualitative detection is, owing to the constituent of deposit is extremely complex, affects the many factors of accuracy in detection, thus be difficult to it is carried out reliably, the detection of high accuracy.
In this case, for the characteristic of soluble organic nitrogen and releasing mechanism in Depth Study deposit, the worker of this area is necessary to seek a kind of precision and reliability is high, can realize the soluble organic nitrogen assay method of qualitative detection.
Summary of the invention
What the present invention solved is to measure the precision of method of settlement soluble organic nitrogen and the problem that reliability is the highest in prior art.And then a kind of be applicable to lake sediment, qualitative determination method of soluble organic nitrogen that accuracy and reliability is high, simple to operate is provided.
The technical scheme that the present invention solves the employing of above-mentioned technical problem is as follows:
The method characterizing settlement soluble organic nitrogen based on high resolution mass spectrum, comprises the following steps:
(1) sediment-water mixed liquor is carried out concussion operation；
(2) the described mixed liquor completing to shake in step (1) operation being carried out ultrasound procedure, supersonic frequency is 60-90Hz, and ultrasonic time is 15-30min；
(3) the described mixed liquor completing ultrasound procedure is centrifuged, centrifugal 5-30min under the rotating speed of 8000-10000r/min；
(4), after completing to be centrifuged, take supernatant and filter, obtain filtrate；
(5) described filtrate is carried out acidification, the pH value of described filtrate is regulated to 1.5-3；Solid-phase extraction column is carried out activation processing, uses the described solid-phase extraction column after activation processing that the filtrate after completing acidification is carried out Solid-Phase Extraction；
(6) solid-phase extraction column completing extraction is carried out drip washing, collect leacheate；
(7) soluble organic nitrogen in high resolution mass spectrometer detection leacheate is used.
The preparation method of the sediment-water mixed liquor in step (1) is: be ground after deposit lyophilization, and the sedimentary particle after grinding crosses 100 mesh sieves, and the sedimentary particle after sieving and water are mixed to form sediment-water mixed liquor；Described sedimentary particle is 1:100-1:10 with the weight ratio of water.
Described sieve after the weight ratio of sedimentary particle and water be 1:50.
The temperature carrying out concussion operation in step (1) is 15-25 °.
Step (4) use the poly tetrafluoroethylene of 0.45 μm described supernatant is filtered.
Solid-phase extraction column described in step (5) is Waters Oasis HLB solid-phase extraction column；The method activating described solid-phase extraction column is: first uses solid-phase extraction column described in methanol rinses, re-uses solid-phase extraction column described in the aqueous hydrochloric acid solution rinse of pH=1.
In step (6), first use solid-phase extraction column described in the aqueous hydrochloric acid solution drip washing of pH=2, remove impurity, re-use solid-phase extraction column described in methanol drip washing, collect methanol leacheate；
In step (7), when using high resolution mass spectrometer to detect the soluble organic nitrogen in described methanol leacheate, first pass through nitrogen and blow described methanol leacheate is concentrated into 0.5-1ml.
The device of settlement soluble organic nitrogen is characterized, including set gradually based on high resolution mass spectrum:
Rocking equipment, for carrying out concussion operation to the mixed liquor of S & W；
Vltrasonic device, for carrying out ultrasound procedure to the described mixed liquor completing concussion operation；
Centrifugal device, for being centrifuged the described mixed liquor completing ultrasound procedure；
Defecator, for filtering the supernatant obtained after described centrifugal device is centrifugal, obtains filtrate；
Solid-phase extraction device, for described filtrate is carried out Solid-Phase Extraction, obtains the leacheate containing soluble organic nitrogen；
High resolution mass spectrometer, for detecting the soluble organic nitrogen in leacheate.
Described defecator is provided with the poly tetrafluoroethylene that aperture is 0.45 μm.
Described solid-phase extraction device is Waters Oasis HLB solid-phase extraction column.
Experimental provision and the method being characterized settlement soluble organic nitrogen by high resolution mass spectrum of the present invention, advantage is:
The present invention utilizes high resolution mass spectrometer to characterize lake sediment, described high resolution mass spectrometer is fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS), the advantage with pinpoint accuracy, high accuracy, it is capable of, from molecular level, complex material is carried out constituent sign, it is achieved the comprehensive assurance to complex material.
