CN113340691B - Method for extracting phosphorus with different occurrence forms in marine sediment - Google Patents
Method for extracting phosphorus with different occurrence forms in marine sediment Download PDFInfo
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 233
- 239000011574 phosphorus Substances 0.000 title claims abstract description 186
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 186
- 239000013049 sediment Substances 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000000243 solution Substances 0.000 claims description 74
- 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 43
- 229910052586 apatite Inorganic materials 0.000 claims description 42
- 239000006228 supernatant Substances 0.000 claims description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 25
- 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
- 230000029087 digestion Effects 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
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 230000001105 regulatory effect Effects 0.000 claims description 13
- 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
- 238000001179 sorption measurement Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 239000007853 buffer solution Substances 0.000 claims description 4
- 238000010304 firing Methods 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
- 239000012530 fluid Substances 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000000872 buffer Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000000284 extract Substances 0.000 abstract description 36
- 238000000605 extraction Methods 0.000 abstract description 13
- 230000009897 systematic effect Effects 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- 238000002156 mixing Methods 0.000 description 13
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 6
- 238000002386 leaching Methods 0.000 description 6
- 229910052573 porcelain Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 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
- 239000000126 substance Substances 0.000 description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 102000005701 Calcium-Binding Proteins Human genes 0.000 description 2
- 108010045403 Calcium-Binding Proteins Proteins 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
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 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
- 230000009467 reduction Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 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
- 101100059533 Capsicum annuum CAFP gene Proteins 0.000 description 1
- 241000289581 Macropus sp. Species 0.000 description 1
- 230000006978 adaptation Effects 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
- 238000004380 ashing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000011978 dissolution method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 208000021302 gastroesophageal reflux disease Diseases 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- 238000004064 recycling Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000005303 weighing Methods 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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- 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
- G01N1/42—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 with different occurrence forms in marine sediments. The extraction method can comprehensively extract the phosphorus in different occurrence forms in the marine sediment, has high extraction rate, and is convenient for systematic research on the phosphorus form in the ocean.
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 for the growth and reproduction of marine plankton and is the basis for the primary productivity of the ocean and the food chain. River input is a main source of phosphorus in the ocean, sediment is an important reservoir of phosphorus in water, the exchange effect of phosphorus between the sediment and the sediment is remarkable, however, the amount of the bio-available phosphorus capable of participating in the exchange depends on the occurrence form of the phosphorus in the sediment, and when factors such as the temperature, the pH value, the biological disturbance and the like of a deposition environment change, only weakly adsorbed phosphorus, closed phosphorus, iron/aluminum adsorbed phosphorus and organic phosphorus can be diffused from the sediment to the overlying water body and are utilized by the organism, so that the content of the phosphorus in the ocean water environment is influenced. Therefore, the occurrence form of phosphorus in the ocean sediment has important significance for quantifying the upper limit of available phosphorus of potential organisms, acquiring relevant information of the sediment environment, knowing the recycling of phosphorus in the ocean and carrying out endogenous pollution control.
The prior art discloses various methods for separating and quantifying phosphorus morphology in marine sediments, most desirably chemical reagent extraction methods, mainly comprising: rutternberg method, jensen (1998) method, kaarina modified method. However, the Rutternberg process focuses only on the separation of clastic phosphorus from autogenous phosphorus, which is inadequate for other forms of phosphorus, such as the second extraction being essentially the sum of aluminum-bound phosphorus (Al-P), iron-bound phosphorus (Fe-P), and closed-cell phosphorus, which is too biased if considered to be Fe-P alone; jensen (1998) improved on the basis of Rutternberg's method, further refined the morphology of phosphorus in the sediment, and divided the main depositional phosphorus into six fractions of weakly adsorbed phosphorus (Lsor-P), iron bound inorganic phosphorus (Fe-P), extractable organic phosphorus (Lea-OP), autogenous apatite (CAFP), clastic apatite (FAP) and stable organic phosphorus (Ref-OP); the Kaarina modified process separates phosphorus in the iron-manganese bound state, which is sensitive to the redox environment, from alumina, phosphorus and organic phosphorus in unreducable iron oxides, but fails to distinguish native clastic phosphorus from autogenous phosphorus in the deposition environment.
