CN103558242B - The extraction of particulate form organophosphorus and assay method in water body - Google Patents
The extraction of particulate form organophosphorus and assay method in water body Download PDFInfo
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- CN103558242B CN103558242B CN201310566056.9A CN201310566056A CN103558242B CN 103558242 B CN103558242 B CN 103558242B CN 201310566056 A CN201310566056 A CN 201310566056A CN 103558242 B CN103558242 B CN 103558242B
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- organophosphorus
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Abstract
The invention discloses the extracting method of particulate form organophosphorus in a kind of water body, it is characterized in that, comprise the following steps: sampling, filtration, freeze-drying, grinding, EDTA-Na
2s
2o
4the step extracting organophosphorus in Phos, NaOH solution is extracted in mixed solution; Also disclose the nuclear magnetic resonance measuring method based on this extracting method simultaneously.Usefulness of the present invention is: the kind that can detect concrete organophosphorus in sample; By filtration in-situ, decrease the change of Organic phosphorus form in sample transportation; The sample size of analysis demand is few, decreases the workload of filtration in-situ; Analysis extraction step is few, not only reduces the phosphorus loss in leaching process, and saves the time analyzing sample; Find after utilizing relative recovery to calculate, the precision of its analytical test of assay method of the present invention is higher.
Description
Technical field
The present invention relates to a kind of extraction and assay method of organophosphorus, be specifically related to extraction and the assay method of particulate form organophosphorus in a kind of water body, belong to chemical field.
Background technology
At present, in water body, the analytical approach of organophosphorus mainly contains: minusing and substep sequential extraction method.For substep sequential extraction method, with reference to Fig. 1, it mainly includes sampling, filtration, freeze-drying, grinding, MgCl
2extract exchangeable species phosphorus, NH
4f extracts aluminium phosphorus, NaOH+Na
2cO
3extraction iron phosphorus, HAc+NaAc use 8 large steps such as hydrochloric acid extraction organophosphorus after extracting spontaneous calcium phosphorus, hydrochloric acid extraction chip calcium phosphorus, calcination, the reagent not only needed is many, and operating process is loaded down with trivial details, the most important thing is, analyze the content that the organic phosphorous content drawn is total organic phosphorus, particulate form organophosphorus Main Morphology and content thereof can not be distinguished.Same problem is there is in minusing with step sequential extraction method.
The particulate form organophosphorus of some kinds is easily converted and is utilized by hydrobiont, and this has great importance to the biogeochemical cycle understanding aquatic ecosystem.But the organophosphorus that existing two kinds of methods extract is only particulate form total organic phosphorus, has both comprised and being easily converted, comprise again difficult bioavailable, this has a certain impact to the biogeochemical cycle tool of accurate understanding aquatic ecosystem.
Summary of the invention
For solving the deficiencies in the prior art, the object of the present invention is to provide the extracting method that a kind of sampling amount is few, extract particulate form organophosphorus in quick easy-operating water body, and the assay method of particulate form organophosphorus in the water body that determination step is few, test accuracy is higher.
In order to realize above-mentioned target, the present invention adopts following technical scheme:
In water body, an extracting method for particulate form organophosphorus, is characterized in that, comprises the following steps:
(1), gather water sample, and utilize the on-the-spot water sample filtration that will gather of vacuum filtering system, collect filter membrane, stored refrigerated;
(2), use deionized water rinsing filter membrane, leave and take washing fluid L
1, then filter membrane is soaked in deionized water, with oscillator vibrates until all solid particles are all separated in water, leaves and takes leaching liquor L
2, merge L
1with L
2obtain solution L
extract;
(3) solution L, is got
extract, freeze drying under-80 DEG C of conditions, obtains solid particulate matter S
0;
(4), abrasive solid particle S
0, by ground solid particulate matter numbering S
1, sealed storage is for subsequent use in the deep freezer of-80 DEG C;
(5), under-20 DEG C of conditions, by solid particulate matter S
1put into the EDTA-Na of pH=4.5
2s
2o
4vibration pre-service is carried out in mixed solution;
(6), mixed liquor is centrifugal under-4 DEG C of conditions, the centrifugal sediment obtained joins in the NaOH solution of 0.1M, extracts under-20 DEG C of conditions;
(7), extract is centrifugal under-4 DEG C of conditions, and supernatant is the final extract of particulate form organophosphorus.
