CN113340691A - Method for extracting phosphorus with different occurrence forms in marine sediments - Google Patents
Method for extracting phosphorus with different occurrence forms in marine sediments Download PDFInfo
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 216
- 239000011574 phosphorus Substances 0.000 title claims abstract description 170
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 170
- 239000013049 sediment Substances 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 37
- 239000000243 solution Substances 0.000 claims description 94
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 63
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 60
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 claims description 44
- 229910052586 apatite Inorganic materials 0.000 claims description 43
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 29
- 239000006228 supernatant Substances 0.000 claims description 27
- 229910052742 iron Inorganic materials 0.000 claims description 22
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 22
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 21
- 229910052782 aluminium Inorganic materials 0.000 claims description 21
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 20
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 18
- 239000011575 calcium Substances 0.000 claims description 18
- 229910052791 calcium Inorganic materials 0.000 claims description 18
- 230000029087 digestion Effects 0.000 claims description 18
- 238000000926 separation method Methods 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 6
- 239000007853 buffer solution Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 4
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 4
- 239000012498 ultrapure water Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 239000000872 buffer Substances 0.000 claims 1
- 239000000284 extract Substances 0.000 abstract description 20
- 238000000605 extraction Methods 0.000 abstract description 15
- 238000011160 research Methods 0.000 abstract description 3
- 230000009897 systematic effect Effects 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 17
- 238000002156 mixing Methods 0.000 description 14
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 9
- 238000002386 leaching Methods 0.000 description 6
- 229910001629 magnesium chloride Inorganic materials 0.000 description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000012530 fluid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 229910004878 Na2S2O4 Inorganic materials 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000000877 morphologic effect Effects 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 description 1
- 102000005701 Calcium-Binding Proteins Human genes 0.000 description 1
- 108010045403 Calcium-Binding Proteins Proteins 0.000 description 1
- 101100059533 Capsicum annuum CAFP gene Proteins 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical compound C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/34—Purifying; Cleaning
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/42—Low-temperature sample treatment, e.g. cryofixation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/44—Sample treatment involving radiation, e.g. heat
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Abstract
The invention provides a method for extracting phosphorus in different occurrence forms from marine sediments. The extraction method can comprehensively extract phosphorus in different occurrence forms in the marine sediments, has high extraction rate, and is convenient for systematic research on phosphorus forms in the marine.
Description
Technical Field
The invention relates to the technical field of environment, in particular to a method for extracting phosphorus with different occurrence forms in marine sediments.
Background
Phosphorus is an essential component of the growth and reproduction of marine plankton and is the basis for marine primary productivity and the food chain. River input is a main source of phosphorus in the ocean, sediments are important reservoirs of phosphorus in water, the exchange effect of phosphorus between the river input and the sediments is obvious, however, the amount of bioavailable phosphorus capable of participating in exchange depends on the occurrence form of phosphorus in the sediments, and when factors such as temperature, pH value and biological disturbance of a sedimentation environment change, only weakly adsorbed phosphorus, close-storage phosphorus, iron/aluminum adsorbed phosphorus and organic phosphorus can diffuse from the sediments to an overlying water body and are utilized by organisms, so that the content of phosphorus in the ocean water environment is influenced. Therefore, the occurrence form of phosphorus in the marine sediments has important significance for quantifying the upper limit of available phosphorus of potential organisms, acquiring relevant information of the sedimentation environment, knowing the recycling of phosphorus in the sea and controlling endogenous pollution.