Based on the fact that the existing multiple phosphorus form grading leaching methods cannot systematically extract and analyze the occurrence forms of phosphorus in sediments, the invention provides a method for extracting phosphorus in different occurrence forms in marine sediments by combining the advantages of various previous grading leaching methods, refines the bioavailable phosphorus, further perfects and focuses on the research requirements of environmental geochemistry.
Disclosure of Invention
In view of this, in order to solve the technical problem that the existing extraction method can not completely extract the phosphorus in different occurrence forms in the sediment, the invention provides a method for extracting the phosphorus in different occurrence forms in the ocean sediment, and aims to systematically and completely extract the phosphorus in different occurrence forms in the ocean sediment.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a method for extracting phosphorus in different occurrence forms in marine sediments, comprising the following steps:
1) Using MgCl with pH 8 2 Extracting a marine sediment sample by taking the solution as an extracting agent, and obtaining residue a and an extracting solution containing weakly adsorbed phosphorus after centrifugal separation;
2) Extracting the residue a in the step 1) by using CDB solution with the pH value of 7.6 as an extracting agent, centrifuging to obtain residue b and supernatant, carrying out high-temperature digestion on the supernatant by using strong acid, cooling to obtain transparent solid, dissolving the transparent solid by using water, and regulating the pH value to 3.0-3.1 to obtain an extracting solution containing closed-state phosphorus;
3) Extracting the residue b in the step 2) by using NaOH solution as an extracting agent, and centrifugally separating to obtain residue c and an extracting solution containing iron/aluminum adsorption phosphorus;
4) Extracting the residue c in the step 3) by using NaAC-HAC buffer solution as an extracting agent, centrifuging to obtain residue d and supernatant, and regulating the pH value of the supernatant to 3.0-3.1 to obtain an extracting solution containing autogenous 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 regulating the pH value of the supernatant to 3.0-3.1 to obtain an extracting solution containing clastic apatite;
6) Burning and cooling the residue e in the step 5) at high temperature, extracting by adopting an HCl solution as an extracting agent, centrifuging to obtain residue f and supernatant, and regulating the pH value of the supernatant to 3.0-3.1 to obtain an extracting solution containing organic phosphorus;
7) And (3) carrying out high-temperature digestion and cooling on the residue f in the step (6), extracting by adopting an HCl solution as an extracting agent, and regulating the pH value of supernatant fluid to 3.0-3.1 after centrifugal separation to obtain an extracting solution containing silicate clastic phosphorus.
Preferably, step 1) the MgCl 2 The concentration of the solution is 1mol/L, and the preparation method comprises the following steps: 203.3g of MgCl 2 ·6H 2 O was dissolved in 1L of ultrapure water with 10% NH 4 OH was adjusted to pH 8.
Preferably, step 2) the CDB solution is prepared using 32.4gC 6 H 5 Na 3 O 7 ·2H 2 O、42gNaHCO 3 、2.87gNa 2 S 2 O 4 Is 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 supernatant fluid in a 100ml digestion tube, and take a mixed solution composed of sulfuric acid, perchloric acid and nitric acid with the volume ratio of 1:2:7 as a digestion agent, wherein the sulfuric acid is preferably pure, the sulfuric acid content is 95-98%, and the density is 1.84g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Nitric acid is high-grade pure, and the content of nitric acid is 65% -68%; perchloric acid is produced by Tianjin Oriental chemical plant.
Preferably, the concentration of the NaOH solution in the step 3) is 0.1mol/L.
Preferably, the NaAC-HAC buffer in step 4) has a pH of 4 and a concentration of 1mol/L.
Preferably, the HCl solution concentration used in the steps 5), 6) and 7) is 1mol/L.
