KR100504303B1 - Determination Method of Ethylenethiourea, Maleic Hydrazide and Isopropylmethylphosphonate in Water Samples - Google Patents
Determination Method of Ethylenethiourea, Maleic Hydrazide and Isopropylmethylphosphonate in Water Samples Download PDFInfo
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- KR100504303B1 KR100504303B1 KR10-2002-0072620A KR20020072620A KR100504303B1 KR 100504303 B1 KR100504303 B1 KR 100504303B1 KR 20020072620 A KR20020072620 A KR 20020072620A KR 100504303 B1 KR100504303 B1 KR 100504303B1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 13
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 title claims abstract description 11
- BGRDGMRNKXEXQD-UHFFFAOYSA-N Maleic hydrazide Chemical compound OC1=CC=C(O)N=N1 BGRDGMRNKXEXQD-UHFFFAOYSA-N 0.000 title claims abstract description 11
- GHZKGHQGPXBWSN-UHFFFAOYSA-N methyl(propan-2-yloxy)phosphinic acid Chemical compound CC(C)OP(C)(O)=O GHZKGHQGPXBWSN-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 239000005983 Maleic hydrazide Substances 0.000 title 1
- 239000000126 substance Substances 0.000 claims abstract description 22
- 238000004817 gas chromatography Methods 0.000 claims abstract description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000004458 analytical method Methods 0.000 claims abstract description 12
- 239000003651 drinking water Substances 0.000 claims abstract description 9
- 235000020188 drinking water Nutrition 0.000 claims abstract description 9
- 239000000383 hazardous chemical Substances 0.000 claims abstract description 7
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 12
- 238000001212 derivatisation Methods 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 238000000605 extraction Methods 0.000 abstract description 9
- 239000002904 solvent Substances 0.000 abstract description 6
- 230000035945 sensitivity Effects 0.000 abstract description 5
- 238000004904 shortening Methods 0.000 abstract description 3
- 238000011109 contamination Methods 0.000 abstract 1
- 238000004949 mass spectrometry Methods 0.000 abstract 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- 230000002265 prevention Effects 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 8
- 238000001514 detection method Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000575 pesticide Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- QRKUHYFDBWGLHJ-UHFFFAOYSA-N N-(tert-butyldimethylsilyl)-N-methyltrifluoroacetamide Chemical compound FC(F)(F)C(=O)N(C)[Si](C)(C)C(C)(C)C QRKUHYFDBWGLHJ-UHFFFAOYSA-N 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000004009 herbicide Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 238000002423 nitrogen--phosphorus detection Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011002 quantification Methods 0.000 description 2
- 238000002098 selective ion monitoring Methods 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- RZYHXKLKJRGJGP-UHFFFAOYSA-N 2,2,2-trifluoro-n,n-bis(trimethylsilyl)acetamide Chemical compound C[Si](C)(C)N([Si](C)(C)C)C(=O)C(F)(F)F RZYHXKLKJRGJGP-UHFFFAOYSA-N 0.000 description 1
- HULNEMMTFGKRCN-UHFFFAOYSA-N 3-methylbutan-2-yl dihydrogen phosphate Chemical compound CC(C)C(C)OP(O)(O)=O HULNEMMTFGKRCN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010033799 Paralysis Diseases 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- 238000000752 ionisation method Methods 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- PVWOIHVRPOBWPI-UHFFFAOYSA-N n-propyl iodide Chemical compound CCCI PVWOIHVRPOBWPI-UHFFFAOYSA-N 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000004454 trace mineral analysis Methods 0.000 description 1
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/40—Concentrating samples
- G01N1/4022—Concentrating samples by thermal techniques; Phase changes
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