The prior art discloses various methods for separating and quantifying the form of phosphorus in marine sediments, and most ideally, a chemical reagent extraction method mainly comprises the following steps: rutternberg method, Jensen (1998) method, Kaarina modified method. However, the Rutternberg process focuses only on the separation of phosphorus from scrap and authigenic phosphorus, and is not sufficient for the separation of other forms of phosphorus, e.g., the second extraction step is actually the sum of aluminum-bound phosphorus (Al-P), iron-bound phosphorus (Fe-P), and occluded phosphorus, which is too biased if considered to be Fe-P alone; jensen (1998) is improved based on the Rutternberg method to further refine the morphology of phosphorus in the deposit, dividing the main sedimentary phosphorus into six fractions of weakly adsorbed phosphorus (Lsor-P), iron-bound inorganic phosphorus (Fe-P), extractable organic phosphorus (Lea-OP), authigenic apatite (CAFP), clastic apatite (FAP) and stable organic phosphorus (Ref-OP); the Kaarina modified process separated phosphorus in the iron manganese bound form sensitive to the redox environment from alumina, phosphorus in non-reducible iron oxides and organophosphorus, but failed to distinguish primary clastic phosphorus from autogenous phosphorus in the deposition environment.
Because many existing phosphorus form grading leaching methods cannot systematically and completely extract and analyze the occurrence forms of phosphorus in sediments, based on the method, the invention integrates the advantages of various previous grading leaching methods, provides a method for extracting phosphorus with different occurrence forms in marine sediments, refines bioavailable phosphorus, further perfects and emphatically considers the research requirements of environmental geochemistry.
Disclosure of Invention
In view of the above, in order to solve the technical problem that the existing extraction method cannot completely extract phosphorus in different occurrence forms in the sediments, the invention provides a method for extracting phosphorus in different occurrence forms in marine sediments, and aims to systematically and completely extract phosphorus in different occurrence forms in marine sediments.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for extracting phosphorus with different occurrence forms in marine sediments comprises the following steps:
1) using MgCl at pH 82Extracting a marine sediment sample by using the solution as an extractant, and performing centrifugal separation to obtain residue a and an extracting solution containing weakly adsorbed phosphorus;
2) extracting the residue a in the step 1) by using a CDB solution with a pH value of 7.6 as an extracting agent, performing centrifugal separation to obtain a residue b and a supernatant, performing high-temperature digestion on the supernatant by using strong acid, cooling to obtain a transparent solid, dissolving the transparent solid by using water, and adjusting the pH value to 3.0-3.1 to obtain an extracting solution containing the occluded phosphorus;
3) extracting the residue b in the step 2) by using NaOH solution as an extracting agent, and performing centrifugal separation to obtain residue c and an extracting solution containing iron/aluminum adsorbed phosphorus;
4) extracting the residue c in the step 3) by using NaAC-HAC buffer solution as an extracting agent, performing centrifugal separation to obtain residue d and supernatant, and adjusting the pH value of the supernatant to 3.0-3.1 to obtain an extracting solution containing authigenic apatite and calcium-bound phosphorus;
5) extracting the residue d in the step 4) by using HCl solution as an extracting agent, centrifuging to obtain residue e and supernatant, and adjusting the pH value of the supernatant to 3.0-3.1 to obtain an extracting solution containing clastic apatite;
6) burning the residue e in the step 5) at high temperature, cooling, extracting by using an HCl solution as an extracting agent, performing centrifugal separation to obtain a residue f and a supernatant, and adjusting the pH value of the supernatant to 3.0-3.1 to obtain an organic phosphorus-containing extracting solution;
7) carrying out high-temperature digestion and cooling on the residue f in the step 6), extracting by using an HCl solution as an extracting agent, carrying out centrifugal separation, and adjusting the pH value of the supernatant to 3.0-3.1 to obtain an extracting solution containing silicate clastic phosphorus.
Preferably, step 1) said MgCl2The concentration of the solution is 1mol/L, and the preparation method comprises the following steps: 203.3g of MgCl2·6H2Dissolving O in 1L of ultrapure water, adding 10% NH4OH to adjust the pH to 8.
Preferably, the CDB solution in the step 2) is prepared by using 32.4gC6H5Na3O7·2H2O、42gNaHCO3、2.87gNa2S2O4Is prepared by dissolving in 500mL of ultrapure water and is prepared on the same day.
