CN101339133A - Calcareous sediment organophosphorus extraction and constitutes analysis method - Google Patents
Calcareous sediment organophosphorus extraction and constitutes analysis method Download PDFInfo
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- CN101339133A CN101339133A CNA2008100219047A CN200810021904A CN101339133A CN 101339133 A CN101339133 A CN 101339133A CN A2008100219047 A CNA2008100219047 A CN A2008100219047A CN 200810021904 A CN200810021904 A CN 200810021904A CN 101339133 A CN101339133 A CN 101339133A
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Abstract
The invention relates to an extracting and composition analyzing method of organic phosphorus of calcareous sediment. The method is characterized in that acidic EDTA solution is used for flushing and centrifuging the sediment; a traditional extraction method that the mixed solution of NaOH and EDTA (NaOH plus EDTA) is used for oscillating, extracting and centrifuging the sediment; a part of the extracted solution of NaOH plus EDTA is tested by a spectrometer to determine the total phosphorus; the rest extracted solution is concentrated; ultimately, the <31>P nuclear magnetic resonance technique (<31>P-NMR) is used for analyzing the composition of organic phosphorus in the extracted solution.
Description
Technical field
The present invention relates to the evaluation analysis to lake rimstone phosphorus, particularly a kind of calcareous sediment organophosphorus extracts and constitutes analysis method, also is fit to high ocean and the river deposit of calcium content.
Background technology
Phosphorus is the restricted factor that eutrophication takes place in the lake.The phosphorus overwhelming majority in the lake is accumulated in sediment.Sediment phosphorus can discharge in a large number to water body under proper condition, causes water quality deterioration and body eutrophication.The release potentiality of sediment phosphorus are main relevant with the occurrence patterns of phosphorus in sediment.At present, about the form of inorganic states phosphorus in sediment and the active relative maturation of analysis thereof, and the research means of organophosphorus is also lacked very much with evaluation method.Rely on traditional method for photometric analysis only can obtain the total amount information of organophosphorus.Using new method and quantitatively obtain the composition information of organophosphorus in the sediment, is to estimate organic phosphorus active and to the key of water systems'phosphorus contribution.
Sediment organophosphorus is formed general two steps of needs of obtaining of information to be finished: 1) organophosphorus in the sediment is extracted; 2) form with the organophosphorus in the instrumental analysis extract.The extracting method over-borrowing of sediment organophosphorus total amount is in view of the soil subject.The general highly basic of selecting is as extraction agent, and its principle is at high OH
-Produce electrostatic repulsion between organophosphorus and the oxide under the race condition, the high-valence cationic bridge that combines with organophosphorus is by low price Na
+Replace, impel organophosphorus to discharge from oxide surface.For improving the extraction efficiency of sediment organophosphorus, the researcher further adds complexometric reagent or material to strong base solution, as resin or ethylenediamine tetraacetic acid, by the complexing polyvalent metal ion, promotes the dissolving of sediment organophosphorus.At present, be extensive use of the extraction agent of the mixed solution (NaOH+EDTA) of NaOH and ethylenediamine tetraacetic acid as sediment organophosphorus.This extraction agent is when being applied to the low sediment of calcium content, and the extraction effect of organophosphorus is comparatively desirable.Yet, when being applied to the high sediment of calcium content,, cause the extraction efficiency of sediment organophosphorus on the low side unusually because calcium and phosphorus precipitate under alkali condition.
The method of measuring the organophosphorus composition has liquid phase
31The P nuclear magnetic resonance (
31P-NMR), technology such as grenz ray fluorescence spectrum, high performance liquid chromatography, enzymolysis.Wherein,
31The P-NMR technology is because of sample pre-treatments is simple, component is differentiated and waited advantage to come into one's own fully.This technology is by the more soil field that is applied to, and is generalized to sedimental analysis gradually.Because
31P-NMR is the hyposensitivity technology, and its analytical effect depends on the extraction effect of back organophosphorus.For rimstone, because of the NaOH+EDTA extraction agent on the low side to the extraction efficiency of sediment organophosphorus,
31The P-NMR analytical effect is unsatisfactory.Especially for some low type organophosphorus of content, by
31The P-NMR technology is obtained its information bigger difficulty.In addition, paramagnetic metal ion (mainly being ferric iron and manganese) too high levels can make in the extract
31Spectral line broadening when P-NMR analyzes overlaps between the different component, causes component identification and quantification difficult.
