CN104383890A - Soil heavy metal ion absorbent and preparation method thereof - Google Patents
Soil heavy metal ion absorbent and preparation method thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
Abstract
The invention discloses a soil heavy metal ion absorbent and a preparation method thereof. The soil heavy metal ion absorbent is prepared by mixing modified corn straws, modified kaolin and potassium humate in a mass ratio of 2 to 5 to 3; the modified corn straws are mainly formed by drying, alkali treatment, acid treatment and drying; the modified kaolin is mainly formed by adding sodium polyphosphate and then roasting. The soil heavy metal ion absorbent disclosed by the invention can be used for obviously enhancing the absorption capability of soil to heavy metal and reducing the migration of the heavy metal in the soil to crops. Tests show that the average lead reducing rate in corn kernels is 15.63%, the average cadmium reducing rate in the corn kernels is 12.15%, and the average arsenic reducing rate in the corn kernels is 7.62%. The average lead reducing rate in rice is 17.8%, the average cadmium reducing rate in the rice is 17.27%, and the average arsenic reducing rate in the rice is 21.84%, and the quality of edible part of the crops is guaranteed.
Description
Technical field
The present invention relates to the planting technology field of heavy metal pollution of soil reparation and crop production safety quality control.
Technical background
Along with the development of process of industrialization nearly decades, various industry as mining industry, Metallurgy Industry, chemical industry etc. the leachate of the waste water that produces and solid waste directly enter water body, along with the distribution of water system and agricultural irrigation water need enter farm environment.Soil is the direct carrier that agricultural product are produced, chemical substance in soil is absorbed by crops and enters agricultural product in agricultural production, whether soil is polluted and pollution level directly affect agricultural product quality and yield (Zhou Qixing edit. healthy agrology-soil health quality and agricultural product security .2005, Beijing: Science Press), therefore, agricultural product quality and safety and soil pollution in close relations.First heavy metal-polluted soil produces Cumulate Sum by agricultural product root absorption and moves in plant, when polluting content and exceeding the maximum acceptable concentration of crops, the edible safety of agricultural product is just difficult to be protected, agricultural product quality survey data display in 2011, there is cadmium pollution in China's 10% rice, the long-term edible generation that can cause human body " Itai-itai diseases ".Therefore, health and the existence of the various life entities comprising the mankind in soil, sewage heavy metal pollution serious harm.Soil, heavy metals pollute and have persistence, the effect such as bioconcentration and amplification, how effectively administer heavy metal wastewater thereby pollute and soil pollution by heavy metal oneself become the problem that the mankind pay close attention to jointly.
At present, China is by nearly 20,000,000 hm of cultivated area of the heavy metal pollutions such as Cd, As and Pb
2, account for 1/5 of total cultivated area, wherein by nearly 1.33 ten thousand hm of cultivated area that Cd pollutes
2relate to 11 and economize 25 areas, every year because heavy metal pollution causes grain drop in production more than 1,000 ten thousand tons, the contaminated by heavy metals grain that can not eat reaches 1,200 ten thousand tons of (Wei Chaoyang etc., heavy metal super-enriched plant and phytoremediation technology progress, Acta Ecologica Sinica, 2001,21 (7): 1196-1203), the whole nation has many areas to develop into the degree of production " cadmium rice ".Within 2000, find the whole nation 2.2 hundred million ton-grain food investigation, in grain, heavy metal Pb, Cd, Hg and As exceeding standard rate reach 10%.2002, Ministry of Agriculture's rice and quality of item supervision and inspection center thereof show national market rice security Examined, exceed standard in rice the most seriously Pb, exceeding standard rate is 28.4%, next is Cd, exceeding standard rate is 10.3%, As and Hg exceeding standard rate is relatively low, be respectively 2.8% and 3.4%, and present certain combined pollution phenomenon (Cheng Wang great etc., the kind of the content of beary metal such as arsenic, cadmium, chromium, nickel, lead and Grain position effect in late japonica rice seed, rice in China science, 2005,19 (3): 273-279).
