CN114590978B - Material for inhibiting release of endogenous phosphorus and arsenic in sediment and using method - Google Patents
Material for inhibiting release of endogenous phosphorus and arsenic in sediment and using method Download PDFInfo
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Abstract
The invention provides a material and method of use for inhibiting the release of endogenous phosphorus and arsenic from a deposit, the material comprising fulvic acid extracted from the deposit; the fulvic acid is a fulvic acid solution obtained by leaching the sediment with an alkaline solution, and then is separated with resin to obtain hydrophobic fulvic acid or hydrophobic acidic fulvic acid. The application utilizes the hydrophobic fulvic acid or the hydrophobic acidic fulvic acid to be mixed with clay minerals or sediments, prepares the formed sediment phosphate and the arsenic release inhibiting material through bonding, and can effectively control the release of phosphorus pollutants and heavy metal arsenic in the sediments when the material acts on the water body sediments. The material prepared by the method is taken from water body sediments, and new pollutants are not introduced into the material while the release of phosphorus and arsenic in the sediments is inhibited.
Description
Technical Field
The invention belongs to the technical field of endogenous pollution control of water, and particularly relates to a material for inhibiting release of endogenous phosphorus and arsenic in sediment and a using method thereof.
Background
The source of pollutants in the water body comprises an external source and an internal source, the external source pollution comprises point source pollution caused by sewage discharge of industrial sewage, domestic sewage and the like, and non-point source pollution entering the water body along with rainwater runoff, farmland drainage and the like. Endogenous contamination is primarily from the release of contaminants from the sediment. In recent years, along with the gradual increase of environmental management strength, exogenous pollution is well controlled, and the proportion of endogenous pollution in the water environment problem is increased, so that the method becomes one of the difficulties which are urgently needed to be solved in the field of current water environmental management.
In this context, endogenous deposit pollution control technology has also become a focus of research in this field. Among the various technical means for controlling the release of the pollutants from the sediments in the prior art, the technology of covering the bottom sediment by adding a control material to cover the bottom sediment so as to isolate the bottom sediment and control the release of the pollutants from the bottom sediment is widely applied in recent years. For example, chinese patent document CN106277672a discloses a method for preparing a sediment-water interface phosphorus release control material, which specifically comprises: (1) Collecting lake sediments, and obtaining sediment powder for later use through freeze drying, grinding and sieving; (2) Taking kaolin, drying, grinding and sieving to obtain kaolin powder for later use; (3) Uniformly mixing the sediment powder and the kaolin powder to form mixed powder for later use; (4) Carrying out oxidation treatment on the mixed powder, and then drying for later use; (5) Modifying the mixed powder oxidized in the step (4) by using an iron salt solution, and then drying for later use; (6) And (4) adding water into the modified mixed powder obtained in the step (5) for soaking, then carrying out extrusion forming, and roasting the formed material to obtain the control material.
The control material in the prior art has stronger adsorption capacity to phosphate, so that the release of phosphorus pollutants in sediments into a water body can be effectively controlled. The phosphorus pollutant is one of key factors influencing water eutrophication, and the inhibition of the release of sediment phosphorus has a remarkable effect on improving the water eutrophication. However, the sediment covering material in the prior art can only control single pollutants, the release factor of the pollutants in the actual sediment is very complex, and the inhibition of the single pollutants is limited for improving the whole water body environment. In addition to phosphorus contaminants, deposits are also a significant reservoir of heavy metal contaminants, with a significant risk of secondary contamination of the heavy metals. The control of heavy metal release from deposits is also a focus of research in the field, since heavy metals cannot be decomposed by organisms and are likely to be converted to more toxic organics within the organism. Therefore, how to explore a material which has a composite control effect, can effectively inhibit the release of heavy metals while inhibiting the release of phosphorus pollutants has great significance for the treatment and restoration of the water environment.
Disclosure of Invention
The invention solves the technical problem that the prior art lacks a material capable of simultaneously inhibiting release of sediment phosphorus and heavy metal pollutants, further provides a material capable of inhibiting release of endogenous phosphorus and heavy metal arsenic in sediment, and also provides a using method of the material.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a material for inhibiting endogenous release of phosphorus and arsenic from a deposit, comprising a fulvic acid component extracted from the deposit; the fulvic acid component is a fulvic acid solution obtained by leaching sediments with an alkaline solution, and is separated by resin to obtain hydrophobic fulvic acid or hydrophobic acidic fulvic acid.