- G01N30/7206—Mass spectrometers interfaced to gas chromatograph
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/18—Water
- G01N33/1826—Organic contamination in water
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G01N33/184—Herbicides, pesticides, fungicides, insecticides or the like
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- G01N2001/4027—Concentrating samples by thermal techniques; Phase changes evaporation leaving a concentrated sample
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Abstract
본 발명은 음용수 및 수질 시료에 함유된 에틸렌티오우레아, 말레산 히드라지드, 이소프로필메틸포스포네이트 등 3종의 유해 물질을 동시 분석하기 위하여 농축하는 방법을 사용하였으며, 농축 후 요오드화메틸과 아세톤을 이용하여 반응시킨 후 3종 유해 물질을 메틸유도체화한 후 그 농도를 결정하는 것을 특징으로 한다. 상기 방법은 기체 크로마토그래피(GC) 또는 기체 크로마토그래피(GC)-질량분석기(MS)를 사용하여 위의 3종 유해 물질의 농도를 분석하는 것으로 이루어진다. 본 발명의 방법에 의해 수질 시료 중에서 분석할 경우, 우수한 감도, 분석 시간의 단축 및 간편성, 경제성, 추출용매 사용시 발생되는 2차 오염의 예방 등을 동시에 얻을 수 있다.In the present invention, a method of concentrating to simultaneously analyze three harmful substances such as ethylenethiourea, maleic acid hydrazide, and isopropylmethylphosphonate contained in drinking water and water samples was used, and after concentration, iodide methyl and acetone were concentrated. After the reaction by using the three kinds of harmful substances, characterized in that after determining the concentration of methyl derivatives. The method consists in analyzing the concentrations of the above three hazardous substances using gas chromatography (GC) or gas chromatography (GC) -mass spectrometry (MS). When analyzing in a water sample by the method of the present invention, it is possible to simultaneously obtain excellent sensitivity, shortening and simplicity of analysis time, economy, and prevention of secondary contamination generated when using an extraction solvent.
Description
본 발명은 음용수 및 수질 시료에서 에틸렌티오우레아, 말레산 히드라지드, 이소프로필메틸포스포네이트 등의 3종 유해 물질을 동시에 검출하는 검출법으로, 더욱 상세하게 상기 3종 물질들을 진공회전증발기를 이용하여 농축한 후, 일정한 반응 시간 및 온도 하에서 요오드화메틸(methyliodide)을 반응시켜 상기 3종의 유해 물질을 유도체화한 후, 이를 직접 기체 크로마토그래피(GC) 또는 기체 크로마토그래피/질량분석기(GC/MS)를 사용하여 분석함으로써 우수한 감도, 분석시간의 단축 및 간편성, 경제성 등으로 수질에서 미량으로 잔류하는 유해 물질 모니터링에 효과적으로 널리 응용될 수 있는 검출법에 관한 것이다.The present invention is a detection method for simultaneously detecting three harmful substances such as ethylene thiourea, maleic acid hydrazide, isopropyl methyl phosphonate in drinking water and water samples, more specifically using the vacuum rotary evaporator After concentration, methyl iodide is reacted under a constant reaction time and temperature to derivatize the three hazardous substances, which are then directly subjected to gas chromatography (GC) or gas chromatography / mass spectrometry (GC / MS). The present invention relates to a detection method that can be effectively and widely applied to monitoring harmful substances remaining in traces in water quality due to its excellent sensitivity, shortening and simplicity of analysis time, and economic efficiency.
분석하고자 하는 3가지의 물질 중 에틸렌티오우레아, 말레산 히드라지드 등은 농약으로 주로 사용되고 있으며 값이 비교적 싸고 적은 양으로도 효과를 볼 수 있기 때문에 세계적으로 폭 넓게 사용되어 왔다[J. Chromatography A 765 (1997) 31-38]. 또한, 이소프로필메틸포스포네이트는 독성을 지닌 물질로 신경계에 마비를 일으키는 물질로 알려져 있다[J. Chromatography B 701 (1997) 9-17]. 이러한 유해 물질의 남용으로 인하여 사용 후에 강이나 호수, 지하수, 토양 등으로 스며들어 환경을 오염시키고 있는 것으로 알려져 있다.Of the three substances to be analyzed, ethylenethiourea and maleic acid hydrazide are mainly used as pesticides and have been widely used worldwide because they are relatively inexpensive and can be effective in small amounts [J. Chromatography A 765 (1997) 31-38]. Isopropylmethylphosphonate is also a toxic substance known to cause paralysis in the nervous system [J. Chromatography B 701 (1997) 9-17]. Due to the abuse of these harmful substances, it is known that they penetrate rivers, lakes, groundwater, soil, etc. after use and pollute the environment.
