KR102015327B1 - Method for inhibiting uptake into plant of organochlorine pesticide present in soil using biochar - Google Patents

Abstract

The present invention relates to a method for inhibiting the absorption of organochlorine insecticide remaining in the soil using biochar in the plant and, more specifically, to a biochar powder derived from oak, which has excellent adsorption capacity for endosulfan and can be very useful as a material of a soil improving agent to stabilize the soil contaminated by endosulfan.

Description

Method for inhibiting uptake into plant of organochlorine pesticide present in soil using biochar}

The present invention relates to a method for inhibiting the absorption of organochlorine insecticides in the plant using bio-tea in the soil.

Pesticides are essential agricultural materials that play a role in controlling pests and weeds from crops, increasing production, improving quality and reducing labor, and have been dropping about 25,000 tons of agricultural land every year since the 1990s. It is similar to Korea and Japan and Italy, which have a intensive agricultural form, and their consumption per unit area (1 ha) is 13.1 kg (based on 2007 usage), and the Economic Cooperation and Development Organization compiled by the Food and Agriculture Organization of the United Nations (FAO) (OECD) National annual average (1990-2003) data show that domestic pesticide use is the number one among 29 countries. As mentioned above, however, pesticides have been a concern of society in that they have high consumption per unit area and are one of the causes of residues or environmental pollution after spraying, despite the advantages of increasing farm household income due to the increase in agricultural productivity.

In order to control pests and weeds, pesticides applied to crops and weeds through atomizers or weeds are ejected into the air as fine particles and attached to the crops. It depends on the method of spraying. In general, emulsions are known to have 50% of the sprayed amount and 30% or less of powder applied to crops, and the rest falls into the soil as it is mixed (typically about 35 to 50%). It has a tendency to be lost due to environmental factors such as loss and photolysis due to, degradation due to metabolism in plants or dilution effect due to enlargement and growth of crop. However, some pesticides and disinfectants may be directly added to the soil. Residual pesticides may remain in the soil either directly or indirectly due to debris, rainfall, or related waters of plants and animals. It may be dislodged and moved to the soil. That is, pesticides attached to crops or pesticides scattered to the atmosphere are eventually moved to soil by rainfall or the like. Particularly, in the case of granulated pesticides, the topsoil is treated directly in the soil, and the topsoil is a major place in direct contact with these pesticides, and at the same time, a decomposition site.

Pesticides that enter the soil can have some effects on humans or livestock when they are absorbed into the crops and used as food or feed. The continuous intake of pesticides remaining in the crops as foods without decomposing the components themselves into toxic compounds has the potential to cause consumer harm such as chronic poisoning. In general, this amount is very small compared to the amount of pesticide absorbed from the soil and remaining in the crop. However, in the case of long-lived components such as organylchlorine pesticide dildrin (dildrin), there is an example that the contamination caused not only the crops at the time of spraying, but also to the soil after the spraying.

In addition, the excessive use of pesticides applied for crop protection will result in a reduction in the species of the ecosystem and the balance between species. Such disturbed ecosystems have a negative impact on productivity, and recovery of a disturbed ecosystem requires a long period of years to decades. As such, the use of pesticides has been effective in controlling pests, but the misuse and abuse of pesticides has caused pollution of the soil environment, resulting in health problems due to pollution of ecosystems and ingestion of foods contaminated with pesticides. It is causing a big negative impact on the public, making it a huge social problem.

Biochar is a material obtained by pyrolyzing biomass and is black carbon, which has recently been recognized as a multifunctional substance related to carbon sequestration, metal immobilization and fertilization of soil. Bio teas are produced by pyrolysis of biomass under a limited oxygen supply, and various types of biomass, poultry compost, livestock manure, sewage sludge and paper sludge, can be applied to the production of bio teas with different properties. Crop residues originating from agricultural by-products may be an essential source for maintaining plant nutrient cycles in soil and maintaining soil or crops. Excessive supply of crop residues, however, caused environmental pollution when the residues were burned directly in the fields or dumped in the sea or on land. Therefore, in order to prevent such negative effects, estimated crop residues of 5.7 × 10 ⁵ tonnes are considered as sources of biofuel or bioenergy in Korea. Since biotea can be made from many kinds of raw materials, the collection and use of such resources is of additional benefit to the environmental system. For example, biotea is widely applied to sequester carbon in soil, increase soil fertility, and immobilize heavy metals and herbicides. One of the most important functions of bio tea is its ability to adsorb organic pollutants in the environment. Structured carbon substrates with medium to high surface areas allow the biocar to act as an adsorbent of organic pollutants, similar to activated carbon. The use of biocar sorbents on organic pollutants is economical and readily available due to the availability of a wider range of feedstocks and the absence of activation processes compared to activated carbon.