Preferably, the high temperature firing temperature in the step 6) is 550 ℃, and the firing time is 4 hours.
Preferably, the strong acid added for digestion in the step 7) is concentrated sulfuric acid and perchloric acid.
Preferably, the method adopts an ascorbic acid reduction phosphomolybdenite method (GB/T12763.4-2007) to respectively measure the content of weak adsorption state phosphorus in the first-step phosphorus form extracting solution, the content of closed storage state phosphorus in the second-step phosphorus form extracting solution, the content of iron/aluminum adsorption state phosphorus in the third-step phosphorus form extracting solution, the content of autogenous apatite and calcium-binding state phosphorus in the fourth-step phosphorus form extracting solution, the content of chip apatite in the fifth-step phosphorus form extracting solution, the content of organic phosphorus in the sixth-step phosphorus form extracting solution and the content of silicate chip state phosphorus in the seventh-step phosphorus form extracting solution.
Compared with the prior art, the invention has the following beneficial effects: the invention extracts and analyzes the phosphorus form in the ocean sediment by a continuous grading leaching method, can fully obtain phosphorus with different occurrence forms from the ocean sediment, and accurately reflects the existence form and bioavailability of the phosphorus in the ocean sediment. The extraction mode of the invention requires less marine sediment sample, and the adopted chemical reagent is simple and has low cost.
Drawings
FIG. 1 is a sample station diagram of embodiments 1-12 of the present invention;
FIG. 2 is a flow chart of the extraction of phosphorus in different occurrence forms in a marine sediment according to the present invention;
FIG. 3 is a schematic diagram showing the distribution of phosphorus in different occurrence forms 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) Mixing marine sediment and magnesium chloride solution with the 1mol/LpH value of 8 uniformly by using a vortex mixer, vibrating and extracting the mixture at room temperature for 2 hours, and centrifugally separating the mixture at the rotating speed of 5000r/min for 15 minutes to obtain residue a and a first-step phosphorus form extracting solution. Wherein the first-step phosphorus form extracting solution obtained in the step contains weak adsorption state phosphorus (Lsor-P), the marine sediment in the step is collected into sediment samples with the surface layer of about 10cm in the studied sea area through a grab bucket type sampler, and ammonia water with the mass concentration of 10wt% is dropwise added into the 1mol/L magnesium chloride solution to adjust the pH value of the magnesium chloride solution to 8.
2) Mixing residue a with CDB solution with pH value of 7.6After shaking extraction for 6 hours, centrifuging for 15 minutes at a rotation speed of 5000r/min to obtain residue b and supernatant; weighing 5ml of supernatant in a digestion tube, adding sulfuric acid, perchloric acid and nitric acid respectively according to the volume ratio of 1:2:7, and then carrying out high-temperature digestion, wherein the sulfuric acid is high-grade pure, the sulfuric acid content is 95% -98%, and the density is 1.84g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Nitric acid is high-grade pure, and the content of nitric acid is 65% -68%; perchloric acid is produced by Tianjin eastern chemical plant until perchloric acid and nitric acid are decomposed completely, and the process is finished when sulfuric acid flows back, transparent solid is formed after cooling, and the liquid after water is added for dissolution is the second-step phosphorus form extracting solution, wherein a water adding boiling dissolution method can be adopted.
The CDB solution was prepared using 32.4gC 6 H 5 Na 3 O 7 ·2H 2 O、42g NaHCO 3 、2.87g Na 2 S 2 O 4 Is dissolved in 500mL of ultrapure water.
In this step, the pH of the second-step phosphorus-form extract is adjusted to 3.0-3.1 with 0.1mol/L sodium hydroxide solution or 10mol/L sodium hydroxide solution to obtain an extract containing occluded phosphorus (Oc-P).
3) Mixing the residue b with 0.1mol/L sodium hydroxide solution uniformly, vibrating and extracting for 18h, and centrifuging at 5000r/min for 15min to obtain residue c and third-step phosphorus form extract.
