CN106520137A - Modifier for reducing methyl mercury pollution in acidic rice field and method thereof - Google Patents
Modifier for reducing methyl mercury pollution in acidic rice field and method thereof Download PDFInfo
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- CN106520137A CN106520137A CN201610973759.7A CN201610973759A CN106520137A CN 106520137 A CN106520137 A CN 106520137A CN 201610973759 A CN201610973759 A CN 201610973759A CN 106520137 A CN106520137 A CN 106520137A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
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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
- B09C1/08—Reclamation of contaminated soil chemically
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
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- C—CHEMISTRY; METALLURGY
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- C09K2101/00—Agricultural use
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention discloses a modifier for reducing methyl mercury pollution in an acidic rice field and a method thereof, which mainly relates to the field of agriculture pollution prevention and treatment. The method comprises basal application of the modifier and moisture management. The preparation method of the modifier is characterized in that weathered coal is prepared to coal-based humic acid, according to the weight percentage, 0.1-0.2% of sodium selenite is added and aged, calcium carbonate with the weight ratio of 1:1.2-1:1.5 is added, and the materials are uniformly mixed. The modifier has the beneficial effect that the modifier is used for the acidic rice field with pH value of 4-6 and the mercury pollution degree of lower than 6 mg/kg, compared with the contrast group, the methyl mercury content of soil and rice is reduce to 60% and more, the pH value of the soil is obviously increased, the modifier has good reappearance, and has the advantages of low cost, high efficiency and easy operation, the paddy rice output and plant biomass are not reduced, and the modifier has high economic effect.
Description
Technical field
The present invention relates to agricultural pollution prevention and control field, specifically reduces modifying agent and the side of acid rice field Methylmercury pollution Riverfish
Method.
Background technology
Mercury (Hg) and its compound particularly methyl mercury (MeHg) is with very strong bio-toxicity, biological concentration faster is put
Big multiplying power and longer brain organ biological half-life, even if there was only the concentration of very little in native water environment, may also pass through food chain
Amplified so as to reach extremely hazardous concentration by bioconcentration.China's soil is particularly arable soil mercury pollution situation and does not allow pleasure
See.According to the first time whole nation Investigation of Soil Pollution publication that on April 7th, 2014 announces, Hg points position exceeding standard rate reaches 1.6%.Root
According to Ministry of Agriculture's Second National irrigating region census report, in about 140 × 10 for counting at that time4km2In irrigating region, it is subjected to heavy metal
Contaminated land area accounts for the 64.8% of the irrigating region gross area, and wherein mercury is one of maximum heavy metal of contaminated area, is averagely contained
Measure as 0.76mg-1·kg.Soil is in water such as experience flood irrigation (dirty to fill), seasonal water logging, flood or alternations of wetting and drying (paddy environment)
When slitting part changes, Mercury in Soil can be made to methylate, methyl mercury content increases and be discharged into water body or big in causing soil
In gas, the methyl mercury exposure of organism is formed.Paddy ecosystem is a type of wetland, and paddy rice is in internal cause season in growth period
Property irrigate so as to also become a kind of special wetlands ecosystems, it is preferable to be that sulfate reducing bacteria and iron-reducing bacteria etc. are provided
Life condition, therefore the rice field of the mercury pollution high risk zone such as mining area periphery, irrigating region methylates habitat with very strong mercury
Condition, mercury are converted into methyl mercury under the bacterial actions such as sulfate reducing bacteria, in a large number and are transported in rice grain, strong to human body
Kang Zaocheng great threats.Confirmation is studied, paddy rice has stronger accumulation ability for methyl mercury, and methyl mercury is easily in rice
Build up in rice.In Southwest China mercury ore area periphery, edible rice is the exposed main path of urban residents' methyl mercury, resident
The 94% of methyl mercury general input is from rice edible (Japan and Europe mostly come from edible fishes).
At present for the repairing and treating of heavy-metal contaminated soil mainly includes physics, biological and chemical method.With place weight
Metallic pollution soil remediation is different, and arable land heavy-metal contaminated soil has certain particularity, it is desirable to do not changing soil purposes
The improvement of contaminated soil is carried out on the premise of less impact crops output, this selection and effect to Treatment process is proposed
Higher requirement.Modifying agent is added in soil, by agronomy regulation and water and fertilizer condition, the biologically effective of mercury in soils is reduced
Property, so as to reduce mercury into plant risk, it is a kind of feasible method of comparison, but for agricultural land soil, except technology
Beyond the governance efficiency of method itself, also want that seeking time is fast, instant effect, low cost, convenient use, can not produce after adding soil
Secondary pollution, it is impossible to affect soil production function, it is impossible to crop growth is produced and is significantly negatively affected.
