CN109913233B - Rice field soil heavy metal passivation modifier - Google Patents
Rice field soil heavy metal passivation modifier Download PDFInfo
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- CN109913233B CN109913233B CN201910347164.4A CN201910347164A CN109913233B CN 109913233 B CN109913233 B CN 109913233B CN 201910347164 A CN201910347164 A CN 201910347164A CN 109913233 B CN109913233 B CN 109913233B
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- 239000002689 soil Substances 0.000 title claims abstract description 128
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 42
- 238000002161 passivation Methods 0.000 title claims abstract description 34
- 239000003607 modifier Substances 0.000 title claims abstract description 26
- 235000007164 Oryza sativa Nutrition 0.000 title description 57
- 235000009566 rice Nutrition 0.000 title description 57
- 240000007594 Oryza sativa Species 0.000 title 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 37
- 239000010457 zeolite Substances 0.000 claims abstract description 37
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- 235000019738 Limestone Nutrition 0.000 claims abstract description 23
- 239000006028 limestone Substances 0.000 claims abstract description 23
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims abstract description 21
- 210000003608 fece Anatomy 0.000 claims abstract description 18
- 235000019796 monopotassium phosphate Nutrition 0.000 claims abstract description 18
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 17
- 239000010871 livestock manure Substances 0.000 claims abstract description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 12
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- 239000000203 mixture Substances 0.000 claims description 8
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- 230000004048 modification Effects 0.000 claims 1
- 238000012986 modification Methods 0.000 claims 1
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- 230000008859 change Effects 0.000 abstract description 8
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- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
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Landscapes
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a paddy field soil heavy metal passivation modifier, which comprises a main agent and an auxiliary agent; the main agent consists of natural zeolite, natural limestone and potassium dihydrogen phosphate; the auxiliary agent comprises animal manure, vermiculite, a decomposing agent and a silicon fertilizer. The soil heavy metal passivation modifier for paddy fields can effectively improve the pH value of soil, reduce the change rate of the soil, reduce the content of active cadmium and arsenic in the soil and the enrichment amount of cadmium and arsenic in crops, and improve the content of available phosphorus in the soil and the enrichment capacity of crops on soil selenium.
Description
Technical Field
The invention relates to a soil conditioner, in particular to a passivation conditioner for farmland cadmium-arsenic combined pollution medium/acid soil, belonging to the technical field of farmland soil environment restoration.
Background
Soil is taken as a root for human production and living, the production and waste stacking of industrial and mining smelting plants tend to pollute surrounding soil, and agricultural production activities performed on the polluted soil tend to form food safety problems; with the release of the national soil pollution condition investigation publication and the soil pollution control action plan, the soil pollution control becomes a research hotspot. At present, the thinking of soil heavy metal pollution treatment has been changed from completely removing heavy metals to implementing a strategy based on risk control.
The existing farmland soil heavy metal pollution in-situ passivation technology mainly comprises physical adsorption, soil pH value improvement, soil redox condition change or crop selection and cultivation with low accumulation of heavy metals, but has poor physical adsorption stability and may be activated again at any time; the pH value is improved, a large amount of limestone is sprayed mainly, acid rain is more in the south area, and long-term lime spraying is needed, so that the problems of soil hardening and the like are caused; secondly, the oxidation-reduction condition of the soil is changed, the field is kept to be flooded throughout the year, the soil environment is made to be a reduction environment, the activity of heavy metals such as cadmium and the like is reduced, but the mode is not beneficial to the good growth of rice, and Cr in the soil is reduced 3+ May be reduced to Cr 6+ The chromium pollution risk is greatly improved; the method for selecting and cultivating the crop varieties with low heavy metal accumulation is a better method, but is still in the stage of variety cultivation test at present.
Disclosure of Invention
Aiming at the defects of the most common cadmium-arsenic combined pollution farmland soil restoration in the prior art, the invention aims to provide the paddy field soil heavy metal passivation modifier which can effectively improve the pH value of soil, reduce the change rate of the soil, reduce the content of active cadmium and arsenic in the soil and the enrichment amount of cadmium and arsenic in crops, and improve the content of available phosphorus in the soil and the enrichment capacity of crops on soil selenium.