The extraction method of the hydrophobic fulvic acid comprises the following steps: (1) Freeze-drying and sieving the sediments, then leaching and centrifuging the sediments by using an alkaline solution under the protection of inert gas, collecting the centrifuged leaching liquor, carrying out membrane, pH value adjustment and water bath heating treatment, and centrifuging again to obtain a fulvic acid solution; (2) Adjusting the fulvic acid solution to be neutral, passing through a pretreated XAD-8 resin column, washing the resin column by using ultrapure water, collecting the fulvic acid solution and ultrapure water which pass through the column, adjusting the pH to 2, passing through the XAD-8 column again, and leaching by using 1 time of column volume of HCl with the concentration of 0.01 mol/L; (3) And (3) backwashing the washed resin column by using 0.25-time column volume of NaOH with the concentration of 0.1mol/L, backwashing by using 1.5-time column volume of ultrapure water, collecting backwashing liquid, adjusting the pH value to be neutral, and performing vacuum freeze drying to obtain the hydrophobic fulvic acid.
The extraction method of the hydrophobic acidic fulvic acid comprises the following steps: (1) Freeze-drying and sieving the sediments, then leaching and centrifuging the sediments by using an alkaline solution under the protection of inert gas, collecting the centrifuged leaching liquor, carrying out membrane, pH value adjustment and water bath heating treatment, and centrifuging again to obtain a fulvic acid solution; (2) Adjusting the fulvic acid solution to be neutral, passing through a pretreated XAD-8 resin column, and washing the resin column by ultrapure water; then, backwashing the resin column by using 0.25 times of the volume of the resin column and 0.1mol/L HCl, and continuously backwashing by using 1.5 times of the volume of the column and 0.01mol/L HCl; (3) Collecting the fulvic acid solution and ultrapure water after column passing in the step (2), adjusting the pH to 2, passing through the XAD-8 column again, and then leaching with HCl which is 1 time of the column volume and has a concentration of 0.01 mol/L;
(4) And (3) backwashing the washed resin column in the step (3) by using 0.25-time column volume of NaOH with the concentration of 0.1mol/L, continuously backwashing by using 1.5-time column volume of ultrapure water, collecting backwashing liquid, adjusting the pH value to be neutral, and performing vacuum freeze drying to obtain the hydrophobic acidic fulvic acid.
In the step (1), the leaching and the centrifuging operation are repeated on a sediment sample until the supernatant is yellow, and the pH value of the supernatant obtained by each centrifuging operation is adjusted to l-2 after the supernatant is mixed, so as to obtain the fulvic acid solution.
In the step (1), the leaching liquor after the pH value is adjusted is heated in a water bath and then stands overnight.
In the step (1), after the liquid is filtered by a 0.45 mu m microporous filter membrane, the pH value is adjusted to l-2, the liquid is heated in a thermostatic water bath at 70 ℃ for 1h, and the liquid is kept stand overnight; and centrifuging to obtain supernatant, namely the fulvic acid solution.
The XAD-8 resin was pretreated prior to use as follows: soaking the mixture in 0.1mol/L NaOH solution for 24 hours to remove impurities; packing the XAD-8 resin subjected to impurity removal and drying by using filter paper, putting the packed resin into a Soxhlet extractor, and carrying out Soxhlet extraction for 12 hours by using an eluent as acetone; after the extraction is finished, soaking the resin into methanol, and filling the resin into a chromatographic column together; the resin was rinsed with ultrapure water until the DOC concentration in the effluent was less than 1mg/L.
The material for inhibiting release of endogenous phosphorus and arsenic in sediment also comprises clay or sediment components, the fulvic acid component is mixed with the clay or sediment components, water is added into the mixture, the mixture is bonded and molded, and the material for inhibiting release of endogenous phosphorus and arsenic in sediment is obtained after drying, wherein the fulvic acid component is used in an amount of 0.5-5 parts by weight, and the clay or sediment components are used in an amount of 95-99.5 parts by weight.
And the sediment powder obtained by air drying, vacuum freeze drying, grinding and sieving sediments taken from a water body is roasted for 4 to 6 hours at the temperature of between 400 and 800 ℃ to obtain the sediment components.