The composition of lake sediment is extremely complex, when utilizing high resolution mass spectrum to measure soluble organic nitrogen therein, it tends to be difficult to be met the response effect of mensuration, do not reach the standard of detection.The experimental provision being characterized lake sediment soluble organic nitrogen by high resolution mass spectrum of the present invention, is disposed with rocking equipment, Vltrasonic device, centrifugal device, defecator, solid-phase extraction column and high resolution mass spectrometer.The present invention by setting gradually concussion, ultrasonic, centrifugal device carries out pre-treatment to described deposit, it is possible to be effectively improved response intensity, reduce detection baseline, thus realize the sign of the high resolution mass spectrum to settlement soluble organic nitrogen.
In order to make of the present invention to characterize the experimental provision of settlement soluble organic nitrogen and the technical scheme of method and clearer by high resolution mass spectrum, below in conjunction with concrete drawings and the specific embodiments, the present invention is further elaborated.
Accompanying drawing explanation
It is the spectrogram that obtains of experimental technique being characterized settlement soluble organic nitrogen by high resolution mass spectrum described in the embodiment of the present invention 1 as shown in Figure 1.
It is the spectrogram that obtains of experimental technique being characterized settlement soluble organic nitrogen by high resolution mass spectrum described in the embodiment of the present invention 2 as shown in Figure 2；
It is the spectrogram that obtains of experimental technique being characterized settlement soluble organic nitrogen by high resolution mass spectrum described in the embodiment of the present invention 3 as shown in Figure 3；
It is the scattergram of high resolution mass spectrum detection error in the embodiment of the present invention 2 as shown in Figure 4；
It is the spectrogram that obtains of experimental technique being characterized settlement soluble organic nitrogen by high resolution mass spectrum described in comparative example 1 of the present invention as shown in Figure 5；
It is the spectrogram that obtains of experimental technique being characterized settlement soluble organic nitrogen by high resolution mass spectrum described in comparative example 2 of the present invention as shown in Figure 6.
Detailed description of the invention
Embodiment 1
The experimental provision used in the present embodiment includes setting gradually: isothermal vibration instrument, for the mixed liquor of S & W carries out concussion operation；Vltrasonic device, for carrying out ultrasound procedure to the described mixed liquor completing concussion operation；Centrifuge, for being centrifuged the described mixed liquor completing to shake ultrasound procedure；Defecator, for filtering the supernatant obtained after described centrifugal device is centrifugal, described defecator is provided with the poly tetrafluoroethylene that aperture is 0.45 μm；Solid-phase extraction device, for described filtrate is carried out Solid-Phase Extraction, obtains the leacheate containing soluble organic nitrogen, and described solid-phase extraction device is provided with Waters Oasis HLB solid-phase extraction column, and the specification of described Waters Oasis HLB solid-phase extraction column is 3ml；High resolution mass spectrometer (FT-ICR MS), for detecting the soluble organic nitrogen in leacheate.
The present embodiment chooses (the 100 ° of 9'59E of lake region in the middle part of Erhai；25 ° of 45'43N, 0-10cm) as sampled point, gather the deposit on top layer with the gloomy sampler of Peter.Select the surface deposit of 0-2cm as sample, use the experimental provision described in the present embodiment that the soluble organic nitrogen in described deposit is characterized, specifically comprise the following steps that
(1) take deposit freeze-dried after be ground, cross 100 mesh sieves, weigh 0.5g sedimentary particle sample and be placed in 100ml centrifuge tube, add 50ml ultra-pure water, the ratio of sedimentary particle and water is 1:100；Being shaken under isothermal vibration instrument by sediment-water mixture, shaking set of time in the present embodiment is 16h, and the concussion rotating speed of isothermal vibration instrument is 220r/min, and temperature is 20 DEG C；As selectable embodiment, be may be configured as 10-20h the concussion time of described sediment-water mixture, concussion rotating speed is 200-300r/min, and temperature is preferably arranged to 20-25 DEG C.