이번 발명에서 분석한 물질은 모두 3 종으로 에틸렌티오우레아, 말레산 히드라지드, 이소프로필메틸포스포네이트 등이다. 이러한 농약을 비롯한 유해물은 이제까지 동시에 분석한 경우는 없다. 또한, 이들 3가지 물질은 일반적인 유기 용매에는 거의 녹지 않으며, 물에 대한 용해도는 매우 낮은 편이다. 이러한 이유로 추출이 매우 어렵다. 이러한 3가지 농약의 특징은 수산기(-OH)와 아미노기(-NH) 등을 가지고 있어서 극성이 큰 편으로, 이들 자체로 분석하는 경우에 미량 분석에 문제가 있거나, 기체 크로마토그래피로는 검출이 불가능한 경우가 있다. 이러한 이유로 인하여 이들 물질을 분석하기 위하여 주로 액체 크로마토그래피를 이용하여 분석하거나, 검출기로 NPD (nitrogen-phosphorus detection)를 이용하여 검출하는 방법이 사용되어 왔다. 그러나, 이렇게 분석을 할 경우 검출한계가 비교적 높고, 여러 가지 유해한 시약을 사용함으로써 2차적인 환경오염을 야기시킬 수 있는 문제점이 지적되었다. 따라서, 신속하고 경제적이며 미량까지 분석이 가능한 안정적인 검출법이 요구되어 왔다.All three substances analyzed in the present invention are ethylenethiourea, maleic acid hydrazide, and isopropylmethylphosphonate. These pesticides and other pests have never been analyzed simultaneously. In addition, these three materials are hardly soluble in common organic solvents, and their solubility in water is very low. For this reason, extraction is very difficult. These three pesticides are characterized by having a hydroxyl group (-OH) and an amino group (-NH), and thus have a high polarity. However, these three pesticides have problems in trace analysis when analyzed by themselves, or cannot be detected by gas chromatography. There is a case. For this reason, in order to analyze these materials, a method of mainly analyzing by using liquid chromatography or detecting by using NPD (nitrogen-phosphorus detection) as a detector has been used. However, this analysis has been pointed out that the detection limit is relatively high, and the use of various harmful reagents can cause secondary environmental pollution. Therefore, there has been a demand for a stable detection method that can be analyzed quickly, economically and in trace amounts.
따라서, 본 발명의 목적은 음용수 및 수질 시료에 함유된 에틸렌티오우레아, 말레산 히드라지드, 이소프로필에틸포스페이트 등 3종의 유해 물질을 신속하고 경제적이며 미량까지 분석이 가능하며, 또한 상기 3종의 유해 물질을 동시에 검출하는 안정적인 검출법을 제공하는 것이다.Therefore, an object of the present invention is to analyze the three harmful substances such as ethylene thiourea, maleic acid hydrazide, and isopropylethyl phosphate in drinking water and water samples in a quick, economical and trace amount, and also It is to provide a stable detection method for simultaneously detecting harmful substances.