Summary of the invention
The purpose of this invention is to provide a kind of calcareous sediment organophosphorus extracts and constitutes analysis method, this method is at the low problem of calcareous sediment organophosphorus extraction ratio, use edta solution (pH=4.5) that sediment is washed earlier, use NaOH+EDTA that the organophosphorus in the sediment is extracted in conjunction with classic method again, by
31The P nuclear magnetic resonance (
31P-NMR) technology is further analyzed the composition of organophosphorus in the extract.This method is applicable to the rimstone of metallic element Ca/ (Fe+Al)＞0.7.
Above-mentioned purpose of the present invention is achieved through the following technical solutions: a kind of calcareous sediment organophosphorus extracts and constitutes analysis method, it is characterized in that adopting earlier the edta solution of slant acidity sediment to be washed also centrifugal, use the mixed solution (NaOH+EDTA) of NaOH and ethylenediamine tetraacetic acid as extraction agent in conjunction with traditional extraction process again, sediment vibrated extract and centrifugal, get part NaOH+EDTA extract then, use the spectrophotometer total phosphorus, to remain the NaOH+EDTA extract and concentrate, use at last
31The P nuclear magnetic resonance technique (
31P-NMR) proportion of composing of all types of phosphorus compounds in the analysis extract is by calculating the composition content information that further obtains organophosphorus in the sediment.
The ratio of its metallic element calcium of said rimstone and iron and aluminium content is greater than 0.7; Its pH of the edta solution of said slant acidity is 4.5; Said spectrometer adopts inductive coupling plasma emission spectrograph.
Concrete steps are as follows:
(1) sediment sample is prepared: gather fresh sediment, and earlier at the freezing 4h that is no less than of ultra low temperature freezer, vacuum drying then, final sample is through grinding, sieving, and the room temperature sealing is preserved;
(2) flushing: sediment sample is mixed vibration with the edta solution of slant acidity in centrifuge tube, the centrifugal then supernatant liquor of outwelling.
(3) organophosphorus extracts: continue to add the mixed liquor of NaOH+EDTA to centrifuge tube, vibration, centrifugal after, get sub-fraction supernatant liquor Instrument measuring total phosphorus;
(4) concentrate: will remain extract and pour revolving bottle into, rotary evaporation in vacuo concentrates, with the freezing preservation of concentrate;
(5)
31The P-NMR sample is prepared: takes out the concentrating sample that is freezing state, at room temperature rises again to liquid state, and centrifugal then removal precipitation, and in solution, add heavy water, carry out
31P-NMR analyzes;
(6)
31P-NMR analyzes: nuclear magnetic resonance analyser is BRUKER AV400,
31P-NMR analyzes and to carry out under 161.98MHz, adopts BRUKER standard chamber BBO probe, about 20 ℃ of environment temperatures, the single sample scanning times between 17000～26000, analysis time between 12h to 18h,
31The P chemical shift is with 85%H
3PO
4Be benchmark, form to differentiate chemical shift with reference to the phosphorus standard specimen, be respectively phosphonic acids 20ppm, aromatic diester 7.4ppm, orthophosphoric acid 6～7ppm, orthophosphoric acid monoesters 4～6ppm, phosphatidase 11～3ppm, DNA 0ppm, pyrophosphoric acid-3.5～-4.5ppm, the terminal phosphorus-3 of poly phosphorus～-4ppm and poly phosphorus in the middle of phosphorus-17～-19ppm;
(7) calculate: obtain by area integral
31The proportion of composing of all types of phosphorus compounds in the P-NMR wave spectrum calculates the concentration of all types of phosphorus compounds according to the extract total phosphorus, calculates the composition content of organophosphorus in the unit weight sediment according to sediment weight.
Advantage of the present invention and beneficial effect: at first,, reduce the content of these ions in the NaOH+EDTA extract, avoid by paramagnetic metal ions such as most of ferrimanganics in the edta solution complexing removal sediment of slant acidity
31The defective that the spectral line broadening that too much causes because of above-mentioned ion when P-NMR analyzes, graph-spectrum quality descend; Secondly, by the most of calcium ion in the edta solution complexing removal sediment of slant acidity, calcium and phosphorus produce precipitation when avoiding next step NaOH+EDTA to extract, and impel a large amount of calcium combined state organophosphoruss to become weak combined state simultaneously, and are extracted by NaOH+EDTA.Above measure can significantly increase the extracted amount of sediment organophosphorus, and makes
31The analytical effect of P-NMR significantly improves.Above-mentioned calcareous sediment organophosphorus extracts and the composition measuring method also is applicable to ocean and the river deposit that calcium content is high.