(2) the described mixed liquor completing to shake in step (1) operation being carried out ultrasound procedure, supersonic frequency is 80 hertz (Hz), and ultrasonic time is 15 minutes (min)；
(3) by complete ultrasonic after the mixture of S & W take out after be immediately placed in centrifuge, centrifugal 10min under 8000r/min (rev/min)；
(4) extract the supernatant after being centrifuged and cross 0.45 μm teflon membrane filter, obtain filtrate standby；
(5) described filtrate is carried out acidification, use the hydrochloric acid of pH=1 to regulate the pH value of filtrate to 1.5；Waters Oasis HLB solid-phase extraction column is carried out activation processing, and concrete grammar, for first using solid-phase extraction column described in 20ml methanol rinses, re-uses solid-phase extraction column described in the aqueous hydrochloric acid solution rinse of 20ml pH=2；Use the described solid-phase extraction column after activation processing that the described filtrate after completing acidification carried out post to process, complete Solid-Phase Extraction；
(6) after completing Solid-Phase Extraction, first use solid-phase extraction column described in the aqueous hydrochloric acid solution drip washing of 20mlpH=2, remove impurity；Re-use solid-phase extraction column described in the methanol drip washing of 12ml, extraction soluble organic nitrogen on solid-phase extraction column is carried out eluting, collects methanol leacheate；
(7) described methanol leacheate being carried out nitrogen to blow, described leacheate is concentrated into 0.5ml, use the soluble organic nitrogen in high resolution mass spectrometer detection leacheate, the high resolution mass spec spectrogram that the present embodiment obtains in the positive-ion mode is as shown in Figure 1；By being analyzed spectrogram peak, the ratio going out peak number overall with detection material for DON is 1846/3940=46.8%.
Data processing and inversion: the mass spectrometric data obtained by high resolution mass spectrometer (FT-ICR MS) imports MFC software, by MFC, element is allocated, Origin is utilized to carry out data mapping analysis, process according to gained spectral data, utilize excel computed in software to go out DBE value, O/C, H/C, N/C, KM (CH2)、KMD(CH2)、KM(COO)、KMD(COO).Concrete computational methods are:
A. under negative ion mode:
O/C=n (O)/n (C)；H/C=n (H)/n (C)；N/C=n (N)/n (C), wherein n (*) represents the atom number of *；
KM(CH2)=(theory mass+1.00794)/1.0011178, theory mass refers to the molecular mass calculated；KM (*) represents the Kendrick mass calculated based on *；
KMD(CH2)=ABS (round [KM (CH2)]-KM(CH2))；
KM (COO)=(theory mass+1.00794) * 1.000231207；
KMD (COO)=ABS (round [KM (COO)]-KM (COO)).
B. under positive ion mode:
O/C=n (O)/n (C)；N/C=n (N)/n (C)；
Time in solution containing Na: H/C=n (H)/n (C), during without Na: H/C=[n (H)-1]/n (C)；
KM(CH2)=(theory mass+1.00794)/1.0011178；
KMD(CH2)=ABS (round [KM (CH2)]-KM(CH2))；
KM (COO)=(theory mass+1.00794) * 1.000231207；
KMD (COO)=ABS (round [KM (COO)]-KM (COO)).
It should be noted that under negative ion mode, normal molecular to be changed into, need plus a H；Under positive ion mode, subtracting H time in solution without Na, during containing Na, nothing is added or subtracted.
After calculating data, first substance for calculation percent abundance (i.e. divided by abundance peak), again data are carried out subregion and screening, filter out the material compositions such as CHO, CHON, CHOS, CHONS, then data analysis is carried out, pass through data analysis, on the one hand may determine that the classification of material, such as protein matter, little molecule acid, macromolecular polymer class and lignin, tannic acid etc. (concrete judgement scope is shown in Table 1), and substantially judge relative proportion according to the abundance ratio between material；Analysis further for data may be used without analysis method common in the art, such as Van Krevelen diagrams (Fan Shi figure) analytic process.Material change contrast can be carried out in course of reaction by Fan Shi figure, carry out product analysis, further relate to the catabolite change of material during reactions change.Can also need according to analyzing, spectral data be carried out category division, as a example by nitrogen, the classes such as CHO, CHON, CHOS, CHONS can be divided into, and make in, in figure, to be analyzed with different labeled by different classes of material.