Repair the difference of control technology principle according to heavy-metal contaminated soil, common heavy metal pollution of soil processing method is broadly divided into three kinds, i.e. chemical method, physical-chemical process and bioanalysis.Chemical Treatment heavy-metal contaminated soil mainly comprises chemical precipitation method and electrolysis, is mainly applicable to the process containing higher concentration heavy metal ion Tailings Dam soil.Physical-chemical process process heavy-metal contaminated soil comprises ion-exchange and membrane separation technique, is applicable to the process containing low concentration heavy metal ion soil.Bioanalysis mainly refers to plant restoration method, and the method refers to the content of beary metal utilizing plant to pass through the effect contaminated soil of reduction such as absorption, precipitation and enrichment or surface water, to reach the object of pollution administration, repairing environment.Bioremediation comprises bio-flocculation process, biosorption process.Biological adsorption be exactly organism and derivative thereof to the suction-operated of heavy metal in medium, comprise the complexing of the different parts heavy metal ion of cell, ion-exchange, absorption and inorganic microdeposit etc.Biosorption process is a kind of brand-new Heavy Metal Pollution Control method in recent years, and efficient with it, cheap advantage causes the interest of people gradually.The research of external this respect from the eighties, the nineties, development was very fast, biosorption process has compared with other heavy-metal contaminated soil processing method can reduce the absorption enriching quantity of crops to heavy metal in soil, and operating cost is low, can reclaim heavy metal and not have the advantage of secondary pollution.And biogenic there is easy immobilization, and special biological adsorption agent can be made as required and Reusability.Therefore, biosorption process has good agricultural environment Heavy Metal Pollution Control application prospect.
The successful implementation of biosorption process, key depends on the development and application of adsorbent.Biological adsorption agent refers generally to can the microbial body of Adsorption of Heavy Metals, comprises algae, bacterium, fungi etc.Growing along with biosorption technology, biological adsorption agent is not only confined to microorganism, some abundant natural materials, particularly cellulose, is considered to the biological adsorption agent with suitable potentiality.Cellulose is the abundantest on the earth, the natural resources that can recover, and has inexpensive, degradable and does not produce the advantages such as pollution to environment.But native cellulose Adsorption of Heavy Metals ability is also not bery strong, just must can become sorbing material of good performance by modification.Calendar year 2001, the research such as Liu Minghua shows, modified spherical cellulose is to Cr
3+adsorbance is 28mg/g; The research such as ， Wang Yu in 2009 shows, modification cane residuals is to Cu
2+adsorbance is up to 58.53mg/g.Can find out, biological adsorption agent wide material sources, wide in variety, many biomaterials have superior Adsorption of Heavy Metals ability.Agricultural crop straw is the agricultural wastes that biomass is huge in the world.Especially the crop straw such as corn, wheat, paddy rice is rich in cellulose components, can play an important role in a lot of fields, but, the agricultural crop straw that existing utilization obstacle causes quite a few is used by low value and directly discarded, and the crop of developing into of agricultural wastes method of modifying and technology of preparing is prepared ion adsorbent and provides theoretical foundation and research direction.
Summary of the invention
The technical problem to be solved in the present invention overcomes in original agricultural cultivation management mode because heavy metal-polluted soil background value is relatively high or sewage irrigation causes Regional Agricultural Products content of beary metal to exceed the safety problem of national food hygienic standard limitation.Therefore, the invention provides a kind of can effectively solve crop production safety have to the soil heavy mental ion adsorption agent of heavy metal-polluted soil efficacy of adsorption and preparation method, improve agricultural product security edible quality to reach, promote the object of the orderly development of agricultural environment and human health.
For solving the problems of the technologies described above and realizing the object of the invention, technical scheme of the present invention is as follows:
1. a soil heavy mental ion adsorption agent, is characterized in that: by following A, B and humic acid potassium three groups
Material is in A:B: the mass ratio of humic acid potassium is that the ratio of 2:5:3 is obtained by mixing;
(1) A group material is the maize straw of modification, and the maize straw of described modification is obtained by following methods:
1. the collection of stalk and pretreatment
Collect the fresh straw of more than the plant root after harvest corn, cut and cut up with a hay cutter into section, the earth and sand and dust of cleaning stalk surface attachment is rinsed with clear water, put natural air drying in the cool, put into again constant temperature oven 50 DEG C dry pulverize to constant weight or shine under natural sunlight dry in the air be dried to constant weight after pulverize, cross 2-4 mesh sieve and namely obtain stalk particle;
2. straw modification
A, in stalk particle: concentration is the mass ratio of the NaOH solution of 1mol/L is the ratio of 1:50, adds the NaOH solution of stalk particle and 1mol/L in a reservoir, after stirring, puts into Tempeerature-constant air shaking table, 40 DEG C soak 18 hours;
After B, immersion, take out stalk particle, supernatant is removed in centrifugation, and it is precipitated as through alkali treatment stalk particle;
C, by through alkali treatment stalk particle and acrylonitrile according to alkali treatment stalk particle: the mass ratio of acrylonitrile is that the ratio of 1:10 is mixed to get mixture, this mixture is put into another container, at 30 DEG C of reaction 20-30min;
D, by step (1) 2. C through reacted stalk particle deionized water washing 2-3 time, then be 12g/L hydrochloric acid soak acid-cleaning by concentration, until the stalk particle pH fully soaked into stalk particle be 7 or pH be 5 ~ 6.9;
E, take out stalk particle through pickling, with deionized water washing until aqueous solution pH is 6.5 ~ 7, then stalk particle is put into constant temperature oven 50 DEG C and dry to constant weight, obtain the maize straw of described modification;
(2) B group material is the kaolin of modification, and the kaolin of described modification is obtained by following methods:
Get kaolinite original ore powder in container, in kaolinite original ore powder: the mass ratio of sodium polyphosphate is that the ratio of 4:1 adds sodium polyphosphate, mix, add distilled water again and stir into pasty state, after leaving standstill half an hour, be placed in constant temperature oven, start baking oven, setting maximum temperature is 100 DEG C, when oven temperature rises to 100 DEG C gradually, maintain 100 DEG C of constant temperature bakings and then move in Muffle furnace for l hour, open Muffle furnace and be warming up to 280 DEG C of roasting temperatures one hour, come out of the stove by kaolin cool to room temperature, namely ground 2-4 mesh sieve obtains the kaolin of modification.