105052646 A of patent CN discloses a kind of method for reducing paddy rice methyl mercury content.The method is by paddy rice
Plant and the mixture of inorganic selenium salt or inorganic selenium salt and sodium sulphate is applied within first 20 days in soil contain reducing methyl mercury in paddy rice
Amount.But the method has several deficiencies, one be when in use between it is upper indefinite.The disclosure proposes Rice Cropping before at least 20 days in soil
The mixture of inorganic selenium salt or inorganic selenium salt and sulfate is added in earth, if but it is also proposed that be advanced to same less than or equal to 10 days
The conclusion of methyl mercury content reduction in paddy rice can be obtained.Two be in use and dosage use on it is more complicated, in practice
It is difficult to grasp, feasibility is poor.After such as be manured into soil the mixture of inorganic selenium salt or inorganic selenium salt and sodium sulphate, need to plough
Soil more than three times, flooding depth are more than 4 centimetres.On dosage, selenium salt sowing amount is calculated with total selenium, and content is 2-3mg/kg,
Sulphates content is 2 times of sulphates content in soil.In practice, peasant is difficult to calculate selenium salt according to the ratio of 2-3mg/kg
Input quantity, it is also not possible to know the actual content of sulfate in soil.Three be the disclosure propose Rice Cropping during hold
Impact of the continuous waterflooding to methyl mercury transformation in rice field still needs further to be studied.Under paddy rice flooding condition, although high price in soil
State selenate radical or selenite radical can be reduced to lower valency selenium, and the validity to form inertia mercury reduction mercury is reacted with inorganic mercury, but
The reducing environment that waterflooding is produced is also beneficial to the activity of sulfate reducing bacteria or iron-reducing bacteria, can promote inorganic states mercury to methyl
The conversion of mercury.And in the operation of actual field, continuously submerging is different from the planting habit of the regular dry field of peasant, a large amount of filling is expended
Water is irrigate, is unfavorable for that agricultural machinery carries out farm work, is also unfavorable for paddy growth.Table is put into practice in many Heavy Metal Pollution Control reparations
Bright, long-term to keep waterflooding to be difficult to land in practice, peasant's acceptance level is low, the Hunan Chang-Zhu-Tan Delta Region carried out for such as 2014
Heavy metal pollution arable land is repaired and main crops production is adjusted in many control measures of pilot work, and growth period duration of rice holding is flooded
Water is most difficult to implement.
105170613 A of patent CN discloses a kind of method that utilization organic carbon reduces methyl mercury content in paddy rice.The public affairs
Open and the stalk batch of agriculture waste is concentrated in Sealing furnace, be compacted, heated up with 10 DEG C/min of speed until after 600 DEG C simultaneously
1 hour is maintained, is crushed after cooling, crossed 1mm sieves, make organic carbon.Organic carbon surface has functional group, can be in soil
Methyl mercury carries out absorption fixation, and then reduces absorption of the rice root to methyl mercury, reduces the content of methyl mercury in paddy rice.The public affairs
Open the organic carbon production process for using complicated, it is more difficult to realize large-scale production, it is difficult to which the land for growing field crops mercury pollution that satisfaction has a large capacity and a wide range is controlled
The needs of reason.
In sum, therefore, for the mercury pollution such as mining area periphery, irrigating region, In The Suburbs of Large And Medium Cities risk area higher
Rice field, need badly the convenient to carry out, regulation effect of research and development significantly, peasant is easy to receive and do not result in the prevention and control rice of secondary pollution
The technology and product of field Methylmercury pollution Riverfish, reduces paddy rice methyl mercury exposure.
The content of the invention
It is an object of the invention to provide reduce the modifying agent and method of acid rice field Methylmercury pollution Riverfish, it is for pH is 4
～6, mercury pollution degree in the acid rice field of below 6mg/kg, compare control and reduce up to 60% with rice methyl mercury content by soil
More than, soil pH is significantly improved, with preferable reappearance and low cost, high efficiency, easily operated, rice yield and plant
Biomass is not reduced, with higher economic effect.
The present invention for achieving the above object, is achieved through the following technical solutions：
The modifying agent of acid rice field Methylmercury pollution Riverfish is reduced, is obtained by following steps：
(A) 0.5～2.0mm sieves are crossed after weathered coal being removed impurity removing, milled；
(B) after sieving, according to ratio of water to coal (mass ratio) 8:1～12:1 adds clear water, stirs, using ultrasonic power
400w～700w carries out ultrasonic activation and processes 30～50min, and room temperature is air-dried；
(C) according to volume ratio 1:1～1:3 add 0.1mol/L HCl, soak 65～80 hours under stirring or oscillating condition,
Rinsed more than 3 times with clear water after filtration, spread out air-dried at room temperature, obtain coal base humic acid；
(D) add the sodium selenite of 0.1-0.2% in the coal base humic acid by weight percentage, after mixing, be aged 2
～4 days；
(E) in the material that step (D) is aged by weight 1:1～1:2 add calcium carbonate, mix, obtain final product.