Table 1
Wherein * AI is aromatic index
Embodiment 2
The experimental provision used in the present embodiment includes setting gradually: isothermal vibration instrument, for the mixed liquor of S & W carries out concussion operation；Vltrasonic device, for carrying out ultrasound procedure to the described mixed liquor completing concussion operation；Centrifuge, for being centrifuged the described mixed liquor completing to shake ultrasound procedure；Defecator, for filtering the supernatant obtained after described centrifugal device is centrifugal, described defecator is provided with the poly tetrafluoroethylene that aperture is 0.45 μm；Solid-phase extraction device, for described filtrate is carried out Solid-Phase Extraction, obtains the leacheate containing soluble organic nitrogen, and described solid-phase extraction device is provided with Waters Oasis HLB solid-phase extraction column, and the specification of described Waters Oasis HLB solid-phase extraction column is 3ml；High resolution mass spectrometer (FT-ICR MS), for detecting the soluble organic nitrogen in leacheate.
The present embodiment chooses (the 100 ° of 9'59E of lake region in the middle part of Erhai；25 ° of 45'43N, 0-10cm) as sampled point, gather the deposit on top layer with the gloomy sampler of Peter.Select the surface deposit of 2-4cm as sample, use the experimental provision described in the present embodiment that the soluble organic nitrogen in described deposit is characterized, specifically comprise the following steps that
(1) take deposit freeze-dried after be ground, cross 100 mesh sieves, weigh 1g sediment sample and be placed in 100ml centrifuge tube, add 50ml ultra-pure water, the weight ratio of sediment sample and water is 1:50；Carrying out sediment-water mixture under isothermal vibration instrument shaking 16h, concussion rotating speed is 220r/min, and temperature is 20 DEG C；
(2) the described mixed liquor completing to shake in step (1) operation being carried out ultrasound procedure, supersonic frequency is 90Hz, and ultrasonic time is 30min；
(3) mixture of the S & W after completing ultrasound procedure is immediately placed in centrifuge after taking out, centrifugal 5min under 10000r/min；
(4) extract the supernatant after being centrifuged and cross 0.45 μm teflon membrane filter, obtain filtrate standby；
(5) described filtrate is carried out acidification, use the hydrochloric acid of pH=1 to regulate the pH value of described filtrate to 2；Waters Oasis HLB solid-phase extraction column is carried out activation processing, and concrete grammar, for first using solid-phase extraction column described in 20ml methanol rinses, re-uses solid-phase extraction column described in the aqueous hydrochloric acid solution rinse of 20ml pH=2；Use the described solid-phase extraction column after activation processing that the described filtrate after completing acidification carried out post to process, complete Solid-Phase Extraction；
(6) after Solid-Phase Extraction completes, first use solid-phase extraction column described in the aqueous hydrochloric acid solution drip washing of 20ml pH=2, re-use solid-phase extraction column described in the methanol drip washing of 12ml, collect methanol leacheate；
(7) described methanol leacheate being carried out nitrogen to blow, described methanol leacheate is concentrated into 1ml, use the soluble organic nitrogen in high resolution mass spectrometer detection leacheate, the high resolution mass spec spectrogram that the present embodiment obtains in the positive-ion mode is as shown in Figure 2；By being analyzed spectrogram peak, the ratio going out peak number overall with detection material for DON is 2148/4610=46.5%.
Embodiment 3
The experimental provision used in the present embodiment includes setting gradually: isothermal vibration instrument, for the mixed liquor of S & W carries out concussion operation；Vltrasonic device, for carrying out ultrasound procedure to the described mixed liquor completing concussion operation；Centrifuge, for being centrifuged the described mixed liquor completing to shake ultrasound procedure；Defecator, for filtering the supernatant obtained after described centrifuge, described defecator is provided with the poly tetrafluoroethylene that aperture is 0.45 μm；Solid-phase extraction device, for described filtrate is carried out Solid-Phase Extraction, obtains the leacheate containing soluble organic nitrogen, and described solid-phase extraction device is provided with Waters Oasis HLB solid-phase extraction column, and the specification of described Waters Oasis HLB solid-phase extraction column is 3ml；High resolution mass spectrometer (FT-ICR MS), for detecting the soluble organic nitrogen in leacheate.
