Behaviour of the Soil Residues of the Acaricide-Insecticide, [$^{14}C$]Acrinathrin;II. Degradation in Soil

살비살충제 [$^{14}C$Acrinathrin 토양 잔류물의 행적 규명;II. 토양중 분해

In order to elucidate the degrading characteristics of the pyrethroid acaricide-insecticide, acrinathrin in two different types of soils, Soil A(pH, 5.8; organic matter, 3.4%; C.E.C., 115 mmol(+)/kg soil; texture, sandy loam) and Soil B(pH, 5.7; organic matter, 2.0%; C.E.C., 71 mmol(+)/kg soil; texture, sandy loam), residualities of the non-labeled compound under the field and laboratory conditions, extractability with organic solvents and formation of non-extractable bound residues, and degradabilities of [$^{14}C$]acrinathrin as a function of aging temperature and aging period were investigated. The half lives of acrinathrin in Soil A treated once and twice were about 18 and 22 days and in Soil B about 13 and 15 days, respectively, in the field, whereas, in the laboratory, those in Soil A and B were about 36 and 18 days, respectively, suggesting that the compound would be non-persistent in the environment. The amounts of $^{14}CO_2$ evolved from [$^{14}C$]acrinathrin in Soil A and B during the aging period of 24 weeks were 81 and 62%, respectively, of the originally applied $^{14}C$ activity, and those of the non-extractable soil-bound residues of [$^{14}C$]acrinathrin were about 70% of the total $^{14}C$ activity remaining in both soils, increasing gradually with the aging period. Degradation of [$^{14}C$]acrinathrin in both soils increased with the aging temperature. Three degradation products of m/z 198(3-phenoxy benzaldehyde), m/z 214(3-phenoxybenzoic acid), and m/z 228(methyl 3-phenoxybenzoate) as well as an unknown were detected by autoradiography of acetone extracts of both soils treated with [$^{14}C$]acrinathrin and aged for 15, 30, 60, 90, 120, and 150 days, respectively, and the degradation pattern of acrinathrin was identical in both soils. Acrinathrin in soil turned out to be degraded to 3-phenoxybenzaldehyde cyanohydrin by hydrolytic cleavage of the ester linkage adjacent to the $^{14}C$ with a cyano group, the removal of hydrogen cyanide therefrom led to the formation of 3-phenoxybenzaldehyde as one of the major products, and the subsequent oxidation of the aldehyde to 3-phenoxybenzoic acid, followed by decarboxylation would lead to the evolution of $^{14}CO_2$.

Pyrethroid계 살비살충제인 acrinathrin의 물리화학적 특성이 상이한 두 토양중에서의 분해특성을 구명하기 위하여 비표지 화합물을 이용한 포장 및 실내조건에서의 잔류성과 표지화합물을 이용하여 유기용매에 의한 추출율과 추출불가 속박잔류물 형성 및 숙성온도와 숙성기간에 따른 분해성을 검토하였다. 포장실험에서 acrinathrin의 반감기는 약제를 1회와 2회 처리시 토양 A에서는 각각 18과 22일, 토양 B에서는 각각 13과 15일, 실내실험에서는 토양 A와 B에서 각각 36과 18일로서 acrinathrin은 환경중에서 분해가 용이함을 시사하였다. 24주의 숙성기간중 [$^{14}C$]acrinathrin이 무기화되어 방출된 $^{14}CO_2$의 양은 토양 A와 B에서 각각 총처리 방사능의 81과 62%이었으며, 유기용매에 의한 추출불가 토양속박 잔류물의 양은 두 토양 모두 약 70%이었고 숙성기간이 증가함에 따라 점진적으로 증가하는 경향이었다. 토양중 acrinathrin의 분해에 미치는 온도($15{\sim}30^{\circ}C$)의 영향은 숙성 온도가 높을수록 컸다. [$^{14}C$]acrinathrin을 토양에 처리한 후 15, 30, 60, 90, 120, 150일간 숙성한 토양의 acetone 추출액을 autoradiography하여 m/z 198 (3-phenoxybenzaldehyde)과 m/z 214(3-phenoxybenzoic acid) 및 m/z 228(methyl 3-phenoxybenzoic acid)의 분해산물과 1종의 미확인 분해산물을 검출하였으며, 분해 양상은 두 토양에서 유사하였다. Acrinathrin은 토양중에서 cyano group이 결합된 탄소($^{14}C$)에 인접한 ester 결합이 가수분해되어 3-phenoxybenzaldehyde cyanohydrin을 형성한 후 뒤이어 HCN이 제거되어 3-phenoxybenzaldehyde를 생성하고 이것이 다시 3-phenoxybenzoic acid로 산화된 후 decarboxylation에 의하여 $^{14}CO_2$가 방출되는 것으로 판단되었다.