Preferably, the high-temperature digestion in the step 2) is to take part of the supernatant fluid to be placed in a 100ml digestion tube, and a mixed solution composed of sulfuric acid, perchloric acid and nitric acid according to the volume ratio of 1:2:7 is used as a digestion agent, wherein the sulfuric acid is super-grade pure, the content of the sulfuric acid is 95-98%, and the density of the sulfuric acid is 1.84g/cm3(ii) a The nitric acid is superior pure, and the content of the nitric acid is 65 to 68 percent; perchloric acid is produced by Tianjin Oriental chemical plant.
Preferably, the concentration of the NaOH solution in the step 3) is 0.1 mol/L.
Preferably, the NaAC-HAC buffer solution in the step 4) has a pH value of 4 and a concentration of 1 mol/L.
Preferably, the concentration of the HCl solution adopted in the step 5), the step 6) and the step 7) is 1 mol/L.
Preferably, the high-temperature burning temperature in the step 6) is 550 ℃, and the burning time is 4 hours.
Preferably, the strong acid added in step 7) is concentrated sulfuric acid and perchloric acid.
Preferably, the content of weakly adsorbed phosphorus in the phosphorus form extract in the first step, the content of occluded phosphorus in the phosphorus form extract in the second step, the content of iron/aluminum adsorbed phosphorus in the phosphorus form extract in the third step, the content of authigenic apatite and calcium-bound phosphorus in the phosphorus form extract in the fourth step, the content of clastic apatite in the phosphorus form extract in the fifth step, the content of organic phosphorus in the phosphorus form extract in the sixth step, and the content of silicate clastic phosphorus in the phosphorus form extract in the seventh step are respectively measured by an ascorbic acid reduced phosphomolybdic blue method (GB/T12763.4-2007).
Compared with the prior art, the invention has the following beneficial effects: the invention extracts and analyzes the form of the phosphorus in the marine sediments by a continuous grading leaching method, can fully obtain the phosphorus with different occurrence forms from the marine sediments, and accurately reflects the existence form and the bioavailability of the phosphorus in the marine sediments. The extraction method of the invention needs less marine sediment samples, and the adopted chemical reagent is simple and has low cost.
Drawings
FIG. 1 is a sampling site map of embodiments 1-12 of the present invention;
FIG. 2 is a flow chart of the process for extracting phosphorus in different forms of occurrence from marine sediments according to the present invention;
FIG. 3 is a schematic diagram of the distribution of phosphorus in different forms of occurrence in examples 1 to 12 of the present invention.
Detailed Description
The invention provides a method for extracting phosphorus with different occurrence forms in marine sediments, which comprises the following steps:
1) uniformly mixing marine sediments and a magnesium chloride solution with the value of 1mol/LpH being 8 by using a vortex mixer, extracting the mixture at room temperature for 2 hours by shaking, and then carrying out centrifugal separation for 15 minutes at the rotating speed of 5000r/min to obtain residue a and a first-step phosphorus form extracting solution. The phosphorus form extracting solution obtained in the step contains weak adsorption state phosphorus (Lsor-P), marine sediments in the step are obtained by collecting a sediment sample with the surface layer being about 10cm in a researched sea area through a grab type sampler, and ammonia water with the mass concentration of 10 wt% is dripped into the magnesium chloride solution with the concentration of 1mol/L to adjust the pH value of the magnesium chloride solution to be 8.