The present embodiment chooses (the 100 ° of 9'59E of lake region in the middle part of Erhai；25 ° of 45'43N, 0-10cm) as sampled point, gather the deposit on top layer with the gloomy sampler of Peter.Select the surface deposit of 4-6cm as sample, use the experimental provision described in the present embodiment that the soluble organic nitrogen in described deposit is characterized, specifically comprise the following steps that
(1) take deposit freeze-dried after be ground, cross 100 mesh sieves, weigh 5g sediment sample and be placed in 100ml centrifuge tube, add 50ml ultra-pure water, the weight ratio of sediment sample and water is 1:10；Carrying out sediment-water mixture under isothermal vibration instrument shaking 16h, concussion rotating speed is 220r/min, and temperature is 20 DEG C；
(2) carrying out ultrasound procedure by completing the described mixed liquor of concussion operation in step (1), supersonic frequency is 90Hz, and ultrasonic time is 30min；
(3) by complete ultrasonic after the mixture of S & W take out after be immediately placed in centrifuge, centrifugal 5min under 10000r/min；
(4) extract the supernatant after being centrifuged and cross 0.45 μm teflon membrane filter, obtain filtrate standby；
(5) described filtrate is carried out acidification, use the hydrochloric acid of pH=1 to regulate the pH value of described filtrate to 3；Waters Oasis HLB solid-phase extraction column is carried out activation processing, and concrete grammar, for first using 20ml methanol to carry out solid-phase extraction column described in rinse, re-uses solid-phase extraction column described in the aqueous hydrochloric acid solution rinse of 20mlpH=2；Use the described solid-phase extraction column after activation processing that the described filtrate after completing acidification carried out post to process, complete Solid-Phase Extraction；
(6) after Solid-Phase Extraction completes, first use solid-phase extraction column described in the aqueous hydrochloric acid solution drip washing of 20mlpH=2, remove impurity, re-use solid-phase extraction column described in the methanol drip washing of 12ml, collect methanol leacheate；
(7) described methanol leacheate being carried out nitrogen to blow, described leacheate is concentrated into 1ml, use the soluble organic nitrogen in high resolution mass spectrometer detection leacheate, the high resolution mass spec spectrogram that the present embodiment obtains in the positive-ion mode is as shown in Figure 3；By being analyzed spectrogram peak, the ratio going out peak number overall with detection material for DON is 1965/4298=45.71%.
High resolution mass spec Fig. 1-3 that deposit described in embodiment 1-3 obtains, signal to noise ratio ＞ 10, baseline values is low, has higher response intensity (intensity), swarming effective, it is possible to meet detection demand well.And its error level is relatively low, there is preferable accuracy.As a example by embodiment 2, its detection error e rror (ppm) scattergram as shown in Figure 4, as can be known from Fig. 4, its detection error e rror (ppm) be concentrated mainly on ± 1 in the range of.
Comparative example
Comparative example 1
Experimental provision in this comparative example and experimental technique with embodiment 1, unique unlike Waters Oasis HLB solid-phase extraction column is replaced with Cleanert IC-Ag/H solid-phase extraction column, be measured with identical sample in embodiment 1.The spectrogram obtained is as shown in Figure 5.
As can be seen from Figure 5, the spectrogram obtained when using Cleanert IC-Ag/H solid-phase extraction column, compared with comparative example 1, the spectrogram baseline in baseline values comparative example to be far above 1, and intensity is more weak, it is difficult to meet examination criteria.