In order to achieve the technical aim, the invention provides a paddy field soil heavy metal passivation modifier, which comprises a main agent and an auxiliary agent; the main agent consists of natural zeolite, natural limestone and potassium dihydrogen phosphate; the auxiliary agent comprises animal manure, vermiculite, a decomposing agent and a silicon fertilizer.
In a preferred scheme, the main agent consists of the following components in parts by mass: 65-70 parts of natural zeolite, 25-28 parts of natural limestone and 2-5 parts of potassium dihydrogen phosphate.
Preferably, the auxiliary agent comprises the following components in parts by mass: 52-61 parts of animal manure, 26-32 parts of vermiculite, 0.5-0.7 part of a decomposing agent and 6-8 parts of a silicon fertilizer.
Preferably, the animal manure comprises at least one of cow manure, sheep manure and pig manure.
In a preferred scheme, the mass ratio of the main agent to the auxiliary agent is 1.8-2.2:0.9-1.1.
The main agent of the paddy field soil heavy metal passivation modifier is mainly used for adsorbing active heavy metal ion cadmium and arsenic in soil. The natural zeolite (main component A (x/q) [(AlO 2 ) x (SiO 2 ) y ]n(H 2 O)) not only has a porous structure, but also contains a large amount of active Ca 2+ 、Na + 、K + Because of the active property, the soil and Cd in the solution of the Cd are easy to be mixed 2+ And As 3+ Ion exchange occurs to cause Cd to 2+ And As 3+ Forms a more stable mineral with the silicon (aluminum) oxygen tetrahedral lattice of zeolite, and reduces the content of active cadmium and arsenic in soil. Monopotassium phosphate (KH) 2 PO 4 ) For modifying zeolite, and adding original Ca in zeolite 2+ Substitution by smaller volumes of K + Thereby increasing the pore volume of the zeolite, changing the electrical property of the end face of the zeolite crystal layer by replacing ions, enhancing the adsorption capacity of heavy metal cations and containing H 2 PO 4 － Through exchange ofThe desorption causes the increase of the pH of the soil, further improving the physicochemical adsorption effect of the zeolite. While natural limestone can be combined with water and H in the soil solution + Reaction to reduce H in soil + Content, stress Cd 2+ 、As 3+ With Ca in zeolite 2+ 、Na + 、K + The substitution is performed, so that the chemical adsorption effect of divalent cadmium ions and trivalent arsenic ions is enhanced. The three are synergistic, the specific surface area of zeolite is increased by increasing the pore volume of zeolite, and the ion exchange efficiency of cadmium, arsenic and the like in soil solution is improved by H 2 PO 4 － And CaCO (CaCO) 3 With H in soil solution + Reaction to reduce H in soil + Content of Ca in soil is increased 2+ Concentration of Ca with higher concentration and higher activity 2+ And K + Cd in stress soil 2+ 、As 3+ Into zeolite with increased pore size and with Ca in silicon (aluminium) oxide tetrahedral lattice 2+ 、K + Ion exchange is carried out on alkaline earth metal or alkali metal ions, and relatively stable minerals are formed with silicon (aluminum) oxygen tetrahedral grids, thereby reducing active Cd in soil 2+ And As 3+ The main agent synthesized by the three components is an effective natural mineral passivating agent for exchanging and adsorbing active cadmium and arsenic in soil. The auxiliary agent comprises mainly cow (sheep) manure, vermiculite, a decomposition agent, a silicon fertilizer and the like, wherein the cow (sheep) manure is mainly used for improving the content of organic matters, nitrogen, phosphorus and potassium and loosening soil, the vermiculite is mainly used for slowing down the pH value mutation, so that the passivation effect of the main agent is stable for a long time, water and soil moisture are preserved, trace elements necessary for the growth of crops such as K, mg, ca, fe are provided, the silicon fertilizer is used for supplementing fast-soluble silicon, the yield and lodging resistance of the rice are improved, the auxiliary agent mixed by the composite auxiliary agent is mainly used for slowing down the pH mutation efficiency, and simultaneously, the organic matters, the trace elements such as nitrogen, phosphorus, potassium, calcium and magnesium necessary for the growth of the crops are enhanced, the content of the silicon fertilizer is improved, and the growth quality of the crops is improved. The heavy metal passivation modifier for the whole paddy field soil can effectively replace and adsorb cadmium ions and arsenic ions in the soil on the premise of not damaging the ecological environment of the farmland, and simultaneously reduce H in the soil + The content and the change efficiency are reduced, and the active cadmium and arsenic in the soil are reducedThe content of cadmium and arsenic in crops, and the content of effective phosphorus in soil is improved, and the selenium enrichment capability of crops to soil is improved.