본 발명은 음용수 및 수질 시료에서 추출이 어려운 상기한 3종의 유해 물질을 효과적으로 분석하기 위하여, 수질 시료를 직접 증발, 농축시킨 후, 상기 3종의 유해 물질을 요오드화메틸과 아세톤을 이용하여 반응시켜 유도체화한 후, 이를 직접 기체 크로마토그래피 또는 기체 크로마토그래피/질량 분석기를 사용하여 3종 유해 물질의 미량 농도를 분석하는 동시 검출법에 그 특징이 있다.In the present invention, in order to effectively analyze the three harmful substances that are difficult to extract from drinking water and water samples, the water samples are directly evaporated and concentrated, and then the three hazardous substances are reacted using methyl iodide and acetone. After derivatization, it is characterized by a simultaneous detection method that analyzes trace concentrations of three hazardous substances by direct gas chromatography or gas chromatography / mass spectrometry.
이와 같은 본 발명을 상세하게 설명하면 다음과 같다.The present invention will be described in detail as follows.
본 발명은 음용수 및 수질 시료로부터 3종 물질을 분석하기 위하여 농축하는 방법을 시행하였다. 이들 물질은 유기 용매에 대한 추출율이 매우 낮기 때문에 용매로 추출하는 데에는 어려움이 있다. 본 발명에서는 이러한 단점을 보완하기 위하여 유기 용매를 사용하여 추출하지 않고 5 - 10 ㎖의 물을 직접 진공회전 증발기를 이용하여 완전히 건조시킨 후 요오드화메틸을 이용하여 3종 유해 물질을 모두 유도체화하며, 이러한 유도체화 반응은 다음 반응식 1과 같다.In the present invention, a method of concentrating to analyze three substances from drinking water and water samples was conducted. These materials are difficult to extract with a solvent because the extraction rate with respect to the organic solvent is very low. In the present invention, 5-10 ml of water is completely dried using a direct vacuum rotary evaporator without using an organic solvent, and then all three harmful substances are derivatized using methyl iodide. This derivatization reaction is shown in Scheme 1 below.
상기 반응식 1의 유도체화 과정에서 3종 물질이 요오드화메틸과의 반응시간이 중요하며, 요오드화메틸의 양은 시료 10 ml 당 약 50 - 150 ㎕, 바람직하게는 50 ㎕가 적당하며, 반응온도는 60 - 90 ℃, 바람직하게는 90 ℃가 적당하며, 반응시간으로는 약 30 - 120분, 바람직하게는 60분으로 상기 유도체화 반응을 수행하면 상기 반응식 1에 표시되어 있는 화합물을 얻을 수 있다. 상기 반응에서 아세톤은 반응시에 충분히 첨가한다. 또한, 탄산칼륨은 반응시에 알칼리 분위기를 만들기 위하여 사용한다. 상기 방법은 3종 물질을 유도체화시키는 최적의 조건이 되며 기체 크로마토그래피 또는 기체 크로마토그래피/질량 분석기에 감도 및 선택성이 좋고 보다 향상된 검출한계를 제공한다.The reaction time of the three substances with methyl iodide is important in the derivatization of Scheme 1, and the amount of methyl iodide is about 50-150 μl, preferably 50 μl, per 10 ml of the sample, and the reaction temperature is 60 −. 90 ° C., preferably 90 ° C., is suitable. The reaction time is about 30-120 minutes, and preferably 60 minutes, whereby the derivatization reaction is carried out to obtain the compound represented by Scheme 1. Acetone is sufficiently added in the reaction. In addition, potassium carbonate is used in order to create an alkaline atmosphere at the time of reaction. The method is an optimal condition for derivatizing the three materials and provides better detection limits with better sensitivity and selectivity for gas chromatography or gas chromatography / mass spectrometry.
유도체화된 3종 유해 물질의 분석은 기체 크로마토그래피 또는 기체 크로마토그래피/질량분석기를 사용하여 분석하게 되며, 구체적으로는 기체 크로마토그래피에 주입시키고, 산화에 불활성인 기체를 이동상으로 사용한다. 이동상으로 사용될 수 있는 기체는 기체 크로마토그래피에 사용되는 통상의 기체이면 가능하다. 바람직하게는 산화에 불활성인 질소, 헬륨 및 수소 등이 있다. 컬럼의 길이와 내경 등은 중간 정도 극성을 가진 컬럼이면 가능하다.Analysis of the derivatized three hazardous substances is carried out using gas chromatography or gas chromatography / mass spectrometry, specifically injected into gas chromatography, using a gas inert to oxidation as the mobile phase. The gas which can be used as the mobile phase can be any conventional gas used for gas chromatography. Preferred are nitrogen, helium and hydrogen which are inert to oxidation. The length and the inner diameter of the column can be a column having a medium polarity.