In aforesaid water body, the extracting method of particulate form organophosphorus, is characterized in that, aforementioned filter membrane is the acetate fiber filter membrane of 0.45 μm.
In aforesaid water body, the extracting method of particulate form organophosphorus, is characterized in that, aforesaid solid particle S
1all by 100 object sieves.
In aforesaid water body, the extracting method of particulate form organophosphorus, is characterized in that, aforementioned EDTA-Na
2s
2o
4mixed solution is by 0.1MEDTA and 2%(w/v) Na
2s
2o
4mix.
In aforesaid water body, the extracting method of particulate form organophosphorus, is characterized in that, in step (5), to vibrate mixed solution 1 time every 20min, the duration of each vibration is 1min, and pretreated T.T. of vibrating is 2h.
In aforesaid water body, the extracting method of particulate form organophosphorus, is characterized in that, in step (6), when sediment starts to extract in NaOH solution, every 30min vibration once, until all samples all forms ice cube.
In water body, an assay method for particulate form organophosphorus, is characterized in that, comprises the following steps:
(1), gather water sample, and utilize the on-the-spot water sample filtration that will gather of vacuum filtering system, collect filter membrane, aforementioned filter membrane is the acetate fiber filter membrane of 0.45 μm, stored refrigerated;
(2), use deionized water rinsing filter membrane, leave and take washing fluid L
1, then filter membrane is soaked in deionized water, with oscillator vibrates until all solid particles are all separated in water, leaves and takes leaching liquor L
2, merge L
1with L
2obtain solution L
extract;
(3) solution L, is got
extract, freeze drying under-80 DEG C of conditions, obtains solid particulate matter S
0;
(4), abrasive solid particle S
0, by ground solid particulate matter numbering S
1, solid particulate matter S
1all by 100 object sieves, sealed storage is for subsequent use in the deep freezer of-80 DEG C;
(5), under-20 DEG C of conditions, by S
1put into the EDTA-Na of pH=4.5
2s
2o
4vibration pre-service is carried out in mixed solution;
(6), mixed liquor is centrifugal under-4 DEG C of conditions, the centrifugal sediment obtained joins in the NaOH solution of 0.1M, extracts under-20 DEG C of conditions;
(7), extract is centrifugal under-4 DEG C of conditions, with kind and the content of the organophosphorus in nuclear magnetic resonance method determination supernatant.
In aforesaid water body, the assay method of particulate form organophosphorus, is characterized in that, in step (5), to vibrate mixed solution 1 time every 20min, the duration of each vibration is 1min, and pretreated T.T. of vibrating is 2h.
In aforesaid water body, the assay method of particulate form organophosphorus, is characterized in that, in step (6), when sediment starts to extract in NaOH solution, every 30min vibration once, until all samples all forms ice cube.
In aforesaid water body, the assay method of particulate form organophosphorus, is characterized in that, the condition of nuclear magnetic resonance is: 90 ° of pulses, circulation delay time 2s, capture time 0.5s, and scanning times is 19000 times,
31the resonant frequency of P is 161.98MHz, and chemical shift is the signal standards relative to 85% phosphoric acid.
Usefulness of the present invention is: by filtration in-situ, decreases the change of Organic phosphorus form in sample transportation; The sample size of analysis demand is few, decreases the workload of filtration in-situ; Analysis extraction step is few, not only reduces the phosphorus loss in leaching process, and saves the time analyzing sample; Nuclear magnetic resonance method of the present invention can not only detect kind and the content of concrete organophosphorus in sample, and can reflect the situation of organophosphorus in water body comparatively accurately, and the accuracy of its analytical test is higher.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of the key step of existing substep sequential extraction method;
Fig. 2 is the process flow diagram of the key step of extracting method of the present invention;
Fig. 3 is the nuclear magnetic resonance figure of particulate form organophosphorus in the water body of Dian Chi sampled point 1;
Fig. 4 is the nuclear magnetic resonance figure of particulate form organophosphorus in the water body of Dian Chi sampled point 2;
Fig. 5 is the nuclear magnetic resonance figure of particulate form organophosphorus in the water body of Hulun nur sampled point;
Fig. 6 is the nuclear magnetic resonance figure of particulate form organophosphorus in the water body of Taihu Lake sampled point 1;
Fig. 7 is the nuclear magnetic resonance figure of particulate form organophosphorus in the water body of Taihu Lake sampled point 2.
