KR100922608B1 - Mixing fumigant and fumigation - Google Patents

Abstract

The present invention is a herbaceous plant, a root plant, moss, fungi that have been identified as factors of biological damage, including bacteria and fungi, which are hardly observed with the naked eye, which give weathering damage to stone cultural properties and stone to be preserved in Korea. Various organisms and microorganisms such as molds, bacteria, algae, lichens, etc. are inhabited in the stone by using gas fumigants without physical removal method or liquid chemicals. For the killing of organisms and microorganisms of stone cultural properties by maintaining the original color of stone cultural properties and safely preserving them for a long time without changing color and material properties of stone cultural properties by allowing them to be completely killed in a short time. As to a mixed fumigation agent and a fumigation method using the same,

Specific solutions of the fumigation method and mixed fumigation for killing organisms and microorganisms of the stone culture property of the present invention,

Steel pipe pipes are used outside the stone cultural properties for fumigation, and 14 wt% of ethylene oxide (Ethylene Oxide, C₂H₄O) and 86 wt% of methyl bromide (CH₃Br) are mixed to stabilize the mixed fumigant gas. The amount used is calculated by administering 150 gr / m³ of mixed gas per 1m³ of fumigation volume as a standard dosage, and the gas concentration in fumigation should be maintained at 100 mg / l or more, but a small fan to promote the diffusion and uniformity of the mixed fumigant gas After the fan is installed, cover the insulation cover to maintain the internal temperature and prevent dew condensation, and cover the film with a polyethylene film of 0.2mm or more in thickness to maintain the gas retaining power. It is possible to measure the concentration of fumigation gas in the middle at the bottom of three places at regular intervals during fumigation treatment from the outside. And fumigation treatment preparation steps,

When administering the mixed fumigant stored in liquefied state, vaporize it completely by using an intermittent vaporizer, and then put it on by a worker who prevents the inhalation of the mixed fumigant by wearing a full face gas mask connected to a high concentration gas tank for organic gas. As such, during the fumigation process, the internal gas concentration is measured periodically using a deferred type 18 interferometer type gas detector to maintain the killing concentration of the organism. Dosing while maintaining the fumigation treatment time fumigation treatment and fumigation treatment step to perform the fumigation treatment 48 hours at 25 ℃ or more, and 72 hours at 15 ~ 25 ℃ based on the internal temperature during fumigation,

After the fumigation treatment with the dosage of the mixed fumigant as described above, after the fumigation ends, the mixed fumigant gas is exhausted to a safe place outside until the final residual gas concentration is 1 ppm or less by using a fan and a duct. After exhausting the fumigation process to terminate the fumigation process by dismantling the outer coating vinyl, steel pipe scaffolding, etc.

To confirm the killing of living organisms and microorganisms, the specimens were collected before and after fumigation and the effects of fumigation treatment through culture experiments and the damage and effects on the Daesan stone cultural property due to the fumigation treatment were the same. The fumigation method for the killing of organisms and microorganisms of stone cultural properties, characterized in that the fumigation effect confirming step of performing a test for the damage of the stone, the remaining of the fumigant, etc. It is a structural feature.

Mixed fumigants, stone cultural properties methyl bromide, ethylene oxide.

Description

Fumigation method using mixed fumigant for killing living organisms and microorganisms of stone cultural property {MIXING FUMIGANT AND FUMIGATION}

The present invention is a herbaceous plant, a root plant, moss, fungi that have been identified as factors of biological damage, including bacteria and fungi, which are hardly observed with the naked eye, which give weathering damage to stone cultural properties and stone to be preserved in Korea. Various organisms and microorganisms such as fungi and bacteria, algae, lichens, etc. are removed from the surface of the stone by using fumigant of gaseous body without physical removal method or liquid chemical. By killing completely in a short time, it is possible to kill the organisms and microorganisms of the stone cultural properties to maintain the original stone material and intrinsic color of the cultural property without change of color and color of the stone cultural property and to preserve it safely for a long time without weathering damage. It relates to a mixed fumigation for and a fumigation method using the same.

Stone cultural properties are represented by pagoda, Buddha statues, monuments, Buddhist temples, temple holdings, and stone castles. In addition, there are numerous stone cultural properties such as bridges, water tanks, dolmens, and stone monuments.

According to 2005 statistics, 67 of 308 national treasures (21.8%), 480 of 1,446 treasures (33.2%) and 547 of 3,071 nationally designated cultural assets, accounting for 17.8%. In addition, 766 (33.2%) out of 2,304 designated cultural properties, and other non-designated cultural properties and stone building, the stone cultural property occupies a large proportion.

Seokguram Rock, Dabo Pagoda, Seokga Pagoda, and Seosan Mae Samjong Buddha are world heritages not only for their historicity and artistry but also for their cultural and educational values. In addition, the stone cultural property of Korea is a cultural property that can represent Korean culture in the world that symbolizes Korean culture.

There are many materials of Korean cultural assets such as wood and stone. Among them, granite is most of them, which can be easily obtained due to the national distribution, and it has the technology to handle tens of tons of stones as seen in dolmens and stone stones. It is because of this.