이하, 본 발명을 다음 실시예에 의거하여 더욱 상세하게 설명하였으나, 본 발명이 다음 실시예에 한정되는 것은 아니다.Hereinafter, the present invention has been described in more detail based on the following examples, but the present invention is not limited to the following examples.
<실시예><Example>
<실시예 1><Example 1>
공시험관을 5개 준비하여 각각의 시험관에 에틸렌티오우레아, 말레산 히드라지드, 이소프로필메틸포스포네이트 등 3종 물질의 표준물질 10 ㎍/㎖ 용액을 각각 50 ㎕씩 넣고, 내부표준 물질인 에틸티오필린 용액 10 ㎍/㎖를 10 ㎕씩 모두 첨가한 후, 여기에 5개의 시험관 중 3개의 시험관에 각각 요오드화메틸, 요오드화에틸, 요오드화프로필을 50 ㎕씩 첨가한 후, 아세톤 150 ㎕를 넣어주고 여기에 탄산칼륨 분말을 약 3 mg 정도 첨가하였다. 이 반응이 진행된 것을 실시예 3에 자세히 나타내었다. 또한, 다른 시험관에는 비스(트리메틸실릴)트리플루오로아세트아미드 (1% TMCS) 50 ㎕와 에틸아세테이트 50 ㎕를 첨가한다. 나머지 마지막 시험관에는 N-(tert-부틸디메틸실릴)-N-메틸트리플루오로아세트아미드 50 ㎕와 에틸아세테이트 50 ㎕ 첨가하여 각각을 80℃에서 1시간 반응시켰다.Five blank test tubes were prepared, and 50 μl of 10 μg / ml standard solution of three substances such as ethylenethiourea, maleic acid hydrazide, and isopropylmethylphosphonate was added to each test tube, and ethyl was used as an internal standard. After adding 10 μl / ml of thiophyllin solution, add 50 μl of methyl iodide, ethyl iodide, and propyl iodide to each of three test tubes, and add 150 μl of acetone. About 3 mg of potassium carbonate powder was added thereto. The progress of this reaction is shown in Example 3 in detail. In addition, 50 μl of bis (trimethylsilyl) trifluoroacetamide (1% TMCS) and 50 μl of ethyl acetate are added to another test tube. In the last test tube, 50 μl of N- (tert-butyldimethylsilyl) -N-methyltrifluoroacetamide and 50 μl of ethyl acetate were added, and each was reacted at 80 ° C. for 1 hour.
그 결과 위의 5가지 반응 중 N-(tert-부틸디메틸실릴)-N-메틸트리플루오로아세트아미드 반응은 일어나지 않았으며, 그 밖의 4가지는 반응이 이루어졌으나, 요오드화메틸을 제외한 나머지 반응은 재현성이 낮았으며, 유도체화한 후 생성물이 반응시킨 것만 반응이 일어났다.As a result, N- (tert-butyldimethylsilyl) -N-methyltrifluoroacetamide reaction did not occur among the above five reactions, and the other four reactions were carried out, except for methyl iodide. Low and only reacted with the product after derivatization.