Preferably, the modifying agent for reducing acid rice field Methylmercury pollution Riverfish, is obtained by following steps：
(A) 1.0mm sieves are crossed after weathered coal being removed impurity removing, milled；
(B) after sieving, according to ratio of water to coal (mass ratio) 10:1 adds clear water, stirs, using ultrasonic power 500w
Carry out ultrasonic activation and process 40 ± 5min, room temperature is air-dried；
(C) according to volume ratio 1:2 add 0.1mol/L HCl, soak 72 hours, shone with bamboo and padded under stirring or oscillating condition
Rinsed more than 3 times with clear water after filtration, spread out air-dried at room temperature, obtain coal base humic acid；
(D) add the sodium selenite of 0.1-0.2% in the coal base humic acid by weight percentage, after mixing, be aged 2
～3 days；
(E) in the material that step (D) is aged by weight 1:1.2-1:1.5 add calcium carbonate, mix, obtain final product.
Preferably, the weathered coal content of humic acid used by the step (A) is in more than 500g/kg.
Preferably, whiteness >=90 of the calcium carbonate for being added in the step (E), granularity >=100 mesh, impurity content≤
0.05%.
The method for reducing acid rice field Methylmercury pollution Riverfish, comprises the following steps：
1) modifying agent base is applied：Entered by 200～300kg/ mus using the modifying agent for reducing acid rice field Methylmercury pollution Riverfish
Row base is applied, and is turned over, harrowed even, the modifying agent is well mixed with 20cm topsoil soils, and water drenching makes soil under moisture state
Balance can carry out rice growing or transplanting after 14 days；
2) water management：After Rice Cropping, the time of infertility remains field face moisture state to results.
The step 1) and step 2) in wetting state refer to that Soil Moisture is maintained at field capacity measured value
70～80%, and soil layer surface is without open fire or ponding.
Contrast prior art, the beneficial effects of the present invention is：
After the modifying agent of the present invention is administered to rice field, by the synergy of various composition, coordinate water management measure, carry
High soil pH and mercury adsorption capacity, reduce validity of the inorganic mercury to the microorganism that methylates, and reduce soil methyl mercury content and rice
Meter Jia Ji mercury contents, improve soil physics, chemistry and biological property, and rice yield and biomass are not reduced.Can be wide
It is general to be applied to the higher acid rice field methyl mercury risk prevention system of mercury pollution risk.
1st, the modifying agent obtained by step (A)～(E) indication of the present invention, its main component include coal base activation humic
Acid, calcium carbonate, sodium selenite.After modifying agent is manured into soil, water management is carried out during Rice Cropping, rice field is reduced
The purpose of Methylmercury pollution Riverfish risk.
The mechanism of action of the modifying agent each component is：
The effect of the coal base humic acid in modifying agent：Weathered coal is to be close to or be exposed to the brown coal of earth's surface, bituminous coal, smokeless
Coal, through the product that the infiltration slacking of air, sunlight, ice and snow dust storm, freezing etc. is formed.China's weathering coal reserves is rich
Richness, about 100,000,000,000 tons.In weathered coal, content of humic acid is very high, and in the good weathered coal of run-of-the-mill, content of humic acid is up to 50%
More than.Coal base activation humic acid is the weathered coal humic acid after ultrasonic activation and pickling, with improved soil, improves fertilizer
Effect, stimulate plant growth, it is degeneration-resistant and improve product quality, as various effects such as trace vector, while to inorganic states mercury
There are stronger absorption and ligand complex ability, reduce biological effectiveness of the inorganic mercury to the microorganism that methylates.Due to humic acid
The difference of source, species and environmental condition, causes the impact of its animal migration and activity to mercury in environment significantly different, to ring
Mercury in border has the double effect suppressed with activation concurrently.The Hg that some of which small molecule fulvic acid is held to soil system with compared with
High activation, and grey humic acid then has depression effect.In the present invention, improved in weathered coal by ultrasonic activation and dissociated
The yield of humic acid.Jing after ultrasonication, weathered coal humic acid acidic groups content, content of phenolic hydroxyl groups and carboxyl-content show
Writing increases.Soak through HCl again, remove part small molecule fulvic acid and its soluble simple organic in weathered coal humic acid,
Purification and the buffer capacity to soil system to mercury pollution is improved, while reducing the impurity contents such as heavy metal.