Generally, the stone is hard and is considered to be safe without damage from the surrounding environment.However, it is weathered quickly due to weathering, acid rain, habitat of living things such as lichens, air pollution, etc. As damage is accelerating and various inhabitants inhabit such as above, in addition to melanin, chlorophyll, and carotenoids, the color of the stone surface is discolored and polluted as shown in FIGS. The discoloration of the stone surface due to the growth of living organisms is regarded as a product of history because most people think that it is high color, but this is a result of overlooking the progression and adaptation ability of microorganisms, and the precious cultural property loses its shape and poses a risk of collapse. There is a situation.

Specifically, by listing the biological damage of the stone cultural property,

1) Roots and mycelia of herbaceous plants, lichens, and sesame roots grow in the tissues and gaps of the stone, and cracks occur due to the pressure of the roots,

2) Desquamation, peeling phenomenon caused by the change of stone into salt and chelate compound by organic acid secreted from lichen, fungus, algae,

3) There is a phenomenon that distorts the aesthetic value of stone patterns and sculptures.

Therefore, in recent years, various conservation methods such as non-destructive safety diagnosis, stone hardening treatment, removal of living organisms and contaminants have been introduced from cultural property conservation scientists and conservation experts.

If you look at the existing technology,

Until now, most of the microorganisms have been removed from the surface of stone cultural properties by physical and chemical (biocidal) methods.

First of all, look at the physical removal method,

The use of tools such as plastic brushes, brushes, bamboo knives, and scalpels to remove these organisms artificially stimulates the growth of microorganisms, which in turn facilitates the growth of microorganisms and the risk of damage caused by tools. There is a problem with this,

Looking at the chemical (biocidal) method,

As a premise, the inappropriate use of biocide may result in the removal of microorganisms, but may add to the damage of the already weak stone cultural properties stone. In order to argue, the stone of the target stone cultural property must be proved that it is not damaged or adversely affected by the preservation treatment.

In this regard, biocide is applied for the killing of these organisms by a chemical method to kill the microorganisms over a period of several days to several months. Kind of,

1) AC322

2) K201 (manufactured by Gongju University)

3) Koretrel (manufactured by Donghae Corporation, Japan)

4) Grade 4 ammonium compound (Anti-Gern Solution, Swiss Clean)

5) Instrusept, Swiss Clean, etc.

The advantages and disadvantages of citing the data published by the National Research Institute of Cultural Heritage published by the National Institute of Cultural Heritage are as follows.

1) As a disadvantage of using biocide, it has 30-50% killing effect after 4 months.

2) When the biocide is treated, brown color changes appear on the treated stone surface.

3) It says that the typical treatment period takes 6-12 months.

4) When the curing agent is used for the stone reinforcement treatment after treating the biocide, the curing agent does not perform its normal function due to the treatment of the biocide, and thus there is a problem of weathering and other wear and deformation of the stone.

Mixed fumigation for killing living organisms and microorganisms of the present inventors stone cultural property and fumigation method using the same is to solve the above problems, specifically

First of all, the present invention has the object of enabling the complete killing of the organisms inhabiting the stone cultural property in a short time, depending on the characteristics of the fumigation treatment using the gas body,

Next, the present invention has another object to maintain the unique material and color without changing the material, color change of the target stone cultural properties and at the same time killing the creatures inhabiting the stone cultural properties and the problems presented in the prior art,

Next, the present invention has a purpose to enable the killing of living organisms while maintaining the original shape of the stone cultural property safely by fumigation treatment to prevent the physical damage generated by applying a direct physical force to the stone cultural property in advance. ,

Next, the application of the present invention after the hardening agent coating treatment for stone reinforcement treatment does not affect the original function of the curing agent at all, so that the object can be used safely in the stone cultural property preservation treatment.

Specific solutions for achieving the purpose of the mixed fumigation for killing organisms and microorganisms of the stone culture property and the fumigation method using the same,