Description of drawings
Fig. 1 classic method and the inventive method compare the extraction ratio of sediment total phosphorus;
Fig. 2 tradition is extracted with extracting method of the present invention the sediment organophosphorus extraction ratio is compared;
Fig. 3 classic method and the inventive method to the extraction of sediment phosphorus with
31The all types of phosphorus compound content that P-NMR obtains after analyzing relatively;
Fig. 4 classic method and the inventive method to the extraction of sediment phosphorus with
31Nuclear magnetic resonance map after P-NMR analyzes relatively.
Embodiment
Required reagent
1.50mM ethylenediamine tetraacetic acid (EDTA): take by weighing 18.6g EDTA (Na salt) and be dissolved into 1.0 liters of deionized waters.
2.0.25M NaOH+50mM EDTA mixed liquor: take by weighing 10g NaOH and 18.6g EDTA (Na salt) and be dissolved into 1.0 liters of deionized waters.
3. heavy water (H
2O
2)
Equipment needed thereby
1. reciprocating type vibrating machine
2. hydro-extractor
3. Rotary Evaporators
4. water-bath type vacuum pump
5. inductive coupling plasma emission spectrograph (ICP-AES)
6.Bruker AV400 nuclear magnetic resonance analyser
Operation steps
1, sediment sample is prepared: gather fresh sediment, at-80 ℃ of freezing 4h of ultra low temperature freezer, be placed on vacuum drying on the freeze drier then.Dry good sediment sample is through grinding, sieve (100 order), and the room temperature sealing is preserved.
2, flushing: claim 2.0g (dry weight) sediment to the 100ml centrifuge tube, add 80ml EDTA (50mM), 25 ℃ of vibrations are after 30 minutes, and centrifugal 20 minutes of 10000rpm removes the upper strata stillness of night.
3, organophosphorus extracts: continue to add 16ml 0.25M NaOH+50mM EDTA extraction agent to centrifuge tube, 25 ℃ vibrated 16 hours, and 10000rpm keeps solution after centrifugal 20 minutes.Get the 2ml extract, adopt the total phosphorus in the ICP-AES analytical solution.
4, concentrate: the residue extract is put into the 100ml revolving bottle, concentrates at 28 ℃ of rotary evaporations, adopts the water-bath type vacuum pump to vacuumize simultaneously, and extract is concentrated into 1ml, and concentrate is put into-15 ℃ of freezing preservations.
5,
31The P-NMR sample is prepared: take out the concentrating sample that is freezing state, at room temperature rise again to liquid state, 10000rpm removes precipitation after centrifugal 10 minutes, adds 10% heavy water in solution, carries out
31P-NMR analyzes.
6,
31P-NMR analyzes: nuclear magnetic resonance analyser is BRUKER AV400,
31P-NMR analyzes and carries out under 161.98MHz, adopts BRUKER standard chamber 5mm BBO probe, 90 ° of pulses, 2 seconds time delay, acquisition time 0.5s, 20 ℃ of environment temperatures.The single sample scanning times is between 17000～26000, and analysis time is between 12h to 18h.
31The P chemical shift is with 85%H
3PO
4Be benchmark, form to differentiate chemical shift with reference to the phosphorus standard specimen, be respectively phosphonic acids (20ppm), aromatic diester (7.4ppm), orthophosphoric acid (6-7ppm), orthophosphoric acid monoesters (4-6ppm), phosphatide (1-3ppm), DNA (0ppm), pyrophosphoric acid (3.5～-4.5ppm), the terminal phosphorus of poly phosphorus (3～-phosphorus 4ppm) and in the middle of the poly phosphorus (17～-19ppm).
7, calculate: obtain by area integral
31The proportion of composing of all types of phosphorus compounds in the P-NMR wave spectrum calculates the concentration of all types of phosphorus compounds according to the extract total phosphorus, calculates the composition content of organophosphorus in the unit weight sediment according to sediment weight.
Embodiment: the NW China part lake sediments such as Qinghai Lake, Er Hai and Qinghai-Tibet unknown lake of selecting Shahu Lake, Gansu, western big lake, Qinghai Province, its sediment character all is Ca/ (Fe+Al)＞0.7, according to this invention step sediment organophosphorus is extracted, and use
31P-NMR analyzes its organophosphorus content and composition.Simultaneously by classic method with each sediment sample weighing 2g in the centrifuge tube of 100ml, directly add 16m 0.25M NaOH+50mM EDTA extraction agent, all the other step 3-7 according to this invention extract and measure sediment organophosphorus.Classic method and the inventive method analytical effect are compared as follows:
1, the inventive method is extracted apparently higher than tradition rimstone total phosphorus, organophosphorus extraction ratio.