The total amount of heavy metal elements such as cadmium, lead, arsenic, mercury, copper, nickel, zinc and the like in the natural zeolite, the natural limestone, the natural dolomite and the vermiculite, which have great influence on crops or human bodies, is within the allowable content range, the components are basically natural minerals, the components are stable, and the activity of the heavy metal elements is relatively low. The adopted monopotassium phosphate is a high-efficiency phosphorus-potassium compound fertilizer raw material, vermiculite is a common plant growth base, silicon fertilizer is a medium element fertilizer, and cattle (sheep) manure is a natural organic fertilizer. The main agent and the auxiliary agent are natural or beneficial materials, and the cost is low.
The preparation method of the paddy field soil heavy metal passivation modifier comprises the following steps: mashing natural zeolite to small particles with the particle size not more than 1mm, preparing monopotassium phosphate into a solution with the concentration of 20g/L, placing the mashed natural zeolite particles into the prepared monopotassium phosphate solution, vibrating and standing for 2 days, adding natural limestone powder with the particle size not more than 0.85 mm, vibrating and stirring uniformly, standing for 1 day, and fully air-drying to obtain a main agent; drying cow dung in an auxiliary agent, stirring and crushing the cow dung until the grain diameter is not more than 1mm, preparing a mixture with the water content of 40-50% by using a small amount of distilled water, sequentially adding a decomposing agent, vermiculite and a silicon fertilizer into the mixture, performing ultrasonic dispersion for 1-1.5 h to prepare a mixed sticky matter, and extruding the sticky matter through a mesh screen with the pore diameter of 3 mm; and (3) placing the mixed main agent under the screen, manufacturing auxiliary agent particles, shaking a main agent hopper, enabling the auxiliary agent particles to fall into the main agent hopper, coating a layer of main agent powder on the surface, and forming.
Compared with the prior art, the paddy field soil heavy metal passivation modifier has the beneficial technical effects that:
(1) the paddy field soil heavy metal passivation modifier can slightly improve the pH value of soil, reduce the change rate of the pH value of the soil, reduce the content of extractable cadmium in the soil and reduce the enrichment of cadmium and arsenic in crops; the content of available phosphorus, potassium, calcium and magnesium in the soil is improved, and the selenium enrichment capability of crops to the soil is improved; the comprehensive effective passivation modifier has the advantages of improving the lodging resistance of rice, improving the acre yield of rice to a certain extent, passivating the heavy metal elements in soil, improving the content of beneficial elements such as potassium, phosphorus, silicon, magnesium and the like, and improving the yield.
(2) The soil heavy metal passivation modifier has obvious synergistic effect among the components, and compared with the single zeolite, limestone and the like serving As the heavy metal passivation agent, the soil heavy metal passivation modifier has more obvious passivation effect on Cd and As, and the yield of rice in the season and the improvement effect on the content of effective phosphorus in the soil are more obvious.
(3) The soil heavy metal passivation modifier has wide sources of raw materials and simple preparation method, and is beneficial to reducing the use cost.
Description of the embodiments
The following examples are intended to further illustrate the present invention, but not to limit the scope of the claims.