The material for inhibiting the release of endogenous phosphorus and arsenic in the sediment is laid above the sediment of the water body by using the material with the dosage of 10-50 kg/m 2 。
The material for inhibiting the release of endogenous phosphorus and arsenic in the sediment has the advantages that:
the inhibition material comprises a hydrophobic fulvic acid component, and when the hydrophobic fulvic acid acts on the sediments of the water body, the release of phosphorus pollutants and heavy metal arsenic in the sediments can be effectively inhibited. The hydrophobic fulvic acid prepared by the method can inhibit the release of phosphorus and arsenic in the sediment, and does not introduce new pollutants. Fulvic Acid (FA) or hydrophilic fulvic acid, which contains a large amount of nitrogen and phosphorus pollutants, is added into a water body, and the pollutants are introduced, so that the effect of inhibiting the release of the pollutants cannot be achieved. The hydrophobic fulvic acid or the hydrophobic fulvic acid acidic component separated by the method has extremely low nitrogen and phosphorus contents, and no new pollutants are introduced.
The hydrophobic acidic fulvic acid or the hydrophobic acidic component obtained by the preparation method can further promote the inhibition effect on phosphorus and arsenic, and both the hydrophobic acidic fulvic acid and the hydrophobic acidic fulvic acid component obtained by the preparation method do not contain a protein-like substance, so that the problem that the protein-like substance in fulvic acid releases nitrogen and phosphorus pollutants under the long-term degradation effect is avoided.
The material in this application can high-efficiently restrain the release of phosphorus, arsenic simultaneously, has the composite control effect to nutrient substance phosphorus and heavy metal arsenic concurrently, has important meaning to the pollution control of actual water.
In order to make the technical solution of the material for inhibiting the release of endogenous phosphorus and arsenic in the deposit according to the present invention more clear, the present invention is further described in detail below with reference to specific examples.
Detailed Description
In the following embodiments, the amount per part by weight is 1kg.
In the following examples 1-4, the XAD-8 resin was pretreated prior to use as follows: soaking the mixture in 0.1mol/L NaOH solution for 24 hours to remove impurities; packing the XAD-8 resin subjected to impurity removal and drying by using filter paper, putting the packed resin into a Soxhlet extractor, and carrying out Soxhlet extraction for 12 hours by using an eluent as acetone; after the rope-lifting is finished, soaking the resin into methanol, and filling the methanol and the resin into a chromatographic column, wherein the diameter of the chromatographic column adopted in the embodiment is 26mm, and the height of the chromatographic column is 50cm; after the completion of the column packing, the resin was rinsed with ultrapure water until the DOC concentration in the effluent was less than 1mg/L.
Example 1
The embodiment provides a material for inhibiting release of endogenous phosphorus and arsenic in sediment, which is prepared from the following raw materials: 0.5 part by weight of fulvic acid component extracted from the sediment; the clay component is bentonite powder obtained by sieving bentonite with a 100-mesh sieve, wherein the usage amount of the bentonite powder is 99.5 parts by weight in terms of dry weight, and the dry weight is the weight when the bentonite powder is dried to constant weight. And uniformly mixing the hydrophobic fulvic acid component and the bentonite powder, adding water, bonding and forming, and drying at 60 ℃ to obtain the material, wherein the amount of the added water is 10 parts by weight during mixing.
Wherein the fulvic acid component is a fulvic acid solution obtained by leaching the sediment with an alkaline solution, and is a hydrophobic fulvic acid component obtained by resin separation, and the specific extraction method comprises the following steps:
(1) Placing the sediment sample at-80 ℃ for vacuum freeze drying, and crushing the dried sediment sample and screening the crushed sediment sample through a 100-mesh fine screen; under the protection of nitrogen, na is used 4 P 2 O 7 ·10H 2 Leaching the sieved sediment by using mixed solution of O and NaOH, and leaching for 16h at constant temperature of 200r/min to obtain leaching liquor, wherein Na in the mixed solution 4 P 2 O 7 ·10H 2 The concentration of O and NaOH are both 0.1mol/L, and the mass ratio of the mixed solution to the deposit during leaching is 10; performing centrifugal operation on the leaching liquor to separate out liquid, wherein the rotating speed of the centrifugal operation is 1000r/min; repeatedly performing the leaching and centrifuging operations on a sediment sample for 2-3 times until the supernatant is yellow, mixing the supernatants obtained by each centrifuging operation, filtering the obtained mixed liquid through a 0.45 mu m microporous filter membrane, adjusting the pH value to l, heating in a constant-temperature water bath at 70 ℃ for 1h, and standing overnight; and centrifuging at the rotating speed of 3000r/min to obtain supernatant, namely the fulvic acid solution.
(2) Adjusting the fulvic acid solution to be neutral, passing through a pretreated XAD-8 resin column, washing the resin column by using ultrapure water with the volume of 1.5 times of the column volume, collecting the fulvic acid solution and the ultrapure water after passing through the column, adjusting the pH to 2 by using HCl with the concentration of 6mol/L, passing through the XAD-8 column again, and then leaching by using HCl with the concentration of 0.01mol/L with the volume of 1 time of the column volume.