The implication of Reference numeral in figure: a-85% phosphate; B-phosphonate; C-DNA; D-pyrophosphate; E-ATP β-phosphonate; F-unknown organophosphorus; G-orthophosphate; H-phosphonate monoesters; I-phosphatide; J-polyphosphinates.
Embodiment
Below in conjunction with the drawings and specific embodiments, concrete introduction is done to the present invention.
One, particulate form organophosphorus in water body is extracted
The general collection capacity of natural water 30L(utilizing hydrophore to gather eutrophication water underwater 50cm is 20-50L, determines according to the content of SS in water body), utilize the on-the-spot water sample filtration that will gather of vacuum filtering system, collect filter membrane, stored refrigerated.What filter membrane was selected is Whatman acetate fiber filter membrane (OE67), and aperture is 0.45 μm.
Collection in worksite 200mL water sample L
0, utilize molybdenum blue colorimetric method to measure the content C of total phosphorus in water (TP) and dissolved total phosphorus acid (TDP)
tP, C
iDP, then the content C of total particulate phosphorus (TPP)
iPPcan be expressed as:
C
IPP=C
TP–C
IDP。
With 30mL deionized water rinsing filter membrane, leave and take washing fluid L
1.
Get flushed filter membrane with tweezers, be immersed in the deionized water of 20mL, use oscillator vibrates 2-3min, until all solid particles are all separated in water, leave and take leaching liquor L
2.
By L
1with L
2combine, be called solution L
extract.Get solution L
extract, freeze drying under-80 DEG C of conditions, obtains solid particulate matter S
0.
Abrasive solid particle S
0, until all solid particulate matters are all by 100 object sieves, by ground solid particulate matter numbering S
1, sealed storage is for subsequent use in the deep freezer of-80 DEG C.
Under-20 DEG C of conditions, with the EDTA-Na of 25mLpH=4.5
2s
2o
4mixed solution (by 0.1MEDTA and 2%(w/v) Na
2s
2o
4mix) to S
1carry out vibration pre-service, to vibrate mixed solution 1 time every 20min, the duration of each vibration is 1min, and pretreated T.T. of vibrating is 2h.
Mixed liquor is got, 10000rmin under-4 DEG C of conditions after 2h
-1centrifugal 10min, isolates supernatant and sediment.Wherein,
Supernatant molybdenum blue colorimetric method measures the concentration of TP contained by it and phosphate anion (DIP) respectively, and C ' made by meter respectively
tPwith C '
dIP, then the corresponding content C of TP and DIP in natural water body
0'
tPand C
0'
dIPcan convert and learn, and EDTA-Na
2s
2o
4the percentage composition W of Phos in mixed extract
1also can calculate:
The centrifugal sediment obtained joins in the NaOH solution of 10mL0.1M, under-20 DEG C of conditions, extract 16h, in the 5-6h of beginning, every 30min vibration once, so that extract, until all samples all forms ice cube, afterwards at-4 DEG C and 10000rmin
-1centrifugal 10min under condition, supernatant is the final extract of particulate form organophosphorus.
Two, particulate form organophosphorus in water body is measured
Get the final extract of particulate form organophosphorus, utilize magnetic nuclear resonance method to test kind and the content of wherein organophosphorus.
Magnetic nuclear resonance method: instrument is Bruker company AV400 nuclear magnetic resonance spectrometer, with 5mmBBO probe, 90 ° of pulses, circulation delay time 2s, capture time 0.5s, scanning times is 19000 times,
31the resonant frequency of P is 161.98MHz, and chemical shift is signal standards that is relative and 85% phosphoric acid.