After constructing the scaffolding using steel pipe pipe outside the stone cultural property for fumigation treatment, 14 wt% of ethylene oxide (Ethylene Oxide, C₂H₄O) and 86 wt% of methyl bromide (CH₃Br) were mixed to stabilize the mixed fumigant gas. The amount used is calculated by administering 150 gr / m³ of mixed gas per 1m³ of fumigation volume as a standard dosage, and the gas concentration in fumigation should be maintained at 100 mg / l or more, but a small fan to promote the diffusion and uniformity of the mixed fumigant gas After the fan is installed, cover the insulation cover to maintain the internal temperature and prevent dew condensation, and cover the film with a polyethylene film of 0.2mm or more in thickness to maintain the gas retaining power. It is possible to measure the concentration of fumigation gas in the middle at the bottom of three places at regular intervals during fumigation treatment from the outside. And fumigation treatment preparation steps,
When administering the mixed fumigant stored in liquefied state, vaporize it completely by using an intermittent vaporizer, and then put it on by a worker who prevents the inhalation of the mixed fumigant by wearing a full face gas mask connected to a high concentration gas tank for organic gas. As such, during the fumigation process, the internal gas concentration is measured periodically using a deferred type 18 interferometer type gas detector to maintain the killing concentration of the organism. Dosing while maintaining the fumigation treatment time fumigation treatment and fumigation treatment step to perform the fumigation treatment 48 hours at 25 ℃ or more, and 72 hours at 15 ~ 25 ℃ based on the internal temperature during fumigation,
After the fumigation treatment with the dosage of the mixed fumigant as described above, after the fumigation ends, the mixed fumigant gas is exhausted to a safe place outside until the final residual gas concentration is 1 ppm or less by using a fan and a duct. After exhausting the fumigation process to terminate the fumigation process by dismantling the outer coating vinyl, steel pipe scaffolding, etc.
To confirm the killing of living organisms and microorganisms, the specimens were collected before and after fumigation and the effects of fumigation treatment through culture experiments and the damage and effects on the Daesan stone cultural property due to the fumigation treatment were the same. Presenting a fumigation method for the killing of organisms and microorganisms in stone cultural properties, characterized in that the fumigation effect confirming step to confirm the damage of the fumigation agent, the remaining of the fumigation agent, etc. do.

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Mixed fumigation for killing organisms and microorganisms of the present invention stone culture material and the fumigation method using the same in the composition of the present invention configured as described above stability, penetration, insecticide strong methyl bromide (Methyl Bromide) and excellent sterilizing power of ethylene oxide (Ethylene Oxide) mixed use And its biocidal power is recognized, and it can completely kill almost all living things in the stone cultural property.

The stone culture fumigation treatment of the stone culture material according to the present invention has a complete killing effect with a short time treatment of 24 to 72 hours and can be obtained in a short time of several days compared to the treatment period of several months according to the use of a conventional biocide. .

In addition, the fumigation treatment for the killing of the stone cultural heritage creatures of the present invention is a gaseous substance using a mixed fumigation agent and does not affect the fumigation object as a colorless and odorless property, the problem appearing in the use of conventional liquid biocide (Biocide) In contrast, the original stone material and its original color can be maintained without changing the material and color of the target stone cultural property.

In addition, after the fumigation treatment, the mixed fumigant is completely scattered in the gaseous state and hardly remains. Therefore, the fumigant does not cause the secondary physical property change due to the remaining of the drug in the use of the conventional liquid biocide. After the treatment, there is an advantage that the neutralization treatment is not necessary to neutralize the pH concentration change due to acidification and alkalizing.

In addition, the conventional liquid biocide treatment (Biocide) treatment is difficult to expect the killing of the organisms in the deep areas overlapping the stones stacked up in the stone, such as stone towers, stone bins and the like by the spraying, coating treatment method, the gas fumigation treatment using the present invention It acts as a sieve and has strong penetrating power, which can bring about perfect killing effect.

In addition, the conventional method for removing living organisms or removing living organisms using biocides is a risk of physical damage due to the direct application of force to a stone cultural property or physical force using a device. It is a fumigation treatment using, so it can be safely processed because it does not apply physical force directly.

In addition, the conventional biocide treatment, cracks and decomposition of the curing agent used during the coating process of the curing agent for the treatment of the remaining liquid biocide and stone to strengthen the structure, but the mixing according to the present invention After using the fumigation agent, it is found that there is no effect on the stone hardener, so it can be safely used for preservation treatment of stone cultural properties.

In the above, the present invention has been illustrated and described with reference to specific preferred embodiments, but the present invention is not limited to the above-described embodiments and is not limited to the spirit of the present invention. Various changes and modifications can be made by those who have

As essential components of the present invention, ethylene oxide (Ethylene Oxide) and methyl bromide (Methyl Bromide), both materials are lipid-soluble chemicals.

Cell membranes of living organisms contain lipids as constituents, so fumigated ethylene oxide (EO) or methyl bromide (MB) can react with lipids on cell membranes or dissolve in cell membranes to modify cell membranes. It is possible to change the proteins that are important for the biological activity, which can cause the loss of cell membrane intrinsic life control function. It is also known to cause toxicity by disturbing the daily metabolism of living organisms, including energy metabolism, as a result of disorders in nervous system tissues.

Methylation reaction by methyl group of methyl bromide (MB) is an important chemical reaction, and -SH, carboxyl, and amine groups of amino acids, proteins, and nucleic acids are known to react with methyl groups to disrupt biological metabolism. have.

Methyl bromide, the most widely used pesticide and biocide in the world, and ethylene oxide, the most widely used as a disinfectant, are mixed in a weight ratio of 86: 14 to maximize the safe use and the treatment effect. The present invention is used as a mixed insecticidal fumigant.

Methylbromide for the killing of herbaceous plants, root plants, moss, fungi (fungus and bacteria), algae, lichens, which are biological damage factors of stone cultural properties (Methyl Bromide) and ethylene oxide (Ethylene Oxide) 86: 14 weight ratio to maximize the safe usability and treatment effect, ie 86 wt% of methyl bromide (CH₃Br) and 14 wt% of ethylene oxide (C₂H₄O) We will apply the fumigation treatment using stable gas chain mixed fumigant (E.O + MB) by mixing%.