Example 1
According to the previous investigation and evaluation results, a thick soil layer with the surface layer of 0-20 cm is adopted in a plain farmland of a river basin in Hunan province, the thick soil layer is gray yellow clay loam rice soil, the gray yellow clay loam rice soil is transported back to a base to be subjected to an indoor culture test, water is injected, the mixture is stirred repeatedly and mixed uniformly, the mixture is left to stand and air-dry until the humidity is 18.5%, the mixture is uniformly divided into 24 parts, each part of soil is subjected to soil sampling test pH, cd, as, cr, cu, pb, zn, the analysis results of the soil tests after uniform mixing are basically consistent, the average pH value is 5.82, the average Cd value is 3.72mg/kg, the average As value is 23.57mg/kg, the average Hg value is 2865 mug/kg, the average Pb value is 53.76mg/kg, the average Cu value is 42.39mg/kg, and the average Cr value is 83.17mg/kg. The soil is slightly acidic as a whole, and the problem of exceeding the total Cd amount exists in the soil environment.
Natural zeolite powder is arrangedZ) Natural limestone powderCA) Mixing natural zeolite powder with natural limestone powderZCA) Natural zeolite powder and potassium dihydrogen phosphateZP) Natural limestone powder and potassium dihydrogen phosphateCAP) Potassium dihydrogen phosphateP) Natural zeolite powder, potassium dihydrogen phosphate and limestone powderZPCA) 7 treatments, simultaneously setting up 1 blank control groupCK) Three times of repetition are set for each treatment, and the dosage of each reagent is 68g/kg of zeolite powder, 26g/kg of limestone powder, 4g/kg of monopotassium phosphate, zeolite powder and lime respectivelyThe granularity of the stone powder is 100 meshes, the stone powder is stirred and mixed evenly after being sprayed, the monopotassium phosphate is prepared into aqueous solution and is mixed evenly after being sprayed,ZPCAtreating, soaking zeolite powder in potassium dihydrogen phosphate solution, mixing with limestone powder, spraying in liquid state, and mixing uniformlyCK) No treatment was performed. After the treatment measures, the soil under each treatment is placed for 30 days at room temperature, later rice (Tian Liang you 682) is sown according to the rice cultivation requirement for cultivation, and the soil under each treatment and rice samples are collected respectively for test analysis after the rice is ripe. Analyzing the pH value, cd and effective cadmium content of the soil, performing five-step morphological analysis on the cadmium, and analyzing the Cd, hg, as, pb, cr, cu content of rice.
The test results show that:
(1) relative toCKThe group of the components is arranged in a group,Z、CA、ZCA、CAPandZPCAthe pH value of the soil is improved to different degrees under the six treatments, whereinZPCAThe best results, the pH value rises to 6.35, the Z treatment effect is relatively poor, and the pH value only rises to 5.91. The pH value of the soil under each treatment is ranked as follows:ZPCA＞ZCA＞CA＞Z＞CAP＞CK≈ZP≈P。
②CKthe Cd content interval in the rice (brown rice) is 1.17-1.42 mg/kg, which is far beyond the Cd limit standard (0.2 mg/kg) in the brown rice, and the other five heavy metals are in the limit range of brown rice pollutants. The Cd and As contents in the rice treated by partial treatment measure are obviously reduced, whereinCAThe Cd content in the treated rice is reduced by 19.39%;Zthe Cd content in the treated rice is reduced by 31.27%, and the As content in the rice is reduced by 17.24%;ZCAthe Cd content in the treated rice is reduced by 39.71%, and the As content is reduced by 18.12%;ZPthe Cd content in the treated rice is reduced by 41.26 percent, and the As content is reduced by 23.47 percent;ZPCAthe Cd content in the treated rice is reduced by 63.29 percent, and the As content is reduced by 27.68 percent.
(3) Relative toCKThe group of the components is arranged in a group,Zthe effective cadmium content in the treated soil is reduced by 58.92 percent,ZPthe effective cadmium content of the treated soil is reduced by 67.17 percent,CAthe effective cadmium in the treated soil is reduced by 53.41 percent,CAPthe effective cadmium of the treated soil is reduced by 52.69 percent,ZCAthe effective cadmium of the treated soil is reduced by 63.84 percent,ZPCAthe effective cadmium content of the treated soil is reduced by 81.76 percent.