2) Mixing the residue a with CDB solution with pH of 7.6, shaking for 6 hr, and extracting with 5Centrifuging at the rotating speed of 000r/min for 15min to obtain residue b and supernatant; measuring 5ml of supernatant fluid into a digestion tube, adding the supernatant fluid, the perchloric acid and the nitric acid respectively according to the volume ratio of 1:2:7, and then carrying out high-temperature digestion, wherein the sulfuric acid is superior pure, the content of the sulfuric acid is 95-98%, and the density of the sulfuric acid is 1.84g/cm3(ii) a The nitric acid is superior pure, and the content of the nitric acid is 65 to 68 percent; perchloric acid is produced by Tianjin oriental chemical plants until perchloric acid and nitric acid are completely decomposed and sulfuric acid is refluxed, a transparent solid is formed after cooling, and liquid obtained after dissolving in water is phosphorus form extracting solution in the second step, wherein a method of adding water and boiling for dissolving can also be adopted.
The CDB solution is prepared by using 32.4gC6H5Na3O7·2H2O、42g NaHCO3、2.87g Na2S2O4Is dissolved in 500mL of ultrapure water to prepare the product.
In the step, the pH of the phosphorus-form extract solution in the second step is adjusted to 3.0-3.1 with 0.1mol/L sodium hydroxide solution or 10mol/L sodium hydroxide solution to obtain an extract solution containing occluded phosphorus (Oc-P).
3) And uniformly mixing the residue b with 0.1mol/L sodium hydroxide solution, shaking for extraction for 18h, and centrifuging at the rotating speed of 5000r/min for 15min to obtain residue c and the phosphorus form extracting solution in the third step.
4) Uniformly mixing the residue c with 1mol/LpH ═ 4 NaAC-HAC buffer solution, shaking for extraction for 5 hours, and centrifuging at the rotating speed of 5000r/min for 15min to obtain residue d and the phosphorus form extracting solution in the fourth step;
in this step, the pH of the extract solution in the phosphorus form in the fourth step is adjusted to 3.0 to 3.1 with 1mol/L hydrochloric acid to obtain an extract solution containing authigenic apatite and calcium-bound phosphorus (Ca-P).
5) Uniformly mixing the residue d with 1mol/L hydrochloric acid, shaking for extraction for 16h, and centrifuging at the rotating speed of 5000r/min for 15min to obtain residue e and a phosphorus form extracting solution in the fifth step;
in this step, the pH of the extraction solution of phosphorus form in the fifth step is adjusted to 3.0 to 3.1 with 0.1mol/L NaOH solution or 10mol/L NaOH solution to obtain an extraction solution containing clastic apatite (De-P).
6) The residue e was transferred to a crucible and placed in a muffle furnace and incinerated at 550 ℃ for 4 hours. Uniformly mixing the ashed and cooled residue e with 1mol/L hydrochloric acid, shaking for extraction for 15h, and centrifuging at the rotating speed of 5000r/min for 15min to obtain residue f and the phosphorus form extracting solution in the sixth step.
In this step, the pH of the phosphorus form extract of the sixth step is adjusted to 3.0 to 3.1 with 0.1mol/L sodium hydroxide solution or 10mol/L sodium hydroxide solution to obtain an extract containing Organic Phosphorus (OP).
7) Transferring the whole residue f into a digestion tube, adding 4ml of high-grade pure concentrated sulfuric acid with the sulfuric acid content of 95-98% and 5 drops of perchloric acid, carrying out high-temperature digestion until the residue is completely whitened, and continuing digestion for 20 min; naturally cooling, mixing with 1mol/L HCl, shaking for 8h, centrifuging at 5000r/min for 15min to obtain phosphorus form extractive solution of the seventh step.
In the step, the pH of the phosphorus form extracting solution in the seventh step is adjusted to 3.0-3.1 by using 0.1mol/L sodium hydroxide solution or 10mol/L sodium hydroxide solution, and the extracting solution containing silicate clastic phosphorus (SIF-P) is obtained.
By adopting the method to extract the phosphorus with different occurrence forms in the marine sediments, the invention can systematically and completely analyze and research the existence form and the bioavailability of the phosphorus in the sea.