Calcium carbonate (CaCO in modifying agent3) effect：After acid ground applies calcium carbonate, acid rice field can be improved with slow
Soil pH value, improves soil physical and chemical property, increases the variable charge of soil surface, improves SOIL CLAY MINERALS, the oxidation of aqueous iron
Thing etc. is to Hg2+Adsorption capacity, reduce its biological effectiveness, Ca in exchangeable calcium and paddy rice can also be improved in soil2+Contain
Amount, due to Ca2+With Hg2+Absorption point position on competitive crops root system, and then mitigate harm of the Hg to crop.Calcium carbonate can also be adjusted
Supply of the section soil to trace element, improves edaphon living condition, strengthens the ventilating permeable of soil, improves soil
Fertilizer-preserving ability.Additionally, calcium carbonate is easy to use, and it is safe when applying, unlike quick lime (CaO) easily burn seedlings or operation of burning
Coal base activation humic acid in personnel, with the present invention is used cooperatively, and effectively can be kept soil from packing together.
Sodium selenite (Na in modifying agent2SeO3) effect：Enrichment of the selenium to mercury in food chain is inhibited.Sub- selenium
After sour sodium is manured into soil, abiologic process can be passed through and the inertia selenium mercury compound HgSe of gluey indissoluble is produced with inorganic states mercury,
Settlement action is reached so as to suppress methylating for mercury, can also be by forming (CH3Hg)2Se complex compounds promote to remove methyl mercury
Methylation.On the other hand, absorption of the paddy rice to Se is higher, then the repulsive interaction for absorbing to methyl mercury is stronger.
Worked in coordination by said components, make the modifying agent of the present invention, raw material is sufficient, and process is simple is easy to operate, easily
Implement, cost, after applied once, to sustainable 1 year of rice field Methylmercury pollution Riverfish risk prevention system effect by 1 year half, be a kind of
Safety, heavy metal modifying agent persistently, effectively, economic, individually can impose on rice field by base, it is also possible to apply after puddling with base fertilizer,
Use manpower and material resources sparingly.
2nd, the effect of water management：The water management of the present invention refers to the holding field face moisture state during Rice Growing
(soil layer surface is without open fire or ponding, 70-80% of the soil water content for field capacity measured value).Moisture state is a kind of
Oxidation environment, can increase substantially soil redox potential (Eh).After Eh brings up to 50mV from -200mV, the soil liquid
In system, MeHg contents significantly decline.Waterflooding environment can be obviously improved the biological effectiveness of total mercury and methyl mercury, particularly,
Under waterflooding environment, sulfate reducing bacteria and iron-reducing bacterium activity strengthen, and are conducive to the formation and transmission of methyl mercury.Give birth in paddy rice
During educating, waterflooding environment is changed into into moisture state (oxidation environment), inorganic states mercury in Countermeasures in Soil-rice System can be significantly inhibited
To the transition process of methyl mercury, enrichment risk of the methyl mercury in rice grain is reduced.The addition of modifying agent can ensure that paddy rice exists
Under moisture state, effective fringe, grain number per spike and grain yield do not have and significantly reduce.
Description of the drawings
Accompanying drawing 1 is different disposal soil methyl mercury content variation tendency in 4 pot experiment embodiment of the embodiment of the present invention
Accompanying drawing 2 is 4 pot experiment different disposal soil pH variation tendency of the embodiment of the present invention
Accompanying drawing 3 is methyl mercury content, plant height, grain number per spike in seed after 4 pot experiment rice harves of the embodiment of the present invention
Accompanying drawing 4 is 5 field test different disposal soil methyl mercury content variation tendency of the embodiment of the present invention
Accompanying drawing 5 is 5 field test different disposal soil pH variation tendency of the embodiment of the present invention
Accompanying drawing 6 is methyl mercury content, plant height, grain number per spike in seed after 5 field test rice harves of the embodiment of the present invention
Specific embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limit the scope of the present invention.In addition, it is to be understood that after the content for having read instruction of the present invention, people in the art
Member can be made various changes or modifications to the present invention, and these equivalent form of values equally fall within scope defined herein.
Involved instrument, reagent, material etc. in following embodiments, unless otherwise noted, have in being prior art
Conventional instrument, reagent, material etc., can be obtained by regular commercial sources.Involved experimental technique in following embodiments, inspection
Survey method etc., unless otherwise noted, is existing normal experiment method in prior art, detection method etc..
Embodiment 1：Reduce the modifying agent of acid rice field Methylmercury pollution Riverfish
Weathered coal takes from one open coal mine of Shanxi Huozhou, and content of humic acid is 623g/kg, and Hg contents are 0.012mg/kg.