(4) Relative toCKThe group, the residual cadmium of Z treatment is increased by 52.75 percent,ZPthe treated residual cadmium content is increased by 79.31 percent,Pthe cadmium content of the treated soil residue state is increased by 12.92 percent,CAthe ratio of the residual cadmium in the treated soil is increased by 18.37 percent,CAPthe ratio of the residual cadmium in the treated soil is increased by 21.32 percent,ZCAthe cadmium content of the treated soil residue state is increased by 53.66 percent,ZPCAthe residual cadmium content in the treated soil is increased by 89.87%.
The test result shows that when the cultivation test is carried out on the cadmium-polluted soil, the monopotassium phosphate, the limestone and the zeolite can repair the Cd-polluted soil, but the combination of the natural zeolite powder, the monopotassium phosphate and the limestone powder has better repairing effect on the Cd-polluted soil, and meanwhile, the total As content in the rice can be obviously reduced, and the reduction rate is highest. It is known that the combined use of natural zeolite powder, monopotassium phosphate and limestone powder can effectively reduce the active contents of cadmium and arsenic in soil, and simultaneously reduce the contents of cadmium and arsenic in rice, and the effect is far better than that of the application of zeolite powder, limestone and monopotassium phosphate singly or in any two combinations, and the combined use of the three has obvious synergistic effect to a certain extent.
Example 2
Ten demonstration fields and two field test fields are set according to the scheme by adopting a test method of district tests and field demonstration, each demonstration field is provided with a treatment, and the actual effect of each scheme on soil and crops under natural conditions is observed; five treatment measures are arranged in the test field, each treatment measure is repeated three times and is compared with one control, and the advantages and disadvantages of the treatment measures under the basically consistent natural farmland environment are compared. The selected test field is a test field of No. TM17 of a test base of a Zhentong wood nest village of Xintian county of Hunan province, and the field area is 0.95 mu. The soil of the test field is light gray yellow rice soil, the texture configuration is compact, the soil texture is clay loam, and the thickness of a plough layer is about 27cm. The average value of the pH value of the soil is 8.0, the soil belongs to alkaline soil, the organic matter content of the soil is 6.01 percent, the main nutrient elements are slightly deficient in potassium, and the effective potassium content is 74.4mg/kg; the main soil environmental problems are represented by the exceeding of the total amount of Cd and Hg, wherein the average content of Cd is 2.18 mg/kg, the average content of effective cadmium is 1.04 mg/kg, and the average content of Hg is 3.14 mg/kg; the content of Cd, hg, as, pb, cr and the like in the rice seeds in the test land all reach the quality standard of agricultural products. The test field is tobacco leaf-rice rotation, spring dry seed tobacco leaf and autumn water seed rice, and the standard exceeding condition of heavy metal such as late rice seed cadmium is relatively serious in general cases, the passivation effect of the soil heavy metal passivation modifier in late rice planting is mainly tested, the tested crop is Hui liangyou 996 hybrid rice, and the field management such as daily fertilization and pesticide application is decided by the farmer by oneself so as to test the actual effectiveness of the soil heavy metal passivation modifier under the natural cultivation condition.
The test scheme is to set modified sepiolite, calcium bentonite, natural zeolite powder, natural limestone powder, organic fertilizer and soil heavy metal passivation modifier (the mass ratio of main agent to auxiliary agent=2:1; the main agent composition comprises 68 parts of natural zeolite, 27 parts of natural limestone, 5 parts of potassium dihydrogen phosphate, the auxiliary agent composition comprises 54 parts of cow dung, 30 parts of vermiculite, 0.6 part of decomposing agent and 8 parts of silicon fertilizer), and the six treatments are respectively set up a blank control and three repetitions, and the application amount of each passivation agent is 200 kg/mu. The substrate content of each heavy metal element of the soil heavy metal passivation modifier is lower than the secondary standard of the soil environment quality, and the total amount of each heavy metal element is 3-4 orders of magnitude lower than the heavy metal element content of the soil. Five passivation improvers are thrown when ploughing, the fields are thrown and rotary tillage is carried out while mixing evenly, after the test fields are ploughed and rotary tillage, a test plot is newly built by soil in the fields, a drainage canal is filled in the test plot and matched with the test plot, a film is covered for water isolation, then the passivation improvers are thrown manually and mixed evenly by manual raking, standing and precipitation are carried out for 3-5 days after the sprinkling and mixing operation, transplanting is started, and the growth condition and the water filling and drainage condition are monitored and recorded regularly in the rice growing process. When harvesting rice, respectively collecting rice seed samples and soil samples according to the cells, respectively harvesting rice according to the cells/fields, bagging, sun-drying, weighing after sun-drying, and comparing the yield difference.