Advantages of mixed fumigant include methoxide bromide (MB), which is widely used as quarantine insecticide fumigant and soil insecticide, due to its strong insecticidal, biocidal, and permeability, and ethylene oxide (EO) used for sterilization of medical devices with excellent sterilization power. As a mixed fumigant, it can be used as an insecticide and sterilizing agent for almost all materials. The mixed fumigant acts as a gas and has a strong penetration and diffusion power, which makes it possible to completely kill organisms to the deep part of the fumigation target. In addition, except for some limited items, there is little harm, so it does not affect the fumigation object, especially the archetype and color of cultural property.

The mixed principle of ethylene oxide (EO) with excellent bactericidal power and methyl bromide (MB) with strong biocidal power is self explosive, so it is essential to use a mixture of stabilized gases in ethylene oxide, which is dangerous to use alone. 86 wt% of methyl bromide (MB) and 14 wt% of ethylene oxide (EO) are the most effective mixing ratios by combining methyl bromide with high digestibility and stabilizing gas to satisfy both bactericidal and biocidal properties. By mixing with the present invention a mixed fumigant is developed.

Therefore, the fumigation treatment using the mixed fumigant has a complete killing effect by the treatment of 24 to 72 hours to obtain the effect of processing in a short time, and acts as a gas body to solve the problems caused by the use of conventional biocide (Biocide) There is no change in the color of the target stone cultural properties, and after the fumigation, the mixed fumigant is completely scattered and hardly remains, causing no secondary physical property change due to the remaining of the drug, and it is acidified and alkaline after the conventional liquid biocide treatment. Neutralization treatment is not required for neutralization due to changes in pH concentration, and it can be applied most stably to the treatment of stone cultural properties by killing stacked stones and bringing almost perfect killing effect on the overlapped parts of the stone. That's how it is.

As a treatment method for removing various living organisms in the stone cultural property, we use the mixed fumigant (Ethylene Oxide + Methyl Bromide) of the present inventors to kill living organisms such as plants, lichens, molds, and fungi that are injured in the stone cultural property. It is the core of fumigation of stone cultural property and the following items must be observed to obtain the most obvious killing effect.

That is, the mixed fumigant of the present invention should be used in a weight ratio of 14 wt% of ethylene oxide (Ethylene Oxide, C₂H₄O) and 86 wt% of methyl bromide (CH3Br).

 In addition, the fumigation method according to the present invention, that is, the most important element of the fumigation treatment process conditions, gas concentration, the treatment time, so must comply with the following treatment criteria.

-The amount of the mixed fumigant (M.B + E.O) is calculated by using 150 gr / m³ of mixed gas per 1 m³ of the fumigation volume as a standard dosage, and the gas concentration in the fumigation is maintained at 100 mg / l or more.

-Fumigation treatment time should be fumigation for 48 hours at 25 ℃ or higher and 72 hours at 15 ~ 25 ℃ based on the internal temperature during fumigation.

In addition, methyl bromide (M.B) does not penetrate the water, and the ethylene oxide (E.O) is phenomena that dissolves in water indefinitely, so the stone cultural properties that are subject to fumigation must maintain a sufficient dry state.

In addition, during the fumigation treatment, the gas concentration in the fumigation is measured and recorded on a regular basis to check the fumigation treatment effect in the concentration state.

Hereinafter, the fumigation method for killing living organisms and microorganisms of the stone culture property of the present invention will be described in detail.

1) Preparation process for fumigation

This step is a preparation step before dosing the mixed fumigant, and when fumigation the stone cultural property in the open air, hypothesis of the double scaffolding using a steel pipe pipe to prevent damage to the cultural property coating, and after completion of the scaffolding hypothesis Cover the insulation cover to maintain the internal temperature and prevent condensation, and cover with specially made polyethylene film (thickness: 0.2mm or more) to maintain gas holding capacity. Seal the adhesive seal.

On the other hand, in the case of a small stone fumigation stone cultural property, the use of special vinyl (thickness: 0.2mm) and adhesive tape to make the fumigation treatment by inserting the stone should be manufactured and used completely.

In particular, in order to implement the present invention on a large stone cultural property in the open air, when the height of the stone cultural property reaches about 10 m, the gas specific gravity of the mixed fumigant (M.B + EO) is 2.82 (air = 1). As it is a heavy condition, the gas concentration fluctuates due to the height between the upper and lower sides of the fumigation object, so that a uniform killing effect can be obtained for the entire stone cultural property. Applying a method to maintain the gas concentration of the mixed fumigant for each layer by installing a layer to install a small fan inside the stone cultural property, which is a closed fumigation treatment object, to promote the diffusion of the mixed fumigant gas and the uniformity of the concentration. do.

Next, the concentration fumigation hoses are installed at the upper, middle, and bottom three places inside the sealed fumigation facility to check the concentration of fumigation gas at regular intervals during the fumigation process from the outside and to measure the fumigation gas concentration. .