On the other hand, Korean Patent Publication No. 2015-0139152 discloses a method for inhibiting antibiotic absorption of plants using bio tea, and Korean Patent No. 1485552 uses carbon dioxide in soil using bio tea derived from corn residues. A method of reducing is disclosed. However, the method of inhibiting the absorption of the organochlorine insecticide remaining in the plant using the bio-tea of the present invention in the soil has not been disclosed yet.

The present invention is derived from the above requirements, the inventors of the present invention, when the cultivated crops in soil treated with oak-derived bio tea powder POC (powdered oak char) and the organic chlorine insecticide endosulphan, By treating the granules of granulated oak char (GOC) and rice husk char (RHC) derived from rice hulls, they showed superior endosulfan adsorption capacity, confirming that the effect of inhibiting the absorption of endosulfates remaining in the soil into crops was remarkable. The present invention has been completed.

In order to solve the above problems, the present invention provides a method for inhibiting the absorption of the organochlorine insecticide in the plant, characterized in that it comprises the step of treating the biochar (biochar) in the soil in which the organochlorine insecticide remains.

The present invention also provides a composition for inhibiting absorption in plants of organochlorine insecticide containing bio-tea powder derived from oak as an active ingredient.

The present invention also provides a soil-improving agent for inhibiting absorption in plants of organochlorine insecticides containing bio-tea powder derived from oak as an active ingredient.

Bio-tea powder derived from oak of the present invention is excellent in adsorption capacity for the endosulfan, it can be very useful as a material of the soil improving agent to stabilize the soil contaminated with the endosulfan.

In order to achieve the object of the present invention, the present invention provides a method of inhibiting the absorption of the organochlorine insecticide in the plant, comprising the step of treating the biochar (biochar) in the soil of the organochlorine insecticide remains. .

In the method according to an embodiment of the present invention, the bio-tea may be a powdered oak char (POC) derived from oak, but is not limited thereto.

In addition, the bio-car may have a adsorption pore volume of 0.08 ~ 1.0 cm ³ / g, a specific surface area of 100 ~ 2000 m ² / g, preferably adsorption pore volume of 0.08 ~ 0.15 cm ³ / g, The surface area may be 255 ~ 285 m ² / g, more preferably the adsorption pore volume is 0.138 cm ³ / g, the specific surface area may be 270 m ² / g, but is not limited thereto.

In addition, the organochlorine insecticides are DDT (Dichloro-Diphenyl-Trichloroethane), BHC (Benzene hexachloride), Myrex (Mirex), Aldrin (Aldrin), Endrin (Dieldrin), Chlorane (Chlordane) ), Toxaphene, heptachlor and heptachlor and endosulfan may be any one or more selected from the group consisting of, preferably endosulfane, but is not limited thereto.

The present invention also provides a composition for inhibiting absorption in plants of organochlorine insecticide containing bio-tea powder derived from oak as an active ingredient.

The present invention also provides a soil-improving agent for inhibiting absorption in plants of organochlorine insecticides containing bio-tea powder derived from oak as an active ingredient.

Bio-tea powder derived from oak of the present invention has excellent adsorption capacity for organochlorine insecticides, in particular, endosulfan, it can be very useful as a material of the soil improving agent to stabilize the soil contaminated with endosulfan.

Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are only for explaining the present invention in more detail, it is obvious to those skilled in the art that the scope of the present invention is not limited by them.

Example  One. Bio tea  Characterization

The pH and electrical conductivity of bio-teas were measured by positive activated carbon (PAC), which was purchased from Shinkol (Tokyo, Japan), and powdered oak char (POC), granulated oak char (GAC) and RHC, which were purchased from local marts in Korea. 1 g of rice husk char powder was weighed and 20 mL of distilled water was added thereto, and shaken at 150 rpm using a shaker for 48 hours. Particle size distribution was classified by particle size using 100g of the four bio-teas of 53μm, 100μm, 0.25mm, 0.5mm, 1mm and 2mm sieve, respectively, C, H, N, O and S element content analysis is an element analyzer Measured using (LECO TruSpec CHN, USA). Specific surface area and pore volume analysis The specific surface area and pore volume were analyzed with 0.5 g of bio-dried bio tea at 180 ° C. for 4 hours using micrometry (ASAP-2020M, Micromeritics). As a result, as shown in Table 1, the powdered oak char (POC) prepared from the oak of the present invention had a pore volume of 0.1 or more, specific surface area of 270 or more, and GOC and RHC. A big difference was shown.