<실시예 2><Example 2>
25 ㎖의 분액 깔대기 2개를 준비하여 10 ㎖의 증류수를 넣고 에틸렌티오우레아, 말레산 히드라지드, 이소프로필메틸포스포네이트 등 3종 유해 물질의 표준물질 10 ㎍/㎖ 용액을 각각 50 ㎕씩 넣고, 내부표준 물질인 에틸티오필린 용액 10 ㎍/㎖를 10 ㎕씩 모두 첨가하였다. 염석 효과를 꾀하기 위하여 2g 정도의 무수 황산나트륨을 넣어준 후 에틸에테르와 메틸렌클로라이드를 2 ㎖씩을 각각 넣었다. 15분간 진탕한 후 추출하였다. 추출 후의 물층을 제거한 다음 추출하여 나온 용매층의 물기를 제거하고 요오드화메틸 50 ㎕와 아세톤 150 ㎕ 탄산칼륨 분말 3 mg을 첨가하여 유도체화 과정으로 들어갔다. 80℃, 1시간 동안 가열한 후 반응을 완성시키고 냉각시킨 다음, 다시 질소 하에서 건조시키고 시료를 에틸아세테이트 용액 100 ㎕로 다시 용해시킨 후 직접 기체 크로마토그래피에 2 ㎕ 주입하여 분석하였다. 본 실시예에서는 추출용매에 따른 추출율을 보기 위한 것이다. 그 결과는 도 1에 나타낸 것과 같고 용매를 사용하여 추출한 결과 거의 추출이 되지 않았으며, 진공회전증발기를 이용한 것만이 좋은 결과를 나타내었다.Prepare two 25 ml separatory funnels, add 10 ml of distilled water, and add 50 µl of 10 µg / ml standard solution of three harmful substances such as ethylenethiourea, maleic acid hydrazide, and isopropylmethylphosphonate. 10 μg / ml of ethylthiophylline solution, which is an internal standard, was added. To achieve the salting effect, 2 g of anhydrous sodium sulfate was added, followed by 2 ml of ethyl ether and methylene chloride, respectively. After shaking for 15 minutes, it was extracted. After the extraction, the water layer was removed, and then the solvent layer extracted was dried. 50 μl of methyl iodide and 150 μl of acetone were added to 3 mg of potassium carbonate powder to enter the derivatization process. After heating at 80 ° C. for 1 hour, the reaction was completed and cooled, dried under nitrogen again, and the sample was dissolved again with 100 μl of ethyl acetate solution, followed by direct injection into 2 μl of gas chromatography. In this embodiment, the extraction rate according to the extraction solvent is intended. The results are as shown in FIG. 1 and the extraction using the solvent was hardly performed. Only the vacuum rotary evaporator showed good results.
<실시예 3><Example 3>
상기 실시예 1 및 2를 통하여 얻은 최적의 조건인 요오드화메틸을 반응 시약으로 사용하고 반응시간 60분, 반응온도 80℃에서 반응시켜서 얻은 용액을 2 ㎕ 취하여, 기체 크로마토그래피 또는 기체 크로마토그래피/질량분석기 등으로 바람직하게는 기체 크로마토그래피/질량분석기에 주입하여 도 2에 나타낸 바와 같이 미량의 3종 유해 물질의 피크와 내부표준물질의 크로마토그램을 얻었다. 도 3은 유도체화된 3종 유해 물질의 질량스펙트럼을 나타내고 있는데, 유도체화된 각각의 분자량과 특성 토막이온이 잘 나타나고 있다. 이와 같은 3종 유해 물질의 농도를 결정하기 위해 사용된 기기로는 휴렛-팩커드(Hewlett-Packard)사의 5972 질량분석기와 여기에 연결된 5890 플러스(plus) 기체 크로마토그래피이다. 사용된 이온화 방법은 전자충격법(electron impact, EI)이며 이온원의 온도는 280 ℃이었다. 정량을 위하여 SIM(Selected Ion Monitoring) 모드가 사용되었으며 선택된 이온은 에틸렌티오우레아의 경우는 기준 피크(base peak)인 m/z 130, 74, 69 등이 사용되었으며, 말레산 히드라지드의 경우는 m/z 140, 69, 112 등이 사용되었으며, 이소프로필메틸포스포네이트는 m/z 137, 111, 93이었다. 내부표준물질의 경우는 m/z 208이 사용되었다. 분석에 사용된 분리관(column)은 길이가 25 m, 내경이 0.25 ㎜, 필름 두께가 0.25 ㎛인 울라트(ultra) 2 컬럼을, 이동상 기체로는 헬륨을 사용하였으며, 흐름 속도는 0.7 ㎖/분이었다. 컬럼의 온도는 초기에 100℃에서 머무른 시간없이 10℃/분 속도로 200℃까지 승온시키고, 다시 20℃/분 속도로 300 ℃까지 승온하였다. 