Test result is shown in Fig. 3 to Fig. 7.
W made by the total content meter of organophosphorus
2'.
Three, the checking of measurement result
Get the same final extract of particulate form organophosphorus, measure the content of TP and DIP in final extract with molybdenum blue colorimetric method respectively, C ' ' made by meter respectively
tPand C ' '
dIP, then the corresponding content C of TP and DIP in natural water body
0' '
tPand C
0' '
dIPcan convert and learn, and the percentage composition W of organophosphorus in NaOH extract
2' ' also can calculate:
Calculate extraction efficiency η:
The result is in table 1.
Table 1 measurement result comparison sheet
| Method of the present invention | Molybdenum blue colorimetric method | W 2‘/ W 2‘’ | |
| Dian Chi sampled point 1 | W 2‘=38.2μg·L -1 | W 2‘‘=41.0μg·L -1 | 93.2% |
| Dian Chi sampled point 2 | W 2‘=26.3μg·L -1 | W 2‘‘=32.0μg·L -1 | 82.2% |
| Hulun nur sampled point | W 2‘=35.8μg·L -1 | W 2‘‘=51.0μg·L -1 | 70.2% |
| Taihu Lake sampled point 1 | W 2‘=126.3μg·L -1 | W 2‘‘=199.0μg·L -1 | 63.5% |
| Taihu Lake sampled point 2 | W 2‘=38.7μg·L -1 | W 2‘‘=40.0μg·L -1 | 96.7% |
In sum, 1, extracting method of the present invention is adopted, 9 kinds of natural organophosphoruss can be extracted, the organophosphorus of some kind is (as DNA, polyphosphate and orthophosphate monoesters) to be easily converted and then bioavailable, the biogeochemical cycle tool understanding P elements in water body is of great significance.
2, based on the nuclear magnetic resonance measuring method of extracting method of the present invention, compared with molybdenum blue colorimetric method, adopt the result of nuclear magnetic resonance method determination on the low side, i.e. W
2'/W
2' ' <1, because the organophosphorus that nuclear magnetic resonance is measured is the main species that in water body, organophosphorus exists, and a large amount of pre-stage test shows W
2'/W
2' ' >60%, which represent the main species that in water body, organophosphorus exists, therefore W
2' can be used for representing the situation of organophosphorus in water body completely.
3, this method is utilized to carry out analyzing measuring to more than 20, whole nation lakes and reserviors, the extraction efficiency of organophosphorus is greater than 82%, measure respond well, in nuclear magnetic resonance measuring water body, the content of main organophosphorus accounts for the ratio of total organic phosphorus all more than 60%, and the trophic level of water body is higher, extraction effect is better.
In addition, extracting method of the present invention, compared with minusing, be the direct extraction method to organophosphorus in water body, its result is more accurate; Compared with continuous chemical analytical approach, step greatly reduces, and saves the time analyzing sample.Therefore, extracting method of the present invention and the assay method based on this extracting method, have outstanding substantive distinguishing features and significant progress.
It should be noted that, above-described embodiment does not limit the present invention in any form, the technical scheme that the mode that all employings are equal to replacement or equivalent transformation obtains, and all drops in protection scope of the present invention.
Claims (8)
1. the extracting method of particulate form organophosphorus in water body, is characterized in that, comprise the following steps:
(1), gather water sample, and utilize the on-the-spot water sample filtration that will gather of vacuum filtering system, collect filter membrane, stored refrigerated;
(2), use deionized water rinsing filter membrane, leave and take washing fluid L
1, then filter membrane is soaked in deionized water, with oscillator vibrates until all solid particles are all separated in water, leaves and takes leaching liquor L
2, merge L
1with L
2obtain solution L
extract;
(3) solution L, is got
extract, freeze drying under-80 DEG C of conditions, obtains solid particulate matter S
0;
(4), abrasive solid particle S
0, by ground solid particulate matter numbering S
1, sealed storage is for subsequent use in the deep freezer of-80 DEG C;
(5), under-20 DEG C of conditions, by solid particulate matter S
1put into the EDTA-Na of pH=4.5
2s
2o
4vibration pre-service is carried out in mixed solution;
(6), mixed liquor is centrifugal under-4 DEG C of conditions, the centrifugal sediment obtained joins in the NaOH solution of 0.1M, extracts under-20 DEG C of conditions;
(7), extract is centrifugal under-4 DEG C of conditions, and supernatant is the final extract of particulate form organophosphorus.