(3) And (3) backwashing the washed resin column by using 0.25-time column volume of NaOH with the concentration of 0.1mol/L, backwashing by using 1.5-time column volume of ultrapure water, collecting all backwashing liquids, adjusting the pH value to be neutral, and performing vacuum freeze drying to obtain the hydrophobic fulvic acid component.
Example 2
The embodiment provides a material for inhibiting release of endogenous phosphorus and arsenic in sediment, which is prepared from the following raw materials: 2 parts by weight of a fulvic acid component extracted from the sediment; and clay components, wherein the clay components are bentonite powder obtained by sieving bentonite with a 100-mesh sieve and then roasting the bentonite powder for 4 hours at 400 ℃. The usage amount of the bentonite powder is 95 parts by weight in terms of dry weight, and the dry weight is the weight when the bentonite powder is dried to constant weight. And uniformly mixing the hydrophobic fulvic acid component and the bentonite powder, adding water, bonding and forming, and drying at 60 ℃ to obtain the material, wherein the amount of the added water is 10 parts by weight during mixing.
Wherein the fulvic acid component is a fulvic acid solution obtained by leaching the sediment with an alkaline solution, and is a hydrophobic fulvic acid component obtained by resin separation, and the specific extraction method comprises the following steps:
(1) Placing the sediment sample at-80 ℃ for vacuum freeze drying, and crushing the dried sediment sample and screening the crushed sediment sample through a 100-mesh fine screen; under the protection of nitrogen, na is used 4 P 2 O 7 ·10H 2 Leaching the sieved sediment by using mixed solution of O and NaOH, and leaching for 16h at constant temperature of 200r/min to obtain leaching liquor, wherein Na in the mixed solution 4 P 2 O 7 ·10H 2 The concentration of O and NaOH are both 0.1mol/L, and the mass ratio of the mixed solution to the deposit during leaching is 10. Performing centrifugal operation on the leaching liquor to separate out liquid, wherein the rotating speed of the centrifugal operation is 1000r/min; repeating the above leaching and centrifuging operation for 2-3 times on a sediment sampleMixing the supernatants obtained by each centrifugation operation until the supernatant is yellow, filtering the obtained liquid with a 0.45 μm microporous membrane, adjusting pH to l, heating in 70 deg.C constant temperature water bath for 1h, and standing overnight; and centrifuging at the rotating speed of 3000r/min to obtain supernatant, namely the fulvic acid solution.
(2) Adjusting the fulvic acid solution to be neutral, passing through a pretreated XAD-8 resin column, washing the resin column by using ultrapure water with the volume of 1.5 times of the column volume, collecting the fulvic acid solution and the ultrapure water after the column is passed through, adjusting the pH to 2 by using HCl with the concentration of 6mol/L, passing through the XAD-8 column again, and then leaching by using HCl with the concentration of 0.01mol/L with the volume of 1 time of the column volume;
(3) And (3) backwashing the washed resin column by using 0.25-time column volume of NaOH with the concentration of 0.1mol/L, backwashing by using 1.5-time column volume of ultrapure water, collecting all backwashing liquids, adjusting the pH value to be neutral, and performing vacuum freeze drying to obtain the hydrophobic fulvic acid component.
Example 3
The embodiment provides a material for inhibiting release of endogenous phosphorus and arsenic in sediment, which is prepared from the following raw materials: 2 parts by weight of a fulvic acid component extracted from the sediment; and (3) taking sediment from a water body, air-drying the sediment at-80 ℃, carrying out vacuum freeze drying, grinding the sediment, and sieving the sediment with a 100-mesh sieve to obtain sediment powder, and roasting the sediment powder at 400 ℃ for 4 hours to obtain the sediment component. The amount of the deposit component used was 98 parts by weight on a dry weight basis. And mixing the hydrophobic fulvic acid component and the sediment component, adding water, bonding and molding, and drying at 60 ℃ to obtain the material, wherein the amount of the added water is 10 parts by weight during mixing.