2. the soil heavy mental ion adsorption agent according to technical scheme 1, is characterized in that: the cool room temperature described in room temperature of being come out of the stove by kaolin described in step (2) is 32 DEG C ~ 15 DEG C.
3. a preparation method for soil heavy mental ion adsorption agent, is characterized in that, by following A, B and humic acid potassium three groups of materials in A:B: the mass ratio of humic acid potassium is that the ratio of 2:5:3 mixes and is described soil heavy mental ion adsorption agent:
(1) A group material is the maize straw of modification, and the maize straw of described modification is obtained by following methods:
1. the collection of stalk and pretreatment
Collect the fresh straw of more than the milpa root after harvest corn, cut and cut up with a hay cutter into section, the earth and sand and dust of cleaning stalk surface attachment is rinsed with clear water, put natural air drying in the cool, again its put into constant temperature oven 50 DEG C dry pulverize to constant weight or shine under natural sunlight dry in the air be dried to constant weight after pulverize, cross 2-4 mesh sieve and namely obtain stalk particle;
2. straw modification
A, in stalk particle: concentration is the mass ratio of the NaOH solution of 1mol/L is the ratio of 1:50, adds the NaOH solution of stalk particle and 1mol/L in a reservoir, after stirring, puts into Tempeerature-constant air shaking table, 40 DEG C soak 18 hours;
After B, immersion, take out stalk particle, supernatant is removed in centrifugation, and it is precipitated as through alkali treatment stalk particle;
C, by through alkali treatment stalk particle and acrylonitrile according to alkali treatment stalk particle: the mass ratio of acrylonitrile is that the ratio of 1:10 is mixed to get mixture, this mixture is put into another container, at 30 DEG C of reaction 20-30min;
D, step (1) 2. C, through reacted stalk particle deionized water washing 2-3 time, then are 12g/L hydrochloric acid soak acid-cleaning by concentration, until the stalk particle pH fully soaked into stalk particle be 7 or pH be 5 ~ 6.9;
E, take out stalk particle through pickling, with deionized water washing until aqueous solution pH is 6.5 ~ 7, then stalk particle is put into constant temperature oven 50 DEG C and dry to constant weight, obtain the maize straw of described modification;
(2) B group material is the kaolin of modification, and the kaolin of described modification is obtained by following methods:
Get kaolinite original ore powder in container, in kaolinite original ore powder: the mass ratio of sodium polyphosphate is that the ratio of 4:1 adds sodium polyphosphate, mix, add distilled water again and stir into pasty state, after leaving standstill half an hour, be placed in constant temperature oven, start baking oven, setting maximum temperature is 100 DEG C, when oven temperature rises to 100 DEG C gradually, maintain 100 DEG C of constant temperature bakings and then move in Muffle furnace for l hour, open Muffle furnace and be warming up to 280 DEG C of roasting temperatures one hour, come out of the stove by kaolin cool to room temperature, namely ground 2-4 mesh sieve obtains the kaolin of modification.
4. the preparation method of the soil heavy mental ion adsorption agent according to technical scheme 3, the described cool room temperature described in room temperature of being come out of the stove by kaolin of step (2) is 32 DEG C ~ 15 DEG C.
5. the soil heavy mental ion adsorption agent described in technical scheme 1 or 2 is reducing the application of crop products content of beary metal.
Compared with the prior art, the invention has the beneficial effects as follows:
The present invention is in a large amount of Literature Consults and previous work basis, take corn stalk as raw material, adopt Chemical Decomposition method, modification is carried out to fresh straw, sufficient mixed preparing is carried out with the modified kaolin of the blunt burning of high temperature and humic acid potassium, form soil heavy mental ion adsorption agent prescription of the present invention, by arranging the heavy-metal contaminated soil adsorption applications test of this formula, coupled ion absorption quantitative analysis and Contrast on effect, develop a kind of soil heavy mental ion adsorption agent that effectively can reduce crop heavy metal content, for ensureing that crop production safety provides significant technical guarantee.