Among six passivating agents adopted in the test, the effect of reducing Cd and As in the paddy by applying the soil heavy metal passivating modifier is best, compared with a blank group paddy sample, the Cd content is reduced by 19.85%, the Cd enrichment coefficient (the cadmium content of rice/the total cadmium content of soil) is reduced by 25.19%, the As content in the rice is reduced by 13.13%, and the As enrichment coefficient is reduced by 34.18%; the Cd content in the rice with lime powder is reduced by 4.19%, the enrichment coefficient is reduced by 6.87%, and the As content has no obvious change (< 1%); the Cd content in the rice by using the natural zeolite powder is reduced by 11.27%, the Cd enrichment coefficient of the rice is reduced by 14.21%, the As content of the rice is reduced by 7.24%, and the enrichment coefficient of the rice is reduced by 15.63%; the other three rice samples had less than 5% change in Cd content and their enrichment factor relative to the blank panel, with no significant change in As.
The modified sepiolite, the natural zeolite powder, the calcium bentonite and the soil heavy metal passivation modifier of the invention are applied to obviously reduce the content of effective cadmium and effective nickel in soil by 40-50%, but the difference among treatment measures is small, the limestone powder is applied to reduce the content of effective cadmium in soil by 32%, and the content of effective cadmium in the soil of the applied organic fertilizer is reduced by 28%; the soil heavy metal passivation modifier of the invention is applied to improve the yield of the rice in season by 6.16%, the organic fertilizer is applied to improve the yield of the rice in season by 4.79%, the zeolite powder is applied to improve the yield of the rice in season by 2.74%, and other treatments have no obvious influence on the yield of the rice in season; the application of the soil heavy metal passivation modifier improves the Se content in rice by 16.4%, the Se enrichment coefficient of rice by 14.5%, the Se content in rice by 8.54% and the enrichment coefficient by 9.02% by only using zeolite powder, the Se content in rice by 4.32% and the enrichment coefficient by only using limestone powder, and the Se content in other treated rice is basically unchanged, and in general, the reagent can improve the Se absorption efficiency of rice relatively most; the application of the soil heavy metal passivation modifier of the invention improves the effective phosphorus content in soil by 25.9%, the application of the calcium bentonite improves the effective phosphorus content in soil by 22.5%, the application of the zeolite improves the effective phosphorus content in soil by 16.18%, and the application of the organic fertilizer improves the effective phosphorus content in soil by 16.16%, so other treatment effects are not obvious.
The test results showed that: under the condition of no other manual intervention, in the actual production of paddy rice planted in paddy fields, the soil heavy metal passivation modifier can effectively reduce the Cd and As content in the paddy rice, reduce the absorption efficiency of the paddy rice on the Cd and As in the soil, reduce the effective cadmium content in the soil, improve the effective phosphorus content in the soil, and increase the yield of the paddy rice and the Se content of the paddy rice. And has better effect than the conventional passivating agents such as sepiolite, bentonite, organic fertilizer and the like in the market at present.
Claims (1)
1. A paddy field soil heavy metal passivation modifier is characterized in that: the composition comprises a main agent and an auxiliary agent according to the mass ratio of 1.8-2.2:0.9-1.1;
the main agent consists of the following components in parts by mass: 65-70 parts of natural zeolite, 25-28 parts of natural limestone and 2-5 parts of potassium dihydrogen phosphate; the potassium dihydrogen phosphate is used for zeolite modification;
the auxiliary agent consists of the following components in parts by mass: 52-61 parts of animal manure, 26-32 parts of vermiculite, 0.5-0.7 part of a decomposing agent and 6-8 parts of a silicon fertilizer;
the animal manure comprises at least one of cow manure, sheep manure and pig manure.
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