Comparative example 2
Experimental provision in this comparative example with embodiment 1, specific experiment method is:
(1) take deposit freeze-dried after be ground, cross 100 mesh sieves, weigh 10g sedimentary particle
Sample is placed in 100ml centrifuge tube, adds 50ml ultra-pure water, carries out shaking 16h under isothermal vibration instrument, and concussion rotating speed is 220r/min, and temperature is 20 DEG C；
(2) carrying out ultrasound procedure by completing the described mixed liquor of concussion operation in step (1), supersonic frequency is 80Hz, and ultrasonic time is 15-30min；
(3) by complete ultrasonic after the mixture of S & W take out after be immediately placed in centrifuge, centrifugal 10min under 8000r/min；
(4) extract the supernatant after being centrifuged and cross 0.45 μm teflon membrane filter, obtain filtrate standby；
(5) described filtrate is carried out acidification, use the hydrochloric acid of pH=1 to regulate the pH value of described filtrate to 1.5；Waters Oasis HLB solid-phase extraction column is carried out activation processing, and concrete grammar, for first using solid-phase extraction column described in 20ml methanol rinses, re-uses solid-phase extraction column described in the aqueous hydrochloric acid solution rinse of 20mlpH=2；Use the described solid-phase extraction column after activation processing that the described filtrate after completing acidification carried out post to process, complete Solid-Phase Extraction；
(6) after completing Solid-Phase Extraction, first use solid-phase extraction column described in the aqueous hydrochloric acid solution drip washing of 20mlpH=2, re-use solid-phase extraction column described in the methanol drip washing of 12ml, collect methanol leacheate；
(7) described leacheate being carried out nitrogen to blow, described leacheate is concentrated into 1ml, use the soluble organic nitrogen in high resolution mass spectrometer detection leacheate, the spectrogram obtained is as shown in Figure 6.
By comparative example 1 and comparative example 2, when the weight ratio of sedimentary particle Yu water is 1:5, the spectrogram obtained compared to embodiment 1, the spectrogram baseline in baseline values comparative example to be far above 1, and intensity is more weak.The present invention is 1:100-1:10 by arranging the weight ratio of deposit and water, at the Detection results that can reach excellence after ultrasonic.
Embodiment described above only have expressed the several embodiments of the present invention, and it describes more concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that, for the person of ordinary skill of the art, without departing from the inventive concept of the premise, it is also possible to make some deformation and improvement, these broadly fall into protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claim.
Claims (10)
1. based on high resolution mass spectrum characterize settlement soluble organic nitrogen method, it is characterised in that include with
Lower step:
(1) sediment-water mixed liquor is carried out concussion operation；
(2) the described mixed liquor completing to shake in step (1) operation is carried out ultrasound procedure, supersonic frequency
For 60-90Hz, ultrasonic time is 15-30min；
(3) the described mixed liquor completing ultrasound procedure is centrifuged, at the rotating speed of 8000-10000r/min
Under be centrifuged 5-30min；
(4), after completing to be centrifuged, take supernatant and filter, obtain filtrate；
(5) described filtrate is carried out acidification, the pH value of described filtrate is regulated to 1.5-3；To solid phase
Extraction column carries out activation processing, after using the described solid-phase extraction column after activation processing to completing acidification
Filtrate carries out Solid-Phase Extraction；
(6) solid-phase extraction column completing extraction is carried out drip washing, collect leacheate；
(7) soluble organic nitrogen in high resolution mass spectrometer detection leacheate is used.
The method characterizing settlement soluble organic nitrogen based on high resolution mass spectrum the most according to claim 1,
It is characterized in that, the preparation method of the sediment-water mixed liquor in step (1) is: by deposit lyophilization
After be ground, will grind after sedimentary particle cross 100 mesh sieves, the sedimentary particle after sieving and water
It is mixed to form sediment-water mixed liquor；Described sedimentary particle is 1:100-1:10 with the weight ratio of water.
The method characterizing settlement soluble organic nitrogen based on high resolution mass spectrum the most according to claim 1,
It is characterized in that, described in sieve after the weight ratio of sedimentary particle and water be 1:50.
The method characterizing settlement soluble organic nitrogen based on high resolution mass spectrum the most according to claim 1,
It is characterized in that, the temperature carrying out concussion operation in step (1) is 15-25 °.
The method characterizing settlement soluble organic nitrogen based on high resolution mass spectrum the most according to claim 1,
It is characterized in that, step (4) uses the poly tetrafluoroethylene of 0.45 μm described supernatant is filtered.
The method characterizing settlement soluble organic nitrogen based on high resolution mass spectrum the most according to claim 1,
It is characterized in that, solid-phase extraction column described in step (5) is Waters Oasis HLB solid-phase extraction column；Right
The method that described solid-phase extraction column carries out activating is: first uses solid-phase extraction column described in methanol rinses, re-uses
Solid-phase extraction column described in the aqueous hydrochloric acid solution rinse of pH=1.