The suitable soil heavy mental ion adsorption agent prescription of the preparation measure that the present invention is suitable for and preparation, enhances the adsorption capacity of soil heavy metal, decreases the migration of heavy metal in soil to crops, ensure that the quality safety of crops Leaf-feeding insects.
With do not add compared with soil heavy mental ion adsorption agent of the present invention, the adsorbance increasing degree of rice soil heavy metal arsenic, lead, cadmium is respectively 50%, 49.1% and 16.7%; The adsorbance increasing degree of red soil heavy metal arsenic, lead, cadmium is respectively 20.5%, 8.4% and 29.3%; The adsorbance increasing degree of purple soil heavy metal arsenic, lead, cadmium is respectively 50%, 41.1% and 64.97%, effectively reduce the transfer of heavy metal in soil to the crops such as corn kernel, rice Leaf-feeding insects, content of beary metal in corn kernel is significantly reduced, wherein plumbous average reduction amplitude 15.63%, cadmium on average reduces amplitude 12.15%, and it is 7.62% that arsenic on average reduces amplitude.In rice, content of beary metal obtains significantly being reduced, wherein plumbous average reduction amplitude 17.8%, and cadmium on average reduces amplitude 17.27%, and arsenic on average reduces amplitude 21.84%.
Preparation method and the using method of soil heavy mental ion adsorption agent of the present invention are all easy and simple to handle, with low cost, draw materials conveniently, are suitable for planting wide popularization and application in industry development at green, non-polluted farm product.
Soil heavy mental ion adsorption agent provided by the present invention can be avoided annual because burning environmental pollution that straw causes in a large number, destroying ecological balance problem simultaneously, carries out the efficient resource utilization of agricultural wastes.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further illustrated, but be only citing, is not construed as limiting the invention.Following examples material therefor is commercially available, is conventional method without specified otherwise.
Embodiment 1 soil heavy mental ion adsorption agent of the present invention and preparation method thereof
A kind of soil heavy mental ion adsorption agent of the present invention, by following A, B and humic acid potassium three groups of materials in A:B: the mass ratio of humic acid potassium is that the ratio of 2:5:3 is mixed:
(1) A group material is the maize straw of modification, and the maize straw of described modification is obtained by following methods:
1. the collection of stalk and pretreatment
Collect the fresh straw of more than the plant root after harvest corn, cut and cut up with a hay cutter into section, the earth and sand and dust of cleaning stalk surface attachment is rinsed with clear water, put natural air drying in the cool, put into again constant temperature oven 50 DEG C dry to constant weight pulverize or under natural sunlight shine dry in the air be dried to constant weight after pulverize, cross 3 mesh sieves namely obtain stalk particle;
2. straw modification
A, in stalk particle: concentration is the mass ratio of the NaOH solution of 1mol/L is the ratio of 1:50, adds the NaOH solution of stalk particle and 1mol/L in a reservoir, after stirring, puts into Tempeerature-constant air shaking table, 40 DEG C soak 18 hours;
After B, immersion, take out stalk particle, supernatant is removed in centrifugation, and it is precipitated as through alkali treatment stalk particle;
C, by through alkali treatment stalk particle and acrylonitrile according to alkali treatment stalk particle: the mass ratio of acrylonitrile is that the ratio of 1:10 is mixed to get mixture, this mixture is put into another container, at 30 DEG C of reaction 20min;
D, by step (1) 2. C wash 2 times through reacted stalk particle deionized water, be 12g/L hydrochloric acid soak acid-cleaning by concentration again, until the pH that stalk particle fully soaks into stalk particle is 7 (measuring the pH value of stalk particle with reference to NY/T1121.2-2006);
E, take out stalk particle through pickling, with deionized water washing until aqueous solution pH is 7, then stalk particle is put into constant temperature oven 50 DEG C and dry to constant weight, obtain the maize straw of described modification;
(2) B group material is the kaolin of modification, and the kaolin of described modification is obtained by following methods:
Get kaolinite original ore powder in container, in kaolinite original ore powder: the mass ratio of sodium polyphosphate is that the ratio of 4:1 adds sodium polyphosphate, mix, add distilled water again and stir into pasty state, after leaving standstill half an hour, be placed in constant temperature oven, start baking oven, setting maximum temperature is 100 DEG C, when oven temperature rises to 100 DEG C gradually, maintain 100 DEG C of constant temperature bakings and then move in Muffle furnace for l hour, open Muffle furnace and be warming up to 280 DEG C of roasting temperatures one hour, come out of the stove by kaolin cool to room temperature 25 DEG C, namely ground 3 mesh sieves obtain the kaolin of modification.
The adsorption applications of embodiment 2 soil heavy mental ion adsorption agent of the present invention on soil type.