Next, install a thermo-hygrometer to measure the temperature and humidity inside the fumigation treatment facility.

Preferably, when the temperature inside the fumigation treatment facility is lower than 15 ° C., in order to maintain an appropriate temperature during the fumigation treatment, an electric heater is installed in the fumigation treatment facility to maintain the temperature during fumigation.

For reference, fumigation guides, danger warnings, and perimeter lines are installed outside the fumigation facilities to control the access of outsiders for safety.

After the preparation step as described above to administer the mixed fumigant as described below will be described below.

2) Mixed fumigation administration and fumigation stage

This step is a key step of the present invention. Before administering the mixed fumigant as a prerequisite, the special vinyl sealing part is carefully checked to confirm the complete sealing condition. The gas must be completely vaporized, that is, maintained in a gaseous state, and the operator wearing the front gas mask connected to a high concentration gas tank of organic gas must not inhale the mixed fumigant gas before administering the mixed fumigant.

Next, during the fumigation process, the internal gas concentration is measured periodically using a deferred type 18 interferometer type gas tester to check to maintain the concentration of living organisms.When the concentration falls below the standard concentration, supplementary administration is performed to exceed the prescribed concentration. The measurement time shall be defined at least three times a day according to the temperature change and measured at the prescribed time.

In addition, during the fumigation treatment, the fume gas leak is checked by using a trace gas detector such as Gastec or Gas leak checker on the sealed part, and in case of leakage, immediately perform a supplementary sealing work.

In addition, during the fumigation process, the temperature and humidity of the inside should be periodically measured using a thermo-hygrometer installed inside the fumigation facility, and the measurement time shall be prescribed at least three times a day according to the temperature change.

3) End of gas exhaust after fumigation

This step is to maintain safety in the present invention, after the end of the fumigation by using a blowing fan (Fan) and a duct (Duct) to exhaust the gas to a safe place outside until the final residual gas concentration is less than 1ppm next,

When the mixed fumigant gas concentration reaches a safe concentration, the outer coating vinyl, steel pipe scaffold, etc. are removed in the reverse order of installation.

For reference, where the mixed fumigant gas is adsorbed, a fan is used to promote desorption of the gas and open for at least 24 hours to completely desorb the gas.

In particular, the residual gas concentration is measured using a gastec-tube for methyl bromide, and the fumigation is terminated after confirming below 1ppm of the allowable concentration prescribed by ACGIH.

4) Confirmation of fumigation effect

In this step, biological samples are collected before and after fumigation to confirm the killing of organisms and microorganisms. It is to install the stone specimen or take the sample directly and perform the experiment to confirm the damage of the stone by the fumigation agent and the residual of the fumigation agent after the fumigation treatment.

1. Stone Fumigation Test of Mixed Fumigation Agent I

   The first experiment on the effects of killing organisms and the effects on the target stones after the fumigation treatment with mixed fumigants was carried out by collecting general stones (stones) inhabited by living organisms such as lichens before applying them directly to the stone cultural properties. .

This is because experimentation with untested methods directly on designated cultural properties may cause damage to cultural properties.

1) Results of analysis on the killing of organisms and the effect of stone by fumigation treatment

① It was confirmed that most of the microorganisms inhabiting the stone surface were killed by the fumigation treatment because of the significant decrease in the number of colonies which appeared as a result of the microbial separation from the samples before and after the fumigation treatment using the mixed fumigation agent. It was found to inhibit the growth of. The evaluation of the effect of lichens on the surface of the stone cultural property is based on the fact that lichens are a symbiosis of fungi and algae, and thus the growth of lichens and microalgae, which is a symbiotic partner of lichens, is affected. Judging.

② As a result of analyzing the samples before and after the fumigation treatment using the mixed fumigant, it was not seen that the new water-soluble salts were formed in the target rocks regardless of the types of the rocks. The samples and fumigation conditions of this study did not affect the chemical reaction of the rocks.

2) Growth control experiment of microorganism by fumigation treatment

In the fumigation treatment with a mixed fumigant (Ethylene Oxide 14% + Methyl Bromde 84%), the samples taken from the rock specimens before and after the fumigation were inoculated and cultured in the separation medium of bacteria and fungi, as shown in FIGS. 5 to 6. The same result was found. As shown in Figure 7 it was confirmed that the number of bacteria and mold colonies significantly reduced after the fumigation treatment. In the case of microalgae and cyanobacteria inoculated into the liquid medium, as shown in Figure 8, when the culture under the same conditions, the sample before the fumigation showed that the culture medium turned green after 2-3 weeks of inoculation. However, in the post-fumigation sample, it was observed that 1 out of 7 samples started to grow after 3 months of inoculation. It is confirmed that the growth of fungi and microalgae, which is a symbiotic partner of lichens, is inhibited by the fumigation treatment.