The method characterizing settlement soluble organic nitrogen based on high resolution mass spectrum the most according to claim 1,
It is characterized in that, in step (6), first use solid-phase extraction column described in the aqueous hydrochloric acid solution drip washing of pH=2,
Remove impurity, re-use solid-phase extraction column described in methanol drip washing, collect methanol leacheate；
In step (7), organic in the solubility using high resolution mass spectrometer to detect in described methanol leacheate
During nitrogen, first pass through nitrogen and blow described methanol leacheate is concentrated into 0.5-1ml.
8. characterize the device of settlement soluble organic nitrogen based on high resolution mass spectrum, it is characterised in that include depending on
Secondary setting:
Rocking equipment, for carrying out concussion operation to the mixed liquor of S & W；
Vltrasonic device, for carrying out ultrasound procedure to the described mixed liquor completing concussion operation；
Centrifugal device, for being centrifuged the described mixed liquor completing ultrasound procedure；
Defecator, for filtering the supernatant obtained after described centrifugal device is centrifugal, is filtered
Liquid；
Solid-phase extraction device, for described filtrate is carried out Solid-Phase Extraction, obtains containing soluble organic nitrogen
Leacheate；
High resolution mass spectrometer, for detecting the soluble organic nitrogen in leacheate.
The device characterizing settlement soluble organic nitrogen based on high resolution mass spectrum the most according to claim 1,
It is characterized in that, described defecator is provided with the poly tetrafluoroethylene that aperture is 0.45 μm.
The dress characterizing settlement soluble organic nitrogen based on high resolution mass spectrum the most according to claim 1
Put, it is characterised in that described solid-phase extraction device is Waters Oasis HLB solid-phase extraction column.
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| CN106546694A (en) * | 2016-11-01 | 2017-03-29 | 青海盐湖工业股份有限公司 | A kind of method for determining organic amine content |
| CN110007035A (en) * | 2019-04-23 | 2019-07-12 | 海南医学院 | The detection device of a variety of alkaline drug abuse and application in a kind of degradation biological sample |
| CN110057899A (en) * | 2019-04-14 | 2019-07-26 | 北京工业大学 | The system and method for anaerobic ammonium oxidation sludge extracellular polymeric molecular structure characterization |
| CN112150044A (en) * | 2020-11-04 | 2020-12-29 | 南京大学 | High-resolution mass spectrum-based method for evaluating nitrogen-containing organic matter removal effect of sewage plant |
| CN113624831A (en) * | 2021-08-05 | 2021-11-09 | 广东农工商职业技术学院 | Method for separating enriched sediment organic nitrogen and determining isotope and content |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106546694A (en) * | 2016-11-01 | 2017-03-29 | 青海盐湖工业股份有限公司 | A kind of method for determining organic amine content |
| CN110057899A (en) * | 2019-04-14 | 2019-07-26 | 北京工业大学 | The system and method for anaerobic ammonium oxidation sludge extracellular polymeric molecular structure characterization |
| CN110057899B (en) * | 2019-04-14 | 2022-01-28 | 北京工业大学 | System and method for characterizing molecular structure of extracellular polymer of anaerobic ammonia oxidation sludge |
| CN110007035A (en) * | 2019-04-23 | 2019-07-12 | 海南医学院 | The detection device of a variety of alkaline drug abuse and application in a kind of degradation biological sample |
| CN110007035B (en) * | 2019-04-23 | 2021-09-14 | 海南医学院 | Detection equipment for degrading multiple alkaline abuse drugs in biological detection material and application |
| CN112150044A (en) * | 2020-11-04 | 2020-12-29 | 南京大学 | High-resolution mass spectrum-based method for evaluating nitrogen-containing organic matter removal effect of sewage plant |
| CN112150044B (en) * | 2020-11-04 | 2022-04-22 | 南京大学 | High-resolution mass spectrum-based method for evaluating nitrogen-containing organic matter removal effect of sewage plant |
| CN113624831A (en) * | 2021-08-05 | 2021-11-09 | 广东农工商职业技术学院 | Method for separating enriched sediment organic nitrogen and determining isotope and content |
| CN113624831B (en) * | 2021-08-05 | 2024-05-10 | 广东农工商职业技术学院 | Method for separating and enriching organic nitrogen in sediment and measuring isotope and content |
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