Prepared by following step：
1mm sieves are crossed after weathered coal is removed impurity removing, milled.According to 10:1 ratio of water to coal (mass ratio) is added in weathering coal dust
Clear water, stirs, in supersonic wave cleaning machine (KQ-500DE types, Kunshan ultrasonic instrument Co., Ltd) processing pond, according to super
Acoustic power 500W, ultrasonic time 40 minutes, carry out ultrasonic activation process.After the completion of activation, weathering coal dust room temperature is air-dried.Press
According to volume ratio 1:2 add 0.1mol/L HCl, soak 72 hours, are sufficiently stirred for or vibrate during immersion.Material after immersion is used
Bamboo shine pad filter, repeatedly with clear water rinse 5 times, spread out at room temperature it is air-dried, obtain coal base activation humic acid.
0.1% sodium selenite is added in coal base activates humic acid, is fully mixed, be aged 3 days.According still further to weight percent
Than adding 1:1.2 calcium carbonate (analyzing pure, Shanghai traditional Chinese medicines), fully mixes, obtains modifying agent.
Embodiment 2：Reduce the modifying agent of acid rice field Methylmercury pollution Riverfish
Weathered coal takes from Tengzhou of Shandong Province Guo Zhuan collieries, and content of humic acid is 743g/kg, and Hg contents are 0.016mg/kg.
Prepared by following step：
0.8mm sieves are crossed after weathered coal is removed impurity removing, milled.According to 12:1 ratio of water to coal (mass ratio) adds in weathering coal dust
Enter clear water, stir, in supersonic wave cleaning machine (KQ-500DE types, Kunshan ultrasonic instrument Co., Ltd) processing pond, according to
Ultrasonic power 650W, ultrasonic time 35 minutes, carry out ultrasonic activation process.After the completion of activation, weathering coal dust room temperature is air-dried.
According to volume ratio 1:3 add 0.1mol/L HCl, soak 78 hours, are sufficiently stirred for or vibrate during immersion.Material after immersion
With bamboo shine pad filter, repeatedly with clear water rinse 8 times, spread out at room temperature it is air-dried, obtain coal base activation humic acid.
0.1% sodium selenite is added in coal base activates humic acid, is fully mixed, be aged 4 days.According still further to weight percent
Than adding 1:1.5 calcium carbonate (analyzing pure, Shanghai traditional Chinese medicines), fully mixes, obtains modifying agent.
Embodiment 3：Reduce the modifying agent of acid rice field Methylmercury pollution Riverfish
Weathered coal takes from Jinan Li Fu collieries colliery, and content of humic acid is 574g/kg, and Hg contents are 0.019mg/kg.
Prepared by following step：
1.5mm sieves are crossed after weathered coal is removed impurity removing, milled.According to 9:1 ratio of water to coal (mass ratio) adds in weathering coal dust
Enter clear water, stir, in supersonic wave cleaning machine (KQ-500DE types, Kunshan ultrasonic instrument Co., Ltd) processing pond, according to
Ultrasonic power 450W, ultrasonic time 50 minutes, carry out ultrasonic activation process.After the completion of activation, weathering coal dust room temperature is air-dried.
According to volume ratio 1:1.5 add 0.1mol/L HCl, soak 70 hours, are sufficiently stirred for or vibrate during immersion.Thing after immersion
Material with bamboo shine pad filter, repeatedly with clear water rinse 4 times, spread out at room temperature it is air-dried, obtain coal base activation humic acid.
0.1% sodium selenite is added in coal base activates humic acid, is fully mixed, be aged 2 days.According still further to weight percent
Than adding 1:1 calcium carbonate (analyzing pure, Shanghai traditional Chinese medicines), fully mixes, obtains modifying agent.
Embodiment 4：Carry out reducing the potted plant experiment of soil Methylmercury pollution Riverfish using modifying agent obtained in embodiment 1
Using the modifying agent and its using method of the potted plant method preliminary examinations present invention to Soil-rice methyl mercury content
Reducing effect.For trying potting soil collection, from the wattenshlick field of Xiangyin County white clay lake home town Hu Cun, (genealogical classification is that the latent letter in bottom is educated
Water separating), basic physical and chemical is shown in Table 1.The rice varieties of plantation are prestige excellent 46.
Basic physical and chemical of the table 1 for examination potting soil
Modifying agent prepares：The modifying agent that gained is prepared using embodiment 1 is tested.
Experiment acceptor prepares：
Pot experiment is carried out in flowerpot, a diameter of 40cm of flowerpot upper limb, and basal diameter is 30cm, a height of 35cm, bottom
There is pallet.Per basin 5kg (wind desiceted soil weight).Add external source Hg (NO according to 5mg/kg3)2Solution (top pure grade, Shanghai traditional Chinese medicines chemistry),
80% field capacity is kept, (Jing pilot studies prove that the fractions distribution of external source Hg tends to after 90 days to be placed in aged at room temperature 90 days
It is stable).
After aging end, base fertilizer (analysis pure urea 2.17g, KH are added in soil2PO40.47g, KCl 1.08g,
After testing, in these fertilizer, mercury and selenium are not detected, and the impact to testing is negligible), fully mix.