시료 주입구의 온도는 250℃이었으며, 기체 크로마토그래프와 질량분석기 연결장치의 온도는 280℃이었다.Using a methyl iodide, which is the optimum condition obtained in Examples 1 and 2, as a reaction reagent, 2 µl of a solution obtained by reacting at a reaction time of 60 minutes and a reaction temperature of 80 ° C was taken, and a gas chromatography or gas chromatography / mass spectrometer Etc., and preferably, injected into a gas chromatography / mass spectrometer to obtain chromatograms of peaks of trace amounts of three harmful substances and internal standards as shown in FIG. Figure 3 shows the mass spectrum of the three derivatized harmful substances, the molecular weight and characteristic fragment ion of each derivatized is well represented. The instrument used to determine the concentrations of these three hazardous substances is Hewlett-Packard's 5972 mass spectrometer and 5890 plus gas chromatography connected thereto. The ionization method used was electron impact (EI) and the temperature of the ion source was 280 ° C. SIM (Selected Ion Monitoring) mode was used for quantification, and m / z 130, 74 and 69, which are base peaks for ethylenethiourea, were used, and m for maleic acid hydrazide. / z 140, 69, 112 and the like were used, and isopropylmethylphosphonate was m / z 137, 111, 93. For internal standards m / z 208 was used. The column used for the analysis was an ultra 2 column having a length of 25 m, an inner diameter of 0.25 mm, a film thickness of 0.25 μm, helium as the mobile phase gas, and a flow rate of 0.7 ml / It was minutes. The temperature of the column was initially raised to 200 ° C. at a rate of 10 ° C./min without the time of staying at 100 ° C., and further raised to 300 ° C. at a rate of 20 ° C./min. The temperature of the sample inlet was 250 ° C. and the temperature of the gas chromatograph and mass spectrometer connection was 280 ° C.
<실시예 4><Example 4>
일부 정수장에서 채취한 시료를 10 ㎖ 취하여 내부표준물질인 에틸티오필린 10 ㎍/㎖를 10 ㎕ 첨가한 후, 진공회전증발기를 이용하여 완전 건조시키고 남아 있는 잔류물에 요오드화메틸을 50 ㎕와 아세톤 100 ㎕를 첨가하여, 80℃에서 60분 동안 가열한 후, 반응을 완성시키고 냉각시킨 다음 다시 질소 하에서 건조시키고, 다시 에틸아세테이트 100 ㎕로 용해시킨 후 2 ㎕를 직접 기체 크로마토그래피에 주입하여 분석하였다. 이러한 분석 방법을 통하여 3종의 유해 물질을 질량분석기를 사용하여 정량하기 위한 검량곡선은 도 4에 나타낸 바와 같고 0.2 ∼ 5.0 ㎍/ℓ농도 범위에서 좋은 직선성을 나타내었다.Take 10 ml of sample from some water purification plant, add 10 µl / ml of ethylthiophylline, an internal standard, and completely dry it using vacuum rotary evaporator. 50 µl of methyl iodide and 100 acetone are added to the residue. After adding 60 μl, heating at 80 ° C. for 60 minutes, the reaction was completed, cooled, dried under nitrogen again, dissolved in 100 μl of ethyl acetate, and then 2 μl was directly injected into gas chromatography for analysis. The calibration curve for quantifying three harmful substances through this analytical method using a mass spectrometer is as shown in Figure 4 and showed a good linearity in the concentration range of 0.2 ~ 5.0 ㎍ / ℓ.