4) Uniformly mixing the residue c with NaAC-HAC buffer solution with the concentration of 1mol/LpH =4, vibrating and extracting for 5 hours, and centrifuging for 15 minutes at the rotation speed of 5000r/min to obtain residue d and a fourth-step phosphorus form extracting solution;
in this step, the pH of the extract of the fourth step of phosphorus formation was adjusted to 3.0-3.1 with 1mol/L hydrochloric acid to obtain an extract containing autogenous apatite and calcium-bound phosphorus (Ca-P).
5) Mixing the residue d with 1mol/L hydrochloric acid uniformly, vibrating and extracting for 16 hours, and centrifuging at a rotation speed of 5000r/min for 15 minutes to obtain residue e and a fifth-step phosphorus form extract;
in this step, the pH of the extract of the fifth step of phosphorus form is adjusted to 3.0-3.1 with 0.1mol/L sodium hydroxide solution or 10mol/L sodium hydroxide solution to obtain an extract containing clastic apatite (De-P).
6) The residue e was transferred to a crucible in its entirety, and then placed in a muffle furnace, and subjected to ashing treatment at 550℃for 4 hours. And uniformly mixing the ashed and cooled residue e with 1mol/L hydrochloric acid, vibrating and extracting for 15h, and centrifuging for 15min at a rotation speed of 5000r/min to obtain residue f and a phosphorus form extract 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 Organic Phosphorus (OP) -containing extract.
7) Transferring the total amount of the 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 20min; naturally cooling, uniformly mixing with 1mol/L HCl, oscillating and extracting for 8 hours, and centrifuging for 15 minutes at a rotation speed of 5000r/min to obtain a seventh-step phosphorus form extract.
In this step, the pH of the seventh-stage phosphorus form extract 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 silicate clastic phosphorus (SIF-P).
By adopting the method to extract the phosphorus with different occurrence forms in the marine sediment, the invention can systematically and completely analyze and research the existence form and bioavailability of the phosphorus in the ocean.
The invention adopts an ascorbic acid reduction phosphomolybdenite method (GB/T12763.4-2007) to respectively measure the content of weak adsorption state phosphorus (Lcor-P) in the first-step phosphorus form extracting solution, the content of closed storage state phosphorus (Oc-P) in the second-step phosphorus form extracting solution, the content of iron/aluminum adsorption state phosphorus (Fe/Al-P) in the third-step phosphorus form extracting solution, the content of autogenous apatite and calcium binding state phosphorus (Ca-P) in the fourth-step phosphorus form extracting solution, the content of chip apatite (De-P) in the fifth-step phosphorus form extracting solution, the content of Organic Phosphorus (OP) in the sixth-step phosphorus form extracting solution and the content of silicate chip state phosphorus (SIF-P) in the seventh-step phosphorus form extracting solution.
The relative content and spatial distribution are further analyzed by using data statistics, analysis software and plotting software such as Excle, origin, surfer.
The invention is described in further detail below with reference to the drawings and examples. The marine sediment samples adopted in the following embodiment of the invention are sediment samples with the surface layer of about 10cm respectively collected at 12 stations of the coastal region of Bohai Bay in 10 months in 2019 by adopting a grab bucket type sampler, are uniformly mixed on site and then are stored in a polyethylene sealing bag, and are stored at 4 ℃, and the sampling stations are shown in figure 1.
Example 1
A method for extracting phosphorus in different occurrence forms in marine sediments, which is described with reference to fig. 2, and comprises the following specific steps:
in 2019, the inventor of the invention respectively collects sediment samples with the surface layer thickness of about 10cm at 12 stations of the coastal region of Bohai Bay by using a grab bucket type sampler, uniformly mixes the sediment samples on site, and then seals the sediment samples in a polyethylene sealing bag for storage at 4 ℃.