Experimentation：
Grouping experiment, respectively control group, modifying agent group and modifying agent+water management group are set.Each group is processed and is repeated
10 times.
Control group：Without modifying agent, moisture condition is to simulate the water management pattern that conventional rice is planted, i.e. early stage is flooded
Water (water surface is higher than Soil Interface 2cm), heading flowering period start the field capacity for maintaining 80%.
Modifying agent group：Addition modifying agent (9g/ basins) while base fertilizer is added, moisture condition is identical with control.
Modifying agent+water management group：On the basis of modifying agent process, it is 80% that rice at whole growth periods keeps soil moisture
Field capacity.
Rice paddy seed is first removed into flat-kernel seed with clear water suspension method, 30%H is then used2O2Seed soaking 30 minutes, is rinsed with clear water
Totally, then proceed to Seed soaking 10 hours, vernalization.After seed rice vernalization, rice shoot was moved after 25 days by the first seedling on raising rice seedling plate
Plant in the basin handled well, per 2 cave of basin, per 1 plant of cave.To ensure growth of seedling, the water surface is added water to after transplanting and is higher by Soil Interface
1cm, waits moisture to start to control moisture after slowly evaporating.
During plantation, moisture condition is ensured by gravimetric method, periodically adds deionized water.Topdress during paddy growth 2 times：
Tillering stage applies pure urea 0.545g, KCl 0.310g of analysis per basin；Heading stage applies analysis pure urea 0.545g, KH per basin2PO4
0.235g、KCl 0.310g。
Sampling and measure：
Soil：The 5th day after Rice Cropping, 35 days, 90 days, 120 days (rice harves) and 160 days are from flowerpot rice root
System nearby gathers pedotheque, determines methyl mercury content, Eh and pH in soil.
Paddy rice：Paddy rice sample overground part and underground part are separated after results, the mud on root system is first carefully washed away with running water
Soil, then the whole plant of deionized water, high purity water cleaning, blot surface moisture, sample analysis paddy rice methyl with blotting paper gauze
Mercury content, plant height, grain number per spike, mass of 1000 kernel.
Critical equipment used by analysis of experiments：For analyzing the full-automatic MeHg analysis systems of soil and paddy rice methyl mercury content
(Merx P＆T-GC-AFS, Brooks Rand Labs, USA).
Interpretation of result：
From accompanying drawing 1 as can be seen that with the growth of implantation time, The Rhizosphere of Rice soil methyl mercury content is totally presented and increased
Trend.After 5th day, the soil methyl mercury content of modifying agent+water management group is substantially less than compareed and modifying agent treatment group (P<
0.05, similarly hereinafter), by the 120th day of rice harves, The Rhizosphere of Rice soil methyl mercury content that control and modifying agent are processed (average,
21.36 μ g/kg and 6.11 μ g/kg are respectively similarly hereinafter), the The Rhizosphere of Rice soil methyl mercury content of modifying agent+water management group is
2.87 μ g/kg, only the 13.4% of control group, reduce more than 85%.To last time soil sampling (160 days), control group
19.34 μ g/kg and 7.55 μ g/kg, modifying agent+water management are respectively with the The Rhizosphere of Rice soil methyl mercury content of modifying agent group
The The Rhizosphere of Rice soil methyl mercury content of group is 3.11 μ g/kg, is the 16% of control group, reduces more than 80%.
After adding modifying agent, compared with control group, soil pH significantly rises (accompanying drawing 2).It is by 120 days of rice harves, right
5.8,6.3 and 6.1 are respectively according to the soil pH of group, modifying agent group and modifying agent+water management group.To last time soil sampling
(160 days), the soil pH of control group, modifying agent group and modifying agent+water management group are respectively 5.7,6.1 and 6.0.It is overall next
See, compared with control group, modifying agent makes soil pH improve more than 0.3.
After rice harves, the seed methyl mercury content difference of control group, modifying agent group, modifying agent+water management group process
For 61.2 μ g/kg, 20.33 μ g/kg and 7.61 μ g/kg (accompanying drawing 3), the seed methyl mercury content of modifying agent+water management group is
The 12.4% of control, have dropped more than 85%；Plant height be respectively 103.1cm (control group), 99.3cm (modifying agent group) and
100.07cm (modifying agent+water management group), no marked difference between three kinds of process；Grain number per spike is respectively 96/plant (control
Group), 113.1/plant (modifying agent group) and 93.2/plant (modifying agent+water management group), the lower grain number per spike of modifying agent process is most
Height, modifying agent+water management process with compare between without difference；Mass of 1000 kernel is respectively 23.1g (control group), 25.3g
(modifying agent group) and 24.3 (modifying agents+water management group), the lower mass of 1000 kernel highest of modifying agent process, modifying agent+water management group
Without marked difference between control group.