3) Experiment to confirm whether the rock is damaged by fumigation treatment

Most of the constituent rocks of the fumigation stone cultural property have a porous structure, and weathering is in serious condition. Even if the mixed fumigant gas is injected into the rock in such a state and the fumigant gas is blown off after the fumigation treatment, the surface contacted with the fume gas may cause chemical change, that is, damage due to a property called sorption. The two processes of sorption are adsorption and desorption. Adsorption is a phenomenon in which dissolved or fumed gas components in water adhere to the surface of rock minerals or foreign substances, and desorption is the chemical on the surface of the mineral. Paper is released in the form of dissolved components or gases. Adsorption can be divided into chemical adsorption associated with chemical bonds and physical adsorption caused by intermolecular interactions. Chemical adsorption mostly irreversibly changes a target substance.

For this reason, the presence or absence of a change in the rock due to the fumigation treatment in which adsorption can occur must be confirmed.

  Changes in the ionic components melted by putting a certain amount of rock sample before and after fumigation in a certain amount of distilled water can be seen as a result of chemical change of the rock due to fumigation. After two weeks of fumigation, the samples were dissolved in distilled water and considered to be the change after almost adsorption and desorption. Table 1 shows the types of rock samples used in the test and the dosage (100gr / ㎥, 300gr / ㎥) and time (24, 48 hours) of the mixed fumigant used to remove the organisms after placing them in a 1m3 confined space. The conditions to apply and fumigation were specified and classified.

Tables 2 to 4 summarize the results of measuring the ionic components dissolved after 8 hours by adding a certain amount of fumigated rock sample to a certain amount of distilled water. After two weeks of fumigation, the sample was dissolved in distilled water, which is a change after almost adsorption and desorption.

In limestone (Table 2), the cations of fresh rock showed less than 0.01% before and after treatment, and there was no change in the difference between before and after fumigation. Unlike other cations Ca ^{2 +} is a large amount as a dissolution show the value of the near 1wt.% To the main components of the limestone or wateuna, the components were also not record the modified value due to a fumigation process. In the surface of the weathered samples is changed limestone relatively large amount of Ca ^{2 +} and SO ₄ ² compared to fresh wonam ^- but they are also similarly detected change in the ion content of the fumigation will not be observed.

In granite (Table 3), there was no difference from that of limestone except that slightly more SO ₄ ^{2 -} was detected in the weathered sample, which was not detected in the raw rock. For a Silt stone (Table 4) has been compared to sinseonam the Ca ^{2 +} less detected in punghwaam This is likely a result of the calcium component shown is eluted during weathering, the result by the fumed process out the ions dissolved more as described above Not observed.

As a result, the analysis of these measurements concludes that the fumigation of the above conditions, regardless of the type of rock, does not indicate that new water-soluble salts are formed in the target rock. This is because the values before and after the fumigation match within the error range. The above rock sample and fumigation conditions did not affect the chemical reaction of the rock.

Table 1. Rock samples and fumigation conditions applied to fumigation tests.

Table 2. Water-soluble ionic components (wt.%) Detected in limestone samples before and after fumigation.

Table 3. Water-soluble ion components (wt.%) Detected in granite samples before and after fumigation.

Table 4. Water-soluble ionic components (wt.%) Detected in siltstone samples before and after fumigation.

2. Stone Fumigation Test of Mixed Fumigation Agent II

The results of the first experiment on the killing effect of organisms and the effects on the target stone after the fumigation with mixed fumigant (M.B + EO) are considered to be sufficient and safe for the stone. The preliminary stage of fumigation of the West Three-tier Stone Pagoda of Gameunsaji Three-storied Pagoda (National Treasure No. 112) in Gyeongju, Gyeongsangbuk-do, Korea. The experiment was conducted.

1) Due to fumigation Killing creatures  Effect and Stone Impact Analysis Results

① After inoculation into the bacterial and fungal separation medium through the pretreatment process, the number of colonies on the solid medium was measured after incubation for 2 weeks. The effect of fumigation was determined by comparing the number of bacteria and molds (colony forming unit / g) isolated from each sample before and after fumigation.The type and number of bacteria and molds separated by samples were different. You can see a dramatic decrease in the number of bacteria and fungi isolated. The results are as shown in FIGS. 9 to 12.

② Most of the ionic components in the sample showed slight change before and after fumigation, but it is difficult to say the difference because the value before and after fumigation is within the error range of measurement. As a result of analysis of these measurements, the fumigation treatment does not indicate that new water-soluble salts are formed in the target rock. In other words, the results of the fumigation sample and the fumigation conditions did not affect the chemical reaction of the rock.

2) Growth control experiment of microorganism by fumigation treatment

Samples were taken from the West Three-tier Stone Pagoda member, which is the subject of this study (FIG. 13). Samples were taken twice and tested before and after fumigation to verify whether the mixed gas of ethylene oxide and methyl bromide is effective for the sterilization of living organisms on rock surfaces.

① Verification of fumigation effect on bacteria and mold

The collected sample was prepared as a powder in a laboratory, and inoculated into a separation medium of bacteria and fungi through a pretreatment process. After incubation for 2 weeks, the number of colonies that appeared on the solid medium was measured. By comparing the number of bacteria and mold (colony forming unit / g) separated from each sample before and after the treatment was determined the effect of the fumigation treatment, the results are as shown in FIG. Depending on the sample, the type and number of bacteria and fungi separated are different, and after fumigation, the number of bacteria and fungi separated is significantly reduced.