1, experiment is for examination material
1.1 participate in the experiment soil
Adsorption test soil picks up from different location, three, Yunnan Province, dissimilar arable soil.Gather soil sample after natural air drying, preparation of milling, for the detection of heavy metal-polluted soil and physicochemical character index, soil basic condition of participating in the experiment sees the following form:
Table 1 is participated in the experiment the basic condition of soil
1.2 tests are arranged and Heavy Metal Reagent
The Heavy Metal Reagent that table 2 adsorption test adds and addition
1.3 experimental technique
Adsorption test prepares two groups, and one group is contrast (CK), and one group is process.Three kinds of soil sample 1.00g that control group took 100 mesh sieves are respectively put in 100mL polyethylene centrifuge tube respectively, arrange three repetitions, totally 9 centrifuge tubes.Note: in table, each data are the mean value of three replications.
The soil heavy mental ion adsorption agent of the present invention described in embodiment 1 that processed group also adds 1.00g except the three kinds of soil sample 1.00g taking 100 mesh sieves according to control group is put in 50mL centrifuge tube respectively.Three repetitions are set, totally 9 centrifuge tubes.
18 centrifuge tubes of the control group and processed group that install test material are added three heavy metal species reagent according to the concentration that arranges in table 2 respectively, and reagent solution uses NaOH solution adjust ph to 5.0 in advance, and the addition of often kind of reagent solution is 20mL.The centrifuge tube having added reagent is at room temperature vibrated after (200r/min) 24h and takes out centrifugal (6000r/min) 30 minutes, with the supernatant in quantitative filter paper (GB/T1914-93) filtering centrifuge tube, solution after filtration is pressed GB/T 17141-1997 method with atomic absorption spectrophotometer respectively and is measured plumbous, cadmium, press by atomic absorption spectrography (AAS) the concentration that GB/T 22105.2-2008 measures arsenic, then calculate heavy metal adsorption amount.
1.3 heavy metal adsorption gauge are calculated
Heavy metal adsorption amount calculates as follows:
q＝(C
i-Ce)×V/m
In formula, q is that heavy metal adsorption amount (mg/kg), Ci and Ce are respectively heavy metal initial soln concentration and balance solution weight metal concentration (mg/L), and V is balance solution volume (mL), m is soil quality (g).Balance solution heavy metal concentration to refer to after Adsorption of Heavy Metals heavy metal concentration in solution.
4, application result
Soil is as a kind of medium carrying heavy metal, inherently possesses certain heavy metal adsorption, contrast (table 3) by the adsorption test of this test, the adsorption capacity aggregate performance of three kinds of soil heavy metal of participating in the experiment is red soil > rice soil > purple soil; From heavy metal element, three class soil are Adsorption of Lead all easily, and relatively weak to the adsorption capacity of arsenic.And add the soil heavy mental ion adsorption agent of the present invention's configuration, the adsorption capacity of soil heavy metal is significantly strengthened, compared with not adding the heavy metal adsorption amount of invention soil heavy mental ion adsorption agent, the absorption amplitude of rice soil arsenic, lead, cadmium increases by 50%, 49.1% and 16.7% respectively; The absorption amplitude of red soil arsenic, lead, cadmium increases by 20.5%, 8.4% and 29.3% respectively; Purple soil 50%, 41.1% and 64.97%.
Table 3 adsorption test balance solution concentration
5, conclusion
The test of different soils ionic adsorption shows, soil heavy mental ion adsorption agent of the present invention effectively can increase the adsorbance of the arsenic of soil heavy metal, lead, cadmium, three soil types of participating in the experiment are by adding soil heavy mental ion adsorption agent of the present invention, the adsorption capacity increasing degree average out to 49.7%, 32.86% and 36.99% of heavy metal arsenic, lead, cadmium.
Table 4 soil type and different disposal heavy metal-polluted soil adsorbance
Embodiment 3 soil heavy mental ion adsorption agent of the present invention reduces the growth condition of corn kernel content of beary metal on heavy-metal contaminated soil.
1, experiment is for examination material
1.1 participate in the experiment soil
Soil of participating in the experiment picks up from Gejiu, Yunnan Province moderate heavy-metal contaminated soil, and the basic physicochemical character of soil is in table 5:
Table 5 is participated in the experiment the basic condition of soil
1.2 participate in the experiment crop: Gejiu is when landlord plants blue or green food corn variety three, and variety name is glutinous No. 8 of good list 108, No. 3, clearance permit and actions and spoken parts in classical Chinese drama.
2, test method
Arrange heavy-metal contaminated soil corn planting pot experiment in Gejiu, test soil is all taken from Zhang Jiazhai village, Datun Town, Gejiu and is closed Yulin corn planting ground soil.Test arrangement three kinds, two soil treatment, three experimental design repeated.Test basin adopts high 60cm, bore to be the plastic tub of 50cm, and every basin fills native 40kg, amounts to dress soil 18 basins.The process adding adsorbent is that the every basin of topsoil soils adds according to the amount of 500g (1.25g adsorbent/kg soil) in control basis, and other control measures are consistent with contrast.Soil conventional index and content of beary metal is measured, the content of beary metal of different corn variety seed under detecting different soils process after corn planting respectively before corn planting.