The above-mentioned collected 12 sediment samples are respectively subjected to extraction and determination of phosphorus in different forms according to the following steps, and a specific implementation flow chart is shown in fig. 2, and the detailed steps are as follows:
step 1 to a 1# wet sediment sample corresponding to 1g dry sample was added 20ml 1mol/L MgCl 2 (ph=8), placing on a vortex mixer, uniformly mixing sediment sample and extractant, placing on a kangaroo oscillator at 25 ℃ for oscillation extraction for 2h at 200r/min, centrifuging at 5000r/min for 15min to obtain residue a and supernatant, and taking the supernatant to obtain the first-step phosphorus form extract. And (3) measuring the content of weak adsorption state phosphorus (Lsor-P) in the first-step phosphorus form extract.
Step 2, 20ml of C having a pH of 7.6 was added to the residue a 6 H 5 Na 3 O 7 ·2H 2 O、NaHCO 3 With Na and Na 2 S 2 O 4 Mixing well, extracting for 6h under shaking at 25deg.C, centrifuging at 5000r/min for 15min to obtain residue b and supernatant, taking 5ml of supernatant, placing into 100ml digestion tube, adding 5ml of strong acid with volume ratio of sulfuric acid, perchloric acid and nitric acid of 1:2:7, then carrying out digestion on the digestion tube, gradually raising temperature, digestion until perchloric acid and nitric acid are decomposed completely, ending with sulfuric acid reflux, cooling, adding water to dissolve white transparent solidThe obtained liquid is the second-step phosphorus form extract, a drop of 2, 4-dinitrobenzene is added, the mixture is uniformly mixed, the pH value of the second-step phosphorus form extract is regulated to 3.0-3.1 by using 0.1mol/L sodium hydroxide solution or 10mol/L sodium hydroxide solution, and the content of closed-state phosphorus (Oc-P) is measured.
And step 3, adding 20ml of 0.1mol/LNaOH into the residue b, uniformly mixing, oscillating and extracting for 18h at 25 ℃, and centrifuging for 15min at a rotation speed of 5000r/min to obtain a residue c and a phosphorus form extract in the third step. And (3) measuring the content of iron/aluminum adsorption phosphorus (Fe/Al-P) in the third-step phosphorus form extract.
And 4, adding 20ml of NaAC-HAC buffer solution with the concentration of 1mol/LpH of 4 into the residue c, uniformly mixing, oscillating and extracting for 5 hours at 25 ℃, centrifuging for 15 minutes at a rotation speed of 5000r/min to obtain a residue d and a fourth-step phosphorus form extract, regulating the pH value of the fourth-step phosphorus form extract to 3.0-3.1 by using 1mol/L hydrochloric acid, and measuring the content of autogenous apatite and calcium-bound 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 16 hours at 25 ℃, centrifuging for 15 minutes at a rotation speed of 5000r/min to obtain a residue e and a fifth-step phosphorus form extract, and adjusting the pH value of the fifth-step phosphorus form extract to 3.0-3.1 by using 0.1mol/L sodium hydroxide solution or 10mol/L sodium hydroxide solution. The content of crushed apatite (De-P) in the fifth step of phosphorus form extract was measured.
And 6, transferring all the residue e into a porcelain crucible, placing the porcelain crucible into a muffle furnace, burning the porcelain crucible for 4 hours at 550 ℃, cooling the porcelain crucible, transferring all the porcelain crucible back into a centrifuge tube, adding 20ml of 1mol/L HCl, uniformly mixing, carrying out oscillation extraction for 15 hours at 25 ℃, centrifuging the porcelain crucible at a rotation speed of 5000r/min for 15 minutes to obtain residue f and a sixth-step phosphorus form extract, and regulating the pH value of the sixth-step phosphorus form extract to 3.0-3.1 by using 0.1mol/L sodium hydroxide solution or 10mol/L sodium hydroxide solution. And (3) measuring the content of Organic Phosphorus (OP) in the phosphorus form extract in the sixth step.