Element composition (%) H / C O / C pH
(1:20) Pore volume
(cm ³ / g) Suface area
(cm ² / g) D ₁₀ ^a C _U ^b C H N O S PAC 89.0 0.4 0.8 9.2 0.3 0.05 0.08 6.5 0.657 1117 0.01 2.0 POC 56.1 0.7 0.5 35.3 0.2 0.16 0.47 10.6 0.138 270 0.09 4.7 GOC 89.5 0.5 0.5 8.9 0.1 0.06 0.07 9.9 0.034 83.99 0.30 2.0 RHC 59.6 1.0 0.6 33.9 0.1 0.20 0.43 7.8 0.004 2.56 0.20 3.3

a: effective size

b: uniformity coefficient

Example  2. Bio tea Adsorption capacity  Confirm

Using an insecticide 'Geolix (endosulfan 35%, emulsion and Korea Sampok)' was prepared by diluting the endosulfan solution of 50 ~ 500 mg / L concentration with distilled water. To 100 mL of the diluted endosulfan solution, 50 mg (Powder) or 100 mg (Granule) of the above four species (POC, GOC, RHC and PAC) were added. The pH of the solution was adjusted to pH 7.0 using 0.1 M HCl and 0.1 M NaOH, shaken at 150 rpm for 48 hours using a shaker, and the maximum adsorption capacity and adsorption intensity were as follows. It was calculated using the Langmuir adsorption isotherm equations. As a result, as shown in Table 2, the adsorption capacity of endosulfane of POC having a physicochemical difference was 700 or more, and the maximum adsorption capacity induced by the Languere adsorption isotherm showed the best adsorption characteristics among the four bio-teas. GOC and RHC showed relatively low maximum adsorption capacities (Table 2).

a: Maximum adsorption capacity (mg / g)

b: Constant related to the energy of net enthalpy of adsorption

q: adsorption amount per gram of adsorbent unit

Bio Tea Langmuir isotherm Equation (r *) a b PAC y = 0.0014x + 0.0006 (0.998 **) 713.8 2.159 POC y = 0.0014x + 0.0022 (0.989 **) 714.8 0.628 GOC y = 0.0031x + 0.0021 (0.979 **) 322.6 1.476 RHC y = 0.0055x + 0.0032 (0.999 **) 181.8 1.719

a: maximum adsorption capacity (mg / g)

b: energy-related constant of the adsorption enthalpy net

** p <0.01

Example  3. Bio Tea  Inhibition of Endosulfan Absorption from Soil to Crop by Treatment

Soil used was collected surface soil of 0 ~ 20㎝ of arable land in Seodun-dong, Suwon-si, Gyeonggi-do. The collected soil was dried for 7 days and filtered using a 2 mm sieve. After drying, 1.4 g of 3% endosulfan powder was treated in 2.4 kg of soil so that the concentration of endosulfan in the filtered soil was 18 mg / kg. Sorbents (POC, GOC, RHC and PAC) were treated with a soil stirrer so that the soil weight was 1.0%. After soil stirring, the radish was sown and the radish was grown for 4 months. The cultivated radish roots were washed in running water, dried at room temperature for 2 hours, then crushed and stored frozen at −20 ° C. until analysis. After harvesting, the soil was dried for 48 hours after harvesting. Endosulfan was pretreated with a sample in a conventional manner, and analyzed under the instrumental analysis conditions of Table 3 below. As a result, when the POC of the present invention is treated with soil with endosulfane, compared with PAC, GOC, and RHC, the amount of endosulfane residue in soil and the amount of endosulfane residue (absorption) in radish were also significantly reduced. It was confirmed that the adsorption capacity for the endosulfan is superior to GOC and RHC (Table 4).

device Agilent 6890 GC column DB-5 (0.25 μm 0.25 m × 0.25 mm) Detector (℃) uECD (280 ℃) Injector (℃) Agilent 7863 Series (260 ° C) Injection volume 2 μl Gas flow rate 1 mL / min Oven Rate (℃ / min) Temp (℃) Hold (min) Initial 150 2 10 280 3 20 300 3

Types of Bio Teas Treated Endosulfan residue in soil at harvest (mg / kg) ^a Nothing
Endosulfate residue Endless Sulfonate Residues Nothing
Bioconcentration factor ^b No treatment 8.639 0.212 0.034 0.025 PAC 12.16 0.070 0.026 0.006 POC 5.972 0.012 0.005 0.002 GOC 10.29 0.295 0.046 0.028 RHC 8.651 0.182 0.038 0.021

a: Endosulfane residues are represented by the sum of the endosulfane derivatives (α-endosulfane, β-endosulfane and endosulfane sulfate).

b: Bioconcentration factor is calculated from crop residue and soil residue at harvest.

Claims (6)

A method of inhibiting endosulfan absorption in plants, comprising the step of treating oak-derived biochar powder in soil in which endosulfan remains. delete delete The bio-tea powder derived from oak has an adsorption pore volume of 0.08 to 1.0 cm ³ / g and a specific surface area of 100 to 2000 m ² / g. Way. A composition for inhibiting absorption in plants of endosulfan containing bio-tea powder derived from oak as an active ingredient. Soil modifier for inhibiting absorption of plants in endosulfan containing bio-tea powder derived from oak as an active ingredient.