3, result of the test
Basin soil of getting derives from Zhang Jiazhai village, Datun Town, Gejiu, and soil pH is 5.7, after testing, in table 6, basin soil heavy metal in soil arsenic, cadmium content are relatively high, and exceed the relevant limitation of " standard of soil environment quality " (GB15618-1995), integrated pollution evaluation is intermediate pollution.
Table 6 basin soil heavy metal analysis data
Through the plantation in a season, the absorption accumulation ability of different corn variety heavy metal shows certain difference.In table 7, three corn varieties itself have different to the heavy metal adsorption in contaminated soil.From corn variety heavy metal uptake of participating in the experiment, plumbous, cadmium aggregate performance is the good lists 108 of actions and spoken parts in classical Chinese drama glutinous No. 8 > clearance permits No. 3 >, and lead in glutinous No. 8 corn kernels of actions and spoken parts in classical Chinese drama, cadmium all exceed China " pollutants in food limitation " (GB 2762-2012) standard limit index.The absorption of arsenic element is then slightly different, and show as glutinous No. 8 of good list 108 > clearance permit No. 3 > actions and spoken parts in classical Chinese drama, this may be relevant with the absorption characteristic of kind heavy metal.
Table 7 different disposal corn kernel content of beary metal detects data
Note: adding sorbent treatment in table 7 is the process adding soil heavy mental ion adsorption agent of the present invention.
Comparative analysis original pollution basin soil and add the corn kernel content of beary metal of the autochthonal length of basin of soil heavy mental ion adsorption agent of the present invention, aggregate performance is for after application of soil heavy mental ion adsorption agent of the present invention, and the content of beary metal in corn kernel all has and significantly reduces.Wherein, reduce and be apparent that lead element the most, compared with contrast (CK), what reduction amplitude was larger is No. 3, clearance permit, and reduction amplitude is the plumbous average reduction amplitude of 20.44%, three kinds is 15.63%; Equally, to cadmium reduce amplitude larger be also No. 3, clearance permit, the range of decrease is that on average to reduce amplitude be 12.15% to 15.21%, three kind cadmiums; By contrast, what reduction amplitude was less is arsenic element, although arsenic content overproof is more than 1 times in planting soil, but because rain fed crop is little to arsenic sensitiveness, thus the arsenic content in corn kernel does not exceed national food hygienic standard limitation, but by adding soil heavy mental ion adsorption agent of the present invention in contaminated soil, also there is certain minimizing in the arsenic transferred in corn kernel, what minimizing amplitude was maximum is glutinous No. 8 of actions and spoken parts in classical Chinese drama, minimum is No. 3, clearance permit, and it is 7.62% that three corn variety arsenic on average reduce amplitude.
4, conclusion
A certain amount of soil heavy mental ion adsorption agent of the present invention is added in, intermediate pollution soil slight at heavy metal, effectively can reduce the transfer of heavy metal in soil to corn kernel, three corn tested varieties by adding soil heavy mental ion adsorption agent of the present invention before contaminated soil corn planting, in corn kernel, the relatively direct corn kernel content of beary metal of planting on contaminated soil of content of beary metal is compared, all obtain reduction by a relatively large margin, plumbous average reduction amplitude is 15.63%, it is 12.15% that cadmium on average reduces amplitude, and it is 7.62% that arsenic on average reduces amplitude.
Embodiment 4 soil heavy mental ion adsorption agent of the present invention reduces the growth condition of Rice Kernel content of beary metal on cadmium pollution soil.
1, experiment is for examination material
1.1 participate in the experiment soil
Soil of participating in the experiment picks up from Yiliang County, Kunming, Yunnan Province Kuang Yuan town Bao Hong villagers' committee water paddy soil.The basic physicochemical character of soil is in table 8:
Table 8 is participated in the experiment the basic condition of soil
1.2 participate in the experiment crop: when landlord transplants rice seedlings kind two, variety name is respectively Chu and obstructs No. 28, excellent 20.
2, test method
Arrange Rice Cropping pot experiment in Yiliang County, test soil all takes from the bright rice seedling bed of Yiliang County, Kunming, Yunnan Province Kuang Yuan town Bao Hong villagers' committee Li Hong.Test arrangement two kinds, two soil treatment, three experimental design repeated.Test tools adopts high 40cm, bore to be the Plastic Drum of 20cm, and every 20 kilograms, basin dress soil, amounts to dress soil 12 basins.The process adding adsorbent is that the every basin of topsoil soils adds according to the amount of 25g (1.25g adsorbent/kg soil) in control basis, and other control measures are consistent with contrast.Soil conventional index and content of beary metal is measured, the content of beary metal of different rice varieties seed under detecting different soils process after Rice Cropping respectively before rice transplanting.