In general, in pot experiment, compared with control group, modifying agent+water management processes lower The Rhizosphere of Rice soil
In methyl mercury content and rice grain, methyl mercury content significantly declines (more than 80%), and soil pH significantly rises (raising
Amplitude is more than 0.3), and there is not decline in rice yield and biomass.
Embodiment 5：Carry out reducing the field experiment of soil Methylmercury pollution Riverfish using modifying agent obtained in embodiment 1
Using field test, the drop of the modifying agent and its using method of the present invention to Soil-rice methyl mercury content is investigated
Poorly efficient fruit.Field test is located at all mouth Pb-Zn deposits in Shaoguan City of Guangdong Province 10 km farmlands nearby, and the soil texture is clay loam, base
This physicochemical property is shown in Table 2.Rice varieties are five Feng You 2168.
2 field test soil physico-chemical property of table
Experimentation：
Grouping experiment, respectively control group, modifying agent group and modifying agent+water management group are set.Different disposal field is used
Ridge bag plastic sheeting separates.4 experimental plots of per group of setting, each experimental plot area is 667 square metres (1 mu), is tested
The field gross area is 8004 square metres (6 mu).
Modifying agent prepares：The modifying agent that gained is prepared using embodiment 1 is tested.
Control group：Any modifying agent is not applied, moisture, agricultural chemicals and chemical fertilizer are managed according to local conventional rice planting type.
Modifying agent group：Modifying agent whole base is applied by the weight according to 300kg/ mus, is then carried out turning over, is harrowed even, makes improvement
Agent is well mixed with 20cm topsoil soils, and water drenching, balance carried out rice growing or transplanting after 14 days.Remaining moisture, agricultural chemicals and change
Fertilizer management is according to local conventional rice planting type.
Modifying agent+water management group：On the basis of the process of modifying agent group, Tu Mianchu is remained during paddy growth
In the moisture state without open fire.Remaining agricultural chemicals and chemical fertilizer control measures are according to local conventional rice planting type.
Sampling and measure：Tillering stage, boot stage, heading stage, milk stage and maturity period in Rice Cropping, according to plum blossom 5
Point sampling method uniformly gathers pedotheque, makes biased sample.Each process gathers 3 biased samples altogether, determines soil respectively
Methyl mercury content, Eh and pH.After rice harves, sample analysis paddy rice methyl mercury content, plant height, grain number per spike, mass of 1000 kernel.
Interpretation of result：
With the growth of Rice Cropping time, The Rhizosphere of Rice soil methyl mercury content is presented growth trend.From rice tillering
Phase, the soil methyl mercury content under modifying agent+water management group is substantially less than compareed and modifying agent is processed, ripe to paddy rice
The The Rhizosphere of Rice soil methyl mercury content of phase, control group and modifying agent group is respectively 6.578 μ g/kg and 2.658 μ g/kg, improvement
The The Rhizosphere of Rice soil methyl mercury content of agent+water management group is 1.487 μ g/kg, only the 22.6% of control group, is reduced
More than 75%.
After adding modifying agent, compared with control group, soil pH significantly rises (accompanying drawing 5).To rice maturity, control group,
The soil pH of modifying agent group and modifying agent+water management group is respectively 4.61,5.03 and 5.48.Compared with control group, modifying agent
Soil pH is made to improve more than 0.4.
After rice harves, the seed methyl mercury content difference of control group, modifying agent group, modifying agent+water management group process
For 18.23 μ g/kg, 5.44 μ g/kg and 3.10 μ g/kg (as shown in Figure 3), the seed methyl mercury of modifying agent+water management group
Content is the 17% of control group, have dropped more than 80%；Plant height is respectively 84.21cm (control group), 82.41cm (modifying agent group)
With 82.1cm (modifying agent+water management group), grain number per spike respectively 97.92/plant (control group), 95.00/plant (modifying agents
Group) and 93.64/plant (modifying agent+water management group), mass of 1000 kernel respectively 24.95g (control group), 23.78g (modifying agents
Group) and 25.03 (modifying agents+water management group).Three kinds process plant height, between grain number per spike and mass of 1000 kernel without difference.
In general, in field test, compared with control group, the lower The Rhizosphere of Rice soil of modifying agent+water management group process
In earth methyl mercury content and rice grain methyl mercury content decline more than 75%, soil pH improve more than 0.4, and rice yield and
Biomass is not reduced.