2. the extracting method of particulate form organophosphorus in water body according to claim 1, it is characterized in that, described filter membrane is the acetate fiber filter membrane of 0.45 μm.
3. the extracting method of particulate form organophosphorus in water body according to claim 1, is characterized in that, solid particulate matter S
1all by 100 object sieves.
4. the extracting method of particulate form organophosphorus in water body according to claim 1, is characterized in that, EDTA-Na
2s
2o
4mixed solution is by 0.1MEDTA and 2% (w/v) Na
2s
2o
4mix.
5. the extracting method of particulate form organophosphorus in the water body according to Claims 1-4 any one, it is characterized in that, in step (5), to vibrate mixed solution 1 time every 20min, the duration of each vibration is 1min, and pretreated T.T. of vibrating is 2h.
6. the assay method of particulate form organophosphorus in water body, is characterized in that, comprise the following steps:
(1), gather water sample, and utilize the on-the-spot water sample filtration that will gather of vacuum filtering system, collect filter membrane, described filter membrane is the acetate fiber filter membrane of 0.45 μm, stored refrigerated;
(2), use deionized water rinsing filter membrane, leave and take washing fluid L
1, then filter membrane is soaked in deionized water, with oscillator vibrates until all solid particles are all separated in water, leaves and takes leaching liquor L
2, merge L
1with L
2obtain solution L
extract;
(3) solution L, is got
extract, freeze drying under-80 DEG C of conditions, obtains solid particulate matter S
0;
(4), abrasive solid particle S
0, by ground solid particulate matter numbering S
1, solid particulate matter S
1all by 100 object sieves, sealed storage is for subsequent use in the deep freezer of-80 DEG C;
(5), under-20 DEG C of conditions, by S
1put into the EDTA-Na of pH=4.5
2s
2o
4vibration pre-service is carried out in mixed solution;
(6), mixed liquor is centrifugal under-4 DEG C of conditions, the centrifugal sediment obtained joins in the NaOH solution of 0.1M, extracts under-20 DEG C of conditions;
(7), extract is centrifugal under-4 DEG C of conditions, with kind and the content of the organophosphorus in nuclear magnetic resonance method determination supernatant.
7. the assay method of particulate form organophosphorus in water body according to claim 6, is characterized in that, in step (5), to vibrate mixed solution 1 time every 20min, the duration of each vibration is 1min, and pretreated T.T. of vibrating is 2h.
8. the assay method of particulate form organophosphorus in water body according to claim 6, it is characterized in that, the condition of nuclear magnetic resonance is: 90 ° of pulses, circulation delay time 2s, capture time 0.5s, and scanning times is 19000 times,
31the resonant frequency of P is 161.98MHz, and chemical shift is the signal standards relative to 85% phosphoric acid.
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| 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 |
| CN107957432A (en) * | 2017-11-25 | 2018-04-24 | 王会会 | A kind of method of phosphorus content in water quality detection instrument detection water |
| CN110057902B (en) * | 2019-04-30 | 2021-09-03 | 中国地质调查局南京地质调查中心 | Sea-land phase deposition environment judgment method for selectively extracting exchangeable strontium-barium ratio in land debris sediment |
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| CN101339133B (en) * | 2008-08-18 | 2010-09-01 | 中国科学院南京地理与湖泊研究所 | Calcareous sediment organophosphorus extraction and constitutes analysis method |
| CN101587101A (en) * | 2009-06-12 | 2009-11-25 | 南京大学 | Analysis method for simultaneously measuring chlorinated aromatic compounds and nitroaromatic compounds in water |
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