② Verification of fumigation effect on photosynthetic organisms (microalgae and cyanobacteria)

In addition to bacteria and fungi, there are microalgae and cyanobacteria that synthesize nutrients necessary for themselves through photosynthesis. Therefore, in order to verify the effects of fumigation on these organisms, the pretreated samples were inoculated into microalgae and cyanobacterial separation media. However, since their growth is slower than bacteria or fungi, it is not possible to verify the effectiveness of the fumigation treatment at the 5th week of inoculation. 14 is a photograph taken three weeks after the inoculation, the growth of microalgae and cyanobacteria was not observed in both samples before and after fumigation.

3) Experiment to confirm whether the rock is damaged by fumigation treatment

In order to investigate the changes that occurred after fumigation of the rock samples collected from the West Samstadal Pagoda, it was investigated by analyzing the ionic components dissolved in distilled water. The instrument used for anion analysis was Ion Chromatography (IC, Dionex ICS-1000), and the cation analysis combined ICP-AES and IC. In order to see the changes that can be observed by fumigation treatment, rock samples collected from four parts were manufactured in powder form and tested.

Tables 1 and 2 summarize the results of the measurement of ionic components dissolved after 8 hours by adding a certain amount of fumigated rock sample to a certain amount of distilled water, and Tables 3 and 4 are converted to weight percent. After two weeks of fumigation, the sample was dissolved in distilled water, which is a change after almost adsorption and desorption.

Table 1. Water soluble cation component (ppm) detected in samples of West Three-Layered Stone Tower before and after fumigation.

Table 2. Water-soluble anion components (ppm) detected in samples of West Three-Layered Stone Towers before and after fumigation treatment

Table 3. Water-soluble cation component (wt.%) Detected in West Three-Layered Stone Tower sample before and after fumigation treatment

Table 4. Water-soluble anion components (wt.%) Detected in samples of West Three-Layered Stone Towers before and after fumigation.

The range of ionic components detected in rock samples before and after fumigation is shown in Table 5 below. Most ionic components show slight changes before and after fumigation, but it is difficult to say the difference because the values before and after fumigation are within the error range of measurement. As a result of analysis of these measurements, the fumigation treatment does not indicate that new water-soluble salts are formed in the target rock. In other words, it is judged that the present rock sample and fumigation condition did not affect the chemical reaction of the rock.

Table 5. Ion component range (ppm) detected in rock samples of West Three-Layered Pagoda before and after fumigation.

3. Fumigation Status of Stone Cultural Property

1) Gameunsaji West Three-story Stone Tower  (National Treasure No. 112) Stone tower

As a part of the treatment method for removing various organisms in the three-story stone tower of Gameunsaji, the fumigation treatment with Ethylene Oxide + Methyl Bromide is used to confirm the killing effect of lichens, molds, and bacteria. ,

After the fumigation treatment, this fumigation treatment was carried out to test the effect of the mixed fumigation agent on the stone.

The mixed fumigation used Ethylene Oxide (C ₂ H ₄ O) 14wt% + Methyl Bromide (CH ₃ Br) 86wt% and fumigation method was applied.

The amount of the mixed fumigant was calculated using 150 gr / m³ of the mixed fumigant per 1 m³ of the fumigation volume, and the gas concentration during the fumigation treatment was maintained at 130 mg / l or more.

In order to confirm the effect of fumigation, the disinfection effect of fumigation was confirmed that the sterilization reaction reagent of the sterilizing indicator paper installed before fumigation was sufficiently discolored and had sterilization effect. Was inoculated into bacterial and fungal isolated media and cultured for 2 weeks to determine the number of colonies on the solid media. The effect of fumigation was determined by comparing the number of bacteria and molds (colony forming unit / g) isolated from each sample before and after fumigation. The type and number of bacteria and molds were different according to the samples, and after fumigation We noticed a significant reduction in the number of bacteria and fungi,

In addition to bacteria and fungi, the stone culture cultural heritage also contains microalgae and cyanobacteria that synthesize nutrients necessary for themselves through photosynthesis. Therefore, in order to verify the effects of fumigation on these organisms, microalgae and cyanobacteria were not observed in the samples after inoculation, even after 3 months of inoculation.

2) Bohyunsa Sawon Garden Ambassador Ohjin Pagoda (Treasure No. 192)

In order to remove the organisms (lichen lichens, sediments, etc.) inhabiting the Bohyun Sasangwon metabolic pagoda, mixed fumigant (Ethylene Oxide + Methyl Bromide) was used to kill the lichens, molds and fungi living in the stone. .

The fumigant used was mixed fumigant (Ethylene Oxide (C ₂ H ₄ O) 14wt% + Methyl Bromide (CH ₃ Br) 86wt%).

The amount of the mixed fumigant was calculated as 150 g / m³ of mixed gas per 1 m³ of the fumigation volume, and the gas concentration was maintained at 100 mg / l or more during the fumigation treatment.