The fulvic acid component is a fulvic acid solution obtained by leaching the sediment with an alkaline solution, and is a hydrophobic fulvic acid component obtained by resin separation, and the specific extraction method comprises the following steps:
(1) Placing the sediment sample at-80 ℃ for vacuum freeze drying, and crushing the dried sediment sample and screening the crushed sediment sample through a 100-mesh fine screen; under the protection of nitrogen, na is used 4 P 2 O 7 ·10H 2 O andleaching the sieved deposit with NaOH mixed solution for 16h at constant temperature of 200r/min to obtain leaching solution, wherein Na in the mixed solution 4 P 2 O 7 ·10H 2 The concentration of O and NaOH are both 0.1mol/L, and the mass ratio of the mixed solution to the deposit during leaching is 10. Centrifuging the leaching solution to separate out liquid, wherein the rotation speed of the centrifugation is 1000r/min; repeating the leaching and the centrifuging operation for 2-3 times on a sediment sample until the supernatant is yellow, mixing the supernatants obtained by each centrifuging operation to obtain the liquid, filtering the liquid by a 0.45 mu m microporous filter membrane, adjusting the pH value to 1, heating for 1h in a constant-temperature water bath at 70 ℃, and standing overnight; and centrifuging at the rotating speed of 3000r/min to obtain supernatant, namely the fulvic acid solution.
(2) Adjusting the fulvic acid solution to be neutral, passing through a pretreated XAD-8 resin column, washing the resin column by using ultrapure water with the volume of 1.5 times of the column volume, collecting the fulvic acid solution and the ultrapure water after the column is passed through, adjusting the pH to 2 by using HCl with the concentration of 6mol/L, passing through the XAD-8 column again, and then leaching by using HCl with the concentration of 0.01mol/L with the volume of 1 time of the column volume;
(3) And (3) backwashing the washed resin column by using 0.25-time column volume of NaOH with the concentration of 0.1mol/L, backwashing by using 1.5-time column volume of ultrapure water, collecting all backwashing liquids, adjusting the pH value to be neutral, and performing vacuum freeze drying to obtain the hydrophobic fulvic acid component.
Example 4
The embodiment provides a material for inhibiting release of endogenous phosphorus and arsenic in sediment, which is prepared from the following raw materials: 2 parts by weight of a fulvic acid component extracted from the sediment; and (3) taking sediment from a water body, air-drying the sediment at-80 ℃, carrying out vacuum freeze drying, grinding the sediment, and sieving the sediment with a 100-mesh sieve to obtain sediment powder, and roasting the sediment powder at 800 ℃ for 4 hours to obtain the sediment component. The amount of the above-mentioned deposit component used was 98 parts by weight on a dry weight basis. And mixing the hydrophobic fulvic acid component with the sediment component, adding water, bonding and molding, and drying at 60 ℃ to obtain the material, wherein the weight part of the added water is 10 parts.
In this embodiment, the fulvic acid component is a fulvic acid solution obtained by leaching the sediment with an alkaline solution, and the hydrophobic acidic fulvic acid is obtained by resin separation, and the specific extraction method includes the following steps:
(1) Putting the sediment sample at-80 ℃ for vacuum freeze drying, and crushing the dried sediment sample to pass through a 100-mesh fine screen; under the protection of nitrogen, na is used 4 P 2 O 7 ·10H 2 Leaching the sieved sediment by using mixed solution of O and NaOH, and leaching for 16h at constant temperature of 200r/min to obtain leaching liquor, wherein Na in the mixed solution 4 P 2 O 7 ·10H 2 The concentration of O and NaOH are both 0.1mol/L, and the mass ratio of the mixed solution to the deposit during leaching is 10. Centrifuging the leaching solution to separate out liquid, wherein the rotating speed of the centrifuging operation is 1000r/min; repeating the leaching and the centrifuging operation for 2-3 times on a sediment sample until the supernatant is yellow, mixing the supernatants obtained by each centrifuging operation to obtain the liquid, filtering the liquid by a 0.45 mu m microporous filter membrane, adjusting the pH value to 1, heating for 1h in a constant-temperature water bath at 70 ℃, and standing overnight; and centrifuging at the rotating speed of 3000r/min to obtain supernatant, namely the fulvic acid solution.
(2) Adjusting the fulvic acid solution to be neutral, passing through a pretreated XAD-8 resin column, and washing the resin column by using ultrapure water with the volume of 1.5 times of the column volume; then, the resin column is backwashed by HCl which is 0.25 times the volume of the resin column and has a concentration of 0.1mol/L, then the resin column is backwashed continuously by HCl which is 1.5 times the volume of the column and has a concentration of 0.01mol/L, and the backwashing of the step is not collected to remove the hydrophobic alkaline fulvic acid component on the resin column.