The present invention is 1.2～2.6 times of traditional method for extracting rate to the extraction ratio of sediment total phosphorus, the extraction ratio of sediment organophosphorus is 1.6-3.7 a times that tradition is extracted, this shows that no matter at sediment total phosphorus or organophosphorus, this invention is extracted all and extracted (Fig. 1 and Fig. 2) significantly better than tradition.
2, the inventive method makes
31Organophosphorus is formed kind among the P-NMR obviously increases, and graph-spectrum quality also is higher than traditional extraction process (Fig. 3 and Fig. 4).Among Fig. 4, A is a traditional extraction process, and B is an extracting method of the present invention, a, phosphonic acids; B, aromatic diester; C, orthophosphoric acid; The d monoesters; E, phosphatide; F, DNA; G, the terminal phosphorus of poly phosphorus; H, pyrophosphoric acid; Phosphorus in the middle of the i, poly phosphorus.
Adopt this method to extract the organophosphorus of rimstone, by
31P-NMR analyzes the information that can obtain polytype organic phosphorus compounds such as monoesters, phosphide, aromatic diester, DNA, pyrophosphate and poly phosphorus.Compare with the inventive method, adopt traditional extraction process, the organophosphorus information that phosphatide, aromatic diester, DNA, pyrophosphate and poly phosphorus equal size are low has weakening or disappearance in various degree.In addition, the content of single type phosphorus compound generally is lower than the inventive method in the classic method, demonstrates fully the inventive method to the advantage on calcareous sediment organophosphorus extraction and the composition analysis.In addition, this method can also be used for high ocean of calcium content and river deposit.
Claims (3)
1, a kind of calcareous sediment organophosphorus extracts and constitutes analysis method, it is characterized in that adopting earlier the edta solution of slant acidity sediment to be washed also centrifugal, mixed solution NaOH+EDTA with NaOH and ethylenediamine tetraacetic acid extracts sediment organophosphorus as extraction agent then, with the total phosphorus in the spectrophotometer NaOH+EDTA extract; After extract concentrated, use
31The P nuclear magnetic resonance technique
31P-NMR analyzes the proportion of composing of all types of phosphorus compounds in the extract, by calculating the composition content information that further obtains organophosphorus in the sediment.
2, extract and constitutes analysis method according to the described calcareous sediment organophosphorus of claim 1, the ratio that it is characterized in that its metallic element calcium of said rimstone and iron and aluminium content is greater than 0.7; Its pH of the edta solution of said slant acidity is 4.5; Said spectrometer is an inductive coupling plasma emission spectrograph.
3, extract and constitutes analysis method according to claim 1 or 2 described calcareous sediment organophosphorus, its concrete steps are as follows:
(1) sediment sample is prepared: gather fresh sediment, and earlier at the freezing 4h that is no less than of ultra low temperature freezer, vacuum drying then, final sample is through grinding, sieving, and the room temperature sealing is preserved;
(2) flushing: sediment sample is mixed vibration with the edta solution of slant acidity in centrifuge tube, the centrifugal then upper solution of removing.
(3) organophosphorus extracts: continue to add the NaOH+EDTA extraction agent to centrifuge tube, then sub-fraction upper solution Instrument measuring total phosphorus is got in vibration, centrifugal;
(4) concentrate: will remain extract and pour revolving bottle into, and concentrate through rotary evaporation in vacuo, at last with the freezing preservation of concentrate;
(5)
31The P-NMR analytic sample is prepared: take out the concentrating sample that is freezing state, at room temperature rise again to liquid state, centrifugal removal precipitation behind the adding heavy water, is carried out in solution
31P-NMR analyzes;
(6)
31P-NMR analyzes: nuclear magnetic resonance analyser is BRUKER AV400,
31P-NMR analyzes and to carry out under 161.98MHz, adopts BRUKER standard chamber BBO probe, about 20 ℃ of environment temperatures, the single sample scanning times between 17000～26000, analysis time between 12h to 18h,
31The P chemical shift is with 85%H
3PO
4Be benchmark, form to differentiate chemical shift with reference to the phosphorus standard specimen, be respectively phosphonic acids 20ppm, aromatic diester 7.4ppm, orthophosphoric acid 6～7ppm, orthophosphoric acid monoesters 4～6ppm, phosphatidase 11～3ppm, DNA 0ppm, pyrophosphoric acid-3.5～-4.5ppm, the terminal phosphorus-3 of poly phosphorus～-4ppm and poly phosphorus in the middle of phosphorus-17～-19ppm;
(7) calculate: obtain by area integral
31The proportion of composing of all types of phosphorus compounds in the P-NMR wave spectrum calculates the concentration of all types of phosphorus compounds according to the total phosphorus concentration of extract, calculates the composition content of organophosphorus in the unit weight sediment according to sediment weight.