The method comprises the steps of respectively measuring the content of weak adsorption state phosphorus (Lsor-P) in an phosphorus form extracting solution in the first step, the content of impoundment state phosphorus (Oc-P) in an phosphorus form extracting solution in the second step, the content of iron/aluminum adsorption state phosphorus (Fe/Al-P) in an phosphorus form extracting solution in the third step, the content of authigenic apatite and calcium binding state phosphorus (Ca-P) in an phosphorus form extracting solution in the fourth step, the content of clastic apatite (De-P) in an phosphorus form extracting solution in the fifth step, the content of Organic Phosphorus (OP) in an phosphorus form extracting solution in the sixth step and the content of silicate clastic phosphorus (SIF-P) in an phosphorus form extracting solution in the seventh step by adopting an ascorbic acid reduction phosphomolybdic blue method (GB/T12763.4-2007).
The relative content and the spatial distribution of the protein are further analyzed by using data statistics, analysis software and mapping software of Excle, Origin, Surfer and the like.
The present invention will be described in further detail with reference to the accompanying drawings and examples. The marine sediment samples adopted in the following embodiments of the invention are sediment samples with the surface layer thickness of about 10cm which are collected at 12 stations of the Bohai Bay offshore area in 2019 and 10 months by adopting a grab type sampler, the sediment samples are sealed in a polyethylene sealed bag after being mixed uniformly on site and stored at 4 ℃, and the sampling stations are shown in figure 1.
Example 1
A method for extracting phosphorus with different occurrence forms in marine sediments is described with reference to FIG. 2, and comprises the following specific steps:
in 2019 and 10 months, the inventor of the invention collects sediment samples with the surface layer thickness of about 10cm at 12 stations in the Bohai Bay offshore area by using grab type samplers, seals the sediment samples in a polyethylene sealing bag after field mixing, and stores the sediment samples at 4 ℃.
The 12 collected sediment samples are respectively extracted and measured according to the following steps, the specific implementation flow chart is shown in figure 2, and the detailed steps are as follows:
And 3, adding 20ml of 0.1mol/LNaOH into the residue b, uniformly mixing, extracting for 18 hours at 25 ℃ by oscillation, and centrifuging for 15 minutes at the rotating speed of 5000r/min to obtain residue c and the phosphorus form extracting solution in the third step. And (3) determining the content of iron/aluminum adsorption state phosphorus (Fe/Al-P) in the phosphorus form extracting solution in the third step.
And 4, adding 20ml of 1mol/LpH NaAC-HAC buffer solution of 4 into the residue c, uniformly mixing, extracting under oscillation at 25 ℃ for 5h, centrifuging at the rotating speed of 5000r/min for 15min to obtain residue d and an phosphorus form extracting solution in the fourth step, adjusting the pH of the phosphorus form extracting solution in the fourth step to 3.0-3.1 by using 1mol/L hydrochloric acid, and measuring the content of the authigenic apatite and the calcium-binding-state phosphorus (Ca-P).
And 5, adding 20ml of 1mol/L HCl into the residue d, uniformly mixing by using a vortex mixer, oscillating and extracting for 16h at 25 ℃, centrifuging for 15min at the rotating speed of 5000r/min to obtain residue e and the phosphorus form extracting solution in the fifth step, and adjusting the pH value of the phosphorus form extracting solution in the fifth step to 3.0-3.1 by using 0.1mol/L sodium hydroxide solution or 10mol/L sodium hydroxide solution. And (4) measuring the content of clastic apatite (De-P) in the phosphorus form extracting solution in the fifth step.
And 6, transferring the residue e into a ceramic crucible, placing the ceramic crucible into a muffle furnace, burning for 4h at 550 ℃, cooling, transferring the residue e back to a centrifuge tube, adding 20ml of 1mol/L HCl, mixing uniformly, extracting for 15h at 25 ℃ in a vibration mode, centrifuging for 15min at 5000r/min to obtain residue f and the phosphorus form extracting solution in the sixth step, and adjusting the pH value of the phosphorus form extracting solution in the sixth step to 3.0-3.1 by using 0.1mol/L sodium hydroxide solution or 10mol/L sodium hydroxide solution. And (4) measuring the content of Organic Phosphorus (OP) in the phosphorus form extracting solution in the sixth step.