(3) Collecting the fulvic acid solution and ultrapure water which pass through the column in the step (2), adjusting the pH to 2, passing through the XAD-8 column again, and then leaching with HCl with the column volume of 1 time and the concentration of 0.01 mol/L;
(4) And (3) backwashing the washed resin column in the step (3) by using 0.25-time column volume of NaOH with the concentration of 0.1mol/L, continuously backwashing by using 1.5-time column volume of ultrapure water, collecting all backwashing liquids, adjusting the pH value to be neutral, and performing vacuum freeze drying to obtain the hydrophobic acidic fulvic acid.
Examples of the experiments
Experimental example 1
To demonstrate the technical effect of the materials described in this application for inhibiting the release of endogenous phosphorus and arsenic from deposits, experimental examples were set up to verify the performance of the materials. The experiment is carried out in the box, and the deposit that is got from yunnan pond bottom has been laid to the bottom half, and the deposit is air-dried, smashes the back stirring to deposit sample is unanimous in guaranteeing each box. The thickness of the sediment is 30 cm, the materials for inhibiting the release of endogenous phosphorus and arsenic in the sediment, which are prepared in the embodiments 1 to 5, are respectively paved above the sediment layer of each independent box body, and the using amount is 10kg/m 2 Equal amounts of overburden water were added to each tank and a 360 day test run was performed using a DGT probe to test the flux of arsenic and phosphorous in the overburden water.
The experimental example was provided with a control group, which only laid a sediment layer at the bottom of the tank, and no inhibiting material above. The results of the experiments are shown in the following table:
from the above experimental results, it can be seen that the material prepared in the present application has excellent inhibitory effect on the release of both phosphorus and arsenic.
Experimental example 2
The components of the hydrophobic fulvic acid component prepared in example 3 and the hydrophobic acidic fulvic acid component and the hydrophobic alkaline fulvic acid component prepared in example 4 were analyzed by using a three-dimensional fluorescence spectroscopy technique, and the results were as follows:
wherein C1 is terrestrial humus, C2 is microbial humus, C3 and C4 are proteinoid substances, and C5 is soil fulvic acid; from the above results, it is understood that both the hydrophobic fulvic acid component and the hydrophobic acidic fulvic acid component prepared by the present invention do not contain a proteinoid substance, and when used as an inhibitory material, the problem of release of nitrogen due to long-term degradation of the proteinoid substance can be prevented.
Comparative example 1
To further demonstrate the technical effect of the materials described in this application for inhibiting the release of endogenous phosphorus and arsenic from deposits, a comparative example was set up, in which the experimental procedure was the same as the experimental example. Comparative example 3 sets of experiments were set, wherein the control materials of 2 experiments were composed of bentonite and an inhibiting component, wherein the amount of the inhibiting component used was 5 parts by weight and the amount of the bentonite used was 95 parts by weight; the inhibiting component and the bentonite are mixed, added with water, bonded and molded, and dried at 60 ℃ to obtain the control material, wherein the amount of the added water is 10 parts by weight during mixing. The Control material prepared by bentonite in the rest 1 group in proportion is used as a Control group (Control).
The inhibitory components of the 2 experiments were hydrophilic fulvic acid component (Hydrohilic FA) and fulvic acid component (FA), respectively.
The preparation method of the fulvic acid component and the hydrophilic fulvic acid component comprises the following steps: placing the sediment sample at-80 ℃ for vacuum freeze drying, and crushing the dried sediment sample and screening the crushed sediment sample through a 100-mesh fine screen; under nitrogen atmosphere, na was used 4 P 2 O 7 ·10H 2 Leaching the sieved deposit with mixed solution of O and NaOH, leaching for 16h at constant temperature of 200r/min to obtain leach liquor, wherein Na in the mixed solution 4 P 2 O 7 ·10H 2 The concentrations of O and NaOH were 0.1mol/L. Centrifuging the leaching solution to separate out liquid, wherein the rotation speed of the centrifugation is 1000r/min; repeating the leaching and the centrifuging operation for 2-3 times on a sediment sample until the supernatant is yellow, mixing the supernatants obtained by each centrifuging operation to obtain the liquid, filtering the liquid by a 0.45 mu m microporous filter membrane, adjusting the pH value to 1, carrying out constant-temperature water bath at 70 ℃ for 1h, and standing overnight; and centrifuging at the rotating speed of 3000r/min to obtain supernatant, namely the fulvic acid solution.
Adjusting the pH of the fulvic acid solution to neutral, and vacuum freeze-drying at-80 deg.C to obtain fulvic acid component (FA).