Step 7, transferring the total amount of the residue f into a digestion tube, adding 4ml of concentrated sulfuric acid and 5 drops of perchloric acid, and continuing to digest for 20min after the digestion instrument is used for digestion until the whole residue f becomes white; naturally cooling, adding 20ml of 1mol/L HCl, transferring to a centrifuge tube, oscillating and extracting for 8h, centrifuging for 15min to obtain seventh-step phosphorus form extract, and adjusting the pH of the seventh-step phosphorus form extract to 3.0-3.1 by using 0.1mol/L sodium hydroxide solution or 10mol/L sodium hydroxide solution. And (3) determining the content of silicate clastic phosphorus (SIF-P) in the phosphorus form extract in the seventh step.
Examples 2 to 12
The marine sediment samples 2# 12 were treated by the method of example 1, respectively, and phosphorus with different occurrence forms was obtained.
The results of the measurements of examples 1-12 are shown in FIG. 3.
As can be seen from fig. 3, the classification extraction method of the present invention can obtain seven kinds of phosphorus in different occurrence forms from the marine sediment sample, and the phosphorus contents in the various forms have significant differences. As shown in fig. 3, each of the changes in the phosphorus content was in the order of clastic apatite (De-P) > Organic Phosphorus (OP) > closed-state phosphorus (Oc-P) > silicate clastic-state phosphorus (SIF-P) > iron/aluminum adsorption-state phosphorus (Fe/Al-P) > autogenous apatite and calcium-binding-state phosphorus (Ca-P) > weakly adsorbed-state phosphorus (Lsor-P), while the average ratio of clastic apatite (De-P), organic Phosphorus (OP), closed-state phosphorus (Oc-P), silicate clastic-state phosphorus (SIF-P), iron/aluminum adsorption-state phosphorus (Fe/Al-P), autogenous apatite and calcium-binding-state phosphorus (Ca-P), weakly adsorbed-state phosphorus (Lsor-P) in the 1-12 samples was: 53.95%, 15.89%, 11.78%, 9.01%, 5.66%, 2.80%, 0.91%.
Wherein the proportions of the weakly adsorbed phosphorus (Lsor-P), the occluded phosphorus (Oc-P), the iron/aluminum adsorbed phosphorus (Fe/Al-P), the autogenous apatite and the calcium-bound phosphorus (Ca-P), the clastic apatite (De-P), the Organic Phosphorus (OP) and the silicate clastic phosphorus (SIF-P) in sample 1# are respectively as follows: 0.76%, 18.99%, 8.22%, 2.69%, 49.19%, 12.30%, 7.85%.
The proportions of weakly adsorbed phosphorus (Lsor-P), occluded phosphorus (Oc-P), iron/aluminum adsorbed phosphorus (Fe/Al-P), autogenous apatite and calcium bound phosphorus (Ca-P), clastic apatite (De-P), organic Phosphorus (OP), and silicate clastic phosphorus (SIF-P) in sample 2# were: 0.85%, 6.25%, 3.37%, 2.28%, 69.09%, 10.56%, 7.61%.
The proportions of weakly adsorbed phosphorus (Lsor-P), occluded phosphorus (Oc-P), iron/aluminum adsorbed phosphorus (Fe/Al-P), autogenous apatite and calcium bound phosphorus (Ca-P), clastic apatite (De-P), organic Phosphorus (OP), and silicate clastic phosphorus (SIF-P) in sample 3# were: 1.16%, 16.24%, 5.87%, 5.76%, 42.51%, 20.75%, 7.72%.
The proportions of weakly adsorbed phosphorus (Lsor-P), occluded phosphorus (Oc-P), iron/aluminum adsorbed phosphorus (Fe/Al-P), autogenous apatite and calcium bound phosphorus (Ca-P), clastic apatite (De-P), organic Phosphorus (OP), and silicate clastic phosphorus (SIF-P) in sample 4# were: 1.04%, 16.21%, 8.08%, 3.28%, 45.27%, 18.93%, 7.19%.