상기 설명한 바와 같이, 본 발명은 동시 추출이 어려운 3종의 유해 물질을 수질 시료 중에서 효과적으로 분석할 수 있도록 하며, 기체 크로마토그래피 또는 기체 크로마토그래피/질량분석기에 대해서 선택적이고 우수한 감도를 가진다. 또한, 물질의 분석에 일반적으로 사용되는 기체 크로마토그래피/질량분석기로 분석하는 최적의 분석조건을 제공한다. 따라서, 본 발명을 이용할 경우, 우수한 감도, 재현성 향상, 정확성, 분석시간의 단축, 저비용 및 간편성 등을 만족시킬 수 있으며, 이로 인해 인체에 유해한 물질인 3종의 유해 물질을 수질 시료에서 동시에 정량적으로 분석할 수 있어 환경 시료, 특히 수질 시료 분석에 폭 넓게 응용할 수 있다.As described above, the present invention makes it possible to effectively analyze three harmful substances in water samples, which are difficult to simultaneously extract, and have selective and excellent sensitivity to gas chromatography or gas chromatography / mass spectrometer. It also provides optimum analytical conditions for analysis with gas chromatography / mass spectrometers commonly used in the analysis of materials. Therefore, when using the present invention, it is possible to satisfy the excellent sensitivity, reproducibility improvement, accuracy, shortening of analysis time, low cost and simplicity. It can be widely applied to the analysis of environmental samples, especially water samples.
도 1은 본 발명에서 추출용매 및 농축에 따른 추출회수율을 나타낸 것이다.Figure 1 shows the extraction recovery rate according to the extraction solvent and concentration in the present invention.
도 2는 본 발명에서 3종 제초제를 기체 크로마토그래피/질량분석기로 분석된 크로마토그램을 나타낸 것이다.2 shows chromatograms of three herbicides analyzed in the present invention by gas chromatography / mass spectrometry.
도 3은 본 발명에서 유도체화된 3종 제초제의 질량스펙트럼을 나타낸 것이다.Figure 3 shows the mass spectrum of the three herbicides derivatized in the present invention.
도 4는 본 발명에서 정량을 위한 검량곡선을 나타낸 것이다.Figure 4 shows the calibration curve for quantification in the present invention.
Claims (6)
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CN106290615B (en) * | 2016-07-29 | 2018-08-21 | 云南省烟草农业科学研究院 | A kind of micro maleic acid hydrazide separation method |
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US5302531A (en) * | 1992-10-22 | 1994-04-12 | Miles Inc. | Composition for the semiquantitative determination of specific gravity of a test sample |
US5935862A (en) * | 1996-01-19 | 1999-08-10 | The United States Of America As Represented By The Secretary Of The Army | Microspot test methods and field test kit for on-site inspections of chemical agents |
KR20030044662A (en) * | 2001-11-30 | 2003-06-09 | 한국과학기술연구원 | Simultaneous determination method of acidic pesticide |
KR20030078097A (en) * | 2002-03-28 | 2003-10-08 | 한국과학기술연구원 | Determination Method of Glyphosate, Endothall and Chloramben in Water Samples |
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US5302531A (en) * | 1992-10-22 | 1994-04-12 | Miles Inc. | Composition for the semiquantitative determination of specific gravity of a test sample |
US5935862A (en) * | 1996-01-19 | 1999-08-10 | The United States Of America As Represented By The Secretary Of The Army | Microspot test methods and field test kit for on-site inspections of chemical agents |
KR20030044662A (en) * | 2001-11-30 | 2003-06-09 | 한국과학기술연구원 | Simultaneous determination method of acidic pesticide |
KR20030078097A (en) * | 2002-03-28 | 2003-10-08 | 한국과학기술연구원 | Determination Method of Glyphosate, Endothall and Chloramben in Water Samples |
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