Examples 2 to 12
Marine sediment samples # 2-12 were treated separately in the manner of example 1 and different forms of phosphorus were obtained.
The results of the measurements of examples 1 to 12 are shown in FIG. 3.
As can be seen from fig. 3, seven different forms of phosphorus can be obtained from the marine sediment sample by the fractional extraction method of the present invention, and the phosphorus content of each form has significant difference. As shown in FIG. 3, the content of each form of the apatite is sequentially clastic apatite (De-P) > Organophosphorus (OP) > occluded phosphorus (Oc-P) > silicate clastic phosphorus (SIF-P) > iron/aluminum adsorbed phosphorus (Fe/Al-P) > authigenic apatite and calcium-bound phosphorus (Ca-P) > weakly adsorbed phosphorus (Lsor-P), and the average ratio of clastic apatite (De-P), Organophosphorus (OP), occluded phosphorus (Oc-P), silicate clastic phosphorus (SIF-P), iron/aluminum adsorbed phosphorus (Fe/Al-P), authigenic apatite, calcium-bound phosphorus (Ca-P) and weakly adsorbed phosphorus (Lsor-P) in 1-12 samples is: 53.95%, 15.89%, 11.78%, 9.01%, 5.66%, 2.80%, 0.91%.
Wherein the proportion of weakly adsorbed phosphorus (Lsor-P), occluded phosphorus (Oc-P), iron/aluminum adsorbed phosphorus (Fe/Al-P), authigenic apatite and calcium-bonded phosphorus (Ca-P), clastic apatite (De-P), Organophosphorus (OP) and silicate clastic phosphorus (SIF-P) in sample No. 1 is respectively as follows: 0.76%, 18.99%, 8.22%, 2.69%, 49.19%, 12.30%, 7.85%.
In sample 2#, the ratios of weakly adsorbed phosphorus (Lsor-P), occluded phosphorus (Oc-P), iron/aluminum adsorbed phosphorus (Fe/Al-P), authigenic apatite and calcium-bound phosphorus (Ca-P), clastic apatite (De-P), Organophosphorus (OP) and silicate clastic phosphorus (SIF-P) are respectively as follows: 0.85%, 6.25%, 3.37%, 2.28%, 69.09%, 10.56%, 7.61%.
In sample No. 3, the weakly adsorbed phosphorus (Lsor-P), occluded phosphorus (Oc-P), iron/aluminum adsorbed phosphorus (Fe/Al-P), authigenic apatite and calcium-bound phosphorus (Ca-P), clastic apatite (De-P), Organophosphorus (OP), and silicate clastic phosphorus (SIF-P) are respectively as follows: 1.16%, 16.24%, 5.87%, 5.76%, 42.51%, 20.75%, 7.72%.
In sample 4#, the ratios of weakly adsorbed phosphorus (Lsor-P), occluded phosphorus (Oc-P), iron/aluminum adsorbed phosphorus (Fe/Al-P), authigenic apatite and calcium-bound phosphorus (Ca-P), clastic apatite (De-P), Organophosphorus (OP) and silicate clastic phosphorus (SIF-P) are respectively as follows: 1.04%, 16.21%, 8.08%, 3.28%, 45.27%, 18.93%, 7.19%.
In sample No. 5, the weakly adsorbed phosphorus (Lsor-P), occluded phosphorus (Oc-P), iron/aluminum adsorbed phosphorus (Fe/Al-P), authigenic apatite and calcium-bound phosphorus (Ca-P), clastic apatite (De-P), Organophosphorus (OP) and silicate clastic phosphorus (SIF-P) are respectively as follows: 1.01%, 8.95%, 7.60%, 2.47%, 52.86%, 16.94%, 10.16%.