The proportions of weakly adsorbed phosphorus (Lsor-P), occluded phosphorus (Oc-P), iron/aluminum adsorbed phosphorus (Fe/Al-P), autogenous apatite and calcium bound phosphorus (Ca-P), clastic apatite (De-P), organic Phosphorus (OP), and silicate clastic phosphorus (SIF-P) in sample 5# were: 1.01%, 8.95%, 7.60%, 2.47%, 52.86%, 16.94%, 10.16%.
The proportions of weakly adsorbed phosphorus (Lsor-P), occluded phosphorus (Oc-P), iron/aluminum adsorbed phosphorus (Fe/Al-P), autogenous apatite and calcium bound phosphorus (Ca-P), clastic apatite (De-P), organic Phosphorus (OP), and silicate clastic phosphorus (SIF-P) in sample 6# were: 1.26%, 17.06%, 3.90%, 3.04%, 54.34%, 13.05%, 7.34%.
The proportions of weakly adsorbed phosphorus (Lsor-P), occluded phosphorus (Oc-P), iron/aluminum adsorbed phosphorus (Fe/Al-P), autogenous apatite and calcium bound phosphorus (Ca-P), clastic apatite (De-P), organic Phosphorus (OP), and silicate clastic phosphorus (SIF-P) in sample 7# were: 0.93%, 9.97%, 7.26%, 3.00%, 51.55%, 19.87%, 7.43%.
Sample 8# the above-mentioned weakly adsorbed phosphorus (Lsor-P), occluded phosphorus (Oc-P), iron/aluminum adsorbed phosphorus (Fe/Al-P), autogenous apatite and calcium-bound phosphorus (Ca-P), clastic apatite (De-P), organic Phosphorus (OP), and silicate clastic phosphorus (SIF-P) had the following ratios: 0.52%, 9.72%, 3.35%, 1.75%, 68.02%, 9.43%, 7.21%.
In sample 9#, the above-mentioned weakly adsorbed phosphorus (Lsor-P), occluded phosphorus (Oc-P), iron/aluminum adsorbed phosphorus (Fe/Al-P), autogenous apatite and calcium-bound phosphorus (Ca-P), clastic apatite (De-P), organic Phosphorus (OP), and silicate clastic phosphorus (SIF-P) have the following ratios: 0.90%, 11.56%, 5.84%, 1.63%, 54.47%, 17.28%, 8.32%.
The proportions of weakly adsorbed phosphorus (Lsor-P), occluded phosphorus (Oc-P), iron/aluminum adsorbed phosphorus (Fe/Al-P), autogenous apatite and calcium bound phosphorus (Ca-P), clastic apatite (De-P), organic Phosphorus (OP), and silicate clastic phosphorus (SIF-P) in sample 10# were: 0.95%, 7.28%, 5.80%, 2.53%, 54.64%, 16.65%, 12.14%.
The proportions of weakly adsorbed phosphorus (Lsor-P), occluded phosphorus (Oc-P), iron/aluminum adsorbed phosphorus (Fe/Al-P), autogenous apatite and calcium bound phosphorus (Ca-P), clastic apatite (De-P), organic Phosphorus (OP), and silicate clastic phosphorus (SIF-P) in sample 11# were: 0.76%, 10.06%, 4.64%, 2.42%, 49.24%, 19.48%, 13.39%.
Sample 12# the ratios of weakly adsorbed phosphorus (Lsor-P), occluded phosphorus (Oc-P), iron/aluminum adsorbed phosphorus (Fe/Al-P), autogenous apatite and calcium bound phosphorus (Ca-P), clastic apatite (De-P), organic Phosphorus (OP), and silicate clastic phosphorus (SIF-P) were respectively: 0.83%, 9.02%, 4.01%, 2.77%, 56.18%, 15.48%, 11.71%.