Dripping the fulvic acid solution into an XAD-8 resin column from the upper end, washing the fulvic acid solution after passing through the column by using ultrapure water with the volume of 1.5 times of the column volume, leaching by using 0.01mol/L HCl with the volume of 1 time of the column volume, collecting leacheate to obtain a hydrophilic fulvic acid solution, and carrying out vacuum freeze drying at-80 ℃ to obtain the hydrophilic fulvic acid component.
The experimental results of this comparative example are as follows:
| As Flux (pg s -1 cm -2 )/360days | P Flux (pg s -1 cm -2 )/360days | |
| COMPARATIVE EXAMPLE 1 (FA) | -1.091 | 4.708 |
| Comparative example 2 (Hydrohilic FA) | 0.755 | -0.904 |
| Comparative example 3 (Control) | 1.092 | 0.032 |
From the comparative experiments, it is found that the fulvic acid component (FA) has a good effect of inhibiting arsenic, but has a very poor effect of inhibiting P. The hydrophilic fulvic acid component (hydrohalic FA) has a good effect of inhibiting phosphorus, but has a poor effect of inhibiting arsenic release, and cannot simultaneously inhibit phosphorus and arsenic release. The material prepared in the application can effectively inhibit the release of phosphorus and arsenic at the same time.
Comparative example 2
DOC (soluble organic carbon), total Phosphorus (TP), and ammonia Nitrogen (NH) for the hydrophobic fulvic acid component prepared in example 2 of the present application, the Fulvic Acid (FA) solution prepared in comparative example 1, and the hydrophilic fulvic acid (hydrohalic FA) solution 4 -N) content was determined as follows:
| DOC(mg/L) | TP(mg/L） | NH 4 -N(mg/L) | |
| fulvic acid solution | 381 | 28.95 | 35.58 |
| Hydrophilic fulvic acid solution | 101 | 27.99 | 44.01 |
| Hydrophobic fulvic acid solution | 155 | 1.10 | 8.29 |
From the results, the proportion of the phosphorus content and the ammonia nitrogen content of the hydrophobic fulvic acid prepared in the application to the DOC is much lower than that of the fulvic acid and the hydrophilic fulvic acid, so that the hydrophobic fulvic acid prepared in the application can inhibit the release of phosphorus and arsenic in deposits, and meanwhile, new pollutants can not be introduced.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. Therefore, the protection scope of the present invention should be subject to the claims.
Claims (8)
1. A material for inhibiting the release of endogenous phosphorus and arsenic from a deposit, comprising a fulvic acid component extracted from the deposit; the fulvic acid component is a fulvic acid solution obtained by leaching sediments with an alkaline solution, and is separated by resin to obtain hydrophobic fulvic acid or hydrophobic acidic fulvic acid;
the extraction method of the hydrophobic fulvic acid comprises the following steps: (1) Freeze-drying and sieving the sediments, then leaching and centrifuging the sediments by using an alkaline solution under the protection of inert gas, collecting the centrifuged leaching liquor, carrying out membrane, pH value adjustment and water bath heating treatment, and centrifuging again to obtain a fulvic acid solution; (2) Adjusting the fulvic acid solution to be neutral, passing through a pretreated XAD-8 resin column, washing the resin column by using ultrapure water, collecting the fulvic acid solution and the ultrapure water after the column passes, adjusting the pH to 2, passing through the XAD-8 resin column again, and leaching by using 1 time of column volume of HCl with the concentration of 0.01 mol/L; (3) Backwashing the washed resin column by using 0.25-time column volume of NaOH with the concentration of 0.1mol/L, backwashing by using 1.5-time column volume of ultrapure water, collecting backwashing liquid, adjusting the pH value to be neutral, and performing vacuum freeze drying to obtain the hydrophobic fulvic acid;
the extraction method of the hydrophobic acidic fulvic acid comprises the following steps: (1) Freeze-drying and sieving the sediments, then leaching and centrifuging the sediments by using an alkaline solution under the protection of inert gas, collecting the centrifuged leaching liquor, carrying out membrane, pH value adjustment and water bath heating treatment, and centrifuging again to obtain a fulvic acid solution; (2) Adjusting the fulvic acid solution to be neutral, passing through a pretreated XAD-8 resin column, and washing the resin column by ultrapure water; then, backwashing the resin column by using 0.25 times of the volume of the resin column and 0.1mol/L HCl, and continuously backwashing by using 1.5 times of the volume of the column and 0.01mol/L HCl; (3) Collecting the fulvic acid solution and ultrapure water which pass through the column in the step (2), adjusting the pH to 2, passing through the XAD-8 resin column again, and then leaching with HCl which is 1 time of the column volume and has the concentration of 0.01 mol/L; (4) And (3) backwashing the washed resin column in the step (3) by using 0.25-time column volume of NaOH with the concentration of 0.1mol/L, continuously backwashing by using 1.5-time column volume of ultrapure water, collecting backwashing liquid, adjusting the pH value to be neutral, and performing vacuum freeze drying to obtain the hydrophobic acidic fulvic acid.