In sample 6#, the ratios of weakly adsorbed phosphorus (Lsor-P), occluded phosphorus (Oc-P), iron/aluminum adsorbed phosphorus (Fe/Al-P), authigenic apatite and calcium-bound phosphorus (Ca-P), clastic apatite (De-P), Organophosphorus (OP) and silicate clastic phosphorus (SIF-P) are respectively as follows: 1.26%, 17.06%, 3.90%, 3.04%, 54.34%, 13.05%, 7.34%.
In sample 7#, the ratios of weakly adsorbed phosphorus (Lsor-P), occluded phosphorus (Oc-P), iron/aluminum adsorbed phosphorus (Fe/Al-P), authigenic apatite and calcium-bound phosphorus (Ca-P), clastic apatite (De-P), Organophosphorus (OP), and silicate clastic phosphorus (SIF-P) are: 0.93%, 9.97%, 7.26%, 3.00%, 51.55%, 19.87%, 7.43%.
In sample No. 8, the weakly adsorbed phosphorus (Lsor-P), occluded phosphorus (Oc-P), iron/aluminum adsorbed phosphorus (Fe/Al-P), authigenic apatite and calcium-bound phosphorus (Ca-P), clastic apatite (De-P), Organophosphorus (OP), and silicate clastic phosphorus (SIF-P) are respectively as follows: 0.52%, 9.72%, 3.35%, 1.75%, 68.02%, 9.43%, 7.21%.
In sample No. 9, the weakly adsorbed phosphorus (Lsor-P), occluded phosphorus (Oc-P), iron/aluminum adsorbed phosphorus (Fe/Al-P), authigenic apatite and calcium-bound phosphorus (Ca-P), clastic apatite (De-P), Organophosphorus (OP), and silicate clastic phosphorus (SIF-P) are respectively as follows: 0.90%, 11.56%, 5.84%, 1.63%, 54.47%, 17.28%, 8.32%.
In sample No. 10, the weakly adsorbed phosphorus (Lsor-P), occluded phosphorus (Oc-P), iron/aluminum adsorbed phosphorus (Fe/Al-P), authigenic apatite and calcium-bound phosphorus (Ca-P), clastic apatite (De-P), Organophosphorus (OP), and silicate clastic phosphorus (SIF-P) are respectively as follows: 0.95%, 7.28%, 5.80%, 2.53%, 54.64%, 16.65%, 12.14%.
In sample 11#, the ratios of weakly adsorbed phosphorus (Lsor-P), occluded phosphorus (Oc-P), iron/aluminum adsorbed phosphorus (Fe/Al-P), authigenic apatite and calcium-bound phosphorus (Ca-P), clastic apatite (De-P), Organophosphorus (OP), and silicate clastic phosphorus (SIF-P) are: 0.76%, 10.06%, 4.64%, 2.42%, 49.24%, 19.48%, 13.39%.
In sample 12#, the ratios of weakly adsorbed phosphorus (Lsor-P), occluded phosphorus (Oc-P), iron/aluminum adsorbed phosphorus (Fe/Al-P), authigenic apatite and calcium-bound phosphorus (Ca-P), clastic apatite (De-P), Organophosphorus (OP), and silicate clastic phosphorus (SIF-P) are: 0.83%, 9.02%, 4.01%, 2.77%, 56.18%, 15.48%, 11.71%.