3, result of the test
Institute gets test soil and derives from Yiliang County, Kunming, Yunnan Province Kuang Yuan town Bao Hong villagers' committee rice terrace, soil pH is 6.9, after testing, in table 9, heavy metal in soil cadmium content is relatively high, exceeds the relevant limitation of " standard of soil environment quality " (GB15618-1995).
Table 9 basin soil heavy metal analysis data
Through the plantation in a season, the absorption accumulation ability of different rice varieties heavy metal shows certain difference.In table 10, two rice varieties itself also have different to the heavy metal adsorption in contaminated soil.From rice varieties heavy metal uptake of participating in the experiment, lead, cadmium, the aggregate performance of arsenic three Heavy Metallic Elements are excellent 20 > Chu stalks 28, although the lead in two kind rice and arsenic all exceed China's " pollutants in food limitation " (GB2762-2012) standard limit index, but add soil heavy mental ion adsorption agent of the present invention in soil, the lead in these two kind rice and the content of arsenic all obtain larger reduction.And Cadmium in Soil exceeds standard, but the Cd concentration of brown rice of these two kinds does not exceed standard.
Comparative analysis initial soil, add the rice grain content of beary metal of the soil-grown of soil heavy mental ion adsorption agent of the present invention, aggregate performance is for after application of soil heavy mental ion adsorption agent of the present invention, and three heavy metal species content in rice grain all reduce significantly.Wherein, reduce and be comparatively apparent that arsenic element, compared with contrast (CK), Chu's stalk 28 reduces amplitudes more greatly 28.86%, and excellent 20 reduction amplitudes are 14.84%, and average reduction amplitude is 21.84%; And cadmium and plumbous reduction amplitude are more or less the same, wherein two kinds are to the reduction amplitude average out to 17.27% of cadmium, to the reduction amplitude average out to 17.8% of lead.
4, conclusion
At heavy metal cadmium Single Pollution soil, (this heavy metal in soil content only has cadmium to exceed standard, claim cadmium Single Pollution soil) a certain amount of soil heavy mental ion adsorption agent of the present invention of middle interpolation, effectively can reduce the transfer of heavy metal in soil to rice grain, two paddy rice tested varieties by adding soil heavy mental ion adsorption agent of the present invention before contaminated soil plantation, in rice, the relatively direct rice grain of planting on this cadmium pollution soil of content of beary metal is compared, content of beary metal all obtains reduction by a relatively large margin, plumbous average reduction amplitude is 17.8%, it is 17.27% that cadmium on average reduces amplitude, it is 21.84% that arsenic on average reduces amplitude.
Table 10 different disposal rice grain content of beary metal detects data
Note: adding sorbent treatment in table 10 is the process adding soil heavy mental ion adsorption agent of the present invention.
Each embodiment above, the mensuration of Arsenic in Soil content is pressed GB/T 22105.2-2008 method and is measured.The mensuration of Lead In Soil content is pressed GB/T 17141-1997 method and is measured.The mensuration of Cadmium in Soil content is pressed GB/T17141-1997 method and is measured.The mensuration of mercury in soils content is pressed GB/T 22105.1-2008 method and is measured.The mensuration of Chromium in Soil content is pressed GB/T 17137-1997 method and is measured.In corn kernel and rice grain, the mensuration of lead content all measures by GB 5009.12-2010 method, the mensuration of cadmium content all measures by GB/T 5009.11-2003 method by the mensuration of GB/T 5009.15-2003 method mensuration, total arsenic content.