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| CN102353567A (en) * | 2011-06-30 | 2012-02-15 | 河北工业大学 | Method for abstracting and enriching organic phosphorus in substrate sludge |
| CN103558242A (en) * | 2013-11-14 | 2014-02-05 | 河南理工大学 | Methods for extracting and measuring granular organic phosphorus in water body |
| CN103776860A (en) * | 2012-10-25 | 2014-05-07 | 中国科学院生态环境研究中心 | Device for concentrating extracting solution during organic phosphorus analysis in deposit sediments |
| CN104459054A (en) * | 2014-12-16 | 2015-03-25 | 上海微谱化工技术服务有限公司 | Analysis method of phosphorus-containing cleaning agent |
| CN104458786A (en) * | 2014-12-16 | 2015-03-25 | 上海微谱化工技术服务有限公司 | Method for analyzing metaphosphate |
| CN104614331A (en) * | 2015-01-27 | 2015-05-13 | 中国环境科学研究院 | Method for simultaneously extracting and analyzing forms of organic phosphorus and inorganic phosphorus in aquatic sediments |
| CN104965049A (en) * | 2015-06-25 | 2015-10-07 | 苏州科技学院 | Method for determining content of active calcium-phosphorus in sediment |
| CN104634806B (en) * | 2015-02-02 | 2017-01-04 | 浙江大学 | Utilize methylenediphosphonate quantified by external standard method liquid31the method of P nuclear magnetic resonance, NMR |
| CN107632037A (en) * | 2017-08-24 | 2018-01-26 | 北京中科乾和环保科技服务有限公司 | Based on liquid phase31The analysis method of organophosphor in the deposit of P NMR technologies |
| CN110749614A (en) * | 2019-11-11 | 2020-02-04 | 南京大学 | Method for rapidly and quantitatively detecting organic phosphorus in soil |
| CN113405879A (en) * | 2021-08-19 | 2021-09-17 | 中国农业科学院农业环境与可持续发展研究所 | Method for improving extraction rate of organic phosphorus in calcareous soil and detection effect of liquid-phase 31P-NMR |
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| CN102353567A (en) * | 2011-06-30 | 2012-02-15 | 河北工业大学 | Method for abstracting and enriching organic phosphorus in substrate sludge |
| CN103776860A (en) * | 2012-10-25 | 2014-05-07 | 中国科学院生态环境研究中心 | Device for concentrating extracting solution during organic phosphorus analysis in deposit sediments |
| CN103558242A (en) * | 2013-11-14 | 2014-02-05 | 河南理工大学 | Methods for extracting and measuring granular organic phosphorus in water body |
| CN104458786B (en) * | 2014-12-16 | 2016-08-24 | 上海微谱化工技术服务有限公司 | The analysis method of metaphosphate |
| CN104459054A (en) * | 2014-12-16 | 2015-03-25 | 上海微谱化工技术服务有限公司 | Analysis method of phosphorus-containing cleaning agent |
| CN104458786A (en) * | 2014-12-16 | 2015-03-25 | 上海微谱化工技术服务有限公司 | Method for analyzing metaphosphate |
| CN104614331B (en) * | 2015-01-27 | 2017-12-22 | 中国环境科学研究院 | The method of organophosphor and Forms of Inorganic Phosphorus in extraction simultaneously and analyzing water body deposit |
| CN104614331A (en) * | 2015-01-27 | 2015-05-13 | 中国环境科学研究院 | Method for simultaneously extracting and analyzing forms of organic phosphorus and inorganic phosphorus in aquatic sediments |
| CN104634806B (en) * | 2015-02-02 | 2017-01-04 | 浙江大学 | Utilize methylenediphosphonate quantified by external standard method liquid31the method of P nuclear magnetic resonance, NMR |
| CN104965049A (en) * | 2015-06-25 | 2015-10-07 | 苏州科技学院 | Method for determining content of active calcium-phosphorus in sediment |
| CN107632037A (en) * | 2017-08-24 | 2018-01-26 | 北京中科乾和环保科技服务有限公司 | Based on liquid phase31The analysis method of organophosphor in the deposit of P NMR technologies |
| CN110749614A (en) * | 2019-11-11 | 2020-02-04 | 南京大学 | Method for rapidly and quantitatively detecting organic phosphorus in soil |
| CN113405879A (en) * | 2021-08-19 | 2021-09-17 | 中国农业科学院农业环境与可持续发展研究所 | Method for improving extraction rate of organic phosphorus in calcareous soil and detection effect of liquid-phase 31P-NMR |
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