Claims (6)
1. the modifying agent of acid rice field Methylmercury pollution Riverfish is reduced, it is characterised in that：It is obtained by following steps：
(A) 0.5～2.0mm sieves are crossed after weathered coal being removed impurity removing, milled；
(B) after sieving, according to ratio of water to coal (mass ratio) 8:1～12:1 adds clear water, stirs, using ultrasonic power 400w
～700w carries out ultrasonic activation and processes 30～50min, and room temperature is air-dried；
(C) according to volume ratio 1:1～1:3 add 0.1mol/L HCl, soak 65～80 hours, filter under stirring or oscillating condition
Rinsed more than 3 times with clear water afterwards, spread out air-dried at room temperature, obtain coal base humic acid；
(D) add the sodium selenite of 0.1-0.2% in the coal base humic acid by weight percentage, after mixing, be aged 2～4
My god；
(E) in the material that step (D) is aged by weight 1:1～1:2 add calcium carbonate, mix, obtain final product.
2. the modifying agent of acid rice field Methylmercury pollution Riverfish is reduced according to claim 1, it is characterised in that：By following steps
It is obtained：
(A) 1.0mm sieves are crossed after weathered coal being removed impurity removing, milled；
(B) after sieving, according to ratio of water to coal (mass ratio) 10:1 adds clear water, stirs, is carried out using ultrasonic power 500w
Ultrasonic activation processes 40 ± 5min, and room temperature is air-dried；
(C) according to volume ratio 1:2 add 0.1mol/L HCl, soak 72 hours under stirring or oscillating condition, shine pad with bamboo and filter
Rinsed more than 3 times with clear water afterwards, spread out air-dried at room temperature, obtain coal base humic acid；
(D) add the sodium selenite of 0.1-0.2% in the coal base humic acid by weight percentage, after mixing, be aged 2～3
My god；
(E) in the material that step (D) is aged by weight 1:1.2-1:1.5 add calcium carbonate, mix, obtain final product.
3. the modifying agent of acid rice field Methylmercury pollution Riverfish is reduced according to claim 1, it is characterised in that：The step (A)
The content of humic acid of the weathered coal for using is in more than 500g/kg.
4. the modifying agent of acid rice field Methylmercury pollution Riverfish is reduced according to claim 1, it is characterised in that：The step (E)
Whiteness >=90 of middle added calcium carbonate, granularity >=100 mesh, impurity content≤0.05%.
5. the method for reducing acid rice field Methylmercury pollution Riverfish, it is characterised in that：Comprise the following steps：
1) modifying agent base is applied：Pressed using the modifying agent that acid rice field Methylmercury pollution Riverfish is reduced as described in any one of Claims 1 to 4
200～300kg/ mus carry out base and apply, and turn over, harrow even, the modifying agent is well mixed with 20cm topsoil soils, and water drenching makes soil
Earth can carry out rice growing or transplanting after balancing 14 days under moisture state；
2) water management：After Rice Cropping, the time of infertility remains field face moisture state to results.
6. the method for reducing acid rice field Methylmercury pollution Riverfish according to claim 5, it is characterised in that：The step 1) and step
It is rapid 2) in moisture state refer to that Soil Moisture is maintained at the 70～80% of water-retaining quantity among field of soil, and surface is without covering water.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109588218A (en) * | 2018-12-25 | 2019-04-09 | 湖南恒凯环保科技投资有限公司 | For reducing the implantation methods of crops mercury content |
| CN111205870A (en) * | 2020-02-28 | 2020-05-29 | 江苏省地质调查研究院 | Passivator and application thereof in repairing moderate and light mercury polluted farmland soil |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102925161A (en) * | 2012-01-18 | 2013-02-13 | 云南省烟草公司昭通市公司 | Broad spectrum heavy metal activity deactivator preparation method |
| CN105052646A (en) * | 2015-09-11 | 2015-11-18 | 南京大学 | Method for decreasing methyl mercury content in rice |
-
2016
- 2016-11-03 CN CN201610973759.7A patent/CN106520137A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102925161A (en) * | 2012-01-18 | 2013-02-13 | 云南省烟草公司昭通市公司 | Broad spectrum heavy metal activity deactivator preparation method |
| CN105052646A (en) * | 2015-09-11 | 2015-11-18 | 南京大学 | Method for decreasing methyl mercury content in rice |
Non-Patent Citations (3)
| Title |
|---|
| XIAOYAN PENG ET AL.: "Reducing total mercury and methylmercury accumulation in rice grains through", 《ENVIRONMENTAL POLLUTION》 * |
| 李家家: "超声波活化风化煤对土壤中Hg形态及土壤酶活性的影响研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
| 范拴喜: "《土壤重金属污染与控制》", 30 November 2011, 中国环境科学出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109588218A (en) * | 2018-12-25 | 2019-04-09 | 湖南恒凯环保科技投资有限公司 | For reducing the implantation methods of crops mercury content |
| CN111205870A (en) * | 2020-02-28 | 2020-05-29 | 江苏省地质调查研究院 | Passivator and application thereof in repairing moderate and light mercury polluted farmland soil |
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