In addition, the method for extracting the phosphorus with different occurrence forms in the marine sediment is verified by using a standard substance (GBW 07333). The method for continuously classifying leaching of phosphorus occurrence forms in the ocean sediment is used for analyzing the phosphorus form of the standard substance (GBW 07333) of the ocean sediment in the yellow sea, and the precision of each step in the seven steps of continuously classifying leaching is as follows: the first step: 2.7%, second step: 4.5%, third step: 1.9%, fourth step: 3.2%, fifth step: 4.1%, sixth step: 1.6%, seventh step: 2.7 percent, and the error range between the total sum of the actual measurement seven-step phosphorus morphology and the standard value is 6.3 percent to 10.3 percent. Therefore, the method for extracting the phosphorus with different occurrence forms in the marine sediment through continuous graded leaching provided by the embodiment of the invention can be applied to the separation and extraction of the phosphorus form in the marine sediment.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (6)
1. A method for extracting phosphorus in different occurrence forms in marine sediments, which is characterized by comprising the following steps:
1) Using MgCl with pH 8 2 Extracting a marine sediment sample by taking the solution as an extracting agent, and obtaining residue a and an extracting solution containing weakly adsorbed phosphorus after centrifugal separation;
2) Extracting the residue a in the step 1) by using CDB solution with the pH value of 7.6 as an extracting agent, centrifuging to obtain residue b and supernatant, carrying out high-temperature digestion on the supernatant by using strong acid, cooling to obtain transparent solid, dissolving the transparent solid by using water, and regulating the pH value to 3.0-3.1 to obtain an extracting solution containing closed-state phosphorus;
3) Extracting the residue b in the step 2) by using NaOH solution as an extracting agent, and centrifugally separating to obtain residue c and an extracting solution containing iron/aluminum adsorption phosphorus;
4) Extracting the residue c in the step 3) by using NaAC-HAC buffer solution as an extracting agent, centrifuging to obtain residue d and supernatant, and regulating the pH value of the supernatant to 3.0-3.1 to obtain an extracting solution containing autogenous 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 regulating the pH value of the supernatant to 3.0-3.1 to obtain an extracting solution containing clastic apatite;
6) Burning and cooling the residue e in the step 5) at high temperature, extracting by adopting an HCl solution as an extracting agent, centrifuging to obtain residue f and supernatant, and regulating the pH value of the supernatant to 3.0-3.1 to obtain an extracting solution containing organic phosphorus;
7) Digesting the residue f in the step 6), cooling, extracting by adopting an HCl solution as an extracting agent, and regulating the pH value of supernatant fluid to 3.0-3.1 after centrifugal separation to obtain an extracting solution containing silicate clastic phosphorus;
step 2) high-temperature digestion is to adopt a mixed solution composed of sulfuric acid, perchloric acid and nitric acid with the volume ratio of 1:2:7 as a digestion agent for part of supernatant;
the concentration of the NaOH solution in the step 3) is 0.1mol/L.
2. The method for extracting phosphorus in different occurrence forms from marine sediments according to claim 1, wherein step 1) said MgCl 2 The concentration of the solution is 1mol/L, and ammonia water with the mass concentration of 10wt% is added dropwise to adjust the pH value of the extractant to 8.
3. The method for extracting phosphorus in different occurrence forms from marine sediments as recited in claim 1, wherein said CDB solution of step 2) is obtained by using 32.4gC 6 H 5 Na 3 O 7 ·2H 2 O、42gNaHCO 3 、2.87gNa 2 S 2 O 4 Is dissolved in 500mL of ultrapure water.
4. The method of claim 1, wherein the NaAC-HAC buffer in step 4) has a pH of 4.
5. The method for extracting phosphorus in different occurrence forms from marine sediments according to claim 1, wherein the concentration of the HCl solution adopted in the steps 5), 6) and 7) is 1mol/L.
6. The method for extracting phosphorus in different occurrence forms from marine sediments according to claim 1, wherein the high-temperature firing temperature in the step 6) is 550 ℃ and the firing time is 4 hours.
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