2. The material for inhibiting release of endogenous phosphorus and arsenic in sediment according to claim 1, wherein in the step (1), the leaching and the centrifuging are repeated on a sediment sample until the supernatant is yellow, and the pH value of the supernatant obtained from each centrifuging is adjusted to l-2 after mixing, so as to obtain the fulvic acid solution.
3. The material for inhibiting the release of endogenous phosphorus and arsenic in sediments according to claim 2, wherein in the step (1), the leaching solution after pH value adjustment is subjected to water bath heating treatment and then is left for overnight.
4. The material for inhibiting release of endogenous phosphorus and arsenic in sediment according to claim 3, wherein in the step (1), the leaching and the centrifugation are repeated on a sediment sample until the supernatant is yellow, after the supernatant obtained from each centrifugation is mixed, the obtained liquid is filtered by a 0.45 μm microporous membrane, the pH value is adjusted to l-2, the mixture is heated in a constant-temperature water bath at 70 ℃ for 1h, and the mixture is allowed to stand overnight; and centrifuging to obtain supernatant, namely the fulvic acid solution.
5. A material for inhibiting endogenous phosphorus and arsenic release from deposits according to any of claims 1-4, wherein the XAD-8 resin in the XAD-8 resin column is pretreated prior to use as follows: soaking the mixture in 0.1mol/L NaOH solution for 24 hours to remove impurities; packing the XAD-8 resin subjected to impurity removal and drying by using filter paper, putting the packed resin into a Soxhlet extractor, and carrying out Soxhlet extraction for 12 hours by using an eluent as acetone; after the extraction is finished, soaking the resin into methanol, and filling the resin into a chromatographic column together; the resin was rinsed with ultrapure water until the DOC concentration in the effluent was less than 1mg/L.
6. The material for inhibiting the release of endogenous phosphorus and arsenic in sediment according to claim 5, further comprising clay or sediment components, wherein the fulvic acid component is mixed with the clay or sediment components, water is added into the mixture, the mixture is bonded and molded, and the material for inhibiting the release of endogenous phosphorus and arsenic in sediment is obtained after drying, wherein the fulvic acid component is used in an amount of 0.5-5 parts by weight, and the clay or sediment components are used in an amount of 95-99.5 parts by weight.
7. The material for inhibiting release of endogenous phosphorus and arsenic in sediment according to claim 6, further comprising sediment components, wherein sediment powder obtained by air drying, vacuum freeze drying, grinding and sieving sediment in water is roasted at 400-800 ℃ for 4-6 hours to obtain the sediment components.
8. Use of a material for inhibiting the release of endogenous phosphorus and arsenic from sediments as claimed in any of claims 1-7, characterised in that the material is laid on top of the sediments in a body of waterThe dosage of the material is 10-50 kg/m 2 。
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Citations (4)
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| JPS5170966A (en) * | 1974-12-16 | 1976-06-19 | Giichi Yamaguchi | |
| CN105043839A (en) * | 2015-09-16 | 2015-11-11 | 中国环境科学研究院 | Method for separating and enriching fulvic acid in soil through activated carbon |
| CN106706404A (en) * | 2017-02-08 | 2017-05-24 | 中国环境科学研究院 | Equipment for extracting hydrophobic fulvic acid in soil by adopting combination of two-stage resins |
| CN112090393A (en) * | 2020-09-04 | 2020-12-18 | 山西大学 | Preparation method of green functional clay repairing material for composite pollution |
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| CN110255767A (en) * | 2019-06-28 | 2019-09-20 | 吉林建筑大学 | The separation method of organic matter in a kind of natural water body |
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| JPS5170966A (en) * | 1974-12-16 | 1976-06-19 | Giichi Yamaguchi | |
| CN105043839A (en) * | 2015-09-16 | 2015-11-11 | 中国环境科学研究院 | Method for separating and enriching fulvic acid in soil through activated carbon |
| CN106706404A (en) * | 2017-02-08 | 2017-05-24 | 中国环境科学研究院 | Equipment for extracting hydrophobic fulvic acid in soil by adopting combination of two-stage resins |
| CN112090393A (en) * | 2020-09-04 | 2020-12-18 | 山西大学 | Preparation method of green functional clay repairing material for composite pollution |
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