In addition, the method for extracting phosphorus with different occurrence forms in marine sediments, which is provided by the embodiment of the invention, is verified by a standard substance (GBW 07333). The phosphorus form analysis of the yellow sea marine sediment standard substance (GBW07333) is carried out by adopting an improved continuous grading leaching method of phosphorus occurrence form in the marine sediment, and the precision of each step in the seven-step continuous grading leaching is as follows: the first step is as follows: 2.7%, and the second step: 4.5%, and the third step: 1.9%, and the fourth step: 3.2%, and the fifth step: 4.1%, and the sixth step: 1.6%, and the seventh step: 2.7 percent, and the error range between the sum of the phosphorus forms of the actual measurement seven steps and the standard value is 6.3 to 10.3 percent. Therefore, the method for extracting phosphorus in different occurrence forms in the marine sediments by continuous fractional leaching, which is provided by the embodiment of the invention, can be applied to the separation and extraction of phosphorus forms in the marine sediments.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A method for extracting phosphorus with different occurrence forms in marine sediments is characterized by comprising the following steps:
1) using MgCl at pH 82Extracting a marine sediment sample by using the solution as an extractant, and performing centrifugal separation to obtain residue a and an extracting solution containing weakly adsorbed phosphorus;
2) extracting the residue a in the step 1) by using a CDB solution with a pH value of 7.6 as an extracting agent, performing centrifugal separation to obtain a residue b and a supernatant, performing high-temperature digestion on the supernatant by using strong acid, cooling to obtain a transparent solid, dissolving the transparent solid by using water, and adjusting the pH value to 3.0-3.1 to obtain an extracting solution containing the occluded phosphorus;
3) extracting the residue b in the step 2) by using NaOH solution as an extracting agent, and performing centrifugal separation to obtain residue c and an extracting solution containing iron/aluminum adsorbed phosphorus;
4) extracting the residue c in the step 3) by using NaAC-HAC buffer solution as an extracting agent, performing centrifugal separation to obtain residue d and supernatant, and adjusting the pH value of the supernatant to 3.0-3.1 to obtain an extracting solution containing authigenic apatite and calcium-bound phosphorus;
5) extracting the residue d in the step 4) by using HCl solution as an extracting agent, centrifuging to obtain residue e and supernatant, and adjusting the pH value of the supernatant to 3.0-3.1 to obtain an extracting solution containing clastic apatite;
6) burning the residue e in the step 5) at high temperature, cooling, extracting by using an HCl solution as an extracting agent, performing centrifugal separation to obtain a residue f and a supernatant, and adjusting the pH value of the supernatant to 3.0-3.1 to obtain an organic phosphorus-containing extracting solution;
7) digesting the residue f in the step 6), cooling, extracting by using an HCl solution as an extracting agent, and after centrifugal separation, adjusting the pH value of the supernatant to 3.0-3.1 to obtain an extracting solution containing silicate clastic phosphorus.
2. The method for extracting phosphorus in marine sediments as claimed in claim 1, wherein said MgCl of step 1)2The concentration of the solution is 1mol/L, and ammonia water with the mass concentration of 10 wt% is dripped to adjust the pH value of the extractant to 8.
3. The method of claim 1, wherein the CDB solution of step 2) is prepared using 32.4gC6H5Na3O7·2H2O、42gNaHCO3、2.87gNa2S2O4Is dissolved in 500mL of ultrapure water to prepare the product.
4. The method for extracting phosphorus with different occurrence forms in marine sediments as claimed in claim 1, wherein the high-temperature digestion in the step 2) is to use a mixed solution of sulfuric acid, perchloric acid and nitric acid with a volume ratio of 1:2:7 as a digestion agent for part of the supernatant.
5. The method for extracting phosphorus with different occurrence forms in marine sediments as claimed in claim 1, wherein the concentration of NaOH solution in step 3) is 0.1 mol/L.
6. The method of claim 1, wherein the NaAC-HAC buffer of step 4) has a pH of 4.
7. The method for extracting phosphorus with different occurrence forms in marine sediments as claimed in claim 1, wherein the concentrations of HCl solutions adopted in the steps 5), 6) and 7) are all 1 mol/L.
8. The method for extracting phosphorus with different occurrence forms in marine sediments as claimed in claim 1, wherein the temperature of high-temperature ignition in step 6) is 550 ℃ and the ignition time is 4 hours.
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