Claims (5)
1. a soil heavy mental ion adsorption agent, is characterized in that: by following A, B and humic acid potassium three groups of materials in A:B: the mass ratio of humic acid potassium is that the ratio of 2:5:3 is obtained by mixing;
(1) A group material is the maize straw of modification, and the maize straw of described modification is obtained by following methods:
1. the collection of stalk and pretreatment
Collect the fresh straw of more than the plant root after harvest corn, cut and cut up with a hay cutter into section, the earth and sand and dust of cleaning stalk surface attachment is rinsed with clear water, put natural air drying in the cool, put into again constant temperature oven 50 DEG C dry pulverize to constant weight or shine under natural sunlight dry in the air be dried to constant weight after pulverize, cross 2-4 mesh sieve and namely obtain stalk particle;
2. straw modification
A, in stalk particle: concentration is the mass ratio of the NaOH solution of 1mol/L is the ratio of 1:50, adds the NaOH solution of stalk particle and 1mol/L in a reservoir, after stirring, puts into Tempeerature-constant air shaking table, 40 DEG C soak 18 hours;
After B, immersion, take out stalk particle, supernatant is removed in centrifugation, and it is precipitated as through alkali treatment stalk particle;
C, by through alkali treatment stalk particle and acrylonitrile according to alkali treatment stalk particle: the mass ratio of acrylonitrile is that the ratio of 1:10 is mixed to get mixture, this mixture is put into another container, at 30 DEG C of reaction 20-30min;
D, by step (1) 2. C through reacted stalk particle deionized water washing 2-3 time, then be 12g/L hydrochloric acid soak acid-cleaning by concentration, until the stalk particle pH fully soaked into stalk particle be 7 or pH be 5 ~ 6.9;
E, take out stalk particle through pickling, with deionized water washing until aqueous solution pH is 6.5 ~ 7, then stalk particle is put into constant temperature oven 50 DEG C and dry to constant weight, obtain the maize straw of described modification;
(2) B group material is the kaolin of modification, and the kaolin of described modification is obtained by following methods:
Get kaolinite original ore powder in container, in kaolinite original ore powder: the mass ratio of sodium polyphosphate is that the ratio of 4:1 adds sodium polyphosphate, mix, add distilled water again and stir into pasty state, after leaving standstill half an hour, be placed in constant temperature oven, start baking oven, setting maximum temperature is 100 DEG C, when oven temperature rises to 100 DEG C gradually, maintain 100 DEG C of constant temperature bakings and then move in Muffle furnace for l hour, open Muffle furnace and be warming up to 280 DEG C of roasting temperatures one hour, come out of the stove by kaolin cool to room temperature, namely ground 2-4 mesh sieve obtains the kaolin of modification.
2. soil heavy mental ion adsorption agent according to claim 1, is characterized in that: the cool room temperature described in room temperature of being come out of the stove by kaolin described in step (2) is 32 DEG C ~ 15 DEG C.
3. a preparation method for soil heavy mental ion adsorption agent, is characterized in that, by following A, B and humic acid potassium three groups of materials in A:B: the mass ratio of humic acid potassium is that the ratio of 2:5:3 mixes and is described soil heavy mental ion adsorption agent:
(1) A group material is the maize straw of modification, and the maize straw of described modification is obtained by following methods:
1. the collection of stalk and pretreatment
Collect the fresh straw of more than the milpa root after harvest corn, cut and cut up with a hay cutter into section, the earth and sand and dust of cleaning stalk surface attachment is rinsed with clear water, put natural air drying in the cool, again its put into constant temperature oven 50 DEG C dry pulverize to constant weight or shine under natural sunlight dry in the air be dried to constant weight after pulverize, cross 2-4 mesh sieve and namely obtain stalk particle;
2. straw modification
A, in stalk particle: concentration is the mass ratio of the NaOH solution of 1mol/L is the ratio of 1:50, adds the NaOH solution of stalk particle and 1mol/L in a reservoir, after stirring, puts into Tempeerature-constant air shaking table, 40 DEG C soak 18 hours;
After B, immersion, take out stalk particle, supernatant is removed in centrifugation, and it is precipitated as through alkali treatment stalk particle;
C, by through alkali treatment stalk particle and acrylonitrile according to alkali treatment stalk particle: the mass ratio of acrylonitrile is that the ratio of 1:10 is mixed to get mixture, this mixture is put into another container, at 30 DEG C of reaction 20-30min;
D, step (1) 2. C, through reacted stalk particle deionized water washing 2-3 time, then are 12g/L hydrochloric acid soak acid-cleaning by concentration, until the stalk particle pH fully soaked into stalk particle be 7 or pH be 5 ~ 6.9;
E, take out stalk particle through pickling, with deionized water washing until aqueous solution pH is 6.5 ~ 7, then stalk particle is put into constant temperature oven 50 DEG C and dry to constant weight, obtain the maize straw of described modification;
(2) B group material is the kaolin of modification, and the kaolin of described modification is obtained by following methods:
Get kaolinite original ore powder in container, in kaolinite original ore powder: the mass ratio of sodium polyphosphate is that the ratio of 4:1 adds sodium polyphosphate, mix, add distilled water again and stir into pasty state, after leaving standstill half an hour, be placed in constant temperature oven, start baking oven, setting maximum temperature is 100 DEG C, when oven temperature rises to 100 DEG C gradually, maintain 100 DEG C of constant temperature bakings and then move in Muffle furnace for l hour, open Muffle furnace and be warming up to 280 DEG C of roasting temperatures one hour, come out of the stove by kaolin cool to room temperature, namely ground 2-4 mesh sieve obtains the kaolin of modification.
4. the preparation method of soil heavy mental ion adsorption agent according to claim 3, the described cool room temperature described in room temperature of being come out of the stove by kaolin of step (2) is 32 DEG C ~ 15 DEG C.
5. the soil heavy mental ion adsorption agent described in claim 1 or 2 is reducing the application of crop products content of beary metal.
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