In order to confirm the effect of fumigation, it was confirmed that the disinfection effect among the fumigation effects was sufficiently discolored due to the discoloration of the sterilization reagent of the sterilizing indicator paper installed before fumigation.

After the fumigation treatment, organisms such as parasites were completely removed artificially using a brush, and a hardening agent (DWR-III, 5%) was applied to the present stone reinforcement treatment.

After that, we have been continually observing whether or not the organism is breeding, but it is confirmed that the organism is not enough to be identified with the naked eye.

3) Tomb of King Muryeong (Historic Site No. 13)

In 1998, fumigation was performed using a mixed fumigant of Ethylene Oxide + Methyl Bromide to remove the organisms living in the Mausoleum of King Muryeong Royal Mausoleum, and killed organisms such as algae and algae that live on the stone surface inside the chamber. .

The fumigant used was mixed fumigant (Ethylene Oxide (C ₂ H ₄ O) 14wt% + Methyl Bromide (CH ₃ Br) 86wt%).

The amount of the mixed fumigant was calculated based on 150 gr / m³ of the fumigant per 1 m³ of the fumigation volume, and the gas concentration was maintained at 100 mg / l or more during the fumigation treatment.

In order to confirm the effect of fumigation, the disinfection effect of fumigation effect was confirmed by the indirect method of incubation experiment of the test bacteria (black mold, Aspergillus niger 1AM 3001) installed before fumigation.

As described above, as well as other detailed experiment results, the present invention kills bacteria and other molds inhabiting stone cultural properties while maintaining the unique color and unique shape of the stone cultural property itself. You can make it possible.

1 to 4 are photographs showing the discoloration, plant habitat and pollution damage state of the stone cultural property due to microbial growth in the conventional stone cultural property

A; Gyeongju Seorakri Three-storied Pagoda, B; Jeongeup Eunseonri Three-story Pagoda, C; Yeongwol Ambassador Award, D; Baekyangsayo Ambassador

5 to 6 are photographs showing the culture results of microorganisms isolated from a sample before and after the present invention;

7 is a diagram showing the number of microbial colonies separated from the sample before and after the present invention,

8 is a picture showing the microalgae and cyanobacteria cultured in the sample before and after the present invention, the left is before the present invention and the right is a picture showing the present invention,

 9 to 12 are comparative pictures of bacteria and fungi isolated from samples before and after the present invention, and comparison pictures confirming that the number of colonies and molds, as well as the number of colonies, marked on the medium after the present invention was significantly reduced;

Figure 13 is a sample taken before the implementation of the present invention by taking a sample from the West Three-tier stone pagoda member

14 is a photograph taken three weeks after the inoculation to inoculate the microalgae and cyanobacteria as a separate medium to the sample before the present invention.

Claims (6)

delete Steel pipe pipes are used outside the stone cultural properties for fumigation, and 14 wt% of ethylene oxide (Ethylene Oxide, C₂H₄O) and 86 wt% of methyl bromide (CH₃Br) are mixed to stabilize the mixed fumigant gas. The amount used is calculated by administering 150 gr / m³ of mixed gas per 1m³ of fumigation volume as a standard dosage, and the gas concentration in fumigation should be maintained at 100 mg / l or more, but a small fan to promote the diffusion and uniformity of the mixed fumigant gas After the fan is installed, cover the insulation cover to maintain the internal temperature and prevent dew condensation, and cover the film with a polyethylene film of 0.2mm or more in thickness to maintain the gas retaining power. It is possible to measure the concentration of fumigation gas in the middle at the bottom of three places at regular intervals during fumigation treatment from the outside. And fumigation treatment preparation steps, When administering the mixed fumigant stored in liquefied state, vaporize it completely by using an intermittent vaporizer, and then put it on by a worker who prevents the inhalation of the mixed fumigant by wearing a full face gas mask connected to a high concentration gas tank for organic gas. As such, during the fumigation process, the internal gas concentration is measured periodically using a deferred type 18 interferometer type gas detector to maintain the killing concentration of the organism. Dosing while maintaining the fumigation treatment time fumigation treatment and fumigation treatment step to perform the fumigation treatment 48 hours at 25 ℃ or more, and 72 hours at 15 ~ 25 ℃ based on the internal temperature during fumigation, After the fumigation treatment with the dosage of the mixed fumigant as described above, after the fumigation ends, the mixed fumigant gas is exhausted to a safe place outside until the final residual gas concentration is 1 ppm or less by using a fan and a duct. After exhausting the fumigation process to terminate the fumigation process by dismantling the outer coating vinyl, steel pipe scaffolding, etc. To confirm the killing of living organisms and microorganisms, the specimens were collected before and after fumigation and the effects of fumigation treatment through culture experiments and the damage and effects on the Daesan stone cultural property due to the fumigation treatment were the same. A fumigation method for killing organisms and microorganisms of stone cultural properties, characterized in that the fumigation effect confirming step to perform a test for confirming the damage of the stone, the remainder of the fumigant, etc. after the fumigation treatment by installing a sample or direct sampling. delete delete delete delete

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